# Procedure Z: Quality Assurance Requirements for X-Ray-Fluorescence Based Multi-Metals Continuous Emission Monitoring Systems at Stationary Sources

Prepared by : Cooper Environmenta l Services, LLC 10180 SW Ni m bus Blvd Suite J6 Portland, Oregon 97223

Revision 1.0 June 9, 2005

# 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 outlin es the continu i ng quality contr o l and quality assuranc e requirem e nts for an x-ray fluorescence based m u lti -m etal CEMS. Procedure Z requires daily checks of th e upscale, zero and vol u m e measurem ent drift. It al so sp ecifies quarterly checks of the x-ray fluorescence calibration and of the volum e m eas urem ent calibration. Finally procedur e Z requir e s th at the entire X R F m u lti m e tal CEMS ac curacy be v e rif i ed on an annual basis.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page i of iv

### List of Symbols b o = The y inte rc ept of the be st f it line b 1 = The slope of the best fit line

i CA = X-ray fluorescence calib ration accuracy

C i C = Corrected CEMS concentration for the i th elem ent

CEMS i C = The concentration of the i thelem ent as reported by the CEMS

CEM i C = The average reported co ncentration of the CEMS for the i th elem ent

PT i CF = Correction factor for pe rcent transpo r t for the i th elem ent

RB i CF = The relative bias corr ection factor for the i th elem ent

L i C = The em ission lim it of the i th elem ent

S i C = Concentration of the i th elem ent at the stack

sm i C = Concentration of the i th elem ent at the sam p ling module or as reported by the XRF multi- m e tals CEMS.

i d = Difference between two paired m easurem ents d = Arithm e tic m ean of differences FS = Full scale value of your CEMS volum e (or flow) m easurem e n t device

0 i L = The calib rated value of the i th elem ent on the zero standard

cem i L = The value of the standard reported by your CEMS

cemo i L = The m easured CEMS response to the zero standard for the i th elem ent

cemu i L = The m easured CEMS response to the i th elem ent in the ups cale standard

std i L = The known value of the XRF calibration check standard

u i L = The value of the i th elem ent of the up scale s t andard
n = Num b er of data points

i PT = The percen t transpo r t of the i th elem ent

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page ii of ivi PT = Average percent transpo r t for the i th elem ent PRB i = Percent relative Bias of the i th elem ent

RM i R = The average of the reference m e thod m easurem e n ts for the i th m e tal

i PRSD = The relative percen t stan dard deviation for the i th m e tal

r = The correlation coefficient SD i = The standard deviation of differences for the i thelem ent V

cemr = Sa m p le gas volum e (or flow) as m easured by the CEMS volum e check device VD = Volum e drif t V

m = Volum e (or flow) reported by your multi-m e tals CEMS

i UD = The upscale drift of the i th elem ent on your CEMS in percent.

x = Arithm e tic m ean
x i = Value of each data point y i = CEMS reported concentration for the i thelem ent ZD i = The zero drift of the i thelem ent on your CEMS in percent

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page iii of iv

### Table of Contents Executive S u mm ary ................................................................................................................... i List of Symbols

......................................................................................................................... ii Table of Contents

..................................................................................................................... iv 1.0 Using Procedure Z

........................................................................................................... 1 1.1 W h at is the purpose and app lic abilityof Procedure Z?

............................................. 1 1.2 W h at are the basic requirem e nts of Pr ocedure Z ?

..................................................... 1 1.3 W h at special definitions apply to procedure Z ?

........................................................ 1 2.0 Interferences, Safety, and Equipm ent Requirem e nts

....................................................... 2 2.1 W h at interferences are as so ciated with procedure Z?

............................................... 2 2.2 W h at do I need to know to ensure the safety of persons using Procedure Z?

........... 2 2.3 W h at equipm ent and supplies do I need?

.................................................................. 3 2.4 W h at reagen ts and stand a rds do I need?

.................................................................... 3 2.5 W h at sam p l e collection, preservation, storag e, and transport proc edures are relevant to Procedure Z?

............................................................................................................... 4 3.0 Quality Con t rol, Calibration, and Standardization

.......................................................... 4 3.1 W h at quality contro l m e asures a r e r e quired by this procedur e f o r m y m u lti-m e tal CEMS?

............................................................................................................................ 4 3.2 W h at calib r a tion ch ecks and audit p r ocedures m u st I pe rf orm f

o r my m u lti-m e tal CEMS?

............................................................................................................................ 4 4.0 Calculations

..................................................................................................................... 7 4.1 W h at calculations and d a ta analysis must I perform ?

................................................ 7 4.2 W h at waste m a nage m e nt procedur es are required for procedure Z?

....................... 13 5.0 Other Requirem e nts and Inform ation

............................................................................ 13 5.1 W h at pollution preventio n m easures mu st I take when using procedure Z?

........... 13 5.2 W h at criteria are ne cess a ry f o r my XRF multi- m e tal CEMS to be in co ntrol and what do I do if it is out of control?

................................................................................ 13 5.3 W h at tables, diagram s and flow charts are relev a n tto Procedur e Z ?

