82 ERDC/CERL TR-05-9 

2) Continuous Emissions Monitoring Systems, CE M systems are in place 

to measure carbon monoxide (CO) and oxygen (02) in the exhaust stack. The 

C EM sampling system includes the following: sample extraction probe, heat 

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

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

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

calibration, which allows the monitors to be calibrated periodically without 

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

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

to 7 percent 0 2 (using data from the 0 2 CEM). 

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

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

box, and a slide chute. The scale reports the measured weight to the PLC via a 

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

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

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

item onto the slide chute, which is over the primary feed conveyor. The WFRMS 

is capable of cycling every 15 seconds. 

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

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

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

continue moving through the furnace and deters possible explosions outside the 

furnace. 

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

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

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

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

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

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

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

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

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

have been established for each ammunition item by controlled testing. The roVES016900 
ERDC/CERL TR-05-9 83 

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

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

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

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

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

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

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

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

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

furnace burner. 

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

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

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

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

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

alternatively so that only one gate is open at any time, thus maintaining the 

negative pressure. 

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

Technology Incorporated. The afterburner is designed to raise the temperature 

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

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

afterburner is capable of heating 4000 scfm of flue gas from 350-450 °F to 1400-

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

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

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

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

conveyor located at the discharge/burner end. The solid waste is typically comprised of the metal casings, melted lead projectiles, and residual ash. The low 

end of the discharge conveyor is located underneath the discharge/burner end of 

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

barricade wall and deposits the waste into containers. 

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

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

VES016901 
84 ERDC/CERL TR-05-9 

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

JT Systems Incorporated. The flue gases from the afterburner are transported 

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

afterburner to 1000 °F entering the baghouse. The baghouse contains 154 cerafil 

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

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

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

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

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

seal on the baghouse assembly. 

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

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

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

inches of water column. 

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

3.2 TEAD Emission Limits During Testing 

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

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

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

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

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

Antimony (Sb) 14 Lead (Pb) 4.3 

Arsenic (As) 0.11 Mercury (Hg) 14 

Barium (Ba) 2400 Nickel (Ni) 930 

Beryllium (Be) 0.20 Selenium (Se) 180 

Cadmium (Cd) 0.26 Silver (Ag) 140 

Chromium (Cr) 0.04 Thallium (Tl) 14 

VES016902 
ERDC/CERL TR-05-9 85 

4.0 EXPERIMENTAL DESIGN 

4.1 General Design 

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

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

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

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

shows the nine elements that will be measured by the XCE M during verification 

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

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

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

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

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

Stack gas metal concentrations will be simultaneously determined by the XCE M 

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

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

for the M29 test run. 

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

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

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

velocity traverse to determine a representative sampling point for the M29 

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

the base of the exhaust stack. The nearest flow disturbances are located 9.8 duct 

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

of the stack) from the sample ports. 

VES016903 
86 ERDC/CERL TR-05-9 

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

Fuze, Bomb, Tail, MK344 Mod 0/1 

Feed Rate: 79 items/hr; Loading (lb/item) 0.2791 

Component Component Quantity (lb/item) 

Component 

Feed Rate 

(lb/hr) 

Butyl Acetate 0.00001 0.0008 

Charcoal 0.00002 0.0016 

Ethyl Alcohol 0.00001 0.0008 

Graphite 0.00541 0.4275 

Lead Azide 0.00028 0.0221 

Lead Monoxide 0.00005 0.0040 

Lead Powder 0.00031 0.0245 

Lead Styphnate 0.00683 0.5398 

Nitrocellulose 0.00002 0.0016 

Nitrostarch 0.00001 0.0009 

PETN 0.00031 0.0245 

Potassium Nitrate 0.00008 0.0063 

Selenium Powder 0.00012 0.0095 

Sulfur 0.00005 0.0040 

Tetryl 0.26555 20.9855 

Toluene 0.00001 0.0008 

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

Elements 

Emission Limits1 Spiking Level1 

Elements 

g/hr ~ fig/ dscm 

Elements ~ ug/ dscm 

g/hr ~ fig/ dscm 

Runs 1-6 Runs 7-12 

As 0.11 17 15 15 

Ba 2,400 360,000 1000 1000 

Cd 0.26 39 35 35 

Cr 0.04 6.5 5.5 5.5 

Hg 14 2,100 100 300 

Ni 930 139,500 200 500 

Pb 4.3 645 NS NS 

Sb 14 2,100 200 500 

Zn NR NR 200 500 

1 The concentration in ug/dscm assumes a stack flow rate of about 6700 dscm/hr 

NR: Not regulated NS: Not Spiked 

VES016904 
ERDC/CERL TR-05-3 87 

CHPPM will conduct the chemical analysis of recovered sample fractions from 

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

will conform to the requirements of M29. Accuracy data for metals analysis will 

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

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

analytical process to the original sample. 

4.2 Test Schedule 

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

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

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

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

4.3 Test Procedures 

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

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

The intent of this approach is to allow comparisons of XCE M data to reference 

method data under constant conditions. 

4.3.1 Spiking approach 

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

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

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

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

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

good mixing. 

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

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

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

VES016905 
88 ERDC/CERL TR-05-9 

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

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

the verification test. 

4.3.2 Reference method sampling 

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

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

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

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

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

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

Pitot tubes undergo a geometric calibration, and thermocouples are calibrated 

using standard two point calibration methods. 

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

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

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

set. 

4.3.3 Reference method analysis 

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

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

M29 section 9.1 protocols and a standard blank subtraction will be made if significant metals are found in the blank. 

CHPPM uses ICP-MS for its metals analysis. The ICP-MS is calibrated using 

solution standards as discussed in section 10.2 of M29. 

4.4 Data Comparisons 

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

that will be used for the verification comparisons. 

VES016906 
ERDC/CERL TR-05-9 89 

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

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

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

relative accuracy and correlation calculations. 

Precision will be determined by analysis of XCE M concentrations when the spike 

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

reported precision will include variability in stack conditions as well as XCE M 

variability. 

Table 4-5. Summary of data to be obtained during XCE M verification test. 

Performance 

Parameter 

Objective 

Comparison 

Based On 

No. of 

Data 

Points 

Accuracy 

Determine degree of quantitative 

agreement with reference method. 

Reference Method 

Results 

12 

Correlation 

Determine degree of correlation 

with reference method. 

Reference Method 

Results 

12 

Precision 

Determine degree of consistency in 

XCEM measured concentrations 

under constant operating 

conditions. 

XCE M reported 

concentrations 

under constant 

operating 

conditions. 

6/run 

Instrument 

Drift 

Determine XCEM ability to 

measure consistently over the 

course of the test. 

Determine 

variation in 

palladium 

concentrations 

determined with 

each XCE M 

measurement 

3/hr 

Span and Zero 

Determine XCE M response under 

maximum and minimum conditions 

XCE M automated 

daily QA routine 

4 

Response Time 

Determine XCE M response time as 

a batch CEM. 

Continuous 

monitoring of metal 

concentrations 

3/hr 

Bias 

Determine if bias exists between 

M29 and the XCEM. 

Reference Method 

Results 

12 

Low Level 

Metal Response 

Determine XCEM performance 

when low metal concentrations are 

present in the stack. 

Arsenic and 

chromium ref. 

Method results 

24 

VES016907 
90 ERDC/CERL TR-05-9 

Instrument drift will be determined by evaluation of XCE M reported palladium 

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

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

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

reported concentrations is maintained. The percent relative standard deviation 

for palladium concentrations will also serve as a determination of XCE M instrument drift during testing. 

XCE M response time will be determined as the time between the start of one 

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

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

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

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

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

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

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

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

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

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

and compared to reported XCE M data. 

The XCEM's ability to measure low-level concentrations of metals will be challenged by Cr, As, and Cd, which are to be present at approximately 5, 15, and 35 

pg/dscm respectively. 

M29 results identified as outliers will be reported, but will not be used for verification. The intent of this approach is to provide a valid set of reference data for 

verification purposes, while also illustrating the degree of variability of the reference method. Identification of outliers will be based upon analysis of percent 

differences in M29 concentrations between sampling trains and trends in data 

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

According to PS-10, the XCE M acts as a batch CEM. Batch CEMs continuously 

sample and concentrate the pollutant on a capture medium. Analysis is performed after sufficient time has elapsed to concentrate the pollutant to levels 

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

response time criteria: 

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

the apphcable standard. 

VES016908 
ERDC/CERL TR-05-9 91 

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

period shall be no greater than 1 hour. 

3. Samphng shall be continuous except in that the pause in sampling when the 

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

averaging period or 5 minutes, whichever is less. 

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

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

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

minutes per hour. 

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

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

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

are determined by analysis of blank filter tape. 

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

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

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

through observation and through communication with the vendors during the 

test. Factors to be noted include the frequency of scheduled maintenance activities, the downtime of the CEM, and the number of staff operating or maintaining 

it during the verification test. 

5.0 STATISTICAL CALCULATIONS 

Statistical calculations will be used to verify the performance of the XCEM as 

described below. In all cases, measurement results from both the reference 

method and the XCE M are reported in units of pg/m3 on a dry basis at 20 °C, 

1 atmosphere pressure, and the actual flue gas 0 2 content. 

5.1 XCEM Concentrations During a Reference Method Run 

Average XCEM concentrations for a given reference method run will be calculated as follows: 

VES016909 
92 ERDC/CERL TR-05-9 

[Eq 5.1] 

where: 

Cj = XCE M time-weighted concentration for element i during M29 test run 

C jj = XCE M reported concentration for element i during time interval j 

n = number of XCEM measurements during test run 

t, = number of minutes XCE M measured element i's concentration during 

time interval j 

5.2 Relative Accuracy 

The relative accuracy (RA) of the XCEM with respect to the reference method 

(M29) will be assessed by: 

\d\ + t" 

RA = —^-xl00 % [Eq 5.2] 

Where d refers to the difference between M29 and the XCE M results, and x corresponds to the M29 result. Sd

 denotes the sample standard deviation of the differences, while t a

n l is the t value for the 100(l-a)th

 percentile of the distribution 

with n' ! degrees of freedom. The RA will be determined for an a value of 0.025 

(i.e., 97.5 percent confidence level, one-tailed). The RA calculated in this way can 

be interpreted as an upper confidence bound for the relative bias of the analyzer, 

PI 

i.e., where the superscript bar indicates the average absolute value of the 

x 

differences of the reference values. If 12 reference method test runs are completed, the RA procedure stated in PS-10 will be followed (i.e., up to three results 

may be omitted from the RA calculation). The impact of the number of data 

points (n) on the RA value will be noted in the verification report. The RA will be 

calculated separately for each metal measured by the XCEM . 

5.3 Correlation with Reference Method 

The degree of correlation of the XCE M with the reference method results will be 

assessed in terms of the correlation coefficient (r2) for metals spiked at more than 

one concentration (i.e., Hg, Ni, Zn, and Sb). 

VES016910 
ERDC/CERL TR-05-9 93 

A second series of intra-method correlations will be determined by comparing the 

relative ratios of metals measured by the XCE M for each of the measurement 

periods. This correlation assumes that no fractionation of the injected species 

occurred during transport. 

5.4 Precision 

Precision will be calculated in terms of the percent relative standard deviation 

(RSD) of a series of XCEM measurements made during stable operation of the 

TEAD, with metals injected at a constant level. This precision will reflect the 

variability in the stack conditions, spiking rate, and XCE M measurements and 

will be identified as a maximum XCE M precision with a note in the verification 

report that the calculated precision is subject to the variability of the test, not 

only the XCE M variabihty. During each M29 sampling run, all readings from 

the XCE M will be recorded and the mean and standard deviation of those recordings will be calculated. Percent precision (P) will then be determined as: 

o n 

P = ^xl0 0 [Eq5.3] 

X 

where SD is the standard deviation ofthe XCEM readings and X is the mean of 

the readings. The same calculation will be performed for each metal measured 

by the XCEM. 

5.5 Span, Zero, and Instrument Drift 

The XCEM has automated daily span and zero checks and reports a palladium 

concentration with each sample to check for instrument drift. Span, zero, and 

instrument drift will be reported in terms of the mean, RSD, and range (maximum and mimmum) of the readings obtained from the XCEM. The percent RSD 

will be calculated as: 

RSD = ~xl0 0 [Eq5.4] 

X 

where X is the mean, and SD is the standard deviation of the daily readings of 

the standard. This calculation, along with the range of data, will indicate the 

day-to-day variation in zero and standard readings. 

VES016911 
94 ERDC/CERL TR-05-9 

5.6 Method 29 and XCEM Bias 

Bias between the two M29 sampling trains and the M29/XCEM data will be determined using an EPA Method 301 approach. The results are tested for statistically significant bias by calculating the t-statistic and determining if the mean of 

the differences between the two sampling trains is significant at the 80-percent 

confidence level. The t-statistic is calculated by finding the SD of the differences 

between the two sampling trains. 

E(<w„ ) 

Where: 

dj = the difference between the two sample train values 

dm = mean of the d; values 

n = number of paired samples 

Using the SD determined in equation 5.5, the t-statistic is then calculated as follows: 

The critical value ofthe t-statistic is 0.8755 for 12 runs. If the calculated t-value 

is greater than the critical value, the bias as defined by M301 is statistically significant. A statistically significant bias in the reference method will be noted in 

the validation report. 

Method 29 data pairs that are determined to be unbiased relative to each other 

will be averaged and used for comparison to the XCEM. Bias between the 

XCE M and average M29 data will be determined using equations 5.5 and 5.6 

with ^ being the difference between the average M29 and XCE M data. 

VES016912 
ERDC/CERL TR-05-9 95 

6.0 MATERIALS AND EQUIPMENT 

6.1 Gases and Chemicals 

6.1.1 Compressed gas 

The XCEM requires about 10 scfm of dry compressed gas to provide a vacuum in 

the extraction system. A small amount of purified compressed gas is also used to 

drive the XCE M pneumatics. The atomizers used for spiking will require about 

10 scfm of dry air. 

6.1.2 Spike injection solutions 

The spike injection solutions include Ba(N03)2, Cd(N03)2, Cr(N03 )3, As 2Os, 

Hg(N03)2, Ni(N03 )2, Zn(N03)2, and SbCl 2. Solutions will be prepared on-site to 

allow for flexibility in responding to background metal concentrations found in 

the TEAD incinerator. 

6.2 Reference Method 

6.2.1 Sampling trains 

CHPPM will supply the glassware, filters, and associated equipment for M29 

sampling. Multiple trains will be supplied so that six trains (i.e., three sampling 

runs with two trains each) may be sampled in a single day; in addition, at least 

two M29 field spikes and a media blank will be analyzed. Preparation, sampling, sample recovery, and cleaning of used trains will be the responsibility of 

CHPPM during this verification test. 

6.2.2 Analysis equipment 

CHPPM will provide laboratory equipment for sample recovery and analysis. 

This will include all chemicals and solutions for rinsing train components and 

recovering impinger samples. 

6.3 TEAD Monitoring Equipment 

The verification will make use of monitoring equipment already integrated into 

the TEAD facility. This equipment includes monitors for major flue gas constituents (02

, C02 ), as well as sensors for temperature and pressure. These devices 

are considered part of the TEAD facility for purposes of this test, and will be operated during this verification according to normal TEAD procedures. 

VES016913 
96 ERDC/CERL TR-05-9 

7.0 QUALITY ASSURANCE/QUALITY CONTROL 

7.1 Assessments and Audits 

7.1.1 Technical systems audits 

Battelle's Quality Manager, will perform a technical systems audit (TSA) once 

during the performance ofthis verification test. The purpose ofthe TSA is to ensure that the verification test is being performed in accordance with this test/QA 

plan, and that all QA/QC procedures are being implemented. In this audit, the 

reference sampling and analysis methods used may be reviewed; the actual test 

procedures compared to those specified in this plan; and data acquisition and 

handhng procedures reviewed. The Quahty Manager will also prepare a TSA 

report, the findings of which must be addressed either by modifications of test 

procedures or by documentation in the test records and report. 

At EPA's discretion, EPA QA staff may also conduct an independent on-site TSA 

during the verification test. The TSA findings will be communicated to testing 

staff at the time ofthe audit, and documented in a TSA report. 

7.1.2 Data quality audit 

Battelle's Quality Manager will audit at least 10 percent of the verification data 

acquired in the verification test. The Quality Manager will trace the data from 

initial acquisition, through reduction and statistical comparisons, and to final 

reporting. All calculations performed on the data undergoing audit will be 

checked. 

7.1.3 Assessment reports 

Each assessment and audit will be documented in accordance with section 2.9.7 

of the QMP for the AMS pilot. Assessment reports will include the following: 

• Identification of any adverse findings or potential problems 

• Space for response to adverse findings or potential problems 

• Possible recommendations for resolving problems 

• Citation of any noteworthy practices that may be of use to others 

• Confirmation that solutions have been implemented and are effective. 

7.1.4 Corrective Action 

The Battelle Quality Manager, during the course of any assessment or audit, will 

notify the technical staff performing experimental activities of any immediate 

VES016914 
ERDC/CERL TR-05-9 97 

corrective action that should be taken. Once the assessment report has been 

prepared, the Verification Testing Leader will ensure that a response is provided 

for each adverse finding or potential problem, and will implement any necessary 

follow-up corrective action. The Quality Manager will ensure that follow-up corrective action has been taken. 

8.0 DATA ANALYSIS AND REPORTING 

8.1 Data Acquisition 

Data acquisition in this verification test includes recording of the response data 

from the XCEM, documentation of sampling conditions and analytical results 

from the reference method, and recording of operational data such as combustion 

source conditions, test temperatures, the times of test activities, etc. 

Cooper Environmental Services will perform data acquisition for the XCE M during the test. For all tests, CES will be responsible for reporting the response of 

the XCE M to the sample provided. The XCEM data must include the results of 

all tests conducted each test day and are to be provided to the test manager at 

the end of each day. The XCE M data must include all individual readings of the 

XCE M (i.e., temperature, pressure, metal concentrations, QA data, etc.) listed by 

time of day. Averaged results over the period of an M29 sampling run will be determined following the test and provided to the test manager prior to release of 

M29 data. 

Other data will be recorded in laboratory record books maintained by TEAD, 

CHPPM, Battelle, MSE-TA, and CES staff involved in the testing. These records 

will be reviewed to identify and resolve any inconsistencies. All written records 

must be in ink. Any corrections to notebook entries, or changes in recorded data, 

must be made with a single line through the original entry. The correction is 

then to be entered, initialed, and dated by the person making the correction. 

In all cases, strict confidentiality of data from the XCE M will be maintained. 

Table 8-1 summarizes the types of data to be recorded; how, how often, and by 

whom the recording is made; and the disposition or subsequent processing of the 

data. The general approach is to record all test information immediately and in 

a consistent format throughout all tests. Data recorded by CES is to be turned 

over to the CERL designated test manager immediately upon completion of each 

test day. 

VES016915 
98 ERDC/CERL TR-05-9 

Table 8-1. Summary of data recording process for the verification test. 

Data Tb Be 

Recorded 

Responsible 

Party 

Where 

Recorded 

How Often 

Recorded 

Disposition of 

Data 

Dates, times of test 

events 

CERL Laboratory 

record books 

Start/end of test, 

and at each 

change of a test 

parameter. 

Used to organize/check test 

results; manually 

incorporated in 

data spreadsheets as necessary. 

Test parameters 

(temperature, analyte identities and 

concentrations, flows, 

etc.) 

TEAD, CERL, 

CHPPM 

Laboratory 

record books 

When set or 

changed, or as 

needed to document stability. 

Used to organize/check test 

results; incorporated in data 

spreadsheets as 

necessary. 

XCEM readings including digital displays, printouts, and 

electronic output. 

CES 

Laboratory 

record books, 

data sheets, or 

data acquisition system, as 

appropriate. 

XCEM data will 

be recorded continuously 

throughout test. 

Data sheets will 

be completed as 

required for each 

test. 

Electronically 

transferred to 

spreadsheets. 

Reference method 

sampling data. 

CHPPM Laboratory 

record books 

At least at 

start/end of ref. 

test, and at 

change of a test 

parameter. 

Used to organize/check test 

results; incorporated in data 

spreadsheets as 

necessary. 

Reference method 

sample analysis, 

chain of custody, and 

results. 

CHPPM 

Laboratory 

record books, 

data sheets, or 

data acquisition system, as 

appropriate. 

Throughout sample handling and 

analysis period. 

Transferred to 

spreadsheets. 

8.2 Data Review 

Records generated in the verification test will receive a one-over-one review 

within 2 weeks after generation. These reviews are to be performed within the 

organization generating the data. These records will then be used to calculate, 

evaluate, and report verification results. These records may include laboratory 

record books; operating data from the combustion source; XCE M data; or reference method analytical results. The review will be documented by the person 

performing the review by adding his/her initials and date to a hard copy of the 

record being reviewed. This hard copy will then be returned to the staff who 

VES016916 
ERDC/CERL TR-05-9 99 

generated or who will be storing the record. Battelle will receive a copy of all 

written and recorded data in the project record books and a copy of the XCE M 

data. 

8.3 Reporting 

Cooper Environmental Services will prepare a summary test report for CERL 

documenting the testing results. The summary report will include a discussion 

of the XCEM performance, testing processes, and a comparison with M29 results. CES will provide Battelle with this summary test report and copies of all 

original raw field and laboratory data. 

Battelle will prepare an ETV verification report and statement for the testing 

that includes the test data and a statistical evaluation ofthe data as described in 

sections 4 and 5. The verification report will briefly describe the ETV program 

and the AMS Center, and will describe the procedures used in verification testing. The results of the verification test will be stated quantitatively, without 

comment on the acceptability of the XCEM's performance. The summary test 

report prepared by CES will serve as the basis for the draft ETV verification report. The ETV verification report and statement will undergo a technical peer 

review. Final approval and distribution of the ETV verification report and 

statement will be conducted as stated in the Generic Verification Protocol for the 

Advanced Momtoring Systems Pilot. 

9.0 HEALTH AND SAFETY 

The verification test described in this test/QA plan will be performed at the 

TEAD facility in Tooele, Utah. All participants in this verification test will adhere to the health and safety requirements of the facility. Vendor staff will be 

operating their equipment only during the verification test. They are not responsible for, nor permitted to, operate the combustion source or perform any 

other verification activities identified in this test/QA plan. Operation of the 

XCE M does not pose any known chemical, fire, mechanical, electrical, noise, or 

other potential hazard. 

A ll visiting staff at the TEAD will be given a site-specific safety briefing prior to 

the installation and operation of the XCEM. This briefing will include a description of emergency operating procedures (i.e., in case of fire, tornado, laboratory 

accident) and identification and location and operation of safety equipment (e.g. 

fire alarms, fire extinguishers, eye washes, exits. Test participants are required 

VES016917 
100 ERDC/CERL TR-05-9 

to wear hearing protection. Steel-toed safety shoes and work gloves are recommended. Eye wear is not required. 

10.0 REFERENCES 

Battelle. (1998). Generic Verification Protocol for the Advanced Monitoring Systems Pilot, Battelle, Columbus, Ohio, November 1998. 

Bryson, S., C. Whitworth, and S. Kujawa. (2000). Final Report - Test and 

Evaluation of an X-Ray Fluorescence Based Multi-Element Metals Continuous 

Emission Monitor. Prepared for U.S. Army Corp of Engineers by MSE-TA, Butte, 

MT. 

Environmental Protection Agency (EPA). (2000). Quality Management Plan 

(QMP) for the ETV Advanced Monitoring Systems Pilot, U.S. EPA Environmental Technology Verification Program, prepared by Battelle, Columbus, Ohio. 

EPA. (1998). EPA Environmental Technology Verification Program Quality and 

Management Plan for the Pilot Period (1995-2000), EPA-600/R-98/064, U.S. Environmental Protection Agency, Cincinnati, OH, May 1998. 

EPA. (1996). Proposed Performance Specification 10 for Multi-Metal Continuous 

Emission Monitors, U.S. Environmental Protection Agency, Washington, DC. 

EPA. (1991). U.S. EPA Method 301 Field Validation of Emission Concentrations 

from Stationary Sources. Federal Register Vol. 56, No. 114. June 13,1991. 

EPA. (1990). U.S. EPA Method 29 Determination of Metal Emissions from Stationary Sources. From EPA's technology transfer website www.epa.gov/ttn. 
ERDC/CERL TR-05-9 101 

Appendix B: Determination of XCEM 

Reported Concentrations 2001 

XCEM Metal Concentration Determination 

To measure metal concentrations in stack gas, the XCE M uses an Aalborg mass 

flow controller to obtain flow rates and a QuanX energy dispersive x-ray fluorescence (XRF) analyzer to determine mass concentrations. The QuanX reported 

mass concentrations are then divided by the total dry flow to obtain concentrations in micrograms per dry standard cubic meter . The entire process is automated by a custom WonderWare® software interface. The original concentrations 

reported during the 2001 test are shown in Table Bl . 

Test data were modified according to a final post-test calibration and evaluation 

of dryer capabilities resulting in an 8 percent increase in reported metal concentrations. All calibration adjustments were completed prior to receiving M29 results. The final reported concentrations with the 8 percent correction are shown 

in XCEM Reported Concentrations (page 15). 

Global Corrections to Reported Concentrations 

Flow Corrections 

For the TEAD vahdation testing, the mass flow meter was cross-checked with a 

Sierra mass flow meter and was determined to be in good agreement. For this 

reason, no changes were made to flow measurements applied to reported concentrations. 

Mass Corrections 

Due to the rapid turn-around time required for this project (6 weeks between 

contract award date and dehvery date), a final XRF calibration was not conducted until after the tests. The XCE M is cahbrated with thin-film standards 

produced by the National Institute of Standards and Testing (NIST) and MicroVES016919 
102 ERDC/CERL TR-05-9 

Matter Inc. (Deer Harbor, WA). These standards, which are 47-mm in diameter, 

are larger than the x-ray beam intensity area. In contrast, the exposed spot on 

the XCEM filter is about 7 mm in diameter and is smaller than the x-ray beam 

intensity area. A global conversion factor is required to convert intensities from 

thin film to spot size. During the final calibration it was determined that a 

global increase of 4.4 percent was required to better account for the thin-film to 

spot conversion factor. 

Dryer Inefficiency Corrections 

The XCE M uses a gas dryer built by Universal Analyzer of Reno, NV. The dryer 

cools gas to a predefined temperature, which condenses the water in the gas 

stream. Water is then removed from the dryer using a pneumatic pump. Following the test, it was determined that manufacturer specifications were not properly defined for the partial vacuum in the XCEM. CES conducted extensive testing on the gas dryer (Table B2) and determined that, under a partial vacuum, 

the XCE M had 3.5 percent water content. For this reason, the XCEM concentrations were increased uniformly by 3.5 percent. 

VES016920 
ERDC/CERL TR-05-9 103 

Table B1. Original XCEM reported concentrations (ug/dscm) uncorrected for calibration and dryer changes. 

Date Start Stop XCNo. RM No. 

