ERDCI CERL T R.05 · 9

Ta ble16. M2 9 eon ce n tra llon s (•glds cm ). RU N P b C d Cr As H Sb A B AVG A B 

### . .we A 8 AVG A B AVG A ll AVG A 8 AVC I 74 7 1 73 31 28 29 3 .5 3.6 3. 6 8 . 1 7.4 7.8 344 320 332 15 4 1 4 8 1 5 1 2 7 5 7 8 77 32 3 2 32 4 .0 4.1 4.0 8.4 8 .0 8 . 2 337 33 1 334 188 1 76 1 82 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 3 7 39 38 3 1 31 3 1 4 .8 5 . 2 5.0 11 . 5 12 .1 1 1. 8 347 301 327 168 1 6 4 166 5 29 26 2 8 32 30 3 1 5.3 5 . 2 52 12 . 3 1 1.1 1 1.7 3 19 3 1 7 3 18 172 1 6 3 168 6 1 48 146 147 32 3 1 3 1 5.0 4 . 7 4.8 11. 6 10 .9 1 1.2 29 1 269 280 160 1 63 1 62 7 1 3 8 132 13 5 32 31 32 5.0 4 .8 4.9 11 .8 11.4 1 1. 6 279 29 1 2 8 5 169 1 59 164 8 131 126 128 33 32 3 2 5. 2 4 .9 5.1 12 .6 11.8 12.2 309 303 306 165 1 58 162 9 

## m 122 122 32 3 2 32 4 .9 5 .4 5 2 12 .0 12.2 12.1 3 12 305 309 1 53 1 6 1 15 7 1 0**~** 129 135 3 1 29 30 5.0 4 .8 4.9 11. 3 1 0 .8 11.0 294 289 292 1 6 4 I l l 15 7 II 119 11 8 1 1 9 32 31 3 1 4 .9 4 .7 4.8 11. 7 l l.S 1 1.6 29 7 293 295 1 62 164 163 12 114 Il l 113 3 1 31 3 1 4 .8 4.8 4.8 11 .9 1 1.7 11 . 8 30 8 278 2 93 1 54 154 154 R

UN Nl Bo Zll So A B AVG A B AVG A B .AVG A B AVG I 209 19 1 200 222 206 214 203 186 195 13 2 144 138 2 235 23l 235 249 24$ 248 216 208 2 1 2 13 1 168 1 49 3 240 22R 234 2 52 243 247 222 208 2 1 l 207 1 99 203 4 207 220 2 13 1 95 211 203 192 20 1 1 96 66 90 78 5 227 235 231 2 1 S 198 207 2 02 1 9 1 196 51 69 63 6 236 2 1 4 225 2 1 7 215 216 218 200 209 13 1 1 08 120 1 230 205 2 1 8 220 204 2 1 2 206 198 202 60 1 4 6 7 8 224 2 13 219 2 1 4 206 210 211 196 204 4 7 4$ 47 9 222 221 221 204 209 206 204 200 202 4 1 )5 38 1 0 2 1 9 192 205 2 18 199 20S 205 1 92 199 88 64 76 II 2 18 2 14 2 16 2 10 210 210 205 20 1 203 44 36 4 0 12 202 1 9 5 1 99 20& 20 1 204 199 1 92 196 31 2 5 2 8 Predicted Stack G as Concentrations 

### Predicted stack gas concentrations were detennined by adding the MSE-TA calculated spik e d concentrations with background concentrations based on XCEM measurements when munit i ons 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 Z n , 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 Inj ect i on 

### D uring !1129 testing , MSE-T A spiked known masses ofPb, Cd, Cr, As, 

### Hg , Sb , N i , B a , and Zn into 

### the stack <Bryson 2002) . These s piked masses were divided by the stack flow to 

### obtain concentrations in jlg/dscm. MSE-TA mass concentration s in solution were cross-checked by submitting aliquots from M29 runs 5 and 6 to 

### an independent laborat ory for analysis (HKM Labs , Butte , MT ) . H KM's re sults were within 7 percent of MSE-TA's estima tes for all elements except As, 43



### VES01134244 ERDC/CERL TR-05-9 

### which was 23 percent lowe r according to HKM than reported by MSE-TA. No adjustments were made to 

### MSE -T A reported data. The potential impact of t he A s difference is discussed in a report by Cooper et aL ( 2002). Mea surements of stack flow by CHPPM were cross-checked v.-ith the stack contin uous v elocity monit or for accurac y and were f ound to be within 6 

### percent of each ot her (Table 17). 

### The CHPPM flows were determined using 

### a v elocity tra v erse at t he same stack height 

### as the XCEM probe and 

### are believed to 

### be more representati v e of true flows than the continuous v eloci ty 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/ 

### Ru n monitor M29A M298 M29 Avg . M29 (dscmlh rl (dscmlhrl (dscmlhrl (dscmlhrl W•l 1 5, 1 73 4. 7 18 4 . 659 4 .689 1 1 0 2 5.037 4 .638 4 . 652 4 . 645 108 3 4 ,998 4 .527 4,532 4 , 530 1 1 0 4 4 ,889 4 ,680 4, 688 4 ,684 104 5 4838 4 ,672 4,6 88 4 ,680 103 6 4970 4 ,578 4,5 80 457 9 109 7 4 , 826 4 607 4,6 1 3 4 6 1 0 105 8 4 785 4 64 1 4 647 4 644 1 03 9 4 , 67 6 4 , 662 4,672 4 , 667 1 00 10 4 , 060 4 ,589 4 ,600 4 , 5 94 11 0 1 1 4,960 4 , 593 4 ,662 4 , 628 1 07 1 2 4 ,879 4 , 6 60 4,67 0 4 , 665 1 05 AVG 4 ,92 4 4 , 6 30 4 , 63 9 4 , 6 35 1 06 Backgro un d me1a l concentrat i o n 

### TEAD incinerated 20 mm TPM55A2 bullets during all 1 2 M29 r u ns . This am munition, which is used for target training , does not contain significant qua ntit ies 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. Ta ble 18 shows XCEM results for elements me a sured on 13 and 15 May while the 20 mm bullets were being burned and MSE

- TA was not spiking into the stack . The 1 3 May metal concentrations were significantly higher than

Persona l c om m u n

ication: M1k e Pattison, U .S. Ar m

y CH PPM. Wl lh Bruce Johno:...eo, CES, J ooe 2002.



## VE S0 113 4 3ERDCICERL 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 , N i , and Sb were below XCEM detection limit s (1 

### Jlg/dscm) and were reported as 0 

### pg/dscm. Table 18. AP E-1236 slack concentrations**(~gld scm)**  with munitions Incineration but no spi k ing . 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 9 08 44 . 5 5.7 49.3 22.6 259 63 . 8 8 . 4 41.3 3 1 . 7 33 1 990 1 5/02 1 5/02 • .€ 1 5/02 3;8 1 9 . 4 1 . 7 1 9.3 6.7 102 Use of Sn as a surro gate for backgro u nd 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 con centrations stem fro m the same source . Since Sn was not spiked by MSE

- TA, its concentration was u s ed a s an indicator ofthe background during spiking periods. The background cont ribution of the other e l ement s was estimated by their relationship to 

### Su according to the equations in Figure 13. Figure 14 shows the XCEM measurements of Sn during M29 te s ting. A s urge 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 t o certify its relatiouship with Sn, it was assunted to behav e in the same manner as the other met als. Combining the 1\ofSE

- TA spik e injection estimates with t he estimated backgl'Ound concentra tions resulted in 

### predicted concent.rations as shown . in Table 19. 45



### VES011344ERDCICERL TR·05-9

XC£M Wd '4. XCEM T O. During**No a~**  XCEM Zinc ,. $. XCE.M T'io D•rlog Non·**SpWa~** Ptriocb: Spiklllf: Ptriods 120 60**00** 

## ........ i 50 

# -**~:** ::;: 40 . 

## • .......**0** 

# -**~** 40**(l SOh**  I I U S!!**~** 20 'i 1)'" .. 0. 0 1•?• .- 4.1411 .:s 2<)**tt: :q~** **llfl l(,** **~JO** 

# -**tl•t>.? ~~**  0 

## • 0 • r

0 200 400 600 800 0 200 400 600 8!>0 'fl a (llefDSCM) r .. tpafDSCMl XCEM Bui'um ' ' "· XCEMTin Ourf•;, N oll Spi king renoch

" 80 

## •**~** 

## • 

# ..... 

# t60 • ..........-: 34<) ; ? O 

# .**~** b· -0.097i .\**+-~ (l$92** **~** 

# i

- : 

# . I k ? .. OA6n: 0 0 200 400 600 800 nn (pJI'()S C.M) Figure 13. Correlation betwee n Sn a nd other APE- 1 236 metals wfth munitions burning and no opiking .

