Approved for public release; distribution is unlimited.ERDC/CERL TR-05-9



# X-Ray Fluorescence-Based Multi-Metal Continuous Emission Monitor Technology Demonstration

K. James Hay, Veera M. Boddu, Bruce E. Johnsen, and John A. Cooper March 2005Construction EngineeringResearch Laboratory

### ERDC/CERL TR-05-9 March 2005



# X-Ray Fluorescence Based Multi-Metal Continuous Emission Monitor: Technology Demonstration

K. James Hay and Veera M. Boddu Construction Engineeri ng Research Laboratory PO Box 9005 Champaign, IL 61826-9005

Bruce E. Johnsen and John A. Cooper Cooper Environmental Services 10170 SW Nimbus Avenue, Suite H5 Portland, OR 97223-4340

Final Report
Approved for public release; distribution is unlimited.



### Prepared for U.S. Army Corps of Engineers Washington, DC 20314-1000

Under Work Unit #CNE-B091ABSTRACT: Army demilitarization incinerators will need to comply with the Hazardous Waste Combustor National Emission Standa rd for Hazardous Air Pollutant s that will regulate metals and metal compounds listed under the Clean Air Act Amendments. A large problem for these incinerator operations is limited knowledge of the typeand quantity of emitted metals, so that compliance may be determined only through trial burn emission tests. A continuous emission monitor (CEM) for multi-metals will provide the emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn strategies for increased production. A user-friendly multi-metal CEM that uses x-ray fluorescence (XRF) as the analytical method and an automated sampling system that provides extractive batch sampling onto a filter tape (XCEM) was de monstrated at the 1236 De activation Furnace at Tooele Army Depot, Utah. The unit was compared to EPA Reference Method 29 during two separate tests (2001 and 2002). The second test was performed after improvements were made to the sample transport and system calibrations. The results indicate that the XCEM has met the proposed Perf ormance Specification 10 for multi-metal CEMs except for relative accuracy requirements for 4 of 9 metals. Its failures are attributed mostly to in adequacies in the reference method. The monitor is proving useful at Tooele and is ready for implementation at other Army demilitarization incinerators.

DISCLAIMER: The contents of this report are not to be used for advertising, pu blication, or promotional purposes. Citation of trade names does not constitute an official endorse ment or approval of the use of such commercial products. All product names and trademarks cited are the property of their respective owners. The findings of this report are not to be construed as an official Department of the Army pos ition unless so designated by other authorized documents. DESTROY THIS REPORT WHEN IT IS NO LONGER NEEDED. DO NOT RETURN IT TO THE ORIGINATOR.ERDC/CERL TR-05-9 iii



# Contents

List of Figures and Tables ..................................................................................................... .......... v

Conversion Factors............................................................................................................. ........... vii

Preface........................................................................................................................ ..................... viii

1 Introduction ................................................................................................................... .............1 Background..................................................................................................................... .... 1 Objective...................................................................................................................... ....... 3 Approach ....................................................................................................................... ..... 4 Mode of Technology Transfer ............................................................................................. 4

2 Field Testing 2001............................................................................................................. .........5 Brief Descripti on of XCEM.................................................................................................. 5

Extraction System.............................................................................................................. ............5 Sampling and Anal ysis System ................................................................................................... ..6
Control System................................................................................................................. .............7 Execution of Field-Te sting Activities ................................................................................... 7

Test Plan...................................................................................................................... ..................8
EPA Verification ............................................................................................................... ..............9
TEAD Inte rface................................................................................................................. .............9 Test Obje ctiv es ................................................................................................................ ............10
Site Descr iption ............................................................................................................... ............ 11 Experimental Design ............................................................................................................ .......14 Results........................................................................................................................ ...... 15

XCEM Reported C oncentrati ons .................................................................................................15 Sampling and Re sponse Time..................................................................................................... 19
Zero and Calibr ation Dr ift..................................................................................................... ........19
Correlation with Re ference Me thod .............................................................................................2 0 Response to Changes in Metal Concent ration ............................................................................25
Relative Accuracy.............................................................................................................. ..........25
Precis ion...................................................................................................................... ................33
Low-Level Meta l Res ponse

....................................................................................................... ..35
Bias .......................................................................................................................... ...................36 Summa ry ........................................................................................................................ .. 37iv ERDC/CERL TR-05-9

3 Transport and Calibrat ion Improvements ............................................................................39 Transport Line Changes ................................................................................................... 39 Recalibration.................................................................................................................. ... 40 Summary of Transport and Calibration Ev aluati ons......................................................... 40

4 M29 Comparison Testing of XCEM 2002 ..............................................................................42
Results........................................................................................................................ ...... 42

Method 29 Co ncentra tions ....................................................................................................... ...42
Predicted Stack Ga s Concentra tions ...........................................................................................43
XCEM Concen trati ons ............................................................................................................ .....47 XCEM Calibration Evaluation Usi ng A QuanX – XR F and ICP/ MS.................................. 53 Precision ...................................................................................................................... ..... 53 Discussion ..................................................................................................................... ... 54

Regulated Elements Typicall y Found in the Feedstream.............................................................54 Regulated Elements Not Typically Found in TEAD Emissi ons.....................................................58 Nonregulate d Meta ls ............................................................................................................ .......63 Summa ry ........................................................................................................................ .. 63

5 XCEM Cost and Status........................................................................................................... .65
Cost Estimates................................................................................................................. . 65

Capital Costs .................................................................................................................. .............65
Annual Costs ................................................................................................................... ............66 Continued Use of the XCEM ............................................................................................ 66

6 Summary and Conclusions....................................................................................................68

References..................................................................................................................... ..................71

Appendix A: Test/QA Plan for Verification of a Continuous Emission Monitor for Multi-metals at Tooele Army Depot (2001)............................................................................73

Appendix B: Determination of XCEM Reported Concentrations 2001...........................101

Appendix C: Transport and Calibration Evalua tions........................................................106

Appendix D: Mercury Calibration a nd Loss Discussion 2002......................................... 117

Abbreviations and Acronyms ..................................................................................................... 125

Report Documentation Page

...................................................................................................... .127ERDC/CERL TR-05-9 v



# List of Figures and Tables

Figures
1 XCEM stilling chamber and sampling cassette....................................................... 6
2 XCEM chassis ......................................................................................................... 7 3 New Component Cont rol Screen for XCEM so ftware interface .............................. 8 4 XCEM housing and transport line, M29 sampling setup, stack, and ceramic baghouse at TEAD ................................................................................................ 10 5 TEAD incinerator setup an d sampling/spikin g locati ons....................................... 13 6 Spiking at base of stac k during validati on testing ................................................. 15
7 Palladium concentratio ns during M29 testing ....................................................... 21
8 XCEM and M29 concentrations duri ng TEAD verifica tion testing......................... 22
9 Correlation between XCEM and M29 fo r elements spiked at two levels .............. 24
10 XCEM and M29 lead concent rations during runs 8–11......................................... 28
11 Ratio of XCEM to M29 concent rations during valid ation testing........................... 30
12 Uncorrected XCEM As concentratio ns versus XCEM Pb concentrations............. 32
13 Correlation between Sn and other APE-1236 metals with munitions burning and no spik ing ....................................................................................................... 46
14 XCEM tin measurement s during M29 testing........................................................ 46
15 XCEM versus M29 l ead for validati on test s .......................................................... 56
16 Percent difference between M29 and the XCEM versus percent of Hg on M29 filt er................................................................................................................ 60
17 2004 CES meta ls moni tor ..................................................................................... 67 C1 Experimental design fo r atomizati on test s .......................................................... 107 C2 XCEM reported concentrations for nonspiked elements......................................113 C3 XCEM reported concentrations and MSE-projected concentrations for spiked elements ...................................................................................................114 D1 Comparison of XCEM x-ray spectra measured during M29 testing and 71 days late r............................................................................................................. 121
D2 Percent difference between M29 and the XCEM vs. percent of Hg on the M29 filt er.............................................................................................................. 123vi ERDC/CERL TR-05-9

Tables
1 Army hazardous waste combustors......................................................................... 2 2 Proposed PS-10 requirem ents................................................................................. 3
3 XCEM test dates and associat ed TEAD incinerat ion feedstream............................ 9 4 Typical operating parameters for the APE-1236 deactiv ation furnace................... 12
5 TEAD metal emission limits during verificati on testing........................................... 12
6 TEAD incinerator metal emi ssion limits and sp iking levels .................................... 14 7 Final reported CEM concentr ations for M 29 testing............................................... 17 8 Upscale and zero concentrations during validat ion testing.................................... 20
9 Correlation betwee n the XCEM and M29............................................................... 25 10 XCEM measured, M29 measured, and MSE-predicted metal concentrations during TEAD validat ion test ing............................................................................... 26 11 Relative accuracy and correl ations ........................................................................ 27
12 Percent differences be tween M29 samp le trai ns ................................................... 34
13 XCEM and M 29 precis ion ...................................................................................... 35
14 Method 301 bias and correction fact or comparison ............................................... 37 15 Summary of XCEM performance rela tive to proposed PS-10 requirements ......... 38
16 M29 conc entrations................................................................................................ 43
17 APE-1236 stack flow rate s during M29 testing ...................................................... 44
18 APE-1236 stack concentrati ons with munitions incineration but no spiking .......... 45 19 Predicted stack concentrations based on MSE-TA spiking and background estimates ................................................................................................................ 47
20 XCEM concentrations............................................................................................. 48 21 Analysis of XCEM filter tape by Columbia Analytical ............................................. 53 22 Predicted (spiked), XCEM, and M29 pr ecision during validation testing ............... 53
23 TEAD emission limits for regulated elements ........................................................ 54 24 Summary of Pb concentration dat a and ratios duri ng M29 test ing ........................ 55 25 Summary of Cd concentration dat a and ratios duri ng M29 test ing........................ 57 26 Summary of Cr concentration dat a and ratios duri ng M29 test ing......................... 58 27 Summary of As concentration dat a and ratios duri ng M29 testing......................... 59 28 Summary of Hg concentration dat a and ratios duri ng M29 test ing........................ 60 29 Summary of Sb concentration dat a and ratios duri ng M29 test ing ........................ 61 30 Summary of Ni concentration dat a and ratios duri ng M29 test ing ......................... 62 31 Summary of Ba concentra tion data during M 29 testing......................................... 62 32 Summary of Zn concentration dat a and ratios duri ng M29 test ing ........................ 63 33 Summary of 2002 M29/XC EM comparison results ................................................ 64ERDC/CERL TR-05-9 vii

B1 Original XCEM reported concentrati ons uncorrected for calibration and dryer changes................................................................................................................ 103
B2 Results of dryer te sts............................................................................................ 105
C1 Flow rates and concentr ations used to calculate at omization concentrations..... 109

C2 Atomization vs. XC EM concentrations................................................................. 109 C3 Total capture mass vs . atomization mass .............................................................111
C4 Lead normalized atomization ma ss vs. total capture............................................111
C5 Method 17 vs. XC EM at TE AD............................................................................. 116 D1 Mercury reported concentrations during Year 2002 M29 validation testing......... 120 D2 Comparison of the location in M29 sampling trains where the Hg was deposited during the 200 1 and 2002 te sts........................................................... 122



# Conversion Factors

Non-SI * units of measurement used in this report can be converted to SI units as follows:

Multiply By To Obtain degrees Fahrenheit (5/9) x (°F – 32) degrees Celsius

* Système International d’Unités (“International System of Measurement”), commonly known as the “metric system.”viii ERDC/CERL TR-05-9



# Preface

This study was conducted for Headquarte rs, Department of the Army under Program Element 063728A, “Environmental Technology Demonstration”; Project002, “Environmental Compliance Technology”; Work Unit CNE-B091, “Hazardous Air Pollutants Technology Demonstrat ions.” The technical reviewer was Thomas Logan, U.S. Environmental Protection Agency.

The work was performed by the Environmental Process Branch (CN-E) of the Installations Division (CN), Constructi on Engineering Research Laboratory (CERL). The CERL Principal Investigator was Dr. K. James Hay. Part of this work was done by Cooper Environmen tal Services under DACA42-02-P-0072 and DACA42-01-C-0022; MSE Technology Applic ations, Inc. under GS-10F-0212K; and the U.S. Army Center for Health Pr omotion and Preventive Medicine. The technical editor was Linda L. Wheatley, Information Technology Laboratory — Champaign. Dr. Kirankumar V. Topudurti is Chief, CN-E, and Dr. John T. Bandy is Chief, CN. The associated Tec hnical Director was Gary W. Schanche. The Director of CERL is Dr. Alan W. Moore.

CERL is an element of the U.S. Army Engineer Research and Development Center (ERDC), U.S. Army Corps of En gineers. The Commander and Executive Director of ERDC is COL James Rowan, and the Director of ERDC is Dr. James R. Houston.ERDC/CERL TR-05-9 1



# 1 Introduction

Background

The U.S. Environmental Protection Agency (EPA) is developing regulations for hazardous waste combustors (HWC) as part of Title III of the 1990 Clean Air Act Amendments (CAAA) in the form of a Na tional Emission Standard for Hazardous Air Pollutants (NESHAP). The U.S. Army possesses a number of demilitarization furnaces that will need to comply with these regulations. Of most concern is meeting the requirements for metals and metal compounds listed under the CAAA. A large problem for these incinerato r operations is limited knowledge of the types and quantities of emitted meta ls. Compliance may be determined only through trial burn emission tests because of this limitation. These tests are expensive and require worst-case scenario burns. The air permits that are thenissued are based on these worst-case burns and impose limitations on the demilitarization facilities. A continuous emi ssion monitor (CEM) for metals would provide the emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn st rategies for increased production and sustainability. In addition, the HWC NESHAP suggests that a CEM would be the preferential method of emission accountability.

Multi-metal CEMs being developed are based on elemental sensors using laserinduced breakdown spectroscopy (LIBS) or inductively coupled plasma (ICP). None of the LIBS monitors has successfully met the EPA-proposed Performance Specification 10 (PS-10; EPA 1996) for continuous multi-metal monitors. Only one of the ICP units, developed by Thermo Jarrell Ash Corporation, has been successful in meeting the relative accuracy (RA) criteria of the PS-10 (Seltzer 2000). This technology appears to have lim itations such as its complexity, high initial costs, and high operating costs. The U.S. Army Engineer Research and Development Center, Construction Engi neering Research Laboratory (ERDC/ CERL) decided to pursue the development of the X-ray fluorescence (XRF)-based continuous emission monitor (XCEM) beca use it had the potential to be a reliable and accurate CEM without these limitations.

The basic approach of the XCEM is to draw a continuous representative sample of stack gas to a stilling chamber where a smaller metered sample is extracted and passed through a chemically treated filt er that collects metals in the particu-2 ERDC/CERL TR-05-9



### late and vapor phases. Following samplin g, the filter is passed through an XRF analyzer where the masses of up to 19 metals are measured. This approach was originally tested in 1997 at an EPA test incinerator, where the filters were analyzed offline (French 1998). Cooper En vironmental Services (CES) further developed this method into an on-line system that was tested under the ERDC/CERL Waste Minimization and Po llution Prevention Program at MSE Technology Applications, Inc.’s (MSE-TA’ s) research incinerator in Butte, Montana (Bryson et al. 2000). The results were encouraging because the XCEM met the PS-10 RA requirements for chromium (Cr) and lead (Pb). Many of the other requirements were unmet, however, and further development was needed. Itwas at this point that ERDC/CERL began funding the development of this technology under their Hazardous Air Pollutants (HAP) program.

The Army currently has 19 existing, new, or planned hazardous waste combustors. Table 1 lists these sites (Josephson 2003).

Table 1. Army hazardous waste combustors.

Location Type Waste Treated Status GO or CO Sierra AD APE 1236 CS Existing GO Tooele AD APE 1236 CS Existing GO Tooele AD APE 1236 Test Furnace – CS Existing GO McAlester AAP APE 1236 CS Existing GO Hawthorne AAP APE 2210 CS New CO Fort Richardson APE 1236 CS New GO Kansas AAP APE 1236 CS Existing CO Crane AAP APE 1236 CS New GO Lake City AAP APE 1236 Off-spec conventional Existing GO Picatinny Arsenal APE 1236 Waste R&D propellants New GO Pine Bluff Arsenal Fluidized Bed Pyrotechnics and Obscurants New GO Pine Bluff Arsenal APE 1236 Off-spec pyrotechnics Existing GO Radford AAP Kiln Off-spec propellants Existing GO Deseret CA Chemical Chem Existing GO Umatilla AD Chemical Chem New GO Pine Bluff Arsenal Chemical Chem New GO Anniston AD Chemical Chem New GO Pueblo CA Chemical Chem Planned GO Anniston AD Kiln De-Painting wastes Planned GO GO – Government Owned CO – Contractor Owned CA – Chemical Activity CS – Conventional Stockpile Chem – Chemical Stockpile APE - Ammunition Peculiar Equipment AD – Army Depot AAP – Army Ammunition PlantERDC/CERL TR-05-9 3



### Objective

The overall objective of the HAP program is to develop cost-effective technologies to help the Army meet current and future demands of HAP regulations. Toward this objective, the XCEM was developed. It was developed to possess characteristics that make it compatible with Ar my operations and expectations, such as user friendliness and affordability. That work is described in a precedent-setting report (Hay et al. 2005). The specific ob jective of this work was to demonstrate the XCEM at an Army installation. Th e desired exit criterion under the HAP Program was for the monitor to meet, under field conditions, the proposed PS-10 requirements, which are described in Table 2.

Table 2. Proposed PS-10 requirements.

Criterion Description Sampling and response time It is required that the sampling time be no longer than one-third of the averaging period for the applicable standard for a batch CEM. The delay between the end of the sampling period an d reporting of the sample analysisshall be no greater than 1 hour. A batch CEM is required to sample continuously except when changing the sampling media, which should be no greater than 5 percent of the averagin g period or 5 minutes, whichever is less. For this study, the averaging period is 12 hours, which means the sampling time should be no longer than 240 minutes, the response time no greater than 60 minutes, and the maximum time allowed for changing the sampling media is 5 minutes. Quality assurance Calibration drift: The calibra tion may not drift or deviate from the referencevalue of the calibration standard used for each metal by more than 5 percent of the emission standard for each me tal. Must allow for determining on a daily basis.Zero drift: The zero point for each metal shall not drift by more than 5 percent of the emission standard for that me tal. Must allow for determining on a daily basis. Span: The CEM response range must include zero and a high level value equal to the span. The span value is defined as 20 times the applicable emission limit for each metal. This is an equipment specification (not tested). RA The RA of the CEM must be no greate r than 20 percent of the mean value of the RM test data in terms of units of emission standard for each metal, or10 percent of the applicable standard, whichever is greater. During verification, the measure of RA at a single concentration level is required for each metal measured for compliance purpose s, and the RA must be determined at three concentration levels for one metal (zero can be one level). Source: EPA 1996.4 ERDC/CERL TR-05-9



### Approach

As a result of encouraging developmen t work (Hay et al. 2005) a new monitor was installed at the 1236 production deactivation furnace at Tooele Army Depot (TEAD), Utah. The monitor was compared to EPA Reference Method 29 (M29) in 2001. The monitor was only partly succe ssful; several improvements were warranted and implemented. A second M29 field-test was conducted a year later. This report includes the description and results from both M29 comparison tests and the modifications that took place in between. The XCEM was demonstrated under this project through contracts with CES and MSE-TA. The U.S. Army Center for Health Promotion and Preven tive Medicine (CHPPM) performed the M29 stack sampling activities described in this report.



### Mode of Technology Transfer

This technology was developed and de monstrated through the ERDC/CERL HAP Program, which uses 6.3 advanced development and field-testing funds. The HAP Program is part of the Army Envi ronmental Quality Technology (EQT) Program. As part of the EQT process, a technology transfer plan is being developed by the Army Environmental Center (AEC ) for this technology as well as other qualified technologies under the HAP program. A User’s Guide and Resource Manual have been developed to accompan y the XCEM for field training and reference (CES 2001a, 2001b). This technology is ready for transfer to Army facilities, and transition has already begun. The Army purchased another XCEM in 2003 for use at the 1236 Test Deactivation Furnace at TEAD.

This report will be made accessibl e through the World Wide Web at: http://www.cecer.army.milERDC/CERL TR-05-9 5



# 2 Field Testing 2001

The XCEM underwent M29 comparison te sting at the TEAD 1236 deactivation furnace in May 2001. This chapter presents a brief description of the XCEM, the testing activities, and the results of the testing.



### Brief Description of XCEM

A new XCEM was developed and built for demonstration at the TEAD facility as described in Hay et al. (2005). The XCEM extracts a sample of stack gas and concentrates the metals of interest on a chemically treated filter tape. Followingcollection, the filter tape is advanced to an analysis area where a laboratorygrade XRF instrument is used to determine metal mass. The system is entirely automated and produces concentration data every 10 to 20 minutes for up to 19 elements of interest. The three major X CEM components are: an extraction system, sampling and analysis system, and control system.

Extraction System

The XCEM extraction system collects a re presentative stack gas sample from thesmokestack and transports the sample to the filter. The system includes a sample probe and insulated sample line. Th e stack gas temperature is monitored in the sample line just before it enters the enclosure that houses the XCEM. The unit only operates when this temperatur e is above the dew point for water. Upon entering into the enclosure, the stack gas passes through a heat-traced stilling chamber with a larger diameter th at slows the gas velocity (Figure 1).Approximately 1 percent of the stack gas that enters the stilling chamber is sampled through an extraction tube for conc entration on a filter. The remaining 99percent of the gas is transported out of the stilling chamber, through a flow meter, and vented or returned to the stack (2 to 3 standard cubic feet per minute, SCFM). An eductor, located downstream of the stilling chamber, is used to pull the stack gas through the extraction system.6 ERDC/CERL TR-05-9

Figure 1. XCEM stilling chamber (verti cal pipe) and sampling cassette (bottom).



### Sampling and Analysis System

Approximately 0.8 liters per minute (Lpm) is extracted and concentrated on a filter tape for analysis. Following filt ration, the extracted stack gas is transported to the XCEM chassis where drying and volume determination take place (Figure 2).

The sampling cassette holds a 4-week supply of filter tape on a reel-to-reel system that is automated to accurately mo ve the tape from the sampling to an analysis position. Sampling and analysis occur simultaneously, resulting in a continuous monitoring system that re ports metal concentration measurements every 10 to 20 minutes.ERDC/CERL TR-05-9 7

Figure 2. XCEM chassis.



### Metal mass on the filter is determined using a modified ThermoNoran QuanXenergy dispersive XRF analyzer. The QuanX is capable of simultaneously measuring 19 elements and a palladium (Pd) quality assurance (QA) standard. Although the QuanX can readily quantify elements with atomic number 13 and above, the XCEM-modified QuanX is most efficient at quantifying and reporting hazardous elements with an atomic number greater than 24 (Cr). Since XRF is nondestructive, the retentate on the filter tape can be reanalyzed if the end-user requires additional data.

Control System

The XCEM is controlled by a personal computer using a custom WonderWare ® 

### (Progressive Software Solutions, Inc., Al bany, OR) software interface (Figure 3).All day-to-day functions of the XCEM are automated, including flow and temperature control, concentration determin ation, and QA routines. Flow, temperature, concentration, pressure, and error messages are automatically recorded in a secure database. The data can readily be imported into Excel or an equivalent program for subsequent evaluation. Flow, temperature, concentration, and pressure measurements are logged in real-time on the screen.



### Execution of Field- Testing Activities

Before shipment to Tooele, the XCEM was tested and an initial calibration was completed. Due to a tight timetable for this project, a final calibration was not conducted until after the tests. Test data were modified according to the final calibration, resulting in an 8 percent incre ase in reported metal concentrations. All calibration adjustments were comp leted prior to receiving M29 results.8 ERDC/CERL TR-05-9

Figure 3. New Component Control Sc reen for XCEM software interface.



### Following installation, preliminary onsite training was conducted for TEAD personnel. Onsite training consisted of an introduction to the XCEM and its capabilities. Although the XCEM has been designed for ease of use, it is recommended that additional training be prov ided to ensure successful integration of the XCEM into incinerator daily operations.

Test Plan

A test plan was developed to verify cap abilities of the XCEM to measure metalsunder typical incinerator conditions (Appendix A). The test plan outlined methodology for comparison testing between EPA M29 and the XCEM at the TEAD incinerator. Specifically, the test plan called for at least 12 EPA M29 tests with each test run lasting 2 hours. Arsenic (As), barium (Ba), Cr, cadmium (Cd), nickel (Ni), mercury (Hg), antimony (Sb), and zinc (Zn) were spiked during the reference method testing to ensure quantifiable concentrations of a wide variety of metals. Lead was also measured for ea ch test but was not spiked because it isfound in quantifiable concentrations in TEAD incinerator emissions under normal operating conditions. The actual dates of the test, associated M29 run numbers, and TEAD incineration feedstream are shown in Table 3.ERDC/CERL TR-05-9 9



### In general, the test plan (Appendix A) wa s followed as written with the following exceptions:

• The Army chose to burn bullets during the first two M29 tests rather than fuses as specified in the test plan.

• The XCEM observed high levels of Pb during the first two test runs. The TEAD operators believe that the high Pb was related to a faulty bypass valve. Consequently, the TEAD site manager de cided to run M29 testing with no ammunition being incinerated until repairs co uld be completed. The repairs were completed after run 11.

• A 13th M29 test run was added.

• Delays in completing a trial burn test at the Army incinerator forced a 2-day postponement in XCEM testing. To make up for lost time, four M29 test runs were completed on both 15 and 16 May.

Table 3. XCEM test dates and associ ated TEAD incineration feedstream. 14 May 15 May 16 May 17 May
Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7 Run 8 Run 9 Run 10 Run 11 Run 12 Run 13

50 Caliber 50 Caliber No Ammo No Ammo No Ammo No Ammo No Ammo No Ammo No Ammo No Ammo No Ammo MK344 Fuses MK344 Fuses



### EPA Verification

Test activities were coordinated with EPA’s Environmental Technology Verification (ETV) program. ETV’s charter is to provide objective and quality assured performance data on environmental technolo gies, so that users, developers, regulators, and consultants have an independent and credible assessment of an instrument’s performance. Battelle Memori al Institute, headquartered in Columbus, OH, is EPA’s partner for the ET V Advanced Monitoring Systems (AMS) Center. The scope of the AMS Center cove rs verification of monitoring methods for contaminants and natural species in air, water, and soil. For these tests, ETV representatives reviewed the test pl an and monitored testing procedures. They also conducted an onsite audit of the Army laboratory that analyzed theM29 samples. CES provided ETV representatives with the XCEM metal concentrations for each test run. The M29 test results were submi tted independently tothe ETV representatives. These data, combined with an evaluation of the quality of the test, have been documented in a final ETV report (Myers et al. 2002).

TEAD Interface

The XCEM sampled the stack gas through a probe and transport line. Ideally, the probe would have been shrouded, which allows for increased flexibility in isokinetic sampling and reduces particulate loss in the probe. However, the shrouded probes are specially manufactu red by Anderson Instruments, Inc.10 ERDC/CERL TR-05-9



### (Smyrna, GA), and procuring the special probe requires significant lead time. With the short project timeline, a more easily built custom probe with a simpler design was supplied by Millennium Instruments, Inc (Spring Grove, IL). The probe was located at the same elevation as the reference method probes within 86 inches of the top of the stack. The XCEM and M29 probes were located approximately 27 feet above the base of the exhaust stack. The nearest flow disturbances were 9.8 duct diameters upst ream (induced draft fan) and 4.3 duct diameters downstream (top of the stack) from the sample ports. These distances are adequate to ensure that these flow disturbances do not affect the sampling. The transport line consisted of approximat ely 35 ft of 1.5-in. diameter stainless steel tubing that extended from the probe to the XCEM shed, which was on the ground near the stack (Figure 4).

Test Objectives

The overall objective of the test was to provide quantitative verification of the performance of the XCEM under field cond itions. EPA’s draft performance specification document PS-10 (EPA 1996) is a proposed description of how to assess the acceptability of a multi-metal CEM upon installation and thereafter.

Figure 4. XCEM housing and transport line, M29 sampling setup, stack, and ceramic baghouse at TEAD.ERDC/CERL TR-05-9 11



### The goals of the verification test were to meet the proposed PS-10 requirements for: 1. Response time and reporting time for a batch CEM. 2. QA by passing daily zero and calibration drift checks. 3. Relative accuracy for the elements in the feedstream of the TEAD incinerator (Sb,Ba, Cd, Cr, and Pb). This includes evaluating the response to change in concentration by testing at least one element at two concentration levels.

A secondary objective was to meet the RA criteria for additional regulated and unregulated metals, which are not typically found in the feedstream (As, Hg, Ni, and Zn).

Additional performance parameters ex amined during the testing included:

• correlation with reference method

• precision

• low-level metal response

• bias.

The XCEM has an automated check for calibration drift that measures a Pd standard with each XCEM test run. Calibration drift was also checked by the automated daily XCEM zero and upscale QA measurements. For the verification test, response time was determined as the time between the start of one sampling period and the beginning of a second sampling period. The effectiveness of the XCEM to measure low concentrations was determined by a comparison to Cr and As reference method concentrations. Bias was identified using EPA Method 301 – Field Validation of Pollutant Measurement Methods from Various Waste Media (EPA 1992).

It was beyond the scope of this verifica tion test to durability for routine longterm use. This test evaluated the perf ormance of a new XCEM over a relativelyshort test period, operated by skilled personnel. It must be noted that the longterm performance may be different from that observed in the testing described here. The XCEM did not exhibit any mech anical problems during the test; it completed more than 150 test runs du ring the week without any downtime.

Site Description

Verification testing took place at TEAD building 1320 deactivation incineratorAPE-1236. The TEAD incinerator, which runs on diesel fuel, is designed to incinerate decommissioned munitions. Typi cal operating parameters for the incinerator are shown in Table 4. The TEAD incinerator is classified as a dry stack12 ERDC/CERL TR-05-9



### with water content ranging from 5 to 10 percent. Typical stack PM concentrations are in the range of 10 micrograms per dry standard cubic meter.

The TEAD incinerator is currently regu lated under the Resource Conservation and Recovery Act (RCRA) for Sb, As, Ba, beryllium (Be), Cd, Cr, Pb, Hg, Ni, selenium (Se), silver (Ag), and thallium (Tl). Of the 12 regulated elements, 5 are typically found in the feedstream: Sb, Ba, Cd, Cr, and Pb. The XCEM wastested for its measurement capabilities of the five elements found in the feedstream as well as As, Hg, Ni, and a nonregulated metal, Zn. These elementswere selected in order to challenge the XCEM over a large range of analysis conditions and elemental concentrations.

For the verification test, metals in th e TEAD incinerator stack gas were regulated under a Temporary Authorization permit (Table 5). Of the 12 regulatedmetals, Pb is the only element that was consistently found in measurable concentrations in the stack gas. Figure 5 shows the deactivation incinerator set up and the locations for sampling and spiking during the test.

Table 4. Typical operating parameters for the APE-1236 deactivation furnace.

Temp. (°F) 1630 Baghouse ∆ P (in. H 2 O) 4 Baghouse Inlet Temperature (°F) 860 Kiln Feed End Draft Pressure (in. H 2 O) -0.2 Kiln Feed End Temperature (°F) 375 Kiln Burner End Temperature (°F) 1000

O 2 – CEM (%) 15 CO (ppm) 8 Stack Temperature (°F) 500 Stack Gas Velocity (ft/sec) 46

Table 5. TEAD metal emission limits during verification testing.

Element Limit (g/hr) Element Limit (g/hr)
Antimony 14 Lead 4.3 Arsenic 0.11 Mercury 14

Barium 2400 Nickel 930 Beryllium 0.20 Selenium 180
Cadmium 0.26 Silver 140
Chromium 0.04 Thallium 14ERDC/CERL TR-05-9 13

XCEMFurnace



### Feed DischargeAfterburner



### Cyclone

Fan Stack

Ceramic BaghouseAir flow



## Top view of TEAD Incinerator Setup XCEMFurnace



### Feed DischargeAfterburner



### Cyclone

Fan Stack

Ceramic BaghouseAir flow



## Top view of TEAD Incinerator SetupScaffolding 

## Stack

XCEM Spiking M29 Sampling 

## Front view of TEAD Stack during Sampling

Air flow FanScaffolding 

## Stack

XCEM Spiking M29 Sampling 

## Front view of TEAD Stack during Sampling

Air flow Fan

Figure 5. TEAD incinerator setup and sampling/spiking locations.14 ERDC/CERL TR-05-9



### Experimental Design

Both the kiln and afterburner were fired wi th diesel fuel for all 13 runs. Duringruns 1 and 2, 50-caliber bullets were incinerated. The XCEM observed unexpected high Pb concentrations during th ese runs, however, which led to a decision not to incinerate additional ammuni tion during the test until repairs to a bypass valve could be made. For this re ason, no ammunition was burned duringruns 3 through 11. Following the bypass repair, two final M29 runs were conducted while incinerating Mark 344 fuses. Table 6 shows the 9 elements that were measured by the XCEM during all 13 of the verification test runs. Eight of these metals were spiked directly into the stack downstream of the controls. These metals were spiked at the level shown in Table 6. Lead, however, was not spiked since the incinerated munitions provide measurable concentrations of Pb without spiking.

Spiking was conducted by MSE-TA using th ree atomizers to inject solutions containing the metals directly into the stac k (Figure 6). Manufacturer specifications for the atomizers determine droplet size distributions based on pressure and airflow rate. For these tests, pressure and flow rate were maintained to keep droplet sizes less than 28 microns in diameter. When dried, the majority of the particle mass was calculated to be in the 1 to 4 micron diameter range. An analysis ofthe M29 concentration data during validation testing indicated that 10 to 15 percent of the spiked metal mass was lost on the probe (CHPPM 2001). This level of probe loss is typical for M29 at an incinerator and, since particulate loss in the probe depends in part on particle size, indicates that the spiked metal particle size was on the same order as a typical incinerator.

