ERDCICERL TR-OS-9 

1 Introduction 

Background 

The U.S. Environmental Protection Agency (EPA) is developing regulations for 

hazardous 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 permits that are then 

issued are based on these worst-case burns and impose limitations on the demilitarization facilities. A continuous emission monitor (CEM) for metals would provide the emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn strategies for increased production and sustainability. 

In addition, the HWC NESHAP suggests that a CEM would be the preferential 

method of emission accountability. 

Multi-metal CEMs being developed are based on elemental sensors using laserinduced 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, developed by Thermo Jarrell Ash Corporation, has been 

successful in meeting the relative accuracy (RA) criteria of the PS-10 (Seltzer 

2000). This technology appears to have limitations such as its complexity, high 

initial costs, and high operating costs. The U.S. Army Engineer Research and 

Development Center, Construction Engineering Research Laboratory (ERDC/ 

CERL) decided to pursue the development of the X-ray fluorescence (XR.F)-based 

continuous emission monitor (XCEM) because it had the potential to be a reliable and accurate CEM without these limitations. 

The basic approach of the XCE.M is to draw a continuous representative sample 

of stack gas to a stilling chamber where a smaller metered sample is extracted 

and pas.<;ed through a chemically treated filter that collects metals in the parti.cu1 

VES011300 
2 ERDC/CERL TR-0~9 

late and vapor phases. Following sampling, the filter 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, where the filters were analyzed offiine (French 1998). Cooper Environmental Services (CES) further developed this method into an on-line system that was tested under the 

ERDC/CERL Waste Minimization and Pollution Prevention Program at MSE 

Teclmology Applications, Inc.'s (MSE-TA's) research incinerator in Butte, Montana (Bryson et al. 2000). The results were encouraging because the XCEM met 

the PS-10 RA requirements for chromium (Cr) and lead (Pb). Many of the other 

requirements were unmet, however, and further development was needed. It 

was at this point that ERDC/CERL began funding the development of this technology under their Hazardous Air Pollutants (HAP) program. 

The Army currently has 19 existing, new, or planned hazardous waste combus· 

tors. Table 1lists these sites (Josephson 2003). 

Table 1. Army hazardous waste combustors. 

Location 1\lpe waste Treated Status GOorCO 

Sierra AD APE 1236 cs Exlstin!l GO 

Tooele AD APE 1236 cs Exlstioo GO 

Tooele AD APE 1236 Test Furnace - CS Existing GO 

McAlester AAP APE 1236 cs Existing GO 

Hawthorne AAP APE 2210 cs New co 

Fori Richardson APE 1236 cs New GO 

KansasAAP APE 1236 cs Exis1ing co 

CraneAAP APE 1236 cs New GO 

Lake City AAP APE 1236 Off·spec conventional Exis1ing GO 

Picatinny Arsenal APE 1236 Waste R&D propellants New GO 

Pine Bluff Arsenal Auldized Bed Pyrotechnics and Obscurants New GO 

Pine Bluff Arsenal APE 1236 Off-spec pyro«echnics 

Radford AAP Kiln Off·SPGC I)<Opellants 

Oeseret CA Chemical Chem 

Umatilla AD Chemical Chem 

Pine Bluff Arsenal Chemical Chem 

Anniston AD Chemical Chem 

PuebloCA Chemical Chem 

Anniston AD Kiln De-Painting wastes 

GO - Gcwemmenl Owned 

CS - Conventional Stockpile 

AD- Army Depot 

CO - CoMrac!Or Owned 

Chern - Chemical Sfod:pi!e A.AP - Army Ammunitlm P1ant 

Existing GO 

Existing GO 

Existing GO 

New GO 

New GO 

New GO 

Planned GO 

Planned GO 

CA- ChelricaiAclMty 

APE 4 A.rrwnunition Peculiar E(JiipmQnt 

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ERDC/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 was developed to possess characteristics that make it compatible with Army operations and expectations, such as 

user friendliness and affordability. That work is described in a precedent-setting 

report (Hay et al. 2005). The specific objective of this work was to demonstrate 

the XCE.M at an Army installation. The desired exit criterion under the HAP 

Program was for the monitor to meet, under field conditions, the proposed PS-10 

requirements, which are described in Table 2. 

Table 2. Proposed PS-10 requirements. 

Criterion DoscriJ>tion 

SafT4)1iog and It is required that the &afr4'liog time be no longer lhan one-1Nrd of the averresponse time aging periOd lor lhe applicable standard lor a balch CEM. The delay be· 

tween the end of the sampling penod and reporting of the sample ana!ysis 

shall be no greater than I hour. A batch CEM Is required to sample continuous!y exoept when changing the sampMng media, which should be no 

greater than 5 percent or the averaging period or 5 minutes, whichever is 

tess. For this study, lhe averaging period is 12 hours, which means the 

sampling time should be no longer than 240 minutes, the response time no 

greater than 60 mWlutes, and the maximum time aUowed for changing the 

samplina media Is 5 minutes. 

Quality assurance Calibration drift: The calibration may not drift or deviate from the reference 

value ollhe calibration standard used for each metal by more than 5 percent of the emission standard fQ( each metal. Must allow for detennining on 

a daily basis. 

Zero drift: The zero point lor each metal shall not drift by more than 5 percent of the emission standard for that metal. Must allow for detenminiog on 

a daily basis. 

Span: The CEM response range must include zero and a high level value 

equal to the span. The span valUe is defined es 20 times the applicable 

emission limit lor each metal. This is an equipment specification (not 

tested). 

RA The RA of the CEM must be no greate< than 20 peccant of the mean value 

ol the RM test data in terms of units of emission standard lor each metal, or 

10 percent ol the applicable standard. whichever Is greater. Duling velifica· 

lion. lhe measure o1 RA at a single concentration level is required for each 

metal measured for cornplianoe purposes. and the RA must be dete<mined 

at three concentration levels for one melal fzero can be one Ieven. 

Source: EPA 1996. 

3 

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4 EROC/CERL TR.05-9 

Approach 

As a result of encouraging development work (Hay 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 EPA Reference Method 29 (M29) in 

2001. The monitor was only partly successful; several improvements were warranted and implemented. A second M29 field-test was conducted a year later. 

This report includes the description and results from both M29 comparison tests 

and the modifications that took place in between. The XCEM was demonstrated 

under this project through contracts with CES and MSE-TA The U.S. Army 

Center for Health Promotion and Preventive Medicine (CHPPM) performed the 

M29 stack sampling activities described in this report. 

Mode of Technology Transfer 

This technology was developed and demonstrated through the ERDC/CERL HAP 

Program, which uses 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 process, 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 Deactivation Furnace at TEAD. 

This report will be made accessible through the World Wide Web at: 

http://www.cecer.army.mil 

VES011303 
ERDC/CERL TR.O!MI 

2 Field Testing 2001 

The XCEM underwent M29 comparison testing at the TEAD 1236 deactivation 

furnace in May 2001. This chapter presents a brief description of the XCEM, the 

testing activities, and the r esults of tho testing. 

Brief Description of XCEM 

A new XCEM was developed and built for demonstration at the TEAD facility as 

described in Hay et al. (2005). The XCEM extracts a sample of stack gas and 

concentrates the metals of interest on a chemically treated filter tape. Following 

collection, the filter tape is advanced to an analysis area where a laboratorygrade XRF instrument is used to determine metal mass. The systom is entirely 

automated and produces concentration data every 10 to 20 minutes for up to 19 

elements ofinterest. The three major XCEM components are: an extraction system, sampling and analysis system, and control system. 

Extraction System 

The XCEM extraction system collects a representative stack gas sample from the 

smokestack and transports the sample to the filter. The system includes a sample probe and insulated sample line. 'rhe stack gas temperature is monitored in 

the sample line just before it enters t.he enclosure that houses the XCEM. The 

unit only operates when this temperature 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). 

Approximately 1 percent ofthe stack gas that enters the stilling chamber is sampled through an extraction tube for cOnCI.lntration on a filter. The remaining 99 

percent of t.he gas is transported out of the stilling chamber, through o flow meter, and vented or returned to the tack (2 to 3 standard cubic feet per minute, 

SCFM). An eductor, located downstream of the stilling chamber, is used to pull 

the stack gas through the extraction system. 

5 

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6 ERDCICERL TR-05·9 

Figure 1. XCEM stilling chamber {vertical pipet and sampling cassette (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 extracted stack gas is transported 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 system that is automated to accurately move the tape from the sampling to an 

analysis position. Sampling and analysis occur simultaneously, resulting in a 

continuous monitoring system that reports metal concentration measurements 

every 10 to 20 minutes. 