Tin During M29 T esting

700. 0 600.0**~y 3**  May 1 4 May IS M a y 16 

# • 500.0 

# • 4

00.0 

# '**~ ~**  

# . 300.0 

# .\•\**~** 200 . 0 

# f\'1 •• , .. 1 00. 0

0 . 0 

# • 890 930 970 1010 Figure 14. X C EM tin measurements during M 29 test ing .



### VES011345ERDC/CERL T R-05·9 XCEM Co ncent ra t i o ns 

### 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 dur ing M29 testing , the XCEM successfully canied out 120 runs with only 2 runs falling outside of the Pd QA 

### criter ion due to 

### air-conditioning proble ms . This r e p re sents an uptim e of 9 8 percent. T

a bl e 19. Pr e d ict ed stack c on c en tration s**(~ ds** **cm)** based o n MSE ·T A spi ldng an d backgro und e s tim ate s .**HllO~UU M**  CADMIUM LEAD ARSENIC NICKEL

R UN M SE BKG P RD MSE BKG PRD M SE BK C P RD MSI: BK C PR . D MSE B KC . I'

RD I 2 .9 0.0 2.9 32.0 9. 4 4 1. 5 0.0 6 7 6 7 1 0 .6 0 . 0 10.6 267 0 .0 267 2 2 .9 0.0 2.9 3 1. 5 8.4 39.8 0.0 6 1 61 10. 7 0.0 1 0 . 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 1 6 . 7 275 0 .0 275 4 5.0 0 .0 5.0 36.5 5. 0 4 1.6 0 .0 41 4 1 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 6 1 1 67 16.0 0.0 16.0 27 1 0. 0 27 1 7 5. 1 0.0 5 . 1 ')7 . 7 6.0 43 . 7 104 46 ISO 16.4 

### o . o 1 6 .4 269 0 . 0 269 3 5. 1 0 .0 5.1 3 7. 1 4 .4 4 1.5 103 3 7 1 40 16 . 2 0.0 1 6.2 267 0.0 267 9 5 .1 0 .0 5. 1 37 . 1 3 .4 40 .5 1 03 3 1 134 16.2 0.0 1 6..2 266 0.0 266 tO 4 .8 0 .0 4 . 8 35 . 3 5. 9 4 1.1 105 46 1 5 1 1 5.2 0.0 1 5.2 27 0 0.0 27 0 II 5.0 0 .0 5 . 0 36.5 3 . 5 39 .9 1 04 32 136 16.0 0.0 16.0 268 0.0 26 8 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 6 1 4 7 10 7 15.2 0 .0 15. 2 26 8 

### o .o 268 S D 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 4 1.2 238 1 96 0.0 1 96 268 29.3 297 3 333 0.0 333 20 1 Sl.6 253 20 1 0.0 20 1 27 5 37.3 312 4 322 

### o . o 322 1 9 4 28.3 223 194 

### o . o 1 94 265 1 9.5 285 5 323 

### o . o 323 1 93 25.0 2 1 8 193 

### o . o 1 93 266 16 .9 283 6 329 0.0 329 1 99 41.6 24 0 199 0 .0 199 27 1 29.6 301 7 327 0 . 0 327 1 97 3 1.9 229 197 0 . 0 197 269 22 .2 291 8 325 0.0 325 1 92 25.9 2 18 192 0 . 0 19'2 267 1 7 .6 285 9 324 

### o.o 324 1 89 22. 1 2 12 1 89 

### o . o 189 266 1 4 . 7 280 10 328 

## o.o 328 1 94 31.6 226 1 94 0. 0 194 270 2 2. 0 292 II 326 0.0 326 1 93 22.5 2 1 5 193 0.0 1 93 268 1 5.0 2 8 3



### VE SO!l346**~** Table 20 . X CEM 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 ). XCE M concenvatlona. 1!1

m 

# ..**~** 

# .. r

# ~

# < rTl (/) 0**~ ~**  w u. 0**Tab~** 20 (Cont' d ) . XC · EM concentrat i on& .

UNWF. IGIITI ;:D A VI! R AG£ m ;a 0

### ~ m ;a 

### ,... 

# ... ;a b 

# t**~**52 ERDC/CERL TR-05- 9

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

# cI [Eq 7] where: C, = XCEM time

- weighted concen tration for element 

### i during M29 

### test run C

ij 

## = 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 per iod. 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 f acto rs w ere too high relative to the calibration standards by 15, 15 , and 7 percent, respectively. The calibration fac

tors 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 discuss i on 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 ofthe stack gas. For this reason, run 961 for Cr was not used dur

ing 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 , X CEM concentrations for run 12 were based on a time-weighted average ofthe 97 min utes that the XCEM produced validated data. The modified XCEM d ata were submitted before receiving the M29 results . No modification to the XC EM data was made after receiving M29 results .



### VES011351ERDC/CERL TR.OS.9 

### XCEM Calibrat i on Evaluation Using A QuanX- XRF and ICPIMS Since XRF analysis is nondestructive, the concenn·ated particul ate 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 h as been approved for measuring PM ,. metals concentrations for EPA's specia tion 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 wee ks after M29 te s ting . With the exception of Hg, which appeared to be 

### lost from the X CEM filter, t he material collected on the filter s e emed to be int act and representative of the sample collected at TEAD . The 

### QuanX calibration evaluation data are shown in Ta b le 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 analysi s. T able 21. Analysis o f XCEM fi« o r lapo by Columbia Analytical (11g/<lsem)

Ru n As Cd C r Ba Hg N i Pb Sb Sn Zn

5 14 .0 36 .4 5 . 0 176 2 74 226 22 174 74 252 6 13 . 3 34 .2 4. 7 159 2 54 220 1 29 152 1 27 245 

### Precision Five elements were spiked by MSE ·TA at a constant rate throughout the t esting: B a , Hg, Ni, Sb , and Zn. Al t hough 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 t hese elements with the XCEM precision about 30 percent lower than M29 ( Table 22). Table 22. Predicted (spiked), XCEM, and M29 prec is ion (%)during validaUon testing . ' Approach Ha S b 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 ' Determ ined by**perc«~ l**  RSO or t 2 concentratiOns repOr'ted Sot' M29 runs. 53



### VESOll35254 EROC/<;1;RL TR-05-9 D isc u ssio n 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 incinera t ion fe e d rates (Table 23; Be is not listed in this table because it cannot be measured by the XCEM). The X CEM succes sfully 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 Elo m en t State Limi t**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 1 0 97 84 Yes As 0 . 11 24 No H

Q 14 3 .036 1 30 130 No Sb 14 3. 036 NR NR No Nl 930 201,740 NR NR N o Sa 2,400 521 , 2 43 NR NR N o 1 Ass001es 4 , 635 dsc:trv'h r based on average rate from T able 1 6. NR : Not**egu ate** **~** MACT : Maximum achievab le contro l tech n o logy (rule) Lead Lead is the element that most often limits incineration rates at APE-1236. The TEAD incinerator has a**~-tate mandated**  P b 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 t o 240 )lg/dscm. The final MACT rnle , which was published 20 April 2004 (FR21210) and will be in effect 3 years after i t promulgates, will further limit the com bined P b and Cd emission rate 

### to 59 )lg ldscm . Currently, Pb concentrations within the munitions are determined for e ach type of ordnance before incineration . Munit ion feed rates into the inciner ator are re stricted using a model that assumes that a fraction of the Pb in the munitions will be transported through the air pollution control device s and emitted from the stack. The effectiveness of t he model depends upon several assumptions in · eluding transport under various meteorological regimes , incinera t or temperature effects, and chemical in ter ac

tions. Dir ect measurement of Pb concentrat ions in 

## VES011353ERDC/C£RL TR-05-9



### t he 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 u sing 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 (Figur e 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. Du ring testing, both M29 and the XCEM reported concentrations ranging from 25 to 150 pg!dscm . The RA for the X CEM 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 co nce ntration**(~g/dsc )**  data and raUos durin g M29 t&sting.

RUN PRD Jlll9 XC Q N CA XC/QN XC/PRD Ml9/PRD XC/Ml9 QN / Ml9 I 67 72 67**~** 0.99 1.0 1**1. 0~**  0.93 0 .94 

### z 61 77 6 7 64 1.04 1.1 1 1. 2 7 0.87 0.84 3 77 9R R l R 4 0.97 1.06 t. Z1 O . R3 U6 4 41 38 36 39 0.93 0.88 0.93 0.95 1.0 3 5 3 6 27 26 26 22 0 . 99 0.73 0 .7 7 0.94 0 .95 6 167 14 7 154 141 1 29 1. 09 0.92 0.8 8 I. O

S 0.96 7 I SO 1 3S 13 7 141 0.97 0.91 0 .90 1.0 1 1.05 8 14 0 1 28 132 1 32 1. 00 0.94 0.92 1.03 1.03 9 134 1 22 128 125 1. 02 0 . 95 0.9 1 1.05 1.03 1 0 l SI 13 S 140 140 1.00 0.9 3 0.89 1.04 1.04 11 1 36 118 12 1 U 9 0.94 0 . 89 0 . 87 1. 02 1.09 

### n 1 28 113 117 126 0 . 93 0.91 0.88 1.04 1. 1 2 AVG. 107 101 101 101 75 0.99 0.94 0.96 0.98 0.99



### s o 47 39 43 43 76 

### o .os 0.09 0. 1 6 0.07 0.09 55



### VESOll35456 ERDC/CERL TR-0 5-9



### 200

### r;:======**----,** 150 

## iy = 

### 1 .09x- 9.601-

-- ='- ------l 

# i R 2 

### =0.98 100 

## -j-J '----_j7£:... ------l 50 -········**+---~----------~** 

### 0 

### 50 

### 100 150 

### 200 1\129 Lead (pgldscm) Figure 1 5. 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 resul t s suggests that an XCEM calibration error may have been responsible for the difference between 1\129 and the XCEM.



### VES011355ERDC/CERL TR-115-9

Table 25 . Summary of Cd concentration**(~g/dscm)** data and raUos during M 29 tesUng.