...................... 16 5.4 W h at references are relevant to Procedure Z ?

......................................................... 18

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page iv of iv

### 1.0 Using Procedure Z 1.1 What is the purpose and app licab ility of Procedu r e Z? The purpose of Procedure Z is to establish the m i nim u m requirem e nts for quality control (QC) and quality assurance (QA) procedures for x-ray fluorescence (XRF) based m u ltim e tals CEMS. These quality control and quality assurance procedures are in place to e n sure the accuracyand valid ityof the data reported by y our m u lti-metal CEMS for em ission com p liance purposes. Y ou m u st m e e tthese m i ni mum requirem e nts if you plan to use your multi-m e tal CEMS for reporting purposes, howev er, we enco urage you to develop a more extensive QA program or to continue with su ch p r ogram s where th ey already exis t. Any XRF multi- m e tals CEMS used to re port to us, th e sta t e, or a local enf o rce m ent agency m u st com p ly with procedure Z imm e diately after the c o m p letion o f the initial perf orm a nce specification test ou tlined in Performance Specification YY i

. 1.2 What are the basic requ irements o f

Procedure Z ? Procedure Z requires you to perform several drift checks and audits whichensure th e accura cy of the data rep o rted by your XRF m u lti-m e tals CEMS. You are required to , on a daily basis, record and calculate zero drift, upscale drift, a nd, a sam p le volum e drift. On a quarterly basis you are required to perform an XRF calibration audit (XFCA) and a sam p le volum e audit (SVA). On an annual basis you are required to execute eith er a linearity audit (LA) or a relative bias audit ( RBA) and, if applicable, a trans port efficiency audit (TEA). The criteria for passing these audits and drift ch ecks are outlined in pr ocedure Z. Procedure Z also summ arizes the requirem e nts for when and if your CEMS fails an audit or drift test. Finally, P r ocedure Z also covers the requirem e nts for and tim elin es associated with periods when your XRF multi-m e tals CEMS is out of control. 1.3 What special definiti ons apply to procedure Z? Linearity A udit: (LA) An assessment of the validity of the origin al line ar correlation of your CEMS. Reference material: A m a terial of known value used to check the calibration drift of your XRF multi- m e tal CEMS. Relative Bias: The difference betw een a reference m e thod or aerosol concentration and the concentration recorded by your CEMS divide d by the concentration of the reference m easurem ent. Relative Bias Audit: (RBA) An assessm ent of the bias in your CEMS. Sample Interface: The portion of the CEMS used for one or more of the following: sam p le acquis ition f r om the stack or duct effluent, s a m p l e transpo r t, sam p le condition i ng, or protection of the m onitor from the effects of stack gas.

Quality Assurance for XRF –Based Multi-Me tal CE M S (Procedure Z ) Page 1 of 18Sample Module: The p o rtion of the XRF multi- m e tal CEMS that traps the m e tals and delivers them to the x-ray fluorescence m odule. Standard Volume Audit: (SVA) This is an evaluation of your XRF m u lti-m e tals CEMS sam p le volum e measurem ent system. This is required if your CEMS uses a volum e m easurem ent to report m e tal concentrations and is accom p lished by comparing the v o lum e m easured by your CEMS with the volum e m eas ured by an independently calibrated device. Transport Effic i ency Audit: (TEA) An assessm e nt of the transport ef ficiency of the sam p le interface of your m u lti-m e tals CEMS. This audi t applies to your XRF multi-m etals CEMS if either the RB A or LA c h allenged only the sam p ling and XRF m odules. Transport System: The portion of the CEMS that tran sports a representative sam p le of source effluent from the sam p le probe to the sample m odul e. X-Ray Fluorescence Ca libration Audit: (XFCA) This is an evaluation of how well the xray fluores cence portion of your m u lti-m e tals CE MS has m a i n tained its o r igin al calib ration. This is accomplished by challenging th e XRF module with a standard of known concentratio n for each metal m easured by your CEMS for compliance. T h e analyzer response is com p ared with the know n concentration of the standard. X-Ray Fluorescence Module: The portion of a n XRF based m u lti-m e tal CEMS which identifies an d m easures m e tal m a sses or concentrations using x-ray fluorescence. XRF Multi-Metals Con t inuous Emission Monitor (CEMS): All of the equipm ent required f o r determ ining m e tal concentr ation s using x-r a y fluorescence as an analytical techn i q u e. The system m a y consist of several m a jor subsystem s including the sam p le interface, the xray fluorescence m odule, the volum e m easurem e n t m odule, diluent analyzer, data recorder, and sam p ling m odule. 

