9403 SW Nimbus Ave

Beaverton, Oregon 97008

www.cooperenvironmental.com Phone 503-670-8127

Fax 503-624-2120

Cooper Environmental Services, LLC Response to Comments from:

Veolia ES Technical Solutions, LLC

Test America and Focus Environmental, Inc

Coalition for Responsible Waste Incineration

Robert Baxter, B3 Systems

Regarding:

Comments Received In Docket ID: EPA-R05-OAR-2014-0280

Agency: Environmental Protection Agency

Air Pollution Control Title V Permit #V-IL-1716300103-2014-10 (DRAFT)

For Veolia ES Technical Solutions, LLC

Prepared by Andrea Geiger, Krag Petterson, and John Cooper

Cooper Environmental Services, LLC (CES) has reviewed the comments provided by 

Veolia and others commenting on Veolia ES Technical Solutions’ (Veolia) Title V permit 

regarding the use of multi-metal continuous emission monitoring system (CEMS)

technology at the Veolia hazardous waste incinerator (HWI). CES is compelled to 

provide the US Environmental Protection Agency (EPA), for the purposes of placing in 

the public record, additional responses to various comments with the intent of:

 Clarifying technical aspects of the Xact multi-metal CEMS functioning and 

performance,

 Dispelling some inaccuracies and misperceptions that are frequently reported in 

commentary from Veolia and their supporting organizations, and

 Supporting the technical and scientific integrity of CES in the development and 

design of our multi-metals monitoring instrumentation.

It is important to state here, for the record, that CES was not involved in nor attempted 

to influence the development of any requirements in the past or present Title V permit 

for Veolia. Veolia’s comment (VES019536, Page 38) that EPA has “demonstrated bias by 

its collusion with Cooper,” is false and misleading. We would like to make it clear that 

no “collusion” has occurred between the USEPA and CES with regard to the Xact multimetal CEMS. We have provided answers to technical and costing questions posed by 

the USEPA, which is fully in line with any instrumentation company’s efforts in describing 

and detailing the specifications and functionality of their instrument. It is natural that the 

company who invented and developed a technology would be the primary source of 

information with regard to that technology and, by no means, places either the 

company or the regulatory body into a position of faltering morality. 
February 10, 2015 Page 2 of 14

CES had no involvement in the development of the current draft Title V permit or the 

draft permit reopening in 2013. In fact, we were not aware of the multi-metal CEMS 

requirement before the permit’s release for public comment. CES has dedicated 

considerable time and resources towards developing a robust technology for 

measuring multi-metals in various conditions. Our focus has always been, and will 

always be, placed on the development of new technologies for measuring multi-metals 

with the intent of protecting human health and the environment. We have not 

participated in any activities that could be considered unlawful or conspiratorial with 

the sole objective of monetary gain.

Particulate Matter Transport Issues

From our review of comments submitted by Veolia, Test America/Focus Environmental, 

Robert Baxter, Michael Fuchs and others, there are several topics frequently mentioned. 

A majority of the comments discuss the problems associated with particulate matter 

(PM) transport. This is an extremely complex topic, and we would like to include our

input on the available research and our knowledge of the Xact’s performance with 

regard to the following topics:

1. Traverse versus single point sampling 

Several commenters have suggested that single point sampling is not able to collect 

a representative sample, because:

a. Variations in particle density can affect accuracy of single point sampling 

systems.

b. Transporting particulate is different from transporting a gas; PM has 

stratification issues, and the Xact has no way of compensating for PM 

stratification.

c. The Xact CEMS cannot provide results consistent with actual stack gases, due 

to stratification.

To respond to the comment regarding both traverse versus single point sampling and

PM stratification, we refer the EPA to prior work conducted using R&P Tapered Element 

Oscillating Microbalance (TEOMTM) monitors to evaluate PM stratification at various 

points in a Coal-Fired Power Plant (CFPP) emission stream. This series of particulate 

matter measurement studies using paired TEOMs prepared by Edward Burgher and 

Gilles Gonnet in a white paper, detail the lack PM stratification in measured stack 

emissions (accessed through Environmental Technology Online). The goals of the studies 

were to demonstrate and validate the capabilities of the TEOM monitor. The first part of 

the study details the validation of the TEOM monitors through comparison with 

reference methods. The second part of the study evaluated the precision of side-byside monitors, while also evaluating the stratification of particulate matter within a stack

(Burgher and Gonnet, 2004). Two identically configured TEOM systems were installed in 
February 10, 2015 Page 3 of 14

adjacent sampling ports; both single-point and traverse measurements were collected. 

In the single point sampling test, the sampling probes were inserted so that each probe 

nozzle was located at the centermost point of the stack, while the traverse test installed 

and configured the TEOMs to measure PM concentrations at three discreet locations 

along the sample traverse line. Results of the testing conducted in the coal-fired power 

plant emission source demonstrated excellent agreement between the co-located 

TEOM monitors (<8% difference), while also showing the sampling locations to be 

essentially non-stratified with respect to particulate matter. 

The full report is provided as Attachment 1 to our comments, with selected tables and 

graphs provided below. The results of the side-by-side TEOM monitoring are depicted in 

Table 6 and Figures 1 and 2 of the article. To demonstrate the precision of the method, 

Figures 1 and 2 were created using two-minute rolling average mass concentrations for 

each system.

An additional study, performed by Jim Peeler and Laura Kinner with Emissions 

Monitoring, Incorporated, was presented at the 2011 Source Evaluation Society’s 

annual conference (Peeler and Kinney, 2011). This study also compared PM 

measurements collected with traverse and single-point sampling methods and found 

that no stratification was present in the stack measured.
February 10, 2015 Page 4 of 14
February 10, 2015 Page 5 of 14

2. Commentary that particle size issues cause an inability of the Xact to collect a 

representative sample.

CES found conflicting theories from the commenters with regard to measurement issues

caused by particle size.

VES016998 Robert Baxter comments:

“...the Xact is unable to obtain a representative sample and will underestimate the 

larger particles, since those (by being trapped on the transport wall and not in the 

center of the stack) will not be sampled, and enhance the concentrations of smaller 

particles.” Mr. Baxter also claims that the (former) Quantitative Aerosol Generator 

(QAG)

1 “produces particles approximately 1 micron in size or less, which is not 

representative of Veolia’s emissions’ particle size distribution (PSD).” The reasoning Bob 

Baxter uses for claiming that the QAG does not appropriately estimate the size fraction 

present in Veolia’s stack gas is primarily based on stack velocities and the ability of the 

velocities present in Veolia’s stack emissions to transport large particles up to 150 

microns (as opposed to the ~1 micron average particle size produced by an older QAG 

model). Mr. Baxter, however, provides no evidence of the actual particle sizes present

in Veolia’s post-treatment emissions. Veolia’s process conditions may well produce 

larger particles, but those larger particles will be eliminated through use of the multiple 

pollution control systems in place. Multiple sources are available stating the 95% - 99% 

collection efficiencies for baghouse control treatment (Somani, 1998; Honghong Yi, 

2006) and that the particulate sizes in the post-treatment emission stream is made up of 

small particles (<1 μm) (Park et al, 2012; Yi et al., 2006). In addition, prior studies have 

shown that metals showed “proportionally higher concentrations in the submicrometer 

particles compared to total mass.” (A.D. Shendrikar, 1983) While large particles, were 

they present in Veolia’s waste stream, could be carried by the velocities found in 

Veolia’s emissions, it is highly unlikely that, following both spray-drier absorber and 

baghouse treatments, particles over 1 micron would be found. As Mr. Baxter references 

in his commentary, PM particles do “act like a gas” for particles <1 μm) (Mueller 

Environmental Designs, Inc, 2015); therefore, the argument that the Xact would not be 

capable of capturing a representative sample based on underestimating larger 

particles does not apply.

From a physical perspective the majority of toxic metals in flue gas of HWI’s exist as fine 

particles (Donnelly, 1991). Regardless, simply because the stack velocities can support 

up to 150 micron particles does not mean that particles of that size will be present in 

stack emissions following pollution control treatments. A 2012 study published in the

Journal of Aerosol and Air Quality Research investigated the filtration and cleaning 

characteristics of a baghouse filtration system (Park et al., 2012). The purpose of the 

 

1 Note: CES has performed significant development of the QAG in recent years. The QAG now 

has the capability of modulating particle size and particle size distributions, and is being 

developed to replace PS11 at coal-fired power plants.
February 10, 2015 Page 6 of 14

study was to identify the capture efficiency for fine particles before and after baghouse

cleaning procedures; they focused on evaluating collection efficiency for PM size 

fractions ranging from 0.45 to 2.5 microns. The researchers found that as particle size 

decreased, the collection efficiency decreased due to lower impaction effect during 

filtration with a fresh filter; however, there was no difference found in the collection 

efficiency for particles over 0.725 microns during any phase of baghouse filter cleaning 

processes. In other words, Mr. Baxter’s concern that the Xact is not verified to produce 

results relatable to Veolia’s waste stream and particle size is unfounded. Even if particle 

sizes produced from the QAG and transported to the Xact are 1 micron or less, that 

particle size fraction is accurately representative of the fine particles remaining 

following baghouse treatment.

In statements conflicting with those of Bob Baxter concerning the particle size 

distribution likely to be present in Veolia’s stack Test America and Focus Environmental 

state clearly that the particulate emissions from a typical hazardous waste incinerator 

equipped with emissions controls are >99 percent less than one micron in aerodynamic 

particle size (page 8 of Test America’s commentary). Oddly, Test America uses this >99% 

less than 1 micron value to claim that the reason the Xact performed better on previous 

the Coal-Fired Power Plant testing is because the particle sizes at a CFPP are larger, so 

in this case, the better performance of the Xact is due to larger particle sizes, which is in 

direct opposition to the reasoning made by Mr. Baxter. The Xact is able to sample and 

analyze a wide range of particle sizes, and the Xact analytical results for a 

representative sample are not dependent on particle size.

3. Concern over particulate matter buildup on transport walls

Veolia’s comments include a series of figures (Figures 1.1 through 1.4 starting on page 

VES 019552) indicating the possibility of particles accumulating with a large chunk of 

particulate breaking off and depositing on the Xact’s filter tape. There are several 

reasons why this statement is neither accurate nor likely. Firstly, the Xact samples a 

subsample from the full emission stream and then collects another smaller subsample of 

that sample (see schematic in Figure 3). The large chuck of built-up PM on the transport 

wall would have to be extremely well distributed across the entire transport line to have 

the possibility of falsely impacting the Xact’s filter and detector. Secondly, Veolia 

argues that particulate would adhere to the transport wall as the gas cools, which 

would lead to greater PM build up on the transport walls. CES uses a heated transport 

line, so the argument that cooling gas emissions would deposit particulate on transport 

walls is simply not an issue. The temperature of the transport line is approximately 190°C,

which is quite close to the maximum temperature at Veolia prior to pollution controls of 

204-216°C (taken from Veolia’s Draft Title V CAA Permit, Operating Parameter Limits 

table, page 15). The temperature may cool after pollution control treatment, but it will 

not cool (or only cool negligibly) in the Xact’s transport system, see representative 

schematic in Figure 3 below. 
February 10, 2015 Page 7 of 14

Figure 3 – Schematic of Xact 640 Transport and Set Up

The sampling module and transport line of the Xact operate under high temperatures 

to prevent condensation of stack gas. Both the main line and the subsample line are 

continuously heated. The Xact 640 requires external heater controls for ensuring that the 

sample transport line is properly heated. The sample line heater controller must be set to

set to190°C which allows for the transport of oxidized mercury species, as well as 

preventing the condensation of water and acid vapors, as well as reducing the 

likelihood of particulate condensation on the transport line walls. In addition, the Xact 

samples a small subsample from the central flow through the transport line, so the large 

particles that might break or flake off from the transport line’s wall, unlikely as that may 

Roof

Exhaust return to stack

Xact

Stack Heated sample line 100-600 lpm

1 lpm XRF analysis area Filter tape

Probe 190°C
February 10, 2015 Page 8 of 14

be, would be extremely unlikely to have an impact on the concentration reading of the 

Xact. 

4. Commentary that the validation of the Xact with the QAG fails to mimic actual 

stack conditions because the emission aerosols are not physically or chemically 

comparable to the forms used in the QAG aerosol.

Page 2 of Test America & Focus Environmental Inc comments (page 2 of 19): 

“...the Xact® CEMS Method 301 validation using the QAG fails to mimic the 

actual conditions in a hazardous waste incinerator stack gas. The specific 

materials used as standards are inappropriate chemically because they are not 

comparable to the actual chemistry and physical state of the compounds 

required to be measured in the stack gas.

Cooper Environmental Services chose soluble metal nitrates [such as chromium 

nitrate, Cr(NO3)3] to prepare the QAG aerosol solutions. Such easily dissolved 

metal compounds generate a matrix that lends itself favorably to the generation 

of the QAG aerosol. However, the aerosol generated using these easily dissolved 

metal nitrate salts in no way chemically compares to the hard-fired, resilient 

metal oxides compounds [such as chromium oxide, Cr2O3] that normally exit 

combustion systems. Combustion temperatures and oxidative conditions 

produce metal emissions, typically oxides, which are very stable and generally 

insoluble in water without the aid of harsh chemical digestion. These tenacious 

chemical properties pose a formidable challenge to a QAG standard design 

which should use chemicals that are the same as the actual exhaust gas matrix 

chemical species.

To prove the Xact CEMS captures a representative sample and provides an 

accurate analytical result, the QAG generated matrix and the chemical species 

that are sampled should be compositionally the same as an actual stack gas. It 

is irrelevant that the X-ray fluorescence (XRF) technology alone can purportedly 

accurately detect metal concentrations on the proprietary reactive filter tape 

regardless of the matrix. The issue is not the analysis technology, but the sample 

collection.”

As the authors acknowledge, the total metals analysis used in the XRF analysis of the 

Xact is independent of oxidation state, chemical matrix, refractory oxides, or difficult to 

dissolve metal compounds. The form of metal compounds would be significant for an 

analysis method such as inductively coupled plasma – mass spectrometry (ICP-MS), but 

it does not apply to total metals analysis of particulates and vapor-phase metals 

captured on the treated filter media of the Xact, because the metals are neither

removed nor dissolved and XRF uses inner shell electron transition lines to quantify the 

amount of metal, which is entirely separate from chemical compound form.
February 10, 2015 Page 9 of 14

The question then is whether the aerosol created by the nebulization of metals dissolved 

in nitric acid solution behave differently, either chemically or physically, from the metal 

oxides likely to be produced from the incineration process. Table 1 shows the typical 

melting points of various metal oxide species along with the melting points of the 

corresponding nitrate salts. The melting point data for the oxide species reinforces the 

fact that these elements are present principally in the particulate phase at the 

temperatures found in Veolia’s stack emissions. Although chromium and arsenic start 

out as nitrate salts, they will decompose to form the oxides at the temperatures found in 

the QAG and the Xact transport line (Malecki et al, 2003). This means that these 

elements, when spiked are both chemically and physically, identical to the species 

being emitted. In addition, it is clear from the table that both the lead and cadmium 

nitrate species will also be in the particulate phase at the temperatures found in the 

stack. This means that these elements will transport in a manner similar to that of the 

stack emissions for these metals. Finally, since all of the material coming in contact with 

the stack gas in the Xact’s transport line and probe is either Teflon coated metal, Teflon 

tubing, or inert metal tubing (Titanium and Hastalloy), it is simply not reasonable that the 

lead and cadmium nitrate or oxide species will react with any of these components.

After the sample has been transported to the instrument, a small sub-sample is 

withdrawn through a reactive filter tape; however, all of the particulate phase species,

whether emitted by the QAG or sampled from stack effluent, are captured on the filter 

tape via a physical – rather than a chemical - filtration process. The characteristics of 

the filter media are such that greater than 99.9% of all particulates 0.3 μm or larger are 

caught on the tape this means that all of the lead, arsenic, cadmium and chromium,

whether generated by the QAG or coming from the stack, are captured on the filter 

tape via this filtration process.

Mercury is the only species from the table that is present to any degree in the vapor 

phase. Mercuric nitrate melts at 79C and is completely in the vapor phase in the QAG 

aerosol. Mercuric oxide, however, if emitted by the species is not in the vapor phase. If 

mercury is present in the particulate phase in Veolia’s effluent it will transport similarly to 

the other vapor phase species. Additionally if it is in the particulate phase it will also be 

captured by the same physical filtration process as the other metals. If mercury is 

present in the vapor phase (and the use of activated carbon at Veolia to control 

mercury suggests that it is) then the vapor phase mercury generated from the QAG 

tests both the transport and capture of vapor phase mercury. 
February 10, 2015 Page 10 of 14

Table 1. Melting Points of Select Hazardous Metal Oxides and Nitrates

Metal

Melting Point (°C)*

Nitrate Oxide

Cd 360 900-1000

Cr+3 Thermally decomposes to oxide 2432

Pb 470 489

As Decomposes to oxide 274 - 315

Hg 79 500

Appx Temp of Xact 640 Transport Line (°C) 190

Maximum Temp of HWI Gas at Control Device Inlet (°C)^ 204 - 216

Footnotes:

*All information sourced from the CRC Handbook of Chemistry and Physics, 95 ed (accessed online 

01/23/2015), with the exception of Cadmium Oxide, which was sourced from International Programme 

on Chemical Safety and the European Commission (accessed online 01/23/2015)

^ Temperature taken from Draft Veolia Permit No. V-IL-1716300103-2014-10, Operating Parameter 

Limits (420°F for Incinerators 2 and 3 and 399°F for Incinerator 4)

In addition to the melting point data shown 

in table 1 CES has performed additional 

testing to evaluate trapping efficiency using 

the X-Ray Filter Method (XFM). The filters set 

up within the XFM include a particulate filter 

followed by a chemically treated filter for 

capturing vapor-phase metals (see Figure 4, 

below). The results of the XFM testing 

demonstrated that 98% of the total sample 

was present in the particulate form, 

demonstrating that the QAG is producing a 

particulate that can effectively mimic the 

particulate phase present for most metals 

(other than vapor phase mercury). The full 

report is included in Attachment 2.
February 10, 2015 Page 11 of 14

5. Budgetary concerns. Veolia states a number of times that CES keeps “its monetary 

options flexible by including variable cost factors that could be used to increase the 

price” (VES019545, page 47).

CES’ pricing is the same for Veolia as for any other customer. Pricing for the variable 

items, such as transport length to accommodate the location of the CEMS in relation to 

the sample port or the amount of filter tape needed for varying sampling intervals, 

depend greatly on an individual facility’s needs. This type of variability (particularly the 

variability due to sample line length) is not unique to CES’ pricing, and it exists for any 

instrumentation company installing a CEMS at a new facility. It is also important to state 

that CES has offered on at least two occasions (phone call on 12/11/2014 and email on 

1/7/2015) to travel to Veolia’s facility so that we can provide a firm quote, yet these

offers were not accepted. Until an evaluation can be performed to prepare an 

informed quote, any commentary on this topic is purely speculative, and should be 

considered as such.

6. Error in operational description, Test America/Focus Environmental comments, page 

3:

“The XACT® CEMS operates on a repeating 15-minute cycle time. For 

approximately 12 minutes of each cycle, a sample of stack gas is extracted via a 

heated sampling probe and drawn through a filter element. The filter element is 

a proprietary, chemically infused material designed to capture metals. The filter 

element is mounted on a reel similar to tape. After sampling, the filter media is 

advanced on the reel to move the sample to the XRF analyzer and expose fresh 

filter media for the next sampling cycle. The filter media advancement and XRF 

analysis takes approximately 3 minutes.”

CES Response: Although some of the factors described in Test America’s description of 

the Xact technology are partially correct, there are several errors. Firstly, it takes 

approximately between 20 to 45 seconds for the tape to advance from the sampling to 

analysis area (not three minutes). The only time that the Xact pauses in its sampling of 

stack gas is during this advancement period, so a 12 minute sample period with three 

minute advancement time is incorrect. The XRF analysis occurs at the same time and 

for the same duration as the subsequent sample is being collected, it is not performed 

during the sample advancement period, as indicated in the Test America-Focus 

Environmental description. 