RU N 

### PRD**~U9** X C Q N CA X C/QN XC /P RD M29 / P

RD XC/M29 IQN / M29 I 41.5 29.4 35.2 29.3 1.20 0 . 85 0.7 1 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. 1 8 0. 71 0.7 1 1.08 0 .91 4 41.6 31.0 37.7 32.6 1.16 0.9 1 0.74 1.22 1.05 5 41.4 30.8 36.4 30.0 36.4 1. 22 0.88 0.74 1. 1 8 0.97 6 45.4 31.2 37 .2 28. 6 34.2 1.30 0. 82 0.69 1. 1 9 0.92 7 4 3 .7 3 1. 8 36 . 6 30. 9 1.19 0 .84 0.73 1.1 5 0.97 8 41.5 3 2.4 37.7 31.1 1.2 1 0. 9 1 0. 78 1.1 6 0.96 9 40 . 5 32. 0 37.4 31.5 1. 19 0.92 0.79 1.1 7 0.98 10 4 1.1 29. 8 34.6 27.9 1.24 0.84 0.73 1.16 0 . 94 11 39 . 9 3 1.3 34.9 30.9 1.13 0.87 0.78 1.1 2 0.99 12 39.0 31.2 35.5 31.6 1.12 0.9 1 0.80 1.14 1.01 AVG . 42.0 3 1 . 5 36.4 30.4 35.3 1.20 0. 87 0.75 1. 16 0 .9 7

SD 2.7 1 .3 1 . 1 1 .4 1 .5 0.05 

## o.os 0 . 04 0.04 0 .04 C h r o mi u m 

### The APE-1236 has an effective Cr emission limit of les s than 10 pgldscm unde r typical stack operating conditions. Since the background Cr concentra t ions were uncertain at the start o f the validation test, MSE -T A spiked a nomina l 8 pgldsc m during M 29 runs 1 and 2 . Following these runs, it was determined that t he background Cr concentrations were insignificant and MSE- TA rai sed their spiking rate to 5 pgidscm for the remainder of the tests. Overall , the XCEM w as consistently 10 percent hi gh er than M29 at both concentration levels (Table 2 6 ) . This r e presen ts a difference of abou t 0.5 pg/ ds cm. The agreement between the XCEM an d Ivf29 at both the 3 and 5 )lg/dscm levels v alidates the ability of the X

C

EM 

### to accurate ly measure 

### C.· at v ery low concen trations. The Cr RA was 15 percent, meeting the PS-10 criterion. Sub s equent measuremen t s of the XCEM filter tape by the CES-QuanX and ICP were 

### wit.hin 3 percent of the M2 9 concentrations . The consistency of M29 with the predicted values and subsequ ent measurements of the XCEM filter tape suggests that the difference bet ween the two methods is 

### due 

### to XCEM error. 57



## VES 0 113 5658 E.RDC/CERL TR ·OS. 9

Tab le 26 . Su mma ry of Cr concentration {J.tWdscm) data an d ratios d u r i ng M29 testing .

RU N 

### PRD 1\'129 XC QN CA X CI Q N XC I PRD M29 fPRD X CIM29 QNIM29 1 2.9 3 . 6 3.7 32 1. 1 6 1. 28 1.24 1.03 0.89 2 2.9 4.0 4. 0 3.2 1.27 1.39 1.38 1.0 1 0.79 3 5.2 6.4 5 .8 4.8 1.20 1.11 1.24 0 . 90 0. 7 5 4 5.0 5.0 5. 8 5. 1 1.14 1. 15 0.99 1. 1 6 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 1.0 1 1.1 4 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. 1 0 1.44 A V G. 4.7 4.9 5 .4 

### s . o 4.8 1.1 0 1.1 6 1. 07 t.I O 1 .02 

### S D O.B 0.7 0 . 8 1 .0 0 .2 0 .14 0. 09 0 . 14 0.08 0. 1 8 Reg ula t ed E lements Not Ty pically Found In TEAD Em issi ons 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 criter i a for Sb (20 percent) and Ba (4 percent), but was hi gh er than M29 for 

### As , Hg , and 

### Ni with rel ative accuracies of 27, 

### 33, and 33 percent, respectively. A

noenlc Arsenic results are shown in T able 27. The XCEM

- reported concentra tion was in good agreement with the post-test analysis of the filte r tape by both QuanX and Columbia Analytical. Their agreemen t indicates that the XCEM calibration was correct 

### to within a few percent . The XCEM con centration is also in good agreement with t he predicted concentration. Although, as discussed ea rlier, the HKM analysis showed a 23 percent lower value fo r the calibration. The XCEM's RA of 27 percent did not meet PS-10 criterion. Overall , the XCEM concentrations were 25 percen t higher than M29 concentrations for A!3. Other potential sou rces errors for the XCEM besides calibration s uch as loss during transport, low filter trapping efficiency , and deposit positioning errors can be ruled out bec a use they would re s ult in XCEM concentrat ions lower than M29 . I t is highly possible t hat the differences in concent ration are due to M29 errors. The XC EM was also highly correlated wit h M29 A!3 (r2:0.85) showing good responsiveness 

### to changes in A!3 concentration.



## VES011357EROCICERL TR.05·9

Table 27 . Summary ofAs conC<>ntratlon (l&gl dscm) data and r aUos durin g M29 test ing. R

UN PIID M29 XC QN CA XC/QN XC/PRO M 29/ PRD XCIM29 Q NIM29 I 10.6 7.8 1 0 .1 9.4 1.07 0.95 0.74 1. 29 1. 20 2 1 0 . 7 8.3 9.3 1 0.2 0 . 9 1 0.88 0 . 17 1. 13 1.2 4 3 16.7 II . S 1 3 .7 1 3 .4 1.02 0.82 0.69 1. 19 1.1 7 4 16. 1 1 1. 9 1 4 .3 1 4.5 0 . 98 0.89 0 . 74 1. 20 1. 22 5 16. 1 11 .8 15 .3 1 4.1 1 4.0 1.1)9 0.95 0.73 1. 30 1.20 6 16.0 11.3 1 3 . 9 13.8 13 .3 1.0 1 0.87 0 .7 1 1.23 1.22 7 16 .4 I I. 7 1 5 . 6 13.7 1.14 0.96 0 .7 1 1. 34 1.18 8 16 . 2 1 2. 3 1 4 .

4 13.8 1. 05 0.89 0 . 76 1. 18 1. 12 9 1 6. 2 12.2 13 .9 1 3. 7 1.02 0.86 0.75 1. 1 4 1. 12 10 15.2 II. I 14.3 13.3 1.07 0.94 0 .73 1. 28 1.20 11 1 6.0 1 1.7 15.5 1 4.7 1.05 0.97 0 .73 1.32 1.25 12 16. 2 1 1. 9 1 4 . 8 1 4 .3 1.03 0 . 9 1 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. 0 2 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 mul ti-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 Tabl e 28. The XCEM and )1;129 concentrations ha d acceptable agreement during runs 

### 1

- 5 with the XC EM 16 percent higher than M29. F ollowing run 5 , however , the XCEM was consistently 34 percent higher than M29. It is 

### believed that these differences are d u e to 

### vaporization of particulate Hg from the M29 filter. During run s 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 s ource of this decrease may be related to 

### the unusually high level of pa r ticulate phase Hg present during t his validat ion tes t. Particulate Hg is captured o n t he M29 quartz fiber filter and can be readily v olatilized 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 fil t er represents particulate phase Hg, which is typically only a couple of percent of the total Hg. 

### As such, M29 does not require 

## VES01135860 ERDC/CERL TR-05-9 refrigeration of the M29 fllter, so it was not cooled whil e being shippe d 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 re l ationship between the level of Hg on the M29 fil t er and the percent difference between M29 and the X CEM. The XC EM filter also showed a loss of about 30 percent of 

### its Hg 

### as demonstrated by an analysis of the spectra available during v alidation testing and a few weeks later when the tape was reanalyzed by the CES QuanX . Interestingly , the C ES tape had previously shown good r etention of vapor phase H g on ero:lier tests (Cooper et al. 2000; Chapter 3 ) so the Hg loss seems 

### to depend upon the quantity in the particulate pha se. See Appendix D for a more detailed discussiolL T

able 28 . Summary of Hg concent r ation (l<g/dscm) data and r atios during M29 te sti ng .

RUN 

### P RD M29 XC Q N' CA 1 XCIQN XC/PRD M29/PRD XC /M29 Q N/ M29 I 324 332 367 25 7 1.42 1. 1 3 1.02 1. 10 0.77 2 325 334 381 25 1 1. 52 1.1 7 1.03 1. 14 0.75 3 333 29 4 365 262 1.39 1.09 0.88 1. 24 0 . 89 4 322 327 368 30 1 1. 22 1.14 1.02 1. 1 3 0.92 5 323 3 1 8 379 308 274 1.23 1. 1 8 0 .99 1. 1 9 0.97 6 329 280 3 7 8 288 254 1.31 1.1 5 0 .8 5 1.35 1.03 7 3 27 285 392 302 1. 30 1 .20 0 .87 1. 37 1.06 8 32 5 306 4 06 294 138 1 .25 0.94 1.33 0.% 9 324 309 405 287 1. 41 1.2 5 0 .95 1.31 0.93 10 328 292 395 282 1 .40 1. 20 0.89 1.3 5 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 AV G. 32 6 3 05 385 282 264 1.37 1.18 0.94 1.17 0 . 93

S D 3.3 '19 1 4 : 19 1 3-8 0. 09 0 . 0 5 0. 06 0.1 0 0.09 I ) M e r c u ry lo st from lllter. 

# = 

# l**50 ~========** **~------------~ ~** **~** 40

_ y = 1. 25x- 4 .3 223 ...... .**~** .. 

