Ma y 2002



# Environmental Technolo **g y**  **Verification Report**
C OOPER 

# E NVIRONMENTAL 

# S ERVICES 

# XCEM M ULTI 

# -M ETALS 

# C ONTINUOUS 

# E MISSION 

# M ONITOR

Prepared by



## Battelle

Under a cooperative agreement with



## U.S. Environmental Protection AgencyMa y 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 (E PA), through its Office of Research and Development, has financ ially 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 e ndorsement or recommendation by the EPA for use.

ii

## Foreword

The U.S. EPA is charged by Congress with protec ting the nation’s air, wa ter, and land resources. Under a mandate of nati onal environmental laws, the Agency strives to formul ate and implement actions leading to a compatible balance between human activities and the ability of natural systems to support and nurture life. To meet th is mandate, the EPA’s Office of Research and Development provides da ta and science support that can be used to solve environmental problems and to build the scien tific knowledge base needed to manage our ecological resources wisely, to understand how pollutant s affect our health, and to pr event or reduce environmental risks. The Environmental Technology Verification (ETV) Program has been established by the EPA to verify the performance characteristics of innovative environm ental 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 e nvironmental technologies into the marketplace. Verification organizations oversee and report verification activities based on testing and quality assurance protocols develope d with input from major stakeholders and customer groups associated with the technology area. ETV cons ists 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 monito ring technologies are needed to assess environm ental quality and to supply cost and performance da ta to select the most appropr iate technology for that assessment. In 1997, through a competitive cooperative agreement, Battelle was awarded EPA funding and support to plan, coor dinate, 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 t echnology 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. Re ference method sampling and chemical analysis were conducted by the U.S. Ar my Center for Health Promo tion and Preventive Maintenance; operations at the Tooele Army Depot were led by Mike Pattison. Steve Bryson of MSE Technology Applications, Inc., Butte, Montana, di rected 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 As 2 

### O 5 

### arsenic oxide Ba barium Ba(NO 3 

### ) 2 

### barium nitrate Be beryllium BTU/hr British thermal units per hour Cd cadmium Cd(NO 3 

### ) 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 CO 2 

### carbon dioxide Cr chromium CrO 3 

### chromium trioxide DLS Directorate of Laboratory Sciences dscm dry standard cubic meter EPA United States Envir onmental Protection Agency ETV Environmental Technolog y Verification program Hg mercury Hg(NO 3 

### ) 2 

### mercury (II) nitrate ID internal diameter K 2 

### (C 4 

### H 2 

### O 6 

### Sb) 2 

### potassium antimony tartrate mg milligram M29 EPA Method 29 M301 EPA Method 301 ml milliliter MSE-TA MSE Technology Applicati ons Inc. (of Butte, Montana) Ni nickel Ni(NO 3 

### ) 2 

### nickel nitrate O 2 

### 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(NO 3 

### ) 2 

### zinc nitrate ZnO zinc oxide � 

### g m i c r o g r a m � 

### g/m 3 

### micrograms per cubic meter

ix

## Chapter 1 Background

The U.S. Environmental Protection Agency (E PA) has created the Environmental Technology Verification (ETV) Program to facilitate the deploy ment of innovative environmental technologies through performance verification and di ssemination of information. The goal of the ETV Program is to further environmental protection by substantially accelerating the acceptance and use of improved and cost-e ffective technologies. ETV seeks to achieve this goal by providing high-quality, peer-revi ewed data on technology perform ance to those involved in the design, distribution, financing, permitting, purch ase, and use of envi ronmental technologies. ETV works in partnership with recognized standa rds and testing organiza tions; with stakeholder groups that consist of buyers, ve ndor organizations, and permitters; and with th e full participation of individual technology developers. The pr ogram evaluates the performance of innovative technologies by developing test plans that are responsive to the needs of stakeholders, conducting field or laboratory tests (as a ppropriate), collecting and analyz ing data, and preparing peerreviewed reports. All evaluati ons are conducted in accordance w ith rigorous quality assurance (QA) protocols to ensure that data of known and ad equate quality are gene rated and that the results are defensible. The EPA’s National Exposure Research Laborator y and its verification organization partner, Battelle, operate the Advanced Monitoring Systems (AMS) Ce nter 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 procedur es and results of the verification test for that instrument, the X-ray based continuous emissi on 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 fo r air, water, and soil. This verification repor t provides results for the verification testing of the XCEM. The fo llowing 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 collec tion, the filter tape adva nces, moving the sample spot to an analysis area where a laboratory-grad e X-ray fluorescence (XRF) instrument is used to determine metal mass. The system is automate d and produces concentr ation data every 10 to 20 minutes for 19 elements of interest. The XC EM 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 thesample 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 wa s 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 f eet 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 offilter 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 dispersiveXRF 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 nonde structive, the filtrate on the tape can be reanalyzed at a later date if th e end-user require s 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, concen tration determination, and QA routines. Flow, temperature, concentration, pressure, and error messages are automatically record ed in a secure database. The data can be imported intoExcel 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 Con tinuous 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 ac tivities provided data fo r verification of the following performance parameters of the XCEM:



