ERDC ICERL TR-OS-9



# 1 Introduction
Background 

### The U.S
. Environmental Protection Agency (EPA) is 

### developing regulations for h azardous waste combustors ( HWC) as part of Title Ill of the 1990 Clean Air Act Amendments (CAAA) in the form of a National Emission Standard for Hazardous Air Pollutants (NESHAP)
. The U.S. Army possesses a number of demilitarization furnaces that will need to comply with these regulations. Of most concern is meeting the requirements for metals and metal compounds listed under the CAAA. A large problem for these incinerator operations is limited knowledge of the types and quantities of emitted metals. Compliance may be determined only through trial burn emission tests because of this limitation
. These tests are expensive and require worst-case scenario burns. The air p ermits that are then issued are based on these wors t- case burns and impose limitations on the demili

tarization facilities. A continuous emission monitor (CEM) for m et

als w ould pro vide the emission data, a tool to he lp meet compliance require ments, and the opportunity to adjust burn strategies for increased production and sustainability. I n addition , the HWC NESHAP suggests t hat a CEM would be 

### the preferential method of emission accountability. Multi-metal CEMs being developed are based on elemental sensors using laser

induced breakdown spectroscopy (LIBS) or inductively coupled plasma (ICP)
. None of the LIBS monitors has successfully met the EPA

-proposed Performance Specification 10 {PS-10; EPA 1996) for continuous multi

- metal monitors. Only one of the ICP units, devel oped by Thermo Jarrell Ash Corporation, has been successful in meeting the relative accuracy (RA) criteria of the PS-10 (Seltzer 2000). Thi s techno l ogy appears to have limita tio n s such as its complexity, high initial costs, and high operating costs. The U.S. Army Engineer Research and Development Center, Construction E ngineering Research Laboratory ( ERDC/ CER L) decided to pursue the development of the X- ray fluorescence (XR
. F)

- based continuous emission m onitor ( X

CEM ) because it had the potential to be a reli

able and accurate CEM without these limitations. The basic ap proach of the X CE.M i s to draw a continuous representat ive sample of s tack gas to a s tilling chamber where a smaller metered sample is extracted and pas.<;ed through a chemically treated filter that collects metals in the parti.cu1



## VES0113002 ERDC/CERL**TR-0~9**


### l ate and vapor phases. F ollowing sampling , t he fi l ter is passed through an XRF analyzer where the masses of up 

## ro 19 metals are measured
. This approach was originally tested in 1997 at an EPA test incinerator, w here the filters were analyzed offiine (French 1998). Cooper E nvironmental Services (CES) further de

veloped this method into an on-line system th at was tested under the ERDC/C ERL Wa ste Minimization and Pollution Prevention Program a t MSE Teclmology Applications, Inc .' s ( MSE- TA's ) re s earch incinerator in Bu tte, Montana (Bryson et al. 2000). The results were encouraging because the XCEM met the PS- 10 RA requirements for chro mium (Cr) and lead ( Pb). Many of the ot her requirements were unmet, however, and further development was needed. It was at this point that ERDC/CERL began fun ding the d evelopment of this 

### technology under their H a zardou s Air Pollutants ( HAP ) program. The Army 

### currently has 19 existing , new , or planned hazardous waste combus · tors. Table 1lists these s ites (Jo sephson 2003). Table 1 . Army hazardous wast e combustors . Locat i on 1\lpe waste Treat ed Status GOorCO S i erra AD APE 1 236 

## cs E xl st in!l GO T ooel e AD APE 1 236 

## cs E xl st ioo GO Tooel e AD AP E 1236 Tes t F urnace - CS E xist ing GO McAlester AAP APE 1236 

## cs E xi st ing GO Hawt h o rne AA P APE 22 1 0 

## cs N e w 

## co Fori Ri cha rdson APE 1236 

## cs New GO Ka n sasAA P APE 1236 

### cs Ex i s1ing 

## co Cra neAA P APE 1236 

### cs New GO La ke Ci ty AA P AP E 1236 Off · spec conven ti ona l Ex i s1ing GO P i catin ny Arsenal APE 1 236 Waste R&D propellants New G O P ine B l uffArsena l Au l di z ed Be d Pyr o t ech ni cs an d Obscurants New GO Pine B l uffArsena l APE 1236 Off-spec pyro« echn ics Radfo rd AAP K iln Off · SPGC I)< Opellan ts O esere t CA Chemica l Chem U matill a AD Chemica l Chem Pi ne B l uffArsena l Chemica l Ch em An niston AD Chemica l Ch em Pue bl oCA Chem ica l Chem An n i ston AD K iln De- P a i nti ng wastes GO - Gcwemm e nl O wned CS - Co n ve n tional S t o

ckpile AD- Ar m y D epot CO - CoMrac!Or Owned C

hern - C h emi cal Sfod:p i! e A.AP - Ar m y Ammuni tlm P1an t Ex i st ing GO Ex i sting GO Ex i sting GO N

e w GO New GO New GO P la n ne d GO P la n ned GO CA - ChelricaiAclMt y AP E 4 A.rrwnu ni tion Pecu l ia r E(Ji i pmQn t



### VESOll30lERDC/CERL TR.OS-9 

### Objective The overall objective of the HAP program is to develop cost-effective technologies to help the Army meet current and future demands of HAP regulations. 'lbward this objective , the XCEM was developed. It w a s d eveloped to possess characteristics that make it comp a tible with Army operations and expectati ons , such as user friendlin e ss and affordability
. Th at work is described in a precedent-setting report (Hay et al. 2005). The specific objective of this work was to demonstrat e the XC E.M at an Army installation. The desired exit criterion u nder the HAP Program was for the monitor to meet, u nder field conditions, t he proposed P S -1 0 requirements, which are described in Table 2
. Table 2
. Proposed PS-10 requirements.

Criterion DoscriJ>tion SafT4) 1 iog and It i s re qu i red that the &afr4'liog time be no l onger lha n one-1Nrd of the averresponse ti me aging periOd l or lhe a ppl i cab l e standard lor a ba lch CEM
. The d el ay be · tween the end of the sam pl i ng peno d and r eporting o f the sample ana !ys i s shall be no g re ater t han I hou r. A batch CEM Is requ i red to samp l e contin u ous!y exoept wh en changing the samp M ng media , wh i ch sho u ld be n o g rea ter t han 5 percent or th e averag i ng period or 5 mi nu tes, whichever is tess
. For th i s s t u d y , lhe averaging peri od i s 1 2 hours, wh i ch means the sampling t ime should be n o longer than 240 mi nu tes, the response tim e no g r

eater t han 60 mWlutes , and the m axi mum time aU owed f o

r changing the sampl i na med ia I s 5 m i nu t es. Quality assurance Cal i bration drift: The cali brati on m ay not d rift or d ev i ate from the re feren ce va l ue ollhe cal i brati on standard us ed for eac h metal by more than 5 percent o f th e emi ssion st andard fQ( each meta l. Must allow f o

r det enn ini ng on a da il y basis
. Zero drift : The zero poin t lor each metal shall not d rift by more tha n 5 percent of t he emission stan d ard for that meta l. Must allow for d etenm i niog on a da il y basis
. Span : The CEM r espons e range must i nclude zero and a high leve l va l ue equa l to the span. The span valUe is defined es 20 ti mes the applicab l e emissio n l i mit lor ea ch meta l. T h is is an equ i pment specification (not tested)
. RA T he RA of the CEM must be no g r eate< than 20 pe c can t of the mean val u e ol th e RM t est d ata in terms of units of emission standard lor each meta l, or 10 percent ol the appl i cab l e standard. wh icheve r Is greate r. Duling velifi ca · li on . lhe measure o1 RA at a sing l e concentration leve l i s r e q ui r ed for each meta l measu r ed for cornp l ia noe purposes. and the RA must be dete<m i n ed at th r ee concentration l eve l s fo r one mela l f ze ro can be one I even. So u rce : EPA 1 996
. 3



### VES0113024 EROC/CERL TR .05-9
Approach As 

### a result of encouraging development work ( Ha y et a!. 2005) a new monitor was installed at the 1236 production deactivation furnace at Tooele Army Depot (TEAD) , Utah. The monitor was compared to E P A 

### Reference Method 29 (M29 ) in 2001. The monitor was only partly successful; several improvements were warrant ed and implemented. 

### A second M29 field

- te st was conducted a year lat er . This report includes the description and r es ults from both M29 comparison 

### tests and the modifications that took pl a ce in between. The XCEM was demonstrated unde r this project through contract s with C ES and MSE- TA The U.S. Army Center for Heal t h Promotion and Preventiv e Medicine (CHPPM) performed the M29 s tack sampling activities described in this report.
Mode of Technology Transfer 

### This tec hn ology was developed and demons t rated through the ERDC/CE R L HAP Program, which use s 6
. 3 advanced development and field-testing funds. The HAP Program is part of the Army Environmental Quality Technology ( EQT ) Pro · gram. As 

### part of the EQT proces s , a technology transfer plan is being developed by the Army Em<ironmental Center (AEC) for this technology as well as other qualified technologies under the HAP program. A 

### User's Guide and Resource Manual have been developed to accompany the XCEM for field training and ref · erence (CES 2001a, 2001b). This technology is ready for transfer to Army facili· ties, and transition has already begun. The Army purchased another XCEM in 2003 for use at the 1236 Test D eactivation Furn a ce at TEAD
. This report will be made accessible through th e World Wide Web at : http://www.cecer.army.mil



### VES011303ERDC/ CERL TR.O!MI



# 2 Field Testing 2001

The XCEM underwent M29 comparison t esting at t h e TEAD 1236 d eactiva tion furnace i n May 2001
. This chapter pre se nts a brief description of the XCEM, the testing activiti es , and the r esults of tho testing.
Br ie f Description of XC EM 

### A new XCEM was de veloped and built for demonstration at th e T EAD facility as de scribed in Hay et a l. ( 2005 )
. The XCEM ex t r acts a sam ple o f stack gas and concent r ates the metals of interest on a chemically treated filter tape . Following co

llection, the filter tape is advanced to an analysi s are a wh ere a l aboratorygrade XRF i nstr ume nt is used 

### to d ete rmi ne metal mass. The systom is ent irely automate d and produces concentration data every 10 

### to 20 min ute s for up to 19 e leme nts ofinterest. The three major X CEM components are: an e xtraction sys tem , sampling and analysis system, an d control system. 

### Extract ion Syste m The XCEM extract io n system collec ts a representati ve stack gas sam ple from the smokes tack and trans ports the sample 

### to the filte r . The s ystem incl udes a sam ple pr obe and insul ated sample line
. 'r h e stack gas temperat ure is monitored in the sam pl e line just before it enter s t.he enc losure that house s t he X CEM
. T h e unit on l y operates when this temperat ure is above the dew point for water . Upon entering into the enclosure, the stack gas passes through a heat-traced stilling chamber with a larger diameter that slows the gas velocity (Figure 

### 1 )
. A

pproximately 1 percent ofthe stack gas that enters the stilling chamber is s ampled throu gh an e xtraction tube for cO n CI.lntration on a filter. The r emaining 99 percent of t.he gas is trans po rted out of t he st illing cham ber, throu gh o flow meter, and vented or returned to the**tack** 

### ( 2 to 3 standard cubic feet per minute , SCFM). An 

### eductor , l ocated down stream of the stillin g ch amber , i s u sed 

### to pull the stack gas thro ugh the extraction system . 5



## VES0 1 13046 ERDCICERL TR-05·9

Figure 1. XCEM stilling chamber {vertical pipe t a nd sampling cassett e (bottom ). Sampling and Analysis System 

### Approximately 0.8 liters per minute {Lpm ) is extracted and concentrated on a filter tape for analysis. Following filtration, the ext racted stack gas 

### is trans
ported to 

### the XCElVI chassis where drying and volume determination take place (Figure 2). 

### The sampling cassette holds a 4

- week supply of filter tape on a reel-to

- reel sys tem that is a utomated to accurately move t he tape from the sampling to an analysis position. Sampling and analysis occur simultaneously, resulting i n a continuous monitoring system that reports metal concent ration measurements every 10 to 20 minutes . 