7. Commentary regarding the Xact’s ability to collect vapor-phase (elemental)

mercury (Hg°)

Test America/Focus Environmental questions the Xact’s ability to capture vapor phase 

mercury, and suggests that the Xact’s better performance (as compared to Method 

29) is related to the particulate nature of emissions from CFPP. It is well known that the 

majority of mercury emissions issuing from CFPPs is primarily in the vapor phase. Hg 
February 10, 2015 Page 12 of 14

deposition currently estimated using contemporary in-stack speciation estimates show

that Hg0is the dominant form (84 - 88%) (Landis et al. 2014; Edgerton et al., 2002; 

Lohman et al, 2006; EPRI, 2006; Kos et al, 2013; Yee-Lin et al, 2012; Lehigh University ERC, 

2007) 

Test America/Focus Environmental also suggest that CFPPs emissions would contain 

significant amounts of carbon which could behave similarly to activated carbon. 

(Activated carbon is used routinely for controlling mercury emissions.) It seems unclear 

to CES why a CFPP would need to use activated carbon injection pollution control 

systems if there is already carbon entrained in their stack emissions that behaves like 

activated carbon and traps vapor-phase mercury. They claim that it is the affinity for 

mercury to adhere to carbon particles that allows the Hg0to be easily captured by the 

Xact CEMS’ reactive filter media (as a particulate). Test America/Focus Environmental

claim that it is this “phenomenon” that explains the Xact’s better performance for 

mercury capture (when compared to Method 29) for coal-fired units. 

It should be noted that there are no references included with the conjectures 

presented in Test America/Focus Environmental’s commentary, but in our research into 

mercury emissions and stack testing, CFPP have, if anything, a higher percentage of 

vapor-phase mercury in their emissions than HWI’s. They would certainly have a higher 

level of consistent vapor phase mercury, since they do not burn the wide variety of 

waste sources incinerated at Veolia. Multiple reports state that particulate mercury in 

CFPP emissions is less than 1% of the total emissions (Lohman et al., 2006). In an 

extensive search of stack-based mercury testing, CES found no published works

regarding the presence of entrained carbon in CFPP emissions and/or that carbon’s 

ability to absorb Hg°.

CES has performed extensive testing on the ability of the Xact to capture vapor-phase 

mercury. In all tests, elemental mercury trapping efficiency exceeded 99%. We are 

attaching a collection of additional data and reports in support of the Xact’s 

performance with regard to mercury and other candidate method comparisons. This 

information, and others with respect to the Xact’s ability to capture vapor-phase 

mercury, is provided as Attachment 2. In addition, CES refers the reader to the multiple

patents granted to CES for our methods developed to capture vapor-phase mercury

(see Attachment 3).

In closing, CES hopes that this commentary provides additional supporting 

documentation with regard to the contrary claims of Veolia and other commenters. 

Overall, CES requests that EPA focus on the science, technology, and factual history of 

both Veolia and the Xact multi-metal CEMS. We feel it is essential to separate an

industry’s negative response to a requirement for installing a specific monitoring 

instrument from the integrity of the science and technology in developing that 

instrument.
February 10, 2015 Page 13 of 14

Note: Additional commentary and supporting documentation provided with CES’

submittal to Veolia’s Draft Permit # V-IL-1716300103-2014-10 on December 19, 2014.

(USEPA Docket ID EPA-R05-OAR-2014-0280)

Works Cited

A.D. Shendrikar, D. E. (1983). Size-dependent penetration of trace elements through a 

utility baghouse. Atmospheric Environment , 1411-1421.

Anil Somani, S. A. (1998). Airborne Particulate Matter: Pollution Prevention and Control. 

In W. B. Group, Pollution Prevention and Abatement Handbook (pp. 235 - 239). 

Washington D.C.: The International Bank for Reconstruction and Development.

Baxter, Robert, 2014. Evaluation of the Xact Multi-Metal CEMS. December 11, 2014.

Byung Hyun Park, S. B.-H. (2012). Filtration Characteristics of Fine Particulate Matters in a 

PTFE/Glass. Aerosol and Air Quality Research, , 1030-1036.

Donnelly, J. (1991). Metals Emissions Control Technologies for Waste Incineration.

Argonne National Library.

Edgerton E, Hartsell BE, Jansen JJ (2012). Paper presented at Air Quality-III: Mercury, 

Trace Elements, and Particulate Matter; 2002 Sep; Arlington, VA.

Electric Power Research Institute (US). Mercury Chemistry in Power Plant Plumes. 

Environmental Research Program final report. Palo Alto, CA: 2006.

Fuchs, Michael. 2014. Comments by Michael Fuchs on behalf of Veolia ES Technical 

Solutions. L.L.C. on the Draft Title V Permit and the Statement of Basis Dated October 

2014

Geiger, Andrea, Krag Petterson, and John Cooper, 2014. Cooper Environmental 

Services, LLC Comments to United States Environmental Protection Agency, Region 5

Air Pollution Control Title V Permit #V-IL-1716300103-2014-10 (DRAFT). December 19, 

2014.

Kos, G, Ryzhkov, A, Dastoor, A, Narayan, J, Steffen, A, Ariya, PA, and Zhang, L: 

Evaluation of discrepancy between measured and modelled oxidized mercury species, 

Atmos. Chem. Phys., 13, 4839-4863.

Landis MS, Ryan JV, ter Schure, AF, Laudal D. 2014 Nov. The Behavior of Mercury 

Emission from a Commercial Coal-Fired Power Plant: The Relationship between Stack 

Speciation and Near-Field Plume Measurements. Environmental Science and 

Technology 48 (22): 186-191.
February 10, 2015 Page 14 of 14

Lehigh University Energy Research Center (US). Evaluation and Comparison of U.S. and 

EU Reference Methods for Measurement of Mercury, Heavy Metals, PM2.5 and PM10

Emissions from Fossil-Fired Power Plants. Final report. Bethlehem, PA: 2007 Feb.

Lohman K, Seigneur C, Edgerton E, Jansen J. 2006 Jun. Modeling Mercury in Power Plant 

Plumes. Environmental Science and Technology 40(12): 3848-3854.

Malecki, A, B Malecka, R Gajerski, and S Labus, 2003. Thermal Decomposition of 

Chromium(III) Nitrate(V) Nanohydrate Different Chromium Oxides Formation. Journal of 

Thermal Analysis and Calorimetry 72: 135-144.

Mueller Environmental Designs, Inc. (2015, February 4). Fundamentals of Gas 

Solids/Liquids Separation. Retrieved from www.muellerenvironmental.com.

Peeler, James and Laura Kinney. 2011, March. Particulate Matter Instrumental Testing 

for CPT Optimization at a Cement Plant Burning Hazardous Waste and Related PM 

Monitoring Issues. Presented at 35th Conference on Stationary Source Sampling and 

Analysis for Air Pollutants. Tucson, AZ.

Test America (William C. Anderson) and Focus Environmental, Inc (Chris McBride), 2014. 

Viability of the Xact Multi-metal CEMS as a Tractable Instrument for the collection of 

metals data related to HWC MACT compliance standards. December 9, 2014.

Veolia, 2014. Comments of Veolia ES Technical Solutions, LLC to Draft Air Pollution 

Control Title V Permit to Operate, Permit No. V-IL-1716300103-2014-10. December 17, 

2014.

Warchol, Dennis, 2014. Comments and Affidavit of Dennis J. Warchol in Support of 

Veolia ES Technical Solutions, LLC. to Draft Air Pollution Control Title V Permit to Operate, 

Permit No. V-IL-1716300103-2014-10. December 12, 2014.

Yi, Honghong, Jiming Hao, Lei Duan, Xinghua Li, and Xingming Guo, 2006. 

Characteristics of Inhalable Particulate Matter Concentration and Size Distribution from 

Power Plants in China. Journal of Air and Waste Management Association. 56: 1243-

1251.
CEM 2004 

Real Time Measurement Of Particulate At Low Concentration From The 

Emission Of Stationary Source In The Steel And Power Industries Using a 

TEOMTM based Emissions Monitor 

Edward C. Burgher 

Rupprecht & Patashnick Co., Inc., 25 Corporate Circle, Albany, New York 12203 

telephone: 518 452-0065 

fax: 518 452-0065 

email: eburgher@rpco.com 

Gilles Gonnet 

Ecomesure, B.P. 13, F-91640 Briis Sous Forges, France 

telephone: 33 1 6490 5555 

fax: 33 1 6490 5566 

email: ecomesur@aol.com

Abstract 

Historically, measurements of particulate matter emissions from large stationary 

sources to comply with regulatory standards have employed a variety of methods 

depending on local agency requirements. More recently, with the establishment of 

regulatory norms for member states of the European Union, new methods have been 

established to provide a common basis for evaluating emission sources. In the USA, 

measurement of PM in emissions sources must be performed in accordance with 

U.S. EPA Method 5 or, in some cases, Method 17. As with the historical methods 

used in Europe and the USA, one of the newer methods, EN 13284-1 is based on 

filtration of particulate matter from a sample collected in-situ and isokinetically and 

requires the filter to be analyzed in a laboratory. The repeatability of a measurement 

made with any of the manual methods can be influenced adversely by factors 

including handling and transport of the filter, conditioning the filter before and after 

the sampling, and filter weighing. Also, because the measurement using the manual 

methods can only represent the average emission over the time period sampled, 

some important data like transitory concentration, stratification in the duct being 

sampled and the influence of the variation in parameters such as velocity, 

temperature and pressure on the particulate concentration is difficult or impossible to 

determine. Consequently, these limitations prompted customers of Rupprecht and 

Patashnick Company to request the company to develop a new method based on its 

patented Tapered Element Oscillating Microbalance (TEOMTM) technology. 

While this new method, named the TEOM Series 7000 Source Particulate Monitor, 

provides an in-situ measurement collected by filtering source gases at isokinetic 

sampling conditions, the filter handling and weighing processes are completely 

different. A filter is placed on the top of the hollow-tube, oscillating element that is 

housed in a temperature controlled mass transducer assembly. As a carefully 

controlled vacuum is applied to the opposite end of the tapered element, source 

gases are extracted from the stack isokinetically and passed through the filter 

thereby capturing any particulate matter that was entrained in the sample gases. As 

the filter weight increases with the accumulation of particulate matter, the frequency 

of oscillation decreases. The change in frequency can be determined in real-time and 

converted to mass. Tracking mass change with collected sample volume over time 

permits calculation of mass concentration measurements that can be continuously 

reported and/or reported as an average over a user specified time period. The 

1
method also incorporates procedures to dry the sample filter prior to and after the 

test in-situ and to recover any residual particulate matter left in the sample inlet 

during sampling thereby eliminating measurement errors introduced by filter 

handling, transport, etc. The ability of the Series 7000 method to measure and report 

data in real-time, can increase the amount of information available for 

characterization of process or control system variability or for calibration/correlation of 

indirect source measurement techniques such as triboelectric, optical or beta 

attenuation. 

Since it is important to understand the agreement between the different methods, 

and characterize the performance of the new, TEOM-based method this paper 

reports on a series of tests comparing the TEOM Series 7000 method to NF EN 

13284-1 (for low concentration emissions), and NFX 44052 (for high concentration 

emissions). Results of the twelve test runs performed at the steel mill indicate that the 

Series 7000 provides a valid measurement equivalent to the reference methods and 

confirms the conclusion of other laboratories like the TÜV Rheinland who evaluated 

the Series 7000 in 2001. The evaluation also allowed evaluation of the Series 7000 

for calibrating or auditing indirect automatic measuring systems for PM. Results of 

the tests also found that the Series 7000 method is well suited for the calibration of 

continuous measuring system using light scattering, transmissiometry or beta 

attenuation methods. The evaluation also showed that the monitor was robust and 

well adapted to the industrial environment while being easy to use and reliable. 

In a second series of tests, conducted at a large, coal-fired power plant located in the 

mid-western U.S., paired TEOM Series 7000’s were used to evaluate the systems’ 

capacity to make precise, real-time measurements with very short measurement time 

response. This precision evaluation was conducted in conjunction with assessment 

of stratification of a PM emissions source with respect to PM at the stack’s normal 

sampling locations. This series of tests found excellent agreement between in the 

paired Series 7000 trains and showed how the Series 7000 method can be used to 

rapidly provide detailed information regarding stratification in a sampling plane. 

Results indicate that the sampling location would be suitable for installation of a PM 

AMS. 

Keywords: particulate matter, source sampling, stack sampling, real-time isokinetic 

PM measurement 

2
Introduction 

As reported in a paper presented at CEM 2002 [Burgher, 2002], Rupprecht & 

Patashnick Co., Inc. developed a new instrumental method for measuring the 

particulate matter concentration in emission sources. This method, named the 

TEOM® Series 7000 Source Particulate Monitor (“TEOM SPM”), incorporates R&P’s 

patented TEOM technology and significantly enhances the amount of particulate 

matter emissions information that can be achieved from conducting an emissions 

testing program. For instance, when siting particulate matter continuous automatic 

measuring systems (“PM AMS”) it is important that the monitor is installed such that it 

will collect a representative sample regardless of the emission unit operating load. 

Secondly, as currently available PM AMS do not directly measure particulate matter 

mass, it is necessary to establish and verify the PM CEMS monitor accuracy over a 

range of operating conditions using methods such as EN-13284-1, EPA Method 5, 

ISO 9096 or the TEOM Series 7000. 

While TEOM SPM method provides an in-situ measurement collected by filtering 

source gases at isokinetic sampling conditions, as does recognized reference 

methods, the filter handling and weighing processes are completely different. With a 

TEOM SPM, a filter is placed on the top of the hollow-tube, oscillating element that is 

housed in a temperature controlled mass transducer assembly. The mass transducer 

is affixed to the end of a long sample probe that allows the mass transducer to be 

positioned in an emission source. By applying a carefully controlled vacuum to the 

opposite end of the tapered element, source gases are extracted from the stack 

isokinetically and passed through the sample filter. The filter captures any particulate 

matter present in the sample gas stream. As particulate matter accumulates, the filter 

weight increases which results in decreasing the tapered element oscillating 

frequency. The change in frequency can be determined in real-time and converted to 

mass. The result is mass concentration measurements that can be continuously 

reported and/or reported as an average over a user specified time period. Sample 

filter conditioning prior to and after the test can also be accomplished in-situ thereby 

eliminating measurement errors introduced by filter handling, transport, etc. The 

ability of the Series 7000 method to measure and report data in real-time, can 

increase the amount of information available for characterization of process or control 

system variability or for calibration/correlation of indirect source measurement 

techniques such as triboelectric, optical or beta attenuation. 

Since it is important to understand the agreement between the different methods 

used to make source PM emissions measurements, this paper reports on a series of 

tests designed to evaluate the performance of the Series 7000 method in comparison 

to NF EN 13284-1 (for low concentration emissions) and NFX 44052 (for high 

concentration emissions). In the first set of tests conducted by the laboratory LECES 

with the support of Ecomesure, the TEOM SPM method was compared to NF EN 

13284-1 and to NFX 44052 in three different sources at a steel mill. Following the 

methods comparison tests, the Series 7000 was then used to calibrate an opacitybased continuous emissions monitor. 

It is also important that the reference method used to calibrate or audit an automatic 

measuring system for PM be inherently precise regardless of source conditions or 

test operators, etc. For example, while European standards such as EN 14181 and 

U.S. standards such as Performance Specification 11 (PS-11) do not explicitly 

include precision requirements for reference method measurements, the correlation 

of the automatic measurement system to the reference method can be significantly 

influenced by the precision of the reference method measurements. To demonstrate 

the precision of the TEOM Series 7000 method when used in real-world test 

3
conditions, a second series of tests, conducted in the fall of 2003, were devised 

testing to evaluate the precision of method in an emission source produced by a 

coal-fired, power plant. This series of test were also designed to investigate 

particulate matter emissions stratification at two sampling locations normally used for 

emissions permit limit compliance determinations. 

Background - Series 7000 Measurement Theory, Configuration and Operation 

The Series 7000 allows sample collection inside a stack or duct through a filter while 

automatically maintaining isokinetic sampling conditions. The filter is affixed to one 

end of the mass transducer thereby allowing the collected particles to be weighed 

continuously resulting in a real-time measurement of the particle mass concentration. 

The TEOM mass transducer uses a short, straight inlet nozzle tube to isokinetically 

sample the flue gas transporting it just a few millimeters to the filter. The mass 

transducer is a hollow tube, clamped on one end and free to vibrate at the other. An 

exchangeable filter cartridge is place over the tip of the free end. This "tapered 

element" vibrates precisely at its natural resonant frequency. A precise electronic 

counter measures the frequency that has a direct relationship with mass. The 

relationship, expressed below, between mass and frequency can be derived from the 

simple harmonic oscillator equation [Patashnick, et.al, 1991]. 

f2 = K0 / m (1) 

where, f = frequency of oscillation 

K0 = calibration constant 

m = mass 

The calibration constant of the tapered element can be established by measuring the 

frequency of the tapered element with a filter of known mass installed and without a 

filter. Applying the relationship described by equation 1, the value of K0 can be 

calculated as shown below: 

K0 = (m2 - m1) / (1/f22 - 1/f12) (2) 

The tapered element system is constructed using non-fatiguing inert material and 

since K0 is a function of the (non-changing) physical characteristics of the tapered 

element system, the tapered element retains its calibration indefinitely. Once K0 has 

been determined for a particular tapered element, it can be used for mass 

measurements. 

If the element is oscillating at the frequency of fa and has a frequency response of fb 

after an unknown mass is collected on the filter (∆m’), ∆m’ can be obtained as a 

function of fa, fb and Ko using the following equation: 

∆m’ = K0(1/fb

2

 - 1/fa

2

) (3) 

Tracking frequency with time provides the mass rate. When the mass rate is 

combined with the sample flow rate through the filter, mass concentration of the 

sampled gases can be directly calculated and in real-time. During normal operation, 

the temperature of the mass transducer is maintained a few degrees above the stack 

temperature to provide the frequency stability necessary for measurement of very 

small mass changes with high temporal resolution. To automatically control isokinetic 

sampling rates, the system incorporates measurement of source gas velocity, 

temperature and gas density / molecular weight. Velocity is measured with a "S" type 

Pitot tube assembly while the gas temperature is measured with a "K" type 

thermocouple. The gas density / molecular weight determination is provided by 

4
measuring carbon dioxide with a non-dispersive, infrared monitor, oxygen with a 

paramagnetic monitor and moisture using a differential flow technique patented by 

R&P. All of these parameters are measured in real-time and input into the system's 

onboard computer to automatically perform the necessary calculations for computing 

isokinetic sampling rates. This information is then used to set and control the 

sampling rate using a measurement-control feedback loop. 

Case Study 1: R&P TEOM Series 7000 Evaluation in Steel Mill Source 

Emissions 

The major objectives of this study were: 

1. Compare R&P TEOM Series 7000 to the European and French Manual Standard 

Method (FR EN 13284). 

2. Evaluate TEOM 7000 real-time data output, ease of use for conducting emissions 

tests, and investigate capability for generating complete results on-site. 

3. Evaluate TEOM 7000 as a method to calibrate an opacimeter as a PM mass 

emissions monitor. 

A series of twelve test runs in three different sources at a steel mill were conducted 

by the laboratory LECES with the support of Ecomesure to compare the TEOM SPM 

method to NF EN 13284-1 and to NFX 44052. All tests were performed under normal 

operating conditions of each emission unit. One TEOM SPM and one (1) manual 

reference method sampling train were operated such that simultaneous, co-located 

samples were collected. The TEOM SPM was operated in the continuous mode 

following the method instructions that are integrated into the system’s computerized 

operating system. All Series 7000 test measurements and analyses were performed 

on-site. The manual method trains were operated in accordance with the NF 

EN13284-1 procedures. Results of the tests are shown below. 

