ERDCICERL TR.05·9 

Table16. M29 eoncentrallons (•gldscm). 

RUN Pb Cd Cr As H Sb 

A B AVG A B . .we A 8 AVG A B AVG A ll AVG A 8 AVC 

I 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 3 1 4.8 5.2 5.0 11.5 12.1 11.8 347 301 327 168 164 166 

5 29 26 28 32 30 3 1 5.3 5.2 52 12.3 11.1 11.7 319 317 318 172 163 168 

6 148 146 147 32 31 3 1 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 m 122 122 32 32 32 4.9 5.4 52 12.0 12.2 12.1 312 305 309 153 16 1 157 

10 ~ 129 135 31 29 30 5.0 4.8 4.9 11.3 10.8 11.0 294 289 292 164 Il l 157 

II 119 118 119 32 31 3 1 4.9 4.7 4.8 11.7 l l.S 11.6 297 293 295 162 164 163 

12 114 Il l 113 31 31 3 1 4.8 4.8 4.8 11 .9 11.7 11.8 308 278 293 154 154 154 

RUN Nl Bo Zll So 

A B AVG A B AVG A B .AVG A B AVG 

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

2 235 23l 235 249 24$ 248 216 208 212 131 168 149 

3 240 22R 234 252 243 247 222 208 21l 207 199 203 

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

5 227 235 231 21S 198 207 202 191 196 51 69 63 

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

1 230 205 218 220 204 212 206 198 202 60 14 67 

8 224 213 219 214 206 210 211 196 204 47 4$ 47 

9 222 221 221 204 209 206 204 200 202 4 1 )5 38 

10 2 19 192 205 2 18 199 20S 205 192 199 88 64 76 

II 2 18 214 216 2 10 210 210 205 201 203 44 36 40 

12 202 195 199 20& 201 204 199 192 196 31 25 28 

Predicted Stack Gas Concentrations 

Predicted stack gas concentrations were detennined 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, A!?,, Hg, Sb, and Ni. 

For Cd, Ba, and Zn, the background correction was small relative to the MSE-TA 

spiked concentrations, which were 17, 15, and 8 percent, respectively. For Pb, 

however, the background accounted for 100 percent of the Pb in runs 1- 5 and 35 

percent ofthe Pb in runs 6-12. 

MSE-TA spike Injection 

During !1129 testing, MSE-TA spiked known masses ofPb, 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 jlg/dscm. MSE-TA mass concentrations in solution were cross-checked by submitting aliquots from M29 runs 5 and 

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

43 

VES011342 
44 ERDC/CERL TR-05-9 

which was 23 percent lower according to HKM than reported by MSE-TA. No 

adjustments were made to MSE-TA reported data. The potential impact of the 

As difference is discussed in a report by Cooper et aL (2002). 

Measurements of stack flow by CHPPM were cross-checked v.-ith the stack continuous velocity monitor for accuracy and were found to be within 6 percent of 

each other (Table 17). The CHPPM flows were determined using a velocity traverse at the same stack height as the XCEM probe and are believed to be more 

representative of true flows than the continuous velocity monitor.* For this reason, the CHPPM flows were used to calculate the predicted concentrations. 

Table 17. APE-1236 S1aCl< flow rotes during M29 testing. 

TEAl> stack Avg. CHPPM TEAl> stack/ 

Run monitor M29A M298 M29 Avg. M29 

(dscmlhrl (dscmlhrl (dscmlhrl (dscmlhrl W•l 

1 5,173 4.7 18 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 4838 4,672 4,688 4,680 103 

6 4970 4,578 4,580 4579 109 

7 4,826 4 607 4,613 4 6 10 105 

8 4 785 4 641 4 647 4 644 103 

9 4,676 4,662 4,672 4,667 100 

10 4,060 4 ,589 4,600 4,594 110 

11 4,960 4,593 4,662 4,628 107 

12 4 ,879 4,660 4,670 4,665 105 

AVG 4,924 4,630 4,639 4,635 106 

Background me1al concentration 

TEAD incinerated 20 mm TPM55A2 bullets during all 12 M29 r uns. This ammunition, which is used for target training, does not contain significant quantities of hazardous elements. However, measurable residual concentrations of Pb, 

Cd, Ba, Zn, and Sn were found in the stack gas from earlier incineration of other 

munitions. Table 18 shows XCEM results for elements measured on 13 and 15 

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

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

Personal communication: M1ke Pattison, U.S. Army CHPPM. Wllh Bruce Johno:...eo, CES, Jooe 2002. 

VES011343 
ERDCICERL TR-05-9 

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

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

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

0 pg/dscm. 

Table 18. APE-1236 slack concentrations (~gldscm) with munitions Incineration but no spiking. 

Date x;;: Pb Cd Ba :n Sn 

0/l.otV.< 899 94.5 11.5 68.7 J; 1.3 487 

900 85.9 5.9 64.8 4: .7 604 

11 ' 

0 

282 

i.4 1( 231 

906 44.7 8.0 18.1 21.2 205 

2 907 54.7 6.0 22.3 23.9 275 

2 908 44.5 5.7 49.3 22.6 259 

63.8 8.4 41.3 31.7 331 

990 

15/02 

15/02 •.€ 

15/02 3;8 

19.4 1.7 19.3 6.7 102 

Use of Sn as a surrogate for background metals 

Figure 13 shows the relationship between Pb, Ba, Zn, and Sn when spiking was 

not occurring. The correlations indicate that Pb, Ba, Zn, and Sn background concentrations stem from the same source. Since Sn was not spiked by MSE-TA, its 

concentration was used as an indicator of the background during spiking periods. 

The background contribution of the other elements was estimated by their relationship to Su according to the equations in Figure 13. Figure 14 shows the 

XCEM measurements of Sn during M29 testing. A surge in Sn concentrations is 

observed each morning after the bypass damper is opened. The surge is followed 

by a gradual decrease in Sn concentrations throughout the day. Although Cd 

was not found in high enough concentrations to certify its relatiouship with Sn, 

it was assunted to behave in the same manner as the other metals. Combining 

the 1\ofSE-TA spike injection estimates with the estimated backgl'Ound concentrations resulted in predicted concent.rations as shown.in Table 19. 

45 

VES011344 
ERDCICERL TR·05-9 

XC£M Wd '4. XCEM TO. During Noa~ XCEM Zinc ,.$. XCE.M T'io D•rlog Non· 

SpWa~ Ptriocb: Spiklllf: Ptriods 

120 60 

00 ........ i 50 

~: -

::;: 40 . 

• ....... 

'i 

~ 40 (l SOh I IU S!! ~ 20 

0 

-1)'" .. 0.01•?• .-4.1411 

.:s 2<) tt: :q~llfll(, ~JO 

- tl•t>.? ~~ 

0 • 0 • r 

0 200 400 600 800 0 200 400 600 8!>0 

'fla (llefDSCM) r .. tpafDSCMl 

XCEM Bui'um ' '"· XCEM Tin Ourf•;, NollSpiking renoch 

" 80 ~ • • ..... t60 • ..........-: 34<) 

; ?O . ~ 

~ b·-0.097i.\ +-~ (l$92 i- : . I k? .. OA6n: 

0 

0 200 400 600 800 nn (pJI'()SC.M) 

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

opiking. 

Tin During M29 Testing 

700.0 

600.0 ~y 3 May 14 May IS May 16 

• 500.0 • 

400.0 ' ~ ~ . 

300.0 

200.0 f\'1 .\•\ •• , .. 

~ 

100.0 

0.0 • 

890 930 970 1010 

Figure 14. XCEM tin measurements during M29 testing. 

VES011345 
ERDC/CERL TR-05·9 

XCEM Concentrations 

XCEM concentrations were determined every 20 minutes for Pb, Cd, Cr, As, Ni, 

Hg, Ba, Sb, Zn, and Sn (Table 20). A Pd rod is permanently mounted in the XRF 

detection area and is measured with every sample. The consistency of the Pd 

concentrations provides QA of the instruments stability during M29 testing, the 

XCEM successfully canied out 120 runs with only 2 runs falling outside of the 

Pd QA criterion due to air-conditioning problems. This represents an uptime of 

98 percent. 

Table 19. Predicted stack concentrations (~ dscm) based on MSE·TA spildng and background 

estimates. 

HllO~UUM CADMIUM LEAD ARSENIC NICKEL 

RUN 

MSE BKG PRD MSE BKG PRD MSE BKC PRD MSI: BKC PR.D MSE BKC .I'RD 

I 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 I I. I 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 4 1.4 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 ')7.7 6.0 43.7 104 46 ISO 16.4 o.o 16.4 269 0.0 269 

3 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 

tO 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 

II 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 2~ 16.2 o.o 16.2 266 o.o 266 

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

SD 0.8 0.0 0.8 2.1 2.7 2.7 53 16 47 2.2 0.0 1.2 1.8 0.0 1.8 

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

3 333 0.0 333 201 Sl.6 253 201 0.0 201 275 37.3 312 

4 322 o.o 322 194 28.3 223 194 o.o 194 265 19.5 285 

5 323 o.o 323 193 25.0 218 193 o.o 193 266 16.9 283 

6 329 0.0 329 199 41.6 240 199 0.0 199 27 1 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 19'2 267 17.6 285 

9 324 o.o 324 189 22. 1 212 189 o.o 189 266 14.7 280 

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

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

VESO!l346 
~ 

Table 20. XCEM concenirations. 

m 

(") 

~ 

~ m 

:u 

... 

;! 

0 

tii 

'I' 

"" 

C/) 

0 

...... -

w 

~ 

...... 
< m 

en 

0 

-

w 

.j>. 

00 

Table 20 (Coni' d). XCEM concent111tlona. 

m 

;a 

§ 

,... 

.... 

, 

0 

~ 

~ 
< 

tTl 

(/) 

0 

w 

.l:. 

\J;) 

Table 20 (Cont'd). XCEM concenvatlona. 

1!1 

m 

.. 

.. 

~ r 

~ 
< 

rTl 

(/) 

0 

~ 

~ 

w 

u. 

0 

Tab~ 20 (Cont'd). XC·EM concentration&. 

UNWF.IGIITI;:D A VI!RAG£ 

m 

;a 

0 

~ m 

;a 

,... 

... 

;a 

b 

t 

~ 
52 ERDC/CERL TR-05-9 

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

c I [Eq 7] 

where: 

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

run 

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

n = Number ofXCEM measurements during test run 

t, = Number of minutes XCEM measured element i's concentration dur· 

ing time interval} coinciding with M29 sampling 

Lt 1 = M29 sampling period. 

All XCEM data used for comparisons to M29 were the same as reported during 

1\1129 testing with the following four exceptions: 

1. During M29 run 1, an evaluation of the calibration factors was undertaken. It 

was observed that Sb, Ba, and Hg calibration factors were too high relative to the 

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

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

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

a complete discussion ofHg calibration). 

3. During run 961, an unusually high Cr number (18 pgldscm- more than 6 SD 

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

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

on the filter tape. The speck was believed to be from contamination that was not 

representative 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 oonditioning failed on 16 May, which meant that the Pd QA 

concentration did not meet the 90-110 percent criterion for XCEM runs 1021 and 

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

concentrations for run 12 were based on a time-weighted average of the 97 minutes that the XCEM produced validated data. 

The modified XCEM data were submitted before receiving the M29 results. No 

modification to the XCEM data was made after receiving M29 results. 

