Xact extracted a sample of effluent downstream of all controls. The extracted effluent was 

dynamically spiked with five different metals (As, Cd, Cr, Pb, Hg) at three different 

concentration levels (27, 92 and 250 pg/dscm) using the QAG. The Xact reported concentration 

was plotted against the reference aerosol concentration and a linear least squares regression fit 

was performed. The accuracy ofthe Xact was evaluated on the basis of slope, correlation 

coefficient and intercept. 

Measurement of Mercury with tbe Xact on Coal Fired Power Plants 

This paper also summarizes the results of two distinct studies evaluating the accuracy ofthe 

Xact's mercuiy measurement on coal fired power plants. During both studies the accuracy of the 

Xact was detennined by comparing it to Method 30B20, a sorbent trap approach to measuring 

mercuiy. The first study was performed on a 585 MW facihty, burning subbituminous coal and 

operating with ESP controls. The Xact was deployed at this facility for three weeks and 

comparison testing took place on one of those days. 

The second study was performed at a 750MW source burning two separate blends of lignite and 

Powder River Basin (PRB) coal (60/40 and 80/20 blends of lignite/PRB). The facihty was 

equipped with an ESP and wet scrubber, but all of the Xact sampling was done downstream of a 

single ESP module and upstream of the wet scrubber. In addition, the facility was testing two 

separate mercuiy control options - activated powdered carbon and EMO, a bromine based 

additive. During the course of the approximately two week test the Xact reported mercury 

concentration was compared to Method 30B measured concentration at several times each day. 

RESULTS AND DISCUSSION 

Method 301 Validation Results 

Diiring the Method 301 validation ofthe Xact the bias, precision and linearity of the Xact were 

detennined by comparing the Xact's reported concentration with reference aerosol concentration 

over three different concentration levels (nominally 20,45 and 110 ug/dscm) and a zero 

concentration. The bias was calculated for each element at each data point using Equation 2 

Bi = • 100 Equation 2 

where: 

Bi— The Xact's bias for the i * element relative to the QAG expressed as a percentage 

Cf1 = The concentration ofthe i * element as measured by the Xact 

CfAG= The concentration of tiie r* element in the QAG aerosol 

The precision of the Xact was calculating by first determining the relative percent standard 

deviation as shown in equation 3. 

VES016800 
Equation 3 

where: 

V-=the total variability of the r* element 

SD(= the standard deviation of the r* element 

C{= the average concentration of the i * element 

Because there is random variability associated with both the QAG aerosol concentration as well 

the Xact measurement, the total variability (V?) is an indicator ofthe overall variability of both 

the QAG aerosol generation and the Xact measurement. The individual variability of just the 

Xact measured concentration then is determined by dividing the total variability by the square 

root of 2 as shown in equation 4. 

vf 

Vi~-fl Equation 4 

where: 

7i=the precision ofthe Xact measurement for the i * element 

V?=the total precision ofthe r* element 

Table 1 summarizes the results for both the average bias and average precision for the Xact for 

each of the five tested elements over all three concentration levels. In general, there was less 

than 10% difference between the Xact reported concentrations and the known concentration of 

the reference aerosol. Only the bias for mercury was determined to be statistically significant and 

6% of the bias was later determined to be due to a calibration error for mercury. The average 

variability of the Xact was also less than 2% for each element indicating that the Xact's 

measurements were extremely precise and consistent. 

Table 1. Xact Method 301 Results for Measurement Bias and Variability 

Element N Average Bias (%) Average Variability 

(%) 

Cr 40 8.2 1.6 

As 40 4.9 1.7 

Hg 40 16 1.4 

Pb 40 7.9 1.5 

Cd 40 5.2 1.9 

Figure 1 shows the overall linear regression for all of the metals tested over all three 

concentration levels and a zero concentration. The slope ofthe linear regression fit was 0.95 

indicating excellent agreement between the Xact measured concentration and the QAG reference 

aerosol. The intercept was slightly greater than 1 pg/dscm indicating very little background bias 

6 

VES016801 
and the correlation coefficient was greater than 0.99 indicating very little scatter in the data and 

good precision.12 

Figure 1. Xact Linearity During Method 301 Validation 

140 

QAG Reference Concentration (pg/dscm) 

Operation ofthe Xact Over Several Years 

The Xact operated for several years at Eh Lilly's hazardous waste incinerator and during that 

tine met all ofthe daily, quarterly and annual quality assurance requirements. Some sample 

upscale cahbration check results from March of 2006 to March of2007 are shown in Figure 2. 

Daring that entire 12 month period the Xact upscale drift exceeded its upscale calibration drift 

criteria on only two occasions. Table 2 shows all the quarterly XRF and flow audit results for 

the entire compliance operation period from 2007 to 2010. During that four year span the Xact 

passed all of its quarterly audit requh ements. Finally, table three shows the results from six 

separate relative accuracy test audits (RATA) over a span of five years. The Xact met the RATA 

criteria in all cases, however, in 2006 and 2008 a small correction factor needed to be applied to 

tie instnunent data for arsenic. 

Figure 2. Daily Upscale Results from March 2006 to March 2007 

VES016802 
8 

VES016803 
Table 2. Quarterly Flow and XRF Audit Results from 2007 to 2010 

Audit 

Year 

Quarter Flow Error 

{%) 

Audit XRF Audit Error (%) 

Year 

Quarter Flow Error 

{%) Cr As Cd Hg Pb 

2O07 1 3.04 1.46 2.18 2.84 1.75 2.34 

2 3.13 3.32 0.13 4.23 2.60 2.96 

2O07 

3 0.68 -3.74 2.18 -4.13 2.36 2.76 

2O07 

4 1.42 6.50 0.36 7.36 4.18 0.40 

2O08 1 NA 0.22 .11 1.20 -0.99 0.87 

2 1.07 1.93 .66 1.82 2.16 2.34 

2O08 

3 0.53 2.96 2.61 3.30 2.53 0.68 

2O08 

4 1.37 1.77 0.72 1.48 0.56 1.06 

2009 1 2.10 0.60 2.94 1.52 3.45 0.46 

2 3.67 1.49 4.09 1.07 1.78 0.30 

2009 

3 0.84 2.00 5.43 2.78 0.72 0.22 

2009 

4 NA NA NA NA NA NA 

2010 1 NA 1.60 5.13 0.45 0.71 2.11 

2 NA 1.61 5.92 1.12 4.00 0.96 

2010 

3 1.68 -3.47 -0.92 -2.82 -2.42 -2.11 

2010 

4 NA 2.00 0.82 2.70 1.83 2.91 

Average 1.77 1.35 2.16 1.66 1.68 1.22 

NA - Data not available 

Table 3. Annual QA G RAT A Results 

Year Slope 

Cr As C d Hg Pb Annual 

Average 

2006 0.83 0.90 0.85 0.82 0.85 0.85 

2006 

(Quarterly) 

0.91 0.77 0.95 0.92 0.93 0.89 

2007 0.84 0.82 0.88 0.84 0.81 0.84 

2008 0.96 0.71 0.98 0.99 0.97 0.92 

2O09 0.96 0.99 0.99 1.10 1.00 1.01 

2010 0.97 1.06 1.11 1.02 1.04 1.04 

Average 

for Each 

Element 

0.91 0.87 0.96 0.95 0.93 0.93 

Results ofthe Evaluation ofthe Xact on a Coal Fired Source 

Table 4 shows the results of the evaluation ofthe Xact's accuracy on a coal fired source. During 

tlie study the Xact was challenged with three concentration levels using CES' quantitative 

aerosol generator. As with the Method 301 testing the Xact effluent was dynamically spiked to 

test for any potential interferences from the coal fired effluent. For each element, the Xact 

9 

VES016804 
reported concentiations were plotted against the known reference aerosol concenhation and a 

least squares regression analysis was performed. In all cases, the Xact slope was between 1.00 

and 1.15 with correlation coefficients greater than 0.99. This indicated that there were no 

measurement matrix effects associated emissions from a coal fired source and that the Xact is 

able to accurately measure many of the key metals of mterest on such a source.21 

Table 4. Results from Accuracy Testing on a Coal Fired Source 

Element N Slope Correlation 

Coefficient 

Cr 28 1.09 >0.99 

As 28 1.14 >0.99 

Cd 28 1.11 >0.99 

Hg 28 1.14 >0.99 

Pb 28 1.00 >0.99 

Mercury Measurement with the Xact on a Coal Fired Power Plant 

Daring testing on a 585 MW coal fired facility equipped with ESP controls the mercury 

concentration as reported by the Xact was compared against method 30B. The percent 

difference between the Xact and Method 30B was 3.53%.22 These results are shown graphically 

in Figure 3. 

Figure 3. Xact Comparison with Method 30B 

§ 

•8 

10 

9 

8 

li 

c 

o 

u 

>» 

2 

• • 

• CES Xact 

• Method 30B 

0 1 2 3 4 5 6 7 8 9 10 11 12 13 

RATA Number 

10 

VES016805 
Additional comparisons have been made between Method 30B and the Xact at another coal fired 

power plant. This 750 MW facility was burning lignite-PRB coal blends and testing two 

different mercury control technologies (powder activated carbon and EMO). Over the entire 

two week period 21 comparisons were made between the Xact and Method 30B under a variety 

of stack effluent conditions. The average percent difference between the Xact and Method 30B 

was 6.0% demonstrating the accuracy ofthe Xact's mercury measurements. The results are 

summarized in Table 5. 

Table 5. Xact Mercury Measurements With and Without Mercury Control 

Fuel 

Conditions 

Date Time Hg 

Controls 

Method 

30B 

(ug/dscm) 

Xact 

(pg/dscm) 

Percent 

Difference 

60% 10/3/12 11:45 Baseline 24.57 22.59 -8.1 

Lignite 10/3/12 14:45 EMO 14.85 15.33 3.2 

40% PRB 10/3/12 16:45 EMO 16.30 15.83 -2.9 

10/5/12 12:15 EMO & 

PAC 

9.25 10.09 9.0 

10/5/12 16:45 EMO & 

PAC 

11.52 12.74 10.6 

10/5/12 17:45 EMO & 

PAC 

4.05 5.88 45.2 

10/6/12 10:45 Baseline 24.03 24.55 2.2 

10/6/12 13:45 EMO & 

PAC 

11.14 12.34 10.8 

10/6/12 15:45 EMO & 

P AC 

5.74 7.97 38.8 

10/6/12 18:45 EMO & 

PAC 

13.92 15.72 13.0 

80% 10/9/12 10:15 Baseline 28.14 25.07 -10.9 

Lignite 10/9/12 12:15 PAC 19.01 19.26 1.3 

20% PRB 10/9/12 16:15 PAC 7.00 7.34 4.9 

10/10/12 10:30 Baseline 23.19 23.98 3.4 

10/10/12 13:45 E MO 18.73 20.22 8.0 

10/10/12 16:45 E MO 20.10 22.10 10.0 

10/10/12 19:45 E MO 18.60 22.11 18.8 

10/10/12 9:00 Baseline 21.57 18.69 -13.4 

10/11/12 9:00 Baseline 24.00 23.53 -1.9 

10/11/12 10:45 E MO 20.52 18.90 -7.9 

10/11/12 11:30 E MO 21.38 19.55 -8.6 

Average Percent Difference Under Baseline Conditions -4.8 

Average Percent Difference with Hg Controls 7.6 

Overall Percent Difference 6.0 

11 

VES016806 
CONCLUSION 

Tke Xact has demonstrated metals measurement accuracy on a variety of source types and with a 

variety of different controls. These sources have included gas fired and coal fired sources with 

ESP and wet scmbbing controls. In addition, the Xact demonstrated accuracy measuring 

mercxuy with at least two different approaches to mercury control - powder activated carbon and 

EMO. In the future the accuracy and precision ofthe Xact will be tested on two secondary lead 

smelters in the Los Angeles Basin area. These tests will include both dynamic spiking tests with 

a reference aerosol as well as comparisons to stack metals measurement methods such as Method 

29. 

