humidity, and lhe weight ofthe solution. Document new readings for these parameters every l hour. Also record bag s of ice added aod time as well as any necessary notes. 9.6 Shut-down T o tum the QAG off after testing , first close the manual ball valve on the nebuli:ring air line and sbu t oiTihc flow . Tum ofT aU of !he heaterS. Next, tum off the drying air Oow and shut down the sampling system. Pump as much of the SOl u tion uut of the dropl e t e ener.uing chamber as**pos~ible** and tum offthe peffitaltic 

### pump, balance , and laptop. Finally , shut off tlte main flow. 9. 7 Post
- Test Procedures 9. 7. I Balan c e Check 

### Check lhe balanc e calibration following the procedure descnlled · n Section 

### 8.2 .3 . 9. 7.2 Flow Meter Check 

### Check the flow meters calibrations following the procedure descibed in Section 

### 8.2 . 3 . 9. 7. 3 Ambient Pressure Reading 

### TilLe a fmal reading ofthe ambient 

### pressure with 

### a NIST-traceable pressure gauge. 9. 7.4 Solrtlion 

### Sample Collect and store 

### an additional 

### 50 ml sample ofthe anal)'le solllion 

### for possible quality assurance checks ot a lat er time if nece ssary. 

### 1 0 . 0 Calc ulations 10

. 1 Generated Aerosol CoiiCeJI/TDiion The following equation i s used to calculate tbe genera t ed aerosol concentration of the i"' element ( Ctt)AC) from the QAG 's recorded parameters :

cs ·QAG**C~ -QAG-**  1 

### (R

- R ) 

### ' F • .. 

## ' E-quatio n I Where:**~.c** 

## = Concentration of the 

### i • element in the QAG's NJST traceable solution.**lo~** Mdhod fora ()I.G : VIJJ Section tO. O Calculations Pag e**l~of23** 

### VES009 1F, = Total flow, i .e. , the combined flow ofnebulizer air and drying air added within the aerosol generat ion system, determined by the flow meter l oca ted between the 

### QAG and the t:"dnsport >Y>1em. R., ; Measured rate of reservoir ma ss l oss , detennined as the s lope of a li near l eas t squares fit of the reservoir mass dma over the period of a tes t or series of te sts . R v = Rate of vapor lo s s is a calculated vatu" hased o n the follow i ng equation: Equ ati on 2 Where : F, = Flow rate of the expanded nebulization air as measured by the flow meter on the nebulizing air line . M . = Mass ofwater vapor 

### in a liter of sa turated air at 

### 32 • f. This value has been well defined and documented : M , (32 ° F) = 4.8 4 7 rug/liter 

### Pe = Pressure of th e expanded gas outside the nebulizer nozzle . Since tbe droplet generating chamber ond the drop let size selector are open to the atmosphere, 

### P, is the atmospheric pre ssure reco rded from t he fie l d barometer readin g. P

, = Absolute 

### pressure of the co mpressed air up stream of 

### the n ebul izer nozzle. calculated by add i ng the atmospheric pressure to tbe gau ge pressure . 

### I

0. 2 Generate d Aerosol C ottcemratiorr Urrce rtainty . The uncertainty of the gene rated aeroso l co n centration ( u**c~)** i s de termi ned**u.~ing** standard propagafun oferror techn i ques 5 relevant to the parameters of Equation l. Tbe un certainty values for the parameters arc those listed as certified uncertain t ies b)' the manufacrurers andfor NIS T . This procedu re is co nsistent**tb** those u sed at N!ST"7JI The uncertainty of the generated a erosol concentrat io n (**C~" )**  is calcula t ed using t he foUoY. i ng equation:

_ c a - QAG I j Equation 3**Ps g~~**  16 of 23 

### VES00990J

### Equation 4 

### Where:

1 Equation 5 

### and 

### uR, . 

## = R ,.

and Equation 

### 6 ( O"P, 

# )1 

# +( 0" 1! )2

P. P, . 10

. 3 Solu tion Conce/1/ration and Flow Rate Set Points To de termine the required sol ution con c entration and 

### Oow rate set poi1ns for given lest 

### run , select a desired concentration of t he QAG's aerosol emissions ( 

## c;-\1• ' 0 ) . 

### Use the expanded form of Equatio n I :

c.• - (J,<(i = 

# c;-!!A" 

# [R
- F M 

# (

1

- f>. )] I 

### F , Cf v 

### p r < 

### Plug in the de s ired concentration ( 

## c, ...e«; ), the estimated rate of mass 

### loss (Rw. see also section 8.3), the mas s of water vapor in a liter of saturated air a t 32 ° F (A/ ,. 

### 32 op • 4.847 mglliter) , the pressure of t he expanded nebulization air (P,), and the absolut e pressure of the compressed nebulizing air 

### ( P c ). Solve for an appropriate combination of solution concent ration ( 

# c;o..c ) and flow rates, bearing in mind that total flow ( F,) equals the expanded flow ofnebulizing air (F,; 

### which must be between I0 and 12 lpm) plus the drying air flow (which can range from 28 to 

### 1990 lpm). / 0.4 

### Aerosol Emission Size Use the following equation to determine the siz e oflbe salt panicles emitted by tl1e 

### QAG:

St!\.:ti-on 10.0 Coln 1 latious Pag e 

### 17of23 

### VES009902Equatio n 7 

### Where : D,. 1 , 

### The d iameter 

### of the salt in 1101 . 

### Duq 

## = The diameter of the liqu1c1 c1roplets in 11m**u~** specified by the nebuli zer manufacturer in )l.nl . 

## c

;- Q•c = The concentration ofth e analyte s tandard in the NJST-tracenb l e solution in 