### ., U R 2 a 

### 0.8055**~** + + • ;:; :><: 30 ....

# ~ ] 20

# +------**--.,...,., ~_/".** **::..._**__ • ___ .. _--_

# -~**i5~** 

# A d**~** 10 

## +----- - - =-- ----- ..-----**~** 

# .,**+-----~----~-----.-- --** **-~** !>.. 0 10 20 30 40 Perce n t of H g o n ii'U9 F il ter Figure 16. Percent difference between M29 an d the XCEM versus percent of H g on M29 filt e r.



### VES011359E RDC /CERL TR.0 5·9 Antimony 

### Antimony results are shown in 

### Tab l e 29. Overall, the XCEM was higher than M29 by about 18 percent, but met RA criteria w i th an RA of 19 . 9 percent. Sub · sequent analysis of the fil t er tape by the CES QuanX was in 

### better agreement with M29. For this reason, it is believed that t he XCEMJM29 differences were due t o XCEM calibration errors of about 15 percent. T

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

R UN PRD M2 9 XC Q N CA XCJQN XC/PRD M291PRD**XC/~U9 N~** **U9**

I 1 92 151 1 84 1 66 1.10 0.96 0.79 1. 2 1 1.10 2 196 1 82 200 177 1.12 1.02 0.93 1.10 0 .97 3 2 0 1 183 190 156 1.21 0.94 0.91 1.03 0 . 85 4 1 94 166 1 89 176 1.08 0.98 0.85 1.1 4 1.06 5 1 93 168 195 172 1 74 1. 1 4 1. 0 1 0 . 87 1.16 1.03 6 199 162 194 1 59 152 1. 22 0.98 0.81 1.20 0 .98 7 197 1 64 198 17 4 1.14 1.0 1 0.83 1.2 1 1.06 8 192 162 1 86 170 1. 09 0.97 0.84 1.15 1.05 9 189 157 195 1 71 1.14 1.03 0.83 1.25 1.09 10 194 157 193 1 62 1.19 0.99 0.81 1.23 1.03 I 1 193 1 63 193 1 80 1.0 7 1.00 0 . 84 1. 1 R 1.10 1 1 190 154 193 1 83 1. 05 1.01 0.81 125 1.19 AVG . 194 164 192 171 1 63 1.13 0.99 0.84 1.18 1.04



### S

D 3 10 5 8 15 0 . 06 0 . 03 0.04 0.06 0.08 N ick e l 

### Validation tes t results for Ni are reported in 

### Table 30. The XCEM w a s about 30 percent higher than M29 and bad a n 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 resul t s 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 analytic al problems . Nickel is not typically fo u nd in 

### TEAD stack emissions and the site 

### bas a 140,000 pg/d s cm stack emi s sion limit. As such, the conservative number s produced by the X CEM should serve to 

### adequately ensure that N i is below the emission limit. 61



## VES01136062 ERD C/C ERL TR -05·9

T

able 30. Summary o f N i conce n trati o n**(~g/dscm)** da ta and ratios d u ring M29 t esti ng.

RUN PRD M 29 X C Q N CA XC/Q N XCIP RD M 29/PRD XC/M2 9 Q N/M2 9 1 2 67 200 270 262 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 27 1 225 281 259 220 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 1 0 270 2 05 285 281 1.02 1.06 0.76 1. 39 1.37 11 268 2 16 288 292 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 . 26 8 2 1 8 28 1 2 77 223 1.02 1. 05 0. 81 1.3 0 1 .28

S D 2.8 12 10 1 2 4 .9 0.04 0. 04 0 .04 0 .09 0 . 11 Ba ri um Barium results for t h e validation tests are shown in Table 31 . F or Ba, tbe predicted co ncentrati ons , M29 results , XCEM results, and QuanX reanalysis 

### all agree to "itbin 10 percent with an XCEM RA of 4 percen t . 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 B a under realistic stack conditions . Ta b le 31 . Su m ma ry o f Ba concentration**(~gldscm)** data and ratios clwing M 29 1 esting. R

U

N P RD J\1 2 9 XC O N C A XC/O N XCIPRD M 29/P RD XC/lll2 9 ION /M 29 I 237 2 14 229 204 1.12 0.96 0.90 1.07 0.95 2 238 248 244 222 1. 1 0 1. 03 1.05 0.9R 0.89 3 253 247 22 8 195 1. 1 7 0.90 0 .98 0.92 0.79 4 223 203 210 201 1.04 0.94 0.9 1 1.03 0.99 5 218 207 230 1 94 176 1.18 1.05 0.95 1.11 0.9 4 6 240 216 222 1 86 159 l.J9 0. 92 0.90 1.03 0 .86 7 229 2 12 215 1 97 1.09 0 . 9 4 0.92 1.02 0.93 8 2 18 2 10 2 15 1 89 1.1 4 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 2 08 198 1 87 1.06 0.88 ().92 0.95 0.90 II 215 2 10 197 2 11 0 . 93 ().92 0.98 0 .94 1.00 12 209 204 20 3 206 0 . 98 0.97 ().98 0.99 I.() I AV G . 2 2 6 2 16 2 16 199 16 7 1. 09 0 . % 0 . 9 5 1. 00 0 .93 

### s o 13 1 6 15 11 13 0. 08 

## o .os 0 . 0 4 0.05 0.06



### V E S011361ERD C /C ERL TR-05 · 9 No n regulated Me tals 

### 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 w it

h X CEII I reported concentrations shown in Table 32. O verall, the XCEM Zn concentrations w er e consistently about 40 percent higher t han M29 . The XCEM Z n concentrations were in good agreement with both the CE S QuanX and Columbia Analytical tape evaluations , indicating that calibra · tion was not the primary source of this difference. It is believed that the differ

ence is primarily due 

### to .M29 errors . Table 32 . S umma ry o f Zn c on c entrati o n (pglcb cm ) data an d r atios d u rin g M291estin g



### R

UN P RD M 29 XC ON CA XC/ON XC/PRD M29/ PRD**XC~ 9**  IO N/l\1 29 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 0.7 1 1 .40 1.43 3 3 12 215 28 7 301 0.96 0.92 0.69 1.34 1.40 4 285 1 96 2 76 303 0.91 0.97 0.69 1.40 l.S4 5**2~3** 1 96 277 282 252 0. 9 8 0.98 0.69 1 .4 1 1.44 6 30 1 209 2 91 283 245 1.03 0.97 0.69 1.39 1.35 7 29 1 202 2 92 301 0.97 1.00 0.69 1.45 1.49 8 285 2 04 293 294 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 1 0 292 1 99 293 298 0.98 1.00 0.68 1.4 7 1.50 11 283 203 286 303 0.94 1.0 1 0.72 1.41 1.49 12 278 1 96 2 79 302 0.92 1. 01 0.7 1 1 .43 1.54 AVG . 290 2 0 2 288 296 24 8 0. 97 0.99 0. 70 1 . 4 2 1 .47



## s o 1 0 7 7 7 5 0.03 0. 03 0. 02 0. 04 0.06 Su m m ary 

### The XCEM met the proposed PS-10 RA requirements for the three poten tial e mission-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 ot h er 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 , 

### H g, 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 X CEM was responsive 

### to c hanges in concentration and showed good correlation wi t h the reference method for elements that 

### were spiked at more titan one level. In addition, tlte XCEM successfully measured low metal concentrat ions as d emonstrated by the XCEM's tracking of M 29 Cr's low concentrations when ch anges of on ly 2 p.g/m·' occurred 63



### VES 0 1136264 ERDC/CERL TR-0 5-9 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 1 0 1 1 01 1 07 4 Yes C d 42 .0 3 1. 5 36.4 1 7 Yes Cr 4. 9 5 . 4 4 . 7 1 5 Yes As 11 . 1 13 . 8 15. .2 27 No Hg 305 385 326 33 No Sb 1 64 1 9 2 1 94 .20 Yes Nl 2 1 8 28 1 268 33 No Ba 2 1 6 2 1 6 226 4 Yes Zn 202 290 288 43 No



## V E S011363EROCICE R L TR-05- 9



# 5 XCEM Cost and Status Cost estimates for the Army 

### to purchase and operate a new X CEM are discussed in this chapter. The v alues are presented in $1,000 units 

### ($K) and were current in July 2004. Also 

### presented is a summary of the continued operation of the XCEM at TEAD and status ofthe technology. Co s t E s timates Capita l Costs 

### Capital costs include : 1. 

### XCE M : 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. 

### Pro be and Transport Lin e : Includes shrouded probe, corrosion resistant transport line , h eat tr a cing, and insul a tion ($ 1 0K ). 3. Shipping 

### and Installation: TypicaUy includes shipping of equipme nt, onsite inst allation, onsite instrument shak edown, a nd final onsite calib ration check. Site 

### will be responsible for lifting and connecting transport line ( $ 2 5 K) . 4. 

### Training: O nsite t raining 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.



## VES01136466 ERDC/CERL TR-05·9 Annual Costs Annual costs include: 1. Consumabl es: 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. Warrant y includes onsite assistance as needed ($25K). The total estimated annual costs are between $32 . 4K and $48.3K. Continued U se of the XCEM Following the conclusion of the M29 tests, the XCEM was used in a series of di

agnostic 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 o f Pb in the emis sions. The XCEM has also been used by the Ammunition Equipment Directorate (AED} on their test furnace at TEAD. The continued u se 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 t heir hazardous wasre incinerators. They have submitted an Alrernative Mo nitoring Plan (AMP) with the EPA with the intention of u sing the monitor for compliance purposes. The AMP should be finalized in the near 