### � Relative accuracy 

### � Correlation with reference method 

### � Precision 

### � Span, zero, and intern al standard drift 

### � Bias 

### � Response time. Relative accuracy, correlation with the refere nce method, and precision (i.e., repeatability at stable test conditions) we re assessed for all of the elements being measured by the XCEM. The reference method in the asse ssment of relative accuracy a nd correlation was EPA Method 29 (3) 

### (M29). Precision was assessed in terms of the variability of XC EM response during periods when the stack gas flow rate and volume and the isokine tic rate were stable. The XCEM has an automated check for drift that measures a Pd intern al 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 dete rmined as the time between the start of one sampling period and the beginni ng 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 (A PE-1236M1) (Figure 3-1). This section describes the TEAD incinerator and the proce dures 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 (S e), silver (Ag), and thallium (Tl). Of the twelve regulated elements, five are ty pically 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. Deactivatio n 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, ga s 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 st andards. The incinerato r 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 component s 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. H 2 O) 4 Baghouse Inlet Temp. ( � F) 860 Kiln Feed End Draft Pressure (in. H 2 O) -0.2 Kiln Feed End Temp. ( � F) 375 Kiln Burner End Temp. ( � F) 1,000 O 2 – CEM (%) 15 CO (ppm) 8 Stack Temp. ( � F) 500 Stack Gas Velocity (ft/sec) 46

5

### � Main Control Panel . The main control panel contains va rious 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 in terlocks, and alarms. The comput er system is an industrialbased machine, running data acquisition software that provides centralized and integrated data management, process graphics, ope rator interface, and report generation.



### � CEMS . CEMS are in place to measure carbon monoxide (CO) and oxygen (O 2 

### ) in the exhaust stack. The CEMS include a sample extraction probe, heat-traced sampling lines, calibration ports, a refrigerate d condenser, a sample pump, f ilters, and flow meters. The sample extraction port is located in the exhaust stack approximately 20 feet above grade. The CEMS include automatic calibra tion, 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 conve yor 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 de posits the ammunition into the rotary furnace feed chute. If an out-of-param eter condition arises, the primar y 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-tem perature end of the k iln 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 reactiv e components from the metal shells. The heat to ignite the ammunition is initially provided by fuel oil form ing 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 as h and the metal compone nts of the ammunition are discharged at the burner end of the rota ry 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 fr eely, depending on the ammunition characteristics. The thick-cast steel walls contain high-order detonations. Feed rates, residence times, and ope rating parameters have been established for each ammunition item by controlled testing. The rotary fu rnace is equipped with a Hauck 783 proportioning burner located at the discharge end. The burne r has a capacity of 3 million British thermal units per hour (BTU/hr) and a nominal turndown ra tio 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 enclos es 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 be neath the retort shroud, creating a negative pressure. The combustion air bl ower creates a negative pressu re 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 fo r particles 10 microns and larg er. 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 valv e. 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 afte rburner. The afterburne r is equipped with a Hauck WR0164 wide-range burner with a cap acity 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 ty pically composed of metal casings, melted lead projectiles, and residual ash. Th e low end of the discharge conveyor is located underneath the discharge/burner end of the rotary furnace. Th e 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 particul ate cleansing for the ga s 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 pr essure 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 aninduced 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 authoriza tion 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 verificati on test took place at the TEAD in cinerator during the week of May 7, 2001. The XCEM verification test occu rred over a four-day period on May 14, 15, 16, and 17, 2001. A total of 13 M29 r uns were conducted, for two hour s each, consisting of three
8

