# 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. Arm **y Corps of Engineers Engineer Research and Developm**  **ent Center Constructi** **on Engineering Research Laboratory**

**Submitted By**


## Cooper Environ**me ntal 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** 

**Cont ract 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 

# EX**ECUTIVE SUMMARY** Cooper Environmental Services (CES) has developed an on

- line multi

-metal **X**

-ray based **C** ontinuous **E**mission **M**onitor (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 M SE

- 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 analys is 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 analys is. 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 analy tical errors. An analys is 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 reanalys is 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 ty pical 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 o f various munitions. Next, a by pass 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 mercury

dedicated 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/m 3)**  **Avg.**

**XC Conc.**  **(μg/m 3)**  **Avg.**

**Pred. Conc.**  **(μg/m 3)**  **Concentrations**

**potentially approach site**  **limit. RA** 

**% Corr.**  **Coeff. (Runs**  **3**
**- 13)**  **Notes**

Pb 101 101 107 Yes **4** 0.98 **Me t PS10 RA criteria.**  Cd 42.0 31.5 36.4 Yes **17** NA **Me t PS10 RA criteria.**  Cr 4.9 5.4 4.7 Yes **15** 0.64 **Me t 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 **Me t PS10 RA criteria.** 
Ni 218 281 268 No 33 NA XCEM uniformly higher than M29 by 30%. Ba 216 216 226 No **4** NA **Me t PS10 RA criteri** **a.**
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. Analys is of XCEM Filter Tape By Columbia Analy

tical 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 Te sting 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 S ystems; 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 DL S 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 Mas s 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 ME**  **THOD 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 CONTINUE** **D USE OF THE XCEM**
**................................ ................................**  **............................. 21**  **5.0 CONCLUSION AND RECOMMENDATIONS** 
**................................ ................................**  **........... 22**  **6.0 REFERENCES** 
**................................ ................................**  **................................ ................................**  **. 23** 



# APPENDICES

APPENDIX A

– HKM Results APPENDIX B

– Columbia Analy tical 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 (Brys on, 2001, Johnsen, 2001). Although no final performance specifications exist for multi

metal 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**  **Sb As**  **Cd Cr** 

**Ba Sn** 

**Zn 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 analys is (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 13 th 

### and May

15 th 

### while the 20 mm bullets were being burned and MSE

- TA was not spiking into the stack. The May

13 th 

### metal concentrations were significantly higher than the May15 th 

### concentrations. This is c onsistent 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 Incin eration But No Spiking (μg/DSCM)** 

**Date Ru** **n 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 byp ass 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 Non**

**Spiking Periods**

y = 0.0977x + 9.0892 R2= 0.4678 0 20 40 60 80

0 200 400 600 800 **Tin (μg/DSCM) B** **a r** **i u** **m (** **μ g** **/ D** **S C** **M )**  **XCEM Lead vs. XCEM Tin During Non Spiking Periods** 

y = 0.1505x + 11.158 R2= 0.8636 0 20 40 60 80 100 120

0 200 400 600 800 **Tin (μg/DSCM) L** **e a** **d (** **μ g** **/ D** **S C** **M )**  **XCEM Zinc vs. XCEM Tin During Non Spiking Periods** 

y = 0.0747x + 4.7411 R2= 0.7159 0 10 20 30 40 50 60

0 200 400 600 800 **Tin (μg/DSCM) Z** **i n** **c (** **μ g** **/ D** **S C** **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 ST** **ART STOP**  **XC RUN**  **XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)**  **M29 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 ST** **ART STOP**  **XC RUN**  **XCEM CONC. (μg/DSCM) CES CONC. (μg/DSCM)**  **M29 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 P M**  **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 P M**  **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 P** **M 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 P** **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 P** **M 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 P** **M 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 P** **M 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 P** **M 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 P** **M 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 P** **M 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 P** **M 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 P** **M 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 P** **M 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 P** **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 P** **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 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 XCEM CONC. (μg/DSCM)**  **CES CONC. (μg/DSCM) M29**  **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**

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

1 j j ij
i 

### t t C C **Equation 1** where:
C i 

### = XCEM time

-weighted concentration for element i during M29 test run C ij 

### = XCEM reported concentration for element i during time interval j n = Number of XCEM measurements during test run t j 

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

during time interval j coinciding with M29 sampling. 

#  j 

### t = M29 sampling period. 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 reanalyz ed 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 analys is 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 reanalys is, filter spots that correlated with M29 runs 5 and 6 were combined and submitted to Columbia Analy tical of Vancouver, WA for analysis using ICP/MS (Table 6). **Table 6. Analysis of XCEM Filter Tape By Columbia Analytical (μg/DSCM)** 

### Ru**n 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: B a, 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 b etter 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 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. 

