METHOD 29 COMPARISON 

TESTING OF AN X-RAY BASED 

CONTINUOUS EMISSION 

MONITOR AT TOOELE ARMY 

DEPOT

Contract No. DACA42-02-P-0072

(TASK 6)

FINAL REPORT

Prepared for

U. S. Army Corps of Engineers

Engineer Research and Development Center

Construction Engineering Research Laboratory

Submitted By

Cooper Environmental Services

10170 SW Nimbus Ave Suite H5

Portland, Oregon 97223

July 31, 2002
METHOD 29 COMPARISON TESTING OF AN X-RAY BASED 

CONTINUOUS EMISSION MONITOR AT TOOELE ARMY 

DEPOT

Contract No. DACA42-02-P-0072

(TASK 6)

FINAL REPORT

Prepared by

B.E. Johnsen, J.A. Cooper, M. Nakanishi, S. Fry

Cooper Environmental Services

10170 SW Nimbus Ave. Suite H5

Portland, OR 97223

Submitted to

K. J. Hay

U. S. Army Corps of Engineers

Engineer Research and Development Center

Construction Engineering Research Laboratory

P. O. Box 9005, CN-E, Champaign, IL 61826-9005

July 31, 2002
i

EXECUTIVE SUMMARY

Cooper Environmental Services (CES) has developed an on-line multi-metal X-ray based 

Continuous Emission Monitor (XCEM) capable of simultaneously measuring 19 elements in 

stack gas emissions every 20 minutes. The U.S. Army purchased an XCEM for monitoring 

emissions at its demunitions incinerator APE-1236 on the Tooele Army Depot (TEAD). In

order to validate the XCEM, a series of 12 comparison tests with EPA’s Method 29 (M29) were 

conducted while the stack was being spiked by MSE-TA of Butte, MT. Results were compared 

to criteria found in EPA’s proposed performance specification 10 for multi-metal continuous 

emission monitors (PS10).

During the testing, the XCEM had an “uptime” of better than 98%, met all quality assurance 

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 (Table ES1).

APE-1236 emissions have the potential to approach state-mandated emission limits for three 

elements: Pb, Cd, and Cr. The XCEM met the PS10 20% relative accuracy criteria for all three 

of these elements with RA’s of 4%, 17%, and 15% respectively. XCEM data was 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 non-regulated element, Zn, was also 

spiked by MSE-TA and examined during validation testing. The XCEM met the RA criteria for 

two of the non-limiting elements Ba (4%) and Sb (20%), 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 As, Ni, and Zn, the 

XCEM calibration was not the primary source of error. Aside from calibration and 

spectral errors, other potential sources of error for the XCEM include loss during 

transport, low filter trapping efficiency, deposit positioning errors, and incorrect flow 

measurements. Each of these error sources is highly unlikely. The first three sources of 

error would only result in XCEM concentrations lower than M29. An incorrect flow 

measurement would have resulted in all metals being uniformly high or low since one 

XCEM flow measurement is applied to all of the metals for each run. For this reason, 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 six weeks later showed a loss of 30% of the Hg from the XCEM filter. M29 

particulate concentrations on the M29 filters 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.
ii

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 lead and zinc during incineration of 

various munitions. Next, a bypass duct was blocked with a metal plate resulting in a 

greater than 90% drop in metal concentrations. Using this data, TEAD was better able to 

understand sources of Pb in the emissions.

Currently, the XCEM is being moved to a newly developed test furnace at TEAD. The 

furnace, operated by the Ammunition Equipment Division, anticipates using the 

instrument to rapidly determine effects of changes in munitions or control strategies.

The continued use of the XCEM to diagnose and assist with process control indicates the 

value of having an installed continuous emission monitor for multi-metals at TEAD. CES 

recommends the adoption of the XCEM as a validated monitor for incinerators such as 

APE-1236. Recent advances in XRF technology have allowed for a miniaturized version 

of the XCEM with better detection limits than the current system. CES also recommends 

that this technology be incorporated into a mobile version of the XCEM for the army’s 

stack testing organization (CHPPM) and an extension of the technology to a mercurydedicated XCEM.

Table ES1. Relative Accuracy and Correlation

NR: Not regulated

NA: Correlation coefficient not available since element was only spiked at one level.

Elem.

Avg. 

M29 

Conc. 

(μg/m3)

Avg. 

XC 

Conc. 

(μg/m3)

Avg. 

Pred. 

Conc. 

(μg/m3)

Concentrations 

potentially 

approach site 

limit. 

RA 

%

Corr. 

Coeff. 

(Runs

3-13)

Notes

Pb 101 101 107 Yes 4 0.98 Met PS10 RA criteria.

Cd 42.0 31.5 36.4 Yes 17 NA Met PS10 RA criteria.

Cr 4.9 5.4 4.7 Yes 15 0.64 Met PS10 RA criteria.

As 11.1 13.8 15.2 No 27 0.85 XCEM uniformly higher 

than M29 by 24%.

Hg 305 385 326 No 33 NA

Met criteria for runs 1-5. 

XCEM higher for runs 6-12. 

Difference likely due to loss 

from M29 filter.

Sb 164 192 194 No 20 NA Met PS10 RA criteria.

Ni 218 281 268 No 33 NA XCEM uniformly higher 

than M29 by 30%.

Ba 216 216 226 No 4 NA Met PS10 RA criteria.

Zn 202 290 288 NR 43 NA XCEM uniformly higher 

than M29 by 42%.
iii

LIST OF TABLES

Table 1. Method 29 Concentrations

Table 2. APE-1236 Stack Flow Rates During M29 Testing

Table 3. APE-1236 Stack Concentrations With Munitions Incineration But No Spiking

Table 4. Predicted Stack Concentrations Based on MSE-TA Spiking and Background Estimates

Table 5. XCEM Concentrations

Table 6. Analysis of XCEM Filter Tape By Columbia Analytical

Table 7. Predicted, XCEM and Method 29 Precision During Validation Testing

Table 8. TEAD Emission Limits

Table 9. Summary of Lead Concentration Data During M29 Testing

Table 10. Summary of Cadmium Concentration Data During M29 Testing

Table 11. Summary of Chromium Concentration Data During M29 Testing

Table 12. Summary of Arsenic Concentration Data During M29 Testing

Table 13. Summary of Mercury Concentration Data During M29 Testing

Table 14. Summary of Antimony Concentration Data During M29 Testing

Table 15. Summary of Nickel Concentration Data During M29 Testing

Table 16. Summary of Barium Concentration Data During M29 Testing

Table 17. Summary of Zinc Concentration Data During M29 Testing

LIST OF FIGURES

Figure 1. Correlation Between Tin and Other APE1236 Metals With Munitions Burning 

and No Spiking.

Figure 2. XCEM Tin Measurements During M29 Testing

Figure 3. XCEM vs. M29 Lead During Validation Testing

Figure 4. Percent Difference Between M29 and the XCEM vs. Percent of Mercury on M29 Filter
iv

LIST OF ABBREVIATIONS

AMS Advanced Monitoring Systems; part of the ETV program

APE Ammunition Peculiar Equipment

As Arsenic

Ba Barium

Cd Cadmium

CEM Continuous Emissions Monitor

CES Cooper Environmental Services of Beaverton, OR

CHPPM Center for Health Promotion and Preventative Maintenance

Cr Chromium

DLS Director of Laboratory Services

DSLP Dry Standard Liters Per Minute

DSCM Dry Standard Cubic Meters

EPA United States Environmental Protection Agency

ETV Environmental Technology Verification program

Hg Mercury

HVM High Volatile Metals (mercury)

LVM Low Volatile Metals (cadmium, lead)

M29 EPA standard method 29 

M301 EPA standard method 301

MACT Maximum Achievable Control Technology 

MFC Mass Flow Controller

MFM Mass Flow Meter

MM-CEM Multi-metal Continuous Emission Monitor

MSE-TA MSE-Technology Applications Inc. of Butte, MT.

