VES 000620.pdf 
US Army Corps 

of Engineers® 

Engineer Research and 

Development Center 

X-Ray Fluorescence-Based Multi-Metal 

Continuous Emission Monitor 

Developmen t 

K. James Hay, Bruce E. Johnsen, and January 2005 

John A. Cooper 

Pressure 

Qamnl p Leak Check Transducer 

sample Valve " 

SAMPL E 

RETUR N 

LINE 

Extractio n 

Syste m 

Samplin g 

a n d 

Analysi s 

Syste m 

Approved for public release; distribution is unlimited. 

VES 00062 
VES 00062 
ERDC/CERL TR-05-3 

January 2005 

X-Ray Fluorescence-Based Multi-Metal Continuous 

Emission Monitor: Development 

K. James Hay 

Construction Engineering Research Laboratory 

PO Box 9005 

Champaign, IL 61826-9005 

Bruce E. Johnsen and John A. Cooper 

Cooper Environmental Services 

10170 SW Nimbus Avenue, Suite H5 

Portland, OR 97223-4340 

Final Report 

Approved for public release; distribution is unlimited. 

Prepared for U.S. Army Corps of Engineers 

Washington, DC 20314-1000 

Under Work Unit #CNE-B091 
ABSTRACT: Army demilitarization incinerators will need to comply with the Hazardous Waste Combustor National Emission Standards for Hazardous Air Pollutants that will regulate metals and metal compounds listed under 

the Clean Air Act Amendments. A large problem for these incinerator operations is limited knowledge of the types 

and quantities of emitted metals. Compliance may be determined only through trial bum emission tests because of 

this limitation. A continuous emission monitor (CEM) for multi-metals will provide the emission data, a tool to help 

meet compliance requirements, and the opportunity to adjust burn strategies for increased production. The XCEM 

multi-metal CEM was developed using x-ray fluorescence (XRF) as the analytical method and an automated sampling system that provides extractive batch sampling onto a filter tape. The system is operated with user-friendly 

WonderWare® software that provides automation, calibration routines, and report generation. A prototype XCEM 

was tested in the laboratory with a spiked gas stream against U.S. Environmental Protection Agency Reference 

Method 29 for four sample runs. The XCEM met the relative accuracy criteria for four of seven metals. A fieldready XCEM was built for demonstration at the 1236 Deactivation Furnace at Tooele Army Depot, Utah. 

DISCLAIMER : The contents of this report are not to be used for advertising, publication, or promotional purposes. 

Citation of trade names does not constitute an official endorsement or approval ofthe use of such commercial products. 

AH product names and trademarks cited are the property of their respective owners. The findings of this report are not to be 

construed as an official Department of the Army position unless so designated by other authorized documents. 

DESTRO Y THIS REPOR T WHE N IT IS N O LONGE R NEEDED . D O NOT RETUR N IT T O TH E ORIGINATOR . 
ERDC/CERL TR-05-3 iii 

Contents 

List of Figures and Tables

 v 

Conversion Factors

 v " 

Preface

 vii i 

1 Introduction

 1 

Background

 1 

Objective

 3 

Approach

 3 

Mode of Technology Transfer

 3 

2 XCEM Development

 4 

XCE M Description

 5 

Extraction System 5 

Sampling and Analysis System 7 

Control System 9 

Integration of Sensors

 1 0 

Operator Accessible Control Screens 10 

Administrator Accessible Control Screens 17 

Sampling Platform Modifications

 1 9 

Quality Assurance Modifications 19 

Ease-of-use Modifications 23 

Safety Modifications 24 

3 Laboratory Testing 25 

Mercury Sampling

 2 5 

Experimental 25 

Mercury RIF Results 25 

Mercury Oxidation Automation 26 

Mercury XCEM Results 27 

Method 29 Comparison Tests

 2 7 

Spike Injection System 27 

Test Design 3 0 

XCEM Results During Method 29 Testing 31 

XCEMvsM29 3 7 

Method 29 and XCEM Precision and Accuracy 39 

VES 00062. 
iv ERDC/CERL TR-05-3 

4 Field-ready XCEM 43 

5 Summary and Conclusions 46 

References 48 

Abbreviations and Acronyms 49 

Report Documentation Page 51 
ERDC/CERL TR-05-3 v 

List of Figures and Tables 

Figures 

1 Schematic of XCE M components minus the control computer 5 

2 XCE M analysis system, computer control, and sampling cassette 6 

3 XCE M sampling cassette

 7 

4 Gas sampling process in the sample cassette 8 

5 X-ray detection process

 8 

6 Component Control screen

 1 1 

7 Diagnostics screen

 1 2 

8 Metal Concentration screen during M29 testing 12 

9 Quality Assurance screen

 1 3 

10 Temperature Trend screen

 1 4 

11 Pressure Trend screen 1 4 

12 Flow Trend screen

 1 5 

13 Concentration Trend screen 15 

14 Data output screen 1 6 

15 Alarm screen 17 

16 Set Q A Ranges screen

 1 8 

17 Set Analog Ranges screen i 9 

18 XCE M QA program

 2 0 

19 PL C control for the XCE M

 2 1 

20 Zero and span test plunger

 2 2 

21 Pd wire-mounted for QA

 2 2 

22 XCE M sampling cassette and XR F control panel 24 

23 Schematic of Hg capture for first phase experiments 26 

24 RIF Hg capture efficiency versus air flow rate through filter 26 

25 XCE M elemental concentrations during M29 testing 32 

26 XCE M cadmium versus other spiked metals during M29 testing 35 

27 Comparisons of XCE M and M29 concentration by run 40 

28 XCE M and M29 normalized concentrations by element 41 

29 New Component Control Screen for XCE M software interface 43 

VES 00062 
vi ERDC/CERL TR-05-3 

30 XCE M cassettes 44 

31 XCE M extraction system and cassette and chassis 44 

32 XCE M with cabinet door open 45 

33 XCE M with computer system installed at TEAD 45 

Tables 

1 Army hazardous waste combustors 2 

2 Evaluation of spike injection options 29 

3 Test conditions during M29 sampling 31 

4 Elemental concentrations at XCE M and M29 Ports during pre- and 

post-tests 36 

5 Relative accuracies of M29 Port versus XCE M Port during pre- and 

post-tests 36 

6 Reported XCE M and M29 concentrations 38 

7 Average metal concentrations for each sampling run 38 

8 XCE M and M29 relative accuracies 39 

VES 
ERDC/CERL TR-05-3 vii 

Conversion Factors 

Non-SI units of measurement used in this report can be converted to SI units as 

follows: 

Multiply By To Obtain 

degrees Fahrenheit (5/9) x (°F - 32) degrees Celsius 

feet 0.3048 meters 

inches 0.0254 meters 

* Systeme International d'Unites (International System of Measurement), commonly known as the metric system. 
viii ERDC/CERL TR-05-3 

Preface 

This study was conducted for Headquarters, Department of the Army under Program Element 063728A. "Environmental Technology Demonstration"; Project 

002, "Environmental Compliance Technology"; Work Unit CNE-B091, "Hazardous Air Pollutants Technology Demonstrations." The peer reviewer was Thomas 

Logan, U.S. Environmental Protection Agency, Office of Air Quality and Planning and Standards, Air Measurements and Quality Group. 

The work was performed by the Environmental Process Branch (CN-E) of the 

Installations Division (CN), Construction Engineering Research Laboratory 

(CERL). The CERL Principal Investigator was Dr. K. James Hay. Part of this 

work was contracted to Cooper Environmental Services under DACA42-02-P0072, DACA42-01-R-008, and DACA42-00-P-0245. The technical editor was 

Linda L. Wheatley, Information Technology Laboratory. Dr. Kirankumar V. 

Topudurti is Chief, CN-E, and Dr. John T. Bandy is Chief, CN. The associated 

Technical Director was Gary W. Schanche. The Director of CERL is Dr. Alan W. 

Moore. 

CERL is an element of the U.S. Army Engineer Research and Development 

Center (ERDC), U.S. Army Corps of Engineers. The Commander and Executive 

Director of ERDC is COL James R. Rowan, EN, and the Director of ERDC is 

Dr. James R. Houston. 
ERDC/CERL TR-05-3 1 

1 Introduction 

Backgroun d 

The U.S. Environmental Protection Agency (EPA) is developing regulations for 

Hazardous Waste Combustors (HWC) as part of Title III of the 1990 Clean Air 

Act Amendments (CAAA) in the form of a National Emission Standards for Hazardous Air Pollutants (NESHAP). The U.S. Army possesses many demilitarization furnaces that will need to comply with these regulations. Of most concern is 

being able to meet the requirements for metals and metal compounds listed under the CAAA. These incinerator operations have a large problem because of 

limited knowledge of the types and quantities of metals emitted. Compliance 

may be determined only through trial bum emission tests because of this limitation. These tests are expensive and require worst-case scenario burns. The air 

permits that are then issued are based on these worst-case burns and impose 

limitations on the demilitarization facilities. A continuous emission monitor 

(CEM) for metals would provide the emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn strategies for increased 

production and sustainability. In addition, the HWC NESHAP suggests that a 

C E M would be the preferential method of emission accountability. 

Multi-metal CEMs being developed are based on elemental sensors using laserinduced breakdown spectroscopy (LIBS) or inductively coupled plasma (ICP). 

None of the LIBS monitors has successfully met the EPA-proposed Performance 

Specification 10 (PS-10 1996) for continuous multi-metal monitors. Only one of 

the ICP units, developed by Thermo Jarrell Ash Corporation, has been successful 

in meeting the relative accuracy (RA) criteria of the PS-10 (Seltzer 2000). The 

multi-metal CEMS technology appears to have practical limitations such as its 

complexity, high initial cost, and high operating costs. The U.S. Army Engineer 

Research and Development Center, Construction Engineering Research Laboratory (ERDC/CERL) decided to pursue the development of the X-ray fluorescence 

(XRF)-based continuous emission monitor (XCEM) because it had the potential 

to be a reliable and accurate CE M without these limitations. 

The basic approach of the XCE M is to draw a continuous representative sample 

of stack gas to a stilling chamber where a smaller metered sample is extracted 

and passed through a chemically treated filter that collects metals in the particu-
2 ERDC/CERL TR-05-3 

late and vapor phases. Following sampling, the filter is passed through an XRF 

analyzer where the masses of up to 19 metals are measured. This approach was 

originally tested in 1997 at an EPA test incinerator, where the filters were analyzed offline (French 1998). Cooper Environmental Services (CES) further developed this method into an online system tested under the ERDC/CERL Waste 

Minimization and Pollution Prevention Program at MSE Technology Applications, Inc.'s (MSE-TA's) research incinerator in Butte, MT (Bryson et al. 2000). 

The results were encouraging because the XCE M met the PS-10 RA requirements for chromium (Cr) and lead (Pb). Many of the other requirements were 

unmet, however, and further development was needed. It was at this point that 

ERDC/CERL began funding the development of XCE M technology under their 

Hazardous Air Pollutants (HAP) program. Table 1 lists the Army's 19 existing, 

new, or planned hazardous waste combustors (Josephson 2003). 

Table 1. Army hazardous waste combustors. 

Location Type Waste Treated Status GO or CO 

Sierra AD A P E 1236 C S Existing G O 

Tooele A D A P E 1236 C S Existing G O 

Tooele A D A P E 1236 Test Furnace - C S Existing G O 

McAlester AA P A P E 1236 C S Existing G O 

Hawthorne AA P A P E 2210 C S New C O 

Fort Richardson A P E 1236 C S New G O 

Kansas AA P A P E 1236 C S Existing C O 

Crane AA P A P E 1236 C S New G O 

Lake City AA P A P E 1236 Off-spec conventional Existing G O 

Picatinny Arsenal A P E 1236 Waste R&D propellants New G O 

Pine Bluff Arsenal Fluidized Bed Pyrotechnics and Obscurants New G O 

Pine Bluff Arsenal A P E 1236 Off-spec pyrotechnics Existing G O 

Radford AA P Kiln Off-spec propellants Existing G O 

Deseret C A Chemical Chem Existing G O 

Umatilla AD Chemical Chem New G O 

Pine Bluff Arsenal Chemical Chem New G O 

Anniston A D Chemical Chem New G O 

Pueblo C A Chemical Chem Planned G O 

Anniston A D Kiln De-Painting wastes Planned G O 

GO - Government Owned CO - Contractor Owned CA - Chemical Activity 

CS - Conventional Stockpile Chem - Chemical Stockpile APE - Army Peculiar Equipment 

AD - Army Depot AAP - Army Ammunition Plant R&D - Research and Development 
ERDC/CERL TR-05-3 3 

Objectiv e 

The overall objective of the HAP program is to develop cost-effective technologies 

to help the Army meet current and future demands of HAP regulations. The 

specific objective of the work reported here was to develop a multi-metal CE M 

for use at an Army installation. It is important that this monitor be easy to 

transition to the Army by incorporating characteristics that make it compatible 

with Army operations and expectations, such as user friendliness and 

affordability. Ultimately, the desired exit criterion under the HAP Program is 

for the monitor to meet the complete requirements of the proposed PS-10 under 

field conditions. This objective will be pursued in a follow-on report. 

Approac h 

The XCE M was developed under this project through contracts with CES 

(DACA42-00-P-0245 and DACA42-01-R-008). A prototype was constructed incorporating necessary improvements determined from the Butte testing, such as 

user friendliness, automation, and the capability to monitor mercury (Hg). This 

prototype was then tested in the laboratory by comparing it against the EPA 

Reference Method 29 (M29). A new monitor was constructed and readied for 

demonstration at the 1236 production deactivation furnace at Tooele Army Depot (TEAD), UT. 

Mod e o f Technolog y Transfe r 

This technology was developed through the ERDC/CERL HAP Program, which 

uses 6.3 advanced development and field-testing funds. The HAP Program is 

part of the Army Environmental Quality Technology (EQT) Program. As part of 

the EQT process, a technology transfer plan is being developed by the Army Environmental Center (AEC) for this technology and other qualified technologies 

under the HAP program. A User's Guide and a Resource Manual have been developed to accompany the XCE M for field training and reference (CES 2001a,b). 

This report will be accessible through the World Wide Web (WWW) at URL: 

http://www.cecer.army.mil 
4 ERDC/CERL TR-05-3 

2 XCEM Development 

Regulators, government agencies, and industry have expressed support for development of instrumentation capable of continuous measurement of metals 

from stationary sources. The EPA recently reemphasized its position in the final 

Maximum Achievable Control Technology (MACT) standard for hazardous waste 

incinerators. In this standard, continuous monitoring is placed at the top of the 

Compliance Monitoring Hierarchy and underscored as the "strong preference" 

(Federal Register [FR] 52925). The incentives provided in the MACT standard 

for using multi-metal CEMs include bypassing feedstock measurement and decreased requirements for performance testing. In addition, end users of multimetal CEMs have real-time access to process control information and the potential for enhanced public acceptance. 

Over the past few years, CES has developed instrumentation capable of continuous multi-metal measurement. The CES approach uses XRF to measure stack 

gas particulate matter (PM) that has been concentrated on a filter. In 1997 CES 

demonstrated the feasibility of this approach using an offline continuous sampling system at an EPA test incinerator in North Carolina (French 1998). Further adaptation of the approach led to an online XCE M capable of determining 

metal concentrations every 10 to 15 minutes. The prototype XCE M was successfully tested in 1999 at the MSE-TA test facility (Bryson et al. 2000). During 

these tests, the XCE M demonstrated an RA for two MACT metals, Cr and Pb, of 

less than 20 percent. Further refinement was needed, however, to meet EPA's 

PS-10. Specifically, the MSE-TA report recommended that the following tasks 

be performed: 

1. Sensor Integration: Integrate temperature and pressure sensors into a userfriendly computer interface. 

2. Sampling Platform Modifications: Modify the sampling platform for improved 

ease-of-use, and integrate an automated quality assurance (QA) program into the 

sampling platform design. 

3. Mercury Sampling: Conduct additional laboratory testing for Hg capture efficiency and automation of XCE M Hg oxidation system. Conduct further Hg RA 

testing. 

4. Spike Injection System: Develop an injection method capable of supplying adequate concentrations of metals for routine testing. Conduct further XCE M RA 

testing using the new spike injection system. 
ERDC/CERL TR-05-3 5 

This chapter presents a general description ofthe XCEM and the improvements to 

the XCEM that address the first two recommendations made in the MSE-TA report: 

sensor integration and sampling platform modifications. 

XCE M Descriptio n 

Figure 1 shows major XCE M components and relative flows. The XCE M comprises three major subsystems: an extraction system, sampling and analysis 

system, and control system. 

Extraction System 

The extraction system is designed to transport a representative sample of stack 

gas from the stack to the filter tape. It includes a probe, 1-inch-diameter tubing, 

stilling chamber, and flow measurement and control components. Temperature 

is measured at five locations, and all tubing prior to the filter is heat traced. 

Pressure 

Leak Check Transducer 

Valve 

SAMPL E 

RETUR N 

LINE 

Extractio n 

Syste m 

Samplin g 

a n d 

Analysi s 

Syste m 

Figure 1. Schematic of XCEM components minus the control computer. 
6 ERDC/CERL TR-05-3 

The extraction system draws an isokinetic sample from the stack using a largediameter probe. The gas is transported to a 3-inch-diameter stilling chamber, 

which slows the gas velocity, decreasing the Stokes number so that small quantitative subsamples can be extracted. The subsample, less than 1 percent of the 

gas sample in the stilling chamber, is removed from the stilling chamber through 

a one-quarter-inch-diameter extraction tube. Inside the extraction tube, a dilution and mixing chamber allows the addition of chlorine and other gases to dry 

and oxidize the sample. The oxidized sample is then drawn through a resinimpregnated filter (RIF) where particulate and vapor phase metallic species are 

concentrated for subsequent XRF analysis. After passing through the filter, the 

gas is dried with a Universal Analyzer dryer, measured with a mass flow controller, and returned to the stack through a diaphragm sampling pump. A postfilter pressure transducer provides assurance that no leaks are present in the 

system. The volume of the remaining 99 percent of the stilling chamber stack 

gas is measured and returned to the stack using a regenerative blower. The entire extraction system is shown in Figure 1. 

The XCE M software interface controls key extraction system components including: thermocouples, a pressure transducer, blower, pump, and several flowmeters. Temperature, flow, and pressure data are automatically recorded in an 

electronic database. Figure 2 shows the sample cassette atop the XRF analyzer 

next to the computer control enclosure. 

Figure 2. XCEM analysis system, computer control, and sampling cassette. 
ERDC/CERL TR-05-3 7 

Sampling and Analysis System 

Once the stack gas subsample leaves the stilling chamber, it is drawn into a 

sample cassette (Figure 3). This cassette contains a stepper motor, infrared tape 

break sensor, and filter tape mounted on reels. Stack gas entering the cassette 

is transported through the extraction tube across a 0.3 cm2 spot on the filter 

tape. Every 12 minutes the filter tape in the cassette is advanced from the sampling location to the analysis position located 1 inch away. A Kevex-Spectrace 

QuanX XRF instrument (Thermo Kevex, Thermo Electron Corp., Waltham, MA) 

then analyzes the metals mass concentrated on the filter. Following analysis, 

the sample is advanced again and collected on a take-up reel. Figure 4 shows a 

schematic of this process. During the XRF analysis, x-rays are emitted from the 

x-ray tube onto the filter tape sample. Resultant x-rays are produced that are 

characteristic of the metals on the sample (Figure 5). These x-rays are detected 

by the XRF detector and a signal that is proportional to the mass for each metal 

is sent to the computer. The computer acquires these signals and compares it to 

known mass per signal ratios developed during calibration. XRF results are 

then reported as micrograms per sample. 

1 

Figure 3. XCEM sampling cassette. 
8 ERDC/CERL TR-05-3 

Gas Sample in 

Extraction Cassette Wheel 

Filtered Gas out 

Figure 4. Gas sampling process in the sample cassette. 

Filter Tap e Sampl e 

CZ. 1. 'L. 1 

Figure 5, X-ray detection process. 

VES 
ERDC/CERL TR-05-3 9 

Since XRF is nondestructive, metal mass on the take-up reel is available if 

needed for subsequent chemical analysis. Each cassette holds a 2-4 week supply 

of tape and is engineered to be portable and easily removed. It is anticipated 

that each XCE M will come with two cassettes, which will enable the operator to 

exchange tapes in a clean environment and transport the entire cassette into the 

field. An additional benefit of having two cassettes is a duplication of components. In the event of equipment failure, the duplicate cassette can be in place 

within a few minutes, decreasing instrument downtime. The cassette is designed to fit directly onto the XRF instrument and includes interlocks to prevent 

the XRF from operating when the cassette is not in place. 

The QuanX energy dispersive XRF has an electronically cooled lithium drifted 

silicon detector. Located immediately above the detector is a permanently 

mounted palladium rod, which is analyzed with each sample to determine if instrument drift is occurring. As an additional QA source, a rod is mounted on a 

pneumatic plunger near the detector. This rod has an epoxy coating with significant quantities of Cadmium (Cd), Cr, Hg, and Pb. Each day the XCE M activates 

the plunger and extends the rod into the analysis area for span and zero tests. 

Detection limits for the XRF are determined by filter blank concentrations and 

analysis time. If a sample is taken every 10 minutes, detection limits for all of 

the MACT metals are less than 3.5 ug/m3 (micrograms per cubic meter). Detection limits can be improved by increasing sampling time. The XRF automatically determines metals concentration and uncertainties. The data are then 

transmitted to a second computer, which runs the WonderWare® software control interface. 

Control System 

XCE M flows and temperatures are controlled using WonderWare® software 

interface on a personal computer. This interface records pressure, temperature, 

metals concentrations, QA data, and sampling times, and prints a hard copy 

report with each sample analysis. An electronic copy of the data is kept in a 

WonderWare® database, which cannot be altered without being flagged. These 

data can be made available over a local intranet or a secure Internet website. A 

second personal computer runs the XRF software. 

Automating the XCE M to make it a user-friendly tool was a primary objective of 

this work. The automation and control features that were developed are 

discussed in the next section. 
10 ERDC/CERL TR-05-3 

Integratio n o f Sensor s 

The MSE-TA report recommended computer control of XCE M components, data 

storage, and QA. In response to this recommendation, the XCE M has been fully 

automated using a WonderWare® software interface. This interface includes a 

variety of screens that allow the user to control components, diagnose problems, 

view concentration trends, and output data. Each screen contains an alarm signal in the lower right-hand corner that flashes if some component of the system 

is not working or if the metals' concentrations exceed user-defined limits. The 

XCE M interface is password protected and can be accessed by either an operator 

with limited XCE M control or an administrator with full user rights. 