XC Time 

(min) As Ba Cd Cr Hg Ni Pb Sb Zn 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

10:45 

11:05 

11:26 

11:48 

12:10 

12:31 

12:53 

11:05 

11:26 

11:48 

12.09 

12:31 

12:53 

13:15 

650 

651 

652 

653 

654 

655 

656 

Run 1 

Run 1 

Run 1 

Run 1 

Run 1 

Run 1 

Run 1 

19:48.0 

21:12.0 

21:32.0 

21:42.0 

21:41.0 

21:51.0 

22:07.0 

74.2 

78.6 

76.8 

78.8 

89.1 

99.9 

57.4 

153 

158 

178 

153 

174 

202 

187 

25.7 

24.0 

24.5 

20.2 

26.1 

29.5 

25.2 

2.8 

2.3 

1.7 

2.0 

2.4 

2.0 

2.2 

55 

101 

145 

192 

224 

238 

262 

318 

403 

432 

415 

435 

477 

428 

1,020 

1,043 

1,064 

1,107 

1,221 

1,487 

656 

314 

345 

334 

327 

349 

369 

358 

275 

293 

296 

292 

317 

344 

322 

Average 

SD 

RSD 

21:24.7 79.2 

13.1 

17 

172 

18 

11 

25.0 

2.8 

11 

2.2 

0.4 

16 

174 

76 

44 

416 

49 

12 

1,086 

249 

23 

342 

19 

5 

306 

23 

8 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

13:58 

14:23 

14:46 

15:09 

15:32 

15:55 

14:23 

14:46 

15:09 

15:32 

15:55 

16:17 

659 

660 

661 

662 

663 

664 

Run 2 

Run 2 

Run 2 

Run 2 

Run 2 

Run 2 

25:09.0 

22:56.0 

22:56.0 

22:54.0 

22:36.0 

22:34.0 

177.3 

165.0 

162.3 

155.7 

146.1 

25.5 

213 

207 

230 

231 

180 

159 

24.8 

27.3 

24.1 

20.7 

27.0 

25.1 

2.2 

1.9 

1.1 

1.9 

1.1 

2.4 

172 

217 

226 

204 

221 

238 

347 

395 

395 

375 

384 

363 

3,168 

3,007 

2,793 

2,484 

2,173 

168 

333 

351 

368 

342 

351 

322 

277 

320 

325 

307 

321 

295 

Average 

SD 

RSD 

23:10.8 138.6 

56.4 

41 

203 

29 

14 

24.8 

2.4 

10 

1.8 

0.5 

30 

213 

23 

11 

377 

19 

5 

2,299 

1,104 

48 

345 

16 

5 

307 

19 

6 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

5/14/01 

17:00 

17:23 

17:44 

18:05 

18:26 

18:47 

17:23 

17:44 

18:05 

18:26 

18:47 

19:07 

667 

668 

669 

670 

671 

672 

Run 3 

Run 3 

Run 3 

Run 3 

Run 3 

Run 3 

22:45.0 

21:00.0 

20:52.0 

20:58.0 

20:53.0 

20:54.0 

20.0 

16.6 

15.0 

14.9 

16.2 

13.6 

117 

130 

146 

162 

155 

136 

23.5 

19.7 

25.0 

26.8 

19.8 

22.2 

3.1 

2.0 

2.4 

2.6 

2.3 

2.2 

240 

244 

246 

248 

236 

230 

366 

359 

386 

379 

383 

383 

110 

84 

55 

51 

56 

60 

309 

310 

329 

336 

326 

333 

297 

295 

315 

314 

308 

321 

Average 

SD 

RSD 

21:13.7 16.0 

2.2 

14 

141 

17 

12 

22.8 

2.8 

12 

2.4 

0.4 

16 

241 

7 

3 

376 

11 

3 

69 

23 

33 

324 

12 

4 

308 

11 

3 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

8:59 

9:18 

9:39 

10:00 

10:21 

10:42 

11:03 

9:18 

9:39 

10:00 

10:21 

10:42 

11:03 

11:24 

684 

685 

686 

687 

688 

689 

690 

Run 4 

Run 4 

Run 4 

Run 4 

Run 4 

Run 4 

Run 4 

19:43.0 

20:34.0 

20:55.0 

21:00.0 

20:58.0 

20:57.0 

20:51.0 

15.6 

17.3 

17.7 

18.2 

18.5 

16.8 

18.3 

134 

161 

124 

142 

176 

134 

170 

19.9 

26.4 

30.7 

28.3 

29.7 

24.7 

26.4 

4.1 

5.8 

5.0 

4.9 

4.7 

4.8 

5.1 

31 

50 

64 

74 

78 

79 

90 

273 

371 

400 

400 

401 

387 

412 

63 

64 

61 

60 

59 

51 

41 

251 

308 

335 

343 

350 

334 

3S1 

218 

295 

323 

322 

319 

314 

339 

Average 

SD 

RSD 

20:42.6 17.5 

1.0 

6 

149 

20 

14 

26.6 

3.6 

14 

4.9 

OS 

10 

67 

20 

30 

378 

48 

13 

57 

8 

14 

325 

36 

11 

304 

40 

13 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

12:06 

12:27 

12:48 

13:09 

13:30 

13:51 

12:27 

12:48 

13:09 

13:30 

13:51 

14:12 

693 

694 

695 

696 

697 

698 

Run 5 

Run 5 

Run 5 

Run 5 

Run 5 

Run5 

20:55.0 

20:52.0 

20:51.0 

20:48.0 

20:57.0 

20:59.0 

19.1 

17.7 

17.4 

18.4 

15.4 

17.6 

164 

159 

141 

168 

171 

168 

29.0 

31.2 

31.8 

31.0 

33.2 

29.8 

5.1 

5.1 

5.6 

4.9 

5.3 

5.0 

86 

90 

94 

106 

113 

120 

408 

398 

386 

416 

416 

411 

46 

50 

48 

43 

42 

35 

354 

343 

335 

357 

364 

361 

328 

322 

314 

333 

338 

331 

Average 

SD 

RSD 

20:53.7 17.6 

1.2 

7 

162 

11 

7 

31.0 

1.5 

5 

5.2 

03 

5 

101 

13 

13 

406 

12 

3 

44 

5 

12 

352 

11 

3 

328 

8 

3 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

5/15/01 

14:54 

15:15 

15:36 

15:57 

16:18 

16:39 

17:00 

15:15 

15:36 

15:57 

16:18 

16:39 

17:00 

17:21 

701 

702 

703 

704 

705 

706 

707 

Run 6 

Run 6 

Run 6 

Run 6 

Run 6 

Run 6 

Run 6 

20:57.0 

20:59.0 

20:58.0 

20:56.0 

20:54.0 

20:55.0 

20:58.0 

18.4 

16.3 

13.9 

14.3 

14.8 

15.9 

15.0 

153 

140 

155 

153 

173 

171 

152 

29.1 

29.5 

29.1 

29.0 

31.6 

30.4 

34.0 

5.0 

5.0 

5.0 

5.5 

4.9 

5.1 

5.7 

127 

135 

132 

130 

155 

152 

154 

422 

431 

410 

398 

395 

409 

428 

36 

36 

45 

44 

34 

33 

42 

363 

358 

358 

344 

352 

360 

359 

348 

350 

335 

324 

326 

336 

342 

Average 

SD 

RSD 

20:56.7 15.5 

1.S 

10 

157 

12 

7 

30.4 

1.9 

6 

5.2 

0J 

6 

141 

13 

9 

413 

14 

3 

38 

5 

13 

356 

6 

2 

337 

10 

3 

VES016921 
104 ERDC/CERL TR-05-9 

Table Bl (Cont'd). Original XCEM reported concentrations (ug/dscm) uncorrected for calibration and dryer 

changes. 

5/15/01 18:03 18:24 710 Run 7 20:55.0 17.9 169 33.0 5.4 143 442 42 367 357 

5/15/01 18:24 18:45 711 Run 7 20:58.0 19.3 154 31.9 5.9 124 443 41 374 366 

5/15/01 18:45 19:06 712 Run 7 20:58.0 17.5 177 26.7 5.6 111 455 42 349 349 

5/15/01 19:06 19:27 713 Run 7 20:59.0 16.9 155 28.6 5.2 112 425 37 347 332 

5/15/01 19:27 19:48 714 Run 7 20:50.0 16.6 162 28.4 5.3 122 388 31 340 312 

5/15/01 19:48 20:09 715 Run 7 20:41.0 15.5 148 30.8 5.1 127 404 28 351 325 

Average 20:S3.5 173 161 29.9 5.4 123 426 37 355 340 

SD 13 11 2.4 03 12 26 6 13 21 

RSD 7 7 8 6 10 6 16 4 6 

5/16/01 8:58 9:18 725 Run 8 20:24.0 30.7 103 30.1 4.8 15 178 268 130 124 

5/16/01 9:18 9:39 726 Run 8 20:33.0 30.8 128 29.5 5.5 19 204 224 124 139 

5/16/01 9:39 10:00 727 Run 8 20:33.0 26.8 134 29.9 5.0 20 205 214 116 140 

5/16/01 10:00 10:20 728 Run 8 20:33.0 26.6 145 27,2 4.9 26 183 184 126 137 

5/16/01 10:20 10:41 729 Run 8 20:26.0 21.7 163 33.6 4.7 31 189 187 125 130 

5/16/01 10:41 11:01 730 Run 8 20:24.0 28.6 141 30.2 5.3 33 200 209 124 139 

5/16/01 11:01 11:22 731 Run 8 20:30.0 26.5 150 30.0 5.3 40 209 199 130 139 

Average 20:29.0 27.4 138 30.1 5.1 26 195 212 125 135 

SD 3.1 19 1.9 0.3 9 12 29 5 6 

RSD 11 14 6 6 34 6 14 4 4 

5/16/01 11:42 12:03 733 Run 9 20:28.0 29.0 169 30.6 4.1 45 195 176 126 136 

5/16/01 12:03 12:23 734 Run 9 20:26.0 22.2 157 30.3 5.2 46 186 158 129 131 

5/16/01 12:23 12:44 735 Run 9 20:21.0 25.5 142 28.5 4.9 45 189 150 132 136 

5/16/01 12:44 13:04 736 Run 9 20:18.0 24.9 191 32.8 6.0 52 206 177 143 141 

5/16/01 13:04 13:25 737 Run 9 20:24.0 23.2 132 28.8 4.8 50 199 140 134 134 

5/16/01 13:25 13:45 738 Run 9 20:19.0 24.8 127 26.6 4.8 54 185 141 134 133 

5/16/01 13:45 14:05 739 Run 9 20:23.0 22.5 139 27.0 4.8 56 211 144 137 132 

Average 20:22.7 24.6 151 29.2 5.0 SO 196 155 133 135 

SD 2.3 23 2.2 O.S 4 10 16 6 3 

RSD 9 15 7 11 9 5 10 4 2 

5/16/01 14:46 15:07 742 Run 10 20:24.0 25.0 144 32.1 5.5 85 194 135 137 135 

5/16/01 15:07 15:27 743 Run 10 20:21.0 33.7 174 34.2 5.0 83 200 242 142 139 

5/16/01 15:27 15:48 744 Run 10 20:23.0 21.4 130 30.0 5.0 76 178 106 124 123 

5/16/01 15:48 16:08 745 Run 10 20:16.0 22.5 178 29.2 5.0 84 193 124 135 138 

5/16/01 16:08 16:28 746 Run 10 20:21.0 21.6 149 33.5 5.1 88 192 100 151 135 

5/16/01 16:29 16:49 747 Run 10 20:20.0 21.6 154 28.6 5.2 88 188 88 130 127 

5/16/01 16:49 17:09 748 Run 10 20:20.0 17.3 129 27.7 5.0 101 173 102 141 127 

Average 20:20.7 233 151 30.8 5.1 86 188 128 137 132 

SD 5.1 19 2.5 0.2 8 10 53 9 6 

RSD 22 13 8 4 9 5 41 6 5 

VES016922 
ERDC/CERL TR-05-9 105 

Table B1 (Cont'd). Original XCEM reported concentrations (ug/dscrn) uncorrected for calibration and dryer 

changes. 

5/16/01 17:32 17:52 750 Run 11 20:21.0 19.9 165 28.9 5.5 94 195 100 139 132 

5/16/01 17:52 18:12 751 Run 11 20:18.0 19.7 136 28.0 4.8 89 193 94 136 130 

5/16/01 18:12 18:33 752 Run 11 20:20.0 19.5 157 27.2 4.9 88 189 96 130 135 

5/16/01 18:33 18:53 753 Run 11 20:18.0 19.7 165 27.9 5.0 88 178 84 136 128 

5/16/01 18:53 19:13 754 Run 11 20:12.0 20.4 141 24.4 5.3 89 177 82 136 131 

5/16/01 19:13 19:34 755 Run 11 20:12.0 20.3 155 30.3 5.1 86 186 82 132 135 

5/16/01 19:34 19:54 756 Run 11 20:17.0 18.7 141 30.7 4.2 78 196 89 136 135 

Average 20.16.9 19.7 151 28.2 5.0 87 188 90 135 132 

SD 0.6 12 2.1 0.4 5 8 7 3 3 

RSD 3 8 8 8 6 4 8 2 2 

5/17/01 11:12 11:32 770 Run 12 20:01.0 25.0 161 24.6 3.8 22 208 157 127 123 

5/17/01 11:32 11:52 771 Run 12 20:08.0 27.4 181 21.5 3.9 33 221 215 147 135 

5/17/01 11:52 12:12 772 Run 12 20:14.0 32.6 161 28.2 4.0 51 206 253 153 146 

5/17/01 12:12 12:32 773 Run 12 20:16.0 25.6 210 22.6 3.7 68 205 189 146 149 

5/17/01 12:32 12:53 774 Run 12 20:12.0 25.1 141 29.3 4.4 73 190 149 146 140 

5/17/01 12:53 13:13 775 Run 12 20:12.0 18.2 164 25.9 4.1 77 189 127 144 133 

5/17/01 13:13 13:33 776 Run 12 20:07.0 20.0 138 26.1 3.8 80 177 129 144 140 

Average 20:10.0 24.9 165 25.4 4.0 58 199 174 144 138 

SD 4.7 24 2.8 0.2 23 15 47 8 9 

RSD 19 15 11 6 40 7 27 6 6 

5/17/01 14:14 14:34 779 Run 13 20:15.0 23.6 150 33.3 4.7 74 186 110 158 136 

5/17/01 14:34 14:54 780 Run 13 20:10.0 24.5 194 31.3 4.9 74 197 113 157 135 

5/17/01 14:54 15:14 781 Run 13 20:09.0 21.9 147 33.4 5.6 76 217 109 155 138 

5/17/01 15:14 15:34 782 Run 13 20:10.0 24.3 129 31.3 5.4 77 197 103 157 138 

5/17/01 15:35 15:55 783 Run 13 20:12.0 26.2 182 37.6 5.4 77 160 119 157 109 

5/17/01 15:55 16:15 784 Run 13 20:02.0 23.8 153 36.2 5.6 69 157 112 154 76 

5/17/01 16:15 16:35 785 Run 13 19:57.0 12.0 87 17.3 3.7 42 65 79 71 20 

Average 20:07.9 22.3 149 31.S 5.0 70 168 107 144 107 

SD 4.7 35 6.7 0.7 12 50 13 32 45 

RSD 21 24 21 14 18 30 12 22 42 

Table B2. Results of dryer tests. 

Day Time 

(min) 

Flow actual 

(sLpm) 

Pressure 

in line 

(psia) 

Web Bulb 

Temp 

<°F) 

Vol of 

air/water 

(L) 

Mass of 

Water 

Collected 

(a) 

Vol of 

Water 

(L) 

Impinger 

% water 

by vol 

1 270 0.82 7.3 150 220.4 7.9 9.8 4.5 

2 200 0.82 7.3 150 163.3 4.7 5.8 3.6 

3 78 0.84 7.3 120 65.5 1.8 2.2 3.4 

4 126 0.83 7.3 168 104.6 2.8 3.5 3.3 

VES016923 
106 ERDC/CERL TR-05-9 

Appendix C: Transport and Calibration 

Evaluations 

Quantitative Spike Injection by CES 

CES Spiking Test Design 

Following calibration, a series of 11 tests were conducted at TEAD to certify the 

calibration and check the ability of the XCEM to transport particulates from the 

top of the shed to the filter tape. The tests included quantitative spiking of various aerosohzed metals into the XCE M transport line immediately prior to entering the shed. The metals were then sampled by the XCEM. The rest of the 

spiked aerosol, about 99 percent of the volume, was sampled by two filters downstream ofthe stilling chamber as illustrated in Figure Cl. 

CES used a Quantitative Spike Injection System (QSIS) to conduct the tests. 

The QSIS includes an atomizer and a drying chamber that generate a simulated 

stack gas containing the metals of interest in -100 ppm of nitric acid. Two 

pumps pulled 80-100 sLpm of the simulated stack gas through the atomization 

system and XCE M stilling chamber. Approximately 1 percent of the simulated 

stack gas was sampled and analyzed by the XCEM. The remaining gas was 

transported out of the XCEM stilling chamber into a manifold containing two 

filter holders. The upstream filter holder contained a 47-mm-diameter membrane filter (MF) while the downstream holder held a 47-mm-diameter quartz 

fiber filter (QFF). After each test, the metal concentrations on the two filters 

were determined using a QuanX XRF, and their total mass, identified as the "Total Capture" concentration, was compared to the theoretical atomization concentration and reported XCEM concentrations. 

VES016924 
ERDC/CERL TR-05-9 107 

ATOMIZATION 

CONCENTRATION 

XCEM 

CONC. 

TOTAL CAPTURE 

CONCENTRATION 

Drying 

Chamber 

Atomizer 

Figure Cl . Experimental design for atomization tests. 

Mass Flow 

Meter Pumps 

Test design for atomization of Pb and Cr (Tests 1-3) 

Three tests were conducted using a solution of Pb and Cr nitrates in 5 percent 

nitric acid. The injected solution had a concentration of 25.4 pg/mL of Pb and 

25.1 pg/mL of Cr. Atomizer concentrations were determined by weighing the solution before and after testing and multiplying the net atomized mass by the 

concentration to determine total micrograms of metal emitted during the test. 

This mass was compared to the total mass on the resin-impregnated and quartz 

fiber filters (RIF and QFF) located downstream ofthe XCEM. 

During these tests, the XCE M reported values every 20 minutes and completed 

30 runs. Atomization chamber and total capture filter temperatures were maintained at about 140 °F while the stilling chamber and cassette were maintained 

at about 225 °F. The mainline flow varied between 88-97 sLpm and the XCE M 

sampled 0.8 sLpm. 

Following the first test, a leak was discovered in the system, so the first test was 

disregarded and a third test was conducted. Data from the first test are included 

in Appendix C, but were not used to evaluate the calibration. 

Test design for atomization of As, Cd, Cr, Ba, Hg, Pb, Se, and Ag (Tests 4-7) 

A second series of four tests was conducted using a NIST traceable stock solution 

of As, Cd, Cr, Ba, Hg, Pb, Se, and Ag (VHG Labs, Inc., Manchester, NH). All 

eight elements were at the same concentration in the stock solution. Two sets of 

VES016925 
108 ERDC/CERL TR-05-9 

duplicate runs were conducted with nominal concentrations at about 250 pg/m3 

for tests 4 and 5 and 125 pg/m3 for tests 6 and 7. Atomization and XCE M temperature and flow conditions were the same as for the Pb and Cr tests. The 

XCEM reported values every 20 minutes and completed an additional 30 runs. 

Test design for atomization of Cd, Ba, Hg, Ni, Pb, and Zn (Tests 8-11) 

The third series of tests used a NIST traceable VHG stock solution of Cd, Ba, Hg, 

Ni, Pb, and Zn. Two sets of duplicate runs were conducted with concentrations 

from runs 8 and 9 cut in half for runs 10 and 11. Atomization and XCE M temperature and flow conditions were the same as for the Pb and Cr test. The 

XCE M reported values every 20 minutes and completed an additional 35 runs 

during these tests. 

CES Spiking Test Results 

Atomization vs. XCEM 

Before and after atomization, the spike injection solution was weighed to determine net change in mass. This mass was divided by the time and flow to determine atomization rate in micrograms per dry standard cubic meter as shown in 

equation 6: 

(m, -mr)-at 

Ct=

K

 ' SJ

 k -106

 [Eq6] 

d-f- t 

where: 

Ck = Gas concentration for element "k" during a test 

i n = Initial mass of atomized solution (g) 

mf = Final mass of atomized solution (g) 

d = Density of solution (g/mL) 

at = Concentration of element "k" in solution (g of element k/mL of solution) 

t = Time (min) 

f = Gas flow rate (dscm/min) 

Data used to calculate predicted metals concentrations based on atomization 

rates are shown in Table Cl. Atomization rate predictions vs. XCE M measured 

concentrations are shown in Table C2. 

VES016926 
ERDC/CERL TR-05-9 109 

Table C1. Flow rates and concentrations used to calculate atomization concentrations. 

Test 

Atom, vol 

(ml) 

As Cd Fe Cr Ba Hg Ni Pb Sb Se Ag Zn Ti 

ml ug/ml ug/ml ug/ml ug/ml us/ml ug/ml ug/ml ug/ml ug/ml ug/ml ug/ml ug/ml us/ml 

1 

2 

3 

4 

5 

6 

7 

8 

9 

10 

11 

56.1 

31.9 

41.8 

30.3 

37.8 

35.5 

32.9 

32.1 

31.3 

36.2 

33.2 

50.6 

50.6 

25.1 

25.1 

50.6 

50.6 

25.1 

25.1 

17.4 

17.4 

8.6 

8.6 

25.1 

25.1 

25.1 

50.6 

50.6 

25.1 

25.1 

50.6 

50.6 

25.1 

25.1 

497.7 

497.7 

246.9 

246.9 

50.6 

50.6 

25.1 

25.1 

99.6 

99.6 

49.4 

49.4 

25.4 

25.4 

25.4 

50.6 

50.6 

25.1 

25.1 

29.9 

29.9 

14.8 

14.8 

50.6 

50.6 

25.1 

25.1 

50.6 

50.6 

25.1 

25.1 

99.6 

99.6 

49.4 

49.4 

Table C2. Atomization vs. XCEM concentrations. 

AS C D C R BA H G 

TES T X C A T XC/A T 

X C A T XC/A T X C I A T XC/A T 

X C | A T 

XC/A T 

X C A T 

XC/A T 

ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

Ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

2 122 106 1.15 

3 126 112 1.12 

4 245 230 1.07 201 230 0.87 260 230 1.13 247 230 1.07 226 230 0.98 

5 230 234 0.98 192 234 0.82 243 234 1.04 247 234 1.06 218 234 0.93 

6 126 126 1.00 105 126 0.83 137 126 1.09 158 126 1.26 120 126 0.95 

7 123 122 1.00 97 122 0.79 126 122 1.03 153 122 1.25 112 122 0.92 

8 63 76 0.82 2384 2183 1.09 50 87 0.57 

9 54 66 0.81 2022 1901 1.06 41 76 0.54 

10 32 38 0.84 1265 1101 1.15 20 44 0.45 

11 33 40 0.82 1214 1152 1.05 28 46 0.61 

AVG . 181 178 1.01 97 117 0.83 169 155 1.09 961 881 1.12 102 121 0.75 

NI PB SE A G Z N 

TES T X C A T XC/A T 

X C A T XC/A T X C A T 

XC/A T 

X C A T 

XC/A T 

X C A T XC/A T 

ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

ug/DSCM 

XC/A T 

2 111 107 1.04 

3 117 113 1.03 

4 266 230 1.16 236 230 1.03 217 230 0.94 

5 247 234 1.06 221 234 0.94 204 234 0.87 

6 137 126 1.09 122 126 0.97 113 126 0.90 

7 121 122 0.99 117 122 0.96 102 122 0.84 

8 450 437 1.03 133 131 1.01 463 437 1.06 

9 383 380 1.01 114 114 1.00 394 380 1.04 

10 243 220 1.10 73 66 1.10 249 220 1.13 

11 226 230 0.98 67 69 0.96 233 230 1.01 

AVG . 326 317 1.03 138 131 1.04 174 178 0.97 159 178 0.89 335 317 1.06 

Reported XCE M concentrations matched expected atomization values for As (101 

percent), Cr (109 percent), Ni (103 percent), Pb (104 percent), Ba (112 percent), 

Se (97 percent), and Zn (106 percent). Mercury XCE M concentrations matched 

atomization rates for runs 4-7 (95 percent), but were low for runs 8-11 (54 percent). During runs 8-11, the outside air temperature dropped dramatically and 

VES016927 
110 ERDC/CERL TR-05-9 

snow was on the transport line. For this reason, the Hg numbers for runs 8-11 

were considered less reliable. 

Both Cd and Ag were low by 10-15 percent relative to the expected concentrations. This difference was either caused by transport inefficiency or cahbration 

error. To determine which source created the discrepancy, a comparison was 

made of the Cd/Ag concentrations relative to other elements captured downstream of the XCEM. The results of these comparisons are discussed in the next 

section. 

Total capture vs. XCEM 

The total flow used for atomization was captured downstream of the XCE M on 

an M F and QFF. These filters were then analyzed at CES and compared to the 

atomized concentrations. The total capture system is downstream of a 90° elbow 

and is not expected to be quantitative; however, the relative concentrations of the 

elements should stay constant. Table B3 shows the total micrograms atomized 

vs. the total captured downstream of the XCEM. Reported Cr concentrations 

have not been corrected for filter absorption, which can be significant on a QFF. 

In this table, it can be seen that the transport efficiency to the filters was dependent on the injection solution. For tests 2 and 3, the transport was about 90 

percent for Pb. The second solution was used for tests 4 through 7, with a resulting transport efficiency of about 85 percent for As, Cd, Ni, Pb, and Se. 

Except for Hg, which can form a vapor, the atomization process results in particles that contain metals in proportion to their concentration in the original solution. Because the elements associated with particles should be in proportion to 

the solution, the results in Table C3 were normalized to Pb to determine relative 

transport efficiencies. These results are shown in Table C4. Both Cd and Ag in 

Table C4 show good agreement with Pb, arsenic, and the other elements. Thus, 

it appears that Cd and Ag were transported with the other elements. From these 

data, it was concluded that the significant difference between Cd/Ag and the 

other elements in Table C2 was not due to transport inefficiency but rather the 

result of calibration error. 

VES016928 
ERDC/CERL TR-05-9 111 

Table C3. Total capture mass (TC) vs. atomization mass (AT). 

As Cd Cr Ba Hg 

Test T C A T FIL/TC T C A T FIL/TC T C A T FIL/TC T C A T FIL/TC T C A T FIL/TC 

ug 

FIL/TC 

ug 

FIL/TC 

ug 

FIL/TC 

ug 

FIL/TC 

ug 

FIL/TC 

2 700 821 0.85 

3 791 1077 0.73 

4 1192 1574 0.76 1192 1574 0.76 917 1574 0.58 1461 1574 0.93 1013 1574 0.64 

5 1535 1963 0.78 1530 1963 0.78 1145 1963 0.58 1884 1963 0.96 1402 1963 0.71 

6 807 914 0.88 781 914 0.85 662 914 0.72 948 914 1.04 689 914 0.75 

7 702 848 0.83 682 848 0.80 571 848 0.67 832 848 0.98 642 848 0.76 

8 454 572 0.79 14746 16374 0.90 

9 446 559 0.80 14631 15976 0.92 

10 286 320 0.89 9142 9158 1.00 

11 218 294 0.74 7263 8418 0.86 

AVG . 1059 1325 0.81 699 881 0.80 850 1235 0.71 6363 6903 0.95 937 1325 0.72 

Ni Pb Se Ag Zn 

Test T C I AT FIL/TC 

T C A T FIL/TC T C 1 AT FIL/TC T C A T FIL/TC T C A T FIL/TC 

ng 

FIL/TC 

fig 

FIL/TC FIL/TC 

ug 

FIL/TC 

f g 

FIL/TC 

2 760 831 0.91 

3 970 1090 0.89 

4 1258 1574 0.80 1196 1574 0.76 1295 1574 0.82 

5 1622 1963 0.83 1550 1963 0.79 1667 1963 0.85 

6 837 914 0.92 806 914 0.88 847 914 0.93 

7 728 848 0.86 702 848 0.83 741 848 0.87 

8 1952 3277 0.60 724 984 0.74 1979 3277 0.60 

9 1906 3197 0.60 713 960 0.74 1933 3197 0.60 

10 1421 1833 0.78 463 550 0.84 1394 1833 0.76 

11 1139 1685 0.68 369 506 0.73 1140 1685 0.68 

AVG . 1604 2498 0.66 887 1062 0.83 1064 1325 0.81 1138 1325 0.87 1611 2498 0.66 

Table C4. Lead normalized atomization mass (AT) vs. total capture (TC). 