### runs on May 14, four runs on May 15, four runs on May 16, a nd 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. Du ring M29 Runs 1 and 2, M17 .50-caliber bullets were incinerated. However, dur ing these runs, the XCEM obs erved 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 incine rate additional ammuniti on during the test until repairs to the bypass valve coul d be made. For this reason, no ammunition was bur ned 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 measur ed 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 incinerate d munitions provide meas urable concentrations of lead without spiking. Note that, for Hg, Ni, Sb, and Zn, different spik e 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 (As 2 

### O 5 

### ), cadmium metal, and chromium trioxide (CrO 3 

### ), dissolved in a dilute nitric acid solution. The second solution cont ained mercury (II) nitrate (Hg(NO 3 

### ) 2 

### ), nickel nitrate (Ni(NO 3 

### ) 2 

### ), and zinc oxide (ZnO), dissolved in dilute nitric acid. The final solution contained potassium antimony tartrate (K 2 

### (C 4 

### H 2 

### O 6 

### Sb) 2 

### ) and barium nitrate (Ba(NO 3 

### ) 2 

### ), dissolved in water. (5) 

### Spiking was conducted by MSE Technology A pplications 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 es tablish droplet size distributions based on pressure and airflow space rate. For these tests, pr essure 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 Li mitations and Target Spiking Levels
� � Emission Limits a ( g/dscm) Target Spiking Level a ( 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 me tals 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 simultane ously determined by the XCEM and two M29 sampling trains. The M29 trains sampled for tw o hours, while XCEM data, which are recorded every 20 minutes, were averaged for the M29 te st run. A total of 13 dua l M29 test runs were performed by the U.S. Army Center for Hea lth 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 w ith reference method data under constant conditions. CHPPM ’s Directorate of Laborator y 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 c onfirmed 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 identifi cation 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 re ference and CEM data were used and compared to quantify the performance of the XCEM. Table 3-5 summarizes th e data used for the ve rification comparisons.
10

### Table 3-5. Summary of Data to be Ob tained During XCEM Verification Test

Performance No. of

Parameter Objective Comparison Based On Data Points a

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 appro ach. M29 results that were iden tified as outliers were reported, but were not used for verificati on. 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 analys is 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 wa s suggested, an effort was made to find an assignable cause for the divergent result. For va lid test runs, M29 concen trations 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 esta blished based on the successive XCEM readings during the M29 runs, when spike injections and incinerator cond itions 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 th e precision of the XCEM. Span and zero determinations also were c onducted daily by the XCEM. The automated XCEM span routine extended a plunger containing four of the metals of intere st (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 readin gs was determined as an indicator of instrument drift. Internal 11

### standard drift also wa s 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 con centrations 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, a nd the average results were compared with the XCEM reported concentrations. The XCEM sampled for 10 to 20 minutes, dependi ng upon the desired detection limits. Within a few seconds of sampling, the exposed tape wa s moved into the XRF analysis region. Analysis required the same amount of time as sampling. Fo llowing analysis, concen trations were determined and recorded in a fraction of a second. Fo r 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 dur ing 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 compre ssed 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(NO 3 

### ) 2 

### , Cd(NO 3 

### ) 2 

### , Cr(NO 3 

### ) 3 

### , As 2 

### O 5 

### , Hg(NO 3 

### ) 2 

### , Ni(NO 3 

### ) 2 

### , Zn(NO 3 

### ) 2 

### , and Sb(NO) 3 

### . Solutions were prepared on-site to allow for flexibility in responding to background metal concentra tions found in the TEAD incinerator. The glassware, filters, and a ssociated equipment for M29 sa mpling were supplied by CHPPM. Multiple trains were supplied so that at least si x trains (i.e., three samp ling 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, sa mple recovery, and cleaning of used trains were the responsibility of CHPPM durin g this verification test. CHPPM provided laborator y equipment for sample recovery and analysis. This included all chemicals and solutions for rins ing train components and recoveri ng 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 [O 2 