Operator Accessible Control Screens 

The computer interface allows the user to view a number of screens that present 

operational data for control of the XCEM . Those screens are presented below. 

Component Control Screen 

The Component Control screen (Figure 6) contains a schematic of the XCE M system. This schematic includes icons representing key XCE M components and 

real-time data for temperatures, pressures, and flows. Adjacent to the schematic, a System Start/Stop button begins and completes sampling with a single 

click. This screen also provides users with the option of manually adjusting individual components of the sampling system. Users logged on as operators can 

control heaters or turn the pump and blower on by double clicking on the appropriate icon and responding to the pop-up dialogue box. Users logged on as administrators have the further capability of controlling flow rates and valves. 

This page is considered the "home page" for the interface and can be accessed 

from any screen by clicking on the house icon in the lower left-hand corner of the 

page. 
ERDC/CERL TR-05-3 11 

| jt~j & |Us « Warns None Screen LDckea Logon ] ' ^ Admin ; fft Reports j Q Trends

 ; 3 Screens ) AtHfffis •- 9/e/oo j 4:57:25 

Component Contrd 1 Metals Conccnb-attans J ) Qualify tesurance j j 

Figure 6. Component Control screen. 

Diagnostics screen 

The Diagnostics screen (Figure 7) is a read-only interface designed to give the 

operator an easy-to-read system status check. The Diagnostics screen displays 

current temperature, flow, QA and metal concentrations and lights indicating if 

the system is functioning properly. Buffer ranges defined by the system administrator for each component are displayed on this screen. Measurements that 

fall within these buffer ranges are given a green light. Measurements slightly 

beyond the range are signified with a yellow light, and data significantly beyond 

the buffer range warrant a red light. Yellow and red lights are listed as alarms 

by the XCE M interface. 

Metals Concentration screen 

Up to 20 real-time metals' concentrations are displayed on the Metals Concentration screen (Figure 8). Operators can graph up to eight of these concentrations 

simultaneously and access a 12-hour rolling average chart that displays High 

Volatile Metals (HVM), Semi-Volatile Metals (SVM), and Low Volatile Metals 

(LVM). The chart was developed in accordance with the MACT rule for hazardous waste incinerators and can be set to include buffer ranges to alert the operator of high metal concentrations in the stack. As with all graphs within the 
12 ERDC/CERL TR-05-3 

XCE M interface, the Metals Concentration graph's time axis can be set to display data for periods between a few hours up to 6 weeks. 

CES Sanpte Line Pies sure CES 

XCE M i Diagnostics : 

awnq Chamber Tetnpersture 

3rtln_ Chamber Intel Twrpf fslme 

' SA Parwrdet Zao Cadmium Current Value 

12-HOUR ROLLING AVERAGE BUT O RANGE 

COMPONENTS 

j HVMtHg) B 0,0 0.9 9.1 

(svM(cd6Pb) , 0.0 0.9 9.1 

[TVM (As a Cr) • . 

0.0 0.9 9,1 

. . . _ _ _ . _ 

STATUS CURRENT BAJFFER RANGE 

! Matnllne Flow (ocfin) 0.0 1.0 9.0 

j CBddan'tFbw (ml. mb) • ' 0.0 3.0 4OQ.0 

] Sample Flow (dslpm) 0,1 1.0 9.0 

j Stad<Terr^.rtjj.. .pC) B: 21.8 16.0 340.0 

j Upper ChAtrter TetnpsraturB t?C} B ' 4CO.0 16.0 340,0 

\ Lower Oamber TemperatLre (°C) B 4CO.0 16.0 340.0 

I Main Flaw Terrperature (.Q • B 21.5 16.0 340.0 

| Filer Temperature {°c> 22.5 36.0 340.0 

] sanpla th e Pressure <psfi) ' B 14.1 0,2 5.0 

QUALITY ASSURANCE 

| Span Metals (cr, Cd, Pb) 

j 2ero Metals (Cr, Cd, Pb) 

STATUS 

_____ [ QA Flow Difference 

rpsladUm 

STATUS 

___ _ 

1 

' 1 S~eenLWod<et| Logon | j & Admin j P i Reports) Q Trends ) • Screens J 00:20 • 

| | CarnfM-VfltGanlrd | J " Dlagia-tlrs "H f [ Metals Caxentratfais f | Qua-lty&swaicB 

Figure 7. Diagnostics screen. 

Inloij. h WmrluwVtrMi'i 

12-HOUR ROLLING AVERAGE 

, 12-HOUR 

RCtUNG 

' GRAPH 

j WM (Hg) 

! SVM (Cd 8. Pb) 

STATUS CUWtENT SUFTOPAMGE 

§ § | 113,66 ug/dscm 0.0 250,0 

! § 185.63 yg/dicin D.O 250.0 

I LVM (As a Cr) • 

198.96 pg/dscm 0,0 250.0 

CURRENT METAL CONCENTRATION UstSamptePeriod: 12:32:26 To 12:44:05 

Etermnt Concentration Element Cc*ncentra_ori 

232.5 

203.S 

1M.4 -

145,3 

116.3 % 

- u p L_I i )^r - -4_P= —'3-. -w-^^t-i^p-

&jg/dscrr)) 

f AS • 

0,0 CO 0.3 

{ Or • a o 

i ' 

Ni 0.4 

{ Cd • 0,0 • r Cu 1,7 

! Hg D. 0.0 i S T H 0,0 

j "p b BB 0.0 Br 2,3 

0.0 Tl 0,0 

j Ag i D.D r V 1,9 

j Sb O.D r Mn 0.0 

I Ba Q.O • r N.U. 

1.9 • r 2143.2 " 

View Trend 

Full Screen 

I S3 _ ^ i User Nam-', adrrfnlstr-lor 

! Screenuntocio-

 f j3 ' Logon j & Admin j ff» , Reports : Q Trends . E3 Screens j Alarms j li/ia/QQ j iOrfOi-7 '. 

CcmporientC_*-d Oi'arjit-tics Metal. OGncentratit-- Quallb/ Assurance 

Figure 8. Metal Concentration screen during M29 testing. 
ERDC/CERL TR-05-3 13 

Quality Assurance screen 

The Quality Assurance screen (Figure 9) is a read-only display that shows historical QA results. Palladium (Pd) is measured with each sample while daily 

span and zero tests for key metals are conducted at user-defined times. The time 

at which the latest QA check was undertaken is also listed in a text box on the 

right-hand side. 

Trends screens 

Trends for temperature, pressure, flow, and metals concentrations are all displayed as individual screens by the XCE M computer interface (Figures 10-13). 

Each screen can display up to eight trends simultaneously and can be customized to include combinations of data from the other trends screens. For example, 

stack temperature and metals concentrations can be graphed simultaneously. 

A ll figures can be printed by using the Print Trend button in the lower righthand comeY of the screen. 

XCEM Diagnostics 

[Sample Line Press StiBig Clmmfiyr Tempera!Ofc i 

Stiiirg Chamber htet Ternpy 

|QA Paiameter Iato cadrfMum Currer. vau_ 

12-HOUR ROLLING AVERAGE STATUS. CURRENT BUFFER RANGE 

j HVM01g> 0.0 0.9 9,1 

\ swfcdapb ) D.0 0,9 9.1 

UvMiAsacr ) • 0.0 a.e 9.1 

COMPONENTS STATUS CURRENT BUFFER RANGE 

Marin a Ftew (scfm) • .0 1.0 s.o 

, Oxidant Ftow (ml/min) • D.O 3.0 400,0 

i Sample Flow (dsfpm) 0.1 1.0 9.0 

' Stad< Temperature fC ) m . 21.B 16.0 340,0 

* Upper Chamber Temperature (=C) B 400.0 16.D 340.0 

| Lower Chamber Terrperature 0_) 11 400.0 16.0 340,0 

• Main Fbw Temperature TO m 21.5 16,0 340.0 

; Filt_p Temperature (°C) 22.6 16.D 340.0 

• Sample Line Pressure (psla) n ^ 14.1 0.2 5,0 

QUALITY ASSURANCE STATUS STATUS 

I SpanMetals(Cr,Cd,Pb) mi | QA Flow Difference n . 

fzer a Metals (Cr, Cd, Pb) ^ PabiU m • 

a

-Name: «dmlrtslr_or (Screen Unlocked f|) ' Logon ] Admin } fjl) Reports \ jfj Trends ! 3 Screens! £ j Alarms j sye/OO j. 5;00;2O 

Canpcnent Control Diagnostics Metals Cancentrations ~j Quality Pwssurante 

Figure 9. Quality Assurance screen. 
14 ERDC/CERL TR-05-3 

lnloui.h WindonViewef 

Ik.. "35 

>03' 5> 

l b 05 

-: 

)Jo-'05 

157. 0 

137. 3 

117. 7 

98. 1 

78. 5 

58. 9 

39: 2 

19. 6 

0 0 '_ ' 

i;- 3i 57 

© Ha * • StillJng Chanter Q Rtter 

H staling chanter Inlet @ swing Chanter Outlet 13 Not Used 

• Not Used 

H Mot Used 

Print Trend 

' u?l l%3 • # fuserNam" adrrfttetrator . i rSwenLoaed~'fl i : & logon } %.Admin i f% Reports j ^Trend s I • Screens | j £ Alarmsj Ii/I3f00 j I3i32.,0? ; 

Concentration Trend j Pressure Trend Temperature Trend 

Figure 10. Temperature Trend screen. 

i it Touch - WinilowVittwui 

• Not Used 

• Not Used 

• fktUsad 

• Hot Used 

• Mot Used 

H Not Used 

f^j l Print Trend 

:

 tj2 O & j User Name: admJmstratar ! screen Locked \\=) Logon j ^ Admin ! Ifsj Reports,' QTrends J £3 Screens J & Alarms 5 U/13/00 > I3i3iil0 ; 

Concentration Trend fl Temperature Trend 

Figure 11. Pressure Trend screen. 

VES 000& 
ERDC/CERL TR-05-3 15 

- WmdowVicwpi 

DeuelopmertJ 

! 

4 , 0 

3 . 5 

3 . 0 

2 . 5 -

2 . 0 • 

1 . 5 -

1 . 0 -

0 . 5 • 

0 . 0 

M Sample Line 

SI Otfoant 

Vi 2 c 

13:28:58 '. M 

I Man Line 

O wot Used 

M Naused 

i Not Used 

i Not used 

f ^ h Print Trend 

'.il l ii i fc* fuserltoee: edmlrjslrelcr 

j ) coitenlratiori Trend j 

Tsweenucted |3 ; ^ Logon j Admin i pi Repbrs j £3 Trends r • Screens ] ff Alarmt j n/13/oo i 13:29.08 : 

J Tempefattire Trend j i 

Figure 12. Flow Trend screen. 

i. In Touch - WindowViewei 

FOe Logic Special 

Nov 05 

03:34: K 

2 3 2 5 

203. 5 

174. 4 

145. 3 

116, 3 

87. 2 

58. 1 

29. 1 

0 . 0 : ' J 

H MjaA-Pd-CV 

• NJIC.Se a 

Nov 05 

06-04:16 

Nov 05 

Oij-34'16 

Nov 05 

11:04-16 

Nov 05 

!3:34:1l5 

I 

i 

I 

I 

i I I 

' j 

L

'W\ 

j ! 

• i 

ji M_ECjCf_CV 

3 MJXJCCLC V 1 H_£C_fto_CV 

Print Trend 

tfl fi3 fl 1

 Wamfl :

 , ", T* I ^eeflTocKed" fig) Logon j. life Admin j- Pi Reports j Q Trends 1 a Screens j % fidarms j n/iajoo j 13:34:31 [ 

Concentration Trend Pressure Trerid ^ J| j ' Tenipeta^e Trend | ]•• 

Figure 13. Concentration Trend screen. 
16 ERDC/CERL TR-05-3 

Data output 

The control program automatically saves QA and metals concentration data. 

XCE M operators have the option to convert the data to a comma-delimited format that is readily opened using Microsoft® Excel or other spreadsheet programs. Using the Data Output screen (Figure 14), the operator can select up to 6 

weeks of historical data. The output is automatically averaged over a userdefined sample period. Data output includes: 

1. Sample date 

2. Sampling time 

3. Concentrations of analyzed elements 

4. Uncertainty in concentrations of analyzed elements 

5. Pressure in sampling loop 

6. Temperatures 

7. Main line, oxidant and sample flows 

8. Data flag and code if red alarm is triggered. 

Data are automatically flagged if a potential problem occurred (i.e., a parameter 

is outside the user-defined QA limits/ranges). The XCE M administrator defines 

acceptable boundaries for all temperature, flow, and pressure readings as well as 

QA parameters, individual metal concentrations, and 12-hour average concentrations. 

START DATE AND TIME 

; Start TlmB Hour 

i Start Time Mtrute 

DURATION OF SAMPLE 

Max length of tine for duration i» six wseks. 

"3 

Fractional values ere edowed. 

(.25D-6hoirs, 1W - 1 Week) 

W =None 

W "Week 

0 =Dsy 

H»Hour 

M -Hrnlte 

SAMPLE INTERVAL 

Max length of time for duration is six weeks. 

Tine Time Period 

tT-acSwial V<AJW ore allowed, 

(2M-2Mnut»i, .5H-30Minutes) 

W = Week 

D "= Day 

H = Hour 

M =Minut& 

S - Second 

CONTROL AND STATUS 

\ CSV 5ave Filename &.\zfs mp\XRFTEST110500 

] Initiate CSV File Write t Save to j OperattoriR NO ERRORS 

i Last Error Message 

I [£g ^ j Use-Name; wtrtrtrrtrattw . [screenUttoctod - ^ logon ' ^.Adm'ml p ) Reports } Q Trends j E3 Screens Alarms jTlf(3foo j &.33-.2a 

i Write/SayB/View CSV File] 

Figure 14. Data output screen. 
ERDC/CERL TR-05-3 17 

For chain-of-custody purposes, neither the operator nor the administrator can 

change the recorded data in the XCE M database without flagging the data. 

Alarms 

When an alarm condition exists, a flashing red alarm signal is shown at the bottom right of each screen and a discussion of the alarm condition is shown in the 

upper right of each computer screen. Detailed information about the alarm can 

be found on the Alarm screen (Figure 15). Alarm conditions include filter tape 

breakage, diagnostic or QA parameters out of the buffer range, sampling cassette 

lids incorrectly mounted, and 12-hour rolling averages out of the buffer range. 

When an alarm condition is remedied, it remains listed in the Alarm screen with 

green, blue, or black font colors. The XCE M will continue to sample despite an 

alarm condition; however, data will be flagged. 

Administrator Accessible Control Screens 

Only an individual logged in as an administrator can set component and QA 

buffer ranges, scale analog readings from the instrument and bypass the normal 

instrumentation routines. Administrator access is password protected. The following screens are only accessible by an administrator. 

XCEM 

.Sample Line Pressure 

Alarms 

.Silling Chamber TerrperBture 

i StOTing Chamber Inlet Temperature 

iQA Parameter Zero Cadmium Current Value 

>113TO?vlC:..U ALAT5M3 

Dale Tima Stale Type Oper Pn Cmt Name Val 

OB Sep 20O0 17000 6 A C K HIHI VW/XCEM/a r 1 Sample Line Pressure W M PI105 14.G798 

08 Sep 2000 17:00:06 A C K HIHI WWXCEM/a c 1 Stillinq Chamber Temperature W W TC003 400 

08 Sep 20D0 17:00:06 A C K HIHI WWXCEM/a c 1 Stillinq Chamber Inlet Temperature W W TC002 400 

08 Sep 2000 17:00:06 A C K LOLO WWXCEM/a e 1 Q A Parameter Zero Cadmium Cmrent Value M QA Zero Cd C V 0 

08 S«p200 0 17:00:06 A C K LOLO WWXCEM/a c 1 O A Parameter Zero Chromium Current Value M OA Zero Cr C V 0 

08 Sep 2000 17:0006 A C K LOLO WWXCEM/a c 1 Q A Parameter Zero Lead Current Value M O A Zero Pb CV 0 

08 Sep 2000 17:00:06 A C K LOLO WWXCEM/a c 1 Q A Parametei Palladium Current Value M Q A P d C V D 

08 Sep 2000 17:00.06 A C K LOLO WWXCEM/a c 1 L V M (As/Cr) 12 Hour Rollinq Averaqe Cunenl Value M LV M 12H C V 0 

08 Sep 2000 17:00:06 A C K LOLO WWXCEM/a e 1 S V M (Cd/Pb) 12 Hour Rollinq Averaqe Current Value M SV M 12H C V 0 

08 Sep 2000 17:00:06 A C K LOLO WWXCEM/a c 1 H V M (Hq) 12 Hour Rollina AvBraqe Current Value M HV M 12H C V 0 

08 Sap 2000 17:0006 A C K LO WWXCEM/a c 2 Main Line Flow W W FI104 0 

08 Sap 2000 17:00:06 A C K LO WWXCEM/a c 2 Sample Line Mass Flow W W FI101 0 

08 Sep 2000 17,00:05 A C K LO WWXCEM/a c 2 Oxidant Mass Flow W W FI102 0 

08 Sep 2000 17:00:06 A C K DSC WWXCEM/a c 1 X RF Plate Not In Position Fault W W ZJ306 FAULT 

08 Sep 2GO0 17:00.06 IJWACK RTN OPR VWAICEM/ac 999 HewAlarm Site/Alarm O FF 

08 Sep 2CO0 17:00:04 IJWACK RTM SYST E administrator 999 Ae-ceesLavel SAccessLevel 9999 

08 Sep 2CO0 17:00:04 UMACK RTN SYST E Wane 9S9 Operator ^Operator adirnnrsl 

08 Sep 2030 16:51:43 A C K RTN OSC None Filler Tape Ereak W W ZI30I IICRI-1AI 

08 Sep 2CO0 16 51:43 UHACK HIHI None Sample Line Pressure W W PHOS 14 0793 

08 Sep 2O30 15:51 43 A C K PI N LOLO Nono Filter Tempouluro WI TCOOE 22.9 

08 Sep 2000 16:51 43 m RTIM LOLO None Stillinq Chamber Outlet Temperature WV'/ TC004 21 3 

08 Sep 2CO0 16.5! 43 UHAC K HIHI None Stilhnu Chamber Temperature VA/V TC003 400 

OS Sep 2CO0 16.51 43 UKAC K H H Hone Stillinq Chamber Inlet Temperature W W TC002 400 

03 Sep 2030 16.51.43 A C K RTN LOLO None Slack Temperature WV'/ TCOOt 22' 

-1 1 " • 

Update Successful 

Jjjj History^] | £ 3 Current J A C K Selected ] [ j|t AC K Ai l 

' fjy j I User Name: administrator i saeen Urtockea j ^ Logon , Admin ; ^ Reports j Trends j a Screens j Alarm s j sfefoo j 5:zoizt j 

^cenfratfEgi Trend ] 3 Pressure Trend Temperature Trend 

Figure 15. Alarm screen. 
18 ERDC/CERL TR-05-3 

Set QA Ranges 

Administrators can set buffer ranges using the Set QA Ranges screen (Figure 

16). Low and high target ranges are entered on this page. Measurements that 

fall within the target range will give a green light on the Diagnostics screen. 

Red light ranges are also defined. When measured data lies between the target 

range and red light range, a yellow light is displayed on the diagnostics screen 

and an alarm is signaled. 

Administrators using the Set QA Ranges screen can also set the hour of the day 

that a QA analysis will occur, conduct an immediate zero/span test or a peak 

shape test, and view milli-ampere (mAmp) readings for instrumentation. 

Set Analog Ranges 

Administrators also have access to the Set Analog Ranges screen for XCE M (Figure 17). This screen relates the 4 to 20 mAmp signal received by components to 

a scale used by the program. For example, a flow meter may have a 4 mAmp 

signal designated as 0 scfm (standard cubic feet per minute) and a 20 mAmp 

signal designated as 12 scfm using this screen. 

CES 

E'i;n srwental Set XCEM Set QA Ranges 

iStiBing Chamber Temperature 

iSMng cnamDer hist Temperature 

iOA Parameter Zero Cadmium Current Value 

SET COMPONENT AND QA RANGES 

Target Range 

Low High 

Red Light 

Law H^fi 

Buffer Range 

Low High 

Red Light 

Low High . 