As Cd C r Ba Hg 

I est T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T 

2 0.92 0.99 0.93 

3 0.82 0.99 0.83 

4 0.95 1.00 0.95 0.95 1.00 0.95 0.73 1.00 0.73 1.16 1.00 1.16 0.80 1.00 0.80 

5 0.95 1.00 0.95 0.94 1.00 0.94 0.71 1.00 0.71 1.16 1.00 1.16 0.86 1.00 0.86 

6 0.96 1.00 0.96 0.93 1.00 0.93 0.79 1.00 0.79 1.13 1.00 1.13 0.82 1.00 0.82 

7 0.96 1.00 0.96 0.94 1.00 0.94 0.78 1.00 0.78 1.14 1.00 1.14 0.88 1.00 0.88 

8 0.63 0.58 1.08 20.4 16.6 1.22 

9 0.63 0.58 1.08 20.5 16.6 1.23 

10 0.62 0.58 1.06 19.7 16.6 1.19 

11 0.59 0.58 1.02 19.7 16.6 1.18 

AVG . 0.96 1.00 0.96 0.78 0.79 1.00 0.79 1.00 0.79 10.6 8.8 1.18 0.84 1.00 0.84 

Test 

Ni Pb Se Ag Zn 

Test 

T C AT TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T T C A T TC/A T 

2 1.00 1.00 1.00 

3 1.00 1.00 1.00 

4 1.00 1.00 1.00 0.95 1.00 0.95 1.03 1.00 1.03 

5 1.00 1.00 1.00 0.96 1.00 0.96 1.03 1.00 1.03 

6 1.00 1.00 1.00 0.96 1.00 0.96 1.01 1.00 1.01 

7 1.00 1.00 1.00 0.96 1.00 0.96 1.02 1.00 1.02 

8 2.70 3.33 0.81 1.00 1.00 1.00 2.73 3.33 0.82 

9 2.67 3.33 0.80 1.00 1.00 1.00 2.71 3.33 0.81 

10 3.07 3.33 0.92 1.00 1.00 1.00 3.01 3.33 0.90 

11 3.09 3.33 0.93 1.00 1.00 1.00 3.09 3.33 0.93 

AVG . 2.88 3.33 0.87 1.00 1.00 1.00 0.96 1.00 0.96 1.02 1.00 1.02 2.89 3.33 0.87 

VES016929 
112 ERDC/CERL TR-05-9 

Evaluation of Stack Transport 

Test Design 

The QSIS tests just discussed in the previous section were able to effectively 

evaluate the XCEM calibration. Since the QSIS was injected at the top of the 

shed, however, more data were needed to determine the transport efficiency of 

the sample line from the stack to the shed. To evaluate the entire transport system and the responsiveness of the XCE M to munitions burning, a second series 

of tests were conducted from 30 April to 2 May in which the TEAD stack was 

spiked by MSE-TA for metals of interest while munitions were incinerated. An 

EPA Reference Method 17 (M17) type train was used to capture a representative 

stack sample of P M near the inlet of the XCE M stack probe. Results of the M17 

tests were then compared with the concurrent XCEM concentrations. 

XCEM Responsiveness to Munitions Destruction 

During the stack spiking, TEAD conducted normal burning operations in which 

they were destroying 20 mm bullets and tracers. The bullets were observed by 

the XCEM to have significant quantities of Pb, Cd, and tin (Sn), while only Sn 

was observed in significant quantities during tracer incineration. These elements were not spiked by MSE-TA. As shown in Figure 38, the XCE M displayed 

good responsiveness to various types of ammunitions burning and stack operation approaches. 

Figure C2 shows the XCEM relationship between Sn and Cd when bullets were 

being destroyed. The high correlation (r2 = 0.94) indicates that the two elements 

were from the same source. A 75 to 90 percent decrease is seen in Cd and Pb 

when tracers are being burned while Sn remains unchanged. Follow up conversations with TEAD personnel indicated that the tracers did not contain Cd and 

Pb, but did contain Sn. Figure C2 also shows the impact of opening and closing 

the bypass valve each day, with concentrations exhibiting spikes during the short 

period that the bypass valve was open. 

One of the intended uses of the XCE M is as a monitor to better understand control efficiencies. The data in Figure 38 were used to help TEAD personnel identify the sources of metals in the stack gas and better control the emissions. Following M29 testing, TEAD stack operators conducted tests in which they used 

the XCEM to determine that the metals emissions could be significantly reduced 

by completely cutting off the bypass system during operation. 

VES016930 
ERDC/CERL TR-05-9 113 

XCE M Run No. j j XCE M Run No. 

Figure C2. XCEM reported concentrations for nonspiked elements. 

XCEM Response vs. MSE-TA Spiking 

From 30 April to 2 May, MSE-TA spiked known concentrations of Ba , Hg, Ni , Sb, 

and Zn. The XCE M relative response to these concentrations is shown in Figure 

B3. 

Other than Zn, which is associated with the incineration feed, the XCE M reported concentrations were slightly less than the MSE-TA predicted concentrations on 30 April and the morning of 1 Ma y (runs 795-837). Following these 

runs, however, the transport line heat tracing was completed and the XCE M 

concentrations were within 5 to 15 percent of MSE-TA estimated concentrations. 

VES016931 
114 ERDC/CERL TR-05-9 

780 SOO 820 840 860 880 

XCKM Run No. 

Figure C3. XCEM reported concentrations and MSE-projected concentrations for spiked elements. 

XCEM Comparisons to Method 17 Results 

To obtain adequate flows and meet stack temperature requirements, quartz fiber 

filters (QFF) were used for the in-stack filter holder for M17 testing. The QFFs 

cannot adequately trap Hg, but were analyzed for the spiked elements Ba, Ni , 

Zn, and Sb as well as the elements Cd and Pb, which were both found in the munitions. A total of 15 valid runs were conducted. Table C5 shows the results. 

Both N i and Zn were spiked together by MSE-TA. For these two metals, the 

XCE M to M17 ratios were 1.18 and 1.09, respectively. Since the XCE M was 

higher than M17, no indication of loss in the transport line was believed to have 

occurred. The uncertainty of the ratios was about 20-25 percent, which was 

VES016932 
ERDC/CERL TR-05-9 115 

primarily the result of variability in the M17 flow measurement and uncertainties in M17 absorption corrections. 

A second solution spiked by MSE-TA contained Ba and Sb. The two elements 

had respective XCE M to M17 ratios of 0.99 and 1.03, which indicated good 

transport efficiencies for elements in this spiked solution. 

Although neither Pb nor Cd was spiked by MSE-TA, significant concentrations of 

both were found in the stack when bullets were being burned. The concentrations changed dramatically when tracers were burned instead of bullets for part 

of run 4. The XCE M and M17 were in good agreement for Pb, but the XCEM 

was significantly higher than M17 for Cd. The Cd results indicated a potential 

XCE M calibration error for Cd. 

During the 3 days of testing, the Pd concentration, which is measured with every 

sample by the XCE M and indicates stability, varied from 90 to 105 percent. The 

higher than normal variability was determined to be associated with high ambient temperatures in the sample shed due to a faulty air conditioner. Installation 

of an improved temperature control system would help remedy this problem in 

the future. 

VES016933 
116 ERDC/CERL TR-05-9 

| WWC | 

3 1 1 3 s s © 1 2 Sj 2 $ 

d 1 s 5 

S s a S 5 2 s a a 

•* 

tS s © S a 8 a s 

s 

I 

ON 8 9 * 2 5 

s 

I 

s 

a vo in 8 s 3 s 

a s § 

£ 

i 1 1 1 1 © 1 § o o 2 2 I s 9 

£ rs 1 a 8 S 

a 

g 

r- £ 

s ts 1 1 o 

(S S s § S a 

00 

„ , 1 1 1 I 2 1 2 1 5 3 

I 1 1 s 1 o 3 

8 s a 1 1 1 

£ 2 

o 1 3 2 1 1 2 1 2 3 1 

s s a s a a 

§ 1 m a a 1 tS 

rCN § a S a 

* 

I 1 I o" 5 l °° 

o 1 ^O ? 

o i s? l 3 

* i s s S v-t § R >n 1 s * 

§ 5 S 5-

O 1 1 i 

1 

| 4:11 PM | | 9:42 A

M | 

| 10:47 A

M | 

| 11:45 A

M | 

| 12:26 P

M | 

| 1:28 P

M | 

| 2:26 P

M | 

| 3:20 P

M | 

| 4:15 P

M | 

| 9:21 A

M | 

| 11:45 A

M | 

| 12:52 P

M | 

| 1:47 P

M | 

| 3:03 P

M | 

| 3:40 P

M | 

i 

! 

! 

I 

| 3:11 P

M | 

| 8:36 A

M | 

| 10:02 A

M | 

| 11:00 A

M | 

| 12:01 P

M | 

| 12:43 P

M | 

| 1:46 P

M | 

| 2:40 P

M | 

| 3:35 P

M | 

| 8:41 A

M | 

| 11:05 A

M | 

| 12:12 P

M | 

| 1:07 P

M | 

| 2:33 P

M | 

| 3:10 P

M | 

i 

! 

! 

I 

| 4/30/02 | | 5/1/02 | | 5/1/02 | | 5/1/02 | | 5/1/02 | | 5/1/02 | | 5/1/02 | | 5/1/02 | | 5/1/02 | | 5/2/02 | | 5/2/02 | | 5/2/02 | | 5/2/02 | | 5/2/02 | | 5/2/02 ] 

i 

! 

1 ! - ts m in SO CO On o — ts t 2 i 

! 

1 ! - ts m in SO CO On 2 i 

! 

! 
ERDC/CERL TR-05-9 117 

Appendix D: Mercury Calibration and 

Loss Discussion 2002 

Introduction 

Mercury (Hg) represents a distinctly different hazardous element from the others included in these tests in that it is more likely to exist in the vapor phase and 

has been shown to exhibit distinctly different transport properties. These properties appear to have contributed to differences in the Hg concentrations measured by the different methods compared in the 2002 test. This appendix discusses the details associated with both the adjustments that were made to the 

XCE M calibration factors and losses of Hg from particulate deposits after sample 

collection. 

Calibration Adjustments 

Two adjustments were made to the Hg results after the first M29 test run was 

started. The first adjustment was a 7 percent increase in the Hg sensitivity factor between M29 run 1 and run 2. The second was a 4 percent increase in the 

sensitivity factor shortly after the completion ofthe tests and before the M29 and 

XCE M results were submitted. The necessity for these adjustments was due in 

part to the volatility of the Hg, which makes it difficult to make stable thin-film 

Hg standards. As such, thin film Hg standards are not available from NIST. 

The standards that are available are relatively unstable and need to be frequently validated. This method limitation is generally minimized by the fact 

that energy dispersive X-ray fluorescence (XRF) sensitivity factors are a 

smoothly varying function of atomic number. This allows Hg sensitivity factors 

to be estimated by interpolation using well-defined sensitivity factors for elements with similar atomic number such as platinum, gold, thallium, lead (Pb), 

and bismuth. The following two adjustments were based on this interpolation 

process and a re-evaluation ofthe best-estimated calibration factor. 

VES016935 
118 ERDC/CERL TR-05-9 

Adjustments During First Day of Testing 

The XCEM underwent mercury calibration during preliminary spiking tests, 

prior to the M29 tests. During these spiking tests, the NIST thin-film standard 

for Pb was not available, and the Hg sensitivity was estimated based on a previous measurement of the Pb NIST standard. This fact was not realized until after 

the preliminary spiking testing started and a review of the preliminary Hg results indicated a potential bias relative to the NIST Pb results. As a result, the 

Hg calibration was adjusted by 7 percent at the earliest possible time, which was 

after M29 run 1 and before run 2. 

Post-Test Adjustments 

The second adjustment to the Hg results of 4 percent was apphed when the calibration factors were reviewed following the M29 tests. A comparison with the 

ratio of Hg to Pb sensitivity factors developed from a more extensive study in the 

laboratory indicated that the 0.838 ratio used during the tests should have been 

0.873. This 4 percent correction was apphed to the XCE M results prior to the 

submission of either the M29 or the XCE M results. 

Losses From PM Fraction 

The XCEM Hg results were, on average, 18 percent greater than the predicted 

concentration, 27 percent greater than the M29 results, 37 percent greater than 

the laboratory XRF measurements of the XCE M deposit spots, and 45 percent 

greater than cold vapor atomic absorption (CVAA) measurements on the XCE M 

deposit spots. Subsequent investigations of these differences strongly suggest 

that the XCE M results are the best estimate of the actual Hg concentrations in 

the stack. It is hypothesized that the large differences between the XCEM Hg 

results and the results from the other methods is due to the loss of Hg from the 

filter deposits after the M29 and XCE M samples were collected and after the 

XCE M original measurements were made. 

Model 

A model has been developed to explain the apparent high XCE M Hg concentrations relative to M29. In this model, Hg is lost from the particulate fraction of 

the M29 and XCE M filters after the initial XCE M measurements were made. 

That is, a substantial fraction of Hg was associated with the particulate fraction, 

and the Hg in this particulate was unstable. Since all of the other analytical 

methods relied on aged samples, the Hg concentration results were low due to 
ERDC/CERL TR-05-9 119 

vaporization of particulate Hg prior to laboratory analysis. A substantial 

amount of experimental data is available, all of which is supportive of this hypothesized model. Most of this experimental data was developed only because of 

the unique characteristics of the XCE M and the fact that the XCEM elemental 

measurement is nondestructive and the spectra from each of the original measurements were archived. 

Experimental 

The initial XCE M measurements were based on the analysis of filter deposits, 

which were a combination of both absorbed vapor phase Hg species and surface 

deposits of particulate Hg species. Each deposit was analyzed using three different X-ray excitation conditions, resulting in spectra that were used to determine 

concentration. All spectra were archived in the XCE M computer. As such, the 

deposit was available for further analysis and testing, and the original spectra 

were available for comparison with subsequently developed spectra. 

Following the vahdation testing at TEAD, CES conducted several tests to better 

understand the Hg concentration differences between M29 and the XCEM. 

• All ofthe XCEM deposit spots corresponding to all of the M29 runs were reanalyzed by CES's laboratory QuanX XRF analyzer 6 weeks after the initial validation test. In addition, 10 XCE M filter deposit spots were analyzed over a 2-

month period to evaluate Hg stability. Spectra from these tests were compared 

with archived spectra from the original validation test. 

• The XCEM deposit spots corresponding to M29 runs 5 and 6 were analyzed 

first by laboratory XRF and then by CVAA by an independent laboratory 

(Columbia Analytical Services). 

• The elemental concentrations in the MSE-TA spiking solutions corresponding 

to M29 runs 5 and 6 were analytically determined by HK M Labs (Butte, MT). 

Results and Discussion 

The Hg results for the original validation test are summarized in Table Dl. 

There is a clear bias of about 26 percent between the XCE M results and the M29 

results. Normally, the M29 results would be accepted as the best estimate of 

stack Hg concentration and it would be assumed that the candidate method 

(XCEM) was in error. However, because of the total QA associated with the 

XCE M and the fact that the XRF analysis is nondestructive, it is possible to conduct further analyses to evaluate the potential cause of this difference. Additionally, the laboratory analysis results for each component of the M29 sampling 

trains (i.e., probe, filter, and back half) were determined separately, and are 

available for interpretation. 

VES016937 
120 ERDC/CERL TR-05-9 

Table D1. Mercury reported concentrations during Year 2002 M29 validation testing. 

RUN PRD M29 XC QN CA PRD XC QN CA RUN 

g/DSCM Normalized to M29 

1 324 332 367 257 0.98 1.10 0.77 

2 325 334 381 251 0.97 1.14 0.75 

3 333 294 365 262 1.13 1.24 0.89 

4 322 327 368 301 0.98 1.13 0.92 

5 323 318 379 308 274 1.02 1.19 0.97 0.86 

6 329 280 378 288 254 1.18 1.35 1.03 0.91 

7 327 285 392 302 1.15 1.37 1.06 

8 325 306 406 294 1.06 1.33 0.96 

9 324 309 405 287 1.05 1.31 0.93 

10 328 292 395 282 1.13 1.35 0.97 

11 326 295 397 286 1.11 1.35 0.97 

12 322 293 389 267 1.10 1.33 0.91 

AVG. 326 305 385 282 264 1.07 1.27 0.93 0.88 

SD 3.3 19 14 19 13.8 0.07 0.10 0.09 0.03 

Loss of mercury from the XCEM filter 

Laboratory XRF measurements (QN). Two months after the validation testing, 

CES's laboratory QuanX XRF analyzer reanalyzed the original XCE M deposit 

samples with good replication for all elements except Hg (see Table 31 in main 

body of text). 

A series of 10 spots on the XCE M filter tape were reanalyzed between 21 June 

2002 and 11 July 2002. The spots, which represent 10 XCEM runs, showed a 

consistent Hg loss of about 30 percent over the 3-week period. Other sources of 

error such as shifts in geometry or instrument instability were eliminated as 

possible systematic sources of error by noting that the other elements were replicated within experimental error to a few percent. 

XCEM measurements (XCEM). To confirm this loss of Hg, five XCE M deposit 

spots were re-analyzed by the TEAD XCEM, which was still operating with the 

same conditions and calibration factors as used during the M29 tests about 2 

months earlier. The X-ray spectra from the original analysis of XCEM runs 939 

to 943 (M29 run 4) are compared in Figure Dl. This comparison clearly shows 

that agreement is good for the two closest analyte peaks for Zn and Pb, but reduction is substantial in the peak intensity for the Hg L-alpha analyte line. A 

comparison of the XCEM Hg concentrations measured during the M29 testing 

(14 May 2002) with those measured with the XCE M on 25 July 2002 indicate a 

31.4 ± 0.4 pg/m3 reduction in measured concentration. Although this reduction 

might be associated with possible systematic errors such as sample positioning, 

this possible source of error was eliminated by comparing other elements such as 

VES016938 
ERDC/CERL TR-05-9 121 

Zn and Pb as well as the ratio of Hg to these elements. The reduction in H g to 

Zn ratio, for example, was 29.1 percent, which is i n good agreement with the Hgmeasured reduction. 

Clearly, Hg was lost from the XCE M deposit after the sample was collected and 

analyzed by the XCEM . As discussed in the following subsection, the available 

data strongly suggest that a substantial portion of the M29 Hg was also lost from 

the M29 P M filter deposits prior to analysis. 

14000 

12000 

10000 

| 8000 

o 6000 

4000 

2000 

0 

• XCEM 051402 B XCEM 072502 

Figure D1. Comparison of XCEM x-ray spectra measured during M29 testing and 71 days later. 

Instability of M29 Hg PM deposit highly likely 

Although there is no direct evidence of the loss of Hg from the M29 samples, 

there is ample indirect evidence that a similar loss to that of the XCE M deposit 

would be expected. This indirect evidence is discussed in the following three 

subsections. 

Train location ofHg deposits. The recovery and analysis of the M29 probe, filter, 

nitric acid impingers, sulfuric acid impingers, and the hydrochloric acid rinse 

were kept separate for both the Ma y 2001 and Ma y 2002 M29 tests. The results 

are summarized and compared i n Table D2. It is interesting to note that, during 

the 2001 testing, only about 1 percent ofthe Hg was deposited on the quartz fiber filter. This is typical of most stack measurements of Hg, so there is little 

concern for tbe stability of the P M deposited on the filter. This is not the case, 

however, for the 2002 Hg measurements. During these latter tests, 18 percent of 

the H g was deposited on the filter during runs 1 through 5, with no Pb in the HgNi-Zn spiking solution. After adding Pb to the spiking solution, the percent of 

Hg depositing on the filter increased to 29 percent for the remaining M29 runs. 

Zinc 

Mercury 

VES016939 
122 ERDC/CERL TR-05-9 

Table D2. Comparison of the location in M29 sampling trains where the Hg was deposited 

during the 2001 and 2002 tests. 

YEAR RUNS FILT. PROBE M2B M3A M3B M3C TOTAL 

Percent on 

Filter 

2001 1-13 1.1 0.1 93 0.4 0.3 5.2 100 

Percent on 

Filter 

Percent on 2002 1-12 24.7 0.1 71 0.2 0.1 4.1 100 

Filter 2002 1-5 18.2 0.2 77 0.3 0.1 4.7 100 

Percent on 

Filter 

2002 6-12 29.4 0.1 67 0.2 0.0 3.7 100 

Mass on 

Filter (ng) 

2001 1-13 6.0 0.2 414 2.2 1.0 26 450 

Mass on 

Filter (ng) 

Mass on 2002 1-12 166 0.8 484 1.6 0.4 28 681 

Filter (ng) 2002 1-5 129 1.1 551 1.9 0.7 34 718 

Mass on 

Filter (ng) 

2002 6-12 191 0.6 437 1.4 0.2 24 654 

It is interesting to note that during the 2001 M29 tests, the reported M29 Hg 

concentrations were 12 percent greater than the predicted concentrations; similar to the 18 percent (12 percent with corrected solution concentrations) measured in 2002 with the XCEM. On the other hand, the 2002 M29 results are 6 

percent less than the predicted concentrations rather than 12 percent greater as 

in 2001. 

These results are certainly consistent with the hypothesis that M29 Hg results 

are low because there was a loss of Hg from the M29 quartz fiber filter between 

the time it was collected on the filter and the time it was analyzed. It is also 

consistent with the fact that many ofthe Hg compounds and amalgams of Hg are 

relatively unstable and have relatively high vapor pressures. Thus, it should not 

be surprising that if there is a substantial portion of the Hg on the filter as there 

was during the 2002 tests, there might be a potential for significant loss due to 

volatilization. It also needs to be noted that the filters were not stored in a controlled environment from the time they were collected until they were delivered 

to the analytical laboratory several days later. During this time, they may have 

been exposed to relatively high ambient temperatures while being transported 

through the western desert from Tooele, UT to California in the back of a closed 

panel truck. 

Correlation with percent Hg on M29 filter. The percent difference between the 

M29 Hg results and the XCEM results is significantly correlated with the percent Hg on the M29 filters as is illustrated in Figure D2. That is, the percent 

difference between the two methods (percent loss from the M29 filter) is dependent on the fraction ofthe total Hg measured in the M29 train that is on the filter. 

This observation is consistent with the proposed hypothesis for the difference 

between the various methods, that is, loss of Hg from the M29 filter. 

VES016940 
ERDC/CERL TR-05-9 123 

e 

50 

o nee Betv 

XCEM 

4o 'y 

30 i 

- 1.25x - 4.3223 

R

2

 = 0.8055 

TS 

£ CS 20 • 

5 

s IO 

IH 0 _ 

0 10 20 30 40 

Percent of Hg on M29 Filter 

Figure D2. Percent difference between M29 and the XCEM vs. percent of 

Hg on the M29 filter. 

Precision 

The difference in the Hg concentrations was not likely due to imprecision in either of the two measurements. Mercury was one of two elements spiked by 

MSE-T A that were clearly not present i n the background stack emissions. Thus, 

the variability in the Hg concentration was due primarily to variability in the 

spiking and stack flow rates. The Hg precision as measured by the XCE M was 

3.8 percent and 6.1 percent for M29, which includes the variability in the two 

parameters above as well as the measurement method variability. 

Mercury to nickel ratio 

Nickel was another element that clearly was not present i n the background, and 

it was in the same spiking solution as the Hg. Thus, the ratio of Hg should not 

vary significantly since the concentrations for these two elements was kept constant for these latest tests. The XCE M measured H g to N i ratio was 1.37 ± 0.015 

(1.1 percent relative) and close to both the M29 ratio, 1.41 ± 0.116 (8.3 percent 

relative), and the predicted concentration ratio based on the measured solution 

concentration ratio of 1.33. It is interesting to note that the XCE M precision is 

significantly better than the M29 ratio precision, both of which should be relatively independent of factors other than the individual method. 

Low Columbia Analytical Services results 

The XCE M deposit samples submitted to Columbia Analytical Services for CVAA 

analysis were extracted 41 days after they were analyzed by CES . Based on an 

assumed linear loss rate, the expected H g concentrations at the time of extracVES016941 
124 ERDC/CERL TR-05-9 

tion would be about 10 percent lower than measured by the CES XRF analyzer. 

The observed difference was 14 percent. 

Conclusion 

The weight of evidence clearly indicates that the XCE M Hg deposit was unstable 

as was the M29 P M deposit on the quartz fiber filter. This instability most likely 

caused the difference between the Hg measured by these two methods and the 

other methods. It is highly likely that, if these losses had not occurred, the 

XCE M would have passed the PS-10 RA tests. 

It is recommended that, in future M29 testing, the filters be immediately sealed 

and cooled to at least 0 °C, stored at below freezing temperatures and digested as 

soon as possible after sampling. 
ERDC/CERL TR-05-9 125 

Abbreviations and Acronyms 

A EC Army Environmental Center 

A ED Ammunition Equipment Directorate 

A MP Alternative Monitoring Plan 

AMS Advanced Monitoring Systems (Center) 

A PE ammunition peculiar equipment 

CAAA Clean Air Act Amendments (of 1990) 

C EM continuous emission monitor 

CERL Construction Engineering Research Laboratory 

CES Cooper Environmental Services 

CHPPM U.S. Army Center for Health Promotion and Preventive Medicine 

CVAA cold vapor atomic absorption 

EPA U.S. Environmental Protection Agency 

EQT Environmental Quality Technology 

ERDC U.S. Army Engineer Research and Development Center 

ETV Environmental Technology Verification (program) 

HAP Hazardous Air Pollutants 

HWC hazardous waste combustors 

ICP inductively coupled plasma 

LIBS laser-induced breakdown spectroscopy 

L VM low volatile metals 

MACT Maximum Achievable Control Technology 

M17 EPA Reference Method 17 

M29 EPA Reference Method 29 

MF membrane filter 

NESHAP National Emissions Standard for Hazardous Air Pollutants 

NIST National Institute of Standards and Technology 

P M particulate matter 

PS-10 EPA Proposed Performance Specification 10 

QA/QC quality assurance/quality control 

VES016943 
126 ERDC/CERL TR-05-9 

QFF quartz fiber filter 

QSIS Quantitative Spike Injection System 

RA relative accuracy 

RCRA Resource Conservation and Recovery Act 

RIF resin-impregnated filter 

RSD relative standard deviation 

SCFM standard cubic feet per minute 

TEAD Tooele Army Depot 

XCE M XRF-based continuous emission monitor 

XRF x-ray fluorescence 

Chemical elements 

Ag silver Pb lead 

As arsenic Pd palladium 

Ba barium Sb antimony 

Be beryllium Se selenium 

Cd cadmium Sn tin 

Cr chromium Tl thallium 

Hg mercury Zn zinc 

Ni nickel 

VES016944 
REPOR T DOCUMENTATIO N PAG E Form Approved 

OMB No. 0704-0188 

Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and mainlaining the 

date needed, and completing and reviewing this collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing 

this burden to Department of Oefense, Washington Headquarters Services, Directorate for Information Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 22202-

4302. Respondents should be aware that notwithstanding any other provision of law. no person shall be subject to any penalty for failing to comply with a collection of information If it does not display a currently 

valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. 

1. REPORT DATE (DD-MM-YYYY) 2. REPORT TYPE 

03-2005 Final 

3. DATES COVERED (From - To) 

4. TITLE AND SUBTITLE 

X-Ray Fluorescence Based Multi-Metal Continuous Emission Monitor: 

Technology Demonstration 

5a. CONTRACT NUMBER 

5b. GRANT NUMBER 

5c. PROGRAM ELEMENT NUMBER 

6. AUTHOR(S) 

K. James Hay, Veera M. Boddu, Bruce E. Johnsen, and John A. Cooper 

5d. PROJECT NUMBER 

622784AT41 

5e. TASK NUMBER 

002 

5f. WORK UNIT NUMBER 

CNE-B091 

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 

U.S. Army Engineer Research and Development Center (ERDC) 

Construction Engineering Research Laboratory (CERL) 

PO Box 9005 

Champaign, IL 61826-9005 

8. PERFORMING ORGANIZATION REPORT 

NUMBER 

ERDC/CERL TR-05-9 

9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 

U.S. Army Corps of Engineers 

441 "G" Street NW 

Washington, DC 20314-1000 

10. SPONSOR/MONITOR'S ACRONYM(S) 

11. SPONSOR/MONITOR'S REPOR T 

NUMBER(S) 

12. DISTRIBUTION / AVAILABILITY STATEMENT 

Approved for public release; distribution is unlimited. 

13. SUPPLEMENTARY NOTES 

Copies are available from the National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161. 

14. ABSTRACT 

Army demilitarization incinerators will need to comply with the Hazardous Waste Combustor National Emission Standard for Hazardous 

Air Pollutants that will regulate metals and metal compounds listed under the Clean Air Act Amendments. A large problem for these incinerator operations is limited knowledge of the type and quantity of emitted metals, so that compliance may be determined only through 

trial burn emission tests. A continuous emission monitor (CEM) for multi-metals will provide the emission data, a tool to help meet 

compliance requirements, and the opportunity to adjust bum strategies for increased production. A user-friendly multi-metal CEM that 

uses x-ray fluorescence (XRF) as the analytical method and an automated sampling system that provides extractive batch sampling onto a 

filter tape (XCEM) was demonstrated at the 1236 Deactivation Furnace at Tooele Army Depot, Utah. The unit was compared to EPA 

Reference Method 29 during two separate tests (2001 and 2002). The second test was performed after improvements were made to the 

sample transport and system calibrations. The results indicate that the XCEM has met the proposed Performance Specification 10 for 

multi-metal CEMs except for some ofthe relative accuracy requirements. Its failures are attributed to inadequacies in the reference 

method. The monitor is proving useful at Tooele and is ready for implementation at other Army demilitarization incinerators. 

