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 Andr ea Geiger, Krag Petterson, and John Coope r

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 E nvironmental P rotection A gency (EPA) , for the purposes of placing in the public record, additional responses to va rious 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 organizati ons, 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 “col lusion” has occurred between the USEPA and CES with regard to the Xact multi

metal 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 det ailing 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 th e current draft Title V permit or the draft permit reopening in 2013. In fact, w e were not aware of the multi

- metal CEMS requirement before the perm it’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 tec hnologies 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 par ticulate matter (PM) transport. This is an extremely complex topic, and we would like to include ou r 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 di fferent from transporti ng 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 a t various points in a Coal

- Fired Pow er Plant ( CFPP ) emission stream

. This series of particulat e matter measurement studies using paired TEOMs prepared by Edward Burgher and
Gilles Gonnet i n a white paper, detail the lack PM stratification in measured stack
emissions (accessed through Environmental Technology Online)

. The goals of the studies

were t o 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

- by

side monitor s, while also evaluating the stratification of particulate matter within a stack ( Burgher and Gonnet, 2004) . Two identically configured TEOM systems were insta lled inFebruary 10, 2015 Page 3 of 14

adjacent sampling ports; b oth 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 thr ee 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 loc ations to be essentially non

- stratified with respect to particulate matter

.

T he full report is provided as A ttachment 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 Emiss ions Monitoring, Inc orporated, 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 p resent in the stack measured

.February 10, 2015 Page 4 of 14February 10, 2015 Page 5 of 14

2. Commentary that p article size issues cause an inability of the Xact to collect a representative sample.

CES found conflicting theories from th e 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 sma ller 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 parti cles up to 150
microns (as opposed to the ~1 micron average particle size produced by an old er 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 part icles does not apply.

From a physical perspective the majority of toxic metals in flue gas of HWI’ s exi st as fine particles (Donnelly, 1991)

. R egardless , s i mply 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
develo ped 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 b aghouse 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 d uring 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 ver ified 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 em issions from a typical hazardous waste incinerator equipped with emissions controls are >99 percent less than one micron in aero dynamic 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
dir ect 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 p articulate matter buildup on transport w alls

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, t he 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 h ave 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

argu e s that particulate would adhere to the transport wall as the gas cools , which
would lea d 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 V eolia ’ s Draft Title V CAA Permit, Operating Parameter Limits table, page 15). The temperature may cool after pollution control treatment, but it will

not coo l (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 to 19 0° C which allows for the transport of oxidized mercury species

, as well as preventing the condensation of water a nd acid vapors, as well as reduc ing the likelihood of particulate condensation on the transport line walls. In addition, the Xact samples a small subsample from the cent r al flow through the transport line , so the large particle s that might break or flake off from the transport line ’ s wall, unlikely as t hat may 1 90 ° CFebruary 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 t he validation of the Xact with the QAG fails to mimic actual
stack conditions because the emiss ion aerosols are not physically or chemically comparable to the forms use d 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 use d 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(NO 3 ) 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, Cr 2 O 3 ] 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 desig n 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

, t he total metals analysis used in the X RF analysis of the Xact is independent of oxidation state

, chemical matrix, refractory oxides, or diffi cult 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 me tals captured on the treated filter media of the Xact

, because the metals are n either

remov ed n or dissolv ed and XRF uses inner shell electron transition lines to quantify the
amount of metal , which is e ntirely 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. T he 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 c hromium and arsen ic 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 mean s 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 te mperatures 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 eithe r 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 instrum ent

, a small sub

- sample is withdrawn through a reactive filter tape ; h owever, al l 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 μ m 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

, a re 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 oxid e, 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 per formed additional testing to evaluate trapping efficiency using
the X

- Ray Fi lter 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 p resent 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 i s 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, p a g e 47).

