May 2002 

Environmental Technology 

Verification Report 

COOPER ENVIRONMENTAL SERVICES 

XCEM 

MULTI-METALS CONTINUOUS EMISSION 

MONITOR 

Prepared by 

Battelle 

Under a cooperative agreement with 

U.S. Environmental Protection Agency

May 2002 

Environmental Technology Verification


Report


ETV Advanced Monitoring Systems Center 

Cooper Environmental Services


XCEM


Multi-Metals Continuous Emission Monitor


by


Jeffrey Myers


Thomas Kelly


Charles Lawrie


Karen Riggs


Battelle


Columbus, Ohio 43201

Notice 

The U.S. Environmental Protection Agency (EPA), through its Office of Research and 

Development, has financially supported and collaborated in the extramural program described 

here. This document has been peer reviewed by the Agency and recommended for public release. 

Mention of trade names or commercial products does not constitute endorsement or 

recommendation by the EPA for use. 

ii 
Foreword


The U.S. EPA is charged by Congress with protecting the nation’s air, water, and land resources. 

Under a mandate of national environmental laws, the Agency strives to formulate and implement 

actions leading to a compatible balance between human activities and the ability of natural 

systems to support and nurture life. To meet this mandate, the EPA’s Office of Research and 

Development provides data and science support that can be used to solve environmental 

problems and to build the scientific knowledge base needed to manage our ecological resources 

wisely, to understand how pollutants affect our health, and to prevent or reduce environmental 

risks. 

The Environmental Technology Verification (ETV) Program has been established by the EPA to 

verify the performance characteristics of innovative environmental technology across all media 

and to report this objective information to permitters, buyers, and users of the technology, thus 

substantially accelerating the entrance of new environmental technologies into the marketplace. 

Verification organizations oversee and report verification activities based on testing and quality 

assurance protocols developed with input from major stakeholders and customer groups 

associated with the technology area. ETV consists of six environmental technology centers. 

Information about each of these centers can be found on the Internet at http://www.epa.gov/etv/. 

Effective verifications of monitoring technologies are needed to assess environmental quality and 

to supply cost and performance data to select the most appropriate technology for that assessment. In 1997, through a competitive cooperative agreement, Battelle was awarded EPA funding 

and support to plan, coordinate, and conduct such verification tests for “Advanced Monitoring 

Systems for Air, Water, and Soil” and report the results to the community at large. Information 

concerning this specific environmental technology area can be found on the Internet at 

http://www.epa.gov/etv/07/07_main.htm. 

iii 
Acknowledgments


The authors wish to acknowledge the several agencies and people who contributed to the conduct 

of this verification. We acknowledge K. James Hay of the U.S. Army Corps of Engineers, 

Engineer Research and Development Center, Construction Engineering Research Laboratory, for 

his overall support and direction of the test activities. We also thank Dee Russell and the staff of 

the conventional munitions deactivation furnace at the Tooele Army Depot for their cooperation 

and guidance in the verification activities. Reference method sampling and chemical analysis 

were conducted by the U.S. Army Center for Health Promotion and Preventive Maintenance; 

operations at the Tooele Army Depot were led by Mike Pattison. Steve Bryson of MSE 

Technology Applications, Inc., Butte, Montana, directed spiking of metal solutions into the 

deactivation furnace flue gas. 

iv 
Contents


Notice ...................................................................... ii 


Foreword ................................................................... iii 


Acknowledgments ........................................................... iv 


List of Abbreviations ......................................................... viii 


1. Background ................................................................ 1 


2. Technology Description ...................................................... 2 


3. Test Design and Procedures .................................................... 4 


3.1 Introduction ....................................................... 4 


3.2 Test Facility ....................................................... 4 


3.3 Test Schedule ...................................................... 8 


3.4 Experimental Design ................................................ 9 


3.5 Data Comparisons ................................................. 10 


3.6 Material and Equipment ............................................ 12 


4. Data Quality .............................................................. 14 


4.1 Deviations from the Test/QA Plan .................................... 14 


4.2 Facility Calibrations ............................................... 15 


4.3 M29 Sampling and Analysis ......................................... 15 


4.3.1 M29 Detection Limits and Blank Results .......................... 15 


4.3.2 M29 Analytical Duplicates ..................................... 16 


4.3.3 M29 Precision ............................................... 17 


4.4 Audits .......................................................... 17 


4.4.1 Technical Systems Audit ...................................... 17 


4.4.2 Performance Evaluation Audits ................................. 19 


4.4.3 Data Quality Audit ........................................... 22 


5. Statistical Methods ......................................................... 23 


5.1 XCEM Concentration .............................................. 23 


5.2 Relative Accuracy ................................................. 23 


5.3 Correlation with Reference Method ................................... 24 


5.4 Precision ........................................................ 24 


v 
5.5 Span, Zero, and Internal Standard Drift ................................. 24 


5.6 M29 Bias and XCEM Bias Relative to M29 ............................. 25 


6. Test Results ............................................................... 26 


6.1 XCEM Concentration .............................................. 26 


6.2 Relative Accuracy ................................................. 31 


6.3 Correlation with Reference Method ................................... 34 


6.4 Precision ........................................................ 34 


6.5 Span, Zero, and Internal Standard Drift ................................. 36 


6.6 XCEM Bias Relative to M29 ........................................ 38 


6.7 Response Time ................................................... 38 


7. Performance Summary ...................................................... 40 


8. References ................................................................ 41 


Appendix A. XCEM Data During M29 Runs ..................................... A-1 


Figures 

Figure 2-1. XCEM Supplied by CES ............................................. 2 


Figure 2-2. XCEM Housing and Gas Transport System at TEAD ...................... 3 


Figure 2-3. XCEM Extraction System, Cassette, and Chassis .......................... 3 


Figure 3-1. Deactivation Incinerator at TEAD Incinerator ............................ 5 


Figure 3-2. TEAD Incinerator Stack ............................................. 8 


Figure 6-1. XCEM and M29 Data During Verification Test .......................... 28 


Figure 6-2. Uncorrected XCEM Arsenic Concentrations vs.


XCEM Lead Concentrations ......................................... 32 


Figure 6-3. Correlation Between XCEM and M29 ................................. 35 


Figure 6-4. XCEM Palladium Internal Standard Readings During M29 Testing .......... 38 


vi 
Tables 

Table 3-1. Typical Operating Parameters for the TEAD Incinerator ................... 5 


Table 3-2. TEAD Incinerator Metal Emission Limits During Verification Testing ........ 8 


Table 3-3. XCEM Test Dates and Associated TEAD Incineration Feedstreams .......... 9 


Table 3-4. Tooele Metal Emission Limitations and Target Spiking Levels ............. 10 


Table 3-5. Summary of Data to be Obtained During XCEM Verification Test .......... 11 


Table 4-1. Estimated Detection Limits for Analysis of Metals by M29 ................ 16 


Table 4-2. Flue Gas Metals Concentrations Determined by Duplicate M29 Trains


at the TEAD Incinerator ............................................ 18 


Table 4-3. Summary of RPD Results from Duplicate M29 Trains


in XCEM Verification ............................................. 19 


Table 4-4. Summary of PE Audit Results on M29 Sampling Equipment


in XCEM Verification Test ......................................... 20 


Table 4-5. Results of Field Spikes of M29 Trains ................................ 21 


Table 6-1. Summary of Results from XCEM and M29 for Each Test Run ............. 27 


Table 6-2. Relative Accuracy Results for XCEM ................................. 32 


Table 6-3. Correlation Between XCEM and M29 ................................. 35 


Table 6-4. XCEM Precision ................................................. 36 


Table 6-5. XCEM Span and Zero Readings During Verification Testing .............. 37 


Table 6-6. XCEM Bias Relative to M29 ........................................ 39 


vii 
List of Abbreviations 

AMS Advanced Monitoring Systems 

Ag silver 

APE Ammunition Peculiar Equipment 

As arsenic 

As2O5 arsenic oxide 

Ba barium 

Ba(NO3)2 barium nitrate 

Be beryllium 

BTU/hr British thermal units per hour 

Cd cadmium 

Cd(NO3)2 cadmium nitrate 

CEM continuous emission monitor 

CEMS continuous emission monitoring systems 

CES Cooper Environmental Services (of Beaverton, Oregon) 

CHPPM Center for Health Promotion and Preventive Medicine, U.S. Army 

CO carbon monoxide 

CO2 carbon dioxide 

Cr chromium 

CrO3 chromium trioxide 

DLS Directorate of Laboratory Sciences 

dscm dry standard cubic meter 

EPA United States Environmental Protection Agency 

ETV Environmental Technology Verification program 

Hg mercury 

Hg(NO3)2 mercury (II) nitrate 

ID internal diameter 

K2(C4H2O6Sb)2 potassium antimony tartrate 

mg milligram 

M29 EPA Method 29 

M301 EPA Method 301 

ml milliliter 

MSE-TA MSE Technology Applications Inc. (of Butte, Montana) 

Ni nickel 

Ni(NO3)2 nickel nitrate 

O2 oxygen 

Pb lead 

Pd palladium 

PE performance evaluation 

PLC programmable logic circuit 

ppm parts per million 

viii 
PS-10	 Performance Standard 10 (EPA’s proposed standard for multi-metal 

CEMS) 

QA	 quality assurance 

QC	 quality control 

QMP	 quality management plan 

RA	 relative accuracy 

RCRA	 Resource Conservation and Recovery Act 

RPD	 relative percent difference 

RSD	 relative standard deviation 

Sb	 antimony 

scfm	 standard cubic feet per minute 

Se	 selenium 

TEAD	 Tooele Army Depot 

Tl	 thallium 

TSA	 technical systems audit 

WFRMS	 waste feed rate monitoring system 

XCEM	 X-ray based continuous emission monitor 

XRF	 X-ray fluorescence 

Zn	 zinc 

Zn(NO3)2	 zinc nitrate 

ZnO	 zinc oxide 

�g 	microgram 

�g/m3	 micrograms per cubic meter 

ix 
Chapter 1


Background


The U.S. Environmental Protection Agency (EPA) has created the Environmental Technology 

Verification (ETV) Program to facilitate the deployment of innovative environmental technologies through performance verification and dissemination of information. The goal of the 

ETV Program is to further environmental protection by substantially accelerating the acceptance 

and use of improved and cost-effective technologies. ETV seeks to achieve this goal by 

providing high-quality, peer-reviewed data on technology performance to those involved in the 

design, distribution, financing, permitting, purchase, and use of environmental technologies. 

ETV works in partnership with recognized standards and testing organizations; with stakeholder 

groups that consist of buyers, vendor organizations, and permitters; and with the full participation 

of individual technology developers. The program evaluates the performance of innovative 

technologies by developing test plans that are responsive to the needs of stakeholders, conducting 

field or laboratory tests (as appropriate), collecting and analyzing data, and preparing peerreviewed reports. All evaluations are conducted in accordance with rigorous quality assurance 

(QA) protocols to ensure that data of known and adequate quality are generated and that the 

results are defensible. 

The EPA’s National Exposure Research Laboratory and its verification organization partner, 

Battelle, operate the Advanced Monitoring Systems (AMS) Center under ETV. The AMS Center 

recently evaluated the performance of a continuous emission monitor for multiple metals in stack 

gas. This verification report presents the procedures and results of the verification test for that 

instrument, the X-ray based continuous emission monitor (XCEM) from Cooper Environmental 

Services (CES). 

1

Chapter 2


Technology Description


The objective of the ETV AMS Center is to verify the performance characteristics of environmental monitoring technologies for air, water, and soil. This verification report provides results 

for the verification testing of the XCEM. The following description of the XCEM is based on 

information provided by the vendor. 

The XCEM (Figure 2-1) extracts a sample of stack gas and concentrates the metals of interest on 

a chemically treated filter tape. Following collection, the filter tape advances, moving the sample 

spot to an analysis area where a laboratory-grade X-ray fluorescence (XRF) instrument is used to 

determine metal mass. The system is automated and produces concentration data every 10 to 

20 minutes for 19 elements of interest. The XCEM components are divided into three major 

categories: the extraction system, the sampling and analysis system, and the control system. 