## 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 Em ission Limits**  **MACT Limit**

**g/hr μg/dscm**  **1** 

### 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 ty pical 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 analys is of the XCEM filter tape by Columbia Analy tical (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 L** **e a** **d (** **μ g** **/ d** **s c** **m )** 



### 3.1.2 **CADMI UM**  The APE

- 1236 state

-mandated emission limit for Cd is about 60 μg/DSCM under ty pical 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 yi elded mixed results with the QuanX XRF within 3% of M29 and the Columbia Analy

tical 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/Q N**  **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 deter mined 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 cons ervatively 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 ta pe 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 analys is 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 conc entrations 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 the se 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 Analy tical ICP/MS results, and incorrect flow measurements would have re sulted 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 M SE

- 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 ty pically 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 analys is 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 PRD**  **1 M29**  **1 XC**  **1 QN**  **1 CA**  **1 XC/QN**  **XC/PRD M29/PRD**  **XC/M29 QN/M29**  **1** 324 332 367 257 1.42 1.13 1.02 1.10 0.77 **2** 325 334 381 251 1.52 1.17 1.03 1.14 0.75 **3** 333 294 365 262 1.39 1.09 0.88 1.24 0.89 **4** 322 327 368 301 1.22 1.14 1.02 1.13 0.92 **5** 323 318 379 308 274 1.23 1.18 0.99 1.19 0.97 **6** 329 280 378 288 254 1.31 1.15 0.85 1.35 1.03 **7** 327 285 392 302 1.30 1.20 0.87 1.37 1.06 **8** 325 306 406 294 1.38 1.25 0.94 1.33 0.96 **9** 324 309 405 287 1.41 1.25 0.95 1.31 0.93 **10** 328 292 395 282 1.40 1.20 0.89 1.35 0.97 **11** 326 295 397 286 1.39 1.22 0.90 1.35 0.97 **12** 322 293 389 267 1.46 1.21 0.91 1.33 0.91 **AVG. 326**  **305 385**  **282 264**  **1.37 1.18**  **0.94 1.27**  **0.93 SD**  **3.3 19**  **14 19**  **13.8 0.09**  **0.05 0.06**  **0.10 0.09**  **1) Mercury lost from filter.** 

### Figure 4. Percent D**ifference Between M29 and the XCEM vs. Percent of Mercury on M29 Filter**

y = 1.25x - 4.3223 R2

### = 0.8055

0 10 20 30 40 50

0 10 20 30 40

**Percent of Hg on M29 Filter P** **e r** **c e** **n t** **D i** **f f** **e r** **e n** **c e** **B e** **t w** **e e** **n 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 Analy

tical. 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 ty

pically 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 reanalys is all agree to within 10% with an XCEM relative accuracy of 4%. Although the stack limit is 500,000 μg/DSCM, ty

pical 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 Analy

tical 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 by pass 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 emiss ions. 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 RECOM MENDATIONS**  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 analys is 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**
Brys on (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.
Brys on (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 S ervices 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 S election 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 ADJUSTME**  **NTS 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 adj ustments 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 adj ustment 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 best

estimated 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 NI ST thin film standard for lead was not availab le and the mercury

sensitivity

was estimated based on a previous measurement of the lead NI ST 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 hy pothesized 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 hy pothesis 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 hy pothesized 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 M2 9 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 analy tical methods relied on aged samples, the mercury

concentration results were low due to vaporization of particulate mercury prior to laboratory

analys is. As discussed in the following subsection, a substantial amount of experimental data is available, all of which is supportive of this hy pothesized 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 analys is 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 analys is 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 analyz ed 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 Analy

tical 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 analys is is non

- destructive, it is possible to conduct further analys es to evaluate the potential cause of this diff

erence. 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 Y ear 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 replic ation 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

- analyz ed 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 analys is 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 analys is. **Figure C.1 Comparison of XCEM X**
**- Ray Spectra Measured During Method 29**  **Testing and Se venty** 
**- One Days Later.** 

0 2000 4000 6000 8000 10000 12000 14000**C o** **u n** **t s** 



### 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 analys is 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 ty pical 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 dep osited 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. Com parison 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 cer

tainly consistent with the hy

pothesis 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 analyz ed. 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 analy tical laboratory

s everal 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 .3 223 R 2

### =0 .8 055

0 10 20 30 40 50

0 10 20 30 40

**Pe rce**  **nt of H**

**g on** **M 29**  **Fi lte**  **r P** **e r** **c e** **n t** **D i** **f f** **e r** **e n** **c e** **B e** **t w** **e e** **n M** **2 9** **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 analys is 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 coo led to at least 0°C, stored at below freezing temperatures and digested as soon as possible after sampling.