Ni Nickel

Pb Lead

PLC Programmable Logic Circuit

PS10 EPA’s proposed Performance Specification 10 for multi-metal CEMS

QA Quality Assurance

QC Quality Control

QN QuanX XRF located at CES

RA Relative Accuracy

RSD Relative Standard Deviation (% RSD equals precision)

Sb Antimony

SVM Semi-volatile metals (arsenic, beryllium, chromium)

TEAD Tooele Army Depot

USACERL U.S. Army Construction Engineering Research Library

XCEM X-ray based Continuous Emission Monitor

XRF X-Ray Fluorescence

Zn Zinc

μg/DSCM Micro-grams per dry standard cubic meter

 
v

TABLE OF CONTENTS

EXECUTIVE SUMMARY............................................................................. i

LIST OF TABLES.......................................................................................iii

LIST OF FIGURES.................................................................................... iii

LIST OF ABREVIATIONS............................................................................iv

1.0 INTRODUCTION............................................................................................................................. 1

2.0 RESULTS .......................................................................................................................................... 1

2.1 METHOD 29 CONCENTRATIONS.................................................................................. 1

2.2 PREDICTED STACK GAS CONCENTRATIONS.......................................................... 2

2.3 XCEM CONCENTRATION DETERMINATION ........................................................... 6

2.4 XCEM CALIBRATION EVALUATION USING A QUANX – XRF AND ICP...........11

2.5 PRECISION.........................................................................................................................12

3.0 DISCUSSION ...................................................................................................................................12

3.1 REGULATED ELEMENTS TYPICALLY FOUND IN THE FEEDSTREAM............12

3.2 REGULATED ELEMENTS NOT TYPICALLY FOUND IN TEAD EMISSIONS ....16

3.3 NONREGULATED METALS ...........................................................................................21

4.0 CONTINUED USE OF THE XCEM .............................................................................................21

5.0 CONCLUSION AND RECOMMENDATIONS ...........................................................................22

6.0 REFERENCES.................................................................................................................................23

APPENDICES

APPENDIX A – HKM Results

APPENDIX B – Columbia Analytical Results

APPENDIX C – Mercury Calibration Discussion
1

1.0 INTRODUCTION

Cooper Environmental Services (CES) has developed an X-ray based multi-metals Continuous 

Emissions Monitor (XCEM) capable of providing near real-time data for up to 19 elements 

found in smoke stack emissions. During the spring of 2001, the XCEM was installed at the 

Tooele Army Depot (TEAD) munitions incinerator. Following installation, a series of 

comparison tests to EPA’s Method 29 (M29) were conducted with the XCEM during May 2001 

(Bryson, 2001, Johnsen, 2001). Although no final performance specifications exist for multimetal CEMs, the results of these tests were compared to EPA’s draft Performance Specification 

10 (PS10). The XCEM met the precision, quality assurance, response time, and response to 

change in concentration criteria of PS10, but only met relative accuracy criteria for three 

elements (chromium, cadmium, and nickel). 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 relative accuracy.

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. Finally, in May 2002 a series of Method 29 tests were conducted to evaluate the 

measurement capabilities of the upgraded XCEM. This report discusses the XCEM results 

relative to the Method 29 testing. A second companion report (Johnsen, 2002) discusses the 

results of the transport line changes and preliminary tests prior to Method 29. 

2.0 RESULTS

2.1 METHOD 29 CONCENTRATIONS

Method 29 (M29) 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 (Pattison, 2002a). 

More than 90% of the paired M29 concentrations were within 10% of each other. Of the eleven 

reported concentrations that were not within 10%, nine were measurements of Sn. Since M29 

has not been approved for Sn (EPA, 1992), CHPPM determined that the M29 Sn values were not 

valid. 

Overall, train A was higher than train B by about 3% with about 78% 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.

M29 data used for comparison to the XCEM is the same as reported in the M29 report (Pattison, 

2002a) with the exception of a one to three percent correction compensating for the laboratory’s 

inadvertent subtraction of an estimated blank concentration when the blank concentrations were 

below the method reporting limit (Severen-Trent, 2002).
2

Table 1. Method 29 Concentrations (μg/DSCM)

A B AVG A B AVG A B AVG A B AVG A B AVG A B AVG

1 74 71 73 31 28 29 3.5 3.6 3.6 8.1 7.4 7.8 344 320 332 154 148 151

2 75 78 77 32 32 32 4.0 4.1 4.0 8.4 8.0 8.2 337 331 334 188 176 182

3 99 96 98 36 34 35 6.7 6.2 6.4 11.7 11.2 11.4 306 283 294 187 180 183

4 37 39 38 31 31 31 4.8 5.2 5.0 11.5 12.1 11.8 347 307 327 168 164 166

5 29 26 28 32 30 31 5.3 5.2 5.2 12.3 11.1 11.7 319 317 318 172 163 168

6 148 146 147 32 31 31 5.0 4.7 4.8 11.6 10.9 11.2 291 269 280 160 163 162

7 138 132 135 32 31 32 5.0 4.8 4.9 11.8 11.4 11.6 279 291 285 169 159 164

8 131 126 128 33 32 32 5.2 4.9 5.1 12.6 11.8 12.2 309 303 306 165 158 162

9 121 122 122 32 32 32 4.9 5.4 5.2 12.0 12.2 12.1 312 305 309 153 161 157

10 140 129 135 31 29 30 5.0 4.8 4.9 11.3 10.8 11.0 294 289 292 164 151 157

11 119 118 119 32 31 31 4.9 4.7 4.8 11.7 11.5 11.6 297 293 295 162 164 163

12 114 111 113 31 31 31 4.8 4.8 4.8 11.9 11.7 11.8 308 278 293 154 154 154

A B AVG A B AVG A B AVG A B AVG

1 209 191 200 222 206 214 203 186 195 132 144 138

2 235 235 235 249 248 248 216 208 212 131 168 149

3 240 228 234 252 243 247 222 208 215 207 199 203

4 207 220 213 195 211 203 192 201 196 66 90 78

5 227 235 231 215 198 207 202 191 196 57 69 63

6 236 214 225 217 215 216 218 200 209 131 108 120

7 230 205 218 220 204 212 206 198 202 60 74 67

8 224 213 219 214 206 210 211 196 204 47 48 47

9 222 221 221 204 209 206 204 200 202 41 35 38

10 219 192 205 218 199 208 205 192 199 88 64 76

11 218 214 216 210 210 210 205 201 203 44 36 40

12 202 195 199 208 201 204 199 192 196 31 25 28

 Hg

 Ni

 Pb Cd Cr As Sb 

 Ba Zn Sn

RUN

RUN

2.2 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 concentration -- 17%, 15%, and 8% respectively. However, for 

Pb, the background accounted for 100% of the Pb in runs 1-5 and 35% of the Pb in runs 6 

through 12.

2.2.1 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 micrograms per dry standard cubic meter (μg/DSCM). MSE-TA mass 

concentrations in solution were cross-checked by submitting aliquots from M29 runs 5 and 6 to 

an independent laboratory for analysis (HKM labs, Butte, MT). HKM’s results were within 7% 
3

of MSE-TA’s estimates for all elements except As which was 23% lower according to HKM labs 

than reported by MSE-TA. Because of the limited HKM data, no adjustments were made to 

MSE-TA reported data. The potential impact of the As difference is discussed in Section 3.0 and 

in a report by Cooper et. al. (Cooper, 2002).

Measurements of stack flow by CHPPM were crosschecked with the stack continuous velocity

monitor for accuracy and were found to be within 6% of each other (Table 2). 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 

(Pattison, 2002b). For this reason, the CHPPM flows were used to calculate the predicted 

concentrations.

Table 2. APE-1236 Stack Flow Rates During M29 Testing

TEAD M29A M29B M29 TEAD/ 

M29

DSCM/ 

HR

DSCM/ 

HR

DSCM/ 

HR

DSCM/ 

HR %

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 5,060 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

RUN
4

2.2.2 Background Metal Concentration

TEAD incinerated 20 mm TPM55A2 bullets during all twelve M29 runs. This ammo, 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 

earlier incineration of other munitions. Table 3 shows XCEM results for elements measured on 

May 13th and May 15th while the 20 mm bullets were being burned and MSE-TA was not spiking 

into the stack. The May 13th metal concentrations were significantly higher than the May15th

concentrations. This 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 

and were reported as 0 μg/DSCM.

Table 3. APE1236 Stack Concentrations With Munitions Incineration But No Spiking (μg/DSCM)

Date 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

AVG. 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

AVG. 19.4 1.7 19.3 6.7 102

2.2.3 Use of Sn as a Surrogate for Background Metals

Figure 1 shows the relationship between Pb, Ba, Zn, and Sn when spiking was not occurring. 

The correlations indicate that Pb, Ba, Zn and Sn background concentrations stem from the same 

source. Since Sn was not spiked by MSE-TA, its concentration was used as an indicator of the 

background during spiking periods. The background contribution of the other elements was 

estimated by their relationship to Sn according to the equations in Figure 1. Figure 2 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 3. 
5

Figure 1. Correlation Between Sn and Other APE1236 Metals With Munitions Burning 

and No Spiking

XCEM Barium vs. XCEM Tin During NonSpiking Periods 

y = 0.0977x + 9.0892

R

2

 = 0.4678

0

20

40

60

80

0 200 400 600 800

Tin (μg/DSCM)

Barium (μg/DSC

M)

XCEM Lead vs. XCEM Tin During NonSpiking Periods 

y = 0.1505x + 11.158

R

2

 = 0.8636

0

20

40

60

80

100

120

0 200 400 600 800

Tin (μg/DSCM)

Lead (μg/DSC

M)

XCEM Zinc vs. XCEM Tin During NonSpiking Periods 

y = 0.0747x + 4.7411

R

2

 = 0.7159

0

10

20

30

40

50

60

0 200 400 600 800

Tin (μg/DSCM)

Zinc (μg/DSC

M)

Figure 2. XCEM Tin Measurements During M29 Testing

Tin During M29 Testing

0.0

100.0

200.0

300.0

400.0

500.0

600.0

700.0

890 930 970 1010

May 13 May 14 May 15 May 16
6

2.3 XCEM CONCENTRATION DETERMINATION

XCEM concentrations were determined every 20 minutes for Pb, Cd, Cr, As, Ni, Hg, Ba, Sb, Zn, 

and Sn (Table 5). A Pd rod is permanently mounted in the XRF detection area and is measured 

with every sample. The consistency of the Pd concentrations provides quality assurance of the 

instruments stability During M29 testing, the XCEM successfully carried out 120 runs with only 

two runs falling outside of the Pd quality assurance criteria due to air conditioning problems. 