The XCEM extraction system collects a representative stack 

gas sample from the stack and transports the sample to the 

filter tape. For this project, the U.S. Army provided the 

sample probe and insulated sample line, as well as the enclosure for housing the XCEM (Figure 2-2). The stack gas 

temperature was monitored where it enters the XCEM 

enclosure, and testing was conducted only when this 

temperature was above the dew point for water. Upon 

entrance into the XCEM housing, the stack gas passes 

through a heat-traced stilling chamber that expands the 

tubing diameter and slows the gas velocity (Figure 2-3). An 

eductor, located downstream of the stilling chamber, is used 

to pull the stack gas through the extraction system. Of the 

two to three standard cubic feet per minute (scfm) that pass 

through the stilling chamber, a sub-sample of approximately 

0.8 liter per minute is extracted and directed through a filter 

tape, concentrating the metals sample for analysis. 

2 

Figure 2-1. XCEM Supplied by 

CES 
Figure 2-2. XCEM Housing and Gas 

Transport System at TEAD 

Following filtration, the stack gas is subsequently 

transported to the XCEM chassis where drying 

and volume determination take place (Figure 2-3). 

The excess (i.e., unfiltered) stack gas is transported out of the stilling chamber through a 

flowmeter and is vented or returned to the stack. 

The sampling cassette holds a four-week supply of 

filter tape on a reel-to-reel system that is automated to accurately move the tape from the 

sampling to the analysis position. Sampling and 

analysis occur simultaneously, resulting in a 

continuous monitoring system that produces metal 

concentration values every 10 to 20 minutes. 

Metal mass on the filter is determined using a 

modified ThermoNoran QuanX energy dispersive 

XRF analyzer. The QuanX is capable of simultaneously measuring 19 elements and a palladium 

(Pd) quality control (QC) standard. Although the 

QuanX can readily quantify elements with atomic 

number 13 and above, the XCEM-modified 

QuanX is most efficient at quantifying and 

reporting hazardous elements with an atomic 

number greater than 24 (Cr). Since XRF is nondestructive, the filtrate on the tape can be 

reanalyzed at a later date if the end-user requires additional data. 

The XCEM is controlled by a personal computer using a custom WonderWare(1) software 

interface. All day-to-day functions of the XCEM have been automated, including flow and 

temperature control, concentration determination, and QA routines. Flow, temperature, 

concentration, pressure, and error messages are automatically recorded in a secure database. The 

data can be 

imported into 

Excel or an equivalent program for 

subsequent 

analysis. Flows, 

temperatures, 

concentrations, 

and pressure are 

logged in real time 

on the screen 

computer monitor. 

3 

Figure 2-3. XCEM Extraction System, Cassette, and Chassis 
Chapter 3


Test Design and Procedures


3.1 Introduction 

This verification test was conducted according to procedures specified in the ETV Test/QA Plan 

for Pilot-Scale Verification of Continuous Emission Monitors for Multi-Metals.

(2) The overall 

objective of the verification test was to provide quantitative evaluation of the performance of the 

XCEM under real-world conditions. The test activities provided data for verification of the 

following performance parameters of the XCEM: 

� Relative accuracy 

� Correlation with reference method 

� Precision 

� Span, zero, and internal standard drift 

� Bias 

� Response time. 

Relative accuracy, correlation with the reference method, and precision (i.e., repeatability at 

stable test conditions) were assessed for all of the elements being measured by the XCEM. The 

reference method in the assessment of relative accuracy and correlation was EPA Method 29(3) 

(M29). Precision was assessed in terms of the variability of XCEM response during periods when 

the stack gas flow rate and volume and the isokinetic rate were stable. The XCEM has an automated check for drift that measures a Pd internal standard with each XCEM test run. Drift also 

was checked by daily XCEM span and zero QA measurements. Bias was identified using EPA 

Method 301(4) (M301) protocols. Response time was determined as the time between the start of 

one sampling period and the beginning of a second sampling period. 

3.2 Test Facility 

Verification testing took place at the U.S. Army’s Tooele Army Depot (TEAD) in Tooele, Utah, 

TEAD Building 1320 deactivation incinerator (APE-1236M1) (Figure 3-1). This section 

describes the TEAD incinerator and the procedures for operating it for this test. The TEAD 

incinerator is currently regulated under the Resource Conservation and Recovery Act (RCRA) 

for antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), cadmium (Cd), chromium (Cr), 

lead (Pb), mercury (Hg), nickel (Ni), selenium (Se), silver (Ag), and thallium (Tl). Of the twelve 

regulated elements, five are typically found in the feedstream–Sb, Ba, Cd, Cr, and Pb, whereas 

only Pb is typically found in the stack gas. The XCEM was tested for its ability to measure the 

4

Figure 3-1. Deactivation Incinerator at TEAD 

five elements found in the feedstream, as well as As, Hg, Ni, and a 

nonregulated metal, zinc (Zn). 

Except for Pb, the stack gas levels 

of these target metals were 

prepared by spiking metal solutions 

into the stack gas at the base of the 

stack.(5) These elements were 

selected to challenge the XCEM 

over a large range of analysis 

conditions and elemental 

concentrations. 

The TEAD incinerator, which runs 

on diesel fuel, is designed to 

incinerate decommissioned 

conventional munitions. Typical 

operating parameters for the incinerator are shown in Table 3-1. The TEAD incinerator is 

classified as a dry stack with water content ranging from 5 to 10%. Typical stack particulate 

matter concentrations are in the 10 milligram per dry standard cubic meter (mg/dscm) range. A 

number of sensors (temperature, gas flow, pressure differential, combustion gases, etc.) are used 

to monitor operating conditions at various points in the system. Signals from these sensors are 

monitored and compared with preset operating standards. The incinerator consists of a main 

control panel, continuous emission monitoring systems (CEMS), waste feed rate monitoring 

system (WFRMS), dual conveyor feed system, rotary furnace, furnace shroud, cyclone, afterburner, discharge conveyor, high-temperature cast ceramic filters baghouse, high-temperature 

draft fan, and exhaust stack. These components of the incinerator are described below. 

Table 3-1. Typical Operating Parameters for the TEAD Incinerator 

Parameter Typical Value 

Afterburner Temp. (�F) 1,630 

Baghouse ∆P (in. H2O) 4 

Baghouse Inlet Temp. (�F) 860 

Kiln Feed End Draft Pressure (in. H2O) -0.2 

Kiln Feed End Temp. (�F) 375 

Kiln Burner End Temp. (�F) 1,000 

O2 – CEM (%) 15 

CO (ppm) 8 

Stack Temp. (�F) 500 

Stack Gas Velocity (ft/sec) 46 

5

� Main Control Panel. The main control panel contains various pieces of control equipment to 

monitor and control the furnace operation. Process controllers are used to control the rotary 

furnace feed end temperature, negative pressure in the furnace, and afterburner temperature. 

A multi-point digital recorder is used to record process parameters. Logic control for the 

furnace is performed by a programmable logic circuit (PLC). The PLC controls the motor 

starters, the WFRMS, safety interlocks, and alarms. The computer system is an industrialbased machine, running data acquisition software that provides centralized and integrated 

data management, process graphics, operator interface, and report generation. 

�	 CEMS. CEMS are in place to measure carbon monoxide (CO) and oxygen (O2) in the 

exhaust stack. The CEMS include a sample extraction probe, heat-traced sampling lines, 

calibration ports, a refrigerated condenser, a sample pump, filters, and flow meters. The 

sample extraction port is located in the exhaust stack approximately 20 feet above grade. The 

CEMS include automatic calibration, which allows the monitors to be calibrated periodically 

without operator intervention. 

� WFRMS. The WFRMS controls the furnace feed rate. The WFRMS consists of a precision 

explosion-proof scale, a push-off box, and a slide chute. The scale reports the measured 

weight to the PLC via a serial communication cable. The PLC verifies that the weight is less 

than or equal to the established limit for the item being incinerated. Once the PLC has 

verified that the weight is acceptable, the push-off box pushes the ammunition item onto the 

slide chute, which is over the primary feed conveyor. The WFRMS is capable of cycling 

every 15 seconds. 

� Dual Conveyor Feed System. The primary waste feed conveyor transports the munitions 

from the WFRMS through the concrete wall into the barricade area. The ammunition is then 

fed onto the secondary feed conveyor, which deposits the ammunition into the rotary furnace 

feed chute. If an out-of-parameter condition arises, the primary feed conveyor is stopped until 

the condition is corrected. However, for safety reasons, the secondary conveyor continues to 

operate. This allows munitions near the high-temperature end of the kiln to continue moving 

through the furnace and deters possible explosions outside the furnace. 

� Rotary Furnace. The rotary furnace is designed to ignite the ammunition items and 

effectively incinerate reactive components from the metal shells. The heat to ignite the 

ammunition is initially provided by fuel oil forming a countercurrent to the movement of the 

ammunition through the rotary furnace. Combustion gases and entrained ash exit the furnace 

adjacent to the feed chute. Nonentrained ash and the metal components of the ammunition 

are discharged at the burner end of the rotary furnace. The ammunition is propelled through 

the 20-foot-long, 30.5-inch-diameter retort toward the burner end by spiral flights. As the 

ammunition approaches the flame, it either detonates or burns freely, depending on the 

ammunition characteristics. The thick-cast steel walls contain high-order detonations. Feed 

rates, residence times, and operating parameters have been established for each ammunition 

item by controlled testing. The rotary furnace is equipped with a Hauck 783 proportioning 

burner located at the discharge end. The burner has a capacity of 3 million British thermal 

units per hour (BTU/hr) and a nominal turndown ratio of 4:1. The feed end temperature of the 

6

furnace ranges between 350 to 450�F, while the discharge end ranges from 800 to 1,100�F 

during normal operation. The rotary furnace is operated under a slight negative pressure. 

� Furnace Shroud. A metal shroud that completely encloses the retort sections, the draft fan, 

and the retort combustion air fan controls fugitive emissions from the rotary furnace. The 

draft fan is used to maintain negative pressure at the feed end of the furnace. The retort 

combustion air fan draws air from the area beneath the retort shroud, creating a negative 

pressure. The combustion air blower creates a negative pressure inside the shroud, which 

pulls any fugitive emissions through the blower and discharges them into the furnace via the 

furnace burner. 

� Cyclone. Large particles are removed from the gas stream by the cyclone. The cyclone has a 

90 to 95% removal efficiency for particles 10 microns and larger. The cyclone rotates clockwise, with inlet and outlet ducts at 90� separation. Collected material is removed from the 

cyclone at the bottom by a double tipping valve. The valve has two gates that are motor 

driven. The gates open alternately so that only one gate is open at any time, thus maintaining 

the negative pressure. 

� Afterburner. The afterburner is built by Southern Technology Incorporated. The afterburner 

is designed to raise the temperature of the exhaust gases exiting from the kiln. This elevated 

temperature, and the added residence time, enhances the complete combustion of the 

explosive. The afterburner is capable of heating 4,000 scfm of flue gas from 350 to 450�F to 

over 1,600�F with a minimum flue gas residence time of 2 seconds. A diesel fuel burner with 

a propane pilot ignition system heats the afterburner. The afterburner is equipped with a 

Hauck WR0164 wide-range burner with a capacity of 8 million BTU/hr and nominal 

turndown ratio of 10:1. 

� Discharge Conveyor. The solid waste exits the furnace by the discharge conveyor located at 

the discharge/burner end. The solid waste is typically composed of metal casings, melted lead 

projectiles, and residual ash. The low end of the discharge conveyor is located underneath the 

discharge/burner end of the rotary furnace. The high end of the conveyor passes through the 

concrete barricade wall and deposits the waste into containers. 