### grams ofanalyte 

### salt per**gra~n** of solution P

.m c 

### The density 

### of the analyte salt in 

### g/m3• 

### P

u . = The density oftbc liquid droplet in 

## sfm'. 11 .0 Do c um e ntation ofQua .lity Co n trol a nd Assuranc e 11.1 Certificlltio ns Prepare a eheck list and con 

### fum the certifications ofNlST-traceable components . Assemble the certifications o fNIST traceability for each component. J

1.2 Field Data 

### Rerords Create and use a data sheet fo r the calibrdtion the balance and flow met ers in t he field. 

### 12 . 0 Pollution Prevention The 

### excess aero so l gene mtcd by the QAG should be trapped in 

### a filter and disposed of acconding to the ap p ropriate regulations. The unused solution sb ould tlso 

### be di sposed of accordi n g to regulation. 

### 13 .0 W as t e Man age m e nt The soi Uiion standard s should be handled according to th eir Ma t erial Safety D ala Sheets.

fruarumeattl**M~** f or a QAG : V 1. 0 Secfiuu J 3 .0 Waste Mnnagomenr Pa11e 1 8 of23 

## VES009903

### 14 . 0 Fi g u r es a nd Tabl es 

# I \



# ""'""' ,- 

# '



# - """' I 

# .. ' I 

# --=:.

# -~ 1.:- 1'\' rl r.u."k -*.



# ""'' •

....... "'"' 

# 'I # C ' olliJbl 

# - So:oiii !JM 

# 'l = S!G a nl 

# · -- Slltt

u tl oll I« Ba!ll 

### c-**au _~**  

### ' I 

# g A. 

### B. Figure I : A . Sc h e m a t ic of flow thr o u gh Q A G co mp o ne nts. B . 0 \ 'e rvl ew o f th e set- up o f l be C ES Q AG.

\

Figu re 2 : Sc h e m atic of t b e C E S Q AG s ta ndard s olull ou control sys t e m,

Pag e 1 9 of 23 

## VE S 009904**·~. ~** **1=r~=** 

# .... 

# -r;-r:ltlf**~** f 

## lfi 

# J. !lt

---·· ;.J Coodmlot !O 

# , .

# ' . ,. 

# .. ,.,.,. 

# ... t ' iber Me"' Regu 111(0t Unitt

Fi gure 3: Schema ti c of the CE S QAG nebuliz er air control sy stem.

Nebuhm hn g .fqoiltJnoc in s

Cbllntber

Nebul izer NolLie

F igure 4 : Sch e mati c of th e CES QAG n ebulizer and d roplet s ize con trol s ystem.



## VES00990S

## ~

Or>ina Ch o mber- 

### 1'- l ieoter(• l Dr)-ing Chamber

,-- 

# • •lJc



# - ' 

# . l.e

J

# ~ I**~** 

# [\ Dty ina Air**P~~u re**  Tube Flow Meter R•gulacor**Hcatc.1~ S)**  t::: 

# - - "


# - - · - DTying Ai

r Ring Fi gure 5: Scb cmad c of the C ES QAG d ry ing air aud dryi n g chamber sys te m.

Page 21 of23 

## VES009906

### Dala Sheet QAG**11~1** 

### Tes1s Ojflliror: Soli. Cone**Do~:** l oc<lloo: Sian illllll' ..**~:** SQOOT• lillol 

# .... """ 

# ... . 

# , _ "::." 

# , _ """"" IIY.II 

# - : Rlo:rl ltYt Pres. i)(jj Jk

# I~ ,. FIDw Ailemp**r.e pcrt**  F1Dw Flor 11!111**~** ' 111111 

### c.s:a S!CII ffi 

## m (sbol l'f l f,i\ 1001 1 

### · •n •• llri 

## m 1\au ( i



# '* .lddld let**~~~t** l&.gs

'IUinlltlentaiMtbxl for 1 OAG : VIIJ Pa ge 2 2 of 23 

## VES 00 99 0 7

### 1 S. O R e f

e r

e nc es I. Scot1 Specially Gases. Scou Gas Mixtures Data: Gas and Liquid Mixture Basics. Plwusteadville , PA: Scott Specialty Gases; 2004. 2. Bureau International des Poids et Mes ures , Intern a tional Electrote.chnical Co mmission, lntemntional Federation ofClinical Chemistry and Laborau>ry Medicine , lntc marloo al Orgauaation for Stnodnrdizarion, International Union of 

### Pure and Applied Chemistry I nternational Union of Pure and Appl ie d Phys ics , lnte:natiooal Organization ofLegal M etro l ogy [BIPM, IEC, !F CC, ISO, IUP A C, IUPAP , OIML) . International Vocabulary of Basi c and Genera J Tenns in Metro l ogy (VIM). Geneva, Switzerland: BIPM, rEC, JFCC, I SO , JUP AC, IUPAP, OlML; 1 993 . Avai l ab l e from: I SO, Geneva, Switzer l and; IS BN 92 -67
- 01075-1. 3 . Smithsonian Phys ical Tables, 9th R ev. Ed . Washington D. C.: S miths onian Inst i tu t ion Press ; 1954. 4 . Scace, G.E. and J.T . Hodges. Uncertainty of tbe NIST 

