# Method X: Determination of Metal Concentrations in Emissions from Stationary Sources (Instrumental Analyzer Procedure)



# DRAFT

June 7, 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

# Method X: Determination of Metal Concentrations in Emissions from Stationary Sources (Instrumental Analyzer Procedure)



# DRAFT

June 7, 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

# Method X: Determination of Metal Concentrations in Emissions from Stationary Sources (Instrumental Analyzer Procedure)

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, DirectorMethod X: Multi-Metals Instrumental Analyzer Procedure Page i of v 

### Executive Summary

Method X is an instrumental analyzer proced ure for the determination of multiple metals using x-ray fluorescence as an analytical technique. Method X specifies the criteria for accuracy stability and precision that must be met by an x-ray fluorescence based instrument analyzer. Method X also describes the emission test procedures associated with an x-ray fluorescence based metals measurement system.Method X: Multi-Metals Instrumental Analyzer Procedure Page ii of v 

### List of Symbols

i B = The background concentration of the i th metal as determined by the instrumental metals measurement system

i CD = X-ray fluorescence calibration drift for the i th metal

L i C = Value of the emission limit for the i th metal

RB i CF = Relative bias correction factor for the i th metal
d i = Difference between paired alternative reference method or reference aerosol and instrumental metals measurement system concentrations for the i th metal

i d = Average difference in concentr ation between the instrumental measurement system and the alterna tive reference method or aerosol

0 i L = Zero reference value for the i th element at the last calibration

IA i L = Concentration reported by the instrume ntal metals measurement system
for the i th metal

IAC i L = Value of the standard reported by th e x-ray fluorescence module for the i th

metal

IAU i L = Response to the i th element in the upscale reference

IAZ i L = Instrumental metals measurement system response for the i th metal to the
zero reference

std i L = Calibrated value of the calibration test standard for the i th element

u i L = Calibrated value of i th element on the upscale reference

n = Number of data points

i PRB = Percent relative bias for the i th metal

RM i R = The concentration of the i th metal in the alternative EPA reference
method data set or refere nce aerosol concentration

RM i R = Average concentration of the i th metal in the alternative EPA reference
method data set or refere nce aerosol concentration

i PRSD = Percent relative sta ndard deviation of the i th metal

i SD = Standard deviation of differences for the i th metal

i UD = Upscale drift of the i th metal of an instrumental metals measurement system in percent VA = Volume or flow measurement accuracy V

c = Volume or flow reported by the instrumental metals measurement system’s volume check device VD = Volume or flow drift V

IA = Volume or flow reported by the instrumental measurement system’s volume or flow sample measurement device V

r = Sample gas volume measured by the independent calibrated reference deviceMethod X: Multi-Metals Instrumental Analyzer Procedure Page iii of v x i = Value of the i th measurement

i ZD = Zero drift of i th metal on an instrumental metals measurement systemMethod X: Multi-Metals Instrumental Analyzer Procedure Page iv of v 