VES011305 
EROCICERL TR-05-9 

Figure 2. XCEM chassis. 

Metal mass on the filter is determined using a modified ThermoNoran QuanX 

energy dispersive XRF analyzer. The QuanX is capable of simultaneously measuring 19 elements and a palladium (Pd) quality assurance (QA) standard. Although 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 is 

nondestructive, the retentate on the filter tape can be reanalyzed if the end-user 

requires additional data. 

Control System 

The XCEM is controlled by a personal computer using a custom WonderWare"' 

(Progressive Software Solutions, Inc., Albany, OR) software interface (Figure 3). 

All day-to-day functions of the XCEM are automated, including flow and temperature 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 evaluation. Flow, temperature, concentration, and pres· 

sure measurements are logged in real-time on the screen. 

Execution of Field-Testing Activities 

Before shipment to 1boele, the XCEM was tested and an initial calibration was 

completed. 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 adjustments were completed prior to receiving M29 results. 

7 

VES011306 
8 ERDCICERL TR·OS..S 

COmponent COniTOI 

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

...... ' --~~ 

Following installation, preliminary onsite 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 successful integration of 

the XCEM into incinerator daily operations. 

Test Plan 

A test plan was developed to verify capabilities of tbe XCEM to measure metals 

under typical incinerator conditions (Appendix A). The test plan outlined meth· 

odology for comparison testing between EPA M29 and the XCEM at the TEAD 

incinerator. Specifically, the test plan called for at least 12 EPA M29 tests with 

each test run lasting 2 how'S. Arsenic (As), barium (Ba), Cr, cadmium (Cd), 

nickel (Nil, mercury (Hg), antimony (Sb), and 1.inc (Zn) 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. 

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ERDC/CERL TR·05·9 

In general, the test plan (Appendix A) was followed as written with 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 XCEM observed high levels ofPb during the first two test mos. The 

TEAD operators believe that the high Pb was 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 test run was added. 

• Delays in completing a trial burn test at the Army incinerator forced a 2-day 

postponement in XCEM testing. To make up for lost time, four M29 test runs 

were completed on both 16 and 16 May. 

Table 3. XCEM test dates and associated TEAD Incineration leedslream. 

14 Ma• 15 Mav 16 Mav 17 Mav 

Run 1 R.., 2 -3 R ... 4 R\Jn5 RIM16 Run 7 RunS Run 9 Roo 10 Run 11 Run 12 Run 13 

50 50 No No No No No No No No No ~IK344 "'K344 

Calibet caliber Anmo Ammo Ammo Ammo Ammo Ammo Ammo Anmo Ammo Fuses FUGG$ 

EPA Verification 

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 partner for the ETV Advanced Monitoring Systems (AMS) 

Center. The scope of the AMS Center covers verification of monitoring methods 

for contaminants and natural species in air, water, and soiL For these tests, 

ETV representatives reviewed the test plan and monitored testing procedures. 

They also conducted an onsite audit of the Army laboratory that analyzed 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 

VES011308 
10 ERDC/CERL TR.OS.9 

(Smyrna, GA), and procuring the special probe requires significant lead time. 

With the 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 probes 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 downstream (top of the stack) from the sample port.~. These distances 

are adequate to ensure that these flow disturbances do not affect the sampling. 

The transport 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). 

Test Objectives 

The overall objective of the test was to provide quantitative verification of the 

performance of the XCEM under field conditions. EPA's draft performance specification document PS-10 (EPA 1996) is a proposed description of how to assess 

the acceptability of a multi-metal CEJ.\I upon installation and thereafter. 

Figure 4. XCEM housing and transport line, M29 

s.amp1ing setup, stack, and ceramic baghouse at TEAO. 

VES011309 
ERDC/CERL TR.05·9 

The goals of the verification test were to meet the 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 feedstream of the TEAD incinerator (Sb, 

Ba, Cd, Cr, and Pb). This includes evaluating the response to change in concen· 

tration by testing at least one element at two concentration levels. 

A secondary objective was to meet the RA criteria for additional regulated and 

unregulated metals, which are not typically found in the feedstream (As, Hg, Ni, 

and Zn). 

Additional performance parameters examined during the testing included: 

• 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 also checked by the 

automated daily XCEM zero and upscale QA measurements. For the verification 

test, response time was determined as the time between the start of one sampling period and the beginning of a BeCQnd 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 EPA Method 

301 - Field Validation of Pollutant Measurement Methods from Various Waste 

Media CEPA 1992). 

It was beyond the scope of this verification test to durability for routine longterm use. This test evaluated the performance of a new XCEM over a relatively 

short test period, operated by skilled personnel. It must be noted that the longterm performance may be different ti·om t hat observed in the testing described 

here. The XCEM did not exhibit any mechanical problems during the test; it 

completed more than 150 test rWls during the week without any downtime. 

Site Description 

Verification testing took place at TEAD building 1320 deactivation incinerator 

APE-1236. The TEAD incinerator, which runs on diesel fuel, is designed to incinei·ate decommissioned munitions. Typical operating parameters for the incinerator are shown in Table 4. The TEAD incinerator is classified as a dry stack 

11 

VES011310 
12 ERDCICERL TR-65·9 

with water 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 is currently •·egulated under tbe Resource Conservation 

and Recovery Act (RCRA) for Sb, As, Ba, beryllium (Be), Cd, Cr, Pb, Hg, Ni, selenium (Se), silver (Ag), and thallium (TI). Of the 12 regulated elements, 5 are 

typically found in tbe feedstream: Sb, Ba, Cd, Cr, and Pb. The XCEM was 

tested for its measurement capabilities of the five elements found in the feed· 

stream as well as As, Hg, Ni, and a nonregulated metal, Zn. These elements 

were selected in order to challenge tile XCEM over a large range of analysis conditions and elemental concentrations. 

For tile Yerification test, metals in the TEAD incinerator stack gas were regulated under a Temporary Authorization permit (Table 5). Of the 12 regulated 

metals, Pb is the only element that was consistently found in measurable con· 

centrations in the stack gas. Figure 5 shows the deactivation incinerator set up 

and the locations for sampling and spiking during the test. 

Table 4 Typical operating parameters for the APE-1236 deactivation fumace 

Temp. (' F) 1630 

Baghouse t.P (in. H,O) 4 

Baghouoe Inlet Temperature (' F) 860 

Kiln Feed End Draft Pressure (in. H,O) ·0.2 

Kiln Feed End Tempemture ("F) 375 

Kiln Butner End Tempe<atute ("F) 1000 

0,- CEM (%) 15 

CO(ppm) 8 

Stack Temperature ('F) 500 

Stack Gas Velocity (ftlsec) 46 

Table 5. TEAD metal emission limits during V8rifleatlon tosting. 

B ement Limit (glhr) Element Limit (g/hr) 

Antimony 14 Lead 4.3 

Arsenic 0.11 Merrury 14 

Barium 2400 Nickel 930 

Beryllium 0.20 Selenium 180 

Cadmium 0.26 Silver 140 

Chromium 0.04 Thallium 14 

VES01 1311 
ERDCJCERL TR-lls-9 

Discharge ,. -

Feed 

Sta~an .,_ 

Ceramic 

XCEM Baghouse 

Top view ofTEAD 

Incinerator Setup 

t 

"'i ,. Stack 

Front view of 

TEAD Stack 

during Sampling 

XCEM 

Air flow 

-

Figure 5. TEAD incinerator setup and Umpllnglsplklng loc.rtions. 

13 

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14 ERDC/CERL TR-05·9 

Experimental Design 

Both the kiln and afterburner were fired with 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, however, which led to a deci· 

sion not to incinerate additional anununition 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 while 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 

these metals were spiked directly into the stack downstream of the controls. 

These metals were spiked at the level shown in Table 6. Lead, however, was not 

spiked since the incinerated munitions provide measurable concentrations 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 pressure and airflow rate. For these tests, pressure and flow rate were maintained to keep droplet sizes Jess than 28 microns in diameter. When dried, the majority of the particle mass was calculated to be in the 1 to 4 micron diameter range. An analysis of 

the M29 concentration data during validation testing indicated that 10 to 15 percent of the spiked metal mass was lost on the probe (CHPPM 2001). Tltis level of 

probe loss is 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. 

Table 6. TEAO incinerator metal emission limits and spiking levels. 