REFERENCES 

1. Eli Lilly and Co. (2005), Alternative Momtoring Petition for the Solid-Liquid Incinerator, 

Tippecanoe Laboratories, Lafayette, IN 47909 

2. Oldham, C3. Air Measurements and Quality Group, Office of Air Planning and 

Standards, U.S. Environmental Protection Agency, Research Triangle Park, NC. Written 

communication with Eli Lilly and Company: Lafayette, IN. 2006 

3. U. S. Envhonmental Protection Agency. Method 301, Field Vahdation of Pollution 

Measurement Methods for Various Media. In Code of Federal Regulations, 40 CFR Part 

56. U.S. Government Printing Office: Washington, DC, 2005 

4. "National Emissions Standards From Coal- Oil-fired Electric Steam Generating Units and 

Standards of Performance for Fossil-Fuel-Fired Electric Utility, mdusuial-CommercialInstitutional Steam Generating Units, Final Rule." Federal Register 77 (February 16, 

2012): 9403-9513. 

5. "National Emissions Standards for Hazardous Air Pollutants for Hazardous Waste 

Combustors (Phase I Final Replacement Standards and Phase II);" Final Rule. Federal 

Register 70, No. 196 (October 12,2005): 59402 -

59450) httD.//ww.epa.gov/fed^gsh/CTA-AIR/2005/October/Dav- 12/al 8824a.pdf. 

Accessed July24,2014. 

6. "Standards of Perfonnance for New Stationary Sources and Emissions Guidelines for 

Existing Sources: Hospital/Medical/Infections Waste Incinerators;" Final Rule. Federal 

Register 74, No. 192 (October 6,2009). http://ww.gpo.gov/fQSVs/pkg/FR-2Q09-10-

Q6/pdf/E9-22928.pdf Accessed July 24.2014. 

7. "National Emission Standards for Hazardous Air Pollutants from the Portland Cement 

Manufacturing Industry and Standards of Performance for Portland Cement Plants;" Final 

Rule. Federal Register 75, No. 174 (September 9, 2010). 

htto://www.epa.gov/ttn/atw/pcem/fr09sel0.pdf. Accessed July 24, 2014 

8. U.S. Envhonmental Protection Agency. Method 29, Detenrunation of Metals Emissions 

from Stationary Sources. In Code of Federal Regulations, 40 CFR 60\ U.S. Government 

Printing Office: Washington, DC, 2005. 

12 

VES016807 
9. "Revised Standards for Hazardous Waste Combustors" Proposed Rule. Federal Register 

61, No. 77 (April 19,19961. http://ww.gro.gov/fdsv^ 

7872.pdf Accessed M v 24.2014. 

10. U.S. Environmental Protection Agency, Region 5. Air Pollution Control Title V Permit to 

Operate. Permit No. V-IL-1716300103-08-01. 

http://ww.regulatioiis.gov/#!documentDetail;D==EPA-R05-OAR-20r2-0649-0001 

Accessed July 24,2014. 

11. "National Emission Standards for Hazardous Air Pollutants: Secondary Lead Smelting" 

Proposed Rule. Federal Register 76, No. 97 (May 19, 

2011) htro.V/ww.epa.gov/ttri/atw/lead^d/irl9mvl l.pdf Accessed July 24. 2014 

12. Yanca, C.A.; Barth, D.C ; Petterson, K.A.; Nakanishi, M.P.; Cooper, J.A.; Johnsen, B.E.; 

Lambert, R.H.; Bivins, D.G.; J. Air and Waste Manage. Assoc. 2006,56,1733-1742. 

13. Rigo, H.G.; Chandler A.J.; J. Air and WasteMange. Assoc. 1999, 49,399-411. 

14. American Society of Mechanical Engineers, Research Committee on Industrial and 

Municipal Waste. Reference Method Accuracy and Precision (ReMAP): Phase 1, 

Precision oj"Manual Stack Emission' Measurements; Report No. CRTD-60; American 

Society of Mechanical Engineers International; Washington, DC, 2001. 

15. U.S. Environmental Protection Agency. Evaluation of Two Methods for the Measurement 

of Mercury Emissions in Exhaust Gases from a Municipal Waste Combustor; EPA 450/4-

92-013. U.S. Government Printing Office: Washington, DC, 1991 

16. U.S. Environmental Protection Agency. Other Test Method 16, Specifications for X-ray 

Fluorescence Based Multi-Metals CEMS at Stationary 

Sources. http://w\w.epa.gov/tln/emc/preUm/otml6.pdf Accessed July_24,2014. 

17. U.S. Environmental Protection Agency Other Test Method 20. Quality Assurance 

Requirements for X-ray Fluorescence Based Multi-Metals CEMS at Stationary 

Sources. htrp://www.epagov/tta/em Accessed July 24, 2014. 

18. Microraatter Co. 4004 Westbrook Mall, Vancouver, B.C. V6T 2A3, Canada. 

19. U.S. Environmental Protection Agency. Compendium Method 10-3.3: Detennination of 

Metals in Ambient Particulate Matter Using X-ray Fluorescence (XRF) Spectroscopy. In 

Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air; 

EPA/625/R-96/010a. U.S. Government Printing Office: Washington, DC, 1999. 

20. U.S. Environmental Protection Agency. Method 30B. Determination of Total Vapor 

Phase Mercury Emissions From Coal-Fired Combustion Sources Using Carbon Sorbent 

Traps. In Code of Federal Regulations 40 CFR 60. U.S. Government Printing Office. 

Washington, DC, 

21. Cooper Envhonmental Services LLC. Feasibility of Monitoring Heavy Metal Emissions 

from a Coal Fired Hazardous Waste Incinerator Using a Multi-Metal Continuous 

13 

VES016808 
Emissions Monitor. EPA Contract ID EP-D-07-026. April 30, 2007. 

22. The Avagadro Group LLC , Continuous X-Ray Fluorescence Mercury Emissions 

Monitor, Unofficial Relative Accuracy Test Audit, April 28th 2009. 

KEYWORDS 

Multi-Metals CEMS, Hazardous Waste Incinerators, X-ray Fluorescence 
VES016810-016945.pdf 
US Army Corps 

of Engineers« 

Engineer Research and 

Development Center 

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 2005 

4mt 

CES 

public release; distribution is unlimited. 

VES016810 
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 Engineering 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-B091 

VES016811 
ABSTRACT: Army demilitarization incinerators will need to comply with the Hazardous Waste Combustor National Emission Standard for Hazardous Air Pollutants 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 type 

and quantity of emitted metals, so that compliance may be determined only through trial bum 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 E M 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 demonstrated at the 1236 Deactivation 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 XCE M has met the proposed Performance Specification 10 for multi-metal CEMs except for 

relative accuracy requirements for 4 of 9 metals. Its failures are attributed mostly to inadequacies 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, publication, or promotional purposes. 

Citation of trade names does not constitute an official endorsement or approval of the use of such commercial products. 

All product names and trademarks cited are the property of their respective owners. The findings ofthis report are not to be 

construed as an official Department of the Army position unless so designated by other authorized documents. 

DESTROY THIS REPORT WHEN IT IS NO LONGER NEEDED. DO NOT RETURN IT TO THE ORIGINATOR. 

VES016812 
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 Description of XCEM 5 

Extraction System 5 

Sampling and Analysis System 6 

Control System 7 

Execution of Field-Testing Activities 7 

Test Plan 8 

EPA Verification 9 

TEAD Interface 9 

Test Objectives 10 

Site Description 11 

Experimental Design 14 

Results 15 

XCEM Reported Concentrations 15 

Sampling and Response Time 19 

Zero and Calibration Drift. 19 

Correlation with Reference Method 20 

Response to Changes in Metal Concentration 25 

Relative Accuracy 25 

Precision 33 

Low-Level Metal Response • 35 

Bias 36 

Summary 37 

VES016813 
iv ERDC/CERL TR-05-9 

3 Transport and Calibration Improvements 39 

Transport Line Changes 39 

Recalibration 40 

Summary of Transport and Calibration Evaluations 40 

4 M29 Comparison Testing of XCEM 2002 42 

Results 42 

Method 29 Concentrations 42 

Predicted Stack Gas Concentrations 43 

XCEM Concentrations 47 

XCEM Calibration Evaluation Using A QuanX - XRF and ICP/MS 53 

Precision 53 

Discussion 54 

Regulated Elements Typically Found in the Feedstream 54 

Regulated Elements Not Typically Found in TEAD Emissions 58 

Nonregulated Metals 63 

Summary 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 Evaluations 106 

Appendix D: Mercury Calibration and Loss Discussion 2002 117 

Abbreviations and Acronyms 125 

Report Documentation Page 127 

VES016814 
ERDC/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 Control Screen for XCEM software interface 8 

4 XCEM housing and transport line, M29 sampling setup, stack, and ceramic 

baghouse at TEAD 10 

5 TEAD incinerator setup and sampling/spiking locations 13 

6 Spiking at base of stack during validation testing 15 

7 Palladium concentrations during M29 testing 21 

8 XCEM and M29 concentrations during TEAD verification testing 22 

9 Correlation between XCEM and M29 for elements spiked at two levels 24 

10 XCEM and M29 lead concentrations during runs 8-11 28 

11 Ratio of XCEM to M29 concentrations during validation testing 30 

12 Uncorrected XCEM As concentrations versus XCEM Pb concentrations 32 

13 Correlation between Sn and other APE-1236 metals with munitions burning 

and no spiking 46 

14 XCEM tin measurements during M29 testing 46 

15 XCEM versus M29 lead for validation tests 56 

16 Percent difference between M29 and the XCEM versus percent of Hg on 

M29 filter 60 

17 2004 CES metals monitor 67 

C1 Experimental design for atomization tests 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 later 121 

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

M29 filter 123 

VES016815 
vi ERDC/CERL TR-05-9 

Tables 

1 Army hazardous waste combustors 2 

2 Proposed PS-10 requirements 3 

3 XCEM test dates and associated TEAD incineration feedstream 9 

4 Typical operating parameters for the APE-1236 deactivation furnace 12 

5 TEAD metal emission limits during verification testing 12 

6 TEAD incinerator metal emission limits and spiking levels 14 

7 Final reported CEM concentrations for M29 testing 17 

8 Upscale and zero concentrations during validation testing 20 

9 Correlation between the XCEM and M29 25 

10 XCEM measured, M29 measured, and MSE-predicted metal concentrations 

during TEAD validation testing 26 

11 Relative accuracy and correlations 27 

12 Percent differences between M29 sample trains 34 

13 XCEM and M29 precision 35 

14 Method 301 bias and correction factor comparison 37 

15 Summary of XCEM performance relative to proposed PS-10 requirements 38 

16 M29 concentrations 43 

17 APE-1236 stack flow rates during M29 testing 44 

18 APE-1236 stack concentrations 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 precision during validation testing 53 

23 TEAD emission limits for regulated elements 54 

24 Summary of Pb concentration data and ratios during M29 testing 55 

25 Summary of Cd concentration data and ratios during M29 testing 57 

26 Summary of Cr concentration data and ratios during M29 testing 58 

27 Summary of As concentration data and ratios during M29 testing 59 

28 Summary of Hg concentration data and ratios during M29 testing 60 

29 Summary of Sb concentration data and ratios during M29 testing 61 

30 Summary of Ni concentration data and ratios during M29 testing 62 

31 Summary of Ba concentration data during M29 testing 62 

32 Summary of Zn concentration data and ratios during M29 testing 63 

33 Summary of 2002 M29/XCEM comparison results 64 

VES016816 
ERDC/CERL TR-05-9 vii 

B1 Original XCEM reported concentrations uncorrected for calibration and dryer 

changes 103 

B2 Results of dryer tests 105 

C1 Flow rates and concentrations used to calculate atomization concentrations 109 

C2 Atomization vs. XCEM concentrations 109 

C3 Total capture mass vs. atomization mass 111 

C4 Lead normalized atomization mass vs. total capture 111 

C5 Method 17 vs. XCEM at TEAD 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 2001 and 2002 tests 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 

Systeme International d'Unites ("International System of Measurement"), commonly known as the "metric system." 

