Candidate Conditional Method ZZ: 

Determination of Metal Concentration in CES’ Xact 

CEMS Stilling Chamber Using Filters and Solid 

Sorbents with X-Ray Fluorescence Analysis 

Draft 

June 23, 2005

Prepared for 

U. S. Environmental Protection Agency 

Research Triangle Park, NC 

Prepared by: 

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223
Candidate Conditional Method ZZ: 

Determination of Metal Concentration in CES’ Xact 

CEMS Stilling Chamber Using Filters and Solid 

Sorbents with X-Ray Fluorescence Analysis 

Draft 

June 23, 2005

Prepared for 

U. S. Environmental Protection Agency 

Research Triangle Park, NC 

Prepared by: 

J.A. Cooper, B.E. Johnsen, K. Petterson, 

C. A. Yanca, M. Nakanishi, D. Barth, S. Fry 

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223
Candidate Conditional Method ZZ: 

Determination of Metal Using Filters and Solid 

Sorbents with X-Ray Fluorescence Analysis 

Prepared by:___________________________________ Date:_________

 Douglas C. Barth, Environmental Scientist 

Prepared by: ___________________________________ Date:_________ 

 Cay A. Yanca, Environmental Scientist 

Prepared by: ___________________________________ Date:_________ 

 Krag Petterson, Environmental Scientist 

Reviewed by: ___________________________________ Date:_________ 

 Bruce E. Johnsen, QA Manager 

Approved by: ___________________________________ Date:________ 

 John A. Cooper, Director 
Standard Operating Procedure for the CES XFM: V1.0 Page i of iii

Executive Summary 

Eli Lilly and Company (Lilly) operates a waste incineration system located at the Tippecanoe 

Laboratories in Lafayette, Indiana. This incinerator system includes an Xact multi-metals 

continuous emissions monitoring system (Xact-CEMS, manufactured by Cooper 

Environmental Services, LLC) for demonstrating attainment with the Hazardous Waste 

Combustor MACT for semi-volatile metals, low-volatile metals, and mercury emissions. 

Lilly must conduct an initial performance evaluation test as well as quarterly and annual 

audits to assure the accuracy of the reported results from the CEMS. Lilly has proposed the 

use of a NIST-traceable reference aerosol generator for relative accuracy and linearity 

determinations. In addition, Lilly is also proposing the use of a new sampling and analysis 

reference method for metals to assure the accuracy of the spiked reference aerosol. 

This appendix describes this new sampling and analysis method used in Method 301 tests 

described in the body of this report and proposed for the above noted initial performance 

evaluation test and annual audits of Lilly’s Xact-CEMS. This new method is an X-ray Based 

Filter Method (XFM) that draws a representative sample of incinerator emissions from the 

Xact-CEMS stilling chamber through a series of reactive and non-reactive filters. The filter 

deposits are non-destructively analyzed by X-Ray Fluorescence (XRF) to determine metal 

concentrations in the filter deposits. Metal concentrations in the emissions are calculated by 

dividing the volume of sampled flue gas into the metal mass measured by XRF. 

This method is applicable to the measurement of chromium (Cr), arsenic (As), cadmium 

(Cd), mercury (Hg), and lead (Pb)) in emissions from Lilly’s hazardous waste incinerator. 

Although the XFM is optimized for these elements, it is applicable to other elements 

including: vanadium (V), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), zinc (Zn), 

silver (Ag), antimony (Sb), barium (Ba), thallium (Tl), tin (Sn), bismuth (Bi), cobalt (Co) and 

selenium (Se). The XFM can quantify flue gas concentrations ranging from less than 0.2 to 

over 2000 μg/dscm. 
6/26/2007 1:54 PM Page ii of v 

Table of Contents 

Executive Summary................................................................................................................... i 

List of Symbols........................................................................................................................ iv 

List of Figures............................................................................................................................v 

1.0 Method Summary.......................................................................................................... 1 

1.1 Principle ................................................................................................................ 1 

1.2 Applicability ......................................................................................................... 1 

1.3 Cautions ................................................................................................................ 1 

2.0 Definitions and Abbreviations ...................................................................................... 2 

3.0 Safety ............................................................................................................................ 2 

4.0 Apparatus ...................................................................................................................... 2 

4.1 Overview............................................................................................................... 2 