Emission Limits' Spiking Level' 

Elements - iJ91dscm 

glhr -iJ9ldscm 

Runs1-6 Runs 7·1 3 

As 0.11 25 14 14 

Ba 2,400 540,000 200 200 

Cd 0.26 58 34 34 

Cr 0.04 10 5 5 

Hg 14 3,145 280 88 

Ni 930 209,000 460 180 

Pb 4 .3 966 NS NS 

Sb 14 3145 520 200 

Zn NR NR 460 180 

' The concentration i'l IJ9fdacm assumes a st&e:k flow rate of about 4500 dscmthr 

NR: Nol regwled NS Nor~ked 

VESOll313 
ERDCICERL TR.05·9 

Figure 6. Spiking at base of stack during validation testing. 

Three separate solutions were prepared for spike iQjection. The ftrSt solution 

contained arsenic oxide (As,O,), Cd metal, and chromium oxide (CrO,.) dissolved 

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 contained 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 XCEM data were recorded every 20 minutes and were 

averaged for comparison to each M29 test run. As a performance audit, two 

blank trains were quantitatively spiked with all nine of the metals. 

CHPPI\fs Directorate of Laboratory Services (DLS) conducted laboratory analysis of the sampling trains. 

Results 

XCEM Reported Concentrations 

Time-weighted average concentrations 

Average XCEM concentrations during the time of one M29 test run were calcu· 

lated using Equation 1. 

15 

VES011314 
16 ERDC/CERL TR-05·9 

(Eq 1) 

where: 

C, = XCEM 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 corrections 

Following M29 testing, but prior to receiving M29 results, CES recalibrated the 

XCEM and determined that a 4.4 percent global change was required for XCEM 

reported concentrations. In addition to the recalibration, CES conducted exten· 

sive testing of the sample line dryer and detemrined that a 3.5 percent correction 

in flow was required 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 discussion 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 Pb interference as discussed in Response to 

Changes in Metal Concentration (page 25). Arsenic corrections were com· 

pleted prior to receiving M29 data. 

The final reported XCEM concentrations are listed in Table 7. Approximately six 

to seven XCEM measurement took place during each M29 run. The "Min. of 

Run" column in Table 7 refers to the number of minutes for that particular 

XCEM (listed as XC in the table) measurement that coincided with the M29 run. 

VES011315 
ERDCICERL TR-Os-9 17 

Tabla 7. Final CEM concentrations for M29 testing. 

RM XC Mia. XC 

No. Dau Start St(lp N(). R~u T""" ... B• C<l Cr Hg Nl , Sb Za Pd 

Run I 5114>0 1 10:45 II :05 650 5.0 119:48.0 20.8 166 27.1 3.1 59 34 3 

:: ~ 340 :191 ?4.1 Run I 5/ 14101 I 1:05 11 :26 651 21.2 11:12.0 24.3 171 26.0 2.5 109 436 312 316 23.& 

kunl 5114101 II :16 11 :48 6.52 21.5 21,J2.0 21.1 192 u.s 1.9 156 467 1. 149 361 320 25.6 

kun I 5/14.<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 12:10 12:31 654 21.7 21:41.0 25.3 U!? 28,2 2.6 242 470 1,319 317 ).42 24.6 

Run I ;;::: ~: 12:$3 :;! z;; ;;·~~:~ ;::! 218 

~:~ 2.2 251 SIS 1::::: 399 372 25.4 

kun I IJ:I S 202 2.4 283 463 386 ).48 _Hl_ 

Th ue \\ "•ble<IA>'O 120.0 I '"2o1.1 2>.6 187 26.9 2.3 194 462 l.l40 372 m 

RunZ l;t4/1)1 13:58 14:23 659 18.3 125:09.0 1.3 230 26.8 2.3 186 

Run2 S/ .~1 14:2l 14:46 660 22.9 12:56.0 3.5 224 29.5 2.0 2~4 !~; ·~~~ ;~~ : ~ Run l 5,1141()1 14:46 15:09 661 22.9 22:56.0 n.o 249 Z6.0 1.2 l« 427 ~~~ 398 )52 25. 1 

Run 2 /1~1 15:09 15:32 (1(;2 22.9 22:54.0 2.3.8 250 22.3 2.0 220 405 2.683 370 332 25.3 

Run 2 

!:::~ : :~:~; !:~ ~ 22.6 

I ;~ :~ ! ~~ 29.! 

~:! 239 4 1S ~~7 379 ).47 25.2 

~ 10.3 27.1 257 392 348 319 24.4 

ri(hledA'I: 120.0 

~ 16.3 2~ 26Jl u 229 410 1.690 375 335 

1 Kun > 511411/1 17>1}0 17:2> .. , 10.0 IS.) J27 25.4 3.4 2S9 39S 11 8 334 32<J 24.6 

Run ) $114..01 11:23 17:44 1>61< 21.0 21:00.0 13.1 140 21.3 2.1 264 38S 9 1 33S 319 25.2 

Ron3 /14.~ 1 17:44 18.:05 669 20.9 20:52.0 13.0 158 27.0 2.5 265 417 60 355 341 l$.4 

Run:l :S!I4R)I 11'::05 11'::26 670 21.0 20:Sit0 1.1.1 175 2&.9 2.9 268 409 55 363 339 Z$.1 

Run.l SIJ.Wl 18:26 18:47 671 20.9 20:S3.0 14.2 J68 21.4 2.4 255 4 13 

~ 352 ~; 24.6 

I Runl 5/14,01 18:47 19:07 672 2<J.3 I 2<J:54.o 11 .2 147 24.0 2.3 249 414 360 I 25.9 

ln ... · 

~'· 8:59 

I 12011 :13.1 13.2 154 24.6 u 260 .... 73 351 

1 Run4 9:18 ... 3J 119:43.0 13.2 14S "·5 4.5 3J 2\1'! •• m ZJ> 25.0 

Run4 S/15101 9:1M 9:39 685 2M 2():'34.0 15.0 113 2~..5 6.2 54 401 69 m ) 19 23.4 

Ruo4 $/ I SA} I 9:39 10:00 686 20.9 20:55.0 15.6 133 3).2 5.4 69 432 66 362 349 24.7 

Runol S/ISJGI 10:00 10:21 687 21.0 21:00.0 16.2 154 30.5 5.3 80 432 64 371 348 23.1 

Run4 91:sJ01 10:1:1 10:42 68S 21.0 20:58.0 16.ti 191 ~2.1 5.0 .. 4:13 64 37l': 344 :s.1 

Run4 5/15101 10:42 11 :03 689 21.0 211:57.0 15.2 145 26.6 5.2 ss 4 18 55 361 339 24,2 I Run4 S/15101 11:03 11:24 690 12.3 1211:51.0 17.4 183 28.5 55 91! .... 45 380 366 25.0 

h'in>< el•hted A" 1120.0 IZ0:4L6 15.8 161 29.8 SA 76 422 •• 361 340 

1 Run S $/IS,'() I 12:06 12:21 693 15.6 I 20:Sl.O 18.0 177 31.4 5.5 93 440 49 

~~; m 24.7 

RunS 5/15101 12:27 12:48 694 20.9 2Q:S2 .. 0 16.2 172 3J.7 55 97 430 S4 34S 24.) 

Run5 5/15101 12:48 13:09 69S 2Q.9 2Q:51.0 16.0 153 ).4.4 6.1 102 417 52 362 )39 23.3 

Run 5 5115101 13:09 1);3<) 696 20-8 21),411.Q 11.) 182 33.4 5.3 114 450 47 386 360 24.6 f:: !i/I.W l 1.1 10 

:~ :~ 691 Zl.O 20:57.0 ~~ ~ 35.8 5.1 122 449 45 ~93 365 25.7 S/IS/01 13:51 698 21.0 I 20:59.o 32.2 $A 129 443 38 390 358 25.2. 

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1 Run

Run7 

7 511 

511

SJO

5101 

I 

1

18

8:

:03 

24 :~; :~ 21.0 

IIU 1 

2

zo

0:58.

ss.o 

0 18.5 

16.9 

:~ 35

).4.5 

.6 5

6.4 

.8 

~ :;! !~ : -:-~ 2<.2 

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~ l11511ll 19:2? 9~ 114 20.8 2():$0.0 t6.Z m 30.1 5.1 132 419 34 367 m 2.5.9 

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.. .,. 16.6 Jl.! 5.A m 461 40 3&3 367 

VES011316 
18 EROC/CERL TR..0$-9 

Table 7 (Cont'd). FINII roportod XCEM concentrations ~g/dscm) for M29 testing. 