This represents an uptime of 98%. 

Table 4. Predicted Stack Concentrations Based on MSE-TA Spiking and Background 

Estimates (μg/DSCM)

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

1 2.9 0.0 2.9 32.0 9.4 41.5 0.0 67 67 10.6 0.0 10.6 267 0.0 267

2 2.9 0.0 2.9 31.5 8.4 39.8 0.0 61 61 10.7 0.0 10.7 268 0.0 268

3 5.2 0.0 5.2 37.5 11.1 48.6 0.0 77 77 16.7 0.0 16.7 275 0.0 275

4 5.0 0.0 5.0 36.5 5.0 41.6 0.0 41 41 16.1 0.0 16.1 265 0.0 265

5 5.0 0.0 5.0 37.2 4.1 41.4 0.0 36 36 16.1 0.0 16.1 266 0.0 266

6 5.0 0.0 5.0 36.9 8.5 45.4 105 61 167 16.0 0.0 16.0 271 0.0 271

7 5.1 0.0 5.1 37.7 6.0 43.7 104 46 150 16.4 0.0 16.4 269 0.0 269

8 5.1 0.0 5.1 37.1 4.4 41.5 103 37 140 16.2 0.0 16.2 267 0.0 267

9 5.1 0.0 5.1 37.1 3.4 40.5 103 31 134 16.2 0.0 16.2 266 0.0 266

10 4.8 0.0 4.8 35.3 5.9 41.1 105 46 151 15.2 0.0 15.2 270 0.0 270

11 5.0 0.0 5.0 36.5 3.5 39.9 104 32 136 16.0 0.0 16.0 268 0.0 268

12 5.1 0.0 5.1 36.6 2.4 39.0 103 26 128 16.2 0.0 16.2 266 0.0 266

AVG. 4.7 0.0 4.7 36.0 6.0 42.0 61 47 107 15.2 0.0 15.2 268 0.0 268

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

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

1 324 0.0 324 192 45.3 237 192 0.0 192 267 32.5 300

2 325 0.0 325 196 41.2 238 196 0.0 196 268 29.3 297

3 333 0.0 333 201 51.6 253 201 0.0 201 275 37.3 312

4 322 0.0 322 194 28.3 223 194 0.0 194 265 19.5 285

5 323 0.0 323 193 25.0 218 193 0.0 193 266 16.9 283

6 329 0.0 329 199 41.6 240 199 0.0 199 271 29.6 301

7 327 0.0 327 197 31.9 229 197 0.0 197 269 22.2 291

8 325 0.0 325 192 25.9 218 192 0.0 192 267 17.6 285

9 324 0.0 324 189 22.1 212 189 0.0 189 266 14.7 280

10 328 0.0 328 194 31.6 226 194 0.0 194 270 22.0 292

11 326 0.0 326 193 22.5 215 193 0.0 193 268 15.0 283

12 322 0.0 322 190 18.4 209 190 0.0 190 266 11.9 278

AVG. 326 0.0 326 194 32.1 226 194 0.0 194 268 22.4 290

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

LEAD ARSENIC

ZINC

RUN

RUN

NICKEL

MERCURY BARIUM ANTIMONY

CHROMIUM CADMIUM
7

Table 5. XCEM Concentrations (μg/DSCM)

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 0.0 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 9:17 AM 902 2.1 20 9.9 0.8 1 0 60 3 227 23

5/13 9:18 AM 9:37 AM 903 0.0 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 0.0 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 0.0 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 910 1 8.0 242 30.8 2.9 347 254 48 187 249 269 8.6 210 27.5 3.2 261 270 51 172 226 296

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 12:59 PM 913 1 8.1 215 32.0 4.1 356 264 59 192 331 279 9.0 210 29.5 3.8 244 247 63 161 318 276

5/13 12:59 PM 1:19 PM 914 1 11.5 223 40.4 3.7 385 278 87 182 484 301 8.5 206 29.9 3.1 263 262 84 159 399 297

5/13 1:19 PM 1:40 PM 915 1 10.9 265 37.4 3.8 371 279 94 190 558 303 8.6 193 27.5 3.0 244 248 88 161 460 286

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

5/13 2:01 PM 2:22 PM 917 9.2 241 36.9 3.5 387 285 79 191 437 313 9.4 229 29.3 3.0 264 284 79 174 374 321

5/13 2:22 PM 2:47 PM 918 10.2 240 35.0 3.2 366 275 77 192 394 297 10.4 231 30.0 3.3 278 293 80 183 353 325

5/13 2:47 PM 3:08 PM 919 2 9.6 272 34.3 3.7 381 278 76 206 389 295 10.3 247 28.8 3.1 268 273 75 173 341 301

5/13 3:08 PM 3:29 PM 920 2 7.1 241 37.5 4.8 394 281 77 191 379 300 10.4 209 28.4 3.2 258 275 69 182 316 303

5/13 3:29 PM 3:50 PM 921 2 11.0 233 39.0 3.7 380 290 72 206 335 302 10.4 231 33.0 3.4 264 288 71 183 306 314

5/13 3:50 PM 4:10 PM 922 2 8.7 255 32.0 3.8 390 294 67 206 338 308 9.4 209 26.5 3.0 230 257 61 171 275 281

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 7:25 AM 926 6.8 136 20.6 3.4 148 142 50 102 253 158 8.3 117 18.0 3.0 93 150 52 87 227 173

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 76 160 314 297

5/14 7:45 AM 8:06 AM 928 3 13.6 210 38.6 6.1 350 259 84 185 417 290 12.8 173 31.7 4.7 253 267 81 145 369 311

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 9:08 AM 931 3 10.5 218 36.7 5.5 347 245 78 175 435 269 14.2 212 32.0 4.9 283 280 87 156 407 318

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

5/14 9:29 AM 9:49 AM 933 3 16.7 218 36.9 5.6 399 286 69 207 391 302

Date START STOP XC 

RUN

M29 XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)

RUN
8

Table 5. XCEM Concentrations (μg/DSCM) (Cont.)

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

5/14 9:49 AM 10:10 AM 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 AM 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 AM 11:53 AM 939 4 14.8 213 37.4 5.3 360 265 40 181 220 273 14.3 179 30.5 4.8 301 274 43 172 203 294

5/14 11:53 AM 12:13 PM 940 4 12.7 208 38.7 6.1 362 262 43 198 216 268 14.3 190 32.2 5.1 319 299 43 175 203 320

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

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 34 182 165 306

5/14 1:35 PM 1:56 PM 945 13.5 183 32.6 5.0 368 273 29 170 191 275 14.4 198 33.3 5.4 312 281 30 163 165 299

5/14 1:56 PM 2:16 PM 946 14.8 33 36.3 6.6 363 268 27 13 165 273 14.0 40 30.3 5.2 291 282 30 10 157 302

5/14 2:16 PM 2:37 PM 947 5 14.1 225 41.3 5.1 369 269 29 196 181 274 14.4 198 30.0 5.2 331 283 30 178 154 299

5/14 2:37 PM 2:57 PM 948 5 17.1 207 35.5 6.2 387 282 26 190 173 286 14.9 190 28.0 5.1 309 266 27 169 149 283

5/14 2:57 PM 3:18 PM 949 5 14.7 235 41.7 6.9 390 281 29 190 167 281 13.7 197 30.4 4.7 300 255 26 164 137 271

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

5/14 3:38 PM 3:59 PM 951 5 15.9 222 36.8 5.9 374 268 22 196 157 271 12.8 186 31.7 4.1 288 242 24 166 129 257

5/14 3:59 PM 4:19 PM 952 5 13.9 258 35.3 6.3 374 271 26 202 155 276 14.2 190 29.7 5.7 309 281 25 184 133 295

5/14 4:20 PM 4:40 PM 953 5 14.1 228 40.7 6.2 395 286 26 209 147 287 16.0 217 35.3 5.7 346 300 27 196 142 319

5/15 6:57 AM 7:18 AM 956 5.6 70 20.5 3.1 148 138 53 70 12 138

5/15 7:18 AM 7:38 AM 957 11.0 191 41.3 5.8 341 273 139 191 216 275 14.0 176 27.5 5.2 286 276 138 154 185 298

5/15 7:38 AM 7:58 AM 958 6 15.6 225 38.9 6.6 386 291 163 195 415 306 15.1 228 30.6 4.8 293 265 154 156 339 296

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 AM 8:39 AM 960 6 15.3 220 34.9 5.9 372 272 152 194 378 281 15.0 170 30.0 5.0 278 253 143 155 324 279

5/15 8:39 AM 9:00 AM 961 6 15.0 220 39.2 18.0 361 279 149 192 325 284 13.2 168 28.3 7.7 272 241 134 153 257 262

5/15 9:00 AM 9:21 AM 962 6 13.9 236 41.3 5.7 375 283 162 195 348 293 15.1 189 29.8 4.8 299 260 142 166 281 283

5/15 9:21 AM 9:41 AM 963 6 12.5 209 33.7 5.9 388 278 150 194 305 292 12.5 175 24.3 4.4 292 269 141 155 250 289

5/15 9:41 AM 10:02 AM 964 6 4.1 227 12.6 2.2 384 283 147 202 300 288 1.9 172 10.1 1.7 285 265 141 149 239 283

5/15 10:02 AM 10:22 AM 965 14.1 197 37.9 5.8 384 277 141 198 270 284 16.3 211 31.2 5.5 330 285 146 166 243 307

Date START STOP XC 

RUN

M29 XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)

RUN
9

Table 5. XCEM Concentrations (μg/DSCM) (Cont.)