Table 6. TEAD incinerator metal emission limits and spiking levels.

Emission Limits 1 Spiking Level 1
~ μg/dscm Elements g/hr ~ μg/dscm Runs 1-6 Runs 7-13
As 0.11 25 14 14 Ba 2,400 540,000 200 200
Cd 0.26 58 34 34 Cr 0.04 10 5 5 Hg 14 3,145 280 88 Ni 930 209,000 460 180 Pb 4.3 966 NS NS Sb 14 3145 520 200
Zn NR NR 460 180

1 The concentration in μg/dscm assumes a stack flow rate of about 4500 dscm/hr NR: Not regulated NS: Not spikedERDC/CERL TR-05-9 15

Figure 6. Spiking at base of stack during validation testing.



### Three separate solutions were prepared fo r spike injection. The first solution contained arsenic oxide (As 2 

### O 5 

### ), Cd metal, and chromium oxide (CrO 3 

### ) dissolved in a dilute nitric acid solution. The second solution contained mercury nitrate (Hg(NO 3 

### ) 2 

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

### ) 2 

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

### (C 4 

### H 2 

### O 6 

### Sb) 2 

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

### ) 2 

### ) dissolved in water (Bryson 2001).

A total of 13 dual M29 test runs were performed over a 4-day period (14–17 May) by the U.S. Army CHPPM Air Quality Surveillance Program. The M29 trains sampled for 2 hr while XCEM data were recorded every 20 minutes and were averaged for comparison to each M29 test run. As a performance audit, two blank trains were quantitatively spiked with all nine of the metals.

CHPPM’s Directorate of Laboratory Serv ices (DLS) conducted laboratory analysis of the sampling trains.



### Results

XCEM Reported Concentrations

Time-weighted average concentrations



### Average XCEM concentrations during the time of one M29 test run were calculated using Equation 1.16 ERDC/CERL TR-05-9



# ∑ ∑

= 

### = j n

j j ij

i 

### t t C C 1 [Eq 1]



### 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 measurements during test run t j 

### = number of minutes XCEM measured element i ’s concentration during time interval j coinciding with M29 sampling. 

# ∑ j 

### t = M29 sampling period.

Data corrections



### Following M29 testing, but prior to rece iving M29 results, CES recalibrated the XCEM and determined that a 4.4 percent global change was required for XCEM reported concentrations. In addition to the recalibration, CES conducted extensive testing of the sample line dryer and determined that a 3.5 percent correction in flow was required since the dryer did not remove all of the moisture in the line. The net result of these changes was to uniformly increase the reported XCEM concentrations by about 8 percent. Appendix B includes a complete discussion of these changes.

In addition to the global changes, it wa s determined that a spectral interference between Pb and As was affecting As concen trations. For this reason, As concentrations were corrected for the Pb interference as discussed in Response to Changes in Metal Concentration (page 25). Arsenic corrections were completed prior to receiving M29 data.

The final reported XCEM concentrations ar e listed in Table 7. Approximately six to seven XCEM measurement took place during each M29 run. The “Min. of Run” column in Table 7 refers to the number of minutes for that particular XCEM (listed as XC in the table) measurement that coincided with the M29 run.ERDC/CERL TR-05-9 17

Table 7. Final reported CEM concentrations ( μ g/dscm) for M29 testing.

RM No. Date Start Stop XC No. Min. of Run XC Time As Ba Cd Cr Hg Ni Pb Sb Zn Pd

Run 1 5/14/01 10:45 11:05 650 5.0 19:48.0 20.8 166 27.7 3.1 59 343 1,102 340 297 24.1 Run 1 5/14/01 11:05 11:26 651 21.2 21:12.0 24.3 171 26.0 2.5 109 436 1,127 372 316 23.8 Run 1 5/14/01 11:26 11:48 652 21.5 21:32.0 21.1 192 26.5 1.9 156 467 1,149 361 320 25.6 Run 1 5/14/01 11:48 12:09 653 21.7 21:42.0 20.7 165 21.8 2.2 207 449 1,196 353 316 25.5 Run 1 5/14/01 12:10 12:31 654 21.7 21:41.0 25.3 187 28.2 2.6 242 470 1,319 377 342 24.6 Run 1 5/14/01 12:31 12:53 655 21.9 21:51.0 21.5 218 31.8 2.2 257 515 1,607 399 372 25.4 Run 1 5/14/01 12:53 13:15 656 7.0 22:07.0 23.8 202 27.2 2.4 283 463 709 386 348 24.2 Time Weighted Avg. 120.0 21:24.7 22.6 187 26.9 2.3 194 462 1,240 372 333 Run 2 5/14/01 13:58 14:23 659 18.3 25:09.0 7.3 230 26.8 2.3 186 375 3,422 360 299 25.6 Run 2 5/14/01 14:23 14:46 660 22.9 22:56.0 3.5 224 29.5 2.0 234 427 3,248 379 345 24.7 Run 2 5/14/01 14:46 15:09 661 22.9 22:56.0 13.0 249 26.0 1.2 244 427 3,017 398 352 25.1 Run 2 5/14/01 15:09 15:32 662 22.9 22:54.0 23.8 250 22.3 2.0 220 405 2,683 370 332 25.3 Run 2 5/14/01 15:32 15:55 663 22.6 22:36.0 31.5 194 29.1 1.2 239 415 2,347 379 347 25.2 Run 2 5/14/01 15:55 16:17 664 10.3 22:34.0 17.8 172 27.1 2.6 257 392 182 348 319 24.4 Time Weighted Avg. 120.0 23:10.8 16.3 224 26.8 1.8 229 410 2,690 375 335 Run 3 5/14/01 17:00 17:23 667 16.0 22:45.0 15.3 127 25.4 3.4 259 395 118 334 320 24.6 Run 3 5/14/01 17:23 17:44 668 21.0 21:00.0 13.1 140 21.3 2.2 264 388 91 335 319 25.2 Run 3 5/14/01 17:44 18:05 669 20.9 20:52.0 13.0 158 27.0 2.5 265 417 60 355 341 25.4 Run 3 5/14/01 18:05 18:26 670 21.0 20:58.0 13.1 175 28.9 2.9 268 409 55 363 339 25.7 Run 3 5/14/01 18:26 18:47 671 20.9 20:53.0 14.2 168 21.4 2.4 255 413 60 352 333 24.6 Run 3 5/14/01 18:47 19:07 672 20.3 20:54.0 11.2 147 24.0 2.3 249 414 65 360 347 25.9 Time Weighted Avg. 120.0 21:13.7 13.2 154 24.6 2.6 260 406 73 351 334 Run 4 5/15/01 8:59 9:18 684 3.3 19:43.0 13.2 145 21.5 4.5 33 294 69 271 235 25.0 Run 4 5/15/01 9:18 9:39 685 20.6 20:34.0 15.0 173 28.5 6.2 54 401 69 333 319 23.4 Run 4 5/15/01 9:39 10:00 686 20.9 20:55.0 15.6 133 33.2 5.4 69 432 66 362 349 24.7 Run 4 5/15/01 10:00 10:21 687 21.0 21:00.0 16.2 154 30.5 5.3 80 432 64 371 348 23.7 Run 4 5/15/01 10:21 10:42 688 21.0 20:58.0 16.6 191 32.1 5.0 84 433 64 378 344 25.1 Run 4 5/15/01 10:42 11:03 689 21.0 20:57.0 15.2 145 26.6 5.2 85 418 55 361 339 24.2 Run 4 5/15/01 11:03 11:24 690 12.3 20:51.0 17.4 183 28.5 5.5 98 446 45 380 366 25.0 Time Weighted Avg. 120.0 20:42.6 15.8 161 29.8 5.4 76 422 62 361 340 Run 5 5/15/01 12:06 12:27 693 15.6 20:55.0 18.0 177 31.4 5.5 93 440 49 383 355 24.7 Run 5 5/15/01 12:27 12:48 694 20.9 20:52.0 16.2 172 33.7 5.5 97 430 54 371 348 24.3 Run 5 5/15/01 12:48 13:09 695 20.9 20:51.0 16.0 153 34.4 6.1 102 417 52 362 339 23.3 Run 5 5/15/01 13:09 13:30 696 20.8 20:48.0 17.3 182 33.4 5.3 114 450 47 386 360 24.6 Run 5 5/15/01 13:30 13:51 697 21.0 20:57.0 14.3 185 35.8 5.7 122 449 45 393 365 25.7 Run 5 5/15/01 13:51 14:12 698 21.0 20:59.0 17.0 181 32.2 5.4 129 443 38 390 358 25.2 Time Weighted Avg. 120.0 20:53.7 16.4 175 33.6 5.6 110 438 47 381 354 Run 6 5/15/01 14:54 15:15 701 7.2 20:57.0 17.8 166 31.4 5.4 137 455 39 392 376 25.6 Run 6 5/15/01 15:15 15:36 702 21.0 20:59.0 15.5 152 31.9 5.4 146 465 39 386 379 24.9 Run 6 5/15/01 15:36 15:57 703 21.0 20:58.0 12.4 167 31.4 5.4 142 443 48 387 362 24.4 Run 6 5/15/01 15:57 16:18 704 20.9 20:56.0 12.9 165 31.3 5.9 140 430 47 372 350 26.2 Run 6 5/15/01 16:18 16:39 705 20.9 20:54.0 14.0 187 34.1 5.3 168 427 36 381 353 24.9 Run 6 5/15/01 16:39 17:00 706 20.9 20:55.0 15.2 185 32.9 5.5 164 442 35 389 363 24.5 Run 6 5/15/01 17:00 17:21 707 8.2 20:58.0 13.7 164 36.7 6.2 166 462 46 387 369 25.0 Time Weighted Avg. 120.0 20:56.7 14.2 170 32.6 5.6 152 443 41 384 363 Run 7 5/15/01 18:03 18:24 710 18.1 20:55.0 16.9 183 35.6 5.8 154 477 45 396 386 24.9 Run 7 5/15/01 18:24 18:45 711 21.0 20:58.0 18.5 166 34.5 6.4 134 478 44 404 395 24.2 Run 7 5/15/01 18:45 19:06 712 21.0 20:58.0 16.5 191 28.8 6.0 120 491 45 377 377 25.3 Run 7 5/15/01 19:06 19:27 713 21.0 20:59.0 16.1 168 30.9 5.6 121 459 40 375 359 25.3 Run 7 5/15/01 19:27 19:48 714 20.8 20:50.0 16.2 175 30.7 5.7 132 419 34 367 337 25.9 Run 7 5/15/01 19:48 20:09 715 18.1 20:41.0 15.1 159 33.3 5.5 137 436 30 379 351 24.3 Time Weighted Avg. 120.0 20:53.5 16.6 174 32.2 5.8 132 461 40 383 36718 ERDC/CERL TR-05-9

Table 7 (Cont’d). Final reported XCEM concentrations ( μ g/dscm) for M29 testing.

RM No. Date Start Stop XC No. Min. of Run XC Time As Ba Cd Cr Hg Ni Pb Sb Zn Pd

Run 8 5/16/01 8:58 9:18 725 15.3 20:24.0 17.6 111 32.5 5.2 17 193 290 141 134 23.8 Run 8 5/16/01 9:18 9:39 726 20.6 20:33.0 20.3 139 31.8 6.0 20 220 242 134 150 24.2 Run 8 5/16/01 9:39 10:00 727 20.6 20:33.0 16.5 145 32.3 5.4 22 222 231 125 151 25.6 Run 8 5/16/01 10:00 10:20 728 20.6 20:33.0 18.0 156 29.4 5.3 28 197 199 136 148 24.6 Run 8 5/16/01 10:20 10:41 729 20.4 20:26.0 12.5 176 36.3 5.1 33 204 202 135 141 24.4 Run 8 5/16/01 10:41 11:01 730 20.4 20:24.0 18.7 152 32.7 5.7 36 216 226 134 150 24.3 Run 8 5/16/01 11:01 11:22 731 2.3 20:30.0 17.1 162 32.4 5.7 44 226 214 141 150 23.9 Time Weighted Avg. 120.0 20:29.0 17.3 148 32.5 5.4 27 210 229 134 146 Run 9 5/16/01 11:42 12:03 733 7.1 20:28.0 21.1 183 33.1 4.5 49 210 190 136 147 25.0 Run 9 5/16/01 12:03 12:23 734 20.4 20:26.0 14.8 170 32.7 5.6 50 201 170 139 142 24.0 Run 9 5/16/01 12:23 12:44 735 20.4 20:21.0 18.8 154 30.7 5.3 49 204 162 142 146 24.1 Run 9 5/16/01 12:44 13:04 736 20.3 20:18.0 16.6 206 35.4 6.5 56 223 191 154 152 24.9 Run 9 5/16/01 13:04 13:25 737 20.4 20:24.0 17.0 143 31.1 5.2 54 215 151 145 145 24.7 Run 9 5/16/01 13:25 13:45 738 20.3 20:19.0 18.6 138 28.8 5.2 59 200 153 145 144 24.5 Run 9 5/16/01 13:45 14:05 739 11.1 20:23.0 16.0 151 29.1 5.2 60 228 155 148 143 25.1 Time Weighted Avg. 120.0 20:22.7 17.3 162 31.6 5.5 54 210 166 145 146 Run 10 5/16/01 14:46 15:07 742 17.2 20:24.0 19.2 156 34.7 6.0 91 210 146 148 146 25.2 Run 10 5/16/01 15:07 15:27 743 20.4 20:21.0 22.3 187 37.0 5.4 89 216 261 154 151 25.6 Run 10 5/16/01 15:27 15:48 744 20.4 20:23.0 17.0 141 32.5 5.4 82 192 115 134 133 24.9 Run 10 5/16/01 15:48 16:08 745 20.3 20:16.0 17.1 192 31.6 5.4 91 208 134 146 149 25.6 Run 10 5/16/01 16:08 16:28 746 20.4 20:21.0 17.5 161 36.2 5.5 95 208 108 163 145 24.2 Run 10 5/16/01 16:29 16:49 747 20.3 20:20.0 18.3 167 30.9 5.6 95 203 95 140 137 24.7 Run 10 5/16/01 16:49 17:09 748 1.2 20:20.0 12.7 139 29.9 5.4 109 186 110 152 137 24.5 Time Weighted Avg. 120.0 20:20.7 18.5 167 33.8 5.5 91 206 143 147 143 Run 11 5/16/01 17:32 17:52 750 6.3 20:21.0 15.7 178 31.3 6.0 101 211 108 150 143 25.0 Run 11 5/16/01 17:52 18:12 751 20.3 20:18.0 15.8 147 30.2 5.2 96 209 102 147 141 25.5 Run 11 5/16/01 18:12 18:33 752 20.3 20:20.0 15.5 170 29.3 5.3 95 204 104 141 145 24.6 Run 11 5/16/01 18:33 18:53 753 20.3 20:18.0 16.4 178 30.2 5.4 95 192 91 147 138 25.6 Run 11 5/16/01 18:53 19:13 754 20.2 20:12.0 17.3 152 26.4 5.8 96 191 89 147 141 24.8 Run 11 5/16/01 19:13 19:34 755 20.2 20:12.0 17.2 167 32.8 5.5 92 201 89 143 146 24.9 Run 11 5/16/01 19:34 19:54 756 12.3 20:17.0 15.0 152 33.2 4.6 84 212 96 147 145 24.0 Time Weighted Avg. 120.0 20:16.9 16.2 163 30.2 5.4 94 201 96 145 143 Run 12 5/17/01 11:12 11:32 770 13.0 20:01.0 17.8 174 26.5 4.1 24 224 170 137 133 24.6 Run 12 5/17/01 11:32 11:52 771 20.1 20:08.0 17.2 195 23.2 4.2 35 238 232 159 146 25.9 Run 12 5/17/01 11:52 12:12 772 20.2 20:14.0 20.5 174 30.5 4.3 55 222 273 165 157 25.3 Run 12 5/17/01 12:12 12:32 773 20.3 20:16.0 16.7 226 24.4 4.0 73 221 204 158 161 25.4 Run 12 5/17/01 12:32 12:53 774 20.2 20:12.0 18.4 153 31.7 4.8 79 206 161 158 151 24.1 Run 12 5/17/01 12:53 13:13 775 20.2 20:12.0 12.3 177 28.0 4.5 83 204 138 155 143 24.4 Run 12 5/17/01 13:13 13:33 776 6.0 20:07.0 14.1 150 28.2 4.1 86 191 140 155 151 26.0 Time Weighted Avg. 120.0 20:10.0 17.0 182 27.5 4.3 62 218 195 156 150 Run 13 5/17/01 14:14 14:34 779 6.1 20:15.0 19.1 162 35.9 5.1 80 201 119 171 146 24.0 Run 13 5/17/01 14:34 14:54 780 20.2 20:10.0 19.9 210 33.9 5.3 80 213 122 170 146 25.3 Run 13 5/17/01 14:54 15:14 781 20.2 20:09.0 17.4 159 36.1 6.1 82 235 117 168 149 25.0 Run 13 5/17/01 15:14 15:34 782 20.2 20:10.0 20.3 140 33.8 5.8 83 212 112 170 150 25.1 Run 13 5/17/01 15:35 15:55 783 20.2 20:12.0 21.3 196 40.7 5.9 84 173 129 169 117 24.4 Run 13 5/17/01 15:55 16:15 784 20.0 20:02.0 19.2 165 39.1 6.0 74 170 121 166 82 25.1 Run 13 5/17/01 16:15 16:35 785 13.1 19:57.0 8.3 94 18.7 4.0 46 70 85 77 22 25.2 Time Weighted Avg. 120.0 20:07.9 18.4 165 34.7 5.6 77 186 116 159 118ERDC/CERL TR-05-9 19



### Sampling and Response Time

The XCEM met PS-10 sampling and respon se time criteria for a batch CEM. These criteria are that (1) the sampling time be no longer than one-third of the averaging period for the applicable standard, (2) the delay between the end of the sampling period and reporting of the sample analysis shall be no greater than 1 hour, and (3) sampling is to be continuous except in that the pause in sampling when sample collection media are changed should be no greater than 5 percent for the averaging period or 5 minutes, whichever is less (EPA 1996). Exhibiting no mechanical problems, the XCEM had an effective up-time of 100 percent during the 40 hours of verificati on testing. The XCEM sampled continuously except for a 4-second period betw een each 20-minute sample run when the filter tape was moved to a new analysis position. XCEM results are reported immediately after each 20-minute analysis resulting in a 20-minute response time between the end of sampling and reporting.

Zero and Calibration Drift

The XCEM has automated daily zero and upscale checks and reports a Pd concentration with each sample to test for calibration drift. To determine the zero check, the XCEM measures an unexposed region of the filter tape. Following the zero check, a plunger is extended into th e analysis region. The tip of the plunger contains Cr, Cd, Hg, and Pb embedded in a resin. Analysis of this spiked resin provides an upscale check for the XCEM.

Zero and upscale checks were conducted on each of the four test days with the results shown in Table 8. Since the zero and upscale checks are evaluations of mass measurements, they are reported as mass per unit area on the filter (μg/spot). Equivalent zero and upscal e concentrations in micrograms per dry standard cubic meter are also shown in Table 8 and reflect the typical sampling rate of 16 L per spot.

Zero values determined during the TEAD test indicate no measurable blank bias in the mass measurement. The XCEM detection limits for Cr, Cd, Hg, and Pbare 0.75, 3.0, 1.0, and 1.0 μg/dscm, respectively. The XCEM zero values were below the detection limits for Cd, Hg, and Pb and only slightly higher than the Cr detection limit.

The upscale check indicated good prec ision for the high concentration mass measurements. The precision over the 4 days was less than 1 percent for Cd, Hg, and Pb and about 2.3 percent for the Cr.20 ERDC/CERL TR-05-9

Table 8. Upscale and zero concentrations during validation testing. Upscale Values (μg) Zero Values (μg) 1 Date Cr Cd Hg Pb Cr Cd Hg Pb 5/14/01 5.23 156 27. 6 30.4 0.012 0.046 0.008 0.008 5/15/01 5.53 158 28. 0 30.9 0.016 0.042 0.008 0.008 5/16/01 5.45 156 27.9 30.8 0.014 0.024 0.010 0.008 5/17/01 5.42 156 27. 9 30.6 0.011 0.024 0.005 0.023

Avg. 5.41 157 27.8 30. 7 0.013 0.034 0.008 0.012 SD 0.13 0.74 0.18 0.23 %RSD 2.33 0.47 0.65 0.76

Equiv. Upscale Values (μg/dscm) 2 Equiv. Zero Values (μg/dscm) 1,2 Date Cr Cd Hg Pb Cr Cd Hg Pb 5/14/01 327 9,765 1, 724 1,898 0.75 2.86 0.50 0.47 5/15/01 346 9,850 1, 750 1,931 1.01 2.65 0.50 0.50 5/16/01 341 9,772 1,742 1,925 0.85 1.50 0.63 0.50 5/17/01 339 9,744 1,746 1,912 0.67 1.50 0.29 1.42

Avg. 338 9,783 1,741 1, 917 0.82 2.13 0.48 0.72 SD 7.88 46.14 11.25 14.64 %RSD 2.33 0.47 0.65 0.76 1) Gray values were nondetects. Nondetect treated as one-half of Detection Limit. 2) Equivalent concentrations determined using 16 liters per sample. SD = standard deviation; RSD = relative standard deviation



### Palladium, which is measured with every sample, also displayed good precision over the 4 days of testing (Figure 7). Overall, the Pd concentration had a precision of about 2.5 percent with all 113 measured Pd concentrations lying within 6 percent of the average concentration. An alysis of the Pd concentration trend in Figure 7 indicates that no significant drif t occurred. Over the 4-day test period, the average Pd concentration changed by less than 1 percent with no observable trending occurring.

Correlation with Reference Method

The comparison between the XCEM and M29 concentration measurements are shown in Figure 8. In this figure the dashes represent the M29 concentration over the sampling period, while the diamonds represent the individual XCEM measurements. The degree of correlation between the XCEM and M29 is shown in Figure 9 and Table 9. Five metals (Ni, Pb, Sb, Zn, and Hg) were present in the stack gas at varying concentrations. Of these elements, Ni, Sb, and Zn showed correlations of 0.95 or better. Lead shows a high correlation of 0.997 for all 13 runs, but a correlation of 0.76 for the 11 runs in which Pb concentrations were used for RA comparisons. Mercury did not show a high correlation between the two methods.ERDC/CERL TR-05-9 21



## Palladium

20 21 22 23 24 25 26 27 28 29 30

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg)



### 5/14/01 5/17/01 5/16/01 5/15/01

Average Palladium Effective Concentration One SD from Avg. Pd Concentration 5% from Avg. Pd Concentration

Figure 7. Palladium concentrations during M29 testing.



### Unlike the other elements, the XCEM Hg co ncentrations were consistently lower than M29, but by a variable amount. During the early runs for each day, the XCEM reported low concentrations relati ve to M29. As the day progressed, the XCEM Hg concentration would gradually increase until it approximated M29reported concentrations. This same increasing Hg concentration trend was observed on each of the four test days (Figure 8).

It is believed that the Hg was lost during transport from the stack to the XCEM. The M29 samples were collected next to the stack and were not transported through a long sample line as the XCEM samples were. The TEAD incinerator was shut down each evening and started in the morning 1 hour before validationtesting. Consequently, the transport line, which was insulated but not heattraced, was cooler during the early runs. Some research indicates that Hg can be lost to a stainless steel surface at low te mperatures (Hall et al. 1990; Wang et al. 1983). In the laboratory, the XCEM was tested with oxidized Hg and met with good success (Hay et al. 2005). The labora tory tests, however, were conducted at elevated line temperatures. It is reco mmended that a shrouded probe and heattraced tubing be used to overcome potential Hg transport problems.22 ERDC/CERL TR-05-9



### Cadmium

0 5 10 15 20 25 30 35 40 45

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01



### Chromium

0 1 2 3 4 5 6 7 8

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01



### Nickel

0 100 200 300 400 500 600

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01



### Lead

0 500 1,000 1,500 2,000 2,500 3,000 3,500 4,000

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01
Figure 8. XCEM and M29 concentrations during TEAD verification testing.ERDC/CERL TR-05-9 23



### Barium

0 50 100 150 200 250 300 350

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01 

### Antimony

0 100 200 300 400 500 600 700 800

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01



### Zinc

0 100 200 300 400 500 600

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01



### Lead (Runs 3-13)

0 100 200 300 400 500

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01

Figure 8 (Cont’d). XCEM and M29 concentr ations during TEAD verification testing.24 ERDC/CERL TR-05-9



### Mercury

0 50 100 150 200 250 300 350

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01


### Palladium

0 5 10 15 20 25 30

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00Conc. (μg/dscm)

5/14/01 5/17/01 5/16/01 5/15/01
Figure 8 (Cont’d). XCEM and M29 concentr ations during TEAD verification testing.

Antimony M29 vs. XCEM

y = 1.6931x + 0.097 R 2 = 0.9609

0 200 400 600 800

0 100 200 300 400 500
XCEMM29

Nickel M29 vs. XCEM

y = 1.0941x - 48.923 R 2 = 0.9482

0 100 200 300 400 500 600

0 100 200 300 400 500
XCEMM29

Mercury M29 vs. XCEM

y = 0.9531x + 95.878 R 2 = 0.4002

0 50 100 150 200 250 300 350 400

0 50 100 150 200 250 300
XCEMM29 Zinc M29 vs. XCEM

y = 1.4087x - 8.3036 R 2 = 0.9766

0 100 200 300 400 500 600

0 100 200 300 400
XCEMM29

Lead M29 vs. XCEM

y = 1.2364x - 37.827 R 2 = 0.9966

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

0 500 1,000 1,500 2,000 2,500 3,000
XCEMM29

Lead Minus High Runs M29 vs. XCEM

y = 0.7191x + 11.915 R 2 = 0.7623

0 50 100 150 200 250

0 50 100 150 200 250
XCEMM29

Figure 9. Correlation between XCEM and M29 for elements spiked at two levels.ERDC/CERL TR-05-9 25

Table 9. Correlation between the XCEM and M29. Spike Ratio 2 High Runs: Low Runs Elem. Correlation (R 2 ) (13 Runs) Correlation (R 2 ) (11 Runs) 1 MSE M29 XCEM
Ni 0.9482 0.9753 2.57 2.52 2.12 Pb 0.9966 0.7623 NS NS NS Sb 0.9609 0.968 2 2.52 2.56 2.51 Zn 0.9766 0.973 8 2.57 2.54 2.50 Hg 0.4002 0.3526 3.09 3.11 2.17 NS: Not spiked 1 Runs 3 through 13 2 High runs are runs 3-7; low runs are runs 8-13



### Response to Changes in Metal Concentration

MSE-TA spiked Ni, Sb, Zn, and Hg at tw o distinct concentration levels. The theoretical ratio, based on spiking, between high and low concentration runs ranged from 2.52 for Sb to 3.09 for Hg (Table 9). Since these four elements are typically not found in the stack gas in sign ificant quantities, it was expected that the theoretical ratio would be measured by both the M29 and XCEM. Except for the XCEM Hg concentrations, both the XCEM and M29 ratios were in very good agreement with the theoretical ratio of concentrations. This agreement, along with the high correlation coefficients, in dicates that the XCEM was precisely and consistently measuring Ni, Sb, Zn, and Pb and was responsive to changing concentrations. In addition, the XCEM’s response to changes in the Pb concentration, which changed by almost two orders of magnitude, was consistent with the M29 results illustrated in Figure 8.

Relative Accuracy

Table 10 shows XCEM, M29 reported conc entrations, and MSE-predicted spike concentrations. The RA of the XCEM with respect to the M29 was determinedusing PS-10 criteria. Of the 13 M29 runs, 11 were used to calculate RA and average concentrations. During runs 1 an d 2, the incinerator experienced problems with a faulty bypass valve, which le d to extremely high Pb concentrations (1,000 to 3,000 μg/dscm). Although the XCEM tracked the problem, and was in fact used to identify and re ctify the problem, it was not felt that these conditions represented the typical operating conditions of the plant. For this reason, runs 1 and 2 were not used to calculate RA and average concentrations.

Since 11 valid reference method test r uns were completed, the RA procedure stated in PS-10 allowed for omission of up to two additional runs from the RAcalculation. Table 11 shows the RA for all 11 runs and the best 9 runs. In general, with the exception of Pb, the omission of two additional runs did not significantly affect RA calculations.26 ERDC/CERL TR-05-9Table 10. XCEM measured, M29 measured, and MSE-predicted metal concentrations (μg/dscm) during TEAD validation testing.XCM29MSEXCM29MSEXCM29MSEXCM29MSEXCM29MSEXCM29MSEXCM29MSEXCM29MSEXCM29MSE12311121872562302730322431942922854623854741,2401,618NS37256554633346747921611122242982232738312432292762814104014662,6903,242NS3756295303354714723139111542012062530303432602862814063774697384NS3515355163344184694161214161255200303436575763182694224524486264NS36164349934049544851612141752411993435356651103182674384184444746NS38162749735445444461412141702711983335356651523192704434734504145NS38469449536351245071712141742791953234366651323182704614864504052NS38371248936754045081712141482622003235365752710492210206184229198NS13427220014621918491711.3714.33162223198323536575541059021017817916677NS145237198146193179101811.4214.16167214197343435665911018820616117514384NS147221197143175175111611.4314.1616323319730333556594101872011861759654NS14525619714320117512179111822142002728264546210888218161177195187NS15623620015018117713181214165248195353636665778482186156163116109NS159286195118173163Avg.(Runs3-13)16111416624019931333456510319717130929630111091250429335237324301SbZnAsBaCdCrRunNo.HgNiPbXC: XCEMNS: Not spikedERDC/CERL TR-05-9 27

Table 11. Relative accuracy and correlations.

Elem. Avg. M29 Conc. ( μ g/dscm) Avg. XC Conc. ( μ g/dscm) Avg. MSE predicted

Conc. ( μ g/dscm) %RA (Runs 3-13) %RA (9 Runs) Notes

Cd 33 31 34 10 8 Met RA criterion.

Cr 6 5.2 5.0 19 15 Met RA criterion.

Ni 296 309 301 11 11 Met RA criterion.

Pb 91 110 NS 45 22

Ba 240 166 199 39 37 Spiked with Sb. XC is consistently low.

Sb 429 250 335 58 55 Spiked with Ba. XC is consistently low.

Zn 324 237 301 37 35 Potential calibration error. XC is consistently low.

As 11.3 16.4 13.6 55 48 XC had correctable Pb interference for As.

Hg 197 103 171 78 68 Consistent pattern of increase throughout day until concentration approaches M29 value. NS: Not spiked XC: XCEM

Cadmium, chromium, and nickel



### The XCEM and M29 reported concentrations for Cd, Cr, and Ni are in good agreement. The average XCEM concentrat ions for these three metals were 31, 5.2, and 309 μg/dscm, respectively, while the M29 average concentrations were33, 6.0, and 354 μg/dscm. The high correlation between the two methods is reflected in the low relative accuracies of 10 percent for Cd, 19 percent for Cr, and 11 percent for Ni. All three elements would have met the RA requirements of the draft PS-10.

The RA for Cr would have been significan tly improved if not for a high bias in the M29 results due to protocol assumptions and high analytical uncertainties in M29 back-half concentrations. EPA M29 protocol requires the assumption that the detection limit be used for the conc entration when the concentration is in fact below the detection limit. In most case s, the detection limit is low relative to the measured concentrations. In the case of Cr, however, it is almost 20 percent of the total Cr found in the M29 sample train.28 ERDC/CERL TR-05-9

Lead



### The average reported XCEM Pb concentration was 110 μg/dscm for runs 3 through 13, while the average M29 concentration was 91 μg/dscm. In general,the XCEM and M29 concentrations were in good agreement. On 16 May, however, both the XCEM and M29 methods reported higher Pb concentration at the start of the day than was observed on 15 May. The XCEM reported a consistent gradual decline in concentrations thro ughout the day while M29 showed a more rapid decrease in concentration (Figure 10). Although the average XCEM and M29 concentrations differed by only about 2 percent for runs 3, 4, 5, 6, 7, 8, 12, and 13, the large difference found in runs 9, 10, and 11 was enough to raise the RA from about 14 percent for these 8 runs to almost 45 percent for all 11 runs. PS-10 allows for 2 of the 11 runs to be dropped. This would have given an RA of 22 percent for the XCEM Pb concentrations.

It is not known why the XCEM and M29 differed on 16 May. The XCEM was able to rapidly transition from much high er concentrations during the first two runs to a much lower concentration during the third run on 14 May and was in good agreement with M29 for the third run on that day. The 14 May XCEM/M29comparisons indicate that the XCEM is responsive to rapid changes in Pb concentration and is resistant to sample line contamination, while M29 data showed good precision and QA/QC for 16 May. Th e XCEM has historically measured Pb accurately with RAs below 20 percent during the MSE-TA test (Bryson 2000) and the laboratory test in 2000 (Hay et al. 2005).

0 50 100 150 200 250 300 350 400 450 500

7:12 9:36 12:00 14:24 16:48 19:12 21:36Concentrations (μg/dscm) 

### XCEM-Pb M29-Pb

Run 8

Run 11 Run 10 Run 9

Figure 10. XCEM and M29 lead concentrations during runs 8–11.ERDC/CERL TR-05-9 29

Barium and antimony



### Barium and antimony were spiked in the same solution and exhibited similarbehavior during M29 testing. For both metals, the average XCEM concentrations were significantly lower than th e M29 reported concentration (30 percent lower for Ba and 40 pe rcent lower for Sb).