Table 1 - Agglomeration Plant Test Results 

Dust Concentration (mg/m3) 

Test Run Automatic Method 

(TEOM SPM) 

Manual Method 

(NF EN 13284-1) 

Relative Difference

(%) 

1 79.9 85.5 -6.5 

2 123.1 115 7.0 

3 88.4 101 -12.5 

4 74.4 83.3 -10.7 

Test Average 91.5 96.2 -4.9 

Test Conditions: Ave. stack temperature: 80°C 

Stack diameter: 2 m 

Ave. stack gas velocity 9 m/s 

Table 2 – Coke Oven Test Results 

Dust Concentration (mg/m3) 

Test Run Automatic Method 

(TEOM SPM) 

Manual Method 

(NF EN 13284-1) 

Relative Difference

(%) 

5 3.0 3.5 -14.3 

6 4.0 4.6 -13.0 

Test Average 3.5 4.1 -13.6 

Test Conditions: 

Condition 5: Stack temperature: 35°C 

Stack diameter: 2 m 

Gas velocity: 18 m/s 

5
Condition 6: Ave. stack 

temperature: 

184°C 

Stack diameter: 4 m 

Ave. stack gas 

velocity: 

5.3 m/s 

Table 3 - Electric Arc Furnace Test Results 

Dust concentration (mg/m3) 

Test Run Automatic Method 

(R&P 7000) 

Manual Method 

(EN 13284-1) 

Relative Difference

(%) 

7 6.8 6.0 13.3 

8 56.2 56.9 -1.2 

9 5.4 5.0 8.0 

10 0.9 0.7 28.6 

11 2.1 1.8 16.7 

12 2.2 2.0 10.0 

Test Average 12.3 12.1 1.7 

Test Conditions: Ave. stack 

temperature: 115°C 

Stack diameter: 2.5 m 

Ave. stack gas velocity: 11 m/s 

In a second set of tests conducted at the steel mill on an agglomeration unit, the 

TEOM SPM was used to calibrate two Oldham EP1000 Opacimeters. The Series 

7000 was installed so that the sample extraction points were near the laser path area 

of the EP1000. The number of TEOM SPM sampling points on the sampling traverse 

axis was determined per the procedures specified in EN 13284-1. The duration of 

each TEOM SPM sample point was approximately five (5) minutes per point. 

Following the completion of each sample traverse line, the EP 1000 was adjusted to 

agree with the traverse average reported by the TEOM SPM. This process was 

repeated until the EP 1000 and R&P 7000 agreed. Result of each calibration test run 

are shown in the following tables. 

Table 4 - Agglomerator Stack 1 

Time R&P 7000 

(mg/m^3) 

Oldham EP 1000 

(mg/m^3) 

Temperature

(°C) Humidity (%) 

8:29 to 9:41 42 81 124 4.7 

10:05 to 11:12 31 61 121 8.8 

13:40 to 14:38 58 45 123 4.7 

15:22 to 16:24 53 34 127 5.5 

10:33 to 10:48 37 46 121 6.6 

11:28 to 11:41 28 40 114 10.1 

13:44 to 14:13 43 45 116 6.5 

Table 5 - Agglomerator Stack 2 

Time R&P 7000 

(mg/m^3) 

Oldham EP 1000 

(mg/m^3) 

Temperature

(°C) Humidity (%) 

9:25 to 9:51 11 4 50 4.4 

10:21 to 10:36 14 21 51 4.6 

10:48 to 11:09 10 17 50 4.7 

6
11:22 to 11:45 14 14 51 2.2 

11:56 to 12:45 10 11 52 6.1 

Case Study 2 : Comparison of TEOM SPM to EPA Method 5 and Stratification 

Analysis 

To illustrate the use of the TEOM SPM for conducting stratification studies to support 

siting of particulate matter automatic measurement systems (PM AMS), one set of 

paired train test runs was performed to investigate the degree of stratification in the 

sampling lines normally used for compliance testing. Prior to the stratification test 

runs, a set of paired train tests were conducted with the monitor’s sample probes 

positioned at fixed locations near the center area of the stack for the purposes of 

evaluate the precision of the monitors used for stratification testing. Testing was 

conducted at a utility plant in the Mid-western U.S. that primarily uses a 

subbituminous coal from the Powder River Basin (PRB) in the State of Wyoming. 

During testing, the plant was operating at normal base load conditions. 

For the stratification tests, both TEOM SPM systems were operated in the traverse 

mode following the method instructions that are integrated into the system’s 

computerized operating system. Stack gas velocity and temperature, sample gas 

molecular weight and gas density measurements used for calculation and setting of 

isokinetic sampling rates were determined using the TEOM SPM onboard 

measurement systems. For the precision test, both TEOM SPM systems were 

operated in the continuous mode. Stack gas velocity and temperature and sample 

gas density and molecular weight determinations were also made using the onboard 

measuring systems. All Series 7000 test measurements and analyses were 

performed on-site. 

First, to investigate the precision of the co-located TEOM SPM systems, two 

identically configured TEOM SPM systems were installed in adjacent sampling ports. 

The sample probes were inserted so that the probe nozzles were located at the 

centermost point of the stack as described in EPA Method 1. After each system’s 

sample filter was desiccated to a stable mass, sample collection was started and test 

measurements were taken for approximately 1.5 hours. Care was taken to start and 

end the test period for each monitor simultaneously to minimize the potential for 

temporal changes in the PM emission rate to influence the precision analysis. 

For the second test investigating PM stratification, the monitors were installed and 

configured to measure PM concentrations at three discrete locations along the 

sample traverse lines for each test port. The probes for each monitor were installed 

in the same ports that were used for the co-location test. Sample measurements 

were taken for about 20 minutes at each traverse point for a total test time of 

approximately one hour. As with the precision test, each monitor was programmed to 

start and end sampling at the same time. 

Results from the co-located precision (co-located) test indicate that the difference 

between the two monitors, when located within the centroid area of the stack, is less 

than 8%, on average. Results for the traverse test found close agreement between 

the monitors at all points including the third traverse points were the same points 

used for the precision test. Since the two monitors showed good agreement during 

the fixed sample location test, and again at all three traverse point locations, it can be 

concluded that stratification of particulate matter is not present, at least in the areas 

tested. Results are summarized below in Table 6 and Figures 1 and 2. The charts 

shown in Figures 1 and 2 are constructed using the two-minute rolling average mass 

7
concentration for each system clearly demonstrating the precision of the method 

even for very short term measurements. 

Table 6 - TEOM SPM – Stratification Analysis 

Coal-fired Power Plant – Midwestern U.S.

Test Type Traverse 

Point 

Distance from 

Wall 

(m) 

TEOM SPM 

Unit 20102 

conc. (mg/m3

) 

TEOM SPM 

Unit 20111 

conc. (mg/m3

) 

Rel. % Diff.

Co-located 2.76 21.1 19.6 7.7% 

Traverse 1 0.41 14.83 15.10 -1.8% 

" 2 1.36 14.38 15.22 -5.7% 

" 3 2.76 15.46 15.70 -1.5% 

" Traverse Test Averages 17.54 16.77 4.5% 

Test Conditions: 

Co-located Test: Ave. stack temperature: 160.0°C 

Stack diameter: 9.3 m 

Ave. stack gas velocity: 19.7 m/s 

Traverse Test: Ave. stack temperature: 152.8°C 

Stack diameter: 9.3 m 

Ave. stack gas velocity: 19.0 m/s 

Figure 1 - Fixed Sampling Location (Co-located) Test 

Coal-fired Power Plant Emission Source (Midwest U.S.) 

Precision Analysis

0

5

10

15

20

25

30

35

40

13:33 13:48 14:02 14:16 14:31 14:45 15:00 15:14

Time (hh:mm)

Mass Concentration (mg/m3

)

TEOM SPM Unit 20111

TEOM SPM Unit 20102

8
Figure 2 - Traverse Test

Coal-fired Power Plant Emission Source (Midwest U.S.)

Stratification Analysis

0

5

10

15

20

25

11:05 11:12 11:19 11:26 11:34 11:41 11:48 11:55 12:02 12:10

Time (hh:mm)

Mass Concentration (mg/m3

)

TEOM SPM Unit 20102

TEOM SPM Unit 20111

 Traverse Point 1

Unit 20102 ave. 14.8 mg/m3

Unit 20111 ave. 15.1 mg/m3 

location: 0.41 m from wall

 Traverse Point 3

Unit 20102 ave. 15.5 mg/m3

Unit 20111 ave. 15.7 mg/m3

location: 2.76 m from wall

 Traverse Point 2

Unit 20102 ave. 14.4 mg/m3

Unit 20111 ave. 15.2 mg/m3 

location: 1.36 m from wall

Conclusions 

The evaluation found that the Series 7000 method is well suited for the calibration of 

continuous measuring systems using light scattering, transmissiometry or beta 

attenuation methods. The evaluation also showed that the monitor was robust and 

well adapted to the industrial environment while being easy to use and reliable. 

Results of the test runs performed at the steel mill indicate that the Series 7000 

provides a valid measurement equivalent to the reference methods and confirms the 

conclusion of other laboratories like the TÜV Rheinland who evaluated the Series 

7000 in 2001. The evaluation also showed that the monitor was robust and well 

adapted to the industrial environment while being easy to use and reliable. 

Results of the testing conducted in the coal-fired power plant emission source 

showed excellent agreement between co-located Series 7000 monitors while also 

showing the sampling locations to be essentially non-stratified with respect to 

particulate matter. Furthermore, testing using the Series 7000 found that stratification 

analysis could be conducted very rapidly with high reliability thereby, minimizing 

impacts on plant operations while potentially reducing the overall costs of conducting 

these types of test programs. 

References 

1. Burgher, E. Rupprecht E. “Validation of a TEOM® - based Source Particulate 

Monitor According to European Reference Method prEN13284-1”. Paper 

presented at CEM 2002 Conference 

2. Patashnick, H.; Rupprecht, E. “Continuous PM-10 Measurements Using the 

Tapered Element Oscillating Microbalance”, J. Air Waste Management 

Association 1991, 41, 1079-1083. 

9
Method 301 Eval.: Appendix L V1.0 Page i of iii

Attachment 2:

Additional Reports and Data in Support of Source and Range 

Extension of Candidate Measurement Methods

Xact Series of Monitoring Instruments

X-ray Filter Method (XFM)

Table of Contents

1. Introduction.............................................................................................................. 1

2. Supplemental Testing Of Candidate Methods...................................................... 2

Laboratory Evaluation of XFM Filter Trapping Efficiency...................................... 2

Collection Efficiency Tests at a PGE Coal-Fired Power Plant in Boardman, Oregon

..................................................................................................................... 5

Laboratory Tests to Determine XFM and Xact Holding Times................................ 6

Method 29 Reference Tests of the Xact at the Toole Army Depot: Extension of 

Concentration Range................................................................................. 11

Ontario-Hydro Reference Tests of the XFM Filter Approach at an EPA Sponsored 

Test on A Wet Midwest Coal-Fired Power Plant ..................................... 15

Method 29 Tests of A Mercury Optimized Xact On A Dry Coal-Fired Power Plant 

At The Iowa Army Ammunition Plant ..................................................... 19

Xact Field Blank Evaluation ................................................................................... 22

Test Summary ......................................................................................................... 23

3. Range Extension..................................................................................................... 24

Sampling Conditions............................................................................................... 24

Elemental Applicability........................................................................................... 25

Applicability of Additional Source Categories....................................................... 31

4. Summary................................................................................................................. 36

5. References............................................................................................................... 37
Method 301 Eval.: Appendix L V1.0 Page ii of iii

List of Figures

Figure 1: Experimental arrangement for trapping efficiency tests. .................................... 3

Figure 2: Elemental mercury injection at CFPP. ................................................................ 5

Figure 3: Test Arrangement for XFM Trapping Efficiency at PGE CFPP......................... 5

Figure 4: Round robin results for PM2.5 Speciation program. ............................................ 7

Figure 5: Mercury retention on reactive filter..................................................................... 9

Figure 6: Comparison of Xact and M29 results during May 2002 testing at the TEAD 

production furnace. ......................................................................................... 11

Figure 7: XRF Reanalysis results for Xact filter reel-to-reel approach. ........................... 11

Figure 8: Xact reported lead concentrations vs. EPA Method 29 for AED tests.............. 14

Figure 9: Comparison of lead and nickel concentrations in stack emissions when 20 mm 

rounds are incinerated (August 16, 2003)....................................................... 15

Figure 10: Modified XFM used during Midwest CFPP tests. .......................................... 16

Figure 11: Correlation of XFM with OH during MRI May 2003 tests. ........................... 17

Figure 12: XFM vs. certified mercury concentrations for spike injection........................ 19

Figure 13: Test design for IAAP reference method tests of the mercury Xact................. 20

Figure 14: Nickel precision during Xact-Hg testing......................................................... 22

Figure 15: Percentage of reported Xact concentrations for lead and mercury while 

measuring field blanks. ................................................................................... 22

Figure 16: CES replicate samples for PM2.5 Speciation program..................................... 29

Figure 17: XRF round robin results for EPA’s PM2.5 Speciation program....................... 29

Figure 18: XRF evaluation of NIST standard 987............................................................ 30

Figure 19: XRF evaluations of NIST Standard 1228........................................................ 30

Figure 20. Source applicability for XFM and Xact-IAP................................................... 34
Method 301 Eval.: Appendix L V1.0 Page iii of iii

List of Tables

Table 1 Summary of mercury chloride trapping efficiency tests........................................ 4

Table 2: Elemental mercury trapping efficiency. ............................................................... 6

Table 3: XFM metal concentration Dec. 2004 and April 2005. ......................................... 7

Table 4: Ratio of Hg concentrations to original concentrations. ........................................ 9

Table 5: Evaluation of two year holding times for reactive filters. .................................... 9

Table 6: Xact and Method 29 reported lead concentrations. ............................................ 13

Table 7: Reported XFM and Ontario-Hydro results for MRI May 2003 tests. ................ 17

Table 8: XFM vs. certified spike concentrations. ............................................................. 18

Table 9: XFM precision tests during Phase II testing....................................................... 19

Table 10: Xact-Hg and Method 29 results for IAAP tests................................................ 21

Table 11: Empirically determined Xact detection limits. ................................................. 23

Table 12: Summary of applicability extension tests......................................................... 24

Table 13: Elements analyzed by XRF for EPA’s PM2.5 Speciation program. ................ 28

Table 15: Summary of test results in support of extending filter approach...................... 35
Method 301 Eval.: Appendix L V1.0 Section 1 Introduction Page 1 of 6

1. Introduction

Data presented in the main body of this report demonstrates the ability of the XFM and XactIAP to accurately and precisely quantify metals in stack emissions over a broad range of 

concentrations. Over the past few years, however, Cooper Environmental Services (CES) has 

conducted numerous additional tests of the XFM and Xact approaches. These tests 

demonstrate the applicability of the filter based approach to a wider range of sources and 

sampling conditions. The purpose of this appendix is to present additional test data in support 

of source and range extension for these two candidate methods.

Both the XFM and Xact candidate methods concentrate a representative stack gas sample on 

a reactive filter, measure the flow, determine metal mass using x-ray fluorescence, and report 

concentrations in micrograms per dry standard cubic meter. Several key parameters influence 

the applicability of the filter based approach. These parameters include:

 Elemental Applicability

 Temperature of Filter During Sampling

 Filter Face Velocity

 Sample Times

 Moisture Content of Stack

 Holding Times

 Interferences

 Source and Control Types

 Filter Collection Efficiency

The supplemental tests discussed in this appendix extend the applicability of the candidate 

methods for these key parameters. This appendix will discuss results from the following 

laboratory and field evaluations:

 Laboratory Filter Trapping Efficiency: A series of tests were conducted at CES to 

evaluate the trapping efficiency of the filter under a variety of sampling conditions. 

These tests extend the candidate methods application for of temperatures, flows, and 

concentrations.

 CFPP Filter Trapping Efficiency: Filters were tested for mercury trapping 

efficiency using flue gas from a PGE coal-fired power plant (CFPP) in Boardman, 

Oregon. 

 Holding Times Evaluation: Tests were conducted to evaluate the holding times for 

the XFM and Xact. Both the Filters were spiked with aerosolized mercury and 

analyzed over a 13 month period. For the Xact, results reported during a reference 

Method 29 test, were compared with a laboratory reanalysis of the filter tape 

conducted two months after collection. 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 2 of 6

 Test of the Xact on a Hazardous Waste Combustor: Conducted in 2002, the Xact 

was compared to EPA Method 29 at an army demilitarization incinerator. The tests 

showed the ability of the Xact to measure lead accurately when concentrations were 

above 2000 g/dscm. 

 EPA Tests of the XFM at a Midwest CFPP: CES tested the XFM filter approach 

during an EPA sponsored evaluation of mercury measurement methods at a Midwest 

CFPP that uses wet air pollution control technology (APCT). These tests, conducted 

in July 2003, compared the XFM and the Ontario-Hydro method for mercury 

concentrations between 1 and 6 g/dscm.

 US Army Tests of The Xact at an Iowa CFPP: The U.S. Army sponsored a series 

of tests in January 2005 to evaluate a mercury-optimized Xact at a CFPP that uses dry 

APCT. For the tests, mercury and arsenic were spiked into a stack gas stream and 

measured by both the Xact and Method 29. 

 Lilly Field Blank Evaluation of the Xact: The Lilly Xact, installed on the T149 

hazardous waste incinerator in May 2004, was operated throughout the summer of 

2004. During this time, the Xact completed about 4000 runs while the stack was not 

burning hazardous waste. These runs were treated as field blanks and were used to 

determine Xact detection limits. 

These tests demonstrate the ability of the candidate methods to operate effectively under a 

wider set of conditions and sources than was presented in the body of the report. 

2. Supplemental Testing Of Candidate Methods

Laboratory Evaluation of XFM Filter Trapping Efficiency

2.a.i Test Design for Evaluation of XFM Vapor Phase Metal Trapping Efficiency

The XFM uses a PTFE membrane for collection of particulate metals. The XFM’s 

PTFE filter is an off-the-shelf product (Teflo P/N R2PJ037) and has been shown by the 

manufacturer1to operate efficiently at temperatures of up to 400°F with a capture 

efficiency of better than 99%1for flow rates of up to 17 lpm/cm2. The PTFE membrane 

used by the XFM is operated within these flow rates and temperatures. 

While PTFE is capable of removing particulates, it cannot remove vapor phase metals 

from a flue gas stream. For this reason, the XFM uses a downstream chemically treated 

REO-7 filter to collect vapor phase metals. In the summers of 2000 and 2002, CES 

conducted a series of laboratory tests of the REO-7 filter’s trapping efficiency for 

vapor phase metals. During each test, mercury was aerosolized and passed through an 

XFM filter holder that had been modified to include two REO-7 filters and a 

downstream Carbon Impregnated Filter (CIF) (Figure 1). The CIF acted as a control to 

ensure that Hg did not pass through both treated filters. Upstream of the filter holder, a 

permeation tube containing mercuric chloride (HgCl2) was mounted in a polyethylene 

container and heated in order to spike the mercury into a filtered air stream. This air 

stream was then diluted and drawn through the filters using a diaphragm pump. The 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 3 of 6

capture efficiency was determined by comparing the concentration on the upstream 

filter relative to the downstream filter according to the following equation:

100





d

i

u

i

u

i

i

C C

C

E

Equation 1

Where: 

Ei = Capture Efficiency of the ith element (%)

u Ci = Concentration of the ith element on the upstream filter

u Ci = Concentration of the ith element on the downstream filter

The first series of tests were completed in the laboratory during May 2000 and 

evaluated the filter efficiency for HgCl2. For these tests, a permeation tube was heated 

to about 100oF within the polyethylene container. A few milliliters of filtered ambient 

air were pulled through the container each minute and became saturated with the 

volatilized mercuric chloride. This saturated air was then combined with 5 lpm of 

filtered ambient air in order to dilute the mercuric chloride concentrations to the 

desired range for the test. The total flow passed through about 10 feet of PFA tubing to 

the modified XFM and was measured using a mass flow meter. The filter temperature 

was varied between 100 to 212oF and the sample rate was kept constant at 1 lpm/cm2. 