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

5/15 10:22 AM 10:43 AM 966 7 13.6 233 36.9 5.9 384 280 137 205 251 283 11.9 187 26.8 4.0 241 226 116 143 189 241

5/15 10:43 AM 11:03 AM 967 7 14.2 212 34.1 6.1 402 294 141 203 254 294 13.3 213 30.7 5.1 301 287 145 169 216 306

5/15 11:03 AM 11:24 AM 968 7 15.4 223 35.5 5.9 396 292 139 208 245 297 14.8 200 31.3 5.3 310 287 145 179 224 304

5/15 11:24 AM 11:45 AM 969 7 17.9 253 34.9 4.9 394 291 138 197 237 296 14.5 193 32.7 5.2 317 303 151 184 214 318

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 5.4 309 288 142 175 201 304

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

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

5/15 12:46 PM 1:07 PM 973 15.6 185 34.7 5.8 396 285 135 186 196 292 13.9 181 29.8 5.2 277 253 120 157 161 267

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 PM 1:48 PM 975 8 15.1 232 33.6 6.8 402 292 128 182 171 287 13.8 185 30.7 4.5 294 274 128 167 146 287

5/15 1:48 PM 2:09 PM 976 8 15.3 202 35.8 4.9 395 286 132 187 192 285 13.6 191 29.9 4.8 302 294 141 170 166 311

5/15 2:09 PM 2:29 PM 977 8 12.9 215 35.1 5.6 412 299 132 188 179 301 14.6 183 31.5 5.2 310 288 133 179 151 301

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 5.1 303 298 137 178 153 311

5/15 2:50 PM 3:10 PM 979 8 16.4 205 39.8 5.8 413 303 130 179 149 300 12.5 171 28.7 4.2 265 256 121 158 128 266

5/15 3:10 PM 3:31 PM 980 8 15.4 200 40.8 4.9 393 289 127 190 157 285 13.8 172 31.3 5.3 289 280 130 169 134 291

5/15 3:31 PM 3:51 PM 981 13.0 215 41.7 6.1 398 290 119 185 133 284 14.0 187 34.8 5.3 323 319 145 192 135 330

5/15 3:51 PM 4:12 PM 982 9 16.1 202 38.8 6.0 406 293 128 198 143 297 13.2 208 31.3 4.6 275 262 119 163 115 272

5/15 4:12 PM 4:32 PM 983 9 14.0 216 34.7 6.3 410 298 132 193 146 301 13.6 200 31.5 5.4 299 288 129 169 128 299

5/15 4:33 PM 4:53 PM 984 9 12.7 217 34.3 6.0 405 295 132 199 136 295 13.1 180 30.4 4.9 263 264 118 172 113 272

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

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

5/15 5:55 PM 6:15 PM 988 15.0 183 29.1 5.0 418 304 123 195 110 299 12.7 193 29.3 5.4 308 309 133 174 100 320

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 PM 990 0.0 13 0.6 0.2 20 1 22 5 120 8 0.0 20 1.2 1.5 19 2 23 2 104 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 4 114 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

5/16 7:25 AM 7:45 AM 996 13.2 216 39.3 7.1 374 268 151 172 290 280 13.0 216 33.8 12.5 287 269 151 158 249 289

5/16 7:45 AM 8:06 AM 997 10 13.7 188 38.5 6.1 404 284 154 182 262 298 14.2 197 32.9 6.9 283 272 146 167 231 294

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 14.1 191 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

5/16 9:28 AM 9:49 AM 3 10 15.1 183 33.2 5.6 387 285 127 202 211 286 14.1 187 28.3 5.0 277 280 132 160 185 295

5/16 9:49 AM 10:09 AM 4 10 16.3 203 37.1 5.4 391 291 128 188 182 292 14.7 203 30.9 5.1 280 290 134 172 164 303

5/16 10:09 AM 10:30 AM 5 18.9 185 36.1 5.8 407 294 127 196 175 297 13.8 205 29.8 4.3 270 274 125 178 151 283

Date START STOP XC 

RUN

M29 XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)

RUN
10

Table 5. XCEM Concentrations (μg/DSCM) (Cont.)

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

5/16 10:30 AM 10:50 AM 6 11 16.2 183 34.6 5.3 393 286 126 202 163 281 14.7 218 32.0 4.8 284 281 129 174 144 292

5/16 10:50 AM 11:11 AM 7 11 15.9 204 34.1 5.2 394 286 119 193 152 285 14.7 209 32.1 5.4 302 305 136 185 141 315

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

5/16 11:31 AM 11:52 AM 9 11 10.6 204 34.3 4.9 405 298 130 192 133 295 14.5 206 29.4 5.2 288 298 128 182 119 309

5/16 11:52 AM 12:13 PM 10 11 23.1 194 37.5 5.4 405 289 112 191 128 290 14.7 216 33.5 5.3 292 299 131 186 116 311

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

5/16 12:33 PM 12:54 PM 12 11 15.6 201 30.3 4.9 374 273 115 189 110 269 12.9 206 29.2 7.6 263 280 121 183 96 288

5/16 12:54 PM 1:14 PM 13 12.5 208 32.3 5.7 386 281 119 198 95 283 14.9 198 33.1 5.0 291 302 130 181 92 312

5/16 1:14 PM 1:35 PM 14 14.8 183 33.2 5.1 402 298 124 211 100 299 13.6 203 33.6 5.2 260 291 126 180 86 300

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 97 308

5/16 1:56 PM 2:16 PM 16 12 14.3 234 33.4 4.9 389 289 118 196 105 279 14.0 208 31.8 6.0 252 286 123 181 87 295

5/16 2:16 PM 2:37 PM 17 12 12.9 184 33.9 5.1 381 281 117 189 90 272 14.7 191 30.2 4.9 264 291 124 178 80 301

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 38.8 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

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

ALL 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

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

M29 XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)

RUN

UNWEIGHTED AVERAGE

St. Dev.

Date START STOP XC 

RUN
11

The XCEM data was then averaged for each M29 run using equation 1:







j

n

j 1

ij j

i

t

C t

C Equation 1

where:

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

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

n = Number of XCEM measurements during test run

tj = Number of minutes XCEM measured element i’s concentration 

during time interval j coinciding with M29 sampling.

  jt = 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. 

During this time, it was observed that Sb, Ba, and Hg calibration factors were 

too high relative to the calibration standards by 15%, 15%, and 7% respectively. 

The calibration factors were changed prior to run 2 (Appendix C).

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

curve by 4% and were changed following the M29 test (see Appendix C for a 

complete discussion of Hg calibration).

3. During run 961, an unusually high Cr number (18 μg/DSCM – more than 6 SD 

from the average during normal spiking conditions) was observed. The spectra 

showed Fe, Cr, and Ni in the same ratio as stainless steel and a speck was noted 

on the filter tape, which was believed to be from contamination that was not 

representative of the stack gas. For this reason, run 961 for Cr was not used 

during the averaging to compare to M29.

4. The XCEM shed’s air conditioning failed on May 16. As such, the Pd QA 

concentration did not meet the 90-110% criteria for XCEM runs 1021 and 1022, 

which represented 23 minutes of M29 run 12. Consequently, XCEM 

concentrations for run 12 were based on a time-weighted average of the 97 

minutes that the XCEM produced validated data.

The modified XCEM data was submitted prior to receiving M29 results. No modification 

to the XCEM data was made after receiving M29 results.

2.4 XCEM CALIBRATION EVALUATION USING A QUANX – XRF AND ICP

Since XRF analysis is nondestructive, the concentrated particulate matter on the filter can 

be reanalyzed at a later date. In order to evaluate the XCEM calibration, CES reanalyzed 

each spot using a QuanX XRF analyzer located at CES. The CES QuanX analyzer is one 
12

of four in the nation that has been approved for measuring PM2.5 metals concentrations 

for EPA’s speciation program. Consequently, the analyzer has undergone a series of 

round robin tests with other labs as well as rigorous quality control checks. The QuanX 

analysis was conducted approximately six 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 is shown in Table 5.