## VES011305EROCIC E RL TR-05-9

Figure 2. X CE M c hass is. 

### Metal mass on the filter is determined using a modified ThermoNoran QuanX energy dispersive XRF analyzer. The QuanX is 

### capable of simul taneously meas uring 19 elements and a palladium (Pd) quality assurance (QA) 

### standard. Al

though the QuanX can readily quantify elements with atomic number 13 and above, the XCEM-modified QuanX is most efficient at quantifying and reporting hazardous elements with an atomic number greater than 24 (Cr). Since XRF i s nondestructive, the retentate on the filter tape can be 

### reanalyzed if the end

- user requires additional data. C

o n trol Sy s tem 

### The XCEM i s controlled b y a personal computer using a custom WonderWare "' (Progressive Software Solutions, Inc., Albany, OR) software interface (Figure 

### 3). All day- t o-day functions of the XCEM are automated, including flow and tem
perature control , concentration determination , and 

### QA routines
. Flow, temperature, concentration, pressure, and error messages are automatically recorded in a secure database
. The data can readily be imported into Excel or an equivalent program for subsequent e valuation. Flow, temperature , concentration, and pres· sure measurements are logged in real -time on the screen.
E xec ut ion o f F i eld - T es ting Activities 

### Before shipment to 

### 1boele, the XCEM was tested and an initial calibration was compl eted. Due to a tight 

### timetable for this**pr~ject,** 

### a fmal calibration was not conducted until after the tests. Test data were modified according to the final calibration, resulting in an 8 percent ine1·ease in reported metal concentrations. All calibration adjustment s were completed prior to 

### receiving M29 results. 7



## VES0113068 ERDCICERL TR·OS..S

COmponent COniTOI

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

# ...... 

# -- '**~~**



### Following in s tallation, preliminary ons ite training was conducted for TEAD per · sonnel. Onsite training consisted of an introduction to the XCEM and 

### its capa · bilities. Although the XCEM has been designed for ease of use, it is recom · mended that additional training be 

### provided to ensure s u ccessful integration of t he XCEM into incinerator daily operations. Test Plan 

### A test plan was developed to verify capabilities of tbe XCEM to measure metals under typ i cal incinerator condit i ons ( Appendix A )
. 

### The t est plan out lined meth· odology for comparison testing bet ween EPA M29 and the XCEM at the TEAD incinerator. Specifically, the te s t plan called for at least 12 EPA M29 t ests with each test run lasting 2 how'S. Arsenic ( As), 

### barium ( Ba ), Cr, cadmium ( Cd), nickel ( Nil, mercury (Hg ), antimony (Sb), and 1 .inc ( Z n ) were spiked during the reference method testing to 

### ensure quantifiable concentrations of a V<'ide variety of metals
. Lead was also measured for each test but was not spiked because it is found in quantifiable concentrations in TEAD incinerator emissions under nor· mal operating conditions. The actual dates of the test, associated M29 run num · hers , and TEAD incineration feedstream are shown in Table 3
.



## VES011307ERDC/CERL TR·05·9
In 

### general, the test plan ( Appendix A) was followed a s written w ith the following exceptions : • The Army chose to burn bullets during the first two M29 tests rather than fuses as specified in the test plan. • The X C EM observed high levels ofPb during the first two test mos. The TEAD operators believe that the high Pb wa s related to a faulty bypass valve. Consequently, the TEAD site manager decided to run M29 testing with no am· munition being incinerated until repairs could be completed. The repairs were completed after run 11. • A 13th M29 t est run was added. • Delays in completing a trial burn test at the Army incinerator forced a 2-day postponement in XCEM testing. T o make up for los t time, four M29 test runs were completed on both 16 and 16 May. Table 3. XCEM t est dates a nd a ssociat ed TE AD Incineration leedslream
. 1 4 M a • 15 M av 1 6 M av 17 M a v R un 1 R .., 2 -3 R
... 4 R\Jn5 RIM16 Run 7 Ru nS R u n 9 Roo 10 Run 11 Ru n 12 R un 1 3 50 50 No No No No No No No No No**~IK344** "'K344 Cal ibet caliber Anmo A m

mo Ammo Ammo Ammo Ammo A m

mo Anmo Amm o Fuses FUGG$ EP A V erifi c ation 

### Test activities were coordinated with EPA's Environmental Technology Verifica · tion (ETV ) program. ETV's charter is to provide objective and quality assured performance data on environmental technologies , so that users, developers, regu· lators , and consultants have an independent and credible assessment of an in· strument's performance. Battelle Memorial Institute, headquartered in Colum · bus, OH , is EPA's partn e r for the ETV Advanced Monitoring Systems (AMS) Center. The scope of the AMS Center covers verification of monitoring met hods for contaminants and natural species in air, water , and s oiL For these tests, ETV representatives reviewed the test plan and monitored testing procedures. They also conducted an onsite audit of the Army laboratory that a n aly zed the M29 samples
. CES provided ETV representatives with the XCEM metal concen· trations for each test run. The M29 test results were submitted independently to the ETV representatives. These data, combined with an evaluation of the qual· ity of the test, have been documented in a final ETV report (.Myers eta!. 2002). TEAD Interface 

### The XCEM sampled the stack gas through a probe and transport line. Ideally, the probe would have been shrouded, which allows for increased flexibility in isokinetic sampling and reduces particulate Joss in the probe
. However, the shrouded probes are specially manufu.ctured by 

### Anderson Instruments, Inc
. 9



## V

E S01130810 ERDC/ C ERL T R.OS.9 

### (Smyrna, GA ) , and procuring the special probe requires significant lead time. With t he short project timeline, a more easily built custom probe with a simpler design was supplied by Millennium Instruments, Inc (Spring Grove , IL)
. The probe was located at the same elevation as the reference method probes within 86 inches of the top of the stack. The XCEM and M29 probe s were located approximately 27 feet above the base of the exhaust stack. The nearest flow disturbances were 9.8 duct diameters upstream (induced draft fan) and 4
. 3 duct diameters downs t ream (to p of the stack ) from the sample**port.~.** 

### T hese distances are adequate to ensure that these flow disturbances do not affect the sampling
. The t ransport line consisted of approximately 35 ft 

### of 1.5 · in
. diameter stainless steel tubing that extended from the probe to the XCEM shed, which was on the ground near the stack (Figure 

### 4 ). Te s t Objectives 

### T h e overall objective of the test was to provide quantitative verification of the performance of the XCEM under field conditions. EPA's draft 

### performance spe ci

fication document PS

- 10 ( E P A 1996) is a proposed description of h ow to assess the acceptability of a multi-metal C EJ.\ I upon ins t allation and ther eafter.

Fi g u r e 4
. XCEM ho us in g an d t ranspo rt line, M 29 s.a mp1ing setu p , stac k, and ceramic b aghous e at TEA O.


## VES011309ERDC/CERL TR.05·9

The goals of the verific atio n test were to meet t he proposed PS

- 10 requirements for: 1. 

### Response time and 

### reporting time for a batch CEM. 2. 

### QA by passing daily zero and calibration drift checks. 3. 

### Rekttive accural.y for the elements in the feeds tream ofthe TEAD incinerator (Sb, Ba, Cd, Cr, and Pb). This includes evaluating the response to change in concen· tration by testing at least one element a t two concentration levels. A secondary objective w as to meet the RA criter ia for additional regula ted and unregulated m etals, which are no t typically found in the feedstream ( As, Hg, Ni , and Zn). Additional performance parameters examined during the te sting incl uded: • correlation with reference method • precision • low-level metal response • bias
. The XCEM has an automated check for calibration drift that measures a Pd standard with each XCEM 

### test run. Calibration 

### drift was al so checked by the automated dai l y XCEM zero and upscale QA measurements . For the verifi cation test, r espo nse time was determined as the time between the start of one sampling period and the beginning of a BeCQn d sampling period
. The effectiveness of the XCEM to measure low concentrations was determined by a comparison to Cr and As reference method concentrations. Bias was identified using E PA Method 301

- Field Valida tion of Pollutant Measurement Methods from Various Waste Media CEPA 1 992). It was beyond the scope of this verification test to durability for ro u tine long

term use. This test evaluated the performance of a new XCEM over a relatively short test peri od , operated by skilled p ersonnel. It must be n oted that the long

term perf ormance may be different ti ·om t hat observed in the testing d escribed here
. The XC EM d id not exhibit any mechanical probl ems during the 

### test; it completed more than 1 50 test rWls during the week without any downtime
. Site Descr ip ti o n Verification testing took place at TEAD building 1320 deactivation incinerator APE

- 123 6
. The TEAD incinerator, which runs on diesel fuel, is designed to in

cinei ·ate decommissioned munition s . Typical operating parameters for the incin

erator are shown in Table 4
. The TEAD incinerator is cl assified as a dry stack 1 1



## VES01131012 ERDCICER L TR-65 ·9
with w a ter content ranging from 5 to 10 percent . Typical stack PM concentrations are in the range of 10 micrograms per dry standard cubic meter. The TEAD incinerator i s cur rently •· egulated under tbe Resource Conservation and Recovery Act (RC RA) fo r Sb, As , Ba, beryllium (Be), Cd , Cr , P b , Hg , Ni , selenium (Se), silver (Ag ) , and thallium ( TI ). Of the 12 regulated e lements, 5 are typically f oun d in tbe feedstrea m : Sb , B a, Cd, Cr, and Pb
. The XC EM was tested for its measurement capabilities of the fi ve e l ements found in the feed· stream as well as As , Hg , N i, and a nonregul ated m etal , Zn. These elements were select ed i n order to ch a llenge tile XCEM over a large range of analy sis conditions and elemental concentrations. For tile Yerification tes t , metals in the TEAD inciner ator stack gas w e

re regulated under a T e mporary Authorization permit ( Table 5 ). Of the 12 regulated metals , Pb is the only e lem ent t hat was consistent l y foun d in measurable con· centrations in the stack gas. Figure 5 shows the deacti v ation incinerator s et up and the locations for samp ling and spiking duri ng the test. Table 4 Typ ical ope ratin g parameters for t he APE-1236 deactivation fumace Temp. ( ' F ) 1 630 Baghouse t.P ( i n. H,O) 4 Baghouoe I nlet Temperat u re ( ' F) 860 Ki l n Fee d End D raft P ressure ( i n . H, O ) · 0 .2 Ki l n Fee d End T em p em t ure (" F) 375 K iln Butner End Tempe<atute ("F) 1 000 0, - CEM (% ) 1 5 CO(ppm) 8 Stack Tem perature ( ' F) 500 Stack Gas Vel o city (ftlsec) 46 Table 5
. TEAD meta l emission limits du r i ng V8rifleatlon tosting. B ement L imit ( glh r ) Element Lim i t (g/hr) An ti mony 1 4 L ead 4
. 3 Arsenic 0 .1 1 M e rrury 1 4 Barium 2400 Ni c kel 930 Berylli u m 0.20 S elen i um 1 80 Cadm i um 0.26 Silver 1 40 Ch romi u m 0
.04 Thallium 1 4