� High-Temperature Cast Ceramic Filters Baghouse. The baghouse is a high-temperature 

cast ceramic collector, used for final particulate cleansing for the gas stream. The baghouse 

was designed and built by JT Systems Incorporated. The flue gases from the afterburner are 

transported to the baghouse by 120 feet of 30-inch-diameter stainless steel ducting. The 

ducting is long enough to produce a temperature drop from 1,600�F at the exit of the 

afterburner to less than 1,000�F entering the baghouse. The baghouse contains 154 cerafil 

ceramic candles that are 5.75 inches in diameter and 10 feet long. This results in a total filter 

area of 2,330 square feet with a filtration velocity of 4.97 feet per second. The baghouse 

operates with a delta pressure range of 0.5 to 6.0 inches of water column. Collected material 

settles into the hopper below and is exhausted through a double tipping gate valve into a 

sealed 55-gallon drum while maintaining an air seal on the baghouse assembly. 

7

� High-Temperature Draft Fan. The gas 

stream is pulled though the baghouse by an 

induced draft fan. The fan is a Fan Equipment Company Model M-21 I.E. The fan is 

capable of pulling 6,700 actual cubic feet 

per minute at a draft (negative pressure) of 

30 inches of water column. 

� Exhaust Stack. The A36 carbon steel, 

circular exhaust stack is approximately 

30 feet high (34 feet with extension) and 

has a nominal ID of 20 inches (Figure 3-2). 

For the verification test, metals in the TEAD 

incinerator stack gas were regulated under a 

temporary authorization permit. The hourly 

emission limits for each regulated metal are 

shown in Table 3-2. Of the 12 regulated metals, 

five are typically found in the feedstream (Pb, 

Sb, Ba, Cd, and Cr); however, Pb is the only 

element that is routinely found in measurable 

concentrations in the stack gas. Consequently, 

the other metals were introduced by spiking 

metals solutions into the stack. 

Table 3-2. TEAD Incinerator Metal Emission Limits During Verification Testing 

Figure 3-2. TEAD Incinerator Stack 

Element Limit (g/hr) Element Limit (g/hr) 

Antimony (Sb) 14 Lead (Pb) 4.3 

Arsenic (As) 0.11 Mercury (Hg) 14 

Barium (Ba) 2,400 Nickel (Ni) 930 

Beryllium (Be) 0.20 Selenium (Se) 180 

Cadmium (Cd) 0.26 Silver (Ag) 140 

Chromium (Cr) 0.04 Thallium (Tl) 14 

3.3 Test Schedule 

Setup for the XCEM verification test took place at the TEAD incinerator during the week of 

May 7, 2001. The XCEM verification test occurred over a four-day period on May 14, 15, 16, 

and 17, 2001. A total of 13 M29 runs were conducted, for two hours each, consisting of three 

8 
runs on May 14, four runs on May 15, four runs on May 16, and two runs on May 17. All nine 

metals of interest were tested during each run; however, lower concentrations of Hg, Ni, Sb, and 

Zn were spiked into the stack gas during the last six runs. 

3.4 Experimental Design 

Both the kiln and afterburner were fired with diesel fuel for all 13 test runs. Table 3-3 shows the 

incinerator feedstreams for the 13 M29 runs. During M29 Runs 1 and 2, M17 .50-caliber bullets 

were incinerated. However, during these runs, the XCEM observed excessively high lead 

concentrations, which were traced to a problem in the bypass damper valve in the incinerator 

baghouse. This led to a decision not to incinerate additional ammunition during the test until 

repairs to the bypass valve could be made. For this reason, no ammunition was burned during test 

Runs 3 through 11. Following the bypass repair, two final M29 runs were conducted while 

incinerating Mark 344 fuses. Table 3-4 shows the emission limits and target spiking concentrations for the nine elements that were measured by the XCEM during all 13 of the verification 

test runs. In all test runs, eight of these metals were spiked directly into the stack upstream of the 

XCEM and M29 sampling locations.(5) These metals were spiked at the level shown in Table 3-4. 

Pb, however, was not spiked since the incinerated munitions provide measurable concentrations 

of lead without spiking. Note that, for Hg, Ni, Sb, and Zn, different spike levels were used in 

Runs 1-7 than in Runs 8-13. 

Table 3-3. XCEM Test Dates and Associated TEAD Incineration Feedstreams 

May 14 May 15 May 16 May 17 

Run Run Run Run Run Run Run Run Run Run Run Run Run 

1 2 3 4 5 6 7 8 9 10 11 12 13 

M17 M17 No No No No No No No No No Mark Mark 

.50 .50 Ammo Ammo Ammo Ammo Ammo Ammo Ammo Ammo Ammo 344 344 

caliber caliber Fuses Fuses 

Three separate solutions were prepared for the spike injections.(5) The first solution contained 

arsenic oxide (As2O5), cadmium metal, and chromium trioxide (CrO3), dissolved in a dilute nitric 

acid solution. The second solution contained mercury (II) nitrate (Hg(NO3)2), nickel nitrate 

(Ni(NO3)2), and zinc oxide (ZnO), dissolved in dilute nitric acid. The final solution contained 

potassium antimony tartrate (K2(C4H2O6Sb)2) and barium nitrate (Ba(NO3)2), dissolved in 

water.(5) Spiking was conducted by MSE Technology Applications Inc. (MSE-TA), using three 

atomizers to inject solutions containing the metals of interest directly into the base of the stack. 

Manufacturer specifications for the atomizers establish droplet size distributions based on 

pressure and airflow space rate. For these tests, pressure and flow rate were maintained to keep 

droplet sizes less than 28 microns in diameter. When dried, the majority of the mass was calculated to be in the one to four micron range. M29 results(6) showed that 10 to 15% of the spiked 

metal mass was collected in the sampling probe of the M29 train. This result is typical for M29 

sampling at an incinerator and may indicate that the spiked metal particle size range was similar 

to other incinerators. Spiking of metals solutions continued at a constant rate throughout 

9

Table 3-4. Tooele Metal Emission Limitations and Target Spiking Levels 

� �

Emission Limitsa ( g/dscm) Target Spiking Levela

 ( g/dscm) 

M29 Runs 1-7 M29 Runs 8-13 

As 25 14 14 

Ba 540,000 200 200 

Cd 58 34 34 

Cr 10 5 5 

Hg 3,145 280 88 

Ni 209,000 460 180 

Pb 966 NS NS 

Sb 3,145 520 200 

Zn NR 460 180 

a The concentration in �g/dscm assumes a stack flow rate of about 4,474 dscm/hr. 


NR = not regulated


NS = not spiked


each test day, to assure constant flue gas metals content. That is, the spiking process was 

continuous, and was not turned on and off, e.g., to coincide with M29 sampling intervals. 

Additional information on the spiking procedures and results can be found in the MSE-TA report 

to the U.S. Army Corps of Engineers.(5) 

Stack gas metal concentrations were simultaneously determined by the XCEM and two M29 

sampling trains. The M29 trains sampled for two hours, while XCEM data, which are recorded 

every 20 minutes, were averaged for the M29 test run. A total of 13 dual M29 test runs were 

performed by the U.S. Army Center for Health Promotion and Preventive Medicine (CHPPM) 

Air Quality Surveillance Program.(6) In all cases, when reference method data were being taken, 

the spiking of the indicated metals was held constant throughout the entire sampling period.(5) 

The intent of this approach was to allow comparisons of XCEM data with reference method data 

under constant conditions. CHPPM’s Directorate of Laboratory Sciences (DLS) conducted 

laboratory analysis of the sampling trains.(6) 

Sample handling, analysis, and all associated QA/QC activities conformed to the requirements of 

M29.(6) Accuracy data for metal analysis were confirmed with two field spikes of the nine 

measured metals into blank sampling trains. Media blanks of the M29 solutions and filter were 

also analyzed. Sample integrity was maintained using chain of custody and a designated sample 

custodian. Unique sample identification numbers were implemented so that final data used for 

verification could be traced back through the analytical process to the original sample. Data 

quality results for the M29 reference data are presented in Section 4.3. 

3.5 Data Comparisons 

This section describes how the reference and CEM data were used and compared to quantify the 

performance of the XCEM. Table 3-5 summarizes the data used for the verification comparisons. 

10

Table 3-5. Summary of Data to be Obtained During XCEM Verification Test 

Performance No. of 

Parameter Objective Comparison Based On Data Pointsa 

Accuracy Determine degree of quantitative 

agreement with reference method 

Reference method results 13 

Correlation Determine degree of correlation with 

reference method 

Reference method results 13 

Precision Determine XCEM precision during 

periods when stack and spiking 

conditions are held constant 

XCEM readings during constant 

operating and spiking conditions 

6 per run 

Span and Zero 

Drift 

Determine XCEM response to 

calibration and blank samples 

XCEM automated daily QA 

routine 

4 

Internal Standard 

Drift 

Determine XCEM ability to measure 

consistently over the course of the test 

Determine variation in palladium 

concentrations determined with 

each XCEM measurement 

6 per run 

Bias Determine if inter-method bias exists Reference method results 13 

between M29 and the XCEM 

Response Time Determine XCEM response time as a 

batch CEM 

XCEM cycle time in continuous 

monitoring of metal 

concentrations 

6 per run 

a

Number of data points used in the verification for each target metal. 

Relative accuracy was verified by comparing the CEM results against the M29 results for each 

metal. The total train results were combined for the relative accuracy calculations. Precision of 

the dual M29 sampling trains for each run was determined by a comparison of the dual M29 

sample runs using an M301 approach. M29 results that were identified as outliers were reported, 

but were not used for verification. The intent of this approach was to provide a valid set of 

reference data for verification purposes, while also illustrating the degree of variability of the 

reference method. Identification of outliers was based upon analysis of percent differences in 

M29 concentrations between sampling trains, and trends in data throughout the test day. In any 

case, where rejection of a reference result was suggested, an effort was made to find an 

assignable cause for the divergent result. For valid test runs, M29 concentrations were averaged 

and compared with reported XCEM data. 

Correlation of the XCEM with M29 was verified using the same data used to assess relative 

accuracy. Correlation was calculated for each metal measured by the XCEM. 

Precision of the XCEM was established based on the successive XCEM readings during the M29 

runs, when spike injections and incinerator conditions were stable. The percent relative standard 

deviation (RSD) of the successive readings was determined for each metal within each M29 run, 

as an indication of the precision of the XCEM. 

Span and zero determinations also were conducted daily by the XCEM. The automated XCEM 

span routine extended a plunger containing four of the metals of interest (Cd, Cr, Hg, and Pb) 

into the analysis area. The plunger was analyzed by the XCEM in the same manner as for a 

sample spot on the tape. Zero readings were determined by analysis of blank filter tape. The 

variation in span and zero readings was determined as an indicator of instrument drift. Internal 

11

standard drift also was determined by evaluation of XCEM-reported palladium concentrations. 

As part of the XCEM QA program, a palladium rod was permanently fixed above the X-ray 

beam and below the filter tape. The palladium rod was measured with each sample and a running 

record of the reported Pd concentrations was maintained. The %RSD for palladium concentrations indicated the XCEM internal standard drift during testing. 

Bias was determined relative to the M29 sample results using M301. First, M29 sample trains 

were compared with each other to determine any significant bias. M29 data sets that did not show 

significant intra-method bias were averaged, and the average results were compared with the 

XCEM reported concentrations. 

The XCEM sampled for 10 to 20 minutes, depending upon the desired detection limits. Within a 

few seconds of sampling, the exposed tape was moved into the XRF analysis region. Analysis 

required the same amount of time as sampling. Following analysis, concentrations were determined and recorded in a fraction of a second. For these tests, the response time was determined 

as the average time from the start of one sampling period to the start of the next sampling period, 

with a delay in the reporting of data that was equivalent to the analysis time. 

Setup and maintenance needs were documented qualitatively, both through observation and 

through communication with the CEM vendor during the test. Factors noted included the 

frequency of scheduled maintenance activities, the downtime of the CEM, and the number of 

staff operating or maintaining it during the verification test. 

3.6 Material and Equipment 

The XCEM requires about 10 scfm of dry compressed gas (e.g., air or nitrogen) to provide a 

vacuum in the extraction system. A small amount of purified compressed gas also is used to 

drive the XCEM pneumatics. The atomizers used for spiking required about 10 scfm of dry air. 