Following the reanalysis, filter spots that correlated with M29 runs 5 and 6 were 

combined and submitted to Columbia Analytical of Vancouver, WA for analysis using 

ICP/MS (Table 6).

Table 6. Analysis of XCEM Filter Tape By Columbia Analytical (μg/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

2.5 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%, 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 five 

percent (Table 7).

Both the XCEM and M29 show good precision for these elements with the XCEM 

precision about 30% lower than M29.

Table 7. Predicted, XCEM and Method 29 Precision During Validation Testing1

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.

3.0 DISCUSSION

3.1 REGULATED ELEMENTS TYPICALLY FOUND IN THE 

FEEDSTREAM

Although 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 8). The XCEM successfully measured all three of the key elements and 

met the 20% relative accuracy requirements in proposed PS-10 with relative accuracies of 

4%, 17%, and 15% respectively.
13

Table 8. TEAD Emission Limits

MACT Limit

g/hr μg/dscm1 μg/DSCM

Pb 4.3 932 Yes

Cd 0.26 56 Yes

Cr 0.04 10 Yes

As 0.11 24 No

Hg 14 3,036 130 No

Sb 14 3,036 NR No

Ni 930 201,740 NR No

Ba 2,400 521,243 NR No

Zn NR NR NR No

1) Assumes 4635 DSCM per hour

NR: Not regulated

State Limit

Elem Potential to Limit 

Feed Rate

240

97

3.1.1 LEAD

Lead is the element which most often limits incineration rates at APE-1236. The TEAD 

incinerator has a state-mandated Pb stack emission limitation of 4.3 g/hr. At typical stack 

flow rates, this equates to about 900 μg/DSCM. EPA’s Hazardous Waste Combustor 

Maximum Achievable Control Technology (MACT) rules, which are scheduled for 

implementation within two years, will further limit the combined Pb and Cd emission rate 

to 240 μg/DSCM. 

Currently, Pb concentrations within the munitions are determined for each type of 

ordnance prior to incineration. Munition feed rates into the incinerator are restricted 

using a model which assumes that a fraction of the lead in the munitions will be 

transported through the air pollution control devices and emitted from the stack. The 

effectiveness of the model is dependent upon several assumptions including transport 

under various meteorological regimes, incinerator temperature effects, and chemical 

interactions. Direct measurement of Pb concentrations in 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 9 shows the Pb results for the MSE/background predicted concentrations (PRD), 

M29, XCEM, 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 seven percent. The XCEM and M29 Pb concentrations 

are also highly correlated with an r2 of 0.98 (Figure 3). 

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

incinerator. Following run five, MSE-TA began spiking an additional 105 μg/DSCM of 

Pb. During testing both M29 and the XCEM reported concentrations ranging from 25 to 
14

150 μg/DSCM. The relative accuracy for the XCEM was 4.4%. This good 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 9. Summary of Lead Concentration Data During M29 Testing (μg/DSCM)

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

1 67 72 67 68 0.99 1.01 1.08 0.93 0.94

2 61 77 67 64 1.04 1.11 1.27 0.87 0.84

3 77 98 81 84 0.97 1.06 1.27 0.83 0.86

4 41 38 36 39 0.93 0.88 0.93 0.95 1.03

5 36 27 26 26 22 0.99 0.73 0.77 0.94 0.95

6 167 147 154 141 129 1.09 0.92 0.88 1.05 0.96

7 150 135 137 141 0.97 0.91 0.90 1.01 1.05

8 140 128 132 132 1.00 0.94 0.92 1.03 1.03

9 134 122 128 125 1.02 0.95 0.91 1.05 1.03

10 151 135 140 140 1.00 0.93 0.89 1.04 1.04

11 136 118 121 129 0.94 0.89 0.87 1.02 1.09

12 128 113 117 126 0.93 0.91 0.88 1.04 1.12

AVG. 107 101 101 101 75 0.99 0.94 0.96 0.98 0.99

SD 47 39 43 43 76 0.05 0.09 0.16 0.07 0.09

Figure 3. XCEM vs. M29 Lead for Validation Tests

y = 1.09x - 9.60

R

2

 = 0.98

0

50

100

150

200

0 50 100 150 200

M29 Lead (μg/dscm)

X

C

E

M

Lea

d (μ

g/dscm)

3.1.2 CADMIUM

The APE-1236 state-mandated emission limit for Cd is about 60 μg/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% of 

the stack’s Cd was from MSE-TA while 20% was estimated to be background. Table 10 

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% higher than M29 with a relative accuracy of 17%. The reanalysis of the 

XCEM filter tape yielded mixed results with the QuanX XRF within 3% of M29 and the 

Columbia Analytical concentrations within 4% 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.
15

Table 10. Summary of Cadmium Concentration Data During M29 Testing (μg/DSCM)

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

1 41.5 29.4 35.2 29.3 1.20 0.85 0.71 1.20 0.99

2 39.8 32.0 35.8 29.4 1.22 0.90 0.80 1.12 0.92

3 48.6 34.6 37.2 31.6 1.18 0.77 0.71 1.08 0.91

4 41.6 31.0 37.7 32.6 1.16 0.91 0.74 1.22 1.05

5 41.4 30.8 36.4 30.0 36.4 1.22 0.88 0.74 1.18 0.97

6 45.4 31.2 37.2 28.6 34.2 1.30 0.82 0.69 1.19 0.92

7 43.7 31.8 36.6 30.9 1.19 0.84 0.73 1.15 0.97

8 41.5 32.4 37.7 31.1 1.21 0.91 0.78 1.16 0.96

9 40.5 32.0 37.4 31.5 1.19 0.92 0.79 1.17 0.98

10 41.1 29.8 34.6 27.9 1.24 0.84 0.73 1.16 0.94

11 39.9 31.3 34.9 30.9 1.13 0.87 0.78 1.12 0.99

12 39.0 31.2 35.5 31.6 1.12 0.91 0.80 1.14 1.01

AVG. 42.0 31.5 36.4 30.4 35.3 1.20 0.87 0.75 1.16 0.97

SD 2.7 1.3 1.1 1.4 1.5 0.05 0.05 0.04 0.04 0.04

3.1.3 CHROMIUM

APE-1236 has an effective Cr emission limit of less than 10 μg/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 μg/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 μg/DSCM for the remainder 

of the tests. Overall, the XCEM was consistently 10% higher than M29 at both 

concentration levels (Table 11). This represents a difference of about 0.5 μg/DSCM. 

The good agreement between the XCEM and M29 at both the 3 and 5 μg/DSCM levels 

validates the ability of the XCEM to accurately measure Cr at very low concentrations.

Subsequent measurements of the XCEM filter tape by the CES-QuanX and ICP were 

within 3% of the M29 concentrations. The consistency of M29 with the predicted values 

and subsequent measurements of the XCEM filter tape indicates that an XCEM 

calibration error of about 10% may have been responsible for any differences between 

the two methods.

The Cr relative accuracy was 15%, meeting PS10 criteria.
16

Table 11. Summary of Chromium Concentration Data During M29 Testing (μg/DSCM)

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

1 2.9 3.6 3.7 3.2 1.16 1.28 1.24 1.03 0.89

2 2.9 4.0 4.0 3.2 1.27 1.39 1.38 1.01 0.79

3 5.2 6.4 5.8 4.8 1.20 1.11 1.24 0.90 0.75

4 5.0 5.0 5.8 5.1 1.14 1.15 0.99 1.16 1.02

5 5.0 5.2 6.1 5.0 5.0 1.22 1.21 1.04 1.16 0.96

6 5.0 4.8 5.8 5.3 4.7 1.09 1.16 0.97 1.20 1.10

7 5.1 4.9 5.6 5.2 1.09 1.10 0.96 1.15 1.05

8 5.1 5.1 5.8 4.8 1.20 1.13 1.00 1.14 0.95

9 5.1 5.2 5.9 5.3 1.10 1.17 1.02 1.14 1.03

10 4.8 4.9 5.4 5.4 1.01 1.14 1.03 1.11 1.10

11 5.0 4.8 5.4 5.5 0.97 1.07 0.96 1.11 1.15

12 5.1 4.8 5.3 6.9 0.76 1.04 0.95 1.10 1.44

AVG. 4.7 4.9 5.4 5.0 4.8 1.10 1.16 1.07 1.10 1.02

SD 0.8 0.7 0.8 1.0 0.2 0.14 0.09 0.14 0.08 0.18

Overall, the XCEM effectively measured the three key elements for the M29 tests. The 

XCEM met relative accuracy criteria, showed good response to changes in concentration, 

and had good response times and correlations.

3.2 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 did not measure Be as part of this test. The XCEM met PS10 measurement criteria for 

Sb (20%) and Ba (4%), but was conservatively higher than M29 for As, Hg, and Ni with 

relative accuracies of 27%, 33%, and 33% respectively. 

3.2.1 ARSENIC

Arsenic results are shown in Table 12. The XCEM reported concentration was in good agreement 

with the post-test analysis of the filter tape by both the 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. 