15. SUBJECT TERMS 

emissions air pollution 

hazardous air pollutants (HAPs) continuous emission monitor (CEM) 

16. SECURITY CLASSIFICATION OF: 17. LIMITATION 

OF ABSTRACT 

SAR 

18. NUMBER 

OF PAGES 

137 

19a. NAME OF RESPONSIBLE PERSON 

K. James Hay 

a. REPORT 

Unclassified 

b. ABSTRACT 

Unclassified 

c. THIS PAGE 

Unclassified 

17. LIMITATION 

OF ABSTRACT 

SAR 

18. NUMBER 

OF PAGES 

137 

19D.TELEPHONE NUMBER (include area code) 

(217) 373-3485 

NSN 7540-01 -280-5500 Standard Form 298 (Rev. 8-98) 

Prescribed by ANSI Std. 239.18 

VES016945 
VES016946-016949.pdf 
Environ. Sci. Technol. 1888, 20, 735-738 

(20) Schwarzenbach, R. P.; Giger, W.j Schaffnei, C ; Wanner, 

O. Environ. Sci. Technol. 1985,19, 322-327. 

(21) Schweiier, C ; Tarradellas, J . Chimin 1980, 34, 609r619. 

(22) Olle, K.| Vermeulen, P. L.; Huteinger, 0. Chemosphere 1977, 

6, 455-469. 

(23) Buser, H. R.; Bosshardt, H . P.; Rappe, C. Chemosphere 

1978, 7,165-172. 

(24) BaUachmiter, K. University of Ulm, Ulm, Federal Republic 

of Germany, personal communication, 1985. 

(25) Harlesa, R, L.; Oswald, E. 0.; Wilkinson, M . K.; Dupuy, A. 

E„ Jr., McDaniel, D. D.; Han, T. Anal. Chem. 1980,52, 

1239-1245. 

Received for review October 21,1985. Accepted February 18, 

1986. 

Adsorption of Mercury Vapor on Particles 

YosWo Otanl," Chlkao Kanaoka, Chlyokl Usui, Saburo Matsul,T and Hltoshl EmI 

Department of Chemical Engineering, Kanazawa University, 2-40-20 Kodatsuno, Kanazawa 920, Japan 

• The adsorption of mercury vapor on particles was 

studied by using soot particles generated by incineration 

of sewage sludge (EP-ash) and activated carbon particles. 

Through the experiments, it was found that, at 298 K, the 

EP-ash has a fairly high adsorption capacity for mercury 

vapor in the order of 10"* g/g, which is between that of the 

ordinary soils and that of activated carbon particles. 

Furthermore, it was found that physical adsorption of 

mercuiy vapor on the studied particles at high temperature 

is described by Dubinin's equation. On the basis of the 

equation, it was shown that tlie EP-ash physically adsorbs 

very little mercury vapor at high temperature, and 

therefore, most mercury in the EP-ash is chemically adsorbed or contained in a form of mercury compounds. 

Nevertheless, the total amount of mercury contained in 

the particles is very little compared to the total mercury 

inthe exhaust gases so that most mercury behaves as a 

vapor even in the presence of particulate matter. 

Introduction 

It has been reported that mercury at a low concentration 

is released into the atmosphere together with combustion 

products resulting from the incineration of sewage sludge 

or municipal garbage. The mercury content in sewage 

sludge is usually 0.2-1.8 mg/kg dry matter, and most of 

the mercury is volatilized by the incineration to give 

mercury concentrations in the emission of about 0.3 

mf/m9(N-m3) (i, 2). Although there is no regulation for 

the mercury emission in waste gases, it is urgent to install 

effective collectors for mercury since it may cause serious 

diseases by accumulating in the human body. 

In incinerators where a large number of soot particles 

and reactive gases are generated at a high temperature, 

it is expected that there are strong interactions between 

mercury vapor and these substances. In order to develop 

an effective mercury control technique, it is necessary to 

conduct quantitative studies on the interaction of mercury 

vapor with particulate matter as well as reactive gases. 

In the previous paper (3), we investigated the existence 

of particulate mercury in a dust-free atmosphere at various 

mercury concentrations and found that mercury mostly 

exists as a vapor even at a concentration 200 times higher 

than the saturation at 273 K. In a dusty atmosphere, 

however, the situation would be more complicated because 

of mercury-particle interaction. 

In the present work, the interaction of mercury vapor 

and particles, i.e., the adsorption of mercury on particles, 

was studied with soot particles obtained from an electrostatic precipitator in a sewage sludge incineration plant 

• Present address: Department of Sanitary Engineering, Kyoto 

University, Voshida-Honmachi, Sakyoku, Kyoto 606, Japan. 

Table I. Chemical Compositions and Physical Properties of 

the Particles 

raw heated activated 

EP-ash EP-ash carbon 

ignition loss, % 35.21 33.37 

chemical component 

C,% 15.35 16.05 

H, % 0.59 0.36 -

- N, % 0.23 0,15 -

SiCV % 6.68 7.49 

CaO, - « % 16,20 7.60 

KjO - , % 1.69 2.06 

MgO, % 0.97 1.06 -

- Al 2Oj, % 2.83 3.16 

Fe, ppm 5.14 5.41 -

- Cd, ppm 531 

Pb, ppm 3470 - -

geometric mean particle 1.6 -1.6 6-2 

diameter, jtm 

geometric standard deviation 1.8 1.8 1.2 

particle density, g/cm3 2.47 

specific surface area (BET - -

-

17.8 716 

method), ms/g 

"Determined by the method specified by JIS-R-2212.

 6 (-), not 

measured. 

(EP-ash) and also with activated carbon particles. 

Experimental Procedures 

Adsorption characteristics of mercury on particles were 

studied by the following experiments: (i) determination 

of mercury in solid particles (desorption method); (ii) 

determination of equilibrium adsorbed mass of mercury 

with packed bed of particles (adsorption method). 

In the experiments, EP-ash sampled from an electrostatic precipitator in a sewage sludge incineration plant 

(raw EP-ash) and the EP-ash heated at 773 K for 8 min 

in nitrogen atmosphere (heated EP-ash) were used with 

activated carbon particles as a reference adsorbent. The 

results of chemical composition analyses of the raw and 

heated EP-ashes and their physical properties are shown 

in Table I with those of the activated carbon particles. 

The details of experiments i and ii are described here, 

(i) Desorption Method. The mercury content in 

particles was measured by trapping thermally desorbed 

mercury in liquid absorbent. Particles were heated in 

nitrogen atmosphere by an infrared image furnace (Shinku-riko Co. Ltd., Model RHL-E25). The desorbed mercury 

was entrained by nitrogen gas and collected in a gas 

washing bottle containing 200 cm8 of 0.2 wt % KMn04 + 

2 N H2S04 (4), The collected mercury was then determined by a flameless atomic absorption spectrophotometer 

(Shimadzu, Model AA-640-13). The desorption method 

was examined by using activated carbon particles con0013-936X/86/0920-0735$01.50/0 © 1986 American Chemical Society Environ, Sci. Technol., Vol. 20, No. 7, 1986 735 

VES016946 
Hg hollow absorption 

colhod lamp lens call | e n . 

I=SM-I==H -

amplifier Table III. Mercury Content In the Haw EP-ash» 

dilutionl 

gas washing cell 

boi lie 

Figure 1. Experimental setup for the measurement of breakthrough 

curves. 

Table II, Experimental Conditions for the Measurement of 

Breakthrough Curves 

packed mass of particles, g 

average particle size, Jim 

flow velocity of air, cm/s 

led depth, cm 

bed diameter, cm 

bed, temperature, K 

mercury vapor concentration, mg/(N-ms) 

EP-Bshes 

0.07 

1.6 

7.4 

0.3 

activated 

carbon 

0.05 

52 

10.4 

0.2 

0.8 

296 

0.14-1.6 

taining known amounts of mercury since the desorption 

efficiency of mercury from particles depends upon the 

heating time and temperature. The mercury-containing 

activated carbon particles were prepared in the following 

manner. One gram of activated carbon particles was 

packed in a 8 mm diameter and 4 cm long bed, through 

which known volume of air containing mercury was passed. 

The total amount of mercury adsorbed in the particles was 

calculated by the total air volume passing through the bed 

and its mercury vapor concentration, When the temperature of particles was kept at 773 K for 8 min during 

desorption, the accuracy of the method was within 5% 

(standard deviation) over mercury contents from 3 x lflr6 

to 4.4 X IO"8 g/g. 

(ii) Adsorption Method. The equilibrium adsorbed 

mass of mercury in particles was determined by measuring 

breakthrough curves of the packed beds. The experimental setup is shown in Figure 1. Air containing a known 

concentration of mercury vapor was passed through the 

packed bed of particles, and the outlet concentration of 

mercury was continuously measured by introducing the 

exit gas directly to the flameless atomic absorption spectrophotometer. The equilibrium adsorbed mass of mercury, q, was obtained by using the following relationship. 

<j = fVo-OdlQ. ) (1) 

where C0 and C are the inlet and outlet concentrations of 

mercury, and Qt is the total air volume flowing into the 

bed. The mercury content was also determined by the 

desorption method. The experimental conditions for the 

measurement of the breakthrough curves are shown in 

Table II. 

Results and Discussion 

The mercury contents in the EP-ash samples measured 

by the desorption method are shown in Table III. The 

average mercury content in the particles is 2.42 X IO"8 g/g 

with a standard deviation of 0.75 x 10"4 g/g. The average 

mercury mercury mercury 

content, content, content, 

sample PPm sample ppm sample ppm 

1 3.73 16 2.75 31 1.41 

2 1.13 17 3.60 32 2.44 

3 1.57 18 3.36 33 1.80 

4 1.74 19 3.48 34 2.83 

5 6.84 20 2.70 35 1.73 

6 1.96 21 2.00 36 1.73 

7 2.19 22 2.76 37 2.67 

6 2.26 23 2.77 38 2.54 

9 2.50 24 2.00 39 2.67 

10 2.40 25 1.20 40 1.93 

11 2.50 26 3.47 41 1.28 

12 1.41 27 1.87 42 2.83 

13 1.70 28 1.47 43 1.56 

14 3.30 29 2.93 44 . 2.90 

15 3.60 30 2.13 45 3.34 

"ppm = 10*8 g/g. 

ro.a 

> 

I 0.6 

S 0.2 

HeaJad EP-as h 

activated carbon 

1 

C «l.O mg/m-N 

1 0.82 

r / 

r 

/ 

! 

/ 

/ 

/ 

0.49 

• 0.44 

0.25 

O O.I 0.2 0.3 0.4 

totol air volume flowing into bed, Ot tnv^-NJ 

Figure 2, Breakthrough curves for the heated EP-ash and activated 

carbon particles. 

content agrees with the previously reported mercury contents in EP-ashes of sewage sludge incinerators (5, 6). 

The breakthrough curves of the heated EP-ash are 

shown in Figure 2 with those of the activated carbon 

particles. The period of zero outlet concentration decreases 

in the following order: activated carbon, heated EP-ash, 

and raw EP-ash. For the same particles, breakthrough 

occurs more rapidly as the mercury concentration increases. 

The equilibrium adsorbed masses of mercury in the 

EP-ashes and the activated carbon particles measured by 

the adsorption method are plotted by hollow symbols in 

Figure 3, together with those of various soils measured by 

Fang (7). First, when the order of these sorbents is compared, it is noted that the EP-ashes, having an adsorption 

capacity of about 10"6 g/g, are between activated carbon 

particles and ordinary soils. In the same figure, the adsorbed masses on the raw and heated EP-ashes measured 

by the desorption method are shown by solid symbols. The 

adsorbed masses on the heated EP-ash measured by both 

adsorption and desorption methods agree with each other 

within experimental error, whereas the adsorbed mass on 

the raw EP-ash measured by the adsorption method is 

lower than that measured by the desorption method since 

the raw EP-ash already contained an average of about 2.42 

X 10"6 g/g mercury. The adsorbed mass on the heated 

EP-ash is higher than that ofthe raw EP-ash, indicating 

that the sampled raw EP-ash is not thermally stable and 

its adsorption capacity may be changed by the heat 

treatment. 

Second, looking at concentration dependence of the 

isotherms, it is found that the heated EP-ash and the raw 

7)0 Environ. Sci. Technol., Vol. 20, No. 7, 1986 

VES016947 
mercury concentration, C- Cmg/rrt'-Nl 

Fljiirs 3. Comparison of adsorption Isotherms ot various adsorbents, 

EP-ash measured by the adsorption method have almost 

the same slope as that of the activated carbon. The 

agreement of the slopes probably indicates that mercury 

vapor is adsorbed on these particles by the same mechanism, i.e., physical adsorption which is the main adsorption 

mechanism on the activated carbon. On the other hand, 

the slope of die raw EP-ash measured by the desorption 

method is smaller than that of the other adsorbents. The 

possible explanation for the weak concentration dependence of the raw EP-ash may be the result of mercury 

content of the raw EP-ash, which is most probably present 

inthe form of mercury compounds. 

When, the above considerations are taken into account 

and the Freundlich isotherm is applied to the data, 

physical adsorption of mercury vapor on the studied 

particles can be expressed by the following equations. For 

the raw EP-ash (by adsorption method) 

(2) 

(3) 

q = (3.5 X lO^Co0 8 7 

For the heated EP-ash 

q = (5.4 X W W 

For the activated carbon 

q = (1.8 X lO-^C/ 3 7 (4) 

where q is the adsorbed mass in g/g and C0 is the equilibrium mercury concentration in g/(N-ms

). 

We have obtained the adsorption isotherms of mercury 

vapor on the raw EP-ashes at room temperature (298 K). 

In order to predict the adsorbed mass of mercury at elevated temperatures, we apply Dubinin's equation to the 

obtained isotherms, confining our consideration to the 

physical adsorption of mercury vapor. In addition, since 

the adsorption capacity of the raw EP-ash was found to 

be changed by the heat treatment, we assume that isotherm ofthe raw EP-ash at high temperature varies between that of the raw EP-ash at room temperature and 

that of the heated EP-ash, following the same concentration dependence, i.e. 

1 2 3 4 

adsorption potential, AxlO"4 

5 

tJ/motl 

Figure 4. Adsorbed masses of mercury on the activated carbon 

particles and EP-ashes as a function of tha adsorption potential. 

where 3.5 X IO"5 < a < 5.4 X 10"* and p = 0.37. The 

Freundlich form of eq 5 is rewritten in the form of Dubinin's equation as 

q - go exp(-A/.E) (6) 

In this equation, q0 is a constant, E the characteristic 

energy of adsorption, and A the Polanyi's potential given 

by 

A = RT ln (P,/Po) (?) 

where R is the gas content, T is the temperature, and P, 

and P0 are the saturated vapor pressure and the adsorption 

equilibrium pressure, respectively. ?0 and E are related 

to a and /J in eq 5 by the following equations: 

>

 = 0! \rt ) 

E = RT/0 

(8) 

(5) 

(9) 

Substitution of a and 0 into eq 8 and 9 yields the constants 

of eq 6 as 

8.2 x icr< < 9 o < 1.3 x irr* (g/g) 

JS = 6.7 X 103 (J/mol) for raw EP-ash (10) 

To test the applicability of Dubinin's equation, the 

equilibrium adsorbed mass was measured at elevated 

temperatures. In the experiment, activated carbon particles were used because mercury vapor is physically adsorbed on both raw EP-ash and activated carbon particles 

and the equilibrium adsorbed mass of the raw EP-ash is 

changed by heat treatment. The experiment with the 

activated carbon can provide information on the temperature dependence of the mercury adsorption in case of 

physical adsorption. The equilibrium adsorbed mass 

measured at various temperature is plotted in Figure 4 as 

a function of the adsorption potential. The data for both 

raw and heated EP-ashes contain only those obtained at 

room temperature. In the figure, the curveB are predicted 

lines by eq 6. The data obtained at various temperatures 

for the activated carbon particles are in fairly good 

agreement with the predicted line, showing that the form 

of eq 6 is applicable to the physical adsorption of mercury 

vapor. 

If we take representative values of the temperature, the 

concentration of mercury vapor, and the dust concentration at the outlet of the electrostatic precipitator as 473 

K, 0.3 mg/(N-ms), and 0.2 g/(N-m3), respectively, then the 

Environ. Sci. Technol., Vol. 20, No. 7, 1986 737 

VES016948 
adsorption potential is A ~ 5.3 X 104

 J/mol. By substitution of this value into eq 6 with the constants given in 

eq 10, the equilibrium adsorbed mass of mercury vapor is 

between 3.0 X IO"8 and 4.8 X 10"* g/g. Thus, the quantity 

of mercury in the particles leaving the precipitator is only 

between 6.0 X IO"10 and 9.6 X 10"10 g for each N-m3 gas 

generated compared with the average mercury concentration 0.3 mg/(N-m8

). This calculation result indicates 

that the raw EP-ash would contain very little mercury 

vapor at high temperatures if the mercury is only physically adsorbed on the particles. However, since about 2.42 

X Kr 6 g/g of mercury was detected in the raw EP-ash in 

average, it can be said that mercury is not adsorbed 

physically on the EP-ash but it is chemically adsorbed or 

contained in the form of chemical compounds. Therefore, 

if we assume that the average mercury content of the 

EP-ash does not change with temperature since the mercury compounds are more stable thermally than metal 

mercury, the amount of mercury at the representative 

condition of the incinerator emission is 4.8 X 10"' g/CN-m3). 

Although this predicted value is about 100 times higher 

than the amount of physically adsorbed mercury, it is still 

only y6oo of the total mercury content in the incinerator 

emission. Therefore, we may conclude that most mercury 

is in the vapor state even in the presence of soot particles. 

Conclusions 

The adsorption experiments lead to the following conclusions: 

(1) The mercury content in the EP-ash sampled from 

an incineration plant is about 2.42 x IO"6 g/g which agrees 

with the previously reported values for the sewage sludge 

incineration dust collected by an electrostatic precipitator. 

(2) The EP-ash has a fairly high mercury adsorption 

capacity on the order of 10"8 g/g compared with the ordinary soils. 

(3) Physical adsorption of mercury vapor at an elevated 

temperature can be predicted by Dubinin's equation. 

(4) Very little physically adsorbed mercury on the raw 

EP-ash occurs at a high temperature,-and most mercury 

is chemically adsorbed or contained as chemical compounds in the EP-ash. 

Acknowledgments 

We express our appreciation for the financial support 

and useful discussions by T. Kasakura, Assistant to the 

General Manager, Environmental System and Equipment 

Division, NGK Insulators, Ltd. 

. Registry No. Hg, 7439-97-6; C, 7440-44-0. 

Literature Cited 

(1) Suzuki, M.; Kubota, H.; Kanaya, K. Kougai to Taisaku 

1985, 21, 69-76. 

(2) Kato, T. Nibon Gaishi Research Report-Kankyo Souchi 

Tokushu, NG K Insulators Ltd., Japan, 1976. 

(3) Otani, Y.; Emi, H.; Kanaoka, C ; Matsui, S. Environ. Sci. 

Technol. 1984,18, 793-796. 

(4) Kitamura, S.; Kondo, M.; Takizawa, Y.; Fujii, M ; Fujiki, 

M . Suigin; Koudansha Press: Tokyo, 1976; p 84. 

(6) Hayashi, S. Sangyo Kougai 1980,16, 714-717. 

(6) Kurihara, S. Kagaku Kogyo 1980, 1, 83-88. 

(7) Fang, S. C. Environ. Sci. Technol, 1978,12, 285-288. 

(8) Astakhov, V. A.; Dubinin, M . M.; Romankov, P. G. Theor. 

Osn. Khim. Tekhn. 1969, 3, 292-295. 

Received for review April IB, 1985. Revised manuscript received 

February 20,1986. Accepted April 8,1986. 

738 Environ. Sci. Technol., Vol. 20, No. 7, 1986 

VES016949 
VES016950-016960.pdf 
This article was downloaded by: [70.88.2.29] 

On: 30 October 2014, At: 13:59 

Publisher: Taylor & Francis 

Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer 

House, 37-41 Mortimer Street, London WIT 3JH, UK 

Journal of the Air 8t Waste Management 

Association 

Publication details, including instructions for authors and subscription information: 

http://www.tandfonline.com/loi/uawm20 

Validation of Three New Methods for 

Determination of Metal Emissions Using a Modified 

Environmental Protection Agency Method 301 

Catherine A. Yanca

 a

 , Douglas C. Barth

 a

, Krag A. Petterson

 a

 , Michael P. Nakanishia 

, John A. Coopera, Bruce E. Johnsen

 b

 , Richard H. Lambertc & Daniel G. Bivinsd 

a

 Cooper Environmental Services, LLC , Portland , OR , USA 

b

 SAIF Co. , Portland , OR , USA 

c

 Engineering Tech Center, Eli Lilly and Co , Indianapolis , IN , USA 

d

 U.S. Environmental Protection Agency , Research Triangle Park , NC , USA 

Published online: 27 Feb 2012. 

To cite this article: Catherine A. Yanca , Douglas C. Barth , Krag A. Petterson , Michael P. Nakanishi , John A. Cooper, 

Bruce E. Johnsen , Richard H. Lambert & Daniel G. Bivins (2006) Validation of Three New Methods for Determination 

of Metal Emissions Using a Modified Environmental Protection Agency Method 301, Journal of the Air & Waste 

Management Association, 56:12, 1733-1742, DOI: 10.1080/10473289.2006.10464578 

To link to this article: http://dx.doi.org/10.1080/10473289.2006.10464578 

PLEASE SCROLL DOWN FOR ARTICLE 

Taylor & Francis makes every effort to ensure the accuracy of all the information (the "Content") 

contained in the publications on our platform. However, Taylor &. Francis, our agents, and our licensors 

make no representations or warranties whatsoever as to the accuracy, completeness, or suitability for any 

purpose of the Content. Any opinions and views expressed in this publication are the opinions and views 

ofthe authors, and are not the views of or endorsed by Taylor 8i Francis. The accuracy ofthe Content 

should not be relied upon and should be independently verified with primary sources of information. 

Taylor and Francis shall not be liable for any losses, actions, claims, proceedings, demands, costs, 

expenses, damages, and other liabilities whatsoever or howsoever caused arising directly or indirectly in 

connection with, in relation to or arising out of the use of the Content. 

This article may be used for research, teaching, and private study purposes. Any substantial or systematic 

reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any 

form to anyone is expressly forbidden. Terms 8i Conditions of access and use can be found at http:// 

www.tandfonline.com/page/terms-and-conditions 

VES016950 
TECHMICAL PAPER ISSN 1047-3289 J. Air & Waste Manage. Assoc. 56:1733-1742 

Copyright 2006 Air & Waste Management Association 

Validation of Three New Methods for Determination of Metal 

Emissions Using a Modified Environmental Protection Agency 

Method 301 

Catherine A. Yanca, Douglas C. Barth, Krag A. Petterson, Michael P. Nakanishi, and 

John A. Cooper 

Cooper Environmental Services, LLC, Portland, OR 

Bruce E. Johnsen 

SAIF Co., Portland, OR 

Richard H. Lambert 

Engineering Tech Center, Eli Lilly and Co., Indianapolis, IN 

Daniel G. Bivins 

U.S. Environmental Protection Agency, Research Triangle Park, NC 

ABSTRACT 

Three new methods applicable to the determination of 

hazardous metal concentrations in stationary source 

emissions were developed and evaluated for use in U.S. 

Environmental Protection Agency (EPA) compliance 

applications. Two of the three independent methods, a 

continuous emissions monitor-based method (Xact) 

and an X-ray-based filter method (XFM), are used to 

measure metal emissions. The third method involves a 

quantitative aerosol generator (QAG), which produces a 

reference aerosol used to evaluate the measurement 

methods. A modification of EPA Method 301 was used 

to validate the three methods for As, Cd, Cr, Pb, and Hg, 

representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal 

categories (low volatile, semivolatile, and volatile). The 

modified procedure tested the methods using more 

stringent criteria than EPA Method 301; these criteria 

included accuracy, precision, and linearity. The aerosol 

generation method was evaluated in the laboratory by 

comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a 

hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, 

Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated 

precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on 

the order of 0.99, confirming the methods' linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the 

reference aerosol.generator should be applicable to additional analytes. EPA recently approved an alternative 

monitoring petition for an HWC at Eli Lilly's Tippecanoe site in Lafayette, IN, in which the Xact is used for 

demonstrating compliance with the HWC MACT metal 

emissions (low volatile, semivolatile, and volatile). The 

QAG reference aerosol generator was approved as a 

method for providing a quantitative reference aerosol, 

which is required for certification and continuing quality assurance of the Xact. 

INTRODUCTION 

Air toxic metals have been associated with a wide range 

of environmental and human health effects, including 

respiratory disorders, pulmonary disorders, and cancer.1

'

2

 EPA regulates the emissions of toxic metals from 

stationary sources under the National Emission Standards for Hazardous Air Pollutants (NESHAP) or Maximum Achievable Control Technology rule.3

 Currently, 

emissions are estimated based on control efficiencies 

established during performance tests and estimated 

feed rates during normal operations. When actual emissions are measured, EPA Reference Method 29 (Method 

29) is used.4 However, Method 29 is based on 30-yr-old 

IMPLICATIONS 

The two measurement methods for determining metal 

emissions validated In this study (the Xact and the XFM) 

include significant improvements in measurement technology. With these two new methods, plant operators can 

make more precise, accurate, and frequent measurements, 

leading to a better understanding of emissions. With the 

new reference aerosol generator validated in this study (the 

QAG), development and evaluation of new measurement 

methods are now more practical. The measurement methods are applicable to a wide range of elements and may be 

applicable to other sources. The aerosol generator may be 

applicable to both organic and inorganic analytes. 

Volume 56 December 2006 Journal of the Air & Waste Management Association 1733 
Yanca et al. 

impinger technology with accuracies and precisions on 

the order of 15%.5-

7

 The method also involves hazardous chemicals, and it requires long turnaround times. It 

is clear that there are opportunities for improvement in 

the current monitoring technology. 

There have been attempts over the past decade to 

improve metals measurement technology by developing multimetal continuous emissions monitoring systems (CEMS). 8

-

1 0

 None of the proposed technologies 

have been approved for compliance demonstration 

other than those discussed in this paper. The new technology presented here includes three new methods applicable to the determination of hazardous metal concentrations in emissions: a multimetal CEMS-based 

method (Xact), a sampling and analysis measurement 

method (X-ray-based filter method [XFM]), and a National Institute for Standards and Technology (NIST--

traceable reference aerosol generating method (QAG). 

The methods and the instruments used to perform the 

methods were developed to provide more precise, accurate, and frequent measurement capabilities than are 

offered by Method 29. The Xact method uses a CEMS 

based on X-ray fluorescence (XRF) analysis of aerosol 

deposits (particulate and vapor phase) on reactive filter 

tape. 111 2 XFM is comparable to Method 29 but uses 

reactive filters (solid sorbants)11'

12

 instead of impingers 

to trap both particulate and vapor phase metals, followed by nondestructive XRF analysis of the filters. The 

quantitative aerosol generator (QAG) is based on nebulization of a metal-containing solution and produces a 

reference aerosol that can be used to validate measurement methods, such as the Xact and XFM. 

To evaluate the performance of the new methods, a 

test plan1 3 based on the requirements of EPA Method 

30114 was developed. Method 301 is a defined procedure 

for validating new pollutant measurement methods that 

could potentially be used to demonstrate compliance 

with permits or other EPA applications. A more stringent 

modification of this procedure was used to validate the 

three methods based on accuracy, precision, and linearity 

criteria. This paper presents: (1) an overview of the three 

methods, (2) the procedure used for validating these 

methods, and (3) the results of the validation tests. Details 

about these instruments and methods, performance specifications, and standard operating procedures are presented elsewhere.15

-

20 

EXPERIMENTAL WORK 

Quantitative Reference Aerosol Generation 

The method for generating a quantitative reference 

aerosol involves the operation of the QAG instrument. 1 5 '

2 1

 Using the QAG, an aerosol of analyte solution droplets is created using a nebulizer.21

-

22

 The droplets are then passed into a settling chamber where the 

large droplets are removed and liquid and vapor phases 

are equilibrated. Droplets <30 \x.m in diameter are allowed to pass into a drying chamber where they are 

dried before being emitted. The aerosol exiting the drying chamber consists of the transport gas, water and 

metal vapor, and dried salt particles. The aerosol emission concentration (Q) is calculated from the analyte 

concentration in the nebulized solution (Cs), the solution emission rate (Rm) corrected for vapor loss (Rv), 

and the total volume of nebulizing, drying, and dilution gas used to create the aerosol (Ft). 