RM llo<r Slt11 SO>p XC I M ia. XC 

Sa Cd Cr Nl Pb Sb z. No. No. nmc As ur 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/1601 10"1 11:01 T.lt 20.4 20:24.0 18.7 Ill 32.7 5.7 36 116 :!26 IJ.I ISO 24.) 

I R...I S/16.01 11:01 11:22 731 u 12<>.30.0 17.1 162 32.4 5.7 "' 226 214 141 ISO 23.9 

tn ... "" ' 12n.J ; ZD:29JI 17.J 1 .. I Jl.S ... 27 ZIO m 1.14 1 .. 

I ...... ::::: II:Al ll:Ol m 7.1 llklS.O 121.1 Ill lll.l 4.5 ~ 210 190 136 147 25.0 

RIOl9 ll:OJ 11:2) 7)4 20.4 21k26.0 14.8 170 32.1 5.6 so 201 170 !l9 141 2•.o 

RWI9 Sl iM) I 12:2) 12;.&4 'Ill 20.4 2<>.21.0 IU ~~ J0.7 5.3 49 ~ 162 142 1 .. 24 .. 1 

Run9 SIIMII 12:44 13:04 n• 20.3 20:1$.0 16.6 2()6 35.4 6.5 56 m 191 IS4 "' 24.9 

Rwt 9 lllii<U I IJ:04 13:.25 737 20,4 20.24.0 11.0 143 31.1 l.l S4 liS Ill 145 145 24.7 

Roo • l/111<0 I ll:ll ll :"-1 

~: ~~ :~~:~ IM 1)3 2$.8 52 59 200 I5J 145 144 24.5 I Rim? 51111<0 I 1) >45 14:05 16.0 lSI 19.1 5.2 60 118 155 148 143 25.1 

lnmr Wri''"'• An l !O.t ZA:!2.7 17.1 s.s M 2!0 166 145 I" 

Run 10 

: " :"'6 15:07 742 17.2 20:24.0 19.2 156 34,7 6.0 91 ZIO 146 143 ... I''·' Run 10 15:07 15:27 74) 20.4 20:2 1.0 21.) 187 37.0 5.4 89 116 261 IS4 151 25.6 

Run 10 !JIM! I 15:27 15:48 '"' 20.4 2<):23.0 17.0 141 32.5 5.4 81 192 liS 134 133 24.9 

A:un 10 !/16/01 15:48 16:08 145 20.3 20: 16.0 17.1 192 31.6 5.4 91 203 134 146 149 25.6 

Run 10 Yl 6t1'1 1 16:08 16:28 746 lOA 20:21.0 17.S 161 36.2 ss 95 208 10& 163 145 24.2 

Run 10 

~~ : :::!: 16:49 

'" 20.3 20:20.0 1&3 167 30.9 5.6 95 103 9S 140 131 24,7 

IRom i O 17:09 148 1.2 20:10.0 12.7 139 29.9 5.4 109 186 110 151 137 I 24.s 

"·· ·~· 0.0 20:10.7 18.5 167 33.8 s.s " 106 143 147 143 

~33 20:11.0 :::: :: S/16.4)1 ~:;; ;: ;~ ~~~ 20: 18.0 ~ ~ ~~~ ~ ~~ ;~ :~ ~ :~ ;~ ~ ~u:n II S/1610 1 18:12 11:33 752 20.3 20:20.0 15.S 170 29.3 53 95 204 104 141 145 24.() 

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Run II SJ10ir)l 11:5) 19:13 754 20.2 20; 12.0 17.3 Il l 26.4 5.8 96 19 1 89 147 14 1 l4.R 

Rlll'lll ~1 6/fll :ll 19::14 

~~! ~; 2(); 12.0 17.2 161 32.J! s.s ~ :!ill R9 l oll 146 24.9 

Run II 5/IMII 19::14 19:$4 20:17.0 ll.O Ill 33.2 4.6 211 96 147 145 124.0 

TIN• I~ ~ 16.2 163 31.2 ... " .lru ~ 145 !4J 

" """ 11 :12 11 :32 710 13.0 17.8 Ji4 265 ~ .. z• ~: rro m m 

Run 12 li17101 II ~2 11 :52 71J 20.1 20:08.0 11.2 195 23.2 4.2 )$ lJ2 159 1 .. I i~ : 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 11.4 153 3J.7 ... 79 206 161 IS& 151 14.1 

. ... 12 5111101 12:5.) ll:ll ns 20.2 20:11..0 12.3 m ~· 4,5 ltl 2(14 Ill! ISS 141 z .... .... 12 5111101 ll:ll ll:ll 716 6.0 20:010 . 14 1 ISO 28.2 4.1 86 191 140 ISS IJI 126.0 

'l'lo ... ' ~· IHJI lC>.IO.I 11.0 18:2 17.5 u ., 211 19!1 I~ I.e! 

..., u 14:14 14:34 m ~~, ::~~ ::; ~~ ~; ;~ : ~; I~ ... u 5111101 14:34 14~ 780 1- :~ :: I~ 

- 13 S/17101 14SI 15:14 711 20.2 20:090 "" IS9 36.1 6.1 82 lll 117 161 149 25.0 

Run 13 5117101 IS:I4 IS:l4 782 20.2 20:10.0 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 "' 113 129 169 111 , ... R\W\ 1l S/11101 U:SJ I&:IS 714 20.0 20:il2.0 19.2 165 39.1 6.0 7< 17D 121 166 2 2.5 I 

R'"' 13 S/11101 16.15 16.3S 715 ll.l 119:57.0 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 186 116 159 Ill 

VESO 11 317 
ERDCICERl TR-05-9 

Sampling and Response Time 

The XCEM met PS-10 sampling and response time criteria for a batch CEM. 

These criteria are that (1) the sampling time be no longer than one-third of the 

averaging 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 to 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 continuously except for a 4-second period between each 20-minute sample run when the 

filter tape was moved to a new analysis position. XCEM results are 1·eported 

immediately after each 20-minute analysis resulting in a 20-minute response 

time between the end of sampling and reporting. 

Zero end Calibration Drift 

The XCEM has automated daily zero and upscale checks and reports a Pd concentration with each sample to test for calibration drift. To determine the zero 

check, the XCEM measures an unexposed region of the filter tape. Following the 

zero check, a plunger is extended into the analysis region. The tip of the plunger 

contains Cr, Cd, Hg, and Pb embedded in a resin. Analysis of this spiked resin 

provides an upscale check for the XCEM. 

Zero and upscale checks were conducted on each of the four test days with the 

results shown in Table 8. Since the zero and upscale checks are evaluations of 

mass measurements, they are reported as mass per unit area on the filter 

(pg/spot). 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 blank bias 

in the mass measurement. The XCEM detection limits for Cr, Cd, Hg, and Pb 

are 0.75, 3.0, 1.0, and 1.0 pg/dscm, respectively. The XCEM zero values were below the 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 

measurements. The precision over the 4 days was less than 1 percent for Cd, 

Hg, and Pb and about 2.3 percent for the Cr. 

19 

VES011318 
20 ERDC/CERL TR.05·9 

Table 8 Upscato and zero concentrations during validation testing 

Upscale Valueslual ~o Values luo\1 

Date Cr I Cd I Hg I Pb Cr I Cd I Ha I 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 30.9 0.016 0.042 0.008 0.008 

5116/01 5.45 156 27.9 30.S 0.014 0.024 0.010 0.008 

5117/01 5.42 156 27.9 30.6 0.011 0.024 0.005 0 .023 

Avg. 5.41 157 27.8 30.7 0.0 13 0.034 0.008 0 .012 

so 0.13 0.74 0 .18 0.23 

%RSD 2 .33 0.47 0 .65 0.76 

Date 

Eauiv. Upscale Values (~g/dscm)' Eauiv. Zero values IUQ/dscml1

" 

Cr I Cd I Hg I Pb Cr I Cd I Ha I Pb 

5114/01 327 9,765 1,724 1,898 0.75 2.86 0.50 0.47 

5115101 346 9,850 1,750 1,931 1.01 2.65 0.50 0.50 

5116/01 341 9,772 1,742 1,925 0.85 1.50 0.63 0.50 

5117/01 339 9,744 1,746 1,912 0.67 1.50 0.29 1.42 

Avg. 338 9,783 1,741 1,917 0.82 2.1 3 0.48 0.72 

so 7.88 46.14 11.25 14.64 

%RSD 2.33 0.47 0 .65 0.76 

1) Gray values were noodetects. Nondetect treated as one-half of Detection Limij, 

2) Equivalent concentrations determined using 16 liters per sample. 