Some question exists, however, as to the predicted concentrations true value since the 

HKM analysis of the MSE-TA solution was 23% lower for As. If the HKM As 

concentrations were used, the predicted concentration would be much closer to M29.

Overall, the XCEM was 25% higher than M29 concentrations for As. Aside from 

calibration errors, other potential sources of error for the XCEM include loss during 

transport, low filter trapping efficiency, deposit positioning errors, spectral interferences, 

and incorrect flow measurements. Each of these error sources is highly unlikely. The 

first three sources of error would only result in XCEM concentrations lower than M29. 

Spectral interferences would not have impacted Columbia Analytical ICP/MS results, and 

incorrect flow measurements would have resulted in all metals being uniformly high or 
17

low since one XCEM flow measurement is applied to all of the metals for each run. For 

this reason, the differences in concentration appear to be due to M29 errors.

The XCEM’s relative accuracy of 27% did not meet PS10 criteria. However, the XCEM 

was conservatively high for this element, which is typically not found in the TEAD 

emissions. The XCEM was also highly correlated with M29 As (r2=0.85) showing good 

responsiveness to changes in As concentration.

Table 12. Summary of Arsenic Concentration Data During M29 Testing (μg/DSCM)

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

1 10.6 7.8 10.1 9.4 1.07 0.95 0.74 1.29 1.20

2 10.7 8.3 9.3 10.2 0.91 0.88 0.77 1.13 1.24

3 16.7 11.5 13.7 13.4 1.02 0.82 0.69 1.19 1.17

4 16.1 11.9 14.3 14.5 0.98 0.89 0.74 1.20 1.22

5 16.1 11.8 15.3 14.1 14.0 1.09 0.95 0.73 1.30 1.20

6 16.0 11.3 13.9 13.8 13.3 1.01 0.87 0.71 1.23 1.22

7 16.4 11.7 15.6 13.7 1.14 0.96 0.71 1.34 1.18

8 16.2 12.3 14.4 13.8 1.05 0.89 0.76 1.18 1.12

9 16.2 12.2 13.9 13.7 1.02 0.86 0.75 1.14 1.12

10 15.2 11.1 14.3 13.3 1.07 0.94 0.73 1.28 1.20

11 16.0 11.7 15.5 14.7 1.05 0.97 0.73 1.32 1.25

12 16.2 11.9 14.8 14.3 1.03 0.91 0.73 1.24 1.21

AVG. 15.2 11.1 13.8 13.3 13.7 1.04 0.91 0.73 1.24 1.19

SD 2.2 1.5 2.0 1.7 0.5 0.06 0.05 0.02 0.07 0.04

3.2.2 MERCURY

Unlike the other elements, Hg is primarily in the vapor phase in typical stack emissions. 

For example, during the 2001 M29 tests at TEAD, the particulate Hg captured on the 

M29 filter and probe represented 1% of the total Hg. The XCEM relies upon a specially 

treated filter membrane to capture the vapor phase Hg while M29 uses an impinger train.

The APE-1236 Hg limit is about 3000 μg/DSCM. Mercury, however, is typically not

present in TEAD stack emissions. Indeed, an earlier multi-metals monitor was certified 

for use at TEAD without even measuring Hg (Seltzer, 1999). For the current validation 

test, Hg was spiked by MSE-TA with results shown in Table 13.

The XCEM and M29 concentrations had acceptable agreement during runs 1-5 with the 

XCEM 16% higher than M29. Had the conditions for runs 1-5 been duplicated for nine runs, 

the XCEM would have met the relative accuracy requirements for Hg. However, following 

run 5, the XCEM was consistently 34% higher than M29. It is believed that these differences 

are due to vaporization of particulate mercury 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% 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 
18

of Hg on the M29 filter increased from 18% in runs 1-5 to 30% in runs 6-12 (Pattison, 

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 refrigeration of 

the M29 filter and it was not cooled while being trucked to California for analysis.

During this time, a significant quantity of the Hg on the filter could have vaporized. 

Figure 4 shows the relationship between the level of Hg on the M29 filter and the percent 

difference between M29 and the XCEM. The high correlation (r2 = 

The XCEM filter also showed a loss of about 30% 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 for vapor phase Hg on earlier tests (Cooper, 2000; Johnsen, 2001) 

so the Hg loss seems to be dependent upon the quantity in the particulate phase. 

Table 13. Summary of Mercury Concentration Data During M29 Testing (μg/DSCM)

RUN PRD1 M291 XC1 QN1 CA1XC/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.

Figure 4. Percent Difference Between M29 and the XCEM vs. Percent of Mercury on M29 Filter

y = 1.25x - 4.3223

R

2

 = 0.8055

0

10

20

30

40

50

0 10 20 30 40

Percent of Hg on M29 Filter

Percent Difference Between

M

2

9

a

n

d

X

C

E

M
19

3.2.3 ANTIMONY

Antimony results are shown in Table 14. Overall, the XCEM was higher than M29 by about 

18%, but met relative accuracy criteria with an RA of 19.9%. 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%.

Table 14. Summary of Antimony Concentration Data During M29 Testing (μg/DSCM)

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

3.2.4 NICKEL

Validation test results for Ni are reported in Table 15. The XCEM was about 30% higher 

than M29 and had a relative accuracy of 34%, which did not meet PS10 criteria. 

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 in the As section, since the XCEM was higher than M29, the difference 

appears to be due to M29 analytical problems.

Nickel is not typically found in TEAD stack emissions and the site has a 140,000 

μg/DSCM stack emission limit. As such, the conservative numbers produced by the 

XCEM should serve to adequately ensure that Ni is below the emission limit.
20

Table 15. Summary of Nickel Concentration Data During M29 Testing (μg/DSCM)

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

1 267 200 270 262 1.03 1.01 0.75 1.35 1.31

2 268 235 283 276 1.02 1.06 0.88 1.20 1.18

3 275 234 262 262 1.00 0.95 0.85 1.12 1.12

4 265 213 269 285 0.95 1.02 0.80 1.26 1.34

5 266 231 274 267 226 1.03 1.03 0.87 1.19 1.15

6 271 225 281 259 220 1.08 1.03 0.83 1.25 1.15

7 269 218 289 285 1.01 1.07 0.81 1.33 1.31

8 267 219 296 281 1.05 1.11 0.82 1.35 1.28

9 266 221 294 283 1.04 1.11 0.83 1.33 1.28

10 270 205 285 281 1.02 1.06 0.76 1.39 1.37

11 268 216 288 292 0.99 1.07 0.81 1.33 1.35

12 266 199 286 294 0.98 1.08 0.75 1.44 1.48

AVG. 268 218 281 277 223 1.02 1.05 0.81 1.30 1.28

SD 2.8 12 10 12 4.9 0.04 0.04 0.04 0.09 0.11

3.2.5 BARIUM

Barium results for the validation tests are shown in Table 16. For Ba, the predicted 

concentrations, M29 results, XCEM results, and QuanX reanalysis all agree to within 

10% with an XCEM relative accuracy of 4%. Although the stack limit is 500,000 

μg/DSCM, typical Ba concentrations found in the stack are in the 0 to 200 μg/DSCM 

range. During these validation tests, the XCEM demonstrated good accuracy relative to 

M29 for Barium under realistic stack conditions.

Table 16. Summary of Barium Concentration Data During M29 Testing (μg/DSCM)

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
21

3.3 NONREGULATED METALS 

Two non-regulated 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 (Pattison, 2002b). Zinc was spiked by MSE-TA with XCEM reported 

concentrations shown in Table 17.

Overall, the XCEM Zn concentrations were consistently about 40% 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. As discussed in the arsenic section, XCEM potential sources of 

error would lead to decreased concentrations. Since the XCEM was higher than M29, it 

is believed that the difference is primarily due to M29 errors.

Table 17. Summary of Zinc Concentration Data During M29 Testing (μg/DSCM)

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

4.0 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 lead and zinc during incineration of 

various munitions. Next, a bypass duct was blocked with a metal plate resulting in a 

greater than 90% drop in metal concentrations. Using this data, TEAD was better able to 

understand sources of Pb in the emissions.

Currently, the XCEM is being moved to a newly developed “test furnace” at TEAD. The 

furnace, operated by the Ammunition Equipment Division, anticipates using the 

instrument to rapidly determine effects of changes in munitions or control strategies.

The continued use of the XCEM to diagnose and assist with process control indicates the 

value of having an installed continuous emission monitor for multi-metals at TEAD.
22

5.0 CONCLUSION AND RECOMMENDATIONS

The XCEM successfully measured the three potential emission limiting elements found 

in APE-1236 which could potentially approach emission limits: Pb, Cd, and Cr. The 

XCEM also successfully measured two other regulated metals: Ba and Sb and were 

conservatively 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. 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 chromium’s low 

concentrations when changes of only two micrograms per cubic meter occurred between 

runs two and three.

The XCEM has continued to be a useful instrument at TEAD for diagnostics and process 

control. CES recommends the adoption of the XCEM as a validated monitor for 

incinerators such as APE-1236. Recent advances in XRF technology have allowed for a 

miniaturized version of the XCEM with better detection limits than the current system. 