### VES01 1311ERDCJCERL TR-lls-9



# - Discharge
,.

Feed

# Sta~an .,_ C e ra mi c X

CE M Ba gho u se 

## Top view ofTEAD Incinerator Set up 

# t "'i Stack 

# ,. Front vi ew of TEAD S tack during Samp lin g

XCEM Air flow 

# -

F igure 5
. TEAD incinerator setup and Umpllnglspl k lng l oc.rtions. 13



## VES01131214 ERDC/CE R L TR-05· 9
Expe rim enta l Desig n 

### Both the kiln and afterburner w ere fired wit h diesel fuel for all 13 runs . During t•uns 1 and 2, 50

-caliber bullets were incinerated. The XCEM observed unex · pected high Ph concentrations during these runs, howe ver, which led to a deci · sion not to incinerate additional anununit i on during the test until repairs to a bypass valve could be made. For this reason , no ammunition was burned during runs 3 through 11. Following the bypass repair , two final M.29 runs were conducted w hile incinerating l'vlark 344 fuses
. Table 6 shows the 9 elements that were measw-ed by the XCEM during all 13 of the verification test runs. Eight of t hese metals were spiked directly into the stack downstream of the controls. These metals were spiked at the level shown in Table 6. Lead, however, w as not s piked since the incinerated munitions provide measurable concentrat i o ns of Pb without spiking. Spiking was conducted by MSE- TA using three atomizers to inject solutions con · taining the metals directly into the stack (Figure 6). Manufacturer specifications for the atomizers determine droplet size distributions based on pressur e and ai rflow rate. F or these tests, pressure and flow rate were maintained to keep drop

let sizes Jess than 28 microns in diameter
. W hen dried, the majority of t he parti

cle mass was calculated to be in the 1 t o 4 micron diameter range. An 

### analysis of the M29 concentration data during vali dation testing indicated that 10 to 15 percent of the spiked metal mass was lost on the probe (CHPPM 2001 )
. Tltis level of probe loss i s typical for M29 at an incinerator and, since particulate loss in the probe depends in part on particle size, indicates that the spiked metal particle size was on the same order as a typical incinerator. Tabl e 6 . TEAO incine ra to r metal emission limits and spi k in g leve l s . Emission Limits' Spiking Level ' Elements

- iJ91dscm glhr -iJ9ldscm R uns1-6 Run s 7 ·1 3 As 0
. 1 1 25 14 1 4 Ba 2 ,400 540,0 0 0 200 200 C d 0
. 26 58 3 4 34 Cr 0
. 04 10 5 5 H

g 1 4 3,1 4 5 280 88 N

i 930 209 , 0 0 0 460 1 80 Pb 4
. 3 966 N S NS Sb 1 4 31 4 5 520 200 Zn NR NR 4 60 180 ' The concentration i'l IJ9fdacm a ssu m es a s t&e: k flow rat e of about 4500 dsc mt hr NR: Nol regwled**NS No** **r~ ked**  

### VESOll313ERDCICERL TR.05·9

F ig ur e 6. S p i king at base of stack during validation testing. 

### Three separate solutions were prepared for spike iQjection
. The ftrSt s olution contained arsenic oxide (As,O,) , Cd metal, and chromium oxide (CrO,.) disso lved in 

### a dilute nitric acid solution. The second solution contained mercury nitrate (Hg(NO, ), ), nickel nitcate (Ni ( NO,),), and zinc oxide (ZnO) dissolved in a dilute nitric acid. The final solution conta i ned antimony tartrate (K ,(C,H,O.,Sbl , ) and barium nitrate (Ba(NO , ), ) dissolved in water (Bryson 2001). A total of 13 dual M29 test 

### runs were performed over a 4-day petiod (14-17 May) by the U.S
. Army CHPPM Air 

### Quality Surveillance Program. The M29 trains sampled for 2 

### hr while X CEM data were recorded every 20 minutes and were averaged for comparison to each M29 test run . As 

### a performance audit, two blank trains w e re quantitatively spiked with all nine of the metals. CHPPI\fs Directorate of Laboratory Services ( D LS) conducted laborat ory analysis of the sampling trai n s.
Results XCEM Reported Concen trat io ns T i me-weig hte d a verage con ce ntra t io n s 

### Average XCEM concentrations during the time of one M29 test run were calcu · lated using Equation 1. 1 5



## VES01131416 ERDC/CERL TR-05·9

(Eq 1 ) 

### where: C , = 

### X CEM time-weighted concentration for element 

### i during M29 test run 

# c, = 

### XCEM reported concentration for element 

### i dwing time intervalj n = 

### number ofXCEM measurements during test run 

### t, = 

### number of minutes XCEM measured element i's concentration during time intervalj coinciding with M29 sampling
.**)** 1 = 

### 1';129 sampling period.
Data co rr ect i on s 

### Following M29 testing, but prior to receiving M29 results, CES recalibrated the XCEM and determined that a 4
. 4 percent global change w as r e quired for XCEM reported concentrat ion s . In addition to the recalib rat ion, C ES conducted exten · sive testing of the sample line dryer and detemrined that a 3
. 5 percent correction in flow wa s r equir ed since the dryer did not remove all of the moisture in the line. The net result of these changes was to 

### wriformly increase the reported XCEM concentrations by about 8 percent. Appendix B includes a complete d i scussion of these changes. In addition to 

### the global changes, it was determined that a spectral interference between Pb and As 

### was affecting As conc. entrations
. For this reason, As 

### concentrations were corrected for the P b interference as discussed in Response to 

### Changes in Metal Concentration ( page 25). Arsenic corrections were com · pleted prior to 

### r eceiving M29 data
. The final reported XCEM concentrations are listed in Table 7. Approximately six to 

### sev e n XCEM measurement took place during each M29 run. The "Min. of Run " col umn in Table 7 ref ers to the number of minute s for that particular XCEM (listed as XC in the table) measurement that coinci ded with the M29 run.



## VES011315ERDCICER L TR-Os-9 17

Tabla 7
. F inal CEM concentrations for M29 testing
.

RM XC Mi a . XC No. Dau Start St(lp N().

## R~u T""" 

# ... B• C<l Cr Hg Nl 

# , Sb Za Pd Ru n I 511 4 > 0 1 1 0 : 4 5 II : 05 6 5 0 5
. 0 1 1 9:4 8 .0 20. 8 1 66 27
. 1 3.1 59 34 3

## ::**~** 340 :191 ?4 .1 Run I 5 / 1

410 1 I 1 :0 5 11 :26 6 5 1 2 1.2 1 1 :12. 0 24.3 1 7 1 2 6
. 0 2 .5 1 09 4 3 6 312 316 23 .& kunl 5114101 II :1 6 11 : 4 8 6.52 21.5 21,J2
. 0 21
. 1 1 92 

### u .s 1. 9 1 5 6 467 1
. 1 49 36 1 320 25. 6 ku n I 5/ 1 4. <ll**11 8**  12 :09 6.53 21.7 21 :42
. 0 20
. 7 165 21.8 2.2 207 449 1, 1 % 353 316 25.5 Run I**511 '01**  1 2 :1 0 1 2: 31 654 21
. 7 21 :4 1. 0 25
. 3 U !? 28 , 2 2
. 6 24 2 4 70 1 ,31 9 317 ).42 2 4 .6 Run I 

# ; ;: : :**~:** 1 2:$3 

# :;! 

# z;;**;; ·~** **~:~** 

# ;::! 2 1 8

## ~:~ 2
. 2 25 1 SIS 

## 1::::: 399 372 25 .4 kun I IJ : I S 202 2. 4 283 463 3 86 ).48

_ Hl_ T h u e \\ "• b le<IA> 'O 120.0 I '"2o1 .1 2>
. 6 187 26.9 2.3 194 4 62 l .l40 372 m R unZ l;t4/1)1 13: 58 14 :23 659 1 8
. 3 1 25:09 .0 1.3 230 26.8 2
. 3 1 86

## !~**; ·~** **~~**

## ;~~ 

# :**~** R un2**S/ .~1**  1 4 :2l 1 4 : 4 6 660 22
. 9 12 : 56 .0 3 .5 224 29
. 5 2.0**2~ 4** 

## ~~~ Run l 5 ,1141() 1 1 4 :46 1 5:09 66 1 22
. 9 22 : 56
. 0 

### n .o 249 Z6
. 0 1.2 l« 427 3 98 )52 2 5. 1 Run 2**/1~ 1**  15:09 1 5: 32 (1(;2 22
. 9 22 :54
. 0 2.3.8 25 0 22.3 2. 0 220 405 2.683 37 0 332 25.3 Run 2

## !:::~**: :~:** **~; !:~** **~** 22
. 6 I

## ;~**:~**

## !

## ~~ 29
. !

## ~:! 2 39 4 1 S

### ~~7 379 ).47 25
. 2

# ~ 1 0. 3 27
. 1 25 7 392 348 3 19 24
. 4 ri(hledA'I: 120.0

# ~ 1 6.3**2~** 26Jl u 229 410 1.6 90 375 335 1 Kun > 511411/ 1 1 7 >1}0 17:2>
.. , 10.0 I S
. ) J 27 25.4 3
. 4 2S9 39S 11 8 33 4 3 2<J 2 4 .6 Run ) $114..0 1 11:23 17 : 44 1>61< 21
. 0 2 1:00
. 0 13.1 140 21.3 2
. 1 264 38S 9 1 33S 3 19 25.2 Ro n3**/14.~ 1**  17 : 44 1 8.:05 669 20
. 9 20:5 2
. 0 13
. 0 1 58 2 7.0 2 .5 2 65 417 60 355 34 1 l$.4 Ru n:l :S !I4R) I 1 1'::05 1 1': : 26 670 21. 0 20:Sit0 1.1
. 1 175 2&.9 2
. 9 268 409 5 5 3 6 3 339 Z$
. 1 Ru n.l S IJ.W l 1 8 :26 1 8 :47 671 20
. 9 20 :S3
. 0 14 .2 J 68 21.4 2 .4 255 4 1 3

## ~ 352

## ~; 24. 6 I R

unl 5/14,0 1 1 8 : 47 1 9:07 672 2<J
. 3 I 2<J :5 4
. o 11 .2 1 47 24
. 0 2.3 24 9 4 14 3 60 

# I 2 5
. 9 l n ... ·

# ~'· 8 : 59 I 120 11 :13.1 13. 2 154 24.6 u 2 60 

# .... 73 351 1 Run4 9:18 

# ... 3J 1 19 : 43
. 0 13 .2 1 4S "· 5 4
. 5 3J 2\1'! 

# •• m ZJ> 25.0 Run4 S /1510 1 9 : 1 M 9:39 685 2M 2() : '34
. 0 15
. 0 113**2~..5** 6.2 54 40 1 69 

### m ) 19 23
. 4 Ruo4 $ / I SA} I 9 : 39 1 0:00 686 20.9 20:55.0 1 5.6 133 3)
. 2 5 .4 69 432 66 362 349 24 .7 Runol S/ISJG I 1 0 :00 1 0 :21 68 7 2 1. 0 21:00
. 0 1 6
. 2 154 3 0
. 5 5
. 3 80 4 32 64 371 348 23 .1 Run4 91:sJ0 1 10 : 1: 1 1 0 : 42 68S 2 1. 0 20:58
. 0 16
. ti 1 9 1**~2 .1**  5
. 0 

# .. 4 :1 3 6 4 37 l': 344 

### :s . 1 Ru n4 5 /1510 1 10 : 42 11 :03 689 2 1. 0 211 : 57
. 0 1 5.2 1 45 26
. 6 5. 2 

### ss 4 1 8 55 3 6 1 339 2 4 ,2 

# I R

un4 S/1510 1 11:03 11 :24 690 1 2.3 1 211 : 51. 0 17 .4 1 83 28.5 55 91! 