! Sample Lhe Mass Flow FU01 (dslpm) 1,0 9,0 0,0 10,0 J'HVMfHg) 0.9 9.1 0,5 9.5 

] Oxidant Mass Flow FI102 (rrJ/mln) 3,0 400.0 • 0.0 459.0 j' SVM(Cd&Pb) 0.9 9.1 D.S 9.5 

HalniSneFkm FIHW (scfm) 1.0 9,0 . 0.0 10.0 j tVM(AsftCf) 0,9 9.1 0,5 9.5 

J SampteUie Pressure PI105 (psla) D 2 5.0 • 0.D e,o i Pe&aAum XW) 0,9 9,1 0.5 9.5 

I Stsck Temperature TC001 C O 16.0 340.0 • 15.G . 350,0 I Span Chrorraum 0.9 9.1 0,5 9,5 

j Chamber Inlet Temperature TC002 ("0 16.0 340.0 : i5.o 350.0 j 5r^C«feniiirrj 0.9 9.1 D.5 9.5 

i Charrfoer Temperature TCG03 i"C) . 16.0 340.0 ' 15.0 350.0 ! Span Lead 0.9 9.1 0,5 9.5 

! Chamber Outlet Temperature TCOTM <»C} 16.0 310,0 15.0 350.0 j Zero Chromium 0.9 9.1 0,5 9.5 

| Filter Temperature TCQQ5 pc) 16,0 34:0,0 15.0 350.0 j Zero Cadmium 0.9 9.1 0,5 9.5 

j QA Fkw* Difference 99.0 100.0 j 2wo Lead 0.9 9.1 0.5 9.5 

QA STATUS AND PARAMETERS 

; Ltf ^ pfSan^AnalvskTirr* ^^-rtnute s 

J Set QA AndysSs Vmo 0 hour 0 minute 

j EnaWo QA Aral^fs i.„n.^.^-^^"3 ^^^^S '< Imrr^l * Peat 5hape Request 

j View Component mA values (^Popup^mft Values Window | \ zerojspan Run status 

j Immediate Zero/Span Request 

Enable Request • | | 

EnaMeRegoftst.. ..1 

Peak Shape Run Status 

- ^ | User Name; whtiirtstrslor : Screen Unlocked ' Logon ! & Admin • p i Reports \ jfjj Trends j £3 Screens j Atanns j G;21J13 j 

| Set Canponent/QA RangBS { 1 Set Analog Ranges ~ | ) loop Turing 

Figure 16. Set QA Ranges screen. 
ERDC/CERL TR-05-3 19 

^5^.TM XCEM Set Analog Ranges f

Tiple Une Press'jf a 

ling Chamber remperalm-e _ 

ling Chamber htet Temperature 

|QA Parameter Zero Cadmium Current Vatu? i n 

ANALOG SCALING VALUES 

Scaling Range 

Maximum Value 

f Sample Line Mass Fbw Meter moi (0-999,9 dspm) 0,0 5.0 ••• • 

\ oxidant Mass Flew Meter FI102 (0-999.9 ml/mm) 0.0 

5oo.o wmmm 

• QA Mass Flow Meter R103 (0-999,9 ds^m) 0.0 5.o ••• • 

l~Maln Lhe Ftow Meter •' R U H <&-999.9.scfm) o.o 

\ Sample Line Pressure Meter P11D5 (0-999.5 psla) 0,0 " r ~B. o mm m -

j Sample Line Flow Setpolnt F1C201 (0-999.9 ds^am) o.o s-o" ' ~ ••• • I 

XRF PARAMETERS 

\ Setcsv File Name 

j Sat CSV Fib Offset 

Piast Fib Exists Btalus Check 

: Set Archival File Patil D:\XRFArchival 

; last Archival Initiate Status 0 

i Set CSV Conversion File Nanie Di^tempNParse Jtesults.exe 

Last Fib Read Status 

Last Archival Status 

(set XRF Results Text Fife Name G:y?esul!s 

I Si' ^ luserMeire: athrinWrator Ta*emUrtocWj|| j £ Logon ) % ifldmrn) g^, Reports \ Q Trends j • Screens ; ^'Alanris I 9/s/ooj 5:;2..o; 

| Set GoTirolenVQA Ranges| \ Set Analog Ranges j | Loop Tuning j j PLC Status f | CSt/Tooi 

Figure 17. Set Analog Ranges screen. 

Samplin g Platfor m Modification s 

The XCE M sampling platform was modified to provide automated QA features 

and improve operator ease-of-use. 

Quality Assurance Modifications 

The XCE M was reengineered to include an automated, user-friendly QA program (Figure 18). A WonderWare® software package has been developed with a 

custom programmable logic controller (PLC) to control key components and independently run QA features (Figure 19). 

QA features for the XCE M focus upon the two numbers required to determine 

stack gas concentration: mass of the metal on the filter and sample volume. 

Metal mass on the filter is determined in micrograms per spot using the XRF 

while sample volume is in dry standard cubic meters per spot as determined by 

mass flow meters. A spot is equal to the area on the filter tape scanned by the 

X RF analyzer. The XCE M program builds in automated redundancy and daily 

QA checks for measuring both mass and volume. Acceptable QA boundaries are 

user-defined. If the measured values fall outside of these boundaries, such as 
20 ERDC/CERL TR-05-3 

when instrument drift occurs, the software package will signal an alarm and flag 

the data. All QA measurements are logged in the XCE M database and are 

available for use by Microsoft® Excel and Access or compatible data management 

programs. 

HH Mass by XR F 

~y Volume by MF M 

Multi-Metal Samvling Train 

M29 

gHir=>Pump 

Automate d Q A 

Mas s b y XR F 

• Every Sample: Pd Internal 

Standard + 5% 

• Periodic: Cu peak shape 

evaluation. 

• Daily Zero (blank) and 

Span (standard) Checks. 

Volum e b y Mas s Flo w Mete r 

• Daily MFM Calibration 

Evaluation. 

• Periodic NIST-Traceable 

Calibration. 

M 

Elementa l Mas s 

Multi Metal Standard (Hg, Cd, Cr, Pb) 

PdWire 

Cu Wire 9 . Tape Analyzed By 

Independent Lab 

Tube Detector 

M F M 1 [J 

^ MFM-2 

Pump 

Additiona l Q A Option s 

• Independent Tape Analysis 

• Quantitative Spiking Sampl e Volum e 

Figure 18. XCEM QA program. 
ERDC/CERL TR-05-3 21 

Figure 19. PLC control for the XCEM. 

Mass measurement QA 

XCE M mass measurements are determined using a KevexSpectrace QuanX 

XRF. For this project, the XRF analyzer was calibrated using thin film standards made by pipetting a National Institute of Standards and Technology 

(NIST)-traceable standard solution containing equal masses of silver (Ag), 

arsenic (As), Cd, Cr, Hg, Pb, and selenium (Se) onto a Mylar film. A series of 10 

standards with varying concentrations were analyzed by the XRF, and a linear 

relationship between x-ray intensity and mass was determined. The XRF is 

stable over a period of months and typically requires calibration only about once 

every 6 months. 

X RF zero and span tests are conducted examining blank filter tape and a metal 

rod attached to a pneumatic plunger mounted below the sampling cassette (Figure 20). At a user-defined time of day, the XCE M begins the QA process by advancing clean, unexposed filter tape into the x-ray beam area and analyzing the 

blank tape as a zero test. Immediately following this test, the plunger extends 

the multi-metal standard rod into the beam area. The rod, which contains relatively high concentrations of Cr, Hg, Cd, and Pb, acts as a span test. The zero/ 

span test typically takes 20 to 30 minutes. 
22 ERDC/CERL TR-05-3 

To check for instrument drift and provide a continuous assurance that the XRF 

is giving precise, repeatable mass measurements, a Pd wire has been permanently mounted in the XRF x-ray beam analysis region (Figure 21). The Pd is 

measured with every sample, allowing for continuous comparison to preceding 

values determined when the instrument was last calibrated. 

Figure 20. Zero and span test plunger. 

, tut 

Figure 21. Pd wire-mounted for QA. 
ERDC/CERL TR-05-3 23 

Flow measurement QA 

In addition to mass measurements, the XCE M assures quality flow measurements using a redundant mass flow meter in-line with the existing flow controller. When QA mass measurements are engaged, the software interface diverts 

flow out of the flow controller and through the second mass flowmeter. The two 

flow rates are then compared. If a significant difference is determined, an alarm 

will be posted and the data will be flagged. Having a redundant flow meter provides two additional benefits. It can act as a back-up method for measuring concentrations if the flow controller breaks down, and the QA mass flow meter can 

be periodically removed and sent out for recalibration without affecting the 

XCE M normal operations. 

Extraction system QA 

The accuracy of the extraction system can be evaluated periodically (e.g., every 6 

to 12 months) by spiking metals directly into the XCEM . A spiking system was 

developed that uses a NIST traceable standard solution and a nebulizer. This 

spiking system, which is inexpensive to operate, demonstrated good precision 

and was able to spike a variety of metals over a wide concentration range. Using 

this approach, XCEM-reported metal concentrations can be compared with results from either an M29 sample train or a filter grab sample. The XCE M spiking system and results of M29 comparison tests are discussed later. 

Ease-of-use Modifications 

In earlier XCE M versions, the sampling platform was permanently mounted to 

the top of the QuanX XRF. The updated XCEM, however, has been reengineered 

to include a sampling cassette that is attached with only four thumbscrews to 

the XRF analysis platform. The sampling cassette is lightweight (about 25 

pounds) and can be removed from the analyzer in under 5 minutes (Figure 3). 

No tools are required to disconnect the electronics' plug, screws, and two pneumatic lines on the cassette. Once removed, the cassette is self-supporting, but a 

special transport plate is available. It is anticipated that the next version of the 

XCE M will come with at least two sampling cassettes. Every 2 to 4 weeks, when 

the XCE M filter tape has been fully exposed, operators will be able to rapidly 

change sampling cassettes and transport the cassette containing the exposed 

tape to a separate work area. In the work area, technicians will be able to 

change filter tapes in a clean environment and conduct routine preventative 

maintenance on the cassette. It is anticipated that a technician would be able to 

carry out these tasks in under an hour. 
24 ERDC/CERL TR-05-3 

Safety Modifications 

The portable sampling cassette contains a mounted filter tape, a stepper motor, 

pneumatic plungers, lead shielding, and a tape breakage sensor (Figures 3, 20, 

and 22). The cassette cover is positioned to trigger interlocks so that sampling 

cannot take place unless the covers and shielding are properly positioned. 

In addition to increased efficiency in exchanging filter tapes, the portable cassette ensures that the tape is not contaminated prior to installation into the unit. 

Another benefit is the system redundancy provided by the cassette. If the stepper motor, plungers, or tape are damaged, the XCE M operator can rapidly exchange cassettes and ensure monitor uptime. 

Figure 22. XCEM sampling cassette and XRF control panel. 
ERDC/CERL TR-05-3 25 

3 Laboratory Testing 

This chapter addresses the last two recommendations that were presented in the 

MSE-TA report (Bryson et al. 2000): Hg sampling and the spike injection system. As discussed in the previous chapter, additional laboratory testing was 

needed to evaluate and optimize the Hg capture efficiency of the automated oxidation system, and to compare XCE M mercury measurements with M29. A 

spike injection system was developed so that M29 comparison tests with six 

metals in addition to Hg could be performed in the laboratory. This chapter also 

presents the results of these M29 comparison tests. 

Mercur y Sampling 

Experimental 

Optimization of the XCE M Hg sampling efficiency was accomplished in two 

phases. In the first phase (Figure 23), elemental Hg was generated using a Hg 

permeation tube in a controlled temperature environment. The elemental Hg 

vapor was then converted to mercuric chloride using chlorine gas. The resulting 

mercuric chloride was then captured on a 47-mm diameter RIF that was backed 

up by a second 47-mm diameter RIF. Any Hg vapor that was not trapped by the 

RIFs was captured with a carbon-impregnated filter (CIF). Analysis of the relative concentrations on the two RIFs and CIF were conducted to determine if 

breakthrough was occurring. In the second phase, Hg was generated using the 

XCE M nebulization system and a stock multi-element standard from VH G Labs, 

Inc. (Manchester, NH). The Hg was injected directly into the XCE M sampling 

system and analyzed in real time. The XCE M real-time data were compared to 

results from a modified EPA M29 sampling train. 

Mercury RIF Results 

The primary purpose of first-phase Hg testing was to determine RIF vapor phase 

Hg capture efficiencies under varying flow, temperature, and oxidant conditions. 

Figure 24 shows a typical capture efficiency curve when flow rates varied. In 

this series of tests, conducted with a filter temperature of 140 °F (60 °C), the primary RIF collected greater than 90 percent of the Hg when flow rates through 
26 ERDC/CERL TR-05-3 

the filter were less than 0.8 dry standard Lpm/cm2 (liters per minute per square 

centimeter). These results indicate that the RIF could capture greater than 90 

percent of vapor phase (elemental) Hg under typical operating conditions. 

Reaction Chamber 

Figure 23. Schematic of Hg capture for first phase experiments. 

100 

12 

£ 75 

C 

O 

o 

O) 

X 

£ 

3 

a 

co 

o 

50 

£ 25 

0 

-•"RIF 1 

RIF2 

-I • CIF 

-•"RIF 1 

RIF2 

-I • CIF 

0.00 0.50 1.00 1.50 

Flow Through Filter (Lpm/cm2) 

Figure 24. RIF Hg capture efficiency versus air flow rate through filter. 

Mercury Oxidation Automation 

The XCE M continuously extracts a small subsample, on the order of 0.5 Lpm, of 

stack gas from the stilling chamber. Prior to collection on the RIF, this subsample enters a dilution/oxidation chamber where an oxidizing agent, such as chlorine gas, is used to convert the elemental Hg to ionic phase Hg, which can then 

be captured on the RIF. The calculations that determine the settings for the oxidant valve, flowmeter, and dilution have all been automated and are fully integrated into the XCE M computer control system. 
ERDC/CERL TR-05-3 27 

Mercury XCEM Results 

During the second phase of Hg testing, the XCE M total Hg measurement capability was determined using an M29 sampling train. Mercuric nitrate and other 

metallic compounds of interest were spiked into the XCE M extraction system 

and were simultaneously collected by the RIF and an M29 sampling train. Four 

M29 tests were conducted, with each test lasting 3 hours. Since the XCE M determined Hg concentrations every 12 minutes, a time-weighted average was 

used to compare XCE M and M29 results. 

Overall the XCE M and M29 Hg concentrations were in good agreement. The average XCE M Hg concentration was 135 ± 8 ug/m3

 (micrograms per cubic meter) 

while the average M29 result was 122 ± 6 ug/m3. On average, an 11 percent difference existed between reported sampling run concentrations, which is within 

M29 uncertainty. No indication of filter trapping inefficiencies was evident because the XCE M reported slightly higher Hg concentrations than M29. During 

testing, about 7 percent of the Hg was in the vapor phase as defined by the M29 

front half/back half measurement. 

The XCEM/M29 Hg RA for the four test runs was 20.4 percent, which when 

rounded to two significant digits marginally meets the PS-10 RA criterion. This 

number was calculated using the method described in PS-10. The RA will decrease with increased numbers of runs, so that it is estimated that the RA would 

decrease to about 18 percent if more runs with similar results had been conducted. 

Overall the M29 results demonstrate that the XCE M can adequately trap and 

measure Hg concentrations under realistic test conditions. 

Method 29 Compariso n Test s 

Spike Injection System 

Approach 

The quality of the XCE M mass measurements is routinely evaluated with the Pd 

quality control standard, zero, and span checks. However, a spiking system is 

required to confirm XCE M transport and collection efficiencies. An ideal spike 

injection system should have the following capabilities: 

• Can inject all MACT metals at levels well above detection limits 

• Repeatable precision 
28 ERDC/CERL TR-05-3 

• Easy and safe to implement 

• Relatively inexpensive to operate 

• Able to produce an aerosol with high transmission efficiency 

• Quantifiable. 

Several options were reviewed which could potentially meet the above criteria 

(Table 2). These options included: 

• Nebulization. A solution containing elements of interest is aspirated into a 

gas stream. The resulting droplets dry and create an aerosol of salt particles. 

• Aerosolization. A spiked powder is suspended in a carrier gas that is injected into the stack gas stream. Methods of aerosolizing a spiked powder include moving a deposit under a gas jet, fluidized bed plus elutriator, or microscrew injection. 

• Evaporation. A compound of a spiking element with a well-defined boiling 

point is raised to a temperature above its boiling point. This takes place in 

an inert carrier gas that is introduced into the stack gas. 

• Combustion/aspiration. A solid or liquid containing spiking elements is 

burned in a carrier gas. The combustion products containing the spiking 

elements are carried into the stack gas with the carrier gas. Oils containing 

a variety of elements are available and could be readily burned. Solids would 

need to be specially prepared and there would be a greater tendency for the 

elements to remain in the ash. 

• Electric spark. A high voltage spark or arc is created between two carbon 

electrodes containing spiking elements. The sparking process generates fine 

particles with the spiked elements. 

• Hydride generation. An inert gas is bubbled through a solution containing 

the spiking elements. Sodium tetraborohydrate is added to the solution. The 

hydride-forming elements are exchanged with the carrier gas and carried to 

the stack. 

• Specialty gas. A commercially prepared and certified gaseous mixture containing the required spiking elements. 

After reviewing the options, nebulization was selected as the preferred alternative due to its simplicity, potential for extended operation, and quantification advantages. Nebulizers have been used to successfully generate aerosols for a 

number of years (Ylatalo et al. 2000; Flagan and Seinfeld 1988; Fuchs and Stutugin 1966). They are relatively inexpensive and easy to use. In addition, NIST 

traceable laboratory standards are available for all metals of interest. These 

standards are available in a wide variety of concentrations (From 1 to 2000 

ug/mL) and have a guaranteed shelf life of 1 year. 
ERDC/CERL TR-05-3 29 

Table 2. Evaluation of spike injection options. 

Option Advantages Disadvantages 

1) Nebulization 

Ease of use 

Low cost 

Readily available standards 

Humidity affects nebulization rate 

Potential water super-saturation in 

stack sample 

2) Aerosol ization 

Ease of use 

Low cost 

Uniformity of powder issues 

Potential agglomeration issues 

Quantification is difficult 

3) Evaporation 

Ease of use 

Low cost 

Loss of large particles to walls 

Different temperatures required for 

different elements 

4) Combustion/ Aspiration 

Ease of use 

Low cost 

Readily available standards 

Carrier particles produced by the 

combustion process 

Potential safety issues 

5) Electric Spark 

Precision 

Ease of use 

Potential safety issues 

Engineering expense 

Quantification difficulties 

6) Hydride Generation 

Ease of use 

Low cost 

Cost of components 

Instability of hydrides 

Not all metals are available 

7) Specialty Ga s Independent certification 

Cost of gas 

Availability of gas 

Design 

During nebulization, compressed air is pushed into the bottom of a nebulizer cup 

containing a liquid solution. The compressed air exits the cup at the top and 

creates a partial vacuum, which draws liquids out with the air. A DeVilbiss 

nebulizer (Illinois Tool Works, Glendale Heights, IL) was used for these tests. 

The nebulizer included an impaction plate designed to prevent large droplets 

from escaping. 

For the M29 testing, the nebulization system produced 100 liters per minute 

(Lpm) of spiked gas with concentrations between 115 and 180 ug/m3 for seven 

metals: Ag, As, Cd, Cr, Hg, Pb, and Se. A commercially available solution standard (VHG Labs, Manchester, NH) was used to spike the gas stream. The standard solution contained 100 ug/mL of each metal in 5 percent nitric acid. For 

each test run, standard solution was added to the nebulizer cup, which was then 

weighed. Following nebulization, the cup was reweighed and the amount of 

nebulized solution was determined. 

About 5 Lpm of spiked aerosol from the nebulizer cup was injected into a vertical 

four-inch diameter pipe. Another 95 Lpm of dry air was drawn into the pipe 

with the spiked aerosol. The pipe, which was 3-ft long, was heat traced and kept 

at about 220 °F (103 °C). The addition of heat and dry air served to rapidly dry 
30 ERDC/CERL TR-05-3 

the nebulized particles. It is estimated that the typical dried particle size was on 

the order of 0.2 microns in diameter once it exited the 4-inch tubing. The combined 100 Lpm of spiked gas was then drawn into the stilling chamber for extraction by the XCE M and M29 probes. 

Spiking evaluation 

The DeVilbiss nebulizer showed good precision over the 4 days of M29 testing. 

The overall nebulization rate, as determined by mass measurements, was 0.23 ± 

0.01 mL/min. This represents a 4 percent relative standard deviation (RSD). 

Following M29 testing, further nebulization tests under more controlled conditions have demonstrated improved precision and an RSD of less than 1 percent. 

Although the nebulizer precision was good during M29 testing, the mass of nebulized solution could not be used to accurately predict stack concentrations. 

Despite the overall quantification issue, nebulization remains a promising approach. The current nebulization system is able to precisely provide all elements 

of interest over a wide range of concentrations allowing for an effective XCE M 

test range of 1-2000 ug/m3. It is relatively inexpensive, safe, and easy to operate, and a wide variety of metals are available as NIST traceable standard solutions. 

Test Design 

To test XCE M accuracy, four modified M29 test runs were conducted from 4-7 

November 2000. During these tests, simultaneous samples were collected by the 

XCE M and an M29 sampling train. Simulated "stack gas" was provided by 

nebulization of a metals solution containing equal concentrations of As, Cd, Cr, 

Hg, Pb, Se, and Ag. The M29 sample probe extracted the stack gas from a 2-

inch-diameter pipe located approximately 3 feet downstream of the XCE M extraction tube. Both sampling sites were at least eight diameters downstream 

and two diameters upstream of any flow disturbance as required by EPA sampling protocols. During testing, XCE M and M29 temperatures, flows, and pressures were held constant. No XCE M dryer was used for the M29 tests since water content was determined to be less than 1 percent of the volume. Test 

parameters are listed in Table 3. 

The M29 sample was collected isokinetically while the XCE M extracted subisokinetically from the stilling chamber. The stilling chamber design slows stack 

gas and allows for non-isokinetic sampling due to its low Stoke's number (Cooper 

et al. 2000). 
ERDC/CERL TR-05-3 31 

Table 3. Test conditions during M29 sampling. 

Test Parameter Test Parameter 

Main Line Flow (scfm) 3.52 ± 0.02 Stilling Chamber Temperature - 230 °F 

XCE M Sample Flow (sLpm) 0.58 + 0.003 Temperature at M29 Impinger Inlet - 230 °F 

M29 Flow (sLpm) 4.1+0.2 Temperature at M29 Impinger Outlet <5 2 °F 

Nebulization Rate (mL/min) 0.23 ± 0.01 M29 Sample Time (min) 180 

Nebulizer Metal Concentration 

(pg/mL) 

100 Ambient Relative Humidity 40 - 60% 

Nebulized Metals 

A s , Cd , Cr, Hg, 

Pb, Se, Ag 

Ambient Temperature 55 - 65 °F 

Metals were nebulized using the XCE M spike injection system. The nebulized 

standard solution, provided by VH G labs, is NIST traceable and contains 

100 ug/mL of each metal in 5 percent nitric acid. Particle size for the test was 

estimated to be on the order of 1 micron or less. During the M29 tests, the nebulization rate was very stable and varied by no more than 5 percent. 

The XCE M exhibited no mechanical or functional problems during the 4-day test 

period, which included over 150 test runs. 

XCEM Results During Method 29 Testing 

XCEM results by element 

The XCE M reported metal concentrations in ug/m3 every 11.7 minutes for each of 

the nebulized metals (Figure 25). Every 2 to 3 hours, spiking was stopped to refill the nebulizer cup. Since the refilling process took about 5 minutes, it reduced 

concentrations for one XCE M sample run. These concentration changes are 

shown as deflections in Figure 25 and illustrate the sensitivity of the instrument 

to changes in metal concentration. The horizontal magenta lines indicate the 

respective metal M29 concentration for the duration of each M29 sample. 