CES also recommends that this technology be incorporated into a mobile version of the 

XCEM for the army’s stack testing organization (CHPPM) and an extension of the 

technology to a mercury-dedicated XCEM.
23

6.0 REFERENCES

Bryson (2001). Final Report – Stack Spiking Report for a Multi-Metal CEMS Test at the 

Tooele Army Depot Deactivation Furnace. Prepared for U.S. Army Corp of Engineers by 

MSE-TA, Butte, MT. Contract No. GS-10F-0212K.

Bryson (2002). US Army CERL, Waste Minimization and Pollution Prevention Program: 

Stack Spiing Report for a Multi-Metal CEMS Test at the Tooele Army Depot 

Deactivation Furnace – 2002. Prepared for U.S. Army Corp of Engineers by MSE-TA, 

Butte, MT.

Cooper (2002. Cooper, J.A., B.E. Johnsen, S.C. Fry, M.P. Nakanishi. “Limitations in the 

Use of EPA Reference Method 29 for Evaluating the Relative Accuracy of Candidate 

Multi-Metal Continuous Emission Monitors.” Cooper Environmental Services Report, 

September 2002.

Cooper, J., B. E. Johnsen, K.J. Hay, 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.

Johnsen, B., J. Cooper, A.C. Milliken (2000). X-Ray Fluorescence Multi-Metals Monitor 

Dat Recording and Calibration Automation and Mercury Sampling. Prepared for U.S. 

Army Corp of Engineers by CES, Beaverton, OR. Contract No. DACA42-00-P-0245. 

Johnsen (2002). Calibration And Transport Evaluation Of An X-Ray Based Continuous 

Emission Monitor At Tooele Army Depot. Prepared by Cooper Environmental Services 

for the U.S. Army Corp of Engineers. Contract No. DACA42-02-P-0072

Pattison, M. (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. Prepared by the U.S. Army Center for Health Promotion and Preventative 

Maintenance.

Pattison, M. (2002a). Air Pollution Management Study No. 43-EL-4755-02 Verification 

of Multi-Metals Continuous Emission Monitor at Tooele Army Depot. Tooele, Utah 

May 13-16, 2002. Prepared by the U.S. Army Center for Health Promotion and 

Preventative Maintenance.

Pattison, M. (2002b). Phone conversation between Mike Pattison (US Army CHPPM) 

and Bruce Johnsen CES June 2002. Mike Pattison phone number: (410) 436-8146.

Cooper, J., B. E. Johnsen, K.J. Hay, 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.
24

MACT (1999). Final Technical Support Document for HWC MACT Standards. Vol III 

Selection of MACT Standards and Technology. Chapter 13. USEPA Contract 68-D2-

0164.

PS-10 (1996), Proposed Performance Specification 10 for Metal CEMS (Proposed 

04/19/96) Found on the EPA website at: http://www.epa.gov/ttn/emc/propperf.html.

Weidenfeld, R. July 9, 2002. Phone conversation between Robert Weidenfeld of Severen 

Trent Lab and John Cooper of CES. Robert Weidenfeld phone number: 916-373-5600.
APPENDIX B

MERCURY CALIBRATION 

ADJUSTMENTS AND VOLATILITY 

LOSSES FROM PARTICULATE MATTER 

FRACTION
C-1

1. INTRODUCTION

Mercury represents a distinctly different hazardous element from the others included in 

this test in that it is more likely to exist in the vapor phase and has been shown to exhibit 

distinctly different transport properties. These properties appear to have contributed to 

differences in the mercury concentrations measured by the different methods compared in 

this test. This appendix discusses the details associated with both the adjustments that 

were made to the XCEM calibration factors and losses of mercury from particulate 

deposits after sample collection.

2. CALIBRATION ADJUSTMENTS

Two adjustments were made to the mercury results after the first test run was started. 

The first adjustment was a 7% increase in the mercury sensitivity factor between M29 

Run 1 and Run 2. The second was a 4% increase in the sensitivity factor shortly after the 

completion of the tests and before the M29 and XCEM results were submitted. The 

necessity for these adjustments was due in part to the volatility of the mercury, which 

makes it difficult to make stable thin-film mercury standards. As such, thin film mercury

standards are not available from NIST. The standards that are available are relatively 

unstable and need to be frequently validated. This method limitation is generally 

minimized by the fact that energy dispersive X-ray fluorescence sensitivity factors are a 

smoothly varying function of atomic number. This allows mercury sensitivity factors to 

be estimated by interpolation using well-defined sensitivity factors for elements with 

similar atomic number such as platinum, gold, thallium, lead and bismuth. The following 

two adjustments were based on this interpolation process and a re-evaluation of the bestestimated calibration factor.

a. Adjustments During First Day of Testing

Mercury calibration of the XCEM prior to the M29 tests was done during preliminary

spiking tests. During these tests, the NIST thin film standard for lead was not available 

and the mercury sensitivity was estimated based on a previous measurement of the lead 

NIST standard. This fact wasn’t realized until the testing started and a review of the 

preliminary mercury results indicated a potential bias relative to the NIST lead results. 

As a result, the mercury calibration was adjusted by 7% during the period between M29 

Run 1 and Run 2.

b. Post-Test Adjustments 

The second adjustment to the mercury results of 4% was applied when the calibration factors 

were reviewed following the tests. A comparison with the ratio of mercury to lead sensitivity

factors developed from a more extensive study in the laboratory indicated that the 0.838 ratio 

used during the tests should have been 0.873. This 4% correction was applied to the XCEM 

results prior to the submission of either the M29 or the XCEM results. 
C-2

3. LOSSES FROM PM FRACTION

a. Introduction

The XCEM mercury results were, on average, 18% greater than the predicted 

concentration, 27% greater than the M29 results, 37% greater than the laboratory XRF 

measurements of the XCEM deposit spots, and 45% greater than the CVAA 

measurements on the XCEM deposit spots. Subsequent investigations of these 

differences strongly suggest that the XCEM results are the best estimate of the actual 

mercury concentrations in the stack. It is hypothesized that the large differences between 

the XCEM mercury results and the results from the other methods is due to the loss of 

mercury from the filter deposits after the M29 and XCEM samples were collected and 

after the XCEM original measurements were made. This hypothesis is described in more 

detail in the following subsection. The experimental measurements are described in 

Subsection C and the results are summarized and discussed in Subsection D. The 

hypothesized model is then evaluated relative to the available data in Subsection E.

b. Model

A model has been developed to explain the apparent high XCEM mercury concentrations 

relative to M29. In this model, mercury is lost from the particulate fraction of the M29 

and XCEM filters after the initial XCEM measurements were made. That is, a substantial 

fraction of mercury was associated with the particulate fraction, and the mercury in this 

particulate was unstable. Since all of the other analytical methods relied on aged 

samples, the mercury concentration results were low due to vaporization of particulate 

mercury prior to laboratory analysis. As discussed in the following subsection, a 

substantial amount of experimental data is available, all of which is supportive of this 

hypothesized model. Most of this experimental data was developed only because of the 

unique characteristics of the XCEM and the fact that the XCEM elemental measurement 

is nondestructive and the spectra from each of the original measurements were archived.

c. Experimental 

The initial XCEM measurements were based on the analysis of filter deposits, which 

were a combination of both absorbed vapor phase mercury species and surface deposits 

of particulate mercury species. Each deposit was analyzed using three different X-ray

excitation conditions, resulting in spectra that were used to determine concentration. All 

spectra were archived in the XCEM computer. As such, the deposit was available for 

further analysis and testing, and the original spectra was available for comparison with 

subsequently developed spectra.

Following the validation testing at TEAD, several tests were conducted by CES to better 

understand the mercury concentration differences between M29 and the XCEM.
C-3

 All of the XCEM deposit spots corresponding to all of the M29 runs were 

reanalyzed by CES’s laboratory QuanX XRF analyzer six weeks after the initial 

validation test. In addition, ten XCEM filter deposit spots were analyzed over a 

period of two months to evaluate mercury stability. Spectra from these tests were 

compared to archived spectra from the original validation test.

 The XCEM deposit spots corresponding to M29 Runs 5 and 6 were analyzed first 

by laboratory XRF and then by cold vapor atomic absorption by an independent 

laboratory (Columbia Analytical Services).

 The elemental concentrations in the MSE-TA spiking solutions corresponding to 

M29 Runs 5 and 6 were analytically determined by HKM labs in Butte, MT. 

d. Results and Discussion

The mercury results for the original validation test are summarized in Table C1. There is 

a clear bias of about 26% between the XCEM results and the M29 results. Normally, the 

M29 results would be accepted as the best estimate of stack mercury concentration and it 

would be assumed that the candidate method (XCEM) was in error. However, because of 

the total quality assurance associated with the XCEM and the fact that the XRF analysis 

is non-destructive, it is possible to conduct further analyses to evaluate the potential cause 

of this difference. Additionally, the laboratory analysis results for each component of the 

M29 sampling trains (i.e. probe, filter, and back half) were determined separately, and are 

available for interpretation. 

Table C.1 Mercury Reported Concentrations During Year 2002 Method 29 Validation Testing.