VES011351 
ERDC/CERL TR.OS.9 

XCEM Calibration Evaluation Using A QuanX- XRF and ICPIMS 

Since XRF analysis is nondestructive, the concenn·ated particulate matter on the 

filter can be reanalyzed at a later date. To evaluate the XCEM calibration, CES 

reanalyzed each spot using a QuanX XRF analyzer located at CES. The CES 

QuanX analyzer is one of four in the nation that has been approved for measuring PM,. metals concentrations for EPA's speciation program. Consequently, the 

analyzer has undergone a series of round robin tests with other laboratories as 

well as rigorous quality control checks. The QuanX analysis was conducted approximately 6 weeks after M29 testing. With the exception of Hg, which appeared to be lost from the XCEM filter, the material collected on the filter 

seemed to be intact and representative of the sample collected at TEAD. The 

QuanX calibration evaluation data are shown in Table 20 as CES Concentration 

(CES CONC.). 

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

combined and submitted to Columbia Analytical (Vancouver, \VA) for analysis 

using ICP/mass spectrometry (MS). Table 21 shows results of this analysis. 

Table 21. Analysis of XCEM fi«or lapo by Columbia Analytical (11g/<lsem) 

Run As Cd Cr Ba Hg Ni Pb Sb Sn Zn 

5 14.0 36.4 5.0 176 274 226 22 174 74 252 

6 13.3 34.2 4.7 159 254 220 129 152 127 245 

Precision 

Five elements were spiked by MSE· TA at a constant rate throughout the testing: 

Ba, Hg, Ni, Sb, and Zn. Although Ba and Zn had background concentrations of 

about 10 percent, their limited variability during testing affected the predicted 

concentrations precision by only a few percent. Overall, these elements were 

spiked with a precision of better than 5 percent. 

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

precision about 30 percent lower than M29 (Table 22). 

Table 22. Predicted (spiked), XCEM, and M29 

precision (%)during validaUon testing.' 

Approach Ha Sb Ni Ba 

Predicted 1.0 1.7 1.1 5.9 

XCEM 3.8 2.5 3.7 6.9 

1.129 6.1 6.1 5.7 7.2 

Zn 

3.5 

2.4 

3.3 

' Determined by perc«~l RSO or t2 concentratiOns repOr'ted Sot' M29 runs. 

53 

VESOll352 
54 EROC/<;1;RL TR-05-9 

Discussion 

Regulated Elements Typically Found In the Feedstream 

Although the APE-1236 is regulated for nine elements, only three elements -

Pb, Cd, and Or - are found in high enough quantities in stack emissions to pot entially limit incineration feed rates (Table 23; Be is not listed in this table because it cannot be measured by the XCEM). The XCEM successfully measured 

all three of the key elements and met the 20 percent RA requirements in proposed PS-10 with RAs of 4, 17, and 15 percent, respectively. 

Tabte 23. TEAO emission limits for regulated elements. 

Interim Final MACT Potential to Lima 

Eloment State Limit MACTUm~ Limit Feed Rate 

gJhr pg/dscm' 11!1/dscm ~g/dscm 

Pb 4.3 932 240 59 Yes 

Cd 0.26 56 Yes 

Cr 0.04 10 97 84 Yes 

As 0.11 24 No 

HQ 14 3.036 130 130 No 

Sb 14 3.036 NR NR No 

Nl 930 201,740 NR NR No 

Sa 2,400 521 ,243 NR NR No 

1 Ass001es 4,635 dsc:trv'hr based on average rate from Table 16. 

NR: Not egu ate~ MACT: Maximum achievable control technology (rule) 

Lead 

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

TEAD incinerator has a ~-tate mandated Pb stack emission limitation of 4.3 g!hr. 

At typical stack flow rates, this equates to about 900 )lg/dscm. EPA's HWC interim maximum achievable control technology (MACT) rule (EPA 1999) currently 

limits Pb and Cd emissions to 240 )lg/dscm. The final MACT rnle, which was 

published 20 April 2004 (FR21210) and will be in effect 3 years after it promulgates, will further limit the combined Pb and Cd emission rate to 59 )lgldscm. 

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

of ordnance before incineration. Munition feed rates into the incinerator are restricted using a model that assumes that a fraction of the Pb in the munitions 

will be transported through the air pollution control devices and emitted from 

the stack. The effectiveness of the model depends upon several assumptions in· 

eluding transport under various meteorological regimes, incinerator temperature 

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

VES011353 
ERDC/C£RL TR-05-9 

the stack gas allows for improved understanding of the relationship between 

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

Table 24 shows the Pb results for the MSEibackground predicted concentrations 

(PRDl, M29, XCEM (XC), the post-test analysis of the XCEM spots using the 

CES QuanX (QN), and the ICP/MS analysis of the XCEM filter tape by Columbia 

Analytical (CAl. In general, the results are in very good agreement with the 

PRD, M29, XCE1Y1, and QN concentrations, agreeing to within 7 percent. The 

XCEM and M29 Pb concentrations are also highly correlated with an r" of 0.98 

(Figure 15). 

Lead in the first fh•e M29 runs was exclusively from residual concentrations in 

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

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

ranging from 25 to 150 pg!dscm. The RA for the XCEM was 4.4 percent. This 

agreement between the XCEM and M29 demonstrates the capability of the 

XCEM to accurately measure Pb at the incinerator under a wide range of concentrations. 

Table 24. Summary of Pb concentration (~g/dsc ) data and raUos during M29 t&sting. 

RUN PRD Jlll9 XC QN CA XC/QN XC/PRD Ml9/PRD XC/Ml9 QN/Ml9 

I 67 72 67 ~ 0.99 1.01 1.0~ 0.93 0.94 

z 61 77 67 64 1.04 1.1 1 1.27 0.87 0.84 

3 77 9R Rl R4 0.97 1.06 t.Z1 O.R3 U6 

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 I. OS 0.96 

7 ISO 13S 137 141 0.97 0.91 0.90 1.0 1 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 0.9 1 1.05 1.03 

10 lSI 13S 140 140 1.00 0.93 0.89 1.04 1.04 

11 136 118 12 1 U9 0.94 0.89 0.87 1.02 1.09 

n 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 

so 47 39 43 43 76 o.os 0.09 0.16 0.07 0.09 

55 

VESOll354 
56 ERDC/CERL TR-05-9 

200 r;:====== ----, 

150 iy = 1.09x- 9.601---='-------l 

i R2 =0.98 

100 -j-J'----_j7£:...------l 

50 -········ 

+---~----------~ 

0 50 100 150 200 

1\129 Lead (pgldscm) 

Figure 15. XCEM versus M29 '-•d for validation tests. 

Cadmium 

The APE-1236 state-mandated emission limit for Cd is about 60 pgldscm under 

typical stack flow rates. Cadmium stack concentrations, which are derived from 

incineration of shell casings, can occasionally approach this limit. For this test, 

approximately 80 percent of the stack's Cd was from MSE-TA, while 20 percent 

was estimated to be background. Table 25 shows the M29 and XCEM results for 

Cd during the validation tests. 

Overall, the XCEM and M29 were in good agreement for Cd. On average, the 

XCEM was about 14 percent higher than M29 with an RA of 17 percent. Thereanalysis of the XCEM filter tape yielded mixed results with the QuanX XRF 

within 3 percent of M29 and the Columbia Analytical concentrations within 4 

percent of the XCEM. The inconsistency between the XCEM and CES-QuanX 

results suggests that an XCEM calibration error may have been responsible for 

the difference between 1\129 and the XCEM. 

VES011355 
ERDC/CERL TR-115-9 

Table 25. Summary of Cd concentration (~g/dscm) data and raUos during M29 tesUng. 

RUN PRD ~U9 XC QN CA XC/QN XC/PRD M29/PRD XC/M29 IQN/M29 

I 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 l.l2 0.92 

3 48.6 34.6 37.2 3 1.6 1. 18 0.71 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 1.1 7 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 o.os 0.04 0.04 0.04 

Chromium 

The APE-1236 has an effective Cr emission limit of less than 10 pgldscm under 

typical stack operating conditions. Since the background Cr concentrations were 

uncertain at the start of the validation test, MSE-TA spiked a nominal 8 pgldscm 

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

background Cr concentrations were insignificant and MSE-TA raised their spiking rate to 5 pgidscm for the remainder of the tests. Overall, the XCEM was consistently 10 percent higher than M29 at both concentration levels (Table 26). 

This represents a difference of about 0.5 pg/dscm. The agreement between the 

XCEM and Ivf29 at both the 3 and 5 )lg/dscm levels validates the ability of the 

XCEM to accurately measure C.· at very low concentrations. 

The Cr RA was 15 percent, meeting the PS-10 criterion. Subsequent measurements of the XCEM filter tape by the CES-QuanX and ICP were wit.hin 3 percent 

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

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

57 

VES011356 
58 E.RDC/CERL TR·OS.9 

Table 26. Summary of Cr concentration {J.tWdscm) data and ratios during M29 testing. 

RUN PRD 1\'129 XC QN CA XCIQN XCIPRD M29fPRD XCIM29 QNIM29 

1 2.9 3.6 3.7 32 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 

s 5.0 52 6.1 5.0 5.0 1.22 1.21 1.04 1.16 0.96 

6 5.0 4.8 5.8 S.J 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 S.J 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 !.I I 1.10 

I I 5.0 4.8 5.4 5.5 0.97 1.07 0.96 I. I I 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 s.o 4.8 1.10 1.16 1.07 t.IO 1.02 

SD O.B 0.7 0.8 1.0 0.2 0.14 0.09 0.14 0.08 0.18 

Regulated Elements Not Typically Found In TEAD Emissions 

APE-1236 is regulated for six additional elements that are not typically found in 

the feedstream in quantities that approach the regulatory limits: As, Hg, Sb, Ni, 

Ba, and Be. The XCEM does not measure Be. The XCEM met PS-10 measurement criteria for Sb (20 percent) and Ba (4 percent), but was higher than M29 for 

As, Hg, and Ni with relative accuracies of 27, 33, and 33 percent, respectively. 

Anoenlc 

Arsenic results are shown in Table 27. The XCEM-reported concentration was in 

good agreement with the post-test analysis of the filter tape by both QuanX and 

Columbia Analytical. Their agreement indicates that the XCEM calibration was 

correct to within a few percent. The XCEM concentration is also in good agreement with the predicted concentration. Although, as discussed earlier, the HKM 

analysis showed a 23 percent lower value for the calibration. 

The XCEM's RA of 27 percent did not meet PS-10 criterion. Overall, the XCEM 

concentrations were 25 percent higher than M29 concentrations for A!3. Other 

potential sources errors for the XCEM besides calibration such as loss during 

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

ruled out because they would result in XCEM concentrations lower than M29. It 

is highly possible that the differences in concentration are due to M29 errors. 

The XCEM was also highly correlated with M29 A!3 (r2:0.85) showing good responsiveness to changes in A!3 concentration. 

VES011357 
EROCICERL TR.05·9 

Table 27. Summary of As conC<>ntratlon (l&gldscm) data and raUos during M29 testing. 

RUN PIID M29 XC QN CA XC/QN XC/PRO M29/PRD XCIM29 QNIM29 

I 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 0.17 1.13 1.24 

3 16.7 II.S 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 1.1)9 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 I I. 7 15.6 13.7 1.14 0.96 0.7 1 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 II. I 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 

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

Sb 2.2 1.5 l .O 1.7 0.5 0.06 0.05 0.02 0.07 0.04 

Mercu ry 

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

emissions. For example, during the 2001 M29 tests at TEAD, the particulate Hg 

captured on the M29 filter and probe represented 1 percent of the total Hg. The 

XCEM relies upon a specially treated filter membrane to capture the vapor 

phase Hg while M29 uses an impinger train. 

The APE-1236 Hg limit is about 3000 pg/dscm. Mercury, however, is typically 

not present in TEAD stack emissions. An earlier multi-metals monitor was certi· 

fied for use at TEAD without measuring Hg (Seltzer 2000). For the current vali· 

dation test, Hg was spiked by MSE-TA with results shown in Table 28. 