The spike injection solutions included Ba(NO3)2, Cd(NO3)2, Cr(NO3)3, As2O5, Hg(NO3)2, 

Ni(NO3)2, Zn(NO3)2, and Sb(NO)3. Solutions were prepared on-site to allow for flexibility in 

responding to background metal concentrations found in the TEAD incinerator. 

The glassware, filters, and associated equipment for M29 sampling were supplied by CHPPM. 

Multiple trains were supplied so that at least six trains (i.e., three sampling runs with two trains 

each) could be sampled in a single day, in addition to at least two M29 field spikes and a media 

blank. Preparation, sampling, sample recovery, and cleaning of used trains were the 

responsibility of CHPPM during this verification test. 

CHPPM provided laboratory equipment for sample recovery and analysis. This included all 

chemicals and solutions for rinsing train components and recovering impinger samples, as well 

as cold vapor atomic absorption or atomic fluorescence spectroscopy equipment for mercury 

determination at the DLS. 

The verification also made use of monitoring equipment already integrated into the TEAD 

facility. This equipment included monitors for major flue gas constituents [O2, carbon dioxide 

12

(CO2)], as well as sensors for temperature and pressure. These devices were considered part of 

the TEAD facility for purposes of this test and were operated during this verification according to 

normal TEAD procedures. 

13

Chapter 4


Data Quality


4.1 Deviations from the Test/QA Plan 

The quality of the verification data was assured by QA/QC procedures, performed in accordance 

with the quality management plan (QMP) for the AMS Center(7) and the test/QA plan(2) for this 

verification test. Deviations from the test/QA plan were documented in the verification records 

during testing at the TEAD facility. Deviations required the approval of Battelle’s AMS Center 

Manager. The following deviations were documented and approved: 

� The higher concentration metal injection solutions were used first, and then the lower 

concentration solutions, which is opposite to the order stated in the test/QA plan. This 

was done at the request of CES staff to provide the stronger signal to assess XCEM 

operation at the start of the verification test. 

� Ba was spiked to produce a level of 200 micrograms per cubic meter (�g/m3

) in the flue 

gas, rather than 1,000 �g/m3

, as stated in the test/QA plan. This change was planned 

before the testing began, but was inadvertently not corrected in the test/QA plan. 

� Four M29 sampling runs per day were performed on May 15 and 16, instead of three runs 

per day, as stated in the test/QA plan. This change was made necessary by delays in the 

start of the verification test. 

� Thirteen M29 runs were performed, instead of 12, as stated in the test/QA plan. The 13 

runs were performed as follows: three on May 14, four on May 15, four on May 16, and 

two on May 17. The 13th M29 run was added to ensure that six runs were completed with 

the low concentration spiking solutions, as planned (the first seven runs having been 

completed with the high concentration spiking solutions). 

� The test/QA plan states that Mark 344 fuses would be the feedstream for the TEAD 

incinerator throughout verification of the XCEM. Because of a shortage of such fuses, 

and subsequent problems with the incinerator baghouse, the Mark 344 fuses were used 

only for the last two M29 test runs (Runs 12 and 13). M17 .50 caliber ammunition was 

fed into the incinerator for the first two test runs (Runs 1 and 2), and no ammunition was 

fed during Runs 3 through 11. 

� The test/QA plan states that both ammunition feed to the incinerator and the injection of 

metals spiking solutions would take place throughout all M29 runs. However, as noted 

above, ammunition was fed to the incinerator only during Runs 1, 2, 12, and 13, with the 

14

result that, in Runs 3 through 11, only the injected metals were present in the flue gas. 

This procedure was made necessary by the failure of a damper valve in the incinerator 

baghouse that would have resulted in exceeding the facility’s emission permit for lead if 

ammunition were fed into the incinerator. 

None of these deviations had any significant effect on the quality of the verification data. 

4.2 Facility Calibrations 

This verification made use of monitoring equipment already integrated into the TEAD facility, 

including CEMs for O2 and CO2, as well as sensors for temperature and pressure. These devices 

were considered part of the TEAD facility and were operated during this verification according to 

normal TEAD procedures. The CEMS included automatic calibration, which caused the monitors 

to be calibrated periodically without operator intervention. The results of the facility CEM calibrations were factored into the data on flue gas conditions reported by the facility for this 

verification. 

Flue gas water content was determined from the impinger weights in the M29 trains, by means of 

an electronic balance located in the M29 train preparation/recovery laboratory at TEAD. That 

balance was the subject of a performance evaluation (PE) audit, as described in Section 4.4.2. 

4.3 M29 Sampling and Analysis 

The preparation, sampling, and recovery of samples from the M29 trains followed all aspects of 

the QA/QC requirements in the method. The CHPPM report on the M29 sampling(6) includes all 

field data sheets, M29 equipment calibration procedures and results, and QA/QC results. 

Stringent sample custody procedures were employed. Samples were either in the direct custody 

of the sample custodian or under lock and key at all times. Sample custody sheets were included 

in the M29 data report provided by CHPPM.(6) Recovered M29 samples were sent for analysis at 

the CHPPM DLS at Aberdeen Proving Ground, Maryland. All sample analyses were completed 

within one month after the completion of the field verification test at TEAD. 

Because of the importance of the M29 data in this verification, the following sections present key 

data quality results from the M29 data. 

4.3.1 M29 Detection Limits and Blank Results 

Any M29 sample fraction showing no detectable concentration of a target metal was assigned 

a concentration equal to the detection limit for that metal. To make such assignments for 

nondetect results, the analytical detection limit for each type of sample was estimated by CHPPM 

staff, based on calibration results and instrument performance criteria.(6) Table 4-1 lists the detection limits estimated in this way for each target metal, in each of the types of sample fractions 

recovered from an M29 train. Based on a typical M29 sample volume of 2.1 dscm, the detection 

15

limits in Table 4-1 correspond almost entirely to flue gas levels of about 1 �g/dscm or less, 

which are negligible in comparison to the actual flue gas levels of the target metals. The only 

exceptions are for Hg and Zn in the impinger samples (6.0 and 4.8 �g, respectively); but, even 

for these metals, the equivalent flue gas metal levels of about 2.9 and 2.3 �g/dscm, respectively, 

are minimal compared with the actual flue gas levels of these metals. 

Table 4-1. Estimated Detection Limits for Analysis of Metals by M29 

Front-Half Impingers/Back- Fractions 

Filter � Rinse � Half Rinsea 

� 3A, 3B, 3Ca,b �

Metal ( g) ( g) ( g) ( g) 

As 0.50 0.20 0.96 n/a 

Ba 2.50 1.00 1.20 n/a 

Cd 0.50 0.20 0.48 n/a 

Cr 2.50 1.00 0.96 n/a 

Hg 0.20 0.20 6.00c 2.20 

Ni 2.50 1.00 1.20 n/a 

Pb 0.50 0.20 1.20 n/a 

Sb 0.50 0.28 0.48 n/a 

Zn 2.50 1.00 4.80 n/a 

a Values are approximate due to varying sample volumes. b Combined. c Elevated due to a required 1:100 dilution (because of high Hg values). 

n/a = not applicable. 

One blank M29 train was prepared and recovered along with the sample trains to establish the 

blank levels of the target metals in the various sampling media. No detectable level of As, Cd, 

Cr, Hg, Pb, or Ni was found on the M29 filter or in any of the impinger sample fractions from the 

blank train. Detectable levels of Ba and Sb were found only in the filter blank (8.1 �g and 

1.14 �g, respectively). This Ba blank level corresponds to about 2% or less of the mass of Ba 

found on the filters from the 13 M29 sample runs, and this Sb blank level corresponds to about 

0.2% or less of the mass of Sb found on those filters. Detectable blank levels of Zn were found 

only on the filter (6.0 �g) and in the probe rinse (3.4 �g). These combined blank levels for Zn 

correspond to about 2.5% or less of the combined mass of Zn found in the filter and probe rinse 

samples from the 13 M29 sample runs. All results were blank corrected. 

4.3.2 M29 Analytical Duplicates 

A total of 206 duplicate analyses for individual metals in M29 sample fractions were reported by 

CHPPM, from over three weeks of sample analysis.(6) These 206 analytical duplicates were 

obtained by injecting the same sample twice and analyzing each sample for the element of 

16

interest. For only one of those results (a sample containing an extremely high Pb level) did the 

second analysis differ from the first by over 10%. Furthermore, for only 27 of those results did 

the second analysis differ from the first by more than 5%. These results indicate excellent 

precision of the M29 analytical results. 

4.3.3 M29 Precision 

The results of the M29 sampling at the TEAD incinerator are shown in Table 4-2. Shown are the 

flue gas concentrations of each target metal determined by each of the duplicate M29 trains 

(designated as Trains A and B) in each of the 13 M29 runs. Inspection of the data shows that, in 

nearly all cases, the duplication of results for all metals was good. To determine whether any bias 

existed between the paired M29 trains, the M301 procedure described in Section 5.6 of this 

report was used. In addition, reproducibility was assessed by calculating the relative percent 

difference (RPD) between the two paired trains for each metal in each M29 run. RPD is defined 

as the difference between the paired M29 results divided by their mean, with the result expressed 

as a percentage. 

Using the M301 procedure, it was determined that there was no statistically significant bias 

between the paired M29 sampling trains for As, Ba, Cd, Cr, Hg, and Pb. A small but significant 

bias (i.e., about 6%) was found for Ni, Sb, and Zn, with Train B results slightly higher than 

Train A results when averaged over all 13 runs. 

The results of the RPD calculations are summarized in Table 4-3, which lists for each target 

metal the average, maximum, and minimum RPD value found from the 13 sets of duplicate M29 

results. The average RPD results for all the metals were 8.4% or less, and the average over all 

M29 runs and all metals was 5.8%. These RPD results indicate close agreement between the 

duplicate M29 trains, even for Ni, Sb, and Zn, which were identified as having a significant bias 

by the M301 calculation. 

Based on these evaluations of the precision of the duplicate M29 trains, no obvious outliers were 

identified in the M29 data. Consequently, no M29 data were excluded; and, for each M29 run, 

the average value of each metal calculated from the duplicate train results was used as the 

reference concentration for verification of the XCEM. 

4.4 Audits 

4.4.1 Technical Systems Audit 

Battelle’s Quality Manager performed an internal technical systems audit (TSA) of the 

verification test, beginning on May 16, 2001, during testing at the TEAD incinerator. The TSA 

ensures that the verification test is conducted according to the test/QA plan(2) and that all 

activities associated with the test are in compliance with the AMS Center QMP.(7) On May 16, 

the Battelle Quality Manager visited the TEAD incinerator test site, toured the test area, and 

observed the performance of XCEM monitoring, M29 sampling, and the introduction of metal 

spike solutions by MSE-TA staff. In this visit, the Quality Manager met with staff from CES, 

17

18


Table 4-2. Flue Gas Metal Concentrations Determined by Duplicate M29 Trains at the TEAD Incinerato

Run 

As Ba Cd Cr Hg Ni Pb S

No. A B A B A B A B A B A B A B A 

1 11.3 10.3 249 264 30.1 30.7 4.4 4.1 295 290 390 380 1463 1773 555 2 11.1 11.0 320 276 39.9 36.3 4.4 4.2 272 280 401 402 3248 3236 625 3 9.3 9.5 196 206 29.6 29.5 4.4 4.1 290 282 375 378 88.0 79.0 539 4 11.9 12.2 247 263 32.1 34.9 6.1 7.9 323 314 439 464 65.4 62.1 629 