SO = standard deviation; RSD = relative standard deviation 

Palladium, which is measured with every sample, also displayed good precision 

over the 4 days of testing (Figure 7). Overall, the Pd concentration had a preci· 

sion of about 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 that 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 M29 concentration measurements are 

shown in Figure 8. In this figure the dashes represent the M29 concentration 

over the sampling period, while the diamonds represent 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 varying 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 correlation between 

the two methods. 

VES011319 
EROC/CERL TR·05-9 

PaUadium 

30 

29 

28 . 

:g 27 

26 

~¥.; :Sii it#. .; 25 

= Q 

u 24 c 

23 • 

22 

2 1 5/1 4/01 5/ 15/01 5/16/01 

20 

7:00 15:00 23:00 7:00 15:00 23:00 7:00 15:00 23:00 

Average Palladium Effective Concentration 

- One SO from Avg. Pd Concentration 

- 5% from A vs;. Pd Concentration 

F'sure 7. PaJia.dium concentrations d-uring M29 testing. 

i 

5/17/01 

7:00 15:00 

Unlike the other elements, the XCEM Hg concentutions were consistently lower 

than M29, but by a variable amount. During the early runs for each day, the 

XCEM reported low concentrations relative to M29. As the day progressed, the 

XCEM Hg concentration would gradually increase until it approximated M29 

r eported concentrations. This 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 not transported 

through a long sample line as 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. Some research indicates that Hg can be 

lost to a stainless steel surface at low temperatures lliall et al. 1990; Wang et al. 

1983). ln the laboratory, the XCEM was tested with oxidized Hg and met with 

good success (Hay et al. 2005). The laboratory tests, however, were conducted at 

elevated line temperatures. It is recommended that a shrouded probe and heat· 

traced tubing be used to overcome potential Hg transport problems. 

21 

VESOI1320 
22 EROC/CERL TR-05-9 

45 Cadmium 

40 

a 35 -

• • :~ ... • 30 • 

~ lS oo;-..;:.z •t • ~ 

2U • • •• 

" • 0 IS 0 

u lfi • S · .. .. • 0 

1:00 IS:OO 23:00 . 15:00 23:00 1<l<l JS:OO 23:00 roo l5:00 

5;(4101 S/15101 i/16/01 5117/01 

8 

Chromium 

' a • ·- :r -.. 

6 ~~':/1): .,~ 

i ' !tl.*hi# " 

• ~ 

~ 4 --- • • ~ .; 

• J ~ • 

u • l 

I 

• - • 0 . 

7:00 IS:OO 23:00 7:00 15:00 .!3:00 7:00 ~:00 23:(11) 1':00 1~:00 

i/14i01 5! 15{()1 5116/01 5/ 1 7.'01 

600 

Nickel 

500 

a ~'+ ..... • .... ~ ~ 400 

~ • . ·- .:; :lOO 

.; lOO ~ ... • -· d • 101) • • • 

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 4/01 i/15/01 i/16/01 Sl 17i01 

4.000 

Lead 

3.500 

a 

~ 

3

2,500 

,000 -

• :r. •• 

.:; 2.000 

J 1,500 -;; 5 1,000 • 

son • 

0 • • 

7<10 15;(1!) 2]:00 7:00 t·S:OO 23:00 1o00 IS:CO lJ.(J() 1:00 --1~ () 

5114101 5115101 5i l6101 5/17101 

Figure 8. XCEM and M29 concentrations during TEAD verification tasting. 

VES011321 
ERDCICERLTR..OS-9 

soo.---------------~~~ad~(R=un==s J~-1~3) ----------------, 

• 

e +------------------------------------------------------~ 

i 300 ~---------------------------------- ------------------ --~ 3 ' • 

• ~ 100 +-------~~------------------------ ~·r--------------- ~ "-, r._ 0 100 - :...--------,--- ---- .._ 

l-------.. ~ ------ t-q~~ ~~~~~~---- ---=~~ ----------· ____ j 

1;01) 15:00 23:01) 7:00 15;00 23:00 7:00 ,,:00 23:00 7!00 ~00 

5114/QI 5/ 15/QL Sl 16/01 5117/01 

Ba.ri11m 3~ r-------------------~~~=-----------------------, 

300 -

-! 2S0 i ·---~ · .. ---------A -~------------- ~-- ~---------- --1 

... ~ lOih -,~·~'~ ---------- ~~ -----------~~ ------------ ~~~·~ ~ ~ l--' .. "0!'-' •'---''-F<~r--------.:~,.":'~ ~\,(C:, ..... .. . 5 • 100 ~ ---------------------------~-~-------- ~t-------------~------------------------------~ 

0 A----- ~----~~ ------------~~--~----.---------~~ 7:00 IS~ l):OO 1:00 I S:OO 13~0 7:00 15:00 7:00 15:00 

S/ 14101 5115101 5116.'0 1 5/17101 

Antimony 800 r---------------------~~~~-----------------------, 

700 -1------ e 6oo t-~ ... ~~-- -----------=---- ------------------------------------~ 

~ oo t----- -- --------------------------------------------------~ 

~ ~ 340000 t==,__,. ~~~·~·=========J~~~~ ========::================== :j 

========:====================~---- --~~~ ========== ~ 0 200 100 -1--------.-------------------- •' .. ,.,. 

+----- ---- ------------ ----------------~ 7:01) lS~ ?l:OO 7:00 U:OO 2.l:OO 1:00 1$:00 7;00 1$:00 

5114101 5115101 5116/01 S/J 7101 

Zinc 000 ,-------------------~==~--------------------~ 

500 +-~ ~-----------------~-------------------------- e --. - " 400 f--.,-.!!!t·- ~ -

i 300 -I-~Ju~~~~.~~------ ~~~ ------------------------~ 

~ ~t================~~---------- ' ~~~;: .,; ======== ,;~~~ . ~~~-------~------------ . o+- ----c...: ------ ---------------- --~------------------~ 7:00 l :'i!O!l 13!00 7:•Xl 1.$:00 7:110 ISiOtl 

5114/01 5/ISlO I 5117/01 

Figura 8 (Con!' d). XCEM and M29 concentrations during TEAD verlflcaUon testing. 

23 

VES011322 
24 ERDCICERL TR-05-9 

JSO. 

Mercury 

300 ---- • 25<\ -- { __ ,...,. .. 200 • 

.;, • 

ISO · <II. 

" ,, • '"" • ,. ~ ~ 

- <.> ;o • / ,-. ~ 0 

1!00 1!1:00 23:00 t.OO S~ 2.);()0 t.OO 1.5:00 21:00 7<>0 IS!Ol) 

S/14101 S/ 1 SIOI 5116101 S/17/01 

Palladium 

'" 

i lS - ... --()~ .,_·~ ~riJ~ 

~ 20 "'"·- ~ ~ IS 

~ 

<5 

10 

' 

0 

.... IS:OO lJ:OO ''"" """ :U;QO 

'''" 15:00 """ 1:00 15:00 

S/14101 SII S/01 5116101 5}11101 

Figure 8 (Cont'd). XCEM and M29 concentrations during TEAO verlflcallon tesllng. 

A.ntlm<~ Y Mlt ,.._ XCEM Zktc ,M29 n ;. XCEM 

""' ... 600 -r- ~9) b. • O.G\'7 . .J ""' y"' Laoi?JI.. l:lO~ /.:' - ~t -u.%09 I ......---- .. ... 0,97~1\ :·-=- i ... ~300 

"" ...r'" '"" - ... ""' • • • ooo ""' "" .. , l<O • ,., 20) "" "" XCI» I XC!M 

~ie}!.tt i\1~ YJ. XCEM lnd M19 Vl, XO!M 

000 

~ !:!: ay-1~~~ m 

""' • LMJ.t. · "ll.m l •..r 13.10 ft••l},o;•J!oti 

§m •t1• 0.9-ili2 ~ z.coo <: 1.:00 

""' li>)O 

'"" ,.. • 0 

0 "' ""' JOO .... ""' " ~·· ,..,, ,.,.., !.001) U IJ!J )JJ(l(l 

xn:M xcr.M 

MtJ"(.U)' f\U9 \'$, XCEM U..d Ml1111~ llf:!;at Ro~ M:l9 \'$, XCf.M 

.... '"' =r ·O.~I9 +lt~•s l '"' ""' • ""' &.~W • _.;. • i~: ; '" -- ,., . .. {1,9»1~ "<tM?' ... ltlO 

...:-- • ·~· 

__..._ R!•O.JOOO . -

•• • "' 

" 0 

0 .. "' "" '" "" "" • .. 100 

XCEM XCRM '"' "" "" 

Figure 9. Correlation between XCEM and M29 for elements spiked at two levels. 