The XCEM to M29 ratios for Ba and Sb were 0.70 ± 0.08 and 0.59 ± .06, respectively (Figure 11). The consistent differe nce in concentrations is reflected in the XCEM and M29 ability to measure Sb at two concentration levels. Antimony was spiked at two different levels that were theoretically 2.52-fold different in concentration. M29 measured a 2.56 fold difference between high and low Sb concentrations while the XCEM showed a similar change with a 2.51 ratio. The XCEM and M29 Sb correlation is reflected in a high R 2 

### value of 0.96 for their correlation plot (in Figure 9).

The average M29 reported concentrations for Ba and Sb were 240 and 429 μg/m3 respectively, which is more than 20 percent higher than the predicted maximum stack concentration based on stack spiking (Table 11). The XCEM Ba and Sb concentrations compared favorably to the MSE-predicted concentrations. The XCEM has an RA of less than 20 percent for Ba when compared directly with the MSE-predicted concentrations.

The differences between the XCEM and pr edicted concentrations are believed to be due to particulate loss in the unheated XCEM transport line and calibration

errors.30 ERDC/CERL TR-05-9

As

0.0 0.5 1.0 1.5 2.0

3 5 7 9 11 13 Run No.Normalized Conc. Ba

0.0 0.2 0.4 0.6 0.8 1.0

3 5 7 9 11 13 Run No.Normalized Conc.

Cd

0.0 0.2 0.4 0.6 0.8 1.0 1.2

3 5 7 9 11 13 Run No.Normalized Conc. Cr

0.0 0.2 0.4 0.6 0.8 1.0

3 5 7 9 11 13 Run No.Normalized Conc.

Hg

0.0 0.2 0.4 0.6 0.8 1.0

3 5 7 9 11 13 Run No.Normalized Conc. Ni

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

3 5 7 9 11 13 Run No.Normalized Conc.

Sb

0.0 0.2 0.4 0.6 0.8 1.0

3 5 7 9 11 13 Run No.Normalized Conc. Zn

0.0 0.2 0.4 0.6 0.8 1.0

3 5 7 9 11 13 Run No.Normalized Conc.

Pb

0.0 0.5 1.0 1.5 2.0 2.5

3 5 7 9 11 13 Run No.Normalized Conc.

Figure 11. Ratio of XCEM to M29 concentrations during validation testing.ERDC/CERL TR-05-9 31

Zinc



### Like Ba and Sb, the XCEM Zn concentratio ns were consistently lower than the M29 concentrations by about 30 percent. XCEM Zn concentrations were highly correlated with M29 (Figure 9) with an R 2 

### value of 0.98. Zinc was spiked at a high concentration level for runs 1 throug h 7 and a 2.57 fold lower level for runs8 to 13. The XCEM was responsive to this difference showing a 2.50 concentration multiplier between the average high and low concentrations, which is in good agreement with the M29 ratio of 2.54.

Unlike Ba and Sb, however, the other elements spiked with Zn showed no indication of uniform loss during transport. Nickel met the PS-10 RA requirements and XCEM Ni concentrations were slight ly higher than M29 Ni concentrations. Mercury, as discussed earlier, had pote ntial transport problems to the XCEM under cooler conditions but was approxim ately equal to M29 concentrations for 4 of the 11 runs. Since the elements spiked in the same solution with Zn did not show systematic loss during transport, it is believed that the low Zn concentrations are not simply a function of transport problems.

CES calibrated the XCEM using thin film standards produced by MicroMatter Inc. (Deer Harbor, WA) and a select few National Institute of Standards and Technology (NIST) traceable standards. During calibration, the NIST standards and MicroMatter standards did not agree for Zn. A decision was made to use theNIST standard, which produced significantly lower reported Zn values. Following testing, it was determined that the NIST Zn standard is not in agreement with the NIST Cu standard and may be in correct. It is believed that the Zn differences are primarily a function of this calibration error. Use of the MicroMatter calibration standard instead of the NIST standard would have given XCEM concentrations about 15 percent higher.

Arsenic



### In general, the XCEM As concentrations were consistently higher than the predicted (spiked) and measured M29 concentrations. During M29 testing, it was observed that Pb concentrations were highly correlated with As (Figure 12). Since no significant As was expected in the background stack gas concentration and the As was spiked at a constant ra te, the observed correlation was determined to be due to an XRF spectral interference. Arsenic concentrations are established using a Ka line, which is overla pped by the La line of Pb. For this reason, in XRF analysis, high Pb concentrations can interfere with As measurements, although the reverse is not true.32 ERDC/CERL TR-05-9



### As a first cut, the interference impact was estimated using the simple linear regression shown in Figure 12. That is, about 5.4 percent of the Pb concentrationwas being added to the measured As concentration. CES adjusted the As numbers accordingly prior to re ceiving M29 data. Even with this first order adjustment, the XCEM final reported As concentrations were still higher than the M29 and predicted concentrations with the grea test deviations occurring during high Pb runs. Overall, the average final reported XCEM concentration was 16.3 μg/dscm while the average M29 conc entration was 11.3 μg/dscm.

Since the XCEM saves each XRF spectrum, it was possible to review individual spectra and adjust for the As/Pb interferen ce using a second spectral resolution approach. This task was completed af ter receiving the M29 data for runs 8through 11 on 16 May. These adjusted XCEM results based on this second spectral analysis approach were within 4 percent of the M29 results.

It is believed that a change in the spec tral resolution approach will resolve the Pb/As overlap problem. The XRF can be calibrated using a variety of methods that will take into account the Pb/As inte rference. For example, during the fall 2000 tests, a calibration method was used that contained both arsenic and Pb. No As/Pb interference was observed during these tests (Hay et al. 2005).



### y = 0.0538x + 15.961 R 2 

### = 0.9891

0 40 80 120 160 200

0 500 1,000 1,500 2,000 2,500 3,000 3,500 XCEM Lead Conc. (μg/m3)XCEM Arsenic Conc. (μg/m3)

Figure 12. Uncorrected XCEM As concentrations versus XCEM Pb concentrations.ERDC/CERL TR-05-9 33

Mercury



### As discussed earlier, the XCEM to M29 Hg ratios varied from run to run. At the beginning of each test day, the XCEM repo rted low Hg concentrations relative to M29. As the day progressed, the XCEM concentration would gradually increase until it approximated M29 reported concen trations. The pattern suggests that the transport line from the stack to the XC EM needed to be heated to a highertemperature to improve transmission efficiency. The use of a heat-traced transport line should improve Hg transmission efficiency.

Interestingly, more than 98 percent of the Hg measured by M29 passed through the filter and was collected in the back ha lf of the sample train indicating that the vast majority of the Hg was in the vapor phase. Since the XCEM had good comparisons to M29 on at least four runs (3, 10, 11, and 13), the test indicates that the XCEM was able to efficiently trap and measure Hg as a vapor.

Precision

Precision was calculated in terms of th e percent relative standard deviation(RSD) of a series of XCEM measurements made during relatively stable operation of the TEAD incinerator, with metals injected at a relatively constant rate. This precision reflects not only the XCEM variability, but also the variability in the stack concentrations, spiking rate, and flow variability.

Method 29 dual sample train precision



### During testing, CHPPM ran dual M29 samp le trains. Percent differences between the two trains are shown in Table 12. Overall, the average metal concentration agreement between the M29 trains was about 6 percent (CHPPM 2001). This result is significantly better than the typical agreement between trains,which is on the order of 15 percent (EPA 1999). This better-than-typical agreement indicates that M29 sampling and analysis were conducted in a precise

manner.

Method 29 vs. XCEM precision



### The spike injection rate was altered on th e first day of testing, 14 May, to ensure spiked emissions were within the site pe rmit limitations. On 17 May, stack conditions were not stable following stack repairs. However, MSE-TA and TEADreported reasonably stable conditions on 15 and 16 May and the spiking precision was estimated at 2 percent. For this reason, the eight runs on 15 and 16 May were used for precision calculations.34 ERDC/CERL TR-05-9



### The average M29 and XCEM precisions for the eight spiked elements on 15 to 16 May are listed in Table 13. The averag e M29 precision for these runs was about 6 percent, while the XCEM average precision was about 10 percent. The XCEM precision, however, was heavily influenced by the highly variable Hg results. For the non-Hg elements, the precision of the XCEM was 3.7 percent, while the average M29 precision for the same group of elements was 6.8 percent.

The XCEM also measures Pd with every sample. The average XCEM Pd concentration was 25 ± 0.6 μg, which gives a precision of about 2.5 percent. Palladium concentrations reflect XRF precision, bu t are independent of flow, spiking, and sampling variability.

Overall then, the XCEM performed in a very consistent manner and exhibited precision on the same order as or slightly better than M29 for all elements except Hg.

Table 12. Percent differences between M29 sample trains. 1


## Run As Ba Cd Cr Hg Ni Pb Sb Zn Avg. % Diff 1 9 -6 -2 7 2 3 -19 -4 -9 7 2 1 15 9 5 -3 0 0 -1 -1 4 3 -2 -5 0 8 3 -1 11 1 5 4 4 -2 -6 -8 -26 3 -5 5 -4 -2 7 5 -9 -12 -6 -15 1 -11 -3 -11 -9 9 6 0 -8 1 0 0 -2 6 -9 -5 3 7 3 -8 -3 -2 0 -6 -1 -9 -7 4 8 1 -3 -5 -4 4 -9 -14 -11 -10 7 9 6 -8 -3 12 0 9 7 3 7 6 10 0 6 -5 -5 -2 11 2 5 5 5 11 -4 -3 -5 -5 -1 -10 -1 -10 -13 6 12 6 14 8 8 0 11 11 5 12 8 13 -2 -14 -1 -1 1 -11 -2 -14 -9 6 Avg. %

Diff. 4 8 4 827 6 77 6

1 Average percent difference is determined by averaging the absolute value of the difference between sample trains.ERDC/CERL TR-05-9 35

Table 13. XCEM and M29 precision.



### Elem. M29 Runs Avg. M29 Conc. (μg/dscm) M29 % RSD Avg. XC Conc. (μg/dscm) XC % RSD (By Run) As 4-11 12 2.3 16 7.6 Ba 4-11 247 9.4 165 5.2 Cd 4-11 34 2.3 32 4.5 Cr 4-11 6 5.7 6 2.6 Hg (high) 4-7 211 0.2 92 35.4 Hg (low) 8-11 103 1.9 67 48.4 Ni (high) 4-7 457 6.5 438 3.6 Ni (low) 8-11 183 10.1 207 2.0 Sb (high) 4-7 669 6.1 375 2.9 Sb (low) 8-11 246 9.0 143 4.2 Zn (high) 4-7 500 7.2 354 3.4 Zn (low) 8-11 197 9.2 144 1.2 Avg. (All elem.) 5.8 10.1 Avg. (No Hg) 6.8 3.7

Low-Level Metal Response

Low-level metal response was determin ed by comparison of M29 and XCEMreported Cr and As concentrations. Neither of these elements is found in significant quantities in TEAD stack emissions and both are regulated to low levelsunder the site-based RCRA limitations. Both elements were spiked as particulates by MSE-TA at low concentrations wi th typical Cr stack concentrations in the 5 μg/dscm range and As in the 14 μg/dscm range.

The XCEM accurately measured Cr relati ve to M29 with an RA of 19 percent. The average XCEM Cr concentration was 5.2 ± 0.9 μg/m3 while the M29 average was 6.0 ± 0.8 μg/m3. The M29 concentrations reported the detection limit for the back half when no Cr was measured, which occurred for more than half of the samples. Since the M29 back half detection limit was about 0.5 μg/m3, the M29 concentrations were biased high by at least 10 percent. Correction for the M29 back-half detection limit improves the RA to better than 10 percent. This consistent agreement between the two method s demonstrates the capability of theXCEM to measure metals at low concentrations even in the presence of high concentrations of interfering elements such as Ba.

As discussed earlier, the XCEM As concentrations were biased by Pb interference. For this reason, the XCEM As conc entrations were routinely higher than the M29 concentrations.36 ERDC/CERL TR-05-9



### Bias

Bias between the two M29 sampling trains and the M29/XCEM data was determined using an EPA Method 301 approach (EPA 1992). The results are tested for statistically significant bias by calculating the t-statistic and determining if the mean of the differences between the tw o sampling trains is significant at the 80-percent confidence level. The t-statisti c is calculated by finding the standard deviation of the differences between the two sampling trains. 

# ( ) ( ) 1 2



### − −

= 

# ∑

n d d SD m i d [Eq 4]



### where:

d i 

### = the difference between the two sample train values d

m 

### = mean of the d i 

### values n = number of paired samples

Using the standard deviation determined in Equation 4, the t-statistic is then calculated as follows:



### ⎟ ⎟ ⎠ ⎞ ⎜ ⎜ ⎝ ⎛ =

n SD d t

d m [Eq 5]



### Based on EPA criteria, a statistically significant bias in a data set exists if the tstatistic value is greater than a critical value (0.88 for 11 runs).

Using Equations 4 and 5 and EPA’s critical value for 11 runs, it was determined that M29 experienced statistically significant bias between the paired sample trains for Ba, Cd, Cr, Hg, Ni, Sb, and Zn. However, the M29 bias was small, on the order of 3 to 6 percent. Furthermore, the bias was not consistent by element with sample Train A being higher for Cr and Hg while Train B was slightlyhigher for As, Ba, Cd, Ni, Sb, and Zn. Overall, the M29 sample trains had an average absolute percent difference of about 6 percent (Table 9). Since the M29 bias for individual elements was relative ly small and no consistent differencesbetween sample trains was noted, it was determined that the average M29 concentration would be used for comparison purposes and no correction would be taken to compensate for bias.ERDC/CERL TR-05-9 37



### Relative to M29, the XCEM showed significant bias for all elements (Table 14).This bias is believed to be a product of XCEM transport and calibration problems. Method 301 outlines a procedure for determining correction factors that can be applied when bias is present. If the Method 301 correction factor had been applied to the XCEM concentrations, the XCEM would have met the 20 percent RA criterion for all of the elements except Hg. Although this method shows the existence of a high level of corre lation, it is important to note that the XCEM correction factors are outside of th e acceptable range for validation of Pb, Ba, Sb, Zn, As, and Hg.

Table 14. Method 301 bias and correction factor comparison.

Element T-Stat Significant Bias Correction Factor RA with Corr. Factor (Runs 3-13) Corrected RA Meets PS-10

Cd 5.33 Yes 1.08 3.9 Yes Cr 6.41 Yes 1.17 6.3 Yes Ni 1.27 Yes 0.96 8.0 Yes Pb 1.87 Yes 0.83 20.2 Yes 1
Ba 9.59 Yes 1.46 8.7 Yes Sb 6.17 Yes 1.73 6.5 Yes Zn 5.64 Yes 1.38 6.1 Yes As 11.75 Yes 0.69 7.8 Yes Hg 3.44 Yes 1.91 35.9 No

1 Using only nine runs as s uggested in PS-10, Pb RA would have been 14 percent.



### Summary

The XCEM was constructed, installed at the TEAD incinerator, and tested against M29. The primary objective was to meet the proposed requirements of PS-10. Following is a list of the individual requirements and discussion of the performance of the XCEM: 1. Response time and reporting time: The XCEM had a response time of 20 minutes, meeting the PS-10 criterion for batch CEMs. It experienced no mechanical problems and had an effective up-time of 100 percent. 2. QA: The XCEM showed a calibration drift of less than 0.5 percent and QA precision of about 2 percent for daily zero and upscale checks. 3. Relative accuracy:

a. The XCEM met PS-10 accuracy criteria for Cd, Cr, and Ni by having relative accuracies that were less than 20 percent.38 ERDC/CERL TR-05-9



### b. The XCEM did not meet the Pb accuracy criterion with an RA of 22 percent.

c. The reported XCEM concentrations we re uniformly high for As due to a spectral resolution problem. d. The XCEM was consistently low for Zn. The Zn differences are believed to be due to an incorrect XCEM calibration standard that lowered the XCEM concentrations by about 15 percent.

e. The XCEM was also consistently low for Ba and Sb. These differences are believed to be a function of transport or calibration problems. f. The XCEM did not successfully measure Hg, which exhibited a concentration pattern that suggests loss to the unheated sample transport line.
g. The XCEM had a correlation (r2) of better than 0.95 for three (Ni, Sb, Zn) of the four elements that were spiked at varying concentrations.

In addition, during the tests the XCEM functioned in a completely automated manner and automatically recorded concen trations, temperatures, flow rates, and QA data. It also showed a precis ion of better than 4 percent for periods when spiking and stack conditions were held relatively constant.

An analysis of reported concentrations using EPA Method 301 correction factors indicates that the XCEM would meet the 20 percent RA criterion for all elements except Hg, once the bias is taken into account. However, the correction factors are outside the acceptable range for validation. Table 15 summarizes the results relative to PS-10.

Table 15. Summary of XCEM performance relative to proposed PS-10 requirements.

Test Goal Met Criterion? Discussion
Sampling and Response Time Yes Exhibited a 100% up-time for test. Sampled for greater than 99.5% of the time. Reported time averaged concentrations every 20 minutes with a 20-minute lag between sampling and reporting.

QA Yes The XCEM exhibited a precision of 1 to 2% for zero drift. The XRF calibration drift was less than 0.5% for the 4 days of testing.

RA Yes for 3 No for 6 elements Met 20% RA criteria for Cd , Cr , and Ni. Had a 22% RA for Pb

. Was systematically biased for Ba , Sb , Zn, and As. Did not successfully measure Hg. For response to change in concentration, had correlation (r 2 ) of 0.95 or better for Ni, Sb, and Zn. Underlined elements are regulated elements typically found in the Tooele feedstream.ERDC/CERL TR-05-9 39



# 3 Transport and Calibration Improvements

During the M29 comparison tests of May 2001, the XCEM met the PS-10 criteria for QA and sampling and response time, bu t only met the RA criterion for three elements (Cr, Cd, and Ni). An evaluation of the test parameters indicated that changes to the transport line, improvements in calibration, and testing of the XCEM vs. stack spiking would improve the XCEM RA.

During the spring of 2002, improvements were made to the XCEM transport line and a second series of preliminary te sts were conducted to better understand calibration and stack spiking efficiency. This chapter discusses the changes to the transport line, calibration, and test results.



### Transport Line Changes

The initial transport line used by the XCEM at TEAD was insulated, but not heat traced. The line, which extended ho rizontally 20 ft, showed problems with Hg transport. During May 2001 testing, XCEM Hg concentrations were lower than M29 values at the beginning of the day when temperatures were lower, but as the line temperature increased, the XCEM Hg concentrations approached M29 results. For this reason, it was determined that the XCEM required a heated transport line.

In March 2002 the XCEM shelter was moved to a location that required only 13 ft of horizontal transport. Following the move, the line was heat traced, insulated, and maintained at 220 oF. In addition, a shrouded probe was installed. The shrouded probe, manufactured by Anderson Instruments, has been shown to minimize the impact of variations in stack velocity on deviations from isokinetic sampling (McFarland and Rodgers 1993). The combined effect of these changes was to minimize Hg and particulate loss in the sample line.40 ERDC/CERL TR-05-9



### Recalibration

During the week of 8 April 2002, CES recalibrated the instrument using thinfilm MicroMatter standards. The thin-film standards are developed by flashing the metal of interest onto a nuclepore filter, resulting in a known concentration of metal in micrograms per square centimeter (μg/cm2). The XRF unit used by the XCEM had not been calibrated since August 2001. Before recalibrating, CESanalyzed the MicroMatter standards (previously purchased by the Army as unknowns) to evaluate the XRF’s stability. The XRF reported values within 10 percent of the calibration standards, which indicated that it had maintained good stability for 9 months and would not have needed recalibration under normal operating conditions.

Following the initial check, several changes were made to the calibration procedure to improve spectral deconvolution. These changes included:

• Development of a representative filt er tape background reference spectra

• Subtraction of the filter tape background spectra

• Development of better pure element reference spectra

• Inclusion of additional elements as background spectra to correct for potential interferences.

Following recalibration, the Army Micro Matter standards were again evaluated as unknowns. The standards were within 1.5 percent of the listed values for all elements except Sb (6 percent) and Ba (15 percent). The accuracy of the Army MicroMatter standards was in question, so they were compared to CES MicroMatter standards at the CES laboratory. Some inconsistencies for Cd and Pb were noted between the Army and the CE S MicroMatter standards. They were also compared with standards from NIST. The results from the analysis of the NIST and CES MicroMatter standards we re compared with the Army MicroMatter standards, and it was determined that the Army standards for Cd and Pb were high by 12 percent and low by 4 pe rcent, respectively. The XRF calibration was adjusted accordingly.



### Summary of Transport and Calibration Evaluations

Changes to the transport line were tested by comparing XCEM concentrations toconcentrations based upon stack spiking estimates and an in-stack EPA Reference Method 17 (M17) filter. Overall, no measurable loss of particulates in the improved XCEM transport line was observed . The calibration was tested using aERDC/CERL TR-05-9 41



### Quantitative Spike Injection System (QSIS) . It was determined that the elemental concentrations were being reported wi thin their expected uncertainties for all elements except Cd and Ag. Appendix C gives descriptions and detailed results of these tests.42 ERDC/CERL TR-05-9



# 4 M29 Comparison Testing of XCEM 2002

In May 2002 a new series of M29 tests were conducted to evaluate the measurement capabilities of the improved XCEM. The test objective was to compare M29 and the XCEM and determine the XCEM RAs. The testing was conducted at TEAD with a test plan similar to the plan used in the 2001 M29 comparison tests. Ten metals were measured by M29 and the XCEM. This chapter presents the results of the M29 sampling, predicted concentrations based on the spiking, and the XCEM sampling. Also presented: a calibration evaluation based on the reevaluation of the XCEM filters, a disc ussion of the precision of the three concentration determinations, and a detailed discussion of the M29 comparison.



### Results

Method 29 Concentrations

Method 29 tests were conducted using du plicate sample trains located at the same stack height as the XCEM probe. In general, the two trains were in good agreement (CHPPM 2002). As shown in Table 16, more than 90 percent of thepaired M29 concentrations were within 10 percent of each other. Of the 11 reported concentrations that were not with in 10 percent, 9 were measurements of Sn. Method 29 has not been approved for Sn (EPA 1992). Tin is not a regulated metal, but measuring it is useful to T EAD for identifying deactivated munitions.

Overall, train A was higher than train B by about 3 percent with about 78 percent of the concentrations in train A being higher than their train B counterpart. An average of trains A and B was used for comparison to the XCEM reported concentrations.

Method 29 data used for comparison to the XCEM is the same as reported in theM29 report (CHPPM 2002) with the exception of a 1–3 percent correction compensating for the laboratory’s inadvertent subtraction of an estimated blank concentration when the blank concentrations were below the method-reporting limit. *

* Personal communication: Robert Weidenfeld, Severen Trent Lab, with John Cooper, CES, 9 July 2002.ERDC/CERL TR-05-9 43

Table 16. M29 concentrations ( μ g/dscm).

A B AVG A B AVG A B AVG A B AVG A B AVG A B AVG 1 74 71 73 31 28 29 3.5 3.6 3.6 8.1 7.4 7.8 344 320 332 154 148 151 2 75 78 77 32 32 32 4.0 4.1 4.0 8.4 8.0 8.2 337 331 334 188 176 182 3 99 96 98 36 34 35 6.7 6.2 6.4 11.7 11.2 11.4 306 283 294 187 180 183 4 37 39 38 31 31 31 4.8 5.2 5.0 11.5 12.1 11.8 347 307 327 168 164 166 5 29 26 28 32 30 31 5.3 5.2 5.2 12.3 11.1 11.7 319 317 318 172 163 168 6 148 146 147 32 31 31 5.0 4.7 4.8 11.6 10.9 11.2 291 269 280 160 163 162 7 138 132 135 32 31 32 5.0 4.8 4.9 11.8 11.4 11.6 279 291 285 169 159 164 8 131 126 128 33 32 32 5.2 4.9 5.1 12.6 11.8 12.2 309 303 306 165 158 162 9 121 122 122 32 32 32 4.9 5.4 5.2 12.0 12.2 12.1 312 305 309 153 161 157 10 140 129 135 31 29 30 5.0 4.8 4.9 11.3 10.8 11.0 294 289 292 164 151 157 11 119 118 119 32 31 31 4.9 4.7 4.8 11.7 11.5 11.6 297 293 295 162 164 163 12 114 111 113 31 31 31 4.8 4.8 4.8 11.9 11.7 11.8 308 278 293 154 154 154

A B AVG A B AVG A B AVG A B AVG 1 209 191 200 222 206 214 203 186 195 132 144 138 2 235 235 235 249 248 248 216 208 212 131 168 149 3 240 228 234 252 243 247 222 208 215 207 199 203 4 207 220 213 195 211 203 192 201 196 66 90 78 5 227 235 231 215 198 207 202 191 196 57 69 63 6 236 214 225 217 215 216 218 200 209 131 108 120 7 230 205 218 220 204 212 206 198 202 60 74 67 8 224 213 219 214 206 210 211 196 204 47 48 47 9 222 221 221 204 209 206 204 200 202 41 35 38 10 219 192 205 218 199 208 205 192 199 88 64 76 11 218 214 216 210 210 210 205 201 203 44 36 40 12 202 195 199 208 201 204 199 192 196 31 25 28 Hg

Ni Pb Sb As Cd Cr

Ba Sn Zn RUN

RUN



### Predicted Stack Gas Concentrations

Predicted stack gas concentrations were determined by adding the MSE-TA calculated spiked concentrations with bac kground concentrations based on XCEM measurements when munitions were being burned but no spiking was occurring. The background was essentially zero for five elements: Cr, As, Hg, Sb, and Ni. For Cd, Ba, and Zn, the background correct ion was small relative to the MSE-TA spiked concentrations, which were 17, 15, and 8 percent, respectively. For Pb, however, the background accounted for 100 percent of the Pb in runs 1–5 and 35 percent of the Pb in runs 6–12.

MSE-TA spike injection



### During M29 testing, MSE-TA spiked known masses of Pb, Cd, Cr, As, Hg, Sb, Ni, Ba, and Zn into the stack (Bryson 2002). These spiked masses were divided by the stack flow to obtain concentrations in μg/dscm. MSE-TA mass concentrations in solution were cross-checked by submitting aliquots from M29 runs 5 and 6 to an independent laboratory for anal ysis (HKM Labs, Butte, MT). HKM’s results were within 7 percent of MSE-TA’s estimates for all elements except As,44 ERDC/CERL TR-05-9



### which was 23 percent lower according to HKM than reported by MSE-TA. No adjustments were made to MSE-TA report ed data. The potential impact of the As difference is discussed in a report by Cooper et al. (2002).

Measurements of stack flow by CHPPM were cross-checked with the stack continuous velocity monitor for accuracy and were found to be within 6 percent of each other (Table 17). The CHPPM flows we re determined using a velocity traverse at the same stack height as the XCEM probe and are believed to be more representative of true flows than the continuous velocity monitor. * For this reason, the CHPPM flows were used to calculate the predicted concentrations.

Table 17. APE-1236 stack flow rates during M29 testing.

Run TEAD stack monitor (dscm/hr) M29A (dscm/hr) M29B (dscm/hr) Avg. CHPPM M29 (dscm/hr) TEAD stack/ Avg. M29 (%) 1 5,173 4,718 4,659 4,689 110 2 5,037 4,638 4,652 4,645 108 3 4,998 4,527 4,532 4,530 110 4 4,889 4,680 4,688 4,684 104 5 4,838 4,672 4,688 4,680 103 6 4,970 4,578 4,580 4,579 109 7 4,826 4,607 4,613 4,610 105 8 4,785 4,641 4,647 4,644 103 9 4,676 4,662 4,672 4,667 100 10 4,060 4,589 4,600 4,594 110 11 4,960 4,593 4,662 4,628 107 12 4,879 4,660 4,670 4,665 105 AVG 4,924 4,630 4,639 4,635 106

Background metal concentration



### TEAD incinerated 20 mm TPM55A2 bullets during all 12 M29 runs. This ammunition, which is used for target traini ng, does not contain significant quantities of hazardous elements. However, measurable residual concentrations of Pb, Cd, Ba, Zn, and Sn were found in the stack gas from earlier incineration of other munitions. Table 18 shows XCEM results for elements measured on 13 and 15 May while the 20 mm bullets were being burned and MSE-TA was not spiking into the stack. The 13 May metal concen trations were significantly higher than

* Personal communication: Mike Pattison, U.S. Army CHPPM, with Bruce Johnsen, CES, June 2002.ERDC/CERL TR-05-9 45



### the 15 May concentrations, which is consis tent with incineration of relatively clean munitions scouring the stack. Ba ckground concentrations for Cr, As, Hg, Ni, and Sb were below XCEM detection lim its (1 μg/dscm) and were reported as 0 μg/dscm.

Table 18. APE-1236 stack concentrations ( μ g/dscm) with munitions incineration but no spiking.



### Date XCEM Run Pb Cd Ba Zn Sn 5/13/02 899 94.5 11.5 68.7 38.3 487 5/13/02 900 85.9 5.9 64.8 42.7 604 5/13/02 901 78.2 8.4 43.6 39.3 466 5/13/02 902 60.0 9.9 20.1 22.9 227 5/13/02 903 68.2 10.0 74.5 26.5 272 5/13/02 904 53.3 12.2 41.1 39.3 282 5/13/02 905 53.8 6.4 10.6 40.3 231 5/13/02 906 44.7 8.0 18.1 21.2 205 5/13/02 907 54.7 6.0 22.3 23.9 275 5/13/02 908 44.5 5.7 49.3 22.6 259 Average 63.8 8.4 41.3 31.7 331 5/15/02 990 22.3 0.6 12.6 8.4 120 5/15/02 991 25.0 4.9 29.4 8.8 135 5/15/02 992 21.4 1.3 5.6 6.7 114 5/15/02 993 8.9 0.1 29.4 2.9 38 Average 19.4 1.7 19.3 6.7 102

Use of Sn as a surrogate for background metals



### Figure 13 shows the relationship between Pb, Ba, Zn, and Sn when spiking was not occurring. The correlations indicate that Pb, Ba, Zn, and Sn background concentrations stem from the same source. Since Sn was not spiked by MSE-TA, its concentration was used as an indicator of the background during spiking periods. The background contribution of the other elements was estimated by their relationship to Sn according to the equation s in Figure 13. Figure 14 shows the XCEM measurements of Sn during M29 testing. A surge in Sn concentrations is observed each morning after the bypass damper is opened. The surge is followed by a gradual decrease in Sn concentratio ns throughout the day. Although Cd was not found in high enough concentrations to certify its relationship with Sn, it was assumed to behave in the same manner as the other metals. Combiningthe MSE-TA spike injection estimates with the estimated background concentrations resulted in predicted concentrations as shown in Table 19.46 ERDC/CERL TR-05-9

XCEM Barium vs. XCEM Tin During NonSpiking Periods

y = 0.0977x + 9.0892
R 2 = 0.4678 0 20 40 60 80

0 200 400 600 800 Tin (μg/DSCM)Barium (μg/DSCM) XCEM Lead vs. XCEM Tin During NonSpiking Periods

y = 0.1505x + 11.158
R 2 = 0.8636 0 20 40 60 80 100 120

0 200 400 600 800 Tin (μg/DSCM)Lead (μg/DSCM) XCEM Zinc vs. XCEM Tin During NonSpiking Periods

y = 0.0747x + 4.7411 R 2 = 0.7159 0 10 20 30 40 50 60

0 200 400 600 800 Tin (μg/DSCM)Zinc (μg/DSCM)

Figure 13. Correlation between Sn and other APE-1236 metals with munitions burning and no spiking.

Tin During M29 Testing

0.0 100.0 200.0 300.0 400.0 500.0 600.0 700.0

890 930 970 1010 May 13 May 14 May 15 May 16

Figure 14. XCEM tin measurements during M29 testing.ERDC/CERL TR-05-9 47



### XCEM Concentrations

XCEM concentrations were determined every 20 minutes for Pb, Cd, Cr, As, Ni, Hg, Ba, Sb, Zn, and Sn (Table 20). A Pd rod is permanently mounted in the XRF detection area and is measured with ev ery sample. The consistency of the Pd concentrations provides QA of the inst ruments stability during M29 testing, the XCEM successfully carried out 120 runs with only 2 runs falling outside of the Pd QA criterion due to air-conditioning pr oblems. This represents an uptime of 98 percent.
Table 19. Predicted stack concentrations ( μ g/dscm) based on MSE-TA spiking and background estimates.