4.2 Extraction assembly.............................................................................................. 3 

4.3 Extraction flow control module ............................................................................ 3 

4.4 Dilution flow control module................................................................................ 3 

4.5 Sample filter holder assembly............................................................................... 3 

4.6 Sample flow control module................................................................................. 3 

5.0 Reagents and Standards ................................................................................................ 4 

5.1 Filter cassette ........................................................................................................ 4 

5.2 Desiccant............................................................................................................... 5 

5.3 XRF standards....................................................................................................... 5 

6.0 Pre-sample Preparation ................................................................................................. 5 

6.1 Test preparation .................................................................................................... 5 

6.2 Pre-test laboratory preparation.............................................................................. 5 

6.3 Sample train preparation....................................................................................... 5 

7.0 Sample Collection......................................................................................................... 6

7.1 Filter holder leak check......................................................................................... 6 

7.2 Setting total flow needle valve.............................................................................. 6 

7.3 Filter temperature range........................................................................................ 6 

7.4 Evaluation of sample meter accuracy ................................................................... 6 

7.5 Filter cassette installation...................................................................................... 7 

7.6 Sampling ............................................................................................................... 7 
6/26/2007 1:54 PM Page iii of v 

7.7 Sample recovery.................................................................................................... 7 

7.8 Post-test Checks.................................................................................................... 7 

8.0 Sample Recovery, Handling and Preservation.............................................................. 7 

9.0 Elemental Analysis ....................................................................................................... 8 

9.1 Analysis................................................................................................................. 8 

9.2 Calibration............................................................................................................. 8 

10.0 Calculations................................................................................................................... 8 

10.1 Flow Correction Factor......................................................................................... 8 

10.2 XFM Measured Aerosol Concentration................................................................ 9 

11.0 Quality Control ............................................................................................................. 9 

11.1 Sampling ............................................................................................................... 9 

11.2 Analysis................................................................................................................. 9

12.0 Method Performance..................................................................................................... 9 

12.1 Range .................................................................................................................. 10 

12.2 Detection Limits.................................................................................................. 10 

13.0 Pollution Prevention.................................................................................................... 10

14.0 Waste Management..................................................................................................... 10 

15.0 Tables and Figures ...................................................................................................... 10

16.0 References................................................................................................................... 17 
6/26/2007 1:54 PM Page iv of v 

List of Symbols 

e-XFM Ci = Concentration of the ith analyte in the emission measured by the XFM 

PTFE Mi = XRF-determined mass of the ith analyte on the PTFE filter 

REO−7 Mi = XRF-determined mass of the ith analyte on the reactive filter (REO-7)

XFM Vt = Total volume (emission plus dilution) sampled by the XFM 

XFM Vd = Volume of dilution air drawn through filters of the XFM 
6/26/2007 1:54 PM Page v of v 

List of Figures 

Figure 1 Flow diagram of the sampling train used in Phase I and II XFM validation tests. .. 12 

Figure 2: Sample train components used in Phase I and II XFM validation tests.................. 13 

Figure 3: Exploded view of the extraction assembly.............................................................. 14 

Figure 4: Schematic diagram of the extraction flow control module. .................................... 14 

Figure 5: Schematic diagram of the dilution flow control module......................................... 15 

Figure 6: Exploded and assembled view of the sample filter holder...................................... 15 

Figure 7: Schematic diagram of the sampling flow control module....................................... 16 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 1 of 17 

1.0 Method Summary 

1.1 Principle 

A representative sample of flue gas is drawn from an Xact CEMS1

 stilling chamber through a 

cassette containing PTFE and reactive filters. The elements in particulate matter (PM) are 

deposited on the PTFE filter while the vapor phase elements are trapped on the reactive filter. 

The elemental mass in each filter deposit is determined by X-Ray Fluorescence (XRF) using 

EPA IO Compendium Method 3.32

. Metal concentrations in stilling chamber flue gas are 

calculated by dividing the volume of the flue gas sampled into the elemental mass measured 

by XRF. 

1.2 Applicability 

This method is applicable to the measurement of metal aerosol concentrations in the XactCEMS stilling chamber. 

1.2.1 Analytes 

This method is applicable to Antimony (Sb), Arsenic (As), Cadmium (Cd), Chromium (Cr), 

Cobalt (Co), Lead (Pb), Manganese (Mn), Mercury (Hg), Nickel (Ni), and Selenium (Se) and 

is generally appropriate for elements with atomic number from about 13 (Al) through 92 (U) 

as noted in IO Compendium Method 3.32

. This sampling method is also applicable to 

Beryllium (Be), if measured with IO Compendium Method 3.43 after non-destructive XRF 

analysis. 