The XCEM and )1;129 concentrations had acceptable agreement during runs 1-5 

with the XCEM 16 percent higher than M29. Following run 5, however, the 

XCEM was consistently 34 percent higher than M29. It is believed that these 

differences are due to vaporization of particulate Hg from the M29 filter. 

During runs 1-5, the Hg solution contained Zn and Ni. Following run 5, Pb was 

added to this solution. Although Hg was spiked at a constant rate, M29 Hg 

concentrations decreased by 8 percent following Pb injection. The source of this 

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

present during this validation test. Particulate Hg is captured on the M29 

quartz fiber filter and can be readily volatilized if the filter is not cooled. Even 

though total M29 Hg decreased following run 5, the fraction of Hg on the M29 

filter increased from 18 percent in runs 1-5 to 30 percent in runs 6-12 (CHPPM 

2002). The Hg captured on the filter represents particulate phase Hg, which is 

typically only a couple of percent of the total Hg. As such, M29 does not require 

VES011358 
60 ERDC/CERL TR-05-9 

refrigeration of the M29 fllter, so it was not cooled while being shipped to 

California for analysis. During t his time, a significant quantity of the Hg on the 

filt.er could have vaporized. Figure 16 shows the relationship between the level 

of Hg on the M29 filter and the percent difference between M29 and the XCEM. 

The XCEM filter also showed a loss of about 30 percent of its Hg as demonstrated by an analysis of the spectra available during validation testing and a 

few weeks later when the tape was reanalyzed by the CES QuanX. Interestingly, 

the CES tape had previously shown good retention of vapor phase Hg on ero:lier 

tests (Cooper et al. 2000; Chapter 3) so the Hg loss seems to depend upon the 

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

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

RUN PRD M29 XC QN' CA1 XCIQN XC/PRD M29/PRD XC/M29 QN/M29 

I 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 

8 325 306 406 294 138 1.25 0.94 1.33 0.% 

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 

u 326 295 397 286 139 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 1.17 0.93 

SD 3.3 '19 14 :19 13-8 0.09 0.05 0.06 0.10 0.09 

I) Mer cury lost from lllter. 

= l 50 ~========~------------~ ~ ~ 40 _y = 1.25x- 4.3223 ...... . ~ .. 

., U R2 a 0.8055 ~ + + • 

;:; :><: 30 .... 

~ ] 20 +--------.,...,.,~_/". ::..._ __ • ___ .._--_ -~ 

i5~ A d ~ 10 +------ - =-------.. -----

., 

~ +-----~----~-----.-----~ 

!>.. 0 10 20 30 40 

Percent of Hg on ii'U9 Filter 

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

VES011359 
ERDC/CERL TR.05·9 

Antimony 

Antimony results are shown in Table 29. Overall, the XCEM was higher than 

M29 by about 18 percent, but met RA criteria with an RA of 19.9 percent. Sub· 

sequent analysis of the filter tape by the CES QuanX was in better agreement 

with M29. For this reason, it is believed that the XCEMJM29 differences were 

due to XCEM calibration errors of about 15 percent. 

Table 29 Summary of Sb concentration (~gldscm) data and ratios during M29 te~Ung. 

RUN PRD M29 XC QN CA XCJQN XC/PRD M291PRD XC/~U9 N~U9 

I 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 20 1 183 190 156 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 

I 1 193 163 193 180 1.07 1.00 0.84 1. 1 R 1.10 

11 190 154 193 183 1.05 1.01 0.81 125 1.19 

AVG. 194 164 192 171 163 1.13 0.99 0.84 1.18 1.04 

SD 3 10 5 8 15 0.06 0.03 0.04 0.06 0.08 

Nickel 

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

percent higher than M29 and bad an RA of 34 percent, which did not meet the 

PS-10 criterion. Although the XCEM Ni concentrations were supported by the 

CES QuanX filter evaluation and predicted roncentrations, the M29 results were 

similar to results from Columbia Analytical. At this time, the XCEM appears to 

have been calibrated correctly. As discussed earlier in the section on Arsenic, 

since the XCEM was higher than M29, the difference appears to be due to M29 

analytical problems. 

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

pg/dscm stack emission limit. As such, the conservative numbers produced by 

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

61 

VES011360 
62 ERDC/CERL TR-05·9 

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

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

1 267 200 270 262 1.03 1.01 0.75 1.35 1.3 1 

2 268 235 283 276 1.02 1.06 0.88 1.20 l.J8 

3 275 234 262 262 1.00 0.95 0.85 l.J2 l.J2 

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 l.JS 

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 1.1 1 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 

1l 266 199 286 294 0.98 1.08 0.75 1.44 1.48 

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

SD 2.8 12 10 12 4.9 0.04 0.04 0.04 0.09 0.11 

Barium 

Barium results for the validation tests are shown in Table 31. For Ba, tbe predicted concentrations, M29 results, XCEM results, and QuanX reanalysis all 

agree to "itbin 10 percent with an XCEM RA of 4 percent. Altbough the stack 

limit is 500,000 pg/dscm, typical Ba concentrations found in the stack are in the 

0 to 200 Jlg/dscm range. During these validation tests, the XCEM demonstrated 

good accuracy relative to M29 for Ba under realistic stack conditions. 

Table 31 . Summary of Ba concentration (~gldscm) data and ratios clwing M29 1esting. 

RUN PRD J\129 XC ON CA XC/ON XCIPRD M29/PRD XC/lll29 ION/M29 

I 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 0.9R 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 l.J9 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 ().92 0.95 0.90 

II 215 210 197 211 0.93 ().92 0.98 0.94 1.00 

12 209 204 203 206 0.98 0.97 ().98 0.99 I.() I 

AVG. 226 216 216 199 167 1.09 0.% 0.95 1.00 0.93 

so 13 16 15 11 13 0.08 o.os 0.04 0.05 0.06 

VES011361 
ERDC/CERL TR-05·9 

Nonregulated Metals 

Two nonregulated metals, Sn and Zn, were measut·ed by the XCEM during validation testing. As discussed earlier, M29 is not approved for Sn, and the M29 Sn 

results were not considered valid. Zinc was spiked by fv!SE-TA with XCEIII reported concentrations shown in Table 32. 

Overall, the XCEM Zn concentrations were consistently about 40 percent higher 

than M29. The XCEM Zn concentrations were in good agreement with both the 

CES QuanX and Columbia Analytical tape evaluations, indicating that calibra· 

tion was not the primary source of this difference. It is believed that the difference is primarily due to .M29 errors. 

Table 32. Summary of Zn concentration (pglcbcm) data and ratios during M291esting 

RUN PRD M29 XC ON CA XC/ON XC/PRD M29/PRD XC~ 9 I ON/l\129 

1 300 195 28R 294 0.9R 0.96 0.65 1.4R 1.5 I 

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 l.S4 

5 2~3 196 277 282 252 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 

so 10 7 7 7 5 0.03 0.03 0.02 0.04 0.06 

Summary 

The XCEM met the proposed PS-10 RA requirements for the three potential 

emission-limiting elements found in APE-1236 that could potentially approach 

emission limits: Pb, Cd, and Cr. The XCE.M also met the RA requirements for 

two other regulated metals Ba and Sb but was high for As, Hg, Ni, and the 

unregulated Zn. An analysis of potential sources of en'or suggests that the 

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

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

concentration and showed good correlation with the reference method for 

elements that were spiked at more titan one level. In addition, tlte XCEM 

successfully measured low metal concentrations as demonstrated by the XCEM's 

tracking of M29 Cr's low concentrations when changes of only 2 p.g/m·' occurred 

63 

VES011362 
64 ERDC/CERL TR-05-9 

between run.q 2 and 3. Table 33 sununarizes the comparison between M29 and 

theXCEM. 

Table 33 S..mmary ol 2002 M29/XCEM comparison results. 

Average M29 Average Avenge Predicted Met PS-10 RA 

Element Cone. XCEMConc. Cone. RA Criterion 

luQ/dscml luQ/dscml luQ/dscml (%) 

Pb 10 1 101 107 4 Yes 

Cd 42.0 31.5 36.4 17 Yes 

Cr 4.9 5.4 4.7 15 Yes 

As 11 .1 13.8 15 . .2 27 No 

Hg 305 385 326 33 No 

Sb 164 192 194 .20 Yes 

Nl 2 18 281 268 33 No 

Ba 2 16 216 226 4 Yes 

Zn 202 290 288 43 No 

VES011363 
EROCICERL TR-05-9 

5 XCEM Cost and Status 

Cost estimates for the Army to purchase and operate a new XCEM are discussed 

in this chapter. The values are presented in $1,000 units ($K) and were current 

in July 2004. Also presented is a summary of the continued operation of the 

XCEM at TEAD and status of the technology. 

Cost Estimates 

Capital Costs 

Capital costs include: 

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

extraction system, computer and control module, software, sampling system, 

enclosure, and calibration equipment, as well as in-house acceptance testing 

($195K). 

2. Probe and Transport Line: Includes shrouded probe, corrosion resistant 

transport line, heat tracing, and insulation ($10K). 

3. Shipping and Installation: TypicaUy includes shipping of equipment, onsite installation, onsite instrument shakedown, and final onsite calibration 

check. Site will be responsible for lifting and connecting transport line 

($25K). 

4. Training: Onsite training for up to six people, including training manuals, 

hands-on training, power point presentations, and customer support following installation ($8K). 

5. Housing: Includes temperature-controlled housing as either an instrument 

grade trailer or a shelter depending upon end-user requirements ($5 to 

$15K). 

The total estimated capital costs are between $243K and $253K. 

VES011364 
66 ERDC/CERL TR-05·9 

Annual Costs 

Annual costs include: 

1. Consumables: Includes 1 year of filter paper and all other consumables. 

This cost will depend on usage. The low estimate is for a typical 40 hr/week 

schedule and the high estimate is for a 24/7 schedule ($5K to $20K). 

2. Labor: Includes changing filter tape (1 hr once every 3 weeks for 24/7 usage; 

once every 2 months for 40 hr/week usage), and regular maintenance (clean· 

ing unit and replacing filters, 6 br every 3 months) 30-41 hr/year x $80/hr 

($2.4K to $3.3K). 

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

maintenance. Warranty includes onsite assistance as needed ($25K). 

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

Continued Use of the XCEM 

Following the conclusion of the M29 tests, the XCEM was used in a series of diagnostic tests to evaluare air pollution control technology installed at APE-1236. 

Using the XCEM, TEAD personnel developed baseline data for Pb and Zn during 

incineration of various munitions. TEAD stack operators also conducted tests 

using the XCEJ\1 in which they determined that the metals emissions could be 

significantly reduced by complerely cutting off the bypass sysrem during operation. Blocking the bypass duct with a metal plare resulted in a grearer than 90 

percent drop in metal concentrations. Using this data, TEAD was better able to 

understand sources of Pb in the emissions. 

The XCEM has also been used by the Ammunition Equipment Directorate (AED} 

on their test furnace at TEAD. The continued use of the XCEJ\1 to diagnose and 

assist with process control indicares the value of having an installed CEM for 

multi-metals at TEAD. More recently (2003), AED purchased a second XCEM 

unit for their test furnace. It was installed during 2004. 

Eli Lilly Corporation hss recently (May 2004) purchased and installed an XCEM 

unit for one of their hazardous wasre incinerators. They have submitted an 

Alrernative Monitoring Plan (AMP) with the EPA with the intention of using the 

monitor for compliance purposes. The AMP should be finalized in the near 

VES011365 
ERDC/CERL TR.05-9 

future. The monitor has been successfully integrated into the data acquisition 

system for the site and generates a 12-hr rolling average as required. 