5 11.3 12.4 226 255 33.5 35.7 5.8 6.7 320 316 395 440 44.8 46.3 593 

6 12.0 12.0 260 283 35.0 34.7 6.1 6.1 318 320 469 477 46.0 43.5 663 

7 12.0 11.6 268 290 33.8 34.8 6.3 6.5 317 319 472 500 51.5 52.1 680 

8 11.6 11.5 257 266 34.3 36.2 6.4 6.6 106 102 197 215 184 212 257 

9 11.7 11.0 215 232 34.2 35.2 7.1 6.3 105 105 185 170 80.1 74.8 241 

10 11.4 11.4 220 207 33.1 34.8 5.9 6.2 99.8 102 170 153 85.3 83.2 227 

11 11.2 11.7 229 237 32.0 33.7 5.8 6.1 101 101 177 195 54.0 54.6 242 

12 9.5 9.0 229 199 28.9 26.7 5.1 4.7 108 108 170 153 197 177 241 

13 11.9 12.1 231 266 36.0 36.5 6.1 6.2 83.9 83.2 148 165 108 110 265 
Table 4-3. Summary of RPD Results from Duplicate M29 Trains in XCEM Verificationa 

RPD Results (%) for Target Metals 

RPD As Ba Cd Cr Hg Ni Pb Sb Zn Overall 

Average 3.5 8.4 4.5 7.5 1.6 6.7 6.4 6.8 7.2 5.8 

Maximum 9.3 14.8 9.4 26.3 3.7 11.0 19.2 14.2 13.3 26.3 

Minimum 0.2 3.3 0.2 0.2 0.2 0.2 0.4 1.3 0.8 0.2 

a

 RPD = (2(A-B)/(A+B)) x 100 

TEAD, CHPPM, and MSE-TA, as well as with the Battelle Verification Testing Leader. The 

Quality Manager reviewed the records of all organizations participating in the verification test 

and visited the M29 sample recovery lab to observe train preparation, sample recovery, and 

record keeping procedures carried out by CHPPM staff. At that time, the Quality Manager 

observed spiking of two M29 trains for performance evaluation audit purposes, as described in 

Section 4.4.2. The TSA was completed on June 12, 2001, when a representative of the Quality 

Manager visited the CHPPM laboratory in Aberdeen, Maryland, to observe M29 analysis 

procedures. All observations from the TSA were documented in a TSA report, which was 

submitted to EPA Quality Management staff on July 27, 2001. No issues were found in the TSA 

that could adversely affect the quality of the data from this verification. The records concerning 

the TSA are stored in the custody of the Battelle Quality Manager. 

4.4.2 Performance Evaluation Audits 

A series of audits was performed to check the quality of reference measurements made in the 

verification test.(2) These audits were performed by Battelle and carried out with the assistance of 

CHPPM staff. 

Table 4-4 summarizes the results of the PE audits on the two sets of M29 sampling equipment 

and on the M29 impinger weighing equipment. The audits of the temperature and flow rate 

measurements of the M29 samplers were conducted on the sampling platform near the top of the 

stack, by a simultaneous measurement with each M29 train and the audit device. The temperature 

audit was conducted both at ambient temperature (approx. 58°F) and at elevated temperature 

(approx. 260°F), by collocating the audit thermocouple and the M29 train thermocouple. The 

balance used to weigh M29 impingers was audited by weighing certified weights. Table 4-4 

shows that the PE results on the M29 flow measurements showed agreement with the audit 

results within about 2%, and the temperature measurements agreed within 1% in absolute 

temperature. Impinger weighing showed agreement within 0.18%. 

19

Table 4-4. Summary of PE Audit Results on M29 Sampling Equipment in XCEM 

Verification Test 

Observed 

Measurement 

Audited Date Audit Method 

Agreement 

(% difference) 

Flow Rate 5/15/01 Comparison to independent flow rate 

measurement 

1.3%a 

2.1%b 

Temperature (absolute) 5/17/01 Comparison to independent temperature 

measurement 

ambient: 0.1%a 

elevated: 1.0%a 

ambient: 0.1%b 

elevated: 0.3%b 

Impinger weighing 5/16/01 Weighing certified weights 0.18% 

a

 Results for Nutech 2010A MST Serial No. 90488 sampling unit. 

b

 Results for Nutech 2010A MST Serial No. 90495 sampling unit. 

Table 4-5 summarizes the PE audit results from spiking samples from two blank M29 trains. 

This PE audit of the M29 analysis was performed by spiking the target metals onto a blank filter, 

and into aliquots of the sample solutions, from two blank M29 trains. The six sample fractions 

from each train that received the metals spikes were 

� Particulate filter 

� 100 ml of 0.1 N HNO3 

� 200 ml HNO3/H2O2 solution + 100 ml of 0.1 N HNO3 

� 100 ml of 0.1 N HNO3 

� 100 ml KMnO4 solution + 33 ml H2O 

� 25 ml of 8 N HCl + 475 ml H2O. 

The first three fractions listed above were each spiked with 1 ml of a solution containing 

20 �g/ml of eight of the target metals (As, Ba, Cd, Cr, Ni, Pb, Sb, and Zn). Also, all six fractions 

listed above were spiked with 1 ml of a solution containing 10 �g/ml of Hg. The spiked filters 

were allowed to dry in the laboratory air before they were sealed for shipment for analysis. 

Table 4-5 shows the results of analysis of the spiked train samples, in terms of both the mass of 

metal found in each sample and the corresponding percent recovery values relative to the amount 

spiked. All spike results were within the target range of 70 to 130% recovery, with the following 

exceptions: 

� Field Spike 1 Filter—Zn. The Zn recovery for the filter was approximately 60%. This may be 

attributed to a high Zn filter blank value (6.0 �g). If the 6.0 �g blank value were not subtracted from this fraction, the recovery would have been approximately 90%. 

20

Table 4-5. Results of Field Spikes of M29 Trains [Mass Recovered (% Recovery)] 

Filtera , Fraction 2a , Fraction 3a , Fraction 4b , Fraction 5b , Fraction 6b , 

ug (%) ug (%) ug (%) ug (%) ug (%) ug (%) 

Field Spike Train 1 

As 15.90 (79.5) 18.10 (90.5) 17.70 (88.5) -- -- --

Ba 22.30 (111.5) 20.70 (103.5) 21.50 (107.5) -- -- --

Cd 17.00 (85.0) 17.90 (89.5) 17.60 (88.0) -- -- --

Cr 17.90 (89.5) 20.10 (100.5) 21.30 (106.5) -- -- --

Hg 1.80c

 (18) NDc 8.30 (83.0) 10.10 (101) NDd 18.60d (186) 

Ni 15.00 (75.0) 19.40 (97.0) 19.70 (98.5) -- -- --

Pb 20.90 (104.5) 19.20 (96.0) 21.70 (108.5) -- -- --

Sb 25.26 (126) 19.40 (97.0) 19.60 (98.0) -- -- --

Zn 12.103

 (60.5) 16.10 (80.5) 19.50 (97.5) -- -- --

Field Spike Train 2 

As 16.90 (84.5) 18.40 (92.0) 17.60 (88.0) -- -- --

Ba 23.10 (115.5) 21.10 (105.5) 22.10 (110.5) -- -- --

Cd 18.20 (91.0) 18.00 (90.0) 18.00 (90.0) -- -- --

Cr 18.70 (93.5) 20.20 (101) 20.80 (104) -- -- --

Hg 3.90c

 (39) 0.26c (2.6) 7.90 (79.0) 10.00 (100) NDd 18.60d (186) 

Ni 15.50 (77.5) 19.50 (97.5) 19.40 (97.0) -- -- --

Pb 23.90 (119.5) 19.40 (97.0) 21.10 (105.5) -- -- --

Sb 25.06 (125.3) 19.80 (99.0) 20.10 (100.5) -- -- --

Zn 14.40 (72.0) 16.80 (84.0) 19.60 (98.0) -- -- --

a Target value is 20 �g/sample (10 �g/sample for Hg) b Only Hg was spiked; target value is 10 �g/sample c Did not meet recovery target d See text 

ND = Non-detect 

21

� Field Spikes 1 and 2 Filter—Hg. The Hg recoveries on the filter field spikes were 18 and 39%, 

respectively. The liquid spike was allowed to dry on the filter over a period of a few hours 

before sealing the petri dish. It may be that some of the Hg was lost from the filter during 

drying or sample recovery. 

� Field Spikes 1 and 2, Fraction 2—Hg. The Hg field spike results for this fraction were very 

low (nondetect and 2.6%, respectively) in both spiked trains. Since a mercury spike should be 

very stable in the HNO3 matrix, the only plausible explanation is that this fraction was inadvertently not spiked with the Hg solution (the remaining metals in this fraction all met the 

target recovery values). 

� Field Spikes 1 and 2, Fractions 5 and 6—Hg. The Hg recoveries for Fraction 5 were 

nondetects. However, the recovery for Fraction 6 was 186%. As part of the sample preparation 

procedure, Fraction 5 was filtered to remove MnO2 precipitate, and it is possible that some or 

all of the Hg was trapped in the MnO2 precipitate (and therefore in the filter). This filter was 

then digested in HCl and combined with Fraction 6. Therefore, it is possible that the Hg 

spiked in Fraction 5 was transferred to Fraction 6 during sample preparation. The combined 

mercury recovery for Fractions 5 and 6 was approximately 93% in both sets of field spikes, 

well within the target range. 

4.4.3 Data Quality Audit 

Battelle’s Quality Manager audited at least 10% of the verification data acquired in the verification test. The Quality Manager traced a representative sample of the data from initial acquisition, 

through reduction and statistical comparisons, to final reporting. 

22

Chapter 5


Statistical Methods


Statistical calculations were used to verify the performance of the XCEM as described below. In 

all cases, measurement results from both the reference method and the XCEM were reported in 

units of �g/m3 on a dry basis at 20�C, 1 atmosphere pressure, and the actual flue gas O2 content. 

5.1 XCEM Concentration 

Average XCEM concentrations for a given reference method run were calculated as follows: 

n 

∑C t ij j 

Ci = j =1 

∑t j 

where: 

Ci = XCEM time-weighted concentration for element i during M29 test run 

Cij = XCEM reported concentration for element i during time interval j 

n = number of XCEM measurements during test run 

tj = number of minutes XCEM measured element i’s concentration during time interval j 

5.2 Relative Accuracy 

The relative accuracy (RA) of the XCEM with respect to M29 was assessed by 

α Sd d + tn−1 

RA = n ×100% 

x 

Where d refers to the difference between corresponding M29 and XCEM results, n is the number 

of runs, and x corresponds to the average M29 result. Sd denotes the sample standard deviation 

of the differences, while t�

n-1 is the t value for the 100(1-α)

th percentile of the distribution with 

23

n-1 degrees of freedom. The RA was determined for an α value of 0.025 (i.e., 97.5% confidence 

level, one-tailed). The RA calculated in this way can be interpreted as an upper confidence bound 

d 

x 

for the relative bias of the analyzer, i.e., , where the superscript bar indicates the average of the 

differences of the reference values. RA was calculated separately for each metal measured by the 

XCEM. 

For both As and Pb, the RA also was determined using only Runs 3 through 13 due to the high 

Pb levels in Runs 1 and 2 and the apparent interference in the As measurement caused by those 

high Pb levels (see Section 6.2). For these calculations, a t-statistic value of 2.28 was used. 

5.3 Correlation with Reference Method 

The degree of correlation of the XCEM with the reference method results was assessed in terms 

of the correlation coefficient (r) and coefficient of determination (r2

) for lead and for those metals 

spiked at more than one concentration (i.e., Hg, Ni, Zn, and Sb). 

5.4 Precision 

Precision was calculated in terms of the percent RSD of a series of XCEM measurements made 

during stable operation of the TEAD, with metals injected at a constant level. This precision 

result reflects the variability in the stack conditions, spiking rate, and XCEM measurements, i.e., 

the calculated precision is subject to the variability of the test, not only the XCEM variability. 

During each M29 sampling run, all readings from the XCEM were recorded, and the mean and 

standard deviation of those recordings were calculated. Precision as percent RSD was determined 

as: 

S D P = × 100 

X 

where SD is the standard deviation of the XCEM readings and x is the mean of the readings. 

The same calculation was performed for each metal measured by the XCEM, for each of the 13 

M29 runs. 