### Table of Contents Executive Summary............................................................................................................. i 1.0 Purpose and Applicability....................................................................................... 1 1.1 Purpose................................................................................................................ 1 1.2 Applicability ....................................................................................................... 1 2.0 Method Summary.................................................................................................... 1 2.1 Principle .............................................................................................................. 1 3.0 Range and Sensitivity ............................................................................................. 1 3.1 Analytical range.................................................................................................. 1 3.2 Sensitivity ........................................................................................................... 1 4.0 Definitions............................................................................................................... 2 5.0 Apparatus and Reagents.......................................................................................... 3 5.1 Measurement system........................................................................................... 3 5.2 Quality assurance and control materials ............................................................. 4 5.3 Metals generator.................................................................................................. 5 5.4 Alternative EPA Reference method.................................................................... 5 6.0 Measurement System Performance Specifications................................................. 5 6.1 Zero drift ............................................................................................................. 5 6.2 Upscale drift........................................................................................................ 5 6.3 Volume drift........................................................................................................ 6 6.4 X-ray fluorescence module calibration drift check............................................ 6 6.5 Volume measurement calibration check............................................................. 6 6.6 Percent relative bias ............................................................................................ 6 6.7 Interference Check.............................................................................................. 6 6.8 Reporting requirements....................................................................................... 6 7.0 Measurement System Performance Test Procedures.............................................. 6 7.1 Measurement system preparation ....................................................................... 6 7.2 Zero drift check................................................................................................... 6 7.3 Upscale drift check ............................................................................................. 7 7.4 Volume drift check ............................................................................................. 7 7.5 X-ray fluorescence calibration drift check.......................................................... 7 7.6 Volume or flow calibration check....................................................................... 7 7.7 Relative bias test ................................................................................................. 8 7.8 Interference check............................................................................................... 9 8.0 Emissions Test Procedure..................................................................................... 10 8.1 Performance tests prior to emissions testing..................................................... 10 8.2 Selection of sampling point .............................................................................. 10 8.3 Sample collection.............................................................................................. 10 9.0 Calculations........................................................................................................... 11 9.1 Arithmetic mean ( x )......................................................................................... 11 9.2 Zero drift ( i ZD ) ................................................................................................ 11 9.3 Upscale drift ( i UD )........................................................................................... 12 9.4 Volume drift (VD) ............................................................................................ 12Method X: Multi-Metals Instrumental Analyzer Procedure Page v of v 9.5 X-ray Fluorescence calibration drift ( i CD ) ...................................................... 12 9.6 Volume or flow calibration drift (VA).............................................................. 13 9.7 Relative bias ( i RB ) ........................................................................................... 13 9.8 Standard deviation (of differences) ( i SD )........................................................ 14 9.9 Percent relative standard deviation ( i RSD ) ...................................................... 14 9.10 Correction factor for relative bias ( RB i CF ) ....................................................... 15 10.0 Safety .................................................................................................................... 15 11.0 Tables, Figures for Method X............................................................................... 15 12.0 References............................................................................................................. 20Method X: Multi-Metals Instrumental Analyzer Procedure Page 1 of 1 

### 1.0 Purpose and Applicability

1.1 Purpose The purpose of Method X is to define the emi ssion test procedures that must be followed when using an instrumental metals measuremen t system that reports metal concentrations in emissions from stationary sources using x-ra y fluorescence as an an alytical technique. These criteria and emission test procedures are in place to assu re the accuracy and reliability of the data produced by the system.

1.2 Applicability This method is applicable to the determinati on of metal concentrations in emissions from stationary sources using an x-ray fluorescence based instrumental metals measurement system.



### 2.0 Method Summary

2.1 Principle A sample of gas is acquired isokinetically from a stack or duct. A portion of that sample source gas is then pulled through a capturing medium where metal analytes are removed from the effluent stream and concentrated. The metal analyte sample is then presented to the x-ray fluorescence module after enough time has elapsed to allow the metal analytes to concentrate sufficiently to be detectable. The masses of metal an alytes reported by the x-ray fluorescence module is divided by the vol ume of stack effluent sampled to obtain the analyte concentration in the source.



### 3.0 Range and Sensitivity

3.1 Analytical range The instrumental metals monitoring system must be able to measure metal concentrations in a range from 20% to 400% of the allowed emission limit for each metal as demonstrated by laborat ory or field trials.

3.2 Sensitivity
The minimum detectable limit of the instrume ntal analyzer depends on the analytical range, the signal-to-noise ratio of the measurement system and the presence of interferences. The minimum detectable lim it must be less than 10% of the applicable emission standard.Method X: Multi-Metals Instrumental Analyzer Procedure Page 2 of 2 

### 4.0 Definitions

Analytical range: The range of metal concentrati ons the instrument can reliably

measure.
Diluent analyzer: The portion of the instrumental metals measurement system that detects the diluent. The d iluent may be detected by the x-ray fluorescence module or by another device or technique.

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 happens to be present in stack or duct effluent that can be used to determine relative bias.

EPA reference method : A method recognized by the United States Environmental Protection Agency as appropriate for the m easurement of a pollutant or pollutants in source emissions.

Instrumental metals analyzer : The portion of the instrumental metals measurement system containing the components nece ssary for the measurement of metal concentrations, including th e sampling module, the x-ray fluorescence module, and the volume measurement module.

Instrumental metals measurement system: All of the equipment required for determining metal concentrations using an x-ray fluorescence based approach. An instrumental metals measurement system ma y consist of several modules including, but not limited to the following: the sample inte rface, the x-ray fluorescence module, the diluent analyzer, the sampli ng module, the volume measur ement module, and the data recorder

Non-quantitative spiking: The process of introducing an unknown concentration of metal or metals into a gas stream.

Quantitative spiking: The process of introducing a know n concentration of metal or metals into a gas stream.