1.2.2 Interferences 

There are no known flue gas components in their typical concentrations that interfere with 

sample collection. Elemental interferences are addressed in IO Compendium Method 3.32

. 

1.2.3 Concentration Range 

The applicable concentration range of this method is from less than 0.2 μg/dscm (Table 1) to 

over 2000 μg/dscm. 

1.3 Cautions 

This method does not include all of the specifications essential to its performance. Some 

material is incorporated by reference. Therefore, to obtain reliable results, persons using this 

method should have a thorough knowledge of at least EPA Methods 14

 and 25 and EPA IO 

Compendium Method 3.32

. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 2 of 17 

2.0 Definitions and Abbreviations 

Accuracy: The agreement between an experimentally determined value and the true value. 

Aerosol: A suspension of solids and/or liquids in a gas. 

Analyte: A species (element, metal, etc.) of interest in an analytical method. 

Detection Limit: The lowest concentration of an element that can reliably be distinguished 

from a zero concentration. 

Interferant: A substance other than the analyte that causes an undesired positive or negative 

output. 

NIST: U. S. Department of Commerce, National Institute of Standards and Technology6, 

Gaithersburg, MD 20899 

Uncertainty: An indication of the degree of reliability of a value usually expressed 

statistically (probability) as a multiple of the standard deviation of a set of measurements. 

Unless otherwise stated, the uncertainty in a mean value of a series of measurements will be 

the standard deviation. In the case of values based on calculations, the uncertainty in the 

value is equal to the propagated uncertainty based on the uncertainties in the parameters used 

in the calculations. 

3.0 Safety 

This method involves the measurement of hazardous materials and the operation of 

equipment with the potential to cause bodily harm. This test method does not address 

appropriate safety and health practices associated with its use. It is the responsibility of the 

user of this test method to establish appropriate safety and health plans prior to performing 

this method. 

4.0 Apparatus 

4.1 Overview 

The sample collection apparatus used for this method is described in the following 

subsection. The equipment required for the XRF analysis of the filters is specified in IO 

Compendium Method 3.32. 

The sample collection equipment consists of the following five major components (Figure 1 

and Figure 2): 

• Extraction assembly 

• Extraction flow control module 

• Dilution flow control module 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 3 of 17 

• Sample filter holder assembly 

• Sample flow control module 

4.2 Extraction assembly 

The extraction assembly (Figure 3) is used to draw flue gas from the Xact stilling chamber 

through the extraction plate via the extraction flow control module (Subsection 4.3). A subsample of this flow is drawn from the extraction assembly through the probe plate by the 

sample flow control module (Subsection 4.6). A dilution plate is directly downstream of the 

probe plate and the stack gas sample is diluted and mixed with CDA prior to passing through 

the filter holder (Subsection 4.5). 

4.3 Extraction flow control module 

This module (Figure 4) uses an eductor to draw flue gas through the extraction assembly. 

The flow rate is controlled by a standard industrial pressure regulator with gauge and 

powered by compressed CDA. The flue gas is then filtered, dried, and denuded of corrosive 

material before it is exhausted back into the stilling chamber. 

4.4 Dilution flow control module 

The dilution flow control module (Figure 5) dries, cleans, controls, measures and totalizes the 

flow of dilution gas. Clean, dry, compressed air is further dried in this module before it is 

used to dilute the sample flue gas. The dilution gas flow and pressure are controlled with a 

regulator, pressure gauge and a needle valve. The flow rate is measured by a mass flow 

meter (D-MFM). A dilution flow integrator (DFI) totalizes the output from the D-MFM and 

reports the total volume of dilution air that has been added to the gas stream. 

4.5 Sample filter holder assembly 

The sample filter holder assembly (Figure 6) is used to trap particulate and vapor phase 

metals in the emission sample. Two filters are contained within a 37 mm polypropylene 

filter cassette inside the filter holder. The first filter is non-reactive PTFE filter and is used to 

trap particulate phase metals. The second filter is a reactive filter that collects vapor phase 

metals6

. Downstream of the filters, a thermocouple provides temperature information to 

ensure that the filters remain within their optimal temperature range of 100° to 180°F. This 

assembly includes a quick disconnect for use with leak checks. 