5.5 Span, Zero, and Internal Standard Drift 

The XCEM performs automated daily internal span and zero checks and also reports a reading 

from a palladium internal standard with each sample to check for internal standard drift. Span, 

zero, and internal standard drift were reported in terms of the mean, relative standard deviation, 

24

and range (maximum and minimum) of the readings obtained from the XCEM. The percent RSD 

was calculated as 

where x is the mean, and SD is the standard deviation of the readings of the span, zero, or 

S D RSD = × 100 

X 

palladium internal standard. 

5.6 M29 Bias and XCEM Bias Relative to M29 

Bias between the paired M29 sampling trains, and between M29 and the XCEM, was determined 

using an M301 approach. The results were tested for statistically significant bias by calculating 

the t-statistic and determining if the mean of the differences between the two sampling trains or 

methods was significant at the 80% confidence level. The t-statistic was calculated by finding the 

standard deviation of the differences between the two sampling trains or methods: 

∑(di −dm )

2 

SDd = (n −1)

Where: 

di = the difference between paired sample train values 

dm = mean of the di

 values 

n = number of paired samples 

The t-statistic was then calculated as follows: 

d 

t = m 

 S Dd 



 

n 

The critical value of the t-statistic was 1.356 for 13 runs (two-tailed test with P=0.20). If the 

calculated t-value was greater than the critical value, the bias as defined by M301 was 

statistically significant. 

M29 data pairs that were determined to be unbiased relative to each other were averaged and 

used for comparison with the XCEM. Bias between the XCEM and average M29 data was 

determined as described above, with di

 being the difference between the average M29 and 

XCEM data. 

25

Chapter 6


Test Results


It was beyond the scope of this verification test to simulate the aging and exposures that may 

affect a multi-metals CEM during routine long-term use. This verification test evaluated the 

performance of a new XCEM over a relatively short test period, in the hands of staff skilled in its 

operation. It must be noted that long-term performance may be different from that observed in 

the testing described here. However, the XCEM did not exhibit any mechanical problems during 

the test, completing more than 150 sampling and analysis cycles during the week without any 

downtime. 

6.1 XCEM Concentration 

Figure 6-1 shows the individual measurements of each target metal made by the XCEM 

(diamonds) and the M29 measurement made at the same period (solid horizontal bars) taken 

from data shown in Appendix A. Lead concentrations are shown on two separate graphs, to more 

clearly show the lower concentrations seen in Runs 11 through 13. Also shown in Figure 6-1 are 

the XCEM readings on the palladium internal standard analyzed with every sample analysis. 

Average XCEM concentrations were calculated for each of the M29 runs according to 

Section 5.1. Table 6-1 summarizes the results of the XCEM measurements for each M29 run, 

showing the average XCEM and corresponding M29 results for each metal. The averages over all 

13 runs are also shown in Table 6-1. Included also is the average for Runs 3 through 13. Runs 1 

and 2 are excluded in this average because of the large lead concentrations that occurred from the 

M17 .50 caliber munitions that were used in those runs. 

26

27


Table 6-1. Summary of Results from XCEM and M29 for Each Test Run 

� Metal Concentration ( g/dscm) 

As Ba Cd Cr Hg Ni Pb Sb 

Run XCEM M29 XCEM M29 XCEM M29 XCEM M29 XCEM M29 XCEM M29 XCEM M29 XCEM M2

1 22 11 186 256 27 30 2 4 189 292 449 385 1169 1618 369 56

2 16 11 220 298 27 38 2 4 229 276 405 401 2498 3242 371 62

3 13 9 152 201 25 30 3 4 259 286 405 377 75 84 349 53

4 16 12 160 255 29 34 5 7 72 318 408 452 61 64 351 64

5 16 12 174 241 33 35 6 6 109 318 437 418 47 46 380 62

6 14 12 169 271 33 35 6 6 151 319 445 473 41 45 384 69

7 16 12 173 279 32 34 6 6 132 318 459 486 40 52 382 71

8 17 12 148 262 32 35 5 7 28 104 211 206 228 198 135 27

9 18 11 163 223 31 35 5 7 54 105 211 178 167 77 144 23

10 18 11 163 214 33 34 6 6 93 101 203 161 138 84 148 22

11 16 11 163 233 30 33 5 6 94 101 202 186 97 54 146 25

12 17 9 178 214 27 28 4 5 62 108 215 161 188 187 155 23

13 18 12 161 248 34 36 5 6 75 84 182 156 115 109 155 28

Average 17 11 170 246 30 34 5 6 119 210 325 311 374 451 267 45

Average 16 11 164 240 31 33 5 6 103 197 307 296 109 91 248 42

(Runs 3-13) 
Antimony 

0 

200 

400 

600 

800 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Arsenic 

0 

50 

100 

150 

200 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Barium 

-50 

50 

150 

250 

350 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Figure 6-1. XCEM and M29 Data During Verification 

Test (diamonds = XCEM, bars = M29) 

28

Cadmium 

0 

10 

20 

30 

40 

50 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Chromium 

0 

2 

4 

6 

8 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Lead (All Runs) 

0 

1,000 

2,000 

3,000 

4,000 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Figure 6-1. XCEM and M29 Data During Verification 

Test (diamonds = XCEM, bars = M29) (continued). 

29

Lead (Runs 3-13) 

0 

100 

200 

300 

400 

500 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Mercury 

0 

100 

200 

300 

400 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Nickel 

0 

100 

200 

300 

400 

500 

600 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Figure 6-1. XCEM and M29 Data During Verification 

Test (diamonds = XCEM, bars = M29) (continued). 

30

Palladium 

0 

10 

20 

30 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Zinc 

0 

200 

400 

600 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 

5/15/01 

12:00 

5/16/01 

6:00 

5/17/01 

0:00 

5/18/01 

Conc. (ug/dscm) 

Figure 6-1. XCEM and M29 Data During Verification Test 

(diamonds = XCEM, bars = M29) (continued). 

6.2 Relative Accuracy 

Table 6-2 lists the percent RA results for all the target metals. These results are based on the 

XCEM and M29 results from all 13 test runs. In addition, RA for Pb and As also was calculated 

based on test Runs 3 through 13, thereby excluding the high Pb concentrations (and apparent 

interference in As measurement) in Runs 1 and 2. Because PS-10 allows basing the calculation of 

RA on nine runs, a recalculation of relative accuracy using Runs 3 through 7 and 10 through 13 

also is presented. The following are specific comments on the RA results for each target metal. 

As 

An RA of 61.3% was found for As. Calculating RA using nine runs gave 53.1%. In general, the 

XCEM As concentrations were consistently higher than those measured by M29 (Figure 6-1). 

However, it was observed that XCEM As concentrations were highly correlated with XCEM Pb 

concentrations (Figure 6-2). 

31

Table 6-2. Relative Accuracy Results for XCEM 

Metal RA (%) RA (%) Using Nine Runs 

Asa 61.3 53.1 

Ba 36.7 38.9 

Cd 14.7 10.8 

Cr 25.4 20.4 

Hg 67.3 81.5 

Ni 13.0 12.8 

Pbb 54.8 36.7 

Sb 53.5 58.6 

Zn 36.8 39.4 a Calculated RA of 52.8% using Runs 3-13 only. b Calculated RA of 46.1% using Runs 3-13 only. 

Reported Arsenic vs. Reported Lead Conc. At TEAD 

0 

20 

40 

60 

80 

100 

120 

140 

160 

180 

200 

0 500 1,000 1,500 2,000 2,500 3,000 3,500 

Pb Conc. (μg/m3) 

As Conc. (μg/m3) 

As Conc = 0.0538 x Conc Pb + 15.961 

r 

2

 = 0.9891 

Figure 6-2. Uncorrected XCEM Arsenic Concentrations vs. XCEM Lead 

Concentrations 

32

Since no significant As was expected in the background stack gas, and the As was spiked at a 

constant rate, the observed correlation is believed to be due to an XRF spectral interference. 

Concentrations of As are established by XRF using a K� line, which is overlapped by the L� line 

of Pb. For this reason, in XRF analysis, high Pb concentrations can interfere with As 

measurements, although the reverse is not true. 

The XCEM vendor has indicated that a change in the spectral resolution approach can resolve the 

Pb/As overlap problem. The XRF can be calibrated using a variety of methods that will take into 

account the Pb/As interference. For example, during previous tests of the XCEM, a calibration 

method was used that contained both As and Pb. No Pb/As interference was observed during 

those tests.(8) 

Ba and Sb 

Ba and Sb exhibited similar behavior during verification testing. For both metals, the average 

XCEM concentrations were significantly lower than the M29 reported concentrations, resulting 

in RAs of 36.7 and 53.5% for Ba and Sb, respectively. 

Cd, Cr, and Ni 

The agreement between XCEM and M29 reported concentrations for Cd, Cr, and Ni is illustrated 

in Figure 6-1 and reflects the RAs of 14.7% for Cd, 25.4% for Cr, and 13.0% for Ni. 

Hg 

As shown in Figure 6-1, at the beginning of each test day, the XCEM reported low Hg 

concentrations relative to M29. As the day progressed, the XCEM Hg reading usually gradually 

increased until it approximated M29 reported concentrations. This pattern suggests that the 

transport line from the stack to the XCEM was slowly equilibrating with the stack Hg level, and 

perhaps needed to be heated to a higher temperature to improve transmission efficiency. The 

M29 results showed that more than 98% of the Hg measured by M29 passed through the filter 

and was collected in the back half of the sample train, indicating that the vast majority of the Hg 

was in the vapor phase. The majority (approximately 80%) of the sample was collected in the 

HNO3 impinger, suggesting that most of the vapor-phase Hg was oxidized rather than elemental. 

This preponderance of oxidized Hg is consistent with the apparently slow equilibration of the 

XCEM inlet system each day. The overall RA for Hg was 67.3%; however, from Table 6-1, it 

can be seen that the XCEM Hg readings were within 20% of the M29 results on five runs (Runs 

2, 3, 10, 11, and 13), all of which took place late in the day when equilibrium of the XCEM inlet 

line would be most nearly complete. 

Pb 

In general, the XCEM and M29 Pb concentrations were similar (Table 6-1 and Figure 6-1). 

Differences of about 25% were observed at the high Pb concentrations in Runs 1 and 2. Also, on 

May 16, both the XCEM and M29 Pb methods reported a higher Pb concentration at the start of 

the day than was observed on the previous day. The XCEM reported a consistent gradual decline 

33

in Pb concentrations throughout the day on May 16, while M29 showed a more rapid decrease in 

concentration (Figure 6-1). On May 14, the XCEM was able to rapidly transition from high 

concentrations during Runs 1 and 2 to a much lower concentration during Run 3 and agreed with 

M29 for that third run (Table 6-1). The May 14 XCEM/M29 comparisons indicate that the 

XCEM is responsive to rapid changes in Pb concentration and is resistant to sample line 

contamination. 

Overall, the XCEM achieved an RA for Pb of 54.8% for all 13 runs and an RA of 46.1% when 

only Runs 3 to 13 were considered. Runs 1, 2, 9, 10, and 11 had the greatest influence on the RA 

values. Calculating RA using only nine runs gave an RA of 36.7%. 

Zn 

Like Ba and Sb, the XCEM Zn concentrations were consistently lower than the M29 concentrations (Figure 6-1). An RA of 36.8% was found for Zn. 

6.3 Correlation with Reference Method 

The degree of correlation between the XCEM and M29 is shown in Figure 6-3 and summarized 

in Table 6-3. Five metals were present in the stack gas at sufficiently varying concentrations to 

support a calculation of correlation, i.e., Hg, Ni, Pb, Sb, and Zn. Of these elements, Ni, Pb, Sb, 

and Zn show coefficients of determination (r2

) of 0.95 or better. The correlation for Pb was 

weaker over Runs 3 through 13 (r2

 = 0.75) than when all 13 runs were included (r2 = 0.997) as a 

result of the influence of the high Pb levels in Runs 1 and 2. Hg did not show a high correlation 

between the two methods (r2=0.388) possibly due to the postulated inlet losses during sampling. 

6.4 Precision 

The XCEM precision results are presented in Table 6-4 for each target metal, and for the Pd 

internal standard, for each M29 run. Precision was calculated in terms of the percent RSD of a 

series of XCEM measurements made during stable operation of the TEAD incinerator, with 

metals injected at a constant rate. Therefore, precision reflects not only the XCEM variability, 

but also the variability in the stack concentrations, spiking rate, and flow variability. 