Sample conditioning system: The portion of the sample in terface that conditions the stack or duct gas to prevent concentration loss and or damage to the x-ray fluorescence module. Examples of sample conditioning incl ude heaters and dilutent gas to prevent the condensation of water vapor.

Sample interface: The portion of the instrumental meta ls measurement system that is used for extracting a sample from the stack or duct. The sample interface may include some or all of the following systems; a sample probe, sample transport system, and sample conditioning systems.Method X: Multi-Metals Instrumental Analyzer Procedure Page 3 of 3 Sampling module: The portion of the instrumental me tals measurement system that traps the metals and delivers them to the x-ray fluorescence module.

Sample probe: The portion of the sample interface th at extracts the gas from the stack or duct.

Sample transport system : The portion of the sample interface which transports the sample stack or duct gas from the downstream end of the sample probe to the sampling module.

Volume drift: The difference in the reading betw een the sample volume or flow measurement device and an independently calibrated volume or flow measurement device.

Volume measurement module: The portion of an instrumental measurement system that determines sample volume.

Upscale drift : The difference in the reading for the upscale reference from the calibrated value after some period of time during which no maintenance or adjustment took place.

X-ray fluorescence module: The portion of the instrumental metals measurement system that uses x-ray fluorescence as analy tical technique to identify metals and to determine metal concentrations.

XRF : x-ray fluorescence.

Zero drift: The difference in the reading for zero input from the calibrated value after some period of time during which no main tenance or adjustment took place.



### 5.0 Apparatus and Reagents

5.1 Measurement system

5.1.1 Sample interface The sample interface must collect a sample of source effluent isokinetically and then transport that effluent to the samp ling module. The sample interface must at least include the following two elements.

1. Sample probe The sample probe may be made of glass, stainless steel, Teflon-coated steel or other mate rial that will prevent loss or contamination of analyte metal or meta ls. The sample probe may also be heated to prevent the conde nsation of water vapor.

2. Sample transport lines Lines made from any material that will transport the analyte metal with minimal particle loss. The transport lines may be heated or allow for the addition of di luent gas to preven t the condensation of water vapor.Method X: Multi-Metals Instrumental Analyzer Procedure Page 4 of 4 5.1.2 Sampling module The sampling module must include a met hod for capturing the metal analytes of interest and presenting them to the x -ray fluorescence module. The sampling module may capture the metals from the enti re volume of the sample interface or it may extract a sub-sample of source effluent.

5.1.3 X-ray fluorescence module The x-ray fluorescence module uses x-ray fl uorescence as an analytical technique to identify and determine the mass of me tal analytes on the capturing medium.

5.1.4 Data recorder
The data recorder should be able to reco rd metals concentrations and instrument status signals (flags) that indicate whether the metals measurement system is performing appropriately.

5.1.5 Volume measurement module This module must accurately measure the volume of effluent drawn through the capture media on a dry basis.

5.2 Quality assurance and control materials

5.2.1 Zero drift reference An instrumental metals monitoring system must include a means to measure zero drift. If feasible this reference should produce an in strumental response indicating the absence of metals. If this is not f easible the zero reference should produce a value between zero and 20% of the emission limit for at least two of the metals measured by the system.

5.2.2 Upscale drift reference An x-ray based instrumental metals mon itoring system must include an upscale drift reference to measure the upscale drift. The upscale drift reference must contain an element measured by each en ergy condition of the XRF analysis. The mass of each metal in the reference must generate an instrumental response between 80 and 200 percent of th e applicable emission limit.

5.2.3 Volume or flow drift check device An instrumental metals measurement syst em must include a means of checking the sample volume drift or flow drift against another internal measurement device.

5.2.4 Volume or flow calibration check device An instrumental metals measurement syst em must include a means of checking the calibration of the volume or flow measur ement device against an externally calibrated measurement device.Method X: Multi-Metals Instrumental Analyzer Procedure Page 5 of 5 5.2.5 X-ray fluorescence calib ration check standards An instrumental metals measurement sy stem must also include a means of checking the calibration for every metal it measures for compliance purposes. NIST traceable thin film standards are an example of a suitable calibration check standard.

5.3 Metals generator A method of metals generation is necessary to determine the relative bias of the metals measurement system and is required for the interference check if it is performed. The following are optional sources of metals that may be used for this purpose.

5.3.1 Quantitative aerosol generator A quantitative aerosol generator produces known metals concentrations in a gas stream The known concentrations of the analytes are compared with the values reported by the instrument al metals measurement system.

