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5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com April 8, 2015

Mr. George Czerniak Director, Air and Radiation Division (A-18J) EPA Region 5 77 West Jackson Boulevard, 18 th Floor Chicago, IL 60604

Re: Response to the Cooper Environmental Services Post-Closure Date Submittal to Docket ID EPA-R05-OAR-2014-0280 on the Viability of the Xact ® Multi-metal Continuous Emissions Monitoring System Required by EPA on the Veolia’s Sauget, Illinois

Hazardous Waste Incinerators for the Collection of Metals Data Related to HWC MACT Compliance Standards.

Dear Mr. Czerniak:

This letter is in response to comments by Cooper Environmental Services (CES) and posted by

EPA relative to our December 2014 submittal to Docket ID EPA-R05-OAR-2014-0280. Our submittal evaluated the viability of using the Xact ® Multi-metal continuous emissions monitoring system (CEMS) for evaluating Hazardous Waste Combustor (HWC) Maximum Achievable Control Technology (MACT) metals emissions compliance of Veolia’s Sauget, Illinois hazardous waste incinerators (HWIs). CES’ comments, submitted in February 2015, well after the draft Title V Air Permit comment period closing date of December 19, 2014, require us to respond at this time.

CES Point 1: Traverse vs. Single Point Sampling, Isokinetics, and Verification Testing We and others commented substantially on the particulate matter (PM) transport issues

associated with accurate continuous metals emissions measurements. 1,2 The Xact ® CEMS obtains samples for analysis via single-point, non-isokinetic sampling. Samples of particle bound constituents obtained in such a manner can not be representative of stack gas effluents for compliance measurements. CES crudely compensates for the non-isokinetic sampling of

the Xact ® CEMS by operation of their units at super-isokinetic conditions in order to avoid consistently collecting data with a low bias and a non-representative sampling reputation.

TEOMTM PM Emission Stratification Study In their own defense of the single-point, non-isokinetic PM sampling aspect, CES’ response

included reference to EPA work that evaluated PM stratification in emissions from a coal-fired power plant (CFPP) using the R&P Tapered Element Oscillating Microbalance (TEOMTM) monitors. The TEOMTM monitor study was conducted in two parts:

1. Validation of the TEOM TM monitors accuracy through comparison with manual reference methods, and 2. Evaluation of the precision of side-by-side TEOM TM monitors. 3Page 2 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com First, we specifically note these same types of measurement comparisons be required if a proper validation of the Xact ® CEMS in terms of accuracy, precision, and bias is to be obtained. To our knowledge, no such complete study of the Xact ® CEMS has ever been performed.

In the CFPP study, the relative difference of the paired TEOM TM monitors averaged 7.7% and 4.5% for co-located and traverse sampling, respectively. CES points to the TEOM TM study as

evidence that PM emissions stratification is not significant. While this may have been the case for a system firing only a single, reasonably unifo rm fuel under relatively stable stack flow conditions, this test in no way substantiates any claim as to the absence of PM stratification in all firing cases. Nor, does this testing substantiate the general absence of PM stratification for a HWI unit where the wastes treated (fuels) vary and firing conditions are constantly changing.

Another PM Stratification Study CES’ response cites another PM stratificati on study involving traverse and single-point sampling. Like the TEOM TM monitor study, no PM stratification was found in that study. However, while metals routinely attach to PM, there is no data presented in this other study, or the previously cited TEOM TM monitors study, to show metals do so uniformly. In March 2015, CES revised and resubmitted the February 2015 submittal to remove the second PM stratification study citation.

TEAD Incinerator Study The testing of the Xact ® CEMS on Tooele Army Depot (TEAD) incinerator in 2001 and 2002 did

involve an evaluation similar to Part 1 above, the Xact ® CEMS versus a paired set of Method 29 trains. The TEAD test conditions were the correct testing configuration for thorough accuracy testing of the Xact ® CEMS. Specifically, the sampling was performed on a stack gas where the concentrations of the target metal analytes were well above the detection limits of

both the Xact ® CEMS and Method 29 such that accuracy and bias of the CEMS could be evaluated. CES has routinely and publicly presented the TEAD data for a select subset of metals, but glaringly excludes data for the other metals tested that failed to meet the required acceptance criteria. As we note in our December 2014 letter, when the TEAD data for all the metals tested are examined, the conclusion can only be the Xact ® CEMS design that was tested was a substantial failure. To our knowledge, a Part 2 study using paired Xact ® CEMS units to evaluate the relative precision has never been performed.