### 2.0 Interferences, Safety, and Equipment Requirements 2.1 What interferences are a ssociated with procedure Z? There m a y be interferences arising from the x -ray fluorescence, the trapping m e dia, or from condensatio n in the effluent gas. C h eck withy our m u lti-metal CEMS m a nufacturer to find out m o re about poten tial interferences. 2.2 What do I need to know to ensure th e safety of persons using Procedure Z? Persons using procedure Z m a y be exposed to hazardous m a terials, equipm ent, and operations. Procedure Z does not pu rport to address all of the sa fety issues associated with its use. It is your responsibil ity to establish appropriate safe ty and health practices before using this procedure. Y ou m a y consult withyour CEMS m a nual and/ or m a nufacturer for precau tions specific to y our m u lti-metal CEMS. If standard reference m e thods are u s ed then you m a y also consult the appr opriate reference m e thods to address safety concerns.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 2 of 182.3 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 m easure m ent device for th e sam p le volum e check. 2.4.1 Zero drift reference Every XRF multi-m e tals CEMS m u st be equipp e d with a ze r o ref e rence that can be checked on a daily basis. This referen ce should produce a CE MS response indicating the absence of m e tals. If this is not f easible this standard should produce a value between zero and 20% of the em ission lim it fo r at leas t two elem en ts m e a s ured by your XRF multi- m e tals CEMS when the instrum e nt is operating a ppropria te ly

. 2.4.2 Upscale drift reference The reference for the upscale drift check s hould generate a response for at least one m e tal from e ach condition used in the XRF an alysis. This response m u st be at least 80 percen t of the em ission lim it. 2.4.3 Sample volu me or flow check If your XRF m u lti-m e tals CEMS m a kes volum e or flow m e asurem ents it must be equipped to perform a da ily sam p le volum e check. 2.4.4 Sample volume audit standard If your XRF m u lti-m e tals CEMS m a kes vol um e or flow m easurem ents, period ic standard volum e or flow audits m u st be perform e d. An independently calibrated volum e or fl ow m easurem ent device or standard such as a Dry Cal ® is required for these aud its. The standard m u st be able to acquire a volum e or flow m e asurem ent at sam p ling rates typical of your XRF multi-m e tals CEMS. 2.4.5 X-ray Fluorescence Calibration Check Standards Your XRF multi-m e tals CEMS m u st in c l ude a m eans of checking th e x -ray fluorescence calib ration agains t an external stan dard. NIST trac eable thin f ilm standard s are an exam ple of a suitab l e x-ra y fluo rescen ce calibra tion check standard. 2.4.6 Reagents and standards for the Linearity Audits and Relative Bias Audits You will ne ed other rea g ents and s t andards f o r th e line a rity audit o r re lative bia s audit. The regents and standa rd s required will d i f f e r depending on h o w these au dits a r e perform e d.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 3 of 182.4.7 Regents and standards for th e Transport Efficiency Audit The regents and standards fo r the transport efficiency audit also depend upon how the audit is perf orm e d. 2.5 What sample collection, preservation, storage, and trans port procedures are relevant to Procedure Z? [reserved]



### 3.0 Quality Control, Calibration, and Standardiz a tion 3.1 What quality control measures are require d by this procedure for my multi-metal CEMS? You m u st develop and implem e nt a quality c ontrol program that, at a m i nim u m includes detailed written procedures for all of the f o llowing activ ities. 1. Procedures f o r perform i ng drift checks on a daily basis, includ ing but not lim ited to, zero drift, upscale drift, and sam p le volum e measurem ent drift. 2. Procedures and m e thods of adjusting your m u lti-m e tal CEMS in respons e to the results of the drift checks. 3. Preventative m a intenance of your XRF m u lti-metals CEMS. 4. Data recording, calculations, and reporting. 5. Procedures f o r required audits, including tr ansport efficiency audits (if necessary), linearity audits, and relative bias audits. 6. Procedures f o r adjusting your CEMS based on audit results. 7. A program of corrective action and stack operation procedures in case of a CEMS m a lfunction and an out of control period. You are required to keep written docum e nt ation of your QA/QC procedures on record and available for inspection for the life of th e CEMS or until you ar e no longer subject to the requirem ents of this procedure. If you fail two consecutive audits you must revise your QA/QC procedures. 3.2 What calibration checks and audit procedur es m u st I perform for my multi-metal CEMS? 3.2.1 Daily drift check proced ures Your XRF multi-m e tals CEMS m u st have th e ca pacity to per f o rm each of the f o llowin g checks on at leas t a dailybasis.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 4 of 18• Z ero drift: You m u st check the zero drift to ensure the stabili ty of your CEMS response to the zero drift reference. Th e zero drift m u st be less than plus or m i nus 20% of the em ission lim it each day. Follow your CEMS m a nufa c turer’s instructions for proper zero drift check procedures.

• Upscale drift: You m u s tcheck the upscale drift to ensure the stability of your XRF multi-m e tal CEMS response to the ups cale standard. The daily up scale drift m u st be less than 15% of th e ups cale referen ce value d e term ined imm e diately after the x-ray fluorescence m odule has been calibrated. Follow your CEMS m a nufacturer’s instructions for pr oper upscale drift check procedures.