Mercuric chloride concentrations ranged from 5 to 880 g/dscm.

Figure 1: Experimental arrangement for trapping efficiency tests.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 4 of 6

2.a.ii XFM Mercuric Chloride Trapping Efficiency Results

Results for the mercuric chloride tests are shown in Table 1. In all cases, the mercuric 

chloride trapping efficiency exceeded 99%, and no measurable amount of mercury was 

found on the back-up treated filter or the CIF. This high trapping efficiency was 

independent of sampling time and demonstrated the ability of the filter to capture 

mercuric chloride at temperatures of up to 212oF with concentrations of up to 880 

g/dscm.

Table 1 Summary of mercury chloride trapping efficiency tests.

Sampling Time Mercuric Chloride 

Conc. Filter Temp. Capture Efficiency

(min) g/dscm oF (%)

10 765 185 >98.3

10 748 185 100.0

20 574 185 100.0

15 58 212 >99.7

15 49 212 >99.3

15 48 212 100.0

15 35 212 100.0

15 31 212 >99.6

15 16 212 100

15 5 212 >99.9

15 77 212 100.0

30 881 100 100.0

30 286 100 100.0

30 387 100 100.0

30 258 100 100.0

30 207 100 >99.7

30 121 100 100.0

30 245 100 >99.7

60 46 212 100.0

60 116 212 >99.1

60 117 212 100.0

60 91 212 >99.7

60 32 212 100.0

60 62 212 100.0

60 20 212 >98.3

60 91 212 100.0

60 90 212 100.0
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 5 of 6

Collection Efficiency Tests at a PGE Coal-Fired Power Plant in Boardman, Oregon

2.a.iii Test Design for CFPP Collection Efficiency Tests

PGE owns and operates a 580 megawatt CFPP near Boardman, OR. This plant has a 

cold side ESP for its primary APCT, resulting in a relatively low water content, SO2

concentrations ranging from 205 to 265 PPM, and NOx concentrations between 165 

and 250 PPM. During the summer of 2002, CES conducted a series of tests to evaluate 

the REO-7 filter’s ability to capture elemental mercury in flue gas. In order to 

adequately determine capture efficiency under a variety of mercury concentrations, 

Using a syringe, elemental mercury was sampled from the head space of a temperature 

regulated pool of mercury in a 20-liter container (Figure 2, Figure 3). The mercury was 

then injected into the stack gas sample line prior to the filter housing. The heated filter 

housing contained two of the treated filters followed by a CIF. The spiked flue gas was 

sampled for seven runs while filter temperatures were maintained at 185°F, flow rates 

varied between 0.7 and 3 lpm and sampling times varied between 20 and 60 minutes 

(Table 2). 

Figure 2: Elemental mercury injection at CFPP.

Figure 3: Test Arrangement for XFM Trapping Efficiency at PGE CFPP
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 6 of 6

2.a.iv Results 

As with the laboratory tests, the mercury trapping efficiency exceeded 99%, with no 

measurable Hg found on the back-up REO-7 or CIF. Elemental mercury concentrations 

ranged from 5 to 880 g/dscm. This high elemental mercury trapping efficiency of the 

filters was independent of time or flow rate and demonstrated the ability of the filter to 

capture mercury in flue gas emissions at temperatures of up to 185oF and 

concentrations of more than 300 g/dscm.

Table 2: Elemental mercury trapping efficiency.

Test 

Run 

No.

Test Conditions Results

Temp. Time Flow Flow Trapping Effic. Hgo Conc. Hgo Conc.

°F Min. lpm lpm/cm2 % μg/cm2 μg/m3

1 183 21 1.55 0.52 >99 1.08 100

2 185 20 2.95 0.98 >99 1.25 64

3 185 30 3.03 1.01 >99 1.23 41

4 183 60 0.73 0.24 >99 4.58 314

5 185 60 1.56 0.52 >99 4.06 130

6 184 60 2.22 0.74 >99 4.99 112

7 185 60 3.05 1.02 >99 3.26 53

Laboratory Tests to Determine XFM and Xact Holding Times

The XFM collects particulate metals on an upstream PTFE filter. During the December 

2004 Phase I tests, the PTFE filter had collected Cr, As, Pb, and Cd at concentrations 

ranging from 20 g/dscm to 125 g/dscm. In order to determine PTFE filter holding 

times, CES reanalyzed filters from seven of these tests (Runs 1-4 and 21-24) in April 

2005. During the five months between the initial and second XRF analysis, the filters 

were stored at room temperature in plastic petrie dishes. Both analyses were conducted 

using XRF following the IO Method 3.3 procedure1.

Overall, the metal concentrations measured in April 2005 were within one percent of 

the concentrations determined five months earlier (Table 3). All elements were within 

4% of their original concentration, with no significant bias shown. The good replication 

of the metal mass demonstrates the ability of the PTFE filters to retain metal 

concentrations over a five month period.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 7 of 6

Table 3: XFM metal concentration Dec. 2004 and April 2005.

Cr As Pb Cd Cr As Pb Cd

RUN1T 1.80 1.64 1.79 1.75 1.74 1.63 1.85 1.79 3.5 0.7 -3.4 -2.2

RUN2T 1.59 1.58 1.63 1.70 1.75 1.62 1.75 1.75 -10.3 -2.5 -7.6 -3.3

RUN3T 1.72 1.63 1.73 1.74 1.76 1.65 1.75 1.75 -2.3 -1.2 -0.9 -0.3

RUN4T 2.02 1.87 2.05 2.00 2.00 1.86 1.99 2.00 1.1 0.7 2.7 0.1

RUN 21T 3.69 3.66 3.67 3.66 3.54 3.60 3.74 3.58 4.1 1.7 -2.1 2.4

RUN 22T 3.62 3.65 3.35 3.53 3.26 3.44 3.40 3.45 10.0 5.5 -1.5 2.2

RUN 23T 3.57 3.64 3.14 3.51 3.31 3.41 3.37 3.37 7.2 6.4 -7.3 3.8

RUN 24T 3.72 3.76 3.29 3.64 3.51 3.64 3.62 3.62 5.7 3.2 -10.1 0.3

AVG. 2.72 2.68 2.58 2.69 2.61 2.61 2.68 2.66 2.4 1.8 -3.8 0.4

μg/spot μg/spot

Percent Difference

Cd

Phase I PTFE (Dec 2004)

Sample 

Phase I PTFE (April 2005)

Cr As Pb

2.a.v Evaluation of PTFE Filters for EPA’s PM2.5 Speciation Program

The PTFE filter matrix used by the XFM for stationary sources has also been applied to 

particulate metals determination in ambient air. As one of three authorized laboratories 

for EPA’s PM2.5 Speciation program2, CES has used XRF protocol IO Method 3.3 to 

determine ambient metal concentrations for thousands of samples collected on PTFE 

filters. Since the XFM also uses the same filter matrix as well as IO Method 3.3, the 

holding times for the Speciation Program PTFE filters are applicable to the XFM. 

As part of the Speciation Program, filters that have already been analyzed by CES are 

shipped to other authorized laboratories for blind round-robin audits. Figure 4 shows 

round-robin concentrations for CES relative to the other two authorized laboratories: 

Chester LabNet of Tigard, OR; and RTI of Research Triangle Park, North Carolina. 

The same samples were repeatedly analyzed over a one year period and their high 

correlation and slope approaching 1.0 demonstrate that no measurable loss of 

particulate metals was found during this time. Concentrations shown in Figure 4 are in 

the 0.5 to 7 μg/filter, which would be equivalent to 2-25 μg/dscm for the XFM, similar 

to the expected metal concentrations typically found in stack emissions. For this 

reason, it is believed that the Speciation Program’s results for the PTFE show that the 

XFM PTFE filters can be safely stored for at least 12 months.

XRF Iron Round Robin Results

y = 0.935x + 0.099

R

2

 = 0.998

0

1

2

3

4

5

6

7

8

0 2 4 6 8 CES (μg/filter)

RTI (μg/filter)

XRF Iron Round Robin Results

y = 0.946x + 0.050

R

2

 = 0.998

0

1

2

3

4

5

6

7

8

0 2 4 6 8

CES (μg/filter)

Chester (μg/filter)

Figure 4: Round robin results for PM2.5 Speciation program.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 8 of 6

2.a.vi Holding Times for Reactive Filters

Test Design to Determine Reactive Filter Holding Time

The XFM captures vapor phase metals on the REO-7 filter while the Xact uses the 

PRO-11 filter to capture these metals. The chemical matrices for these two filters are 

identical except for the application of a dopant for trapping of elemental mercury. This 

dopant is added to the REO-7 prior to XFM sampling, but is added to the PRO-11 

during Xact sampling. Following collection of metals, the two filters have identical 

chemistry. For this reason, holding times for vapor phase metals for the PRO-11 are 

considered to be the same as for the REO-7.

Using the same test arrangement shown in Figure 1, CES exposed filters to elemental 

mercury and mercuric chloride. Tests were conducted in June and August 2002 and the 

filters were reanalyzed at three month and six month intervals. CES also repeatedly 

analyzed elemental Hg concentrations on reactive filters that were spiked while 

collecting CFPP flue gas at the Boardman, OR CFPP as discussed in the previous 

section. 

All filters were kept at room temperature and analyzed using IO Method 3.3.

Test Results for Reactive Filter Holding Times

Mercury concentrations were normalized to the XRF results from the original test date 

and are shown in Figure 5 and Table 4. Retention efficiency ranged from 93 to 98% for 

the first six months for both types of mercury and was about the same for the laboratory 

and CFPP filters. Overall, the mercury loss was between 0.3 and 0.8% per month for 

the first six months, within the 5-10% analysis uncertainty in the XRF analysis. For this 

reason, it is believed that the reactive filter holding time for vapor phase metals is at 

least six months and that no correction for Hg loss is needed during this time.

These filters were reanalyzed after two years and were found to have lost about 10% of 

the original mercury (Table 5). This finding was independent of mercury phase or 

laboratory or field application. A linear model was developed which assumes the 

mercury loss from the reactive filter to be constant over time. This model showed that, 

when using a correction factor that assumes a loss of about 0.5% per month, the 

mercury concentrations measured after two years were, on average, within 10% of the 

original mercury concentrations. The good agreement for all of the test types supports 

the use of a correction factor of 0.5% per month for filters that have been archived for 

more than six months. This would allow the holding time to extend to at least two 

years.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 9 of 6

0.00

0.20

0.40

0.60

0.80

1.00

1.20

Lab (Hg) Lab (HgCl2) CFPP (Hg) Ratio to Orig Analysis

Month 3 Month 6

Figure 5: Mercury retention on reactive filter.

Table 4: Ratio of Hg concentrations to original concentrations.

Date HG1 HG2 HG3 HG4 HG5 HG6 AVG

6/6/2002 1.000 1.000 1.000 1.000 1.000 1.000 1.000

11/19/2002 0.979 1.010 0.953 1.015 0.996 0.970 0.987

1/23/2003 0.992 1.063 0.871 0.964 0.930 1.002 0.970

Date AVG.

8/30/2002 1.00

11/19/2002 0.96

1/23/2003 0.93

Date AVG.

8/16/2002 1.00

11/19/2002 1.12

1/23/2003 0.96

1.00

1.11

0.99

1.00

1.14

0.93

1.00

0.98

0.93

CF-HG-1 CF-HG-2

Laboratory (Hg°)

CFPP (Hg°)

Laboratory (HgCl2)

HgCl2-1

1.00

0.93

0.92

HgCl2-2

Table 5: Evaluation of two year holding times for reactive filters.

Parameter Units

Hg 22 Hg23 Hg13 Hg15 Hg19 Hg21 HgCl2 2 HgCl2 3 815 3T 815 7T

Jun-02 Jun-02 Jun-02 Jun-02 Jun-02 Jun-02 Aug-02 Aug-02 Aug-02 Aug-02

Jul-04 Jul-04 Jul-04 Jul-04 Jul-04 Jul-04 Jul-04 Jul-04 Jul-04 Jul-04

Months month 25.9 25.9 25.9 25.9 25.9 25.9 23.1 23.1 23.6 23.6

Correction Rate % per mo. 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Original Conc. μg/cm2 0.93 0.91 0.91 0.87 0.90 0.91 7.33 14.34 1.23 14.34

Final Conc. μg/cm2 0.89 0.89 0.77 0.80 0.86 0.89 6.95 12.16 1.21 12.16

Final Corrected Conc. μg/cm2 1.02 1.02 0.89 0.93 0.99 1.01 7.07 12.28 1.33 12.28

Final Corr./ Original % 1.11 1.12 0.99 1.07 1.11 1.12 0.96 0.86 1.08 0.86

Filter

Orig Test Date

Final Test Date

Average

Lab (Hg°) Lab (HgCl2

) CFPP (Hg°)

1.08 0.91 0.97

2.a.vii Evaluation of the Impact of Xact Reel-to-Reel Approach

Test Design for Evaluation of Reel-to-Reel Approach

Since the Xact filter matrix is the same as the XFM, the filter tape holding time should 

be the same as the XFM. The Xact tape; however, is collected using a reel-to-reel 

system that wraps the exposed filter back onto a spool. Some potential exists for the 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 10 of 6

metals collected on the tape to be compromised by subsequent samples wrapping 

around the uptake spool. The abrasion would affect particulates to a greater degree than 

vapor phase metals since a higher percentage of the particulates are collected on the 

surface of the tape. For this reason, CES conducted an evaluation of lead particulates 

that had been collected during a field test at a Hazardous Waste Combustor (HWC).

The US Army owns and operates a HWC production furnace at the Tooele Army 

Depot (TEAD) in Tooele, UT. This incinerator is used to destroy outdated ordinance 

including bullets, tracer munitions, and small explosives. Destruction of these 

munitions can produce Pb, Cr, and Cd in the APE-1236 style incinerator stack 

emissions. For this reason, the US Army conducted a series of tests of the Xact in order 

to evaluate its applicability to the TEAD location3.

In May 2002, an early model of the Xact was tested relative to EPA Method 29. During 

these tests, monitored by the Battelle’s Environmental Technology Verification 

program4, the Xact used a PRO-7 tape to concentrate metals, including Pb, that were 

found in emissions from the production furnace. Although the Xact was a prototype, it 

used the same type of tape as the current Xact and had the same reel-to-reel filter tape 

approach. Twelve Method 29 (M29) test runs were conducted by the US Army’s 

Center for Health Promotion and Preventive Maintenance (CHPPM) with 

concentrations varying from 5 to 300 g/dscm for seven metals including As, Cd, Cr, 

Hg, and Pb. The Xact reported 114 samples during this testing which were then 

averaged for the 12 M29 runs.

Following the tests, the filter tape was stored at room temperature at CES. Two months 

after the testing was completed, the 114 sample points on the tape were unwound from 

the spool and reanalyzed for Pb using the CES QuanX XRF analyzer and the results 

were compared to the original concentrations reported by the Xact.

Test Results for Evaluation of Reel-to-Reel Approach

For the field tests, the Xact Pb was in very good agreement with Method 29 with a 

relative accuracy of 4% (Figure 6). Results showed lead concentrations varying from 

20 to more than 150 g/dscm with a correlation between the standard reference method 

and the Xact prototype of better than 0.98. After the tests in the field were completed, 

the filter tape spool was stored for two months and was reanalyzed by a laboratory 

QuanX XRF analyzer during July 2002. The laboratory analysis of the 114 Xact runs 

showed a retention rate of 97 ± 5% for the lead on the filter tape (Figure 7). Since the 

uncertainty of the prototype Xact was on the order of 5%, the results indicate that the 

Xact filter tape approach did not significantly damage the original samples during 

collection or storage.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 11 of 6

M29 vs. Xact Prototype

y = 1.09x - 9.60

R

2

 = 0.98

0

20

40

60

80

100

120

140

160

180

0 50 100 150 200

M29 Pb (μg/dscm)

Xact Pb (μg/dscm)

Figure 6: Comparison of Xact and M29 results during May 2002 testing at the TEAD 

production furnace.

y = 0.9727x + 3.4259

R

2

 = 0.9685

0

20

40

60

80

100

120

140

160

180

0 50 100 150 200

Xact Conc. (μg/m3); May, 2002

Lab Conc. (μg/m3) July, 2002

Figure 7: XRF Reanalysis results for Xact filter reel-to-reel approach.

Method 29 Reference Tests of the Xact at the Toole Army Depot: Extension of Concentration Range 

The Phase I and II tests demonstrated the ability of the Xact to measure concentrations 

ranging from 20 to more than 120 g/dscm. CES, however, has conducted other reference 

Method tests which extend the concentration applicability for the Xact. This section 

discusses Xact testing completed at a HWC for metal concentrations from 0 to more than 

2000 g/dscm.

In 2002, CES was contracted by the US Army’s Ammunition Equipment Directorate (AED), 

located at the Tooele Army Depot (TEAD) in Tooele, Utah, to install the Xact at an AED 

research furnace and assist with a series of tests of new Air Pollution Control Technology. 

This research furnace is of the same design as the one discussed in Section 0, but is used by 

the Army to evaluate changes in incineration and monitoring technologies prior to 

implementing these changes world-wide.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 12 of 6

The research furnace employs the APE 1236 design that includes a rotary furnace, a cyclone, 

oil-fired afterburner, ceramic filter baghouse, and an exhaust stack. The ceramic baghouse 

operates at 750°F and the Xact sampling port is approximately 450°F. Water content is 

typically on the order of 5-10%. The APE 1236 style furnace incinerates small caliber 

munitions up to 20 mm in diameter including fuses and bullets. These munitions have the 

potential to emit chromium, cadmium, barium, lead and other toxic metals. Of these metals, 

lead emissions are the most likely to approach regulatory limits and were the sole focus of 

the reference method test. 

The AED test evaluated the effectiveness of the baghouse approach to reduce lead emissions. 

The baghouse employs a bypass system to allow the baghouse to reach its required operating 

temperature prior to reception of stack gas. Although a valve is used to close off the bypass 

during normal operations, earlier experiments at the production furnace using the Xact 

indicated that the bypass valve might be a considerable source of lead emissions. For the

preliminary tests, the baghouse was allowed to achieve required temperatures and then the 

bypass was disconnected and closed off with flanged plates. Following the sealing of the 

bypass, the lead concentration dropped considerably. It was hypothesized that the valve in 

the bypass was not adequately sealing off the duct work during normal operations. For this 

reason, a more comprehensive test was proposed and the Xact was installed at the AED test 

furnace to provide immediate feedback and comparison data for reference Method 29.

2.a.viii Test Design

Following installation of the Xact, a series of reference method tests were conducted by 

AED to evaluate the effectiveness of alternative Air Pollution Control Technology 

strategies. These tests included an analysis of the impact of temperature changes and an 

evaluation of the lead emissions impact when the bypass for the ceramic baghouse was 

sealed. During testing, the U.S. Army’s Center for Health Promotion and Preventive 

Medicine (CHPPM) conducted fifteen standard EPA method test runs in order to 

determine the Pb concentration. The Xact operated concurrently with these tests 

producing near-real time lead concentration data.

Prior to these tests, the AED incinerator was rebuilt using all new components. The 

first reference method test was conducted prior to incinerating any munitions and acted 

as a blank since no munitions had ever been processed by the newly built furnace. The 

next six test runs conducted by AED were designed to duplicate the typical lead 

concentrations found on other APE1236 furnaces. The first two runs were conducted 

using 50 mm munitions and the next three runs were completed while the incinerator 

processed 20 mm tracers (Table 6). 