To evaluate the XCE M instrument stability, a Pd rod is situated directly above 

the x-ray tube and provides Pd concentrations with every sample. For these 

tests, the Pd QA rod had an effective concentration of 140 ± 1.0 ug during the 4-

day test period with a precision of better than 1 percent (Figure 25). The consistent Pd concentrations during M29 testing indicate that no XRF instrument drift 

occurred. 
32 ERDC/CERL TR-05-3 

ARSENIC 

200 

0 

M29-1 M29-2 M29-3 M29-4 

Nov. 4 Nov. 5 Nov. 6 

1 

Nov. 7 

348 363 378 

Nebulizer Refilled 

393 408 423 437 

Sample ID No. 

452 467 482 

CADMIU M 

200 

175 

_ 150 -j 

| 125 

ec 

* 100 

I 75 i 

50 

25 

0 

M29-1 

rtfff 

Nov. 4 

348 363 378 

• Nebulizer Refilled 

M29-3 M29-4 

Nov. 6 Nov. 7 

408 423 437 

Sample ID No. 

452 467 482 

CHROMIU M 

M29-2 

Nov. 5 

M29-3 

Nov. 6 

M29-4 

Nov. 7 

348 363 378 

Nebulizer Refilled 

393 408 423 437 

Sample ID No. 

452 467 482 

Figure 25. XCEM elemental concentrations during M29 testing. 
ERDC/CERL TR-05-3 

348 363 378 

• Nebulizer Refilled • Nebulizer Keuucu_ ——-

Fig^C^nt^ ^

 dUrin 9 teStm9

-
34 ERDC/CERL TR-05-3 

SILVER 

200 

a. 

u 

B © 

M29-2 M29-3 M29-4 

Nov. 6 Nov. 7 

348 363 378 

Nebulizer Refilled 

393 408 423 437 

Sample ID No. 

452 467 482 

PALLADIUM 

200 

175 

150 

S 125 

en 

.S* 1 nrv 

c 

o 

O 

75 

50 

25 

0 

M29-1 M29-2 M29-3 M29-4 

Nov. 4 Nov. 5 Nov. 6 Nov. 7 

348 363 378 393 408 423 437 452 467 482 

Sample ID No. 

PALLADIUM 

Be 

a 

o 

U 

QJ 

> 

Average Palladium effective concentration Sample ID No. 

One SD from Avg. Pd Concentration 

5% from Avg. Pd Concentration 

Figure 23 (Cont'd). XCEM elemental concentrations during M29 testing. 
ERDC/CERL TR-05-3 35 

XCE M metal concentrations during the 4 days of testing were highly correlated. 

For example, in comparison to Cd, all of the metals exhibited a correlation of 

0.95 or better and had a slope between 0.95 and 1.17 (Figure 26). The choice of 

Cd was purely arbitrary, and similar relationships would be seen if another 

metal was chosen. The slope is expected to be close to 1 because all the metals 

were spiked with the same concentration. Differences in correlation are expected 

to be due primarily to XRF calibration and spectral measurement uncertainties. 

The high degree of correlation and relatively uniform slope indicate good uniformity in the relative concentration ofthe spiked stack gas. 

f 15 0 

5 0 

0 

5 0 10 0 15 0 

Cadmium Cone (ug/m3) 

2 0 0 

y= 1.04x+ 0.49 

R

z

 = 0.98 

y= 1.04x+ 0.49 

R

z

 = 0.98 

5 0 10 0 15 0 

Cadmium Cone (ug/m3) 

2 0 0 

0 5 0 10 0 15 0 20 0 

Cadmium Cone (ug/m3) 

„ 25 0 

5 0 10 0 15 0 

Cadmium Cone (ug/m3) 

5 0 10 0 15 0 

Cadmium Cone (ug/m3) 

]y = 0.9Sx + 0.83 

R

J

 = 0.97 

5 0 10 0 15 0 

Cadmium Cone (ug/m3) 

2 0 0 

Figure 26. XCEM cadmium versus other spiked metals during M29 testing. 
36 ERDC/CERL TR-05-3 

Pre- and post-tests at XCEM Port versus Method 29 port 

QA testing was conducted before and after each of the four M29 test runs. During QA testing, an open-faced filter holder containing an RIF and CIF was used 

to collect a grab sample from the M29 port. This filter combination, developed by 

CES, is called a Hazardous Elemental Sampling Train (HEST), and has been 

tested in a variety of stack environments as a way of quickly evaluating stack 

gas metal concentrations (Johnson et al. 1998). The HEST samples were analyzed using a laboratory XRF and compared to the XCE M reported concentrations for the concurrent run. Results for the pre- and post-tests are shown in 

Table 4. Overall, the XCE M reported average metal concentration was 138 ± 13 

ug/m3 while the M29 port test average concentration was 126 ± 12 ug/m3 (including Ag). Comparing the average metal concentration is important because all 

metals were spiked at identical concentrations. Especially useful is comparing 

the average concentrations for all metals during one sampling event (e.g.. run 2 

pre-test or run 3 post-test). It appears that the averages are within the standard 

deviation between the two ports and that the deviations are similar. Using the 

M29 port results as the "true" value, the XCE M reported concentrations fell 

within the 20 percent RA criterion in PS-10 for all metals except Ag (Table 5). 

These calculations were performed using the eight sets of sample values for each 

metal. The M29 port concentration for Ag was low by 17 percent relative to all 

other reported metal concentrations, while the XCE M Ag concentration was in 

good agreement with reported concentrations for other spiked metals. 

Table 4. Elemental concentrations at XCEM and M29 Ports during pre- and post-tests. 

As Cd Cr Hg Pb Se Ag XCEM (No Ag) M29 (No Ag) 

TEST 

x c 

M29 

Port 

XC M29 

Port xc 

M29 

Port x c 

M29 

Port x c 

M29 

Port xc 

M29 

Port x c 

M29 

Port Avg SD % 

RSD Avg SD % RSD 

PRE 115 no 122 110 132 114 126 123 123 115 123 110 117 96 124 6 5 114 5 5 

1 POST 138 146 137 147 165 152 148 166 153 150 147 147 133 126 148 10 7 151 8 5 

PRE 141 138 147 140 167 143 156 154 150 142 149 138 139 115 152 9 6 143 6 4 

2 POST 133 141 136 148 148 146 147 163 139 145 136 143 131 117 140 6 4 148 8 5 

PRE 128 109 124 115 144 118 134 125 120 117 130 113 1 17 87 130 8 6 116 5 5 

3 POST 122 118 120 119 135 123 129 133 121 122 125 119 118 95 125 6 4 123 5 4 

PRE 120 120 136 122 133 124 128 135 116 122 125 121 118 95 126 7 6 124 6 5 

POST 128 116 137 116 142 122 133 133 120 122 128 118 121 90 131 8 6 121 6 5 

AV( RAGE 128 125 132 127 146 130 137 142 130 129 133 126 124 103 134 6 5 130 6 5 

Table 5. Relative accuracies of M29 Port versus XCEM Port during pre- and post-tests. 

Element RA Meets EPA-Proposed Criterion1 

Arsenic 8.8 Yes 

Cadmium 11.3 Yes 

Chromium 17.0 Yes 

Mercury 8.3 Yes 

Lead 4.4 Yes 

Selenium 10.5 Yes 

Silver 27.6 No 

1

 EPA-proposed PS-10 for Multi-Metal CEMs requires an RA Criterion of 20%. 
ERDC/CERL TR-05-3 37 

XCEM vs M29 

XCEM and M29 analytical data 

During M29 testing, the XCE M reported stack gas concentrations for As, Cd, Cr, 

Hg, Pb, and Se in ug/m3. In addition to an electronic copy, the XCE M printed a 

hard copy of the results after each test run. Metals concentrations used in this 

report are the same as the XCE M hardcopy output with the exception of corrections to As and Hg concentrations. After testing and before receiving the M29 

results, the XRF was recalibrated using a duplicate/new set of calibration standards. At that time, it was determined that the original standards' Hg concentrations were too low by 17 percent, giving a reported concentration that was too 

high. As such, the XCEM-reported Hg concentrations were reduced by 17 percent. 

Except for Hg, all of the elements were in good agreement following calibration. 

During recalibration, however, it was discovered that a 10 percent As correction 

factor, which had been used in the shakedown period, had accidentally been left 

in the XRF calibration equation. All XCE M concentrations used in this report 

were determined without the use of correction factors. Accordingly, the XCEM -

reported As concentrations were reduced by 10 percent. 

After making these corrections, CES received the M29 data from an independent 

laboratory, Chester LabNet. Included with the M29 data were results from 

blank and spike tests. No changes were made to M29 laboratory results with the 

exception of a blank subtraction to account for Se in the M29 blank. 

XCEM vs M29 test results 

XCE M and M29 concentrations for the four M29 test runs are shown in Table 6. 

Reported concentrations for the two methods are in good agreement for all elements except Ag. 

No apparent overall bias is evident between the two methods. Indeed, the overall average non-Ag metal concentrations reported by the two methods are within 

a few percent of each other. This trend holds true for each sample run (Table 7) 

and indicates that it is probable that no particulate loss occurred in the sampling 

system. 
38 ERDC/CERL TR-05-3 

Table 6. Reported XCEM and M29 concentrations. 

Element Method Concentration Avg. % Element Method Run 1 Run 2 Run 3 Run 4 Average Diff. 

As 

XCE M 

M29 

128 

140 

131 

149 

120 

129 

117 

130 

124 

137 10 

C d XCE M 

M29 

131 

158 

138 

166 

121 

156 

124 

151 

129 

158 19 

C r 

XCE M 

M29 

149 

152 

156 

159 

139 

153 

131 

146 

144 

152 

6 

Hg 

XCE M 

M29 

139 

117 

145 

131 

131 

118 

126 

121 

135 

122 -11 

Pb XCE M 

M29 

139 

120 

140 

131 

127 

111 

117 

96 

131 

114 -15 

Se 

XCE M 

M29 

134 

122 

141 

146 

127 

132 

123 

130 

131 

132 

1 

Ag 

XCE M 

M29 

128 

10 

133 

9 

120 

10 

117 

53 

125 

21 -951 

XCE M 

(NoAg) 

Avg 

S D 

% RS D 

137 

8 

6 

142 

8 

6 

127 

7 

5 

123 

5 

4 

132 

7 

5 4 

M29 

(NoAg) 

Avg 

S D 

% RS D 

135 

18 

13 

147 

14 

10 

133 

18 

14 

129 

20 

15 

136 

17 

13 

4 

Table 7. Average metal concentrations for each sampling run. 

M29 Run 

No. 

XCEM Avg. Metal 

Cone, (pg/m3) 

M29 Avg. Metal Cone. 

(ug/m3) 

Percent 

Difference 

Run 1 137 135 1.5 

Run 2 142 147 3.4 

Run 3 127 133 4.5 

Run 4 123 129 4.6 

Average 132 136 3.5 

1

 Metal concentrations are an average of As, Cd, Cr, Hg, Pb, and Se for each run. 

The strong average concentration correlation is reflected in the positive RA results (Table 8). Even with only four sampling runs, the RA for As, Cr, Hg, and 

Se meets the PS-10 RA criterion of 20 percent. During formal M29 certification, 

a minimum of nine runs is recommended by EPA's proposed PS-10. Had the 

XCE M been tested for nine runs, it is estimated (by using a value of nine for the 

number of sample runs in the PS-10 RA calculation) that Pb would have also met 

the RA criterion. The only MACT metal that would not meet the RA criterion 

was Cd with an RA of 23 percent. Since M29 Cd concentrations were, on average, 15 percent higher than other M29 reported concentrations, it is believed 

that differences in the Cd concentration are a function of a high M29 bias as discussed in the next section. 
ERDC/CERL TR-05-3 39 

Table 8. XCEM and M29 relative accuracies. 

RAwith Est. RA 

Element Four M29 with Nine 

Runs M29 Runs 

Arsenic 14.3 13.0 

Cadmium 22.7 21.6 

Chromium 13.1 11.0 

Mercury 20.4 17.8 

Lead 21.3 19.3 

Selenium 16.2 13.2 

Silver 721.7 662.6 

In contrast to the other spiked metals, Ag XCE M and M29 concentrations do not 

show good agreement. The average Ag concentration during M29 testing was 

reported as 21 ± 21 ug/m3, while the XCE M Ag concentrations during the four 

runs was 131 ± 8 ug/m3. This M29 average Ag concentration is more than five 

standard deviations from the average M29 non-Ag concentration of 136 ± 18. 

Although the pre- and post-test results did indicate some potential difference in 

the Ag concentrations, the average reported M29 port concentration of 103 ± 15 

ug/m3 was still five-fold higher than the M29 test run results. The laboratory 

that performed the M29 analysis believes some analytical problems were possible for Ag and cites the fact that Ag and Sb are the only elements exempted from 

spike recovery criteria by the standard method. For these reasons (and since the 

Ag spike did not meet the 80 to 120 percent recovery criterion), it is believed that 

the M29 Ag numbers were inaccurate. 

The consistency between the overall average XCE M and M29 concentrations is 

important because it indicates that particle loss did not occur during testing. 

The consistency in the elemental concentrations also indicates that elemental 

fractionation was not occurring. Except for Ag, all 24 reported metal concentrations during each of the test runs were within the combined 5 percent XCE M and 

13 percent M29 uncertainties (Figure 27). 

Method 29 and XCEM Precision and Accuracy 

As discussed in the last section, no indication of particle loss or chemical fractionation was observed by either method during M29 testing. As such, all elements should have been present in equal concentrations at both the XCE M and 

M29 ports. In this situation, a hypothetical unbiased method's reporting of elemental concentrations for a given sample run would be randomly distributed 

above and below the "true" elemental concentration. The average elemental concentration would then be a method's best estimate of the "true" concentration in 

the stack, and the range of distributions around and about the average 
40 ERDC/CERL TR-05-3 

concentration would reflect the method's precision. Elemental concentrations 

consistently and significantly above or below the average concentration would 

indicate measurement problems. Figure 28 shows elemental concentrations for 

each sample run that have been normalized to the average elemental concentration. Normalized concentrations in Figure 28 were calculated using 

Equations 1 and 2. 

_ 200 -| j | nxcEMl 

S T T _ 1"M29 j 

As Cd Cr Hg Pb Se Ag * 

200 

"Si 160 

120 

* 80 

40 

-i 1 1 OXCEM 

T T 1RIJN2I WM29 

As Cd Cr Hg Pb Se Ag 

200 

M 160 

g 120 

•43 

* 80 

S 40 

-| 1 1 DXCEM 

T T [ R U N 31 [•M29 

m i l 

As Cd Cr Hg Pb Se Ag 

„ 200 

R U N 4 

• XCEM 

• M29 

Hit 

As Cd Cr Hg Pb Se Ag 

* Expected concentration of all elements should be the same. 

Figure 27. Comparisons of XCEM and M29 concentration by run. 
ERDC/CERL TR-05-3 41 

Cadmium DXCE M 

Figure 28. XCEM and M29 normalized concentrations by element. 
42 ERDC/CERL TR-05-3 

[Eq1l 

where, 

Xn = Normalized XCE M concentration for an element during a sampling run 

Xc = Reported XCE M concentration for an element during a sampling run 

X - Average of reported XCE M As, Cd, Cr, Hg, Pb, and Se concentrations 

during a sampling run 

Mn - Normalized M29 concentration for an element during a sampling run 

Me = Reported M29 concentration for an element during a sampling run 

M = Average of reported M29 As, Cd, Cr, Hg, Pb, and Se concentrations during a sampling run. 

In Figure 28, all XCE M normalized concentrations are within 10 percent of the 

average elemental concentration, and two-thirds of the values are within 5 percent of the average elemental concentration. This is consistent with an XCE M 

estimated one-sigma uncertainty of 5 percent. For the M29 samples, however, 

only As and Se have all reported concentrations within 10 percent of the average 

M29 elemental concentration. Two-thirds of the M29 values are within 13 percent of the M29 average, which is consistent with a M29 one-sigma precision of 

13 percent. Interestingly, M29 Cd and M29 Pb concentrations have the greatest 

deviation from the M29 average, 16 percent high and 16 percent low, respectively, and are the two elements with the highest RAs relative to the XCEM. 

The M29 Cd is, on average, 19 percent higher than the XCEM , and the M29 Hg 

is, on average, 11 percent lower. This indicates that much of the RA difference 

between the XCE M and M29 for Cd and Pb may be a product of M29 bias. 

Overall, the normalized concentrations indicated one-sigma uncertainties of 

about 5 percent for the XCE M and 13 percent for the M29. This M29 uncertainty is in good agreement with the EPA uncertainty estimate of 10 to 15 

percent (MACT 1999b). The M29 normalized concentrations showed significant 

inter-elemental differences indicating a possible method bias, which could be 

responsible for RA differences. 

[Eq2] 

where, 
ERDC/CERL TR-05-3 43 

4 Field-ready XCEM 

CES constructed a new XCE M for testing at the TEAD facility. This prototype 

incorporates all the changes described in the previous chapters. It also includes 

a modified ThermoNoran QuanX energy dispersive XRF analyzer (Thermo 

Kevex) for metal detection. The QuanX is capable of simultaneously measuring 

19 elements and a Pd QA standard. In addition, an eductor downstream of the 

stilling chamber is used to pull the stack gas through the extraction system. 

This change is indicated in the slightly modified main component screen of the 

custom WonderWare* (Progressive Software, Albany, OR) software interface 

(Figure 29). 

t2l fti 3 S •lUserNsme earHrtsfrstof j Screen UntocKed ^ Logon 1 i^Jj Admin \ f (ft Reportsi fcl Trends j 3 Sneuns i Alarms' I 'stzsjoi | "io;35:2e J 

j j SetQflRangee \ | Set QA Paramo hers ) | j Set AnalogRangei | ] Loop li^n g j ] PLC Status ( j CSV Tod 11 I/f Faw ; | | 

Figure 29. New Component Control Screen for XCEM software interface. 

As described in the previous chapters, all day-to-day functions of the XCE M have 

been automated including flow and temperature control, concentration determination, and QA routines. Flow, temperature, concentration, pressure, and error 

messages are automatically recorded in a secure database. The data can readily 

be imported into excel or an equivalent program for subsequent analysis. Flows, 
44 ERDC/CERL TR-05-3 

temperatures, concentrations, and pressure are logged in real-time on the 

screen. Images of the new XCE M and its components are shown in Figures 30-

33. Installation of this unit at TEAD is described in more detail in a follow-on 

technical report. 

Figure 30. XCEM cassettes. 

Figure 31. XCEM extraction system and cassette (left) and chassis (right). 
45 

ERDC/CERL TR-05-3 

Figure 32. XCEM with cabinet door open. 

VES 00067 
46 ERDC/CERL TR-05-3 

5 Summary and Conclusions 

The XCE M has been developed to provide for automated operations. It now includes features that improve ease-of-use and QA. The XCE M extraction, measurement, and data recording systems have been fully automated using a flexible 

WonderWare® software interface. The revised XCE M has been equipped with 

an automated daily zero and span check, as well as a mechanism for checking 

instrument drift, with every sample. 

The XCE M RIF displayed good capture efficiencies for vapor phase Hg under 

reasonable temperature and flow conditions. The XCE M measured the mercuric 

nitrate injected during M29 comparison tests with a 20.4 RA using four test 

runs. This number meets the EPA's proposed PS-10 RA criterion when rounded 

to two significant digits. It is estimated that a larger number of test runs would 

bring that value below 20, so that the XCE M will likely also meet the RA criterion for Hg in future testing. 

A nebulization spiking approach was used to provide very precise concentrations 

of all MACT metals over a wide range of concentrations (1 to 2000 mg/cm3). The 

XCE M agreed well with the M29 test runs for all elements except Ag. The 

XCE M displayed better precision than M29 and was able to report data every 12 

min during the 4-day test period. M29 Ag concentrations differed dramatically 

from any other M29 or XCE M reported concentration. For this reason, and because of laboratory QA issues, it is believed that the low M29 Ag concentrations 

are a result of M29 sampling or analysis error. 

The XCE M met the proposed PS-10 RA criteria for As, Cr, Hg, and Se with only 

four sample runs. It is estimated that the XCE M would also have met the Pb RA 

criterion if nine tests had been conducted. Cadmium, with an RA of 23 percent, 

did not meet the RA criterion. 

Although the simulated stack gas contained the metals of interest and relatively 

high concentrations of nitric acid (~100 ppm), the simulated stack gas did not 

contain sulfur dioxide, fly ash, or nitrogen dioxide as might be seen in an actual 

incinerator stack. For this reason, additional testing under actual stack conditions is needed to ensure that the XCE M can perform as well in the field as it did 

for these tests. 
ERDC/CERL TR-05-3 47 

A new XCE M incorporating the changes made in this report was constructed and 

installed at TEAD where it underwent M29 comparison tests under real incinerator conditions. The installation and field testing of the XCE M at TEAD are 

presented in a follow-on technical report. 
48 ERDC/CERL TR-05-3 

References 

Bryson, S., C. Whitworth, and S. Kujawa. (2000). Final Report - Test and Evaluation of an X-Ray 

Fluorescence Based Multi-Element Metals Continuous Emission Monitor. Prepared for U.S. 

Army Corp of Engineers by MSE-TA, Inc., Butte, MT. 

Cooper Environmental Services (CES). (2001a). "XCEM User's Guide," Beaverton, OR, 2001. 

. (2001b). "XCEM Resource Manual," Beaverton, OR, 2001. 

Cooper, J., B.E. Johnsen, K.J. Hay, and W. Watson (2000). Continuous Hazardous Element 

Analysis System for Ambient and Emissions Monitoring. Presented at regional AWMA 

Conference: Recent Advances in the Science and Management of Air Toxics. April 10, 2000. 

Flagan, R.C., and J.H. Seinfeld (1988). Fundamentals of Air Pollution Engineering, Prentice-Hall, 

Englewood Cliffs, NJ, pp 59-62, 146-159, 359-384. 

French, N. (1998). 1997 Performance Testing of Multi-Metal Continuous Emissions Monitors. 

Summary Report Prepared for the U.S. EPA and U.S. DOE by Sky+, Napa, CA. 

Fuchs, N.A., and A.G. Stutugin. (1966). Aerosol Science, edited by CN Davies, Academic Press, 

London, pp 1-30. 

Johnsen, B., J. Cooper, and B. Richards (1998). Evaluation of a Hazardous Elemental Sampling 

Train During EPA's Continuous Emission Momtoring Test. Presented at Pacific Northwest 

AWMA Conference and International Conference on Incineration and Thermal Treatment 

Technologies. October 1, 1998. 