CES’ pricing is the same for Veolia as for any other customer. Pricing for t he 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 sampl ing intervals

, depend greatly on an individual facility ’s needs . This type of varia bility (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 th e s e offer s were not accepted. Until an evaluation can be performed to prepare an informed quote, any commentary on this topic is purely speculativ e, and shoul d 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 de signed 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 a dvancement 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 2 0 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 indicat ed in the Test America

- Focus
Environmental d escription

.

7. Commentary regarding the Xact ’ s ability to collect v apor

- phase (elemental)

m ercury (Hg ° )

Test Americ a/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 C FPP . It is well known t hat the

ma jority of mercury emissions issuing from CFPPs is primarily in the vapor phase. HgFebruary 10, 2015 Page 12 of 14

deposition currently estimated using contemporary in

- stack speciation estimates show that Hg 0 i s 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 trap s vapor

- phase mercury

. They claim that it is the affinity for mercury to adhere to carbon par t icles that allows the Hg 0 to be easily captured by the
Xact CEMS ’ reactive filter media (as a particulate). Test A merica/Focus Environmental
claim that it is this “phenomenon” that explains the Xact’s better performance for

mercury c apture (when compared to Method 29) for coal

- fired units.

It should be noted that t here are no references included with the conjectures presented in Test America /F o cus Environmental ’ s commentary, but in our research into mercury emissions and stack testing, CFPP have, if any thing, 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 st ate 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 multipl e patents granted to CES for our methods developed to ca pture vapor

- phase mercury (see Att a chment 3)

. In closing, CES hopes that this commentary provides additional supporting
documentation with regard to the contrary claims of Ve olia and other commenters. Overall, CES requests that EPA foc us on the science, technology, and factual history of
both Veolia and the Xact multi

- metal CEMS. We feel it is essential to separate a n industry ’ s n egative respo nse to a requirement for install ing a specific monitoring

i nstrument from the integrity of the science and technology in d evelop ing 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.

A nil Somani, S. A. (1998). Airborne Particulate Matter: Pollution Prevention and Control. In W. B. Group, Pollution Prevention and A b atement 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 Pa rk, 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 Bas is Dated October

2014

Geiger, Andrea, Krag Petterson, and John Cooper, 2014. Cooper Environmental
Services, LLC Comments t o United States Environmental Protection Agency , Region 5

Air Pollution Control Title V Permit #V

- IL

- 1716300103

- 2014

- 10 (DRAFT) . Dec e mber 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., 1 3, 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, PM 2.5 and PM 10 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 M al ecka, R Gajerski , and S Labus , 2003 . Thermal Decomposition of Chromium(III) Nitrate(V) Nanohyd rate Different Chromium Oxides F ormation. Journal of Thermal Analysis and Calorimetry 72 : 135

- 144.

Mueller Environmental Designs, Inc. (2015, February 4). Fu ndamentals of Gas Solids/Liquids Separation. Retrieved from www.muellerenvironmental.com.

Peeler, James and Laura Kinney. 2011 , March. Particula te Matter Instrumental Testing for CPT Optimization at a Cement Plant Burning Hazardous Waste and Related PM Monitoring Issues

. Presented at 35 th Conference on Stationary Source Sampling and Analysis for Air Pollutants. Tucson , AZ.

Test America (William C. Anderson) and F o cus En vironmental, 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 Solution s, LLC to Draft Air Pollution

Co ntrol 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 Co ntrol 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 G uo, 2006.

Characteristics of Inhalable Particulate Matter Concentr ation 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 TEOM TM 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 standar ds 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 source s 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

1method 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

2Introduction

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 t hat 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 veri fy 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 themethods 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 prec ise 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

3conditions, 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 meas urement 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/f2 2 - 1/f1 2 ) (2)

The tapered element system is construct ed 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 K 0 has been determined for a particular tapered element, it can be used for mass
measurements.