### Low Frost
- Point Humidity Genemtor. Gaithersburg, 

### MD: National In s titute of Srondards and Tec hnol ogy; 2004. 

### 5 . McC l av e, J.T .. 

### F.H. Dietrich, Jl , and T. Sincicb. Statistics , 7th 

### Ed. Upper Saddle RiYer. NJ: Prentice 

### HaU; 1997. 6. Taylor, 

### B.N . an d C.E. Kuyatl G u idel ines for Ev alua t in g and Expres sing 

### th e U ncertai nty of NIST Measurement R esults. Gaithersburg, 

### MD: Nationallnstirute of Standards and Technolo gy (NJ S T]; 1994 . Available from : NIST , Gaithersb urg, MD; TN 1 297. 7. Al!lCrican National Standftfd<**Tn~tituteJNatiooal** Conference of S tand ar ds L<lbomtories (ANSIINCSL]. U.S. Guide to the Expre ssion of Uncertainty in Measurement. Washington, D. C: ANSUNCSL; 1997 . Available from: NCSL In t ern a tional , Wa shi ngton , D. C; Z540-2

- 1 996. 

### 8. M ay , 

### K.R . The Collison n e bu lizer: description, performance 

### and application. Aerosol Scien ce 1973 ; 4: 253 -24 3.

IA..........,Mdhod for aQA O · Vl.O Pag e 2 3 of23 

## VE$009908

# VES009909
. pdf

## VES009 9 09

# Performance S pecification YY: S pecification s and Te s t Procedur es for X-Ray Fluor es cence Based M ulti-M e tals C ontinuous E mi ss ion Monitoring Sys tem s at S tationary Sour ce s

Prepared by: Cooper "Environmental S en • lccs , L L C 

### 10180 SW Nimbus Blvd SuiteJ6 Po nland , Orego n 97223

R evi sion : 1 .0 

### J une , 2005



## VES009910

## VES009911

### VES009912

# Performance Specification YY: S pecifications and Test Procedures for X-Ray Fluorescence Based Multi-Metals Continuous Emission Monitoring Systems at Stationary Sources

Prepared b y : D ate: , _ _ _ Krag A. Petterson, Environmen tal Scie ntis t R eview ed by : Date : __ _ Cay A . Ya n ca, Environmental S ci e n tist R evi ewed b y : Dat e: _ _ _ Br uce E. Johnson, Q A M anager Ap prov ed by: D a t , e:

__ _ John A . Cooper, D i r ector



### VES00991 3

### Exec uti ve S ummar y Performance Specification YY details the performance requirements for • multi-metals continuous emissions monitor t hat utilizes x-ray 

### nuorescence (XRF) as an 

### ana lytical technique. Each XRf based multi-metal s CEMS must meet the criteria for accuracy, stab ili ty, arul in s trumental response laid out in thi s document . In addition, every XRF multi· metals CEMS must meet the instaUati on requirements in PS

- YY and the on -g oing quality control and qua l ity a ssurance 

### procedures set forth In**pro~;c<lu c**  Z if it is u sed for**em t~** **<inns** 

### comp lian ce purposes .

Page i 

### of iv 

### YE S0099ll

### b . = b t 

## CA 1 c 

## C

f c c £.1/S**~** I 

# c c •.v I c 

### CF."' I c 

### CF.,.. I E 

## C

' a 

### ' 

# cs

I c 

### Li s t of Sy mb o l s They intercept oft he best tit line The s lop e of th e best fit line X-rn y fluorescence calibration accuracy Corrected CEMS co n centration for the ;•• element The con centrntion of the i,. element as reported by the CEMS The avernge reported co nce ntrJtion of the CEMS for the 

## i" e l ement Correction f.1ctor for percent transport for lhe i'b element The relativ e bias correction factor for the ith element The emission limit ofthe i 111 el ement C onc entration oft he i"' cle ment at the stack C ' M

1 • Concentration of the ilh e l ement at t he samplin g mod ul e 

### or a s reported by the 

### XRF mu lti -m e tal s C EMS . d l d 

### FS**~** 

### L " '"

I 

# c-

I**£'~~-** I 

### E/J J:



# ' ll 

### PT, P T, 

### PRB, a
= =

c**~** 

# -

= =

c 

### • • D ifference between two paired measurements Arithmetic mean ofdifferences Full sca l e value ofyo u r CEM S volwne (o r flow ) meas w e ment devi ce The vnl u " of t he i "' eleme nt on the zero s tand ard**determ~ted** imme di atel y after calibra t i

o n The value of the ca lib rntion c h..ck s tandard reported by your CEMS T h e me as ured CEMS res pon se to the zer o s tandard for t h e i do element Th e measur ed CE MS rest>Onse to the i m e l eme nt in t he u ps cale s tan dard 

### n1 e known va l ue of the c a lib r a tio n cheek standa rd The ca librat ed valu e of the 

### i' • e lement of t be up s cale standard Number of da ta po i nts T h e percent tran sp ort o f the i 111 element A verag e percent transport f or the 