• Daily volu m e or flowcheck: You must check the sam p le volum e or flow m easure m ent to verify th e accuracy o f the volum e m easurem e n t on your CEMS. This volum e check m u st be done at the norm a l sa mpling rate for the CEMS. Your CEMS is out of control if the one day value ex ceeds 20% o f the full scale of the volum e or flow m eas urem ent device. Follow your CEMS m a nufacturer’s inst ructions for proper volum e or flow check procedures. 3.2.2 Audit procedures Audit procedures and criteria are listed below. These requ irem ents are also summarized in Table 1 in section 5.3. 1. X-Ray Fluorescence Ca libration Audit (XFCA): You m u st perform an XFCA once each quarter. To perform anXFCA you m u st challeng e the x-ray fluorescence m odule of your m u lti-metal CEMS with a stand a rd of known concentratio n for each metal m easured by your CEMS for compliance purposes and com p are the value reported by the CEMS with the known value of the standard. If you wish you m a y m a ke onl y one measurem ent of a standard for each elem ent. If your multi-m etal CE MS fails on the in itial m easure m ent you m a y make two m o re m e asurem ents of each stan dard and average all th ree m easure m ents. If the average CEMS response over the three m easurem e n ts deviates by less than 10% from the know n standard the CE MS has passed the XFCA. I f the averag e ex ceeds 10% y our CEMS has failed the XFCA and i s out-of-control. You m u st follow the pr ocedures outlin ed in S e ction 5.2. An XFCA is required once per quarter. The m i ni m u m allowed tim e between each audit is two months and the m a xi m u m allowed tim e is four months. 2. Sample volume (or flo w ) audit (SVA): You must perform a sam p le volum e audit of your XRF m u lti-m e tals CEMS at le ast once per qua rter and pr io r to any linearity or relative accuracy audit. To perform a n SVA you must independently m easure the volum e of sa m p le gas extracted from the stack or duct over the sam p ling period. You m a y ma ke this m easurem ent either at the inlet or outlet of your CEMS. You must m a ke volum e m eas urem ents during three d i fferent sam p ling cycles and the m easurem ents m u st be able to make corre ction s f o r m o isture content if necessary.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 5 of 18If your CEMS m easures flow and totali zes that flow to determ ine volume you m a y perfor m a flow audit instead. You m u st make flow m e asurem ents during three d i fferent sam p ling cycles and fo r each sampling cycle you m u st make at least 3 to 5 sim u ltaneous m easurem e n ts of flow on your CEMS and on the independent flow m easurem ent device. Y ou m u st calculate the erro r from each set of m easurem ents according to equa tion 6 and then calculate the averag e error in the flow during each sam p ling period. Finally you m u st calculate the average erro r from all three sam p lin g periods an d this av erag e m u st be less than 10% of the independent flow or volum e measurem ent device. A sa m p le volum e audit is required on a quarterly basis. The m i ni m u m required tim e between each SVA is at leas t tw o m onths while the m a xim u m allowed tim e between audits is four m onths. Accuracy Audits: As ou tlin ed in Per f o rm ance Specif ica tion YY it is acceptable d u ring th e initial performan ce specification tes tto assess the accuracy an d precis i on of the XRF a nd sam p ling m odules of your XRF multim e tal CEMS separately from the samp le interface. You m a y also do th is during the Linearity or Relati ve Bias Audits that are required f o r Procedure Z. If you choose to challenge the sam p li ng m odule and XRF system s separately from the sampling interface you m u st also p e rform a Transport Efficiency Audit (TEA). If you challenge the en tire XRF multi-m etals CEMS during the Linear ity an d Relativ e Bias Audits you are not required to perfor m an independent check of the CEMS trans port efficiency. For the purposes of Procedure Z you are required to perf orm either a linearity audit or a relative bias audit, but not both. You are also not required to perform the sam e kind of tests for the audit as were perfor m e d during the initi al performance specification test. For ex am ple, if a linearity te st was pe rformed during the initial accuracy tes t s, either a relativ e bias aud it or a linearityaudit is acceptable. There are four different options av aila ble for the accuracy au dits dep e nding on whether or not a linearity or relative bias audit is perform e d and depending on whether or n o t the en tire CEMS is challenged by the audit. T h e audit requirem e nts are listed below. Linearity Audits Option A In this op tio n a line a rity audit is perf orm e d on the entire CEMS. The types of m e tals generation and their associated requirem e nts are identical to those for Option A in perform a nce specification YY section 3.1.4. 1 If you do not m e et the linearity criteria you must apply a correction according to the procedures outlin ed in p e rf orm a nce specif i ca tion YY. 1 Option B In this op tio n a line a rity audit is pe rf orm e d on the sam p ling and XRF modules of the CEMS separately from the samp le interface. The typ e s of m e tals generation and their associat ed requ irem ents are identical to those for Option B