Improvements have been made to the technology since the original XCEM was 

tested. In a new XCEM (2004), the QuanX XRF instrument has been replaced 

with a custom XRF detection approach improving the detection limit to 0.1- 0.2 

f.1g/dscm from 1-3 ,..gtdscm (15-minute sample time). The monitor can now 

monitor up to 25 metals simultaneously. The software has been upgraded to 

accommodate the physical changes and to improve the ease of integration to 

external data acquisition systems. The physical size of the monitor has also 

decreased. Figure 17 shows the 2004 XCEM model from CES (Xact is the 

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

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

known aerosolized metal concentration. CES believes that using the QAG is a 

reliable, consistent, and accurate method for ensw'ing that the calibration has 

been entered correctly. The QAG is CUlTently being evaluated by the EPA for use 

in compliance applications . 

• 

~ 

CES 

--- • • 

Figure 17. 2004 CES metals mon~or. 

67 

VESOJJ366 
68 ERDC/CERL TR-05-9 

6 Summary and Conclusions 

A new prototype XCEM was constructed and installed at the TEAD APE-1236 

incinerator. It underwent an M29 comparison test during a 4-day period in May 

2001. During this test, the monitor functioned in a completely automated manner and automatically recorded the test data. The objective of the test was to 

meet the requirements of the proposed PS-10. 

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

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

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

the Q/1. criterion with a precision no more than 2 percent for zero and upscale 

checks, and a calibration drift of 0.5 percent. The XCEM met the PS-10 RA criterion (less than or equal to 20 percent) for three of the nine metals tested: Cd, 

Cr, and Ni. The RA for Pb was 22 percent. The results for Ba, Sb, Zn, and As 

showed systematic biases. It is believed that the monitor did not successfully 

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

0.95 or better for Ni, Sb, and Zn. 

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

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

to minimize Hg and PM loss in the sample line. In April 2002, several improvements were made to the calibration procedure, and the XCEM was recalibrated. 

The transport system was evaluated by performing a comparison test between 

the XCEM, predicted concentrations based on spiking, and Ml7 frlter sampling. 

No measurable loss in particulates was observed. The recalibration was evaluated using a QSIS. The resulting elemental concentrations were within their 

expected uncertainties for all elements except Cd and Ag. 

In May 2002, a series of 12 comparison tests with EPA's M29 were conducted. 

During this testing, the XCEM had an "uptime" of better than 98 percent, met 

all QA parameters, and had a precision that was better than M29. The XCEM 

also showed good correlation vvith Method 29 for elements that bad significant 

variability in concentration during testing. 

VESOII367 
ERDC/CERL TR-05-9 

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

limite for three elements: Pb, Cd, and Cr. The XCEM met the PS-10 20 percent 

RA criterion for all three of these elements. XCEM data were also compared to 

M29 data for five elements that are typically found in concentrations well below 

the site emission limite: As, Hg, Sb, Ni, and Ba. A final nonregulated element, 

Zn, was also spiked and examined during validation testing. The XCEM met the 

RA ctiterion for Ba and Sb, but was uniformly high relative to M29 for As, Ni, 

Zn,andHg. 

An error analysis was conducted to determine the source of the difference be· 

tween M29 and the XCEM. Calibration errors and spectral interferences were 

checked by reevaluating the XCEM filter with CES's QuanX and submitting fil. 

ter samples to an independent laboratory for analysis. The results indicate that, 

for Cd, Cr, and Sb, calibration appeared to cause some error, even though these 

elements still met the RA criterion. However, for As, Ni, and Zn, the XCEM cali· 

bration was not the primary source of error. Other potential XCEM sources of 

error such as loss during transport, low filter trapping efficiency, and deposit positioning errors are highly unlikely because they would result only in XCEM con· 

centrations lower than M29. The differences in concentration for As, Ni, and Zn 

appear to be due to 1\129 analytical errors. 

An analysis of Hg on the XCEM filter determined that particulate phase Hg was 

being vaporized over time. A comparison ofXCEM spectra generated during the 

test with reanalysis 6 weeks later showed a loss of 30 percent of the Hg from the 

XCEM filter. M29 particulate concentrations on the M29 filters were 15 to 30 

times higher than typical and were highly correlated with differences between 

the XCEM and M29. The filters, which were not cooled while being shipped to 

the l'vl29 laboratory, could have lost the Hg prior to analysis. It is evident that 

the most significant obstacle in meeting the PS-10 RA criterion for the XCEM is 

the accuracy problems of the comparative reference method (M29). 

It was observed for both M29 comparison tests that the best method for calibrating the XCEM had not been determined. Both tests revealed some errors in cali· 

bration with some corrections made after the M29 tests but prior to the XCEM 

result submissions. This may cause some speculation over the performance of 

the monitor because the calibration rules seemed to change after the tests 

started. Because this monitor samples in a nondestructive manner, the results 

can be reanalyzed and vetified at a later date. It is these analyses that allow the 

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

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

VES011368 
70 ERDC/CERL TR-05-9 

field, a reliable, consistent, and accurate calibration protocol needs to be estab· 

lished. 

With the assistance of the XCEM, TEAD was able to identify that blocking the 

bypass duct on the 1236 furnace "ith a metal plate resulted in a greater than 90 

percent drop in metal concentrations. The continued use of the XCEM to diag· 

nose and assist with process control at TEAD indicates the value of having an 

installed CEM for multi-metals. 

The current cost estimates for the Army to purchase and operate a new XCEM 

are between $243,000 and $253,000 in capital costs, and between $32,400 and 

$48,300 for annual costs. These figures were current in July 2004. Recently, 

AED and Eli Lilly purchased XCEJ';1s for their furnaces. Improvements in the 

XCEM have resulted in a monitor that can measure 25 metals simultaneously 

and with det~tion limits between 0.1 and 0.2 jJg/dscm. In addition, CES has re· 

cently developed the QAG spiking method that will provide a reliable, consistent, 

and accurate means for ensuring that the calibration has been entered correctly. 

VES011369 
EROC/CERL TR.Os-9 

References 

Bry'SOn. S. (2001). Final Report- Stack Spiking Report for a Multi-Metal CEMS Testat the Tooele 

Army Depot Deactivation Furnace. Pret"'.red for U.S. Army C'.orp• of Engine""' hy MSETA. lnc.1 Butte, MT. 

---,...,.--· (2002). US Army Construction Engineering Reoearch Labor.tory (CEllL), Wasta 

Minimization and Pollution Prevention Program: Stack Spiking Repo1-t for a Multi·M~tal 

C~IS Test at the Tooele Army Depot Deactivation Furuace - 2002. Prepared lor U.S. 

Army Corps of Engjn..,rs by MSE-TA. Inc., 6u~, MT. 

Bry1;0n, S., C. Whitwonb, and S. Kuja,va. (2000). Final Report- Test and Evaluation of an X-Ray 

Fluo.....,..MO Bas<ld Multi-Eiemont Motals Continuous Emission Monit01·. Prepared for 

U.S. Army Corp of Engineers by MSE-TA. Inc., Butte, MT. 

Center for Health Promotion and Preventive Medicme (CHPPM). (2001). Air Polbttion 

Management Study No. 43·EL·649g.()1 Verification of Multi-Metals Continuous Emission 

Monitor at 1'ooele Army Depot. Tooele, Utah, May 14-17, 2001. 

- - ---· (2002). All· Pollution Management Study No. 43-EL-<!755-02 Verification of MultiMt!ta]s Continuous Emission Monitor at'fooe)eA.l·my Depot. Tooola, Utah, 'May 13-16, 

2002. 

Cooper Em·ironmenta.l Serviees (CES). (200la). "XCEM User's Guide.,'' B~averton, OR. 

-----· (2001b). ''XCEM Rosourco Manu a~ • Beaverton, OR. 

Cooper, J., B. E. Johnsen, K.J. Hay, and W. Wals<ln (2000). Continuous Hazardous Element 

Analysis Syst~m for Aillbi~nt and Emissions Monit.oring. Pt<."S4ilnted at regional AWMA 

Ccmference: Rooent Advances in tihe Science and Management of Air Toxics. AprillO, 

2000. 

Cooper, J.A., B. E. Johnsen, S.C. Fry, and M.P. Nakanishi. (2002). "Limitations in the Use of EPA 

Reference l\lethod 29 for Evaluating the Relative Accw·acy of Candidate Multi-Metal 

Continuous Emission Monitors." CES Report. September 2002. 

Envb·onmemal Protection Agency (EPA). (1992). Metbod~0 Field Validation of PoUut., nt 

Measurement Methods from Various Waste Media. Found on the EPA website at: 

http:/lwww.epa.gov/ttnlemclpromgote/m-301.pdf. 

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

04/19196) Found on the EPA webaite at: htiJ\'/lwww.fnr..gov/ttn/f'md nromwd .html. 

-----· (1999}. Final Standards tOr Hazardous Air Pollutants fOt Hazardous Waste 

Combuotors; Final Rule. FR52$27-FR53077, Vol64. No. 189. 

71 

VES011370 
72 ERDCICERL TR-05-9 

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

Waste Combuswrs (Phase I final Replacement Standords and Phase U): Proposed Rule. 

FR21197·21385, Vol69, No. 76. 

French. N. (1998). 1997 Pe.rformanc0 Testing o-fMulti·Metal Continuous Emissions Monitors. 

Summnry Report Prepared for the U.S. EPA and U.S. DOE by Sky+, Napa, CA. 

Hall. B., 0. Lindqvist, and E. Ljunstrom. (1990). Mercury Chemish'y in Sitnulated Flue Oases 

Ated to Wosto Incineration CondiOOns.. Envi.,.on. Sci. Techno!., Vol 24, No. 1. 

Hay. K .• J., B. E. Johnsen, and J. Cooper (2005). X· Ray Fluorescence-Based Multi-Metal 

Continuous Emission 'Monitor: Development. U.S. Army Engineer Research and 

Development Center (ERDC)JCERL Teclmical Report (TR)·05·3, January 2001>. 

Josephson, Paul (2003). Hazardous Waste Combuswr Management Plan - AEC (for Table 1). 

Lemieux. P .. J. Ryan. N. French, W. futos (1998). Resulte of the September 1997 DOE/EPA 

De.mo.nstratian ofMulti-Matal Continuous Emission Monitoring Technologies. Presented 

at International Conf~n ec on Incineration and Thermal Treatment Technologies. 

McFarl•nd, A.R, and .J.C. Rodgers. (1993). Single-Point Representative Sampling with Shrouded 

Probes. Los Alamos National Laboratory, LA·12612·MS, August 1993. 

Myt>.rs, J., T. Kelly, C. Lawrie. and K. Rigga. (2002). Environmental Technology Verit.cation 

Report: Cooper Environmental Services, XCEM Multi·Metals Continuous Emiafiion 

Monitor. May 2002. From EPA website: 

http://www .epa.gov/etv/pd&fvrvs/02_ vr_cooper_xmc.:em.pdf. 

Seltzer, M.D. (2000). "Performance Testing of a Multi metals Continuou-s Emissions Manitor.:o J. 

Air IVaste Mgt. A..oc., Vol 62, No. 6. 

Wang, R.G., M.A. Dillon, and D. Spe.nc:e. {1983). J()u.rnol fJ/Chem. Phy.~ .. 79 (2) 1 1100. 

VES01137l 
ERDC/CERL TR-G5-9 73 

Appendix A: Test/QA Plan for Verification 

of a Continuous Emission 

Monitor for Multi-metals at 

Tooele Army Depot (2001)* 

1.0 INTRODUCTION 

1.1 Test Description 

This test/quality assurance (QA) plan provides detailed proeedures for a veri.fica· 

tion test for an X-Ray Fluorescence-based Continuous Emissions Monitor 

(XCEM) used to measure metals in source emissions. The. U.S. Army Construe· 

tion Engineering fu!search Laboratory (CERL) will perform the verification test. 