Ca = y(Rm-Rv) (1) 

Quantitation of the emitted aerosol is made possible by: 

(1) using a large reservoir of NIST-traceable analyte solution to minimize the impact of evaporation on solution 

concentration, (2) continuously measuring the solution 

emission rate (R^) with a NIST-traceable balance, (3) precise control of nebulizer conditions, and (4) stable control 

of the maximum droplet size introduced into the generator's drying chamber such that only aerosols with high 

transport efficiencies are generated. The reference aerosol 

produced by the QAG is process NIST traceable and can be 

used in addition to its other applications to challenge and 

evaluate the accuracy, precision, and linearity of the measurement methods. It is applicable to both metal and 

nonmetal species. 

Metal Concentration Measurement 

Xact. The Xact method of metals measurement uses a 

CEMS, called the Xact CEMS, that collects and analyzes 

a sample of emissions using filter-based technology and 

nondestructive XRF. 1 5-

2 3

 During sample collection, the 

Xact CEMS directs a continuous flow of stack gas 

through a stilling chamber where its velocity is reduced 

(i.e., stilled). A continuous subsample is taken from the 

stilling chamber and drawn through chemically-reactive filter tape, which traps both particulate and vaporphase metals.11

-

12'23

 The volume of the sample flow is 

measured, and the filter tape deposits are advanced to a 

position where they are analyzed for metal mass using 

XRF analytical procedures similar to those listed in 

EPA's Compendium Method IO-3.3.24 The Xact CEMS 

then divides the XRF-determined mass per sample by 

the volume per sample and simultaneously reports concentrations for =s20 analyte metals every 15 min. During analysis of the current sample, the next sample is 

automatically collected. In the Xact CEMS, sampling 

and analysis is performed continuously in the same 

instrument except for the time required to advance the 

tape (~3 sec) and the time required for automated 

quality assurance checks (~1 hr, once per day). Detection limits for the Xact CEMS are listed in Table 1 and 

range from 0.1 (xg/dry standard cubic meter (dscm) to 

~6 fj,g/dscm with 15-min sampling times. These limits 

can be lowered significantly by varying sampling and 

analysis conditions. Both the XFM and Xact methods 

are generally applicable to elements with atomic numbers ranging from 13 (Al) to 92 (U). 

XFM. Like the Xact, the XFM uses filter-based technology 

to collect a representative sample of emissions followed 

by nondestructive XRF analysis of the sample.15'

23

 For 

sample collection, the XFM sampling train connects to a 

stilling chamber, such as the one used for the Xact CEMS. 

A representative sample of stack gas is continuously directed into the stilling chamber (at —30-100 L/min), and 

1734 Journal of the Air & Waste Management Association Volume 56 December 2006 
Yanca etal. 

Table 1. Xact and XFM detection limits. 

Xact" XFM" 

Element (ug/dscm) ((j.g/dscm) 

Cr 0.3 0,08 

As 0.1 0.08 

Cd 2.4 0.8 

Hg 0.3 0.14 

Pb 0.6 0.12 

Mn 0.2 0.08 

Co 0.3 0.08 

NI 0.3 0.06 

Se 0.1 0.08 

A8 4.2 0.6 

Sb 6.2 1.6 

Cu 0.5 0.08 

Fe 0.9 0,12 

Zn 0.2 0.06 

Br 0.4 0.2 

Sr 0.3 0.18 

Tl 0.3 0.14 

Lab Air or 

Stack Gas Xact Stilling XFM 

Chamber Sample Train 

Quantitative 

Aerosol 

Generator 

(QAG) 

Exhaust 

Figure 1. Experimental arrangement for laboratory and field tests. 

NIST traceability of the generation and measurement 

methods, inductively coupled plasma (ICP) analysis conducted at an independent laboratory (Chester LabNet, 

Tigard, OR) confirmed the standard solution concentrations used in the QAG and the filter deposit measurements made by the XFM method. 

Notes: "95% Confidence, interference free, 15-mln sample. "95% confidence, 

Interference free, 30-min sample. 

the XFM pulls a subsample of —1 L/min into its sampling 

train. The subsample is diluted and cooled before being 

drawn through a stacked filter cassette containing a polytetrafiuoroethylene filter followed by a chemically reactive niter.11

-

12

-

23

 Particulate-phase metals are trapped on 

the nonreactive polytetrafluoroethylene filter, whereas 

vapor-phase metals, including Hg, are collected on the 

chemically reactive filter or solid sorbent. After sample 

collection, the filter cassettes are removed from the sampling train, and the resulting filter deposits are analyzed 

for metal mass using nondestructive XRF procedures similar to those listed in EPA's Compendium Method IO3.3.24

 The filters do not require handling during any part 

of the XFM procedure, and they can be readily shipped to 

a laboratory for analysis or analyzed in the field. The 

emissions concentration is calculated by dividing the 

XRF-determined metal mass by the volume of emissions 

that passed through the filters. Typical sample times are 

30 min, and analysis turnaround times can be on the 

order of a few hours with a field-portable XRF analyzer. 

Detection limits typically range from 0.06 ug/dscm to 1.6 

u-g/dscm with 30-min sample times (Table 1). Substantially lower detection limits can be attained by varying 

sampling and analysis conditions. 

Method Independence 

The QAG-generated aerosol concentration is independent 

of the aerosol concentrations measured by the Xact and 

XFM. Method independence is confirmed using NIST 

traceability and additional procedures. The concentration 

of the aerosol produced by the QAG is procedurally traceable to NIST through nebulized solution standards and 

QAG operating parameters. The XFM- and Xact-measured 

concentrations are both analytically NIST traceable 

through thin film standards and NIST Standard Reference 

Materials 1832 and 1833. In addition to the independent 

Validation Methodology 

The procedures used to validate the QAG, XFM, and Xact 

were based on EPA Method 301. This EPA method is 

required when new methods of measuring analytes are to 

be used on a source in lieu of the standard reference 

method. Method 301 establishes accuracy and precision 

capabilities of a new method by comparing its determined 

concentrations with those of an accepted reference 

method. The resulting bias between concentrations from 

the two methods is used as an indicator of accuracy. 

Simultaneous method measurements are used to determine precision. Following normal Method 301 procedures, the Xact and XFM measurement methods would be 

tested against Reference Method 29. However, the precision and accuracy of Method 29, which are on the order 

of 15%,s-

7

 were insufficient for verifying the precisions 

and accuracies believed to be attainable with the Xact and 

the XFM (i.e., potential precision <5% and accuracy 

<5%). The validation procedure presented in this section 

is a modified Method 301 in which Method 29 comparisons were replaced with QAG reference aerosol comparisons.13

 This modified method was more stringent than 

Method 301, because it included more replicate runs, 

sequential measurements instead of simultaneous measurements, additional validation criteria (e.g., linearity), 

and independent NIST traceability of results. 

The first step in the modified Method 301 procedure 

required laboratory validation of the QAG emissions, and 

the second step was a field validation of the XFM and Xact 

measurements. The general experimental arrangement 

used for both laboratory and field tests is schematically 

illustrated in Figure 1. First, the QAG generated an aerosol, which was blended with laboratory air for laboratory 

tests and stack gas for field tests. The aerosol flow was then 

directed into the Xact CEMS stilling chamber15'

17

-

19

 from 

which the Xact CEMS and XFM simultaneously withdrew 

representative samples. After sampling, the XFM filters 

were removed and analyzed, whereas the Xact automatically reported metal concentrations every 15 min for the 

duration of the test. It should be noted that an Xact CEMS 

located at the Cooper Environmental Services facility was 

Volume 56 December 2006 Journal ot the Air & Waste Management Association 173S 
Yanca et al. 

used in the laboratory tests, and an Xact CEMS located at 

Eli Lilly and Company's Tippecanoe facility in Lafayette, 

IN, was used in the field. 

QAG Laboratory Validation. The QAG was evaluated in a 

series of laboratory tests15 in which a QAG-generated 

aerosol was combined with ambient laboratory air and 

simultaneously sampled by the Xact CEMS and XFM sampling train. The theoretical QAG concentration calculated 

using ec[ 1 was then compared with the actual concentrations measured with the Xact and XFM to determine the 

accuracy, precision, and linearity of the QAG method. All 

of the QAG-generated aerosols contained As, Cd, Cr, Pb, 

and Hg, representing the volatile, semivolatile, and lowvolatility metal categories as defined in the NESHAP HWC 

rule.3 Tests were conducted at four concentration levels 

(high, mid, low, and blank) ranging from 0 to >130 

u,g/dscm. In these laboratory tests, the QAG aerosol concentrations were compared with results from a total of 22 

XFM and 135 Xact runs. Only Xact runs that corresponded with simultaneous XFM runs were used for accuracy and precision determinations. All of the runs for 

both methods were used in the linear regression analysis. 

The XFM sample time was 30 min per run and the Xact 

was 15 min; concentrations from two Xact runs were 

averaged to represent a 30-min sample period for comparison with the XFM. All of the methods were performed 

according to specifications set forth by their test method 

and standard operating procedures.15-

20 

Xact and XFM Field Validation. The Xact and the XFM 

were evaluated in a series of field tests conducted at a 

hazardous Waste incinerator, where an Xact CEMS was in 

operation.15 For each field test, the validated QAG was 

used to generate a reference aerosol of known concentration, which was spiked into the hazardous waste incinerator flue gas. This dynamically-spiked flue gas was transported to the Xact CEMS stilling chamber where it was 

simultaneously sampled by the Xact CEMS and XFM sampling train. Measured concentrations from each method 

were compared with the QAG-spiked stack gas concentration to determine the accuracy and precision of the Xact 

and XFM methods. All of the QAG-generated aerosols 

contained As, Cd, Cr, Pb, and Hg, and tests were conducted at four concentration levels (high, mid, low, and 

blank) ranging from 0 to >130 p-g/dscm. During these 

field tests, a total of 24 XFM and 192 Xact runs were 

compared with the QAG aerosol concentrations. Again, 

only corresponding Xact/XFM runs were used for accuracy and precision determinations, but all of the runs 

were used for linear regression analysis. During these 

tests, the background concentrations of the stack gas were 

negligible relative to the spiked stack gas concentrations. 

All of the methods were performed according to specifications set forth by their test method and standard operating procedures.15

-

20 

Validation Criteria 

Criteria for method validation were based on Method 301 

bias and precision requirements and were either equal to 

those listed in Method 301 or were more stringent. A 

general criterion for all of the vahdation tests was that a9 

1736 Journal of the Air & Waste Management Association 

runs had to be used to demonstrate acceptable values for 

accuracy, precision, and linearity.2S Accuracy, precision, 

and linearity criteria are defined and discussed below. 

Accuracy. Accuracy for the ith element 04,) is defined as 

bias (JBV ug/dscm) divided by the theoretical or reference 

concentration of the QAG generated aerosol (CP4 0, u.g/ 

dscm), expressed as a percent. 

A, = 7^-10 0 (2) 

Bias is the difference between the mean measured aerosol 

concentration (Cf, >g/dscm) and the theoretical or reference concentration (Cp*0

, (j-g/dscm). 

B, = Cr* - CP A G (3) 

For the QAG, accuracy values <20% were defined as acceptable for validation. For the measurement methods, 

this same criterion was required for accuracy values determined at concentrations at or near the emission limit as 

required by Method 301. In addition to meeting the 

above accuracy criterion, the bias was required to be insignificant relative to the uncertainty in the bias. In this 

case, the uncertainty in the bias for the ith element (Uf) is 

the square root of the sum of the uncertainty in the QAG 

aerosol concentration (UpAG) squared and the standard 

deviation of the mean of the measurement method 

concentration (SDMf) squared, as shown in following 

equation; 

Uf = 7(UPAG)

2

 + (SDMf1)

2

 (4) 

where the QAG propagated uncertainty was estimated to 

be ~5% during the laboratory and field tests.15 Bias was 

considered significant at the 95% confidence level if B, > 

2Uf. If B, was found to be significant, a correction factor 

was required. The correction factor (CF,) is calculated by 

dividing the concentration of the QAG aerosol (CP A G ) by 

the concentration of the measurement method (Cf). 

CF,=-gM- (5) 

Precision. Total precision for the ith element (P\) is defined as percent relative standard deviation (PJ?SD,), or the 

standard deviation (5D,) divided by the mean concentration (C,) of a given method determined from sequential 

measurements. 

P| = -^-100 (6) 

Because there is random variability associated with both 

the QAG aerosol concentration, as well as the measured 

aerosol concentration, the total precision (Pf) is an indicator of the combined variability introduced by all 

Volume 56 December 2006 
Yanca etal. 

Table 2. QAG accuracy determined during laboratory tests. 

Low Concentration Mid Concentration High Concentration 

(-20 ng/tlscm) (-65 ug/dscm) (-130 ug/dscm) Average All Runs 

Measurement 

Method Element N Accuracy A, % SD N Accuracy A, % SD N Accuracy A, % SO N Accuracy A, % SD 

Xact 

XFM 

Cr 

As 

Hg 

Pb 

Cd 

Cr 

As 

Hg 

Pb 

Cd 

1.7 

1.9 

2.3 

2.9 

2.8 

2.5 

2.5 

6.3 

2.2 

6.2 

1.0 

1.7 

1.4 

2.1 

1.8 

1.9 

1.2 

1.1 

2.2 

3.4 

24 

24 

24 

24 

24 

12 

12 

12 

12 

12 

1.4 

4.1 

1.3 

1.5 

1.7 

2.7 

3.0 

3.5 

2.3 

2.0 

1.4 

1.7 

1.0 

0.8 

0.9 

2.7 

3.0 

3.0 

2.6 

1.4 

2.4 

4.9 

0.6 

1.6 

2.0 

1.5 

2.6 

6.7 

2.3 

1.1 

0.3 

1.0 

0.5 

1.1 

1.5 

1.4 

1.5 

5.1 

1.5 

0.8 

40 

40 

40 

40 

40 

20 

20 

20 

20 

20 

1.6 

3.8 

1.3 

1.8 

2.0 

2.4 

2.8 

4.7 

2.3 

2.6 

1.2 

1.9 

1.1 

1.2 

1.2 

2.3 

2.4 

3.5 

2.2 

2.5 

Mores: SD = standard deviation. 

components of the generation-measurement system; that 

is, QAG and measurement method. For this series of tests, 

the magnitude of the QAG precision is considered to be 

the same as the measurement method. Therefore, the 

individual precision of the QAG or measurement method 

(P,) is defined as the combined, or total, precision (Pf) 

divided by the square root of 2. 

P^PRSD^^ (7) 

A precision =£10% was required for the method to satisfy 

established validation requirements. 

Linearity. Evaluation of linearity was based on parameters 

derived from a linear least squares regression analysis of 

the theoretical or reference concentrations and the measured concentrations. Although slope and intercept of the 

regression line were considered, the key linearity criterion 

was the correlation coefficient (r). The QAG and both 

Table 3. QAG precision determined during laboratory tests. 

measurement methods must have a correlation coefficient (r) that is 3=0.85 for method validation. 

RESULTS AND DISCUSSION 

QAG Validation 

Accuracy. QAG accuracy results for each of the five metals 

tested are listed in Table 2. This table includes results from 

a comparison of theoretical QAG concentrations with 40 

Xact and 20 corresponding XFM measurements. Concentrations ranged from a low of —20 |xg/dscm to a high of 

-130 (Ag/dscm. The QAG demonstrated accuracies <7% 

for all of the elements at each concentration level, well 

below the 20% validation threshold. These results show 

that average QAG accuracy for all runs ranged from a low 

of 1.3% for Hg as measured with the Xact to a high of 

4.7% for Hg as measured with the XFM. The overall average accuracy including all five elements, all three concentration levels, and both methods is 2.5 ± 2.3%. None of 

the biases were determined to be significant, In addition, 

independent ICP analysis of a nebulized solution and 

Low Concentration Mid Concentration High Concentration 

(-20 pg/dscm) (-65 ug/dscm) (-130 ug/dscm) Average All Runs 

Measurement — 

Method Element N Precision P, % N Precision P,% H Precision P, % n Precision P,% 

Xact 

Cr 8 1.7 24 1.1 8 1.7 40 1.0 

As 8 2.0 24 1.0 8 2.0 40 1.2 

Hg 8 2.0 24 0.7 8 2.0 40 1.1 

Pb 8 2.0 24 0.8 8 2.0 40 1.3 

Cd 8 2.5 24 1.5 8 2.5 40 1.7 

XFM 

Cr 4 1.3 12 2.3 4 1.3 20 1.5 

As 4 1.8 12 2.2 4 1.8 20 1.7 

Hg 4 0.8 12 2.8 4 0.8 20 2.4 

Pb 4 1.7 12 2.2 4 1.7 20 1.6 

Cd 4 2.3 12 1.9 4 2.3 20 1.7 

Volume 56 December 2006 Journal of the Air S Waste Management Association 1737 
Yanca et al, 

Table 4. QAG linearity determined during laboratory tests. 

o 

O 

o 

© 

X) 

o 

o 

O 

Method 

Element n R Slope SD Intercept SD 

XFM 

Cr 22 0.999 1.02 0.005 -0.54 0.35 

As 22 0.999 1.05 0.005 -0.71 0.38 

Hg 22 0.999 0.99 0.004 -0.01 0.32 

Pb 22 0.999 1.02 0.007 -1.13 0.51 

Cd 22 0.999 0.98 0.008 072 0.56 

Xact 

Cr 135 0.999 1.01 0.004 -0.42 0.25 

As 135 0.999 0.98 0.004 0.31 0.26 

Hg 135 0.999 1.04 0.004 -0.67 0.25 

Pb 135 0.999 1.00 0.005 -0.41 0.30 

Cd 135 0.998 0.98 0.005 0.27 0.35 

Notes: SD = standard deviation. 

selected filter samples were supportive of the XFM measured concentrations. Clearly, these results demonstrate 

that the QAG is an accurate method for generating a 

reference aerosol containing metal concentrations in the 

range from 20 to 130 |i.g/dscm. 

Precision. Precision for the QAG and the measurement 

methods tested in the field was determined from sequential measurements taken during a period of ~4 hr. The 

results from these tests are presented in Table 3. The QAG 

demonstrated precisions well below the 10% validation 

threshold; average precisions were better than 3% for all 

of the elements at each concentration level. The average 

QAG precision for all of the runs ranged from a low of 1% 

for Cr as measured with the Xact to a high of 2.4% for Hg 

as measured with XFM. Including all five of the elements, 

all three of the concentration levels, and both measurement methods, the average QAG precision was 2.2%. 

These results show that the QAG is a precise method for 

generating aerosols in the concentration range from 20 to 

130 u-g/dscm. 

Linearltf. Linearity of the QAG was analyzed with linear 

least-squares regressions of the measured aerosol concentrations compared with the theoretical concentrations 

over all of the concentration levels. Correlation coefficients (r), slopes, and intercepts from these regressions are 

presented for each element in Table 4. The correlation 

coefficients for all of the elements as determined with 

each measurement method were >0.99, well above the 

acceptability requirement of 0.85. Slopes ranged from a 

low of 0.98 to a high of 1.05, all within 5% of unity (i.e., 

1.00). Intercepts ranged from -0.01 to -1.13 and were all 

<1% of the concentration range. Plots of the regression 

analyses using all 5 of the metals combined are presented 

for the Xact in Figure 2 and for the XFM in Figure 3. The 

QAG again demonstrated correlation coefficients of 0.99, 

and slopes were within 0.4% of 1.00. Intercepts were 

<0.3% ofthe concentration range. A final regression analysis of all of the measured versus theoretical QAG data 

yielded a 0.998 correlation coefficient, a slope within 

0.2% of unity (0.998 ± 0.002), and an intercept <0.1% of 

140 

I 120 

1 100 

i 

1 80 

I 60 

c 

o 

S 40 

£ 

3 20 

' 0.999X - 0.103 

r = 0.998 

n = 675 

0 Cr 

A As 

• Hg 

Pb! 

+ Cd 

20 40 60 80 100 120 

Theoretical Concentration (pgldscm) 

140 

Figure 2. QAG linearity as determined by the Xact using all five 

elements. 

the concentration range (-0.04 ± 0.16). This strong linear relationship between the theoretical QAG aerosol concentrations and the independently measured concentrations demonstrates the ability of the QAG to produce 

aerosols quantitatively over a wide range of concentrations. 

Xact Method Validation 

Accuracy. The Xact met the 20% validation criterion for 

accuracies demonstrated at the high concentration level 

(Table 5). For the measurement methods, this level is 

expected to be most representative of concentrations near 

the emission limit as required by Method 301. For the 24 

high-concentration runs, the Xact accuracies ranged from 

1.8% for As to a high of 13% for Hg. The Xact average 

accuracies for all 40 runs ranged from a low of 4.9% for As 

to a high of 16% for Hg. The average Xact accuracy calculated using all five of the elements was 4.7 ± 4.3% for 

the high concentration and 8.3 ± 7.2% for all three of the 

concentration levels. 

Bias was insignificant for four of the five metals but 

was significant for Hg at all of the concentration levels. A 

post-test investigation of this bias revealed a 6% calibration error, although these runs were retained in the dataset without correction. Assuming correct calibration, the 

Hg accuracies would have been on the same order as the 

accuracies of the other four elements; for example, the Hg 

accuracy at the high concentration level would be —7% (i.e., 

140 

120 

100 

80 

60 

40 

20 

0 

y = 0.996x - 0.286 

r = 0.997 

n = 110 

20 40 60 80 100 120 

Theoretical Concentration (ug/dscm) 

140 

Figure 3. QAG linearity as determined by the XFM using all five 

elements. 

1738 Journal oi the Air& Waste Management Association Volume 56 December 2006 

VES016956 
Yanca etal. 

Table 5. Xact accuracy determined during field tests. 

Low Concentration Mid Concentration High Concentration 

(-20 pg/dscm) (-45 ug/dscm) (-110 pg/dscm) Average All Runs 

Element N Accuracy A, % SD N Accuracy A, % SD N Accuracy A, % SD N Accuracy A, % SD 

Cr 8 7.4 2.9 8 20 1.6 24 4.5 1.7 40 8.2 6.5 

As 8 3.3 2.4 8 16 1.9 24 1.8 0.7 40 4.9 5.7 

Hg 8 14" 2.1 8 25a 1.7 24 13a 1.0 40 16" 5.2 

Pb 8 13 1.4 8 20 1.4 24 2.4 1.5 40 7.9 7.4 

Cd 8 3.6 2.6 8 16 1.7 24 2.1 0.8 40 5.2 5.7 

fVotes.- SD = standard deviation;

 aBlas was determined to be significant for this value. 

6% of the 13% accuracy can be attributed to the calibration 

error). This identified error can be readily corrected and 

future Mas, thus, eliminated. As a result, a correction factor 

was not required. In addition to the calibration error, the 

average accuracies for both the Xact and XFM (discussed 

below) were somewhat impacted by biases in the middle 

concentration runs. These biases appear to be the result of 

an increased difficulty in maintaining proper QAG operating conditions in the field compared with the laboratory. 

The biases were not significant, and these runs were retained 

in the dataset. The results presented in Table 5 demonstrate 

a high accuracy for the Xact measurement method even 

with the Hg calibration error and midconcentxation biases. 

Furthermore, these results suggest even better accuracies 

with correct Hg calibrations. 

Precision. The Xact demonstrated better than 4% for all of 

the concentration levels, well below the 10% validation 

threshold (Table 6). The average precision for all of the 

Xact runs ranged from a low of 1.4% for Hg to a high of 

1.9% for Cd. Over all five ofthe elements and all three of 

the concentration levels, the total average precision for 

the Xact was calculated as 1.6%. These results demonstrate the high precision of the Xact over a wide range of 

concentrations. 

Linearity. Xact linearity was evaluated with linear leastsquares regression analysis of the Xact-measured concentrations compared with the QAG-spiked stack gas reference concentrations over all of the concentration levels. 

Regression parameters for each element are presented in 

Table 7. Xact correlation coefficients for all of the elements were >0.99, easily surpassing the 0.85 requirement. Slopes for all of the metals ranged from 0.87 for Hg 

to a high of 1.02 for Pb. Intercepts ranged from -0.79 to 

-1.09, all <1% of the concentration range. A plotted 

regression analysis for all 5 of the metals combined (Figure 4) produced a correlation coefficient of 0.995, a slope 

within 5% of unity (0.952 ± 0.003), and an intercept <2% 

of the concentration range (-1.10 ± 0.18). The strong 

linear relationship between the Xact concentrations and 

the reference concentrations confirms the Xact linear response and high precision over a wide range of concentrations and demonstrates its ability to accurately measure metals over this range. 

XFM Validation 

Accuracy. The XFM accuracy results for each element are 

presented in Table 8. At the high concentration level, the 

XFM accuracies ranged from 3.5% for Hg to 5.8% for Pb, 

all well below the 20% validation requirement. None of 

the biases were significant relative to their uncertainty. 

The average XFM accuracy for all of the runs ranged from 

a low of 6% for Cd and As to a high of 7.9% for Pb. 

Combining data from all five of the elements, the average 

XFM accuracy was calculated as 4.7 ± 3.1% for the high 

concentration level and 6.5 ± 4.5% for all three of the 

concentration levels. These results clearly demonstrate 

the high accuracy of the XFM measurement method. 

Precision. The XFM precisions (Table 9) all met the 10% 

validation criterion and were better than 7% at all of the 

concentration levels. The average XFM precision for all of 

Table 6. Xact precision determined during field tests. 

Low Concentration Mid Concentration High Concentration 

(-20 ^g/dscm) (-45 pg/dscm) (-110 pg/dscm) Average All Runs 

Element H Precision P, % N Precision P, % N Precision P, % N Precisian P, % 

Cr 8 2.2 f ! 1.4 24 1.3 40 1.6 

As 8 I 2.4 f i 1.6 24 1.0 40 1.7 

Hg 8 I 1.7 f i 1.6 24 0.83 40 1.4 

Pb 8 I 1.2 f i 1.3 24 2.0 40 1.5 

Cd 8 i3.4 i i 1.4 24 0.83 40 1.9 

Volume 56 December 2006 Journal of the Air & Waste Management Association 1739 
Yanca et al. 

Table 7. Xact linearity determined during field tests. Table 10. XFM linearity determined during field tests. 

Element N R Slope SD Intercept SD Element N R Slope SD Intercept SD 

Cr 192 0.997 0.951 0.00505 -1.08 0.297 Cr 24 0.997 1.04 0.0174 -1.61 1.39 

As 192 0.998 0.982 0.00487 -0.994 0.287 As 24 0.997 1.07 0.0180 -2.72 1.43 

Hg 192 0.998 0.869 0.00412 -0.788 0.243 Hg 24 ' 0.996 1.04 0.0209 -1.80 1.67 

Pb 192 0.999 1.02 0.00387 -1.09 0.220 Pb 24 0.995 1.07 0.0221 -2.08 1.81 

Cd 192 0.997 0.970 0.00573 -0.802 0.337 Cd 24 0.997 1.05 0.0171 -1.61 1.36 

Notes: SD = standard deviation. Notes: SO = standard deviation. 

•8 

CS 

<s 

00 

00 

o 

o 

I Q 

the runs ranged from a low of 1.8% for Cr and As and to 

a high of 3.7% for Pb. The total average XFM precision 

was calculated as 2.6% over all five ofthe elements and all 

three of the concentration levels. These results demonstrate that the XFM met this acceptance criterion and is 

precise over a wide range of concentrations. 

140 

120 

100 

80 

c ! 60 

c 

a 

u 

c 

0 

40 

8 

13 

20 

X 

y - 0.952X -1.10 

r = 0.995 

rt = 960 

0 Cr 

A. As 

D Hg 

X Pb 

+ Cd 

O 20 40 60 80 100 120 

QAG Reference Concentration (ug/dscm) 

Figure 4. Xact linearity using all five elements. 

Table 8. XFM accuracy determined during field tests. 

Linearity. The results of the XFM linearity evaluation are 

presented on Table 10. These parameters were determined 

with linear least-squares regression analysis of the XFMmeasured concentrations compared with the QAG-spiked 

stack gas concentrations over all of the concentration 

levels. XFM correlation coefficients for all elements were 

a0.99, well above the 0.85 acceptance value. Slopes for all 

of the metals ranged from 1.04 to 1.07, all within 7% of 

unity. Intercepts were all <3% of the linearity test concentration range and ranged from -1.61 to —2.72. A 

plotted regression analysis for all 5 of the metals combined is presented for the XFM in Figure 5. The combined 

metal regression yielded a correlation coefficient of 0.996, 

a slope within 5% of 1.00 (1.05 ± 0.01), and an intercept 

<2% of the full concentration range (-1.96 ± 0.6). The 

strong correlation of the XFM concentrations with the 

reference concentrations demonstrates the ability of the 

XFM to accurately measure a wide range of concentrations and confirms its precision over this range. 