### ;•b element Relative Bi a s ofthe i• el em ent Pa ge ii of iv 

### VES009 9 l5

### Rt.u**~** 

### PRSD ,= r = SD !**~ ~**  

## = VD = 

## v

..**~** 

### UD 1 = X 

## = X

t**~** Y

1 

### ZD; = The av erage of the reference method mea s urements for th e 

### i" tnctal The relative percem standard deviation for the i 1 • metal The correlation coefficient The standard dev iation of differences for lhe i 1 b element Sample gas volume ( o r flow) as measured by t h e CEMS vo l ume cheek device Vo lu m e drift Volume (or flow) reponed by your mu l ti-metal s CEMS The upscale drift of the i'h element on your CEMS in percent. Arithmetic mean Value of each data point CEMS reponed concentration fo r th e i 111 element The zero drift ofth e ilh element on yo ur CEMS in perc ent

l'age iii of iv 

## VES009916

### Table of Content s 1.0 Using PS- YY .......................................... . .... . ...... . . .... ................... ... . .... .. .. . ................. . .. I 1.1 V.bat is the p urpose and applicabi li ty of Performance Speci fication YY? .. ...... ... ... I 1.2 What wiU 

### be di scussed i n PS

- YY ? ........ .... .... .... ...... .... .................. .. ........ .. .. . ..... ...... . I 1. 3 

### What arc the instaUation and pre-performance specification test req u irements? .. ... 2 1.4 

### Wha t special definitions apply toPS- YY? .. ........ ..... .. .............. . ............................ .. 3 

### 2. 0 Interferences , Saf e ty , and Equipment Requirements ............... . .......... .... ..... .............. .. . 5 2.1 Are there any 

### potent i a l**in terference** **~** 

### fo r my 

### XRF multi

- metal 

### CEMS ? ...... ... .. . .... .. 5 2.2 What do 1 need to know to 

### en su re the safety of person s using PS- YY ? .................. 

### 5 2.3 What equipment and supplies do I ne ed ? ..... ....... . .. . .. .............................. .. ............... 

### 5 2.4 Wltat regents and standards do I need ? ..... .. .. .. .... .... .. .. . .... .... .. .. .. .. ...... .... ........ ...... .. ... 6 3.0 Perf orman ce Evaluation Procedures and Reporting . ....... ........ .. ................. ... ....... .... ... 6 3.1 Wbat i s the 

### purpose of the 

### initial p erformance specification tests 

### and what i s required to perf orm 

### the t ests ? .... .... ...... .... ...... ...... ...... .... ...... .... ................ .... ........ .. ............... 6 

### 3 . 2 How do I report the results of the init ial performanc e specification t est? ... ....... .... 1 2 4 .0 Petformance Criteria and Calcu l ations ........ . ... ...... .................. .. ................................. 13 4 . 1 

### Wbat 

### are the performance c riteria for my XRF multi -metals CEMS? .. .. .. ............. 1 3 

### 4. 2 What calcnl ation s, equations , and data analyses are needed ? . .. ... .... .. .. ....... ...... ... .. 14 5.0 O the r Requirements and Information .... ........ .............................................. ...... .... ..... 20 5 . 1 Wha t 

### q ua lity control 

### measures are required? ...... .. ........ .. .... . ............. .. ... ................. 

### 20 5.2 What ca librati on 

### and standardizat i on procedures must I perform ? .... .. .................. 

### 20 5.3 What 

### pollution prevention procedures must I f ollo w? [reserved ] .......... ........ .... .... 2 0 5 .4 What waste management procedure s must l use ? . ...... ... ........ ... .......... .... ........ .. .. .. .. 20 

### 5.5 What 

### ref e rence table s and figures are relevant toPS

- YY ? .... .... .............. .. ............. 

### 20 5 .6 What ref erences appl y toPS

- YY? ... ......... .... .. ..................... .... .... ......... . .......... .. ..... 30

Page iv ofiv 

### VES009917

### 1.0 Using PS-YY 1.1 What is the purpose and applicability of Perf or

man ce Specificati on !1'? / . / ./ Purpose 

### The p u

rpos e of P erforma n ce Spec ification YY is to esta bli s h t h e perfonnance require me nts that must be 

### me . t by a 

### multi

- metals cont mu ous emi ssio n rnuuitoring sys tem ( CEMS) t ha t utili z e s x- rny fluor es cen ce (XRF) 

### to determi ne m etal concentrat i ons in sta tionary sources. A ssura n ce 

### of t he co ntinuing qu alit y of tb e CEMS data rnuy be ac hie ve d b y foUowing tbc procedures defined in**Proc dure**  Z- XRF Based Multi

- Metal CEMS Qualit y Assurance Pro ced ures. 1.1. 2 Application 

### PS-YY appli es to 

### you if 

### you intend to 

### u se an 

### XRF multi

- metals CEMS for purposes of**~'tablishing** 

### com p liance wi t h federal reg ulati ons for m e ta l em iss io ns from 

### statio nar y s ources. 1 . 1.3 M eas urem e nt Capabilities A 

### multi-metals CEM.S 

### must be capable of mea suring total con cent rati on s o f at leas t two 

### metd!S in 

### the units of t he applicabl e stand ard or in units that 

### em be co n verted to unit s of the 

### appl i cable s tandard . I. I .4 O ther Monitorin g 

### lf your 

### XRF based multi

- metal s CEM S i s c apab le of rep orting a me tal concentration in the units oftbe**exi>~** n:gulo t ion no additional 

### monitoring is 

### n ecessary . ifyo ur CEMS 

### does not report conce ntrat i ons in the u nits of the existing standar d then ot her mor.itoring (e.g., 

### oxyg en , t cm p erarure , and pr es sure) are n ecess ary to co nv ert th e uni ts repo rte d by your CEMS to the u nits of the standard. 1. 2 What will be discussed in PS-YY? PS- YY 