If the element is oscillating at the frequency of f a and has a frequency response of f b after an unknown mass is collected on the filter ( ∆ m’), ∆ m’ can be obtained as a function of f a , f b and K o using the following equation:

∆ m’ = K 0 (1/f b 2 - 1/f a 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 stabilit y necessary for measurement of very small mass changes with high temporal resolu tion. 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

4measuring 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 t he 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. st ack 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

5Condition 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
A ve. 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

611:22 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 m easurement 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 precisi on 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 we re 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-lo cated) 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

7concentration 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/m 3 ) TEOM SPM Unit 20111 conc. (mg/m 3 ) 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. sta ck temperature: 160.0°C

Stack diameter: 9.3 m Ave. stack gas velocity: 19.7 m/s

Traverse Test: Ave. sta ck 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

8Figure 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/m 3

Unit 20111 ave. 15.1 mg/m 3

location: 0.41 m from wall Traverse Point 3 Unit 20102 ave. 15.5 mg/m 3

Unit 20111 ave. 15.7 mg/m 3

location: 2.76 m from wall Traverse Point 2 Unit 20102 ave. 14.4 mg/m 3

Unit 20111 ave. 15.2 mg/m 3

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.

9Method 301 Eval. : Appendix L V 1.0 

### Page i of iii 

# Attachment 2:

Additional Reports and Data in Support of Source and R ange Extension of Candidate Measurement Methods

Xact Series of Monitoring I n struments

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 Ef

ficiency 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 Mi dwest 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

................................ ................................ ................................ ............... 37Method 301 Eval. : Appendix L V 1.0 

### 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 PM 2.5 

### Speciation program.

................................ ............ 7

Figu re 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: Mo dified 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 PM 2.5 

### Speciation program.

................................ .... 29
Figure 17: XRF round robin results for EPA’s PM 2.5 

### 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

................................ ................... 34Method 301 Eval. : Appendix L V 1.0 

### Page iii of iii 

## List of Tables

Table 1 Summary of mercury chloride trapping efficiency te sts.

................................ ....... 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 test s.

................ 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.

..................... 35Method 301 Eval. : Appendix L V 1.0 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 X act

IAP 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

c oncentrations.

 

### 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 V 1.0 Section 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 concentr ations 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 te sts, 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 a n Iowa CFPP : The U.S. Army sponsored a series of tests in January 2005 to evaluate a mercury

- optim ized 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 in cinerator 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 limit s.

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
manufacturer 1 

### to operate efficiently at temperatures of up to 400°F with a capture efficiency of better than 99% 1 

### for 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 cap able 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 Fil ter (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 (HgCl 2 

### ) was mounted in a polyethylene

con tainer 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. TheMethod 301 Eval. : Appendix L V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 3 of 6

capture efficiency was determined by comparing the concentration on the upstream
filter r elative to the downstream filter according to the following equation:

Equation 1

W here:

E i 

### = Capture Efficiency of the i th 

### element (%)

= Concentration of the i th 

### element on the upstream filter

= Concentration of the i th 

### element on the downstream filter

The first series of tests were completed in the laboratory during May 2000 and evaluated the filter efficiency for HgCl 2 

### . For these tests, a permeation tub e 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 temper ature was varied between 100 to 212oF and the sample rate was kept constant at 1 lpm/cm 2



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

Figure 1 : Experimental arrangement for trapping efficiency t ests

.Method 301 Eval. : Appendix L V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 4 of 6

2.a.ii XFM Merc uric 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 bac k

- 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 t ests

.

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 4 8 212 100.0

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 90 212 100.0Method 301 Eval. : Appendix L V 1.0 Section 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 own s 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, SO 2 

### concentrations ranging from 205 to 265 PPM, and NO x 

### concentrations between 165 and 250 PPM. During t he 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 m ercury 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 fi lter 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 va ried between 20 and 60 minutes ( Table 2 ).

Figure 2 : Elemental mercury injection at CFPP.

Figure 3 : Test Arrangement for XFM Trapping Efficiency at PGE CFPPMethod 301 Eval. : Appendix L V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 6 of 6

2.a.iv Results

As with t he 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 in dependent 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 effic iency.