Coal-Fired Power Plant Study Later studies of an “improved” version of the Xact ® CEMS design were performed by CES on

two CFPPs. 4 One study involved dynamically enrichi ng a slipstream of CFPP stack gas with multiple metals using the Quantitative Aeroso l Generator (QAG). This study compared the

variance between the Xact ® CEMS reported concentrations and the “known” concentration of the generated aerosol. The stated purpose of this study was to evaluate “any potential

interferences from the coal-fired effluent” . The second study involved the Xact ® CEMS versus paired Method 30B sampling for mercury. The sampling point for this study was performed between the electrostatic precipitator (ESP) and wet scrubber. Neither study involved direct sampling of the stack gas in the stack versus Method 29 or Method 30B as required by Performance Specification 10 (PS-10).Page 3 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com Eli Lilly Validation Study In the Eli Lilly (Lilly) testing of the Xact ® CEMS, Method 29 comparisons were replaced with QAG reference aerosol comparisons. 5 Similar to the CFPP study, the QAG was used to enrich a slipstream of stack gas that was then sampled non-isokinetically. We comment in ourDecember 2014 letter and again later in this letter about the representativeness of the QAGsimulated emissions as related to particulate behavior. As would be expected under such controlled conditions, consistent results were obtained. However, at no time was there any testing performed with direct comparisons of the Xact ® CEMS to Method 29 sampling of actual

incinerator emissions.

ETV Ambient Air Monitor Study The EPA, via the Environmental Technology Verification (ETV) Program, evaluated the Xact ®

625. CES has posted the summary of this particular study on its website(http://cooperenvironmental.com/wp-content/uploads/2014/08/Xact625_ETVReportsummary.pdf ) and included the summary as an attachment the December 2014 submittal to Docket ID EPA-R05-OAR-2014-0280. The full report can be found at EPA’s website (http://nepis.epa.gov/Adobe/PDF/P100FK6B.pdf ). The mission of the ETV is to facilitate the deployment of innovative or improved env ironmental technologies through performance verification and dissemination of information thereby accelerating the acceptance and use of improved and cost-effective technologies. 6 This particular study was performed by Battelle. The reason CES does not include the full ETV study is evident when the full report is

examined.

The ETV study evaluated the ability of the Xact® 625 as an ambient air monitor to provide quantitative measurements of metals in particu late matter with an aerodynamic diameter less than 10 micrometers (PM 10 ). The ETV study compared the Xact® 625 results to concurrent ambient air monitoring being performed at sites in East Liverpool and Marietta, Ohio. The existing monitor, a Partisol Plus 2025 Sequential Ambient Particulate Sampler, was operated in

accordance with EPA Method IO-3.1 and served as the reference method. A total of 23 metals were reported hourly by the Xact® 625 over a per iod of approximately 80 days. Daily averages of the Xact® 625 metals readings that exceeded the daily quantitation limits (“QLs”) of the analyzer were compared to corresponding results determined for 19 of the 23 target metals by analysis of the filters from the Partisol Plus 2025 monitor performed via inductively coupled plasma/mass spectrometry (ICP/MS).

The poor performance and lack of verification of the Xact® 625 is commented upon throughout the document. Of the 19 metals examined by both methodologies, the Xact® 625 results for 12 metals were almost always below the respective QLs of the Xact® 625, and consequently no comparisons could be made to the reference results. For this reason, the Xact® 625 could not be evaluated for 12 of 19 metals. Additionally, the ETV study notes that the Xact® reported a nearly constant and unrealistic ambient concentration of molybdenum (Mo) due to an incorrect energy window for that metal in the X-ray fluorescence (XRF) analysis. The ETV study acknowledged that, for purposes of t he experiment, the Xact technology was not accurate for measurement of molybdenum (Mo). Of the 23 ambient air metals determined by the Xact® 625, only six (6) were left to be possibly verified: calcium (Ca), manganese (Mn), selenium (Se), zinc (Zn), copper (Cu), and lead (Pb). The ETV study noted that:Page 4 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com “the daily average Xact® 625 results were highly correlated and in close quantitative agreement with ICP/MS analysis results for most of the six metals, and ... the Xact® 625 achieved data completeness of over 95%.”

.