Josephson, Paul. (2003). Hazardous Waste Combustor Management Plan - AEC. 

Maximum Achievable Control Technology. (1999). Final Standards for Hazardous Air Pollutants 

for Hazardous Waste Combustors. Federal Register 52828-FR53077, Vol. 64, No. 189. 

. (1999b). Final Technical Support Document for HWC MACT Standards. Vol III. 

Selection of MACT Standards and Technology. Chapter 13. USEPA Contract 68-D2-0164. 

PS-10 (1996), Proposed Performance Specification 10 for Metal CEMS (Proposed 04/19/96) Found 

on the EPA website at: http://www.epa.gov/ttn/emc/propperf.html. 

Seltzer, M.D. (2000). "Performance Testing of a Multimetals Continuous Emissions Monitor", J. Air 

Waste Mgt. Assoc., Vol. 60, No. 6. 

Ytalatalo, S., H. Toivonen, and J. Lehtinen. (2000). Authentication of Air Samples by Aerosol. 

Aerosol Science and Technology 33:419-426. 
ERDC/CERL TR-05-3 49 

Abbreviations and Acronyms 

A EC U.S. Army Environmental Center 

CAAA Clean Air Act Amendments (of 1990) 

C E M continuous emission monitor 

CERL Construction Engineering Research Laboratory 

CES Cooper Environmental Services 

CIF carbon-impregnated filter 

EPA U.S. Environmental Protection Agency 

ERDC U.S. Army Engineer Research and Development Center 

EQT Environmental Quality Technology 

H AP Hazardous Air Pollutants 

HEST Hazardous Elemental Sampling Train 

H V M high volatile metals 

HWC hazardous waste combustors 

ICP inductively coupled plasma 

LIBS laser-induced breakdown spectroscopy 

L V M low volatile metals 

M29 EPA Reference Method 29 

mAmp milli-ampere 

MACT Maximum Achievable Control Technology 

MSE-TA M SE Technology Applications, Inc. 

NESHAP National Emission Standards for Hazardous Air Pollutants 

NIST National Institute of Standards and Technology 

P LC programmable logic controller 

P M particulate matter 

PS-10 EPA Performance Specification 10 

QA quality assurance 

RA relative accuracy 

RIF resin-impregnated filter 

RSD relative standard deviation 
50 ERDC/CERL TR-05-3 

SCFM standard cubic feet per minute 

S VM semi-volatile metals 

TEAD Tooele Army Depot (Utah) 

XCE M XRF-based continuous emission monitor 

X RF x-ray fluorescence 

Chemical elements 

Ag silver 

As arsenic 

Cd cadmium 

Cr chromium 

Hg mercury 

Pb lead 

Pd palladium 

Se selenium 

VES 000675 
REPORT DOCUMENTATION PAGE Form Approved 

OMB No. 0704-0188 

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

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

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

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

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

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

01-2005 Final 

3. DATES COVERED (From - To) 

4. TITLE AND SUBTITLE 

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

Development 

5a. CONTRACT NUMBER 

Sb. GRANT NUMBER 

5c. PROGRAM ELEMENT NUMBER 

6. AUTHOR(S) 

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

5d. PROJECT NUMBER 

622784AT41 

5e. TASK NUMBER 

002 

5f. WORK UNIT NUMBER 

CNE-B091 

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

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

Construction Engineering Research Laboratory (CERL) 

PO Box 9005 

Champaign, IL 61826-9005 

8. PERFORMING ORGANIZATION REPORT 

NUMBER 

ERDC/CERL TR-05-3 

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

U.S. Army Corps of Engineers 

441 "G" Street N W 

Washington, DC 20314-1000 

10. SPONSOR/MONITOR'S ACRONYM(S) 

11. SPONSOR/MONITOR'S REPORT 

NUMBER(S) 

12. DISTRIBUTION / AVAILABILITY STATEMENT 

Approved for public release; distribution is unlimited. 

13. SUPPLEMENTARY NOTES 

Copies are available from the National Technical Infonnation Service, 5285 Port Royal Road, Springfield, V A 22161. 

14. ABSTRACT 

Army demilitarization incinerators will need to comply with the Hazardous Waste Combustor National Emission Standards for Hazardous Air Pollutants that will regulate metals and metal compounds listed under the Clean Air Act Amendments. A large problem for 

these incinerator operations is limited knowledge ofthe types and quantities of emitted metals. Compliance may be determined only 

through trial burn emission tests because of this limitation. A continuous emission monitor (CEM) for multi-metals will provide the 

emission data, a tool to help meet compliance requirements, and the opportunity to adjust burn strategies for increased production. The 

XCE M multi-metal CE M was developed using x-ray fluorescence (XRF) as the analytical method and an automated sampling system 

that provides extractive batch sampling onto a filter tape. The system is operated with user-friendly WonderWare® software that provides automation, calibration routines, and report generation. A prototype XCE M was tested in the laboratory with a spiked gas stream 

against U.S. Environmental Protection Agency Reference Method 29 for four sample runs. The XCE M met the relative accuracy criteria for four of seven metals. A field-ready XCE M was built for demonstration at the 1236 Deactivation Furnace at Tooele Army Depot, Utah. 

15. SUBJECT TERMS 

emissions 

continuous emission monitor (CEM) 

hazardous wastes 

demilitarization 

incinerators 

16. SECURITY CLASSIFICATION OF: 17. LIMITATION 

OF ABSTRACT 

18. NUMBER 

OF PAGES 

19a. NAME OF RESPONSIBLE PERSON 

K. James Hay 

a. REPORT 

Unclassified 

b. ABSTRACT 

Unclassified 

c. THIS PAGE 

Unclassified SAR 60 

19b. TELEPHONE NUMBER (include area code) 

(217) 373-3485 

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

Prescribed by ANSI Std. 239.18 

VES 00068 
VES 000681 .pdf 
Performance Specification YY: 

Specifications and Test Procedures for X-Ray 

Fluorescence Based Multi-Metals Continuous 

Emission Monitoring Systems at Stationary Sources 

DRAFT 

June 8, 2005 

Submitted to: 

The Environmental Protection Agency 

Research Triangle Park, NC 

Prepared by: 

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223 
Performance Specification YY: 

Specifications and Test Procedures for X-Ray 

Fluorescence Based Multi-Metals Continuous 

Emission Monitoring Systems at Stationary Sources 

DRAFT 

June 8, 2005 

Prepared by: 

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

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

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223 
Performance Specification YY: 

Specifications and Test Procedures for X-Ray 

Fluorescence Based Multi-Metals Continuous 

Emission Monitoring Systems at Stationary Sources 

Prepared by: Date:_ 

Krag A. Petterson, Environmental Scientist 

Reviewed by: Date: 

Cay A. Yanca, Environmental Scientist 

Reviewed by: Date: 

Bruce E. Johnson, QA Manager 

Approved by: Date: 

John A. Cooper, Director 
Executive Summary 

Performance Specification Y Y details the perfonnance requirements for a multi-metals 

continuous emissions monitor that utilizes x-ray fluorescence (XRF) as an analytical 

technique. Each XRF based multi-metals CEMS must meet the criteria for accuracy, 

stability, and instrumental response laid out in this document. In addition, every XRF multimetals CEMS must meet the installation requirements in PS-YY and the on-going quality 

control and quality assurance procedures set forth in procedure Z if it is used for emissions 

compliance purposes. 

Specifications for XRF-Based Multi-Metals CEM S (PS-YY) Page i of iv 
b0 

CA, 

Cf 

QCEMS 

QCEU 

CF" = 

CF,RB = 

C, £ = 

List of Symbols 

The y intercept of the best fit line 

The slope ofthe best fit line 

X-ray fluorescence calibration accuracy 

Corrected CEMS concentration for the i t h element 

The concentration ofthe i t h element as reported by the CEMS 

The average reported concentration ofthe CEMS for the i t h element 

Correction factor for percent transport for the it h element 

The relative bias correction factor for the i t h element 

The emission limit ofthe i t h element 

X RF multid, = 

1 

FS 

jcemo 

jcemu 

Lf 

n 

PT< 

PTi 

PRBi 

Concentration of the i t h element at the stack 

Concentration of the i t h element at the sampling module or as reported by the 

•metals CEMS. 

Difference between two paired measurements 

Arithmetic mean of differences 

Full scale value of your CEMS volume (or flow) measurement device 

The value of the i t h element on the zero standard determined immediately after 

calibration 

The value ofthe calibration check standard reported by your CEMS 

The measured CEMS response to the zero standard for the i t h element 

The measured CEMS response to the i" 1 element in the upscale standard 

The known value of the calibration check standard 

The calibrated value ofthe i t h element of the upscale standard 

Number of data points 

The percent transport of the i t h element 

Average percent transport for the i t h element 

Relative Bias of the i t h element 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page ii of iv 
The average ofthe reference method measurements for the i t h

 metal 

PRSDt = The relative percent standard deviation for the i t h

 metal 

r = The correlation coefficient 

SD, = The standard deviation of differences for the i * element 

Vcemr Sample gas volume (or flow) as measured by the CEMS volume check device 

VD = Volume drift 

vm = Volume (or flow) reported by your multi-metals CEMS 

UD, = The upscale drift ofthe i , h

 element on your CEMS in percent. 

x = Arithmetic mean 

X / Value of each data point 

CEMS reported concentration for the i t h element 

ZD, = The zero drift of the i t h

 element on your CEMS in percent 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page iii of iv 

VES 00068! 
Table of Contents 

1.0 Using PS-YY 1 

1.1 What is the purpose and applicability of Perfonnance Specification YY? 1 

1.2 What will be discussed in PS-YY? 1 

1.3 What are the installation and pre-performance specification test requirements? 2 

1.4 What special definitions apply to PS-YY? 3 

2.0 Interferences, Safety, and Equipment Requirements 5 

2.1 Are there any potential interferences for my XRF multi-metal CEMS? 5 

2.2 What do I need to know to ensure the safety of persons using PS-YY? 5 

2.3 What equipment and supplies do I need? 5 

2.4 What regents and standards do I need? 6 

3.0 Performance Evaluation Procedures and Reporting 6 

3.1 What is the purpose of the initial performance specification tests and what is 

required to perform the tests? 6 

3.2 How do I report the results of the initial performance specification test? 12 

4.0 Performance Criteria and Calculations 13 

4.1 What are the performance criteria for my XRF multi-metals CEMS? 13 

4.2 What calculations, equations, and data analyses are needed? 14 

5.0 Other Requirements and Information 20 

5.1 What quality control measures are required? 20 

5.2 What calibration and standardization procedures must I perform? 20 

5.3 What pollution prevention procedures must I follow? [reserved] 20 

5.4 What waste management procedures must I use? 20 

5.5 What reference tables and figures are relevant to PS-YY? 20 

5.6 What references apply to PS-YY? 30 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page iv of iv 
1.0 Using PS-YY 

/. 1 What is the purpose and applicability of Performance Specification YY? 

1.1.1 Purpose 

The purpose of Perfonnance Specification Y Y is to establish the performance 

requirements that must be met by a multi-metals continuous emission monitoring 

system (CEMS) that utilizes x-ray fluorescence (XRF) to determine metal 

concentrations in stationary sources. Assurance of the continuing quality of the CEMS 

data may be achieved by following the procedures defined in Procedure Z-XRF 

Based Multi-Metal CEMS Quality Assurance Procedures. 

1.1.2 Application 

PS-YY applies to you if you intend to use an XRF multi-metals CEMS for purposes of 

establishing compliance with federal regulations for metal emissions from stationary 

sources. 

1.1.3 Measurement Capabilities 

A multi-metals CEMS must be capable of measuring total concentrations of at least 

two metals in the units of the applicable standard or in units that can be converted to 

units of the applicable standard. 

1.1.4 Other Monitoring 

If your XRF based multi-metals CEMS is capable of reporting a metal concentration in 

the units of the existing regulation no additional monitoring is necessary. If your 

CEMS does not report concentrations in the units of the existing standard then other 

monitormg (e.g., oxygen, temperature, and pressure) are necessary to convert the units 

reported by your CEMS to the units of the standard. 

1.2 What will be discussed in PS-YY? 

PS-YY covers two basic topics: (1) the instrument requirements for a XRF based multimetals CEMS and (2) the requirements that each XRF multi-metals CEMS must meet during 

the initial performance specification test. 

1.2.1 Instrument Requ irements 

A multi-metals CEMS must be able to accurately report the concentrations of at least 

two metals. It may do so by extracting a representative sample (path or point samplmg 

may be used if the sample is representative) of stack effluent and capturing the metal 

analytes of interest on a medium. The CEMS must have a cycle time that is less than 

one third the period of the applicable standard. The range of the instrument must be 

from 10 percent to at least 400% of the applicable regulation as determined by field or 

Specifications for XR F Based Multi-Metals CEM S (PS-YY)) Page 1 of 1 
laboratory tests. Finally, the instrument or operator must be able to perform daily 

upscale, blank, and flow quality assurance checks to ensure the accuracy, precision, 

and stability ofthe instrument and its data. 

1.2.2 Initial Performance Specification Tests 

The purpose ofthe initial perfonnance specification test is to establish the stability, 

accuracy, and precision of your XRF multi-metals CEMS. The performance 

specification test can be divided into two phases: (1) the stability test, and (2) the 

accuracy test. 

The stability test consists of a seven day check of the zero and upscale calibration drift 

and is done prior to the accuracy testing. For the accuracy tests, three methods of 

metals generation (quantitative spiking, non-quantitative spiking, and stack operation) 

and two methods of data analysis (percent relative bias, and linearity) are available. 

The sampling and XRF modules of your CEMS may also be tested separately from 

your stack sampling interface. Some options may be better than others depending on 

your multi-metals CEMS, or the conditions existing at your stack. 

1.3 What are the installation and pre-performance specification test requirements? 

1.3.1 Installation Requirements 

The sampling location of an XRF multi-metals CEMS should be downstream of all 

pollution control equipment at a position where the metals concentrations are directly 

representative or can be corrected so as to be representative of total emissions from the 

stationary source. It is recommended that the sampling location be at least two 

equivalent diameters downstream of the nearest control devices, point of pollution 

generation, bend, or other point at which a change in pollutant concentration or flow 

disturbance may occur. The sampling location is also recommended to be at least two 

equivalent diameters upstream from the exhaust. The equivalent diameter is calculated 

according 40 CFR Part 60, Appendix A, Method 1, Section 2.1'. 

Either point or path sampling may be used. For point sampling the measurement point 

should be no less than 1.0 meter from the stack or duct wall or located over the 

centroidal area of the stack or duct cross section. For a path sampling CEMS the 

effective measurement path should be (1) totally within the inner area bounded by a 

line 1.0 meter from the stack or duct wall, or (2) have at least 70 percent ofthe path 

within the inner 50 percent of the stack diameter or duct cross section. The sample 

collection and instrumental analyzer portions of your XRF multi-metals CEMS may be 

located any distance from the sampling point provided the transmission efficiency from 

the sampling point to the sample collection point can be determined and meets the 

criteria outlined later in this performance specification. It is also recommended that the 

sampling probe for your multi-metal CEMS be located at point without stratification. 

You may test for stratification at the proposed CEMS sampling point by using either 

P M (as outlined in PS-11), velocity tests as described in Method 22, or metals 

concentrations using Method 29 or an acceptable alternative. 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 2 of2 
1.3.2 Sampling Requirements 

Your multi-metal CEMS should sample from the source at a flow rate which is within 

10 percent of true isokinetic. If your multi-metal CEMS does not maintain an 

isokinetic sampling rate you must use actual site-specific data or data from a similar 

installation to prove to us, the State, and/or local enforcement agency that isokinetic 

sampling is not necessary. 

1.3.3 Pre-Test Preparation Requirements and Suggestions 

Prior to the initial performance specification test you need to ensure that your multimetal CEMS data logger accurately records emissions levels as well as signals (flags) 

that indicate both normal and abnormal operation. Prior to start of the seven day 

stability test the daily drift measurements (upscale and zero values) should be 

monitored to ensure that the instrument is operating in an appropriate and stable 

manner. We recommend that you use your XRF multi-metal CEMS for a sufficient 

length of time to become comfortable with its operation prior to the start ofthe initial 

performance specification test. 

1.4 What special definitions apply to PS-YY? 

Calibration Drift: The difference in the CEMS output readings from the established 

reference value after a stated period of operation during which no unscheduled maintenance 

or adjustment took place. 

Cycle Time: The time between when the stack gas first comes in contact with the 

concentrating media and when the concentration value for that sample is reported. 

Data Recorder: The portion of the CEMS that provides a record of analyzer output 

including metal concentrations, flags which indicate normal operation, and flags indicating 

abnormal operation. The data recorder may record other pertinent data such as effluent flow 

rates, and various instrument temperatures. 

Diluent module: The part of the CEMS in which any diluent is added and measured. 

Drift Calibration Standard: A standard containing a constant amount of metal used to 

establish the drift in the x-ray fluorescence module response. 

Emission Limit: The emission limit for a single metal is equal to the maximum amount 

allowed under the applicable regulation for its category assuming all of the other metals in its 

category were not present. 

Element of Opportunity: An element that is present in the stack effluent and can be used to 

establish transport efficiency. 

Instrument Measurement Range: The range of metal concentrations the instrument can 

reliably measure from the lowest concentration to the highest. The instrument measurement 

range may be different for different metals. If the upper end of the measurement range is 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 3 of 3 
more than four times the emission limit, the upper limit does not need to be definitively 

established. 

Path Sampling CEMS: A CEMS that samples the source effluent along a path greater than 

10 percent of the equivalent diameter of the stack or duct cross section. 

Point Sampling CEMS: A CEMS that samples the source effluent at a single point. 

Non-Quantitative Spiking: The process of introducing an unknown amount of metal or 

metals into the effluent or sample stream. 

Quantitative Spiking: The process of introducing a known amount metal or metals into the 

effluent or sample stream. 

Percent Relative Bias: The difference between a reference value and the CEMS measured 

value divided by the reference value. 

Reference material: A material of known value used to check the calibration drift of your 

XRF multi-metal CEMS. 

Sample Interface: The portion of the CEMS used for one or more of the following: sample 

acquisition, sample transport, sample conditioning, or protection ofthe monitor from the 

effects of stack gas. 

Sampling module: The portion of an x-ray fluorescence based multi-metal CEMS that traps 

the metals and delivers them to the XRF module. 

Spiking: The process of introducing metals into the effluent stream or the sampling stream. 

Transport Efficiency: The percent of metal that is transported from the sample probe to a 

point as close as possible to the sampling module. 

Upscale Drift: The upscale drift is the difference in the reported value for the upscale 

reference from its value at the last calibration, divided by the value at the last calibration. It 

is used to monitor the stability of the x-ray fluorescence analysis. 

X-Ray Fluorescence (XRF) Module: The portion of an XRF based multi-metal CEMS 

which identifies and measures metal masses or concentrations using x-ray fluorescence. 

XRF Multi-Metals Continuous Emission Monitoring System (CEMS): All of the 

equipment required for determining metal concentrations using x-ray fluorescence as an 

analytical technique. The system may consist of several major subsystems including but not 

limited to the following the sample interface, the x-ray fluorescence module, diluent module, 

data recorder, sampling module and volume measurement module. 

Zero Drift: The zero drift is the difference in the CEMS readings for the zero reference from 

their values after the most recent calibration, divided by the emission limit for each element. 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 4 of 4 
2.0 Interferences, Safety, and Equipment Requirements 

2.1 Are there any potential interferences for my XRF multi-metal CEMS? 

There may be interferences arising from the x-ray fluorescence analysis, the trapping media, 

or from condensation in the effluent gas. Check with your multi-metal CEMS manufacturer 

to find out more about potential interferences. 

2.2 What do I need to know to ensure the safety of persons using PS- YY? 

People using PS-YY may be exposed to hazardous material, operational hazards, and 

hazardous site conditions. PS-YY does not address all the safety issues associated with its 

use. It is your responsibility to ensure the safety of persons using PS-YY. Some helpful 

references may include the CEMS manual, the CEMS manufacturer, other reference 

methods, and on-site safety regulations. 

2.3 What equipment and supplies do I need? 

2.3.1 Equipment for the CEMS 

1. Sample interface: This portion of the CEMS must present a sample of source 

effluent to the sampling module that is directly representative or can be 

corrected so as to be representative of source. To accomplish this, the sample 

interface may contain, among other things, heaters or heating systems, and 

dilution air. 

2. Sampling module: The sampling module must collect and trap all the analytes 

of mterest from a representative sample of stack effluent without significant 

loss. The trapped analytes then must be presented to the XRF module. 

3. XRF module: The XRF module uses x-ray fluorescence to determine the mass 

or concentration of metal captured by the sampling module. 

4. Volume measurement module: This portion ofthe CEMS measures the 

volume of source effluent from which the metal analytes were captured in the 

sampling module. This volume along with the data from the XRF to determine 

concentration of source effluent. 

5. Diluent Module: If your multi-metals CEMS uses a diluent such as air or 

nitrogen it is added to the effluent sample and measured using the diluent 

module. 

6. Quality assurance and quality control materials: Your multi-metal CEMS 

must possess the necessary equipment to perform daily upscale and zero 

checks. Your multi-metal CEMS must also possess the equipment to perform a 

daily check ofthe sample volume at normal sample flow rates. 

7. Data recorder: Your XRF multi-metal CEMS must be able to record metal 

concentrations and instrument status signals (flags). 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 5 of 5 
2.3.2 Other Equipment Needed for the Performance Specification Test 

PS-YY does not specify all the equipment and supplies necessary for the performance 

specification tests. Some of this information is included in the applicable reference 

methods (e.g., Method 29 or an acceptable alternative). 

2.4 What regents and standards do I need? 

2.4.1 Zero Drift Reference 

Your multi-metals CEMS must include a standard for the measurement of the daily 

zero drift. This reference should produce a CEMS response indicating the absence of 

metals. If this is not feasible this standard should produce a value between zero and 

20% ofthe emission limit for at least two elements measured by your XRF multimetals CEMS when the instrument is operating appropriately. 

2.4.2 Upscale Drift Reference 

The reference for the upscale drift check should generate a response for at least one 

metal from each condition used in the XRF analysis. This response must be at least 80 

percent of the emission limit. 