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

measuring metals in stack emissions generated by their demilitarization incin· 

erators. The U.S. Environmental Protection Agency's (EPA's) Environmental 

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

are buying and permitting. 

Battelle Memorial Institute, headquartered in Columbus, Ohio, is EPA's partuet· 

for the ETV Advanced Monitoring Systems (A.MS) Center. The scope of the AMS 

Center covers verification of monitoring methods for contaminants and natural 

species in air, water, and soil. Verification testing will follow procedures specified in this test/QA plan and the quality reqwrements in the "Quality Manage· 

rnent Plan for the ETV Advanced Monitoring Systems Pilot" (EPA 2000). 

Prepared klt CERL by Cooper EnWonmental SeMoes, Beaverton, OR, 8 May 2001, 

VES011372 
74 ERDC/CERL TR-05-9 

Testing will take place at the Tooele Army Depot <TEAD) deactivation furnace 

located in Tooele, UT. 

1.2 Test Objective 

The objective of the verification test is to quantify the performance of the XCEM 

by comparison to reference metal measurements under full-scale conditions at a 

combustion facility. 

1.3 Organization and Responsibilities 

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

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

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

be responsible for spiking the stack, and the U.S. Army Center for Healt h Promotion and Preventive Maintenance (CHPPM) will conduct the r eference method 

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

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

individuals are detailed in the following paragraphs. 

Dee 

Tom James Russell 

Kelly Hay TEAD 

Battelle CERL Facility 

Manager 

I 

John Steve Mike 

Cooper Bryson Pattison 

CES MSE-TA CHPPM 

XCEM Stack Ref. 

Vendor Spiking Measure. 

Figure 1-1. Organizational Chart for Verification Tests 

1.3.1 Construction Engineering Research Laboratory 

Dr. K. James Hay is the CERL verification testing leader. Dr. Hay will ha\'e 

overall responsibility for ensuring that the technical, schedule, and cost goals 

established for the verification test are met. If questions arise concerning QA 

VES011373 
ERDC/CERL TR.05·9 

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

Dr. Hay will: 

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

verification test. 

• Have overall responsibility for development of a test/Q;\ plan. 

• Revise the draft test/Q;\ plan in response to reviewer's comments. 

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

• Serve as the primary point of contact for CES representatives. 

1.3.2 Battelle 

Dr. Thomas J. Kelly is the ETV AMS Center's Verification Testing Leader. In 

this role, Dr. Kelly will be responsible for reviewing the test/QA plan, evaluating 

field-testing to ensw·e that the test/Q;\ plan is being followed, and developing an 

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

Quality Manager. As such, he will be responsible for assessing that quality requirements of this test/QA plan are met. More specifically, these Battelle staff 

will: 

• Review the draft test/QA plan. 

• Coordinate Battelle and EPAIETV staff during verification testing. 

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

• Report test quality problems to CERL. If significant quality problems are 

observed and not rectified, Battelle can discontinue the test as an ETV verification. 

• Pl·epare a draft ETV verification repo1t and statement using test data and 

summary test report provided by CES. 

• Oversee revision of the draft ETV verification report and statement in response to re'>iewer's comments. 

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

report and statement. 

• Conduct a te<:hnical system audit and report results of that audit. 

1.3.3 Tooele Anny Depot 

The verification test will be conducted in collaboration with Dee Russell of 

TEAD. Mr. Russell's responsibilities are: 

• Coordinate the operation of the facility during verification testing. 

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

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

• Contribute to the development of the draft test/Q;\ plan. 

75 

VES011374 
76 ERDCICERL TR.05-9 

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

• Review the draft tes!IQA plan. 

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

• Review draft reports. 

• Assemble trained staff to operate the TEAD incinerator. 

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

the verification test. 

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

• Ensure that operating conditions and procedures for the TEAD incinerator 

are recorded during the verification test. 

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

• Provide support in responding to any issues raised in assessment reports and 

audits related to facility operation. 

1.3.4 Cooper Environmental Services 

Cooper Environmental Services of Beaverton, OR manufactures the XCEM. 

CES staff will: 

• Develop the draft test/QA plan and submit plan to CERL, Battelle, TEAD, 

CHPPM, and MSE-TA staff. Revise the test/QA plan in accordance with reviewers' comments. 

• Approve the final test!QA plan. 

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

oftheXCEM. 

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

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

• Commit a trained technical member of staff to operate, maintain, and repair 

the XCEM throughout the verification test. 

• Participate in verification testing, including providing data acquisition for 

the XCEM. 

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

• Prepare a summary test report for CERL. The summary test report will he 

used as the basis for the ETV verification report. 

• Review the draft verification report and verification statement. 

1.3.5 Center for Health Promotion and Preventive Medicine 

Reference method testing will be conducted by CHPPM under the direction of 

Mike Pattison. :M.r. Pattison will: 

• Review the draft test/QA plan. 

• Adhere to the quality requirements in this test!QA plan. 

VESOII375 
ERDCICERL TR.OS-9 

• Assemble trained technical staff to conduct reference method sampling for 

the verification test. 

• Contract for and oversee laboratory analysis of the reference method sam· 

pies. 

• Provide reference method analytical and quality assurance results and date 

in an agreed-upon format to Battelle, CES, and/or CERL as needed. 

· • Provide support in responding to any issues raised in assessment reports and 

audits related to facility operation. 

1.3.6 MSE Technology Applications, Inc. 

1\ISE-TA will be responsible for injection of the metals of interest into the TEAD 

incinerator. MSE·TA will: 

• Quantitatively spike metals of interest into the TEAD incinerator down· 

stream of the controls. 

• Provide measurable concentrations of the metals of interest at the XCEM and 

reference method sampling points. 

• Ensure that particle size for the metals of interest are representative of typi· 

cal stack gas conditions. 

• Ensw-e that all applicable regulatory emission limits are maintained. 

1.3.7 U.S. Environmental Protection Agency 

EPA manages the. ETV program and partners with Battelle for the ETV AMS 

Center. As such, EPA has the option to conduct a technical systems audit of the 

verification test. In addition, EPA will participate in the peer review of the 

test/QA plan to be prepared by CES and the ETV verification report to be pre· 

pared by Battelle. 

2.0 APPLICABILITY 

2.1 Subject 

This test/QA plan is applicable to the verification testing of a commer cially 

available continuous emission monitor (CEM) system for determining multi· 

metal concentrations in combustion source emissions. The system being tested 

is an X-ray Fluorescence-based CEl\1 (XCEM) manufactured by CES. The XCEM 

extracts a representative stack gas sample and concentrates the particulate matter and gas phase hazardous metals on a filter, which is then analyzed with x· 

ray fluorescence (XRF) using an adapted QuanX analyzer. A prototype of the 

77 

VES011376 
78 ERDC/CERL TR-05-9 

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

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

Verification testing will be conducted at TEAD. The TEAD facility has a wellch!ll-acterized feedstream and was the site for multi-metal CEM tests conducted 

in 1999. 

The TEAD site has a deactivation furnace, APE-1236, for incineration of munitions. The incinerator is currently regulated under the Resource Conservation 

and Recovery Act (RCRA) for antimony, arsenic, barium, beryllium, cadminum, 

chromium, lead, mercury, nickel, selenium, silver, and thallium (Sb, As, Ba, Be, 

Cd, Cr, Pb, Hg, Ni, Se, Ag, and Tl). Of the twelve regulated elements, five are 

typically found in the feedstream: Sb, Ba, Cd, Cr, and Pb. The XCEM will be 

verified for its measurement capabilities of the five elements found in the feedstream as well as As, Hg, Ni and a nonregulated metal, zinc (Zn). These elements were selected in order to challenge the XCEM over a large range of analysis conditions and elemental concentrations. 

EPA Method 29 (M29) is currently recognized as the most suitable procedure to 

determine multi-metal concentrations in source emissions (EPA 1990). Method 

29 draws stack gas through a filter and a series of impingers providing a 1· to 

3-hour average concentration. For the verification testing, a battery of twelve 2-

hour l\f29 tests will be conducted by CHPPi\l Analysis of the M29 sample train 

will be under the direction of CHPPM and will include, as a minimum, determination of the nine elements measured by the XCE!'of. 

2.2 Scope 

The overall objective of the verification test described in this plan is to provide 

quantitative verification of the performance of the XCEM under real-world con· 

ditions. EPA has published a draft performance specification document desig· 

nated as PS-10 (EPA 1996) as a proposed description of how to assess the acceptability of a multi-metal CEM upon installation and thereafter. The goals of the 

verification test will be met if the XCEM meets the proposed PS-10: 

1. Relatiw accuracy criteria for the elements in the feedstream of the Thoele incinerator (Sb, Ba, Cd, Cr, and Pb). 

2. Quality assurance criteria by passing daily zero, span, and drift checks. 

3. Response time and reporting time criteria for a bstch CE~L 

4. Measurement criteria by testing several elements at two concentration levels (Hg, 

Ni, Zn, and Sb). 

VES011377 
ERDC/CERL TR.()5-9 

A secondary objective is to meet the relative accuracy criteria for additional regulated and unregulated metals, which are not typically found in the feedstream 

(As, Hg, Ni, and Zn). 

The performance parameters that are addressed by this testJQA plan include: 

• Relative accuracy 

• Correlation with reference method 

• Precision 

• Instrument drift 

• Span and zero 

• Response time 

• Bias 

• Low level metal response. 

Relative accuracy, correlation with the reference method, and precision (i.e., repeatability at stable test conditions) will be assessed for the elements being 

measured by the XCEM. Instrument drift will be based upon the precision of the 

daily XCEM span and zero QA measurements. The XCEM has a built-in additional check for instrument drift which measures a palladium standard with 

each XCEM test run. For the verification test, response time will be determined 

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

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

less than 6 and 18 pg/dscm respectively. 

It is beyond the scope of this verification test to simulate the aging and exposures that may affect an XCEM during routine long-term use. This verification 

test evaluates the performance of a new XCEM over a relatively short test period, in the hands of staff skilled in its operation. It must be noted that the longterm performance may be different from that observed in the testing described 

here. The effort spent in installing and maintaining the XCEM will be documented, however, and the amount of time the XCEM is operational over the veri· 

fication test period will be recorded, to assess data completeness. 

3.0 SITE DESCRIPTION 

Verification testing will take place at the TEAD building 1320 deactivation in· 

cineraror APE-1236 (Figure 3-1). This section of the test/QA plan describes the 

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

79 

VES011378 
80 ERDCICERL TR..05-9 

3. 1 Test Facility 

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

shown in Table 3-l. The TEAD incinerator is classified as a dry stack with water 

cont<~nt ranging from 5 to 10 percent. Typical stack PM concentrations are in the 

10 mg/dscm range. A number of sensors (temperature, gas flow, pressure differential, combustion gases, etc.) are used to monitor operating conditions at vari· 

ous points in the system. Signals from these sensors are monitored and compared to preset operating standards. The incinerator consists of a main control 

panel, OEMS, Waste Feed Rate Monitoring System (WFR.t'LS), dual conveyor 

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

fan, and exhaust stack. 

1) Main Control Pan el. The main control panel contains various pieces of 

control equipment to monitor and control the furnace operation. Process controllers are used to control the rotary furnace feed end temperature, negative pressure in the furnace, and afterburner temperature. A multi-point digital recorder 

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

by a PLC. The PLC controls the motor stal-ters, the WFRMS, safety interlocks, 

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

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

Figure 3-1. TEAD Deactivation Incinerator Building 1320. 