Summary 

A summary of each method's perfonnance in reference to 

the validation criteria is presented in Table 11. This table 

Low Concentration Mid Concentration High Concentration 

1 —20 pg/dscm) (-45 pg/dscm) (-110 pg/dscm) Average All Runs 

Element N Accuracy A, % SD N Accuracy A, % SD N Accuracy A, % SD N Accuracy A, % SD 

Cr 4 6.0 3.4 4 12 1.3 12 4.0 2.4 20 6.0 3.9 

As 4 1.7 1.0 4 13 2.5 12 5.0 2.9 20 6.0 4.7 

Hg 4 5.5 3.4 4 15 3.8 12 3.5 3.4 20 6.1 5.5 

Pb 4 8.0 6.4 4 14 2.3 12 5.8 4.0 20 7.9 5.2 

Cd 4 6.7 2.0 4 9.0 2,5 12 5.1 2.5 20 6.2 2.8 

Notes: SD = standard deviation. 

Table S. XFM precision determined during field tests. 

Low Concentration Mid Concentration High Concentration 

(-20 pg/dscm) (~ 45 pg/dscm) -110 pg/dscm) Average All Runs 

Element N Precision P, % N Precisian P, % N Precisian P, % N Precision P, % 

Cr 4 2,3 4 1.0 12 2.2 20 1.8 

As 4 1.5 4 2.0 12 1.9 20 1.8 

Hg 4 2,3 4 3.2 12 2.9 20 2.8 

Pb 4 6.5 4 1.9 12 2.7 20 3.7 

Cd 4 4.7 4 2.0 12 2.4 20 3.0 

1740 Journal of the Air & Waste Management Association Volume 56 December 2006 

VES016958 
Yanca et al. 

© 

CN 

S3 

o 

Os 

CN 

cs 

oo 

00 

d 

•s 

o 

o Q 

140 

120 

100 

80 

60 

40 

20 

y1.05x-1.9 6 

r = 0.996 

n = 120 

20 40 60 80 100 120 

QAO Reference Concentration (ug/dscm) 

Figure S. XFM linearity using all five elements. 

clearly shows that the three methods easily passed all of 

the required criteria for all five of the metals. 

CONCLUSIONS 

The three independent methods discussed in this paper 

met EPA Method 301 requirements for compliance applications and are precise, accurate, and linear tools applicable to the determination of hazardous metal concentrations in emissions. The QAG and the Xact technologies 

have currently been approved by EPA for compliance 

demonstration at a HWC. 2 6 In addition to the five elements measured with these tests, the methods are expected to be applicable to most hazardous elements in 

stack and fugitive emissions from stationary sources, as 

well as in the ambient environment. The QAG reference 

aerosol generator could, thus, be used as a generally applicable reference aerosol generator for research, method 

certification, and audits. The XFM measurement methods 

could be used for performance testing, initial certification, 

and continuing quality assurance audits of multimetal 

CEMS. Finally, the Xact could be used to demonstrate 

ongoing compliance through its use as a CEMS, and its 

technology could be extended to an instrumental analysis 

procedure with applications similar to the XFM. 

In addition to the results presented in this paper, all 

three methods have demonstrated high precisions and 

accurades in other field and laboratory tests.27-

30

 The 

measurement methods have also consistently demonTable 11. Summary of validation results. 

Parameters Criteria QAG Method XFM Method Xact Method 

No. of runs (n) a9 20 12 24 

Accuracy (A) s20% <5% <6%a <7%a

'

b 

Precision (P) £10% <3% <4% <4% 

Linearity (i) >0.85 0,99 0.99 0.99 

Notes: "Results from high concentration level; "Assuming correct calibration 

of Hg. 

strated frequent sampling times, rapid analysis turnaround times (15 min for the Xact and 2 hr for the XFM 

if a field-portable analyzer is used), and low detection 

limits. Analysis is nondestructive, and the methods can be 

independently audited with the QAG. In addition to metals, the QAG can potentially generate aerosols of both 

organic and inorganic analytes. 

REFERENCES 

1. Prieditis, H.; Adamson, I.Y. Comparative Pulmonary Toxicity of Various Soluble Metals Found in Urban Particulate Dust; Exp. Lung. Res. 

2002, 28, 563-576. 

2. Monn, C ; Becker, S. Cytotoxicity and Induction of Proinflammatory 

Cytokines from Human Monocytes Exposed to Fine (PM2.5) and 

Coarse Particles (PM10-2.S) in Outdoor and Indoor Air; Toxicol. Appl. 

Pharmacol 1999, ISS, 245-252. 

3. U.S. Environmental Protection Agency. National Emissions Standards 

for Hazardous Air Pollutants for Source Categories. In Code of Federal 

Regulations, 40 CFR 63; U.S. Government Printing Office: Washington, 

DC, 2005. 

4. U.S. Environmental Protection Agency. Method 29, Determination of 

Metals Emissions from Stationary Sources. In Code of Federal Regulations, 40 CFR 60; U.S. Government Printing Office: Washington, DC, 

2005. 

5. U.S. Environmental Protection Agency. Evaluation of Two Methods for 

the Measurement of Mercury Emissions in Exhaust Gases from a Mumcipal 

Waste Combustor; EPA 450/4-92-013. U.S. Government Printing Office: 

Washington, DC, 1991. 

6. Rigo, H.G.; Chandler A.J. Quantitation Limits for Reference Methods 

23, 26, and 29; /. Air & Waste Manage. Assoc. 1999, 49, 399-411, 

7. American Society of Mechanical Engineers, Research Committee on 

Industrial and Municipal Waste. Reference Method Accuracy and Precision (ReMAP): Phase 1, Precision of Manual Stack Emission Measurements; 

Report No. CRTD-60; American Society of Mechanical Engineers International: Washington, DC, 2001. 

8. Zhang, H.; Yuen, F.Y.; Singh, J.P. Evaluation of the Potential of LaserInduced Breakdown Spectroscopy for Detection of Trace Element in 

Liquid; /. Air& Waste Manage. Assoc. 2002, 51, 681-687. 

9. Seltzer, M.D. Performance Testing of a Multimetals Continuous Emissions Monitor. /. Air & Waste Manage. Assoc. 2000, 50, 6. 

10. Sky +, Inc. 1997 Performance Testing of Multi-Metal Continuous Emissions Monitors; DOE/ID-10665. U.S. Department of Energy, Idaho Operations Office: Idaho Falls, ID, 1998. 

11. Cooper, J.A; Fry, S.C; Johnsen, B.E. Apparatus and Methods for Removing Mercury from Fluid Stream. U.S. Patent 6,770,250 B2, 2004. 

12. Cooper, J.A; Fry, S.C; Johnsen, B.E. Apparatus and Methods for Removing Mercury from Fluid Stream. U.S. Patent 6,872,370 B2, 2005. 

13. Draft Test Plan for Validating a Reference Procedure for Measuring the 

Concentration of Metals in Eli Lilly and Company's Hazardous Waste 

Incinerator Stack Gas; Cooper Environmental Services: Portland, OR, 

2004. 

14. U.S. Environmental Protection Agency. Method 301, Field Validation 

of Pollution Measurement Methods for Various Media. In Code of 

Federal Regulations, 40 CFR 56; U.S. Government Printing Office: 

Washington, DC, 2005. 

15. Method 301 Evaluation of Three Methods for Multi-Metals Measurement 

and Validation; Cooper Environmental Services: Portland, OR, 2006. 

16. Barth, D.C; Yanca, C.A.; Petterson, K.A., Nakanishi, M.P.; Cooper, 

J.A.; Johnsen, B.J.; Lambert, R. H. Aerosol Sci. Tech., submitted for 

publication. 

17. Determination of Metal Concentration in CES'XactCEMS Stilling Chamber 

Using the CES XFM; Cooper Environmental Services: Portland, OR, 

2006. 

18. Determination of Metal Concentrations from Stationary Sources Using the 

CES XFM; Cooper Environmental Services: Portland, OR, 2006. 

19. Specifications and Test Procedure for X-Ray Fluorescence Based MultiMetals Continuous Emissions Monitoring Systems at Stationary Sources; 

Cooper Environmental Services: Portland, OR, 2006. 

20. Quality Assurance Requirements for X-Ray Fluorescence Based Multi-Metals 

Continuous Emissions Monitoring Systems at Stationary Sources; Cooper 

Environmental Services: Portland, OR, 2006. 

21. Cooper, J.A.; Barth, D.B.; Nakanishi, M.P.; Petterson, K.A.; Yanca, CA . 

A Quantitative, Traceable-to-NIST, Reference Aerosol Generator for 

Evaluating Aerosol Speciation Monitors and Measurement Methods. 

In Proceedings ofthe Air & Waste Management Association's Symposium 

on Air Quality Measurement Methods and Technology, Durham, NC, May 

9-11, 2006; A&WMA: Pittsburgh, PA, in press. 

22. May, K.R. The Collison Nebulizer. Description, Performance & Application. /. Aerosol. Sci. 1973, 4, 235-243. 

23. Cooper, J.A.; Barth, D.B.; Nakanishi, M.P.; Petterson, K.A.; Yanca, CA . 

New Filter-Based Methods for Precise, Accurate, and Timelier Measurement of Metal Emissions. In Proceedings of the Air & Waste Management 

Volume 56 December 2006 Journal of the Air & Waste Management Association 1741 

VES016959 
Yanca et al. 

t 

o 

O 

o 

OS 

ts 

cs 

oo 

oo 

Association's Symposium on Mr Quality Measurement Methods and Technology, Durham, NC, May 9-11, 2006; A&WMA: Pittsburgh, PA, in 

press. 

24. U.S. Environmental Protection Agency. Compendium Method 10-3.3: 

Determination of Metals in Ambient Particulate Matter Using X-Ray 

Fluorescence (XRF) Spectroscopy. In Compendium of Methods for the 

Determination of Inorganic Compounds in Ambient Air; EPA/625/R-96/ 

010a. U.S. Government Printing Office: Washington, DC, 1999. 

25. Watson, J.G.; Lioy, P.J.; Mueller, P.K. The Measurement Process: Precision, Accuracy and Validity. In Air Sampling Instruments for Evaluation 

of Atmospheric Contaminants, 6th ed.; Lioy, PJ; Lioy, M.J.Y; Eds.; American Conference of Governmental Industrial Hygienists: Cincinnati, 

OH, 1983; pp 2-7. 

26. Oldham, C.B. Air Measurements and Quality Group, Office of Air 

Quality Planning and Standards, U.S. Environmental Protection 

Agency, Research Triangle Park, NC. Written communication with EU 

Lilly and Company: Lafayette, IN. 2006. 

27. Hay, KJ.; Boddu, V.M.; Johnsen; B.E.; Cooper, J.A. X-Ray FluorescenceBased Multi-Metal Continuous Emission Monitor Technology Demonstration; ERDC/CERL-TR-05-3; U.S. Army Corps of Engineers Engineer 

Research and Development Center: Champaign, IL, 2005. 

28. Installation and Use of an X-Ray Based Continuous Emissions Monitor for 

AED Treatability Study; Cooper Environmental Services: Portland, OR, 

2003. 

29. Re-design and Field Testing of an X-Ray Fluorescence Multi-Metals Monitor 

at the Iowa Army Ammunition Plant, Middleton, Iowa Coal Fired Boiler; 

Cooper Environmental Services: Portland, OR, 2005. 

30. Hay, K.J.; Johnsen, B.E,; Ginochio, P.R.; Cooper, J.A. Relative Accuracy 

Testing of an X-Ray Fluorescence-Based Mercury Monitor at CoalFired Boilers; /. Air & Waste Manage. Assoc. 2006, 56, 657-665. 

About the Authors 

Catherine Yanca, Douglas Barth, Krag Petterson, and Michael Nakanishi are environmental scientists at Cooper Environmental Services, LLC. John Cooper is the president of 

Cooper Environmental Services, LLC. Bruce Johnsen is a 

claims adjuster at SAIF Co. Richard Lambert is an engineering consultant at the Engineering Tech Center, Eli Lilly 

and Co. Daniel Bivins is the work assignment manager for 

the Emission Measurement Center of the Office of Air Quality Planning and Standards, U.S. Environmental Protection 

Agency. Address correspondence to: John Cooper, Cooper 

Environmental Services, LLC, 10180 SW Nimbus Ave., Suite 

J6, Portland, OR 97223; phone: +1-503-624-5750; fax +1-

503-624-2120; e-mail: Jacooper@cooperenviranmental.com. 

o 

O 

1742 Journal of the Air & Waste Management Association Volume 56 December 2006 

VESO16960 
VES016961-016974.pdf 
CR(» I 

CoaWon lor ResponsiblB Waste Ircnerafon 

MEMBE R COMPANIES 

Clean Harbors Environmental Services 

Dow Chemical U.S.A. 

E. I. Du Pont de Nemours 

Eastman Chemical Company 

INVISTA S.&r.l. 

3M 

Ross Incineration Services, Inc. 

Veolia ES Technical Services, LLC 

GENERATOR MEMBERS 

Eli Lilly and Company 

ASSOCIATE MEMBERS 

AECOM 

B3 Systems 

Compliance Strategies & Solutions 

Coterie Environmental, LLC 

Focus Environmental, Inc. 

Foster Wheeler USA 

Franklin Engineering Group, Inc. 

METCO Environmental, Inc. 

SAIC 

SGS Analytical Perspectives, LLC 

Strata-G, LLC 

TestAmerica Laboratories, Inc. 

TRC Environmental Corporation 

URS Corporation 

INDIVIDUAL MEMBERS 

Ronald E. Bastian, PE 

Ronald 0. Kagel, PhD 

ACADEMI C MEMBERS 

(Includes faculty from:) 

Clarkson University 

Colorado School of Mines 

Lamar University 

Louisiana State University 

Mississippi State University 

New Jersey Institute of Technology 

University of California - Berkeley 

University of Dayton 

University of Kentucky 

University of Maryland 

University of Utah 

April 1,2013 

George Czerniak 

U.S. EPA 

77 W. Jackson Blvd. (A-18J) 

Chicago, IL 60604. 

Attn: Docket ID No. EPA-R05-OAR-2012-0649 

The Coalition for Responsible Waste Incineration (CRWI) 

appreciates the opportunity to submit comments on Veolia ES 

Technical Solutions draft Title V Permit. CRWI is a trade 

association comprised of 23 members. Veolia ES Technical 

Solutions is a member of CRWI. 

E PA is proposing to make major changes to Veolia's permit. 

CRWI has concerns about the following four issues associated 

with the draft permit. 

1. EPA should not remove the term "NESHAP" in section 

2.1(C)(1). 

2. Region 5 should correct the discrepancies between the 

draft permit and the Statement of Basis, should allow for 

upward extrapolation of mercury feed rates, and calculate 

the mercury feed rate on actual analytical data rather than 

theoretical calculations. 

3. Region 5 should not require the facility to install, calibrate, 

operate, and maintain a multi-metals CEMS. 

4. Region 5 should modify the sampling and analysis 

requirements. 

44121 Harry Byrd Highway, Suite 225 

Ashburn, V A 20147 

Phone: 703-431-7343 

E-mail: mel@crwi.org 

Web Page: http://www.crwi.org 

VES016961 
Docket ID No. EPA-R05-OAR-2012-0649 

Specific comments on each of the issues listed above are attached. Thank you for the 

opportunity to comment on this draft Title V permit. If you have any questions, please 

contact me at (703-431-7343 or mel@crwi.org). 

Sincerely yours, 

Melvin E. Keener, Ph.D. 

Executive Director 
Docket ID No. EPA-R05-OAR-2012-0649 3 

Specific Comments 

1. EPA should not remove the term "NESHAP" in section 2.1 (C)(1). 

On page 11 ofthe draft permit, Region 5 proposed to delete the term "NESHAP" in 

section 2.1(C)(1). We suggest that Region 5 reconsider deleting that term because 

if finalized as proposed, this provision will eliminate the ability to burn any waste 

containing beryllium. Since the Region talks about feed rates of beryllium in other 

sections of the draft permit and in the Statement of Basis, we do not believe this was 

intended. In this case "beryllium NESHAP containing waste" refers to waste that 

was generated when complying with the beryllium NESHAP. The language in the 

original permit was intentional and should be retained. 

2. Region 5 should correct the discrepancies between the draft permit and the 

Statement of Basis, should allow for upward extrapolation of mercury feed rates, and 

calculate the mercury feed rate based on actual analytical data rather than 

theoretical calculations. 

In the Statement of Basis (see page 14), EPA proposes to allow upward 

extrapolation of the SVM and LVM feed rate used during the test to the historical 

highest 12-hour rolling average. EPA's decision was based on guidance provided in 

the preamble of the first hazardous waste combustor MACT final rule (64 Fed. Reg. 

52,946-47, September 30,1999). CRWI supports the decision by Region 5 to allow 

upward extrapolation for SVMs and LVMs. We would like to point out that there are 

two discrepancies on feed rate limits between the Statement of Basis, Table 2 (page 

17) and the draft permit (page 12 of 134). For Unit 2, the Statement of Basis shows 

a feed rate limit for LVM as 68.5 Ib/hr while the draft permit has a value of 84 Ib/hr. 

For Unit 4, the Statement of Basis has a feed rate limit for SVM of 98.1 Ib/hr while 

the draft permit has a value of 64 Ib/hr. CRWI believes that this is a simple 

translation error and suggests that the Agency determine which one is correct. 

While Region 5 is allowing upward extrapolation of SVM and LVM, they are not 

using upward extrapolation for mercury. The stated reasons for this are that Unit 4 

uses carbon injection and that the facility spiked mercury during the test runs. 

However, Units 2 and 3 do not have carbon injection. So the only reason Region 5 

uses for not allowing extrapolation for Units 2 and 3 is on page 18 ofthe Statement 

of Basis. 

Mercury was spiked as part of the comprehensive performance test. The 

intended purpose of metal spiking when conducting comprehensive tests is to 

enable a facility to verify compliance with MACT limits under worst-case 

conditions. To protect workers, EPA does not encourage unnecessary spiking of 

metals during comprehensive tests. Therefore, if a facility spikes metals when 

conducting comprehensive tests, the metal spike rates and the native mercury 

content of the waste should be used to set the feedrate limit with little or no 

VESO16963 
Docket ID No. EPA-R05-OAR-2012-0649 4 

extrapolation, provided the corresponding stack emissions assure compliance 

with all MACT limits with an ample margin of safety. 

(Statement of Basis at 18, footnotes omitted) 

While part of this statement is correct (regarding the protection of workers), the 

statement that if a facility spikes metals during a test, the metal spike rates should 

be used is incorrect. If the Agency would go back to the same document they quote 

in justifying the upward extrapolation for SVM and LVM (the 1999 final rule) and look 

at footnote 240, they would find that EPA Headquarters fully intended for this 

method to apply to mercury as well: 

Footnote 240. Although this extrapolation discussion is presented in context of 

semivolatile and low volatile metal feedrates, similar provisions could be 

implemented for mercury feedrates. 

(64 Fed. Reg. 52,946) 

In addition, Region 5 contradicts EPA Headquarters guidance when they state that 

the spiked rate should be used in setting the feed rate limits. In the same quote from 

the 1999 rule that is in the Statement of Basis, EPA Headquarters states: 

Further, we expect that some spiking would be desired to increase confidence in 

the measured, performance test feedrate levels that will be used to project 

feedrate limits (i.e., the errors associated with sampling and analyzing 

heterogeneous feedstreams can be minimized by spiking known quantities). 

(Statement of Basis at 14 and 64 Fed. Reg. 52,946) 

Thus, under certain circumstances, spiking is desired to increase the confidence of 

the measurements and the extrapolated values. Region 5 has no basis for not 

allowing upward extrapolation of mercury feed rates and in fact, not allowing 

extrapolation for mercury is contrary to the guidance quoted by the Agency. Also, 

Region 5's current position that upward extrapolation of mercury is not allowed may 

have unintended consequences. If facilities cannot use upward extrapolation, they 

will be forced to spike mercury at higher rates than needed to get the operational 

flexibility required to operate. This will nullify all of the benefits (reduction of mercury 

emissions, protections of workers, purchase of excess mercury that must be 

disposed of later, etc.) from allowing upward extrapolation. 

The technical basis for upward extrapolation is laid out in the Technical Support 

Document (Volume 4, Chapter 6.3, page 6-7) ofthe 1999 hazardous combustor final 

rule. There is nothing in the technical support document that sets an upper limit on 

extrapolation. In fact, EPA's graph (Figure 6.1) shows that upward extrapolation will 

be a conservative estimator of actual emissions at any level above where it is 

VES016964 
Docket ID No. EPA-R05-OAR-2012-0649 5 

measured. Thus, the emission levels predicted at higher feed rates based on linear 

extrapolation are greater than or equal to the actual emissions. Obviously, the upper 

limit has to be the promulgated emission limit. In the initial hazardous waste 

combustor final rule (64 FR 52,828, September 30,1999), EPA made a policy 

decision to limit extrapolation to the highest historical feed rates (64, FR 52,946-7). 

There is an extensive discussion on this in the preamble of that rule. It should be 

emphasized that the decision to limit to historical levels is a policy decision, not a 

decision based on technical information. In the same paragraph where the Agency 

made the policy decision, they left some flexibility in this decision by adding a 

sentence that says "Extrapolation approaches that request feedrate limits that are 

significantly higher than the historical range of feedrates should not be approved." 

(64 FR 52,946-7). It is our understanding that other states and regions allow 

upward extrapolation up to 3 times the historical maximum feed rate. We suggest 

that Region 5 should not limit the upward extrapolation to the historical limits if other 

information can be used to show that such emissions rates are below the emission 

limits and are protective of human health and the environment. 

In addition, Region 5 modified the calculation ofthe spike rates to match the 

minimum purity ofthe reagent instead of using the actual laboratory analysis of the 

spiked materials (see footnote 2, Table 2, Statement of Basis, page 17). This is 

surprising since both Region 5 and the facility took samples of the spiking solutions. 

The facility analyzed these samples and used the analytical data to propose mercury 

feed rates. Surely actual analytical data on the amount of mercury fed is superior to 

a theoretical analysis. We see no reason to use theoretical calculation when actual 

analysis from either Veolia or EPA is available. CRWI strongly suggests that Region 

5 recalculate the feed rates based on the analytical data from the test and allow 

upward extrapolation where appropriate (Units 2 and 3) to set the feed rate limits for 

mercury. 

3. Region 5 should not require the facility to install, calibrate, operate, and maintain a 

multi-metals CEMS. 

Region 5 is proposing that Veolia install and operate a multi-metals CEMS for at 

least one year. CRWI has several concerns about this requirement. 

It is inappropriate to use a Title V permit to force Veolia to install a multi-metals 

CEMS. 

A Title V permit is supposed to be a compilation of emissions limits, monitoring 

requirements, and reporting requirements that are developed as a part ofthe 

regulations for that source category. This facility is regulated under Subpart EEE. A 

multi-metal CEM S is not required under Subpart EEE. We do not feel it is proper to 

use the Title V process to add entirely new and untested requirements, especially 

when the Agency has not provided adequate justification. The Agency has the 

authority to require a facility to install instruments and gather data for either 

VES016965 
Docket ID No. EPA-R05-OAR-2012-0649 6 

rulemaking or enforcement but not through the Title V permitting process. This does 

not appear to be either a rulemaking or an enforcement action. Rather it seems to 

be a thinly disguised research project that Region 5 wants the facility to run. 

EPA has made a number of statements on multi-metal CEM S that are incorrect, 

misleading or unsubstantiated. 

In the Statement of Basis, the Agency makes several statements for which they 

have not provided any documentation to show that they are correct. In addition, 

there are a number of statements that are either incorrect or misleading. The 

statements that have no supporting documentation are listed below. 

a. "The uncertainties caused by feedstream analysis are largely solved when an EPAapproved CEMS is used to directly measure emissions." (Statement of Basis at 21) 

b. "Second, modern multi-metals CEMS have been shown to be more accurate and 

reliable than feedstream analysis for monitoring mercury and other hazardous metal 

emissions from combustion of heterogeneous feedstreams." (Statement of Basis at 

22). 

c. "Without a CEMS, most emission excursions from combustion of such 

heterogeneous feedstreams would go undetected." (Statement of Basis at 22). 

The Agency has not provided any documentation or citations to show these statements 

to be correct. The courts have stated (Northeast Maryland, 358 F.3d at 954) that EPA 

must provide proof of its statements, not just make unsupported assertions. If 

everything the Agency said above were correct, one would assume that multi-metals 

CEMS would be required in a number of the recent combustion MACT rules. However, 

it is not required in any of them. 

In addition, the Agency makes a number of statements that are either incorrect or 

misleading. 

a. "Multi-metals CEMS are commercially available and have been demonstrated to be 

reliable for measuring mercury and other metal emissions from hazardous waste 

combustors." (Statement of Basis at 22). 

When the Statement of Basis was written, the Xact was offered by Pall Corporation. 

This is no longer correct. Pall no longer manufactures and sells the Xact unit. The 

marketing rights to the Xact have reverted to Cooper Environmental Services. It 

should also be noted that this instrument is not an instrument that is carried in 

inventory. If a facility wanted to purchase an Xact unit, Cooper Environmental 

Services has indicated that it would take them at least six months to build it. This is 

the time to build the instrument itself and does not include time to develop the sitespecific sampling train or the time to develop the software interface between the 

instrument and the facility's control systems. The software development process 

(custom software for that site) would take several months after the instrument was 

installed. Only one Xact unit has been installed and operated for an extended period 

VES016966 
Docket ID No. EPA-R05-OAR-2012-0649 7 

of time at only one hazardous waste combustor, the combustor at Evoniks 

Tippecanoe Laboratories. Due to frequent maintenance issues and equipment 

failure, that Xact unit is no longer operating. 

b. "EPA has approved the use of multi-metals CEMS as alternative monitoring 

methodologies at hazardous waste combustors." (Statement of Basis at 22). 

The Agency has approved alternative monitoring requirements for one hazardous 

waste combustor - not hazardous waste combustors as stated. This process took 

three years forthe facility to get approval. While the Army allowed the CEMS 

company to install and test an Xact unit on the Tooele Army Depot research and 

development furnace, it is not included as a part of the facility's permit nor has it 

been included as a part of HWC MACT testing (CRWI obtained this information from 

personal communications with the operating facility). 

c. "EPA has performed side-by-side evaluations of multi-metals CEMS with EPA 

Method 29 of Appendix A-8 to 40 C.F.R. Part 60 at industrial waste incinerators and 

found good correlation between the two methods. 75 Fed. Reg. 31962 (June 4, 

2010)." (Statement of Basis at 22-23). 

This reference is from the proposed CISWI rule. The preamble of this proposed rule 

states. 

EPA believes multi-metals CEM S can be used in many applications, including 

CISWI. EPA has monitored side-by-side evaluations of multi-metals CEMS 

with EPA Method 29 of appendix A- 8 of 40 CFR part 60 at industrial waste 

incinerators and found good correlation. EPA also approved the use of 

multimetals CEMS as an alternative monitoring method at hazardous waste 

combustors. EPA believes it is possible to adapt proposed PS-10 

(Specifications and Test Procedures for Multi-metals Continuous Monitoring 

Systems in Stationary Sources) of appendix B of 40 CFR part 60 or other 

EPA performance specifications to allow the use of multimetals CEMS at 

CISWI. We request comment on the appropriateness of using multi-metals 

CEMS instead of initial performance tests coupled with PM CEMS and other 

surrogates. The procedures used in proposed PS-10 for the initial accuracy 

determination use the relative accuracy test, a comparison against a 

reference method. EPA is taking comment on an alternate initial accuracy 

determination procedure, similar to the one in section 11 of PS-15 using the 

dynamic or analyte spiking procedure. 

While the statement above is in the proposed rule, the final rule did not require 

multi-metals CEMS. In the preamble of the final rule, EPA made the following 

statements in response to comments on including multi-metal CEMS. 