4.6 Sample flow control module 

This module (Figure 7) controls the flow rate of diluted flue gas through the filters and 

measures the total sample flow. After passing through the filters, the gas is dried and 

corrosive species removed prior to determining the dry gas flow rate with a mass flow meter. 

4.6.1 Desiccant Dryer 

Downstream of the filter holder, a desiccant dryer is used to remove moisture prior to flow 

measurement. The XFM reports concentrations as mass per dry standard volume. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 4 of 17 

4.6.2 Corrosive Trap 

Following the desiccant dryer, the diluted flue gas is drawn through a corrosive trap designed 

to remove corrosive flue gas species. 

4.6.3 Total Flow MFM 

The total mass flow meter (T-MFM) measures the total flow (1-2 dslpm) passing through the 

filters. This flow meter produces a 4-20 mA signal which is read and totalized by the total 

flow integrator (TFI). The total sample volume is calculated by subtracting the dilution 

volume from the total volume. 

4.6.4 Vacuum Gauge 

A vacuum gauge capable of reporting a vacuum between 0 and 29 in. Hg is used to ensure 

that a vacuum can be maintained in the XFM during leak checks. Monitoring of this gauge 

during sample collection provides continuing quality assurance of vacuum and filter 

integrity. 

4.6.5 Needle Valve 

A needle valve is used for fine control of the total flow rate during sampling. Generally, little 

adjustment of the needle valve is necessary after the initial adjustment to achieve the desired 

flow. 

4.6.6 Two-way Valve 

A manual two-way valve located just upstream of the vacuum pump is used to perform presample leak checks. This valve can also be used as a course flow adjustment to regulate the 

total flow passing through the filter. 

4.6.7 Vacuum Pump 

A diaphragm vacuum pump is used to pull the emission and dilution gas sample through the 

filters. The filtered, cleaned and dried gas sample that passes through the pump is then 

returned to the stack. 

5.0 Materials, Reagents and Standards 

5.1 Filter cassette 

One 37 mm diameter PTFE (Teflo7 or equivalent) and one 37 mm diameter REO-78

 filter for 

trapping particulate and vapor phase metals are required by this method for each run. The 

two filters should be pre-loaded into a labeled 37 mm diameter filter cassette in a clean, dry 

environment prior to the test run. Filter cassettes should be stored in a labeled Petri dish 

before and after sampling. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 5 of 17 

5.2 Desiccant 

The XFM sample dryer requires an indicating desiccant (Agilent Silica Gel Grade 409

 or 

equivalent). A single dryer cartridge may be used for multiple runs as long as the desiccant 

remains below the removal capacity specified by the manufacturer. 

5.3 XRF standards 

XRF thin-film standards for metals of interest should be used to calibrate the XRF prior to 

operation according to IO Method 3.32. Standards should have a known mass per area 

(μg/cm2) to within five percent. 

6.0 Pre-sample Preparation 

6.1 Test preparation 

The complexity of this method is such that, in order to obtain reliable results, both testers and 

analysts must be trained and experienced with the test procedures, including source 

sampling; sample handling; safety equipment and procedures; analytical calculations; 

reporting; and the specific procedural descriptions throughout this method. 

6.2 Pre-test laboratory preparation 

Check filters visually against light for irregularities, flaws, or pinhole leaks. Prior to 

shipping, load one upstream PTFE filter and one downstream REO-7 filter for each run into a 

labeled filter cassette and place into a labeled Petri dish for transport. Provide one loaded 

filter cassette for a QA field blank. 

Before each series of tests, the flow rates for both the total flow and the dilution flow 

integrators should be checked against a certified NIST-traceable meter. The flow reading on 

the integrator should be within five percent of the reading on the certified NIST traceable 

meter. 

6.3 Sample train preparation 

6.3.1 Sample flow rates and sample time 

Sample and dilution flow rates may range from 0.5 to 1.0 slpm, but should not vary by more 

than ten percent during a test run. Sample time should be between 10 and 50 minutes. 

6.3.2 Extraction assembly and dilution flow module leak checks and sampling rate 

The extraction and dilution assembly must be leak checked prior to mounting on the XactCEMS sampling port. To perform this leak check, cap the port adaptor with a rubber stopper 

and insert the extraction assembly plug (Figure 3). Connect the dilution line for compressed 

air to the dilution plate port and cap the 3/8”extraction plate port. Pressurize the assembly to 

5 psi and close the dilution flow shut-off valve. The gauge reading should be stable (±5%) 

for 30 seconds. Following a successful leak check, remove the stopper and 3/8” cap nut. The 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 6 of 17 

extraction assembly and dilution line can now be mounted on the Xact-CEMS stilling 

chamber sampling port. 