### covers two basic top ics: (I) the 

### instrument requirements fo r a XRF 

### based multim

et

a l

s CEMS and (2) the 

### requirement s that eac h XRF 

### mult i -metals CE M S must meet during 

### the initial performance sp ec ification t es t. 1 . 2 . 1 1ns trwn e nt Requ i rements A 

### multi-metals CEMS mu s t be able to accurately rep o rt t h e co n centra ti o n s ofat least two 

### meta l s. It may do 

### so by 

### ex tra c tin g a 

### repre senta tive samp le (pa th 

### or point samp li n g m

a y be 

### use d if the sam pl e is representative) of stack effluent and 

### ca pturin g the metal a nslyl es of interest on a me di u m . The CE M S mu st bave a 

### cy cle time 

### th a t is less than one third r he period of the app licable standard. The range oftbe instrwncnt m ust be 

### from l 0 percent t o atleast400% o f dte : op p li cab le regulatio n as de t e rmin e d by field or P

age I 

### of30

### VES009918laboralory tests. FinaJly. the instrument or operator must be able to p e rform da il y upscale, blank, and flow q uality assurance cbec.Jcs to ensure the accuracy , precision, and st1biliry oftl1e instrument and its data . 1 . 2 . 2 Inilia/ Performanc e Specification Tests The purpose of the initial performance specification test is to estab l ish t he stab i lity, •cc uracy, ""d precision of your XRF multi-metals CEMS. 11te perfomlWlce speci t ication test can be divided ittto two p h ases: (I) t1 1e stabiUty tt>t , and (2) the accnrncy test. The Stabili t y t est consists ofa seven day check of the zero and upscale calibration drift and i1 done prior to the accuracy testing. F or the uccuracy tests , t hree meth ods of meta l s g enerati on ( q uantitative spiking, non-quantitative spiking, and stack operation) and two methods of data analysis (percent relative bias. and lineariy) are available. The sam pli ng and 

### XRF m odul es of your 

### CEMS may also be tested separately from your stack sampling interface. Some options may be better than olhers depending on your multi-metals CEM S, or the condi tions existing a t your stac k. 1 . 3 What are the insrallatto n and pre-peiforma nce specifica t ion tesr requirements? 1 . 3.i lnstallalion Requiremen t s The samp li ng location of an XRF multi-me tals CEMS shou l d be downstream ofa ll pollution control equipment at a position where the metals concentrations are directly representative or can be corrected so 

### as to be r epresenta ti ve of tollll emissions from the sta t ionary source. I t is recommended that tl1e sampling location be at least two equivalent diameters dow n stream oft he neares t control d ev ices , po i n t of pollutio n gene ra t ion, bend , or ot h

er poin t a t which a cha n ge i. n poUutant concentration or flow dismrbaoce may occur . Tbe sampling l ocat i on i s ulso recommen d ed t o be at lea<t two equivalent diame t ers upstream from 

### the exhaust. 

### The equivalent diameter is calculated according 40 CFR Par160, Appendix A. Method I , Section 2 . 1;. Either point or path samp ling may he used. For point samp ling th e meas u rement. point s h oul d he no less than 1.0 meter 

### from the stack or duc t wall 

### or Jccated over the cemroidal area ofthe stack or duct cross section. For a path samp ling CEMS t h

e ell'ective meas u rement pa t h sho u ld be ( I ) 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 of t he path withi n the i n ner 50 percen t of t he s t ack diameter o r d uct c ross section. lhe sample collect;on and instrumental analyzer portions ofyour 

### XRF multi

-metal s CEMS may be located any distance 

### from th e s a mpl i ng poin t provi ded t he transm i ssion efticie n cy from the sampling point to the sample coUectioo point can be determined and meets the**cr~eria** outlined later in this performance specification . It is also recommended t h

at t h

e sam pli ng probe for your m u

l ti

- metal CEMS be located at point without stratification. You may test for s tratification a t the proposed C EM S sam pl iJ1g point by us ing e i t h e r**P~ 1**  (as o u tl i

ned in PS-ll). velocity tests as described in Method 

### 2 u . or metal s concentrations using Method 29 or an accep t ab l e alternative. Page 2 of30 

### V E S0 099191.3 .2 Samp lin g RequiremcniS Your multi-mew I CEMS should samp l e from the source at a flow rate which is within I 0 peteent of true isok . inetic. If yo ur multi

- metal CEMS does no t mai n ta in an is okinetic s ampling rate you must us e ac tual site-specific data or dzta from a similar installation to prove to us , tbe State , and/or local enJorcement agen c y that isokinetic samp ijng i s not necessary. 1.3.3 Pro
- Test Preparation R eq uirem ents ond Sltggestions Prior to th e initi al perf ormance speeification test you need to eru;ure that your multi

meta l CE.MS data Jo gger accurate l y record s emissions l evels as well as sig n als (flags) that i n

dicate botlt nonnal and abnormal operation. Prior to start of the seven day**stabi~ty** test the dai l y drift measureme nts (upsca l e an d ze ro values) s hou l d be monitored to en s ure th a t the instrument is operating i n an appropriate and stable manner . We recommen d that you use your XRF mu l ti

- metal CBMS for a s uft1cicnt length of rime . to become comfortable with it s**per~tion** prior to the >'tart o f the initial**perf~nn an** **ce** specification tes t. 1.4 Wha1 