5.3.2 Non-quantitative aerosol generator A non-quantitative aerosol generator produces metals at unknown concentrations in a gas stream. To use this approach the concentrations of metals produced by the non-quantitative aerosol gene rator must be measured using an independent alternative EPA reference method. The concentration from the alternative reference method can then be compared to the concentration reported by the instrumental measurement system to determine percent relative bias.

5.3.3 Source operation The metal used during the relative bias te st can also be produced by operating the source. The metal or metals produced in routine operation can then be measured by an appropriate alternat ive EPA reference method. The concentration, as determined by the alternative referen ce method is then compared with the concentration from the instrumental meta ls measurement system. The metal used as the analyte for this test is called an element of opportunity.

5.4 Alternative EPA Reference method Some of the procedures to determine percent re lative bias require the use of an alternative EPA reference method. The alternative refe rence method must be able to accurately measure the concentration of the metal used during the bias test.



### 6.0 Measurement System Perf ormance Specifications

6.1 Zero drift The zero drift, calculated using Equation 3, mu st be less than 20% of the applicable emission limit for each element and each measurement.

6.2 Upscale drift The upscale drift, calculated using Equati on 4, must be less than 15% of the value determined immediately after calibration for each metal on the upscale reference.Method X: Multi-Metals Instrumental Analyzer Procedure Page 6 of 6 6.3 Volume drift The volume or flow drift, calculated using E quation 5, must be less than 10% of the full scale value of the flow or volume measurement device.

6.4 X-ray fluorescence module calibration drift check The x-ray fluorescence calibration drift, calcul ated using Equation 6, must be less than 10% of the known value of the standard fo r each metal measured by the instrumental analyzer for reporting purposes.

6.5 Volume measurement calibration check The volume or flow measurement made by the instrumental system shall be less than 10% (calculated using Equation 7) of the volume or flow measurement made by the externally calibrated volume or flow measurement device.

6.6 Percent relative bias If the percent relative bias ( calculated using Equation 8) is less than 15% and the relative standard deviation (calcula ted using Equation 11) is le ss than 10% no correction is required. If the relative percent bias exceeds 15% and the relative st andard deviation is less than 10% then a correcti on factor must be applied to the data using Equation 12. If the relative percent standard deviation exceed s 10% a correction factor cannot be applied and the instrumental metals measurement system must be adjusted or repaired before it can be used.

6.7 Interference Check The average percent relative bias must be less than 15% and the relative standard deviation must be less than 10%.

6.8 Reporting requirements An instrumental metals measurement system mu st report a concentration in the units of the applicable standard or in units that can be converted to the applicable standard.



### 7.0 Measurement System Perfor mance Test Procedures The following procedures must be performed prior to emissions testing.

7.1 Measurement system preparation Assemble the measurement system following th e manufacturer’s instructions. Adjust all flow rates and heaters to the settings that will be used during sampling. The following tests are required after the measur ement system has been assembled.

7.2 Zero drift check A zero drift check must be performed before and after each day of emissions testing. The zero drift check must be performed acco rding to the procedures provided by the instrumental system’s manufacturer. If the in strumental metals measurement system fails the zero drift check it must be repaired or recalibrated and all the emission test runs performed since the last successful zero drif t check shall be consid ered invalid. AfterMethod X: Multi-Metals Instrumental Analyzer Procedure Page 7 of 7 appropriate repairs have been made the system must pass a zero drif t check before testing can resume. If changes are made to the cal ibration of the x-ray fluorescence module the measurement system must also pass an x-ray fluorescence calibration drift check.

7.3 Upscale drift check An upscale drift check must be performed befo re and after each day of emissions testing according to the procedures provided by the ma nufacturer. If the instrumental metals measurement system fails the upscale drift check it must be repaired or recalibrated and all emission test results acquired since the last successful upscale drift check shall be considered invalid. After appr opriate repairs have been made to the system, it must pass an upscale drift check before emissions testi ng can resume. If changes are made to the calibration of the x-ray fluor escence module the measurement system must also pass an x-ray fluorescence calibration drift check.

7.4 Volume or flow drift check A volume drift check must be performed before and after each day of emissions testing according to the procedures provided by the instrumental manufacturer. This is an internal check of the volum e or flow measurement against another flow or volume measurement device. If the instrumental me tals measurement system fails the volume or flow drift check the vo lume module must be repaired or adjusted and all emissions test results acquired since the last successful volume or flow drift check shall be considered invalid. The measurement system must successf ul pass a volume or flow drift check and a volume or flow calibration drift check before emissions testing can resume.