VES016817 
viii ERDC/CERL TR-05-9 

Preface 

This study was conducted for Headquarters, Department of the Army under Program Element 063728A, "Environmental Technology Demonstration"; Project 

002, "Environmental Comphance Technology"; Work Unit CNE-B091, "Hazardous Air Pollutants Technology Demonstrations." 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), Construction Engineering Research Laboratory 

(CERL). The CERL Principal Investigator was Dr. K. James Hay. Part of this 

work was done by Cooper Environmental Services under DACA42-02-P-0072 and 

DACA42-01-C-0022; MSE Technology Applications, Inc. under GS-10F-0212K; 

and the U.S. Army Center for Health Promotion 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 Technical 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 Engineers. The Commander and Executive 

Director of ERDC is COL James Rowan, and the Director of ERDC is Dr. James 

R. Houston. 

VES016818 
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 National 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 incinerator operations is limited knowledge of 

the types and quantities of emitted metals. Comphance 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 then 

issued are based on these worst-case burns and impose limitations on the demilitarization facilities. A continuous emission monitor (CEM) for metals would provide the emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn strategies 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 limitations such as its complexity, high 

initial costs, and high operating costs. The U.S. Army Engineer Research and 

Development Center, Construction Engineering Research Laboratory (ERDC/ 

CERL) decided to pursue the development of the X-ray fluorescence (XRF)-based 

continuous emission monitor (XCEM) because it had the potential to be a rehable and accurate CEM without these hmitations. 

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 filter that collects metals in the particuVES016819 
2 ERDC/CERL TR-05-9 

late and vapor phases. Following sampling, 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 Environmental Services (CES) further developed this method into an on-line system that was tested under the 

ERDC/CERL Waste Minimization and Pollution 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. It 

was 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 

McAlesterAAP 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 Plant 

VES016820 
ERDC/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 Army operations and expectations, such as 

user friendliness and affordability. That work is described in a precedent-setting 

report (Hay et al. 2005). The specific objective of this work was to demonstrate 

the XCEM at an Army installation. The 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 and reporting of the sample analysis 

shall 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 averaging 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 calibration may not drift or deviate from the reference 

value of the calibration standard used for each metal by more than 5 percent of the emission standard for each metal. 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 metal. 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 greater than 20 percent of the mean value 

of the RM test data in terms of units of emission standard for each metal, or 

10 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 purposes, and the RA must be determined 

at three concentration levels for one metal (zero can be one level). 

Source: EPA 1996. 

VES016821 
4 ERDC/CERL TR-05-9 

Approach 

As a result of encouraging development 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 successful; 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 Preventive Medicine (CHPPM) performed the 

M29 stack sampling activities described in this report. 

Mode of Technology Transfer 

This technology was developed and demonstrated through the ERDC/CERL HAP 

Program, which uses 6.3 advanced development and field-testing funds. The 

HAP Program is part of the Army Environmental 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 accompany the XCEM for field training and reference (CES 2001a, 2001b). This technology is ready for transfer to Army facihties, 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 accessible through the World Wide Web at: 

http://www.cecer.army.mil 

VES016822 
ERDC/CERL TR-05-9 5 

2 Field Testing 2001 

The XCEM underwent M29 comparison testing at the TEAD 1236 deactivation 

furnace in May 2001. This chapter presents a brief description ofthe XCEM, the 

testing activities, and the results ofthe 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. Following 

collection, 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 XCEM components are: an extraction system, sampling and analysis system, and control system. 

Extraction System 

The XCEM extraction system collects a representative stack gas sample from the 

smokestack and transports the sample to the filter. The system includes a sample probe and insulated sample line. The 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 temperature 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 that 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 concentration on a filter. The remaining 99 

percent 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. 

VES016823 
6 ERDC/CERL TR-G5-9 

Figure 1. XCEM stilling chamber (vertical 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 nitration, the extracted stack gas is transported to the XCE M 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 move the tape from the sampling to an 

analysis position. Sampling and analysis occur simultaneously, resulting in a 

continuous monitoring system that reports metal concentration measurements 

every 10 to 20 minutes. 

VES016824 
ERDCfCERL TR-05-9 7 

Figure 2. XCEM chassis. 

Metal mass on the filter is determined using a modified ThermoNoran QuanX 

energy dispersive XR F analyzer. The QuanX is capable of simultaneously measuring 19 elements and a palladium (Pd) quality assurance (QA) standard. Al -

though 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 XR F is 

nondestructive, the retentate on the filter tape can be reanalyzed if the end-user 

requires additional data. 

Control System 

The XCE M is controlled by a personal computer using a custom WonderWare" 

(Progressive Software Solutions, Inc., Albany, OR) software interface (Figure 3). 

A l l day-to-day functions of the XCE M are automated, including flow and temperature control, concentration determination, and Q A 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 XCE M 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 increase in reported metal concentrations. 

A l l calibration adjustments were completed prior to receiving M29 results. 

VES016825 
8 ERDC/CERL TR-05-9 

XCEM 

sctccnLWocfic-ci Logon ^ Admin p: Reports Trends 3 Sciccne ^Alarms' 6fcS{0i . 10:35:» 

Set qft Ranges 11 set qfl Parameters j | SetanaloqRanijes j | Loop Tuning 

Figure 3. New Component Control Screen for XCEM software interface. 

Following installation, preliminary onsite training was conducted for TEA D personnel. Onsite training consisted of an introduction to the XCE M and its capabilities. Although the XCE M has been designed for ease of use, it is recommended that additional training be provided to ensure successful integration of 

the XCE M into incinerator daily operations. 

Test Plan 

A test plan was developed to verify capabilities of the XCE M to measure metals 

under typical incinerator conditions (Appendix A). The test plan outlined methodology for comparison testing between EPA M29 and the XCE M at the TEA D 

incinerator. Specifically, the test plan called for at least 12 EP A 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 each test but was not spiked because it is 

found in quantifiable concentrations in TEA D incinerator emissions under normal operating conditions. The actual dates of the test, associated M29 run numbers, and TEA D incineration feedstream are shown in Table 3. 

VES016826 
ERDC/CERL TR-05-9 9 

In general, the test plan (Appendix A) was 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 decided to run M29 testing with no ammunition being incinerated until repairs could 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 associated 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. ETVs charter is to provide objective and quality assured 

performance data on environmental technologies, so that users, developers, regulators, and consultants have an independent and credible assessment of an instrument's performance. Battelle Memorial Institute, headquartered in Columbus, OH, is EPA's partner for the ETV Advanced Monitoring Systems (AMS) 

Center. The scope of the AMS Center covers verification of monitoring methods 

for contaminants and natural species in air, water, and soil. For these tests, 

ETV representatives reviewed the test plan and monitored testing procedures. 

They also conducted an onsite audit of the Army laboratory that analyzed the 

M29 samples. CES provided ET V representatives with the XCEM metal concentrations for each test run. The M29 test results were submitted independently to 

the 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 manufactured by Anderson Instruments, Inc. 

VES016827 
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 XCE M and M29 probes were located 

approximately 27 feet above the base of the exhaust stack. The nearest flow 

disturbances were 9.8 duct diameters upstream (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 approximately 35 ft of 1.5-in. diameter stainless 

steel tubing that extended from the probe to the XCE M 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 XCE M under field conditions. EPA's draft performance specification document PS-10 (EPA 1996) is a proposed description of how to assess 

the acceptability of a multi-metal CE M upon installation and thereafter. 

Figure 4. XCEM housing and transport line, M29 

sampling setup, stack, and ceramic baghouse at TEAD. 

VES016828 
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 examined 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 verification test to durability for routine longterm use. This test evaluated the performance of a new XCEM over a relatively 

short 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 mechanical problems during the test; it 

completed more than 150 test runs during the week without any downtime. 

Site Description 

Verification testing took place at TEAD building 1320 deactivation incinerator 

APE-1236. The TEAD incinerator, which runs on diesel fuel, is designed to incinerate decommissioned munitions. Typical operating parameters for the incinerator are shown in Table 4. The TEAD incinerator is classified as a dry stack 

VES016829 
12 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 regulated 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 was 

tested for its measurement capabilities of the five elements found in the feedstream as well as As, Hg, Ni, and a nonregulated metal, Zn. These elements 

were selected in order to challenge the XCEM over a large range of analysis conditions and elemental concentrations. 

For the verification test, metals in the TEAD incinerator stack gas were regulated under a Temporary Authorization permit (Table 5). Of the 12 regulated 

metals, 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 AP (in. H2O) 4 

Baghouse Inlet Temperature (°F) 860 

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

Kiln Feed End Temperature (°F) 375 

Kiln Burner End Temperature (°F) 1000 

0 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 IVlercury 14 

Barium 2400 Nickel 930 

Beryllium 0.20 Selenium 180 

Cadmium 0.26 Silver 140 

Chromium 0.04 Thallium 14 

VES016830 
ERDC/CERL TR-05-9 13 

Dischaige 

u 

i 

Cyclone 

o 

Slack. 

Fan 

FeedTop view of TEAD 

Incinerator Setup 

Ceramic 

Baghouse 

Stack 

Front view of 

TEAD Stack 

during Sampling 

Fan Air flow 

XCEM 

Figure 5. TEAD incinerator setup and sampling/spiking locations. 

VES016831 
14 ERDC/CERL TR-05-9 

Experimental Design 

Both the kiln and afterburner were fired with diesel fuel for all 13 runs. During 

runs 1 and 2, 50-caliber bullets were incinerated. The XCEM observed unexpected high Pb concentrations during these runs, however, which led to a decision not to incinerate additional ammunition during the test until repairs to a 

bypass valve could be made. For this reason, no ammunition was burned during 

runs 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 three atomizers to inject solutions containing the metals directly into the stack (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 of 

the 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. 

Elements 

Emission Limits1 Spiking Level1 

Elements 

g/hr - Mg/dscm 

Elements - ug/dscm 

g/hr - Mg/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 pg/dscm assumes a stack flow rate of about 4500 dscm/hr 

NR: Not regulated NS: Not spiked 

VES016832 
ERDC/CERL TR-05-9 15 

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

Three separate solutions were prepared for spike injection. The first solution 

contained arsenic oxide (As 2 05 ), Cd metal, and chromium oxide (Cr03 ) dissolved 

in a dilute nitric acid solution. The second solution contained mercury nitrate 

(Hg(NO: J) 2 ), nickel nitrate (Ni(N03 ) 2 ), and zinc oxide (ZnO) dissolved in a dilute 

nitric acid. The final solution contained antimony tartrate (K,,(C,H2 0BSb)„) and 

barium nitrate (Ba(N03 ) 2 ) dissolved i n 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 CHPP M Air Quality Surveillance Program. The M29 trains 

sampled for 2 hr while XCE M 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 Services (DLS) conducted laboratory analysis of the sampling trains. 

Results 

XCEM Reported Concentrations 

Time-weighted average concentrations 

Average XCE M concentrations during the time of one M29 test run were calculated using Equation 1. 

VES016833 
16 ERDC/CERL TR-05-9 

where: 

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

C^ = XCEM reported concentration for element i during time interval j 

n = number of XCEM measurements during test run 

t = number of minutes XCEM measured element i's concentration during 

time interval j coinciding with M29 sampling. 

i = M29 sampling period. 

Data corrections 

Following M29 testing, but prior to receiving 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 was determined that a spectral interference 

between Pb and As was affecting As concentrations. 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 are 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. 