### special definitions apply fiJ PS · YY ? Calibrati o n Dr ift: T h e difference in the C EMS o utp ut rea din gs fr om t he established r eference value ufter a sta ted period of operation during which no unscheduled maintenance or adjus t ment too k p l ace. Cycle Tha e : Th e time betw een when the stack g as fi rst co mes in contact w itb the c on centra tin

g media and when the concentration valu e for that samp l e is reported. D ata Rec o rder: The portion oftlte CEMS that provides a record ofan al yzer output including metal co ncentrations , flags which i ndicate norma l opero tion, a nd flag• indir.llt ing abnonnal operation. The data recorder may record other pertinent data such as effiucot flow rates, a nd vari ou s in strume nt te mpe ratures. D iluen t mo du le: Th e part of the CEM S in w h ic h any diluent i s added and measured . Drift Cal brati o n Sta ndard: A stand ard containing a constant annoum of met al used to establish the drill in the x - ray flu orescence mod ul e respons e. Emis5ion L imit: The emission limit for a si ngle m eta l i s equal to th e maximum amoun t aUowed u nder the app l icab l e regulation for its category assuming a ll of th e other metals in its category were not present. Eleme n t 

## or Op p o rt unity: An e l e ment that i s present in the stack effluent and can be used to estab li sh transport effi c iency. Instr ume n t M ens uremen t Ran ge: The range of metal concentrati ons th e instrtJment can reliably measure from the l owest co ncentrat ion to th e highest. The instrum ent m e asurement rang e may 

### be different for different metals. If the upper end of the measurement range is 

### Page3 of30 

## VES009920more than four ti mes tbe emission limit. the upper limit does not need to 'le definitively es tabli s hed. P atb S a mpling CEM S: A CEMS that s ampl es th e sou rce effl u ent along 

### a path greater than 10 percent oftbe e quivalent diameter of the swck or duct cross section . Point Sampling CEMS: A CEMS that samp l es the so urce effluent at u single point. Non-Q u anti tuti v e S piki ng: The process of introducing un unknown umounl ofmctnl o r metals into the effluent or srunple stream. Quantitative S piki n g: The process of introducing a known amo unt m etal or metals into th e effluent or sample s1re am . P e r cent Rei a liv e Bia s : T he difference between a ref erence value and the CEMS measured value divided by t h

e r eference va lue . Refere n ce m ate rial : A material of known va lue used to check the calibration driH of your 

### XRF multi -metal CEMS. Sampl e T n

t erf3ce: The portion ofthe CEMS 

### used for one or more of the following: sample acquisitio n, sample t ransport, sample condit i oning. or protectio n of th e monitor from the 

### effects of

### nack gas . Samplin g mod · ul e: l'be portion of an x-ray lluore scence based mul ti

- metal CEMS that traps the m etals and delivers them to the 

### XRF mo du le . Spiking: The process of introducing metals into the effluent stream or the samp ling stream.**Tran ~1>or** **t** Efficiency: The**pe~nt** of me"' I that is transported from the sample probe 10 a po int a s c l ose as po ssible t o the sam pling module . Up sca l e Drift: The upscale drifl is t h e difference in the re pon ed vahJ e for the up scale reference from its value at the last calibration, divided b y the value at the la st calibrat ion . It i s used t o monitor the stabil i ty of the x-ray fluorescence analysis. X
- Ray Fl uorescen ce (XRF) Module: The ponion ofan XRF based multi-metal CEMS whi ch identifies and measures metal mli$ses or conce ntrations using x-ray nuores ccnce. XRF Multi-Metals C ont i nu ou s E mi ssion Monito ring System (C EI\tS): AU o f the equipment required for detennining metal concentrations using x-rdy fluorescence as an analytical technique. The sys te m may co nsist of several majo r s ub sys;ems including but not limited to the foUowing the sample interface, the x-ray fluorescenc e module , di lu ent module , data re corder , sampling m od u le l Uld volume measurement module . Zero D rift: T he zero d rift is the difference in the CEMS readi n gs for the zero reference from their values after the most recent ca lib ration , d i vi d ed by t he emission l imit for eac h e lem e nt. Pag e 4 of30 

### VES009921

### 2 . 0 in ter f e

r e n ces , S afe t y , a nd E qu ipme nt Req uir e me nt s 2.1 

### Are tl: e re a11 y 

### pot e mia/ in terfereucesfor my XRF 

### multi

- m e ral CEMS? Ther e may be i n terferences ari sing from th e x-ray fluorescence analysis, the trapping media, o r from condensati oo in the effluen t gas. Check with your m ul ti

-m etal CEMS manufacturer to find ou t more about p o tentia l in terf erences. 2.2 What do I n eed 

### to know to 

### <'11Sure the safety of persons using PS-YY? Peop l e usir.g PS- YY may be exp osed to hazardous m a teria l , operational hazards. and bazatdo us $ite conditions. PS- YY does not addres s all the saf ety issues associated with its use. It i s yi>ur respo ns ibility to ensure tl1e safety of person s using PS

- YY. Some he lpful references may include tile CEMS ma . nual, the CEMS manufacturer , o ther ref erence m

eth ods, and on -site saf ety regulations. 2.3 Wha l 

### eq uipm e nt and su pplie s do I 

### need ? 2. 3.1 

### Eqw'pmem for the CEMS I. S ampl e i nte rfac e: Ths portion of th e CEMS must present a sample of source effl u c o

u to the sam pl ing module tha t i

s directly represen tative or can be corrected so as to be representative of source . To accomp li sh thi s , the samp l e interface may contain , amo n g other things, heaters or beating systems, and dilution air . 