The flow from the Xact-CEMS stilling chamber through the extraction assembly should be 

maintained in the range of 15-30 slpm. The XFM extraction assembly temperature should be 

above 220°F. 

7.0 Sample Collection 

7.1 Filter holder leak check 

A filter holder leak check must be performed after the filter cassette has been loaded in the 

filter holder. To perform this check, seal the filter holder assembly with the filter holder cap 

nut (Figure 6), turn on the pump and allow the vacuum to reach 15 in Hg. Close the sample 

flow shut-off valve (Figure 4), turn off the pump, and record the initial pressure and the 

pressure after 30 seconds. To pass this check, the change in pressure must be less than five 

percent of the initial pressure. Disengage the sampling train quick disconnect to release the 

vacuum (Figure 6). 

7.2 Setting total flow needle valve 

The total flow rate (sample and dilution) that passes through the filter is controlled by a 

needle valve (Figure 7). To determine the needle valve’s initial set point, place a loaded 

blank filter cassette into the filter holder and leak check as stated above. Install the filter 

holder onto the extraction assembly, which is at operating conditions. Open the sample shutoff valve fully and turn on the sample pump. Set the needle valve so that the T-MFM reads 

the desired sampling rate. Then close the shut-off valve and turn off the pump. For each 

sample run, the shut-off valve will be used to start the sampling flow while the needle valve 

should be used to make minor flow adjustments as needed after the sampling has started. 

7.3 Filter temperature range 

Since filter holder temperature can increase at the start of the run, it is recommended that the 

filter temperature be maintained at about 140°F before sampling begins and should not 

exceed 180°F at any time during sampling. 

7.4 Evaluation of sample meter accuracy 

Prior to the first run, the accuracy of the T-MFM should be checked using a NIST-traceable 

flow meter and stack gas. Mount the filter holder containing a filter cassette, attach the NISTtraceable flow meter to the sample flow outlet, turn on the sample pump, open the ball valve 

and allow stack gas to pass through the filter, T-MFM and NIST-traceable meter. Compare 

the T-MFM value to the NIST flow meter. The values should be within five percent. If they 

differ by more than five percent, a correction should be made using the formula in Section 

10.1. Disconnect the NIST flowmeter and place a new filter cassette in the filter holder 

before starting the first sample run. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 7 of 17 

7.5 Filter cassette installation 

For each run, fill out the XFM Field Data Sheet (Table 2), identifying the date, run, operator, 

XFM module I.D. no., and filter I.D. numbers, and date, time, and other data for the test run. 

Insert filter cassette into the filter holder and conduct a filter holder leak check. 

7.6 Sampling 

Prior to sampling, zero the total flow integrator. At a time concurrent with the start of an 

Xact sample run, start the XFM sample pump, open the ball valve, and record the initial 

dilution volume and start time. Sample for 10 to 50 minutes, recording temperatures, 

pressures, and volumes every five minutes. Use the dilution and total flow needle valves to 

ensure that the flow rates are constant and monitor the filter temperature to ensure that it 

remains below 180°F. When sampling is complete, close the shut-off valve, turn off the 

vacuum pump and immediately record the dilution volume, total volume and sample run end 

time on the worksheet. 

Note: It is recommended that a post-test sample flow leak check not be conducted since the 

test may compromise the sample collected on the filter. 

7.7 Sample recovery 

After removing the filter holder from the extraction assembly, disassemble the filter holder 

and remove the filter cassette. Return the filter cassette with filters to the original Petri dish, 

and seal the dish with tape. Do not separate the PTFE and reactive filters from the filter 

cassette. Document any abnormalities on the filter and ship to the appropriate laboratory for 

analysis. 

7.8 Post-test Checks 

The following checks need to be made after the last test run is complete and before packing 

the equipment for return shipment. 

7.8.1 Flow Agreement Check 

Calibration of the dilution and total mass flow meters should be checked following the same 

procedure as in subsection 7.3. 

7.8.2 Extraction assembly and dilution flow module assembly leak checks 

The extraction assembly and dilution flow module leak check should be performed according 

to the same procedures found in subsection 6.3. 