[EPA] Response: For the operations and facilities subject to the rule, we 

believe that the combination of periodic compliance emissions testing and 

VES016967 
Docket ID No. EPA-R05-OAR-2012-0649 8 

continuous monitoring of operational and parametric control measure 

conditions is appropriate for assuring ongoing compliance. The rule allows a 

source owner or operator to install and operate CEMS in lieu of some testing 

and parametric monitoring requirements. This process requires source 

owners to propose site-specific monitoring plans for approval. These plans 

would include CEMS PS and periodic QA/QC steps to assure the quality of 

the alternative monitoring data. Currently, EPA has the requisite CEMS PS 

for Hg monitoring systems and not for multiple metals CEMS. 

(76 FR 15,736, March 21, 2011) 

John Cooper (the developer of the Xact technology) submitted extensive 

comments supporting the use of the Xact multi-metals CEMS. EPA's responses 

to comments document is EPA-HQ-OAR-0119-2494. EPA's responses to Mr. 

Cooper's comments with page numbers are below. 

[EPA] Response 5 [page 1074]. At this time, EPA does not have promulgated 

performance specifications for multimetal CEMS and thus the final rule does 

not contemplate a requirement to use such monitoring or address these 

monitors directly. See preamble Section III.C. for a discussion on the testing 

and monitoring requirements in the final rule. See also response to EPA-HQOAR-2003-0119-1133.2, excerpt 12. 

[EPA] Response 12 [page 1072]. We recognize and agree that an integrating 

multiple metals CEMS operates in a manner fundamentally different than the 

instrumental metals CEMS for which draft Performance Specification 10 was 

developed. Since EPA does not have a published performance specification 

for metals CEMS, instrumental or integrating, the source owner must prepare 

a site-specific monitoring plan in order to apply the metals CEMS option. The 

monitoring plan need not imitate existing CEMS performance specifications 

(e.g., sampling frequency) but should be structured to address those 

characteristic operations ofthe CEM S relecting (sic) the operating principle 

and associated QA/QC procedures. 

In addition, the New York Department of Environmental Conservation (DEC) 

submitted a short comment opposing the use of multi-metals CEMS. They state, 

"The DEC believes that multi-metals and PM CEMS are inadequate to indicate 

the complex nature of incinerator emissions." [page 1078]. EPA responded: 

For the operations and facilities subject to the rule, we believe that the 

combination of periodic compliance emissions testing and continuous 

monitoring of operational and parametric control measure conditions is 

appropriate for assuring ongoing compliance. The rule allows for the source 

owner or operator to install and operate continuous emissions monitoring 

systems in lieu of some testing and parametric monitoring. This process 

VES016968 
Docket ID No. EPA-R05-OAR-2012-0649 9 

requires source owners to propose site-specific monitoring plans for approval. 

These plans would include CEM S performance specifications and periodic 

quality assurance and quality control steps to assure the quality ofthe 

alternative monitoring data. Currently, EPA has the requisite CEMS 

performance specifications for mercury monitoring systems and not for 

multiple metals CEMS. 

While the statement at the beginning of this section is an accurate quote from the 

proposed rule, that proposed rule did not document that this statement is correct. 

In fact, in the final rule, EPA declined to require multi-metals CEMS in spite of 

extensive comments submitted by the developer ofthe Xact system. The 

rationale the EPA provided was that the Agency had not promulgated a 

performance standard. It should be pointed out that OTM 16 and OTM 20 

already existed at the time EPA made the decision not to require multi-metal 

CEM S as a requirement in the CISWI rule. Since the Agency did not recognize 

OTM 16 and OTM 20 as valid performance specifications when they responded 

to Mr. Cooper's comments on the CISWI Rule, they cannot now use them in 

Veolia's circumstance. 

d. "In addition, performance specifications and quality assurance (QA) procedures 

are now available for both mercury and multi-metals CEMS. 2 4 EPA has published 

performance specifications and QA procedures for multi-metal CEMS as OTM 16 

(Specifications and Test Procedures for X-ray Fluorescence Based Multi-Metals 

Continuous Emission Monitoring Systems at Stationary Sources) and OTM 20 

(Quality Assurance Requirements for X-Ray-Fluorescence Based Multi-Metals 

Continuous Emission Monitoring Systems at Stationary Sources). 2 5 Moreover, 

multi-metals CEMS are an accepted option for metals emission compliance in the 

recently promulgated mercury and air toxics (MATS) rule. 77 Fed. Reg. 9303 

(February 16, 2012). Therefore, the multi-metals CEMS has been proven to be 

reliable for measuring actual emissions of HAP metals from a hazardous waste 

combustor such as Veolia." (Statement of Basis at 23) 

Further, Footnotes 24 and 25 of the Statement of Basis state: 

Footnote 24.Performance Specification 10 (for multi-metals CEMS) and 

Performance Specification 12 for mercury CEM S were proposed in 1996 in 

conjunction with the original HWC MACT. However, because the multimetals and mercury CEMS measurement technologies had not been fully 

developed and demonstrated, neither performance specification was 

promulgated. Between 2003 and 2005, Performance Specification 12A for 

mercury CEMS was proposed and promulgated in conjunction with the Clean 

Air Mercury Rule (CAMR) after extensive demonstration of mercury CEMS 

and identification of appropriate performance parameters. In 2007, CAMR 

was vacated by the U.S. Court of Appeals for the District of Columbia, which 

called into question the legality of using Performance Specification 12A. It 

VES016969 
Docket ID No. EPA-R05-OAR-2012-0649 10 

has since been re-proposed in conjunction with amendments to the Portland 

Cement NESHAP. See http://www.epa.g0v/ttn/emc/m0nit0r.html#metals 

Footnote 25.See http://www.epa.gov/ttn/emc/prelim/otm16.pdfand 

http://www.epa.gov/ttn/emc/prelim/otm20.pdf. 

OTM 16 and 20 are not promulgated performance specifications. When CRWI 

suggested EPA use published OTMs for HCI monitors in the Portland Cement 

MACT reconsideration rule, the Agency declined to use these specifications 

giving the following reasons (EPA-HQ-OAR-2011-0817-0846, page 78): 

Other Test Methods (OTM 22 and 23) were provided on our website for 

evaluation and/or use by the stakeholder community and to encourage 

development of field test data supporting the procedures described in these 

methods. Significant improvements and additions to these OTM procedures 

are necessary before they will meet EPA's HCI CEMS performance 

specification requirements. EPA's efforts to prepare and distribute a 

technology neutral Performance Specification embraces the key components 

of OTM 22 and 23. If a facility manager believes that there is an alternative 

procedure that can better meet the HCI compliance monitoring requirements 

in this rule, they always have the option to submit it as an alternative test 

method under 63.7(f) as previously mentioned. 

In at least two rulemakings, EPA Headquarters has declined to use OTM during the 

rulemaking or declined to require CEMS because there was no promulgated 

performance specification for that instrument. In addition, Region 5 states in the 

Statement of Basis (page 21) that "the HWC MACT does not mandate the use of 

CEMS to document compliance with the HWC MACT limits for mercury, LVM, SVM, 

or chlorine based in part on EPA's determination that performance specifications for 

mercury or multi-metals CEMS were not yet available at the time of finalization of 

that rule." We believe that it is disingenuous at best for Region 5 to say that 

performance specifications and quality assurance procedures are now available for 

multi-metal CEMS. If a facility had asked to put such a CEMS on, the Agency would 

require them to submit an alternative monitoring application and the process of 

approving that application would have taken several years. 

e. EPA set forth in its Statement of Basis (at footnote 33) that: 

"The U.S. Army has also successfully installed and evaluated a multi-metals 

CEMS on one of its hazardous waste incinerators. Hay et al. (2005). EPA 

also understands that the U.S. Department of Defense has purchased three 

XactTM units for use at army munitions incinerators. Finally, multi-metals 

CEMS are an accepted option for metals emission compliance in the utility 

mercury and air toxics (MATS) rule that was recently promulgated by EPA." 

(Statement of Basis at 24). 

VES016970 
Docket ID No. EPA-R05-OAR-2012-0649 11 

A hypertext search ofthe MATS rule did not show any reference to a multimetals CEMS. Thus, the statement that a multi-metals CEMS is an acceptable 

option in the MATS rule is not correct. 

, While it is correct that the Army purchased and installed three Xact units, none 

have ever used for compliance with Subpart EEE. CRWI asked Army personnel 

the current status of the multi-metals CEMS at their facilities. Their responses 

are below. 

Tooele Army Depot research and development furnace: This unit only 

operates from time to time to establish new "recipes" for new feed items. It's 

actually not covered by any ofthe site permits, as long as it stays under a 

certain number of hours of operation. We've never tested it for HWC MACT 

and it isn't included in the NOC. I would not consider this a realistic example 

of multi-metal CEMS operating on a daily basis. 

Tooele Army Depot production furnace: This unit was operational on the 

furnace for a period of time. They no longer operate the CEMS on the unit. I 

think once they finished up the prove-out for Cooper, it was shut down. 

Crane Army Ammunition Activity production furnace: It was installed, has 

been started up for an initial qualification, then shut down, and has never 

been used. 

CRWI encourages Region 5 to contact these facilities to verify that these 

statements are correct. 

f. "Yanca ef al. evaluated both the XactTM and the QAG using a modified EPA 

Method 301 at a hazardous waste combustor by comparing measured and 

reference aerosol concentrations. The authors found that both the XactTM and 

the QAG met the Method 301 validation criteria with precisions and accuracies 

on the order of 5 percent over a wide range of concentrations." (Statement of 

Basis at 24). 

This statement is accurate forthe operating conditions and the flue gas 

conditions at the Evoniks hazardous waste combustor. However, this has not 

been verified at any other facility. 

g. "In 2010-2011, EMC deployed the XactTM 625 fence line multi-metals monitor at two 

sites in Ohio in coordination with EPA Region 5, EPA Office of Research and 

Development (ORD) and Ohio EPA. The XactTM625 reports hourly ambient air 

metals concentrations in near real-time, which allows for faster data acquisition and 

decision making over conventional filter-based monitoring methods. EPA's Ohio 

studies show excellent comparability between the XactTM 625 and conventional, 

filter-based, metals monitoring methods." (Statement of Basis at 25). 
Docket ID No. EPA-R05-OAR-2012-0649 12 

This is not a valid comparison. Ambient air monitoring is relatively simple due to 

the ambient air matrix. Flue gas sampling at high temperature and moisture 

content is a totally different problem. It is much more difficult to get a consistent 

flue gas sample to the instrument. Thus, any comparison of sampling the flue 

gas of a hazardous waste combustor to ambient air monitoring ignores too many 

variables to be valid. 

h. "The use of a multi-metals CEMS is the only sure way to verify that Veolia's 

feedstream analysis procedures and the proposed feedrate limits are sufficient to 

assure continuous compliance with the HWC MACT limits." (Statement of Basis at 

25). 

As already discussed, due to the lack of performance specifications for multi-metals 

CEMS, there is no way of determining whether data from the CEMS is accurate. 

Therefore, this statement is inaccurate. 

The vast majority of the statements Region 5 has placed in the Statement of Basis 

are not supported by anything in the official record or in the public record. The facts 

are that an Xact unit was intermittently operated on one hazardous waste combustor 

for a number of years. Due to frequent maintenance issues and equipment failure, 

the facility removed the CEMS from service permanently in 2011. While an Xact unit 

was installed on three other facilities, it was never used on those three units to 

comply with Subpart EEE. 

A CEMS cannot be used for compliance unless it has a promulgated performance 

specification or unless the facility submits and the Agency approves an alternative 

monitoring application. 

EPA has not promulgated a performance specification for a multi-metals CEMS. 

Without a performance specification, the Agency cannot use this instrument for 

compliance unless they approve an alternative monitoring application. It should be 

noted that the facility has not submitted an application. In addition, the courts 

(Portland Cement Association v. Ruckelshaus, 480 F.2d 375,396 (D.C. Cir. 1973), 

cert, denied, 417 U.S. 921 (1974)) have made it clear that compliance can only be 

shown using the same methods used to develop the standards. Since Method 29 

was used to develop the data used to set the standards in Subpart EEE, Method 29 

is the only way a facility can show compliance unless the Agency approves an 

alternative monitoring application. 

OTM 16 and 20 are site-specific methods and are not applicable to Veolia's 

operations. 

OTM 16 and 20 were written specifically for Eli Lilly and Co.'s (Lilly) source and 

instrument. While they would provide a starting place for another facility to develop 

VES016972 
Docket ID No. EPA-R05-OAR-2012-0649 13 

their own site-specific method, one cannot assume that either could be used at 

another facility without significant modification. For example, the sample transport 

system in OTM 16 provides for a protocol for including the sample transport system 

into the instrument validation using either dynamic spiking of known gases or 

comparison to another method (instrumental or reference, M29, filters/tubes and 

Ohio Luminex, etc.). This was written specifically for the Lilly system using a Sigrist 

sampling system. It is not at all clear that an appropriate sample transport system 

could be designed and developed for Veolia's stack gas conditions. Lilly spent 

considerable time and resources in developing both the laboratory and stack data 

underlying these methods. It is also not clear whether this instrument would tie into 

Veolia's daily operations, alarms, and QA/QC procedures. It is likely that these two 

OTMs would need extensive work before they would be usable forthe conditions in 

Veolia's stack. 

In addition, there is a good chance that the current QAG will not be able to produce 

quantitative mass of metals in the ranges required to calibrate/test the Xact. The 

QAG operates as a dynamic spiking into the probe/sample loop of the Xact system. 

Operation of this unit is dependent on the type of probe used, the flow in the sample 

loop, and gas conditions. Lilly spent a year developing this device to present the 

mass of metals specific to its sample loop (flow/moisture, etc.). 

In summary, a Title V permit is not the appropriate place to add entirely new and 

unproven monitoring requirements to a EEE source. The Agency has made a 

number of statements that are unsubstantiated, incorrect, or misleading in an effort 

to show that multi-metals CEMS are off-the-shelf instruments that can simply be 

purchased and easily placed on a stack. These instruments are expensive, custom 

built, require a great amount of resources to install, calibrate, maintain, and operate, 

and ultimately after spending considerable amounts of money, may fail to provide 

the data expected. Installing and operating a multi-metals CEMS would take several 

years to accomplish. It would take several more years to gather data and to 

determine whether that data is an accurate representation of what is emitted from 

the stack. EPA has not promulgated a performance standard for multi-metals CEMS 

and until they do so, these instruments cannot be used for compliance purposes 

without an approved alternative monitoring application. CRWI does not see how 

Region 5 can justify the expenditure of resources for a "research project" when it has 

been established that other methods - namely those required in the existing EEE 

regulations - should be used to show compliance. 

4. Region 5 should modify the sampling and analysis requirements. 

CRWI has safety and public health concerns regarding this requirement that waste 

be sampled within 24 hours of receipt. Waste arrives at facilities at all hours and in 

all conditions. It is not always feasible to accept and safely analyze waste within 24 

hours of receipt. If this requirement were imposed, facilities could be forced to 

choose between accepting the waste and risk violating their permit by not sampling 

VES016973 
Docket ID No. EPA-R05-OAR-2012-0649 14 

the waste within 24 hours, or refusing the waste and forcing carriers with loads of 

hazardous waste to wait in areas that are far less safe than inside the gates of the 

facility. We believe that the timetable for sampling waste and any supplemental 

analysis requirements are more appropriately handled under RCRA and the facility's 

Part B permit. Further, CRWI is concerned that EPA is requiring analysis simply for 

the sake of doing analysis. As written, the draft permit requires the analysis of waste 

that has little or no chance of containing metals. 

CRWI finds it highly ironic that Region 5 is requiring the facility to report non-detects 

at the reporting limit. CRWI has been trying (unsuccessfully) for many years to get 

the Agency to recognize that the reporting limit is the only defensible number that 

can be used. However, since the Agency rejected this idea when finalizing Subpart 

EEE, Region 5 cannot now change the rule and require that all non-detects be 

reported at the reporting limit. We agree with Region 5 that the reporting limit is the 

only defensible number but the Agency has to be consistent. Whatever method was 

used to set the standards has to be the one that is used to show compliance. Thus, 

Region 5 cannot require non-detects to be reported at the reporting limit. This would 

inflate the values and potentially create compliance issues where none actually 

exist. Further, it places the facility in the untenable position of certifying the 

accuracy of EPCRA (Emergency Planning and Community Right-to-Know Act) 

reports. 

Finally, we would note that EPA Headquarters is currently taking comments on a 

revised waste analysis plan guidance document. We believe that it is premature to 

include any changes in waste analysis plans until EPA finalizes that document. 

CRWI suggests that these provisions be removed. 

VES016974 
VES016975-016983.pdf 
Unled States Solid Waste and EPA-530-R-92-011 

EnvbonmentalPnteeSon- Emergency Response FB92-154947 

Agency (OS-322V^ March 1992 

Technical

 p**2*i 5ub , . 

Implementation 

Document for EPA's 

Boiler and Industrial 

Furnace Regulations 
TECHNICAL IMPLEMENTATION 

DOCUMENT 

FOR EPA's 

BOILER AND INDUSTRIAL FURNACE 

REGULATIONS 

U.S. Environmental Protection Agency 

Office of Solid Waste 

401 M Street, S.W. 

Washington, D.C. 20460 

March 1992 
compounds in order of destruction difficulty. The two 

methods that are commonly used in permitting are the 

heat of combustion index and the thermal stability index 

(TSLo02), 

In the heat of combustion index, the compounds 

which have the lowest heat of combustion are ranked as 

most difficult tb destroy. This index is listed in 

. Guidance Manual for Hazardous Waste Incinerator 

Permits (11) and other documents. 

The TSL0O2 index was developed by the 

University of Dayton Research Institute (UDR1) under 

contract to EPA. In the TSLo02 index, compounds are 

ranked according to their thermal stability under low 

oxygen conditions. The compounds that require the 

highest temperatures to achieve destruction are ranked 

as most difficult to destroy. The TSLo02 ranking relies 

on te&t& tha: ' ' i«ri»»'» ifi tfa "^T"V.",nrf tc 

temperatures ui up i _ aui~b:.z ^Luwipuere 

and measure their degree of destruction after 2 seconds. 

Representative compounds from all major groupiogs of 

40 CFR Pari 261, Appendix VIII compounds have been 

tested, and the index for the remainder have been 

estimated. The TSL0O2 index is still being refined as a 

result of ongoing experimental studies. 

A copy of the ranking, which includes 

experimental results through tbe end of the 1990 fiscal 

year, is included in Appendix H. Applicants should use 

the most current index available when developing a trial 

burn plan. When this ranking is used, it is 

recommended that POHCs be selected from those 

compounds br which actual experimental data exist. 

Guidelines br the use of the TSL0O2 index are 

included in Appendix D of Guidance on Setting Permit 

Conditions aad Reporting Trial Burn Results (23). 

The BIF Rule allows the selection of surrogate 

POHCs, i.e., compounds which are not present in the 

waste and/or are not listed in Appendix VM of 40 CFR 

261. The use of surrogate POHCs may be proposed if 

the compounds present in the waste are impractical for 

POHC selection because of the considerations listed 

above, or because of high cost, high toxicity, sampling 

and analysis problems or if the facility believes it is 

more appropriate to select POHCs for which 

experimental data exist. A permit appUcant seeking the 

use of surrogate POHCs must submit, in the trial burn 

plan, adequate documentation of the relationship 

between the DRE of the surrogate POHC and the 

DREs of the Appendix VHI compounds in the waste. 

Two surrogate POHC concepts that have been advanced 

are the use of SF, and/or the use of POHC "soups.* 

The pros and cons of SFB have been discussed in the 

BIF preamble (56 FR 7147, February 21,1991). 

1Q£ Extrapolation/Interpolation of Metals 

Emissions Data 

Extrapouuion/uuerpolation of test data can be 

used to develop operating Emits (e^» metals feed rate 

Emits) from test data obtained at operating conditions 

that are different from the limits. Extrapolation means 

setting limits outside the bounds (above or below) of 

test results, and interpolation means setting operating 

limits between the bounds of the test results. . 

This subsection discusses the specific, 

circumstances in which extrapolation/interpolation may 

•b* 'siwl; «or setting prtmit qrxrating limits. Because 

£«iapoi«u'.'a/I.iter^>;-.itii of data is valid only in 

certain cicumstances, and because EPA is able to 

provide onh/ limited oversight during interim status, it 

should not be used for compliance certification. 

Operating conditions demonstrated during . the 

compliance test provide the basis for limits established 

in the compliance certification, as discussed in Section 

5.0. 

105.1 Theoretical Background 

ExtrapoIation/iDterpoIation of test data must 

consider the relationship between the emissions rate of 

a metal from a BIF and the feed rate of the metal. 

Because this relationship is not linear, 

extrapolation/interpolation may result in 

nonconservative Emits, and is therefore inappropriate in 

some cases. 

The emission rate of a metal depends on 

numerous operating r^rameters, including the feed rate 

of the metal, APCS parameters, gas velocity, operating 

temperatures, etc. The feed rate of a metal to a BIF 

varies as a result of (1) changes in the concentration of 

metals in the feed materials to the BIF (wastes, fuels, 

and raw materials); and (2) changes in the feed rates of 

the various materials to the BIF. Consider a simple 

ease where metals are being fed to a BIF from a single 

-nonpumpable feed stream. The expected effect of 

increasing the metals feed rate on metals emissions from 

a BIF, where the other operating parameters are held 

constant, is shown in Figure 10-1. 

BJF\SECT10.B1F 10-14' 
1 

1 

- ZoneI | 

(Viponzfttioa) J 

I 

ZoneS 

^ 1 FisarelO-l(a) 

Metal Feed Rate in Liquid 

i 

I 

ZoneI ] 

(Vaporization) j (Botraioineat) 

1 Figure 10-l(b) 

Metal Feed Rate in Solid 

(Liquid Feed Rate it Coutaat) 

i I 1 1 

ZoneI | Zone II l Zone IU 

1 1 

^ \ 1 

l 

i • 1 Figra 104(c). 

Metal Feed Rate ia Liquid 

(Solid Feed Rate fcCooatant) 

Figure 10-L Typical Relatioaalrtp Between Metab Feed Bafr and Fmtmdnni- Rate 

10-15 

I 

! 

I 

I 

I 

i 

1 

ti 

VES016978 
For low metals feed rates, metals behavior is 

controlled mainly by vaporization (Zone I), as shown in 

Figure 10-l(a). Metals tend to vaporize until the 

combustion gas becomes saturated with metal 

compounds. The quantity ef a given metal that will 

saturate the gas is detennined by the effective vapor 

pressure of the metal, which depends on the 

temperature, and may depend on the concentration of 

cMcrine, oxygen, and/or sulfur in the gas. If tiie vapor 

pressure is high enough to completely vaporize the 

metal without saturating the gas (Le., at relatively low 

metal feed rates), an increase in the metals feed rate 

results in an equivalent (1 to I) increase in the amount 

oi metals emitted. Eventually, as the metals feed rate 

continues to increase, the gas becomes saturated with 

metal compounds. 

After the saturation level is reached, the metals 

fcisir.non rate becomes a function of the particle 

Ci'-uusicw race, ouii mtuit- :,.iictui4ti&ii cu tLose 

particles (Zone IT). The total metals emissions rate 

continues to increase with increasing metals feed rates 

because of increased metal concentrations in the 

entrained ash particles. However, because no additional 

amount of metal can vaporize, die metals emissions rate 

in Zone II does not increase as rapidly as in Zone I. 

A more complex case is one in which metals are 

being fed to a BIF from both liquid and solid feed 

streams, Tne cxr^aed effett of an maease in the feed 

rate of metals in the solids feed stream when Ihe other 

operating parameters are held constant is shown in 

Figure 10-1 (b). This is similar to the simple single feed 

source case of Figure 10-l(a) except that there b an 

obset in metals emissions as the feed rate of metals in 

tbe solid feed stream approaches zero because of the 

emissions from the liquid feed stream. 

Tbe expected effect of increasing the feed rate 

of metals from the hquid feed stream on metal 

emissions, where the other operating parameters arc 

held constant, is shown in Figure 10-l(c). For low metal 

feel rates, metal behavior is controlled mainly by 

vaporization (Zone I}.. Metals from both feed streams 

tend to completely vaporize until the combustion gas 

bc^mes saturated with metal compounds. As the feed 

rate of metals from the liquid stream becomes higher 

than the saturation point (Zone II), all of the metals fed 

with the liquid feed stream will vaporize; however, only 

a portion of the metals fed with the solid feed stream 

will vaporize, aad the remainder will remain in the ash. 

In tins example, further increases in metal feed 

rates result in a slight increase in metal emission rates 

because of the increase in die metals concentration of 

the entrained particles. Frnally, a point is reached where 

the metals in the Squid feed stream alone aire sufficient 

to saturate the gas. As metal feed rates increase beyond 

this point (Zone IU), further increases in the feed rate 

of metals in hquid feed streams result in a direct 

increase in the amount of entrained metals. 

The relationship between metal feed rates and 

mend emissions is fin ear within each of these three 

zones. Furthermore, the contributions of the liquid and 

the solid feed streams are expected to be additive. 

Thus, as long as tiie extrapolation/interpolation is 

conducted over a limited range (Le, not over either of 

the breakpoints of Figure 104(c)), extrapolation/ 

interpolation is appropriate, for situations where the 

metal feed rate changes in both the solid and the liquid 

feed streams, and the Mowing equations apply: 

SF. - SF, + 

LFL - LF4 * 

EL - E, 

Et-JE * 

(SF, - SFj) 

(LF, - LFj) 

where: 

SF - feed-rate of the metal in the solid feed 

stream 

LF * feed rate .of the metal in the liquid feed 

stream 

E emission rate of the metal 

» " test condition 1 

test condition 2 

t the extrapolated or interpolated limit 

condition 

The above theoretical treatment assumes that 

there is a single stable solid form of the metal over the 

range of extrapolation. In situations where the metal 

has an affinity for the cuhker/aggregate/slag (e.g, 

arsenic), there may be a number of stable complexes, 

and the saturated vapor pressure may change with the 

BIF\$ECT10.BIF 10-16 

VES016979 
concentration of metals in the solids. - in this case, 

Figure 10-1 would be expected to change as follows: 

• Zone I would be unaffected. The metal 

emissions rate in the ^porization" zone would 

be linear with the metals feed rate. 

• A sharp break at the saturation point, would 

still be evident 

• An increased metal feed rate in Zones TX and 

in would result in an increase (probably 

aoalinear) in vaporization with a 

conespondingly nonlinear increase in the metal 

emission rate. The nonlinear impact would be 

greater in Zone II than in Zone lit 

However, because the nonlinear relationship is likely to 

be approximately linear over a s&u £ migc, tlh -l'.-.-..-.. 

necessarily preclude the use of the above extrapolation/ 

interpolation equations over a small range of metal feed 

rates. -

10.5.2 Extrapolation to Different Feed Rates 

Figures 10-2(a) and (b) illustrate examples of 

extrapolation/interpolation of test data to establish 

metal feed rates, using the above theoretical background 

on metal emissions. In Figure 10-2(a), tbe measured 

metal emissions (Point 1} are greater than the allowable 

emissions, determined from dispersion modeling, A 

linear extrapolation back to tbe allowable maximum 

emissions level (Point 2) provides a proposed metal feed 

rate limit (Point 3). However, because of the 

nonlinearicy of the metals emission curve, the actual 

emissions produced at the proposed feed rate limit 

(Point 4) are still higher than the maximum allowable 

leveL The largest allowable metal feed rate should be 

smaller /Point 5). Because of this type of 

noncouservaove result, a downward linear extrapolation 

of data is not recommended; actual data should be used 

in this situation. 

In Figure 10-2(b), the measured metal 

emissions (Point 1) are below the allowable emissions. 

In this case, the extrapolation to Point 2 would produce 

a lower proposed teed rate limit (Point 3) than that 

winch should actually be allowed (Point 5). Therefore, 

upward extrapolation would be theoretically conservative 

ia this case.' Such upward extrapolation may be 

reasonable for justification of limited (e.g^ 720 hours) 

testing at higher metals feed rates; however, it is not 

generally recommended for letting permit limit* because 

of the lack of validation data. 

One situation which may warrant the use of 

upward extrapolation is when the projected emissions at 

the extrapolated feed rates are far below the Tier DI (or 

Tier D) emission limits. For example, suppose a facility 

runs a trial burn using typical waste wuhout spiking, and 

the metal emissions are 20 times lower than the Tier ffl 

limits.. In this case, the permit writer could reasonably 

allow upward extrapolation to set a metals feed rate 

limit somewhat higher (e«, double the feed rate based 

on the trial burn). This would theoretically result in 

metal emissions which are 10 times lower than the Tier 

HI limit. Allowing extrapolation in such eases would 

eliminate the need for expensive metals spiking to 

achieve flexible, but still conservative, metals feed rate 

limits. 