### 2. S amp ling modul e: The samp l ing module must collect and trap aU the analytcs of interest**from~** re presentative samp l e of s tack eftluent without s ignificant loss . The trapped analyte s then must be pre sented to the XRF module . 3. XRF modu l e: The XRF mo d ule uses x- ra y fl uo re scence to det ermine tbe m ass or concentrati on of m etal captured by the sampling mod u l e. 4. Vo l ume measurement modul e: This portion of th e CEM S measures the volume of source effiue nt from which th e metal analytes were captured in the sampling module. Th is vo l ume a l ong with the data from tbe XRF to d e term ine co n centration of source effluent. 

### 5. O llu c n t Module: Lfyour multi

- metals CEMS uses a diluent suc h as a ir or nitrogen it is added to tbe effl u ent sample a n d me:JSured using the diluent modu l e. 6. Quality assurance a n d quall ty contro l m aterials: Your mu lti

- metal CEMS m

u st possess tb e necessary equipment to perfo nn daily**~sca e**  a nd zero c h ecks. Your multi-meta l CEMS must also possess the equipment to perform a dail y check of the samp l e vo lume at normal sam ple Oow rates. 7 . D ata record er: Your XRF mu lti -me tal CEMS must be2ble to recotd metal concentrati ons and ins tru me nt status sig nal s (flag s). Spcdftcad oo> (or XRF 8aM'd MtJto.r..,.\ 1 tUis CllMS (PS ·YYJ Page 5 of30 

### VES0099222.3.2 Otlrer Equipment Needed for 1 he P erfom •an ce Specification Test 

### P S

- YY does not specify all the equip ment and supp lies necessary for lhe performance specificnt i on te s ts. Som e oftb i s informatio n is included in the a pp i icab le re feren ce methods (e.g .• Metho d 29 

### o r an 

### acceptab lealtemalive ). 2.4 What 

### regenls and srandardr do I 

### need ? 2.4 . 1 Zero Drifi Referen c e 

### Yourmulti-mclals CEM S musl include 

### a standard for th e measurement of th e daily zero drift. Thi s reference s hould produce a CEM S response indicating the ab s ence of meta l s. If this is no t. feasible this standard sho ul d produce a value between ze ro and**~/oo ftbe**  

### emi ss ion limit for at least two elements measured by your 

### XRF multi

m

etals CE MS when lb e inst rument is 

### operating appro pri asely. 2.4 . 2 

### Upscale Drift Refere nce The reference for the upscale drift check should generale a response for at least one metal from each condition used in the XRF analysi s . Thi s response mu st be at lea st 80 percent ofthe emiss io n limit 2 . 4.] Volume Drift measurement d evice 

### During the init i al p erfb nnance specification test th e volume measurement must be corr.pared on a daily basis against an internal vo lume or fl ow measurement device. Tn i• vo lume or flow rneasuremenl device must be calibraled independently of the sample volume or fl ow mcn suremont device and mu<t he 

### as ac cu rate or more accurate than the sample volume or How measurement device. 2 .4.4 X-ray Fluor es cen ce Calibrariafl Che c k Standard s 

### Yo ur XRF multi-metals GEMS must include u means of c hecking the :t-ra y flu<>resc ence calibration against an ex1ema l stand anl. N I ST traceable thin film standards are an example of a suitable x- ray fluor escence calibrn : ion check s landard . 

### 3. 0 P erforman ce Evaluation Proced ures and Reporting 3.1 What is the purpos e of the initio/ peiformancr specification tesLr a mi whlll is required 

### t o perform 

### rile rests ? Th e purpose of t he initial perfom1a nc e sp eci fic ation tests i s to determine t he bias, precisi o n, stab ility , and cycle time of your mu lti- metal CEMS .

Page 6 of30 

### VES0099233.1.1 Pretest Preparatio" Prior to tbe srnrt of your initial perfomtaoce specifi . catio n t ests you must be sure that your CEMS i s insmlle d ac cording to th e specifications laid out in this document After installing your XRF multi-metals CEMS we recommend that you use the CEMS for a p eri od of ti me to familiarize yourse l f with its operatio n. We al so recommend that you conduct daily c heck s ofth e z.ero an d upscale dri ft to ver i fy that the instrument is functioning properly . Wh en you are confident that tbe instrument i s performing satisfac t orily it is t ime to prepare fo r th e initia l performance spec it cat ion tests. 3 . 1 . 2 X-ray Fluorescence Calihratirm Chec k 

### If yo ur CE MS mea sures m ore me tals for compliance p urposes than will be evaluated during the CEMS accuracy testing described l ater in thi s doc ume n t you m ust per fonn a calib rati on chec k of the x-ray fluo resc enc e mod u l e for these additio na l metals. During the**~libration** check you must challenge the x-ray fluorescence trodu l e with a s tand ard or**~tandards** for e-•ch m eta l m ea sured by your XRF mu lt i

- meta l CEMS. Each metal must be measured at least three times and tbe error 

### is calculated according to

Equat i o n 13 for eac h measurement The average error of the three measurements must be l ess than 10% of the ca librati on stand ar d 's value for each me ta l , if no t your CE MS may not be properly calibrated . The x-ray fluoresce n ce calibration c heck may**occ~r** at anytime d uring th e initial perf m

mancc s pec ificati on tesL. 3 . U Stability

- The 7
- day CalibraJion . Drij i T ests Prio: to the start of the ac curac y tes t you m u st perf onn 