2.4.3 Volume Drift measurement device 

During the initial performance specification test the volume measurement must be 

compared on a daily basis against an internal volume or flow measurement device. 

This volume or flow measurement device must be calibrated independently of the 

sample volume or flow measurement device and must be as accurate or more accurate 

than the sample volume or flow measurement device. 

2.4.4 X-ray Fluorescence Calibration Check Standards 

Your XRF multi-metals CEMS must include a means of checking the x-ray 

fluorescence calibration against an external standard. NIST traceable thin film 

standards are an example of a suitable x-ray fluorescence calibration check standard. 

3.0 Performance Evaluation Procedures and Reporting 

3.1 What is the purpose of the initial performance specification tests and what is required 

to perform the tests? 

The purpose of the initial performance specification tests is to detennine the bias, precision, 

stability, and cycle time of your multi-metal CEMS. 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 6 of 6 
3.1.1 Pretest Preparation 

Prior to the start of your initial performance specification tests you must be sure that 

your CEMS is installed according to the specifications laid out in this document. After 

installing your XRF multi-metals CEMS we recommend that you use the CEMS for a 

period of time to familiarize yourself with its operation. We also recommend that you 

conduct daily checks ofthe zero and upscale drift to verify that the instrument is 

functioning properly. When you are confident that the instrument is performing 

satisfactorily it is time to prepare for the initial performance specification tests. 

3.1.2 X-ray Fluorescence Calibration Check 

If your CEMS measures more metals for compliance purposes than will be evaluated 

during the CEMS accuracy testing described later in this document you must perform a 

calibration check of the x-ray fluorescence module for these additional metals. During 

the calibration check you must challenge the x-ray fluorescence module with a standard 

or standards for each metal measured by your XRF multi-metal CEMS. Each metal 

must be measured at least three times and the error is calculated according to 

Equation 13 for each measurement. The average error of the three measurements 

must be less than 10% of the calibration standard's value for each metal, if not your 

CEMS may not be properly calibrated. The x-ray fluorescence calibration check may 

occur at anytime during the initial performance specification test.. 

3.1.3 Stability - The 7-day Calibration Drift Tests 

Prior to the start of the accuracy test you must perform a calibration drift test for a 

period of at least seven days. The purpose of this test is to verify that the instrument 

operation is stable. During the calibration drift test period you must determine the 

magnitude of the zero calibration drift (as calculated in Section 4.2.9), the upscale 

calibration drift (as calculated in Section 4.2.8), and the volume (or flow) drift 

(calculated using Equation 14) at least once each day. During the stability tests no 

adjustments or calibrations may be made to the CEMS. The results of the stability test 

must be reported along with the results ofthe accuracy tests. 

3.1.4 CEMS Accuracy 

The accuracy of your XRF multi-metal CEMS may be determined using one of the 

following four options. 

1. Option A: Linearity test of the entire CEMS 

2. Option B: Linearity test of the XRF and sampling modules separately from the 

sample interface. 

3. Option C: Relative bias test ofthe entire CEMS. 

4. Option D: Relative bias test of the XRF and sampling modules separately 

from the sample interface. 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 7 of 7 
There are also several options for generating the metals that will be analyzed by your 

multi-metal CEMS including, metals that are generated as a by-product of nonnal stack 

operation, quantitative spiking, and non-quantitative spiking. Regardless of the 

generation option you choose you must be able to produce concentrations for some of 

the analytes of interest at 80 to 120 percent of the emission limit. All of the CEMS and 

reference method measurements must be conducted while sampling flue gas. 

You do not need to test every metal that your CEMS measures, however, you must 

generate at least one metal from each category of metals measured by your CEMS for 

the accuracy tests. For instance, if your XRF multi-metals CEMS measures semivolatile, low volatile, and high volatile metals you must test at least one metal from 

each of those categories. (Low volatile metals may also be used to verify the capture 

efficiency and detection of non-enumerated metals). You must also prove that the 

X RF module is properly calibrated to measure the elements that are not being 

measured during the accuracy test by following the procedures described in Section 

3.1.2. The test requirements for each option are explained below and summarized in 

Table 1. 

• Linearity Test Requirements (Options A and B): The bias and precision of 

your XRF multi-metals CEMS may be determined by checking the linearity of 

the instrument response over a series of concentrations. If quantitative spiking 

is used, then the concentration of the aerosol is paired with a reported CEMS 

concentration acquired at the same time. Each data point is then plotted with 

the spiked concentration on the X axis and the reported CEMS concentration on 

the Y axis. If either non-quantitative spiking or stack by product is used, then 

the reported CEMS concentration is plotted on the Y axis versus the 

concentration reported by method 29 or a suitable alternative. 

Linear least squares regression analysis is then used to fit the data points to a 

line. If you challenge only the XRF module and the sampling module the slope 

of this line, which is an indication of the accuracy of your XRF multi-metal 

CEMS, is required to be between 0.85 and 1.15 for each metal. The coefficient 

of correlation must be greater than 0.90 and is an indication ofthe precision of 

your multi-metal CEMS. Finally, the intercept of this best fit line must be less 

than 20% ofthe applicable emission limit. If you challenge the entire CEMS 

system and do not meet the slope or intercept criteria you must apply a 

correction factor according to the procedures in Section 4.2.12. You are, 

however, still required to have a correlation coefficient of 0.90 or greater. 

To perform the linearity test you must be able to generate at least three 

concentration levels for one metal from each class of metals (high volatile, low 

volatile and semi-volatile) measured by your CEMS. The three levels must 

incorporate at least a two fold concentration change and one level must be 

between 80 and 120 percent of the emission limit. You may acquire a blank 

sample if you wish, either by sampling ambient air, or by operating the source 

in such a way that metals are not produced (e.g., burning only natural gas). At 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 8 of 8 
least three measurements are required at each concentration level and a total of 

15 measurements are required overall. You may make additional 

measurements, however, you must report all the results. If you are not using 

quantitative spiking you must make 15 corresponding measurements using 

method 29 or a suitable alternative. We recommend using duel trains for the 

reference method measurement to identify and screen the reference method data 

for imprecision and bias. 

Additional requirements for each ofthe two linearity test options are outlined 

below. You may also want to refer to figures 1 through 8 for guidance on 

which option to choose. 

Option A: Total CEMS Linearity 

In option A the entire CEMS system is challenged during the linearity tests. 

Any one of the three methods of metals generation may be used during the test. 

Some ofthe testing requirements associated with metals generation are outlined 

below 

1. Metals generated as a result of stack operation 

If metals for the test are generated as a result of stack operation you must 

measure the concentration ofthe metals in the stack using method 29 or a 

suitable alternative and compare the values with those reported by your 

CEMS. We recommend using dual reference method trains to screen the 

reference method for precision and bias. 

2. Non-quantitative spiking 

You may either spike non-quantitatively into the stack or duct itself or into 

the transport system as close as possible to the sample probe. If you spike 

into the source you must measure the concentration in the source using 

method 29 or a suitable alternative. This measurement is then compared to 

the result of your CEMS. If you choose to spike into the transport line you 

must measure the concentration immediately downstream of the spike point 

with a method 29 or a suitable alternative and compare that measurement 

with the concentration reported by your CEMS. 

3. Quantitative Spiking 

You may spike a quantitative aerosol directly into the source or into the 

transport line as close as possible to sample probe. Either way the known 

spiked concentration is compared with that measured by the CEMS. 

Option B: Linearity for Sampling and XRF Modules Only 

In option B only the sampling and XRF modules of your multi metals CEMS 

are challenged with a linearity test. You must also complete a transport 

efficiency test along with the linearity test. The procedures for perfomiing a 

transport efficiency test are described in section 3.1.5. The procedures for 

option B associated with each metals generation option are listed below. 

1. Metals generated as a result of stack operation 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 9 of 9 

VES 000696 
If metals concentrations for the accuracy test are generated as a result of 

stack operation you must measure the concentration of the metals as close as 

possible to the sampling module using method 29 or a suitable alternative 

and compare the values with those reported by your CEMS. We recommend 

using dual reference method trains to screen the reference method for 

precision and bias. 

2. Non-quantitative spiking 

You may either spike non-quantitatively into the stack or duct itself or into 

the transport system. Either way you must measure the concentrations of the 

analytes as close as possible to the sampling module and compare that 

concentration with that reported by your multi metal CEMS. 

3. Quantitative Spiking 

You must spike at a location as close as possible to the sampling module and 

compare the known spiked concentration with that reported by your CEMS. 

• Relative Bias Test Requirements (Options C and D): There are two relative 

bias options available: one that challenges the entire CEMS and one that 

challenges the sampling and XRF modules separately from the sample 

interface. Either option requires at least 12 CEMS measurements be made at a 

concentration level 80 to 120 percent of the emission limit for a metal from 

each category of metals analyzed by your XRF multi metal CEMS. If you are 

not using quantitative spiking you must also have at least 12 corresponding runs 

of method 29 or a suitable alternative at this concentration level. We 

recommend using dual trains for the reference method to screen the data for 

imprecision and bias. 

Additionally, for at least one metal measured at the emission limit or for a 

surrogate metal that can be measured by your CEMS (such as iron) you must 

test the CEMS at three different concentration levels. These three levels must 

incorporate at least a two-fold change in concentration and one of the levels 

must be between 80 and 120 percent of the emission limit (the concentration of 

the emission limit for the surrogate metal is equal to that for the metal measured 

by your CEMS with the highest emission limit). You are required to obtain at 

least three measurements at each concentration level and are required to have a 

total of at least 12 measurements. You must report the results of all 

measurements. The relative bias is an indicator of accuracy and should be 

calculated using equation 5 for each element. Also, the percent relative 

standard deviation, which is an indicator of precision, should be calculated for 

each metal 

Ifyou challenge the entire CEMS system and you do not meet the test criteria 

you may apply a correction factor to your CEMS data. Calculate a correction 

factor for each metal in the relative bias test according to the equation found in 

section 4.2.13. If you challenge the sampling and XRF modules separately 

from the sample interface you may not apply a correction factor to the data 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 10 of 10 

VES 00069/ 
from the relative bias test, you may, however, apply a correction factor to the 

results of the transport efficiency test. For the metal that was spiked over 

several concentrations you must perform linear least squares regression analysis 

on the data. The correlation coefficient for this fit must be better than 0.90. 

This is to demonstrate that the instrument response is valid over its applicable 

range. If the criteria for this test is met then the correction factors are assumed 

to be valid over the range of the instrument. 

Option C 

In accuracy test option C the entire CEMS is subjected to a relative bias test. 

The options for metals generation and the associated spiking and reference 

method requirements are the same as those for Option A under the linearity 

tests. 

Option D 

In accuracy test option D only the XRF and sampling modules are subjected to 

a relative bias test. The options for metals generation and their associated 

spiking and reference method requirements are the same as those for Option B. 

You are also required to perform a transport efficiency test. 

3.1.5 Transport Efficiency Test 

You must perform a transport efficiency test if you have only challenged the sampling 

and XRF modules during the accuracy tests (options B and D). Any one ofthe four 

methods described below are valid ways of determining percent transport for your 

multi-metals CEMS. 

• Particulate Matter (PM): In this approach particulate matter is measured 

concurrently in two locations, (1) in the stack effluent stream as close as 

possible to your multi-metals CEMS sample interface, and (2) at a point in the 

transport system as close as possible to the sampling module. You may use any 

standard reference method to measure P M including Method 5, Method 5i, or 

Method 17 (40 CFR 60, Appendix A) 3'

4

'

5

. Particulate matter must be generated 

by operating the source. You must acquire at least 12 paired concentration 

measurements (each pair consists ofthe measurement made as close as possible 

to the sample interface and the measurement made as close as possible to the 

sampling module. The percent transmission is calculated for each pair using 

equation 6 and the overall percent transmission is determined by calculating the 

average of all twelve runs. 

• Element of opportunity: Alternatively, transport efficiency can be detennined 

using a surrogate metal such as iron or zinc that is commonly present in stack 

effluent. Method 29 (40 CFR 60, Appendix A) 6 or a suitable alternative can be 

used to measure the metal concentration in the stack effluent stream as close as 

possible to the sample probe and at a point in the transport system as close as 

possible to the sampling module. Also, if your XRF multi-metals CEMS is 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 11 of 11 
capable of measuring the element of interest, you may compare the measured 

concentration on the CEMS with that measured in the stationary source using 

the reference method. Transport efficiency is calculated using equation 6. You 

are required to make at least twelve paired concentration measurements to 

determine the mean transport efficiency. 

• Non-quantitative spiking: An aerosol containing a surrogate metal or a metal 

analyte can be spiked non-quantitatively into the stack or duct gas stream or 

into the transport system as close as possible to the sampling probe. The 

concentration of the spiked metal is measured by method 29 (40 CFR 60, 

Appendix A) 5 or a suitable alternative as close as possible to the CEMS' sample 

probe and by another Method 29 or a suitable alternative as close as possible to 

the sampling module. Ifyou spike directly into the transport line you must 

make your upstream concentration measurement as close as possible to the 

spike location and your downstream measurement as close as possible to the 

sampling module. If your XRF multi-metals CEMS is capable of measuring the 

spiked metal, you may compare its reported concentration with the in source 

metals measurement or with the upstream in transport line measurement to 

calculate transport efficiency according to equation 6. You are required to 

make at least twelve paired concentration measurements to determine the mean 

transport efficiency. 

• Quantitative Spiking: An aerosol containing a surrogate metal or a metal 

analyte can be spiked quantitatively into the stack or duct gas stream or into the 

transport system as close as possible to the sampling probe. The concentration 

may be measured on the CEMS or by using method 29 or a suitable alternative 

as close as possible to the sampling module. This measurement is then 

compared with the known concentration ofthe spiked aerosol to determine the 

percent transport. 

3.1.6 Dual Train Requirements 

Ifyou use a reference method (eg., method 29 or 5i) during the linearity, relative bias, 

or transport efficiency tests it is recommended that you use dual trains to screen the 

reference method for bias and imprecision. 

3.1.7 Cycle Time Requirements 

The cycle time for your XRF multi-metals CEMS should be no greater than one-third 

of the averaging period for the applicable standard. During all phases of the 

performance specification test including the CEMS must use the same cycle time as 

will be used during day to day operation. 

3.2 How do I report the results of the initial performance specification test? 

Summarize the results of the calibration drift and accuracy tests in tabular form. Include all 

data sheets, calculations, and records of CEMS measurements necessary to substantiate the 

performance of the CEMS and any other devices or methods (e.g., method 29). The CEMS 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 12 of 12 
measurements shall be reported to the agency in units of ug/m3

 on a dry basis, corrected to 

20°C. 

4.0 Performance Criteria and Calculations 

4.1 What are the performance criteria for my XRF multi-metals CEMS? 

You must demonstrate that your XRF multi-metal CEMS has adequate stability, precision, 

accuracy, cycle time and data reporting capabilities to determine if your facility is in 

compliance with metal emission standards or operating pennit limits as specified in 

applicable regulations or permits. You will demonstrate this capacity by showing that your 

X RF multi-metal CEMS meets the following performance criteria. 

4.1.1 7-day Drift Check Criteria - Stability 

Upscale Drift: The upscale drift as calculated in section 4.2.8 must be less than 15% of 

the original calibration value of the upscale reference each day for seven consecutive 

days. 

Zero Drift: The zero drift as calculated in Section 4.2.9 must be less than 20% of the 

emission limit each day for seven consecutive days. 

Volume or Flow Drift: The volume or flow drift as calculated in Section 4.2.11 must 

be less then 20% of the full scale value of the flow or volume measurement device each 

day for seven consecutive days. 

4.1.2 X-Ray Fluorescence Calibration Drift Criteria 

For each metal measured by your multi-metal CEMS for compliance purposes the xray fluorescence calibration drift must be less than 10% of the value of the standard. 

(Note: you are not required to calculate the XRF calibration drift for those metals used 

during the bias and precision testing). 

4.1.3 Relative Bias Criteria - Accuracy and Precision 

The relative bias of the instrument must be less than 15% and the relative percent 

standard deviation (RSD) must be 10% or less if you challenge the XRF and sampling 

modules of your CEMS separately from your transport system. If you challenge your 

entire CEMS and it does not meet the above relative bias criteria you must apply a 

correction factor to the results reported by your CEMS. The correction factor is 

calculated using the equation in section 14.2.13. Also, the correlation coefficient for a 

least squares linear regression fit of the metal that was spiked at three different 

concentration levels must be greater than 0.90. This is to help assure that the 

correction factor is applicable over the range of the instrument. 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 13 of 13 
4.1.4 Linearity Test Criteria Accuracy and Precision 

Ifyou choose to do linearity tests to determine the accuracy and precision of your XRF 

multi-metals CEMS the slope of the least squares linear fit should be between 0.85 and 

1.15. The correlation coefficient must be 0.90 or better and the intercept should be less 

than 20% of the applicable emission limit. If you challenge only the XRF module and 

the sampling module of your CEMS you must meet the above criteria. If you 

challenge your entire CEMS and you do not meet the slope or intercept criteria you 

must adjust the results reported by your CEMS, you must however, still meet the 

correlation coefficient criteria. The correction factor is calculated according to the 

procedures in section 4.2.12. 

4.1.5 Transport efficiency - Accuracy 

If the average transport efficiency is between 90 and 110 percent, then no correction 

for transport efficiency needs to be applied to concentrations reported by your XRF 

multi-metals CEMS. If, however, your average transport efficiency is less than 90 

percent or more than 110 percent then you must use a correction factor. You may use 

your transmission efficiency test data to establish a correction factor that would change 

the reported CEMS concentrations for each metal to a value that would reflect 100% 

transmission efficiency. 

4.1.6 Cycle time - Appropriate Reporting 

The cycle time for your XRF multi-metals CEMS must be no greater than one-third of 

the averaging period for the applicable standard. 

4.2 What calculations, equations, and data analyses are needed? 

4.2.1 Arithmetic Mean 

Calculate the arithmetic mean of a data set as follows. 

Equation 1 

Where : 

x Arithmetic mean 

n Number of data points 

Value of each data point 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 14 of 14 
4.2.2 Arithmetic Mean of Difference 

To calculate the arithmetic mean of difference use the above equation substitute d for x. 

Where 

D . _ (JCEMS _ R R M Equation 2 

Where: 

ccms = j^e concentration of the i t h

 element as reported by the CEMS 

RRM _ concenn -atio n of the i t h

 element as reported by the reference 

method or aresol 

4.2.3 Standard Deviation (of differences) 

Equation 3 

Where: 

SDi = The standard deviation of differences for the i * element 

n = The number of data points 

di = The difference between the concentration measured by the 

reference method or the concentration of the reference aerosol and the 

concentration reported by the CEMS. 

4.2.4 Percent relative standard deviation 

SD Equation 4 

PRSD, ==i x 100 

R

m 

Where: 

RfM = The average of the reference method data set or the reference 

aerosol concentration for the i t h element 

PRSD, = The relative percent standard deviation for the i t h metal 

4.2.5 Relative Bias 

TM <

 = lbif x10 0

 Equations 

Ri 

Specifications for XR F Based Multi-Metals CEM S (PS-YY) Page 15 of 2 
Where di is the mean difference, RfM

 is the average ofthe reference method 

data set or the average aerosol concentration for the i t h element, and PRBi is 

the relative bias for the i * element 

4.2.6 Percent Transmission 

PT =-VxlO O 

Cf Equation 6 

Where: 

Cf = Concentration of the i t h element at the stack 

C-"' = Concentration of the i t h element at the sampling module or as 

reported by the XRF multi-metals CEMS. 

PT. = The percent transport of the i t h element 

Report the average percent transport (PT) of all measurements for each 

element that was tested (only one element is required though more can be 

tested). 

4.2.7 Best Fit Line for Linearity Test 

Calculate the linear correlation equation given below. 

y = b0+blx Equation 7 

Where: 

b0 = The y intercept 

b\ = The slope 

The intercept is calculated according to the following equation. 

b0=y-bxx Equation 8 

Where: 

1 

2> X 

n 

y 

The slope of the line is calculated according to equation below. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 16 of 30 
1

^ j ( x i -x)(y i - y ) 

_ J^I Equation 9 

The linear correlation coefficient is calculated according to the following equation. 

n 

]T(x. -x)(y, -y) 

1=1 Equation 10 

I ;=i /=i 

4.2.8 Upscale Drift 

Wceim _ ja I Equation 11 

CZD. = — -xlOO 

Where: 

UD, = The upscale drift of the i * element on your CEMS in percent. 

jcemu = Th e measure( j CEMS response to the i l h element in the upscale 

standard 

L" = The calibrated value of the i t h element of the upscale standard 

4.2.9 Zero Drift 

I Equation 12 

ZD,. = ^——p^xlOO 

Cf 

ZDj = The zero drift of the i * element on your CEMS in percent 

jcemn _ Tn e measure( j CEMS response to the zero standard for the i 1 

element 

L° = The calibrated value of the i , h element on the zero standard 

Cf = The emission limit of the i t h element 

4.2.10 X-Ray Fluorescence Calibration Accuracy 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 17 of 30 
Wcem _ jstd I Equation 13 

CA: —17-^x100 

Lf 

Where: 

CA, = X-ray fluorescence calibration accuracy 

U.m = The value of the standard reported by your CEMS 

Lf - The known value of the standard 

4.2.11 Daily Sample Volume Check 

VD = \Vcmr~

Vm\ x 100 Equation 14 

FS 

Where: 

VD = Volume drift 

Vcemr = Sample gas volume (or flow) measured by the CEMS volume 

check measurement device 

V„, = Sample gas volume (or flow) reported by your multi-metal CEMS 

FS = Full scale value of the CEMS volume (or flow) measurement 

device 

4.2.12 Linearity Test Correction Factors (Applicable only when the linearity test 

challenges the entire CEMS) 

1. Correction equation if CEMS does not meet either the slope or the intercept 

criteria. 

~ ^ Equation 15 

Where: 

Cf = corrected CEMS concentration for the 1t h element 

yt = CEMS reported concentration for the i t h element 

bo = the intercept of the least squares linear regression line 

bi = the slope of the least squares linear regression line 

2. Correction factor if CEMS meets intercept criteria, but does not meet the 

slope criteria. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 18 of 30 
C, c

=y,.-Z>0 Equation 16 

3. Correction factor if CEMS meets slope criteria but does not meet intercept 

criteria. 