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 0.2 4 >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
2 005. 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 procedure 1



### .

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 t he metal mass demonstrates the ability of the PTFE filters to retain metal concentrations over a five month period.Method 301 Eval. : Appendix L V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 7 of 6 Table 3 : XFM metal concentration Dec. 2004 and April 2005.

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

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 PM 2.5 

### Speciation program 2



### , 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 measurab le 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 typicall y 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.

Figure 4 : Round robin results for PM 2.5 

### Sp eciation program.Method 301 Eval. : Appendix L V 1.0 Section 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 thes e 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

mer cury 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 resul ts 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 laborator y 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 meta ls 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 indep endent 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 V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 9 of 6 Figure 5 : Mercury retention on reactive filter.

Table 4 : Ratio of Hg concentrations to origi nal concentrations.

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

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 theMethod 301 Eval. : Appendix L V 1.0 Section 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 reas on, 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 t ests of the Xact in order to evaluate its applicability to the TEAD location 3



### .
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

program 4 

### , 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 sampl es 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 r eanalyzed 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 Metho d 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 V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 11 of 6

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

urnace

.

Figure 7 : XRF Reanalysis results for Xact filter reel

- to

- reel a pproach

.

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 test s 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 cont r acted by the US Army’s Ammunition Equipment Directorate (AE D), 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 Secti on 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 V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 12 of 6

The research furnace employs the APE 1236 design that includes a rotary furnace, a cy clone,
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 lim its 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 pr ior 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 th at 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 f or 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 t he 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 refer ence 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
concentration s 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 b y 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 V 1.0 Section 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 signifi cant concentrations by either the Xact or M29. In general, the Xact was highly correlated with M29 with an r 2 

### 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 M2 9 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 wh en 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 i n 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 bag house 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 V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 14 of 6

Figure 8 : Xact reported lead concentrations vs. EPA Method 29 for AED tes ts.

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 non

regulated 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 da y 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 16 th 

### , the proje cted 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 V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 15 of 6

Figure 9 : Comparison of lead and tin concentrations in stack e missions w hen 20 mm

rounds are i ncinerated (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 Xac t 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 method 6 

### . 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
NO x 

### control, a lime spray dryer absorber for SO 2 

### control, and a fabric filter for particulate control. These con trols resulted in a relatively high water content and low
SO 2 

### and NO x 

### . 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 r uns. Two of the five duplicate OH trains, runs 2 and 6, were not withinMethod 301 Eval. : Appendix L V 1.0 Section 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
cha llenged 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 Xac t 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 w as 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 wasMethod 301 Eval. : Appendix L V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 17 of 6

omitted due to a plant upset and highly variable mercury concentrations. For 11 of th e 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
1 4 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 repr esented 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.

Figure 11 : Correlation of XFM with OH du ring MRI May 2003 tests.

Table 7 : Reported XFM and Ontario

- Hydro results for MRI May 2003 tests.

a) Includes particulate and vapor phase oxidized Hg b) Valid if OH Duplicates < 30% difference

The XFM relative mercury speciat ion results (% Hg°) were also in excellent agreement
with the OH results as shown in Table 7 . The 12

- run average unsigned mean differenceMethod 301 Eval. : Appendix L V 1.0 Section 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 observ ed 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 condu cted 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 (unk nown) 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 f or 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 a re 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/dscm 7 

### . 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 concentration s with a relative accuracy of 11 % compared to the OH standard reference method. The XFM p recision 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 mercur y concentrations, the XFM and OH percentages of oxidized mercury were in good agreement for that run.

Table 8 : XFM vs. certified spike concentrations.Method 301 Eval. : Appendix L V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 19 of 6 Figure 12 : XFM vs. certified mercury concentrations for spike i njection

.

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 2B 1

-- 8B 2.77

3A 2.8 7 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

- opt imized Xact in anticipation of the unit being installed at the IAAP 8 

### . 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 analys is 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 10 th 

### through the 12 th 

### . Dual Method 29 trains were operated by the US Army’s Cen ter 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 t he Xact approach to CFPP applications.Method 301 Eval. : Appendix L V 1.0 Section 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 o f 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 f

or 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 ha lf 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 conside red 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 thisMethod 301 Eval. : Appendix L V 1.0 Section 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 u sed for evaluating the
Xact

- Hg accuracy.