MSE BKG PRD MSE BKG PRD MSE BKG PRD MSE BKG PRD MSE BKG PRD

1 2.9 0.0 2.9 32.0 9.4 41.5 0.0 67 67 10.6 0.0 10.6 267 0.0 267 2 2.9 0.0 2.9 31.5 8.4 39.8 0.0 61 61 10.7 0.0 10.7 268 0.0 268 3 5.2 0.0 5.2 37.5 11.1 48.6 0.0 77 77 16.7 0.0 16.7 275 0.0 275 4 5.0 0.0 5.0 36.5 5.0 41.6 0.0 41 41 16.1 0.0 16.1 265 0.0 265 5 5.0 0.0 5.0 37.2 4.1 41.4 0.0 36 36 16.1 0.0 16.1 266 0.0 266 6 5.0 0.0 5.0 36.9 8.5 45.4 105 61 167 16.0 0.0 16.0 271 0.0 271 7 5.1 0.0 5.1 37.7 6.0 43.7 104 46 150 16.4 0.0 16.4 269 0.0 269 8 5.1 0.0 5.1 37.1 4.4 41.5 103 37 140 16.2 0.0 16.2 267 0.0 267 9 5.1 0.0 5.1 37.1 3.4 40.5 103 31 134 16.2 0.0 16.2 266 0.0 266 10 4.8 0.0 4.8 35.3 5.9 41.1 105 46 151 15.2 0.0 15.2 270 0.0 270 11 5.0 0.0 5.0 36.5 3.5 39.9 104 32 136 16.0 0.0 16.0 268 0.0 268 12 5.1 0.0 5.1 36.6 2.4 39.0 103 26 128 16.2 0.0 16.2 266 0.0 266 AVG. 4.7 0.0 4.7 36.0 6.0 42.0 61 47 107 15.2 0.0 15.2 268 0.0 268

SD 0.8 0.0 0.8 2.1 2.7 2.7 53 16 47 2.2 0.0 2.2 2.8 0.0 2.8

MSE BKG PRD MSE BKG PRD MSE BKG PRD MSE BKG PRD 1 324 0.0 324 192 45.3 237 192 0.0 192 267 32.5 300 2 325 0.0 325 196 41.2 238 196 0.0 196 268 29.3 297 3 333 0.0 333 201 51.6 253 201 0.0 201 275 37.3 312 4 322 0.0 322 194 28.3 223 194 0.0 194 265 19.5 285 5 323 0.0 323 193 25.0 218 193 0.0 193 266 16.9 283 6 329 0.0 329 199 41.6 240 199 0.0 199 271 29.6 301 7 327 0.0 327 197 31.9 229 197 0.0 197 269 22.2 291 8 325 0.0 325 192 25.9 218 192 0.0 192 267 17.6 285 9 324 0.0 324 189 22.1 212 189 0.0 189 266 14.7 280 10 328 0.0 328 194 31.6 226 194 0.0 194 270 22.0 292 11 326 0.0 326 193 22.5 215 193 0.0 193 268 15.0 283 12 322 0.0 322 190 18.4 209 190 0.0 190 266 11.9 278 AVG. 326 0.0 326 194 32.1 226 194 0.0 194 268 22.4 290

SD 3.3 0.0 3.3 3.4 11 13 3.4 0 3 2.8 8 10 LEAD ARSENIC

ZINC RUN

RUN NICKEL

MERCURY BARIUM ANTIMONY CHROMIUM CADMIUM48 ERDC/CERL TR-05-9Table 20. XCEM concentrations.AS BA CD CR HG NI PB SB SN ZN AS BA CD CR HG NI PB SB SN ZN5/13 7:57 AM 8:17 AM 899 0.0 69 11.5 1.2 2 1 95 0 487 385/13 8:17 AM 8:37 AM 900 0.4 65 5.9 0.6 1 0 86 0 604 435/13 8:37 AM 8:57 AM 901 0.2 44 8.4 0.3 2 1 78 1 466 395/13 8:57 AM 9:17 AM 902 2.1 20 9.9 0.8 1 0 60 3 227 235/13 9:18 AM 9:37 AM 903 0.0 75 10.0 1.3 0 0 68 5 272 275/13 9:37 AM 9:57 AM 904 2.2 41 12.2 0.9 1 2 53 1 282 395/13 9:57 AM 10:17 AM 905 0.0 11 6.4 0.7 1 0 54 5 231 405/13 10:17 AM 10:37 AM 906 1.3 18 8.0 0.3 1 0 45 3 205 215/13 10:37 AM 10:57 AM 907 0.0 22 6.0 0.6 1 1 55 5 275 245/13 10:57 AM 11:17 AM 908 1.4 49 5.7 0.4 1 1 45 3 259 235/13 11:17 AM 11:36 AM 909 8.5 129 26.4 3.4 218 200 44 106 250 2105/13 11:37 AM 11:57 AM 910 1 8.0 242 30.8 2.9 347 254 48 187 249 269 8.6 210 27.5 3.2 261 270 51 172 226 2965/13 11:57 AM 12:17 PM 911 1 10.1 202 33.2 3.2 360 257 46 170 238 273 10.8 188 28.0 2.6 264 268 46 176 224 2955/13 12:18 PM 12:38 PM 912 1 9.1 222 35.0 3.7 365 273 47 184 268 283 9.5 222 31.9 3.6 269 277 57 172 271 3065/13 12:38 PM 12:59 PM 913 1 8.1 215 32.0 4.1 356 264 59 192 331 279 9.0 210 29.5 3.8 244 247 63 161 318 2765/13 12:59 PM 1:19 PM 914 1 11.5 223 40.4 3.7 385 278 87 182 484 301 8.5 206 29.9 3.1 263 262 84 159 399 2975/13 1:19 PM 1:40 PM 915 1 10.9 265 37.4 3.8 371 279 94 190 558 303 8.6 193 27.5 3.0 244 248 88 161 460 2865/13 1:40 PM 2:01 PM 916 1 12.6 256 34.1 3.7 371 280 83 181 471 302 11.3 208 29.5 2.8 260 276 83 170 411 3125/13 2:01 PM 2:22 PM 917 9.2 241 36.9 3.5 387 285 79 191 437 313 9.4 229 29.3 3.0 264 284 79 174 374 3215/13 2:22 PM 2:47 PM 918 10.2 240 35.0 3.2 366 275 77 192 394 297 10.4 231 30.0 3.3 278 293 80 183 353 3255/13 2:47 PM 3:08 PM 919 2 9.6 272 34.3 3.7 381 278 76 206 389 295 10.3 247 28.8 3.1 268 273 75 173 341 3015/13 3:08 PM 3:29 PM 920 2 7.1 241 37.5 4.8 394 281 77 191 379 300 10.4 209 28.4 3.2 258 275 69 182 316 3035/13 3:29 PM 3:50 PM 921 2 11.0 233 39.0 3.7 380 290 72 206 335 302 10.4 231 33.0 3.4 264 288 71 183 306 3145/13 3:50 PM 4:10 PM 922 2 8.7 255 32.0 3.8 390 294 67 206 338 308 9.4 209 26.5 3.0 230 257 61 171 275 2815/13 4:11 PM 4:31 PM 923 2 10.5 231 38.0 3.9 374 278 59 196 309 291 10.2 207 29.3 3.1 240 275 58 172 261 3015/13 4:31 PM 4:52 PM 924 2 9.1 230 33.3 4.4 360 273 47 191 221 280 11.0 228 30.9 3.5 245 292 49 187 198 3185/14 7:04 AM 7:25 AM 926 6.8 136 20.6 3.4 148 142 50 102 253 158 8.3 117 18.0 3.0 93 150 52 87 227 1735/14 7:25 AM 7:45 AM 927 13.8 201 42.8 5.6 309 243 79 178 359 283 14.6 211 35.8 4.7 222 260 76 160 314 2975/14 7:45 AM 8:06 AM 928 3 13.6 210 38.6 6.1 350 259 84 185 417 290 12.8 173 31.7 4.7 253 267 81 145 369 3115/14 8:06 AM 8:26 AM 929 3 14.8 216 39.7 6.2 353 265 95 189 508 294 13.2 182 33.1 5.2 247 256 96 156 443 3005/14 8:27 AM 8:47 AM 930 3 14.5 229 34.7 5.1 354 250 80 187 431 277 13.6 207 30.0 4.3 254 250 78 153 378 2835/14 8:47 AM 9:08 AM 931 3 10.5 218 36.7 5.5 347 245 78 175 435 269 14.2 212 32.0 4.9 283 280 87 156 407 3185/14 9:08 AM 9:29 AM 932 3 12.2 275 37.0 6.2 380 266 81 193 431 292 13.3 199 31.5 4.9 271 259 78 168 373 293Date START STOPXCRUNXCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)M29RUNERDC/CERL TR-05-9 49Table 20 (Cont’d). XCEM concentrations.AS BA CD CR HG NI PB SB SN ZN AS BA CD CR HG NI PB SB SN ZN5/14 9:49 AM 10:10 AM 934 15.7 99 35.6 6.4 391 278 60 63 340 2945/14 10:10 AM 10:31 AM 935 13.2 58 36.2 5.8 356 261 61 45 317 2785/14 10:31 AM 10:51 AM 936 15.5 170 40.0 5.4 354 258 51 161 304 2755/14 10:51 AM 11:12 AM 937 15.0 21 38.2 6.2 373 275 47 12 282 2875/14 11:12 AM 11:32 AM 938 14.6 182 36.0 5.6 373 277 46 181 268 2875/14 11:32 AM 11:53 AM 939 4 14.8 213 37.4 5.3 360 265 40 181 220 273 14.3 179 30.5 4.8 301 274 43 172 203 2945/14 11:53 AM 12:13 PM 940 4 12.7 208 38.7 6.1 362 262 43 198 216 268 14.3 190 32.2 5.1 319 299 43 175 203 3205/14 12:13 PM 12:34 PM 941 4 14.2 197 34.1 4.9 353 256 36 188 203 266 14.5 213 31.6 5.1 304 284 42 170 193 3025/14 12:34 PM 12:54 PM 942 4 12.4 224 37.1 5.9 380 280 36 187 194 285 13.7 205 32.7 5.2 305 285 39 179 179 3055/14 12:54 PM 1:15 PM 943 4 16.1 207 39.7 6.0 376 278 33 189 167 280 14.8 215 33.3 5.4 286 275 33 177 164 2915/14 1:15 PM 1:35 PM 944 4 15.6 209 38.9 6.6 376 276 29 193 182 282 15.5 204 34.7 5.0 292 291 34 182 165 3065/14 1:35 PM 1:56 PM 945 13.5 183 32.6 5.0 368 273 29 170 191 275 14.4 198 33.3 5.4 312 281 30 163 165 2995/14 1:56 PM 2:16 PM 946 14.8 33 36.3 6.6 363 268 27 13 165 273 14.0 40 30.3 5.2 291 282 30 10 157 3025/14 2:16 PM 2:37 PM 947 5 14.1 225 41.3 5.1 369 269 29 196 181 274 14.4 198 30.0 5.2 331 283 30 178 154 2995/14 2:37 PM 2:57 PM 948 5 17.1 207 35.5 6.2 387 282 26 190 173 286 14.9 190 28.0 5.1 309 266 27 169 149 2835/14 2:57 PM 3:18 PM 949 5 14.7 235 41.7 6.9 390 281 29 190 167 281 13.7 197 30.4 4.7 300 255 26 164 137 2715/14 3:18 PM 3:38 PM 950 5 16.1 220 30.6 5.8 378 275 25 195 157 273 14.1 200 28.2 5.1 311 269 26 166 143 2865/14 3:38 PM 3:59 PM 951 5 15.9 222 36.8 5.9 374 268 22 196 157 271 12.8 186 31.7 4.1 288 242 24 166 129 2575/14 3:59 PM 4:19 PM 952 5 13.9 258 35.3 6.3 374 271 26 202 155 276 14.2 190 29.7 5.7 309 281 25 184 133 2955/14 4:20 PM 4:40 PM 953 5 14.1 228 40.7 6.2 395 286 26 209 147 287 16.0 217 35.3 5.7 346 300 27 196 142 3195/15 6:57 AM 7:18 AM 956 5.6 70 20.5 3.1 148 138 53 70 12 1385/15 7:18 AM 7:38 AM 957 11.0 191 41.3 5.8 341 273 139 191 216 275 14.0 176 27.5 5.2 286 276 138 154 185 2985/15 7:38 AM 7:58 AM 958 6 15.6 225 38.9 6.6 386 291 163 195 415 306 15.1 228 30.6 4.8 293 265 154 156 339 2965/15 7:58 AM 8:19 AM 959 6 13.5 221 40.1 5.8 387 286 150 194 262 297 14.8 201 32.8 5.9 296 270 138 169 224 2925/15 8:19 AM 8:39 AM 960 6 15.3 220 34.9 5.9 372 272 152 194 378 281 15.0 170 30.0 5.0 278 253 143 155 324 2795/15 8:39 AM 9:00 AM 961 6 15.0 220 39.2 18.0 361 279 149 192 325 284 13.2 168 28.3 7.7 272 241 134 153 257 2625/15 9:00 AM 9:21 AM 962 6 13.9 236 41.3 5.7 375 283 162 195 348 293 15.1 189 29.8 4.8 299 260 142 166 281 2835/15 9:21 AM 9:41 AM 963 6 12.5 209 33.7 5.9 388 278 150 194 305 292 12.5 175 24.3 4.4 292 269 141 155 250 2895/15 9:41 AM 10:02 AM 964 6 4.1 227 12.6 2.2 384 283 147 202 300 288 1.9 172 10.1 1.7 285 265 141 149 239 2835/15 10:02 AM 10:22 AM 965 14.1 197 37.9 5.8 384 277 141 198 270 284 16.3 211 31.2 5.5 330 285 146 166 243 307Date START STOPXCRUNXCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)M29RUN50 ERDC/CERL TR-05-9Table 20 (Cont’d). XCEM concentrations.AS BA CD CR HG NI PB SB SN ZN AS BA CD CR HG NI PB SB SN ZN5/15 10:22 AM 10:43 AM 966 7 13.6 233 36.9 5.9 384 280 137 205 251 283 11.9 187 26.8 4.0 241 226 116 143 189 2415/15 10:43 AM 11:03 AM 967 7 14.2 212 34.1 6.1 402 294 141 203 254 294 13.3 213 30.7 5.1 301 287 145 169 216 3065/15 11:03 AM 11:24 AM 968 7 15.4 223 35.5 5.9 396 292 139 208 245 297 14.8 200 31.3 5.3 310 287 145 179 224 3045/15 11:24 AM 11:45 AM 969 7 17.9 253 34.9 4.9 394 291 138 197 237 296 14.5 193 32.7 5.2 317 303 151 184 214 3185/15 11:45 AM 12:05 PM 970 7 15.5 180 44.6 5.0 384 284 136 196 227 289 13.2 194 30.9 5.4 309 288 142 175 201 3045/15 12:05 PM 12:26 PM 971 7 17.2 192 31.8 6.1 382 286 129 191 208 290 14.5 202 32.7 5.5 314 298 143 182 192 3125/15 12:26 PM 12:46 PM 972 7 13.0 230 40.7 5.7 399 292 133 188 215 292 12.1 178 26.0 4.5 268 253 122 156 173 2655/15 12:46 PM 1:07 PM 973 15.6 185 34.7 5.8 396 285 135 186 196 292 13.9 181 29.8 5.2 277 253 120 157 161 2675/15 1:07 PM 1:27 PM 974 8 14.4 188 41.4 6.1 406 296 133 189 183 288 13.9 193 31.7 4.9 294 272 129 166 155 2845/15 1:27 PM 1:48 PM 975 8 15.1 232 33.6 6.8 402 292 128 182 171 287 13.8 185 30.7 4.5 294 274 128 167 146 2875/15 1:48 PM 2:09 PM 976 8 15.3 202 35.8 4.9 395 286 132 187 192 285 13.6 191 29.9 4.8 302 294 141 170 166 3115/15 2:09 PM 2:29 PM 977 8 12.9 215 35.1 5.6 412 299 132 188 179 301 14.6 183 31.5 5.2 310 288 133 179 151 3015/15 2:29 PM 2:50 PM 978 8 12.3 240 41.2 5.8 410 302 137 190 173 296 14.3 217 33.9 5.1 303 298 137 178 153 3115/15 2:50 PM 3:10 PM 979 8 16.4 205 39.8 5.8 413 303 130 179 149 300 12.5 171 28.7 4.2 265 256 121 158 128 2665/15 3:10 PM 3:31 PM 980 8 15.4 200 40.8 4.9 393 289 127 190 157 285 13.8 172 31.3 5.3 289 280 130 169 134 2915/15 3:31 PM 3:51 PM 981 13.0 215 41.7 6.1 398 290 119 185 133 284 14.0 187 34.8 5.3 323 319 145 192 135 3305/15 3:51 PM 4:12 PM 982 9 16.1 202 38.8 6.0 406 293 128 198 143 297 13.2 208 31.3 4.6 275 262 119 163 115 2725/15 4:12 PM 4:32 PM 983 9 14.0 216 34.7 6.3 410 298 132 193 146 301 13.6 200 31.5 5.4 299 288 129 169 128 2995/15 4:33 PM 4:53 PM 984 9 12.7 217 34.3 6.0 405 295 132 199 136 295 13.1 180 30.4 4.9 263 264 118 172 113 2725/15 4:53 PM 5:14 PM 985 9 14.7 219 38.4 6.1 395 284 123 190 130 284 13.2 189 30.7 4.9 274 278 122 172 110 2885/15 5:14 PM 5:34 PM 986 9 13.3 186 39.3 5.5 403 291 127 194 120 286 14.6 200 34.2 6.9 310 305 133 183 113 3165/15 5:34 PM 5:55 PM 987 9 13.0 170 39.4 5.5 415 301 129 197 124 297 14.1 184 31.0 5.2 303 296 131 169 101 3055/15 5:55 PM 6:15 PM 988 15.0 183 29.1 5.0 418 304 123 195 110 299 12.7 193 29.3 5.4 308 309 133 174 100 3205/15 6:15 PM 6:36 PM 989 4.5 97 16.5 2.3 147 76 48 68 107 79 5.3 81 12.7 2.8 100 72 46 52 87 795/15 6:36 PM 6:59 PM 990 0.0 13 0.6 0.2 20 1 22 5 120 8 0.0 20 1.2 1.5 19 2 23 2 104 95/15 6:59 PM 7:19 PM 991 0.0 29 4.9 0.6 13 2 25 2 135 9 0.0 29 0.0 0.1 15 1 26 5 115 105/15 7:19 PM 7:38 PM 992 0.4 6 1.3 0.0 10 0 21 4 114 75/15 7:38 PM 7:58 PM 993 0.0 29 0.1 0.4 9 0 9 0 38 35/16 7:05 AM 7:25 AM 995 11.9 183 37.8 8.6 286 247 140 155 269 259 14.3 159 30.3 10.0 203 254 140 153 232 2765/16 7:25 AM 7:45 AM 996 13.2 216 39.3 7.1 374 268 151 172 290 280 13.0 216 33.8 12.5 287 269 151 158 249 2895/16 7:45 AM 8:06 AM 997 10 13.7 188 38.5 6.1 404 284 154 182 262 298 14.2 197 32.9 6.9 283 272 146 167 231 2945/16 8:06 AM 8:26 AM 998 10 16.7 208 38.2 6.1 397 284 150 182 244 301 13.7 186 28.8 4.7 269 273 143 160 203 2925/16 8:26 AM 8:47 AM 999 10 12.0 210 25.4 3.7 403 290 144 198 262 296 9.5 195 21.5 6.1 286 282 142 160 214 2965/16 8:47 AM 9:08 AM 1 10 14.1 191 35.7 5.3 396 284 137 197 236 294 14.4 178 28.8 5.0 287 285 140 166 208 3045/16 9:08 AM 9:28 AM 2 10 13.9 208 37.3 6.0 385 281 134 195 216 286 14.2 179 28.0 5.1 290 290 140 162 192 305Date START STOPXCRUNXCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)M29RUNERDC/CERL TR-05-9 51Table 20 (Cont’d). XCEM concentrations.AS BA CD CR HG NI PB SB SN ZN AS BA CD CR HG NI PB SB SN ZN5/16 10:30 AM 10:50 AM 6 11 16.2 183 34.6 5.3 393 286 126 202 163 281 14.7 218 32.0 4.8 284 281 129 174 144 2925/16 10:50 AM 11:11 AM 7 11 15.9 204 34.1 5.2 394 286 119 193 152 285 14.7 209 32.1 5.4 302 305 136 185 141 3155/16 11:11 AM 11:31 AM 8 11 14.4 193 35.9 5.8 382 280 118 183 143 278 15.3 196 28.8 7.0 275 279 122 172 125 2865/16 11:31 AM 11:52 AM 9 11 10.6 204 34.3 4.9 405 298 130 192 133 295 14.5 206 29.4 5.2 288 298 128 182 119 3095/16 11:52 AM 12:13 PM 10 11 23.1 194 37.5 5.4 405 289 112 191 128 290 14.7 216 33.5 5.3 292 299 131 186 116 3115/16 12:13 PM 12:33 PM 11 11 12.7 202 33.5 5.6 401 290 125 198 129 286 14.4 226 30.2 5.0 274 291 128 179 111 3015/16 12:33 PM 12:54 PM 12 11 15.6 201 30.3 4.9 374 273 115 189 110 269 12.9 206 29.2 7.6 263 280 121 183 96 2885/16 12:54 PM 1:14 PM 13 12.5 208 32.3 5.7 386 281 119 198 95 283 14.9 198 33.1 5.0 291 302 130 181 92 3125/16 1:14 PM 1:35 PM 14 14.8 183 33.2 5.1 402 298 124 211 100 299 13.6 203 33.6 5.2 260 291 126 180 86 3005/16 1:35 PM 1:56 PM 15 12 15.3 234 35.4 5.2 395 288 118 194 106 291 13.9 203 31.0 5.1 286 301 130 191 97 3085/16 1:56 PM 2:16 PM 16 12 14.3 234 33.4 4.9 389 289 118 196 105 279 14.0 208 31.8 6.0 252 286 123 181 87 2955/16 2:16 PM 2:37 PM 17 12 12.9 184 33.9 5.1 381 281 117 189 90 272 14.7 191 30.2 4.9 264 291 124 178 80 3015/16 2:37 PM 2:57 PM 18 12 14.6 179 35.9 5.2 376 284 113 195 82 273 14.4 211 32.5 5.4 268 296 127 181 89 3045/16 2:57 PM 3:18 PM 19 12 16.9 196 38.8 5.9 406 291 120 191 94 286 14.5 213 32.3 12.4 274 297 127 189 85 3031 10.1 232 34.7 3.6 365 269 66 184 371 2872 9.3 244 35.7 4.1 380 282 66 199 328 2963 13.7 228 37.3 5.8 364 262 81 189 436 287 13.4 194 31.7 4.8 262 262 84 156 394 3014 14.3 210 37.6 5.8 368 269 36 189 197 276 14.5 201 32.5 5.1 301 285 39 176 184 3035 15.1 228 37.4 6.0 381 276 26 197 162 278 14.3 197 30.5 5.1 313 271 27 175 141 2876 12.9 223 34.4 5.4 379 282 153 195 333 291 12.5 186 26.6 4.9 288 260 142 158 273 2837 15.3 218 36.9 5.7 392 288 136 198 234 292 13.5 195 30.2 5.0 294 277 138 170 201 2938 14.5 212 38.3 5.7 404 295 131 186 172 292 13.8 188 31.1 4.9 294 280 131 170 148 2939 13.9 202 37.5 5.9 406 294 128 195 133 293 13.7 194 31.5 5.3 287 282 125 171 113 29210 14.6 199 35.1 5.5 395 286 139 192 230 293 13.5 189 28.5 5.4 282 282 140 164 199 29811 15.5 197 34.3 5.3 393 286 120 193 137 284 14.5 211 30.7 5.8 283 290 128 180 122 30012 14.8 205 35.5 5.3 389 286 117 193 96 280 14.3 205 31.6 6.8 269 294 126 184 87 303ALL 13.7 216 36.2 5.3 385 281 100 193 236 287 13.8 196 30.5 5.3 287 278 108 170 186 2955.1 69 10.7 2.2 129 94 44 68 116 89 3.0 36 5.7 1.7 52 49 43 34 93 51XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)M29RUNUNWEIGHTED AVERAGESt. Dev.Date START STOPXCRUN52 ERDC/CERL TR-05-9



### The XCEM data were then averaged for each M29 run using equation 7:



# ∑ ∑

= 

### = j n

1 j j ij

i 

### t t C C [Eq 7]



### 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 measurements during test run t j 

### = Number of minutes XCEM measured element i ’s concentration during time interval j coinciding with M29 sampling 

# ∑ j 

### t = M29 sampling period.

All XCEM data used for comparisons to M29 were the same as reported during M29 testing with the following four exceptions: 1. During M29 run 1, an evaluation of the calibration factors was undertaken. It was observed that Sb, Ba, and Hg calibration factors were too high relative to thecalibration standards by 15, 15, and 7 percent, respectively. The calibration factors were changed prior to run 2 (Appendix D). 2. Hg calibration factors were determined to be high relative to the calibration curve by 4 percent and were changed foll owing the M29 test (see Appendix D for a complete discussion of Hg calibration). 3. During run 961, an unusually high Cr number (18 μg/dscm – more than 6 SD from the average during normal spiking conditions) was observed. The spectra showed Fe, Cr, and Ni in the same ratio as stainless steel and a speck was noted on the filter tape. The speck was believed to be from contamination that was notrepresentative of the stack gas. For this reason, run 961 for Cr was not used during the averaging to compare to M29. 4. The XCEM shed’s air conditioning failed on 16 May, which meant that the Pd QA concentration did not meet the 90–110 pe rcent criterion for XCEM runs 1021 and 1022. These runs represented 23 minutes of M29 run 12. Consequently, XCEMconcentrations for run 12 were based on a time-weighted average of the 97 minutes that the XCEM produced validated data.

The modified XCEM data were submitted before receiving the M29 results. No modification to the XCEM data was made after receiving M29 results.ERDC/CERL TR-05-9 53



### XCEM Calibration Evaluation Using A QuanX – XRF and ICP/MS

Since XRF analysis is nondestructive, th e concentrated particulate matter on the filter can be reanalyzed at a later date. To evaluate the XCEM calibration, CES reanalyzed each spot using a QuanX XRF analyzer located at CES. The CESQuanX analyzer is one of four in the nation that has been approved for measuring PM 2.5 

### metals concentrations for EPA’s speciation program. Consequently, the analyzer has undergone a series of round robin tests with other laboratories as well as rigorous quality control checks. The QuanX analysis was conducted approximately 6 weeks after M29 testing. With the exception of Hg, which appeared to be lost from the XCEM filter, the material collected on the filter seemed to be intact and representative of the sample collected at TEAD. The QuanX calibration evaluation data are shown in Table 20 as CES Concentration (CES CONC.).

Following the reanalysis, filter spots that correlated with M29 runs 5 and 6 were combined and submitted to Columbia Analytical (Vancouver, WA) for analysis using ICP/mass spectrometry (MS). Table 21 shows results of this analysis.

Table 21. Analysis of XCEM filter tape by Columbia Analytical ( μ g/dscm). Run As Cd Cr Ba Hg Ni Pb Sb Sn Zn

5 14.0 36.4 5.0 176 274 226 22 174 74 252
6 13.3 34.2 4.7 159 254 220 129 152 127 245



### Precision

Five elements were spiked by MSE-TA at a constant rate throughout the testing: Ba, Hg, Ni, Sb, and Zn. Although Ba and Zn had background concentrations of about 10 percent, their limited variability during testing affected the predicted concentrations precision by only a few percent. Overall, these elements were spiked with a precision of better than 5 percent.

Both the XCEM and M29 show good precision for these elements with the XCEM precision about 30 percent lower than M29 (Table 22).

Table 22. Predicted (spiked), XCEM, and M29 precision (%) during validation testing. 1
Approach Hg Sb Ni Ba Zn
Predicted 1.0 1. 7 1.1 5.9 3.5 XCEM 3.8 2.5 3.7 6.9 2.4 M29 6.1 6.1 5.7 7.2 3.3

1 Determined by percent RSD of 12 concentrations reported for M29 runs.54 ERDC/CERL TR-05-9



### Discussion

Regulated Elements Typically Found in the Feedstream

Although the APE-1236 is regulated for nine elements, only three elements —Pb, Cd, and Cr — are found in high enough quantities in stack emissions to potentially limit incineration feed rates (Table 23; Be is not listed in this table because it cannot be measured by the XCEM). The XCEM successfully measuredall three of the key elements and met the 20 percent RA requirements in proposed PS-10 with RAs of 4, 17, and 15 percent, respectively.

Table 23. TEAD emission limits for regulated elements.

State Limit Interim MACT Limit Final MACT Limit Potential to Limit Feed Rate Element g/hr μg/dscm 1 μg/dscm μg/dscm
Pb 4.3 932 Yes Cd 0.26 56 240 59 Yes Cr 0.04 10 Yes As 0.11 24 97 84 No Hg 14 3,036 130 130 No Sb 14 3,036 NR NR No Ni 930 201,740 NR NR No Ba 2,400 521,243 NR NR No

1 Assumes 4,635 dscm/hr based on average rate from Table 16. NR: Not regulated; MACT: Maximum achievable control technology (rule)

Lead



### Lead is the element that most often limits incineration rates at APE-1236. The TEAD incinerator has a state-mandated Pb stack emission limitation of 4.3 g/hr.At typical stack flow rates, this equates to about 900 μg/dscm. EPA’s HWC interim maximum achievable control technolo gy (MACT) rule (EPA 1999) currently limits Pb and Cd emissions to 240 μg/dscm. The final MACT rule, which waspublished 20 April 2004 (FR21210) and will be in effect 3 years after it promulgates, will further limit the combined Pb and Cd emission rate to 59 μg/dscm.

Currently, Pb concentrations within the munitions are determined for each type of ordnance before incineration. Munition feed rates into the incinerator are restricted using a model that assumes that a fraction of the Pb in the munitions will be transported through the air pollu tion control devices and emitted fromthe stack. The effectiveness of the model depends upon several assumptions including transport under various meteorolog ical regimes, incinerator temperature effects, and chemical interactions. Dire ct measurement of Pb concentrations inERDC/CERL TR-05-9 55



### the stack gas allows for improved under standing of the relationship betweenmunitions incineration and stack emission rates as well as an enhanced mechanism for regulating feed rates.

Table 24 shows the Pb results for the MS E/background predicted concentrations (PRD), M29, XCEM (XC), the post-test analysis of the XCEM spots using the CES QuanX (QN), and the ICP/MS analysis of the XCEM filter tape by Columbia Analytical (CA). In general, the result s are in very good agreement with the PRD, M29, XCEM, and QN concentrations, agreeing to within 7 percent. The XCEM and M29 Pb concentrations are also highly correlated with an r2 of 0.98 (Figure 15).

Lead in the first five M29 runs was exclusively from residual concentrations in the incinerator. Following run 5, MS E-TA began spiking an additional 105 μg/dscm of Pb. During testing, both M29 and the XCEM reported concentrations ranging from 25 to 150 μg/dscm. The RA for the XCEM was 4.4 percent. This agreement between the XCEM and M29 demonstrates the capability of the XCEM to accurately measure Pb at the incinerator under a wide range of concentrations.

Table 24. Summary of Pb concentration ( μ g/dscm) data and ratios during M29 testing.

RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 67 72 67 68 0.99 1.01 1.08 0.93 0.94 2 61 77 67 64 1.04 1.11 1.27 0.87 0.84 3 77 98 81 84 0.97 1.06 1.27 0.83 0.86 4 41 38 36 39 0.93 0.88 0.93 0.95 1.03 5 36 27 26 26 22 0.99 0.73 0.77 0.94 0.95 6 167 147 154 141 129 1.09 0.92 0.88 1.05 0.96 7 150 135 137 141 0.97 0.91 0.90 1.01 1.05 8 140 128 132 132 1.00 0.94 0.92 1.03 1.03 9 134 122 128 125 1.02 0.95 0.91 1.05 1.03 10 151 135 140 140 1.00 0.93 0.89 1.04 1.04 11 136 118 121 129 0.94 0.89 0.87 1.02 1.09 12 128 113 117 126 0.93 0.91 0.88 1.04 1.12 AVG. 107 101 101 101 75 0.99 0.94 0.96 0.98 0.99

SD 47 39 43 43 76 0.05 0.09 0.16 0.07 0.0956 ERDC/CERL TR-05-9



## y = 1.09x - 9.60 R 2 

## = 0.98

0 50 100 150 200

0 50 100 150 200 M29 Lead (μg/dscm)XCEM Lead (μg/dscm)

Figure 15. XCEM versus M29 lead for validation tests.

Cadmium



### The APE-1236 state-mandated emission li mit for Cd is about 60 μg/dscm under typical stack flow rates. Cadmium stac k concentrations, which are derived from incineration of shell casings, can occasionally approach this limit. For this test, approximately 80 percent of the stack’s Cd was from MSE-TA, while 20 percent was estimated to be background. Table 25 shows the M29 and XCEM results for Cd during the validation tests.

Overall, the XCEM and M29 were in good agreement for Cd. On average, theXCEM was about 14 percent higher than M29 with an RA of 17 percent. The reanalysis of the XCEM filter tape yi elded mixed results with the QuanX XRF within 3 percent of M29 and the Columbia Analytical concentrations within 4 percent of the XCEM. The inconsistency between the XCEM and CES-QuanX results suggests that an XCEM calibration error may have been responsible for the difference between M29 and the XCEM.ERDC/CERL TR-05-9 57

Table 25. Summary of Cd concentration ( μ g/dscm) data and ratios during M29 testing.



### RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 41.5 29.4 35.2 29.3 1.20 0.85 0.71 1.20 0.99 2 39.8 32.0 35.8 29.4 1.22 0.90 0.80 1.12 0.92 3 48.6 34.6 37.2 31.6 1.18 0.77 0.71 1.08 0.91 4 41.6 31.0 37.7 32.6 1.16 0.91 0.74 1.22 1.05 5 41.4 30.8 36.4 30.0 36.4 1.22 0.88 0.74 1.18 0.97 6 45.4 31.2 37.2 28.6 34.2 1.30 0.82 0.69 1.19 0.92 7 43.7 31.8 36.6 30.9 1.19 0.84 0.73 1.15 0.97 8 41.5 32.4 37.7 31.1 1.21 0.91 0.78 1.16 0.96 9 40.5 32.0 37.4 31.5 1.19 0.92 0.79 1.17 0.98 10 41.1 29.8 34.6 27.9 1.24 0.84 0.73 1.16 0.94 11 39.9 31.3 34.9 30.9 1.13 0.87 0.78 1.12 0.99 12 39.0 31.2 35.5 31.6 1.12 0.91 0.80 1.14 1.01 AVG. 42.0 31.5 36.4 30.4 35.3 1.20 0.87 0.75 1.16 0.97

SD 2.7 1.3 1.1 1.4 1.5 0.05 0.05 0.04 0.04 0.04

Chromium



### The APE-1236 has an effective Cr emissi on limit of less than 10 μg/dscm under typical stack operating conditions. Sinc e the background Cr concentrations were uncertain at the start of the validation test, MSE-TA spiked a nominal 3 μg/dscm during M29 runs 1 and 2. Following these runs, it was determined that the background Cr concentrations were insign ificant and MSE-TA raised their spiking rate to 5 μg/dscm for the remainder of the tests. Overall, the XCEM was consistently 10 percent higher than M29 at both concentration levels (Table 26). This represents a difference of about 0.5 μg/dscm. The agreement between the XCEM and M29 at both the 3 and 5 μg/dscm levels validates the ability of the XCEM to accurately measure Cr at very low concentrations.