VES011323 
EROCICERL TR-05-9 

Table 9. Correlation between the XCEM and M29 

CorrolaUon (R') CorrelaHon (R') Spike Ratio2 

Elem . Hlah Runs: Low Runs (13 Runs) (11 Runs)

1 

MSE M29 XCEM 

Ni 0.9482 0.9753 2.57 2.52 2.12 

Pb 0.9966 0.7623 NS NS NS 

Sb 0.9609 0.9682 2.52 2.56 2.51 

Zn 0.9766 0.9738 2.57 2.54 2.50 

Ha 0.4002 0.3526 3.09 3.11 2.17 

NS. Not sp1ked 1 Runs 3 through 13 2 Hi!;fl runs are runs 3-7: low n.ms are runs 8·13 

Response to Changes in Metal Concentration 

MSE-TA spiked Ni, Sb, Zn, and Hg at two distinct concentration levels. The 

theoretical ratio, based on spiking, between high and low concentration runs 

ranged from 2.52 for Sb to 3.09 for Hg (Table 9). Since these four elements are 

typically not found in the stack gas in significant quantities, it was expected that 

the theoretical ratio would be measured by both the M29 and XCEM. Except for 

the XCEM Hg concentrations, both the XCEM and M29 ratios were in very good 

agreement with the theoretical ratio of concentrations. This 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 XCEM's response to changes in the Pb concentration, which changed by almost two orders of magnitude, was consi.stent with the 

M29 results illustrated in Figure 8. 

Relative Accuracy 

Table 10 shows XCEM, M29 reported concentrations, and MSE-predicted spike 

concentrations. The RA of the XCEM with respect to the M29 was determined 

using PS-10 criteria. Of the 13 M29 runs, 11 were used to calculate RA and average concentrations. During runs 1 and 2, the incinerator experienced problems with a faulty bypass valve, which led to extremely high Pb concentrations 

(1,000 to 3,000 pg!dscm). Although the XCEM tracked the problem, and was in 

fact used to identify and rectify the problem, it was not felt 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 method test runs were completed, the RA procedure 

stated in PS-10 allowed for omission of up to two additional runs from 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 

VESOll324 
< m 

cz; 

0 

..., 

...., 

...,. 

Tabkl1 0. XCEM measured, M29 meaaurod, and MSE1'radlcted metal concentrations (llg/dscm) during lEAD validation toot ing 

R .. "' ..... XC MU 

I 23 II 

l 16 11 

J IJ 9 

4 16 12 

5 16 12 

6 .. 12 

1 11 12 

8 17 ll 

9 11 11.37 

10 18 11.42 

II 16 11 .43 

12 11 9 

13 II 12 

Avg. 

(Rwn 16 II 

3-13) 

XC: XCEM 

NS: Nol spiked 

MS£ 

12 

ll 

II 

" 

I• 

14 

.. 

.. 

. ... 33 

1<4. 16 

14.16 

II 

14 

14 

llo Cd 

XC M:J:f MSE XC >U 9 1\ (i"J~ XC 

187 256 230 l7 JO ll l 

~~ 2"' m l7 ). )I 2 

l$4 101 l06 1S JO JO J 

161 2SS 200 JO )4 )6 j 

17~ Z'l 199 )4 l! lS 6 

110 271 198 ll JS JS • 

114 119 19) l2 ) 4 36 • 

148 262 200 l'2 JS 36 s 

162 2ll 198 32 JS )6 s 

167 214 197 )4 )4 JS 6 

163 233 197 lO ll lS 5 

182 214 200 27 28 26 4 

165 248 195 35 )6 )6 6 

100 240 19ll l l Jl J• ~ 

Cr n, ~jj Pb 

.,., 1\lS£ XC Mlf MS£ XC Ml:9 MS£ XC ~Uf MSE 

4 l I~ 292 285 461 38S 47< I .lAO 1.618 "'S 

4 ) m l76 2:&1 410 <01 

- Z..090 1.242: NS 

• J 260 W> 281 ... 317 ..., 73 .. ,.-:; 

1 s 76 318 m 4!2 4S2 4<$ 62 64 I'S 

6 s 110 318 167 33 411 ... 41 "" NS 

6 s ISl 319 210 443 413 •so •I •s NS 

6 s Ill )IS 210 461 486 4SO •• 52 NS 

1 s 21 104 9l 210 206 1114 229 198 NS 

1 s s.a lOS 90 210 118 119 166 17 NS 

6 s 91 10 1 ss 2Q6 16 1 175 143 84 NS 

• s 94 101 Sl 201 186 175 9() S4 NS 

s 4 62 108 88 218 161 177 195 187 NS 

6 ; 71 lW 82 186 156 163 116 109 NS 

' ~ IOJ 197 171 l09 296 JOI 110 " 

Sb 

XC 1!11'19 MS£ 

J7l 56S 546 

17) 62<1 ~10 

m SJS Sl6 

)61 643 499 

JAI 627 • 91 

)84 694 49' 

)IJ 712 ·~ 1)4 272 200 

14S ll7 191 

147 221 197 

1<4·5 256 197 

156 2J6 200 

1S9 286 195 

250 429 335 

z. 

XC Ml' 

lll 467 

m 471 

))4 4 11 

)40 49S 

lSI •s.a 

l6l Sl2 

367 SotO 

146 219 

146 193 

14) m 

14) 201 

ISO 181 

118 Ill 

m )24 

MS£ 

479 

•n 

469 

«! 

... 

4l0 

.,., 

184 

179 

m 

m 

111 

163 

301 

ll! 

m 

~ 

~ m 

"' ,... 

... 

"' :\: 

., 
ERDCICERL TR-05-9 

Tabl<l11. Relative accuracy and correlations. 

Avg. M29 

Elom. Cone. 

I (~g/dscm) 

Cd 33 

Cr 6 

Ni 296 

Pb 9 1 

Ba 240 

Sb 429 

Zn 324 

As 11.3 

Hg 197 

NS: Not spil<ed 

XC: XCEM 

Avg. MSE 

Avg. XC Pfedicted 

Cone. Cone. 

(~gldscm) . (ugldscm) 

31 34 

5.2 5.0 

309 301 

110 NS 

166 199 

250 335 

237 301 

16.4 13.6 

103 171 

Cadmium, chromium, and nickel 

'loRA ~oRA Notes 

(Runs 3-13) I (9 Runs) 

10 8 Met RA criterion. 

19 15 Met RA criterion. 

11 11 Met RA criterion. 

45 22 

39 37 Spiked wllh Sb. XC Is 

consistenllv low. 

58 55 

Spiked wllh Ba. XC is 

consistefltly low, 

37 35 Potential calibrallon error. 

XC is consisteniiY low. 

55 48 

XC had correctable Pb 

interlerence for As. 

Consistent pattem of 

78 68 increase throughout day 

until concentration 

aPIJ(OSChes M29 value. 

The XCEM and M29 reported concentrations for Cd, Cr, and Ni are in good 

agreement. The average XCEM concentrations for these three metals were 31, 

5.2, and 309 pg/dscm, respectively, while the M29 average concentrations were 

33, 6.0, and 354 pgldscm. The high correlation between the two met.hods is reflected in the low relative accuracies of 10 percent for Cd, 19 percent for Cr, 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 significantly improved if not for a high bias in 

the M29 results due to protocol assumptions and high analytical uncertainties in 

M29 back-half concentrations. EPA M29 protocol requires the assumption that 

the detection limit be used for the concentration when the concentration is in 

fact below the detection limit. In most cases, the detection limit is low relative to 

the measured concentrations. In the case of Cr, however, it is almost 20 percent 

of the total Cr found in the M29 sample train. 

'ZI 

VESOll326 
28 EROC/CERL TR.05·9 

Lead 

The average 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. On 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, the large difference found in runs 9, 10, and 11 was enough to raise the 

RA from about 14 percent for these 8 runs to almost 45 percent for all 11 runs. 