# .... 45 3 80 366 25.0 h'in>< el•hted A " 1 120 .0 I Z0: 4 L6 15
. 8 161 29.8 SA 76 422 

# • • 361 340 1 Run S $/IS,'() I 12:06 12:21 69 3 15. 6 I 20:Sl.O 1 8 .0 177 31.4 5.5 9 3 440 49

## ~~; m 24 .7

Ru nS 5/1510 1 12:27 1 2:48 6 94 20.9 2Q: S2
. . 0 1 6 .2 172 3J.7 55 97 430 S4 34S 24 .) Run5 5/ 1 510 1 1 2 : 4 8 13:09 69S 2Q. 9 2Q :51. 0 1 6
. 0 1 53 ).4 .4 6.1 10 2 417 52 3 6 2 )39 23.3 Run 5 511510 1 13:09 1);3<) 696 20-8 21) ,4 11.Q 11 .) 1 8 2 33.4 5.3 114 450 47 386 360 2 4. 6 

# f: : !i/ I. W l**1.1 10** 

## :~**:~** 69 1 Z l. O 20 : 57.0

## ~~**~** 35 .8 5
. 1 1 22 449 4 5**~93** 365 25
. 7 S/IS/0 1 1 3 :5 1 698 2 1. 0 I 20:5 9
. o 32.2 $A 1 29 443 38 390 358 25.2.

# ~-**,** 

# ' " " " 1 11 0 .0 111.4 47 38 1 35< I 

## K••• 1>:1> 7 U I 7:! 1 >0:)7.1) 11
. • 

# . 

# .. >1.4 >.4 

### m 4)> 3 9 392 376 2 5. 6 R11n6 S/15.10 1 IS : I S I S,. 1 0 2 2 1.0 ZO :S9.o ll.l Ill 31. 9 5 .4 146 465 3 9 3 86 3 79 2 4 .9 Rmt6 5 / 1 510 1 15;36 I S:S7 7 0 3 2 1.0 2 U :58.

0 1 2 .4 1 6 7 31.4 S
. 4 142 44 3 48**3~7** 362 l 4 .4 Run6 5 1 1 SA.l l 15:5 1 1 6 : 1 & 1 0 4 20. 9 2 U: 56 .0 1 2
. . 9 1 6S 31.3 5 .9 140 4 3 0 47 372 350 l6.l R u n6 5 / 1 5101 16 : 1 8 1 6 : 3 9 105 2 0. 9 2 0 : 5 4.0 14. 0 1 87 ).4 .1 5.3 1 6 8 4 27 3 6 3 8 1 353 2 4 .9 Run6 5/ 1 5101 16 : '39 1 7 : 00 7 06 2 0. 9 2 0 :55
. 0 1 5.2 I SS 32
. 9 55 h \4 442 35 3 89 363 2 4
. l [ Ru"6 S/1 SJO I 17 : 00 1 7 :2 1 707**~** 

### ! 20 58
. 0 13.7 1 64 3 6
. 7**~** 1 66 4 6 2 46 3 8 7 .\69 I 2 s . o A"' 1 120.0 1 2 11<56.7 14.2 170 JU 5 .6 15% 44J 41 384 

# -:-**~** 1 Run 7 511 SJO I 18 : 03

## :~**;**

## :~ II U 1

### zo ss. o 16. 9

## :~ 35 .6 5
. 8

## ~ 

# :;!**!~** 

# : Run7 5 1 1

510 1 1 8: 24 21.0 20: 58. 0 18.5 ).4 .5 6.4 2<.2 Run7 5 /1511l l llt : 45 1 9 : 06 71l 2.1. 0 ZO:SS.o 1 6 .$ 19 1 28 .8 6 .0 120 4 9 1 45 31 1 371 2 5 .3 Run7 .5 1JSIO I 1 9:(1(; 1 9:27 713 2 1
. 0 20:5 9
. 0 1 6
. 1 1 6 8 30.9 5.6 121 459 40 31S 35 9 25.3

# ~ l11511ll 1 9:2?**9~** 114 20.8 2():$ 0
. 0 t6.Z m 30
. 1 5.1 132 419 34 367 m 2 .5
. 9 5 11 s- n 1 1 9:48 20 : 09 115 1 8
. 1 20:41.0 iS .! 159 33.3 5.5 137 436 3 0 379 351 24. 3 

# .. ., . 1 6 .6 Jl.! 5.A m 461 40 3&3 367



### VES01131618 EROC/CERL TR..0$-9

T

able 7 ( Con t' d ). F I NII roport o d X CEM concentrations**~g/dscm )**  for M2 9 testing. RM llo<r Slt11 S O>p X C I M ia. XC Sa C d Cr Nl Pb Sb z. No. No. 

### nmc As u r Pd 

# .... . 

# . ...**~~:** K:
. SI

## :~: 

# :**~! :;~:~** 

## ~;~

## :~~ 1 n 5 52 17 193 1'lO 141 

# ::**~~** 

# ..... 9:11 l U 6.0 20 220 242 1} 4 

# . ... S/1601 9'.J9 10:00 

### n1 lM 20:33.0 165**s** 32.3 5.4 l2 l22 lJI I2S Ill lU 

# ..... Sll601 10:00 10:20 7ll 20.6 lO:JJ.O 1@.0 156 29
. 4 5.3 18 197 199 136 lOS 24.6 

# ..... S/161)1 10:20 10
. 41 

### n9 20
. 4 20:26.0 125 116 l6..l 5 .1 JJ 204 202 m 141 14.4

.... & S/1 601 10"1 11:01 T.lt 20. 4 20:24.0 18 .7 Ill 32.7 5.7 36 116 :!26 I J.I ISO 2 4 .) I R...I S/16.01 11:01 11:22 731 u 1 2<>.30.0 17.1 162 32.4 5. 7 

# "' 226 21 4 14 1 ISO 23.9 tn
... 

# "" ' 12 n.J ; ZD :29JI 17.J 1
.. I Jl.S 

# ... 27 ZI O 

### m 1 .14 1
.. 

### I
...... 

# ::::: II:Al ll:Ol 

### m 7.1 llklS.O 1 21.1 Ill lll.l 4 .5**~** 210 190 136 147 25
. 0 RIOl9 ll :OJ 11:2) 7)4 20.4 21k26.0 1 4 .8 170 32.1 5
. 6 

### so 20 1 170 !l9 1 4 1 

### 2 • . o RWI9 S l i M) I 1 2:2) 1 2 ;.&4 'Ill 20. 4 2<>.21.0 I U**~~** J0
. 7 5.3 4 9**~** 162 1 4 2 1
.. 24
.. 1 Run9 S I I MI I 1 2:44 1 3 : 04 

## n• 20.3 20: 1 $ .0 1 6.6 2()6 35.4 6.5 56 

### m 191 I S4 

# " ' 24.9 Rwt 9 lllii<U I IJ : 04 1 3:.25 737 20,4 20 .24
. 0 11. 0 14 3 3 1.1 l.l S4 liS Il l 145 145 24 .7 Roo • l/ 1 11<0 I l l:ll l l : "-1

## ~:

## ~~**:~~: ~**  I M 1 )3 2$.8 5 2 59 200 I5J 145 144 24 .5 

### I Ri m ? 51 1 11<0 I 1 ) > 45 14 : 05 1 6 .0 l S I 19
. 1 5
. 2 60 11 8 155 14 8 143 25.1 lnm r 

## W ri' '"' • An l !O. t ZA : !2. 7 17
. 1 s .s M 2!0 1 66 145 I" Run 10

## : " :"' 6 15 : 0 7 7 4 2 17
. 2 20:24
. 0 1 9.2 1 56 3 4, 7 6 .0 9 1 Z I O 146 14 3 

# .. . I''·' R

u n 1 0 15 : 0 7 15: 27 74) 20 .4 20 : 2 1. 0 21.) 1 87 37. 0 5.4 8 9 11 6 261 I S4 1 5 1 2 5
. 6 R

un 10 !J I M! I 1 5:27 15:48 

# ' "' 20.4 2<) : 23. 0 1 7.0 141 32.5 5
. 4 81 1 92 liS 1 34 1 33 24.9 A: un 1 0 !/16/0 1 15 :48 16: 08 1 45 20.3 20: 1 6
. 0 1 7 .1 1 9 2 31. 6 5.4 9 1 203 1 34 146 1 4 9 25
. 6 R

un 1 0 Yl 6t1'1 1 1 6:0 8 1 6:2 8 7 4 6 l OA 20:2 1. 0 1 7
. S 1 6 1 36 .2 

### s s 9 5 208 10& 1 6 3 1 45 24.2 R

un 1 0

## ~~**:** 

# : : :

! : 1 6:49 

# ' " 20.3 20:20
. 0 1 & 3 1 6 7 30
. 9 5.6 9 5 103 9S 140 131 24 ,7 I R

o m i O 17 : 09 14 8 1. 2 20 : 10
. 0 1 2
. 7 1 39 29
. 9 5.4 1 09 1 86 11 0 151 1 37 I 24 .s

# "··**·~ ·** **0. 0**  20:10
. 7 18.5 1 67 33.8 

### s.s 

# " 106 143 147 143

### ~33 20 : 1 1. 0

## ~

## ~**~~ ~** **~**

## ~~**;~**

## :~**~ :~** **;~ ~** **:::: ::**  S/16 .4)1

### ~:;;**;: ;~** **~~ ~**  20: 1 8 .0**~u:n** II S/ 1 610 1 1 8:12 11 :33 752 20.3 20:20 .0 1 5 .S 170 29.3 53 9 5 204 104 14 1 1 4 5 24
. () R'un II 5 1 1 610 1 11:n 18 :S3 

### m 20 .3 ZO ; I I.O 1 6.4 1 78 3 0.2 S A 9 5 192 9 1 147 l l i 25
. < Ru n II SJ10ir )l 11:5) 1 9:13 754 20. 2 20 ; 1 2
. 0 1 7
. 3 I l l 2 6
. 4 5 .8 96 1 9 1 89 147 1 4 1 l4
. R R

lll'lll**~1 6/fll** **:ll** 1 9 : :14

## ~~!**~;** 2(); 1 2.0 17 .2 1 61 32.J! 

### s.s

## ~ :!il l R 9 l oll 146 24
. 9 Run II 5 / I MII 1 9::14 1 9:$4 20 : 1 7
. 0 ll
. O I ll 33.2 4 .6 211 96 147 145 1 24
. 0 TIN •**I~**