After these tests, the bypass was sealed by placing metal plates on both the bypass inlet 

and outlet. The earlier experiments were then repeated while 20 and 50 mm munitions 

were incinerated. CHPPM conducted a total of fifteen tests (tests 1-15) while the Xact 

was used for tests 1-12, 16, and 17. The Xact and M29 were both operating during tests 

1-12.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 13 of 6

2.a.ix Xact and Method 29 Test Results

Lead concentrations in stack emissions for the Xact and Method 29 (M29) tests are 

shown in Table 6. No other elements were measured in significant concentrations by 

either the Xact or M29. In general, the Xact was highly correlated with M29 with an r2

of 1.000 and an intercept of one on a scale of 0 to 2,200 μg/dscm. The Xact showed a 

consistent 5% low bias relative to M29 which is within the M29 uncertainty of 15% 

and the Xact uncertainty of 5%. The relative accuracy of the Xact was 4%, well below 

the suggested 20% RA limit found within proposed Performance Specification 10 for 

Multi-Metal CEMs 5.

A dramatic shift in concentrations was found when the bypass was sealed. The lead 

concentration went from the 1000s range for 50 mm munitions and 100s range for 20 

mm tracers to less than 15 μg/dscm for both types of munitions. Subtracting the M29 

blank bias of 7 μg/dscm found during run 1, resulted in no measurable lead in the stack 

emissions following the sealing of the bypass.

The low lead concentration with the sealed bypass was independent of temperature 

regime or munitions input. Both M29 and the Xact measured arsenic, cadmium, and 

chromium with all reported concentrations below five μg/dscm for both methods. Since 

proposed MACT limits for lead combined with cadmium are in the 240 μg/dscm range 

for existing incinerators, the APE1236 test furnace demonstrated the ability of the high 

temperature baghouse to effectively meet the MACT limits for metal emissions when 

the bypass is sealed. The good agreement of the Xact showed its applicability to metal 

concentrations of more than 2200 g/dscm.

Table 6: Xact and Method 29 reported lead concentrations.

Test 

No. Munitions Type Restricted Bypass

Xact Pb 

Conc.

Method 29 

(CHPPM)*

μg/dscm μg/dscm

1 No Ammo/blank No 0.0 7.1

2 50 mm No 1,406 1,442

3 50 mm No 1,866 1,984

4 20 mm No 213 214

5 20 mm No 135 134

6 20 mm No 55 53

7 50 mm No 2,185 2,321

8 20 mm Yes 4.2 0.5

9 20 mm Yes 1.6 0

10 20 mm Yes 1.1 0

11 20 mm Yes 0.9 1.4

12 50 mm Yes 2.7 0

Blank subtracted based on Test 1.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 14 of 6

Xact vs. Method 29 Lead

y = 0.9445x - 1.0267

R

2

 = 0.9997

0

500

1,000

1,500

2,000

2,500

0 500 1,000 1,500 2,000 2,500

M29 Pb Conc. (μg/dscm)

Xact Pb Conc. (μg/dscm)

Figure 8: Xact reported lead concentrations vs. EPA Method 29 for AED tests.

2.a.x Xact Tests of Other Metals

The AED tests illustrate the value of using a multi-metals CEMS. The Xact also 

measured 15 other metals besides lead, all of which were below detection limits except 

for tin. Method 29 is not authorized to measure Sn and did not measure this nonregulated metal during the test. The Xact, however, found that tin and lead were highly 

correlated for the 20 mm rounds, but that almost no Sn was found when 50 mm rounds 

were incinerated. This correlation for tin and lead can be used to determine the relative 

contribution of the 20 mm munitions to the stack emissions. 

During the August 16, 2002 tests, AED incinerated 20 mm tracers with the 

corresponding positive concentration results for tin. The lead peak observed at noon on 

August 16, 2002, however, was not correlated with a rise in tin (Figure 9). Since no tin 

is associated with the 50 mm munitions, this lead peak was probably caused by 

contamination in the ductwork from the 50 mm rounds incinerated the day before. This 

finding is important since the regulated rate for which munitions can be burned is 

limited by the total lead measured in the emissions while incineration is occurring. 

Had the M29 test been conducted on the morning of August 16th, the projected lead 

emissions rate associated with the 20 mm round would have been high by more than 

40%. That is, almost half of the lead associated with the morning concentrations was 

due to contamination in the ductwork from incineration done the day before. The site 

would be required to operate at almost half of its operating capacity due to the false 

positives for lead due to emissions from the day before.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 15 of 6

0

20

40

60

80

100

120

10:30 AM 11:45 AM 1:00 PM 2:15 PM 3:30 PM 4:45 PM

Lead Conc. (μg/DSCM)

Lead

Tin

Figure 9: Comparison of lead and tin concentrations in stack emissions when 20 mm 

rounds are incinerated (August 16, 2003).

2.a.xi Conclusion

The Xact was moved to the AED site and successfully measured lead relative to 

Method 29. The lead concentrations for these independent tests ranged from less than 

10 to more than 2200 g/dscm. The Xact demonstrated its ability to accurately measure 

metals at these high concentration levels and showed the potential for incorrectly 

associating emissions with waste types when a multi-metals CEMS is not used.

Ontario-Hydro Reference Tests of the XFM Filter Approach at an EPA Sponsored Test on A Wet 

Midwest Coal-Fired Power Plant

2.a.xii Test Design

The Midwest Research Institute (MRI) was contracted by the US EPA to conduct an 

evaluation of Hg measurement approaches at a Midwest CFPP. The tests, which took 

place in two phases (May and August 2003), compared candidate approaches to the 

Ontario-Hydro (OH) reference method6. CES participated in these tests using a 

modified XFM filter holder that was engineered to be placed directly in the stack.

The CFPP consisted of a coal-fired generating unit with state-of-the-art pollution 

controls including an ammonia injection and selective catalytic reduction (SCR) for 

NOx control, a lime spray dryer absorber for SO2 control, and a fabric filter for 

particulate control. These controls resulted in a relatively high water content and low 

SO2 and NOx. Fuel for the facility is coal from the Powder River Basin, Jacob’s Ranch 

site.

A total of twelve OH runs were conducted during the Phase I tests with duplicate trains 

for five of the runs. Two of the five duplicate OH trains, runs 2 and 6, were not within 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 16 of 6

40% of each other and the data was not considered valid. One additional run, Run 8, 

was taken during plant upset conditions with rapidly rising stack temperatures and 

variable mercury concentrations and the OH data was considered to be questionable by 

MRI. The remaining nine runs were considered valid and were used for comparison to 

the modified XFM.

In addition to comparing the XFM to the OH method, the CES filter approach was also 

challenged by injecting elemental Hg directly into the sampling train using mercury 

standards from several Spectra Gas Cylinders. Five spike injection tests were 

conducted with three of these tests occurring while CES operators were not present.

During Phase II, the precision of the XFM was evaluated by using paired sample trains 

with the XFM inlets located within six inches of each other. A total of 11 XFM runs 

were completed during Phase II. Although MRI conducted OH testing during Phase II, 

the XFM was not operated at the same time due to space and time restrictions. 

The XFM used for these tests was modified to be inserted directly into the stack. This 

approach allowed the filter collection efficiency to be challenged while maintaining 

space on the platform for the MRI stack testers. In addition to the filter holder 

modifications, the filter holder was also modified to report oxidized and elemental Hg. 

This allowed the results to be compared to the OH approach and also challenged filters 

used by both the Xact and the XFM. For these tests, the PRO-11 filter was included 

upstream of the XFM REO-7 reactive filter. The PRO-11 filter was used to trap 

oxidized and particulate Hg while the REO-7 was collected the remaining elemental 

Hg. A carbon impregnated filter was placed downstream of these filters to ensure that 

breakthrough was not occurring. (Figure 10). 

Figure 10: Modified XFM used during Midwest CFPP tests.

2.a.xiii Results and Discussion

The XFM results relative to the OH method are shown in the regression plot shown in 

Figure 11 and listed in Table 7. A total of 12 OH runs were conducted with each run 

lasting two hours. For each OH run, two 50 minute XFM samples were collected by 

CES. In general, the XFM and the OH were in very good agreement with a relative 

accuracy of about 11% for the nine valid runs, well within the 20% criteria for 

alternative methods specified by EPA’s proposed Performance Specification 12. Three 

of the 12 OH test runs were omitted from all candidate method comparisons. Runs 2 

and 6 were omitted because of poor OH replication (>40% difference) and run 8 was 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 17 of 6

omitted due to a plant upset and highly variable mercury concentrations. For 11 of the 

12 runs, the total mercury concentration ranged from about one to five μg/m3 with 90% 

in the form of elemental mercury. During run number 8, the stack gas temperatures 

increased significantly, total mercury increased to over 20 μg/m3 and averaged about 

14 μg/m3 during the two hour OH test run. During this upset period, the elemental 

mercury concentration dropped from 4 μg/m3 to 2 μg/m3, but the oxidized mercury 

concentration increased about 300 fold; i.e., from about 0.04 μg/m3 to about 12 μg/m3, 

and represented about 85% of the total mercury. The high correlation (r2 = 0.962) and 

low intercept of the MSC with the OH for the nine valid runs indicates good agreement 

between the two methods.

y = 0.9092x + 0.1501

R

2

 = 0.9615

0

1

2

3

4

5

6

0 1 2 3 4 5 6

OH (μg/dscm)

XFM (μg/dscm)

Figure 11: Correlation of XFM with OH during MRI May 2003 tests.

Table 7: Reported XFM and Ontario-Hydro results for MRI May 2003 tests.

OH MSC

RUN RUN START STOP OXIDa ELEM. TOT. AVG. OH-1 OH-2 AVG. Validb MSC OH % Diff

1A 1-May 13:20 14:15 <0.03 0.74 0.74 >95.9

1B 1-May 14:26 15:19 <0.04 1.42 1.42 >97.2

2A 2-May 10:20 11:11 0.12 2.77 2.89 96.0

2B 2-May 11:20 12:10 <0.08 2.59 2.61 >96.9

3A 2-May 14:41 15:31 0.10 1.63 1.74 94.0

3B 2-May 15:40 16:30 0.19 1.30 1.49 87.4

4A 5-May 10:00 10:50 <0.04 1.38 1.38 >97.1

4B 5-May -- -- -- -- -- NM

5A 5-May 14:10 14:50 <0.05 1.75 1.75 >97.1

5B 5-May 15:00 15:50 <0.04 2.70 2.70 >98.5

6A 6-May 9:28 10:18 <0.04 4.58 4.58 >99.1

6B 6-May 10:27 11:17 <0.04 4.19 4.19 >99.0

7A 6-May 15:27 16:17 <0.04 3.35 3.35 >98.8

7B 6-May 16:26 17:16 <0.04 3.67 3.67 >98.9

8A 7-May 15:21 16:06 19.46 3.62 23.08 15.7

8B 7-May 16:13 17:03 11.80 3.12 14.91 20.9

9A 8-May 9:20 10:10 0.54 4.39 4.93 89.1

9B 8-May 10:17 11:07 0.34 4.22 4.56 92.5

10A 8-May 12:21 13:06 0.29 3.84 4.13 93.0

10B 8-May 13:16 14:06 0.29 4.01 4.30 93.2

11A 9-May 9:22 10:12 0.12 3.41 3.53 96.5

11B 9-May 10:21 11:11 0.18 3.04 3.21 94.5

12A 9-May 13:50 14:40 <0.08 3.57 3.57 >97.8

12B 9-May 14:49 15:39 0.18 4.09 4.27 95.8 -2.4

Percent Hg°

2.6

-3.1

-8.4

-1.6

-1.0

99.1

99.2

3.36

-- Yes

94.1

96.5

99.2

15.2

4.22

3.37

3.92

98.9

99.4

3.88

1.88

5.57

4.14

14.27

4.75

20.3

94.2

99.5

-3.5

-0.3

99.0

98.6

-0.4

-3.5

5.24

4.26

3.35 Yes -3.6

9

10

11

12

5

6

7

8

1

2

3

4

1.33

4.20

1.64

1.50

2.23

4.39

3.51

19.00

1.08

2.75

1.61

1.38

DATE

XFM (μg/dscm)

1.36

1.50

4.26

3.33

3.88

1.29

5.34 3.05

1.64 --

1.50

1.88 --

6.91 4.22

--

4.14 --

14.27 --

Yes

No

Yes

Yes

TIME OH

Yes

Yes

Yes

No

Yes

Yes

5.24 --

a) Includes particulate and vapor phase oxidized Hg 

b) Valid if OH Duplicates < 30% difference

The XFM relative mercury speciation results (% Hg°) were also in excellent agreement 

with the OH results as shown in Table 7. The 12-run average unsigned mean difference 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 18 of 6

in the % Hg° from the two methods was 4.2%. The largest oxidized Hg concentration 

was observed during Run 8 in which the dominating oxidized Hg concentration was 

changing rapidly. In addition, the OH and XFM were both stopped in the middle of the 

run due to the plant upset and the XFM runs covered only 100 of the 120 minutes of the 

OH run during which the mercury concentration was changing rapidly. Thus, the XFM 

clearly demonstrated its responsiveness to changing relative Hg speciation and 

demonstrated a high degree of accuracy in the relative species apportionment.

In addition to the stack tests, a series of runs were made comparing the XFM reported 

concentrations to a direct injection of elemental mercury from a Spectra Gases mercury 

canister (Table 8, Figure 12). The first two tests were conducted using a known 

concentration of 8 μg/dscm with XFM reported concentrations of 8.1 and 8.2 μg/dscm 

respectively. The MSC results are well within the Spectra Gases listed uncertainty of 

20%. Following the initial tests, another series of three blind (unknown) tests were 

conducted by MRI with no CES personnel present. These blind tests used equivalent 

certified concentrations of 8, 19 and 19 μg/dscm respectively with the XFM results 

closely correlated at 8.4, 18.3, and 17.9 μg/dscm. The mean XFM recovery for the three 

blind tests was 98.4% with a standard deviation of 5.4% and a range from 94 to 105%. 

Again, the small percentage difference was well within the listed 20% uncertainty of 

the Spectra canisters. 

Phase II precision results for the modified XFM are shown in Table 9 Since the Phase I tests 

had indicated good agreement with the standard method for the XFM, the July tests were 

limited to a demonstration of the XFM precision relative to the typical OH test run. Overall, the 

XFM reported concentrations ranging from 1.6 to 3.2 g/dscm and had a precision of 21%. 

According to the OH standard operating procedure, the OH has a 34% precision when 

concentrations are less than 3 μg/dscm7. Of the eleven runs, nine were below 3 g/dscm. The 

XFM precision for these runs was 24%, significantly better than the reported OH precision.

Overall, the XFM was able to effectively measure mercury concentrations with a relative 

accuracy of 11% compared to the OH standard reference method. The XFM precision was 

better than the OH for the low concentrations present in the stack and the XFM was able to 

consistently determine concentrations to within 10% of the gas canister standards. Although 

only one OH run was present with significant oxidized mercury concentrations, the XFM

and OH percentages of oxidized mercury were in good agreement for that run.

Table 8: XFM vs. certified spike concentrations.

XFM Std.

μg/dscm μg/dscm

STD. Known 1-May 8.1 8.0

STD. Known 1-May 8.2 8.0

STD. Blind 8-May 8.4 8.0

STD. Blind 8-May 18.3 19.0

STD. Blind 8-May 17.9 19.0

Average

Standard Deviation

Date % Recovery

101.0

Injection Type

102.5

104.6

96.4

94.3

99.8

4.3
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 19 of 6

0

2

4

6

8

10

12

14

16

18

20

1 2 3 4 5 Hg Conc (μg/dscm)

Injected Conc

XFM

Figure 12: XFM vs. certified mercury concentrations for spike injection.

Table 9: XFM precision tests during Phase II testing.

XFM RUN Total (μg/m3) % Diff. XFM RUN Total (μg/m3) % Diff.

1A 2.22 0.4 7A 2.79 14.9 1B 2.21 7B 3.24

2A 2.16

--

8A 2.33 17.5 2B1

-- 8B 2.77

3A 2.87

16.7 9A 2.02 23.0 3B 2.43 9B 2.55

4A 1.57 35.5 10A 1.95 25.0 4B 2.25 10B 2.51

5A 2.10 37.3 11A 2.05 34.6 5B 3.06 11B 2.90

6A 3.29 8.8

6B 3.01

1) Filter was damaged during sampling.

Method 29 Tests of A Mercury Optimized Xact On A Dry Coal-Fired Power Plant At The Iowa Army 

Ammunition Plant

2.a.xiv Test Design for IAAP Tests

The US Army owns and operates a coal-fired boiler at their Iowa Army Ammunition 

Plant (IAAP). CES was contracted by the Army Corp of Engineers to develop and test 

a Hg-optimized Xact in anticipation of the unit being installed at the IAAP8. This unit, 

called the Xact-Hg, uses the same filter technology and XRF analysis approach as the 

multi-metal Xact CEMS, but is simplified to measure only a few elements and has 

XRF analysis conditions designed to improve Hg detection limits. The Xact-Hg was 

installed at the IAAP in January 2005 and was tested against a series of twelve Method 

29 runs on January 10th through the 12th. Dual Method 29 trains were operated by the 

US Army’s Center for Health Promotion and Preventive Medicine (CHPPM) and 

results were reported independently to the Corp of Engineers. Although the unit tested 

at the IAAP was optimized for Hg, the identical filter technology and XRF demonstrate 

the applicability of the Xact approach to CFPP applications. 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 20 of 6

Earlier tests performed by CES indicated that mercury concentrations in the coal were 

below detection limits. For this reason, mercury and arsenic were spiked into the stack 

gas during testing (Figure 13). Arsenic is analyzed under the same conditions as Hg 

and the spiking of As acted as a control. Although the spiking was non-quantitative, it 

was able to consistently produce Hg concentrations between 20 and 40 μg/dscm and As 

concentrations of about 20 μg/dscm. Spiking was conducted using a nebulizer to 

aerosolize a 5% nitric acid solution containing the arsenic and mercury as nitrates. The 

aerosolized metals were dried in a heated chamber where they were combined with 10-

20 lpm of stack gas for a combined flow of about 40 lpm. This flow was conducted 

through a manifold where the majority was extracted by the Xact-Hg and the two M29 

sample trains.

The M29 sample trains used a custom glass lined heat-traced probe and a standard front and 

back half to sample a constant volume for each two hour test. For these tests, the Xact-Hg 

sampling period was 30 minutes and the M29 trains commenced sampling at the start of an 

Xact-Hg run and completed sampling at the end of the fourth Xact-Hg run.

Figure 13: Test design for IAAP reference method tests of the mercury Xact.

2.a.xv Results and Discussion for IAAP Tests

Twelve M29 runs were conducted during the three day test with four runs completed 

each day. The paired M29 trains were in very good agreement with each other with an 

average difference of less than 2%. The Xact-Hg operated in a mechanically sound 

manner for all twelve runs; however, in runs one and two the Xact-Hg energy 

alignment was not completed and the results are not considered valid. The energy 

alignment process, which takes less than 30 minutes for the Xact-Hg and is performed 

automatically by the Xact-IAP, is conducted by introducing a copper standard to the 

detector. The Xact-Hg determines the energy peak for the standard and evaluates if this 
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 21 of 6

peak matches the theoretical energy location (8.046 kV). If a shift has occurred, then 

all of the peaks are realigned to match the copper standard’s peak. Runs three through 

twelve were conducted after the energy alignment and were used for evaluating the 

Xact-Hg accuracy.

Table 10 compares M29 and Xact-Hg results for runs 3 through 12. Overall, the XactHg and M29 were in good agreement for all 10 valid runs with the average XactHg/M29 Hg ratio within 9% and Xact-Hg/M29 As ratio within 13%. 

Performance Specifications 10 and 12 specify that the best nine runs are used to 

determine the accuracy of a candidate approach. The relative accuracy calculation in 

these specifications includes a bias and precision term and requires the tested CEMS to 

be less than 20%. For the IAAP tests, runs 4-12 were used to calculate relative 

accuracy for both mercury and arsenic. The mercury RA was 16.9% and the arsenic 

RA was 16.3%. The good agreement between the candidate method and reference 

method demonstrates the ability of the Xact-Hg to effectively measure mercury and 

arsenic in the IAAP Coal-Fired burner emissions.