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 6 of 18in perform a nce specification YY section 3.1.4. 1 A transport efficiency audit must also be com p leted. Relativ e Bia s Audit Option C In this op tio n a relativ e bias aud it is pe rform e d on the entire CEMS. The types of m e tals generation and their associated requirem e nts are id entical to th ose for Option C in perform a nce specification YY section 3.1.4. 1 If your CEMS fails to m eet the criteria you must apply a correction f actor accord ing to th e procedures in perform a nce specification YY. 1 Option D In this op tio n a relativ e bias aud it is perform e d on the sam p ling and XRF modules of the CEMS separately fro m the sam p l e interface. The types of m e tals generation and their associated requirem e nts are iden tical to thos e for Option D in perform a nce specification YY section 3.1.4. 1 A transport efficiency audit m u st als o be com p leted. An accuracyaudit is req u ired on an annual basis. The m i ni mum ti m e between success i ve accuracy audits is 9 m onths while th e m a xi m u m allowed tim e is 15 months. 3. Transport Effic i ency Audit (TEA): You are required to perform a TEA only if you choose to challenge the sam p li ng and XRF m odules of your XRF multim e tals CEMS separately from the sa mpling interface. The procedures for perform i ng a TEA are the sam e as those for determ ining the transpo r t ef ficiency during the initial perf ormance specification tes ta nd are outlined in Perform a nce Specificatio n YY . If the transport efficiency of your CEMS is between 90 and 110 percen t no correctio n is n ecessary. If your transport efficiency is less than 90 percent or greater than 110 percent then you must establish a correction factor acco rding to th e p r ocedures o u tlin ed in section 3.1.7 o f Perfor m a nce Specificatio n YY 1 . The m i ni m u m tim e between success i ve transport efficiency tests is 9 m onths while the m a xi m u m allowed tim e is 15 m o nths. 

### 4.0 Calculati o ns 4.1 What calculations and data analysis must I perform? 4.1.1 Arithmetic Mean Calculate th e arithm etic m ean of a data set as follows 

# ∑ = i x n x 1 Equation 1

W h ere :
x = Arithm e tic m ean
n = Num b er of data poin t s

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 7 of 18x i = Value of each data point 4.1.2 Arithmetic Mean of Difference To calculate the arithm e tic m ean of differe nce us e the above equation sub s titu te d for x . Then

i i i y x d

− = Equation 2 Where x and y are paired data points fr om the CEMS and eith er the reference aerosol or the reference m e thod. 4.1.3 Daily Zero Drift

100 0 × − = L i i cemo i i C L L ZD Equation 3

W h ere: ZD i = The zero drift of the i thelem ent on your CEMS in percent

cemo i L = The m easured CEMS response to the zero standard for the i th elem ent

0 i L = The calib rated value of the i th elem ent on the zero standard

L i C = The em ission lim it of the i th elem ent 4.1.4 Daily Upsca l e Drift

100 × − = u i u i cemu i i L L L UD Equation 4

W h ere:

i UD = The upscale drift of the i th elem ent on your CEMS in percent.

cemu i L = The m easured CEMS response to the i th elem ent in the ups cale standard

u i L = The calib rated value of the i th elem ent of the ups cale s t andard
4.1.5 Daily Sample Volume Check

100 × − = FS V V VD m cemr Equation 5

W h ere:

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 8 of 18VD = Volum e drif t V

cemr = Sa m p le gas volum e or fl ow m easured by the CEMS volum e or flow check m easurem ent device V

m = Sa m p le gas volum e or fl ow reported by your m u l ti-m e tal CEMS FS = Full sca l e va lue of the CEMS volume m easure m ent device 4.1.6 Sample Volume Audit Accuracy

100 × − =

r m r V V V VA Equation 6

W h ere: VA = Volum e or flow m easurem ent accuracy V

r = Sa m p le gas volum e or fl ow m easured by the independent calib rated reference device V

m = Sa m p le gas volum e or fl ow reported by your m u l ti-m e tal CEMS 4.1.7 X-Ray Fluorescen ce Calibr a tion Aud it Calibra tio n

100 × − = std i std i cem i i L L L CA Equation 7

W h ere:

i CA = X-ray fluorescence calib ration accuracy

= The value of the standard reported by your CEMS cem i L

std i L = The known value of the standard 4.1.8 Relative Bias

100 × = RM i i i R d PRB Equation 8

W h ere i d is th e m ean difference, RM i R is the average of the reference m e thod set or reference aero s ol concentratio n for the i th elem ent, and PRB i is the rela tive b i as f o r the i th elem ent 4.1.9 Transport E fficiency

Quality Assurance for Batch Multi-M e tals CE MS (Proce dure Z ) Page 9 of 18100 × = S i i i C C PT sm Equation 9 W h ere: S i C = Concentration of the i th elem ent at the stack

sm i C = Concentration of the i th elem ent at the sam p ling module or as reported by the XRF m u l ti-m e tals CE MS.

i PT = The percen t transpo r t of the i th elem ent Report the average percent transport ( P T ) of all m easurem ents for each elem ent that was tested (only one el em ent is required though more can be tested). 4.1.10 Linearity Audit – Least Squares Linear Regression Calculate th e linear co rrelat ion equation given below.

x b b y ˆ +

= o 1 Equation 10
W h ere: b o = The y inte rc ept b 1 = The slope The intercep t is calcu l ated accord ing to the follow i ng equation

.
x b y b

− = o 1 Equation 11
W h ere: 

# ∑

= = n

i i x n x 1 1 

# ∑

= = n

i i y n y 1 1
The slope of the line is calcul ated according to equation below.