## ~ 1 6. 2 1 63 31 .2 

# ... "
. lru**~** 145 !4 J

" """ 11 : 12 11 :3 2 710 13.0 17
. 8 Ji 4 26 5**~** 

# .. z •

## ~: rro 

### m 

### m I

## i~**:** R

un 12 li 17101 II**~2** 11 :52 71J 20
. 1 20:08.0 11.2 1 95 23.2 4 .2 )$ lJ2 159 1
.. Rom 12 5111101 II :S2 12 :12 712 20
. 2 10:14.0 20.S J: .o 30.5 4.3 55 

### m 213 165 

### m 25.) Rnnll 5111101 12:12 12:)2 713 20
. ) 20:16.0 16.7 226 l U 4 .0 13 221 204 IS& 161 25.4 RDI112 lil1101 1200 ll:Sl 

# , . 20.1 20:11
. .0 11. 4 1 53 3 J.7 

# ... 79 206 161 IS& 151 14.1

. ... 12 5111101 1 2 :5.) ll : ll 

### ns 20.2 20:11..0 12.3 m

## ~· 4,5 ltl 2(14 Ill! ISS 14 1 

### z ... .

.... 12 5111101 ll : ll ll:ll 716 6.0 20:010 . 14 1 ISO 28.2 4
. 1 86 191 140 ISS IJI 1 26
. 0

'l'lo
... '**~·** IH JI lC>. I O.I 11
. 0 1 8:2 17.5 u 

# ., 2 11 1 9!1**I~** I.e!
..., u 14 : 1 4 14:34 

### m**~~,**

## ::~~ 

# ::;**~~ ~;** 

## ;~ 

# :**~; I~** 

## :~ 

# ::**I~** ... u 5111101 14:34**14 ~**  7 80 1-

- 13 S /17101 1 4SI 15 : 1 4 711 20.2 20:090 

# "" IS9 36.1 6.1 82 lll 117 1 61 149 25
. 0 Run 13 5117101 IS : I 4 IS:l4 782 20.2 20: 1 0.0 10.3 140 33.1 5.8 83 212 111 110 ISO 2ll R• 13 lil7>01 IS"$**IS~$** 7&3 20.2 20:11:0 11.J 196 .:0.1 S.9 

# "' 113 129 1 69 111 

# , 

# ... R\W\ 1l S/ 1 1101 U:SJ I &:IS 7 14 20.0 20:il2.0 19.2 165 39
. 1 6.0 7< 17D 121 1 66**2** 2.5 I R'"' 13 S/11101 16
. 15 16 .3S 7 15 ll
. l 1 19:57.0 8J 94 18 .7 4 .0 <6 70 IS 

### n 12 ilH


# .... . l l lt
. O l
. l
... H ISA 165 >4. 7 5. 6 7l 1 86 11 6 1 59 Il l



### VE S O11 3 17E RD CICERl T R-05-9
Sa m p lin g an d Res pon s e Ti me 

### The X CEM met PS

- 10 sampling a nd respon s e ti me criteria for a batch CEM. These criteria are that (1) the sampling time be no longer than one-third of the a veraging period for the applicable standard, (2) the delay between the end of the sampling period and reporting of the sample analysis shall be no greater than 1 hour, and (3) sampling is t o be 

### continuous except in that the pause in sampling when sample collection media are changed should be no greater than 5 percent for the averaging period or 5 minutes, whichever is less <EPA 1996 )
. Exhibiting no mechanical problems , the XCEM had an effective up-time of 100 percent during the 40 hours of verification testing. The XCEJI.-1 sampled continu

ously except for a 4-second period between each 20-minute s a mp le run when the filter tape was moved to a new analysis position. X C E M results are 1 · eported immediately after each 20

- minute analysis resulting in a 20-minute response time between the end of sampling and reporting. Z

e ro en d Ca li b ra t i o n D rift 

### The XCEM has automated daily zero and upsca le checks and reports a Pd concentration with each sampl e to test for calibration drift
. To determine the zero check, the X CEM measures an une xpos e d region of the filter tape. Following the zero check, a plunger is extended into the an alysis region
. T he tip of the plunger contains C r, Cd, H g , and Pb embedded in a resin. Anal y sis of this spiked resin provides an upscale che ck for the XCEM
. Zero and upscale checks were conducted on each of the four test days with the results shown in Table 8
. S ince the zero and upscale checks are evaluations of mass measurements , they are reported as mass per unit area on the filter (pg/s pot). Equivalent zero and upscale concentrations in micrograms per dry standard cubic meter are also shown in Table 8 and reflect the typical sampling rate of 16 L per spot. Zero values determined during the TEAD test indicate no measurable blan k bias in t he mass measurement. The XCEM detection limits for C r, Cd , Hg , and P b are 0.75, 3
. 0 , 1.0, and 1.0 pg/dscm, respectively. The XCEM zero values were be

low t he detection limits for Cd, Hg, 

### and Ph and only slightly higher than the Cr detection limit. The upscale check indicated good precision for the high concent.ration mass m e asurem e nts . The pre cision ove r the 4 days was les s than 1 percent for Cd, Hg, and Pb and about 2.3 percent for the Cr. 19



## VES 0 1131820 ERDC/CERL TR.05·9

Table 8 Upscato and z ero concentrations during validation testing Upsca le Valueslual**~o** Values lu o\ 1 Dat e 

## I I I I I Ha 

### I C r Cd H g Pb Cr Cd Pb 5114/01 5
. 23 156 27
. 6 30
.4 0
.012 0
.046 0.008 0
.008 5115/01 5.53 158 28 .0 3 0
. 9 0
. 016 0.042 0.008 0.008 51 1 6/01 5.45 1 56 27
. 9 30.S 0
.014 0
.024 0.01 0 0.008 5117/01 5.42 1 56 27 .9 30
. 6 0. 011 0
.024 0.005 0
.023

Avg
. 5.41 1 57 27.8 30
. 7 0
. 0 1 3 0.034 0
.008 0
.0 12 

## so 0
. 13 0.74 0
. 1 8 0
. 23 %RSD 2
. 33 0
.47 0
. 65 0
. 76

Date Eauiv. Upscale V alues**(~g/dscm)'** Ea uiv. Zero values I UQ/dscml 1 " Cr 

### I Cd 

### I Hg 

### I Pb Cr 

### I Cd 

### I H a 

### I Pb 51 1 4/0 1 327 9, 765 1 ,724 1,898 0
.75 2.86 0
. 50 0
.4 7 51 1 510 1 346 9,850 1 ,750 1, 931 1.01 2.65 0.5 0 0.50 51 1 6/0 1 34 1 9, 772 1 , 742 1, 925 0
. 85 1. 50 0.63 0.50 5117/01 339 9,744 1 , 746 1, 9 1 2 0
. 6 7 1. 50 0
. 29 1.42

Avg. 338 9,783 1 ,7 41 1, 917 0
. 82 2 .1 3 0 .48 0
. 72 

## so 7
. 88 46.14 11.25 1 4.64 %RSD 2.33 0.47 0
. 65 0
. 76 1) Gray values were noodet ects . N ondetect t reated as one-hal f of Det ection Limij, 2) Equivalent concentrations determined usi ng 16 liters per sample . SO = standa rd deviation ; RSD = relative standa rd devi ation 

### Palladium, which is 

### measured with every sample , also displayed good precision over t he 4 days of testing (Figure 7). Overall, the Pd concentration had a preci· sion of abo ut 2.5 percent with all 113 measured Pd concentrations lying within 6 percent of the ave1-age concentration. Analysis of the Pd concentration trend in Figure 7 indicates t h at no significant drift occurred. Over the 4-day test period, the average Pd concentration changed by less than 1 

### percent with no observable trending occurring
. Correlation with Reference Method 

### The comparison between the XCEM and M2 9 concentration measurements are shown in Figure 8. In thi s figure the dashes represent the M29 concentration over the samp l ing period, while the diamonds repres ent the individual XCEM measurements. The degree of correlation between the XCEM and M29 is 

### shown in Figure 9 and Table 9
. Five metals ( Ni , Pb, Sb, Zn, and Hg) were present in the stack gas at varyi ng concentrations. Of these elements, Ni , Sb, and Zn showed correlations of 0.95 or better. Lead shows a high correlation of 0
. 997 for all 13 

### runs, but a correlation of 0.76 for the 11 runs in which Pb concentrations were used for RA comparisons. Mercury did not show a high corre l ation between t he two methods
. 

## VES011319EROC/CERL TR·05-9


## PaUadium 30 

### 29 28
. 

# :g 27 26

# ~¥.; 

# :Sii it#. .; 

### 25 

# = Q 

### 24 

# c u 23 

### • 22 2 1 5/1 4 /0 1 5 / 15 /01 5/16 / 01 20

7:00 1 5:00 23:00 7:00 15 : 00 23:00 7:00 15: 00 23:00 Average Palladiu m Effective Concentration

- One SO from Avg. Pd Con centration

- 5% from A vs;. Pd Con centration F'sure 7 . PaJia.dium concentrations d-ur ing M29 testing. 

# i

5 / 17 / 01 7 :00 1 5:00

Unlike the other elements, the XCEM Hg concentutions were consistently lower t han M29, but by a variable amount. During the early runs for each day , the XCEM reported low concentrations relat i ve to M29. As the day progressed, t he XCEM Hg concentration would gradually increase until it approximated M29 r e ported concentrations. Thi s same increasing Hg concentration trend was ob · served on each of the four test days (Figure 8 ). 

### Jt is believed that the Hg was lost during transport from the stack to the XCEM. The M29 samples were collected next to the stack and were n ot transported t hrough a long sample line a s the XCEM samples were. The TEAD incinerator was shut down each evening and started in the morning 1 hour before validation t esting. Consequently, the transport line, which was insulated but not heattraced, was cooler during the early runs. Som e research indicates that Hg can be l os t to a stainless steel surface at low temperatures lliall et 

### al. 1990; Wang et al. 1983). ln the l aboratory , the XCEM was tested wi th oxidized Hg and met wi th good success (Hay et al. 2005). The la boratory tests, however, were conducted at elevated line temperatures. It 

### is recommended t hat a shrouded probe and heat· traced tubing be used to overcome potential Hg transport problems
. 21



### VESOI132022 EROC/C ERL TR-05-9

45 Cadmi um 40 

# - a 35 

## • 

# •

# :~ ... • 30 

### •

# ~ l S 

# oo;-..;:.z • t •**~** 2U 

### • 

## • 

## • • 

## " • 0 I S 0 u l fi 

### • S · 

# .. 

# .. • 0 1 :00 I S :OO 23:00**.** 1 5 :00 23 :00 1<l<l JS :OO 23 : 00 

### roo l5:00 5 ;( 410 1 S / 15 1 0 1 i/ 16/0 1 511 7/0 1
8 Chromiu m 

## ' 

# a • ·- :r 

# -.. 6

### ~~**':/1): .,~**  

# i ' !tl.*hi# " 

## •**~** 

## • •**~ ~**  4 

# --- .; J

### ~ • 

## • • l u I 

# - • 

## • 0
. 7 :00 I S:OO 23 :00 7 :00 1 5:0 0 .!3:00 7: 00**~: 00**  23 :(1 1) 1':00**1~: 00**  i/ 1

4 i0 1 5 ! 15 {()1 5 11 6/0 1 5 / 1

7 .'