### , carbon dioxide 12

### (CO 2 

### )], 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/m 3 

### ) in the flue gas, rather than 1,000 � 

### g/m 3 

### , 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 O 2 

### and CO 2 

### , as well as sensors for temper ature 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 au tomatic calibration, whic h caused the monitors to be calibrated periodically w ithout operator intervention. The re sults 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 im pinger 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 pe rformance 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 procedur es were employed. Samples were either in the direct custody of the sample custodian or under lock and key at all times. Sample cust ody sheets were included in the M29 data repor t provided by CHPPM. (6) 

### Recovered M29 samples we re sent for analysis at the CHPPM DLS at Aberdeen Proving Ground, Mary land. All sample analys es were completed within one month after the completion of the field verifica tion 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 calibrati on 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 entir ely 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 Rinse a � 3A, 3B, 3C a,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 6.00 c 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 d ilution (because of high Hg values). n/a = not applicable.


### One blank M29 train was prepared and recovered along with the sa mple trains to establish the blank levels of the targ et metals in the various sampling medi a. No detectable level of As, Cd, Cr, Hg, Pb, or Ni was found on the M29 filter or in any of the impi nger 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 corres ponds to about 2% or less of the mass of Ba found on the filters from the 13 M29 sample runs, and this Sb blank le vel 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 me tals in M29 sample fr actions 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,
1718�Table 4-2. Flue Gas Metal Concentrations Determined by Duplicate M29 Trains at theTEAD Incinerator (g/m3)RunAsBaCdCrHgNiPbSbZnNo.ABABABABABABABABAB111.310.324926430.130.74.44.129529039038014631773555575447487211.111.032027639.936.34.44.22722804014023248323662563446947339.39.519620629.629.54.44.129028237537888.079.0539532429407411.912.224726332.134.96.17.932331443946465.462.1629656491500511.312.422625533.535.75.86.732031639544044.846.3593661433475612.012.026028335.034.76.16.131832046947746.043.5663725499524712.011.626829033.834.86.36.531731947250051.552.1680745520559811.611.525726634.336.26.46.6106102197215184212257287209230911.711.021523234.235.27.16.310510518517080.174.82412341991861011.411.422020733.134.85.96.299.810217015385.383.22272161801711111.211.722923732.033.75.86.110110117719554.054.6242269187214129.59.022919928.926.75.14.71081081701531971772412301921701311.912.123126636.036.56.16.283.983.2148165108110265306166181

### Table 4-3. Summary of RPD Results from Duplicate M29 Trains in XCEM Verification a
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 rec overy lab to observe train prep aration, 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 la boratory in Aberdeen, Maryla nd, to observe M29 analysis procedures. All observations from the TSA we re documented in a TSA report, which was submitted to EPA Quality Manage ment 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 HNO 3 

### � 200 ml HNO 3 

### /H 2 

### O 2 

### solution + 100 ml of 0.1 N HNO 3 

### � 100 ml of 0.1 N HNO 3 

### � 100 ml KMnO 4 

### solution + 33 ml H 2 

### O 

### � 25 ml of 8 N HCl + 475 ml H 2 

### O. 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)]

Filter a , Fraction 2 a , Fraction 3 a , Fraction 4 b , Fraction 5 b , Fraction 6 b , 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 1.80 c (18) ND c 8.30 (83.0) 10.10 (101) ND d 18.60 d (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 12.10 3 (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 3.90 c (39) 0.26 c (2.6) 7.90 (79.0) 10.00 (100) ND d 18.60 d (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 fi eld spike results for this fraction were very low (nondetect and 2.6%, respectively) in both sp iked trains. Since a mercury spike should be very stable in the HNO 3 

### matrix, the only plausible explanati on 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 th e sample preparation procedure, Fraction 5 was filtered to remove MnO 2 