VES016834 
ERDC/CERL TR-05-9 17 

Table 7. Final reported CEM concentrations (pg/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 

Runl 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 I 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 

TimeW eighted Avg. 120.0 21:24.7 22.6 187 26.9 23 194 462 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 

TimeW eighted 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 5/14/0! 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 

TimeW eighted 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 

Run5 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 

TimeW eighted 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 

Rim 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 

TimeW eighted 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 40 383 367 

VES016835 
18 ERDC/CERL TR-05-9 

Table 7 (Cont'd). Final reported XCEM concentrations (pg/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 

Run 8 

Run 8 

Run 8 

Run 8 

Run 8 

Run 8 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

8:58 

9:18 

9:39 

10:00 

10:20 

10:41 

11:01 

9:18 

9:39 

10:00 

10:20 

10:41 

11:01 

11:22 

725 

726 

727 

728 

729 

730 

731 

15.3 

20.6 

20.6 

20.6 

20.4 

20.4 

2.3 

20:24.0 

20:33.0 

20:33.0 

20.33.0 

20:26.0 

20:24.0 

20:30.0 

17.6 

20.3 

16.5 

18.0 

12.5 

18.7 

17.1 

111 

139 

145 

156 

176 

152 

162 

32.5 

31.8 

32.3 

29.4 

36.3 

32.7 

32.4 

5.2 

6.0 

5.4 

5.3 

5.1 

5.7 

5.7 

17 

20 

22 

28 

33 

36 

44 

193 

220 

222 

197 

204 

216 

226 

290 

242 

231 

199 

202 

226 

214 

141 

134 

125 

136 

135 

134 

141 

134 

150 

151 

148 

141 

150 

150 

23.8 

24.2 

25.6 

24.6 

24.4 

24.3 

23.9 

TimeW eighted Avg. 120.0 20:29.0 17.3 148 32.5 5.4 27 210 229 134 146 

Run 9 

Run 9 

Run 9 

Run 9 

Run 9 

Run 9 

Run9 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

11:42 

12:03 

12:23 

12:44 

13:04 

13:25 

13:45 

12:03 

12:23 

12:44 

13:04 

13:25 

13:45 

14:05 

733 

734 

735 

736 

737 

738 

739 

7.1 

20.4 

20.4 

20.3 

20.4 

20.3 

11.1 

20:28.0 

20:26.0 

20:21.0 

20:18.0 

20:24.0 

20:19.0 

20:23.0 

21.1 

14.8 

18.8 

16.6 

17.0 

18.6 

16.0 

183 

170 

154 

206 

143 

138 

151 

33.1 

32.7 

30.7 

35.4 

31.1 

28.8 

29.1 

4.5 

5.6 

5.3 

6.5 

5.2 

5.2 

5.2 

49 

50 

49 

56 

54 

59 

60 

210 

201 

204 

223 

215 

200 

228 

190 

170 

162 

191 

151 

153 

155 

136 

139 

142 

154 

145 

145 

148 

147 

142 

146 

152 

145 

144 

143 

25.0 

24.0 

24.1 

24.9 

24.7 

24.5 

25.1 

TimeW eighted Avg 120.0 20:22.7 17.3 162 31.6 5.5 54 210 166 145 146 

Run 10 

Run 10 

Run 10 

Run 10 

Run 10 

Run 10 

Run 10 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

14:46 

15:07 

15:27 

15:48 

16:08 

16:29 

16:49 

15:07 

15:27 

15:48 

16:08 

16:28 

16:49 

17:09 

742 

743 

744 

745 

746 

747 

748 

17.2 

20.4 

20.4 

20.3 

20.4 

20.3 

1.2 

20:24.0 

20:21.0 

20:23.0 

20:16.0 

20:21.0 

20:20.0 

20:20.0 

19.2 

22.3 

17.0 

17.1 

17.5 

18.3 

12.7 

156 

187 

141 

192 

161 

167 

139 

34.7 

37.0 

32.5 

31.6 

36.2 

30.9 

29.9 

6.0 

5.4 

5.4 

5.4 

5.5 

5.6 

5.4 

91 

89 

82 

91 

95 

95 

109 

210 

216 

192 

208 

208 

203 

186 

146 

261 

115 

134 

108 

95 

110 

148 

154 

134 

146 

163 

140 

152 

146 

151 

133 

149 

145 

137 

137 

25.2 

25.6 

24.9 

25.6 

24.2 

24.7 

24.5 

TimeW eighted Avg 120.0 20:20.7 18.S 167 33.8 5.5 91 206 143 147 143 

Run 11 

Run 11 

Run 11 

Run 11 

Run 11 

Run 11 

Run 11 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

5/16/01 

17:32 

17:52 

18:12 

18:33 

18:53 

19:13 

19:34 

17:52 

18:12 

18:33 

18:53 

19:13 

19:34 

19:54 

750 

751 

752 

753 

754 

755 

756 

6.3 

20.3 

20.3 

20.3 

20.2 

20.2 

12.3 

20:21.0 

20:18.0 

20:20.0 

20:18.0 

20:12.0 

20:12.0 

20:17.0 

15.7 

15.8 

15.5 

16.4 

17.3 

17.2 

15.0 

178 

147 

170 

178 

152 

167 

152 

31.3 

30.2 

29.3 

30.2 

26.4 

32.8 

33.2 

6.0 

5.2 

5.3 

5.4 

5.8 

5.5 

4.6 

101 

96 

95 

95 

96 

92 

84 

211 

209 

204 

192 

191 

201 

212 

108 

102 

104 

91 

89 

89 

96 

150 

147 

141 

147 

147 

143 

147 

143 

141 

145 

138 

141 

146 

145 

25.0 

25.5 

24.6 

25.6 

24.8 

24.9 

24.0 

TimeW eighted Avg 120.0 20:16.9 16.2 163 30.2 5.4 94 201 96 145 143 

Run 12 

Run 12 

Run 12 

Run 12 

Run 12 

Run 12 

Run 12 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

11:12 

11:32 

11:52 

12:12 

12:32 

12:53 

13:13 

11:32 

11:52 

12:12 

12:32 

12:53 

13:13 

13:33 

770 

771 

772 

773 

774 

775 

776 

13.0 

20.1 

20.2 

20.3 

20.2 

20.2 

6.0 

20:01.0 

20:08.0 

20:14.0 

20:16.0 

20:12.0 

20:12.0 

20:07.0 

17.8 

17.2 

20.5 

16.7 

18.4 

12.3 

14.1 

174 

195 

174 

226 

153 

177 

150 

26.5 

23.2 

30.5 

24.4 

31.7 

28.0 

28.2 

4.1 

4.2 

43 

4.0 

4.8 

4.5 

4.1 

24 

35 

55 

73 

79 

83 

86 

224 

238 

222 

221 

206 

204 

191 

170 

232 

273 

204 

161 

138 

140 

137 

159 

165 

158 

158 

155 

155 

133 

146 

157 

161 

151 

143 

151 

24.6 

25.9 

25.3 

25.4 

24.1 

24.4 

26.0 

Time W eighted Avg. 120.0 20:10.0 17.0 182 27.5 43 62 218 195 156 150 

RunB 

RunB 

RunB 

Run 13 

RunB 

RunB 

RunB 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

5/17/01 

14:14 

14:34 

14:54 

15:14 

15:35 

15:55 

16:15 

14:34 

14:54 

15:14 

15:34 

15:55 

16:15 

16:35 

779 

780 

781 

782 

783 

784 

785 

6.1 

20.2 

20.2 

20.2 

20.2 

20.0 

13.1 

20:15.0 

20:10.0 

20:09.0 

20:10.0 

20:12.0 

20:02.0 

19:57.0 

19.1 

19.9 

17.4 

20.3 

21.3 

19.2 

8.3 

162 

210 

159 

140 

196 

165 

94 

35.9 

33.9 

36.1 

33.8 

40.7 

39.1 

18.7 

5.1 

5.3 

6.1 

5.8 

5.9 

6.0 

4.0 

80 

80 

82 

83 

84 

74 

46 

201 

213 

235 

212 

173 

170 

70 

119 

122 

117 

112 

129 

121 

85 

171 

170 

168 

170 

169 

166 

77 

146 

146 

149 

150 

117 

82 

22 

24.0 

25.3 

25.0 

25.1 

24.4 

25.1 

25.2 

Time Weighted Avg. 120.0 20:07.9 18.4 165 34.7 5.6 77 186 116 159 118 

VES016836 
ERDC/CERL TR-05-9 19 

Sampling and Response Time 

The XCEM met PS-10 sampling and response time criteria for a batch CEM. 

These criteria are that (1) the sampling time be no longer than one-third ofthe 

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 verification testing. The XCEM sampled continuously except for a 4-second period between 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 ofthe filter tape. Following the 

zero check, a plunger is extended into the 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 

(ug/spot). Equivalent zero and upscale 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 XCE M detection limits for Cr, Cd, Hg, and Pb 

are 0.75, 3.0, 1.0, and 1.0 pg/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 precision 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. 

VES016837 
20 ERDC/CERL TR-05-9 

Table 8. Upscale and zero concentrations during validation testing. 

Date 

Upscale Values (pg) Zero Values (ug)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 

Date 

Equiv. Upscale Values (ug/dscm)2 Equiv. Zero Values (pg/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. Analysis of the Pd concentration trend in 

Figure 7 indicates that no significant drift 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. 

VES016838 
ERDC/CERL TR-05-9 21 

Palladium 

30 | - - - 1 

29 | j 

28 j 

~>

 2 7

 i 

2£ 25 -

 mm m

 miMwyiii— I I mil IIIII 'ivTimnimf nihility— M fiiiptr»rT»»»Mmy^uiiiiL»iM mmm^^^^ ||if " ninm 

i

 2 5

 ! .-t&6 

23 j 

22 •! 

21 5/14/01 5/15/01 5/16/01 5/17/01 | 

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

— — 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 XCE M Hg concentrations were consistently lower 

than M29, but by a variable amount. During the early runs for each day, the 

XCE M reported low concentrations relative to M29. As the day progressed, the 

XCE M Hg concentration would gradually increase until it approximated M29 

reported concentrations. This same increasing Hg concentration trend was observed on each of the four test days (Figure 8). 

It is believed that the H g 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 XCE M samples were. The TEA D incinerator 

was shut down each evening and started in the morning 1 hour before validation 

testing. 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 temperatures (Hall et al. 1990; Wang et al. 

1983). In the laboratory, the XCE M was tested with oxidized Hg and met with 

good success (Hay et al. 2005). The laboratory tests, however, were conducted at 

elevated line temperatures. It is recommended that a shrouded probe and heattraced tubing be used to overcome potential H g transport problems. 

VES016839 
22 ERDC/CERL TR-05-9 

Cadmium 

45 • - -

41) • - - V 

s ; „ I • * *** * * « * * . 

i is i 

U 10 l ---- - - ^ — - * 

5 1 • 

o I • • A . 

7:00 [5:0(1 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

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

Chromium 

8 -- - : - -

if l TV^ r T^j^^ 

i ~Di ^ eseass; «s»w * * * • 

; j 3 • **> • 

'

 1 * " ? » 

0 , * , , , , 

7:00 IS:W) 23:00 7:0(1 15:00 23:011 7:0(1 15:00 23:00 7(10 1 vOO 

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

Nickel 

600 -

„ 500 * , 

j l 300 * * 

0 - » •- * — - -----

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:01) 23:0(1 7:00 15:00 

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

Lead 

4,000 ----- - -

3,500 « 

_ wjmr 

£ 3.000 • 

| 2,500 * 

J 2,000 

H I 500 

(j 1,000 -- - - ----- - - -

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

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

Figure 8. XCEM and M29 concentrations during TEAD verification testing. 

VES016840 
ERDC/CERL TR-05-9 23 

Lead (Runs 3-13) 

— 400 -

I 

^ 300 j 

5 * 

. J 200 : 

' c 

•° » 

o • • 

; • 

.150 

300 — 

I 250 - * 

i f 200 - ^ 

-»• ~ 7* •> 

§ 100 

Barium 

800 

700 

? 600 

u 

-o 500 

"ofc 400 

300 

o 

U 200 

100 

0 

Antimony 

Zinc 

600 

500 

£ 

in 400 

3. 300 

£ 

c 200 

c 

10D 

0 

15:1)0 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

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

-• • - — —- • --*\ 

50 - - - -- --- j 

* • • i 

<)••.* • i 

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

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

• • • 

t • \ • m • 

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

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

• , • - , - m — — ,-+ — 

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 

5/14/01 5/15/01 5/16/01 5/17/0! 

Figure 8 (Cont'd). XCEM and M29 concentrations during TEAD verification testing. 

VES016841 
24 ERDC/CERL TR-05-9 

)5(l 

31)0 • 

? 251)

 ; 

"Si 200 : • 

a. 

150 i • 

u 

e 

o 

ion • 

U 

50 i • 

0 J • 

15:00 

5/14/01 

Mercury 

7:00 15:00 23:00 

5/15/01 

7:00 15:01) 23:00 

5/16/01 

/ ; 

7:00 15:00 

5/17/01 

% 20 

•a 

1 '5 

i io 

o 

U 

Palladium 

ii in 

7:01) 15:00 

5/14/01 

7:00 ! 5:00 

5/15/01 

7:00 15:00 

5/16/01 

7:00 15:00 

5/17/01 

Figure 8 (Cont'd). XCEM and M29 concentrations during TEAD verification testing. 

Antimony M29 vs. XCE M 

soil 

601) 

400 

200 

100 200 300 400 

XCE M 

Nickel M29 vs. XCE M 

Mercury M29 vs. XCE M 

Zinc M29 vs. XCK M 

[>00 

500 

400 

300 

200 

XCE M 

Lead M29 vs. XCE M 

500 i.DOO 1,500 2.0(H) 2.500 3.000 

XCE M 

Lead Minus High Runs M29 vs. XCK M 

Figure 9. Correlation between XCEM and M29 for elements spiked at two levels. 

VES016842 
ERDC/CERL TR-05-9 25 

Table 9. Correlation between the XCEM and M29. 