0 1
600 N ick e l 500 

## a**~'+** 

### . ... . 

## • 

# ....**~ ~**  400**~** 

## • 

# . 

# · - .:; :lOO .; lOO**~** 

### ... 

### • 

# - · d 

## • 1 01) 

## • • 

## • 0 

## • 

# .. 1: 00 IS:OO 13!00 1!( 1(1 IS!OO tl:OO 7: (1() IS: OO l);OO 1: (10 15; 00 511 4/0 1 i/ 15/0 1 i/ 16/ 01 S l 17i01
4
.000 Lead 3.500 

## a 

# - 3,000**~** 2,500 

## • 

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. (J() 1: 00**1~ ()**  5 11 4 1 01 5115 1 0 1 5i l 610 1 5/ 1 7 1

01 Figure 8
. XCEM a nd M29 concentrations duri ng TEAD verification t asting.



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. XCEM and M29 concentrations du r ing TEAD verlflcaUon testing
. 23



### VES01132224 ERDCICERL TR-05-9

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. 

## V ES0 1 1323ER OC ICE RL TR-05-9

Tab l e 9
. Co rr el a tion b e tw ee n th e XC E M an d M29 Corrol aUon (R') Correl a H on ( R' ) Sp i ke Rati o 2 E le m . H lah Runs: L o w R un s (1 3 R un s ) (11 Runs ) 1 M S E M29 XCE M Ni 0
. 9482 0
. 9753 2
. 57 2
. 52 2. 1 2 Pb 0.996 6 0.7 6 23 N S N S NS S b 0.9 609 0.9682 2
. 52 2.56 2.5 1 Zn 0
. 9 7 6 6 0. 97 38 2
. 57 2. 54 2.50 H

a 0 .400 2 0
. 3526 3
. 09 3 .11 2. 1 7 N S. Not sp 1 k ed 1 Ru n s 3 through 1 3 2 Hi!;fl runs are runs 3-7: low n.ms are r u ns 8 ·1 3 Res ponse to Ch an ges i n M e t

a l Concen trati on MSE-TA spiked Ni, Sb , Zn , and H g at two distinct concentra tion l evels. The theoretical ratio, based on spiking, between high and low concentra t ion runs ranged from 2.52 for Sb to 3.09 for Hg (Table 9). Since these four elem e nts are typically not found in the stack gas in signific an t qu antit i es , i t was expected that the theoretical ratio would be measured by b o th the M29 and XCEM. Except for the XCEM Hg concentration s, both the XCEM and M29 ratios were in very good agreement with the the oretic al ratio of concentrations. T hi s agreement, along with the high correlation coefficients, indicates that the XCEM was precisely and consistently measuring Ni, Sb , Zn, and Pb and was responsive to changing concentrations
. 

### In addition , the XC EM 's respo n se to change s in the Pb concentration, which changed by almo st t wo orders of magnitude, was consi
. stent with the M29 results illustrated in Figure 8. Re lative Accurac y Table 10 shows XCEM , M29 reported concentrations , and MSE-predicted spike concentrations. The RA of the XCEM with respect to the M 29 was determined using PS-10 criteria. Of the 13 M29 runs, 11 were used to calculate RA and a verage con centrations
. During runs 1 and 2, the incinerator experienced problems with a faulty bypass valve, which led to extremely high Pb co n centrations (1,000 to 3,000 pg!dscm)
. Although the XC EM tracked the problem , a n d was in fact used to identify and rectify the problem, it was not fe lt that these conditions represented the typical operating conditions of the plant. For this reason, runs 1 and 2 were not used to calculate RA and average concentrations. Since 11 valid reference m ethod test r uns were completed, the RA procedure stated in PS-10 allowed for omission of up to two additional runs f ro m the RA calculation
. Table 11 shows the RA for all 11 rnns and the best 9 runs. 

### In general, with the exception of Pb, the omission of two additional runs did not significantly affect RA calculations
. 25



### V E SOll324

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Cone. C one.**(~gldscm)** . (u g ldscm)

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. 4 1 3.6

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## I ( 9 Ru n s) 1 0 8 Met RA cr i t erion
. 1 9 1 5 Met RA cr i t erion
. 1 1 1 1 Met RA cri t erion
. 45 22 3 9 37 Spi ked wllh Sb. XC I s con si sten ll v low
. 58 55 Sp i ke d w llh Ba. X C is consist efl tl y low, 37 35 P o ten t ial ca l i brallon erro r. X C i s consis t eniiY l ow . 55 48 XC had correcta b l e Pb in t

e rl e rence f or As. Consistent pattem of 78 68 increase t h roughout d ay until c oncentration aPIJ(OSChes M29 val u e .



### T he XCEM and M29 reported concentrations for C d , Cr, 

### and Ni are in good agreement. The average XC E M concentrations for these three metals w e re 31, 5.2 , and 309 pg/dscm, respectively, while the M29 average conc e ntrations were 33, 6.0, and 354 pgldscm
. The high correlation between the tw o met .hods is reflected in the low rel ative accuracies of 10 percent for Cd , 19 percent for C r , and 11 percent for Ni. All three clements would have met the RA requirements of the draft PS-10. The RA for Cr would have been significant ly impro v ed if not for a high bias in the M 29 resul ts due to protocol assumptions and high analyt i cal uncertainties in M29 back-half concentrations
. E PA M29 protoco l requires the assumption that the detection limit be used fo r the concentration when the concentration is in fact below the detection limit. In 

### most cas es, the detection limit is low rela t ive to the me a sured concentra tions. In 

### the case of Cr, however , it is almost 20 percent of the total Cr found in the M29 sample train. 'ZI



### VESOll32628 EROC/CERL TR.05 · 9



### Le ad The a verage reported XCEM Pb concentration was 110 pg!dscm for runs 3 through 13, while the average M29 concentration was 91 pg!dscm
. In general, the XCEM and M29 concentrations were in good agreement. O n 16 May , how· ever, both the XCEM and M29 methods reported higher Pb concentration at t.he start of the day t . han was observed on 15 May. The XCEM reported a consistent gradual decline in concentrations throughout the day while M29 showed a more rapid decrease in concentration (Figure 10)
. Although the average XCEM and M29 concentrations differed by only about 2 percent for runs 3 , 4, 5, 6, 7, 8, 12, and 13, th e large diff e rence found in run s 9, 10 , and 11 wa s enough to raise the RA from about 14 percent for these 8 runs to almost 45 percent for all 11 run s . PS

- 10 allows for 2 of the 11 runs to be dropped. This would have given an RA of 22 percent for t he XCEM Pb concentrations. It is not known why the XCEM and M29 diffet·ed on 16 May. The XCEM was able to rapidly transition from much higher concent ratio n s during the first two runs t o a muclt lower concentration during the third run on 14 May and was i n good agreement with M29 for the third run on that day. The 14 May XCEMI!'vi29 comparisons indicate that the XCEM is responsive to rapid changes in Pb con · centration and is resistant to sample line contamination, while M29 data showed good precision and QA/QC for 16 May
. The XCEM has histor ically measured Pb accurately with RAs below 20 percent during the MSE · TA test (Bryson 2000) and the laboratory tes t in 2000 ( Hay et al. 2005).
500 45 0 

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# -·- · · ••• R un 9 -- Ru n 10 Kan 11 9 : 36 12 : 00 1 4:24 16 : 48 19 : 12 21:36 Flgure10. XCE M and M 291ead concentrat ions during ru ns 8-11.



### VES011327E ROC ICERL TR-05-9

Bari um and antimony 

### Barium and antimony were spiked in the same solution and exhibited simil ar behavior d u ring M2 9 testing. For both metals , the av e rag e X CEM concentra
tions were significantly lower than the M'29 reported concentration (30 percent lower for Ba and 40 percent lower for Sb )
. The XCEM to .M:29 ratios for Ba and Sb wer e 0. 7 0 :1: 0.08 and 0.59 :1: .06, respectiv ely ( Figure 11). The consistent difference in concentrations is reflected in t he XCEM a nd M29 

### ability to measure Sb at t w o concentration levels. , Antimony was spiked at two different levels that were 

### theoretically 2.52-fold different in concentration. M29 measured a 2.56 fold difference between high 

### and low Sb concentrations while the XCEM showed a similar change with a 2.51 ratio. The X

CEM and M29 Sb correlation is 

### reflected in a high 

### R ' value of 0 .96 for their correlation plot ( in 

### Figure 9). The average M29 reported concentra tions for Ba and Sb were 240 and 429 pgfmS respectively, w hich is more than 20 percent higher than the predicted maximum stack concentration based on stack spiking (Table 11). 

### The X CEM Ba and Sb concentrations compared favorably t o the MSE-predicted concentrations. The XCEM has an 

### RA of 

### less than 20 percent for Ba when compared directly with the MSE

- predicted concentrations. The differences between the XC E M and predicted concentrations are b e lieved 

### to be due to particulate loss in 

### the unheated XCEM transport line an d calibration errors . 29



### VESO!l32830

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. R atio of X CEM to M29 concentrations duri ng valida ti on t ostlng.



### V ESOl l329EROC/CERL TR.OS.9


### Zinc Like Ba and Sb, the XCEM Zn concentrations were consistently lower than the M29 concentrations by about 30 percent. XCEM Z n concentrations were highly correlated with M29 (Figure 9 ) with an R' value of 0.98. Zinc was spiked at a high concentration level for runs 1 through 7 and a 2
. 57 fold lower level for runs 8 to 13. The XCEM was responsive to 

### this difference showing a 2.50 concentration multiplier between the average high and low con centt-ations, which is in good agreement with the M29 ratio of2
. 54
. Unlike Ba and Sb, however, the other e lements spiked with Zn showed no indication o f uniform loss during transport. Nickel met the PS-10 RA requirements and XCEM Ni concentrations were slightly higher 

### than M29 Ni concentrations. Mercury, as discussed earlier, had potential transport problems to the XCEM under cooler conditions but was approximately equal 

### to M29 concentrations for 4 of the 11 runs. Since the elements spiked in the same solution with Zn did not show systematic loss during transport, it is believed that the low Zn concentrations are not simply a function of transport problems. CES calibrated the XCEM using thin film standards produced by MicroMatter Inc. (Deer Harbor, WA) and a select few National Institute of Standards and Thchnology (NIST) traceable standards
. During calibration, the NIST standards and Micro Ma tter standards did not agree for Zn. A decision was made to use the NIST standard, which produced significantly lower reported Zn val ues . Following testing, it was determined that the NlST Zn standard is not in agreement with the NIST Cu standard and may be incorrect
. It is believed that the Zn differences are primarily a function of this calibration error. Use of the MicroMa t
ter calibration standard instead of the NIST standard would have given XCEM concentrations about 15 percent higher. Ars en i c 

### In general, the XCEM As concentrations were consistent ly higher than the predicted (spiked) and measured M29 concentrations. During M29 testing, it was observed that Pb concentrations were highly correlated with As 

### (Figure 12). Since no significant 

### As was expected in the background stack gas concentrat i on and the As 

### was spiked at a constant rate, the observed correlation was determined to be 

### due to an XRF spectral interference. Arsenic concent rations are es · tablished using aKa line, which is overlapped by the La 

### line of Pb. For this 

### reason, in XRF analysis, high Pb concentrations can interfere**"~th** As 

### measurements, alt hough the reverse i s not true. 31



### VES01133032 ERDCICERL T R-05 · 9



### As a first cut , the interference impact was estimated using 

### the simple linear regression shown in Figure 

### 12. That is, 

### about 5.4 percent of the Pb concentration was being added to the m easured As 

### concentration. CES adjusted the As 

### numbers accordingly prior to receiving M29 data. Even with this first orde r ad j ustment. the X CE.M final reported As concentrations were still higher than the M29 and predicted concentrations with 

### the greatest deviations occurring during high Pb runs . Overall, the average final reported XCEM concentration was 16.3 pgldscm while the average M29 concent r ation was 11 .3 pgldscm
. Since the 

### XCEM saves each XRF spectru m , it was possible to review individual spectra and adjust for tho AsiPb interference using 

### a second spectral resolution approach. 'l'his task was completed after receiving the M29 data for runs 8 through 11 on 16 May. These adjusted XCEM results based on this second spect ral analysis appro•tch were within 4 percent of the M29 results. lt is believed that a change in 

### tho spectral resolution approach will resolve the 

### PbiAs over l ap problem. The XRF can be calibrated using a variety of method s that will take into account the Pb/As interference. For example, during the fall 2000 tests, a calibration method was u sed that contained both arsenic and Pb. No As/Pb interference was observed during these tests (Hay ct a!. 