This statement appears initially to be a positive finding for the Xact® 625, however, the part concerning data completeness simply acknowledges that the Xact® 625 generated data 95% of the time over the analysis period. The definitive portion of the statement is “...close quantitative agreement with ICP/MS analysis results for most of the six metals.” The study goes on to clarify that out of the six (6) metals that could be evaluated, the Xact® 625 could only provide unbiased results for four (4) metals: calcium (Ca), manganese (Mn), selenium (Se), and zinc (Zn). The test results for copper (Cu) and lead (Pb) exhibited substantial problems of bias.

The HWC MACT rule regulates the emissions of six (6) metals from HWIs: arsenic (As), beryllium (Be), cadmium (Cd), chromium (Cr), l ead (Pb), and mercury (Hg). Of the ETV study short list of metals, lead (Pb) is the only metal of HWC MACT interest, and the results for lead (Pb) were substantially biased The lead (Pb) results for 52 data points exhibited a high bias that ranged from 8.7 to 339% and averaged nearly 75%. The study does note that part of the lead (Pb) bias is due to the blank level of 1 ng/m 3 on the Xact® 625 sample media (tape).

The ETV study notes the following relative to the quality control (calibration) checks of the

Xact® 625:

The results of the automated daily internal QC checks performed by the Xact 625 were reviewed approximately weekly, each time data were downloaded from the instrument. Those results showed stability in Xact 625 operations throughout the entire period of operation at both the East Liverpool and Marietta sites. Over that entire period the relative standard deviation (RSD) of the Pd [palladium] internal standard readings determined in every Xact 625 XRF analysis was 2.04%. The instrument’s average flow error was -0.69% (± 0.004%), where the value in parentheses is the standard deviation (SD) of the daily flow check results. The average accuracy relative to upscale rod check standards analyzed daily was 100.21% (±0.004%) for Cr, 100.55% (±0.013%) for Cd, and 99.79% (±0.007%) for Pb, where accuracy of 100% represents perfect agreement with the upscale rod check standard.

The Xact® technology, when checked against its own standards, appears to perform superbly. However, the ETV study lead (Pb) results demonstrate the Xact® technology has significant bias issues when compared to the reference method.

A careful reading of the ETV study, like the earlier TEAD study, shows that the Xact technology could not be adequately verified for 19 of the 23 metals that the Xact was designed to target. The ETV study includes the following disclaimer:

“EPA and Battelle make no expressed or implied warranties as to the performance of the technology and do not certify that a technology will always operate as verified.”Page 5 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com CES Point 1 Summary Metals emissions compliance measurement has two parts: 1) sampling, and 2) analysis. The CFPP and Lilly studies address only one-half of the emissions compliance process, specifically the analysis portion. The CFPP and Lilly studies do not include comparisons of the Xact ®

CEMS to analysis results where the sampling was performed isokinetically. The TEAD and ETV studies expose the bias of the sampling portion of Xact ® CEMS. The data from TEAD and ETV studies show the results are varying and generally biased high. The high bias is due to the super isokinetic sampling aspect of the Xact ® CEMS purposefully performed so as to avoid a low bias reputation. Unless the samples for analysis are obtained isokinetically, the Xact ®

CEMS results can never be valid for demonstrating metals emissions compliance.

CES’ response is a broad diversion from the fact that the Xact ® CEMS has never undergone a rigorous validation testing process involving a direct comparison with Method 29 under the same sampling conditions. For the study to be technically defensible, sampling must be of a stack gas where the concentrations of the target metal analytes are well above the detection

limits of both the Xact ® CEMS and Method 29 , and the sampling is performed isokinetically. Only then can accuracy, precision, and bias be appropriately assessed. Until such testing is performed, the Xact ® CEMS can not be accepted or used for any emissions compliance purposes. The EPA has failed to require complete validation of this technology by CES before requiring Veolia to deploy the Xact ® CEMS on the Sauget HWIs.

CES Points 2 & 3: Particle Size and Saltation during Sample Acquisition Particles of various sizes exist in a stack gas stream. Cross-sectional velocities within the stack may not be uniform, and may vary. As such, particle quantities and sizes may or may not be evenly distributed within the stack. Particles in any moving fluid (gas or liquid) making transitional changes in direction within a conduit (duct, stack, line, or pipe) will not be evenly distributed, and will to some degree make impact with the conduit surfaces, regardless of particle size. The degree to which such impaction and possible deposition (saltation) occurs is a function of particle size and quality (e.g., adherence properties). Similarly, settling of particles occurs in horizontal runs due to gravitational impacts and other factors.