PRD M29 XC QN CA PRD XC QN CA

1 324 332 367 257 0.98 1.10 0.77

2 325 334 381 251 0.97 1.14 0.75

3 333 294 365 262 1.13 1.24 0.89

4 322 327 368 301 0.98 1.13 0.92

5 323 318 379 308 274 1.02 1.19 0.97 0.86

6 329 280 378 288 254 1.18 1.35 1.03 0.91

7 327 285 392 302 1.15 1.37 1.06

8 325 306 406 294 1.06 1.33 0.96

9 324 309 405 287 1.05 1.31 0.93

10 328 292 395 282 1.13 1.35 0.97

11 326 295 397 286 1.11 1.35 0.97

12 322 293 389 267 1.10 1.33 0.91

AVG. 326 305 385 282 264 1.07 1.27 0.93 0.88

SD 3.3 19 14 19 13.8 0.07 0.10 0.09 0.03

μg/DSCM

RUN

Normalized to M29
C-4

i. Loss of Mercury From the XCEM Filter

a. Laboratory XRF Measurements (QN)

Two months after the validation testing, CES’s laboratory QuanX XRF analyzer 

reanalyzed the original XCEM deposit samples with good replication for all elements 

except mercury (see Table 5 in main body of text).

A series of ten spots on the XCEM filter tape were reanalyzed between on 6/21/02 and 

7/11/02. The spots, which represent 10 XCEM runs, showed a consistent mercury loss of 

about 30% over the three-week period. Other sources of error such as shifts in geometry

or instrument instability were eliminated as possible systematic sources of error by noting 

that the other elements were replicated within experimental error to a few percent.

b. XCEM Measurements (XCEM)

To confirm this loss of mercury, five XCEM deposit spots were re-analyzed by the 

TEAD XCEM, which was still operating with the same conditions and calibration factors 

as used during the M29 tests about two months earlier. The X-ray spectra from the 

original analysis of XCEM Run Numbers 939 to 943 (M29 Run Number 4) are compared 

in Figure C1. This comparison clearly shows that there is good agreement for the two 

closest analyte peaks for zinc and lead, but a substantial reduction in the peak intensity

for the mercury L-alpha analyte line. A comparison of the XCEM mercury

concentrations measured during the M29 testing (5-14-02) with those measured with the 

XCEM on 7-25-02 indicate a 31.4 ± 0.4 μg/m3 reduction in measured concentration. 

Although this reduction might be associated with possible systematic errors such as 

sample positioning, this possible source of error was eliminated by comparing other 

elements such as zinc and lead as well as the ratio of mercury to these elements. The 

reduction in mercury to zinc ratio, for example, was 29.1%, which is in good agreement 

with the mercury-measured reduction.

Clearly, mercury was lost from the XCEM deposit after the sample was collected and 

analyzed by the XCEM. As discussed in the following subsection, the available data 

strongly suggests that a substantial portion of the M29 mercury was also lost from the 

M29 PM filter deposits prior to analysis.

Figure C.1 Comparison of XCEM X-Ray Spectra Measured During Method 29 

Testing and Seventy-One Days Later.

0

2000

4000

6000

8000

10000

12000

14000

 

C

o

u

nts

XCEM 051402 XCEM 072502

Zinc

Mercury

Lead
C-5

ii. Instability of M29 Mercury PM Deposit Highly Likely

Although there is no direct evidence of the loss of mercury from the M29 samples, there 

is ample indirect evidence that a similar loss to that of the XCEM deposit would be 

expected. This indirect evidence is discussed in the following three subsections.

c. Train Location of Mercury Deposits

The recovery and analysis of the M29 probe, filter, nitric acid impingers, sulfuric acid 

impingers and the hydrochloric acid rinse were kept separate for both the May 2001 and 

May 2002 M29 tests. The results are summarized and compared in Table C2. It is 

interesting to note that during the 2001 testing, only about 1% of the mercury was 

deposited on the quartz fiber filter. This is typical of most stack measurements of 

mercury, and as such there is little concern for the stability of the PM deposited on the 

filter. However, this is not the case for the 2002 mercury measurements. During these 

latter tests, 18% of the mercury was deposited on the filter during runs 1 through 5 with 

no lead in the mercury-nickel-zinc spiking solution. After adding lead to the spiking 

solution, the percent of mercury depositing on the filter increased to 29% for the 

remaining M29 runs. 

Table C2. Comparison of the Location in M29 Sampling Trains Where the Mercury 

Was Deposited During the 2001 and 2002 Tests.

YEAR RUNS FILT. PROBE M2B M3A M3B M3C TOTAL

2001 1-13 1.1 0.1 93 0.4 0.3 5.2 100

2002 1-12 24.7 0.1 71 0.2 0.1 4.1 100

2002 1-5 18.2 0.2 77 0.3 0.1 4.7 100

2002 6-12 29.4 0.1 67 0.2 0.0 3.7 100

2001 1-13 6.0 0.2 414 2.2 1.0 26 450

2002 1-12 166 0.8 484 1.6 0.4 28 681

2002 1-5 129 1.1 551 1.9 0.7 34 718

2002 6-12 191 0.6 437 1.4 0.2 24 654

Percent on 

Filter

Mass on 

Filter (μg)

It is interesting to note that during the 2001 M29 tests, the reported M29 mercury

concentrations were 12% greater than the predicted concentrations; similar to the 18% 

(12% with corrected solution concentrations) measured this year with the XCEM. On the 

other hand, the 2002 M29 results are 6% less than the predicted concentrations rather 

than 12% greater like last year.

These results are certainly consistent with the hypothesis that M29 mercury results are 

low because there was a loss of mercury from the M29 quartz fiber filter between the 

time it was collected on the filter and the time it was analyzed. It is also consistent with 

the fact that many of the mercury compounds and amalgams of mercury are relatively 

unstable and have relatively high vapor pressures. Thus, it should not be surprising that 

if there is a substantial portion of the mercury on the filter as there was during the 2002 
C-6

tests, there might be a potential for significant loss due to volatilization. It also needs to 

be noted that the filters were not stored in a controlled environment from the time they

were collected until they were delivered to the analytical laboratory several days later. 

During this time, they may have been exposed to relatively high ambient temperatures 

while being transported through the western desert from Tooele, UT to California in the 

back of a closed panel truck.

d. Correlation with Percent Mercury on M29 Filter

The percent difference between the M29 mercury results and the XCEM results is 

significantly correlated with the percent mercury on the M29 filters as is illustrated in 

Figure C2. That is, the percent difference between the two methods (percent loss from 

the M29 filter) is dependent on the fraction of the total mercury measured in the M29 

train that is on the filter. This observation is consistent with the proposed hypothesis for 

the difference between the various methods, that is loss of mercury from the M29 filter. 

Figure C2. Percent Difference Between M29 and the XCEM vs. Percent of Mercury 

on the M29 Filter

y = 1.25x - 4.3223

R

2

 = 0.8055

0

10

20

30

40

50

0 10 20 30 40

Percent of Hg on M29 Filter

Percent Difference Between

M29

a

n

d

X

C

E

M

ii. Precision

The difference in the mercury concentrations was not likely due to imprecision in either 

of the two measurements. Mercury was one of two elements spiked by MSE-TA which 

were clearly not present in the background stack emissions. Thus, the variability in the 

mercury concentration was due primarily to variability in the spiking and stack flow 

rates. The mercury precision as measured by the XCEM was 3.8% and 6.1% for M29, 

which includes the variability in the above two parameters as well as the measurement 

method variability.
C-7

iii. Mercury to Nickel Ratio

Nickel was another element that clearly was not present in the background, and it was in 

the same spiking solution as the mercury. Thus, the ratio of mercury should not vary

significantly since the concentrations for these two elements was kept constant for these 

latest tests. The XCEM measured mercury to nickel ratio was 1.37 ± 0.015 (1.1% 

relative) and close to both the M29 ratio, 1.41 ± 0.116 (8.3 % relative), and the predicted 

concentration ratio based on the measured solution concentration ratio of 1.33. It is 

interesting to note that the XCEM precision is significantly better than the M29 ratio 

precision, both of which should be relatively independent of factors other than the 

individual method. 

iv. Low Columbia Analytical Services Results

The XCEM deposit samples submitted to Columbia Analytical Services for CVAA 

analysis were extracted 41 days after they were analyzed by CES. Based on an assumed 

linear loss rate, the expected mercury concentrations at the time of extraction would be 

about 10% lower than measured by the CES XRF analyzer. The observed difference was 

14%.

4. CONCLUSION

The weight of evidence clearly indicates that the XCEM mercury deposit was unstable as 

well as the M29 PM deposit on the quartz fiber filter. This instability was most likely the 

cause of the difference between the mercury measured by these two methods and the 

other methods. It is highly likely that if these losses had not occurred, the XCEM would 

have passed the PS10 relative accuracy tests.

It is recommended that in future M29 testing, the filters be immediately sealed and 

cooled to at least 0°C, stored at below freezing temperatures and digested as soon as 

possible after sampling.