Elem. 

Correlation (R2) 

(13 Runs) 

Correlation (R2) 

(11 Runs)1 

Spike Ratio2 

Elem. High Runs: Low Runs 

Correlation (R2) 

(13 Runs) 

Correlation (R2) 

(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 0.9682 2.52 2.56 2.51 

Zn 0.9766 0.9738 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 two 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 significant 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, indicates 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 concentrations, and MSE-predicted spike 

concentrations. The RA of the XCEM with respect to the M29 was determined 

using PS-10 criteria. Of the 13 M29 runs, 11 were used to calculate RA and average concentrations. During runs 1 and 2, the incinerator experienced problems with a faulty bypass valve, which led to extremely high Pb concentrations 

(1,000 to 3,000 pg/dscm). Although the XCEM tracked the problem, and was in 

fact used to identify and rectify the problem, it was not felt that these conditions 

represented the typical operating conditions ofthe plant. For this reason, runs 1 

and 2 were not used to calculate RA and average concentrations. 

Since 11 valid reference method test runs were completed, the RA procedure 

stated in PS-10 allowed for omission of up to two additional runs from the RA 

calculation. 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. 

VES016843 
Table 10. XCEM measured, M29 measured, and MSE-predicted metal concentrations (pg/dscm) during TEAD validation testing. 

Run 

As Ba Cd Cr Hg Ni Pb Sb Zn 

No. XC M29 MSE xc M29 MSE XC M29 MSE XC M29 MSE XC M29 MSE XC M29 MSE XC M29 MSE XC M29 MSE XC M29 MSE 

1 23 11 12 187 256 230 27 30 32 2 4 3 194 292 285 462 385 474 1,240 1,618 NS 372 565 546 333 467 479 

2 16 11 12 224 298 223 27 38 31 2 4 3 229 276 281 410 401 466 2,690 3,242 NS 375 629 530 335 471 472 

3 13 9 11 154 201 206 25 30 30 3 4 3 260 286 281 406 377 469 73 84 NS 351 535 516 334 418 469 

4 16 12 14 161 255 200 30 34 36 5 7 5 76 318 269 422 452 448 62 64 NS 361 643 499 340 495 448 

5 16 12 14 175 241 199 34 35 35 6 6 5 110 318 267 438 418 444 47 46 NS 381 627 497 354 454 444 

6 14 12 14 170 271 198 33 35 35 6 6 5 152 319 270 443 473 450 41 45 NS 384 694 495 363 512 450 

7 17 12 14 174 279 195 32 34 36 6 6 5 132 318 270 461 486 450 40 52 NS 383 712 489 367 540 450 

8 17 12 14 148 262 200 32 35 36 5 7 5 27 104 92 210 206 184 229 198 NS 134 272 200 146 219 184 

9 17 11.37 14.33 162 223 198 32 35 36 5 7 5 54 105 90 210 178 179 166 77 NS 145 237 198 146 193 179 

10 18 11.42 14.16 167 214 197 34 34 35 6 6 5 91 101 88 206 161 175 143 84 NS 147 22! 197 143 175 175 

11 16 11.43 14.16 163 233 197 30 33 35 5 6 5 94 101 87 201 186 175 96 54 NS 145 256 197 143 201 175 

12 17 9 11 182 214 200 27 28 26 4 5 4 62 108 88 218 161 177 195 187 NS 156 236 200 150 181 177 

13 18 12 14 165 248 195 35 36 36 6 6 5 77 84 82 186 156 163 116 109 NS 159 286 195 118 173 163 

Avg. 

(Runs 16 11 14 166 240 199 31 33 34 5 6 5 103 197 171 309 296 301 110 91 250 429 335 237 324 301 

3-13) 

85 

XC: XCEM 

NS: Not spiked 

VES016844 
ERDC/CERL TR-05-9 27 

Table 11. Relative accuracy and correlations. 

Elem. 

Avg. M29 

Cone, 

(ug/dscm) 

Avg. XC 

Cone, 

(ug/dscm) 

Avg. MSE 

predicted 

Cone, 

(ug/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. XCis 

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 concentrations for these three metals were 31, 

5.2, and 309 pg/dscm, respectively, while the M29 average concentrations were 

33, 6.0, and 354 pg/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 significantly 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 concentration when the concentration is in 

fact below the detection limit. In most cases, 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. 

VES016845 
28 ERDC/CERL TR-05-9 

Lead 

The average reported XCE M Pb concentration was 110 pg/dscm for runs 3 

through 13, while the average M29 concentration was 91 pg/dscm. In general, 

the XCE M and M29 concentrations were i n good agreement. On 16 May, however, both the XCE M and M29 methods reported higher Pb concentration at the 

start of the day than was observed on 15 May. The XCE M reported a consistent 

gradual decline in concentrations throughout the day while M29 showed a more 

rapid decrease in concentration (Figure 10). Although the average XCE M 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 R A of 

22 percent for the XCE M Pb concentrations. 

It is not known why the XCE M and M29 differed on 16 May. The XCE M was 

able to rapidly transition from much higher 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/M2 9 

comparisons indicate that the XCE M 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. The XCE M has historically measured Pb 

accurately with RAs below 20 percent during the MSE-T A test (Bryson 2000) and 

the laboratory test in 2000 (Hay et al. 2005). 

500 

^

 45 0

 • * XCEM - P b 

| 400 - • M29-Pb 

I 350 • 

I 250 • 

e 

o 

U 

* •• • 

200 - •••»•• • # * 

150

 Run 8

 * • 

ioo 

50 • Ru „ 9 Run , 0 •••••• • | ; 

7:12 9:36 12:00 14:24 16:48 19:12 21:36! 

Figure 10. XCEM and M29 lead concentrations during runs 8-11. 

VES016846 
ERDC/CERL TR-05-9 29 

Barium and antimony 

Barium and antimony were spiked in the same solution and exhibited similar 

behavior during M29 testing. For both metals, the average XCEM concentrations were significantly lower than the M29 reported concentration (30 percent 

lower for Ba and 40 percent 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 difference 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 R2 value of 0.96 for their correlation plot (in Figure 9). 

The average M29 reported concentrations for Ba and Sb were 240 and 429 pg/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 predicted concentrations are believed to 

be due to particulate loss in the unheated XCEM transport line and calibration 

errors. 

VES016847 
30 ERDC/CERL TR-05-9 

2.0 

iii. o 

As 

• • 

• 

• • 

7 9 

Run No. 

1.0 

0.8 

B 

0.6 

a 

1 0.4 

1 e 0.2 

0.0 

Ba 

11 13 

1.2 

g 1.0 

5 0.8 

| 0-6 

I 0.4 

| 0.2 

0.0 

Cd 

7 9 

Run No. 

Cr 

• • • • • 

_ * * 

7 9 

Run No. 

11 13 

1.0 

g O.g 

a 

« 0.6 

I 0.4 

S 

6 0.2 

z 

0.0 

Hg 

7 9 

Run No. 

11 13 

Ni 

1 0.6 

1 0.4 

11 13 

1.0 

I °-8 

« 0.6 

I 0.4 

S 

S 0.2 

Z 

0.0 

Sb 

• • 

• • 

7 9 11 13 

Run No. 

Zn 

• • 

Run No. 

Pb 

• 

• • 

• < 

• • 

11 13 

Figure 11. Ratio of XCEM to M29 concentrations during validation testing. 

11 13 

VES016848 
ERDC/CERL TR-05-9 31 

Zinc 

Like Ba and Sb, the XCEM Zn concentrations were consistently lower than the 

M29 concentrations by about 30 percent. XCEM Zn concentrations were highly 

correlated with M29 (Figure 9) with an R2 value of 0.98. Zinc was spiked at a 

high concentration level for runs 1 through 7 and a 2.57 fold lower level for runs 

8 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 slightly higher than M29 Ni concentrations. 

Mercury, as discussed earlier, had potential transport problems to the XCEM 

under cooler conditions but was approximately 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 the 

NIST 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 incorrect. 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 rate, the observed correlation was determined to be due to an XRF spectral interference. Arsenic concentrations are established using a Ka line, which is overlapped 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. 

VES016849 
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 ofthe Pb concentration 

was being added to the measured As concentration. CES adjusted the As numbers accordingly prior to receiving 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 greatest deviations occurring during high 

Pb runs. Overall, the average final reported XCEM concentration was 16.3 

pg/dscm while the average M29 concentration was 11.3 pg/dscm. 

Since the XCEM saves each XRF spectrum, it was possible to review individual 

spectra and adjust for the As/Pb interference using a second spectral resolution 

approach. This task was completed after receiving the M29 data for runs 8 

through 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 spectral 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 interference. 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). 

200 

XCEM Lead Cone. (ug/mJ) 

Figure 12. Uncorrected XCEM As concentrations versus XCEM Pb concentrations. 

VES016850 
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 XCE M reported low Hg concentrations relative to 

M29. As the day progressed, the XCEM concentration would gradually increase 

until it approximated M29 reported concentrations. The pattern suggests that 

the transport line from the stack to the XCEM needed to be heated to a higher 

temperature 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 half 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 the 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 variabihty, 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 sample 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 the first day of testing, 14 May, to ensure 

spiked emissions were within the site permit limitations. On 17 May, stack conditions were not stable following stack repairs. However, MSE-TA and TEAD 

reported 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. 

VES016851 
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 average 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 pg, which gives a precision of about 2.5 percent. Palladium 

concentrations reflect XRF precision, but 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 8 2 7 6 7 7 6 

i Average percent difference is determined by averaging the absolute value of the difference between sample 

trains. 

VES016852 
ERDC/CERL TR-05-9 35 

Table 13. XCEM and M29 precision. 

IT lam M29 Avg. M29 Cone. M29% Avg. XC Cone. X C % RSD 

iLicni. Runs (Ug/dscm) RSD (ug/dscm) (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 determined 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 levels 

under the site-based RCRA hmitations. Both elements were spiked as particulates by MSE-TA at low concentrations with typical Cr stack concentrations in 

the 5 pg/dscm range and As in the 14 pg/dscm range. 

The XCEM accurately measured Cr relative to M29 with an RA of 19 percent. 

The average XCEM Cr concentration was 5.2 ± 0.9 pg/m3 while the M29 average 

was 6.0 ± 0.8 pg/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 pg/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 methods demonstrates the capability of the 

XCEM 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 concentrations were routinely higher than 

the M29 concentrations. 

VES016853 
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 two sampling trains is significant at the 

80-percent confidence level. The t-statistic is calculated by finding the standard 

deviation ofthe differences between the two sampling trains. 

dj = the difference between the two sample train values 

d„ = mean of the d. values 

n = number of paired samples 

Using the standard deviation determined in Equation 4, the t-statistic is then 

calculated as follows: 

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 slightly 

higher 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 relatively small and no consistent differences 

between 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. 

[Eq4] 

where: 

[Eq5] 

VES016854 
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 correlation, it is important to note that the 

XCEM correction factors are outside of the 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 

RAwith 

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 Yes1 

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 

Using only nine runs as suggested 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 ofthe 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. 

VES016855 
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 were 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 concentrations, temperatures, flow rates, 

and QA data. It also showed a precision 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% RAfor Pb. 

Was systematically biased for Ba, Sb, Zn, and As. Did not 

successfully measure Hg. For response to change in 

concentration, had correlation (r2) of 0.95 or better for Ni, Sb, and 

Zn. Underlined elements are regulated elements typically found 

in the Tooele feedstream. 

VES016856 
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, but 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 tests 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 horizontally 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

 2F. 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. 

VES016857 
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 (pg/cm2). The XRF unit used by 

the XCEM had not been calibrated since August 2001. Before recalibrating, CES 

analyzed 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 filter tape background reference spectra 

• Subtraction ofthe 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 MicroMatter standards were again evaluated 

as unknowns. The standards were within 1.5 percent ofthe 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 CES MicroMatter standards. They were 

also compared with standards from NIST. The results from the analysis of the 

NIST and CES MicroMatter standards were 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 percent, respectively. The XRF calibration 

was adjusted accordingly. 

Summary of Transport and Calibration Evaluations 

Changes to the transport line were tested by comparing XCEM concentrations to 

concentrations 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 a 

VES016858 
ERDC/CERL TR-05-9 41 

Quantitative Spike Injection System (QSIS). It was determined that the elemental concentrations were being reported within 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 ofthe 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 discussion 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 duplicate 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 the 

paired M29 concentrations were within 10 percent of each other. Of the 11 reported concentrations that were not within 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 TEAD 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 the 

M29 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. 