Equation 17 

4.2.13 Relative Bias Correction Factors 

j RRM Equation 18 

CF RB 

A NCEM 

R RM 

Where: 

CFTM = The relative bias correction factor for the i t h element 

QCEM _ Tn e averag e reported concentration of the CEMS for the i 

element 

R f 4 = The average of the reference method measurements for the i t h 

metal 

4.2.14 Percent transport correction factor 

D T

 l Equation 19 

C F p r = = 

PTt 

Where 

CF^ = Correction factor for percent transport for the i t h element 

PTj = Average percent transport for the i t h element 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 19 of 30 
5.0 Other Requirements and Information 

5.1 What quality control measures are required? 

Quality control measures for an XRF multi-metal CEMS are addressed in procedure Z 

"Quality Assurance Requirements for X-Ray Fluorescence Based Multi-Metals Continuous 

Emission Monitors." 

5.2 What calibration and standardization procedures must I perform ? 

Refer to your CEMS owner's manual and manufacturer to determine what calibration and 

standardization procedures are required for your multi-metal CEMS. 

5.3 What pollution prevention procedures must Ifollow? [reserved] 

5.4 What waste management procedures must I use? 

A ll chemicals used to produce a reference aerosol or in performing standard methods need to 

be disposed of properly. 

5.5 What reference tables and figures are relevant to PS-YY? 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 20 of 20 
Table 1. Initial Performance Specii ication Tests and Criteria 

Test 

Category 

Test Test Requirements Test Criteria 

Seven Day 

Stability 

Zero Drift Monitor zero standard for 7 

consecutive days under normal 

operating conditions 

< 20% drift every day for seven 

consecutive days 

Seven Day 

Stability 

Upscale Drift Monitor upscale standard for 7 

consecutive days under normal 

operating conditions 

< 15% drift every day for seven 

consecutive days 

Seven Day 

Stability 

Flow Drift Monitor flow drift for 7 consecutive 

days under normal operating 

conditions 

< 20% drift every day for seven 

consecutive days 

Calibration 

X-Ray Fluorescence 

Calibration Drift Check 

Test a standard for each element 

measured for compliance by your 

CEMS 3 times 

< 10% drift for every element 

measured for compliance by 

your CEMS 

Accuracy 

Option A 

Perform a linearity test on 

entire CEMS 

• At least one metal from each 

category 

• Need at least 3 concentration 

levels which include a 2 fold 

cone, change and the emission 

limit 

• If spiking, spike into source, or 

spike into transport line as close 

as possible to the probe 

• Slope = 0.85 to 1.15 

• r>0.90 

• intercept < 20% of emission 

limit 

• if the above criteria are met 

then no correction 

• if not met apply a correction 

(correlation criteria must be 

met) 

Accuracy 

Option B 

• Perform a linearity test 

on sampling module 

and XRF module only 

• Determine transport 

efficiency separately 

• At least one metal from each 

category 

• Need at least 3 concentration 

levels which include a 2 fold 

cone, change and the emission 

limit 

• Spike or measure concentrations 

with reference method as close as 

possible to the sampling module 

Linearity Criteria 

• Slope = 0.85 to 1.15 

• r>0.90 

• intercept < 20% of emission 

limit 

• the linearity criteria must be 

met 

Percent Transport Criteria 

• 90<PT<110 

• If percent transport criteria 

are not met apply a Accurac correction factor 

y 

Option C 

Perform a relative bias test 

on entire CEMS 

• At least one metal from each 

category at 80 to 120 percent of 

emission limit 

• One other metal at 3 cone, levels 

which include a 2 fold cone, 

change and the emission limit 

• If spiking, spike into source or 

spike into transport line as close 

as possible to the probe 

Percent relative Bias 

RB< 15% 

%RSD< 10% 

r > 0.90 for metal with three 

fold cone, change 

• If Criteria not met apply a 

correction factor (correlation 

coefficient criteria must be 

met) 

Accuracy 

Option D 

• Perform a relative bias 

test on sampling 

module and XRF 

module only 

• Determine transport 

efficiency separately 

• At least one metal from each 

category at 80 to 120 percent of 

emission limit 

• One other metal at 3 cone, levels 

which include a 2 fold cone, 

change and the emission limit 

• Spike or measure concentrations 

with reference method as close as 

possible to the sampling module 

Percent Relative Bias Criteria 

RB<15% 

%RSD< 10% 

r > 0.90 for metal with three 

fold cone, change 

Percent Transport Criteria 

• 90<PT<110 

• If percent transport criteria 

are not met apply a 

correction factor 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 21 of 21 
Methods of Metals 

Generation for 

Accuracy Tests 

Quantitative 

Spiking 

NonQuantitative 

Spiking 

Stack Operation 

Figure 1: Types of metals generation available for accuracy tests. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 22 of 22 
Quantitative 

Spiking 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 23 of 23 
Non-Quantitative 

Spiking 

Challenge the cniinc batch MultiMclals System. N o independent 

measure o f transport efficiency. 

Y o u can challenge the sampling 

module and pollutant analyser 

portion of your butch M M CiiM S 

separately rmm the transport sy>tem, 

however, you wil l also have to 

determine transport efficiency. 

No 

C

Y o u may use either ^""V 

linearity testing or ) 

relative bias. ^ / 

Figure 3: Flow chart for using non-quantitative spiking during the accuracy tests. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 24 of 24 
Metals Generated During 

Stack Operation 

cd by. 

Can I generate 

'concentrations at +/- 20% ofthe' 

Emission Limit for a metal from 

vcach class of metals mcasui 

my CEMS? 

Yes 

N o 

You need to use a different 

melhod lo cenerale metals. 

N o • ( You must use relative bias. 

Yes 

: :— \ 

You may use either linearity \ 

testing or relative bias. J 

Figure 4: Flow chart for using stack operation to generate metals concentrations. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 25 
Transport 

Efficiency 

1 r 

PM 

Measurment 

Element of 

Opportunity 

Figure 5: Species available for transport tests 

Specifications for XR F Multi-Metals CEM S (PS-YY) 
P M Measurnicm 

Yes 

* 

Use Method 5, 5i or 17 to 

measure P M cone, at (ho 

slack and al your CEMS . 

Calculate transport 

efficiency. 

Figure 6: Procedure for percent transport using PM. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 27 of 27 

VES 000714 
Compare the 

concentration on or near 

the CEMS with the 

concentration measured 

at the stack. Calculate 

transport efficiency. 

Y ou must establish a correlation to \ 

correct for transport efficiency. J 

/ No correction laclor is necessary. \ 

[ You have completed the transport J 

V efficiency test. J 

Figure 7: Procedure for percent transport determination using an element of 

opportunity. 

Specifications for XR F Multi-Metals CEM S (PS-YY) 

Page 28 of 28 

VES 000715 
. /Choos e Ncw \ 

N u \ Species J 

Non-Quantitative 

Spike 

Select transport line or 

N c*M Choose New Species 

Select In Slack or 

H a * \ Choose New Specie: 

. /ChooseNcw S 

Species J 

Compare the concentration 

on or near the CEMS with 

the concentration measured 

at the stack. Calculate 

transport efficiency. 

Y o u must establish a 

correlation to correct for 

transport efficiency. 

f N o correction factor is ^ 

( necessary. Yo u have completed 

V the transport efficiency test. J 

Figure 8: Procedure of percent transport determination using spiking. 

Specifications for XR F Multi-Metals CEM S (PS-YY) 

Page 29 of 29 

VES 000716 
5.6 What references apply to PS-YY? 

1. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 1: Sample 

and Velocity Traverses for Stationary Sources. Washington, DC: EPA; 2004. 

Available: http://www.epa.gov/ttn/emc/promgate/m-01.pdf via the Internet. Accessed 

May 8, 2005. 

2 United States. Environmental Protection Agency [EPA}. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 2: 

Determination of Stack Gas Velocity and Volumetric Flow Rate. Washington, D.C: 

EPA; 2004. Available: http://www.epa.gov/ttn/emc/promgate/m-02.pdf via the 

Internet Accessed May 10,2005. 

3. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 5: 

Determination of Particulate Matter Emissions from Stationary Sources. Washington, 

DC: EPA; 2004. Available: http://www.epa.gov/ttn/emc/promgate/m-05.pdf via the 

Internet. Accessed May 10, 2005. 

4. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 5i: 

Determination of Low Level Particulate Matter Emissions from Stationary Sources. 

Washington, DC: EPA; 2004. Available: http://www.epa.gov/hwcmact/frhwc5.pdf via 

the Internet. Accessed May 10, 2005. 

5. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 17: 

Determination of Particulate Matter Emissions from Stationary Sources. Washington, 

DC: EPA; 2004. Available: http://www.epa.gov/ttn/emc/promgate/m-17.pdf via the 

Internet. Accessed May 10, 2005. 

6. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 29. 

Determination of Metals Emissions from Stationary Sources. Washington, DC: EPA; 

2004. Available: http://www.epa.gov/ttn/emc/promgate/m-29.pdf via the Internet. 

Accessed May 18, 2005. 

Specifications for XR F Multi-Metals CEM S (PS-YY) Page 30 of 30 

VES 000717 
VES 000718.pdf 
Procedure Z: Quality Assurance Requirements for 

X-Ray-Fluorescence Based Multi-Metals 

Continuous Emission Monitoring Systems at 

Stationary Sources 

DRAFT 

June 9, 2005 

Submitted to: 

The Environmental Protection Agency 

Research Triangle Park, NC 

Prepared by: 

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223 
Procedure Z: Quality Assurance Requirements for 

X-Ray-Fluorescence Based Multi-Metals 

Continuous Emission Monitoring Systems at 

Stationary Sources 

DRAFT 

June 9, 2005 

Prepared by: 

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

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

Prepared by: 

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite J6 

Portland, Oregon 97223 
Procedure Z: Quality Assurance Requirements for 

X-Ray-Fluorescence Based Multi-Metals 

Continuous Emission Monitoring Systems at 

Stationary Sources 

Prepared by: Date:_ 

Krag A. Petterson, Environmental Scientist 

Reviewed by: Date: 

Cay A. Yanca, Environmental Scientist 

Reviewed by: Date: 

Bruce E. Johnson, QA Manager 

Approved by: Date: 

John A. Cooper, Director 
Executive Summary 

Procedure Z outlines the continuing quality control and quality assurance 

requirements for an x-ray fluorescence based multi-metal CEMS. Procedure Z requires daily 

checks of the upscale, zero and volume measurement drift. It also specifies quarterly checks 

of the x-ray fluorescence calibration and of the volume measurement calibration. Finally 

procedure Z requires that the entire XRF multi metal CEMS accuracy be verified on an 

annual basis. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page i of iv 

VES 000721 
b0 

bi 

CA, 

Cf 

QCEMS 

QCEM 

CFf7 

CFTM 

Cf 

Cf 

C

sm 

d 

FS 

A 

juemo 

i f 

L

u

, 

n 

PT, 

List of Symbols 

The y intercept of the best fit line 

The slope of the best fit line 

X-ray fluorescence calibration accuracy 

Corrected CEMS concentration for the i t h element 

The concentration ofthe i t h element as reported by the CEMS 

The average reported concentration ofthe CEMS for the i t h element 

Correction factor for percent transport for the i t h element 

The relative bias correction factor for the i l h element 

The emission limit of the i t h element 

Concentration of the i t h element at the stack 

Concentration of the i t h element at the sampling module or as reported by the 

XRF multi-metals CEMS. 

Difference between two paired measurements 

Arithmetic mean of differences 

Full scale value of your CEMS volume (or flow) measurement device 

The calibrated value of the i t b element on the zero standard 

The value of the standard reported by your CEMS 

The measured CEMS response to the zero standard for the it h element 

The measured CEMS response to the i t h element in the upscale standard 

The known value ofthe XRF calibration check standard 

The value ofthe i t h element of the upscale standard 

Number of data points 

The percent transport ofthe i * element 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page ii of iv 
PTi = Average percent transport for the i element 

PRBi = Percent relative Bias of the i t h element 

RfM = The average of the reference method measurements for the i t h metal 

PRSD, = The relative percent standard deviation for the i' h metal 

r = The correlation coefficient 

SDi = The standard deviation of differences for the it t l element 

Vcemr = Sample gas volume (or flow) as measured by the CEMS volume check device 

VD = Volume drift 

V,„ = Volume (or flow) reported by your multi-metals CEMS 

UDj = The upscale drift of the it h element on your CEMS in percent. 

x = Arithmetic mean 

X, = Value of each data point 

Vi = CEMS reported concentration for the i t h element 

ZD, = The zero drift of the it h element on your CEMS in percent 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page iii of iv 
Table of Contents 

Executive Summary i 

List of Symbols ii 

Table of Contents iv 

1.0 Using Procedure Z 1 

1.1 What is the purpose and applicability of Procedure Z? 1 

1.2 What are the basic requirements of Procedure Z? 1 

1.3 What special definitions apply to procedure Z? 1 

2.0 Interferences, Safety, and Equipment Requirements 2 

2.1 What interferences are associated with procedure Z? 2 

2.2 What do I need to know to ensure the safety of persons using Procedure Z? 2 

2.3 What equipment and supplies do I need? 3 

2.4 What reagents and standards do I need? 3 

2.5 What sample collection, preservation, storage, and transport procedures are relevant 

to Procedure Z? 4 

3.0 Quality Control, Calibration, and Standardization 4 

3.1 What quality control measures are required by this procedure for my multi-metal 

CEMS? 4 

3.2 What calibration checks and audit procedures must I perform for my multi-metal 

CEMS? 4 

4.0 Calculations 7 

4.1 What calculations and data analysis must I perform? 7 

4.2 What waste management procedures are required for procedure Z? 13 

5.0 Other Requirements and Information 13 

5.1 What pollution prevention measures must I take when using procedure Z? 13 

5.2 What criteria are necessary for my XRF multi-metal CEMS to be in control and 

what do I do if it is out of control? 13 

5.3 What tables, diagrams and flow charts are relevant to Procedure Z? 16 

5.4 What references are relevant to Procedure Z? 18 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page iv of iv 
1.0 Using Procedure Z 

/. 1 What is the purpose and applicability of Procedure Z? 

The purpose of Procedure Z is to establish the minimum requirements for quality control 

(QC) and quality assurance (QA) procedures for x-ray fluorescence (XRF) based multimetals CEMS. These quality control and quality assurance procedures are in place to ensure 

the accuracy and validity of the data reported by your multi-metal CEMS for emission 

compliance purposes. You must meet these minimum requirements ifyou plan to use your 

multi-metal CEMS for reporting purposes, however, we encourage you to develop a more 

extensive QA program or to continue with such programs where they already exist. Any 

XRF multi-metals CEMS used to report to us, the state, or a local enforcement agency must 

comply with procedure Z immediately after the completion ofthe initial performance 

specification test outlined in Performance Specification YY 1. 

1.2 What are the basic requirements of Procedure Z? 

Procedure Z requires you to perform several drift checks and audits which ensure the 

accuracy of the data reported by your XRF multi-metals CEMS. You are required to, on a 

daily basis, record and calculate zero drift, upscale drift, and, a sample volume drift. On a 

quarterly basis you are required to perform an XRF calibration audit (XFCA) and a sample 

volume audit (SVA). On an annual basis you are required to execute either a linearity audit 

(LA) or a relative bias audit (RBA) and, if applicable, a transport efficiency audit (TEA). 

The criteria for passing these audits and drift checks are outlined in procedure Z. Procedure 

Z also summarizes the requirements for when and if your CEMS fails an audit or drift test. 

Finally, Procedure Z also covers the requirements for and timelines associated with periods 

when your XRF multi-metals CEMS is out of control. 

1.3 What special definitions apply to procedure Z? 

Linearity Audit: (LA) An assessment of the validity ofthe original linear correlation of 

your CEMS. 

Reference material: A material of known value used to check the calibration drift of your 

X RF multi-metal CEMS. 

Relative Bias: The difference between a reference method or aerosol concentration and the 

concentration recorded by your CEMS divided by the concentration ofthe reference 

measurement. 

Relative Bias Audit: (RBA) An assessment of the bias in your CEMS. 

Sample Interface: The portion of the CEMS used for one or more of the following: sample 

acquisition from the stack or duct effluent, sample transport, sample conditioning, or 

protection ofthe monitor from the effects of stack gas. 

Quality Assurance for XR F -Based Multi-Metal CEM S (Procedure Z) Page 1 of 1 
Sample Module: The portion of the XRF multi-metal CEMS that traps the metals and 

delivers them to the x-ray fluorescence module. 

Standard Volume Audit: (SVA) This is an evaluation of your XRF multi-metals CEMS 

sample volume measurement system. This is required if your CEMS uses a volume 

measurement to report metal concentrations and is accomplished by comparing the volume 

measured by your CEMS with the volume measured by an independently calibrated device. 

Transport Efficiency Audit: (TEA) An assessment of the transport efficiency of the sample 

interface of your multi-metals CEMS. This audit applies to your XRF multi-metals CEMS if 

either the RBA or L A challenged only the sampling and XRF modules. 

Transport System: The portion ofthe CEMS that transports a representative sample of 

source effluent from the sample probe to the sample module. 

X-Ray Fluorescence Calibration Audit: (XFCA) This is an evaluation of how well the xray fluorescence portion of your multi-metals CEMS has maintained its original calibration. 

This is accomplished by challenging the XRF module with a standard of known 

concentration for each metal measured by your CEMS for compliance. The analyzer 

response is compared with the known concentration ofthe standard. 

X-Ray Fluorescence Module: The portion of an XRF based multi-metal CEMS which 

identifies and measures metal masses or concentrations using x-ray fluorescence. 

XRF Multi-Metals Continuous Emission Monitor (CEMS): All of the equipment required 

for determining metal concentrations using x-ray fluorescence as an analytical technique. 

The system may consist of several major subsystems including the sample interface, the xray fluorescence module, the volume measurement module, diluent analyzer, data recorder, 

and sampling module. 

2.0 Interferences, Safety, and Equipment Requirements 

2.1 What interferences are associated with procedure Z? 

There may be interferences arising from the x-ray fluorescence, the trapping media, or from 

condensation in the effluent gas. Check with your multi-metal CEMS manufacturer to find 

out more about potential interferences. 

2.2 What do I need to know to ensure the safety of persons using Procedure Z? 

Persons using procedure Z may be exposed to hazardous materials, equipment, and 

operations. Procedure Z does not purport to address all ofthe safety issues associated with 

its use. It is your responsibility to establish appropriate safety and health practices before 

using this procedure. You may consult with your CEMS manual and/or manufacturer for 

precautions specific to your multi-metal CEMS. If standard reference methods are used then 

you may also consult the appropriate reference methods to address safety concerns. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 2 of2 
2.3 What equipment and supplies do I need? 

[reserved] 

2.4 What reagents and standards do I need? 

Reference materials for the zero and upscale drifts along with a reference measurement 

device for the sample volume check. 

2.4.1 Zero drift reference 

Every XRF multi-metals CEMS must be equipped with a zero reference that can be 

checked on a daily basis. This reference should produce a CEMS response indicating 

the absence of metals. If this is not feasible this standard should produce a value 

between zero and 20% of the emission limit for at least two elements measured by your 

X RF multi-metals CEMS when the instrument is operating appropriately. 

2.4.2 Upscale drift reference 

The reference for the upscale drift check should generate a response for at least one 

metal from each condition used in the XRF analysis. This response must be at least 80 

percent of the emission limit. 

2.4.3 Sample volume or flow check 

If your XRF multi-metals CEMS makes volume or flow measurements it must be 

equipped to perform a daily sample volume check. 

2.4.4 Sample volume audit standard 

If your XRF multi-metals CEMS makes volume or flow measurements, periodic 

standard volume or flow audits must be performed. An independently calibrated 

volume or flow measurement device or standard such as a Dry Cal® is required for 

these audits. The standard must be able to acquire a volume or flow measurement at 

sampling rates typical of your XRF multi-metals CEMS. 

2.4.5 X-ray Fluorescence Calibration Check Standards 

Your XRF multi-metals CEMS must include a means of checking the x-ray 

fluorescence calibration against an external standard. NIST traceable thin film 

standards are an example of a suitable x-ray fluorescence calibration check standard. 

2.4.6 Reagents and standards for the Linearity Audits and Relative Bias Audits 

You will need other reagents and standards for the linearity audit or relative bias audit. 

The regents and standards required will differ depending on how these audits are 

performed. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 3 of 3 
2.4.7 Regents and standards for the Transport Efficiency Audit 

The regents and standards for the transport efficiency audit also depend upon how the 

audit is performed. 

2.5 What sample collection, presentation, storage, and transport procedures are relevant 

to Procedure Z? 

[reserved] 

3.0 Quality Control, Calibration, and Standardization 

3.1 What quality control measures are required by this procedure for my multi-metal 

CEMS? 

You must develop and implement a quality control program that, at a minimum includes 

detailed written procedures for all of the following activities. 

1. Procedures for performing drift checks on a daily basis, including but not limited 

to, zero drift, upscale drift, and sample volume measurement drift. 

2. Procedures and methods of adjusting your multi-metal CEMS in response to the 

results ofthe drift checks. 

3. Preventative maintenance of your XRF multi-metals CEMS. 

4. Data recording, calculations, and reporting. 

5. Procedures for required audits, including transport efficiency audits (if necessary), 

linearity audits, and relative bias audits. 

6. Procedures for adjusting your CEMS based on audit results. 

7. A program of corrective action and stack operation procedures in case of a CEMS 

malfunction and an out of control period. 

You are required to keep written documentation of your QA/QC procedures on record 

and available for inspection for the life ofthe CEMS or until you are no longer subject to 

the requirements of this procedure. Ifyou fail two consecutive audits you must revise 

your QA/QC procedures. 

3.2 What calibration checks and audit procedures must I perform for my multi-metal 

CEMS? 

3.2.1 Daily drift check procedures 

Your XRF multi-metals CEMS must have the capacity to perform each ofthe following 

checks on at least a daily basis. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 4 of 4 
• Zero drift: You must check the zero drift to ensure the stability of your CEMS 

response to the zero drift reference. The zero drift must be less than plus or 

minus 20% ofthe emission limit each day. Follow your CEMS manufacturer's 

instructions for proper zero drift check procedures. 

• Upscale drift: You must check the upscale drift to ensure the stability of your 

X RF multi-metal CEMS response to the upscale standard. The daily upscale 

drift must be less than 15% of the upscale reference value determined 

immediately after the x-ray fluorescence module has been calibrated. Follow 

your CEMS manufacturer's instructions for proper upscale drift check 

procedures. 