The Xact-Hg was consistently about ten percent lower than M29 for both Hg and As. 

M29 results indicated that more than 95% of the mercury was in the “back half” of the 

sample train, suggesting that it was in vapor phase. In contrast, essentially all of the 

arsenic was on the M29 filter which is only capable of capturing particulate phase 

metals. The consistent 10% bias between the Xact-Hg and M29 for both metals 

indicates that the Xact-Hg captured both metals equally and that there is no indication 

of additional bias due to filter trapping inefficiency for the vapor phase mercury. 

In order to evaluate precision and drift, nickel was analyzed with each run (Figure 14). 

The overall precision for the nickel was 1.2% with no observable outliers. The good 

precision of the nickel demonstrates that the Xact-Hg did not have significant problems 

with drift or precision.

Table 10: Xact-Hg and Method 29 results for IAAP tests. 

RUN

MERCURY ARSENIC

M29 Train XACTHG

XACTHG/ M29

M29 Train XACTHG

XACTTrain-1 Train-2 AVG Train-1 Train-2 AVG HG/ M29

1 11.2 10.8 11.0 (a) (a) 24.4 22.2 23.3 (a) (a)

2 22.2 21.8 22.0 (a) (a) 25.0 25.3 25.2 (a) (a)

3 33.6 33.0 33.3 27.4 0.82 27.3 28.5 27.9 20.6 0.74

4 38.4 39.4 38.9 30.5 0.78 25.7 25.3 25.5 20.1 0.79

5 29.2 26.7 28.0 26.1 0.93 20.7 21.4 21.1 18.6 0.88

6 40.9 42.8 41.8 39.0 0.93 24.5 24.2 24.4 22.3 0.92

7 37.5 37.7 37.6 36.4 0.97 19.5 19.4 19.4 16.7 0.86

8 31.1 31.8 31.5 34.7 1.10 19.2 18.8 19.0 17.2 0.91

9 39.0 38.8 38.9 32.7 0.84 19.2 17.1 18.2 16.5 0.90

10 26.9 25.0 25.9 24.4 0.94 21.8 21.1 21.5 18.8 0.87

11 32.5 33.3 32.9 27.1 0.82 21.5 20.6 21.0 19.0 0.90

12 25.0 23.4 24.2 22.2 0.92 18.7 17.9 18.3 16.3 0.89

AVG 33.4 33.2 33.3 30.0 0.91 21.8 21.4 21.6 18.6 0.87
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 22 of 6

a) Runs 1 and 2 were not considered valid due to the Xact-Hg not having proper energy alignment.

0

50

100

150

200

250

1/10

0:00

1/10

12:00

1/11

0:00

1/11

12:00

1/12

0:00

1/12

12:00

1/13

0:00

Nickel Conc. (mass/analysis)

Figure 14: Nickel precision during Xact-Hg testing.

Xact Field Blank Evaluation

Xact analytical detection limits are determined by evaluating XRF analyses of blank filter 

concentrations. After installation of the Lilly Xact at the T149 incinerator, the instrument 

underwent shakedown testing for several months while the stack was either not in operation 

or burning natural gas. This period offered an opportunity to evaluate the Xact blank 

concentrations using actual field data. An evaluation was made using all 3876 Xact samples 

collected at Lilly’s T149 incinerator between July 19th and September 16, 2004. Typical 

results for two representative elements, Pb and Hg are shown in Figure 15 with detection 

limits identified as the 95th percentile value for the field blanks. A summary of all Xact 95th

percentile detection limits is shown in Table 11.

These results are in good agreement with the smaller data set generated during validation 

testing and are, in all cases, more than an order of magnitude below the required limits set by 

the HWC MACT.

Mercury Blank Measurements at T1491 

0

0.5

1

1.5

2

2.5 0-0.01 0.03-0.04 0.06-0.07 0.09-0.1 0.12-0.13 0.15-0.16 0.18-0.19 0.21-0.22 0.24-0.25 0.27-0.28 0.3-0.31 0.33-0.34 0.36-0.37 0.39-0.4 0.42-0.43 0.45-0.46 0.48-0.49 0.51-0.52 0.54-0.55

Concentration (μg/dscm) Percent of Hg

95th Percentile

Lead Blank Measurements at T1491

0

1

2

3

4

5

6 0-0.02 0.06-0.08 0.12-0.14 0.18-0.2 0.24-0.26 0.3-0.32 0.36-0.38 0.42-0.44 0.48-0.5 0.54-0.56 0.6-0.62 0.66-0.68 0.72-0.74 0.78-0.8 0.84-0.86 0.9-0.92 0.96-0.98 1.02-1.04 1.08-1.1

Concentration (μg/dscm) Percent of Pb

95th Percentile

1) 51% of Mercury and 16% of Lead Measurements were reported as 0 and are not listed.

Figure 15: Percentage of reported Xact concentrations for lead and mercury while 

measuring field blanks.
Method 301 Eval.: Appendix L V1.0Section 2 Supplemental Testing Of Candidate Methods Page 23 of 6

Table 11: Empirically determined Xact detection limits.

Elem

Xact Detection 

Limits1 Elem

Xact Detection 

Limits1

g/dscm g/dscm

CR 0.2 AG 4.6

AS 0.1 SB 6.1

CD 2.4 CU 0.4

HG 0.3 FE 0.8

PB 0.5 ZN 0.2

MN 0.2 BR 0.4

CO 0.3 SR 0.3

NI 0.3 TL 0.3

SE 0.1

1) 95% of 3876 Xact blank measurements at T149 Incinerator

Test Summary

A summary of the tests discussed in this appendix is shown in Table 12.
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 24 of 6

Table 12: Summary of applicability extension tests.

Lab Filter 

Trapping 

Efficiency

Trapping 

Efficiency 

at CFPP

CES

 (Hg 

Spike)

Field 

(HgXFM)

Field 

(PbXact)

AED Test of 

Xact at 

Research 

Furnace

EPA XFM 

Tests at a 

Midwest 

CFPP

US Army Xact 

tests at an 

Iowa CFPP

2004 2005 2000 2002 2001 2002 2002 2003 2003 2005 2001-2005

M301 

Test for 

QAG

M301 

Test for 

XFM & 

Xact

>99% 

HgCl2 

trapping 

> 99% 

Elem Hg 

trapping

>95% 

Retent. 

Of Hg

>95% 

Retent. 

Of Hg

>97% 

Retent. 

Of Pb

Xact vs. M29; 

Had RA for Pb 

of 4%

XFM vs. OH; 

Had RA of 

11% for Hg

Xact-Hg vs. 

M29; Had RA 

of <20% for 

Hg, As

NA

As, Cd, 

Cr, Pb, 

Hg

As, Cd, 

Cr, Pb, 

Hg

Particulate 

Metals; Hg Hg Hg Hg Pb Pb Hg Hg, As

XFM and Xact Validated 

for: As, Cd, Cr, Hg, Pb, 

Se, and Ni

XFM/ 

Xact Elem. Hg μg/dscm NM 42-304 20-40 100 NM 1-304 μg/dscm

XFM/ 

Xact Oxid. Hg μg/dscm 5-881 NM 20-40 NM NM 1-881 μg/dscm

XFM oF NA 170 NA 300 NA 185 NA NA 160 NA 200°F in-stack XFM; No 

limit for extractive XFM

XFM oF 170 170 100-212 185 70 185 NA NA 160 NA 212°F

XFM μg/dscm 20-130 20-120 NA NM NA NM NA NA NM NA 20-150 μg/dscm

XFM slpm 1.5 1.5 0.4 0.4 1 0.4 NA NA 0.3 NA 0.3-1.5 slpm

XFM min. 30 30 10-60 20-60 30 20-60 NA NA 50 NA 10-60 min.

XFM days 30 30 30 30 365 365 NA NA 30 NA Up to 365 days

XFM NA NA Wet NA Dry NA Dry NA NA Wet NA Applicable to wet and 

dry APCT

XFM NA NA HWC NA CFPP NA CFPP NA NA CFPP NA Applicable to HWC and 

CFPP.

Xact oF NA 170 NA NA NA NA 450 450 NA 200 Up to 450°F Stack 

Temp.

Xact oF 160 170 NA NA NA NA 180 180 NA 160 135-180°F

Xact μg/dscm 20-130 20-120 NA NA NA NA 20-160 0-2200 NA 9-22 0-2200 μg/dscm

Xact lpm 0.7 0.7 NA NA NA NA 0.8 0.8 NA 0.7 0.6-0.8 slpm

Xact min. 15 15 NA NA NA NA 12 12 NA 30 12-30 min.

Xact days NM NM NA NA NA NA 60 NA NA NM Up to 60 days

Xact NA NA Wet NA NA NA NA Wet Dry NA Wet Applicable to wet and 

dry APCT

Xact NA NA HWC NA NA NA NA HWC HWC NA CFPP Applicable to HWC and 

CFPP.

1) Normalized to XFM flow range of 0.3 cm2

2) Mercury

NM: Not Measured

NA: Not Applicable

HWC or CFPP 

Test

4-40

Summary

NA

Hg 

Conc. 

Range

Elements

1-14

Particulate Metals 

Conc. Range

Flow Range

Stack Temperature

Temp. of Filter 

During Sampling

Particulate Metals 

Conc. Range

Flow Range1

Sample Times

Holding Times

Temp. of Filter 

During Sampling

Wet or Dry Stack 

Chemistry

Wet or Dry Stack 

Chemistry

HWC or CFPP 

Test

Holding Time Eval.

20-130 20-120

Sample Times

Holding Times

Year

Parameter

Stack Temperature

M29 Test Mercury Reference Tests

Summary of Test 

Results Method Units Phase I Tests

Phase II 

Tests

Trapping Efficiency

3. Range Extension

Sampling Conditions

3.a.i Filter Temperature During Sampling

The XFM uses an upstream PTFE filter for collection of particulate metals and a 

downstream REO-7 filter for the trapping of vapor phase metals. The PTFE filter is an 

off-the-shelf product (Teflo P/N R2PJ037) and has been shown by the manufacturer1 

to operate efficiently at temperatures of up to 400°F with a capture efficiency of better 

than 99% for flow rates of up to 17 lpm/cm2. The PTFE membrane used by the XFM is 

operated within these flow rates and temperatures.

Phase I and II XFM tests were conducted with filter temperatures at 170°F and the 

dominant mercury form in the vapor phase. The XFM concentrations were 94% of the 
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 25 of 6

QAG in Phase I and 100% in Phase II, with no indication that the REO-7 filter 

temperature affected capture efficiency. Applicable REO-7 testing extends the 

applicable temperature range to about 185°F. These tests include:

 Mercuric chloride capture efficiency tests conducted in the laboratory at 

temperatures between 100 and 212°F with capture efficiency greater than 99%.

 Elemental mercury capture efficiency tests conducted at the PGE CFPP at 

temperatures up to 185°F. Capture efficiency was greater than 99%.

The Xact PRO-11 filter captures both particulate and vapor phase metals. As with the 

REO-7, the PRO-11 has an efficiency of better than 99% for Particulates9.This filter 

was tested for particulate capture efficiency during the AED bypass evaluation. During 

this reference method test, the filter was operated at 180°F and effectively captured 

particulate Pb at concentrations of up to 2200 g/dscm. 

Mercury was predominantly in the vapor phase during both phases of Method 301 

testing. During Phase I, the Xact filter temperature was 160°F with reported mercury 

concentrations equal to 97% of the QAG predicted. During Phase II, filter temperature 

was 170°F with the Xact at 88% of the QAG predicted mercury concentration. As 

discussed in the main body of this report, the Xact mercury collection efficiency did 

not appear to be affected by temperature during either Phase. Other tests support this 

conclusion including the IAPP tests, where the PRO-11 filter temperature was 160°F 

with good relative accuracy for vapor phase mercury versus Method 29. 

The upper limit for the PRO-11 filter’s vapor phase capture efficiency should be the 

same as the REO-7. The PRO-11 uses the same filter matrix and dopant as the REO-7, 

but is treated with the dopant during sampling instead of being pre-treated. This 

difference should not impact the sampling efficiency of the filter. For this reason, it is 

believed that the PRO-11 filter, like the REO-7 can effectively sample vapor phase 

metals at temperatures of up to 185°F.

3.a.ii Filter Face Velocity

3.a.iii Sampling Times

During Phase I and II, the XFM sampling time was 30 minutes. This time was 

extended to 60 minutes during the laboratory HgCl2 tests and PGE CFPP elemental Hg 

tests. In both cases, the collection efficiency was greater than 99% for concentrations 

of Hg in excess of 300 g/dscm. The XFM was also successfully operated with 50 

minute sampling times during the EPA sponsored tests at the Midwest CFPP with Hg 

in the 1 to 5 g/dscm range.

Elemental Applicability

Phase I and II tests discussed in the main body of this report establish the quantitative ability 

of the XFM and Xact to measure five metals: As, Cd, Cr, Pb, and Hg. The candidate 

methods, however, are also applicable to a wider range of additional metals. This section 
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 26 of 6

discusses relevant regulatory information, tests, and data that are applicable for determining 

the range of metals that can be measured by the XFM and Xact.

3.a.iv Applicability to Beryllium 

The Clean Air Act classifies eleven metals and their compounds as Air Toxics: 

Antimony (Sb), Arsenic (As), Beryllium (Be), Cadmium (Cd), Chromium (Cr), Cobalt

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

These metals have been sorted by volatility in the Maximum Achievable Control 

Technology MACT rules to include:

 Non-enumerated Metal compounds (NM): Sb, Co, Mn, Ni, Se

 Low Volatile Metal compounds (LVM): As, Be, Cr

 Semi-volatile metal compounds (SVM): Pb, Cd

 High Volatile Metals (HVM): Hg

The elements tested in Phase I represented three of the categories: LVM, SVM, and 

HVM. These metals were selected because of their regulatory importance under the 

Clean Air Act’s Maximum Achievable Control Technology (MACT) rules and their 

applicability to XRF. 

Of the eleven air toxic metals, all except Be can be measured with XRF. Although XRF 

is not amenable to quantitative Be determination, it can be expected that this metal 

would be trapped with the same efficiency as the other two LVMs – As and Cr. For the 

Method 301 tests presented in the main body of this report, the candidate methods and 

the QAG reference aerosol were within 8% of each other for both As and Cr with 

concentrations ranging from 20 to 120 g/dscm. These results demonstrated the ability 

of the two filter approaches to quantitatively capture LVMs, and it is expected that the 

XFM and Xact filters would be just as effective at trapping Beryllium. Since XRF is 

non-destructive, the candidate methods’ filters can be reanalyzed by ICP (IO Method 

3.410) or a different analytical approach in order to determine Be concentrations.

3.a.v Applicability to Non-enumerated Metals

In the MACT rules, non-enumerated metals are assumed to have a volatility that is so 

low that they can be correlated with a source’s Particulate Matter (PM) concentration 

and are thus regulated as a part of the PM emissions standard. As such, any approach 

that can quantitatively capture PM and measure these metals should be validated as an 

acceptable method for determination of non-enumerated metals concentrations in 

source emissions. Since all five of the non-enumerated methods can be measured by 

XRF using IO Method 3.311, the key parameter for determining applicability is filter 

trapping efficiency for PM. 

Filter trapping efficiency for PM is a function of pore size, tortuousity, and face 

velocity. The PTFE filter used by the XFM was designed for PM10 and PM2.5

monitoring in aggressive environments and has been found to collect more than 99.8% 

of particles with diameters less than 3 m1. This efficiency will only be improved with 
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 27 of 6

larger particles. Similarly, the PRO-11 filter, with pore sizes of 0.45 m, has been 

found to effectively filter particulates and has a particulate retention efficiency of better

than 99%9.

The quantitative trapping efficiency for the filters used by the candidate methods was 

demonstrated in Phase I and II, where more than 98% of the Pb and Cr were captured 

on the XFM’s upstream PTFE filter. Since PTFE filters are only capable of collecting 

particulate phase metals, it can be concluded that almost all of the Pb and Cr was in the 

particulate phase for these tests. The Xact PRO-11 results were within 7% of the XFM 

PTFE concentrations for both Pb and Cr, and both approaches were within 10% of the 

QAG predicted concentrations. The consistency between the two independent methods 

and the reference aerosol confirmed that both the PRO-11 and PTFE filters have good 

trapping efficiency for particulate metals. For this reason, it is believed that both the 

XFM and Xact-IAP are applicable to the non-enumerated air toxic metals.

3.a.vi Applicability to Other Elements

In addition to the air toxic metals listed above, the XRF filter approach is applicable to 

a number of other elements. XRF can effectively measure elements with an atomic 

number greater than aluminum and, as discussed above, the filters have been shown to 

quantitatively trap particulate metals. The wide range of XRF applicability is illustrated 

by an evaluation of the XRF results for EPA’s PM 2.5 Speciation program.

EPA has developed a monitoring network for collection and evaluation of ambient 

PM2.5 metals. For this program, particulate samples are collected on PTFE filters and 

analyzed for 48 metals by XRF using IO Method 3.3 (Table 13). Four XRF analyzers 

from three laboratories were pre-qualified for the program and were required to 

replicate 10% of their analyses and periodically reanalyze filters from the other labs as 

part of a round-robin program. All three laboratories used IO Method 3.3 for XRF 

analysis. CES, as a participant in this program, analyzed more than 2000 PTFE filters 

and completed more than 200 replicates.

Figure 16 shows the results of the CES replicates for this program for six elements: Si, 

S, K, Ca, Fe, and Zn. In all cases, the slope ranged from 0.99 to 1.01 with correlations 

(r2) greater than 0.99. The concentrations on these filters ranged from 0.1 to 6 g/cm2, 

which would be equivalent to about 4 to 240 g/dscm for the Xact and XFM, 

representative of the concentrations of metals in a typical stationary source. The good 

agreement between these replicates demonstrates the ability of XRF to reproducibly 

quantify a wide-variety of metals over a large concentration range.

The independence of the XRF reproducibility is shown in Figure 17. This figure 

summarizes round robin results for filters analyzed by Cooper Environmental (CPR), 

Chester LabNet of Tigard, OR (770, 771), and Research Triangle Institute of RTP, NC 

(RTI). The slopes for each of the four independent XRF analyzers measured against 

their mean is 1.0 ± 0.05 and their correlations (r2) are greater than 0.99. The filters 

selected for the round-robin test were at least six month old and were rotated to the labs 

for six months as unknowns in order to ensure data integrity. 
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 28 of 6

XRF accuracy is ensured by repeated evaluations of thin-film standards provided by 

NIST. During the PM2.5 Speciation Program, CES reanalyzed two NIST standards 

every three months with the results shown in Figure 18 and Figure 19. These standards 

represent a wide diversity of elements including Si, S, K, Ca, Fe, Zn, Cu, Mn, Co, Si, 

and Al. The XRF percent yield remained within 15% of the NIST assigned 

concentration for the entire two year span for all 11 elements. 

The ability of the divergent labs to reproduce independent results for this wide variety 

of elements and the NIST-traceable nature of XRF demonstrate the applicability of the 

XRF analytical approach to determine concentrations for the 48 elements evaluated in 

the PM2.5 Speciation program.

Table 13: Elements analyzed by XRF for EPA’s PM2.5 Speciation program.