VES016860 
ERDC/CERL TR-05-9 43 

Table 16. M29 concentrations (ug/dscm). 

RUN 

Pb Cd Cr As • Sb 

RUN 

A B A VG A B A VG A B A VG A B A VG A B A VG A B A VG 

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 

RCN 

Ni Ba Zn Sn 

RCN 

A B A VG A B A VG A B A VG A B A VG 

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 

Predicted Stack Gas Concentrations 

Predicted stack gas concentrations were determined by adding the MSE-TA calculated spiked concentrations with background 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 correction 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 pg/dscm. MSE-TA mass concentrations in solution were cross-checked by submitting aliquots from M29 runs 5 and 

6 to an independent laboratory for analysis (HKM Labs, Butte, MT). HKM's results were within 7 percent of MSE-TA's estimates for all elements except As, 

VES016861 
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 reported 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 were 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 training, 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 earher 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 concentrations were significantly higher than 

* Personal communication: Mike Pattison, U.S. Army CHPPM, with Bruce Johnsen, CES, June 2002. 

VES016862 
ERDC/CERL TR-05-9 45 

the 15 May concentrations, which is consistent with incineration of relatively 

clean munitions scouring the stack. Background concentrations for Cr, As, Hg, 

Ni, and Sb were below XCEM detection limits (1 ug/dscm) and were reported as 

0 pg/dscm. 

Table 18. APE-1236 stack concentrations (ug/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 ofthe background during spiking periods. 

The background contribution of the other elements was estimated by their relationship to Sn according to the equations 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 concentrations 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. Combining 

the MSE-TA spike injection estimates with the estimated background concentrations resulted in predicted concentrations as shown in Table 19. 

VES016863 
46 ERDC/CERL TR-05-9 

XCKM Lead vs. XCKM Tin Durinu NonSpiking Periods 

XCE M Zinc vs. XCE M Tin During NonSpiking Periods 

200 400 600 

Tin (ug/DSCM) 

200 400 600 

Tin (ug/DSCM) 

800 

XCKM Barium vs. XCKM Itu During NonSpiking Periods 

! 0 200 400 600 800 

| Tin Oig/DSCM) 

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

spiking. 

Tin During M29 Testing 

May 13 May 14 May 15 M a y 16 

Figure 14. XCEM tin measurements during M29 testing. 

VES01r 
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 every sample. The consistency of the Pd 

concentrations provides QA of the instruments 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 problems. This represents an uptime of 

98 percent. 

Table 19. Predicted stack concentrations (ug/dscm) based on MSE-TA spiking and background 

estimates. 

CHROMIUM CADMIUM LEAD ARSENIC NICKEL 

RUN 

MSE B KG PRD MSE BKG PRD MSE B KG PRD MSE B KG 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 

RUN 

MERCURY BARIUM ANTIMONY ZINC 

RUN 

MSE B KG PRD MSE BKG PRD MSE B KG 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 

VES016865 
Table 20. XCEM concentrations. 

Date START STOP 

XC M29 XCEM CONC. (fig/DSCM) CES CONC. (ug/DSCM) Date START STOP 

RUN RUN AS BA CD CR HG NI PB SB SN ZN AS BA CD CR HG NI PB SB SN ZN 

5/13 7:57 AM 8:17 AM 899 O.O 69 11.5 1.2 2 1 95 0 487 38 

5/13 8:17 AM 8:37 AM 900 0.4 65 5.9 0.6 1 0 86 0 604 43 

5/13 8:37 AM 8:57 AM 901 0.2 44 8.4 0.3 2 1 78 1 466 39 

5/13 8:57 AM 9:1 7 AM 902 2.1 20 9.9 0.8 1 0 60 3 227 23 

5/13 9:18 AM 9:37 AM 903 O.O 75 10.0 1.3 0 0 68 5 272 27 

5/13 9:37 AM 9:57 AM 904 2.2 41 12.2 0.9 1 2 53 1 282 39 

5/13 9:57 AM 10:17 AM 905 O.O 11 6.4 0.7 1 0 54 5 231 40 

5/13 10:17 AM 10:37 AM 906 1.3 18 8.0 0.3 1 0 45 3 205 21 

5/13 10:37 AM 10:57 AM 907 O.O 22 6.0 0.6 1 1 55 5 275 24 

5/13 10:57 AM 11:17 AM 908 1.4 49 5.7 0.4 1 1 45 3 259 23 

5/13 11:17 AM 11:36 AM 909 8.5 129 26.4 3.4 218 200 44 106 250 210 

5/13 11:37 AM 11:57 AM •)10 1 8.0 242 30.X 2.9 347 254 48 187 249 269 8.6 210 27.5 3.2 261 270 51 172 226 296 

5/13 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 46 176 224 295 

5,13 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 57 172 271 306 

5/13 12:38 PM 12:50 PM 913 ] 8.1 215 32.0 4.1 356 264 59 192 331 279 9.0 210 29.5 3.8 244 247 63 161 318 276 

5/13 12:5') PM 1:19 I'M 914 1 11.5 223 40.4 3.7 3X5 278 87 182 484 301 8.5 206 29.9 3.1 263 262 84 159 399 297 

5/13 1:1') PM 1 Mi I'M 915 1 10.9 265 37.4 3.8 371 279 94 190 55K 303 8.6 193 27.5 3.0 244 248 88 161 460 286 

5/13 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 83 170 411 312 

2:01 I'M 2:22 I'M <i; " 36.9 3.5 387 285 79 191 437 313 9.4 229 29.3 3.0 264 284 79 174 374 321 

2:22 I'M 2:47 I'M u | s •I 2 2^0 35.0 •i n 366 275 77 192 394 297 10.4 231 30.0 3.3 278 293 80 183 353 325 

5/13 2:47 PM 3:08 PM 919 2 9.6 272 34.3 3.7 381 278 76 20ft 389 295 10.3 247 28.8 3.1 268 273 75 173 341 301 

5/13 3:08 PM 3:29 PM 920 2 7.1 241 37.5 4.8 394 281 77 191 379 J00 10.4 209 28.4 3.2 258 275 69 182 316 303 

* M 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 71 183 306 314 

5713 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 61 171 275 281 

5'13 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 58 172 261 301 

5/13 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 49 187 198 318 

5/14 7:04 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 ! ; 

5/14 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 7fi 160 314 ;.i • 

5'I4 7:45 AM X:(l(, \ M 928 3 13.6 210 38.6 6.1 350 259 84 185 417 290 12.8 173 31.7 4.7 253 267 81 145 369 311 

5/14 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 96 156 443 300 

5/14 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 78 153 378 283 

5/14 8:47 AM 9:118 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 31S 

5/14 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 78 168 373 293 

o 

VES016866 
Table 20 (Cont'd). XCEM concentrations. 

Date START STOP 

XC M29 XCEM CONC. (ug/DSCM) CES CONC. (ug/DSCM) 

Date START STOP 

RUN RUN AS BA CD CR HG NI PB SB SN ZN AS BA CD CR HG NI PB SB SN Z N 

5/14 9:4') AM 10:10 A M 934 15.7 99 35.6 6.4 391 278 60 63 340 294 

5/14 10:10 AM 10:31 AM 935 13.2 58 36.2 5.8 356 261 61 45 317 278 

5/14 10:31 AM 10:51 AM 936 15.5 170 40.0 5.4 354 258 51 161 304 275 

5/14 10:51 AM 11:12 A M 937 15.0 21 38.2 6.2 373 275 47 12 282 287 

5/14 11:12 AM 11:32 AM 938 14.6 182 36.0 5.6 373 277 46 181 268 287 

5/14 11:32 A M 11:53 AM •)3<i 4 14.8 213 37.4 5.3 360 265 40 181 220 273 14.3 179 30.5 4.8 301 274 43 172 203 294 

5/14 11:53 A M 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 43 175 203 320 

5/14 12:13 PM 12:34 I'M 941 4 14.2 197 34.1 4.9 353 256 36 188 203 266 14.5 213 31.6 5.1 304 284 42 170 193 302 

5/14 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 39 179 179 305 

5/14 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 33 177 164 291 

5/14 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 3U<. 

5'14 1:35 PM 1:56 PM 945 13.5 183 5.0 368 29 1 70 191 275 14.4 198 33.3 5.4 312 281 30 16.3 165 •i>ii 

5/14 1:56 I'M 2:16 PM 946 14.8 33 36.3 6.6 363 '68 13 165 ">"73 14.0 40 30.3 5.2 291 >- 30 10 157 

5/14 2:16 PM 2:37 PM 947 5 M.I 225 41.3 5.1 369 269 29 196 181 274 1 1.4 198 30.0 5.2 331 283 30 178 154 2W 

5/14 2:37 PM 2:57 PM 948 5 17.1 207 35.5 6.2 387 282 26 19U 173 286 14." 190 2S.0 5.1 3119 266 27 169 149 283 

5/14 2:57 PM 3:18 I'M 949 5 14.7 235 41.7 6.9 390 281 29 190 167 281 13.7 197 3U.4 4.7 300 255 26 164 137 271 

5/14 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 26 166 143 286 

5'I4 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 24 166 129 257 

5'14 3:59 I'M 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 25 184 133 295 

5/14 4:21) I'M 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 31)0 27 196 142 319 

5/15 6:57 AM 7:18 AM 956 5.6 70 20.5 3.1 148 13>i 70 12 138 

5/15 7:18 AM 7:38 A M 957 11.0 191 41.3 5.8 341 ?7~ 139 191 216 275 14.0 176 27.5 5.2 286 276 138 154 185 298 

5/15 7:38 AM 7:58 AM 958 6 15.6 225 38.9 h.h 386 291 163 195 415 306 15.1 228 30.6 4.8 293 265 154 156 339 296 

5/15 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 5.9 296 270 138 169 224 292 

5/15 8:19 A M 8:39 AM 960 6 15.3 220 34.9 5.9 372 272 152 194 378 281 15.0 170 lil.il 5.0 278 253 143 155 324 279 

5/15 8:39 A M 9:00 A M 961 6 1S.0 220 39.2 18.0 361 279 149 192 325 284 13.2 168 28.3 7.7 272 241 134 153 257 262 

5'I5 9:00 A M 9:21 A M 962 6 13.9 236 41.3 5.7 375 283 162 195 348 293 15.1 189 29.H 4.8 299 260 142 166 281 283 

5/15 9:21 AM 9:41 A M 963 6 12.5 209 V V 5.9 388 278 150 194 305 292 12.5 175 24.3 4.4 292 269 141 155 250 289 

5/15 «):4I AM 10:02 AM 964 6 4.1 22^ I2.fi 1.1 384 283 147 202 300 288 1.9 172 1(1.1 1.7 285 265 141 149 239 283 

5/15 10:02 A M 10:22 AM 965 14.1 l'<- 37.9 5.8 384 277 141 198 270 284 16.3 211 31.2 5.5 330 285 146 166 243 307 

VES016867 
18 

Table 20 (Cont'd). XCEM concentrations. 