## VES011365ERDC/C E RL 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 X CEM 

### was tested. In a new X CEM (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 physic al changes and to improve the ease of integration to e x ternal 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 t h e X CEM). 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



### VESOJJ36668 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 functio ned in a completely automated manner and automa tically recorded the test data. The objective of the test w a s to meet the requirements of the proposed P S

- 10 . The monitor met the PS-10 sampling and response time criterion by having an effective up-time of 10 0 percent and reporting time averaged concentrations e v ery 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 X CEM met the PS-10 RA cri

terion (less than or equal to 20 percent) for three of the nine metals tested: Cd , Cr, and Ni . The RA for P b was 22 percent. The results for Ba, Sb , Zn, and As 

### showed syste matic biases. It is 

### be lie ved 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 f or Ni , Sb, and 

### Zn. In March 2002, the XCEM was moved to a closer location, heat traced, insul ated, and equipped with a shrouded probe . T he 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 w as e valu

ated using a QSIS. T he resulting elemental concentrations were within their expected uncertainties for all elements except Cd and A g. In May 2002, a series of 1 2 comparison tests with E P A'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 w as better than M29. The XCEM also s ho w e d good correlation vvith Method 29 for elements that bad significant variability in 

### concentration during testing .



### VESOII367ERDC/CERL TR-05-9 APE-1236 emissions have the potential to approach s t ate-mandated emission limite for three elements: Pb, Cd, and Cr. The XCEM met the PS -1 0 20 percent RA criterion for all three of these elements. XCEM data w ere also compared to M29 data for five elements that are typically found in concentrations w ell below the site emission limite: As, Hg , Sb, N i , 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 Q uanX 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, e ven 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 t he 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 we re 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 accurac y 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 rule s seemed to change after the tests started. Because this monitor samples in a nondestructive manner, the results can be reanalyzed and vetified at a l ater date. It is these analyses that allow the determination of the sources of error , including calibration. This has clearly benefited t he development of the XCEM calibration procedures with each subsequent test. However, to ensure confidence in t he monitor's eventual use in the



## VES0 1136870 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 continu ed 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 estimate s for the Army to purchase and operate a new XCEM are between $243,000 and $253,000 in capital costs, and between $3 2,400 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 ens uring that the calibration has been entered correctly.



## VES011369EROC/CERL TR.Os-9



# References

Br

y'SOn. S . (200 1). Fina l Report

- Stack Spiking Report fo r a Mult i

-

Metal CEMS Testa t the Tooele Army Depot Deactivation Furnace. Pret "'.red for U. S . Army C'.orp• of Engine""' h y MSE

TA. lnc . 1 Butte, MT.

---,...,.--· (2002) . US Army Construction Engineering Reoearch Labor.tory (CEllL), Wasta Minimization and Pollut ion Prevention Program: Stack Spiking Repo1-t for a**Multi·M~tal C~IS**  Test at the Tooel e Army Depot Deactivation Furuace

- 2002 . Pr epared l or U.S. Army Corps o f Engjn..,rs by M SE-TA. Inc . ,**6u~,** MT . Br

y1;0n, S ., C. Whitwonb, an d S . Kuja,va. (2000). Final Report

- Test and E val uation ofan X

- Ray Fluo.....,..MO Bas<ld Multi

- Eiemont Motals Continuous Emission Monit01 ·. Prepared f or U.S. Army Corp o f Engineers by MSE-TA. Inc ., Butte, MT . Center fo r Health Promotion and Preventive Medicme (CHPPM). ( 2001) . Air Po lbt tion Management Study No. 43 · EL ·649g.()1 Verification o f Multi

- Metals Contin uous Emiss ion Monitor at 1' ooele Army Depot. Tooele, Utah , May 14-1 7 , 200 1.

- - --- · (2002). All· Pollu tion Management Study No. 43 -EL-<!7 55-02 Ve rificat ion of Mu l ti

Mt!ta] s Continuous Emission Monitor at'fooe)eA.l·my De pot . Tooo la, U tah, ' M

ay 13-16, 2002 . Cooper Em ·i ronm enta.l Servie es (CES). (200la) . "XCEM User's Guide.,''**B~averton,** OR.

----- · (2001b). ''XCEM R osou rco Manu**a~**• Beavert on , OR. Cooper, J. , B. E . Johnsen, K.J . Hay, and W . Wals<ln (2000). Conti nu ous Hazardous E lement Anal ysis**Syst~m** for**Aill bi~nt**  and Emiss ions Monit.o ring. Pt<. "S4ilnted at regional AWMA Cc

m

fe ren ce : 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). "L i mitations in t he Use of EPA Reference l\lethod 29 f or Evaluating the Relative Accw·acy o f Candidate Mul ti- M e t al Cont inuous Emission Monitors ." CES Report. September 2002. Envb ·onmema l Protection Agency (EPA) . (1 992) .**Metbod~0** Fiel d Validati on of PoU ut.

, nt Measurement Methods from Various Waste Med ia. Found on the EPA website at: http:/lwww.epa.gov/ttnlemclpromgote/m-301 . pdf.

----· (1996). PS

- 10, Proposed Performance Spec ifi

cation 10 f or Metal CEMS (Proposed 04/ 19 196) Found on the E PA weba ite at: hti J \ '

/lwww . fnr. . gov/ ttn/ f'm d nromw d .h tm l.

----- · (1 999}. Final Standards tOr Hazardous Air Pollutants f Ot H azardous Waste Combuotor s ; Final Rule . FR52$ 27

-FR53077, Vol64. No . 189. 71



## VES01137072 ERDCICERL TR-05-9

----- · (2004). National Emission Standards for Hazardous Air Pollutants for Hazardous Waste Combuswrs (Phase I final Replacement S tandords and Phase U): Proposed Rul e. FR21197 · 2 1 385, Vol69, No. 76. French. N. (1998). 1997 Pe.rformanc 0 Testing o-fMulti·Metal Continuous Em issio ns 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 Fluoresc ence-Based Multi-Metal Continuous Emi ssion ' Monitor: Development. U . S. Army Engineer Research and Developm ent Center (ERDC)JCERL Teclm ical Report (TR) · 05 · 3, January 2001>. Josephson, Pau l (200 3). Hazardous Waste Combuswr Management Plan

- AEC (for Tabl e 1 ). Lemieux. P .. J. Ry an. N. French, W. futos (1998). Resul te of the September 199 7 DOE/EPA De. mo.nstratian ofMul ti - Matal Continuous Emission Monitoring Technol ogies. Presented a t International**Conf~n ec**  on Incineration and Thermal Treatment Technolo gies . McFarl•nd, A.R, and .J . C . Rodgers. (1993). Singl e-Point Repre s enta ti ve Sampl ing 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 R

epor t : Cooper Environm ental Services, XCEM Mul ti ·Metal s Cont i nuous Emia fiion Moni tor. May 2002. From EPA website: http :// www .epa.gov/etv/pd&fvrvs/ 0 2

_vr_c ooper_xmc. : em.pdf . Seltzer , M.D. (2000). "Performance Testing of a Mul ti

metals Cont inuou-s Emi ssions 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.



### VES01137lERDC/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 T es t De scr iption 

### This test/quality assurance ( QA) 

### plan provides detailed proeedures for a veri.fica · t ion test for an X

- Ray Fluorescence-based Continuous Emissions Monitor (X CEM) used to measure metals in source emissions. The . U .S. Army Construe · tion Engineering fu!search Laborat ory (CERL) will 

### perform the verifica t ion 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 objectiv e and quality assured performance data on environmental technologies, so that users, developers , regula

tors, and consultants have an in dependent 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) .

Pre pared klt CER L by Cooper E nWonmenta l SeMoes , Beaverton, OR , 8 Ma y 200 1 ,



## VES0113727 4 E R

D

C/CER L 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 qu a ntify the p erformance of the XCEM by comparison to reference metal meas urements under full-scale conditions at a combustion facility. 1 . 3 Org an ization and Responsi b iliti e s The CERL, TEAD, and Battelle 

### will perform and evaluate the verification test in cooperation with Cooper Environmental Services (CES), which will provide the X CEM for verification. M SE Technology A pplications , Butte, MT ( M SE

- TA) will be r e sponsible f or 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 organiz ation chart in Figure 1-1 sho ws 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

C E S MSE-T A CHPPM 

### X

CEM Stack Ref. Ven dor Spiking Measure. Figure 1

- 1. Organizational Chart for Verification Tests 1 . 3 .1 Con struct i on Engin ee ring Res e arch Laborato ry Dr. K. James Hay is the C ERL 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



### V E S011373ERDC/CERL TR.05·9 

### problems , Dr. Hay has t he a uthority 

### to stop or delay the test. As 

### the test leader, Dr. Hay will: 

### • Coordinate TEAD , 

### Battelle, CHPPM , M S E -TA and CES staff to conduct the verification test. • Have overall re sponsibility 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 repr esentatives. 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 t est/Q;\ plan is being followed , and d e v eloping 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 qualit y requirements of this test/QA plan are met. More specifically, these Battelle staff will: 

### • Review the 

### draft test/Q A plan . • Coordinate Battelle and EPAIETV staff during v erification 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 verifica

tion. • 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 

### v erification report and statement in response to re'>iewer's comments. • Coordinate technical peer reviews of the test/QA plan and ETV verification report and s tatement. • Conduct a te<:hnic al system audit and report results of t hat audit. 1 . 3 . 3 Tooe l e Anny Depot 