Table 6-4 shows that average results for Ba, Cd, Cr, Ni, Sb, and Zn were in the range of 6 to 12% 

RSD; and, for these metals, very few RSD values exceeded 15%. Run 13 produced the highest 

RSD values for several of these metals. As (16% RSD), Hg (18% RSD), and Pb (21% RSD) 

exhibited higher average RSD values. The average percent RSD for As was strongly affected by 

the result from Run 2 (65% RSD); excluding that value, an average of 11.9% RSD would result. 

For Hg, the percent RSD values from the first run on each test day (i.e., Runs 1, 4, 8, and 12) 

ranged from 30 to 44%, whereas all other percent RSD values ranged from 3 to 18%, and 

averaged 9.6%. Thus, the precision for Hg was strongly influenced by the sampling difficulties 

noted above that occurred at the start of each test day. For Pb, percent RSD values were generally 

34

Antimony M29 vs. XCEM Lead M29 vs. XCEM 

800 4000 

M29 (ug/dscm) 600 

400 

200 

0 

y = 1.71x - 0.54 

r2 = 0.96 

Mercury M29 vs. XCEM 

0 

100 

200 

300 

400

M29 (ug/dscm) M29 (ug/dscm) M29 (ug/dscm) 

y = 1.33x - 47.70 

r2 = 1.00 

3000 

2000 

1000 

0 

0 200 400 600 0 1000 2000 3000 

XCEM (ug/dscm) XCEM (ug/dscm) 

Lead Minus High Runs M29 vs. XCEM 

y = 0.73x + 11.68 

r2 = 0.75 

0 

50 

100 

150 

200 

250 

0 100 200 300 

XCEM (ug/dscm) 

M29 (ug/dscm)

y = 0.95x + 97.23 

r2 = 0.39 

0 100 200 300 

XCEM (ug/dscm ) 

Nickel M29 vs. XCEM 

y = 1.11x ­ 51.28 

r2 = 0.95 

0 

100 

200 

300 

400 

500 

600 

M29 (ug/dscm) 

Zinc M 29 vs. XCEM 

600 

y = 1.42x - 7.79 

r2 = 0.97 

400 

200 

0 

0 200 400 600 0 100 200 300 400 

XCEM (ug/ds cm ) XCEM (ug/dscm ) 

Figure 6-3. Correlation Between XCEM and M29 

Table 6-3. Correlation Between XCEM and M29 

Element r Correlation (r2) 

Hg 0.623 0.388 

Ni 0.976 0.953 

Pb 0.998 0.997 

Sb 0.980 0.960 

Zn 0.987 0.973 

35

Table 6-4. XCEM Precision 

Percent RSD 

Run As Ba Cd Cr Hg Ni Pb Sb Zn Pd 

1 8 11 11 16 44 12 23 5 8 3 

2 65 14 10 30 11 5 48 5 6 2 

3 10 12 12 16 3 3 33 4 3 2 

4 9 14 14 10 30 13 14 11 13 3 

5 8 7 5 5 13 3 12 3 3 3 

6 13 7 6 6 9 3 13 2 3 3 

7 7 7 8 6 10 6 16 4 6 3 

8 14 14 6 6 34 6 14 4 4 3 

9 12 15 7 11 9 5 10 4 2 2 

10 16 13 8 4 9 5 41 6 5 2 

11 5 8 8 8 6 4 8 2 2 2 

12 16 15 11 6 40 7 27 6 6 3 

13 25 24 21 14 18 30 12 22 42 2 

Average 16 12 10 11 18 8 21 6 8 2 

higher and more variable than for other elements. Values as high as 41% RSD were found, even 

excluding the first two test runs. As noted above, this may be due in part to real variability in the 

lead level in the stack gas. 

6.5 Span, Zero, and Internal Standard Drift 

Span and zero checks were conducted on each of the four test days, with the results shown in 

Table 6-5. Since the span and zero checks are evaluations of mass measurement results, they are 

reported as mass per unit area on the filter (�g/spot). Equivalent span and zero concentrations in 

micrograms per dry standard cubic meter also are shown in Table 6-5 and reflect the typical 

sampling rate of 16 liters per spot. 

36

Table 6-5. XCEM Span and Zero Readings During Verification Testing 

Date 

Span Readings ( �

g) Zero Readings ( �g)1 

Cd Cr Hg Pb Cd Cr Hg Pb 

5/14/01 156 5.23 27.6 30.4 0.024 0.012 0.008 0.008 

5/15/01 158 5.53 28.0 30.9 0.024 0.016 0.008 0.008 

5/16/01 156 5.45 27.9 30.8 0.024 0.014 0.008 0.008 

5/17/01 156 5.42 27.9 30.6 0.024 0.006 0.008 0.023 

Average 157 5.41 27.8 30.7 0.024 0.012 0.008 0.018 

Date 

Equiv. Span Values ( �

g/dscm)2 Equiv. Zero Values ( �g/dscm)1,2 

Cd Cr Hg Pb Cd Cr Hg Pb 

5/14/01 9,765 327 1,724 1,898 1.50 0.75 0.50 0.50 

5/15/01 9,850 346 1,750 1,931 1.50 1.01 0.50 0.50 

5/16/01 9,772 341 1,742 1,925 1.50 0.85 0.50 0.50 

5/17/01 9,744 339 1,746 1,912 1.50 0.38 0.50 1.44 

Average 9,783 338 1,741 1,917 1.50 0.75 0.50 0.73 

SD 46.14 7.88 11.25 14.64 

% RSD 0.47 2.33 0.65 0.76 

1 Shaded values were nondetects. Nondetect treated as 1⁄2 of detection limit. 2 Equivalent concentrations determined assuming 16 liters of gas sampled. The span check indicated no trend in span results and 

good precision over the four days of testing. The precision (as percent RSD) of the span results over the four days was less 

than 1% for Cd, Hg, and Pb and about 2.3% for Cr. 

The XCEM span readings show no significant trend with time and exhibit percent RSD values of 

0.47 to 2.33. These results show that day-to-day variation in the XCEM span response was 

minimal over the four test days. 

Zero values determined during the TEAD test indicate no measurable zero drift in the mass 

measurement. The XCEM detection limits for Cd, Cr, Hg, and Pb are 3.0, 0.75, 1.0, and 

1.0 �g/dscm, respectively. The average XCEM zero values were below the detection limits for 

Cd, Hg, and Pb, and only slightly higher than the Cr detection limit. 

The Pd internal standard, which is measured with every sample, also displayed stable readings 

and good precision over the four days of testing (Figure 6-4). Overall, the Pd reading had a 

precision (percent RSD) of approximately 2.5%, with all 113 measured Pd readings lying within 

6% of the average reading. Analysis of the Pd trend in Figure 6-4 indicates that no significant 

drift occurred, i.e., over the four-day test period, the average daily Pd reading changed by less 

than 1.0%. 

37

Palladium 

21 

22 

22 

23 

23 

24 

24 

25 

6:00 

5/14/01 

0:00 

5/15/01 

18:00 12:00 6:00 0:00 

5/15/01 5/16/01 5/17/01 5/18/01 

Conc. (

μg/dscm) 

Pd 

Ave PD 

One std Dev 

5% from Average 

Figure 6-4. XCEM Palladium Internal Standard Readings During 

M29 Testing 

6.6 XCEM Bias Relative to M29 

Using the M301 approach, the XCEM results for all the target metals were found to be 

significantly biased relative to the corresponding results from M29, as shown in Table 6-6. Thus, 

a significant positive and negative bias was found even for Cd, Cr, and Ni, for which the overall 

average concentrations determined by the XCEM differed little from those determined by M29 

(see Table 6-1). 

6.7 Response Time 

The XCEM sampled continuously except for a four-second period between each 20-minute 

sample run when the filter tape was moved to a new analysis position. Thus, the cycle time for 

the XCEM as a batch analyzer is 20 minutes and 4 seconds. Also, XCEM results are reported 

immediately after analysis, resulting in a 20-minute lag time between the end of sampling and 

reporting. 

38

Table 6-6. XCEM Bias Relative to M29 

Element t-stat t-critical Significant Bias 

As 8.8068 1.356 Yes 

Ba 11.4506 1.356 Yes 

Cd 4.15447 1.356 Yes 

Cr 6.28591 1.356 Yes 

Hg 3.92706 1.356 Yes 

Ni 6.16179 1.356 Yes 

Pb 1.77641 1.356 Yes 

Sb 7.42625 1.356 Yes 

Zn 6.81789 1.356 Yes 

39

Chapter 7


Performance Summary


In comparisons with results from M29, the XCEM relative accuracy for Cd, Cr, and Ni was less 

than 26%. The remaining metals (As, Ba, Hg, Pb, Sb, and Zn) had RA values between 37 and 

67%. The reported XCEM concentrations were uniformly high for As. The XCEM was consistently low for Zn, Ba, and Sb. XCEM Hg readings were very low at the start of each test day, 

rising gradually until they stabilized. This behavior is possibly a result of equilibration of the 

XCEM inlet line with vapor phase mercury. The best agreement of XCEM and M29 Hg results 

(within about 20%) was found with M29 runs conducted late in the test day, when XCEM 

readings had stabilized. When calculated using nine runs, the RA for Cd, Cr, and Ni was between 

11 and 20% and the remaining metals had an RA between 36% (Pb) and 82% (Hg). 

Correlation of XCEM and M29 results was calculated for five elements that varied enough 

during the test to justify this comparison. For Ni, Pb, Sb, and Zn, r2 values exceeding 0.95 were 

found, although the r2 value for Pb decreased to 0.75 when the high Pb levels in Runs 1 and 2 

were excluded. For Hg, an r2

 value of 0.39 was found, due, in part, to the equilibration issue 

noted above. 

The XCEM’s precision, as RSD of successive readings with stable metal concentrations, ranged 

from 6 to 21% over the nine target metals. This precision includes variability in the metals 

injection and the test facility, as well as in the XCEM itself. 

XCEM span and zero drift were assessed over the four test days. Daily span readings of Cd, Cr, 

Hg, and Pb exhibited percent RSD values of 0.47 to 2.33 and no significant trends over time. 

Zero readings for all four elements were near or below the respective detection limits on all test 

days. The RSD of the XCEM’s Pd internal standard was approximately 2.5%, with no significant 

trend over time. 

The XCEM results showed statistically significant positive and negative bias relative to M29 

results for all the target metals, based on M301 procedures. 

The XCEM functioned in an automated manner and automatically recorded concentrations, 

temperatures, flow rates, and QA data. It exhibited no mechanical problems, had an effective uptime of 100%, and a response time of 20 minutes. 

40

Chapter 8


References


1.	 Progressive Software, Albany, Oregon, 2001. 

2.	 Test/QA Plan for Pilot-Scale Verification of Continuous Emission Monitors for MultiMetals, Battelle, Columbus, Ohio, May 2001. 

3.	 Determination of Metal Emissions from Stationary Sources, U.S. Environmental Protection 

Agency, Method 29, February 2000. 

4.	 Field Validation of Pollutant Measurement Methods from Various Waste Media, U.S. 

Environmental Protection Agency, Method 301, December 1992. 

5.	 Stack Spiking Report for a Multi-Metals CEMS Test at the Tooele Army Depot Deactivation 

Furnace, prepared for U.S. Army Corps of Engineers by MSE Technology Applications, 

Inc., Butte, Montana, June 2001. 

6.	 Verification of Multi-Metals Continuous Emission Monitor at Tooele Army Depot. Air 

Pollution Management Study No. 43-EL-6498-01, Tooele, Utah, May 14-17, 2001, prepared 

by the U.S. Army Center for Health Promotion and Preventive Medicine, 2001. 

7.	 Quality Management Plan (QMP) for the ETV Advanced Monitoring Systems Pilot, Version 

2.0, U.S. EPA Environmental Technology Verification Program, Battelle, Columbus, Ohio, 

October 2000. 