7.5 X-ray fluorescence calibration drift check The x-ray fluorescence module calib ration drift check must be performed before the start of sample measurement and is only performed once per visit to a site. A calibration drift check should also be performed if the x-ray fluorescence module is recalibrated for any reason during the emissions test.

During a calibration drift check the x-ray fluor escence analyzer is challenged with NIST traceable standards. The calibration of ever y element that will be measured during the emission test must be checked. Each standard must only to be checked once. If the calibration drift exceeds plus or minus 10% of the standard’s value the instrument must be recalibrated and retested for that element.

7.6 Volume or flow calibration check If the instrumental metals measurement system determines volume or flow as part of its metals concentration measurement, a volume or flow calibration check must be performed. This check must be performed at le ast once per site visit prior to the start of emissions testing. The check must also be executed if adjustments are made during emissions testing to the flow or volume measurement devices.

If the instrumental metals measurement system determines volume, as opposed to flow, the value reported by th e system during one sample run must be compared to the value reported by an independently ca librated standard such as a dry gas meter. The samplingMethod X: Multi-Metals Instrumental Analyzer Procedure Page 8 of 8 time during the volume measurement must be equi valent to the sampling time that will be used during emissions testing.

If the instrumental metals measurement system measures flow and totalizes that flow to produce a volume, a flow calibration check may be performed in lieu of a volume calibration check. For this calibration chec k, the flow reported by the instrumental metals measurement system is compared with an independently calibrated flow measurement device such as a NIST traceable Dry Cal ® at 3 to 5 points throughout a single sampling period. The error of each measurement is calculated and the average error computed.

If the instrumental metals measurement syst em fails a volume or flow calibration drift check the volume measurement module may n eed repair. The system must pass another volume or flow calibration drift check before emissions testing can resume.

7.7 Relative bias test The percent relative bias must be determined using at least one metal which may be an analyte measured for compliance purposes or a surrogate metal (e.g., iron) that can be measured by the instrumental metals measurem ent system. At least three measurements are required to establish the average relati ve bias. If the instrumental metals measurement system is being compared to an alternative EPA reference method, at least three simultaneous measurements with the a lternative reference me thod are necessary. The requirements for the relative bias test associated with the three possible metals generation requirements are outlined below.

7.7.1 Option 1: Quantitative spiking In this approach to determining bias, an aerosol of known concentration produced according to the specifica tions laid out in PS-QRAG 1 is spiked into the sample transport line as close as po ssible to the sample probe. This concentration should be between 80 and 120 percent of the emission limit. (If a surrogate metal is spiked then the concentration shoul d be at 80 to 120 percent of the emission limit for the analyte metal with the highest emission limit). The concentration reported by the instrumental metals measurement system is compared with the known concentration of the spiked aerosol and the percent relative bias and the percent relative standard deviat ion are calculated.

7.7.2 Option 2: Elements of opportunity In this approach the instrumental meta ls measurement system may be used to determine if an element of opportunity is pr esent in the source. If one is present, the concentration of that metal must be determined using an alternative EPA reference method sampling from the stack or from a point in the transport line as close as possible to the sample pr obe. The alternative reference method concentration is compared with the c oncentration reported by the instrumental metals monitoring system. The element of opportunity should be present at concentrations well above method detection li mits to be used in the relative bias
test.Method X: Multi-Metals Instrumental Analyzer Procedure Page 9 of 9 7.7.3 Option 3: Non-quantitative spiking
An aerosol at a concentration level be tween 80 and 120 percent of the emission limit is spiked either into the source or in to the sample interface as close as possible to the probe. The metal concentration may be determined using a suitable alternative EPA reference method. The al ternative reference method concentration is compared with the measurement made by the instrumental metals measurement system. If the metal is spiked into th e source the alternative reference method may be located either directly in the source or in the transport line as close as possible to the sample probe. If the metal is spiked into the transport line then the reference method measurements must be made as cl ose as possible to the spiking location.

7.8 Interference check
An interference check tests for interferents in the source emissions that inhibit or prevent the measurement of analyte metals. For th is reason, the instrume ntal analyzer must sample flue gas during the interference chec k. This check must be performed for each model of x-ray fluorescence instrumental metals analyzer the first time that model is used on a particular source category. The results of this test must then be retained and submitted along with the emissions test results whenever the instrumental metals analyzer is used on that particular source category. If an instrumental metals measurement system fails an interference test it may not be used for emissions test on that particular source category until it does pass an interference check.