Table 10 compares M29 and Xact

- Hg results for runs 3 through 12. Overall, the Xact

Hg and M29 were in good agreement for all 10 valid runs with the average Xact

Hg/M29 Hg ratio within 9% an d 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 ter m 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 mo re 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 an d drift, nickel was analyzed with each run ( Fig ure 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
wi th drift or precision.

Table 10 : Xact

- Hg and Method 29 results for IAAP tests.

RUN MERCURY ARSENIC

M29 Train XACT

HG XACT

HG/ M29 M29 Train XACT

HG XACT

HG/ M29 Train

- 1 Train

- 2 AVG Train

- 1 Train

- 2 AVG

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 0.87Method 301 Eval. : Appendix L V 1.0 Section 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.



### Fig ure 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 T14 9 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 evalua tion was made using all 3876 Xact samples collected at Lilly’s T149 incinerator between July 19 th 

### and September 16, 2004. Typical results for two representative elements, Pb and Hg are shown in Figure 15 with detection
limits iden tified as the 95 th 

### percentile value for the field blanks. A summary of all Xact 95 th 

### percentile detection limits is shown in Table 11

.
These results are in good agreement with the smaller data set generated during validation
testi ng and are, in all cases, more than an order of magnitude below the required limits set by
the HWC MACT.

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 V 1.0 Section 2 Supplemental Testing 

### Of Candidate Methods Page 23 of 6 Table 11 : Empirically determined Xact detection limits.

Elem Xact Detection

Limits 1 Elem Xact Detection
Limits 1

 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 V 1.0 Section 3 Range Extension 

### Pa ge 24 of 6 Table 12 : Summary of applicability extension tests.



## 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 manufacturer 1 

### to operate efficiently at temperatures of up to 400°F with a capture efficiency of better
than 99% fo r 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 co ncentrations were 94% of theMethod 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 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:

 

### Mercu ric 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 effi ciency 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 Particulates 9 

### .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
testi ng. 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 re lative 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 dopan t 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 HgCl 2 

### 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 s ectionMethod 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 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 a s 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
Tech nology 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 excep t 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 bod y 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
3.4 10 

### ) or a different analytical approach in o rder 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 t hus 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 emission s. Since all five of the non

- enumerated methods can be measured by XRF using IO Method 3.3 11 

### , 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 PM 10 

### and PM 2.5 

### monitoring in aggressive environments and has been found to collect more than 99.8% of particles with diameters less than 3  m 1 

### . This efficiency will only be improved withMethod 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 27 of 6

l arger 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 ca ndidate 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 inde pendent 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 me tals.

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
PM 2.5 

### 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

- qual ified 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 pr ogram, 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 s tationary 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 analyze rs 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 integr ity.Method 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 28 of 6

XRF accuracy is ensured by repeated evaluations of thin

- film standards provided by NIST. During the PM 2.5 

### 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 ele ments evaluated in
the PM 2.5 

### 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 PbMethod 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 29 of 6 Figure 16 : CE S replicate samples for PM 2.5 

### Speciation program.

Figure 17 : XRF round robin results for EPA’s PM 2.5 

### Speciation program.Method 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 30 of 6 Figure 18 : XRF evaluation of NIST standard 987.