VES011379 
ERDC/CERL TR-05·9 81 

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

Typical Operating Parameters fot· the 

APE-1236 Deactivation Furnace 

Afterbume1· Temp. ("F) 1600 

Baghouse AP (in. HzO) H 

Baghouse Temp ("F) 680 

Kiln Feed End Draft Pressure (in. fuO) 0.3 

Kiln Feed End Temp ("F) 600 

Kiln Burner End Temp (°F) 1200 

02-CEM(%) 14 

CO (ppm) 11 

Stack Temp. ("F) 550 

Stack Gas Velocity (ft/sec) 46 

Stack Pressure (in. H20) 0.3 

Figure 3-2. TEAD Incinerator Stack. 

VES011380 
82 EROC/CERL TR-05-9 

2) Continuous Emissions Monitoring Systems. CEM systems are in place 

to measure carbon monoxide (CO) and oxygen <O.> in the exhaust stack. The 

CEM sampling system includes the following: sample extraction probe, heat 

traced sampling lines, calibration ports, refrigerated condenser, sample pump, 

filters, and flow meters. The sample extraction port is located in the exhaust 

stack approximately 20 feet above grade. The CEM system includes automatic 

calibration, which allows the monitors to be calibrated periodically "~thout 

operator intervention. The CO monitor is a NDffi analyzer with 0-200 ppm and 

0-3,000 ppm dual range capability. The output from the CO monitor is corrected 

to 7 percent 0, (using data from the 0 , CEM). 

3) Waste Feed Rate Monitoring System. The WFRMS controls the furnace 

feed rate. The WFRMS consists of a precision explosion proof scale, a push-off 

box, and a slide chute. The scale reports the measut-ed weight to the PLC via a 

serial communication cable. The PLC verifies that the weight is less than or 

equal to the established limit for the item being incinerated. Once the PLC has 

verified that the weight is acceptable, the push-off box pushes the ammunition 

item onto the slide chute, which is over the primary feed conveyor. The WFRI\18 

is capable of cycling every 15 seconds. 

4) Dual Conveyor Feed System. The primary waste feed conveyor transports the munitions from the WFRMS t.hrough the concrete wall into the barricade area. The ammunition is then fed onto the secondary feed conveyor, which 

deposits the ammunition into the rotary furnace feed chute. If an out-ofparameter condition arises, the primary feed conveyor is stopped until the condition is corrected. For safety reasons, however, the secondary conveyor continues 

to operate. This allows munitions near the high temperature end of the kiln to 

continue moving through the furnace and deters possible explosions outside the 

furnace. 

5) Rotary Furnace. The rotary furnace is designed to ignite the ammunition 

items and effectively incinerate reactive components from the metal shells. The 

heat to ignite the ammunition is initially provided by fuel oil forming a countercurrent to the movement of the ammunition through the rotary furnace. Combustion gases and entrained ash exit the furnace adjacent to the feed chute. 

Non-entrained ash and the metal components of the ammunition are discharged 

at the burner end of the rotary furnace. The ammunition is propelled through 

the 20 ft long, 30.5 inch diameter retort toward the burner end by spiral flights. 

As the ammunition approaches the flame, they either detonate or burn freely, 

depending on the ammunition characteristics. The thick cast steel walls contain 

high order detonations. Feed rates, residence times, and operating parameters 

have been established for each ammunition item by controlled testing. The roVESOll38l 
EROC/CERL TR-05-9 

tary furnace is equipped with a Hauck 783 proportioning burner located at the 

discharge end. The burner has a capacity of 3 million BTU/hr and a nominal 

turndown ratio of 4:1. The feed end temperature of the furnace ranges between 

350-450 •F while the discharge end ranges from 800-1100 •F during normal operation. The rotary furnace is operated under a slight negative pressure. 

6) Furnace Shroud. A metal shroud that completely encloses the ret01t sections, the draft fan, and the retort combustion ait· fan controls fugitive emissions 

from the rotary furnace. The draft fan is used to maintain negative pressure at 

the feed end of the furnace. The retort combustion air fan draws air from t.he 

area beneath the retort shroud, creating a negative pressure. The combustion 

air blower creates a negative pressure inside the shroud, which pulls any fugitive emissions through the blower and discharges them into the furnace via the 

furnac.e burner. 

7) Cyclone. Large particles from the gas stream are removed by the cyclone. 

The cyclone has a 90-95 percent removal efficiency for particles 10 microns and 

larger. The cyclone has a clock-wise rotation, with inlet and outlet ducts at 90° 

separation. Particles are removed from the cyclone at the bottom by a double 

tipping valve. The valve has two gates that are motor driven. The gates open 

alternatively so that on)y one gate is open at any time, thus maintaining the 

negative pressure. 

8) Afterburner. The afterburner is built to AED specifications by Southern 

Technology Incorporated. The afterburner is designed to raise the temperature 

of the exhaust gases exiting from the kiln. This elevated temperature, and the 

added residence time, enhances the complete combustion of the explosive. The 

afterburner is capable of heating 4000 sefm of flue gas from 350-450 •F to 1400-

1600 •F with a minimum flue gas residence time of 2 seconds. A diesel fuel 

burner with a propane pilot ignition system heats the afterburner. The afterburner is equipped with a Hauck WR0164 wide range burner with a capacity of 8 

million BTU/hr and nominal turndown ratio of 10:1. 

9) Discharge Conveyor. The solid waste exits the furnace by the discharge 

conveyor located at the discharge/burner end. The solid waste is typically com· 

prised of the metal casings, melted lead projectiles, and residual ash. The low 

end of the discharge conveyor is located underneath the discharge/burnet· end of 

the rotery furnace. The high end of the conveyor passes through the concrete 

barricade wall and deposits the waste into containers. 

10) High Temperature Cast Ceramic Filters Baghouse. The baghouse is a 

high temperature cast ceramjc collector, used for final particulate cleansing for 

83 

VES011382 
84 ERDC/CERL TR-05-9 

the gas stream. The baghouse was designed and built to AED specifications by 

JT Systems Incorporated. The flue gases from the afterburner are transp011:ed 

to the baghouse by 120 ft of 30-inch diameter stainless steel ducting. The ducting is long enough to produce a temperature drop from 1600 oF at the exit of the 

afterburner to 1000 oF entering the baghouse. The baghouse contains 154 ceraiil 

ceramic candles that are 5.75 inches in diameter and 10ft long. This results in a 

total filter area of 2330 square feet with a filtration velocity of 4.97 feet/second. 

The baghouse operates with a delta pressure range of 0.5 to 6.0 inches of water 

column. The particles settle into the hopper below and are exhausted through a 

double tipping gate valve into a sealed 55-gallon drum while maintaining an air 

seal on tl1e baghou.se assembly. 

11) High Temperature Draft Fan. The gas steam is pulled though theAPCS 

by an induced draft fan. The fan is a Fan Eqnipment Company Model M-21 I.E. 

The fan is capable of pulling 6700 ACFM at a draft (negative pressure) of 30 

inches of water column. 

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

3.2 TEAD Emission Limits During Testing 

For the verification test, metals in the TEAD incinerator stack gas are regulated 

under a Temporary Authorization permit as shown in Table 3-2. Of t.he 12 regulated metals, 5 are typically found in the feedstream (Pb, Sb, Ba, Cd, and Cr); 

however, Pb is the only element that is routinely found in measurable concentrations in the stack gas. 

Table 3-2. TEAD metal emission linlits during verification testing. 

Element Limit (g/hr) Element Limit (g/hr) 

Antimony (Sb) 14 Lead (Ph) 4.3 

Arsenic (As) 0.11 Me1·cury (Hg) 14 

Barium (Ba) 2400 Nickel (Ni) 930 

Beryllium (Be) 0.20 Selenium (Se) 180 

Cadmium (Cd) 0.26 Silver (Ag) 140 

Chromium (Cr) 0.04 Thallium (TI) 14 

VES011383 
ERDCICERL TR-05-9 

4.0 EXPERIMENTAL DESIGN 

4.1 General Design 

For all tests, both the kiln and the afterburner will be fired with diesel fuel while 

incinerating Mark 344 fuses (NSN number 1325000090348) with a feed rate of 

79 per hour. The chemical composition of the fuses is shown in Table 4-1. For 

these fuses, lead is the restrictive element limiting the feed rate. Table 4-2 

shows the nine elements that will be measured by the XCEM during verification 

testing. Eight of these metals will be spiked directly into the stack downstream 

of the controls. These metals will he spiked at the level shown in Table 4-2. 

Lead, however, will not be spiked since the incinerated munitions provide measurable concentrations of lead without spiking. 

Spiking will be conducted by MSE-TA using three or four atomizers to inject solutions containing the metals of interest either directly into the stack or into a 

chamber that dries the solution prior to entering the stack. The atomizer provides liquid droplets that, when dried, yield fme. salt particles that. are representative of typical stack aerodynamic diameters. 

Stack gas metal concentrations will be simultaneously determined by the XCEM 

and two Method 29 (M29) sampling trains. The M29 trains \viii sample for two 

hours while XCEM data, which is recorded every 20 minutes, will be averaged 

for the M29 test run. 

A total of 12 dual M29 test run.~ will be performed by CHPPM. Each run will inelude two M29 sampling trains in order to determine reference method precision. 

Method 301 will be applied to M29 data to determine bias between the reference 

method sampling trains. Prior to testing, CHPPM will conduct an EPA Method 2 

velocity traverse to determine a representative sampling point for the M29 

probes. The XCEM and M29 probes will be located approximately 27 feet above 

the base of the exhaust stack. The nearest flow distm'hances are located 9.8 duct 

diameters upstream (induced draft fan) and 4.3 duct diameters downstream itop 

of the stack) from the sample ports. 

85 

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86 ERDC/CERL TR·OS.9 

Table 4-1. Composition of munitions incinerated during metals testing. 

Fuze, Bomb , Tail, MK344 Mod 0/1 

Feed Rate: 79 it em slhr; Loading (lblitem) 0.2791 

Component Qua n- Com ponent 

Com ponent Feed Rate tlty (lb/item) (lb/br) 

Butyl Acetate 0.00001 0.0008 

Charcoal 0.00002 0.0016 

Ethyl Alcohol 0.00001 0.0008 

Graphite 0.00541 0.4275 

Lead Azide 0.00028 0.0221 

Lead Monoxide 0.00005 0.0040 

Lead Powder 0.00031 0.0245 

Le.ad Styphnate 0.00683 0.5398 

Nitrocellulose 0.00002 0.0016 

Nitrostru:ch 0.00001 0.0009 

PETN 0.00031 0.0245 

Potassium Nitrate 0.00008 0.0063 

Selenium Powder 0.00012 0.0095 

Sulfur 0.00005 0.0040 

Tetryl 0.26555 20.9855 

Toluene 0.00001 0.0008 

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

Emission Limits1 S piking Levell 

Elements - j!g/ dsem 

glbr - j!g/ dscm 

Runs 1-6 Runs 7-12 

As 0. 11 17 15 15 

Ba 2,400 360,000 1000 1000 

Cd 0.26 39 35 35 

Cr 0.04 6.5 5.5 5.5 

Hg 14 2100 100 300 

Ni 930 139,500 200 500 

Pb 4.3 645 NS NS 

Sb 14 2,100 200 500 

Zn NR NR 200 500 

1 The concentration in 11g/dscm assumes a stack flow rate of about 6700 dscmllll' 

NR: Not regulated NS: Not Spiked 

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CHPPM will conduct the chemical analysis of recovered sample fractions from 

the M29 trains. Sample handling, analysis, and all assoeiated QA/QC activities 

will conform to the requirements ofM29. Accuracy data for metals analysis will 

be confirmed with two field spikes of the nine measured metals into blank sampling trains. Media blanks of the M29 solutions and filter will also be analyzed. 