## ∑ ∑

= =

− − −

= n

1 i 2 i 1 i i i 1 ) x x ( ) y y )( x x ( b n Equation 12

The linear correlation co efficient is calcul ated according to the following equation.

Quality Assurance for XRF –Based Multi-Me tals CE MS (Procedure Z ) Page 10 of 18

## ∑ ∑

∑

= = =

− − −

−

= n

i i n

i i

i i i
y y x x y y x x r

1 2
1 2

1 ) ( ) ( ) )( ( n Equation 13

4.1.11 Standard Deviation (of differences)

1 1 2 2

− ∑ ∑

−

= ⎟ ⎠ ⎞ ⎜ ⎝ ⎛

n d

n d SD i i
i Equation 14
W h ere: SD i = The standard deviation of differences for the i thelem ent
n = The num ber of data points d

i = The difference between the concentration m easured by the reference m e thod or the concentration of the reference aerosol and the CE MS reported concentration. 4.1.12 Percent standard deviation
100 × = RM i i i R PRSD SD Equation 15

W h ere:
RM i R = The average of the reference m e thod data set for the i th elem ent

i PRSD = The relative percen t stan dard deviation for the i th m e tal

4.1.13 Linearity Test Correction Factors (A pplicable only when the linearity test challeng es the entire CEMS) 1. Correction equation if CEMS does not m eet eith er the s l ope or the inte rc ept criteria.

1 0 b b y C i

C i − = Equation 16

W h ere:

Specifications for Batch Multi-Metal s CEMS (PS

- YY ) Page 11 of 18= Corrected CEMS concentration for the i C i C th elem ent y i = CEMS reported concentration for the i thelem ent b 0 = The inte rcep t of the lea s t squares line a r reg r ess i o n line b 1 = The slope of the least squares linear regression line
2. Correction factor if CEMS m eets interc ept c r iter ia, but doe s not m eet the slope criteria.

1 b y C i

C i = Equation 17

3. Correction factor if CEMS m eets slope criteria but does not m eet intercept criteria.

0 b y C i

C i − = Equation 18 4.1.14 Relative Bias Correction Factors

CEM i RM i

RM i i RB i C R

R

d CF = + = 1 1 Equation 19

W h ere:
RB i CF = The relative bias co rrect i on fact or for t h e i th elem ent

CEM i C = The average reported co ncentration of the CEMS for the i th elem ent

RM i R = The average of the reference m e thod m easurem e n ts for the i th
me t a l 4.1.15 Percent trans port correction factor

i PT i PT CF 1
= Equation 20
W h ere
PT i CF = Correction factor for percent transpo r t for the i th elem ent

i PT = Average percent transpo r t for the i th elem ent

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 12 of 184.2 What waste management procedur es are required for procedure Z? All chem icals used to produce a reference aeroso l or in perform i ng standard m e thods need to be disposed of properly. Please cons ult the appropriate reference m e thods.


### 5.0 Other Requiremen ts and Information 5.1 What pollution preventio n measures mu st I take when using procedure Z ? [reserved] 5.2 What cr iteria are necess a ry for my X RF multi-metal CEMS to be in contro l and what do I do if it is out of control? 5.2.1 Required C o rrective Action for Dr ift Checks an d Audits

• Daily Z ero Drift: If the one day drift exceeds 20 % you are required to rerun your zero d r ift reference. If the XR F multi-m e tal CEMS m eets the criteria during the second test you m a y continue to operate. If the C E MS fails to m eet the zero drif t criteria again then it is out of control. It is recommended that you exam ine the zero drift standard for def ects. After repairs to th e CEMS are com p leted you are required to perform at least five successfu l zero d r ift checks within a 24 hour period. After the fi ve checks have been successfully com p leted then you CEMS is in control. If the repairs were m a de to the XRF module of the m u lti-m e tals CEMS you are also required to co mplete an x-ray fluorescence calib ration audit (XFCA) to verify the accuracyof your x-ray fluorescence calib ration.

• Daily Upscale Drift: If the one day drif t exceeds 15% you are required to retest the upsca le drif t ref e r e n ce. If the X R F m u lti-m e tals CEMS m eets the criter ia during the second test you m a y continue to operate, however, if the CEMS fails the second upscale drift check it is out of control. It is recom m e nded that you exam ine the upscale d r ift standard for defects. After repairs to the CEMS are com p leted you are required to perform atleast five successfu l upscale drift checks with in a 24 hour period. After the five d r ift checks are successfully com p leted the CEMS is back in con trol. Again, if repairs wer e m a de to the XRF module of the m u lti-m e tal CEMS you are also requ ired to succes sfully com p lete an x-ray fluorescence calib ration audit (XFCA) to verif y the a c c u racy of

the calib r a tion.