Element Symbol Element Symbol

Sodium Na Chromium Cr

Magnesium Mg Manganese Mn

Aluminum Al Iron Fe

Silicon Si Cobalt Co

Phospohorus P Nickel Ni

Sulfur S Copper Cu

Chlorine Cl Zinc Zn

Potassium K Gallium Ga

Calcium Ca Arsenic As

Scandium Sc Selenium Se

Titanium Ti Bromine Br

Vanadium V Rubidium Rb

Strontium Sr Lanthanum La

Yttrium Y Cerium Ce

Zirconium Zr Samarium Sm

Niobium Nb Europium Eu

Molybdenum Mo Terbium Tb

Silver Ag Hafnium Hf

Cadmium Cd Tantalum Ta

Indium In Tungsten W

Tin Sn Iridium Ir

Antimony Sb Gold Au

Cesium Cs Mercury Hg

Barium Ba Lead Pb
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 29 of 6

Silicon Replicates

y = 1.0209x + 0.0033

R

2

 = 0.9973

y = 1.0066x + 0.0071

 = 0.9975

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0 0.2 0.4 0.6 0.8 1 1.2 1.4

Original (μg/cm2) Replicate (μg/cm2)

Sulfur Replicates

y = 1.0041x - 0.0013

R

2

 = 0.9999

y = 1.0045x - 0.0011

0

1

2

3

4

5

6

7

0 1 2 3 4 5 6 7

Original (μg/cm2) Replicate (μg/cm2)

Potassium Replicates

y = 0.9966x + 0.0003

R

2

 = 0.9953

0

0.05

0.1

0.15

0.2

0.25

0.3

0 0.05 0.1 0.15 0.2 0.25 0.3

Original (μg/cm2) Replicate (μg/cm2)

Calcium Replicates

y = 1.0076x - 2E-05

R

2

 = 0.9981

0

0.1

0.2

0.3

0.4

0.5

0.6

0 0.1 0.2 0.3 0.4 0.5 0.6

Original (μg/cm2) Replicate (μg/cm2)

Iron Replicates

y = 0.9951x + 0.0005

R

2

 = 0.9996

0

0.2

0.4

0.6

0.8

1

1.2

1.4

0 0.2 0.4 0.6 0.8 1 1.2 1.4

Original (μg/cm2) Replicate (μg/cm2)

Zinc Replicates

y = 1.0032x - 0.0001

R

2

 = 1

0

1

2

3

4

5

6

0 1 2 3 4 5 6

Original (μg/cm2) Replicate (μg/cm2)

Figure 16: CES replicate samples for PM2.5 Speciation program.

Figure 17: XRF round robin results for EPA’s PM2.5 Speciation program.
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 30 of 6

NIST-987 Si

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

NIST-987 K

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

NIST-987 Ti

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

NIST-987 Fe

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

NIST-987 Zn

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

NIST-987 Pb

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

Figure 18: XRF evaluation of NIST standard 987.

NIST -1228 Cu

80

85

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

NIST-1228 Ca

85

90

95

100

105

110

115

Jun-01 Nov01Apr-02 Sep-02 Jan-03 Jun-03 Nov03 Percent Yield

NIST-1228 Mn

90

95

100

105

110

Jun-01 Nov01Apr-02 Sep-02 Jan-03 Jun-03 Nov03 Percent Yield

NIST-1228 V

90

95

100

105

110

Jun-01 Nov01Apr-02 Sep-02 Jan-03 Jun-03 Nov03 Percent Yield

NIST-1228 Co

90

95

100

105

110

Jun-01 Nov-01 Apr-02 Sep-02 Jan-03 Jun-03 Nov-03 Percent Yield

Figure 19: XRF evaluations of NIST Standard 1228.
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 31 of 6

3.a.vii Summary of Elemental Applicability

The filter based approach is valid for the five MACT metals tested in Phase I and II: 

Cr, As, Cd, Hg, and Pb. Chromium and As are listed by the MACT as Low Volatile 

Metals along with Be. These metals are classified together due to their similar chemical 

properties, and the XFM and Xact filter approaches should be able to quantitatively 

collect Be with the same efficiency as Cr and As. However, since XRF detection limits 

for Be are too high, the element will need to be analyzed by another method such as IO 

3.4.

Extension of the candidate methods to other elements depends upon effective filter 

trapping efficiency and XRF analysis. Both the XFM PTFE filter and the Xact PRO-7 

filter have shown quantitative collection efficiencies for particulate metals, LVMs, 

SVMs, and HVMs. Metals within these categories should be effectively captured by 

the two approaches.

XRF is applicable for elements with an atomic number greater than Aluminum. Data 

from the EPA’s PM2.5 speciation program suggests that XRF analysis is a precise, 

accurate method for measuring metals on filters. For this reason, the CES proposes that 

the Xact and XFM filter approach be made applicable to the 48 elements listed in Table 

13.

Applicability of Additional Source Categories

As discussed earlier, the filter-based sampling approach has been successfully tested on two 

hazardous waste incinerators (Eli Lilly’s T149 incinerator and the TEAD demunitions 

furnace) as well as three coal-fired boilers (EPA’s 2003 Midwest CFPP test; PGE’s 

Boardman, OR CFPP; and the US Army’s CFPP in Burlington, IA). Each of these tests 

showed good relative accuracy and trapping efficiencies. Using a question and answer 

approach, this section discusses testing and key parameters that determine the applicability of 

the filter-based approach to other source categories.

What factors and/or issues need to be considered when evaluating the applicability of 

the filter-based method to other sources?

Both the XFM and Xact-IAP sample particulate and vapor phase metals from an emissions 

source and analyze for mass using XRF. Key factors, then, for the filter-based methods can 

be broken into two categories: analysis and sampling. Analysis concerns include XRF 

interferences due to stack gas constituents and potential impacts due to variability in analysis 

conditions. Potential sampling concerns arise from particle collection factors, vapor phase 

collection factors, stack gas chemistry concerns, and the potential impacts from various 

source categories (Figure 20). 
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 32 of 6

How is the filter-based XRF analysis approach impacted by source type and control 

technology?

For both the XFM and Xact-IAP, the XRF mass determination is conducted in an 

environmentally controlled environment that is physically separated from the sampling 

location. Although the Xact-IAP XRF analysis region is only a few inches away from the 

sampling region while the XFM analysis is conducted in a remote laboratory, both sets of 

XRF components are essentially identical and sample under similarly controlled temperature 

and chemistry conditions. This constancy in analysis conditions allows the metal mass 

determination to be conducted in an identical manner without regard to source type, sampling 

conditions, or control technology. 

Even though XRF sampling conditions are constant, XRF accuracy still has the potential to 

be impacted by high levels of interfering elements on the filter presented for analysis. XRF 

elemental interferences, however, are well-characterized and are taken into account when 

deconvoluting the XRF data. In addition, many of the key constituents of flue gas that 

distinguish source categories (e.g., SOx, Cl2, NOx, CO, CO2, H2O, O2, and N2) are essentially 

invisible to the XRF during metal mass determination. Overall, then, as long as the filter is 

sampled within the particle loading specifications defined in the SOP, elemental interferences 

will not result in a measurable impact regardless of source type or control, and the XRF 

analysis is independent of source type or control technology.

How is the filter-based sampling approach for particulate metals impacted by source 

type and control technology?

Both the XFM and Xact-IAP use physical means to capture particulate metals and chemical 

means to trap vapor phase species. As discussed earlier, the particulate capture rate for both 

the XFM’s PTFE filter and the Xact’s REO-7 is greater than 99% when operated within the 

sampling parameters listed in Section 7.3. This efficiency is dependent upon pore size, 

tortuousity, and face velocity and is independent of emission type or chemistry under normal 

operating conditions. For this reason, particulate sampling for the XFM and Xact-IAP is 

generally applicable to all source types and control technology.

How is the filter-based sampling approach for vapor phase metals impacted by source 

chemistry and control technology?

Unlike the physical filtration mechanism used to collect particulate metals, vapor phase 

metals react with the chemically treated filter and bind to the filter substrate. Some potential 

exists for stack gas constituents to impact this chemical process and disrupt the filter 

collection efficiency. For the filter-based approach, many stack gas constituents do not 

impact the chemical filtration process including CO, CO2, N2, O2, and vapor phase H2O. 

These gaseous compounds are not trapped on the filter and do not influence the filter 

chemistry, allowing for good collection efficiency regardless of concentration. Oxidants 

within the gas stream such as Cl2 only improve the vapor phase collection efficiency. Thus, 

only acid-base constituents such as ammonia (NH3), NOx, and SOx have the potential to 

impact vapor phase collection efficiency.
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 33 of 6

In theory, basic stack gas constituents such as NH3 might have the potential to impact the 

vapor phase trapping efficiency. This possibility was evaluated by evaluating the XFM Hg 

collection efficiency during the EPA’s test of mercury measurement approaches at a Midwest 

CFPP. The plant used a state-of-the-art ammonia injection and selective catalytic reduction 

(SCR) for NOx control6. Despite the presence of ammonia, the XFM reactive filter 

demonstrated an 11% relative accuracy relative to the Ontario-Hydro method for Hg 

concentrations ranging from 1 to 5 g/dscm. This test suggests that the chemical process 

used to trap the Hg was not greatly influenced by the basicity of the stack gas emissions.

Like ammonia, acid gas constituents (i.e., NOx, and SOx) have the potential to impact vapor 

phase collection efficiency. However, it is important to note that there is no indication that 

acid gasses have affected the vapor phase filter trapping efficiency. Indeed, the 99+% 

trapping efficiency for elemental Hg at the Boardman site was completed with measured NOx

concentrations of 200 ppm and SOx concentrations of about 225 ppm. In fact, the QAG itself 

nebulizes an acidic nitric acid solution resulting in acid concentrations that are higher than 50 

ppm. For these reasons, it is not believed that acid gas concentrations significantly affect the 

sampling process.

What sources should be generally applicable to XFM and Xact-IAP sampling?

Sources with metal present in their emissions can be broadly defined in two categories: 

fugitive sources and duct sources. Fugitive sources include emissions from processes such as 

field-burning, slag-pouring, unducted roof top emissions, demolition activities, and forest 

fires. These sources are characterized by relatively low (less than 200 ppm) concentrations of 

acid gases and should not impact vapor phase metal sampling by the XFM or Xact-IAP. 

Because the sampling parameters and chemistry of these sources are less rigorous than the 

testing completed on the waste incinerators and coal-fired boilers, both filter based 

approaches are believed to be generally applicable to fugitive sources.

The second broad category for metal emissions is ducted sources including incinerators, 

boilers, kilns, smelters, plating operations, foundries, and other industrial sites featuring 

ducting of metal-laden emissions and air pollution control technology. As discussed earlier, 

the filter-based approach has shown consistent success over the past few years while 

sampling at two hazardous waste incinerators and three coal-fired boilers. These sites 

represent a wide range of controls (wet scrubbers, ESPs, high temperature ceramic 

baghouses, ammonia injection, selective catalytic reduction, lime spray dryer absorber for 

SO2 control, and a fabric filter for particulate control). In each case the relative accuracy in 

comparison to the QAG, Method 29, and the Ontario Hydro method was better than 20%. In 

general, the filter-based approaches have been accurate regardless of control technology type, 

moisture content and stack chemistry.
Method 301 Eval.: Appendix L V1.0 Section 3 Range Extension Page 34 of 6

Figure 20. Source applicability for XFM and Xact-IAP

Filter-Based 

Approach

(XFM & Xact-IAP)

Analytical

(XRF)

Sampling 

(Particle & Vapor 

Phase Filters)

Independent of 

Source Type

Generally 

Applicable

Particle Sampling Vapor Phase 

Sampling

Generally 

Applicable

Emissions

Constituents with 

No Impact

Emissions 

Constituents with 

Potential Impact

Cl2

CO

CO2

N2

O2

H2O

NOx

SOx

NH3

Low Concentration 

Fugitive Sources 

High Concentration 

Duct Sources

Generally 

Applicable

Generally 

Applicable

Generally 

Applicable
Method 301 Eval.: Appendix L V1.0 Section 4 Summary Page 35 of 6

Table 14: Summary of test results in support of extending filter approach.

Test Summary Test

Concentration Range

Particulate Metals 3-2200 μg/dscm 1, 2

Elemental Mercury 1-314 μg/dscm 3, 4

Oxidized Mercury 1-880 μg/dscm 3, 5

Holding Time

XFM: Particulate Filter 12 Months 6, 7

XFM: Vapor Phase Filter 24 Monthsa 8

Xact 12 Months 6, 7, 8, 9

Stack Type & Conditions

Filters acceptable for Wet Stacks 3, 10, 11

Filters acceptable for Dry Stacks 1, 2, 4, 9

HWC Filters acceptable for HWC applications 1, 2, 9, 11

CFPP Filters acceptable for CFPP applications 3, 4, 10

Stack Temperature 450°F 1, 2

Filter Temperature

XFM Particulate Filter 400°F 12

XFM Vapor Phase Filter 185°F 4, 5

Xact Particulate/Vapor Phase Filter 185°F

Sampling Time

XFM 60 min 4, 5

Xact 30 min 10

Sampling Flow Rate

XFM 4.5 lpm/cm2 4, 12

Xact 2.4 lpm/cm2 12

Field Blank Det. Limits less than 2 μg/dscmb 11

a) Correction factor of 0.5%/month required after six months.

b) One-sigma limits based upon analysis of 3899 filters measurements at Lilly's T149 Incinerator

1 HWC at TEAD production furnace.

2 HWC at TEAD research furnace.

3 EPA test at Midwest CFPP.

4 CES Test at Oregon CFPP.

5 CES Laboratory Tests.

6 Reevaluation of Phase I Filters.

7 EPA PM2.5 Speciation Program7

; Reevaluation of Phase I Filters.

8 CES Laboratory Evaluation of XFM Filters.

9 CES Reanalysis of Xact Filter Tape from TEAD tests.

10 Xact Test at IAAP CFPP.

11 Evaluation of Blank Filters at Lilly's T149 Incinerator.

12 Manufacturers Specifications

13 Phase II Tests at Lilly's T149 Incinerator

Parameter

Moisture
Method 301 Eval.: Appendix L V1.0 Section 4 Summary Page 36 of 6

4. Summary

The data presented in this Appendix extends the applicability and range of the XFM and Xact 

filter based approaches as follows:

 Filter Temperature of up to 185°F

 Face Velocity of slpm/cm2

 Sampling times for the XFM of up to 60 minutes

 Holding times for both the XFM and Xact of 12 months.

 Applicability of the two candidate methods to Incinerators, Kilns, Smelters, Boilers, 

and CFPP.

 Applicability of the XFM and Xact to sites with Filters, ESPs or wet scrubbers for 

APCT.

 Extension to include the 48 elements listed in Table 13.
Method 301 Eval.: Appendix L V1.0 Section 5 References Page 37 of 6

5. References

1. Pall Life Sciences. 2003. Laboratory Filtration and Separation Catalog. pp.30-31.

2. Jayanty, RKM. 2002. PM2.5 Chemical Speciation Nationwide Network and its 

Challenges. Symposium on Air Quality Measurement Methods and Technology –

2002. San Francisco, CA.

3. Hay, K.J., V.M. Boddu, B.E. Johnsen, J.A. Cooper. January 2005. Report No. 

ERDC/CERL-TR-05-3. X-Ray Fluorescence-Based Multi-Metal Continuous 

Emission Monitor Technology Demonstration. US Army Corps of Engineers: 

Engineer Research and Development Center.

4. Myers, J., T. Kelly, C. Lawrie, K. Riggs. May 2002. Environmental Technology 

Verification Report. ETV Advanced Monitoring Systems Center: Cooper 

Environmental Services XCEM Multi-Metals Continuous Emission Monitor. Found 

on the web at http://www.epa.gov/etv/etvoice/02-10.html.

5. US EPA PS-10. Proposed Performance Specification 10 – Specifications and Test 

Procedures for Multi-Metals Continuous Monitoring Systems at Stationary Sources. 

U.S. Environmental Protection Agency, Office of Air Quality Planning and 

Standards, Emissions Measurement Center, August 1997.

6. Hosenfeld, J., Sept. 2003. Long-Term Field Evaluation of Mercury (Hg) Continuous 

Emission Monitoring Systems: Coal-Fired Power Plant Equipped With Dry Flue Gas 

Desulfurization/Fabric Filtration Emission ControlsPhase III (Field Work Performed 

May-July 2003). Final Report for U.S. Environmental Protection Agency. EPA 

Contract 68-D2-01-002 Work Assignment 3-04. MRI Project No. 110130.3.004.

7. ASTM D6784-02. Standard Test Method for Elemental, Oxidized, Particle-Bound 

and Total Mercury in Flue Gas Generated from Coal-Fired Stationary Sources 

(Ontario Hydro Method), 2002.

8. Cooper, J.A., B.E. Johnsen, P. Ginochio. April 2005. Re-design and Field Testing of 

an X-Ray Fluorescence Multi-Metals Monitor at the Iowa Army Ammunition Plant, 

Middleton, Iowa Coal Fired Boiler. Submitted to US Army Corp of Engineers: 

Engineer Research and Development Center under contract no. W9132T-04-P-0065.

9. Ahmed, K. of Pall Corporation personal communication to CES’ B.E. Johnsen June 

3, 2005. Results of Air Techniques TDA-100A standard DOP Test.

10. 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.

11. 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/R-96/010a.

 
CEM 2004 

Real Time Measurement Of Particulate At Low Concentration From The 

Emission Of Stationary Source In The Steel And Power Industries Using a 

TEOMTM based Emissions Monitor 

Edward C. Burgher 

Rupprecht & Patashnick Co., Inc., 25 Corporate Circle, Albany, New York 12203 

telephone: 518 452-0065 

fax: 518 452-0065 

email: eburgher@rpco.com 

Gilles Gonnet 

Ecomesure, B.P. 13, F-91640 Briis Sous Forges, France 

telephone: 33 1 6490 5555 

fax: 33 1 6490 5566 

email: ecomesur@aol.com

Abstract 

Historically, measurements of particulate matter emissions from large stationary 

sources to comply with regulatory standards have employed a variety of methods 

depending on local agency requirements. More recently, with the establishment of 

regulatory norms for member states of the European Union, new methods have been 

established to provide a common basis for evaluating emission sources. In the USA, 

measurement of PM in emissions sources must be performed in accordance with 

U.S. EPA Method 5 or, in some cases, Method 17. As with the historical methods 

used in Europe and the USA, one of the newer methods, EN 13284-1 is based on 

filtration of particulate matter from a sample collected in-situ and isokinetically and 

requires the filter to be analyzed in a laboratory. The repeatability of a measurement 

made with any of the manual methods can be influenced adversely by factors 

including handling and transport of the filter, conditioning the filter before and after 

the sampling, and filter weighing. Also, because the measurement using the manual 

methods can only represent the average emission over the time period sampled, 

some important data like transitory concentration, stratification in the duct being 

sampled and the influence of the variation in parameters such as velocity, 

temperature and pressure on the particulate concentration is difficult or impossible to 

determine. Consequently, these limitations prompted customers of Rupprecht and 

Patashnick Company to request the company to develop a new method based on its 

patented Tapered Element Oscillating Microbalance (TEOMTM) technology. 

While this new method, named the TEOM Series 7000 Source Particulate Monitor, 

provides an in-situ measurement collected by filtering source gases at isokinetic 

sampling conditions, the filter handling and weighing processes are completely 

different. A filter is placed on the top of the hollow-tube, oscillating element that is 

housed in a temperature controlled mass transducer assembly. As a carefully 

controlled vacuum is applied to the opposite end of the tapered element, source 

gases are extracted from the stack isokinetically and passed through the filter 

thereby capturing any particulate matter that was entrained in the sample gases. As 

the filter weight increases with the accumulation of particulate matter, the frequency 

of oscillation decreases. The change in frequency can be determined in real-time and 

converted to mass. Tracking mass change with collected sample volume over time 

permits calculation of mass concentration measurements that can be continuously 

reported and/or reported as an average over a user specified time period. The 

1
method also incorporates procedures to dry the sample filter prior to and after the 

test in-situ and to recover any residual particulate matter left in the sample inlet 

during sampling thereby eliminating measurement errors introduced by filter 

handling, transport, etc. The ability of the Series 7000 method to measure and report 

data in real-time, can increase the amount of information available for 

characterization of process or control system variability or for calibration/correlation of 

indirect source measurement techniques such as triboelectric, optical or beta 

attenuation. 