PS-10 allows for 2 of the 11 runs to be dropped. This would have given an RA of 

22 percent for the 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 concentrations during the first two 

runs to a muclt lower concentration during the third run on 14 May and was in 

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 historically measured Pb 

accurately with RAs below 20 percent during the MSE·TA test (Bryson 2000) and 

the laboratory test in 2000 (Hay et al. 2005). 

500 

450 

'B400 ~ 

~ 

~ 350 

.e 300 

.~ 250 

e 200 ~ 

li ISO 

= 8 100 

so 

0 

7:12 

• 

• XCEM-Pb 

• M29·Pb 1-

• 

•• • •• •. . RunS •• •••••• - .· .... ...... -·-·· ••• 

Run 9 --Run 10 Kan 11 

9:36 12:00 14:24 16:48 19:12 21:36 

Flgure10. XCEM and M291ead concentrations during runs 8-11. 

VES011327 
EROCICERL TR-05-9 

Barium and antimony 

Barium and antimony were spiked in the same solution and exhibited similar 

behavior during M29 testing. For both metals, the average XCEM concentrations 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 0.70 :1: 0.08 and 0.59 :1: .06, respectively (Figure 11). The consistent difference in concentrations is reflected in the 

XCEM and M29 ability to measure Sb at two 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 

XCEM 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 concentrations for Ba and Sb were 240 and 429 pgfmS 

respectively, which is more than 20 percent higher than the predicted maximum 

stack concentration based on stack spiking (Table 11). The XCEM Ba and Sb 

concentrations compared favorably to 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 XCEM and predicted concentrations are believed to 

be due to particulate loss in the unheated XCEM transport line and calibration 

errors. 

29 

VESO!l328 
30 

A$ 

~=!...-! · ·=--=--· -:-· · :=·-- ---~ · ! 

' 9 II U 

j ~~ .. . .....-........ c: . . . . , ;,; (l,l -- ····-·-··--------------l· 

] M ·· -· ~~ ·----------------~ ;eC . 

Oh · , 

5 1 • II 

R~t~~ No. " 

H< hr--------! ----~~--, 

.

.

3 .. ~---------------~ 

~ t·-··_-· ... -L·_··_· __ • __ -_-_;- ==--_-_-_-_-_-_-_-_-_-_-_-_-,~ M~----5 ---------------- II ~ " -·· 

Sb Lit,-------""---------. 

~ 8 t--------------1 0 • • 1 ().6 F--.-.. -..... - ..,,--.- ..4---''--.---''--J. 

~ (1,4 +----------------l 

s ., t---------------1 

~----------------~----1 1 9 

Runx .. II " J.! ,-------' '--------... A:: • -----·· 

11.0 ---- ··- .... -- -''-------* -t 7.oJ+----------------~ 

• • 

.,;.., ______________ .J 

l II ll 

ERDC/CERL TR-0$·9 

Ba 

··~t~ .-- ,-------,--.----'·'-~ 

r

~o2 +---------·-·-f~----------------~ 

•L-------.----- ---~ J • " " 

... .-------'0"--------, 

! ~~ f--.--- ·-·--- _.~ ..... ------·::....~ 

f .J 

I o.<f-----------1 

l "'" 1. ------------------------ '·•'-! ______________ ~ 

' 1 • II 

RW~No. " 

,-------~N~I _____ -..-, 

~~ ~r=f .--~· · ~:~ ·g 

' ' ' II " 

,.T ----------~Z~o--------, 

! '' ,; _ _,•::_ ___ • __ •::__!•c__. ____ • ___ i 

1 '' I r +-· ------··-

. ,, ~~ ==========================j 0 .. -'-

., ' RitA No- ' " " 

Figure 11. Ratio of XCEM to M29 concentrations during validation tostlng. 

VESOl l329 
EROC/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 Zn 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 concentt-ations, which is in 

good agreement with the M29 ratio of2.54. 

Unlike Ba and Sb, however, the other elements spiked with Zn showed no indication of 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 Matter standards did not agree for Zn. A decision was made to use the 

NIST standard, which produced significantly lower reported Zn values. 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 MicroMatter calibration standard instead of the NIST standard would have given XCEM 

concentrations about 15 percent higher. 

Arsenic 

In general, the XCEM As concentrations were consistently 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 concentration 

and the As was spiked at a constant rate, the observed correlation was determined to be due to an XRF spectral interference. Arsenic concentrations 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, although the reverse is not true. 

31 

VES011330 
32 ERDCICERL TR-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 measured As concentration. CES adjusted the As numbers accordingly prior to receiving M29 data. Even with this first order adjustment. the XCE.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 concentration was 11.3 pgldscm. 

Since the XCEM saves each XRF spectrum, 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 spectral 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 overlap problem. The XRF can be calibrated using a variety of methods 

that will take into account the Pb/As interference. For example, during the fall 

2000 tests, a calibration method was used that contained both arsenic and Pb. 

No As/Pb interference was observed during these tests (Hay ct a!. 2006). 

200 

-

~ 160 

,5 

.. 

~ 

B 120 

u 

'E 

u 

M 

< 

80 

~ 

tl 

>< 

40 

0 

0 

y c 0.0538x + J 5.961 

~ • 0.989! 

500 I ,000 1,500 2,000 2,500 3,000 3,500 

XCEM Le:td Con<. (Jil:/m') 

Figure 12. Uncorrected XCEM As concenlnrtions versus XCEM Pb conuntrations. 

VES01133l 
ERDCICERL TR.C5·9 

Mercury 

As discussed earlier, the XCEM to M29 Hg ratios varied from run to run. At the 

beginning of each teat day, t he XCEM reported low Hg concentrations relative to 

M29. As the day progressed, tho XCEM concentration would gradually increase 

until it approximated M29 reported concentrations. The pattorn b-uggcsts that 

the transport line from the stack to the XCEM needed to be heated to a higher 

temperature to improve transmission efficiency. The use of a heat-traced trans· 

port line should improve Hg tTanemission efficiency. 

Interestingly, more than 98 percent of the Hg measured by M29 passed through 

the filter and was coUected in the back half of the sample train indicating that 

the vast majority of the Rg was in the vapor phase. Since the XCE~1 had good 

comparisons to M29 on at least four runs {3, 10, 1.1, and 13), the test indicates 

that the XCEM was able to efficiently trap and measure Rg as a vapor. 

Precision 

Precision was calculated in terms of the percent relative standard deviation 

(RSD) of a series of XCEM measurements made during relatively stable opera· 

tion of the TEAD incinerator, with metals injected at a relatively constant rate. 

This precision reflects not only the XCEM variability, but also the variability in 

the stack concentrations, spiking rate, and flow variability. 

Method 29 dual sample train precision 

During testing, CHPPM ran dual M29 sample trains. Percent differences 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 result is significantly better than the typical agreement between trains, 

which is on the order of 15 percent (EPA 1999). This better-than-typical agreement indicates that M29 sampling and analysis were conducted in a precise 

manner. 

Method 29 vs. XCEM precision 

The spike injection rate was altered on t he first day of testing, 14 May, to ensure 

spiked emissions were within the site permit limitations. On 17 May, stack oon· 

ditions were not stable following stack repairs. However, MSE-TA and TEAD 

reported reasonably stable conditions on 15 and 16 May and the spiking preci· 

sion was estimated at 2 percent. For this reason, the eight runs on 15 and 16 

May were used for precision calculations. 

33 

VES0ll332 
ERDC/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. The XCEM 

precision, however, was heavily influenced by the highly variable Hg results. 

For the non-Hg elements, the precision of the XCEM W8ij 3. 7 percent, while the 

average M29 precision for the same group of elements waa 6.8 percent. 

The XCEM also measures Pd with every sample. The average XCEM Pd concen· 

tration was 25 :t 0.6 pg, which gives a precision of about 2.5 percent. Palladium 

concentrations reflect XRF precision, but are independent of flow, spiking, and 

sampling variability. 

Overall then, tho XCEM performed in a very consistent manner and exhibited 

precision on the same ordel· as or slightly bette•· than M29 for al.l elements except 

Hg. 

Table 12. Percent dlffe,..ncao between M29 sample trains.' 

Run As 811 Cd Cr Hg Ni Pb Sb 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 -15 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 12 0 9 7 3 7 6 

10 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~ ~ dllr"rence is dttwmiaed by ·~i.nc Lbe ~t.bso!ute vflllle ul tbtl dill't-h!noo beL'fiooll llllnlllle 

tra.ics. 

VES011333 
ER.DC/CERL TR.Os-9 

Table 13 XCEM ond M29 precision. 