• Daily Sample Volume Check: If your sam p le volum e or fl ow drift exceeds 20% it has failed the daily volum e check and you m u st perform another daily volum e check. If the CEMS passes the second check you m a y continue to operate. If your CEMS fails the second te st it is out of control and your CEMS must be repaired. After repairs have been m a de the CEMS must successfully com p lete five sam p le volum e checks w ithin a 24 hour period. Upon successful com p letion of the five checks your CEMS is back in control. If the repairs

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 13 of 18were m a de to a volum e or flow m easur em ent device you are also required to successf ullycom p lete a sam p le volum e audit (SVA).

• Quarter l y S a mple Volu me Audit (S VA): Your XRF mu lti m e tals CEMS is out of control if volum e (or flow) meas ured by your CEMS differs from that m easured by the independent standard by m o re th an 10% per c ent. A f a ilur e of this aud it m a y indic a te that rep a ir s n eed to be m a de to the vo lum e m easurem ent system . Upon com p letion of these repa irs you must perform and pass another SVA.

• Quarterly X-Ray Fluorescence Ca libration Audit (XFCA): The respo n se of your XRF multi-m etals CEMS m u st be with in 10% of the standard’s value for each m e tal m easured for com p liance purposes b y your CEMS. If your CEMS f a ils the XF CA initia lly, rerun e ach s t andard two m o re tim es and take the average of the three m e a s urem ents. If the average CEMS response m eets the XFCA criteria you m a y continue to operate, however, if the CEMS fails to m eet the cr ite ria then it is out of control. After the CEMS has been repaired you must com p l e te another XFCA. Upon su ccessf u l com p letion of the XFCA the CEMS is back in control.

• Annual CEMS Accuracy Tests Linearity Audit Option A (Linear ity aud i t of the entir e CEMS). If you challenge the en tire CEMS system (including sam p ling interface an d the sam p ling and XRF modules) with a linearity audit you do not need to apply a correction factor to your CEMS data if it m eets the following criteria: 1. a slope between 0.85 and 1.15 2. the correlation coefficient equal to 0

. 90 or m o re 3. an inte rcep t of less than 20 percen t o f the em ission lim it If your CEMS does not m eet the slope or intercept criteria you m u st apply a correction factor accord ing to the p r ocedures described in Perform a nce Specification YY Section 4.2.12. 1 Your CEMS, however, must still m eet the corre lation c r iteria. If your CEMS fails the linearity test it is out of contro l. After the n ecessary repairs a r e m a de it m u st pass a line a rity or relative bias testto be considered back in con trol. Option B (Linearity audit of the sampling m odule and XRF module only followed by a TEA) If you challenge the sam p ling and X R F m odules separately from the sam p le inte rface, yo ur XRF m u lti-m e tal CEMS is out of contro l if th e line a r least squares regression analysis of your aud it data does not m eet the following criteria for each of the metals m easured by your CEMS for c o m p liance purposes:

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 14 of 181. a slope between 0.85 and 1.15 2. the correlation coefficient equal to 0

. 90 or m o re 3. an inte rcep t of less than 20 percen t o f the em ission lim it If your XRF m u lti-m e tals CEMS fails a lin earity audit you m u st m a ke the necessary repairs to your CEMS and successf ullycom p lete either a relativ e bias audit o r a lin earity audit bef o re it is c onsidered to be back in control. You m u st also com p lete a transport efficiency audit (TEA) along with your linea rity aud it. Relativ e Bia s Audit Option C (Relative bias test of the en tire CEMS) If your CEMS m eets 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( PRSD) exceeds 10% 3. the correlation coefficient (r) for lin earit y portion of the relative bias audit is less th an 0.9 0 If your XRF m u lti-m e tals CEMS fails to m eet the relative b i as criteria you m a y apply a co rrection factor accord ing the procedur es described in perform a nce specification YY Section 4.2.13 . However, if your CEMS fails to m eet either the percent relative standard deviation criteria or the correlation coefficient criteria it is out of control. If your XRF multi-m e tal CEMS fails a relative b i as audit it m u st successfully com p ete another linea r ity or relativ e bias aud it to be considered in contro l. Option D (Perform a relative bias teston the sampling and XRF modules) Your XRF mu lti-m e tals CEMS is out of control if : 1. the percent relative bias ( PRB ) exceeds 15% 2. the percent relative standard deviation( PRSD) exceeds 10% 3. the correlation coefficient (r) for lin earit y portion of the relative bias audit is less th an 0.9 0 You m u st successf ully c o m p lete ano t her RBA or a line a rity a udit bef o re y our CEMS is considered to be in control. You m u st also success f ully com p lete a transport efficiency audit along wi th the relative bias audit. Transport Effic i ency Audit (TEA): A TEA is only required if you challenge your sam p ling XRF modules separately fr om your sam p le interface (Options B and D). If the percent transport is between 90 and 110 percent no correction f actor is n e c e ssary, how ever, if the p e rcen t tr ans port is less than 90 perce n t or greater than 110 percent then you m u st apply a correcti on factor to the results reported by your m u lti m e tal CEMS. The procedures for applying a co rrection factor using the equation in Section 4.1.15.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 15 of 185.2.2 General out of control guidelines

• Out of control period : The out of control period begins im m e diately after the f a iled dr if t test or aud it and is ove r immediately following th e successful com p letion of required procedures associated with the f a ilure of the audit test. During the out of control period you m a y not use the data generated by your XRF mu lti- m e tal CEMS f o r com p liance purpos es.