Since it is important to understand the agreement between the different methods, 

and characterize the performance of the new, TEOM-based method this paper 

reports on a series of tests comparing the TEOM Series 7000 method to NF EN 

13284-1 (for low concentration emissions), and NFX 44052 (for high concentration 

emissions). Results of the twelve test runs performed at the steel mill indicate that the 

Series 7000 provides a valid measurement equivalent to the reference methods and 

confirms the conclusion of other laboratories like the TÜV Rheinland who evaluated 

the Series 7000 in 2001. The evaluation also allowed evaluation of the Series 7000 

for calibrating or auditing indirect automatic measuring systems for PM. Results of 

the tests also found that the Series 7000 method is well suited for the calibration of 

continuous measuring system using light scattering, transmissiometry or beta 

attenuation methods. The evaluation also showed that the monitor was robust and 

well adapted to the industrial environment while being easy to use and reliable. 

In a second series of tests, conducted at a large, coal-fired power plant located in the 

mid-western U.S., paired TEOM Series 7000’s were used to evaluate the systems’ 

capacity to make precise, real-time measurements with very short measurement time 

response. This precision evaluation was conducted in conjunction with assessment 

of stratification of a PM emissions source with respect to PM at the stack’s normal 

sampling locations. This series of tests found excellent agreement between in the 

paired Series 7000 trains and showed how the Series 7000 method can be used to 

rapidly provide detailed information regarding stratification in a sampling plane. 

Results indicate that the sampling location would be suitable for installation of a PM 

AMS. 

Keywords: particulate matter, source sampling, stack sampling, real-time isokinetic 

PM measurement 

2
Introduction 

As reported in a paper presented at CEM 2002 [Burgher, 2002], Rupprecht & 

Patashnick Co., Inc. developed a new instrumental method for measuring the 

particulate matter concentration in emission sources. This method, named the 

TEOM® Series 7000 Source Particulate Monitor (“TEOM SPM”), incorporates R&P’s 

patented TEOM technology and significantly enhances the amount of particulate 

matter emissions information that can be achieved from conducting an emissions 

testing program. For instance, when siting particulate matter continuous automatic 

measuring systems (“PM AMS”) it is important that the monitor is installed such that it 

will collect a representative sample regardless of the emission unit operating load. 

Secondly, as currently available PM AMS do not directly measure particulate matter 

mass, it is necessary to establish and verify the PM CEMS monitor accuracy over a 

range of operating conditions using methods such as EN-13284-1, EPA Method 5, 

ISO 9096 or the TEOM Series 7000. 

While TEOM SPM method provides an in-situ measurement collected by filtering 

source gases at isokinetic sampling conditions, as does recognized reference 

methods, the filter handling and weighing processes are completely different. With a 

TEOM SPM, a filter is placed on the top of the hollow-tube, oscillating element that is 

housed in a temperature controlled mass transducer assembly. The mass transducer 

is affixed to the end of a long sample probe that allows the mass transducer to be 

positioned in an emission source. By applying a carefully controlled vacuum to the 

opposite end of the tapered element, source gases are extracted from the stack 

isokinetically and passed through the sample filter. The filter captures any particulate 

matter present in the sample gas stream. As particulate matter accumulates, the filter 

weight increases which results in decreasing the tapered element oscillating 

frequency. The change in frequency can be determined in real-time and converted to 

mass. The result is mass concentration measurements that can be continuously 

reported and/or reported as an average over a user specified time period. Sample 

filter conditioning prior to and after the test can also be accomplished in-situ thereby 

eliminating measurement errors introduced by filter handling, transport, etc. The 

ability of the Series 7000 method to measure and report data in real-time, can 

increase the amount of information available for characterization of process or control 

system variability or for calibration/correlation of indirect source measurement 

techniques such as triboelectric, optical or beta attenuation. 

Since it is important to understand the agreement between the different methods 

used to make source PM emissions measurements, this paper reports on a series of 

tests designed to evaluate the performance of the Series 7000 method in comparison 

to NF EN 13284-1 (for low concentration emissions) and NFX 44052 (for high 

concentration emissions). In the first set of tests conducted by the laboratory LECES 

with the support of Ecomesure, the TEOM SPM method was compared to NF EN 

13284-1 and to NFX 44052 in three different sources at a steel mill. Following the 

methods comparison tests, the Series 7000 was then used to calibrate an opacitybased continuous emissions monitor. 

It is also important that the reference method used to calibrate or audit an automatic 

measuring system for PM be inherently precise regardless of source conditions or 

test operators, etc. For example, while European standards such as EN 14181 and 

U.S. standards such as Performance Specification 11 (PS-11) do not explicitly 

include precision requirements for reference method measurements, the correlation 

of the automatic measurement system to the reference method can be significantly 

influenced by the precision of the reference method measurements. To demonstrate 

the precision of the TEOM Series 7000 method when used in real-world test 

3
conditions, a second series of tests, conducted in the fall of 2003, were devised 

testing to evaluate the precision of method in an emission source produced by a 

coal-fired, power plant. This series of test were also designed to investigate 

particulate matter emissions stratification at two sampling locations normally used for 

emissions permit limit compliance determinations. 

Background - Series 7000 Measurement Theory, Configuration and Operation 

The Series 7000 allows sample collection inside a stack or duct through a filter while 

automatically maintaining isokinetic sampling conditions. The filter is affixed to one 

end of the mass transducer thereby allowing the collected particles to be weighed 

continuously resulting in a real-time measurement of the particle mass concentration. 

The TEOM mass transducer uses a short, straight inlet nozzle tube to isokinetically 

sample the flue gas transporting it just a few millimeters to the filter. The mass 

transducer is a hollow tube, clamped on one end and free to vibrate at the other. An 

exchangeable filter cartridge is place over the tip of the free end. This "tapered 

element" vibrates precisely at its natural resonant frequency. A precise electronic 

counter measures the frequency that has a direct relationship with mass. The 

relationship, expressed below, between mass and frequency can be derived from the 

simple harmonic oscillator equation [Patashnick, et.al, 1991]. 

f2 = K0 / m (1) 

where, f = frequency of oscillation 

K0 = calibration constant 

m = mass 

The calibration constant of the tapered element can be established by measuring the 

frequency of the tapered element with a filter of known mass installed and without a 

filter. Applying the relationship described by equation 1, the value of K0 can be 

calculated as shown below: 

K0 = (m2 - m1) / (1/f22 - 1/f12) (2) 

The tapered element system is constructed using non-fatiguing inert material and 

since K0 is a function of the (non-changing) physical characteristics of the tapered 

element system, the tapered element retains its calibration indefinitely. Once K0 has 

been determined for a particular tapered element, it can be used for mass 

measurements. 

If the element is oscillating at the frequency of fa and has a frequency response of fb 

after an unknown mass is collected on the filter (∆m’), ∆m’ can be obtained as a 

function of fa, fb and Ko using the following equation: 

∆m’ = K0(1/fb

2

 - 1/fa

2

) (3) 

Tracking frequency with time provides the mass rate. When the mass rate is 

combined with the sample flow rate through the filter, mass concentration of the 

sampled gases can be directly calculated and in real-time. During normal operation, 

the temperature of the mass transducer is maintained a few degrees above the stack 

temperature to provide the frequency stability necessary for measurement of very 

small mass changes with high temporal resolution. To automatically control isokinetic 

sampling rates, the system incorporates measurement of source gas velocity, 

temperature and gas density / molecular weight. Velocity is measured with a "S" type 

Pitot tube assembly while the gas temperature is measured with a "K" type 

thermocouple. The gas density / molecular weight determination is provided by 

4
measuring carbon dioxide with a non-dispersive, infrared monitor, oxygen with a 

paramagnetic monitor and moisture using a differential flow technique patented by 

R&P. All of these parameters are measured in real-time and input into the system's 

onboard computer to automatically perform the necessary calculations for computing 

isokinetic sampling rates. This information is then used to set and control the 

sampling rate using a measurement-control feedback loop. 

Case Study 1: R&P TEOM Series 7000 Evaluation in Steel Mill Source 

Emissions 

The major objectives of this study were: 

1. Compare R&P TEOM Series 7000 to the European and French Manual Standard 

Method (FR EN 13284). 

2. Evaluate TEOM 7000 real-time data output, ease of use for conducting emissions 

tests, and investigate capability for generating complete results on-site. 

3. Evaluate TEOM 7000 as a method to calibrate an opacimeter as a PM mass 

emissions monitor. 

A series of twelve test runs in three different sources at a steel mill were conducted 

by the laboratory LECES with the support of Ecomesure to compare the TEOM SPM 

method to NF EN 13284-1 and to NFX 44052. All tests were performed under normal 

operating conditions of each emission unit. One TEOM SPM and one (1) manual 

reference method sampling train were operated such that simultaneous, co-located 

samples were collected. The TEOM SPM was operated in the continuous mode 

following the method instructions that are integrated into the system’s computerized 

operating system. All Series 7000 test measurements and analyses were performed 

on-site. The manual method trains were operated in accordance with the NF 

EN13284-1 procedures. Results of the tests are shown below. 

Table 1 - Agglomeration Plant Test Results 

Dust Concentration (mg/m3) 

Test Run Automatic Method 

(TEOM SPM) 

Manual Method 

(NF EN 13284-1) 

Relative Difference

(%) 

1 79.9 85.5 -6.5 

2 123.1 115 7.0 

3 88.4 101 -12.5 

4 74.4 83.3 -10.7 

Test Average 91.5 96.2 -4.9 

Test Conditions: Ave. stack temperature: 80°C 

Stack diameter: 2 m 

Ave. stack gas velocity 9 m/s 

Table 2 – Coke Oven Test Results 

Dust Concentration (mg/m3) 

Test Run Automatic Method 

(TEOM SPM) 

Manual Method 

(NF EN 13284-1) 

Relative Difference

(%) 

5 3.0 3.5 -14.3 

6 4.0 4.6 -13.0 

Test Average 3.5 4.1 -13.6 

Test Conditions: 

Condition 5: Stack temperature: 35°C 

Stack diameter: 2 m 

Gas velocity: 18 m/s 

5
Condition 6: Ave. stack 

temperature: 

184°C 

Stack diameter: 4 m 

Ave. stack gas 

velocity: 

5.3 m/s 

Table 3 - Electric Arc Furnace Test Results 

Dust concentration (mg/m3) 

Test Run Automatic Method 

(R&P 7000) 

Manual Method 

(EN 13284-1) 

Relative Difference

(%) 

7 6.8 6.0 13.3 

8 56.2 56.9 -1.2 

9 5.4 5.0 8.0 

10 0.9 0.7 28.6 

11 2.1 1.8 16.7 

12 2.2 2.0 10.0 

Test Average 12.3 12.1 1.7 

Test Conditions: Ave. stack 

temperature: 115°C 

Stack diameter: 2.5 m 

Ave. stack gas velocity: 11 m/s 

In a second set of tests conducted at the steel mill on an agglomeration unit, the 

TEOM SPM was used to calibrate two Oldham EP1000 Opacimeters. The Series 

7000 was installed so that the sample extraction points were near the laser path area 

of the EP1000. The number of TEOM SPM sampling points on the sampling traverse 

axis was determined per the procedures specified in EN 13284-1. The duration of 

each TEOM SPM sample point was approximately five (5) minutes per point. 

Following the completion of each sample traverse line, the EP 1000 was adjusted to 

agree with the traverse average reported by the TEOM SPM. This process was 

repeated until the EP 1000 and R&P 7000 agreed. Result of each calibration test run 

are shown in the following tables. 

Table 4 - Agglomerator Stack 1 

Time R&P 7000 

(mg/m^3) 

Oldham EP 1000 

(mg/m^3) 

Temperature

(°C) Humidity (%) 

8:29 to 9:41 42 81 124 4.7 

10:05 to 11:12 31 61 121 8.8 

13:40 to 14:38 58 45 123 4.7 

15:22 to 16:24 53 34 127 5.5 

10:33 to 10:48 37 46 121 6.6 

11:28 to 11:41 28 40 114 10.1 

13:44 to 14:13 43 45 116 6.5 

Table 5 - Agglomerator Stack 2 

Time R&P 7000 

(mg/m^3) 

Oldham EP 1000 

(mg/m^3) 

Temperature

(°C) Humidity (%) 

9:25 to 9:51 11 4 50 4.4 

10:21 to 10:36 14 21 51 4.6 

10:48 to 11:09 10 17 50 4.7 

6
11:22 to 11:45 14 14 51 2.2 

11:56 to 12:45 10 11 52 6.1 

Case Study 2 : Comparison of TEOM SPM to EPA Method 5 and Stratification 

Analysis 

To illustrate the use of the TEOM SPM for conducting stratification studies to support 

siting of particulate matter automatic measurement systems (PM AMS), one set of 

paired train test runs was performed to investigate the degree of stratification in the 

sampling lines normally used for compliance testing. Prior to the stratification test 

runs, a set of paired train tests were conducted with the monitor’s sample probes 

positioned at fixed locations near the center area of the stack for the purposes of 

evaluate the precision of the monitors used for stratification testing. Testing was 

conducted at a utility plant in the Mid-western U.S. that primarily uses a 

subbituminous coal from the Powder River Basin (PRB) in the State of Wyoming. 

During testing, the plant was operating at normal base load conditions. 

For the stratification tests, both TEOM SPM systems were operated in the traverse 

mode following the method instructions that are integrated into the system’s 

computerized operating system. Stack gas velocity and temperature, sample gas 

molecular weight and gas density measurements used for calculation and setting of 

isokinetic sampling rates were determined using the TEOM SPM onboard 

measurement systems. For the precision test, both TEOM SPM systems were 

operated in the continuous mode. Stack gas velocity and temperature and sample 

gas density and molecular weight determinations were also made using the onboard 

measuring systems. All Series 7000 test measurements and analyses were 

performed on-site. 

First, to investigate the precision of the co-located TEOM SPM systems, two 

identically configured TEOM SPM systems were installed in adjacent sampling ports. 

The sample probes were inserted so that the probe nozzles were located at the 

centermost point of the stack as described in EPA Method 1. After each system’s 

sample filter was desiccated to a stable mass, sample collection was started and test 

measurements were taken for approximately 1.5 hours. Care was taken to start and 

end the test period for each monitor simultaneously to minimize the potential for 

temporal changes in the PM emission rate to influence the precision analysis. 

For the second test investigating PM stratification, the monitors were installed and 

configured to measure PM concentrations at three discrete locations along the 

sample traverse lines for each test port. The probes for each monitor were installed 

in the same ports that were used for the co-location test. Sample measurements 

were taken for about 20 minutes at each traverse point for a total test time of 

approximately one hour. As with the precision test, each monitor was programmed to 

start and end sampling at the same time. 

Results from the co-located precision (co-located) test indicate that the difference 

between the two monitors, when located within the centroid area of the stack, is less 

than 8%, on average. Results for the traverse test found close agreement between 

the monitors at all points including the third traverse points were the same points 

used for the precision test. Since the two monitors showed good agreement during 

the fixed sample location test, and again at all three traverse point locations, it can be 

concluded that stratification of particulate matter is not present, at least in the areas 

tested. Results are summarized below in Table 6 and Figures 1 and 2. The charts 

shown in Figures 1 and 2 are constructed using the two-minute rolling average mass 

7
concentration for each system clearly demonstrating the precision of the method 

even for very short term measurements. 

Table 6 - TEOM SPM – Stratification Analysis 

Coal-fired Power Plant – Midwestern U.S.

Test Type Traverse 

Point 

Distance from 

Wall 

(m) 

TEOM SPM 

Unit 20102 

conc. (mg/m3

) 

TEOM SPM 

Unit 20111 

conc. (mg/m3

) 

Rel. % Diff.

Co-located 2.76 21.1 19.6 7.7% 

Traverse 1 0.41 14.83 15.10 -1.8% 

" 2 1.36 14.38 15.22 -5.7% 

" 3 2.76 15.46 15.70 -1.5% 

" Traverse Test Averages 17.54 16.77 4.5% 

Test Conditions: 

Co-located Test: Ave. stack temperature: 160.0°C 

Stack diameter: 9.3 m 

Ave. stack gas velocity: 19.7 m/s 

Traverse Test: Ave. stack temperature: 152.8°C 

Stack diameter: 9.3 m 

Ave. stack gas velocity: 19.0 m/s 

Figure 1 - Fixed Sampling Location (Co-located) Test 

Coal-fired Power Plant Emission Source (Midwest U.S.) 

Precision Analysis

0

5

10

15

20

25

30

35

40

13:33 13:48 14:02 14:16 14:31 14:45 15:00 15:14

Time (hh:mm)

Mass Concentration (mg/m3

)

TEOM SPM Unit 20111

TEOM SPM Unit 20102

8
Figure 2 - Traverse Test

Coal-fired Power Plant Emission Source (Midwest U.S.)

Stratification Analysis

0

5

10

15

20

25

11:05 11:12 11:19 11:26 11:34 11:41 11:48 11:55 12:02 12:10

Time (hh:mm)

Mass Concentration (mg/m3

)

TEOM SPM Unit 20102

TEOM SPM Unit 20111

 Traverse Point 1

Unit 20102 ave. 14.8 mg/m3

Unit 20111 ave. 15.1 mg/m3 

location: 0.41 m from wall

 Traverse Point 3

Unit 20102 ave. 15.5 mg/m3

Unit 20111 ave. 15.7 mg/m3

location: 2.76 m from wall

 Traverse Point 2

Unit 20102 ave. 14.4 mg/m3

Unit 20111 ave. 15.2 mg/m3 

location: 1.36 m from wall

Conclusions 

The evaluation found that the Series 7000 method is well suited for the calibration of 

continuous measuring systems using light scattering, transmissiometry or beta 

attenuation methods. The evaluation also showed that the monitor was robust and 

well adapted to the industrial environment while being easy to use and reliable. 

Results of the test runs performed at the steel mill indicate that the Series 7000 

provides a valid measurement equivalent to the reference methods and confirms the 

conclusion of other laboratories like the TÜV Rheinland who evaluated the Series 

7000 in 2001. The evaluation also showed that the monitor was robust and well 

adapted to the industrial environment while being easy to use and reliable. 

Results of the testing conducted in the coal-fired power plant emission source 

showed excellent agreement between co-located Series 7000 monitors while also 

showing the sampling locations to be essentially non-stratified with respect to 

particulate matter. Furthermore, testing using the Series 7000 found that stratification 

analysis could be conducted very rapidly with high reliability thereby, minimizing 

impacts on plant operations while potentially reducing the overall costs of conducting 

these types of test programs. 

References 

1. Burgher, E. Rupprecht E. “Validation of a TEOM® - based Source Particulate 

Monitor According to European Reference Method prEN13284-1”. Paper 

presented at CEM 2002 Conference 

2. Patashnick, H.; Rupprecht, E. “Continuous PM-10 Measurements Using the 

Tapered Element Oscillating Microbalance”, J. Air Waste Management 

Association 1991, 41, 1079-1083. 

9
Page | 1

Attachment 3. 

Summary of Patents Relative to Xact Stack, Fence Line and 

Ambient Monitors

The following is a summary of current Cooper Environmental Service LLC United States and 

European patents relevant to the Xact technology

I. U.S. Patent No. 6,872,370; Apparatus and Methods for Removing Mercury from Fluid Streams

Issued 03/29/05.

II. U.S. Patent 6,770,250; Apparatus and Methods for Removing Mercury from Fluid Streams.

Issued 08/03/04.

III. U.S. Patent No. 7,381,388; Method for Removing Mercury from a Gas Stream Using IodineDoped Dilution Gas.

Issued 06/03/08

IV. U.S. Patent No. 7,572,419; Apparatus and Methods for Removing Mercury from Fluid Streams.

Issued 08/11/2009

V. U.S. Patent No. 7,539,282; XRF Analyzer.

Issued 05/26/2009

VI. European Patent No. 1558361 (03774822.5)

German, French, United Kingdom, Italian, Swedish

VII. Quantitative Aerosol Generator 

Application submitted to US Patent Office

VIII. Diffusion Denuding with Moving Surface

Application submitted to US Patent Office

IX. Sample Fluid Stream Probe

Application submitted to US Patent Office