8.0 Sample Recovery, Handling and Preservation 

Open the filter cassettes in a clean work area and note the condition of the filters. Carefully 

remove the filters from the filter cassettes and place each filter sampling side up in a 

separately labeled Petri slide. Filters should be stored in archives at temperatures less than 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 8 of 17 

5°C. The filters remain in archives until they are scheduled for analysis. Following XRF 

analysis the filters may be returned to storage and analyzed again at a later date or they may 

be submitted for analysis for beryllium (Be) according to the procedures outlined in 

Compendium Method IO 3.43

.

9.0 Elemental Analysis 

9.1 Analysis 

The analytical procedures are similar to those in Compendium Method IO-3.32 “Standard 

Operating Procedure for the X-Ray Fluorescence Analysis of PM2.5 Deposits on Teflon 

Filters”. These methods address the application of energy dispersive X-ray fluorescence 

spectrometry (EDXRF) to the determination of elemental composition of particulate matter 

deposits on filters. 

9.2 Calibration 

The X-ray fluorescence analyzer is calibrated using thin film standards of a known 

concentration (usually in μg/cm2). Potential manufacturers of thin film standards are listed in 

Compendium Method IO-3.32

 For each element, a calibration sensitivity factor is obtained by 

dividing the x-ray intensity (counts/sec./mA) by the concentration of the standard (μg/cm2). 

Generally these standards are larger than the area of the exciting X-ray beam while the XFM 

deposition spot is smaller than the beam. For this reason, a thin film to spot ratio must be 

established during calibration. This thin film to spot ratio is determined empirically by using 

a single standard of a known concentration with the same area as the XFM deposition spot. 

This ratio is determined for each analysis condition and is applied to each element in that 

analysis condition. 

10.0 Calculations 

10.1 Flow Correction Factor 

Before each series of tests, the flow rates for both the total integration and the dilution 

integrator should be checked against a certified NIST-traceable meter. The flow reading on 

the integrator ( FFI ) should be within five percent of the reading on the certified NIST 

traceable meter ( FNist ) and recorded in the field notes. If they are not within five percent, the 

noted difference must be used to calculate a correction factor (CFF ) as defined below: 

FI

Nist

F F

F

CF = Equation 1
6/26/2007 XFM for Xact-CEMS SOP V1 Page 9 of 17 

10.2 XFM Measured Aerosol Concentration 

The XFM-determined concentration of the five MACT metals in the sampled flue gas is 

based on a measurement of the metal mass deposited on the XFM filters and the sample 

volume that passed through the filters. The XRF analysis results yield the metal masses in 

μg of each reported metal per filter. The total sample volume is determined by subtracting 

the dilution volume from the total volume. These parameters are used in Equation 2 to 

calculate the concentration of each analyte as shown below: 

XFM

d

XFM

t

REO

i

PTFE

e XFM i

i V V

M M C −+ =

−

−

7

Equation 2

Where: 

e-XFM Ci = Concentration of the ith analyte in the emission measured by the 

XFM (μg/dscm) 

PTFE Mi = XRF-determined mass of the ith analyte on the PTFE filter (μg) 

REO−7 Mi = XRF-determined mass of the ith analyte on the reactive filter 

(REO-7; μg)

XFM Vt = Total volume (emission plus dilution) sampled by the XFM (dscm) 

XFM Vd = Volume of dilution air drawn through filters of the XFM (dscm) 

11.0 Quality Control 

11.1 Sampling 

The sampling quality control requirements include performing all necessary leak checks and 

checking the flow readings against a NIST traceable standard. The following is a list of all 

necessary sampling quality control procedures. 

1. Extraction assembly leak check (See subsection 6.3) 

2. Dilution assembly leak check (See subection 6.3) 

3. Sample filter holder assembly leak check (See subsection 7.1) 

4. Flow calibration check (See subsection 7.3) 

11.2 Analysis 

Quality control and assurance procedures are performed in accordance with Compendium 

IO-3.32

. 

12.0 Method Performance 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 10 of 17 

12.1 Range 

The applicable concentration range is from less than 0.2 μg/dscm to over 2000 μg/dscm. 

12.2 Detection Limits 

The interference free detection limits at the 95% confidence levelError! Bookmark not defined. are 

given in Table 1 assuming a sampling rate of 0.7 slpm and a sampling time of 30 minutes. 

Actual method detection limits are based on actual source sampling and analytical results. If 

required, the method in-stack detection limits can be improved over those shown in Table 1 

by either increasing the stack gas volume sampled, the sample time, or XRF analytical time. 