The procedures for the interference test are very similar to the sample interface relative bias test. For each test the relative bias and relative percent standard deviation are calculated. As with the relative bias test th ere are three options for performing (only one of the options must be executed) the inte rference check based on the type of metals generation performed: 1) Option A. Quan titative spiking, 2) Option B. Element of opportunity, and 3) Option C. Non-quantitat ive spiking. The inference check, however, is testing for bias resulting from problems with the capture of metal analytes in the sampling module or problems with the x-ray fluorescence, while the relative bias test determines the instrumental metals measuremen t system bias primarily resulting from the sample interface.

7.8.1 Option A: Interference check with quantitative spiking For the interference check the quantitative spike injection point should be located as close as possible to the sampling module. Only one metal, either an analyte that will be measured or a surrogate must be spiked. The concentration level of the analyte or surrogate metal in the b ackground should be checked using the instrument analyzer. It is recommended that the spiked metal not be present at detectable concentrations in the stack. If it is present, the bias may be calculated by subtracting the average bac kground concentration using equation 9. At least nine sampling periods of 15 minutes or longe r are required. The known concentration of the spiked metal is compared with the concentration reported by the instrumental analyzer to determine percent relative bias.Method X: Multi-Metals Instrumental Analyzer Procedure Page 10 of 10 7.8.2 Option B: Interference check w ith an element of opportunity The element of opportunity may be any meta l present in the stack gas that can be measured by the instrumental metals analyzer and by an alternative EPA reference method and is present at high enough concen trations to be used. The alternative reference method must placed as close as possible to the sampling module and concentration reported by the method is compared with that reported by the instrumental metals analyzer. Nine si multaneous runs of both the alternative reference method and the instrument al analyzer are required.

7.8.3 Option C: Interference check using non-quantitative spiking. For option C the non-quantitative spike inje ction point may be anywhere upstream of the sampling module. An alternative EPA reference method is required to use Option C and it must be located as close as possible to the sampling module. Only one metal, either an analyte that will be measured during the emissions test or a surrogate such as iron, must be spiked. As for the element of opportunity nine simultaneous runs of the alternative refere nce method and the instrumental analyzer are required.



### 8.0 Emissions Test Procedure

8.1 Performance tests prior to emissions testing The appropriate measurement system performa nce tests must be completed according the procedures in sections 7.1 to 7.8 prio r to the start of emissions testing.

8.2 Selection of sampling point It is recommended that the sampling locati on be at least two equivalent diameters downstream of any control devices, point of pollution generation, be nd or other point at which a change in pollution concentration or flow disturbance may occur and be at least two equivalent diameters upstream of the exhaus t. The equivalent diameter is calculated according 40 CFR Part 60, Appendix A, Method 1, Section 2.1. 2

8.3 Sample collection

8.3.1 Traverses An instrumental metals measurement sy stem must sample at the appropriate traverse points as outlined in Method 1 2 or another EPA approved alternative for the selection of sampling points. A sampli ng run consists of sampling all required traverse points over a period of 15 minutes to one third the ap plicable regulation, depending on source conditions and metal con centrations. If feasible all traverse points must be sampled for approxi mately equal lengths of time.

8.3.2 Isokinetics An instrumental metals measurement system must acquire a representative sample of source effluent by either sampling at a flow rate that is plus or minus10% of isokinetic or by using another means approved by the EPA. VelocityMethod X: Multi-Metals Instrumental Analyzer Procedure Page 11 of 11 measurements to determine the percent of isokinetic must be performed according to EPA approved procedures such as those outlined in Method 2. 3

8.3.3 Possible additional measurements Additional measurements may be required to report the results in units of the applicable standard. Among these are s ource moisture content and percent oxygen
content.



### 9.0 Calculations

9.1 Arithmetic mean ( x )



# ∑
= i x n x 1 Equation 1

Where :

n = Number of data points

x i = Value of the i th measurement

9.1.1 Arithmetic mean of a difference. To calculate the arithmetic mean of difference use the above equation substitute d i for x i . The

i i i y x d

− = Equation 2

Where x and y are paired data points from the instrumental metals measurement system and either the reference aerosol or the alternative reference method.