• Daily volume or flow check: You must check the sample volume or flow 

measurement to verify the accuracy ofthe volume measurement on your 

CEMS. This volume check must be done at the normal sampling rate for the 

CEMS. Your CEMS is out of control if the one day value exceeds 20% of the 

full scale of the volume or flow measurement device. Follow your CEMS 

manufacturer's instructions for proper volume or flow check procedures. 

3.2.2 Audit procedures 

Audit procedures and criteria are listed below. These requirements are also 

summarized in Table 1 in section 5.3. 

1. X-Ray Fluorescence Calibration Audit (XFCA): You must perform an 

XFC A once each quarter. To perform an XFC A you must challenge the x-ray 

fluorescence module of your multi-metal CEMS with a standard of known 

concentration for each metal measured by your CEMS for compliance purposes 

and compare the value reported by the CEMS with the known value of the 

standard. If you wish you may make only one measurement of a standard for 

each element. If your multi-metal CEMS fails on the initial measurement you 

may make two more measurements of each standard and average all three 

measurements. If the average CEMS response over the three measurements 

deviates by less than 10% from the known standard the CEMS has passed the 

XFCA. If the average exceeds 10% your CEMS has failed the XFCA and is 

out-of-control. You must follow the procedures outlined in Section 5.2. An 

XFC A is required once per quarter. The minimum allowed time between each 

audit is two months and the maximum allowed time is four months. 

2. Sample volume (or flow) audit (SVA): You must perform a sample volume 

audit of your XRF multi-metals CEMS at least once per quarter and prior to any 

linearity or relative accuracy audit. To perform an SVA you must 

independently measure the volume of sample gas extracted from the stack or 

duct over the sampling period. You may make this measurement either at the 

inlet or outlet of your CEMS. You must make volume measurements during 

three different sampling cycles and the measurements must be able to make 

corrections for moisture content if necessary. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 5 of 5 
If your CEMS measures flow and totalizes that flow to determine volume you 

may perform a flow audit instead. You must make flow measurements during 

three different sampling cycles and for each sampling cycle you must make at 

least 3 to 5 simultaneous measurements of flow on your CEMS and on the 

independent flow measurement device. You must calculate the error from each 

set of measurements according to equation 6 and then calculate the average 

error in the flow during each sampling period. Finally you must calculate the 

average error from all three sampling periods and this average must be less than 

10% of the independent flow or volume measurement device. 

A sample volume audit is required on a quarterly basis. The minimum required 

time between each SVA is at least two months while the maximum allowed 

time between audits is four months. 

Accuracy Audits: As outlined in Performance Specification Y Y it is 

acceptable during the initial performance specification test to assess the 

accuracy and precision of the XRF and sampling modules of your XRF multimetal CEMS separately from the sample interface. You may also do this 

during the Linearity or Relative Bias Audits that are required for Procedure Z. 

If you choose to challenge the sampling module and XRF systems separately 

from the sampling interface you must also perform a Transport Efficiency 

Audit (TEA). If you challenge the entire XRF multi-metals CEMS during the 

Linearity and Relative Bias Audits you are not required to perform an 

independent check of the CEMS transport efficiency. For the purposes of 

Procedure Z you are required to perform either a linearity audit or a relative 

bias audit, but not both. You are also not required to perform the same kind of 

tests for the audit as were performed during the initial perfonnance 

specification test. For example, if a linearity test was performed during the 

initial accuracy tests, either a relative bias audit or a linearity audit is 

acceptable. 

There are four different options available for the accuracy audits depending on 

whether or not a linearity or relative bias audit is performed and depending on 

whether or not the entire CEMS is challenged by the audit. The audit 

requirements are listed below. 

Linearity A inlits 

Option A 

In this option a linearity audit is performed on the entire CEMS. The types of 

metals generation and their associated requirements are identical to those for 

Option A in performance specification Y Y section 3.1 A 1 If you do not meet 

the linearity criteria you must apply a correction according to the procedures 

outlined in performance specification YY. 1 

Option B 

In this option a linearity audit is perfonned on the sampling and XRF modules 

of the CEMS separately from the sample interface. The types of metals 

generation and their associated requirements are identical to those for Option B 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 6 of 6 
in performance specification Y Y section 3.1.4.1

 A transport efficiency audit 

must also be completed. 

Relative Bias Audit 

Option C 

In this option a relative bias audit is performed on the entire CEMS. The types 

of metals generation and their associated requirements are identical to those for 

Option C in performance specification Y Y section 3.I.4.1 If your CEMS fails 

to meet the criteria you must apply a correction factor according to the 

procedures in performance specification YY. 1 

Option D 

In this option a relative bias audit is performed on the sampling and XRF 

modules of the CEMS separately from the sample interface. The types of 

metals generation and their associated requirements are identical to those for 

Option D in performance specification Y Y section 3.1.4.1 A transport 

efficiency audit must also be completed. 

An accuracy audit is required on an annual basis. The minimum time between 

successive accuracy audits is 9 months while the maximum allowed time is 15 

months. 

3. Transport Efficiency Audit (TEA): You are required to perform a TEA only 

if you choose to challenge the sampling and XRF modules of your XRF multimetals CEMS separately from the sampling interface. The procedures for 

performing a TEA are the same as those for determining the transport efficiency 

during the initial performance specification test and are outlined in Performance 

Specification YY 1. If the transport efficiency of your CEMS is between 90 and 

110 percent no correction is necessary. If your transport efficiency is less than 

90 percent or greater than 110 percent then you must establish a correction 

factor according to the procedures outlined in section 3.1.7 of Performance 

Specification YY 1. The minimum time between successive transport efficiency 

tests is 9 months while the maximum allowed time is 15 months. 

4.0 Calculations 

4.1 What calculations and data analysis must 1 perform? 

4.1.1 Arithmetic Mean 

Calculate the arithmetic mean of a data set as follows 

Equation 1 

Where: 

x Arithmetic mean 

n Number of data points 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 7 of 7 

VES 000731 
x, = Value of each data point 

4.1.2 Arithmetic Mean of Difference 

To calculate the arithmetic mean of difference use the above equation substitute d for x. 

Then 

Equation 2 

di — X; - yi 

Where x and y are paired data points from the CEMS and either the reference 

aerosol or the reference method. 

4.1.3 Da ily Zero Drift 

\Lc

j

emo-L]\ Equation 3 

ZD, =

J

 -^-^xlOO

 H 

Cf 

Where: 

ZD, = The zero drift of the i t h element on your CEMS in percent 

jcemo = measured CEMS response to the zero standard for the i element 

L] = The calibrated value of the i t h element on the zero standard 

Cf = The emission limit of the i t h element 

4.1.4 Daily Upscale Drift 

\jcemu _ ju Equation 4 

UD, =

 ]— ^xlOO H 

L" 

Where: 

UD, = The upscale drift of the i t h element on your CEMS in percent. 

jcemu = T j j e Assured CEMS response to the i * element in the upscale 

standard 

L! = The calibrated value ofthe i t h element ofthe upscale standard 

4.1.5 Daily Sample Volume Check 

V D

 = \VTM>" -

V

"'\ x 10 0 Equation 5 

FS 

Where: 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 8 of 8 
VD = Volume drift 

Vcemr = Sample gas volume or flow measured by the CEMS volume or 

flow check measurement device 

Vm = Sample gas volume or flow reported by your multi-metal CEMS 

FS = Full scale value of the CEMS volume measurement device 

4.1.6 Sample Volume Audit Accuracy 

VA = 

V r

~

V m \ x ioo Equation 6 

Where: 

V A = Volume or flow measurement accuracy 

Vr = Sample gas volume or flow measured by the independent 

calibrated reference device 

V,„ = Sample gas volume or flow reported by your multi-metal 

CEMS 

4.1.7 X-Ray Fluorescence Calibration Audit Calibration 

\rcem TStdl . . _ 

A

 _ A Equation 7 

CA, =

 ]

- ^xlOO

 M 

Lf 

Where: 

CA, = X-ray fluorescence calibration accuracy 

Lf" = The value of the standard reported by your CEMS 

Lf = The known value of the standard 

4.1.8 Relative Bias 

TM ' =| i x10 0 Equations 

R. 

Where di is the mean difference, R*M is the average ofthe reference method 

set or reference aerosol concentration for the it h element, and PRBi is the 

relative bias for the i t h element 

4.1.9 Transport Efficiency 

Quality Assurance for Batch Multi-Metals CEM S (Procedure Z) Page 9 of 9 

VES 000733 
PT, =-VxlO O 

C Equation 9 

Where: 

Cf = Concentration of the i t h

 element at the stack 

C-'" = Concentration of the i t h element at the sampling module or as 

reported by the XRF multi-metals CEMS. 

PT The percent transport of the i' element 

Report the average percent transport (PT ) of all measurements for each 

element that was tested (only one element is required though more can be 

tested). 

4.1.10 Linearity Audit - Least Squares Linear Regression 

Calculate the linear correlation equation given below. 

y = ba +Z?,x Equation 10 

Where: 

b0 = The y intercept 

b\ = The slope 

The intercept is calculated according to the following equation. 

b0=y-blx 

Where: 

1 " 

1 " 

The slope of the line is calculated according to equation below. 

n 

bi= M _ 

Equation 11 

Equation 12 

The linear correlation coefficient is calculated according to the following equation. 

Quality Assurance for XR F -Based Multi-Metals CEM S (Procedure Z) Page 10 of 18 
4.1.11 Standard Deviation (of differences) 

SD, 

Y.di1 [Zdi | 

n 

n-\ 

Equation 14 

Where: 

SDi = The standard deviation of differences for the i * element 

n = The number of data points 

dj = The difference between the concentration measured by the 

reference method or the concentration of the reference aerosol and the CEMS 

reported concentration. 

4.1.12 Percent standard deviation 

SD Equation 15 

PRSD, ==ixl0 0 

R

m 

Where: 

R

 m

 = The average of the reference method data set for the i t h element 

PRSDf = The relative percent standard deviation for the i * metal 

4.1.13 Linearity Test Correction Factors (Applicable only when the linearity test 

challenges the entire CEMS) 

1. Correction equation if CEMS does not meet either the slope or the intercept 

criteria. 

QC _ y-< ~ b0 Equation 16 

Where: 

Specifications for Batch Multi-Metals CEM S (PS-YY) Page 11 of 18 
Cf = Corrected CEMS concentration for the i t h

 element 

y, = CEMS reported concentration for the i * element 

bo = The intercept of the least squares linear regression line 

bi = The slope of the least squares linear regression line 

2. Correction factor if CEMS meets intercept criteria, but does not meet the 

slope criteria. 

C

?=yt-K Equation 17 

3. Correction factor if CEMS meets slope criteria but does not meet intercept 

criteria. 

QC _ ZL Equation 18 

4.1.14 Relative Bias Correction Factors 

Equation 19 

CFTM -

 1

 -

R

m 

Where: 

CF,m = The relative bias correction factor for the i t h element 

C f m - The average reported concentration of the CEMS for the i * 

element 

Rf11 = The average of the reference method measurements for the i t h 

metal 

4.1.15 Percent transport correction factor 

CFPT = =L Equation 20 

PT, 

Where 

CF,PT = Correction factor for percent transport for the il l ) element 

PTi = Average percent transport for the i t h element 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 12 of 18 
4.2 What waste management procedures are required for procedure Z? 

A ll chemicals used to produce a reference aerosol or in performing standard methods need to 

be disposed of properly. Please consult the appropriate reference methods. 

5.0 Other Requirements and Information 

5.1 What pollution prevention measures must I take when using procedure Z? 

[reserved] 

5.2 What criteria are necessaiy for my XRF multi-metal CEMS to he in control and what 

do I do if it is out of control? 

5.2.1 Required Corrective Action for Drift Checks and Audits 

• Daily Zero Drift: If the one day drift exceeds 20% you are required to rerun 

your zero drift reference. If the XRF multi-metal CEMS meets the criteria 

during the second test you may continue to operate. If the CEMS fails to meet 

the zero drift criteria again then it is out of control. It is recommended that you 

examine the zero drift standard for defects. After repairs to the CEMS are 

completed you are required to perform at least five successful zero drift checks 

within a 24 hour period. After the five checks have been successfully 

completed then you CEMS is in control. If the repairs were made to the XRF 

module of the multi-metals CEMS you are also required to complete an x-ray 

fluorescence calibration audit (XFCA) to verify the accuracy of your x-ray 

fluorescence calibration. 

• Daily Upscale Drift: If the one day drift exceeds 15% you are required to retest 

the upscale drift reference. If the XRF multi-metals CEMS meets the criteria 

during the second test you may continue to operate, however, if the CEMS fails 

the second upscale drift check it is out of control. It is recommended that you 

examine the upscale drift standard for defects. After repairs to the CEMS are 

completed you are required to perform at least five successful upscale drift 

checks within a 24 hour period. After the five drift checks are successfully 

completed the CEMS is back in control. Again, if repairs were made to the 

X RF module of the multi-metal CEMS you are also required to successfully 

complete an x-ray fluorescence calibration audit (XFCA) to verify the accuracy 

of the calibration. 

• Daily Sample Volume Check: If your sample volume or flow drift exceeds 

20% it has failed the daily volume check and you must perform another daily 

volume check. If the CEMS passes the second check you may continue to 

operate. If your CEMS fails the second test it is out of control and your CEMS 

must be repaired. After repairs have been made the CEMS must successfully 

complete five sample volume checks within a 24 hour period. Upon successful 

completion of the five checks your CEMS is back in control. If the repairs 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 13 of 13 
were made to a volume or flow measurement device you are also required to 

successfully complete a sample volume audit (SVA). 

• Quarterly Sample Volume Audit (SVA): Your XRF multi metals CEMS is 

out of control if volume (or flow) measured by your CEMS differs from that 

measured by the independent standard by more than 10% percent. A failure of 

this audit may indicate that repairs need to be made to the volume measurement 

system. Upon completion of these repairs you must perform and pass another 

SVA. 

• Quarterly X-Ray Fluorescence Calibration Audit (XFCA): The response of 

your XRF multi-metals CEMS must be within 10% of the standard's value for 

each metal measured for compliance purposes by your CEMS. If your CEMS 

fails the XFC A initially, rerun each standard two more times and take the 

average of the three measurements. If the average CEMS response meets the 

XFCA criteria you may continue to operate, however, if the CEMS fails to meet 

the criteria then it is out of control. After the CEMS has been repaired you 

must complete another XFCA. Upon successful completion of the XFC A the 

CEMS is back in control. 

• Annual CEMS Accuracy Tests 

Linearity A udit 

Option A (Linearity audit of the entire CEMS). 

Ifyou challenge the entire CEMS system (including sampling interface and the 

sampling and XRF modules) with a linearity audit you do not need to apply a 

correction factor to your CEMS data if it meets the following criteria: 

1. a slope between 0.85 and 1.15 

2. the correlation coefficient equal to 0.90 or more 

3. an intercept of less than 20 percent ofthe emission limit 

If your CEMS does not meet the slope or intercept criteria you must apply a 

correction factor according to the procedures described in Performance 

Specification Y Y Section 4.2.12." Your CEMS, however, must still meet the 

correlation criteria. 

If your CEMS fails the linearity test it is out of control. After the necessary 

repairs are made it must pass a linearity or relative bias test to be considered 

back in control. 

Option B (Linearity audit of the sampling module and XRF module only 

followed by a TEA) 

If you challenge the sampling and XRF modules separately from the sample 

interface, your XRF multi-metal CEMS is out of control if the linear least 

squares regression analysis of your audit data does not meet the following 

criteria for each of the metals measured by your CEMS for compliance 

purposes: 

Qualify Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 14 of 14 
1. a slope between 0.85 and 1.15 

2. the correlation coefficient equal to 0.90 or more 

3. an intercept of less than 20 percent of the emission limit 

If your XRF multi-metals CEMS fails a linearity audit you must make the 

necessary repairs to your CEMS and successfully complete either a relative bias 

audit or a linearity audit before it is considered to be back in control. 

You must also complete a transport efficiency audit (TEA) along with your 

linearity audit. 

Relative Bias Audit 

Option C (Relative bias test of the entire CEMS) 

If your CEMS meets the following criteria it has passed the relative bias audit 

and you do not need to apply a correction factor to your CEMS. 

1. the percent relative bias (PRB) exceeds 15% 

2. the percent relative standard deviation(Pi?XD) exceeds 10% 

3. the correlation coefficient (r) for linearity portion of the relative bias audit is 

less than 0.90 

If your XRF multi-metals CEMS fails to meet the relative bias criteria you may 

apply a correction factor according the procedures described in performance 

specification Y Y Section 4.2.131. However, if your CEMS fails to meet either 

the percent relative standard deviation criteria or the correlation coefficient 

criteria it is out of control. If your XRF multi-metal CEMS fails a relative bias 

audit it must successfully compete another linearity or relative bias audit to be 

considered in control. 

Option D (Perform a relative bias test on the sampling and XRF modules) 

Your XRF multi-metals CEMS is out of control if: 

1. the percent relative bias (PRB) exceeds 15% 

2. the percent relative standard deviation(PicSD) exceeds 10% 

3. the correlation coefficient (r) for linearity portion of the relative bias audit is 

less than 0.90 

You must successfully complete another RB A or a linearity audit before your 

CEMS is considered to be in control. You must also successfully complete a 

transport efficiency audit along with the relative bias audit. 

Transport Efficiency Audit (TEA): A TEA is only required if you challenge 

your sampling XRF modules separately from your sample interface (Options B 

and D). If the percent transport is between 90 and 110 percent no correction 

factor is necessary, however, if the percent transport is less than 90 percent or 

greater than 110 percent then you must apply a correction factor to the results 

reported by your multi metal CEMS. The procedures for applying a correction 

factor using the equation in Section 4.1.15. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 15 of 15 
5.2.2 General out of control guidelines 

• Out of control period: The out of control period begins immediately after the 

failed drift test or audit and is over immediately following the successful 

completion of required procedures associated with the failure of the audit test. 

During the out of control period you may not use the data generated by your 

X RF multi-metal CEMS for compliance purposes. 

• Reporting guidelines: You must include in your report to us, the state, or local 

enforcement agency the results of the failed audit or drift check, the corrective 

action that was taken, and the results of the successful audit or drift check. 

• Rules governing auditing time periods: The X-Ray Fluorescence Calibration 

Audit (XFCA) and the Sample Volume Audit (SVA) are required once a 

quarter. Two months must pass between successive quarterly audits and no 

more than four months may pass.. The Linearity Audit (LA) and the Relative 

Bias Audit (RBA) are required on an annual basis. Successive LAs and RBAs 

must be separated by at least nine months and no more than 15 months. 

5.3 What tables, diagrams and flow charts are relevant to Procedure Z? 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 16 of 16 
Table 1: Continuing QA Procedures for XRF Multi-Metals CEMS 

Test 

Frequency 

Test Test Procedures Passing Criteria 

Daily 

Zero Drift Check zero standard and calculate drift < 20% drift each day 

Daily Upscale Drift Check upscale standard and calculate drift < 15% drift each day 

Volume or Flow Drift Check flow drift and calculate drift < 20% drift each day 

Quarterly 

X-Ray Fluorescenc e 

Calibratio n Audit 

Test a standard for each element measured for 

compliance by your CEM S (1 time per 

standard) 

• < 10% difference for every 

element measured for 

compliance by your CEM S 

• If criteria not initially met you 

may take the average of 3 

measurements 

Quarterly 

Sample Volum e 

(or Flow) Audit 

Volume 

• Compare CEM S volume against a standard 

during 3 sampling cycles 

• Average all three 

Flow 

• 3 to 5 flow measurements with standard 

and CEM S per sample cycle 

• Measure in 3 CEM S sample cycles 

• Calculate average difference between 

CEM S and standards over all 

measurements 

<10% difference from the standard 

Annually 

Option A 

Perform a linearity test on 

entire CEM S 

• At least one metal from each category 

• Need at least 3 concentration levels which 

include a 2 fold cone, change and the 

emission limit 

• If spiking, spike into source, or spike into 

transport line as close as possible to the 

probe 

• Slope = 0.85 to 1.15 

• r>0.90 

• intercept < 20% of emission 

limit 

• if above criteria is met then no 

correction 

• if not met apply a correction 

Annually 

Option B 

• Perfon n a linearity test 

on sampling and XR F 

modules only 

• Determine transport 

efficiency separately 

• At least one metal from each category 

• Need at least 3 concentration levels which 

include a 2 fold cone, change and the 

emission limit 

• Spike or measure concentrations with 

reference method as close as possible to the 

sampling module 

Linearity Criteria 

• Slope = 0.85 to 1.15 

• r>0.90 

• intercept < 20% oTemission 

limit 

• the linearity criteria must be met 

Percent Transport Criteria 

• 90<PT<110 

• If percent transport criteria are 

not met apply a correction 

Annually factor 

Option C 

Perform a relative bias test 

on entire CEM S 

• At least one metal from each category at 80 

to 120 percent of emission limit 

• One other metal at 3 cone, levels which 

include a 2 fold cone, change and the 

emission limit 

• If spiking, spike into source or spike into 

transport line as close as possible to the 

probe 

• Percent relative Bias 

• RB<15 % 

• %RSD<10 % 

• r > 0.90 for metal with three 

fold cone, change 

• If Criteria not met apply a 

correction factor (correlation 

coefficient criteria must be met 

Annually 

Option D 

• Perform a relative bias 

test on sampling and 

X R F modules only 

• Determine transport 

efficiency separately 

• At least one metal from each category at 80 

to 120 percent of emission limit 

• One other metal at 3 cone, levels which 

include a 2 fold cone, change and the 

emission limit 

• Spike or measure concentrations with 

reference method as close as possible to the 

sampling module 

Percent Relative Bias Criteria 

• RB<15 % 

• %RSD<10 % 

• r > 0.90 for metal with three 

fold cone, change 

Percent Transtrort Criteria 

• 90<PT<110 

• If percent transport criteria are 

not met apply a correction 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 17 of 17 

VES 000741 
5.4 What references are relevant to Procedure Z? 

1. Performance Specification YY : Specifications and Test Procedures for Batch MultiMetals Continuous Emission Monitoring Systems at Stationary Sources. 2005. 

Quality Assurance for XR F Based Multi-Metals CEM S (Procedure Z) Page 18 of