CES’ comments include a schematic of the Xact ® 640 CEMS sample transport and setup. The

Xact ® CEMS utilizes a single-point probe in the stack. The indicated sampling rate is 100-600 liters per minute (lpm). The heated transfer line (maintained at 190 o C) from the stack probe includes turns and horizontal runs. From the heated transfer line/stilling chamber, the Xact ®

CEMS sample acquisition system extracts a small slipstream (~1 lpm) which is drawn across

the Xact ® CEMS filter media. A sample that is not obtained isokinetically and travels via such an extended and circuitous pathway can not be repres entative of the particle distribution within the stack. In fact, the sample acquisition is doubly non-isokinetic; the single point sampling in the stack is non-isokinetic and the sub-sample taken from the transfer line/stilling chamber is also non-isokinetic. Therefore, the sample obtained for analysis can not be comparable to that obtained isokinetically using the manual methods, and where any probe deposited metals are also recovered for analysis via reagent rinses.

Any compensating measures (sampling rate adjustments, etc.) in the Xact ® CEMS sample acquisition operation will not result in consistently accurate and precise measurements ofPage 6 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com metals emissions. Any sample collections that are conducted under non-isokinetic conditions can not be representative, and therefore can not be accurate.

CES Point 4: QAG Operation and Representative Sampling CES appears to have completely missed the point of our comments related to representativeness of QAG generated emissions. The point is that the chemical and physical properties of the surrogate aerosol emissions generated by the QAG in no way correlate to the actual chemical and physical properties of actual emissions encountered in source emissions. The metal nitrate aerosols have very different chemical and physical properties than the hard fired metal oxides encountered in actual stack gas emissions. Therefore, the surrogate aerosols will behave in a considerably different wa y than a real stack gas matrix and should not be considered as an acceptable choice for this application. If a QAG is to be considered an acceptable accuracy evaluator system to prove that the Xact CEMS works (which given the dynamic conditions in stack emissions, it is seriously questionable), then at a minimum, the evaluators should require the use of the same chemical oxide forms as will be encountered in actual stack gas to be used for the standardization. The metal nitrate mists are not representative and should not be used for this reason.

A particular point of objection is the use of the QAG for the performance of what CES denotes as a Relative Accuracy Test Audit (RATA). CES’ “RATA” methodology for the Xact ® CEMS redefines the term. As we previously stated in our December 2014 letter, the Xact ® CEMS “RATA” protocol which entails dynamically spiking a series of reference aerosol concentrations using the QAG and comparing the Xact ® CEMS responses to the documented concentrations, is akin to a calibration error (CE) test. A RATA, as historically understood and performed under the EPA air regulations, requires using a reference method (RM), in this case another CEMS, operated concurrently. The CES claim about passing numerous “RATA” tests is not accurate pursuant to EPA’s typical definition of “RATA”.

CES Point 6: Xact ® CEMS Sampling Cycle and Analysis Times and Duration We acknowledge the error with regard to the sampling cycle and analysis times and durations in our description of the current the Xact ® CEMS design. However, the point remains that pauses or stops in the Xact ® CEMS sampling operation is likely to cause particulate settling in the quiescent environment portion of the instru ment transport system, no matter how small the portion or how short the duration. Sampling interruptions logically imply that particulate sampling bias is likely.

CES Point 7: Vapor Phase Mercury Sampling and Analysis With regard to our comments relative to impacts of carbon in the stack gas on the performance

of the Xact ® CEMS in measuring mercury emissions from CFPPs, we offer the following citation from an EPA update on controlling mercury emissions from CFPPs:

Mercury may be present in the flue gas in several forms. The specific chemical form – known as the speciation – has a strong impact on the capture of mercury by boiler air pollution control (APC) equipment.* Mercury may be present in the flue gas as elemental mercury vapor (Hg 0 ), as a vapor of an oxidized mercury species (Hg 2+

), and as particulate-bound mercury (Hg p ).Page 7 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com Heterogeneous (gas-solid, surface catalyzed) mercury oxidation is more complex and depends upon the availability of surfaces having electrophylic groups that attract the electron-rich Hg 0 atom. The heterogeneous reactions occur mostly on fly ash surfaces or boiler surfaces, especially if the fly ash contains high amounts of unburned carbon. A proposed heterogeneous oxidation mechanism indicates the chlorination of carbon by HCl is a first step toward heterogeneous oxidation of Hg 0 to HgCl 2 , and adsorption of the mercury onto the carbon. The mercury that is adsorbed onto solid surfaces, such as fly ash or unburned carbon, is the particulate-bound mercury, Hg p , which can be captured by downstream PM control devices. Hence, fly ash characteristics – especially carbon - as well as coal chlorine content play an important role in mercury speciation and capture.