9.2 Zero drift ( i ZD )

100 0

× −

= L i i IAZ i
i C L L ZD Equation 3

Where:

i ZD = Zero drift of i th metal on the instrumental metals measurement system in percentMethod X: Multi-Metals Instrumental Analyzer Procedure Page 12 of 12 IAZ i L = Instrumental metals measurement system response for the i th

metal to the zero reference

0 i L = Zero reference value for the i th element at the last calibration

L i C

L i R = Value of the emission limit for the i th metal

9.3 Upscale drift ( i UD )

100 × −

= u i u i IAU i
i L L L UD Equation 4

Where:

i UD = Upscale drift of the i th metal of an instrumental metals measurement system in percent.

IAU i L = Response to the i th element in the upscale reference

u i L = Calibrated value of i th element on the upscale reference

9.4 Volume drift ( VD )

100 × −

= FS V V VD c IA Equation 5

VD = Volume or flow drift V c = Volume or flow reported by the instrumental metals measurement system’s volume check device V IA = Volume or flow reported by the instrumental measurement system’s volume or flow sample measurement device FS = The full scale value of the volume or flow measurement device

9.5 X-ray Fluorescence calibration drift ( i CD )Method X: Multi-Metals Instrumental Analyzer Procedure Page 13 of 13 100 × −

= std i std i IAC i
i L L L CD Equation 6

Where:

i CD = x-ray fluorescence module drift for the i th metal

IAC i L = Value of the standard repor ted by the x-ray fluorescence
module for the i th metal

std i L = Calibrated value of the calibration test standard for the i th

element

9.6 Volume or flow calibration drift ( VA )

100 × −
=

r IA r V V V VA Equation 7

Where: VA = Volume (or flow) measurement accuracy V r = Sample gas volume (or flow) measured by the independent calibrated reference device V IA = Sample gas volume (or flow) reported by the instrumental metals measurement system

9.7 Relative bias ( i RB )

100 × = RM i i

i R d PRB Equation 8

Where:

i PRB = Percent Relative Bias for the i th metal

i d = Average difference between the instrumental metals measurement system and the altern ative reference method or aerosolMethod X: Multi-Metals Instrumental Analyzer Procedure Page 14 of 14 9.7.1 For option A: interference ch eck using quantitative spiking Substitute the following equation for i d when using quantitative spiking in the presence of a significant and stable b ackground concentration of the spiked metal

RM i i IA i i R B L d

− − = Equation 9

Where:

IA i L = Concentration reported by the instrumental metals measurement system for the i th metal

i B = The background concentration of the i th metal as determined by the instrumental metals measurement system

RM i R = Concentration of reference aer osol or concentration reported by
the alternative EPA reference method for the i th metal

9.8 Standard deviation (of differences) ( i SD )

1 1 2 2

− ∑ ∑

−

= ⎟ ⎠ ⎞ ⎜ ⎝ ⎛

n d

n d SD i i

i Equation 10

Where:

i SD = Standard deviation of differences for the i th metal
d i = Difference between paired alternative reference method or reference aerosol and the instrume ntal metals measurement system concentrations for the i th metal

9.9 Percent relative standard deviation ( i RSD )

100 × = RM i i i R SD PRSD Equation 11

Where:

i PRSD = Percent relative sta ndard deviation of the i th elementMethod X: Multi-Metals Instrumental Analyzer Procedure Page 15 of 15 RM i R = Average concentration of the i th metal in the alternative EPA
reference method data set or reference aerosol concentration

i SD = Standard deviation of the inst rumental measurement system
concentrations for the i th metal

9.10 Correction factor for relative bias ( RB i CF )

IA i RM i

RM i i RB i L R

R

d CF =

+ = 1 1 Equation 12

Where:

RB i CF = Relative bias correction factor for the i th metal

RM i R = Average of the alternative re ference method data set or the
reference aerosol conc entration for the i th metal

i d = The average difference between the instrumental measurement system and the alternative reference method or reference aerosol for the i th metal (where d i is calculated according to the following equation)

RM i IA i i R L d

− = Equation 13

Where:

IA i L = Concentration reported by the instrumental metals measurement system for the i th metal

RM i R = Concentration of reference aeros ol or concentration reported by
the alternative EPA reference method for the i th metal



### 10.0 Safety People using method X may be e xposed to hazardous material s, operational hazards and dangerous site conditions. Method X does not pur port to address all of the safety issues associated with its use. Consult the instrumental metals measurement system manufacturer for safety proce dures related to its use. Confer with the site safety manager concerning safety procedures particular to the emission test site and review all appropriate material safety data sheets when working with chemical hazards.