Date START STOP 

X C M29 XCE M CONC. (ug/DSCM) C ES CONC . (fig/DSCM) 

Date START STOP 

RUN RUN AS BA C D CR HG M PB SB SN ZN AS BA CD C R HG NI PB SB SN ZN 

5/15 111:22 AM 10:43 A.M 966 7 I3.fi 233 36.9 5.9 384 280 137 205 251 283 11.9 187 26.8 4.0 241 226 116 143 189 241 

5/15 10:43 AM 11:113 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 3(16 

5/15 11:03 AM 11:24 AM 968 7 15.4 223 35.5 5.9 396 292 139 208 245 297 14.8 201) 31.3 5.3 310 287 145 179 224 304 

5/15 11:24 AM 11:45 AM 964 7 17.9 253 34.9 4.9 394 291 138 197 237 296 14.5 193 32.7 5.2 317 303 151 184 214 318 

5/15 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 2(11 304 

5/15 12:05 PM 12:26 I'M 971 7 17.2 192 31.8 6.1 382 286 129 191 208 290 14.5 202 32.7 5.5 314 298 143 182 192 312 

5/15 12:26 I'M 12:46 I'M 972 7 13.0 230 40.7 5.7 399 292 133 188 215 292 12.1 178 26.0 4.5 268 253 122 156 173 265 

5/15 1 2:46 I'M 1:07 PM 973 15.6 1 85 34.7 5.8 396 285 135 186 196 292 1 "> •• 181 29.K . - 277 253 120 1 57 161 267 

5/15 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 4.9 294 272 129 166 155 284 

5/15 1:27 I'M 1:48 PM 975 8 15.1 232 33.6 6.8 402 292 128 182 171 287 13.8 185 30.7 4.5 294 274 128 167 146 287 

5/15 1:48 I'M 2:09 I'M 97ft X 15.3 202 35.8 4.9 395 286 132 187 192 285 13.6 191 29.9 4.8 302 294 141 170 166 311 

5/15 2:0V I'M 2:29 PM 977 8 12.9 215 35.1 5.6 412 299 132 188 P9 301 14.6 183 31.5 5.2 310 288 133 179 151 301 

5/15 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 S.1 303 298 137 178 153 311 

5/15 2:50 PM 3:10 PM 979 8 16.4 205 39.8 5.8 413 303 130 179 149 3110 12.5 171 28.7 4.2 265 256 121 158 128 266 

5'IS 3:111 I'M 3:31 PM 9X11 8 15.4 200 40.8 4.9 393 289 127 190 157 285 13.8 172 31.3 5.3 289 280 130 169 134 291 

\i ] *\ 3:31 I'M 3:51 I'M 13.0 215 41 7 398 290 119 1 85 284 14.0 187 34.8 5.3 323 319 145 192 330 

5/15 3:51 PM 4:12 PM 982 9 16.1 202 38.8 6.0 406 293 12X 198 143 297 13.2 208 31.3 4.6 275 262 119 163 115 272 

5/15 4:12 I'M 4:32 PM 9X3 9 14.0 216 34.7 6.3 410 298 132 193 146 301 13.6 2011 31.5 5.4 299 288 129 169 128 299 

5/15 4:33 I'M 4:53 PM •>X4 9 12.7 217 34.3 6.0 405 295 132 199 136 295 13.1 180 30.4 4.9 263 264 118 172 113 272 

5/15 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 4.9 274 278 122 172 110 288 

5'15 5:14 I'M 5:34 PM 986 9 13.3 186 39.3 5.5 403 291 127 194 120 286 14.6 200 34.2 6.9 310 305 133 183 113 316 

5/15 5:34 I'M 5:55 PM 987 9 13.0 170 39.4 5.5 415 301 129 197 124 297 14.1 184 31.0 5.2 303 296 131 169 101 305 

5/15 5:55 I'M 6:15 PM 988 15.0 183 29.1 5.0 418 304 123 195 110 299 12.7 193 20.3 5.4 308 133 174 100 320 

5/15 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 79 

5/15 6:36 PM 6:59 I'M 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 9 

5/15 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 10 

5/15 7:19 PM 7:38 PM 992 0.4 6 1.3 0.0 10 0 21 4 1 14 7 

5/15 7:38 PM 7:58 PM 993 0.0 29 0.1 0.4 9 0 9 0 38 3 

5/16 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 10.0 203 254 140 153 232 276 

5/1'. 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 ^K9 

516 7:45 4M 8:06 AM 997 10 13.7 188 38.5 6.1 404 284 154 182 262 298 14.2 197 32.9 6.9 283 272 146 167 231 294 

5/16 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 4.7 269 273 143 160 203 292 

5:16 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 6.1 286 282 142 160 214 296 

5; 16 8:47 AM 9:08 AM 1 10 14.1 19) 35.7 5.3 396 284 137 197 236 294 14.4 178 28.8 5.0 287 285 140 166 208 304 

5/16 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 5.1 290 290 140 162 192 305 

tn 

73 

D 

O 

O 

m 

73 

VES016868 
Table 20 (Cont'd). XCEM concentrations. 

Date START STOP 

XC Y129 XCEM CONC. (ug/DSCM) CES CONC. (ug/DSCM) Date START STOP 

RUN RUN AS BA CD CR HG NI PB SB s\ / \ AS BA CD CR HG NT PB SB SN Z N 

5/Id 10:3(1 AM 10:50 AM 6 11 16.2 183 34.6 5.3 393 286 126 202 163 281 14.7 218 32.0 4.8 284 281 129 174 144 292 

10:511 A.M 11:11 A M 7 11 15.9 204 34.1 5.2 394 286 119 193 152 285 14.7 209 32.1 5.4 302 305 136 185 141 315 

5/16 11:11 AM 11:31 A M 8 11 14.4 193 35.9 5.8 382 280 118 183 143 278 15.3 196 28.8 7.0 275 279 122 172 125 286 

5/16 11:31 A M 11:52 A M 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 MW 

5/16 11:52 AM 12:13 P.M 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 31 1 

5/16 12:13 I'M 12:33 PM 11 11 12.7 202 33.5 5.6 401 290 125 198 129 286 14.4 226 30.2 5.0 274 291 128 179 111 301 

5/16 12:33 PM 12:54 PM 12 11 15.6 201 311.3 4.9 374 273 115 189 110 269 12.9 206 29.2 7.0 263 280 121 183 9(i 288 

5/16 12:54 PM 1:14 PM 13 12.5 208 32.3 5 7 386 281 1 19 198 95 283 :4 'i 198 33.1 5.0 291 302 130 181 92 : i .. 

5/16 1 I'M 1:35 I'M 14 14.8 183 33 9 s 1 402 298 124 211 100 701) i (i 203 33.6 * ? 260 291 . _'f, 180 86 -IH 

5/16 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 .'•OK 

5/16 1:56 PM 2:16 PM 16 12 14.3 234 33.4 4.9 389 289 118 196 105 279 14.11 208 31.8 6.0 252 286 123 181 87 295 

5/16 2:16 P.M 2:37 PM 17 12 12.9 184 .13.0 5.1 381 281 117 189 90 272 14.-

" 191 30.2 4.9 264 291 124 178 80 301 

5/16 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 89 304 

5/16 2:57 PM 3:18 PM 19 12 16.9 196 18.8 5.9 406 291 120 191 94 286 14.5 213 32.3 12.4 274 297 127 189 85 303 

1 10.1 232 34.7 3.6 365 269 66 184 371 287 

2 9.3 244 35.7 4.1 380 282 66 199 328 296 

3 13.7 228 37.3 5.8 364 262 81 189 436 287 13,4 194 31.7 4.8 262 262 84 156 394 301 

4 14.3 210 37.6 5.8 368 269 36 189 197 276 14.5 201 32.5 5.1 301 285 39 176 184 303 

5 15.1 228 37.4 6.0 381 276 26 197 162 278 14.3 197 30.5 5.1 313 271 27 175 141 287 

6 12.9 223 34.4 5.4 379 282 153 195 333 291 12.5 186 26.6 4.9 288 260 142 158 273 283 

UNW EIGHTED AVERAGE 7 15.3 218 36.9 5.7 392 288 136 198 234 292 13.5 195 30.2 5.0 294 277 138 170 201 293 

8 14.5 212 38.3 5.7 404 295 131 186 172 292 13.8 188 31.1 4.9 294 280 131 170 148 293 

9 13.9 202 37.5 5.9 406 294 128 195 133 293 13.7 194 31.5 5.3 287 282 125 171 113 292 

10 14.6 199 35.1 5.5 395 286 139 192 230 293 13.5 189 28.5 5.4 282 282 140 164 199 298 

11 15.5 197 34.3 5.3 393 286 120 193 137 284 14.5 211 30.7 5.8 283 290 128 180 122 300 

12 14.8 205 35.5 5.3 389 286 117 193 96 280 14.3 205 31.6 6.8 269 294 126 184 87 303 

A LL 13.7 216 36.2 5.3 385 281 100 193 236 287 13.8 196 30.5 5.3 287 278 108 170 186 295 

St. Dev. 5.1 69 10.7 2.2 129 94 44 68 116 89 3.0 36 5.7 1.7 52 49 43 34 93 51 

VES016869 
52 ERDC/CERL TR-05-9 

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

n 

[Eq7] 

where: 

C; = XCEM time-weighted concentration for element i during M29 test 

run 

C^ = XCEM reported concentration for element i during time interval j 

n = Number of XCEM measurements during test run 

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

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 the 

cahbration standards by 15,15, and 7 percent, respectively. The calibration factors were changed prior to run 2 (Appendix D). 

2. Hg cahbration factors were determined to be high relative to the cahbration 

curve by 4 percent and were changed following the M29 test (see Appendix D for 

a complete discussion of Hg cahbration). 

3. During run 961, an unusually high Cr number (18 ug/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 not 

representative ofthe 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 percent criterion for XCEM runs 1021 and 

1022. These runs represented 23 minutes ofM29 run 12. Consequently, XCEM 

concentrations for run 12 were based on a time-weighted average ofthe 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. 

VES016870 
ERDC/CERL TR-05-9 53 

XCEM Calibration Evaluation Using A QuanX - XRF and ICP/MS 

Since XRF analysis is nondestructive, the 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 CES 

QuanX analyzer is one of four in the nation that has been approved for measuring PM 2 S

 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 (ug/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. 

VES016871 
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 measured 

all 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. 

Element State 

B/hr 

Limit 

Mg/dscm1 

Interim 

MACT Limit 

pg/dscm 

Final MACT 

Limit 

Mg/dscm 

Potential to Limit 

Feed Rate 

Pb 4.3 932 240 59 Yes 

Cd 0.26 56 

240 59 

Yes 

Cr 0.04 10 97 84 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 

' 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 pg/dscm. EPA's HWC interim maximum achievable control technology (MACT) rule (EPA 1999) currently 

limits Pb and Cd emissions to 240 pg/dscm. The final MACT rule, which was 

published 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 pg/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 pollution control devices and emitted from 

the stack. The effectiveness of the model depends upon several assumptions including transport under various meteorological regimes, incinerator temperature 

effects, and chemical interactions. Direct measurement of Pb concentrations in 

VES016872 
ERDC/CERL TR-05-9 55 

the stack gas allows for improved understanding of the relationship between 

munitions incineration and stack emission rates as well as an enhanced mechanism for regulating feed rates. 

Table 24 shows the Pb results for the MSE/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 results 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 r 2 of 0.98 

(Figure 15). 

Lead in the first five M29 runs was exclusively from residual concentrations in 

the incinerator. Following run 5, MSE-TA began spiking an additional 105 

pg/dscm of Pb. During testing, both M29 and the XCEM reported concentrations 

ranging from 25 to 150 pg/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 (pg/dscm) data and ratios during M29 testing. 

RUN PRD M29 XC ON CA XC/QN XC/PRD M29/PRD XC/M29 ON/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 0.09 

VES016873 
56 ERDC/CERL TR-05-9 

E 200 

0 50 100 150 200 

M29 Lead (ug/dscm) 

Figure 15. XCEM versus M29 lead for validation tests. 

Cadmium 

The APE-1236 state-mandated emission limit for Cd is about 60 ug/dscm under 

typical stack flow rates. Cadmium stack 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, the 

XCEM was about 14 percent higher than M29 with an RA of 17 percent. The reanalysis of the XCEM filter tape yielded 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. 

VES016874 
ERDC/CERL TR-05-9 57 

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

RUN PRD M29 XC 9 N 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 

1 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 emission limit of less than 10 ug/dscm under 

typical stack operating conditions. Since the background Cr concentrations were 

uncertain at the start of the validation test, MSE-TA spiked a nominal 3 pg/dscm 

during M29 runs 1 and 2. Following these runs, it was determined that the 

background Cr concentrations were insignificant and MSE-TA raised their spiking rate to 5 pg/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 pg/dscm. The agreement between the 

XCEM and M29 at both the 3 and 5 pg/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 ofthe XCEM filter tape by the CES-QuanX and ICP were within 3 percent 

of the M29 concentrations. The consistency of M29 with the predicted values 

and subsequent measurements of the XCEM filter tape suggests that the difference between the two methods is due to XCEM error. 

VES016875 
58 ERDC/CERL TR-05-9 

Table 26. Summary of Cr concentration (ug/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 U O 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 elements 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 was 

correct 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 besides calibration such as loss during 

transport, low filter trapping efficiency, and deposit positioning errors can be 

ruled out because they would result in XCEM 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. 