Other flue gas species – especially SO 3 and H 2 O – have also been shown to affect mercury speciation, tending to suppress Hg 0 oxidation to Hg 2+ . This is due to competition for active sites on the surface of carbon or other flue gas solids. In general, bituminous coals tend to have higher chlorine contents and also tend to produce higher levels of unburned carbon (UBC) in the fly ash. As a result, the flue gas from the burning of bituminous coals tends to contain higher amounts of Hg 2+

species while that of subbituminous and lignite coals tends to contain more Hg 0 vapor.

*Note: In general it is thought that Hg 0 will not be removed by pollution control equipment without first converting it to another form of mercury – either Hg 2+

or Hg p. However, there is also the possibility for interaction between a charged surface and the elemental mercury vapor. These interactions may be in the form of electrostatic, van de Waals, and polarization energies (elemental mercury vapor is polarizable). 7

The principles associated with mercury capture and emissions control from CFPPs equally apply to the Xact ® CEMS filter media. Relying on EPA’s work cited above, we conclude our comments are accurate relative to the better performance of the Xact ® CEMS in measuring mercury emissions from CFPPs being partially attributable to the absorption of mercury on unburned carbon and subsequent PM capture.

Conclusion

The Xact ® CEMS fails to match the results obtained with EPA reference methods when direct comparisons are made and these data are understood. The Xact ® CEMS does not obtain samples isokinetically and can not be accurate. The high bias of the Xact ® CEMS-determined metals emissions resulting from super isokinetic operation falsely overstates metals emissions.

The Xact ® CEMS measured metals emissions data are not usable or reliable for continuous metals emissions compliance demonstration for a HWI.Page 8 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com Please contact us to discuss the specifics of our comments or any questions you may have.

Regards,

William C. Anderson, PhD Senior Analytical Project Manager

TestAmerica, Inc.

Chris E. McBride, PE Consultant/Principal

Focus Environmental, Inc.Page 9 of 9

5815 Middlebrook Pike Knoxville, TN 37921 tel 865.291.3000 fax 865.584.4315 www.testamericainc.com 1 Baxter, Robert, 2014. Evaluation of the Xact Multi-Metal CEMS . December 11, 2014.

2 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 St atement of Basis Dated October 2014

3 Real Time Measurement Of Particulate At Low Co ncentration 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; Gille s Gonnet, Ecomesure, B.P. 13.

4 Review of Monitoring Experience with Xact ®

Multi-Metal Continuous Emissions Monitor , Paper #29; Krag Petterson, Cooper Environmenta l Services, LLC, Beaverton OR; 33 rd International Conference on Thermal Treatment Technologies & Hazardous Waste Combustors, October 13-15, 2014, Baltimore,

MD.

5 Validation of Three New Methods for Determ ination of Metal Emissions Using a Modified Environmental Protection Agency Method 301 , ISSN 1047-3289 Journal of the Air & Waste Management. Association, 56:1733–1742 (2006); Cat herine A. Yanca, Douglas C. Barth, Krag A. Petterson, Michael P. Nakanishi, and John A. Cooper , Cooper Environmental Services, LLC, Portland, OR; Bruce E. Johnsen, SAIF Co., Portland, OR; Rich ard H. Lambert, Engineering Tech Center, Eli Lilly and Co., Indianapolis, IN; Daniel G. Bivins, U.S. Environmental Protec tion Agency, Research Triangle Park, NC

6 Environmental Technology Verification Report, Cooper Environmental Services LLC Xact 625

Particulate Metals Monitor , Prepared by Battelle Under a cooperative agreement with U.S. Environmental Protection Agency, EPA/600/R-12/680, September 2012

7 Control of Mercury Emissions from Coal Fir ed Electric Utility Boilers: An Update Air Pollution

Prevention and Control Division National Risk Mana gement Research Laboratory Office of Research and Development, U.S. Environmental Protection A gency, Research Triangle Park, NC. February 18,

2005.