### 2006 )
. 200



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500 I ,000 1 ,500 2,000 2 , 500 3,000 3,500 XCEM L e:td Con<. (Jil: / m') Figure 1 2
. Uncorrected XCE M As concenlnrtions versus XC EM Pb conuntrations.



### VES01133lERDCICERL TR.C5·9
Mercury As discussed earlier, the X CEM to M29 Hg ratios varied from run to run. At the beginning of each teat day, t h e XCEM reported l ow Hg concentrations relative 

### to M29. As the day progress e d, tho XCE M concen tration woul d gradually increase until it approximated M 29 r eported concentrations. The pattorn b-uggcsts that the transport line from the stack to the X C EM needed 

### to be heated to a higher temperature 

### to improve transmission efficiency. Th e use of a hea t-traced trans· port line should improve Hg tTa n emission efficiency. Interestingly, more than 98 percent of the Hg measured by M29 passed through the filte r and was coUected in the back half of the sample train indicating that the vast majority of the R g was in the vapor phase. Since the**XCE~1** had good comparisons 

### to M29 on at l east four run s { 3, 10 , 1.1, and 1 3 ), the test indicates that the XCEM was able to e fficiently trap and measure Rg as a vapor. Precision Precision was ca lcula ted in te rm s of the percent r elative standard d eviation (RSD ) of a series of XCEM measurements made during rel ati ve l y stabl e opera · t io n of t he TEAD incinerator, with metals injected at a rela tivel y co n stant rate . This precision reflects not only the X CEM variability , bu t also t h e variability in t he stack concentrations, spiking rate , and flow vari a bili ty . Method 29 dual sample train precision During testing, CHPPM ran dual M29 sampl e 

### trains. Percent d ifferences be· tween the two trains are shown in Table 12
. OveralL the average metal concen· tration agreement between the M29 trains was about 6 percent ( CHPPM 2001 ). Thjs r esult i s significantly better tha n the typical agreement between trains, which is on the order of 15 percent ( EPA 1999). This better-t han -typical agreement indicates tha t M29 sam pling and analysis were con ducted in a preci s e manner. M ethod 29 vs . XCE M precis i on The s pike inject ion rate was altered on t he first day of testing , 1 4 May , to ensure spiked emiss ions were within the site permit limitations
. On 17 May , stack oon· ditions were not stable following stack r epairs. However, MSE-TA an d TEAD reported reasonab ly stab l e conditi ons on 15 and 16 May and the spiking preci · s i on was estimated at 2 percent. For this reason, the eight runs on 1 5 and 16 May were used for precis i on calculations. 33



### VES0ll332ERDC/CERl TR-45-9

The average M29 and XCEM precisions for the eight spiked elements on 15 to 16 

### May are listed in Table 

### 13. The average 

### M29 precision for these runs 

### was about 6 percent, while the XCEM average precision -...-as about 10 percent. T he XCEM preci sion, however, was heavily influe nced by the highly variab l e H g r esults. For the non-Hg elements, the p recision of the XCEM W8ij 3
. 7 percent, whil e the average M29 precision for the same group of elements waa 6. 8 percent. The 

### XCEM als o measures Pd wi th every sample
. 

### Th e average 

### XCEM Pd concen · trati on was 25 :t 0.6 pg, which gives a precision of about 2.5 percent. Palladium concentrations reflect XRF precision , but are independ ent of fl ow, s piking, an d sampling variability
. Overall then , tho XCEM p e rformed i n a ver y con sistent manner and exhibited precision on the same ordel· as or slightly bette•· t han M 29 for al
. l elements ex cept Hg
. Table 12. Percent dlffe,..ncao between M29 sample trains. ' Run As 

### 811 Cd C r H g 

### Ni Pb S b 

### Zn Avg. % Diff I 

### 9 

### ·6 ·2 7 

### 2 3 

### -19 -4 

### -9 7 

### 2 I 

### 15 9 

### 5 

### · 3 0 0 - 1 · I 4 3 

### ·2 · 5 0 8 

### 3 .) 11 

### 1 

### 5 4 4 

### -2 

### -6

- 8

- 26 

### 3 -5 5 -4 

### -2 7 

### 5 

### -9
- 12


### - 6 -1 5 I -II 

### -3 

### -II -9 

### 9 6 0 -8 I 

### 0 0 

### -2 

### 6 

### -9 -5 3 7 3 -8 

### -3 

### -2 0 -6 -I 

### -9 -7 4 

### 8 I


### - 3

- 5 -4 

### 4


### -9 -14 

### - J I



### - 10 7 

### 9 6 

### -8

- 3 

### 1 2 

### 0 

### 9 7 3 

### 7 6 

### 1 0 0 

### 6 -5 -5 -2 II 

### 2 

### 5 5 5 11 

### -4 -3 

### -5 -5 -I 

### -10 -I 

### -10 -13 

### 6 12 6 

### 14 

### 8 

### 8 0 II 

### II 

### 5 12 

### 8 

### 13 -2 -14 -1 

### -I I -II 

### ·2 -14 -9 

### 6 Avg.% 4 

### 8 4 

### 8 

### 2 7 

### 6 7 7 

### 6



### Dlff
. 1**A\•er~ ~**  d l lr"rence is dttwmiaed b y**·~i.nc** Lbe**~t.bso!ute** vfllll e ul tbtl dill' t- h!noo beL 'fiooll llllnl l lle tra.ics.



### VES0113 3 3ER
. DC/CERL TR.Os-9

Table 13 XCEM ond M29 precision. 

### Elem. 1\119 Avg
. Ml9 Co n e. !\ U9**~. A~-g.**  XC Co n <. XC % RSD R un s 

### {l!gf d K
. m) 

### RS D ( Jl gf d scm) (B y Run ) As 4-11 12 2
. 3 16 

### 76 

### Ba 4

- 11 247 9.4 165 5
. 2 

### Cd 4-ll 34 

### 2.3 32 4
. 5 Ct 4- 11 

### 6 5
. 1 6 

### 2
. 6 Hg (high) 4-7 211 0.2 

### 92 3 5 .4 HI!; (low) 8-11 103 1.9 67 48.4 

### Ni (high) 4-7 457 6
. 5 438 

### 3.6 Ni (low) 8

- ll 183 10
. 1 207 2
. 0 Sb (high) 4-7 669 6
. 1 

### 375 2. 9 Sb (low) 8·11 246 9
. 0 143 4.2 

### Zn(high) 4-7 500 

### 7
. 2 35 4 3.4 

## Zn (low) 8-11 197 9
. 2 144 1.2 Avg. (All • lem. ) 5
. 8 1 0. 1 Avg.**(No ~)**  6
. 8 3.7 L ow -Level Me tal R e . sponse 

### Low-level mota! response was detennined 

### by comparison of M29 and XCEM· reported Cr and As concentrations. Neither of thes e e lements is found in signifi

cant quantities in 'rEAD stack emwions and both 

### are regulated to 

### low 

### Je, • els onder t.be**si~based** 

### RCRA limitations. B oth elements were s piked as particulates by 

### MSE- TA at low concentrations with typical Cr 

### stack concentrations in the 5 Jlg/dscm range and As 

### in the 14 pg/dscm range . The X CEM accurately measured Cr relative 

### to M29 with on RA of 19 percent . ' rhe average X C

EM Cr concentration was 5.2 :!: 

### 0.9 )lgfm' 

### while the 11129 average w as 6
. 0 :t 

### 0
. 8 pglm • . The M29 concentratio ns reported the detectio n limit fo r the back half when no Cr was measured, which 

### occurred for more 

### than half of the samples. Since the M 29 back half detection limit was about 0.5 

### Jlglm •, the M29 

### concentrations were biased high by at least 10 percent. Correction for the M29 back

-half detection limit improves the RA to 

### b ette r th an 1 0 percent. T h is consis· 

### tent agreement between the two methods demonstrates the 

### capability of the 

### XCEM 

### to m easure metsls at low concentrations even in th e presence of high 

### con· centmtions ofinterfering elements such as Ba
. As discussed 

### earlier, the XCEM As 

### concentrations were biased by Pb interference. For this reason, the X C E..l\1 A s concentrations w e r e routinely highor tha n the M29 concentrations
.



### VES01133436 ERDCICERL TR-o5-9



### B ias Bias between the two M29 sampling 

### trains and the M29/XCEM data 

### was**de~r ·**  nrined using an EPA l\fethod 301 approach ( EPA 1992). The results are tested for statistically significant bias by calculating the t ·statistic and deternrining if the mean of the differences between the two sampling trains 

### is signijicant at the SO-percent confidence leveL The !.-statistic iR calculated by finding the standard deviation of the differences between the two sampling 

### train s. 

# so , =
where: 

## L(d ,-d.Y (n- 1 )

d, c the difference between the two sompl o t rnin vnlues d
. " mean of the 

### d, vnlues

n "' number of paired samples [Eq4]

Using the standa rd devi a tion deternrined in Equation 4 , the t-statistic 

### is then calculated as follows: 

# id. i 

# (7n) [Eq 5]

Based on EPA criteria, a s t atistically significant bias in a data set exists if the 

### t· statistic value is greaw than a critical \'lllue ( 0.88 for 11 runs)
. Using Equations 4 and 6 and EPA' s critical value f o

r 11 runs, it was**de~rnrined** t hat M29 experienced statistically significant bias between tho paired sample trains for Ba, Cd, Cr, Hg, Ni, Sb , and Zn
. However, the ltt29 bias 

### was small, on the order of 3 to 6 peroent. Furthermore , the bias wa s not oonsisteot by element with sample Train A being higher for Cr and Hg while Train B was slightly higher for As , B a, Cd, N i, Sb , and Zn. Overall , the M29 sample trains had an 8\ '· erage**a.bsolu~** percent difference of abo u t 6 percent ('!'able 9). Since the M29 bias for individual elements was relati\ · ely small and no consistent differences between sam ple trains was noted , 

### it was determined that t ho average M29 con· centration would be used for comparison purposes and no CO<Teetioo would be taken to**compensa~** for bias.