The Cr RA was 15 percent, meeting the PS-10 criterion. Subsequent measurements of the XCEM filter tape by the CES-QuanX and ICP were within 3 percent of the M29 concentrations. The consistency of M29 with the predicted valuesand subsequent measurements of the XCEM filter tape suggests that the difference between the two methods is due to XCEM error.58 ERDC/CERL TR-05-9

Table 26. Summary of Cr concentration ( μ g/dscm) data and ratios during M29 testing.



### RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 2.9 3.6 3.7 3.2 1.16 1.28 1.24 1.03 0.89 2 2.9 4.0 4.0 3.2 1.27 1.39 1.38 1.01 0.79 3 5.2 6.4 5.8 4.8 1.20 1.11 1.24 0.90 0.75 4 5.0 5.0 5.8 5.1 1.14 1.15 0.99 1.16 1.02 5 5.0 5.2 6.1 5.0 5.0 1.22 1.21 1.04 1.16 0.96 6 5.0 4.8 5.8 5.3 4.7 1.09 1.16 0.97 1.20 1.10 7 5.1 4.9 5.6 5.2 1.09 1.10 0.96 1.15 1.05 8 5.1 5.1 5.8 4.8 1.20 1.13 1.00 1.14 0.95 9 5.1 5.2 5.9 5.3 1.10 1.17 1.02 1.14 1.03 10 4.8 4.9 5.4 5.4 1.01 1.14 1.03 1.11 1.10 11 5.0 4.8 5.4 5.5 0.97 1.07 0.96 1.11 1.15 12 5.1 4.8 5.3 6.9 0.76 1.04 0.95 1.10 1.44 AVG. 4.7 4.9 5.4 5.0 4.8 1.10 1.16 1.07 1.10 1.02

SD 0.8 0.7 0.8 1.0 0.2 0.14 0.09 0.14 0.08 0.18



### Regulated Elements Not Typically Found in TEAD Emissions

APE-1236 is regulated for six additional el ements that are not typically found in the feedstream in quantities that approach the regulatory limits: As, Hg, Sb, Ni,Ba, and Be. The XCEM does not measure Be. The XCEM met PS-10 measurement criteria for Sb (20 percent) and Ba (4 percent), but was higher than M29 for As, Hg, and Ni with relative accuracies of 27, 33, and 33 percent, respectively.

Arsenic



### Arsenic results are shown in Table 27. The XCEM-reported concentration was in good agreement with the post-test analysis of the filter tape by both QuanX and Columbia Analytical. Their agreement indicates that the XCEM calibration wascorrect to within a few percent. The XCEM concentration is also in good agreement with the predicted concentration. Although, as discussed earlier, the HKM analysis showed a 23 percent lower value for the calibration.

The XCEM’s RA of 27 percent did not meet PS-10 criterion. Overall, the XCEM concentrations were 25 percent higher than M29 concentrations for As. Other potential sources errors for the XCEM be sides calibration such as loss during transport, low filter trapping efficiency , and deposit positioning errors can be ruled out because they would result in X CEM concentrations lower than M29. It is highly possible that the differences in concentration are due to M29 errors.The XCEM was also highly correlated with M29 As (r2=0.85) showing good responsiveness to changes in As concentration.ERDC/CERL TR-05-9 59

Table 27. Summary of As concentration ( μ g/dscm) data and ratios during M29 testing.

RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 10.6 7.8 10.1 9.4 1.07 0.95 0.74 1.29 1.20 2 10.7 8.3 9.3 10.2 0.91 0.88 0.77 1.13 1.24 3 16.7 11.5 13.7 13.4 1.02 0.82 0.69 1.19 1.17 4 16.1 11.9 14.3 14.5 0.98 0.89 0.74 1.20 1.22 5 16.1 11.8 15.3 14.1 14.0 1.09 0.95 0.73 1.30 1.20 6 16.0 11.3 13.9 13.8 13.3 1.01 0.87 0.71 1.23 1.22 7 16.4 11.7 15.6 13.7 1.14 0.96 0.71 1.34 1.18 8 16.2 12.3 14.4 13.8 1.05 0.89 0.76 1.18 1.12 9 16.2 12.2 13.9 13.7 1.02 0.86 0.75 1.14 1.12 10 15.2 11.1 14.3 13.3 1.07 0.94 0.73 1.28 1.20 11 16.0 11.7 15.5 14.7 1.05 0.97 0.73 1.32 1.25 12 16.2 11.9 14.8 14.3 1.03 0.91 0.73 1.24 1.21 AVG. 15.2 11.1 13.8 13.3 13.7 1.04 0.91 0.73 1.24 1.19

SD 2.2 1.5 2.0 1.7 0.5 0.06 0.05 0.02 0.07 0.04

Mercury



### Unlike the other elements, Hg is primarily in the vapor phase in typical stack emissions. For example, during the 2001 M29 tests at TEAD, the particulate Hg captured on the M29 filter and probe represented 1 percent of the total Hg. The XCEM relies upon a specially treated filter membrane to capture the vapor phase Hg while M29 uses an impinger train.

The APE-1236 Hg limit is about 3000 μg/dscm. Mercury, however, is typicallynot present in TEAD stack emissions. An earlier multi-metals monitor was certified for use at TEAD without measuring Hg (Seltzer 2000). For the current validation test, Hg was spiked by MSE-TA with results shown in Table 28.

The XCEM and M29 concentrations had acceptable agreement during runs 1–5 with the XCEM 16 percent higher than M29. Following run 5, however, the XCEM was consistently 34 percent higher than M29. It is believed that these differences are due to vaporization of particulate Hg from the M29 filter.

During runs 1–5, the Hg solution contained Zn and Ni. Following run 5, Pb was added to this solution. Although Hg was spiked at a constant rate, M29 Hg concentrations decreased by 8 percent followi ng Pb injection. The source of this decrease may be related to the unusually high level of particulate phase Hg present during this validation test. Pa rticulate Hg is captured on the M29 quartz fiber filter and can be readily volatilized if the filter is not cooled. Even though total M29 Hg decreased following run 5, the fraction of Hg on the M29 filter increased from 18 percent in runs 1–5 to 30 percent in runs 6–12 (CHPPM 2002). The Hg captured on the filter represents particulate phase Hg, which is typically only a couple of percent of th e total Hg. As such, M29 does not require60 ERDC/CERL TR-05-9



### refrigeration of the M29 filter, so it was not cooled while being shipped to California for analysis. During this time, a significant quantity of the Hg on the filter could have vaporized. Figure 16 shows the relationship between the level of Hg on the M29 filter and the percent difference between M29 and the XCEM.

The XCEM filter also showed a loss of about 30 percent of its Hg as demonstrated by an analysis of the spectra available during validation testing and a few weeks later when the tape was reanalyzed by the CES QuanX. Interestingly, the CES tape had previously shown good retention of vapor phase Hg on earlier tests (Cooper et al. 2000; Chapter 3) so the Hg loss seems to depend upon thequantity in the particulate phase. See Appendix D for a more detailed discussion.

Table 28. Summary of Hg concentration ( μ g/dscm) data and ratios during M29 testing.

RUN PRD 1 M29 1 XC 1 QN 1 CA 1 XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 324 332 367 257 1.42 1.13 1.02 1.10 0.77 2 325 334 381 251 1.52 1.17 1.03 1.14 0.75 3 333 294 365 262 1.39 1.09 0.88 1.24 0.89 4 322 327 368 301 1.22 1.14 1.02 1.13 0.92 5 323 318 379 308 274 1.23 1.18 0.99 1.19 0.97 6 329 280 378 288 254 1.31 1.15 0.85 1.35 1.03 7 327 285 392 302 1.30 1.20 0.87 1.37 1.06 8 325 306 406 294 1.38 1.25 0.94 1.33 0.96 9 324 309 405 287 1.41 1.25 0.95 1.31 0.93 10 328 292 395 282 1.40 1.20 0.89 1.35 0.97 11 326 295 397 286 1.39 1.22 0.90 1.35 0.97 12 322 293 389 267 1.46 1.21 0.91 1.33 0.91 AVG. 326 305 385 282 264 1.37 1.18 0.94 1.27 0.93

SD 3.3 19 14 19 13.8 0.09 0.05 0.06 0.10 0.09 1) Mercury lost from filter.



### y = 1.25x - 4.3223 R 2 

### = 0.8055

0 10 20 30 40 50

0 10 20 30 40 Percent of Hg on M29 FilterPercent Difference BetweenM29 and XCEM

Figure 16. Percent difference between M29 and the XCEM versus percent of Hg on M29 filter.ERDC/CERL TR-05-9 61

Antimony



### Antimony results are shown in Table 29. Overall, the XCEM was higher thanM29 by about 18 percent, but met RA criteria with an RA of 19.9 percent. Subsequent analysis of the filter tape by the CES QuanX was in better agreement with M29. For this reason, it is belie ved that the XCEM/M29 differences were due to XCEM calibration errors of about 15 percent.

Table 29. Summary of Sb concentration ( μ g/dscm) data and ratios during M29 testing.



### RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 192 151 184 166 1.10 0.96 0.79 1.21 1.10 2 196 182 200 177 1.12 1.02 0.93 1.10 0.97 3 201 183 190 156 1.21 0.94 0.91 1.03 0.85 4 194 166 189 176 1.08 0.98 0.85 1.14 1.06 5 193 168 195 172 174 1.14 1.01 0.87 1.16 1.03 6 199 162 194 159 152 1.22 0.98 0.81 1.20 0.98 7 197 164 198 174 1.14 1.01 0.83 1.21 1.06 8 192 162 186 170 1.09 0.97 0.84 1.15 1.05 9 189 157 195 171 1.14 1.03 0.83 1.25 1.09 10 194 157 193 162 1.19 0.99 0.81 1.23 1.03 11 193 163 193 180 1.07 1.00 0.84 1.18 1.10 12 190 154 193 183 1.05 1.01 0.81 1.25 1.19 AVG. 194 164 192 171 163 1.13 0.99 0.84 1.18 1.04

SD 3 10 5 8 15 0.06 0.03 0.04 0.06 0.08

Nickel



### Validation test results for Ni are reported in Table 30. The XCEM was about 30 percent higher than M29 and had an RA of 34 percent, which did not meet the PS-10 criterion. Although the XCEM Ni concentrations were supported by the CES QuanX filter evaluation and predic ted concentrations, the M29 results were similar to results from Columbia Analytical. At this time, the XCEM appears to have been calibrated correctly. As discussed earlier in the section on Arsenic , since the XCEM was higher than M29, the difference appears to be due to M29 analytical problems.

Nickel is not typically found in TEAD stack emissions and the site has a 140,000 μg/dscm stack emission limit. As such, the conservative numbers produced by the XCEM should serve to adequately ensure that Ni is below the emission limit.62 ERDC/CERL TR-05-9

Table 30. Summary of Ni concentration ( μ g/dscm) data and ratios during M29 testing.



### RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 267 200 270 262 1.03 1.01 0.75 1.35 1.31 2 268 235 283 276 1.02 1.06 0.88 1.20 1.18 3 275 234 262 262 1.00 0.95 0.85 1.12 1.12 4 265 213 269 285 0.95 1.02 0.80 1.26 1.34 5 266 231 274 267 226 1.03 1.03 0.87 1.19 1.15 6 271 225 281 259 220 1.08 1.03 0.83 1.25 1.15 7 269 218 289 285 1.01 1.07 0.81 1.33 1.31 8 267 219 296 281 1.05 1.11 0.82 1.35 1.28 9 266 221 294 283 1.04 1.11 0.83 1.33 1.28 10 270 205 285 281 1.02 1.06 0.76 1.39 1.37 11 268 216 288 292 0.99 1.07 0.81 1.33 1.35 12 266 199 286 294 0.98 1.08 0.75 1.44 1.48 AVG. 268 218 281 277 223 1.02 1.05 0.81 1.30 1.28

SD 2.8 12 10 12 4.9 0.04 0.04 0.04 0.09 0.11

Barium



### Barium results for the validation tests are shown in Table 31. For Ba, the predicted concentrations, M29 results, XCEM results, and QuanX reanalysis all agree to within 10 percent with an XCEM RA of 4 percent. Although the stack limit is 500,000 μg/dscm, typical Ba concen trations found in the stack are in the 0 to 200 μg/dscm range. During these validation tests, the XCEM demonstrated good accuracy relative to M29 for Ba under realistic stack conditions.

Table 31. Summary of Ba concentration ( μ g/dscm) data and ratios during M29 testing.

RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 237 214 229 204 1.12 0.96 0.90 1.07 0.95 2 238 248 244 222 1.10 1.03 1.05 0.98 0.89 3 253 247 228 195 1.17 0.90 0.98 0.92 0.79 4 223 203 210 201 1.04 0.94 0.91 1.03 0.99 5 218 207 230 194 176 1.18 1.05 0.95 1.11 0.94 6 240 216 222 186 159 1.19 0.92 0.90 1.03 0.86 7 229 212 215 197 1.09 0.94 0.92 1.02 0.93 8 218 210 215 189 1.14 0.99 0.97 1.02 0.90 9 212 206 202 193 1.04 0.95 0.98 0.98 0.94 10 226 208 198 187 1.06 0.88 0.92 0.95 0.90 11 215 210 197 211 0.93 0.92 0.98 0.94 1.00 12 209 204 203 206 0.98 0.97 0.98 0.99 1.01 AVG. 226 216 216 199 167 1.09 0.96 0.95 1.00 0.93

SD 13 16 15 11 13 0.08 0.05 0.04 0.05 0.06ERDC/CERL TR-05-9 63



### Nonregulated Metals

Two nonregulated metals, Sn and Zn, were measured by the XCEM during validation testing. As discussed earlier, M29 is not approved for Sn, and the M29 Sn results were not considered valid. Zinc was spiked by MSE-TA with XCEM reported concentrations shown in Table 32.

Overall, the XCEM Zn concentrations were consistently about 40 percent higher than M29. The XCEM Zn concentrations were in good agreement with both theCES QuanX and Columbia Analytical tape evaluations, indicating that calibration was not the primary source of this di fference. It is believed that the difference is primarily due to M29 errors.

Table 32. Summary of Zn concentration ( μ g/dscm) data and ratios during M29 testing.

RUN PRD M29 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 QN/M29

1 300 195 288 294 0.98 0.96 0.65 1.48 1.51 2 297 212 297 303 0.98 1.00 0.71 1.40 1.43 3 312 215 287 301 0.96 0.92 0.69 1.34 1.40 4 285 196 276 303 0.91 0.97 0.69 1.40 1.54 5 283 196 277 282 252 0.98 0.98 0.69 1.41 1.44 6 301 209 291 283 245 1.03 0.97 0.69 1.39 1.35 7 291 202 292 301 0.97 1.00 0.69 1.45 1.49 8 285 204 293 294 1.00 1.03 0.72 1.44 1.44 9 280 202 293 293 1.00 1.05 0.72 1.45 1.45 10 292 199 293 298 0.98 1.00 0.68 1.47 1.50 11 283 203 286 303 0.94 1.01 0.72 1.41 1.49 12 278 196 279 302 0.92 1.01 0.71 1.43 1.54 AVG. 290 202 288 296 248 0.97 0.99 0.70 1.42 1.47

SD 10 7 7 7 5 0.03 0.03 0.02 0.04 0.06



### Summary

The XCEM met the proposed PS-10 RA requirements for the three potential emission-limiting elements found in AP E-1236 that could potentially approach emission limits: Pb, Cd, and Cr. The XCEM also met the RA requirements for two other regulated metals Ba and Sb but was high for As, Hg, Ni, and the unregulated Zn. An analysis of potential sources of error suggests that theXCEM numbers for As, Hg, Ni, and Zn best reflect actual stack gas concentrations. However, calibration errors we re noted for Cd, Cr, and Sb even though they met the RA requirements. The XCEM was responsive to changes in concentration and showed good correla tion with the reference method for elements that were spiked at more than one level. In addition, the XCEM successfully measured low metal concentrations as demonstrated by the XCEM’s tracking of M29 Cr’s low concentrations when changes of only 2 μg/m 3 

### occurred64 ERDC/CERL TR-05-9



### between runs 2 and 3. Table 33 summarizes the comparison between M29 and the XCEM.

Table 33. Summary of 2002 M29/XCEM comparison results.

Element Average M29 Conc. ( μ g/dscm) Average XCEM Conc.

( μ g/dscm) Average Predicted Conc. ( μ g/dscm) RA (%) Met PS-10 RA Criterion

Pb 101 101 107 4 Yes Cd 42.0 31.5 36.4 17 Yes Cr 4.9 5.4 4.7 15 Yes As 11.1 13.8 15.2 27 No Hg 305 385 326 33 No Sb 164 192 194 20 Yes Ni 218 281 268 33 No Ba 216 216 226 4 Yes Zn 202 290 288 43 NoERDC/CERL TR-05-9 65



# 5 XCEM Cost and Status

Cost estimates for the Army to purchas e and operate a new XCEM are discussed in this chapter. The values are presented in $1,000 units ($K) and were current in July 2004. Also presented is a summary of the continued operation of the XCEM at TEAD and status of the technology.



### Cost Estimates

Capital Costs

Capital costs include:

1. XCEM: Includes x-ray fluorescence (XRF) spectrometer, operations manuals, extraction system, computer and cont rol module, software, sampling system, enclosure, and calibration equipment, as well as in-house acceptance testing ($195K).

2. Probe and Transport Line: Includes shrouded probe, corrosion resistant transport line, heat tracing, and insulation ($10K).

3. Shipping and Installation: Typically includes shipping of equipment, onsite installation, onsite instrument shakedown, and final onsite calibration check. Site will be responsible for lifting and connecting transport line ($25K).

4. Training: Onsite training for up to six people, including training manuals, hands-on training, power point presen tations, and customer support following installation ($8K).

5. Housing: Includes temperature-controlled housing as either an instrument grade trailer or a shelter depending upon end-user requirements ($5 to $15K).

The total estimated capital costs are between $243K and $253K.66 ERDC/CERL TR-05-9



### Annual Costs

Annual costs include:

1. Consumables: Includes 1 year of filter paper and all other consumables. This cost will depend on usage. The low estimate is for a typical 40 hr/week schedule and the high estimate is for a 24/7 schedule ($5K to $20K).

2. Labor: Includes changing filter tape (1 hr once every 3 weeks for 24/7 usage;once every 2 months for 40 hr/week usage), and regular maintenance (cleaning unit and replacing filters, 6 hr every 3 months) 30–41 hr/year × $80/hr ($2.4K to $3.3K).

3. Warranty: Includes 1-year full-service warranty covering all parts and maintenance. Warranty includes onsi te assistance as needed ($25K).

The total estimated annual costs are between $32.4K and $48.3K.



### Continued Use of the XCEM

Following the conclusion of the M29 tests, the XCEM was used in a series of diagnostic tests to evaluate air pollution control technology installed at APE-1236. Using the XCEM, TEAD personnel develope d baseline data for Pb and Zn during incineration of various munitions. TE AD stack operators also conducted tests using the XCEM in which they determined that the metals emissions could be significantly reduced by completely cutt ing off the bypass system during operation. Blocking the bypass duct with a metal plate resulted in a greater than 90 percent drop in metal concentrations. Using this data, TEAD was better able to understand sources of Pb in the emissions.

The XCEM has also been used by the Ammunition Equipment Directorate (AED) on their test furnace at TEAD. The cont inued use of the XCEM to diagnose and assist with process control indicates th e value of having an installed CEM for multi-metals at TEAD. More recently (2003), AED purchased a second XCEM unit for their test furnace. It was installed during 2004.

Eli Lilly Corporation has recently (May 2004) purchased and installed an XCEM unit for one of their hazardous waste incinerators. They have submitted an Alternative Monitoring Plan (AMP) with the EPA with the intention of using the monitor for compliance purposes. The AMP should be finalized in the nearERDC/CERL TR-05-9 67



### future. The monitor has been successfully integrated into the data acquisition system for the site and generates a 12-hr rolling average as required.

Improvements have been made to the technology since the original XCEM was tested. In a new XCEM (2004), the QuanX XRF instrument has been replaced with a custom XRF detection approach improving the detection limit to 0.1–0.2
μ g/dscm from 1–3 μ g/dscm (15-minute sample time). The monitor can now monitor up to 25 metals simultaneously. The software has been upgraded to accommodate the physical changes and to improve the ease of integration to external data acquisition systems. The physical size of the monitor has also decreased. Figure 17 shows the 2004 XCEM model from CES (X act is the marketing name that CES has given the XC EM). CES has developed, in the last year, a quantitative aerosol generator (QAG) that is capable of delivering a known aerosolized metal concentration. CES believes that using the QAG is a reliable, consistent, and accurate method for ensuring that the calibration has been entered correctly. The QAG is curre ntly being evaluated by the EPA for use in compliance applications.

Figure 17. 2004 CES metals monitor.68 ERDC/CERL TR-05-9



# 6 Summary and Conclusions

A new prototype XCEM was constructed and installed at the TEAD APE-1236 incinerator. It underwent an M29 comparison test during a 4-day period in May 2001. During this test, the monitor func tioned in a completely automated manner and automatically recorded the test da ta. The objective of the test was to meet the requirements of the proposed PS-10.

The monitor met the PS-10 sampling and re sponse time criterion by having an effective up-time of 100 percent and repo rting time averaged concentrations every 20 minutes (20-minute lag between sampling and reporting). It also met the QA criterion with a precision no mo re than 2 percent for zero and upscale checks, and a calibration drift of 0.5 pe rcent. The XCEM met the PS-10 RA criterion (less than or equal to 20 percent) for three of the nine metals tested: Cd, Cr, and Ni. The RA for Pb was 22 percent . The results for Ba, Sb, Zn, and As showed systematic biases. It is believed that the monitor did not successfullymeasure Hg because of loss to the unheated sample line. With regard to response to change in concentration, the XCEM results had a correlation (r 2 

### ) of 0.95 or better for Ni, Sb, and Zn.

In March 2002, the XCEM was moved to a cl oser location, heat traced, insulated, and equipped with a shrouded probe. The combined effect of these changes wasto minimize Hg and PM loss in the sample line. In April 2002, several improvements were made to the calibration proc edure, and the XCEM was recalibrated. The transport system was evaluated by performing a comparison test between the XCEM, predicted concentrations based on spiking, and M17 filter sampling.No measurable loss in particulates was observed. The recalibration was evaluated using a QSIS. The resulting elemental concentrations were within their expected uncertainties for all elements except Cd and Ag.

In May 2002, a series of 12 comparison tests with EPA’s M29 were conducted. During this testing, the XCEM had an “uptime” of better than 98 percent, met all QA parameters, and had a precision that was better than M29. The XCEM also showed good correlation with Meth od 29 for elements that had significant variability in concentration during testing.ERDC/CERL TR-05-9 69



### APE-1236 emissions have the potential to approach state-mandated emission limits for three elements: Pb, Cd, and Cr. The XCEM met the PS-10 20 percent RA criterion for all three of these elemen ts. XCEM data were also compared to M29 data for five elements that are typi cally found in concentrations well below the site emission limits: As, Hg, Sb, Ni, and Ba. A final nonregulated element, Zn, was also spiked and examined during validation testing. The XCEM met the RA criterion for Ba and Sb, but was unifo rmly high relative to M29 for As, Ni, Zn, and Hg.

An error analysis was conducted to dete rmine the source of the difference between M29 and the XCEM. Calibration errors and spectral interferences werechecked by reevaluating the XCEM filter with CES’s QuanX and submitting filter samples to an independent laboratory for analysis. The results indicate that, for Cd, Cr, and Sb, calibration appeared to cause some error, even though theseelements still met the RA criterion. However, for As, Ni, and Zn, the XCEM calibration was not the primary source of e rror. Other potential XCEM sources of error such as loss during transport, low filter trapping efficiency, and deposit positioning errors are highly unlikely because they would result only in XCEM concentrations lower than M29. The differenc es in concentration for As, Ni, and Zn appear to be due to M29 analytical errors.

An analysis of Hg on the XCEM filter determined that particulate phase Hg was being vaporized over time. A comparison of XCEM spectra generated during the test with reanalysis 6 weeks later showed a loss of 30 percent of the Hg from the XCEM filter. M29 particulate concentratio ns on the M29 filters were 15 to 30 times higher than typical and were high ly correlated with differences between the XCEM and M29. The filters, which were not cooled while being shipped to the M29 laboratory, could have lost the Hg prior to analysis. It is evident that the most significant obstacle in meeting the PS-10 RA criterion for the XCEM is the accuracy problems of the comparative reference method (M29).

It was observed for both M29 comparison tests that the best method for calibrating the XCEM had not been determined. Bo th tests revealed some errors in calibration with some corrections made af ter the M29 tests but prior to the XCEM result submissions. This may cause so me speculation over the performance of the monitor because the calibration rules seemed to change after the tests started. Because this monitor samples in a nondestructive manner, the results can be reanalyzed and verified at a later da te. It is these analyses that allow the determination of the sources of error, including calibration. This has clearly benefited the development of the XCEM ca libration procedures with each subsequent test. However, to ensure confidence in the monitor’s eventual use in the70 ERDC/CERL TR-05-9



### field, a reliable, consistent, and accurate calibration protocol needs to be established.

With the assistance of the XCEM, TEAD was able to identify that blocking the bypass duct on the 1236 furnace with a metal plate resulted in a greater than 90percent drop in metal concentrations. The continued use of the XCEM to diagnose and assist with process control at TEAD indicates the value of having an installed CEM for multi-metals.

The current cost estimates for the Army to purchase and operate a new XCEM are between $243,000 and $253,000 in capital costs, and between $32,400 and $48,300 for annual costs. These figures were current in July 2004. Recently, AED and Eli Lilly purchased XCEMs for th eir furnaces. Improvements in the XCEM have resulted in a monitor that can measure 25 metals simultaneously and with detection limits between 0.1 and 0.2 μ g/dscm. In addition, CES has recently developed the QAG spiking method that will provide a reliable, consistent, and accurate means for ensuring that the calibration has been entered correctly.ERDC/CERL TR-05-9 71



# References

Bryson, S. (2001). Final Report – Stack Spiking Report for a Multi-Metal CEMS Test at the Tooele Army Depot Deactivation Furnace. Prepared for U.S. Army Corps of Engineers by MSETA, Inc., Butte, MT.

____________. (2002). US Army Construction Engine ering Research Laboratory (CERL), Waste Minimization and Pollution Pr evention Program: Stack Spiking Report for a Multi-Metal CEMS Test at the Tooele Army Depot Deactiva tion Furnace – 2002. Prepared for U.S. Army Corps of Engineers by MSE-TA, Inc., Butte, MT.

Bryson, S., C. Whitworth, and S. Kujawa. (2000). Final Report – Test and Evaluation of an X-Ray Fluorescence Based Multi-Element Metals Continuous Emission Monitor. Prepared for U.S. Army Corp of Engineers by MSE-TA, Inc., Butte, MT.

Center for Health Promotion and Preventive Medicine (CHPPM). (2001). Air Pollution Management Study No. 43-EL-6498-01 Verificati on of Multi-Metals Continuous Emission Monitor at Tooele Army Depot. Tooele, Utah, May 14-17, 2001.

____________. (2002). Air Pollution Management Stud y No. 43-EL-4755-02 Verification of MultiMetals Continuous Emission Monitor at To oele Army Depot. Tooele, Utah, May 13-16, 2002.

Cooper Environmental Services (CES). (2001a). “XCEM User’s Guide,” Beaverton, OR.

____________. (2001b). “XCEM Resource Manual,” Beaverton, OR.

Cooper, J., B. E. Johnsen, K.J. Hay, and W. Watson (2000). Continuous Hazardous Element Analysis System for Ambient and Emissions Monitoring. Presented at regional AWMA Conference: Recent Advances in the Scienc e and Management of Air Toxics. April 10, 2000.

Cooper, J.A., B.E. Johnsen, S.C. Fry, and M.P. Nakanishi. (2002). “Limitations in the Use of EPA Reference Method 29 for Evaluating the Relative Accuracy of Candidate Multi-Metal Continuous Emission Monitors.” CES Report, September 2002.

Environmental Protection Agency (EPA). (1992). Method 301 – Field Validation of Pollutant Measurement Methods from Various Waste Media. Found on the EPA website at: http://www.epa.gov/ttn/emc /promgate/m-301.pdf.

____________. (1996). PS-10, Proposed Performance Specification 10 for Metal CEMS (Proposed 04/19/96) Found on the EPA website at: http://www.epa.gov/ttn/emc/propperf.html

.

____________. (1999). Final Standards for Hazard ous Air Pollutants for Hazardous Waste Combustors; Final Rule. FR52827-FR53077, Vol 64, No. 189.72 ERDC/CERL TR-05-9

____________. (2004). National Emission Standards for Hazardous Air Pollutants for Hazardous Waste Combustors (Phase I final Replacemen t Standards and Phase II); Proposed Rule. FR21197-21385, Vol 69, No. 76.

French, N. (1998). 1997 Performance Testing of Multi-Metal Continuous Emissions Monitors. Summary Report Prepared for the U.S. EPA and U.S. DOE by Sky+, Napa, CA.

Hall, B., O. Lindqvist, and E. Ljunstrom. (1990) . Mercury Chemistry in Simulated Flue Gases related to Waste Incineration Conditions. Environ. Sci. Technol ., Vol 24, No. 1.

Hay, K. J., B. E. Johnsen, and J. Cooper ( 2005). X-Ray Fluorescence-Based Multi-Metal Continuous Emission Monitor: Developmen t. U.S. Army Engineer Research and Development Center (ERDC)/CERL Techni cal Report (TR)-05-3, January 2005.

Josephson, Paul (2003). Hazardous Waste Co mbustor Management Plan – AEC (for Table 1).

Lemieux, P., J. Ryan, N. French, W. Haas (1998). Results of the September 1997 DOE/EPA Demonstration of Multi-Metal Continuous Emis sion Monitoring Tech nologies. Presented at International Conference on Incinera tion and Thermal Treatment Technologies.

McFarland, A.R., and J.C. Rodgers. (1993). Single-Point Representative Sampling with Shrouded Probes. Los Alamos National Laboratory, LA-12612-MS, August 1993.

Myers, J., T. Kelly, C. Lawrie , and K. Riggs. (2002). Environmental Technology Verification Report: Cooper Environmenta l Services, XCEM Multi-Metals Continuous Emission Monitor, May 2002. From EPA website: http://www.epa.gov/etv/pdfs/vrvs/02_vr_cooper_xmcem.pdf.

Seltzer, M.D. (2000). “Performance Testing of a Multimetals Continuous Emissions Monitor,” J. Air Waste Mgt. Assoc. , Vol 62, No. 6.

Wang, R.G., M.A. Dillon, and D. Spence. (1983). Journal of Chem. Phys. , 79 (2), 1100.ERDC/CERL TR-05-9 73



# Appendix A: Test/QA Plan for Verification of a Continuous Emission Monitor for Multi-metals at Tooele Army Depot (2001) *

1.0 INTRODUCTION

1.1 Test Description

This test/quality assurance (QA) plan prov ides detailed procedures for a verification test for an X-Ray Fluorescence -based Continuous Emissions Monitor(XCEM) used to measure metals in source emissions. The U.S. Army Construction Engineering Research Laboratory (CER L) will perform the verification test. The U.S. Army is interested in identifying an effective means of continuouslymeasuring metals in stack emissions generated by their demilitarization incinerators. The U.S. Environmental Protection Agency’s (EPA’s) Environmental Technology Verification (ETV) Program w ill verify the test procedures and results. The purpose of the ETV is to provide objective and quality assured performance data on environmental technologi es, so that users, developers, regulators, and consultants have an independen t and credible assessment of what they are buying and permitting.

Battelle Memorial Institute, headquartered in Columbus, Ohio, is EPA’s partner for the ETV Advanced Monitoring Systems (AMS) Center. The scope of the AMS Center covers verification of monitori ng methods for contaminants and naturalspecies in air, water, and soil. Verification testing will follow procedures specified in this test/QA plan and the quality requirements in the “Quality Management Plan for the ETV Advanced Monitoring Systems Pilot” (EPA 2000).

* Prepared for CERL by Cooper Environment al Services, Beaverton, OR, 8 May 2001.74 ERDC/CERL TR-05-9



### Testing will take place at the Tooele Ar my Depot (TEAD) de activation furnace located in Tooele, UT.

1.2 Test Objective

The objective of the verification test is to quantify the performance of the XCEM by comparison to reference metal measur ements under full-scale conditions at a combustion facility.

1.3 Organization and Responsibilities

The CERL, TEAD, and Battelle will perform an d evaluate the verification test in cooperation with Cooper Environmental Se rvices (CES), which will provide the XCEM for verification. MSE Technology Applications , Butte, MT (MSE-TA) will be responsible for spiking the stack, an d the U.S. Army Center for Health Promotion and Preventive Maintenance (CH PPM) will conduct the reference method testing. The organization chart in Figure 1-1 shows the individuals who will have responsibilities in the verification te st. The specific responsibilities of these individuals are detailed in the following paragraphs.

Figure 1-1. Organizational Chart for Verification Tests

1.3.1 Construction Engineering Research Laboratory



### Dr. K. James Hay is the CERL verification testing leader. Dr. Hay will have overall responsibility for ensuring that the technical, schedule, and cost goals established for the verification test are met. If questions arise concerning QA Tom Kelly Battelle

John Cooper

CES XCEM Vendor Dee Russell TEAD Facility Manager

Mike Pattison CHPPM Ref. Measure. James

Hay CERL

Steve Bryson MSE-TA

Stack SpikingERDC/CERL TR-05-9 75



### problems, Dr. Hay has the authority to stop or delay the test. As the test leader, Dr. Hay will:

• Coordinate TEAD, Battelle, CHPPM, MSE-TA and CES staff to conduct the verification test.

• Have overall responsibility for development of a test/QA plan.

• Revise the draft test/QA plan in response to reviewer’s comments.