Increasing the volume sampled by a factor of two results in a corresponding two fold 

increase in the detection limits. XRF detection limits improve with the square root of the 

analysis time. 

13.0 Pollution Prevention 

The exhaust from the sample flow module is vented to the atmosphere after passing through 

the sampling filters, dryer and corrosive gas denuder. There are no reagent solutions 

generated in this method. 

14.0 Waste Management 

Sample filters are archived for one year and then disposed as non-hazardous waste. 

15.0 Tables and Figures 

Table 1: XFM Detection LimitsError! Bookmark not defined.

Element Symbol Analytical 

(ng/spot) 

In-stack 

(μg/dscm) 

Antimony Sb 23.0 2.20 

Arsenic As 1.3 0.12 

Cadmium Cd 13.0 1.2 

Chromium Cr 1.3 0.12 

Cobalt Co 1.3 0.12 

Lead Pb 1.7 0.16 

Manganese Mn 1.3 0.12 

Mercury Hg 2.1 0.20 

Nickel Ni 0.8 0.08 

Selenium Se 1.3 0.12 

Silver Ag 8.4 0.80 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 11 of 17 

Table 2. XFM Field Data Sheet 

Ext

Temp.

Filter

Temp.

Samp. 

Flow

Dil. 

Flow

Flow 

Vac.

Dil. 

Flow 

Pres.

Ext. 

Flow 

Vac.

Ext. 

Flow 

Pres.

Drier

Pres.

°F °F liters liters in. Hg in. Hg in. Hg in. Hg in. Hg

NOTES:

F)Total Test Vol. (E-D)

G) Net Sample Vol. (F-C)

E) Final Total Vol.

D) Initial Total Vol.

C) Dil. Air for Test (B-A)

B) Final Tot. Vol. (Dil. Air)

A) Init. Tot. Vol. (Dil. Air)

Start Time

Stop Time

Operator(s):

Leak Check

Post-test Filter Ev.

Pre-test Filter Eval.

Date

Run No.

XFM Module No.

PTFE Filter No.

REO-7 Filter No.

Time

XFM FIELD DATA SHEET
6/26/2007 XFM for Xact-CEMS SOP V1 Page 12 of 17 

Figure 1 Flow diagram of the sampling train used in Phase I and II XFM validation 

tests. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 13 of 17 

Figure 2: Sample train components used in Phase I and II XFM validation tests. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 14 of 17 

Figure 3: Exploded view of the extraction assembly. 

Figure 4: Schematic diagram of the extraction flow control module. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 15 of 17 

Figure 5: Schematic diagram of the dilution flow control module. 

Figure 6: Exploded and assembled view of the sample filter holder. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 16 of 17 

Figure 7: Schematic diagram of the sampling flow control module. 
6/26/2007 XFM for Xact-CEMS SOP V1 Page 17 of 17 

16.0 References

1 Xact-CEMS. X-ray Based Continuous Emissions Monitoring System for Multi-Metals. 

Manufactured by Cooper Environmental Services, LLC. Portland, OR. 

www.cooperenvironmental.com. 

2 EPA Compendium of Methods for the Determination of Inorganic Compounds in 

Ambient Air. June, 1999. Compendium Method IO-3.3 Determination of Metals in 

Ambient Particulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy. EPA/625/R96/010a. 

3 EPA Compendium of Methods for the Determination of Inorganic Compounds in 

Ambient Air. June, 1999. Compendium Method IO-3.4 Determination of Metals in 

Ambient Particulate Matter Using Inductively Coupled Plasma (ICP) Spectroscopy. 

EPA/625/R-96/010a. 

4 EPA Method 1. Sample and Velocity Traverses for Stationary Sources. 

5 EPA Method 2. Determination of Stack Velocity and Volumetric Flow Rate (Type S Pitot 

Tube). 

6 NIST. National Institute of Standards and Technology. Gaithersburg, Md. 

www.NIST.gov. 

7 Teflo Filter. 2003. Manufactured by Pall Life Sciences Laboratory Filtration and 

Separation Catalog. pp.30-31. 

8 REO-7. Manufactured by Cooper Environmental Services, LLC. Portland, OR. 

www.cooperenvironmental.com. 

9 Agilent Dryer. Manufacturered by Agilent technologie. Found on the web at: 

http://www.chem.agilent.com