Sample integrity will be maintained by use of a chain-of-custody and a designated sample custodian. Unique sample identification numbers ";n be implemented so that final data used for verification can be traced back through the 

analytical process to the original sample. 

4.2 Test Schedule 

Set-up for the verification testing is scheduled for May 10. XCEM verification 

testing is tentatively scheduled for May 11, 12, 14, and 15. Three .M29 test runs 

are planned for each day with each run lasting 2 hours. All nine metals of interest will be tested during each run; however, lower concentutions of Ni, Sb, Hg, 

and Zn are scheduled for the first six runs as shown in Table 4-2. 

4.3 Test Procedures 

In all cases when reference method data is being taken, the introduction of the 

indicated metals will be held constant throughout the entire sampling period. 

The intent of this approach is to allow comparisons of XCEM data to reference 

method data under constant conditions. 

4.3.1 Spiking approach 

Spiking will be conducted by MSE-TA of Butte, MT. Three atomizers are used to 

quantitatively inject nitric acid solutions containing the metals of interest. The 

solution will be ixijected either directly into the stack or into a drying chamber, 

which opens to the stack. The spiked solution will enter the stack through a port 

located at the base of the-stack. This port was successfully used in earlier multimetal CEM tests at Thoele and is directly downstream of a draft fan allowing for 

good mixing. 

Manufacturer specifications for the atomizers determine droplet si:r.e distributions based on pressure and air flow rate. For these tests, pressure and flow rate 

will be maintained to keep droplet sizes less than 28 microns in diameter. When 

dried, the majority of the mass is expected to be in the one to four micron range. 

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Each atomizer has been gravimetrically calibrated by MSE-TA to determine 

mass emission rates over the range of pressure and air flow rates expected for 

the verification test. 

4.3.2 Reference method sampling 

CHPPM's Air Quality Surveillance Program will conduct reference method sampling. Dual sample trains will be used to collect metals data employing standard 

operating procedures from M29. Full sample custody procedures will be employed during the test using sample custody sheets and sample custody seals. 

Samples will be under either direct custody or lock and key at all times. Per 

M29 protocol, media blanks from the same lot as used during testing will be 

taken and treated in the same manner as the test run samples. 

Dry gas meters are calibrated both pre- and post-tests with a wet test meter. 

Pitot tubes undergo a geometric calibration, and thermocouples are calibrated 

using standard two point calibration methoda. 

As a performance audit, two blank trains will be quantitatively spiked with all 

nine of the metals of interest. These spikes will be conducted on sampling media, including the filter and impinger solutions, from the same lots used during 

testing. A spike recovery target of 80 to 120 percent of injected solution has been 

set. 

4.3.3 Reference method analysis 

Reference method analyses will be conducted by CHPPM's Directorate of Laboratory Services (DLS). Analysis will follow standard M29 protocol with the following exception: the front half analysis will include separate reported \•alues for 

both the front half rinse and the filter. Blank values will be determined using 

!1.129 section 9.1 protocols and a standard blank subtraction will be made if significant metals are found in the blank 

CHPPM uses ICP-1\>IS for its metals analysis. The ICP-MS is calibrated using 

solution standards as discussed in section 10.2 ofM29. 

4.4 Data Comparisons 

This section describes how the reference and CEM data will be used and compared to quantify the performance of the XCEM. Table 4-5 summarizes the data 

that will be used for the verification comparisons. 

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Relative accuracy and correlation will be det~rmined by comparing the CEM results against the M29 results, for each metal. .M29 results for the probe, front 

half, and back half will be reported separately to evaluate potential particle Joss 

in the XCEM tubing. However, the total train results will be combined for the 

relative accuracy and correlation calculations. 

Precision will be determined by analysis of XCEM concentrations when the spike 

injection rate and stack conditions are held constant. It is recognized that the 

reported precision will include variability in stack conditions as well as XCEM 

variability. 

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

Performance Comparison 

No. of 

Objective Data Parameter Based On Points 

Accuracy Determine degree of quantitative Reference Method 12 agreement with refer ence method. Results 

Col'relation Determ.ine eg~·ee of correlation Reference Method 12 "'ith reforenco method. Rooults 

Determine degree of consistency in XCEM reported 

ooncentrations 

Precision XCEM measured concentrations under constant 6/run under constant operating operating conditions. conditions. 

Determine 

variation in 

Instrument 

Determine XCEM ability to pslladiurn 

Drift measure consistently over the concentrations 3/hr 

course of the test. determined with 

eacbXCEM 

ml.:!asurement 

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

Determine XCEM response time as 

C-ontinuous 

Response Time a batch CEM. monitoring of metal 3/hr 

concentrations 

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

Low Level Determine XCEM performance Arsenic and 

Metal Response 

when low metal conL--entrations are chromium ref. 24 

present in the stack. Method results 

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Instrument drift will be determined by evaluation of XCEM reported palladium 

concentrations. As part of the XCEM quality assurance program, a palladium 

rod has been permanently fixed above the x-ray beam and below the filter tape. 

The palladium rod is measured with each sample, and a running record of the 

reported concentrations is maintained. The percent relath•e standard deviation 

for palladium concentrations will also sen•e as a determination of XCEM in· 

strument drift during testing. 

XCEM response time will be determined as the time between the start of one 

sampling period and the beginning of a second sampling period. The XCEM 

samples for 10 to 20 minutes, depending upon the desired detection limits. 

Within a few seconds of sampling, the exposed tape is moved into the XRF analysis region. Analysis requires the same amount of time as sampling. Following 

analysis, concentrations are determined and recorded in a fraction of a second. 

For these testa, the response time will be determined as the average time from 

the start of one sampling period to the start of the next sampling period with a 

delay in the reporting of data that is equivalent to the analysis time. 

Bias between the dual M29 sampling trains for each run will be determined by a 

comparison of the dual M29 sample runs using an EPA Method 301 approach for 

paired sampling trains. For valid test runs, M29 concentrations will be averaged 

and compared to reported XCEM data. 

The XCEM's ability to measure low-level concentrations of metals will be chal· 

lenged by Cr, As, and Cd, which are to be present at approximately 5, 15, and 35 

pg/dscm I·especti,•ely. 

M29 resulta identified as outliers will be reported, but will not be used for verifi· 

cation. The intent of this approach is to provide a valid set of reference data for 

verification purposes, while also illustrating the degree of variability of the ref· 

erence method. Identification of outliers will be based upon analysis of percent 

differences in M29 concentrations between sampling trains and trends in data 

throughout the test day. In any case, where rejection of a reference result is suggested, effort will be made to find an assignable cause for the divergent result. 

According to PS·lO, the XCEM acts as a batch CEM. Batch CEMs continuously 

sample and concentrate the pollutant on a capture medium. Analysis is per· 

formed after sufficient time has elapsed to concentrate the pollutant to levels 

that are detectable by the analyzer. PS-10 requires that batch CEMS meet three 

response time criteria: 

1. The sampling time shall be no longer than one-third of the averaging period for 

the applicable standard. 

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2. The delay between the end of the sampling period and reporting of the analysis 

period shall be no greater than 1 hour. 

3. Sampling shall be continuous except in that the panse in sampling when the 

sample collection media is changed should be no greater than 5 percent of the 

averaging period or 5 minutes, whichever is less. 

TEAD incinerator emissions are regulated by two standards: Resource Conservation and Recovery Act (RCRA} limits in grams per hour and t he maximum 

achievable control technology (MACT) r ule, which regulates using a 12-hour rolling average. Since the RCRA limits are more stringent, the response time shall 

be limited to 20 minutes for the TEAD tests with sampling occurring at least 57 

minutes per hour. 

Span and zero determinations will be conducted daily by the XCEM_ The automated XCEM span routine extends a plunger containing metals of interest into 

the analysis area. The plunger is then analyzed by the XCEM and the data 

compared with the known metal concentrations on the plunger. Zero readings 

are determined by analysis of blank filter tape. 

The XCEM filter analysis is nondestructive and the exposed tape remains available for subsequent analysis. In cases where unexplained discrepancies exist 

between XCEM and M29 data, a post-test filter tape analysis will be considered. 

Setup and maintenance needs will be documented qualitatively by Battelle, both 

through observation and through communication with the vendors during the 

test. Factors to be noted include the frequency of scheduled maintenance activities, the downtime of the CEM, and the number of staff operating or maintaining 

it during the verification test. 

5.0 STATISTICAL CALCULATIONS 

Statistical calculations will be used to verify the performance of the XCEM as 

described below. In all cases, measurement results from both the reference 

method and the XCEI\II are reported in units of )lg/m' on a dry basis at 20 oc, 

1 atmosphere pressure, and the actual flue gas 0, content. 

5.1 XCEM Concentrations During a Reference Method Run 

Average XCEM concentrations for a given reference method run will be calculated as follows: 

91 

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where: 

c, 

c, 

n 

t; 

= 

= 

= 

= 

[Eq 5.11 

XCEM time-weighted concentration for element i during 1\129 test run 

XCEM reported concentration for element i during time intervalj 

number of XCEM measurements during test run 

number of minutes XCEM measured element i's concentration during 

time intervalj 

5.2 Relative Accuracy 

The relative accuracy (RA) of the XCEM with respect to the reference method 

(M29) will be assessed by: 

!Eq 5.2] 

Where d refers to the difference between M29 and the XCEM results, and x cor· 

responds to the M29 result. 84 denotes the sample standard deviation of the differences, while t"&, is the t value for the 100(1-a)"' percentile of the distribution 

with n·• degrees of freedom. The RA will be determined for an a value of 0.025 

(i.e., 97.5 percent confidence level, one-tailed). The RAcalculated in this way can 

be interpreted as an upper confidence bound for the relative bias of the analyzer, 

i.e., ~ , where the superscript bar indicates the average absolute value of the 

X 

differences of the reference \•alues. If 12 reference method test runs are completed, the RAprocedmoe stated in PS-10 will be followed (i.e., up to three results 

may be omitted from the RA calculation). The impact of the number of data 

points (n) on the RA value will be noted in the verification rep01t. TheRA will be 

calculated separately for each metal measured by the XCEM. 

5.3 Correlation with Reference Method 

The degree of correlation of the XCEM with the reference method results will be 

assessed in terms of the correlation coefficient (r') for metals spiked at more than 

one concentration (i.e., Hg, Ni, Zn, and Sb). 

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ERDCICERL TR..,S-9 

A second series of intra-method correlations will be determined by comparing the 

relative ratios of metals measured by the XCEM for each of the measurement 

periods. This con·elation assumes that no fractionation of the injected species 

occurred during transport. 

5.4 Precision 

Precision will be calculated in terms of the percent relative standard deviation 

(RSD) of a series of XCEM measurements made during stable operation of the 

TEAD, with metals injected at a constant level. This precision will reflect the 

variability in the stack conditions, spiking rate, and XCEM measurements and 

will be identified as a maximum XCEM precision with a note in the verification 

report that the calculated precision is subject to the variabil.ity of the test, not 

only the XCEM variability. During each M29 sampling run, all readings from 

the XCEM will be recorded and the mean and standard deviation of those recordings will be calculated. Percent precision (P) will then be determined as: 

SD P= xJOO 

X [Eq 5.3] 

where SD is the standard deviation of the XCEM readings and X is the mean of 

the readings. The same calculation will be performed for each metal measured 

bytheXCEM. 

5.5 Span, Zero, and Instrument Drift 

The XCEM has automated daily span and zero checks and reports a palladium 

concentration with each sample to check for instrument drift. Span, zero, and 

instrument drift will be reported in terms of the mean, RSD, and range (maximum and minimum) of the readings obtained from the XCEM. The percent RSD 

will be calcnlated as: 

SD RSD .dOO 

X [Eq 5.4] 

where X is the mean, and SD is the standard deviation of the daily readings of 

the standard. This calculation, along with the range of data, will indicate the 

day-to-day variation in zero and standard readings. 