• Have overall responsibility for ensuring that this test/QA plan is followed.

• Serve as the primary point of co ntact for CES representatives.

1.3.2 Battelle



### Dr. Thomas J. Kelly is the ETV AMS Center’s Verification Testing Leader. In this role, Dr. Kelly will be responsible fo r reviewing the test/QA plan, evaluating field-testing to ensure that the test/QA pl an is being followed, and developing an ETV verification report and statement. Mr. Charles Lawrie is the AMS Center’s Quality Manager. As such, he will be re sponsible for assessing that quality requirements of this test/QA plan are met. More specifically, these Battelle staff will:

• Review the draft test/QA plan.

• Coordinate Battelle and EPA/ETV sta ff during verification testing.

• Observe the CHPPM/MSE-TA/CES team in their performance of the verification test.

• Report test quality problems to CERL. If significant quality problems are observed and not rectified, Battelle can di scontinue the test as an ETV verification.

• Prepare a draft ETV verification report and statement using test data and summary test report provided by CES.

• Oversee revision of the draft ETV verification report and statement in response to reviewer’s comments.

• Coordinate technical peer reviews of the test/QA plan and ETV verification report and statement.

• Conduct a technical system audit and report results of that audit.

1.3.3 Tooele Army Depot



### The verification test will be conducte d in collaboration with Dee Russell of TEAD. Mr. Russell’s responsibilities are:

• Coordinate the operation of the facility during verification testing.

• Coordinate the installation of the XCEM at the TEAD incinerator.

• Communicate needs for safety and other tr aining of staff working at the facility.

• Contribute to the development of the draft test/QA plan.76 ERDC/CERL TR-05-9



### • Provide input on facility operating co nditions and procedures for the summary and ETV verification report.

• Review the draft test/QA plan.

• Provide input for the summary test re port and ETV verification report.

• Review draft reports.

• Assemble trained staff to operate the TEAD incinerator.

• Ensure that the facility is fully functional prior to the times/dates needed in the verification test.

• Oversee technical staff in facility operation during the verification test.

• Ensure that operating conditions and procedures for the TEAD incinerator are recorded during the verification test.

• Review and approve all data and records related to facility operation.

• Provide support in responding to any issues raised in assessment reports and audits related to facility operation.

1.3.4 Cooper Environmental Services



### Cooper Environmental Services of Be averton, OR manufactures the XCEM. CES staff will:

• Develop the draft test/QA plan and submit plan to CERL, Battelle, TEAD, CHPPM, and MSE-TA staff. Revise the te st/QA plan in accordance with reviewers’ comments.

• Approve the final test/QA plan.

• Participate in required safety training at the test facility before installation of the XCEM.

• Attend a pre-study site visit to revi ew facility requirements for testing.

• Provide an XCEM for the duration of the verification test.

• Commit a trained technical member of staff to operate, maintain, and repair the XCEM throughout the verification test.

• Participate in verification testing, including providing data acquisition for the XCEM.

• Provide data from the XCEM at the conclusion of each test day.

• Prepare a summary test report for CERL. The summary test report will be used as the basis for the ETV verification report.

• Review the draft verification repo rt and verification statement.

1.3.5 Center for Health Promot ion and Preventive Medicine



### Reference method testing will be conduc ted by CHPPM under the direction of Mike Pattison. Mr. Pattison will:

• Review the draft test/QA plan.

• Adhere to the quality requirements in this test/QA plan.ERDC/CERL TR-05-9 77



### • Assemble trained technical staff to co nduct reference method sampling for the verification test.

• Contract for and oversee laboratory an alysis of the reference method samples.

• Provide reference method analytical and quality assurance results and data in an agreed-upon format to Battelle, CES, and/or CERL as needed.

• Provide support in responding to any issues raised in assessment reports and audits related to facility operation.

1.3.6 MSE Technology Applications, Inc.



### MSE-TA will be responsible for injection of the metals of interest into the TEAD incinerator. MSE-TA will:

• Quantitatively spike metals of intere st into the TEAD incinerator downstream of the controls.

• Provide measurable concentrations of the metals of interest at the XCEM and reference method sampling points.

• Ensure that particle size for the metals of interest are representative of typical stack gas conditions.

• Ensure that all applicable regulatory emission limits are maintained.

1.3.7 U.S. Environmental Protection Agency



### EPA manages the ETV program and partners with Battelle for the ETV AMS Center. As such, EPA has the option to conduct a technical systems audit of the verification test. In addition, EPA will participate in the peer review of the test/QA plan to be prepared by CES and the ETV verification report to be prepared by Battelle.



### 2.0 APPLICABILITY

2.1 Subject

This test/QA plan is applicable to the verification testing of a commerciallyavailable continuous emission monitor (CEM) system for determining multimetal concentrations in combustion source emissions. The system being tested is an X-ray Fluorescence-based CEM (XCEM) manufactured by CES. The XCEM extracts a representative stack gas samp le and concentrates the particulate matter and gas phase hazardous metals on a filter, which is then analyzed with xray fluorescence (XRF) using an adapted QuanX analyzer. A prototype of the78 ERDC/CERL TR-05-9



### XCEM was assessed at the MSE-TA test facility in Butte, MT (Bryson 2000) and has been redesigned for increased ea se-of-use and automated QA routines.

Verification testing will be conducted at TEAD. The TEAD facility has a wellcharacterized feedstream and was the si te for multi-metal CEM tests conducted in 1999.

The TEAD site has a deactivation furnace, APE-1236, for incineration of munitions. The incinerator is currently re gulated under the Resource Conservation and Recovery Act (RCRA) for antimony, arsenic, barium, beryllium, cadminum, chromium, lead, mercury, nickel, selenium , silver, and thallium (Sb, As, Ba, Be, Cd, Cr, Pb, Hg, Ni, Se, Ag, and Tl). Of the twelve regulated elements, five are typically found in the feedstream: Sb, Ba, Cd, Cr, and Pb. The XCEM will beverified for its measurement capabilities of the five elements found in the feedstream as well as As, Hg, Ni and a nonregulated metal, zinc (Zn). These elements were selected in order to challeng e the XCEM over a large range of analysis conditions and elemental concentrations.

EPA Method 29 (M29) is currently recognized as the most suitable procedure to determine multi-metal concentrations in source emissions (EPA 1990). Method 29 draws stack gas through a filter and a series of impingers providing a 1- to 3-hour average concentration. For the veri fication testing, a battery of twelve 2- hour M29 tests will be conducted by CHPPM. Analysis of the M29 sample trainwill be under the direction of CHPPM and will include, as a minimum, determination of the nine elements measured by the XCEM.

2.2 Scope

The overall objective of the verification test described in this plan is to provide quantitative verification of the perfor mance of the XCEM under real-world conditions. EPA has published a draft performance specification document designated as PS-10 (EPA 1996) as a proposed description of how to assess the acceptability of a multi-metal CEM upon installation and thereafter. The goals of the verification test will be met if the XCEM meets the proposed PS-10: 1. Relative accuracy criteria for the elements in the feedstream of the Tooele incinerator (Sb, Ba, Cd, Cr, and Pb). 2. Quality assurance criteria by passing daily zero, span, and drift checks. 3. Response time and reporting time criteria for a batch CEM. 4. Measurement criteria by testing several elements at two concentration levels (Hg, Ni, Zn, and Sb).ERDC/CERL TR-05-9 79



### A secondary objective is to meet the relati ve accuracy criteria for additional regulated and unregulated metals, which are not typically found in the feedstream (As, Hg, Ni, and Zn).

The performance parameters that are addressed by this test/QA plan include:

• Relative accuracy

• Correlation with reference method

• Precision

• Instrument drift

• Span and zero

• Response time

• Bias

• Low level metal response.

Relative accuracy, correlation with the reference method, and precision (i.e., repeatability at stable test conditions) will be assessed for the elements being measured by the XCEM. Instrument drift will be based upon the precision of the daily XCEM span and zero QA measurem ents. The XCEM has a built-in additional check for instrument drift which measures a palladium standard with each XCEM test run. For the verification test, response time will be determinedas the time between the start of one sampling period and the beginning of a second sampling period. Bias will be identi fied using EPA method 301 protocols as discussed in section 5.6. Low-level meta l response will be determined by a comparison to chromium and arsenic referenc e method concentrations, which will be less than 6 and 18 μg/dscm respectively.

It is beyond the scope of this verificati on test to simulate the aging and exposures that may affect an XCEM during ro utine long-term use. This verification test evaluates the performance of a new XCEM over a relatively short test period, in the hands of staff skilled in its oper ation. It must be noted that the longterm performance may be different from that observed in the testing describedhere. The effort spent in installing and maintaining the XCEM will be documented, however, and the amount of time the XCEM is operational over the verification test period will be reco rded, to assess data completeness.



### 3.0 SITE DESCRIPTION

Verification testing will take place at the TEAD building 1320 deactivation incinerator APE-1236 (Figure 3-1). This sect ion of the test/QA plan describes the TEAD incinerator and the procedures for operating it for this test.80 ERDC/CERL TR-05-9



### 3.1 Test Facility

The TEAD incinerator, which runs on diesel fuel, is designed to incinerate decommissioned munitions. Typical operat ing 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 percent. Typi cal stack PM concentrations are in the10 mg/dscm range. A number of sensors (temperature, gas flow, pressure differential, combustion gases, etc.) are used to monitor operating conditions at various points in the system. Signals from these sensors are monitored and compared to preset operating standards. Th e incinerator consists of a main control panel, CEMS, Waste Feed Rate Monitori ng System (WFRMS), dual conveyor feed system, rotary furnace, furnace shro ud, cyclone, afterburner, discharge conveyor, high temperature cast ceramic f ilters baghouse, high temperature draft fan, and exhaust stack.

1) Main Control Panel . The main control panel contains various pieces of control equipment to monitor and control the furnace operation. Process controllers are used to control the rotary furn ace 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 PLC. The PLC controls the motor st arters, the WFRMS, safety interlocks, and alarms. The computer system is an industrial-based machine running data acquisition software, which provides ce ntralized and integrated data management, process graphics, operator in terface, and report generation.

Figure 3-1. TEAD Deactivation Incinerator Building 1320.ERDC/CERL TR-05-9 81



### Table 3-1. Typical operating parameters for the APE-1236 deactivation furnace. Typical Operating Parameters for the APE-1236 Deactivation Furnace Afterburner Temp. (°F) 1600 Baghouse ∆ P (in. H 2 

### O) 9 Baghouse Temp (°F) 680 Kiln Feed End Draft Pressure (in. H 2 

### O) 0.3 Kiln Feed End Temp (°F) 600 Kiln Burner End Temp (°F) 1200
O 2 

### – CEM (%) 14 CO (ppm) 11 Stack Temp. (°F) 550 Stack Gas Velocity (ft/sec) 46 Stack Pressure (in. H 2 

### O) 0.3

Figure 3-2. TEAD Incinerator Stack.82 ERDC/CERL TR-05-9



### 2) Continuous Emissions Monitoring Systems . CEM systems are in place to measure carbon monoxide (CO) and oxygen (O 2 

### ) in the exhaust stack. The CEM sampling system includes the followi ng: sample extraction probe, heat traced sampling lines, calibration ports, refrigerated condenser, sample pump, filters, and flow meters. The sample extraction port is located in the exhaust stack approximately 20 feet above grade. The CEM system includes automatic calibration, which allows the monitors to be calibrated periodically without operator intervention. The CO monitor is a NDIR analyzer with 0-200 ppm and 0-3,000 ppm dual range capability. The output from the CO monitor is corrected to 7 percent O 2 

### (using data from the O 2 

### CEM).

3) Waste Feed Rate Monitoring System . 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 report s 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.

4) Dual Conveyor Feed System . The primary waste feed conveyor transports the munitions from the WFRMS thro ugh the concrete wall into the barricade area. The ammunition is then fed onto the secondary feed conveyor, whichdeposits the ammunition into the rotary furnace feed chute. If an out-ofparameter condition arises, the primary feed conveyor is stopped until the condition is corrected. For safety reasons, however, the secondary conveyor continues to operate. This allows munitions near the high temperature end of the kiln to continue moving through the furnace and deters possible explosions outside the furnace.

5) Rotary Furnace . The rotary furnace is designed to ignite the ammunition items and effectively incinerate reactive components from the metal shells. The heat to ignite the ammunition is initially provided by fuel oil forming a countercurrent to the movement of the ammuniti on through the rotary furnace. Combustion gases and entrained ash exit the furnace adjacent to the feed chute. Non-entrained ash and the metal components of the ammunition are discharged at the burner end of the rotary furnace. The ammunition is propelled through the 20 ft long, 30.5 inch diameter retort to ward the burner end by spiral flights. As the ammunition approaches the flame, they either detonate or burn freely, depending on the ammunition characteristic s. The thick cast steel walls contain high order detonations. Feed rates, re sidence times, and operating parameters have been established for each ammunition item by controlled testing. The ro-ERDC/CERL TR-05-9 83



### tary furnace is equipped with a Hauck 783 proportioning burner located at the discharge end. The burner has a capacity of 3 million BTU/hr and a nominal turndown ratio of 4:1. The feed end te mperature of the furnace ranges between350-450 °F while the discharge end ranges from 800-1100 °F during normal operation. The rotary furnace is operat ed under a slight negative pressure.

6) Furnace Shroud . A metal shroud that completely encloses the retort sections, the draft fan, and the retort combus tion air fan controls fugitive emissions from the rotary furnace. The draft fan is used to maintain negative pressure at the feed end of the furnace. The retort combustion air fan draws air from the area beneath the retort shroud, creating a negative pressure. The combustionair blower creates a negative pressure inside the shroud, which pulls any fugitive emissions through the blower and discharges them into the furnace via the furnace burner.

7) Cyclone. Large particles from the gas stream are removed by the cyclone. The cyclone has a 90-95 percent removal efficiency for particles 10 microns and larger. The cyclone has a clock-wise rota tion, with inlet and outlet ducts at 90° separation. Particles are removed from the cyclone at the bottom by a double tipping valve. The valve has two gates that are motor driven. The gates open alternatively so that only one gate is open at any time, thus maintaining the negative pressure.

8) Afterburner . The afterburner is built to AED specifications 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 4000 scfm of flue gas from 350-450 °F to 1400- 1600 °F with a minimum flue gas residence time of 2 seconds. A diesel fuel burner with a propane pilot ignition sy stem heats the afterburner. The afterburner is equipped with a Hauck WR0164 wide range burner with a capacity of 8 million BTU/hr and nominal turndown ratio of 10:1.

9) Discharge Conveyor . The solid waste exits the furnace by the discharge conveyor located at the discharge/burner end. The solid waste is typically comprised of the metal casings, melted lead projectiles, and residual ash. The low end of the discharge conveyor is locate d underneath the discharge/burner end of the rotary furnace. The high end of the conveyor passes through the concrete barricade wall and deposits the waste into containers.

10) High Temperature Cast Ceramic Filters Baghouse . The baghouse is a high temperature cast ceramic collector, used for final particulate cleansing for84 ERDC/CERL TR-05-9



### the gas stream. The baghouse was designed and built to AED specifications by JT Systems Incorporated. The flue gase s from the afterburner are transportedto the baghouse by 120 ft of 30-inch diameter stainless steel ducting. The ducting is long enough to produce a temperat ure drop from 1600 °F at the exit of the afterburner to 1000 °F entering the baghouse. The baghouse contains 154 cerafil ceramic candles that are 5.75 inches in diam eter and 10 ft long. This results in a total filter area of 2330 square feet with a filtration velocity of 4.97 feet/second. The baghouse operates with a delta pressure range of 0.5 to 6.0 inches of water column. The particles settle into the hopper below and are exhausted through a double tipping gate valve into a sealed 55-gallon drum while maintaining an air seal on the baghouse assembly.

11) High Temperature Draft Fan . The gas steam is pulled though the APCS by an induced draft fan. The fan is a Fan Equipment Company Model M-21 I.E. The fan is capable of pulling 6700 ACFM at a draft (negative pressure) of 30 inches of water column.

12) Exhaust Stack . The A36 carbon steel, circular exhaust stack is approximately 30 ft high (34 ft with extension) and has a nominal ID of 20 inches (Figure 3-2).

3.2 TEAD Emission Limits During Testing

For the verification test, metals in the TEAD incinerator stack gas are regulatedunder a Temporary Authorization permit as shown in Table 3-2. Of the 12 regulated metals, 5 are typically found in th e feedstream (Pb, Sb, Ba, Cd, and Cr);however, Pb is the only element that is routinely found in measurable concentrations in the stack gas.
Table 3-2. TEAD metal emission limits during verification testing.
Element Limit (g/hr) Element Limit (g/hr)

Antimony (Sb) 14 Lead (Pb) 4.3

Arsenic (As) 0.11 Mercury (Hg) 14
Barium (Ba) 2400 Nickel (Ni) 930
Beryllium (Be) 0.20 Selenium (Se) 180
Cadmium (Cd) 0.26 Silver (Ag) 140
Chromium (Cr) 0.04 Thallium (Tl) 14ERDC/CERL TR-05-9 85



### 4.0 EXPERIMENTAL DESIGN

4.1 General Design

For all tests, both the kiln and the afterburner will be fired with diesel fuel while incinerating Mark 344 fuses (NSN number 1325000090348) with a feed rate of 79 per hour. The chemical composition of the fuses is shown in Table 4-1. For these fuses, lead is the restrictive element limiting the feed rate. Table 4-2 shows the nine elements that will be meas ured by the XCEM during verification testing. Eight of these metals will be spiked directly into the stack downstream of the controls. These metals will be sp iked at the level shown in Table 4-2.Lead, however, will not be spiked since the incinerated munitions provide measurable concentrations of lead without spiking.

Spiking will be conducted by MSE-TA usin g three or four atomizers to inject solutions containing the metals of interest either directly into the stack or into a chamber that dries the solution prior to entering the stack. The atomizer provides liquid droplets that, when dried, yiel d fine salt particles that are representative of typical stack aerodynamic diameters.

Stack gas metal concentrations will be simultaneously determined by the XCEM and two Method 29 (M29) sampling trains. The M29 trains will sample for two hours while XCEM data, which is record ed every 20 minutes, will be averaged for the M29 test run.

A total of 12 dual M29 test runs will be performed by CHPPM. Each run will include two M29 sampling trains in order to determine reference method precision. Method 301 will be applied to M29 data to determine bias between the reference method sampling trains. Prior to testin g, CHPPM will conduct an EPA Method 2 velocity traverse to determine a repr esentative sampling point for the M29 probes. The XCEM and M29 probes will be located approximately 27 feet above the base of the exhaust stack. The neares t flow disturbances are located 9.8 duct diameters upstream (induced draft fan) and 4.3 duct diameters downstream (top of the stack) from the sample ports.86 ERDC/CERL TR-05-9



### Table 4-1. Composition of munitions incinerated during metals testing. Fuze, Bomb, Tail, MK344 Mod 0/1 Feed Rate: 79 items/hr; Loading (lb/item) 0.2791

Component Component Quantity (lb/item) Component Feed Rate (lb/hr) Butyl Acetate 0.00001 0.0008 Charcoal 0.00002 0.0016 Ethyl Alcohol 0.00001 0.0008 Graphite 0.00541 0.4275 Lead Azide 0.00028 0.0221 Lead Monoxide 0.00005 0.0040 Lead Powder 0.00031 0.0245 Lead Styphnate 0.00683 0.5398 Nitrocellulose 0.00002 0.0016 Nitrostarch 0.00001 0.0009 PETN 0.00031 0.0245 Potassium Nitrate 0.00008 0.0063 Selenium Powder 0.00012 0.0095 Sulfur 0.00005 0.0040 Tetryl 0.26555 20.9855 Toluene 0.00001 0.0008

Table 4-2. Tooele metal emission limitations and spiking levels.

Emission Limits 1 

### Spiking Level 1 

### ~ μg/ dscm Elements g/hr ~ μg/ dscm Runs 1-6 Runs 7-12 As 0.11 17 15 15 Ba 2,400 360,000 1000 1000 Cd 0.26 39 35 35 Cr 0.04 6.5 5.5 5.5 Hg 14 2,100 100 300 Ni 930 139,500 200 500 Pb 4.3 645 

### NS NS Sb 14 2,100 200 500 Zn NR NR 200 500

1 The concentration in μg/dscm assumes a stack flow rate of about 6700 dscm/hr NR: Not regulated NS: Not SpikedERDC/CERL TR-05-9 87



### CHPPM will conduct the chemical analysis of recovered sample fractions from the M29 trains. Sample handling, analysis, and all associated QA/QC activities will conform to the requirements of M29. Accuracy data for metals analysis willbe confirmed with two field spikes of the nine measured metals into blank sampling trains. Media blanks of the M29 solutions and filter will also be analyzed.Sample integrity will be maintained by use of a chain-of-custody and a designated sample custodian. Unique sample identification numbers will be implemented so that final data used for veri fication can be traced back through the analytical process to the original sample.

4.2 Test Schedule

Set-up for the verification testing is sc heduled for May 10. XCEM verification testing is tentatively scheduled for May 11, 12, 14, and 15. Three M29 test runs are planned for each day with each run last ing 2 hours. All nine metals of interest will be tested during each run; howe ver, lower concentrations of Ni, Sb, Hg, and Zn are scheduled for the first six runs as shown in Table 4-2.

4.3 Test Procedures

In all cases when reference method data is being taken, the introduction of the indicated metals will be held constant throughout the entire sampling period. The intent of this approach is to allo w comparisons of XCEM data to reference method data under constant conditions.

4.3.1 Spiking approach



### Spiking will be conducted by MSE-TA of Butte, MT. Three atomizers are used to quantitatively inject nitric acid solutions containing the metals of interest. The solution will be injected either directly into the stack or into a drying chamber, which opens to the stack. The spiked so lution will enter the stack through a portlocated at the base of the stack. This port was successfully used in earlier multimetal CEM tests at Tooele and is directly downstream of a draft fan allowing for good mixing.

Manufacturer specifications for the atom izers determine droplet size distributions based on pressure and air flow rate. For these tests, pressure and flow rate will be maintained to keep droplet sizes less than 28 microns in diameter. When dried, the majority of the mass is expected to be in the one to four micron range.88 ERDC/CERL TR-05-9



### Each atomizer has been gravimetrically calibrated by MSE-TA to determine mass emission rates over the range of pr essure and air flow rates expected for the verification test.

4.3.2 Reference method sampling



### CHPPM’s Air Quality Surveillance Progra m will conduct reference method sampling. Dual sample trains will be used to collect metals data employing standard operating procedures from M29. Full sa mple custody procedures will be employed during the test using sample custody sheets and sample custody seals. Samples will be under either direct custod y or lock and key at all times. Per M29 protocol, media blanks from the same lot as used during testing will be taken and treated in the same manner as the test run samples.

Dry gas meters are calibrated both pre- an d post-tests with a wet test meter. Pitot tubes undergo a geometric calibra tion, and thermocouples are calibrated using standard two point calibration methods.

As a performance audit, two blank trains will be quantitatively spiked with allnine of the metals of interest. These spikes will be conducted on sampling media, including the filter and impinger solutions, from the same lots used during testing. A spike recovery target of 80 to 120 percent of injected solution has been
set.

4.3.3 Reference method analysis



### Reference method analyses will be conduc ted by CHPPM’s Directorate of Laboratory Services (DLS). Analysis will fo llow standard M29 protocol with the following exception: the front half analysis will include separate reported values for both the front half rinse and the filter. Blank values will be determined using M29 section 9.1 protocols and a standard blank subtraction will be made if significant metals are found in the blank.

CHPPM uses ICP-MS for its metals anal ysis. The ICP-MS is calibrated using solution standards as discussed in section 10.2 of M29.

4.4 Data Comparisons

This section describes how the referenc e and CEM data will be used and compared to quantify the performance of the XCEM. Table 4-5 summarizes the data that will be used for the verification comparisons.ERDC/CERL TR-05-9 89



### Relative accuracy and correlation will be determined by comparing the CEM results against the M29 results, for each metal. M29 results for the probe, front half, and back half will be reported sepa rately to evaluate potential particle loss in the XCEM tubing. However, the total train results will be combined for the relative accuracy and correlation calculations.

Precision will be determined by analysis of XCEM concentrations when the spike injection rate and stack conditions are held constant. It is recognized that the reported precision will include variabilit y in stack conditions as well as XCEM variability.

Table 4-5. Summary of data to be obtained during XCEM verification test.

Performance

Parameter Objective Comparison Based On No. of Data Points
Accuracy Determine degree of quantitative agreement with reference method. Reference Method Results 12

Correlation Determine degree of correlation with reference method. Reference Method Results 12

Precision Determine degree of consistency in XCEM measured concentrations under constant operating conditions. XCEM reported concentrations under constant operating conditions. 6/run

Instrument Drift Determine XCEM ability to measure consistently over the course of the test. Determine variation in palladium concentrations determined with each XCEM measurement 3/hr

Span and Zero Determine XCEM response under maximum and minimum conditions XCEM automated daily QA routine 4

Response Time Determine XCEM response time as a batch CEM. Continuous monitoring of metal concentrations 3/hr

Bias Determine if bias exists between M29 and the XCEM. Reference Method Results 12

Low Level Metal Response Determine XCEM performance when low metal concentrations are present in the stack. Arsenic and chromium ref. Method results 2490 ERDC/CERL TR-05-9



### Instrument drift will be determined by evaluation of XCEM reported palladium concentrations. As part of the XCEM quality assurance program, a palladium rod has been permanently fixed above the x-ray beam and below the filter tape. The palladium rod is measured with each sample, and a running record of the reported concentrations is maintained. The percent relative standard deviation for palladium concentrations will also serve as a determination of XCEM instrument drift during testing.

XCEM response time will be determined as the time between the start of one sampling period and the beginning of a second sampling period. The XCEM samples for 10 to 20 minutes, depending upon the desired detection limits.Within a few seconds of sampling, the exposed tape is moved into the XRF analysis region. Analysis requires the same amount of time as sampling. Following analysis, concentrations are determined an d recorded in a fraction of a second. For these tests, the response time will be 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 is equivalent to the analysis time.

Bias between the dual M29 sampling trains for each run will be determined by a comparison of the dual M29 sample runs using an EPA Method 301 approach for paired sampling trains. For valid test r uns, M29 concentrations will be averaged and compared to reported XCEM data.

The XCEM’s ability to measure low-level concentrations of metals will be challenged by Cr, As, and Cd, which are to be present at approximately 5, 15, and 35 μg/dscm respectively.

M29 results identified as outliers will be reported, but will not be used for verification. The intent of this approach is to provide a valid set of reference data forverification purposes, while also illustrating the degree of variability of the reference method. Identification of outliers will be based upon analysis of percent differences in M29 concentrations between sampling trains and trends in data throughout the test day. In any case, wh ere rejection of a reference result is suggested, effort will be made to find an assignable cause for the divergent result.

According to PS-10, the XCEM acts as a batch CEM. Batch CEMs continuouslysample and concentrate the pollutant on a capture medium. Analysis is performed after sufficient time has elapsed to concentrate the pollutant to levels that are detectable by the analyzer. PS- 10 requires that batch CEMS meet three response time criteria: 1. The sampling time shall be no longer than one-third of the averaging period for the applicable standard.ERDC/CERL TR-05-9 91



### 2. The delay between the end of the sampling period and reporting of the analysis period shall be no greater than 1 hour. 3. Sampling shall be continuous except in that the pause in sampling when the sample collection media is changed should be no greater than 5 percent of the averaging period or 5 minutes, whichever is less.

TEAD incinerator emissions are regulated by two standards: Resource Conservation and Recovery Act (RCRA) limits in grams per hour and the maximum achievable control technology (MACT) rule, which regulates using a 12-hour rolling average. Since the RCRA limits are more stringent, the response time shall be limited to 20 minutes for the TEAD te sts with sampling occurring at least 57 minutes per hour.

Span and zero determinations will be conducted daily by the XCEM. The automated XCEM span routine extends a plunger containing metals of interest into the analysis area. The plunger is then analyzed by the XCEM and the data compared with the known metal concentrations on the plunger. Zero readings are determined by analysis of blank filter tape.

The XCEM filter analysis is nondestructive and the exposed tape remains available for subsequent analysis. In cases where unexplained discrepancies exist between XCEM and M29 data, a post-test filter tape analysis will be considered.

Setup and maintenance needs will be docu mented qualitatively by Battelle, both through observation and through communi cation with the vendors during the test. Factors to be noted include the fr equency of scheduled maintenance activities, the downtime of the CEM, and the number of staff operating or maintaining it during the verification test.



### 5.0 STATISTICAL CALCULATIONS

Statistical calculations will be used to verify the performance of the XCEM as described below. In all cases, measur ement results from both the reference method and the XCEM are reported in units of μg/m 3 

### on a dry basis at 20 °C, 1 atmosphere pressure, and the actual flue gas O 2 

### content.

5.1 XCEM Concentrations During a Reference Method Run

Average XCEM concentrations for a give n reference method run will be calculated as follows:92 ERDC/CERL TR-05-9



# ∑ ∑

= 

### = j n

j j ij

i 

### t t C C 1 

### [Eq 5.1]

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 measurements during test run
t j 

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

5.2 Relative Accuracy

The relative accuracy (RA) of the XCEM with respect to the reference method (M29) will be assessed by:



### % 100 1


### x x n S t d RA d

n α

− 

### +

= [Eq 5.2]

Where d refers to the difference between M29 and the XCEM results, and x corresponds to the M29 result. S d 

### denotes the sample standard deviation of the differences, while t α n-1 

### is the t value for the 100(1- α ) th 

### percentile of the distribution with n -1 

### degrees of freedom. The RA will be determined for an α value of 0.025 (i.e., 97.5 percent confidence level, one-taile d). The RA calculated in this way can be interpreted as an upper confidence bound for the relative bias of the analyzer,

i.e., 

### x d , where the superscript bar indicates the average absolute value of the

differences of the reference values. If12 reference method test runs are completed, the RA procedure stat ed in PS-10 will be followed (i.e., up to three results may be omitted from the RA calculation). The impact of the number of data points (n) on the RA value will be noted in the verification report. The RA will be calculated separately for each metal measured by the XCEM.

5.3 Correlation with Reference Method

The degree of correlation of the XCEM wi th the reference method results will be assessed in terms of the correlation coefficient (r 2 

### ) for metals spiked at more than one concentration (i.e., Hg, Ni, Zn, and Sb).ERDC/CERL TR-05-9 93



### A second series of intra-method correlati ons will be determined by comparing the relative ratios of metals measured by the XCEM for each of the measurement periods. This correlation assumes that no fractionation of the injected species occurred during transport.

5.4 Precision

Precision will be calculated in terms of the percent relative standard deviation (RSD) of a series of XCEM measurements made during stable operation of the TEAD, with metals injected at a constant level. This precision will reflect the variability in the stack conditions, spik ing rate, and XCEM measurements and will be identified as a maximum XCEM prec ision with a note in the verification report that the calculated precision is subject to the variability of the test, not only the XCEM variability. During each M29 sampling run, all readings fromthe XCEM will be recorded and the mean and standard deviation of those recordings will be calculated. Percent pr ecision (P) will then be determined as:



### 100 x X SD P = [Eq 5.3]

where SD is the standard deviation of the XCEM readings and 

### X is the mean of the readings. The same calculation will be performed for each metal measured by the XCEM.

5.5 Span, Zero, and Instrument Drift

The XCEM has automated daily span and zero checks and reports a palladium concentration with each sample to check for instrument drift. Span, zero, and instrument drift will be reported in te rms of the mean, RSD, and range (maximum and minimum) of the readings obtained from the XCEM. The percent RSD will be calculated as:



### 100 x X SD RSD 

### = [Eq 5.4]

where 

### X is the mean, and SD is the standard deviation of the daily readings of the standard. This calculation, along with the range of data, will indicate the day-to-day variation in zero and standard readings.94 ERDC/CERL TR-05-9



### 5.6 Method 29 and XCEM Bias

Bias between the two M29 sampling trains and the M29/XCEM data will be determined using an EPA Method 301 approach . The results are tested for statistically significant bias by calculating the t-statistic and determining if the mean of the differences between the two sampling tr ains is significant at the 80-percent confidence level. The t-statistic is calcul ated by finding the SD of the differences between the two sampling trains. 

# ( ) ( ) 1 2



### − −

= 

# ∑

n d d SD m i d 

### [Eq 5.5]

Where:

d i 

### = the difference between the two sample train values d

m 

### = mean of the d i 

### values n = number of paired samples

Using the SD determined in equation 5.5, the t-statistic is then calculated as follows:



### ⎟ ⎟ ⎠ ⎞ ⎜ ⎜ ⎝ ⎛ =

n SD d t

d m 

### [Eq 5.6]

The critical value of the t-statistic is 0.8755 for 12 runs. If the calculated t-valueis greater than the critical value, the bias as defined by M301 is statistically significant. A statistically significant bias in the reference method will be noted in the validation report.

Method 29 data pairs that are determined to be unbiased relative to each other will be averaged and used for comparis on to the XCEM. Bias between the XCEM and average M29 data will be determined using equations 5.5 and 5.6 with d i 

### being the difference between the average M29 and XCEM data.ERDC/CERL TR-05-9 95



### 6.0 MATERIALS AND EQUIPMENT

6.1 Gases and Chemicals

6.1.1 Compressed gas



### The XCEM requires about 10 scfm of dry compressed gas to provide a vacuum in the extraction system. A small amount of purified compressed gas is also used to drive the XCEM pneumatics. The atomiz ers used for spiking will require about 10 scfm of dry air.

6.1.2 Spike injection solutions



### The spike injection solutions include Ba(NO 3 

### )2, Cd(NO 3 

### )2, Cr(NO 3 

### )3, As 2 

### O 3 

### , Hg(NO 3 

### )2, Ni(NO 3 

### )2, Zn(NO 3 

### )2, and SbCl 2 

### . Solutions will be prepared on-site to allow for flexibility in responding to bac kground metal concentrations found in the TEAD incinerator.