8.	 Johnsen, B., J. Cooper, A. C. Milliken. X-Ray Fluorescence Multi-Metals Monitor Data 

Recording and Calibration Automation and Mercury Sampling, prepared for U.S. Army 

Corps of Engineers by CES, Beaverton, Oregon, Contract No. DACA42-00-P-0245, 2000. 

41

Appendix A


XCEM Data During M29 Runs

Appendix A


XCEM Data During M29 Runs


XC 

Date Start Stop No. RM No. As Ba Cd Cr Hg Ni Pb Sb Zn Pd 

(micrograms/dscm) 

05/14/2001 10:45 11:05 650 Run 1 20.8 166 27.7 3.1 59 343 1,102 340 297 24.1 

05/14/2001 11:05 11:26 651 Run 1 24.3 171 26.0 2.5 109 436 1,127 372 316 23.8 

05/14/2001 11:26 11:48 652 Run 1 21.1 192 26.5 1.9 156 467 1,149 361 320 25.6 

05/14/2001 11:48 12:09 653 Run 1 20.7 165 21.8 2.2 207 449 1,196 353 316 25.5 

05/14/2001 12:10 12:31 654 Run 1 25.3 187 28.2 2.6 242 470 1,319 377 342 24.6 

05/14/2001 12:31 12:53 655 Run 1 21.5 218 31.8 2.2 257 515 1,607 399 372 25.4 

05/14/2001 12:53 13:15 656 Run 1 23.8 202 27.2 2.4 283 463 709 386 348 24.2 

05/14/2001 13:58 14:23 659 Run 2 7.3 230 26.8 2.3 186 375 3,422 360 299 25.6 

05/14/2001 14:23 14:46 660 Run 2 3.5 224 29.5 2.0 234 427 3,248 379 345 24.7 

05/14/2001 14:46 15:09 661 Run 2 13.0 249 26.0 1.2 244 427 3,017 398 352 25.1 

05/14/2001 15:09 15:32 662 Run 2 23.8 250 22.3 2.0 220 405 2,683 370 332 25.3 

05/14/2001 15:32 15:55 663 Run 2 31.5 194 29.1 1.2 239 415 2,347 379 347 25.2 

05/14/2001 15:55 16:17 664 Run 2 17.8 172 27.1 2.6 257 392 182 348 319 24.4 

05/14/2001 17:00 17:23 667 Run 3 15.3 127 25.4 3.4 259 395 118 334 320 24.6 

05/14/2001 17:23 17:44 668 Run 3 13.1 140 21.3 2.2 264 388 91 335 319 25.2 

05/14/2001 17:44 18:05 669 Run 3 13.0 158 27.0 2.5 265 417 60 355 341 25.4 

05/14/2001 18:05 18:26 670 Run 3 13.1 175 28.9 2.9 268 409 55 363 339 25.7 

05/14/2001 18:26 18:47 671 Run 3 14.2 168 21.4 2.4 255 413 60 352 333 24.6 

05/14/2001 18:47 19:07 672 Run 3 11.2 147 24.0 2.3 249 414 65 360 347 25.9 

05/15/2001 8:59 9:18 684 Run 4 13.2 145 21.5 4.5 33 294 69 271 235 25.0 

A-1

XC 

Date Start Stop No. RM No. As Ba Cd Cr Hg Ni Pb Sb Zn Pd 

(micrograms/dscm) 

05/15/2001 9:18 9:39 685 Run 4 15.0 173 28.5 6.2 54 401 69 333 319 23.4 

05/15/2001 9:39 10:00 686 Run 4 15.6 133 33.2 5.4 69 432 66 362 349 24.7 

05/15/2001 10:00 10:21 687 Run 4 16.2 154 30.5 5.3 80 432 64 371 348 23.7 

05/15/2001 10:21 10:42 688 Run 4 16.6 191 32.1 5.0 84 433 64 378 344 25.1 

05/15/2001 10:42 11:03 689 Run 4 15.2 145 26.6 5.2 85 418 55 361 339 24.2 

05/15/2001 11:03 11:24 690 Run 4 17.4 183 28.5 5.5 98 446 45 380 366 25.0 

05/15/2001 12:06 12:27 693 Run 5 18.0 177 31.4 5.5 93 440 49 383 355 24.7 

05/15/2001 12:27 12:48 694 Run 5 16.2 172 33.7 5.5 97 430 54 371 348 24.3 

05/15/2001 12:48 13:09 695 Run 5 16.0 153 34.4 6.1 102 417 52 362 339 23.3 

05/15/2001 13:09 13:30 696 Run 5 17.3 182 33.4 5.3 114 450 47 386 360 24.6 

05/15/2001 13:30 13:51 697 Run 5 14.3 185 35.8 5.7 122 449 45 393 365 25.7 

05/15/2001 13:51 14:12 698 Run 5 17.0 181 32.2 5.4 129 443 38 390 358 25.2 

05/15/2001 14:54 15:15 701 Run 6 17.8 166 31.4 5.4 137 455 39 392 376 25.6 

05/15/2001 15:15 15:36 702 Run 6 15.5 152 31.9 5.4 146 465 39 386 379 24.9 

05/15/2001 15:36 15:57 703 Run 6 12.4 167 31.4 5.4 142 443 48 387 362 24.4 

05/15/2001 15:57 16:18 704 Run 6 12.9 165 31.3 5.9 140 430 47 372 350 26.2 

05/15/2001 16:18 16:39 705 Run 6 14.0 187 34.1 5.3 168 427 36 381 353 24.9 

05/15/2001 16:39 17:00 706 Run 6 15.2 185 32.9 5.5 164 442 35 389 363 24.5 

05/15/2001 17:00 17:21 707 Run 6 13.7 164 36.7 6.2 166 462 46 387 369 25.0 

05/15/2001 18:03 18:24 710 Run 7 16.9 183 35.6 5.8 154 477 45 396 386 24.9 

05/15/2001 18:24 18:45 711 Run 7 18.5 166 34.5 6.4 134 478 44 404 395 24.2 

05/15/2001 18:45 19:06 712 Run 7 16.5 191 28.8 6.0 120 491 45 377 377 25.3 

05/15/2001 19:06 19:27 713 Run 7 16.1 168 30.9 5.6 121 459 40 375 359 25.3 

05/15/2001 19:27 19:48 714 Run 7 16.2 175 30.7 5.7 132 419 34 367 337 25.9 

05/15/2001 19:48 20:09 715 Run 7 15.1 159 33.3 5.5 137 436 30 379 351 24.3 

05/16/2001 8:58 9:18 725 Run 8 17.6 111 32.5 5.2 17 193 290 141 134 23.8 

05/16/2001 9:18 9:39 726 Run 8 20.3 139 31.8 6.0 20 220 242 134 150 24.2 

05/16/2001 9:39 10:00 727 Run 8 16.5 145 32.3 5.4 22 222 231 125 151 25.6 

05/16/2001 10:00 10:20 728 Run 8 18.0 156 29.4 5.3 28 197 199 136 148 24.6 

A-2

XC 

Date Start Stop No. RM No. As Ba Cd Cr Hg Ni Pb Sb Zn Pd 

(micrograms/dscm) 

05/16/2001 10:20 10:41 729 Run 8 12.5 176 36.3 5.1 33 204 202 135 141 24.4 

05/16/2001 10:41 11:01 730 Run 8 18.7 152 32.7 5.7 36 216 226 134 150 24.3 

05/16/2001 11:01 11:22 731 Run 8 17.1 162 32.4 5.7 44 226 214 141 150 23.9 

05/16/2001 11:42 12:03 733 Run 9 21.1 183 33.1 4.5 49 210 190 136 147 25.0 

05/16/2001 12:03 12:23 734 Run 9 14.8 170 32.7 5.6 50 201 170 139 142 24.0 

05/16/2001 12:23 12:44 735 Run 9 18.8 154 30.7 5.3 49 204 162 142 146 24.1 

05/16/2001 12:44 13:04 736 Run 9 16.6 206 35.4 6.5 56 223 191 154 152 24.9 

05/16/2001 13:04 13:25 737 Run 9 17.0 143 31.1 5.2 54 215 151 145 145 24.7 

05/16/2001 13:25 13:45 738 Run 9 18.6 138 28.8 5.2 59 200 153 145 144 24.5 

05/16/2001 13:45 14:05 739 Run 9 16.0 151 29.1 5.2 60 228 155 148 143 25.1 

05/16/2001 14:46 15:07 742 Run 10 19.2 156 34.7 6.0 91 210 146 148 146 25.2 

05/16/2001 15:07 15:27 743 Run 10 22.3 187 37.0 5.4 89 216 261 154 151 25.6 

05/16/2001 15:27 15:48 744 Run 10 17.0 141 32.5 5.4 82 192 115 134 133 24.9 

05/16/2001 15:48 16:08 745 Run 10 17.1 192 31.6 5.4 91 208 134 146 149 25.6 

05/16/2001 16:08 16:28 746 Run 10 17.5 161 36.2 5.5 95 208 108 163 145 24.2 

05/16/2001 16:29 16:49 747 Run 10 18.3 167 30.9 5.6 95 203 95 140 137 24.7 

05/16/2001 16:49 17:09 748 Run 10 12.7 139 29.9 5.4 109 186 110 152 137 24.5 

05/16/2001 17:32 17:52 750 Run 11 15.7 178 31.3 6.0 101 211 108 150 143 25.0 

05/16/2001 17:52 18:12 751 Run 11 15.8 147 30.2 5.2 96 209 102 147 141 25.5 

05/16/2001 18:12 18:33 752 Run 11 15.5 170 29.3 5.3 95 204 104 141 145 24.6 

05/16/2001 18:33 18:53 753 Run 11 16.4 178 30.2 5.4 95 192 91 147 138 25.6 

05/16/2001 18:53 19:13 754 Run 11 17.3 152 26.4 5.8 96 191 89 147 141 24.8 

05/16/2001 19:13 19:34 755 Run 11 17.2 167 32.8 5.5 92 201 89 143 146 24.9 

05/16/2001 19:34 19:54 756 Run 11 15.0 152 33.2 4.6 84 212 96 147 145 24.0 

05/17/2001 11:12 11:32 770 Run 12 17.8 174 26.5 4.1 24 224 170 137 133 24.6 

05/17/2001 11:32 11:52 771 Run 12 17.2 195 23.2 4.2 35 238 232 159 146 25.9 

05/17/2001 11:52 12:12 772 Run 12 20.5 174 30.5 4.3 55 222 273 165 157 25.3 

05/17/2001 12:12 12:32 773 Run 12 16.7 226 24.4 4.0 73 221 204 158 161 25.4 

05/17/2001 12:32 12:53 774 Run 12 18.4 153 31.7 4.8 79 206 161 158 151 24.1 

A-3

XC 

Date Start Stop No. RM No. As Ba Cd Cr Hg Ni Pb Sb Zn Pd 

(micrograms/dscm) 

05/17/2001 12:53 13:13 775 Run 12 12.3 177 28.0 4.5 83 204 138 155 143 24.4 

05/17/2001 13:13 13:33 776 Run 12 14.1 150 28.2 4.1 86 191 140 155 151 26.0 

05/17/2001 14:14 14:34 779 Run 13 19.1 162 35.9 5.1 80 201 119 171 146 24.0 

05/17/2001 14:34 14:54 780 Run 13 19.9 210 33.9 5.3 80 213 122 170 146 25.3 

05/17/2001 14:54 15:14 781 Run 13 17.4 159 36.1 6.1 82 235 117 168 149 25.0 

05/17/2001 15:14 15:34 782 Run 13 20.3 140 33.8 5.8 83 212 112 170 150 25.1 

05/17/2001 15:35 15:55 783 Run 13 21.3 196 40.7 5.9 84 173 129 169 117 24.4 

05/17/2001 15:55 16:15 784 Run 13 19.2 165 39.1 6.0 74 170 121 166 82 25.1 

05/17/2001 16:15 16:35 785 Run 13 8.3 94 18.7 4.0 46 70 85 77 22 25.2 

A-4