### precipitate, and it is possible that some or all of the Hg was trapped in the MnO 2 

### precipitate (and therefore in the filter). This filter was then digested in HCl and combined with Fr action 6. Therefore, it is possible that the Hg spiked in Fraction 5 was transferred to Frac tion 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 AuditBattelle’s Quality Manager audited at least 10% of the verification data acquired in the verification test. The Quality Manager traced a representa tive 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 th e XCEM as described below. In all cases, measurement results from both the re ference method and the XCEM were reported in units of � 

### g/m 3 

### on a dry basis at 20 � 

### C, 1 atmosphere pressure, and the actual flue gas O 2 

### content.

5.1 XCEM Concentration Average XCEM concentrations for a given reference method r un were calculated as follows:

n 

## C t 

# ∑ ij j 

## C i 

## = j = 1 

# ∑ t j


### where:
C i 

### = XCEM time-weighted concentration for element i during M29 test run C ij 

### = XCEM reported concentration for element i during time interval j n = number of XCEM measur ements during test run t j 

### = number of minutes XC EM 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 

## S d 

## d + t n − 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. S d 

### 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 calcu lated in this way can be inte rpreted as an upper confidence bound


### d

x for the relative bias of the analyzer, i.e., , wher e the superscript bar indicates the average of the differences of the reference values. RA was calcu lated 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 cal culations, 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) a nd coefficient of determination (r 2 

### ) for lead and for those metals spiked at more than one concentr ation (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: 

# ∑ ( d i 

### − d m 

# ) 2 

### SD d 

### = 

# ( n
− 1 

# )

Where:
d i 

### = the difference between paired sample train values d m 

### = mean of the d i 

### values n = number of paired samples
The t-statistic was then calculated as follows: 

## d t = m 

##  S D d 

##  

   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 d i 

### 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 th e 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 pe rformance may be different from that observed in the testing described here. Howe ver, 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 th e same period (solid horizontal bars) taken from data shown in Appendix A. Lead concentra tions are shown on two se parate 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 calcula ted for each of the M29 runs according to Section 5.1. Table 6-1 summarizes the results of the XCEM measuremen ts 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.

2627Table 6-1. Summary of Results from XCEM and M29 for Each Test Run�Metal Concentration (g/dscm)AsBaCdCrHgNiPbSbZnRunXCEM M29XCEM M29XCEM M29XCEM M29XCEM M29XCEM M29XCEM M29XCEM M29XCEM M291221118625627302418929244938511691618369565330467216112202982738242292764054012498324237162933147131391522012530342592864053777584349535332418416121602552934577231840845261643516433294955161217424133356610931843741847463806273534546141216927133356615131944547341453846943635127161217327932346613231845948640523827123675408171214826232355728104211206228198135272146219918111632233135575410521117816777144237145193101811163214333466931012031611388414822114217511161116323330335694101202186975414625614220112179178214272845621082151611881871552361481811318121612483436567584182156115109155286116173Average1711170246303456119210325311374451267455250346Average161116424031335610319730729610991248429235324(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 Da ta 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 Da ta During Verification Test (diamonds = XCEM, ba rs = 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 Da ta During Verification Test (diamonds = XCEM, ba rs = 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 c onsistently higher than those measured by M29 (Figure 6-1). However, it was observed that XCEM As concentrations were highly co rrelated with XCEM Pb concentrations (Figure 6-2).

31

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

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

As a 

### 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 Pb b 

### 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 b ackground stack gas, and the As was spiked at a constant rate, the observed corre lation is believed to be due to an XRF spectral interference. Concentrations of As are es tablished 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 reso lution 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, dur ing previous tests of the XCEM, a calibration method was used that contained both As and Pb. No Pb/As interfere nce was observed during those tests. (8)


### Ba and Sb
Ba and Sb exhibited similar be havior during verification testin g. 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 pr ogressed, 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 majo rity (approximately 80%) of the sample was collected in the HNO 3 