6.2 Reference Method

6.2.1 Sampling trains



### CHPPM will supply the glassware, filters, and associated equipment for M29 sampling. Multiple trains will be supplie d so that six trains (i.e., three sampling runs with two trains each) may be sampled in a single day; in addition, at leasttwo M29 field spikes and a media blank will be analyzed. Preparation, sampling, sample recovery, and cleaning of used trains will be the responsibility of CHPPM during this verification test.

6.2.2 Analysis equipment



### CHPPM will provide laboratory equipment for sample recovery and analysis. This will include all chemicals and solutions for rinsing train components and recovering impinger samples.

6.3 TEAD Monitoring Equipment

The verification will make use of monito ring equipment already integrated intothe TEAD facility. This equipment includes monitors for major flue gas constituents (O 2 

### , CO 2 

### ), as well as sensors for temperature and pressure. These devices are considered part of the TEAD facility fo r purposes of this test, and will be operated during this verification ac cording to normal TEAD procedures.96 ERDC/CERL TR-05-9



### 7.0 QUALITY ASSURANCE/QUALITY CONTROL

7.1 Assessments and Audits

7.1.1 Technical systems audits



### Battelle’s Quality Manager, will perform a technical systems audit (TSA) once during the performance of this verification test. The purpose of the TSA is to ensure that the verification test is being performed in accordance with this test/QA plan, and that all QA/QC procedures are being implemented. In this audit, the reference sampling and analysis methods used may be reviewed; the actual test procedures compared to those specified in this plan; and data acquisition and handling procedures reviewed. The Qu ality Manager will also prepare a TSA report, the findings of which must be a ddressed either by modifications of test procedures or by documentation in the test records and report.

At EPA’s discretion, EPA QA staff may also conduct an independent on-site TSA during the verification test. The TSA findings will be comm unicated to testing staff at the time of the audit, and documented in a TSA report.

7.1.2 Data quality audit



### Battelle’s Quality Manager will audit at le ast 10 percent of the verification data acquired in the verification test. The Quality Manager will trace the data from initial acquisition, through reduction and statistical comparisons, and to final reporting. All calculations performed on the data undergoing audit will be checked.

7.1.3 Assessment reports



### Each assessment and audit will be documented in accordance with section 2.9.7 of the QMP for the AMS pilot. Assessment reports will include the following:

• Identification of any adverse findings or potential problems

• Space for response to adverse findings or potential problems

• Possible recommendations for resolving problems

• Citation of any noteworthy practices that may be of use to others

• Confirmation that solutions have been implemented and are effective.

7.1.4 Corrective Action



### The Battelle Quality Manager, during the course of any assessment or audit, will notify the technical staff performing ex perimental activities of any immediateERDC/CERL TR-05-9 97



### corrective action that should be taken. Once the assessment report has been prepared, the Verification Testing Leader will ensure that a response is provided for each adverse finding or potential pr oblem, and will implement any necessary follow-up corrective action. The Quality Manager will ensure that follow-up corrective action has been taken.



### 8.0 DATA ANALYSIS AND REPORTING

8.1 Data Acquisition

Data acquisition in this verification test includes recording of the response data from the XCEM, documentation of samplin g conditions and analytical results from the reference method, and recording of operational data such as combustion source conditions, test temperatures, the times of test activities, etc.

Cooper Environmental Services will perform data acquisition for the XCEM during the test. For all tests, CES will be responsible for reporting the response of the XCEM to the sample provided. The XCEM data must include the results of all tests conducted each test day and are to be provided to the test manager at the end of each day. The XCEM data must include all individual readings of the XCEM (i.e., temperature, pressure, metal concentrations, QA data, etc.) listed bytime of day. Averaged results over the period of an M29 sampling run will be determined following the test and provided to the test manager prior to release of M29 data.

Other data will be recorded in laborato ry record books maintained by TEAD, CHPPM, Battelle, MSE-TA, and CES staff involved in the testing. These records will be reviewed to identify and resolve any inconsistencies. All written records must be in ink. Any corrections to noteb ook entries, or changes in recorded data, must be made with a single line through the original entry. The correction is then to be entered, initialed, and date d by the person making the correction.

In all cases, strict confidentiality of data from the XCEM will be maintained.

Table 8-1 summarizes the types of data to be recorded; how, how often, and by whom the recording is made; and the disposition or subsequent processing of the data. The general approach is to record all test information immediately and in a consistent format throughout all tests. Data recorded by CES is to be turned over to the CERL designated test manage r immediately upon completion of each test day.98 ERDC/CERL TR-05-9



### Table 8-1. Summary of data recordin g process for the verification test.

Data To Be Recorded Responsible Party Where Recorded How Often Recorded Disposition of Data

Dates, times of test events CERL Laboratory record books Start/end of test, and at each change of a test parameter. Used to organize/check test results; manually incorporated indata spreadsheets as necessary. Test parameters(temperature, analyte identities and concentrations, flows, etc.) TEAD, CERL, CHPPM Laboratory record books When set or changed, or asneeded to document stability. Used to organize/check testresults; incorporated in data spreadsheets as
necessary.

XCEM readings including digital displays, printouts, and electronic output. CES Laboratory record books, data sheets, ordata acquisition system, as appropriate. XCEM data willbe recorded continuously throughout test. Data sheets will be completed as required for each test. Electronically transferred to spreadsheets.

Reference method sampling data. CHPPM Laboratory record books At least at start/end of ref. test, and at change of a test parameter. Used to organize/check testresults; incorporated in data spreadsheets as
necessary.

Reference method sample analysis, chain of custody, and results. CHPPM Laboratory record books, data sheets, ordata acquisition system, as appropriate. Throughout sample handling and analysis period. Transferred to spreadsheets.



### 8.2 Data Review

Records generated in the verification te st will receive a one-over-one review within 2 weeks after generation. These reviews are to be performed within the organization generating the data. These records will then be used to calculate, evaluate, and report verification results. These records may include laboratory record books; operating data from the combustion source; XCEM data; or reference method analytical results. The review will be documented by the person performing the review by adding his/her in itials and date to a hard copy of the record being reviewed. This hard copy will then be returned to the staff whoERDC/CERL TR-05-9 99



### generated or who will be storing the reco rd. Battelle will receive a copy of all written and recorded data in the projec t record books and a copy of the XCEM data.

8.3 Reporting

Cooper Environmental Services will pr epare a summary test report for CERL documenting the testing results. The su mmary report will include a discussionof the XCEM performance, testing processes, and a comparison with M29 results. CES will provide Battelle with this summary test report and copies of all original raw field and laboratory data.

Battelle will prepare an ETV verification report and statement for the testing that includes the test data and a statistical evaluation of the data as described in sections 4 and 5. The verification repo rt will briefly describe the ETV programand the AMS Center, and will describe the procedures used in verification testing. The results of the verification test will be stated quantitatively, without comment on the acceptability of the XCEM ’s performance. The summary test report prepared by CES will serve as the basis for the draft ETV verification report. The ETV verification report and statement will undergo a technical peer review. Final approval and distribution of the ETV verification report and statement will be conducted as stated in the Generic Verification Protocol for the Advanced Monitoring Systems Pilot.



### 9.0 HEALTH AND SAFETY

The verification test described in this test/QA plan will be performed at the TEAD facility in Tooele, Utah. All partic ipants in this verification test will adhere to the health and safety requirements of the facility. Vendor staff will beoperating their equipment only during the verification test. They are not responsible for, nor permitted to, operate the combustion source or perform any other verification activities identified in this test/QA plan. Operation of the XCEM does not pose any known chemical, fire, mechanical, electrical, noise, or other potential hazard.

All visiting staff at the TEAD will be give n a site-specific safety briefing prior tothe installation and operation of the XCEM. This briefing will include a description of emergency operating procedures (i.e ., in case of fire, tornado, laboratory accident) and identification and location and operation of safety equipment (e.g. fire alarms, fire extinguishers, eye washes , exits. Test participants are required100 ERDC/CERL TR-05-9



### to wear hearing protection. Steel-toed safety shoes and work gloves are recommended. Eye wear is not required.



### 10.0 REFERENCES

Battelle. (1998). Generic Verification Prot ocol for the Advanced Monitoring Systems Pilot, Battelle, Columbus, Ohio, November 1998.

Bryson, S., C. Whitworth, and S. Kujawa. (2000). Final Report – Test and Evaluation of an X-Ray Fluorescence Based Multi-Element Metals Continuous Emission Monitor. Prepared for U.S. Army Corp of Engineers by MSE-TA, Butte, MT.

Environmental Protection Agency (E PA). (2000). Quality Management Plan(QMP) for the ETV Advanced Monitoring Systems Pilot, U.S. EPA Environmental Technology Verification Program, prepared by Battelle, Columbus, Ohio.

EPA. (1998). EPA Environmental Technology Verification Program Quality andManagement Plan for the Pilot Period (1995-2000), EPA-600/R-98/064, U.S. Environmental Protection Agency, Cincinnati, OH, May 1998.

EPA. (1996). Proposed Performance Specif ication 10 for Multi-Metal Continuous Emission Monitors, U.S. Environmental Protection Agency, Washington, DC.

EPA. (1991). U.S. EPA Method 301 Field Va lidation of Emission Concentrations from Stationary Sources. Federal Regi ster Vol. 56, No. 114. June 13, 1991.

EPA. (1990). U.S. EPA Method 29 Determination of Metal Emissions from Stationary Sources. From EPA’s techno logy transfer website www.epa.gov/ttn.ERDC/CERL TR-05-9 101



# Appendix B: Determination of XCEM Reported Concentrations 2001

XCEM Metal Concentration Determination

To measure metal concentrations in stack gas, the XCEM uses an Aalborg massflow controller to obtain flow rates and a QuanX energy dispersive x-ray fluorescence (XRF) analyzer to determine mass concentrations. The QuanX reported mass concentrations are then divided by the total dry flow to obtain concentrations in micrograms per dry standard cubi c meter . The entire process is automated by a custom WonderWare ® 

### software interface. The original concentrations reported during the 2001 test are shown in Table B1.

Test data were modified according to a final post-test calibration and evaluation of dryer capabilities resulting in an 8 pe rcent increase in reported metal concentrations. All calibration adjustments we re completed prior to receiving M29 results. The final reported concentrations with the 8 percent correction are shown in XCEM Reported Concentrations (page 15).



### Global Corrections to Reported Concentrations

Flow Corrections

For the TEAD validation testing, the ma ss flow meter was cross-checked with a Sierra mass flow meter and was determined to be in good agreement. For this reason, no changes were made to flow me asurements applied to reported concentrations.

Mass Corrections

Due to the rapid turn-around time requir ed for this project (6 weeks between contract award date and delivery date), a final XRF calibration was not conducted until after the tests. The XCEM is calibrated with thin-film standards produced by the National Institute of Standards and Testing (NIST) and Micro-102 ERDC/CERL TR-05-9



### Matter Inc. (Deer Harbor, WA). These standards, which are 47-mm in diameter, are larger than the x-ray beam intensity area. In contrast, the exposed spot on the XCEM filter is about 7 mm in diameter and is smaller than the x-ray beam intensity area. A global conversion factor is required to convert intensities from thin film to spot size. During the final calibration it was determined that a global increase of 4.4 percent was required to better account for the thin-film to spot conversion factor.

Dryer Inefficiency Corrections

The XCEM uses a gas dryer built by Universal Analyzer of Reno, NV. The dryer cools gas to a predefined temperature, which condenses the water in the gas stream. Water is then removed from th e dryer using a pneumatic pump. Following the test, it was determined that ma nufacturer specificatio ns were not properly defined for the partial vacuum in the XCEM. CES conducted extensive testing on the gas dryer (Table B2) and determined that, under a partial vacuum, the XCEM had 3.5 percent water content. For this reason, the XCEM concentrations were increased uniformly by 3.5 percent.ERDC/CERL TR-05-9 103

Table B1. Original XCEM reported concentrations ( μ g/dscm) uncorrected for calibration and dryer changes.

Date Start Stop XC No. RM No. XC Time (min) As Ba Cd Cr Hg Ni Pb Sb Zn
5/14/01 10:45 11:05 650 Run 1 19:48.0 74.2 153 25.7 2.8 55 318 1,020 314 275 5/14/01 11:05 11:26 651 Run 1 21:12.0 78.6 158 24.0 2.3 101 403 1,043 345 293 5/14/01 11:26 11:48 652 Run 1 21:32.0 76.8 178 24.5 1.7 145 432 1,064 334 296 5/14/01 11:48 12:09 653 Run 1 21:42.0 78.8 153 20.2 2.0 192 415 1,107 327 292 5/14/01 12:10 12:31 654 Run 1 21:41.0 89.1 174 26.1 2.4 224 435 1,221 349 317 5/14/01 12:31 12:53 655 Run 1 21:51.0 99.9 202 29.5 2.0 238 477 1,487 369 344 5/14/01 12:53 13:15 656 Run 1 22:07.0 57.4 187 25.2 2.2 262 428 656 358 322 Average 21:24.7 79.2 172 25.0 2.2 174 416 1,086 342 306 SD 13.1 18 2.8 0.4 76 49 249 19 23 RSD 17 11 11 16 44 12 23 5 8

5/14/01 13:58 14:23 659 Run 2 25:09.0 177.3 213 24.8 2.2 172 347 3,168 333 277 5/14/01 14:23 14:46 660 Run 2 22:56.0 165.0 207 27.3 1.9 217 395 3,007 351 320 5/14/01 14:46 15:09 661 Run 2 22:56.0 162.3 230 24.1 1.1 226 395 2,793 368 325 5/14/01 15:09 15:32 662 Run 2 22:54.0 155.7 231 20.7 1.9 204 375 2,484 342 307 5/14/01 15:32 15:55 663 Run 2 22:36.0 146.1 180 27.0 1.1 221 384 2,173 351 321 5/14/01 15:55 16:17 664 Run 2 22:34.0 25.5 159 25.1 2.4 238 363 168 322 295 Average 23:10.8 138.6 203 24.8 1.8 213 377 2,299 345 307 SD 56.4 29 2.4 0.5 23 19 1,104 16 19 RSD 41 14 10 30 11 5 48 5 6

5/14/01 17:00 17:23 667 Run 3 22:45.0 20.0 117 23.5 3.1 240 366 110 309 297 5/14/01 17:23 17:44 668 Run 3 21:00.0 16.6 130 19.7 2.0 244 359 84 310 295 5/14/01 17:44 18:05 669 Run 3 20:52.0 15.0 146 25.0 2.4 246 386 55 329 315 5/14/01 18:05 18:26 670 Run 3 20:58.0 14.9 162 26.8 2.6 248 379 51 336 314 5/14/01 18:26 18:47 671 Run 3 20:53.0 16.2 155 19.8 2.3 236 383 56 326 308 5/14/01 18:47 19:07 672 Run 3 20:54.0 13.6 136 22.2 2.2 230 383 60 333 321 Average 21:13.7 16.0 141 22.8 2.4 241 376 69 324 308 SD 2.2 17 2.8 0.4 7 11 23 12 11 RSD 14 12 12 16 3 3 33 4 3

5/15/01 8:59 9:18 684 Run 4 19:43.0 15.6 134 19.9 4.1 31 273 63 251 218 5/15/01 9:18 9:39 685 Run 4 20:34.0 17.3 161 26.4 5.8 50 371 64 308 295 5/15/01 9:39 10:00 686 Run 4 20:55.0 17.7 124 30.7 5.0 64 400 61 335 323 5/15/01 10:00 10:21 687 Run 4 21:00.0 18.2 142 28.3 4.9 74 400 60 343 322 5/15/01 10:21 10:42 688 Run 4 20:58.0 18.5 176 29.7 4.7 78 401 59 350 319 5/15/01 10:42 11:03 689 Run 4 20:57.0 16.8 134 24.7 4.8 79 387 51 334 314 5/15/01 11:03 11:24 690 Run 4 20:51.0 18.3 170 26.4 5.1 90 412 41 351 339 Average 20:42.6 17.5 149 26.6 4.9 67 378 57 325 304 SD 1.0 20 3.6 0.5 20 48 8 36 40 RSD 6 14 14 10 30 13 14 11 13

5/15/01 12:06 12:27 693 Run 5 20:55.0 19.1 164 29.0 5.1 86 408 46 354 328 5/15/01 12:27 12:48 694 Run 5 20:52.0 17.7 159 31.2 5.1 90 398 50 343 322 5/15/01 12:48 13:09 695 Run 5 20:51.0 17.4 141 31.8 5.6 94 386 48 335 314 5/15/01 13:09 13:30 696 Run 5 20:48.0 18.4 168 31.0 4.9 106 416 43 357 333 5/15/01 13:30 13:51 697 Run 5 20:57.0 15.4 171 33.2 5.3 113 416 42 364 338 5/15/01 13:51 14:12 698 Run 5 20:59.0 17.6 168 29.8 5.0 120 411 35 361 331 Average 20:53.7 17.6 162 31.0 5.2 101 406 44 352 328 SD 1.2 11 1.5 0.3 13 12 5 11 8 RSD 7 7 5 5 13 3 12 3 3

5/15/01 14:54 15:15 701 Run 6 20:57.0 18.4 153 29.1 5.0 127 422 36 363 348 5/15/01 15:15 15:36 702 Run 6 20:59.0 16.3 140 29.5 5.0 135 431 36 358 350 5/15/01 15:36 15:57 703 Run 6 20:58.0 13.9 155 29.1 5.0 132 410 45 358 335 5/15/01 15:57 16:18 704 Run 6 20:56.0 14.3 153 29.0 5.5 130 398 44 344 324 5/15/01 16:18 16:39 705 Run 6 20:54.0 14.8 173 31.6 4.9 155 395 34 352 326 5/15/01 16:39 17:00 706 Run 6 20:55.0 15.9 171 30.4 5.1 152 409 33 360 336 5/15/01 17:00 17:21 707 Run 6 20:58.0 15.0 152 34.0 5.7 154 428 42 359 342 Average 20:56.7 15.5 157 30.4 5.2 141 413 38 356 337 SD 1.5 12 1.9 0.3 13 14 5 6 10 RSD 10 7 6 6 9 3 13 2 3104 ERDC/CERL TR-05-9

Table B1 (Cont’d). Original XCEM reported concentrations ( μ g/dscm) uncorrected for calibration and dryer changes.

5/15/01 18:03 18:24 710 Run 7 20:55.0 17.9 169 33.0 5.4 143 442 42 367 357 5/15/01 18:24 18:45 711 Run 7 20:58.0 19.3 154 31.9 5.9 124 443 41 374 366 5/15/01 18:45 19:06 712 Run 7 20:58.0 17.5 177 26.7 5.6 111 455 42 349 349 5/15/01 19:06 19:27 713 Run 7 20:59.0 16.9 155 28.6 5.2 112 425 37 347 332 5/15/01 19:27 19:48 714 Run 7 20:50.0 16.6 162 28.4 5.3 122 388 31 340 312 5/15/01 19:48 20:09 715 Run 7 20:41.0 15.5 148 30.8 5.1 127 404 28 351 325 Average 20:53.5 17.3 161 29.9 5.4 123 426 37 355 340 SD 1.3 11 2.4 0.3 12 26 6 13 21 RSD 7 7 8 6 10 6 16 4 6

5/16/01 8:58 9:18 725 Run 8 20:24.0 30.7 103 30.1 4.8 15 178 268 130 124 5/16/01 9:18 9:39 726 Run 8 20:33.0 30.8 128 29.5 5.5 19 204 224 124 139 5/16/01 9:39 10:00 727 Run 8 20:33.0 26.8 134 29.9 5.0 20 205 214 116 140 5/16/01 10:00 10:20 728 Run 8 20:33.0 26.6 145 27.2 4.9 26 183 184 126 137 5/16/01 10:20 10:41 729 Run 8 20:26.0 21.7 163 33.6 4.7 31 189 187 125 130 5/16/01 10:41 11:01 730 Run 8 20:24.0 28.6 141 30.2 5.3 33 200 209 124 139 5/16/01 11:01 11:22 731 Run 8 20:30.0 26.5 150 30.0 5.3 40 209 199 130 139 Average 20:29.0 27.4 138 30.1 5.1 26 195 212 125 135 SD 3.1 19 1.9 0.3 9 12 29 5 6 RSD 11 14 6 6 34 6 14 4 4

5/16/01 11:42 12:03 733 Run 9 20:28.0 29.0 169 30.6 4.1 45 195 176 126 136 5/16/01 12:03 12:23 734 Run 9 20:26.0 22.2 157 30.3 5.2 46 186 158 129 131 5/16/01 12:23 12:44 735 Run 9 20:21.0 25.5 142 28.5 4.9 45 189 150 132 136 5/16/01 12:44 13:04 736 Run 9 20:18.0 24.9 191 32.8 6.0 52 206 177 143 141 5/16/01 13:04 13:25 737 Run 9 20:24.0 23.2 132 28.8 4.8 50 199 140 134 134 5/16/01 13:25 13:45 738 Run 9 20:19.0 24.8 127 26.6 4.8 54 185 141 134 133 5/16/01 13:45 14:05 739 Run 9 20:23.0 22.5 139 27.0 4.8 56 211 144 137 132 Average 20:22.7 24.6 151 29.2 5.0 50 196 155 133 135 SD 2.3 23 2.2 0.5 4 10 16 6 3 RSD 9 15 7 11 9 5 10 4 2

5/16/01 14:46 15:07 742 Run 10 20:24.0 25.0 144 32.1 5.5 85 194 135 137 135 5/16/01 15:07 15:27 743 Run 10 20:21.0 33.7 174 34.2 5.0 83 200 242 142 139 5/16/01 15:27 15:48 744 Run 10 20:23.0 21.4 130 30.0 5.0 76 178 106 124 123 5/16/01 15:48 16:08 745 Run 10 20:16.0 22.5 178 29.2 5.0 84 193 124 135 138 5/16/01 16:08 16:28 746 Run 10 20:21.0 21.6 149 33.5 5.1 88 192 100 151 135 5/16/01 16:29 16:49 747 Run 10 20:20.0 21.6 154 28.6 5.2 88 188 88 130 127 5/16/01 16:49 17:09 748 Run 10 20:20.0 17.3 129 27.7 5.0 101 173 102 141 127 Average 20:20.7 23.3 151 30.8 5.1 86 188 128 137 132 SD 5.1 19 2.5 0.2 8 10 53 9 6 RSD 22 13 8 4 9 5 41 6 5ERDC/CERL TR-05-9 105

Table B1 (Cont’d). Original XCEM reported concentrations ( μ g/dscm) uncorrected for calibration and dryer changes.

5/16/01 17:32 17:52 750 Run 11 20:21.0 19.9 165 28.9 5.5 94 195 100 139 132 5/16/01 17:52 18:12 751 Run 11 20:18.0 19.7 136 28.0 4.8 89 193 94 136 130 5/16/01 18:12 18:33 752 Run 11 20:20.0 19.5 157 27.2 4.9 88 189 96 130 135 5/16/01 18:33 18:53 753 Run 11 20:18.0 19.7 165 27.9 5.0 88 178 84 136 128 5/16/01 18:53 19:13 754 Run 11 20:12.0 20.4 141 24.4 5.3 89 177 82 136 131 5/16/01 19:13 19:34 755 Run 11 20:12.0 20.3 155 30.3 5.1 86 186 82 132 135 5/16/01 19:34 19:54 756 Run 11 20:17.0 18.7 141 30.7 4.2 78 196 89 136 135 Average 20:16.9 19.7 151 28.2 5.0 87 188 90 135 132 SD 0.6 12 2.1 0.4 5 8 7 3 3 RSD 3 8 8 8 6 4 8 2 2

5/17/01 11:12 11:32 770 Run 12 20:01.0 25.0 161 24.6 3.8 22 208 157 127 123 5/17/01 11:32 11:52 771 Run 12 20:08.0 27.4 181 21.5 3.9 33 221 215 147 135 5/17/01 11:52 12:12 772 Run 12 20:14.0 32.6 161 28.2 4.0 51 206 253 153 146 5/17/01 12:12 12:32 773 Run 12 20:16.0 25.6 210 22.6 3.7 68 205 189 146 149 5/17/01 12:32 12:53 774 Run 12 20:12.0 25.1 141 29.3 4.4 73 190 149 146 140 5/17/01 12:53 13:13 775 Run 12 20:12.0 18.2 164 25.9 4.1 77 189 127 144 133 5/17/01 13:13 13:33 776 Run 12 20:07.0 20.0 138 26.1 3.8 80 177 129 144 140 Average 20:10.0 24.9 165 25.4 4.0 58 199 174 144 138 SD 4.7 24 2.8 0.2 23 15 47 8 9 RSD 19 15 11 6 40 7 27 6 6

5/17/01 14:14 14:34 779 Run 13 20:15.0 23.6 150 33.3 4.7 74 186 110 158 136 5/17/01 14:34 14:54 780 Run 13 20:10.0 24.5 194 31.3 4.9 74 197 113 157 135 5/17/01 14:54 15:14 781 Run 13 20:09.0 21.9 147 33.4 5.6 76 217 109 155 138 5/17/01 15:14 15:34 782 Run 13 20:10.0 24.3 129 31.3 5.4 77 197 103 157 138 5/17/01 15:35 15:55 783 Run 13 20:12.0 26.2 182 37.6 5.4 77 160 119 157 109 5/17/01 15:55 16:15 784 Run 13 20:02.0 23.8 153 36.2 5.6 69 157 112 154 76 5/17/01 16:15 16:35 785 Run 13 19:57.0 12.0 87 17.3 3.7 42 65 79 71 20 Average 20:07.9 22.3 149 31.5 5.0 70 168 107 144 107 SD 4.7 35 6.7 0.7 12 50 13 32 45 RSD 21 24 21 14 18 30 12 22 42

Table B2. Results of dryer tests.

Day Time (min) Flow actual (sLpm) Pressure in line (psia) Web Bulb Temp

(°F) Vol of air/water (L) Mass of Water Collected (g) Vol of Water

(L) Impinger % water

by vol

1 270 0.82 7.3 150 220. 4 7.9 9.8 4.5
2 200 0.82 7.3 150 163. 3 4.7 5.8 3.6
3 78 0.84 7.3 120 65. 5 1.8 2.2 3.4
4 126 0.83 7.3 168 104. 6 2.8 3.5 3.3106 ERDC/CERL TR-05-9



# Appendix C: Transport and Calibration Evaluations

Quantitative Spike Injection by CES

CES Spiking Test Design

Following calibration, a series of 11 test s were conducted at TEAD to certify the calibration and check the ability of the XCEM to transport particulates from the top of the shed to the filter tape. The te sts included quantitative spiking of various aerosolized metals into the XCEM tr ansport line immediately prior to entering the shed. The metals were then sampled by the XCEM. The rest of thespiked aerosol, about 99 percent of the volume, was sampled by two filters downstream of the stilling chamber as illustrated in Figure C1.

CES used a Quantitative Spike Injection System (QSIS) to conduct the tests. The QSIS includes an atomizer and a dr ying chamber that generate a simulated stack gas containing the metals of interest in ~100 ppm of nitric acid. Two pumps pulled 80-100 sLpm of the simulated stack gas through the atomization system and XCEM stilling chamber. Approximately 1 percent of the simulated stack gas was sampled and analyzed by the XCEM. The remaining gas was transported out of the XCEM stilling chamber into a manifold containing two filter holders. The upstream filter holder contained a 47-mm-diameter membrane filter (MF) while the downstream holder held a 47-mm-diameter quartz fiber filter (QFF). After each test, the metal concentrations on the two filterswere determined using a QuanX XRF, and their total mass, identified as the “Total Capture” concentration, was compared to the theoretical atomization concentration and reported XCEM concentrations.ERDC/CERL TR-05-9 107

Figure C1. Experimental design for atomization tests.

Test design for atomization of Pb and Cr (Tests 1–3)



### Three tests were conducted using a solution of Pb and Cr nitrates in 5 percent nitric acid. The injected solution had a concentration of 25.4 μg/mL of Pb and 25.1 μg/mL of Cr. Atomizer concentrations were determined by weighing the solution before and after testing and multiplying the net atomized mass by the concentration to determine total microgram s of metal emitted during the test. This mass was compared to the total mass on the resin-impregnated and quartz fiber filters (RIF and QFF) located downstream of the XCEM.

During these tests, the XCEM reported values every 20 minutes and completed 30 runs. Atomization chamber and total ca pture filter temperatures were maintained at about 140 °F while the stilling chamber and cassette were maintained at about 225 °F. The mainline flow varied between 88-97 sLpm and the XCEM sampled 0.8 sLpm.

Following the first test, a leak was discover ed in the system, so the first test was disregarded and a third test was conducted. Data from the first test are included in Appendix C, but were not used to evaluate the calibration.

Test design for atomization of As, Cd, Cr, Ba, Hg, Pb, Se, and Ag (Tests 4–7)



### A second series of four tests was conduc ted using a NIST traceable stock solution of As, Cd, Cr, Ba, Hg, Pb, Se, and Ag (VHG Labs, Inc., Manchester, NH). All eight elements were at the same concentration in the stock solution. Two sets of108 ERDC/CERL TR-05-9



### duplicate runs were conducted with no minal concentrations at about 250 μg/m3for tests 4 and 5 and 125 μg/m3 for tests 6 and 7. Atomization and XCEM temperature and flow conditions were the sa me as for the Pb and Cr tests. The XCEM reported values every 20 minutes and completed an additional 30 runs.

Test design for atomization of Cd, Ba, Hg, Ni, Pb, and Zn (Tests 8-11)



### The third series of tests used a NIST traceable VHG stock solution of Cd, Ba, Hg, Ni, Pb, and Zn. Two sets of duplicate r uns were conducted with concentrationsfrom runs 8 and 9 cut in half for runs 10 and 11. Atomization and XCEM temperature and flow conditions were the same as for the Pb and Cr test. The XCEM reported values every 20 minutes and completed an additional 35 runs during these tests.

CES Spiking Test Results

Atomization vs. XCEM



### Before and after atomization, the spike injection solution was weighed to determine net change in mass. This mass was divided by the time and flow to determine atomization rate in micrograms per dry standard cubic meter as shown in equation 6:



### t f d a m m C k f i
k



### ⋅ ⋅ ⋅ −

= ) (

· 10 6 [Eq 6]



### where:

C k 

### = Gas concentration for element “k” during a test

m i 

### = Initial mass of atomized solution (g)

m f 

### = Final mass of atomized solution (g) d = Density of solution (g/mL)

a k



### = Concentration of element “k” in solution (g of element k/mL of solution) t = Time (min) f = Gas flow rate (dscm/min)

Data used to calculate predicted metals concentrations based on atomization rates are shown in Table C1. Atomizatio n rate predictions vs. XCEM measured concentrations are shown in Table C2.ERDC/CERL TR-05-9 109

Table C1. Flow rates and concentrations u sed to calculate atomization concentrations.

Test Atom. vol (ml) As Cd Fe Cr Ba Hg Ni Pb Sb Se Ag Zn Ti ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml μg/ml 1 56.1 25.1 25.4 2 31.9 25.1 25.4 3 41.8 25.1 25.4 4 30.3 50.6 50.6 50.6 50.6 50.6 50.6 50.6 50.6 5 37.8 50.6 50.6 50.6 50.6 50.6 50.6 50.6 50.6 6 35.5 25.1 25.1 25.1 25.1 25.1 25.1 25.1 25.1 7 32.9 25.1 25.1 25.1 25.1 25.1 25.1 25.1 25.1 8 32.1 17.4 497.7 99.6 29.9 99.6 9 31.3 17.4 497.7 99.6 29.9 99.6 10 36.2 8.6 246.9 49.4 14.8 49.4 11 33.2 8.6 246.9 49.4 14.8 49.4

Table C2. Atomization vs. XCEM concentrations.

XC AT XC AT XC AT XC AT XC AT

2 122 106 1.15 3 126 112 1.12 4 245 230 1.07 201 230 0.87 260 230 1.13 247 230 1.07 226 230 0.98 5 230 234 0.98 192 234 0.82 243 234 1.04 247 234 1.06 218 234 0.93 6 126 126 1.00 105 126 0.83 137 126 1.09 158 126 1.26 120 126 0.95 7 123 122 1.00 97 122 0.79 126 122 1.03 153 122 1.25 112 122 0.92 8 63 76 0.82 2384 2183 1.09 50 87 0.57 9 54 66 0.81 2022 1901 1.06 41 76 0.54 10 32 38 0.84 1265 1101 1.15 20 44 0.45 11 33 40 0.82 1214 1152 1.05 28 46 0.61 AVG. 181 178 1.01 97 117 0.83 169 155 1.09 961 881 1.12 102 121 0.75

XC AT XC AT XC AT XC AT XC AT

2 111 107 1.04 3 117 113 1.03 4 266 230 1.16 236 230 1.03 217 230 0.94 5 247 234 1.06 221 234 0.94 204 234 0.87 6 137 126 1.09 122 126 0.97 113 126 0.90 7 121 122 0.99 117 122 0.96 102 122 0.84 8 450 437 1.03 133 131 1.01 463 437 1.06 9 383 380 1.01 114 114 1.00 394 380 1.04 10 243 220 1.10 73 66 1.10 249 220 1.13 11 226 230 0.98 67 69 0.96 233 230 1.01 AVG. 326 317 1.03 138 131 1.04 174 178 0.97 159 178 0.89 335 317 1.06 XC/AT μg/DSCM TEST

TEST XC/AT μg/DSCM XC/AT μg/DSCM μg/DSCM XC/AT XC/AT μg/DSCM

XC/AT μg/DSCM XC/AT μg/DSCM AG ZN XC/AT μg/DSCM XC/AT μg/DSCM XC/AT μg/DSCM HG

NI PB SE AS CD CR BA



### Reported XCEM concentrations matched ex pected atomization values for As (101 percent), Cr (109 percent), Ni (103 percent ), Pb (104 percent), Ba (112 percent), Se (97 percent), and Zn (106 percent). Mercury XCEM concentrations matched atomization rates for runs 4–7 (95 percent ), but were low for runs 8–11 (54 percent). During runs 8–11, the outside air temperature dropped dramatically and110 ERDC/CERL TR-05-9



### snow was on the transport line. For this reason, the Hg numbers for runs 8–11 were considered less reliable.

Both Cd and Ag were low by 10–15 percent relative to the expected concentrations. This difference was either caused by transport inefficiency or calibration error. To determine which source creat ed the discrepancy, a comparison was made of the Cd/Ag concentrations relati ve to other elements captured downstream of the XCEM. The results of these comparisons are discussed in the next section.