### 11.0 Tables, Figures for Method XMethod X: Multi-Metals Instrumental Analyzer Procedure Page 16 of 16 Table 1. Performance Test Procedures and Passing Criteria For Metals IAP Test Procedure Criteria Frequency
Zero drift Run zero standard at least 2 times per sampling day <20% drift Before and after each day of sampling Upscale drift Run upscale standard at least 2 times per sampling day <15% drift from original calib. Before and after each day of sampling Volume Drift Run volume drift check at least 2 times per sampling day <20% drift from independent flow device. Before and after each day of sampling X-ray Fluorescence

Calibration Drift Check Run a standard for each metal measured for compliance
purposes <10% for each element Once each time the instrument is set up in a particular location

Volume Measurement Calibration Check • 1 sampling period

• For flow 3 to 5 measurements of flow during a sampling cycle

• Calculate difference or for flow average difference <10% Once each time the instrument is set up at a particular location

Option 1 Quantitative spiking at stack

• 3 measurements of instrumental metals measurement system

• Only one metal must be spiked • RB<15%

• %RSD<10%

• If RB criteria not met apply a correction

Option 2 Element of opportunity

• Determine identity of element of opportunity

• Run the instrumental method and the alt. reference method simultaneously

• Analyze alt. reference method and compare results • RB<15%

• %RSD<10%

• If RB criteria not met apply a correction

Sample Interface Relative Bias Option 3 Non-quantitative spike

• Spike into stack or transport line

• Run the instrumental method and the alt. reference method simultaneously

• At least three cycles of the instrumental metals measurement system

• At least three alt. reference method measurements

• Analyze alt. reference method and compare

• Only one metal must be spiked • RB<15%

• %RSD<10%

• If RB criteria not met apply a correction Once each time instrument is set up at particular location

Interference Check See table 3 for Interference check options and procedures • Relative Bias<15%

• %RSD<10%

• No correction factor allowed. Once per instrument model on each source categoryMethod X: Multi-Metals Instrumental Analyzer Procedure Page 17 of 17 Table 2. Spiking and Alternative EP A Reference Method Options for Sampling Bias Tests Source of Metals for Bias Test Location of Spike (if applicable) Location of Alternative EPA Reference Method (if applicable)

Quantitative Spike In transport line as close as possible to sample probe. N/A

Option A In stack In stack

-orIn transport line as close as possible to the sample probe Non-Quantitative Spike

Option B In transport line as close as possible to the sample probe In transport line immediately downstream of spike location Option A In stack Element of Opportunity N/A

Option B In transport line as close as possible to the sample probe

Table 3. Spiking and Alternative EPA Re ference Method Locations for Interference Checks Metals Generation Options Spiking Location (if applicable) Location of Alternative EPA Reference Method (if applicable) Option A: Quantitative spiking As close as possible to the sampling module N/A

Option B: Element of opportunity N/A As close as possible to the sampling module Option C: Non-quantitative spiking Anywhere upstream of the alternative EPA reference method As close as possible to the sampling moduleMethod X: Multi-Metals Instrumental Analyzer Procedure Page 18 of 18 Figure 1 Alternative Reference Method or Spiking Location for the Relative Bias Test with (1) Quantitative Spiking , with (2) Non-Quantitative Spiking into the source and using the Alternative Reference Method in the Transport Line, or with (3) an Element of Opportunity using the Alternative Reference Method in the Transport Line.Method X: Multi-Metals Instrumental Analyzer Procedure Page 19 of 19 Figure 2. Using Non-Quantitative Spiking into the Transport Line During the Relative Bias Test

Figure 3. Using Non-Quantitative Spiking or an Element of Opportunity with the Alternative Reference Method in the Sou rce During the Relative Bias Test.Method X: Multi-Metals Instrumental Analyzer Procedure Page 20 of 20 

### 12.0 References 1 Performance Specification XX. Perfor mance Specifications for A Quantitative Reference Aerosol Generator. 2005

2 United States. Environmental Protec tion 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.

3 United States. Environmental Protecti on Agency [EPA]. Technology Transfer Network. Emissions Measurement Center . Promulgated Methods. Method 2. Determination of Stack Gas Velocity and Volumetric Flow Rate (Type S Pitot Tube). Washington, DC. EPA, 2004. Available: http://www.epa.gov/ttn/emc/promgate/m-02.pdf via the internet. Accessed June 6, 2005.