Elem. 1\119 Avg. Ml9 Cone. !\U9 ~. A~-g. XC Con<. XC % RSD 

Runs {l!gfdK.m) RSD (Jlgfdscm) (By 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 35.4 

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 7.2 354 3.4 

Zn (low) 8-11 197 9.2 144 1.2 

Avg. (All •lem.) 5.8 10.1 

Avg. (No ~) 6.8 3.7 

Low-Level Metal Re.sponse 

Low-level mota! response was detennined by comparison of M29 and XCEM· 

reported Cr and As concentrations. Neither of these elements is found in significant quantities in 'rEAD stack emwions and both are regulated to low Je,•els 

onder t.be si~based RCRA limitations. Both elements were spiked 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 XCEM accurately measured Cr relative to M29 with on RA of 19 percent. 

'rhe average XCEM Cr concentration was 5.2 :!: 0.9 )lgfm' while the 11129 average 

was 6.0 :t 0.8 pglm•. The M29 concentrations reported the detection limit for the 

back half when no Cr was measured, which occurred for more than half of the 

samples. Since the M29 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 better than 10 percent. This consis· 

tent agreement between the two methods demonstrates the capability of the 

XCEM to measure metsls at low concentrations even in the presence of high con· 

centmtions of interfering elements such as Ba. 

As discussed earlier, the XCEM As concentrations were biased by Pb interference. For this reason, the XCE..l\1 As concentrations were routinely highor than 

the M29 concentrations. 

VES011334 
36 ERDCICERL TR-o5-9 

Bias 

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 trains. 

so, = 

where: 

L(d,-d.Y 

(n-1) 

d, c the difference between the two somplo trnin vnlues 

d. " mean of the d, vnlues 

n "' number of paired samples 

[Eq4] 

Using the standard deviation deternrined in Equation 4, the t-statistic is then 

calculated as follows: 

id.i 

(7n) [Eq 5] 

Based on EPA criteria, a statistically 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 for 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 was not oonsisteot by element 

with sample Train A being higher for Cr and Hg while Train B was slightly 

higher for As, Ba, Cd, Ni, Sb, and Zn. Overall, the M29 sample trains had an 8\'· 

erage a.bsolu~ percent difference of abou t 6 percent ('!'able 9). Since the M29 

bias for individual elements was relati\·ely small and no consistent differences 

between sample trains was noted, it was determined that tho average M29 con· 

centration would be used for comparison purposes and no CO<Teetioo would be 

taken to compensa~ for bias. 

VES011335 
ERDCICERL TR-4S.9 

Relative to M29, the XCEM showed significant bias for all elements (Table 14). 

This bias is believed to be a product of XCEM transport and calibration problems. Method 301 outlines a procedure for determining correction factors that 

can be applied 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 

percent RA criterion for nlJ of the elements except Hg. Although this method 

shows the existence of a high level of correlation, it is important to note that the 

XCEM correction factors are outside of the acceptable range for validation of Pb, 

Ba, Sb, Zn, As, and Hg. 

Table 14. Method 301 bias and cor"'ction factor comparison. 

Significant Correction RA with Corrected RA 

Element T.stat Corr. Factor Blaa Factor !Runs 3·13) Meets PS-10 

Cd 5.33 Yes 1.08 3.9 Yes 

Cr 6.41 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 11.75 Yes 0.69 7.8 Yes 

Hg 3.44 Yes 1.91 35.9 No 

1 U~onlyr1ne runs as suggested"' PS-10. PbRAwouldhave been 1• percent 

Summary 

The XCEM was constructed, installed at the TEAD incinerator, and tested 

against M29. The primary objective was to meet the proposed requirements of 

PS-10. FoUowing is a list of the individual requirements and discUJlsion of the 

performance of the XCEM: 

1. Response time and reporting time: The XCEM had a response time of 20 

minutes, meeting the PS-10 criterion for batch CEM.s. It experienced no me· 

chanical problems and had an effective up-time of 100 peroent. 

2. QA: The XCEM showed a calibration 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 less than 20 percent. 

VES011336 
38 EROC/CERL 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 Zn. The Zn differences are believed 

to be due to an incorrect XCEM ca.libration standard that lowered the 

XCEM concentrations by about 15 percente. The XCEM was also consistently low for Ba and Sb. These differences 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 recorded concentrations, temperatuTes, now rates, 

and QA data_ It also showed a precision of better than 4 percent for periods 

when spiking and stack conditions were held relatively constant. 

An analysis of reported conccntrr1tions using EPA Method 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 acceptable range for validation. Table 15 summarizes the results 

relative to PS-10. 

Tabfe1 5 St.mmary of XCEM performance ralatlve to proposed P5-10 requirements 

Test Goal - Criterion? Discussion 

sampling and Elchlb~ed a 100% up.&ne for tesl ~led kl< greater than 

Yes 99.5% or the time. Reported time averaged eonoentratlontl avery Response Time 20 minulos with a 20-minute lag -n S\ll!l>ling_and reoortlno. 

QA Yes Tho XCEM exhibijed a precision or 1 to 2% lor zero drift. The 

XRF calibration drift was less than 0.5% for the 4 davs or teslinn. 

Met 20% RA criteria lor J<!l, Q!, and Ni. Had a 22% RA lor fll. 

Yes for 3 Was systamalically biased for§;!, Sb. Zn. nod As. Old not 

RA No for 6 suocessfufly meaS<J<e Hg. For response to change In 

coocontratlon. had correlatlon (r') of 0.95 or benor for Nl, Sb. and 

elements Zn. Unclerlined elements are regulated elements typically found 

in lhe Tooele leedstream. 

VES011337 
ERDC/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 response time, but only met the RA criterion for three 

elements (Cr, Cd, and Ni). An evaluation of t.he test parameters indicated that 

changes to t.he transport line, improvements in calibration, and testing of the 

XCEM vs. stack spiking would improve the XCEM RA. 

During the spring of 2002, improvements were made to the XCEM transport line 

and a second series of preliminary tesb were conducted to better understand 

calibration and stack spilcing efficiency. This chapter discusses the changes to 

the transport line, calibration, and test •·osults. 

Transport Line Changes 

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. During 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 XCE.M Hg concentrations approached 

M29 results. For this reason, it. was determined that the XCEM required a 

heated transport line. 

In March 2002 t.he XCEM shelter was moved to a location that required only 13 

ft of horizontal transport. Following the move, the line was heat traced, insu· 

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 1993). The combined effect of these changes 

was to minimize Hg and particulate loss in the sample line. 

39 

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Recallbratlon 

During the week of 8 April 2002, CES recalibrated the instrument using thinfilm MkroMatter standards. The thin-film standards are developed by flashing 

the metal of interest onto a nuclepore filter, resulting in a known concentration 

of metal in micrograms per square centimeter (Jlgfcm2) . The XRF unit used by 

the XCEM had not been calibrated since Augu;~t 2001. Before recalib•·aling, CES 

analyzed the MicroMatter 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 standards, which indicated that it had maintained good 

stability for 9 months and would not have needed recalibration under normal 

operating conditions. 

Following the initial check, several changes were made to the calibration procedure to improve spectral deconvolution. These changes included: 

• Development of a representative 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 within 1.5 percent of the listed values for all 

elements except Sb (6 percent) and Ba (15 percent). Tbe accuracy of the Army 

MicroMatter standards was in question, so they were compared to CES MicroMatter standards at the CES laboratory. Some inconsistencies for Cd and Pb 

were noted between the Army and the CES l.'.ticroMatter standards. They were 

also compared with standards from NIST. The resull.s from the analysis of the 

NlST and CES MicroMatter standards were compared with the Army Microl\1at· 

ter standards, and it was determined 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 to the transport line were tested by comparing XCEM concentrations to 

concentrations based upon stack spiking estimat-es and an in-stack EPA Reference Method 17 (Ml7) filter. Overall, no measurable loss of particulates in the 

improved XCEM transport line was observed. The calibration was tested using a 

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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. 

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42 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 conducted 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 XCEM 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. 

Results 

Method 29 Concentrations 

Method 29 tests were conducted using duplicate sample trains located at the 

same stsck height as the XCEM probe. In general, the two trains 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 other. 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 deactivated munitions. 

Overall, train A was higher than train B by about 3 percent with about 78 percent of the concentrations in train A being higher than their train B counterpart. 

An average of trains A and B was used for comparison to the XCEM reported 

concentrations. 

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.* 

Person!¥ oommunica!Son: Robert Weldenfe!d, Se\leren Trent Lab, with John Cooper, CES, 9 July 2<102. 

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