### VES011335ERDCICERL TR-4S.9


### Relative to M29, the XCEM showed significant bias for all e l ements (Table 1 4)
. This bias is believed to be a product of XCEM transport and calibration prob

lems. Method 30 1 outlines a procedure for determining correction factors that can be 

### appli e d when bias is present. 

### If the Method 301 correction factor had been applied to the XCEM concentt·ations, the XCEM would have met the 20 p ercent RA criterion for 

### nlJ of the e lements except Hg. Although t hi s method shows the existence of a hi g h l eve l of correlation, it is important to note that the XCEM correction factors are outside of the acceptab l e rang e for validation of Pb , Ba, Sb , Zn , As, 

### and Hg.
T

able 14
. Method 30 1 bias and cor"'ction factor comparison
. Sign ificant Correction RA wi th Corrected RA E

lement T.stat Corr
. Factor Blaa Factor !Runs 3·13) Meets P S- 1 0 Cd 5.33 Yes 1
.08 3
. 9 Yes Cr 6 .4 1 Yes 1
. 17 6
. 3 Yes Ni 1. 27 Yes 0.96 8
. 0 Yes Pb Ul7 Yes 0.83 20
. 2 Yes ' Ba 9.59 Yes 1
.46 8
.7 Yes Sb 6
. 17 Yes 1 .73 6
.5 Yes Zn 5
.64 Yes 1
. 38 6. 1 Yes As 1 1
. 75 Yes 0
. 69 7.8 Yes Hg 3
. 44 Yes 1
. 91 35.9 No 1**U~onlyr1 ne**  runs as suggested"' PS-10. PbRAwouldh ave been 1 • percent 

### Summary The XCEM was constructed, installed at the TEAD incinerator, and tested against M29
. The primary objective was to meet t he proposed requirements of PS-10. FoUowing i s a list of the i ndividual requirements and di scUJlsion of the p e rformance of the XC E M: 1. Response time and reporting time: 

### T he XCEM had a response time of 20 minutes, meeting the P S-10 criterion for batch CEM.s
. It experienced no me · chanical problems and had an effective up - time of 1 00 peroent. 2. QA : 

### The XCEM showed a cal ibration drift of less than 0.5 pereent and QA precision of about 2 percent for daily zero and upscale checks. 3. Relalive accuracy: 

### a. The XCEM met PS-10 accuracy criteria for Cd, 

### Cr, and Ni 

### by having rela· tive accuracies that wero le ss than 20 percent.



### V E S01133638 EROC/CER L TR-*-9

b. The XCEM did not meet the Pb accuracy criterion with an RA of 22 percent. c . The reported XCEM concontration.s were uniformly high for As due to 

### a spectral resolution problem. d. The XCEM was consistentlY low 

### for Z n. The Zn differences 

### are believed 

### to be d ue to an incorrect XCEM ca.libration standard that lowered the XCEM concentrations by about 

### 1 5 percente. The XCEM was also consistently low for Ba and Sb
. These difference s ore believed 

### to be a function of 

### transpott or calibration problems
. f. The XCEM did not successfully measure Hg , which exhibited 

### a ooncontl'ation pattern that suggests loss to the unheated sample transport line
. g. The XCEM had a correlation ( t") of better than 0.95 for tltrce (Ni, Sb , Zn) of the four elements that were spiked at varying concentrations. In addition, during the tests the XCEM functioned in a completely automated manner and automatically re corded concentrations, temperatuTes, now rates, and QA data_ It also showed 

### a precision of better t han 4 percen t for periods when spiking and stack conditions were held relatively con stant . An analysis of reported conccntrr1tions using EPA M e thod 301 correction factors indicates that the XCEM would meet the 20 percent RA criterion for all clements except Hg, once the bias is taken into account. However , the correction factors are outside the acceptab le 

### range for validation. Tabl e 15 summarizes 

### the results relative to PS-10. Tabfe1 5 St.mmary of XCE M performance ralatlve to proposed P 5-10 requirements Test Goal - Criterion? Discussion samp l i ng and**Elchlb~ed** a 100% up.&ne for tesl**~led** kl< greater than Yes 99.5% or the time
. Reported ti me averaged eonoentratlontl avery Response Time 20 minulos with a 20-minute l ag -n S\ll!l>ling_and reoortlno. QA Ye s Tho XCEM exh i bijed a precision or 1 t o 2% lor zero d ri ft
. The XRF calib r ation drift was less than 0
. 5% f o r t h e 4 davs or t es linn
. Met 20% RA criteria lor J<!l, Q!, and N i. H ad a 22% RA lor

### fll
. Yes for 3 Was systa ma li cally bi ased for§;!, Sb
. Zn. nod A s . Old not RA No for 6 suocessfufly meaS<J<e Hg
. For res po nse to change In coocon tratlon
. had correlatlon (r') o f 0.95 or be no r for Nl , Sb
. and elements Zn
. Uncle rl i n ed elements are regu l a ted elements typica l ly found i n lhe Tooele leedstream.



## VES011337E RDC/CERL TR-Gs-9



# 3 Transport and Calibration Improvements During the M29 comparison tests of May 2001, the XCEM met the PS-10 criteria for 

### QA and sampling and re sponse time , but only met the RA criterion for three elements ( Cr, Cd , and Ni )
. An evaluation of t.he test parameters indicated that ch ang es to t.he transport line , improvements in calibration, a nd testing of the X

CEM vs. stack spiking would improve the XCEM RA. During the spring of 2002, improvements were made to the XCEM tran s port line and a second series of preliminary tesb were conducted to better unders tand calibration and stack spilcing efficiency. This chapter discusses the changes to the transport line, calibration , and test •· os ul ts.
T r ansport Line C h a n ge s The initial transport line used by the XCEM at TEAD was insulated , but not heat traced. The line, which extended horizontnlly 20 ft, showed problems with Hg transport . Durin g May 2001 testing, XCEM Hg concentrations were lower than M29 values at the beginning of the day wnen temperatures were lower, but as the line temperature increased, the X CE
. M Hg concentrations approached M29 results. For this rea son, it. was determined that the XC E M required a heated transport line. In March 2002 t.he XCEM s helter was moved to a location that required only 13 ft of horizontal transpo rt. Following th e move , the line was heat traced, in s u · lated, and maintained at 220 

### <F. In addition, a shrouded probe was installed. Tho shrouded probe, manufactured by Anderson Instruments, has been shown to minimize the impact of variations in stack velocity on deviations from isokinctic sampling ( McFarland and Rodgers 199 3 ). The combined effect of these changes was to minimize Hg and particulate loss in the sample line
. 39



## VES011338ERDC I C ERL**TR -0~** **9**


### Recallbratl on During the week of 8 April 2002, CES recalibrated the instrument using thin 

### film MkroMatter standards. The thin-film standards a re developed by flashing the metal of interest onto a nu c lepore filter, resulting in a known concentration of metal in micrograms per square centimeter ( Jlgfcm2 )
. 

### The XRF unit used by t h e XCEM had not been calibrated since**Augu;~t** 

### 2001. Before recalib•·aling, CES analyzed the Mi cro Matter standards ( previously purchased by the Army as un · knowns) to evaluate the XRF's stability. The XRF reported values within 10 per· cent of the calibration s tandards, which indicated that it had maintained good stability for 9 months and would not have n eeded recalibration under normal operating conditi ons. Foll owing the initial check, se vera l changes were made to the calibration proce dure to improve spectral deconvolution. These changes included: • Development of a repres entative filter tape background refe.-ence spectra • Subtraction of the filter tapo background spectra • Development of better pure element reference spectra • Inclusion of additional elements as background spectra to correct for potentia 1 

### interferences
. Following recalibration , the Army MicroMattcr standards were again evaluated as unknowns. The standards were w ithin 1 .5 percent of the listed values for all elements except Sb (6 percent ) and B a (1 5 percent). Tbe accuracy of the Army MicroMatter standards was in question, so they were compared to CES MicroMatter standards at the CES laboratory. Some incons istencies for Cd and Pb were noted between t he Army and the CES l.'.ticroMa tte r standards
. They were also compared with standards fro m NIST. The re sull.s f r om the analysis of the NlST and CES MicroMatter standards were comp ared with the Army 

### Microl\1at · ter s tandards , and it wa s d e termined that the Army standards for Cd and Pb were high by 12 percent and low by 4 percent, respectively. The XRF calibration was adjusted accordingly
. Summary of Transport and Calibration Evaluations Changes t o the transport l ine were tested by comparing XCEM concentrat ions to concentrations based upon stack spiking estimat-es and an in-stack EPA Reference Method 17 (Ml7 ) filter
. Overall, no measurab l e loss of particulates in the improved XCEM transport line was observed. The calibration was tested using a



### VES011339ERDCJCERL TR-05-9
Quantitative Spike Injection System ( QSIS)
. It was detennined that the elemental concentrations were being reported within their expected uncertainties foa· all elements except Cd and Ag. Appendix C gives descriptions and detailed results of these tests . 4 1



### VES01134042 EROCICERL TR-05-9



# 4 M29 Comparison Testing of XCEM 2002
In May 2002 a new series of M29 tests were conducted to evaluate the measure· ment capabilities ofthe improved XCEM. The test objective was to compare M29 and the XCEM and determine the XCEM RAs. The testing was conduct ed at TEAD with a test plan similar to the plan used in t .he 2001 M29 comparison tests. Ten metals were measured by M29 and the XCEM
. This chapter presents the results of the l\'129 sampling, predicted concentrations based on the spiking, and the X CEM sampling. Also presented : a calibration evaluation based on the reevaluation of the XCEM filters, a discussion of the precision of the three concentration determinations, and a detailed discussion of the M29 comparison.
Re su l ts Method 29 Concen trations 

### Method 29 tests were conducted using duplicate sample trains located at the same stsck height as the XCEM probe. 

### In general, the two t rains were in good agreement ( CHPPM 2002). As shown in Table 16, more than 90 percent of the paired M29 concentrations were within 10 percent of each oth e r. Of the 11 re· ported concentrations that were not within 10 percent, 9 were measurements of Sn
. Method 29 has not been approved for Sn (EPA 1992 ). 'l 'in is not a regulated metal, but measuring it is useful to TEAD for identifying deactiv ated munitions. Overall, train A was higher than train B by about 3 percent with about 78 percent of the concentrations in train A being h igher than their t rain B counterpart. An 

### average of trains A and B was used for comparison to the XCEM reported concentrations. Method 29 dats used for comparison to the XCEM is the same as reported in the M29 report (CHPPM 2002) with the exception of a 1-3 percent correction compen · sating for the laboratory ' s inadvertent subtraction of an estimated blank concen· tration when the blank concentrations were below the method-reporting limit.*

Pe r son!¥ oommu ni ca!Son: Robert Weldenfe ! d, Se\leren T rent Lab , with John Cooper , CES , 9 Ju ly 2<102 .



### VES011341