### The verification tes t will 

### be conducted in collaboration wit h Dee Russell of TEAD . 

### Mr . Rus sell's responsibilities are: • Coordinate the operation of the facility during verification tes t ing . • Coordinate the installation of 

### the XCEM at the TEAD 

### incinerator . • Communicate needs for safety and other training of 

### staff working at the facil

ity . • Contribute 

### to the development of the draft test/Q;\ plan. 75



### VES01137476 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 opera tion. • Provide support in responding to any i s sues raised in assessment reports and audits related to facility operation. 1.3 . 4 Coop er Envi ronme n tal Services Cooper Environmental Services of Beaverton, OR m a nufactures the XC EM. CES staff will : • Develop the draft test/QA plan and submit plan to CERL, Battelle , TEAD , CHPP M, and MSE-TA staff. Revise the test/QA plan in accordance with review

ers' comments. • Approve the final test!QA plan . • Participate in required safety training at the test facility before installation oftheXCEM . • A ttend a pre-study site visit to review facility requirements for testing. • Provide an XCEM for the duration ofthe verification test. • Commit a trained technical member of staff to operate, maintain, and repair the XCEM throughout the verification test . • Participa te in verification testing, including providing data acquisition for the XCEM. • Provide data from t he XCEM at the conclusion of each test day. • Prepare a summary test report for C ERL . The summary test report will he us ed as the basis for the ETV verification report. • Review the draft verification report and verification statement. 1 . 3.5 Center for Hea l th P r om otion 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. 

### VESOII375ERDCICERL 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 respon ding to any issues raised in assessment reports and

audits relate d to facility oper ation. 1.3.6 MSE Tech n o l ogy Appli cati o n s, I nc. 

### 1\ISE-TA will be responsible for injection of the metals of interest i n to the TEAD incinerator. MSE ·TA 

### will: • Quantitatively spike metals of interest into the TEAD incinerator down · stream of t he controls. • Provide measurable concentrations of the metal s of interest at the XCEM and r e

f er e n ce method sampling points . • E n sure t hat part icle s ize fo r the metals of interest are representative of typi · cal s tack gas conditions. • Ensw-e that all applicable regulatory e mission limits are maintained. 1 . 3 . 7 U .S. Environme n ta l Prote c tio n A g en cy 

### EPA manages the. ETV program and partners with Battelle for the ETV AMS Center. As such, EPA has the option to conduct a t echnical systems audit of the verification test. I n addition , EP A 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 B attelle. 2 . 0 APP LI CA BILITY 2 . 1 Subj ect 

### Thi s test/QA p lan is applicable to the verification testing of a commer c ially available continuous emission monitor (CEM) system for determining mult i· 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 met als on a filter, which is then analyzed with x· ray fluorescence (XRF) using an adapted QuanX analyzer . A prototype of the 77



## VES 0 1137678 ERDC/CERL T R-05-9 

### X

CE:M was assessed at the MSE-TA test facility in Butte, MT (B ryson 2000) and has been rede signed for increased ease-of-use and automated QA 

### routines. Verification testing will be conducted at 

### TEAD . The TEAD facility has a well

ch!ll-acterized feedstream and w a s the site for multi-metal CEM te sts conducted in 1 999 . 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 t hallium 

### (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 ele

ments wer e selected in order to challenge the XCEM ov er a large range of analy

sis conditions and elemental concentrations. EPA Method 29 (M29) is current ly recognized as the most suitable procedure to determine multi

-metal concentrations in source emissions (EP A 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 i n clude, as a minimum, determination of the nine e lements 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 h as published a draft performance spec ification document desig· nated as PS-10 (E PA 1996) as a proposed description of how to assess 

### the acceptability of a mul ti

-met al CEM upon installation and thereafter. The goals of the verification test 

### will be met ifthe XCEM meets the proposed PS-10: 1. 

### Relatiw accuracy criteria for the elements in the feedstream ofthe Thoele incin

### erator (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 e l ements at two concentration levels (Hg, Ni, Zn, and Sb ).



## VES011377ERDC/CERL TR.()5-9 

### A secondary object ive 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 te stJQA plan include: • Relative accuracy • Correlation with reference method • Precision • Instrument drift 

### • Span and zero • Response time • Bias • Low level metal response. Relative accuracy, correlat ion with the reference method, and pre cision (i. e . , repeatability at stable te st conditions) will be asse ssed 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 b u ilt-in additional check for instrument drift which measures a pall adium 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 v erification tes t to simulate the aging and expo sures that may affect an XCEM during routine long

- term use. This verification test evaluates the performance of a new XCEM over a relatively short tes t period, in 

### the hands of staff skilled in its operation. I t 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 t ake 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



## VES01137880 ERDCICERL TR..05-9 3. 1 Te st Facility 

### The TEAD incinerator, which runs on diesel fuel, is designed to incinerate de

commissioned 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 differ

ential, 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 fi lters baghouse, high temperature draft; fan, and exhaust stack. 1) Main 

### Con t rol Pan e l . The main control panel contains various pieces of control equipment to monitor and control the furnace operation. Process control

lers are used to control the rotary furnace feed end temperature , negative pressur e in the furnace, and afterburner temp er a ture. A multi

- point digital recorder is used to record process parameters. Logic control for the furnace is performed by a PLC. T h e PLC cont rols the motor stal-ters, the WFRMS, safety inter locks, and alarms. The computer system is an industrial

- based machine running data acquisition software , which provides centralized and integrated data man agement , process graphics, operator interface, and report generation.

Figure 3

- 1. TEAD Deactivation Incinerator Building 1320.



### V E S0 1 1379E RDC/CERL TR-05·9 81 

### Table 3-1 . Typical operating parameters for the APE

- 1236 deactivation furnace. Typica l Operating P arameters fo t· the AP E- 12 36 D eactivatio n Furnace Afterb ume1 · Temp. ("F) 

### 1 600 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. H 2 0) 

### 0.3

Figure 3

-2. TEAD Incinerator Stack.



## VES01138082 EROC/C ERL TR -05-9 2 ) Continuou s Emissions Monitoring System s . CEM systems are in place to measure carbon monoxid e (CO) and oxygen 

## <O. > in the exhaust stack . The CEM sampling system includes the following: sample extraction p r obe , heat traced sampl ing lines, calibration ports, refrigerated condenser, sample pump, filte r s, and flow meters. The sample extraction port is lo cated 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 sca le , a push-off box, and a slide chute. The scale repo rts the measut-ed weight to the PLC via a seria l communication cable. The P LC verifies that the weight is les s than or equal to the established limit for t he item being incinerated. Once the P LC 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 1 5 seconds. 4 ) Dual Conveyor Feed System . The primary w as te feed conveyor transports the munitions from the WFRMS t.hrough the concrete w all into t he barricade area. The ammunition is then fed on to the secondary feed conveyor, which deposits the ammunition into the rotary furnace feed chute . If an out-ofparameter condition arises, the p rimary feed conveyor is stopped until the condi

t ion is corrected. For safety reasons, however, t he secondary conveyor continues t o operate. This allow s munitions near the high temperature end of the 

### kiln to continue moving through the furnace and deters possible explosion s outside the furnace. 5 ) Rotary Furnace . The rot ary furnace is designed to ignite t h e ammunition items and effectively incinerate re ac tive components from the metal s hells. The heat to ignite the ammunition is initially provided by fu el oil forming a countercurrent to the movement of the ammunition through the rotary furnace. Combustion gases and entrained ash exit the furn ace a djacent to the f eed chute. Non-entrained ash and the metal components of the ammunition are discharged at the burner end of the r o tary furnace . The ammunition is propelled through the 20 ft long , 30 . 5 inch diameter r etort toward the burner end by spiral flights . As t he ammunition approaches the flame, they either detonate or burn freely , depending on the ammunitio n characteristics. The t hick cast steel walls contain high order detonations . F eed rates, res idence times, and operating parameters have been established for each ammunition item by controlled testing. The ro

### VESOll38lEROC/CERL TR-05-9 tary furnace is equipped with a Hauck 7 83 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 t he discharge end ranges from 800

- 1100 •F during normal operation. The rotary furnace is operated under a slight negative pressure. 6 ) F urnace Shroud. A metal shroud that completely enclo ses 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) C ycl o n e. 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 va l ve has two gates that are motor driven . The gates open alternativel y so that on)y one gate is open at any time, thus maintaining the negative pressure. 8) Afterburne r . The afterburner is built to AED specifications by Southern Technology Incorporated. The afterburner is designed to raise the t emperature of the exhaust gases exiting from the kiln. This elevated temperature , and the added residence time, enhances the complet e combustion of the explosive. The afterburner is capable of heating 4000 sefm of fl ue gas from 350-450 •F to 1400- 1 600 • 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 after

burner 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



## VES01138284 ERDC/CERL TR-05-9 the gas stream . The baghouse was designed and built to AED specifications by JT Systems Incorporated. T he flue gases from the afterburner are transp011:ed to the baghouse by 1 20 ft of 30-inch diameter stainless steel ducting. The duct

ing is long enough to produce a temperature drop from 1600 oF at the exi t of the afterburner to 1000 oF entering the baghouse . The baghouse cont ains 154 ceraiil ceramic candles that are 5.75 inches in diameter and 10ft long. This results in a total filter area of 2330 square fee t w it

h 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 be l ow and are exh austed 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 i s approximately 30 ft high (34ft with extension) and has a nominal ID of 20 i n ches (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 t h at is routinely found in measurable concentrations in the stack ga s . Table 3