Figure 19 : XRF evaluations of NIST S tandard 1228

.Method 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 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 a long 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 B e 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
filt er 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 demuniti ons 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

app roach, 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. Analys is 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 con cerns, and the potential impacts from various source categories ( Figure 20 ).Method 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 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 w ithout 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. X RF 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., SO x 

### , Cl 2 

### , NO x 

### , CO, CO 2 

### , H 2 

### O, O 2 

### , and N 2 

### ) 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 mea ns 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 appl icable 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 phas e 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, CO 2 

### , N 2 

### , O 2 

### , and vapor phase H 2 

### O. 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 Cl 2 

### only improve the vapor phase collection efficiency. Thus, only acid

- base constituents such as ammonia (NH 3 

### ), NO x 

### , and SO x 

### have the potential to impact vapor phase collection efficiency.Method 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 33 of 6

In theory , basic stack gas constituents such as NH 3 

### 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 Mi dwest CFPP. The plant used a state

- of

- the

- art ammonia injection and selective catalytic reduction (SCR) for NO x 

### control 6 

### . Despite the presence of ammonia, the XFM reactive filter demonstrated an 11% relative accuracy relative to the Ontario

- Hydro method fo r 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., NO x 

### , and SO x 

### ) have the poten tial 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 NO x 

### concentrations of 200 ppm and SO x 

### 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) co ncentrations 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 industria l 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
SO 2 

### 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 chemis try.Method 301 Eval. : Appendix L V 1.0 Section 3 Range Extension 

### Pa ge 34 of 6

Figure 20

. Source applicability for XFM and Xact

- IAP Filter

- Based Approach (XFM & Xact

- IAP)

Analytical (XRF) Sampling ( Particle & Vapor
Phase Filter s )

Independent o f Source Type

Generally Applicable Particle Sampling Vapor Phase Sampling

Generally Applicable Emissions

Constituents with No Impact Emissions
Constituents with Potential Impact

Cl 2 CO
CO 2 N 2 O 2 H 2 O NO
x S O
x NH 3

Low Concentration Fugitive Sources High Concentration
Duct Sources

Generally Applicable Generally Applicable Generally ApplicableMethod 301 Eval. : Appendix L V 1.0 Section 4 Summary 

### Page 35 of 6

Table 14 : Summary of test results in support of extending filter approach.Method 301 Eval. : Appendix L V 1.0 Section 4 Summary 

### Page 36 of 6



## 4. Summary

The data presented in t his 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 V 1.0 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 Tech nology

– 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 Sta tionary 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: Co al

- 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 Pr oject 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. Compen dium 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 TEOM TM 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 standar ds 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 source s 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

1method 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

2Introduction

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 t hat 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 veri fy 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 themethods 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 prec ise 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

3conditions, 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 meas urement 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/f2 2 - 1/f1 2 ) (2)

The tapered element system is construct ed 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 K 0 has been determined for a particular tapered element, it can be used for mass
measurements.

If the element is oscillating at the frequency of f a and has a frequency response of f b after an unknown mass is collected on the filter ( ∆ m’), ∆ m’ can be obtained as a function of f a , f b and K o using the following equation:

∆ m’ = K 0 (1/f b 2 - 1/f a 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 stabilit y necessary for measurement of very small mass changes with high temporal resolu tion. 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

4measuring 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 t he 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. st ack 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

5Condition 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
A ve. 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

611:22 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 m easurement 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 precisi on 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 we re 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-lo cated) 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

7concentration 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/m 3 ) TEOM SPM Unit 20111 conc. (mg/m 3 ) 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. sta ck temperature: 160.0°C

Stack diameter: 9.3 m Ave. stack gas velocity: 19.7 m/s

Traverse Test: Ave. sta ck 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

8Figure 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/m 3

Unit 20111 ave. 15.1 mg/m 3

location: 0.41 m from wall Traverse Point 3 Unit 20102 ave. 15.5 mg/m 3

Unit 20111 ave. 15.7 mg/m 3

location: 2.76 m from wall Traverse Point 2 Unit 20102 ave. 14.4 mg/m 3

Unit 20111 ave. 15.2 mg/m 3

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 M onitor s

The f ollowing 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 Removin g Mercury from Fluid Streams

Issued 03/29/05

.

II. U.S. Patent 6,770,250; Apparatus and Methods for Remov ing Mercury from Fluid Streams.

Issued 08/03/04

.

III. U.S. Patent No. 7,381,388; Method for Removing Mercury from a Gas Stream U sing Iodine

Doped 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 t o US Patent Office