10.53 Interpolation to Different Feed Rates 

An approach that is subject to fewer 

uncertainties, is interpolation between data points. This 

approach is illustrated in Figure 10-3. Suppose two tests 

were conducted in a trial burn, each at a different 

metals feed rate. One test (Point 1) resulted in 

emissions above the limit, and one test (Point 2) 

resulted in emissions below the limit. These two points 

define the actual emissions curve observed during the 

test over the range of metal feed rates' that were 

examined. If the range of feed rates was small, linear 

interpolation can be used as shown in the figure to 

detennine the metal feed rate that just meets the limit 

(Point 3), and the theoretical metal feed rate limit that 

corresponds to the maximum pernrissibte emission rate 

can be established (Point 4). 

In considering this approach, the 

owner/operator and pennit writer should carefully 

review the overall range in metal feed rates represented 

by the available test data, as well as the variation in 

other operating parameters, to ensure that the linear 

bterpolation is applicable. For example, in a situation 

where one test was conducted at metal feed rates above 

the saturation point and one test below the saturation 

point, interpolation could result in error. Because it is 

not pffmnWe to determine whether the data points 

straddle the saturation point, EPA recommends 

?jtfjifr»fflyjnfc the feed rate l"T"ts at the demonstrated 

levels (Point 2) m these situations and does not 

recommend the use of interpolation. 

BIF\SECn0.BIF 10-17 
FfgoxelO-2(a) 

Figure 10-2(b) 

Figure 10-2, i^nffpf ^f^ftf flf Kttrapftlitfwi qf Traf ftrrn Daft 

10-18 
VES016982 
where available data show they pose ntinhnai risk to 

human health and the environment. These include: 

• BIFs burning low risk wastes; and 

• Specific types of bouers burning certain classes 

of waste. 

The facility must submit documentation that 

demonstrates that the BIF meets the requirements of 

the low risk waste exemption or special operating 

requirements (SOR) as specified in 1270.22(a). In 

addition, under §270.22(a)(6), it is possible to submit 

data in lieu of a trial burn if the data demonstrate a 

unit's compliance with the BIF Rule. 

10.6.1 Low Risk Waste Exemption 

Section 266.109 allows EPA to waive the DRE 

trial bum standard for certain boilers and industrial 

furnaces, and if the BIF is exempt irom the DRE List 

bum, possibly the trial burn for particulate matter 

(PM).31 These facilities are not exempt from other 

portions of RCRA regulations, such as notification of 

hazardous waste activities, the need to obtam permits 

for storage of hazardous wastes, or other BlF emissions 

standards. 

To qualify for the low risk waste exemption, the 

device must first satisfy, the foUowing operating 

requirements of 5266.109(a)(1): 

1. At least 50% of the fuel (the prunary fuel) is a 

fossil fuel fuel derived from a fossil fuel, tall 

oil, or, if approved on a casc-by-case basis by 

the appropriate regulatory authority, other 

nonhazardous fuel with combustion 

characteristics similar to fossil fuel The 

percentage of primary fuel is determined on the 

basis of either the heat input (le, Btu/hr from 

the primaiy versus all fuels) or the mass feed 

rate (Le, lb/hr of the primary fuel versus the 

waste fuel), depending on which method results 

in the lower mass liazardous waste feed rate. 

% The primary and hazardous waste fuels have a 

minimum as-fired heating value of8,000 Btu/lb. 

4. The stack gas eoncenrration of CO is £100 

ppmv houriy rollmg average (on a dry basis 

corrected to 7%Oj). The device is not eligible 

for the alternative standard for HC emissions 

(<20 ppmv hourly rolling average, reported as 

propane, on a dry basis corrected to 7%,Oa) if 

the BIF falls under the low risk wasteexemption. 

5. The waste does not contain nor is it derived 

from acutely hazardous (dicodn-listed) wastes 

fisted under $26131 (specifically, the waste 

streams F020, P021, F022, F023, F026, and 

F027, which are related to the. manufacture, 

disposal, and use of chlorophenols, 

chlorobenzenes, cblorobexanes, and 

hexachlorophene). 

In addition, the foUowing actions must be 

implemented to ismoustraie lost u*e Ull w3> sot pose 

unacceptable adverse risks to human health: 

. • Identify and quantify the nonmetal compounds 

hsted in 40 CFR Part %%, Appendix VHI that 

could be present in tbe hazardous waste; 

• Calculate reasonable, worst-case emission rates 

for each constituent identified above; 

• Use air dispersion modeling to predict the 

maximum. annual average ground-level 

concentration of the constituents identified 

above; and 

• Ensure that ground-level concentrations of the 

constituents predicted above do not exceed 

levels established in J266.106(a)(2)(iv). 

These procedures require calculation of the 

worst-case emissions of the Appendix Vm organics 

which may be fed to the BIF, a value that can be used 

in a maximum exposed mdividual (MET) exposure 

calculation for tbe system. The hazard levels are 

determined following the procedures for dispersion 

3. . The hazardous waste is fired directly into tiie 

. primary fuel flame zone. 

"A wnver from the PM complines ten required under interim ttatus a rot milable under the Um rttkw«te ettmptkw. 

BIF\SECno.BIF 

10-20 

VES016983 
VES016984-016988.pdf 
Technical Support Document for HWC MACT Standards 

Volume IV: 

Compliance with the HWC MACT Standards 

U.S. Environmental Protection Agency 

Office of Solid Waste and Emergency Response (5305) 

1200 Pennsylvania Avenue, NW 

Washington, D.C. 20460 

September 2005 
maximum limits as determined by the PCDD/PCDF and metals testing in cases where 

compliance with these standards are conducted under separate performance test conditions. 

Metal capturing sorbents ~ Sorbents such as kaolin, bauxite, silica, alumina, and clays, are 

currently being developed to control semivolatile metals emissions. No hazardous waste burning 

facilities are currently intentionally using these control techniques, however they may in the 

future. The sorbents can be added directly to the feed, or injected separately downstream of the 

combustor. Operating parameter requirements may be analogous to carbon injection and dry 

scrubbing technologies discussed in other Sections. In site-specific cases where waste and other 

feedstream materials may potentially contain these types of metal capturing ingredients, 

monitoring of waste composition during the comprehensive performance testing (and during 

subsequent regular operation) may be appropriate in cases where it might be expected that 

composition of wastes and/or feed materials are likely to significantly change. 

6.3 Extrapolation 

The "upward" extrapolation of SVM and LV M feedrates and associated emissions rates 

from levels demonstrated during the comprehensive performance test to higher allowable 

feedrate and emissions rates can be requested on a site-specific basis. Linear upward 

extrapolation from the "origin" (at a metal feed and emissions rate of zero) can be conservatively 

used to allow for higher metals feedrate limits while continuing to ensure that the facility is 

within the MACT emissions limits. 1 0 This is because metals system removal efficiencies tend to 

stay the same or increase as the feedrate increases. This has been shown based on theory and 

statistical analysis of experimental test results. This applies to all metals types and volatility 

groupings. 

The conservative nature of the "upward" extrapolation procedure is shown in Figure 6-1. 

Tlie emissions level predicted at a higher feedrate based on linear extrapolation through the 

origin and from measured emissions levels at a lower feedrate is greater than or equal to the 

actual emissions levels at the higher feedrate (based on the expected relationship between metals 

feed and emissions rates). Alternatively, because "downward" extrapolation may not always be 

conservative, as also shown in Figure 6-1, it is generally not allowed. 

Downward extrapolation is permitted for normal emissions-based standards (see Section 

2 and Appendix B) 

A request for the use of extrapolation for setting allowable metals feedrate limits must be 

contained in the comprehensive performance test plan, which is submitted to EPA at least 1 year 

We note that allowing upward extrapolation of performance test feedrates to establish feedrate limits (while 

ensuring that the emission standard would not be exceeded) precludes the need for sources to spike toxic metals 

excessively during performance testing to achieve feedrates at the high-end of normal operations. Spiking toxic 

metals poses a health risk to workers, increases the environmental loading of toxic metals, and increases the cost of 

performance testing. 

6-9 

VES016985 
prior to the actual testing. The extrapolation methodology will be reviewed and approved by the 

Agency. The extrapolation submittal must discuss: 

• Rationale for the selection of the comprehensive performance test metals feedrates, and 

desired extrapolated feedrates. In particular, the feedrate levels must at a minimum 

represent those in typical "normal" waste streams. It should also reflect the potential 

variability and fluctuation in normal waste metals levels, which will depend on the 

heterogeneity and other characteristics ofthe waste. The discussion should include a 

listing ofthe various waste streams that are treated, and results of historical metals 

characterization efforts. This is to ensure that the amount of extrapolation that is needed 

is minimized. 

• Rationale for the selection of the physical form and species of the metals used, also based 

on expected waste characteristics. 

• A maximum extrapolated feedrate that would be desired, again considering the historical 

metal feedrate data. Specifically, EPA does not want sources to extrapolate to allowable 

feedrates that are significantly higher than their historical range of feedrates. The 

requested extrapolated feedrates should be limited to the upper end of historical metals 

feedrate ranges that a source has actually fed, unless the source documents that future 

operations will necessitate higher metals feedrate limits. 

6-10 

VES016986 
Downward Extrapolation 

Metal Feed Rate 

Upward Extrapolation 

Actual metals 

Metal Feed Rate 

Figure 6-1. Basis for metal feedrate extrapolation guidance. 

6-11 

VES016987 
• Discussion of characterization procedures to be used to ensure that metals 

feedratesand emissions rates documented in the comprehensive performance test plan are 

highly accurate. Some spiking will likely be required to increase confidence in the 

measured feedrate levels used to project higher allowable feedrate limits. Errors 

associated with sampling and analyzing heterogeneous waste streams can be minimized 

by spiking known quantities. 

Also, after the performance testing, the Agency will review the testing and extrapolation results 

to confirm that they have been interpreted properly and that the extrapolation procedure is 

appropriate for the source. 

The extrapolation procedure that is to be used will depend on the extent and quality ofthe 

metals feedrate and emissions data. To ensure that the extrapolation is "conservative" in nature 

(i.e., produces projected emissions levels at the projected feedrate that are upper bounds on that 

expected), it is recommended that the extrapolation be based on either the lowest SRE within a 

test condition, or some statistically based analysis procedure. This might include: 

• For cases where a large amount of data has been compiled from different feedrate levels 

(for example, through many tests over the years), extrapolation from a statistically based 

analysis ofthe specific facility data may be appropriate, such as from a worst case test 

condition average considering typical statistical variability of the within-test condition 

runs, or a linear regression ofthe condition average (or individual run) feedrate and 

emissions rate data, considering some upper confidence limit bound. 

• For cases where more limited and/or widely spread data are available, extrapolation from 

the worst case lowest observed SRE that is not an outlier. 

• Extrapolation from a single test burn condition based on determination ofthe "Upper 

Confidence Limit". Specifically, this involves using a single test condition average, and 

a "within test condition" standard deviation based on either site specific data or the 

demonstrated variation observed in other similar type tests. 

• For small extrapolations to feedrates relatively close to demonstration testing levels, more 

aggressive extrapolations may be warranted, such as those from a test condition median 

or average. Alternately, for larger extrapolations, a more conservative procedure is 

generally appropriate. 

6-12 
VES016989-016996.pdf 
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY *§2L\ REGIONS 

V ^ Z Z ? 77 WEST JACKSON BOULEVARD 

S ^*T ^ CHICAGO, IL 60604-3590 

FEB 2 7 7.004 

REPLY TO THE ATTENTION) OF 

Bet h Brock , Team Leade r 

(AE-17J ) 

Environmenta l Service s 

E l i Lill y an d Company ISOF l i 

Tippecano e Laboratorie s " 

L650 Lill y Road 

Lafayette , Indian a 47909-920 1 

R e : El i Lill y an d Company, Tippecano e Laboratorie s 

Alternativ e Monitorin g Petitio n fo r T149 Solid-Liquid . 

Incinerato r Unde r Hazardou s Wast e Combusto r MACT 

Dea r Ms. Brock : 

The Nationa l Emiss io n Standard s fo r Hazardou s Ai r Pollutant s fro m 

Hazardou s Wast e Combustors, 40 C.F.R . Par t 63, Subpar t EEE , (HWC 

MACT) require s th e owner o r operato r o f a hazardou s wast e 

incinerato r t o submit t o th e Unite d State s Environmenta l 

Protectio n Agenc y (U.S . EPA) a comprehensiv e performanc e tes t 

(CPT) pla n an d continuou s monitorin g syste m (CMS) performanc e 

evaluatio n tes t plan . The CPT Pla n must includ e th e informatio n 

specifie d i n 40 C.F.R . § 63.1207(f ) (1) (i) throug h (xxvii) . Th e 

CNS performanc e evaluatio n tes t pla n must includ e th e informatio n 

specifie d i n th e Appendi x t o th e HWC MACT. Pursuan t t o 40 C.F.R . 

§ 63.1209(g) , regulate d entitie s ma y als o submit an applicatio n 

t o U.S . EPA fo r approva l o f alternativ e monitorin g requirement s 

t o document complianc e wit h th e emissio n standard s o f th e HWC 

MACT. 

On Septembe r 30, 2003, El i Lill y an d Company (El i Lilly ) 

submitte d t o U.S . EPA severa l documents require d unde r th e HWC 

MACT fo r it s solid-liqui d hazardou s wast e incinerato r locate d a t 

t h e Tippecano e Laboratorie s i n Shadeland , Indiana . Thi s lette r 

serve s t o respon d t o you r Alternativ e Monitorin g Application . 

E l i Lill y operate s a Solid-liqui d Incineratio n Syste m a t th e 

Tippecano e Lab s facility , referre d t o as Therma l Oxidize r 149 

Recycled/Recyclable . Printed with Vegetable Oil Based Inks on 100% Recycled Paper (50% Postconsumer) 
2 

(T149) . The T149 incinerato r i s equippe d wit h an ai r pollutio n 

contro l system (APCS) tha t include s a quenc h system , 

condenser/absorber , and a Hydro-Soni c scrubber . The alternativ e 

monitorin g petition s submitte d by El i Lill y pertai n t o th e 

condenser/absorbe r and th e Hydro-Soni c scrubber . Specifically , 

E l i Lill y is seekin g approva l fo r th e following : 

1 . A waive r o f the requiremen t t o establis h an operatin g 

paramete r limi t (OPL) o n th e maximum solid s conten t o f th e 

scrubbe r solution , o r th e minimum blowdown rat e and eithe r 

t h e minimum scrubbe r tan k volum e o r leve l a t th e 

condenser/absorber . 

2 . A waive r o f th e requiremen t t o establis h an OPL o n th e 

minimum pressur e dro p acros s th e condenser/absorber . 

3 . A waive r o f th e requiremen t t o establis h an OPL o n th e 

minimum liqui d fee d pressur e a t th e condenser/absorber . 

4 . A waive r o f th e requiremen t t o establis h a n OPL o n th e 

minimum scrubbe r wate r pH a t th e condenser/absorber . 

5 . A waive r o f th e requiremen t t o establis h a n OPL on th e 

minimum liqui d t o ga s rati o o r minimum liqui d an d maximum 

flu e gas flo w rate s a t th e condenser/absorber . 

6. A n alternativ e OPL fo r th e minimum pressur e dro p across th e 

Hydro-Soni c scrubber . El i Lill y propose s t o establis h a n 

alternativ e OPL base d o n a n equivalen t differentia l pressur e 

tha t would be calculate d base d o n a n equatio n develope d b y 

t h e manufacture r o f th e Hydro-Soni c scrubber . 

Pursuan t t o 40 C.F.R . § 63.8(f)(2) , afte r receip t an d 

consideratio n o f writte n application , th e Administrato r may 

approv e alternative s t o an y monitorin g methods o r procedure s o f 

thi s part . Pursuan t t o 40 C.F.R . § 63.1209(g ) (1) (ii) , i f th e 

owner o r operato r documents tha t neithe r an operatin g paramete r 

limi t i n 40 C.F.R . § 63.120 9 no r a n alternativ e operatin g 

paramete r limi t i s needed t o ensur e complianc e wit h a n emissio n 

standar d i n th e HWC MACT, th e owne r o r operato r may request tha t 

t h e Administrato r waiv e th e requiremen t fo r th e operatin g 

VES016990 
3 

parameter limit . Based on the informatio n you provide d i n you r 

reques t and on additiona l informatio n supplie d by Mike Foste r o f 

E l i Lilly , U.S. EPA i s approvin g you r request s 1 and 6 and 

disapprovin g request s 2 throug h 5 . Detail s o f the 

approvals/disapprovals/comment s fo r each reques t are provide d 

below. 

Condenser/Absorber 

The APCS servin g the T14 9 incinerato r include s as a second stage , 

a condenser/absorber . The condenser/absorbe r consist s o f spra y 

nozzles , packin g and a liqui d collector . Causti c and make-up 

water ar e introduce d i n th e condenser/absorber . 

The condenser/absorbe r provide s additiona l conditionin g o f th e 

combustion gases from the quench syste m prio r t o routin g them t o 

t he Hydro-Sonic scrubber . Accordin g t o Mike Foster , the primar y 

functio n of the condenser/absorbe r i s t o provid e some residenc e 

time and cooling.fo r the combustio n gases so tha t the combustio n 

gases ar e a t an optima l velocit y an d th e entraine d particle s ar e 

of an optima l siz e fo r removal a t th e Hydro-Soni c scrubber ; ther e 

i s no significan t particulat e contro l a t th e condenser/absorber . 

In terms o f the HWC MACT, th e condenser/absorbe r meets th e 

definitio n of a low energy wet scrubber . 

The followin g fiv e alternativ e monitorin g request s pertai n t o th e 

condenser/absorbe r specifically . 

1 . A waiver of the requirement t o establish , an operatin g 

parameter limi t (OPL) on the maximum solid s content o f the 

scrubbe r solution , o r the minimum blowdown rat e and eithe r 

t he minimum scrubber tank volume o r leve l at the 

condenser/absorber. 

The regulatio n a t 40 C.F.R. § 63.1209 (m) (1) (i ) (B) (l j require s 

source s equippe d wit h a wet scrubbe r t o establis h an OPL t o 

ensure tha t the solid s conten t o f th e scrubbe r liqui d does not 

exceed level s durin g the performanc e test . A facilit y must 

establis h one of th e followin g OPLs: a) a limi t on th e solid s 

conten t o f th e scrubbe r liqui d usin g a CMS o r by manual samplin g 

and analysis ; or b) establis h a minimum blowdown rat e usin g a CMS 

and eithe r a minimum scrubbe r tan k volume o r liqui d leve l usin g a 

CMS . 

VES016991 
4 

E l i Lill y i s requestin g tha t the requiremen t fo r thi s OPL be 

waived fo r the condenser/absorber. El i Lill y provide s th e 

followin g reason fo r waivin g thi s OPL. El i Lill y state s tha t 40 

C.F.R. § 63.1209(m) applie s onl y t o particulat e contro l device s 

and the condenser/absorber does no t serv e as a particulat e 

contro l device ; the Hydro-Sonic scrubbe r i s th e particulat e 

contro l device . 

Based on our revie w of the bloc k flo w diagra m of the APCS 

provide d i n the reques t and discussion s wit h Mr. Foste r o f El i 

Lilly , U.S. EPA approves El i Lilly' s request . U.S. EPA has 

determine d tha t sinc e the maximum solid s conten t of the scrubbe r 

solution , or the minimum blowdown rat e and eithe r the minimum 

scrubbe r tank volume o r liqui d leve l ar e bein g measured a t th e 

Hydro-Sonic scrubber, thi s OPL does not need t o be measured a t 

t he condenser/absorber. 

2. A waiver of the requirement t o establis h an OPL on the 

minimum pressure drop acros s th e condenser/absorber. 

The regulatio n at 40 C.F.R. § 63.1209 (o) (3) (ii ) require s source s 

equipped wit h a low energy wet scrubbe r t o establis h a minimum 

pressur e drop acros s th e scrubbe r base d on manufacturer' s 

specifications . Facilitie s must comply wit h the OPL on an hourl y 

rollin g average. 

E l i Lill y i s requestin g tha t th e requiremen t fo r thi s OPL be 

waived. The justificatio n provide d simpl y state s tha t th e 

condenser/absorbe r i s not th e HC1/C12 contro l device ; th e HydroSoni c scrubbe r is . 

U.S. EPA i s denying thi s request . Based on th e bloc k flo w 

diagram o f th e APCS and furthe r discussion s wit h Mr. Foste r at 

E l i Lilly , U.S. EPA believe s i t i s likel y tha t ther e i s some HCL 

removal occurrin g a t th e condenser/absorber . The HCL i s removed 

throug h th e liqui d t o gas interface . Therefor e i t i s appropriat e 

t o establis h an OPL on th e on th e minimum pressur e drop acros s 

t he condenser/absorber . 

3. A waive r of the requirement t o establis h an OPL on the 

VES016992 
5 

minimum liqui d feed pressur e a t the condenser/absorber . 

The regulatio n at 40 C.F.R. § 63.1209(o) (3) (iii ) require s source s 

equipped wit h a low energy wet scrubbe r t o establis h an OPL on 

t he minimum liqui d fee d pressur e t o th e wet scrubbe r based on th e 

manufacturer's specifications . Facilitie s must comply wit h th e 

OPL on an hourl y rollin g average . 

E l i Lill y i s requestin g tha t th e requiremen t fo r th e OPL on th e 

minimum liqui d fee d pressur e be waive d a t the condenser/absorber . 

The justificatio n provide d simpl y state s tha t th e 

condenser/absorber i s not th e HC1/C12 contro l device ; th e 

polishin g scrubbe r is . 

U.S. EPA i s denyin g thi s request . Base d on th e bloc k flo w 

diagram of the APCS and furthe r discussion s wit h Mr. Foste r a t 

E l i Lilly , U.S. EPA believe s i t i s likel y tha t ther e i s some HCL 

removal occurrin g a t the condenser/absorber . The HCL i s removed 

throug h the liqui d t o gas interface . Therefor e i t i s appropriat e 

t o establis h an OPL on the on th e minimum liqui d fee d pressur e a t 

t h e condenser/absorbe r t o ensur e a minimum liqui d fee d i s at 

leas t th e amount as durin g the performanc e test . 

4 . A waiver of the requirement t o establis h an OPL on the 

minimum scrubber water pH a t th e condenser/absorber. 

The regulatio n a t 40 C.F.R. § 63.1209(o) (3) (iv ) require s tha t fo r 

wet scrubbers , an OPL must be establishe d on th e minimum pH on an 

hourl y rollin g average as th e averag e pH durin g th e performanc e 

tes t runs . El i Lill y i s requestin g tha t thi s OPL fo r th e 

condenser/absorbe r be waive d becaus e th e Hydro-Sonic scrubbe r i s 

t h e fina l aci d gas contro l device , no t th e condenser/absorber . 

U.S. EPA i s denyin g thi s request . Base d on th e bloc k flo w 

diagram of the APCS tha t was submitted , El i Lill y adds a mixtur e 

of causti c and make-up wate r t o th e APCS at th e 

condenser/absorber , not a t th e Hydro-Soni c scrubber . Therefore , 

i t i s appropriat e t o establis h an OPL on the pH of th e 

caustic/wate r solutio n as i t enter s th e condenser/absorbe r t o 

ensure tha t the pH o f thi s solutio n i s a t leas t tha t of the 

solutio n used durin g th e performanc e test . 

VES016993 
6 

5 . A waiver of the requirement t o establis h an OPL on the 

minimum liqui d to gas rati o oar the minimum liqui d and 

maximum flu e gas flow rates . 

The regulatio n at 40 C.F.R. § 63 .1209 (o) (3) (v) require s source s 

equipped wit h a wet scrubbe r t o establis h an OPL on eithe r the 

minimum liqui d t o gas ratio , o r th e minimum scrubbe r wate r 

flowrat e and the maximum flu e gas flowrat e as an hourl y rollin g 

average based on the average o f th e tes t runs . 

E l i Lill y i s requestin g tha t th e requiremen t fo r thi s OPL be 

waived fo r the condenser/absorber . The justificatio n provide d 

simpl y state s tha t the condenser/absorbe r i s not the HC1/C12 

contro l device ; the polishin g scrubbe r is . U.S. EPA i s denyin g 

t he reques t t o waive thi s OPL. 

Afte r discussio n wit h Mr. Foster , El i Lill y i s now requestin g t o 

s e t th e minimum gas flo w rat e t o the.manufacturer s recommended 

flo w rat e of 937 gpm o r lowe r i f demonstrate d durin g th e CPT. 

U.S. EPA approves El i Lilly' s reques t t o se t th e minimum liqui d 

fee d rat e t o the recommended minimum by the manufacture r o r lowe r 

i f demonstrated durin g the CPT. 

Hydro-Sonic Scrubber 

The coole d and saturate d combustio n gases exitin g the 

condenser/absorber ente r the Hydro-Soni c scrubbe r where 

particulate , includin g metal s and organi c compounds bound t o th e 

particulate , and aci d gases, includin g HCI, ar e removed. As a 

venturi-typ e scrubber , the Hydro-Soni c scrubbe r meets th e 

definitio n of a high-energ y wet scrubbe r under th e HWC MACT. 

The followin g alternativ e monitorin g reques t pertain s t o th e 

Hydro-Sonic scrubbe r specifically . 

6 . An alternativ e OPL fo r the minimum pressur e drop acros s th e 

Hydro-Sonic scrubber. El i Lill y proposes t o establis h an 

alternativ e OPL based on an equivalen t differentia l pressur e 

tha t would be calculate d base d on an equatio n developed by 

t he manufacturer of the Hydro-Soni c scrubber . 

The regulatio n a t 40 C.F.R. § 63.1209 (m) (1) (i ) (A) require s tha t 

Eor source s equipped wit h hig h energ y wet scrubbers , an OPL on 

VES016994 
7 

t he minimum pressur e drop acros s th e scrubbe r on an hourl y 

average be establishe d based on th e average o f the tes t runs 

However, i n the case o f El i Lilly' s Hydro-Soni c scrubber , steam 

i s injecte d i n orde r t o enhance scrubbin g efficiency , but thi s 

causes a reductio n i n the measured pressur e drop acros s the 

scrubber . To take thi s int o account , El i Lill y i s proposin g an 

alternativ e OPL based on the equivalen t differentia l pressur e 

acros s the Hydro-Sonic scrubber . The equivalen t differentia l 

pressur e would be calculate d base d on measured differentia l 

pressur e and the steam fee d rate . El i Lill y propose s t o initiat e 

an automati c waste fee d cutof f when th e rollin g hour average 

equivalen t differentia l pressur e i s les s tha n th e OPL minimum 

equivalen t differentia l pressure . 

E l i Lilly' s experienc e a t it s facilit y i n Kinsale , Ireland , 

suggests tha t the equatio n develope d by Hydro-Soni c Systems fo r 

equivalen t differentia l pressur e i s ver y conservative , and woul d 

lea d t o excessiv e steam usage. U.S. EPA has evaluate d th e model 

from the Kinsale , Irelan d and th e additiona l informatio n provide d 

by Mr. Foste r i n the Octobe r 1, 2003 e-mail . U.S. EPA i s 

approvin g you r reques t t o use th e model wit h th e conditio n tha t 

E l i Lill y maintain s a minimum equivalen t differentia l pressur e o f 

2 5 inches . Thi s equivalen t differentia l pressur e was provide d i n 

t h e supportin g informatio n provide d i n th e supportin g dat a fro m 

Hydro-Soni c Systems and submitte d t o U.S. EPA by Mr. Foster . I f 

E l i Lill y i s stil l intereste d i n lookin g int o developin g a site -

specifi c model, U.S.- EPA wil l conside r th e model, provide d tha t 

E l i Lill y submits al l th e supportin g dat a t o U.S. EPA. El i Lill y 

must involv e U.S. EPA i n th e development of th e model tha t El i 

Lill y shoul d submit fo r U.S. EPA's approva l withi n 240 days fro m 

t h e CPT. 

VES016995 
8 

I f you have any question s about thi s letter , pleas e contac t Sara h 

Marshall , of my staff , 312-886-6797. 

Sincerel y yours , 

George\T. Cze-fitiak, Chie f 

Air^Enforce^ien t ar^d Compliance Assuranc e Branc h 

c c : Phi l Perry , Chie f 

A i r Compliance Branch 

Indian a Department o f Environmenta l Management 

Raymond Schic k 

A i r Compliance Sectio n 

Indian a Department o f Environmenta l Management 

VES016996 
VES016997-017002.pdf