- 2. T EAD metal emission linlits during verification testing. Element Limit ( g/

hr) E l ement Limit ( g/

hr) Antimony (Sb) 14 Lead (Ph) 4. 3

Arsenic (As ) 0.11 Me1·cury (Hg) 14 Barium (Ba) 2400 Ni c kel (Ni ) 930 Beryllium (Be) 0.20 Seleni um (Se) 180 Cad mium (Cd) 0 . 26 S ilver (Ag) 140 Chrom i um (C r) 0 . 0 4 Tha llium (TI) 1 4



## VES011383ERDCICERL TR-05-9 4.0 EXPERIMENTAL DESIGN 4 . 1 Genera l Design 

### For all tests, both the kiln and the afterburner will be fired with diesel fuel while incinerating Ma rk 344 fuses 

### (NSN number 1325000090348) with a feed 

### rate of 79 per hour. The chemica l compos ition 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 metal s will he 

### spiked at the level shown in Table 4

- 2. Lead , however, will not be spik e d since the incinerated munitions provide mea s urable concentrations of lead without spiking. Spiking will 

### be conducted by MSE-TA using three or four atomizers to inject sol utions containing the met als 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 d a ta, 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 in

elude 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 n earest flow distm'hances are located 9 . 8 duct diameters upstream (induced draft fan) and 4.3 duct diameters downstream i top of the stack) from the sample ports. 85



## VES01138486 ERDC/CER L TR· OS.9

Table 4-1. Composition of munitions incinerated during metals testing. F uz e , Bom b , T ail , MK3 44 Mo d 0 / 1 Feed R ate : 7 9 it e m slhr ; Lo a din g (lbli tem) 0 . 2 7 9 1 C omponent Qua n - Com ponent Com pon e nt F ee d Rate t l ty (lb /item ) (l b/br ) B u tyl Aceta te 0.0000 1 0.0008 Charcoal 0.00002 0.0016 Ethyl Alcohol 0.0000 1 0.0008 G

r aphite 0.00541 0.4275 Lead Azide 0 . 00028 0 . 022 1 Lead Monoxid e 0.00005 0.0040 Lead Powder 0.00031 0.02 45 Le.ad S typhnate 0.00683 0.5398 Nitroce llulose 0 . 00002 0.0016 Nitrost ru:ch 0 . 00001 0 . 0009 PETN 0.00031 0.0245 Pot assium Nitrate 0 . 00008 0.0063 Selenium Powder 0.00012 0.0095 Sul fur 0 . 00005 0.0040 Te t ryl 0.26555 20.9855 To luene 0.00001 0.0008

Table 4-2. Tooele metal emission limitations and spiking levels. Emiss io n Limits 1 S p iki ng Lev el l E l ement s - j!g/ d s em glbr

- j! g/ d scm Ru ns 1 -6 Runs 7 -1 2 As 0. 11 17 1 5 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 1 39,500 200 500 Pb 4.3 645 NS NS Sb 14 2,100 200 500 Zn 

### NR NR 200 500 1 The concent ration in 11g/dscm assumes a stack fl ow rate of about 6700 dscmllll' NR: Not regulated NS: Not Spik e d



### VE SOll385E RDC/CERL TR-05-9 CHPPM 

### will conduct the chemical analysis of recovered sample fractions from t he 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 samp l e identification numbers 

## ";n be implemented so that final data used for verification can be traced back through the an a lytical process to the original sampl e . 4.2 Te s t Schedule Set-up for the verification testing is scheduled for May 10. XCEM verification testing is t entatively 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 T est P rocedures In all cases when reference method data is being taken, the introduction of the indicated metals will be held constant throughout the e ntire 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 approac h 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 l ocated at the base of the

- stack. This port was successfully used in earlier multi

metal 

### 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 t hese tests , pressure and flow rate 

### will be maintained to keep droplet sizes les s than 28 microns in diameter. When dried, t he majority of the mass is expected to be in the one to four micron range. 87



### VESOI138688 ERD C/CERL TR.05- 9 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 refere nce met hod sampling. Dual sample trains will be u sed to collect metals data employing standard operating procedures from M29. Full s a mple custody procedures will be employed during the tes t using sample custody sheets and samp le custody s eals. Samples will be under either direct custody or lock and k ey 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-te sts 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 quant itative ly spiked wi t h a ll nine of t he metals of interest. These spikes will be conducted on sampling media , inc l uding the filter and i mpinger solutions, from the same lots used during tes t ing . A spike recovery target of80 to 120 percent of injected solution has been 

### set.4 . 3 . 3 Refe re nce meth od analysis Reference method analy ses will be conducted by C HPPM' s D irectorate of Laboratory Services ( DLS ). Analysis will follo w standard M29 protocol with the fo llowing exception: the front half analysis will include separate reported \• alu e s for both the front half rinse and the filter. Blank value s will be deter mined using !1.129 section 9 . 1 p r otocols and a standard blank subtraction will be made if sig

nificant metals are found in the blank CHPPM uses ICP-1\>IS for i t s met als analysis . The ICP

- MS is calibrated using s olution standards as discussed in section 1 0.2 ofM29. 4.4 Data Compa ris ons This section describes how the reference and CEM data will be used and compared to quantify the performance of the XCEM . Table 4

-5 summarize s the data that w ill be used for the verification comparisons.



## VES011387ERDC/CERL**TR~S-9** 

### 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 b e determined by analysis of 

### XCEM concentrations when the spike i njection rate and stack conditions are held constant. It is 

### recogni zed that the reported precision will include variability in stack condit i ons as well as 

### XCEM variability . Ta ble 

### 4-5. Summary of data to 

### be obtained during 

### X CEJI.i v erification test. Performanc e Compari son No. 

### of Objective 

### Da t a Param eter B ase d On Points

Accuracy Determine d egree of quanti tative Reference Method 1 2 agreement w i th refe r ence method. Res ults Col'rela tion Determ. ine**eg~·ee** ofcorrelation Reference Method 12 "'ith reforenco method. Roo u lts Deter mine degree ofcon siste n cy in XCEM rep or ted oo n centrations Precision X C EM measured concen tr

ations u n der constant 6/ ru n u nder c onstant operating operati ng con d i tions. conditions. Determine variatio n in Instr ument Determine XCEM ability to pslladiurn Drift measu re consistently over the conce ntrations 3/hr course of the test. determined with eacbXCEM ml.:! as urem en t Span and Zero Determ ine XCEM response under XCEM automated 4 maxi mum and minimu m conditionR daily 

### QA routi ne Determine XCEM response time as C-ontinuous Response Ti me a batch CEM . monitoring of metal 3/h r concentration s Bias D eter mine if bias exists between Reference Method 12 M29 and the XCEM. Resul ts Low Level Determin e XCEM per f ormance Arsenic and M etal Response whe n low metal conL --entrations are chromi u m ref. 24 present in t he stack. Met hod resul ts 89



## VESOJJ38890 ERDC/CERL TR·OS.9 

### Instrument drift 

### will be determined by evaluation of XCEM reported palladium concentrations. As part of the XCEM quality assurance program, a palladium rod has been permanently fixed above the x- ray beam and below the filter tape. The palladium rod is measured with each sample, and a running record of the reported concentrations is maintained. The percent 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 e quivalent 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 d ivergent 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 ofthe averaging period for the applicable standard. 

## VES011389ERDCICERL**TR.O~** 2. The delay between the end ofthe 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 Conser

vation and Recovery Act (RC RA} 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 metal s of interest in to the analysis area. The plunger is then analyzed by the XCEM and the data compared with the known metal concentrations on the plun ger . 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 M 29 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 CALCULAT I ONS 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



## VES01139092 ERDC/CER L TR-05·9

where: 

## c , c ,

n t; = = = = [ Eq 5.11

XCEM time-weighted concentration for eleme nt i durin g 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 t ime intervalj 5. 2 Rela ti ve A c curac y T he relative a ccurac y (RA ) of the XCEM with respect to the reference method (M29) will be ass e ssed by: !Eq 5 . 2] Where d refers to the difference between M 29 and the XCEM results, and x cor· responds to the M29 result. 

### 8 4 denotes the sample standard d eviation of the differences , while t " & , is the t value for the 100(1-a )"' percentile of the distribution with n · • degr e es 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 r e lative bias of the analyzer , i.e.,

# ~ , where t he superscript bar indicates the average absolute value of the X differences of the reference \ • alues. If 12 reference me thod test runs are completed, the RAprocedmoe stated in PS-10 will be followed (i.e. , up t o 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 ca l culated separately for each metal measured by the XCEM. 5. 3 Correla t ion w i t h R e f

erence M e t

h od The degree of correlation o f the XCEM with the ref e rence me thod results will be assessed in terms ofthe correlation coefficient (r ' ) for metals spiked at more than one concentration (i. e., Hg, Ni, Zn, an d Sb).