• Reporting guidelines : You m u st include in your repor t to us, the state, or local enforcem ent agency the results of th e fa iled aud i t or dr if t che c k, the co rre ctive action that was taken, and th e resu lts of the successful audit or drift check.

• Rules governing auditing time periods: The X-Ray Fluorescence Calib r ation Audit (XFCA) and the S a m p le Volum e Audit (SVA) are req u ired once a quarter. Two m onths must pass betweensucces sive quarterly audits and no more than four m onths may pass.. Th e Linear ity Audit (LA) and the Rela tive Bias Audit (RBA) are required on an a nnual basis. Successiv e LAs and RBAs must be separated by at least nine m ont hs and no m o re than 15 m onths. 5.3 What tables, diagrams and flow char ts are relevant to Procedure Z?

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 16 of 18Table 1: Continuing QA Procedures for XRF Multi-Metals CEMS Test Frequency Test Test Proced ures Passing Criteria
Zero Drift Check zero standar dand calculate dri f t < 20% drif t each day Upsc ale Drift Check upscale standard and calculate drif t < 15% drif t each day Daily Vol u m e or Fl o w Drift Check f l ow drif t and calculate drif t < 20% drif t each day X-Ray Fl uores cence

Calib ratio n Aud it Test a standard f o r

each ele m ent m e a s ured f o r co m p liance by y our CEM S ( 1 tim e per stan d a rd ) • < 10% differ e nce f o r

ever y ele m ent m easur ed f o r co m p liance by y our CEM S • If criteri a not initia lly m e t you m a y take the avera g e of 3 m e asure m ents Quarterly Sam p le Vo lu me (o r Fl ow ) Au di t Volu m e • Co m p a r e CE MS v o lu m e against a sta ndard dur ing 3 sam p ling cy cles • Average all three Flow • 3 to 5 flow m easurem ents with standar d and CE M S per sam p le cy cle • Measure in 3 C E M S sa m p le cyc l es • Calculate average dif f e rence between CE M S and standar d s over all m e asure m ents <10% diff erence f r o m the standard

Option A
Pe rform a li ne a r ity te ston entir e CEM S • At least one m e tal f r o m each cat egory • Need at le ast 3 concentration levels w h ich include a 2 fold co nc. change and the e m ission li m it • If spiking, spike into source, or spike into transport line as cl ose as possible to the pr obe • Slope = 0. 85 to 1. 15 • r > 0. 90 • inter cept < 20% of em ission li m it • if above cr iter i a is m e t then no correction • if not m e t applya cor r ection Option B

• Pe rform a li ne a r ity te st on sampling and XRF modules only • Determ ine trans port e ffi ci e n cy se pa rat e ly • At least one m e tal f r o m each cat egory • Need at le ast 3 concentration levels w h ich include a 2 fold co nc. change and the e m ission li m i t • Spike or m easur e c oncentrations with r e fer e nce m e thod as close as possible to the sam p ling m odule Linearit y Crit eria • Slope = 0. 85 to 1. 15 • r > 0. 90 • inter cept < 20% of em ission li m it • the linearity crit eri a m u st be m e t Percent Transport Criteria • 90< PT< 110 • If percent transport crite ria a r e not m e t apply a co r r ection f actor Option C
Perform a relativ e bias test on entire CEMS • At least one m e tal f r o m each cat egory at 80 to 120 per cent of em ission lim it • One other m e tal at 3 conc. levels which include a 2 fold co nc. change and the e m ission li m it • If spiking, spike into sour ce or spike into transport line as cl ose as possible to the pr obe • Percent relative Bi as • RB< 15% • %RSD < 10% • r > 0.90 for m e tal with three fold conc. change • I f Cr iter i a not m e t applya cor

r ection factor (cor r e lation coef f i cient criteria m u st be m e t Annually

Option D

• Perform a relativ e bias test on sampling and XRF modules only • Determ ine trans port e ffi ci e n cy se pa rat e ly • At least one m e tal f r o m each cat egory at 80 to 120 per cent of em ission lim it • One other m e tal at 3 conc. levels which include a 2 fold co nc. change and the e m ission li m it • Spike or m easur e c oncentrations with r e fer e nce m e thod as close as possible to the sam p ling m odule Percent Relat i ve B i as Criteri a • RB< 15% • %RSD < 10% • r > 0.90 for m e tal with three fold conc. change Percent Transport Criteria • 90< PT< 110 • If percent transport crite ria a r e not m e t apply a co r r ection

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 17 of 185.4 What references are re levant to Procedure Z? i . Perform a nce Specification YY: Specifications and Test Pro ce dures f o r Batch Multi-Meta ls Continuous Em ission Monitoring System s at Stationary Sources. 2005.

Quality Assurance for XRF Based M u lti-Metals C E MS (Procedure Z ) Page 18 of 18