93 

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5.6 Method 29 and XCEM Bias 

Bias between the two M29 sampling trains and the M29/XCEM data will be determined using an EPA Method 301 approach. The results are tested for statistically significant bias by calculating the t-statistic and determining if the mean of 

the differences between the two sampling trains is significant at the SO-percent 

confidence. level. The t-statistic is calculated by finding the SO of the differences 

between the two sampling trains. 

Where: 

L;(d,-d.} 

{n - 1) 

d, = the difference between the two sample train values 

d. = mean of the d, values 

n = number of paired samples 

[Eq 5.5) 

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

(Eq 5.6) 

The critical value of the t-statistic is 0.8755 for 12 runs. If the calculated t-value 

is greater than the critical value, the bias as defined by M301 is statistically significant. A statistically significant bias in the reference method will be noted in 

the validation report. 

Method 29 data pairs that are determined to be unbiased relative to each other 

will be averaged and used for comparison to the XCEM. Bias between the 

XCEM and average M29 data will be determined using equations 5.5 and 5.6 

with d, being the difference between the average M29 and XCEM data. 

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6.0 MATERIALS AND EQUIPMENT 

6.1 Gases and Chemicals 

6.1.1 Compressed gas 

The XCEM requires about 10 sclin of dry compressed gas to provide a vacuum in 

the extraction system. A small amount of purified compressed gas is also used to 

drive the XCEM pneumatics. The atomizers used for spiking will require about 

10 scfm of dry air. 

6.1.2 Spike Injection solutions 

The spike injection solutions include Ba(N0,)2, Cd(N0,)2, Cr(N0,)3, As,O,, 

Hg(N0,)2, Ni(N0,)2, Zn(N03)2, and SbCL,. Solutions will be prepared on-site to 

allow for flexibility in responding to background metal concentrations found in 

the TEAD incinerator. 

6.2 Reference Method 

6.2.1 Sampling trains 

CHPP:M will supply the glassware, filters, and associated equipment for M29 

sampling. Multiple trains will be supplied so that six trains (i.e., three sampling 

runs with two trains each) may be sampled in a single day; in addition, at least 

two M29 field spikes and a media blank will be analyzed. Preparation, sampling, sample recovery, and cleaning of used trains will be the responsibility of 

CHPPM during this verification test. 

6.2.2 Analysis equipment 

CHPPM will provide labomtory equipment for sample recovery and analysis. 

This will include all chemicals and solutions for rinsing train components and 

recovering impinger samples. 

6.3 TEAD Monitoring Equipment 

The verification will make use of monitoring equipment already integrated into 

the TEAD facility. This equipment includes monitors for major flue gas constituents ( 0 ,, CO,), as well as sensors for temperature and pressure. These devices 

are considered part of the TEAD facility for purposes of this test, and will be operated during this verification according to normal TEAD procedures. 

95 

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7.0 QUALITY ASSURANCE/QUALITY CONTROL 

7.1 Assessments and Audits 

7.1.1 Technical systems audits 

Battelle's Quality Manager, will perform a technical systems audit (TSA) once 

during the performance of this verification test. The purpose of the TSA is to ensure that the verification test is being performed in accordance with this test/QA 

plan, and that all QArQC procedures are being implemented. In this audit, t.he 

reference sampling and analysis methods used may be reviewed; the actual test 

procedures compared to those specified in this plan; and data acquisition and 

handling procedures reviewed. The Quality Manager will also prepare a TSA 

report, the findings of which must be addressed either by modifications of test 

procedures or by documentation in the test records and report. 

At EPXs discretion, EPA QA staff may also conduct an independent on-site TSA 

duting the verification test. The TSA findings will be communicated to t.esting 

staff at the time of the audit, and documented in a TSA report. 

7.1.2 Data quality audit 

Battelle's Quality Manager will audit at least 10 percent of the verification data 

acquired in the verification test. The Quality Manager will trace the data from 

initial acquisition, through reduction and statistical comparisons, and to final 

reporting. All calculations performed on the data undergoing audit will be 

checked. 

7.1.3 Assessment reports 

Each assessment and audit will be documented in accordance with section 2.9.7 

of the QMP for the AMS pilot. Assessment reports will include the following: 

• Identification of any adverse findings or potential problems 

• Spac.e for response to ad,•erse findings or potential problems 

• Possible recommendations for resolving problems 

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

• Confirmation that solutions have been implemented and are effective. 

7.1.4 CorrectlveAetion 

The Battelle Quality Manager, during the course of any assessment or audit, will 

notify the technical staff perfonning experimental activities of any immediate 

VES011395 
ERDCICERL TR-()5-9 

corrective action that should be taken. Once the assessment report has been 

prepared, the Verification Testing Leader will ensure that a response is provided 

for each adverse finding or potential problem, and will implement any necessary 

follow-up corrective action. The Quality Manager will ensure that follow-up cor· 

rective action has been taken. 

8.0 DATA ANALYSIS AND REPORTING 

8.1 Data Acquisition 

Data acquisition in this verification test includes recording of the response data 

from the XCEM, documentation of sampling conditions and analytical results 

from the reference method, and recording of operational data such as combustion 

souroe conditions, test temperatures, the times oftest activities, etc. 

Cooper Environmental Services will perform data acquisition for the XCEM during the test. For all tests, CES will be responsible for reporting the response of 

the XCEM to the sample provided. The XCEM data must include the results of 

all tests conducted each test day and are to be provided to the test manager at 

the end of each day. The XCEM data must include all individual readings of the 

XCEM (i.e . , temperature, pressure, metal concentrations, QA data, etc.) listed by 

time of day. Averaged results over the period of an M29 sampling run will be determined following the test and provided to the test managet· prior to release of 

M.29data. 

Other data will be recorded in laboratory record books maintained by TEAD, 

CHPPM, Battelle, MSE-TA. and CES staff involved in the testing. These records 

will be reviewed to identify and resolve any inconsistencies. All written records 

must be in ink. Any corrections to notebook entries, or changes in recorded data, 

must be made with a single line through the original entry. The correction is 

then to be entered, initialed, and dated by the person making the correction. 

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

Table 8-1 summarizes the types of data to be recorded; how, how often, and by 

whom the recording is made; and the disposition or subsequent processing of the 

data. The general approach is to record all test information immediately and in 

a consistent format throughout all tests. Data recorded by CES is to be turned 

over to the CERL designated test manager immediately upon completion of each 

t.est day. 

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Table 8-1. Summary of data recording process for the verification test. 

Data To Be Responsible Wher e How Often Disposition of 

Recorded P arty Recorded Recorded Data 

Used to organ· 

Start/end of test, izelcheck test 

Oates, times oftest Laboratory and at each results; manually 

events CERL reoord books change of a test incorporated in 

data spread- parameter. shootsasn~ 

sary. 

Test parameters Used too~n

When set or izo/eheck test (temperature, ana- TEAD,CERL, Laboratory changed, or as results; incorpo- lyte identitie:; and CHPPM record books needed to docu· rated in data concentrations, flows, ment stability. spreadsheets as etc.) necessary. 

XCEM data will 

Laboratory be recorded conXCEM reading>; in- record books, tinuously Electronically eluding digital dis· CES dat..<t shee ~ or t hroughout test. tr.ansfarred to playa, priotout<J. and data acquisi· Oota sheets "ill spreadsheets. electronic output. tion system, as _ be completed as 

appropriate. required for each 

test. 

At least at 

Used to organ· 

stnrtlend ofref. ize/chec;k teot 

Reference method CHPPM Laboratory test, and at results; incorposampling dota. record books rated in data change of. rest 

spreadsheets as 

parameter. 

necessary. 

Laboratory 

Reference method re<ord books. Throughout som· sample. analysis, CHPP:M data sheets, or pie handling and Transferred to 

chain of enstody1 and data aequisi- analysis period. opreadsheel$. 

results. tion .sy~m. as 

appropriate. 

8.2 Data Review 

Records generated in the verification test will receive a one-<>ver-<>ne review 

within 2 weeks after generation. These reviews are to be performed within the 

organization generating the data. These t·ecords \\111 then be used to calculate, 

evaluate, and report verification results. These records may include laboratory 

record books; operating data fi·om the combustion source; XCEM data; or reference method analytical results. The review will be documented by the person 

performing the review by adding his/bet· initials and date to a bard copy of the 

record being reviewed. This hard copy will then be returned to the staff who 

VES011397 
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generated or who will be storing the record. Battelle will receive a copy of all 

written and recorded data in the project record books and a copy of the XCEM 

data. 

8.3 Reporting 

Cooper Environmental Services will prepare a summary test report for CERL 

documenting the testing results. The summary report will include a discussion 

of the XCEM performance, testing processes, and a comparison with M29 results. CES will provide Battelle with this summary test report and copies of all 

original raw field and laboratory data. 

Battelle 'vill prepare an ETV verification report and statement for the testing 

that includes the test data and a statistical evaluation of the data as described in 

sections 4 and 5. The verification report will briefly describe the ETV program 

and the AMS Center, and will describe the procedures used in verification testing. The results of the verification test will be stated quantitatively, u~thout 

comment on the acceptability of the XCEM's performance. The summary test 

report prepared by CES will serve as the basis for the draft ETV verification report. The ETV verification report and statement will undergo a technical peer 

review. Final approval and distribution of the ETV verification report and 

statement will be conducted as stated in the Generic Verification Protocol for the 

Advanced Monitoring Systems Pilot. 

9.0 HEALTH AND SAFETY 

The verification test described in this testJQA plan will be performed at the 

TEAD facility in Thoele, Utah. All participants in this verification test will adhere to the health and safety requirements of the facility. Vendor staff will be 

operating their equipment only during the verification test. They are not responsible for, nor permitted to, operate the combustion source or perform any 

other verification activities identified in this test/QA plan. Operation of the 

XCEM does not pose any known chemical, fire, mechanical, electrical, noise, or 

other potential hazard. 

All visiting staff at the TEAD will be given a site-specific safety briefing prior to 

the installation and operation of the XCEM. This briefmg 'vill include a description of emergency operating procedures (i.e., in case of fire, tornado, laboratory 

accident) and identification and location and operation of safety equipment (e.g. 

fire alarms, fire extinguishers, eye washes, exits. Test participants are required 

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

10.0 REFERENCES 

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

Bryson, S., C. Whitworth, and S. Kujawa (2000). Final Report - Test and 

Evaluation of an X-Ray Fluorescence Based Multi-Element Metals Continuous 

Emission Monitor. Prepared for U.S. Army Corp of Engineers by MSE-TA, Butte, 

MT. 

Environmental Protection Agency (EPA). (2000). Quality Management Plan 

(QMP) for the ETV Advanced Monitoring Systems Pilot, U.S. EPA Env:h·onmental Technology Verification Program, prepared by Battelle, Columbus, Ohio. 

EPA (1998). EPA Environmental Technology Verification Program Quality and 

Management Plan for the Pilot Period (1995-2000), EPA-600/R-98/064, U.S. En· 

vironmental Protection Agency, Cincinnati, OH, May 1998. 

EPA. (1996). Proposed Performance Specification 10 for Multi-Metal Continuous 

Emission Monitors, U.S. Environmental Protection Agency, Washington, DC. 

EPA (1991). U.S. EPA Method 301 Field Validation of Emission Concentrations 

from Stationary Sources. Federal Register VoL 56, No. 114. June 13, 1991. 

EPA (1990). U.S. EPA Method 29 Determination of Metal Emissions from Stationary Sources. From EPA's technology transfer website www.epa.gov/ttn. 

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