## VESOIJ391ERDCICERL TR..,S-9 A second series of int r a - method correlations will be determined by comparing t he relative ratios of metals measured by the XCEM for each of the measurement periods. This con · elat ion assumes that no fractionation of the injected species occurred during transport. 5

. 4 Precisi on Precision will b e 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 variabili ty in the stack condition s, spiking rate, and XCEM measurements and will be identified as a maximum XCEM precision with a note in the verification report t hat 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 r ecordings will be calculated. Percen t precision (P ) will then be determined a s: 

### SD**P= xJOO**  X [Eq 5 .3]

wh ere SD is the standard devi at ion of th e XCEM r e adings and 

## X i s the mean of the readings . The same calculation 

### will be performed for each metal measured bytheXCEM. 5 . 5 Span , Zero, and Instrument D rift The XCEM h as automated daily span and zero checks and reports a palladium concentration with each sample to check for instrument d rift. Span, zero, and instrumen t drift will be reported in terms of the mean , RSD , and range (maxi

mum a nd minimum) of the readings obtained from the X CE M . The percent RSD will be calcnlated as: SD**RSD .dOO**  X [Eq 5.4] where 

## X i s 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 s tandard readings. 93



## VES01139294 ERO C/CEIU. TR -05- 9

5

. 6 Method 29 and XCEM B ias Bias between the two M29 sa m pling trains and the M29/XCEM data will be determined using an EPA Method 301 approach . The results are tested for statisti

cally s ignificant bias by calculating the t-statistic and determining if the mean of the differences betwee n the two sampling trains is significant at the SO

- percent confidence .level. The t-stati s tic is calculated by finding t he SO of the differences between the two sampling trains.

Where: 

## L; (d,- d.} {n

- 1)

d , 

### = the difference between t he two sample train values d. 

## = mean of the d , values

n = number of pair ed samples [ Eq 5 . 5)

Using th e SD determined in equation 5 . 5, the t-statistic is then calculated as follows: (Eq 5.6)

The critical value of the t-stati stic is 0.8755 for 12 runs . 

### Ift he calculated t- value is greater than the critical value, the bias as defi ned by M301 is statistically sig

nificant. A statistically significant bias in the reference method will be noted in the validation r e port. Method 29 data pairs that are d etermined to be unbiased relative to each othe r will be averaged and u sed for comparison to the XC E M . B ia s between the X

CEM and a verage M29 data will be determined using equations 5.5 and 5.6 with 

### d, being the difference between t he average M29 and XCEM data.



### VE S011393ERDCICERL TR -05-9 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 . T he a t omizers used for spiking will require about 10 scfm ofdry air. 6 . 1.2 Sp ike I njecti on soluti ons The spike injection solutions include Ba(N0,)2, Cd ( N0 , )2 , Cr( N0,)3, As,O , , Hg(N0 , )2, Ni(N0,)2 , Zn( N0 3 )2, and SbCL,. Solutions will be prepared on- site to allow for flexibility in responding to background metal concentrations found in t he TEAD incinerator. 6.2 Refer ence Method 6 . 2 . 1 Sampling trains CHPP:M will supply the glassware, filters , and associated equipment for M2 9 sampling. Multiple trains will be supplied so that six trains (i.e., three sampling runs with two trains ea ch) 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 Ana lysi s equipment CHPPM will provide labomtory equipment for sample recovery and analysis. Thi s will include all chemicals and solutions for rinsing t rain components and recovering i mpinger samples. 6.3 TEAD Monitoring Equipment The verification will make use of monitoring equipment already integrated int o the TEAD facility. T his equipment includes monitors for major flue gas constitu

e nts (0 , , CO , ), as well as sensors for temperature and pressure. The s e 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



### V ES01139496 EROCICERL TR.OS-9 7.0 QUALIT Y ASSURANCE/QUALITY CONTROL 7

.1 A sse ss m ents and Audit s 7. 1 . 1 T e

c hni cal s y s tems au dits Battelle's Qua lity 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 t he test records and report. At EPXs discretion , EPA QA staff may also conduct an independent on-s ite TSA duting the verification test. The TSA findings will be comm unicated to t.esting staff at the time of the audit, and documented in a TSA report. 7 .1 . 2 Data q ua li t y 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 A ssess me nt r e p orts Each assessment and audi t 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 o f any noteworthy practices that may be of use to others • Confirmation that solutions have been implemented and are effective. 7. 1.4 C orrectlveAetion The Battelle Quality Manager, during the course of any assessment or audit, will notify the technical staff perfonning e xperim ental activities of any immediate 

## VES011395ER D CICERL 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 E nv ironmental Services will perform data acquisition for the X CEM 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 d ay and are to be 

### provided to the test manag er at the end of each day. Th e XCEM data must include all indiv idual readings of the XC E M (i.e . , temperature, pressure, metal concentrations, 

### QA data, etc.) listed by time of da y. Averaged re sults 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 involv ed in the testing. These records will 

### be reviewed to identify and resolve any inconsistencies. All written recor ds must be in i nk. 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, s trict confidentiality of data from the XCEM will be 

### maintained. Table 8

- 1 sum marizes 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 CE RL designated test manager immediately upon completion of each t.est day. 97



## VESOI139698 ERDC/CERL TR-05-9 

### Table 8-1. Summary of dat a recording proces s for the verification test. Data To Be Responsible Wher e How Often Disposition of R ecorded P arty Recorded Recorded D ata Used to organ · Start/end o f tes t , izelcheck tes t Oates , times oftest Laboratory and at each results; manual ly events CERL reoord books change of a test incorporated i n data spread

- parameter.**shootsasn~** sary. Test parameters Used**too~n** When set or izo/eheck test (temperat ure, ana- TEAD,CERL, Laboratory changed, or as results; incorpo - lyte i denti tie:; and CHPPM record books needed to docu · rated in data concent rations, flow s , ment stability. spreadsheets as etc.) necessar y . XCEM dat a will Laboratory be recorded conXCEM reading>; in- record books , tinuously E lectronically eluding digital dis · CES dat..<t**shee ~**  or t hroughout test . tr.ansfarred to playa, priotout<J. and data acqui si· O ota sheets " ill spreadsheets . electronic output. tion system , a

_ s be compl eted as appropriate . requi red for each test. At le ast at Used to organ· stnrtlend ofref. ize/chec;k teot Reference m et

hod CHPPM Laboratory test , and at results; incorposampling dota. record books rated in data change of. re st s preadsheets as pa r amete r. necessary. Laboratory Reference method re<ord books. Throughout som · sample. analysis , CHPP:M data sheets, or pie handling and Transferred to chain of enstody 1 and data aequis i- analysis period . opreadsheel$ . results . tion**.sy~m.** as appropriate. 8 . 2 Data Review 

### Records generated in the verific ation t est 

### will receive a one-<> v er-<>ne review within 2 weeks after generation. These reviews are t o be performed within the organiza tion generating th e data. These t·ecords \\111 then be 

### used t o calculate, evaluate, and report verification results. These records may include laboratory record books; operating data fi · om the combustion source; XCEM data; or refer

ence met hod analytical results. The review will be 

### documented by the person performing the review by adding h is/bet · initials and date t o a bard cop y of the record being reviewed. Thi s hard copy will then be returned to the staff who 

## VES011397ERDC/CERL T R -05·9 

### generated or who will be storing the record . Battelle will receive a copy o f all written and recorded data in the project rec ord books and a copy of the XCEM data. 8.3 Reporti ng 

### Cooper Environmental Services will 

### prepare a summary 

### test report for CE R L documenting the testing results. The summary report will include a discussion of the X CEM performance , testing processes, and a comparison with M 29 results . CES will 

### provide Battelle with this summary te s t 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 d escribed in s ec tions 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 v erification test will be stated quantitatively ,**u~thout** 

### commen t on the acceptabilit y o f t he 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 und ergo a technical peer review. Final approval and distribution of the ETV verification report and statement will be conducted as stated in the G eneric Verification Protocol for the Advanced Monitoring Systems Pilot . 

### 9 . 0 HEALTH AND SAFETY The v erification test described in this testJQA plan will 

### be performed at the TEAD facility in Thoele, Utah. All participants in this verification test will 

### adhe re to the health and safety requirements of the facility. Vendor staff 

### will be operating the ir equipment only during the verification test. They are not re sponsible f or

, nor permitted to , operate th e combustion source or perform any other verification activities identified in this test/QA plan. Operation of the XCEM does not pose any known che mical, fire, mechanical , electrica l, noise, or other potent ia l 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 descrip

t ion 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 99



### VESOI!398100 EROCIC E

RL TR-05·9



### t o wear hearing prot ection. Steel-toed safety shoes and work gloves are recommended . Eye wear 

### is not required . 10 .0 R EFE R EN C E S 

### B attelle. ( 1998 ) . Generic V erification Protocol for the Advanced Monitoring Systems Pilot, B at t elle, Columbus, Ohio , November 

### 1998 . Bryson, S . , C. Whitworth, and S. Kujawa (2000). Final Report

- Test and Evaluation of an X-Ray Fluorescen ce Based Multi

- Element Met als Continuous Emission Monitor. Prepared for U . S. Army Corp of E ngineers by MS E

- TA, Butte , MT. E nvironmental Protection Agency (EPA). ( 2000) . Quality Managemen t Plan (QMP ) for the ETV Advanced Monitoring Systems Pilot, U . S. EPA Env:h · onmental Technology Verification Program, prepared by Battelle, Columbus , Ohio . E P A (1998). EP A Environmental Technology Verification Program Qua lity and Managemen t Plan for the P ilot Period ( 1 995-2000), EPA

-600/R-98/0 64 , U . S . En · vironmental Protection Agency, Cincinnati, OH , May 1 998. EPA. (1996). Proposed Performance Sp e cification 10 for Multi -Metal Continuous Emission Monitors, U .S. Environmental Protect i on Agency, Washington, DC. E PA (1991) . U . S. EPA Method 301 Field V alidati on of Emission Concentration s from Stationary Sources . Federal Register VoL 56, No. 114. June 13 , 1 9 91. E P A ( 1990). U . S . EP A Method 29 Determina ti on of Metal Emissions from 

### Stationary Sources. From EPA's technology transfer w ebsite www. epa.gov/ttn .



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