VES016876 
ERDC/CERL TR-05-9 59 

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

RUN PRD M29 XC ON 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 13.8 133 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 2001M29 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 pg/dscm. Mercury, however, is typically 

not 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 following Pb injection. The source of this 

decrease may be related to the unusually high level of particulate phase Hg 

present during this validation test. Particulate 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 the total Hg. As such, M29 does not require 

VES016877 
60 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 the 

quantity in the particulate phase. See Appendix D for a more detailed discussion. 

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

RUN PRD M29 XC QN1 C A1 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. 

0 10 20 30 

• 

40 

Percent of Hg on M29 Filter 

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 than 

M29 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 believed that the XCEM/M29 differences were 

due to XCEM calibration errors of about 15 percent. 

Table 29. Summary of Sb concentration (pg/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 predicted 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 

pg/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. 

VES016879 
62 ERDC/CERL TR-05-9 

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

RUN PRD M29 XC ON 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 pg/dscm, typical Ba concentrations found in the stack are in the 

0 to 200 pg/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 (ug/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 0.06 

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ERDC/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 the 

CES QuanX and Columbia Analytical tape evaluations, indicating that calibration was not the primary source of this difference. It is believed that the difference is primarily due to M29 errors. 

Table 32. Summary of Zn concentration (ug/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 APE-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 the 

XCEM numbers for As, Hg, Ni, and Zn best reflect actual stack gas concentrations. However, calibration errors were noted for Cd, Cr, and Sb even though 

they met the RA requirements. The XCEM was responsive to changes in 

concentration and showed good correlation 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 pg/m3 occurred 

VES016881 
64 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 

Cone, 

(pg/dscm) 

Average 

XCEM Cone, 

(pg/dscm) 

Average Predicted 

Cone, 

(pg/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 No 

VES016882 
ERDC/CERL TR-05-9 65 

5 XCEM Cost and Status 

Cost estimates for the Army to purchase 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 ofthe technology. 

Cost Estimates 

Capital Costs 

Capital costs include: 

1. XCEM: Includes x-ray fluorescence (XRF) spectrometer, operations manuals, 

extraction system, computer and control 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 presentations, 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. 

VES016883 
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 x $80/hr 

($2.4Kto$3.3K). 

3. Warranty: Includes 1-year full-service warranty covering all parts and 

maintenance. Warranty includes onsite 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 developed baseline data for Pb and Zn during 

incineration of various munitions. TEAD stack operators also conducted tests 

using the XCEM in which they determined that the metals emissions could be 

significantly reduced by completely cutting 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 continued use of the XCEM to diagnose and 

assist with process control indicates the 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 near 

VES016884 
ERDC/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 XCE M was 

tested. In a new XCE M (2004), the QuanX XR F instrument has been replaced 

with a custom XR F detection approach improving the detection limit to 0.1—0.2 

ug/dscm from 1-3 ug/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 XCE M model from CES (Xact is the 

marketing name that CES has given the XCEM) . CE S has developed, in the last 

year, a quantitative aerosol generator (QAG) that is capable of delivering a 

known aerosolized metal concentration. CE S believes that using the QA G is a 

reliable, consistent, and accurate method for ensuring that the calibration has 

been entered correctly. The QA G is currently being evaluated by the EPA for use 

in compliance applications. 

CES 

Meuli Monitor 

Figure 17. 2004 CES metals monitor. 

VES016885 
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 functioned in a completely automated manner and automatically recorded the test data. The objective of the test was to 

meet the requirements ofthe proposed PS-10. 

The monitor met the PS-10 sampling and response time criterion by having an 

effective up-time of 100 percent and reporting time averaged concentrations 

every 20 minutes (20-minute lag between sampling and reporting). It also met 

the QA criterion with a precision no more than 2 percent for zero and upscale 

checks, and a calibration drift of 0.5 percent. 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 successfully 

measure Hg because of loss to the unheated sample line. With regard to response to change in concentration, the XCEM results had a correlation (r2

) of 

0.95 or better for Ni, Sb, and Zn. 

In March 2002, the XCEM was moved to a closer location, heat traced, insulated, 

and equipped with a shrouded probe. The combined effect of these changes was 

to minimize Hg and PM loss in the sample line. In April 2002, several improvements were made to the calibration procedure, 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 Method 29 for elements that had significant 

variability in concentration during testing. 

VES016886 
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 elements. XCEM data were also compared to 

M29 data for five elements that are typically 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 uniformly high relative to M29 for As, Ni, 

Zn, and Hg. 

An error analysis was conducted to determine the source of the difference between M29 and the XCEM. Calibration errors and spectral interferences were 

checked 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 these 

elements still met the RA criterion. However, for As, Ni, and Zn, the XCEM calibration was not the primary source of error. 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 differences 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 concentrations on the M29 niters were 15 to 30 

times higher than typical and were highly 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 ofthe comparative reference method (M29). 

It was observed for both M29 comparison tests that the best method for calibrating the XCEM had not been determined. Both tests revealed some errors in calibration with some corrections made after the M29 tests but prior to the XCEM 

result submissions. This may cause some 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 date. It is these analyses that allow the 

determination of the sources of error, including cahbration. This has clearly 

benefited the development of the XCEM calibration procedures with each subsequent test. However, to ensure confidence in the monitor's eventual use in the 

VES016887 
70 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 90 

percent 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 their 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 pg/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. 

VES016888 
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 Engineering Research Laboratory (CERL), Waste 

Minimization and Pollution Prevention Program: Stack Spiking Report for a Multi-Metal 

CEMS Test at the Tooele Army Depot Deactivation 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 Verification of Multi-Metals Continuous Emission 

Monitor at Tooele Army Depot. Tooele, Utah, May 14-17, 2001. 

. (2002). Air Pollution Management Study No. 43-EL-4755-02 Verification of MultiMetals Continuous Emission Monitor at Tooele 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 Science 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.eov/ttn/emc/propperf.html. 

. (1999). Final Standards for Hazardous Air Pollutants for Hazardous Waste 

Combustors; Final Rule. FR52827-FR53077, Vol 64, No. 189. 

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. (2004). National Emission Standards for Hazardous Air Pollutants for Hazardous 

Waste Combustors (Phase I final Replacement Standards and Phase H); Proposed Rule. 

FR2U97-21385, 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: Development. U.S. Army Engineer Research and 

Development Center (ERDC)/CERL Technical Report (TR)-05-3, January 2005. 

Josephson, Paul (2003). Hazardous Waste Combustor Management Plan - AE C (for Table 1). 

Lemieux, P., J . Ryan, N. French, W. Haas (1998). Results ofthe September 1997 DOE/EPA 

Demonstration of Multi-Metal Continuous Emission Monitoring Technologies. Presented 

at International Conference on Incineration 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 Environmental Services, XCE M 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. 

VES016890 
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 provides 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 (CERL) will perform the verification test. 

The U.S. Army is interested in identifying an effective means of continuously 

measuring metals in stack emissions generated by their demilitarization incinerators. The U.S. Environmental Protection Agency's (EPA's) Environmental 

Technology Verification (ETV) Program will verify the test procedures and results. The purpose of the ETV is to provide objective and quality assured performance data on environmental technologies, so that users, developers, regulators, and consultants have an independent 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 ofthe AMS 

Center covers verification of monitoring methods for contaminants and natural 

species 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 Environmental Services, Beaverton, OR, 8 May 2001. 

VES016891 
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Testing will take place at the Tooele Army Depot (TEAD) deactivation 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 measurements under full-scale conditions at a 

combustion facility. 

1.3 Organization and Responsibilities 

The CERL, TEAD, and Battelle will perform and evaluate the verification test in 

cooperation with Cooper Environmental Services (CES), which will provide the 

XCEM for verification. MSE Technology Applications, Butte, MT (MSE-TA) will 

be responsible for spiking the stack, and the U.S. Army Center for Health Promotion and Preventive Maintenance (CHPPM) will conduct the reference method 

testing. The organization chart in Figure 1-1 shows the individuals who will 

have responsibilities in the verification test. The specific responsibilities of these 

individuals are detailed in the following paragraphs. 

Tom 

Kelly 

Battelle 

Dee 

Russell 

TEAD 

Facility 

Manager 

John 

Cooper 

CES 

XCEM 

Vendor 

Steve 

Bryson 

MSE-TA 

Stack 

Spiking 

Mike 

Pattison 

CHPPM 

Ref. 

Measure. 

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 

VES016892 
ERDC/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 contact 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 for reviewing the test/QA plan, evaluating 

field-testing to ensure that the test/QA plan is being followed, and developing an 

E TV verification report and statement. Mr. Charles Lawrie is the AMS Center's 

Quality Manager. As such, he will be responsible 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 staff 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 discontinue 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 conducted in collaboration with Dee Russell of 

TEAD. Mr. Russell's responsibilities are: 

• Coordinate the operation ofthe facility during verification testing. 

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

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

• Contribute to the development ofthe draft test/QA plan. 

VES016893 
76 ERDC/CERL TR-05-9 

• Provide input on facility operating conditions and procedures for the summary and ETV verification report. 

• Review the draft test/QA plan. 

• Provide input for the summary test report 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 Beaverton, 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 test/QA plan in accordance with reviewers' comments. 

• Approve the final test/QA plan. 

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

ofthe XCEM. 

• Attend a pre-study site visit to review 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 report and verification statement. 

1.3.5 Center for Health Promotion and Preventive Medicine 

Reference method testing will be conducted 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. 

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• Assemble trained technical staff to conduct reference method sampling for 

the verification test. 

• Contract for and oversee laboratory analysis 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 interest into the TEAD incinerator downstream ofthe 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 commercially 

available 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 sample 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 the 

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XCEM was assessed at the MSE-TA test facility in Butte, MT (Bryson 2000) and 

has been redesigned for increased ease-of-use and automated QA routines. 

Verification testing will be conducted at TEAD. The TEAD facility has a wellcharacterized feedstream and was the site 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 regulated 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 be 

verified 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 challenge 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 verification testing, a battery of twelve 2-

hour M29 tests will be conducted by CHPPM. Analysis of the M29 sample train 

will 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 performance of the XCE M 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,andSb). 

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A secondary objective is to meet the relative 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 measurements. 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 determined 

as the time between the start of one sampling period and the beginning of a second sampling period. Bias will be identified using EPA method 301 protocols as 

discussed in section 5.6. Low-level metal response will be determined by a comparison to chromium and arsenic reference method concentrations, which will be 

less than 6 and 18 pg/dscm respectively. 

It is beyond the scope of this verification test to simulate the aging and exposures that may affect an XCEM during routine 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 operation. It must be noted that the longterm performance may be different from that observed in the testing described 

here. 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 recorded, 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 section of the test/QA plan describes the 

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

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3.1 Test Facility 

The TEA D incinerator, which runs on diesel fuel, is designed to incinerate decommissioned munitions. Typical operating parameters for the incinerator are 

shown in Table 3-1. The TEA D incinerator is classified as a dry stack with water 

content ranging from 5 to 10 percent. Typical stack P M concentrations are in the 

10 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 tbe system. Signals from these sensors are monitored and compared to preset operating standards. The incinerator consists of a main control 

panel, CEMS , Waste Feed Rate Monitoring System (WFRMS), dual conveyor 

feed system, rotary furnace, furnace shroud, cyclone, afterburner, discharge conveyor, high temperature cast ceramic filters baghouse, high temperature draft 

fan, and exhaust stack. 

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 furnace feed end temperature, negative pressure in the furnace, and afterburner temperature. A multi-point digital recorder 

is used to record process parameters. Logic control for the furnace is performed 

by a PLC. The PLC controls the motor starters, the WFRMS , safety interlocks, 

and alarms. The computer system is an industrial-based machine running data 

acquisition software, which provides centralized and integrated data management, process graphics, operator interface, and report generation. 

Figure 3-1. TEAD Deactivation Incinerator Building 1320. 

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Table 3-1. Typical operating parameters for the APE-1236 deactivation furnace. 

Typica l Operatin g Parameters fo r the 

APE-1236 Deactivation Furnac e 

Afterburner Temp. (°F) 1600 

Baghouse AP (in. H2 0 ) 9 

Baghouse Temp (°F) 680 

Kil n Feed End Draft Pressure (in. H2O) 0.3 

Kil n Feed End Temp (°F) 600 

Kil n Burner End Temp (°F) 1200 

Oa - CE M (%) 14 

CO (ppm) 11 

Stack Temp. (°F) 550 

Stack Gas Velocity (ft/sec) 46 

Stack Pressure (in. H2O) 0.3 

Figure 3-2. TEA D Incinerator Stack. 

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