### impinger, suggesting that most of the vapor- phase Hg was oxidized rather than elemental. This preponderance of oxidized Hg is consistent with the appare ntly 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 t ook 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 obs erved at the high Pb concentrations in Runs 1 and 2. Also, on May 16, both the XCEM and M29 Pb methods reporte d a higher Pb concentration at the start of the day than was observed on the previous day. The XCEM reported a cons istent gradual decline 33

### in Pb concentrations throughout the day on Ma y 16, while M29 showed a more rapid decrease in concentration (Figure 6-1). On May 14, the XC EM 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 Ma y 14 XCEM/M29 comparisons indicate that the XCEM is responsive to rapid changes in Pb c oncentration and is resi stant 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 we re 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, P b, Sb, and Zn. Of these elements, Ni, Pb, Sb, and Zn show coefficients of determination (r 2 

### ) of 0.95 or better. The correlation for Pb was weaker over Runs 3 through 13 (r 2 

### = 0.75) than when all 13 runs were included (r 2 

### = 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 (r 2 

### =0.388) possibly due to the postula ted 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 st able 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 va lues exceeded 15%. Run 13 produced the highest RSD values for several of thes e 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 per cent RSD values ranged from 3 to 18%, and averaged 9.6%. Thus, the precision for Hg was st rongly influenced by the sampling difficulties noted above that occurred at the start of each test day. For Pb, percent RS D 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 r 2 = 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 r 2 = 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 r 2 = 0.75

0 50 100 150 200 250

0 100 200 300 **XCEM (ug/dscm) M29 (ug/dscm)** 

y = 0.95x + 97.23 r 2 = 0.39
0 100 200 300 **XCEM (ug/dscm )**

**Nickel M29 vs. XCEM** y = 1.11x ­ 51.28 r 2 = 0.95

0 100 200 300 400 500 600**M29 (ug/dscm) Zinc M 29 vs. XCEM** 
600 y = 1.42x - 7.79 r 2 = 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 (r 2 ) 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, th is 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 th e four test days, with the results shown in Table 6-5. Since the span and zero checks are ev aluations 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 c ubic meter also are shown in Ta ble 6-5 and reflect the typical sampling rate of 16 liters per spot.

36

### Table 6-5. XCEM Span and Zero Readin gs 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 tr end 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 i ndicate no measurable zero drift in the mass measurement. The XCEM de tection 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 hi gher than the Cr detection limit. The Pd internal standard, which is measured w ith 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%, w ith 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 peri od, the average daily Pd reading changed by less than 1.0%.

37Palladium

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 5/18/01Conc. (μg/dscm)

Pd Ave PD One std Dev 5% from Avera g e 

### Figure 6-4. XCEM Palladium Intern al Standard Readings During M29 Testing

6.6 XCEM Bias Relative to M29 Using the M301 approach, the XCEM results fo r all the target meta ls 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 concentr ations 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 agreemen t of XCEM and M29 Hg results (within about 20%) was found with M29 runs c onducted late in the te st 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 calcula ted for five elements that varied enough during the test to justify this comparison. For Ni, Pb, Sb, and Zn, r 2 

### values exceeding 0.95 were found, although the r 2 

### value for Pb decreased to 0.75 when the high Pb levels in Runs 1 and 2 were excluded. For Hg, an r 2 

### value of 0.39 was found, due, in pa rt, to the equilibration issue noted above. The XCEM’s precision, as RSD of successive readin gs 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 te st 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 sta ndard 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 au tomated 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 Softwa re, Albany, Oregon, 2001.
2. Test/QA Plan for Pilot-Scal e Verification of Continuous Emission Monitors for MultiMetals , Battelle, Columbus, Ohio, May 2001.
3. Determination of Metal Emi ssions from Stationary Sources , U.S. Environmental Protection Agency, Method 29, February 2000.
4. Field Validation of Pollutant Measurem ent 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 En gineers by MSE Technology Applications, Inc., Butte, Montana, June 2001.
6. Verification of Multi-Metals Continuous Em ission 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 ET V Advanced Monitoring Systems Pilot , Version 2.0, U.S. EPA Environmental Technology Verifi cation 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-1XC 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-2XC 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-3XC 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

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