Total capture vs. XCEM



### The total flow used for atomization was captured downstream of the XCEM on an MF and QFF. These filters were then analyzed at CES and compared to the atomized concentrations. The total captur e system is downstream of a 90° elbow and is not expected to be quantitative; ho wever, the relative concentrations of the elements should stay constant. Table B3 shows the total micrograms atomized vs. the total captured downstream of th e XCEM. Reported Cr concentrations have not been corrected for filter absorptio n, which can be significant on a QFF.In this table, it can be seen that the transport efficiency to the filters was dependent on the injection solution. For tests 2 and 3, the transport was about 90 percent for Pb. The second solution was us ed for tests 4 through 7, with a resulting transport efficiency of about 85 percent for As, Cd, Ni, Pb, and Se.

Except for Hg, which can form a vapor, the atomization process results in particles that contain metals in proportion to their concentration in the original solution. Because the elements associated with particles should be in proportion to the solution, the results in Table C3 were normalized to Pb to determine relative transport efficiencies. These results are shown in Table C4. Both Cd and Ag in Table C4 show good agreement with Pb, arsenic, and the other elements. Thus, it appears that Cd and Ag were transpor ted with the other elements. From these data, it was concluded that the significant difference between Cd/Ag and the other elements in Table C2 was not due to transport inefficiency but rather the result of calibration error.ERDC/CERL TR-05-9 111

Table C3. Total capture mass (TC) vs. atomization mass (AT).

TC AT TC AT TC AT TC AT TC AT

2 700 821 0.85 3 791 1077 0.73 4 1192 1574 0.76 1192 1574 0.76 917 1574 0.58 1461 1574 0.93 1013 1574 0.64 5 1535 1963 0.78 1530 1963 0.78 1145 1963 0.58 1884 1963 0.96 1402 1963 0.71 6 807 914 0.88 781 914 0.85 662 914 0.72 948 914 1.04 689 914 0.75 7 702 848 0.83 682 848 0.80 571 848 0.67 832 848 0.98 642 848 0.76 8 454 572 0.79 14746 16374 0.90 9 446 559 0.80 14631 15976 0.92 10 286 320 0.89 9142 9158 1.00 11 218 294 0.74 7263 8418 0.86 AVG. 1059 1325 0.81 699 881 0.80 850 1235 0.71 6363 6903 0.95 937 1325 0.72

TC AT TC AT TC AT TC AT TC AT

2 760 831 0.91 3 970 1090 0.89 4 1258 1574 0.80 1196 1574 0.76 1295 1574 0.82 5 1622 1963 0.83 1550 1963 0.79 1667 1963 0.85 6 837 914 0.92 806 914 0.88 847 914 0.93 7 728 848 0.86 702 848 0.83 741 848 0.87 8 1952 3277 0.60 724 984 0.74 1979 3277 0.60 9 1906 3197 0.60 713 960 0.74 1933 3197 0.60 10 1421 1833 0.78 463 550 0.84 1394 1833 0.76 11 1139 1685 0.68 369 506 0.73 1140 1685 0.68 AVG. 1604 2498 0.66 887 1062 0.83 1064 1325 0.81 1138 1325 0.87 1611 2498 0.66 Test Test

FIL/TC μg FIL/TC μg FIL/TC μg FIL/TC μg

FIL/TC μg FIL/TC μg Hg

Zn μg FIL/TC FIL/TC μg FIL/TC μg FIL/TC μg

Ni Pb Se Ag As Cd Cr Ba

Table C4. Lead normalized atomization mass (AT) vs. total capture (TC).

TC AT TC/AT TC AT TC/AT TC AT TC/AT TC AT TC/AT TC AT TC/AT 2 0.92 0.99 0.93 3 0.82 0.99 0.83 4 0.95 1.00 0.95 0.95 1.00 0.95 0.73 1.00 0.73 1.16 1.00 1.16 0.80 1.00 0.80 5 0.95 1.00 0.95 0.94 1.00 0.94 0.71 1.00 0.71 1.16 1.00 1.16 0.86 1.00 0.86 6 0.96 1.00 0.96 0.93 1.00 0.93 0.79 1.00 0.79 1.13 1.00 1.13 0.82 1.00 0.82 7 0.96 1.00 0.96 0.94 1.00 0.94 0.78 1.00 0.78 1.14 1.00 1.14 0.88 1.00 0.88 8 0.63 0.58 1.08 20.4 16.6 1.22 9 0.63 0.58 1.08 20.5 16.6 1.23 10 0.62 0.58 1.06 19.7 16.6 1.19 11 0.59 0.58 1.02 19.7 16.6 1.18 AVG. 0.96 1.00 0.96 0.78 0.79 1.00 0.79 1.00 0.79 10.6 8.8 1.18 0.84 1.00 0.84

TC AT TC/AT TC AT TC/AT TC AT TC/AT TC AT TC/AT TC AT TC/AT 2 1.00 1.00 1.00 3 1.00 1.00 1.00 4 1.00 1.00 1.00 0.95 1.00 0.95 1.03 1.00 1.03 5 1.00 1.00 1.00 0.96 1.00 0.96 1.03 1.00 1.03 6 1.00 1.00 1.00 0.96 1.00 0.96 1.01 1.00 1.01 7 1.00 1.00 1.00 0.96 1.00 0.96 1.02 1.00 1.02 8 2.70 3.33 0.81 1.00 1.00 1.00 2.73 3.33 0.82 9 2.67 3.33 0.80 1.00 1.00 1.00 2.71 3.33 0.81 10 3.07 3.33 0.92 1.00 1.00 1.00 3.01 3.33 0.90 11 3.09 3.33 0.93 1.00 1.00 1.00 3.09 3.33 0.93 AVG. 2.88 3.33 0.87 1.00 1.00 1.00 0.96 1.00 0.96 1.02 1.00 1.02 2.89 3.33 0.87 Ni Test Test

Zn Ag Se Pb As Cd Cr Ba Hg112 ERDC/CERL TR-05-9



### Evaluation of Stack Transport

Test Design

The QSIS tests just discussed in the pr evious section were able to effectively evaluate the XCEM calibration. Since the QSIS was injected at the top of the shed, however, more data were needed to determine the transport efficiency of the sample line from the stack to the shed . To evaluate the entire transport system and the responsiveness of the XCEM to munitions burning, a second series of tests were conducted from 30 April to 2 May in which the TEAD stack was spiked by MSE-TA for metals of interest while munitions were incinerated. An EPA Reference Method 17 (M17) type train was used to capture a representative stack sample of PM near the inlet of th e XCEM stack probe. Results of the M17 tests were then compared with th e concurrent XCEM concentrations.

XCEM Responsiveness to Munitions Destruction

During the stack spiking, TEAD conducted normal burning operations in which they were destroying 20 mm bullets and tracers. The bullets were observed by the XCEM to have significant quantities of Pb, Cd, and tin (Sn), while only Sn was observed in significant quantities during tracer incineration. These elements were not spiked by MSE-TA. As shown in Figure 38, the XCEM displayedgood responsiveness to various types of ammunitions burning and stack operation approaches.

Figure C2 shows the XCEM relationship between Sn and Cd when bullets were being destroyed. The high correlation (r2 = 0.94) indicates that the two elements were from the same source. A 75 to 90 percent decrease is seen in Cd and Pbwhen tracers are being burned while Sn remains unchanged. Follow up conversations with TEAD personnel indicated th at the tracers did not contain Cd and Pb, but did contain Sn. Figure C2 also shows the impact of opening and closing the bypass valve each day, with concentrat ions exhibiting spikes during the short period that the bypass valve was open.

One of the intended uses of the XCEM is as a monitor to better understand control efficiencies. The data in Figure 38 were used to help TEAD personnel identify the sources of metals in the stack gas and better control the emissions. Following M29 testing, TEAD stack operator s conducted tests in which they used the XCEM to determine that the metals emissions could be significantly reduced by completely cutting off the by pass system during operation.ERDC/CERL TR-05-9 113

XCEM Lead

0 100 200 300 400 500 600 700 800 900

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3)

N o Amm

Tracers Bypass Open

Cadmium

0 100 200 300 400 500 600 700 800

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Tracer

N o Amm Bypass Open Tin

0 200 400 600 800 1,000 1,200 1,400 1,600 1,800

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Tracer

N o Amm Bypass Open XCEM Sn vs. XCEM Cd y = 2.36x + 25.96 R 2 = 0.94

0 500 1,000 1,500 2,000

0 200 400 600 800 Cadmium (μg/dscm)Tin (μg/dscm)

* Concentrations when fuses being

Figure C2. XCEM reported concentrations for nonspiked elements.



### XCEM Response vs. MSE-TA Spiking

From 30 April to 2 May, MSE-TA spiked kn own concentrations of Ba, Hg, Ni, Sb, and Zn. The XCEM relative response to these concentrations is shown in Figure B3.

Other than Zn, which is associated with the incineration feed, the XCEM reported concentrations were slightly le ss than the MSE-TA predicted concentrations on 30 April and the morning of 1 May (runs 795–837). Following these runs, however, the transport line heat tracing was completed and the XCEM concentrations were within 5 to 15 perce nt of MSE-TA estimated concentrations.114 ERDC/CERL TR-05-9

Barium

0 200 400 600 800 1,000 1,200

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Ba-XCEM Ba-MSE Mercury

0 50 100 150 200 250 300 350 400 450 500

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Hg-XCEM Hg-MSE

Nickel

0 100 200 300 400 500 600

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Ni-XCEM Ni-MSE Antimony

0 100 200 300 400 500 600

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Sb-XCEM Sb-MSE

Zinc

0 200 400 600 800 1,000 1,200

780 800 820 840 860 880 XCEM Run No.Conc. (μg/m3) Zn-XCEM Zn-MSE

\

Figure C3. XCEM reported concentrations and MSE- projected concentrations for spiked elements.



### XCEM Comparisons to Method 17 Results

To obtain adequate flows and meet stack temperature requirements, quartz fiber filters (QFF) were used for the in-stack f ilter holder for M17 testing. The QFFs cannot adequately trap Hg, but were analyzed for the spiked elements Ba, Ni,Zn, and Sb as well as the elements Cd and Pb, which were both found in the munitions. A total of 15 valid runs were conducted. Table C5 shows the results.

Both Ni and Zn were spiked together by MSE-TA. For these two metals, the XCEM to M17 ratios were 1.18 and 1.09, respectively. Since the XCEM was higher than M17, no indication of loss in the transport line was believed to have occurred. The uncertainty of the ratios was about 20–25 percent, which wasERDC/CERL TR-05-9 115



### primarily the result of variability in the M17 flow measurement and uncertainties in M17 absorption corrections.

A second solution spiked by MSE-TA contained Ba and Sb. The two elements had respective XCEM to M17 ratios of 0.99 and 1.03, which indicated good transport efficiencies for elements in this spiked solution.

Although neither Pb nor Cd was spiked by MSE-TA, significant concentrations ofboth were found in the stack when bullets were being burned. The concentrations changed dramatically when tracers were burned instead of bullets for part of run 4. The XCEM and M17 were in good agreement for Pb, but the XCEM was significantly higher than M17 for Cd . The Cd results indicated a potential XCEM calibration error for Cd.

During the 3 days of testing, the Pd conc entration, which is measured with every sample by the XCEM and indicates stability, varied from 90 to 105 percent. The higher than normal variability was determin ed to be associated with high ambient temperatures in the sample shed due to a faulty air conditioner. Installation of an improved temperature control syst em would help remedy this problem in the future.116 ERDC/CERL TR-05-9Table C5. Method 17 vs. XCEM at TEAD.*XC M17 X/M XC M17 X/M XC M17 X/M XC M17 X/M XC M17 X/M XC M17 X/M1 4/30/02 3:11 PM 4:11 PM 650 716 0.91 401 301 1.33 552 466 1.18 192 208 0.92 176 134 1.31 363 348 1.042 5/1/02 8:36 AM 9:42 AM 567 677 0.84 448 363 1.23 674 595 1.13 213 239 0.89 192 158 1.21 248 258 0.963 5/1/02 10:02 AM 10:47 AM 471 605 0.78 313 284 1.10 539 548 0.98 194 222 0.87 159 134 1.19 214 238 0.904 5/1/02 11:00 AM 11:45 AM 544 533 1.02 236 177 1.33 353 302 1.17 99 99 0.99 58 43 1.36 173 138 1.255 5/1/02 12:01 PM 12:26 PM 708 859 0.82 222 230 0.97 430 459 0.94 200 257 0.78 171 161 1.06 210 207 1.026 5/1/02 12:43 PM 1:28 PM 131 104 1.25 231 186 1.24 506 450 1.12 198 202 0.98 153 122 1.25 38 35 1.087 5/1/02 1:46 PM 2:26 PM 281 348 0.81 208 196 1.06 487 504 0.97 205 236 0.87 161 141 1.14 144 158 0.918 5/1/02 2:40 PM 3:20 PM 432 642 0.67 218 246 0.88 495 591 0.84 210 248 0.85 154 151 1.02 232 293 0.799 5/1/02 3:35 PM 4:15 PM 416 515 0.81 217 217 1.00 477 528 0.90 207 238 0.87 152 142 1.07 221 257 0.8610 5/2/02 8:41 AM 9:21 AM 419 362 1.16 226 1601.42 269 199 1.35 307 220 1.40 70 48 1.45 220 168 1.3111 5/2/02 11:05 AM 11:45 AM 476 333 1.43 219 149 1.47 555 446 1.24 331 273 1.21 220 151 1.45 254 167 1.5212 5/2/02 12:12 PM 12:52 PM 410 518 0.79 221 231 0.96 485 510 0.95 279 275 1.02 169 150 1.13 251 238 1.0613 5/2/02 1:07 PM 1:47 PM 446 346 1.29 230 1681.37 359 268 1.34 150 108 1.38 70 50 1.42 239 151 1.5914 5/2/02 2:33 PM 3:03 PM 451 541 0.83 227 237 0.96 432 487 0.89 244 258 0.95 171 145 1.17 259 554 0.4715 5/2/02 3:10 PM 3:40 PM 487 331 1.47 229 165 1.39 453 325 1.40 256 174 1.47 170 107 1.58 254 383 0.66Average459 495 0.99 256 221 1.18 471 445 1.09 219 217 1.03 150 122 1.25 221 239 1.03Standard Deviation0.26 0.20 0.18 0.22 0.17 0.30RunBaStart StopZnNiDateSbCdPb* XC and M17 concentrations in μg/dscm; XC = XCEM; X/M = XCEM/M17.ERDC/CERL TR-05-9 117



# Appendix D: Mercury Calibration and Loss Discussion 2002

Introduction

Mercury (Hg) represents a distinctly different hazardous element from the others included in these tests in that it is more likely to exist in the vapor phase and has been shown to exhibit distinctly diffe rent transport properties. These properties appear to have contributed to di fferences in the Hg concentrations measured by the different methods compared in the 2002 test. This appendix discusses the details associated with both the adjustments that were made to the XCEM calibration factors and losses of Hg from particulate deposits after sample collection.



### Calibration Adjustments

Two adjustments were made to the Hg results after the first M29 test run wasstarted. The first adjustment was a 7 percent increase in the Hg sensitivity factor between M29 run 1 and run 2. The second was a 4 percent increase in the sensitivity factor shortly after the completion of the tests and before the M29 and XCEM results were submitted. The nece ssity for these adjustments was due in part to the volatility of the Hg, which makes it difficult to make stable thin-film Hg standards. As such, thin film Hg standards are not available from NIST. The standards that are available are re latively unstable and need to be frequently validated. This method limitatio n is generally minimized by the fact that energy dispersive X-ray fluoresc ence (XRF) sensitivity factors are a smoothly varying function of atomic number. This allows Hg sensitivity factors to be estimated by interpolation using well-defined sensitivity factors for elements with similar atomic number such as platinum, gold, thallium, lead (Pb), and bismuth. The following two adjustments were based on this interpolation process and a re-evaluation of the best-estimated calibration factor.118 ERDC/CERL TR-05-9



### Adjustments During First Day of Testing

The XCEM underwent mercury calibration during preliminary spiking tests, prior to the M29 tests. During these spiking tests, the NIST thin-film standardfor Pb was not available, and the Hg sensitivity was estimated based on a previous measurement of the Pb NIST standard. This fact was not realized until after the preliminary spiking testing started an d a review of the preliminary Hg results indicated a potential bias relative to the NIST Pb results. As a result, the Hg calibration was adjusted by 7 percent at the earliest possible time, which was after M29 run 1 and before run 2.

Post-Test Adjustments

The second adjustment to the Hg results of 4 percent was applied when the calibration factors were reviewed following the M29 tests. A comparison with the ratio of Hg to Pb sensitivity factors deve loped from a more extensive study in the laboratory indicated that the 0.838 ratio used during the tests should have been 0.873. This 4 percent correction was app lied to the XCEM results prior to the submission of either the M29 or the XCEM results.



### Losses From PM Fraction

The XCEM Hg results were, on average, 18 percent greater than the predicted concentration, 27 percent greater than th e M29 results, 37 percent greater than the laboratory XRF measurements of the XCEM deposit spots, and 45 percent greater than cold vapor atomic absorption (CVAA) measurements on the XCEM deposit spots. Subsequent investigations of these differences strongly suggest that the XCEM results are the best estimate of the actual Hg concentrations in the stack. It is hypothesized that th e large differences between the XCEM Hg results and the results from the other methods is due to the loss of Hg from the filter deposits after the M29 and XCEM samples were collected and after the XCEM original measurements were made.

Model

A model has been developed to explain the apparent high XCEM Hg concentrations relative to M29. In this model, Hg is lost from the particulate fraction of the M29 and XCEM filters after the initial XCEM measurements were made. That is, a substantial fraction of Hg was associated with the particulate fraction, and the Hg in this particulate was unstable. Since all of the other analytical methods relied on aged samples, the Hg concentration results were low due toERDC/CERL TR-05-9 119



### vaporization of particulate Hg prior to laboratory analysis. A substantialamount of experimental data is available, all of which is supportive of this hypothesized model. Most of this experimental data was developed only because of the unique characteristics of the XCEM and the fact that the XCEM elementalmeasurement is nondestructive and the spectra from each of the original measurements were archived.

Experimental

The initial XCEM measurements were based on the analysis of filter deposits, which were a combination of both absor bed vapor phase Hg species and surface deposits of particulate Hg species. Ea ch deposit was analyzed using three different X-ray excitation conditions, resulting in spectra that were used to determine concentration. All spectra were archived in the XCEM computer. As such, the deposit was available for further analysis and testing, and the original spectra were available for comparison with subsequently developed spectra.

Following the validation testing at TEAD , CES conducted several tests to better understand the Hg concentration differences between M29 and the XCEM.

• All of the XCEM deposit spots corresponding to all of the M29 runs were reanalyzed by CES’s laboratory QuanX XRF analyzer 6 weeks after the initial validation test. In addition, 10 XCEM filter deposit spots were analyzed over a 2- month period to evaluate Hg stability. Spectra from these tests were compared with archived spectra from the original validation test.

• The XCEM deposit spots corresponding to M29 runs 5 and 6 were analyzed first by laboratory XRF and then by CVAA by an independent laboratory (Columbia Analytical Services).

• The elemental concentrations in the MSE-TA spiking solutions corresponding to M29 runs 5 and 6 were analytically determined by HKM Labs (Butte, MT).

Results and Discussion

The Hg results for the original validation test are summarized in Table D1. There is a clear bias of about 26 percent between the XCEM results and the M29 results. Normally, the M29 results would be accepted as the best estimate of stack Hg concentration and it would be assumed that the candidate method (XCEM) was in error. However, because of the total QA associated with theXCEM and the fact that the XRF analysis is nondestructive, it is possible to conduct further analyses to evaluate the po tential cause of this difference. Additionally, the laboratory analysis results for each component of the M29 sampling trains (i.e., probe, filter, and back half) were determined separately, and are available for interpretation.120 ERDC/CERL TR-05-9

Table D1. Mercury reported concentrations during Year 2002 M29 validation testing. PRD M29 XC QN CA PRD XC QN CA

1 324 332 367 257 0.98 1.10 0.77 2 325 334 381 251 0.97 1.14 0.75 3 333 294 365 262 1.13 1.24 0.89 4 322 327 368 301 0.98 1.13 0.92 5 323 318 379 308 274 1.02 1.19 0.97 0.86 6 329 280 378 288 254 1.18 1.35 1.03 0.91 7 327 285 392 302 1.15 1.37 1.06 8 325 306 406 294 1.06 1.33 0.96 9 324 309 405 287 1.05 1.31 0.93 10 328 292 395 282 1.13 1.35 0.97 11 326 295 397 286 1.11 1.35 0.97 12 322 293 389 267 1.10 1.33 0.91 AVG. 326 305 385 282 264 1.07 1.27 0.93 0.88

SD 3.3 19 14 19 13.8 0.07 0.10 0.09 0.03 μg/DSCM RUN Normalized to M29

Loss of mercury from the XCEM filter



### Laboratory XRF measurements (QN). Two months after the validation testing, CES’s laboratory QuanX XRF analyzer reanalyzed the original XCEM deposit samples with good replication for all elements except Hg (see Table 31 in main body of text).

A series of 10 spots on the XCEM filter tape were reanalyzed between 21 June 2002 and 11 July 2002. The spots, which represent 10 XCEM runs, showed a consistent Hg loss of about 30 percent over the 3-week period. Other sources of error such as shifts in geometry or in strument instability were eliminated as possible systematic sources of error by no ting that the other elements were replicated within experimental error to a few percent.

XCEM measurements (XCEM) . To confirm this loss of Hg, five XCEM deposit spots were re-analyzed by the TEAD X CEM, which was still operating with the same conditions and calibration factors as used during the M29 tests about 2 months earlier. The X-ray spectra from the original analysis of XCEM runs 939 to 943 (M29 run 4) are compared in Figure D1. This comparison clearly showsthat agreement is good for the two closest analyte peaks for Zn and Pb, but reduction is substantial in the peak intensity for the Hg L-alpha analyte line. A comparison of the XCEM Hg concentrations measured during the M29 testing (14 May 2002) with those measured with the XCEM on 25 July 2002 indicate a 31.4 ± 0.4 μg/m 3 

### reduction in measured concentration. Although this reduction might be associated with possible systemat ic errors such as sample positioning, this possible source of error was eliminat ed by comparing other elements such asERDC/CERL TR-05-9 121



### Zn and Pb as well as the ratio of Hg to these elements. The reduction in Hg toZn ratio, for example, was 29.1 percent, which is in good agreement with the Hgmeasured reduction.

Clearly, Hg was lost from the XCEM deposit after the sample was collected and analyzed by the XCEM. As discussed in the following subsection, the available data strongly suggest that a substantial portion of the M29 Hg was also lost from the M29 PM filter deposits prior to analysis.



## 0 2000 4000 6000 8000 10000 12000 14000Counts



### XCEM 051402 XCEM 072502 

## Zinc Mercury

Lead

Figure D1. Comparison of XCEM x-ray spectra measured during M29 testing and 71 days later.

Instability of M29 Hg PM deposit highly likely



### Although there is no direct evidence of the loss of Hg from the M29 samples, there is ample indirect evidence that a similar loss to that of the XCEM deposit would be expected. This indirect eviden ce is discussed in the following three subsections.

Train location of Hg deposits . The recovery and analysis of the M29 probe, filter, nitric acid impingers, sulfuric acid im pingers, and the hydrochloric acid rinse were kept separate for both the May 2001 and May 2002 M29 tests. The results are summarized and compared in Table D2. It is interesting to note that, duringthe 2001 testing, only about 1 percent of the Hg was deposited on the quartz fiber filter. This is typical of most stack measurements of Hg, so there is little concern for the stability of the PM deposited on the filter. This is not the case, however, for the 2002 Hg measurements. Du ring these latter tests, 18 percent ofthe Hg was deposited on the filter during runs 1 through 5, with no Pb in the HgNi-Zn spiking solution. After adding Pb to the spiking solution, the percent of Hg depositing on the filter increased to 29 percent for the remaining M29 runs.122 ERDC/CERL TR-05-9

Table D2. Comparison of the location in M29 sampling trains where the Hg was deposited during the 2001 and 2002 tests. 

### YEAR RUNS FILT. PROBE M2B M3A M3B M3C TOTAL

2001 1-13 1.1 0.1 93 0.4 0.3 5.2 100 2002 1-12 24.7 0.1 71 0.2 0.1 4.1 100 2002 1-5 18.2 0.2 77 0.3 0.1 4.7 100 2002 6-12 29.4 0.1 67 0.2 0.0 3.7 100 2001 1-13 6.0 0.2 414 2.2 1.0 26 450 2002 1-12 166 0.8 484 1.6 0.4 28 681 2002 1-5 129 1.1 551 1.9 0.7 34 718 2002 6-12 191 0.6 437 1.4 0.2 24 654 Percent on Filter

Mass on Filter (μg)

It is interesting to note that during the 2001 M29 tests, the reported M29 Hg concentrations were 12 percent greater than the predicted concentrations; similar to the 18 percent (12 percent with co rrected solution concentrations) measured in 2002 with the XCEM. On the other hand, the 2002 M29 results are 6 percent less than the predicted concentrat ions rather than 12 percent greater as in 2001.

These results are certainly consistent wi th the hypothesis that M29 Hg results are low because there was a loss of Hg fr om the M29 quartz fiber filter between the time it was collected on the filter and the time it was analyzed. It is also consistent with the fact that many of the Hg compounds and amalgams of Hg are relatively unstable and have relatively high vapor pressures. Thus, it should not be surprising that if there is a substantia l portion of the Hg on the filter as there was during the 2002 tests, there might be a potential for significant loss due to volatilization. It also needs to be noted that the filters were not stored in a controlled environment from the time they were collected until they were delivered to the analytical laboratory several days later. During this time, they may have been exposed to relatively high ambien t temperatures while being transported through the western desert from Tooele, UT to California in the back of a closed panel truck.

Correlation with percent Hg on M29 filter . The percent difference between theM29 Hg results and the XCEM results is significantly correlated with the percent Hg on the M29 filters as is illustrated in Figure D2. That is, the percent difference between the two methods (perce nt loss from the M29 filter) is dependent on the fraction of the total Hg measured in the M29 train that is on the filter. This observation is consistent with the proposed hypothesis for the difference between the various methods, that is, loss of Hg from the M29 filter.ERDC/CERL TR-05-9 123



### y = 1.25x - 4.3223
R 2 

### = 0.8055

0 10 20 30 40 50

0 10 20 30 40 Percent of Hg on M29 FilterPercent Difference BetweenM29 and XCEM

Figure D2. Percent difference between M29 and the XCEM vs. percent of Hg on the M29 filter.

Precision



### The difference in the Hg concentrations was not likely due to imprecision in either of the two measurements. Mercury was one of two elements spiked by MSE-TA that were clearly not present in the background stack emissions. Thus, the variability in the Hg concentration was due primarily to variability in the spiking and stack flow rates. The Hg precision as measured by the XCEM was 3.8 percent and 6.1 percent for M29, whic h includes the variability in the two parameters above as well as the measurement method variability.

Mercury to nickel ratio



### Nickel was another element that clearly was not present in the background, and it was in the same spiking solution as the Hg. Thus, the ratio of Hg should notvary significantly since the concentrations for these two elements was kept constant for these latest tests. The XCEM measured Hg to Ni ratio was 1.37 ± 0.015 (1.1 percent relative) and close to both the M29 ratio, 1.41 ± 0.116 (8.3 percent relative), and the predicted concentratio n ratio based on the measured solution concentration ratio of 1.33. It is interesting to note that the XCEM precision issignificantly better than the M29 ratio precision, both of which should be relatively independent of factors other than the individual method.

Low Columbia Analytical Services results



### The XCEM deposit samples submitted to Co lumbia Analytical Services for CVAA analysis were extracted 41 days after they were analyzed by CES. Based on an assumed linear loss rate, the expected Hg concentrations at the time of extrac-124 ERDC/CERL TR-05-9



### tion would be about 10 percent lower than measured by the CES XRF analyzer. The observed difference was 14 percent.



### Conclusion

The weight of evidence clearly indicates that the XCEM Hg deposit was unstable as was the M29 PM deposit on the quartz fiber filter. This instability most likely caused the difference between the Hg measured by these two methods and the other methods. It is highly likely that, if these losses had not occurred, the XCEM would have passed the PS-10 RA tests.

It is recommended that, in future M29 test ing, the filters be immediately sealed and cooled to at least 0 °C, stored at be low freezing temperatures and digested as soon as possible after sampling.ERDC/CERL TR-05-9 125



# Abbreviations and Acronyms

AEC Army Environmental Center AED Ammunition Equipment Directorate AMP Alternative Monitoring Plan AMS Advanced Monitoring Systems (Center) APE ammunition peculiar equipment CAAA Clean Air Act Amendments (of 1990)
CEM continuous emission monitor CERL Construction Engineering Research Laboratory CES Cooper Environmental Services CHPPM U.S. Army Center for Health Promotion and Preventive Medicine CVAA cold vapor atomic absorption EPA U.S. Environmental Protection Agency EQT Environmental Quality Technology ERDC U.S. Army Engineer Rese arch and Development Center ETV Environmental Technology Verification (program)
HAP Hazardous Air Pollutants
HWC hazardous waste combustors ICP inductively coupled plasma LIBS laser-induced breakdown spectroscopy
LVM low volatile metals MACT Maximum Achievable Control Technology
M17 EPA Reference Method 17
M29 EPA Reference Method 29
MF membrane filter
NESHAP National Emissions Standard for Hazardous Air Pollutants NIST National Institute of Standards and Technology PM particulate matter PS-10 EPA Proposed Perf ormance Specification 10 QA/QC quality assurance/quality control126 ERDC/CERL TR-05-9



### QFF quartz fiber filter QSIS Quantitative Spike Injection System RA relative accuracy
RCRA Resource Conservati on and Recovery Act RIF resin-impregnated filter
RSD relative standard deviation SCFM standard cubic feet per minute TEAD Tooele Army Depot
XCEM XRF-based continuous emission monitor XRF x-ray fluorescence



### Chemical elements

Ag silver
As arsenic
Ba barium Be beryllium
Cd cadmium
Cr chromium Hg mercury
Ni nickel Pb lead Pd palladium Sb antimony
Se selenium
Sn tin
Tl thallium
Zn zinc

## REPORT DOCUMENTATION PAGE Form Approved OMB No. 0704-0188 Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing da ta sources, gathering and maintaining the data needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden to Department of Defense, Washington Headquarters Services, Directorate for Information Operations and Reports (070 4-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202- 4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty f or failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 1. REPORT DATE (DD-MM-YYYY) 03-2005 2. REPORT TYPE Final 3. DATES COVERED (From - To)

5a. CONTRACT NUMBER

5b. GRANT NUMBER 4. TITLE AND SUBTITLE X-Ray Fluorescence Based Multi-Metal Continuous Emission Monitor: Technology Demonstration

5c. PROGRAM ELEMENT NUMBER

5d. PROJECT NUMBER 622784AT41 5e. TASK NUMBER 002 6. AUTHOR(S) K. James Hay, Veera M. Boddu, Bruce E. Johnsen, and John A. Cooper

5f. WORK UNIT NUMBER CNE-B091 8. PERFORMING ORGANIZATION REPORT

NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) U.S. Army Engineer Research and Development Center (ERDC) Construction Engineering Research Laboratory (CERL) PO Box 9005 Champaign, IL 61826-9005 ERDC/CERL TR-05-9

9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM(S) U.S. Army Corps of Engineers 441 "G" Street NW Washington, DC 20314-1000 11. SPONSOR/MONITOR’S REPORT NUMBER(S)

12. DISTRIBUTION / AVAILABILITY STATEMENT Approved for public release; distribution is unlimited.

13. SUPPLEMENTARY NOTES Copies are available from the National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161.

14. ABSTRACT

Army demilitarization incinerators will need to comply with th e Hazardous Waste Combustor Natio nal Emission Standard for Hazard ous Air Pollutants that will regulate metals and metal compounds lis ted under the Clean Air Act Amendments. A large problem for th ese incinerator operations is limited knowledge of the type and quantity of emitted metals, so that compliance may be determined only through trial burn emission tests. A continuous emission monitor (CEM) for multi-metals will provide the emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn strategies for increased production. A user-friendly multi-metal C EM that uses x-ray fluorescence (XRF) as the analy tical method and an automated sampling system that provides extractive batch sampling onto a filter tape (XCEM) was demonstrated at the 1236 Deactivation Furnace at Tooele Army De pot, Utah. The unit was compared to EPA Reference Method 29 during two separate tests (2001 and 2002). The second test was performed after improvements were made to t he sample transport and system calibrations. The results indicate that the XCEM has met the propo sed Performance Specification 10 for multi-metal CEMs except for some of the re lative accuracy requirements. Its failures ar e attributed to inadequacies in the ref erence method. The monitor is proving useful at Tooele and is ready for implementa tion at other Army demilitarization incinerators.

15. SUBJECT TERMS emissions air pollution hazardous air pollutants (HAPs) continuous emi ssion monitor (CEM)
16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES 19a. NAME OF RESPONSIBLE PERSON K. James Hay a. REPORT Unclassified b. ABSTRACT Unclassified c. THIS PAGE Unclassified SAR 137 19b. TELEPHONE NUMBER (include area code) (217) 373-3485

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