### a calibrntio n drift t est fo r 

### a pe . riod ofat least seven day s. The purpose of this test is t o verify that the in strume nt operation is stable. During th e ca lib ratio n drift te st period you mJSt determine the 

### mOWJitude oftlte 

### zero calibration drift 

### (us cal culated in Section 

### 4 2.9) , tlte upsc al e cali brat io n drift (as ca l c ul ated in Section 4 .2.!1), and the vo lume ( uo flow) drift (calc ulated using Equation 14) at l east once eac h d ay. Duri ng t h

e srnbility tests no adjustments or c.alib ra tion s may be m ade to the CEMS . The results of the stability test mu..<t be reported along with tbe results o ft h e acc uracy t ests. J./.4 CEMSAccuraC)J Theaccumcy of your XRf multi-m eta l C EM S may be detennin«< using one of the follawing four options . L Option A: Line arity test of th e entire C EM S 2 . Option B: Lineari ty test of t he XRF a nd sam pling mo d u l es sep arat e ly fr om th e sample interface . 3. Option C: Relative bias test of the entire CEMS. 

### 4. Option D: Relative bias test of the 

### XRF and sampliog modu l es separate l y from t h

e sa mple i n terf ace. Page 7 of30 

### VES009924There are also several options for generating the metals that will be analyzed by your mul ti -m etal CEMS in cl udin g, metals that arc generate d as a by-pro:luct of nonnal stack operation, quantitative spiking, and non-quantitative spiking.. Regardless of the generation option you choose you mu st be able to produce concentrations for some of the analytes of interest at 80 to 120 percent of the emission lim iL All oftheCEMS and referen ce method measurements must be conducted whi l e sampling nue gas. Yo u do no t need to t e st every m etal th at yo ur CEMS measures, however, you must generate at le ast one metal from each category of metals measured by your Cl:lMS for the accuracy 

### tests . For instance , if your XRF multi-metals CEMS measures 

### semivo l atile , l ow volatile. an d high volatile metals you must test at l ea st**on~** metal from each of those categories. (Low volatile metals may also be used to verify the capture efficiency and detection of non - enumerat ed metal s). You must also prove thnt the 

### XRF m odule is p rop erly calibrated to measure the elements that 

### are not being measu red d u ring tb e accuracy test by following t he procedures de scribed in Section 3 . 1.2. The test requirements for each option 

### are explained below and summarized in Table I. Unearity T est Requlreme . nts ( Options A and B): The b 1 as and precision of your 

### XRF mu lti -metals CEMS may be detennined by check ing t h e linearity of the instrument response over a series ofconcentrations . If quantitative spiking 

### is used. then 01 e concentration of the aerosol 

### is pa ire d with 

### a repo ned CEMS concentration acquired at the 

### same time . Each data po in t i s th en plotted with the spiked concentration oo th e X ax is an d th e reported CEMS concentration on theY axis. Ifeither non-quantitative spiking or stack by product is used, t hen the reported CEMS co nc entration i s plotted o n the Y 

### ax i s versus the concentration reported by m e thod 29 or a suitab l e a lternative. Linear l east squares regression analysis is th en used to fit the data points to a line. Ifyou challenge only the XRF module and th e sampli ng module the s lope of thi s line, which i s 

### an indicati o n of the accuracy of your 

### XRF multi-metal CEMS . is required to be between 0.&5 and 1. 15 for each metal. Th e co effi cien t of correlation must be greater than 0.90 and is an indication of the precision of your multi

- metal CEMS. Finally, th e intercept of this best fit line must be less than 

### 200/o oftb e appl ic abl e em i ssion limit. If you challenge the entire CEMS system and do not meet the s lo pe or intercept cr i teria you mus t apply a correctio n factor according to the procedure s in Section 4.2.12 . You arc, however, still required to have 

### a correlation coeffici ent o r0 . 90 or greater. To perform the linearity test yott must be able to generate at least three concentration levels for one metal fro•n each class ofmetals (high volatile , low vo lati le and sem i-v o latil e) measured by your CEMS
. The three levels must incorporate at least a two fold concentra tion cb an ge an d one level must be between 80 and I 20 percent of the emission limit. You may acquire a blank sample if you wisl 1 , 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 Page 

### & of30 

## VE$009925l east thr ee measurement s are require d a t each co ncentration l evel and a t otal of 

### IS measurements are required 

### overall . You may make addi t i on al measurements, however, yo u must report all the resu lt s. If you are not using qu antitati ve spiki ng you m ust make I S correspo nd ing mea sureme n t s usin g method 29 or a suitable alternative. We recommend using duel trains for the reference method measure m ent to identify and screen the reference method data for imprecision and bias . Addi tional requit -cm ents for each of the twu li ne arity t es t op tio ns are outlined below. You may a l so want to refer t o figures I through 8 for gu idan ce on which op ti on to choose. Option A : Total CEM S Linearltv fn opt i on A the e ntire CE MS sys tem i s challenged d uring th e l i neari ty test s. Any one of the three meLhods of melal s ge neration m ay be used during th e test. S ome ofthe testi ng requirements associated with metals generation are outlined be l ow 1. Metal s ge nerated 

### as a result of stack operation Ifmeta l s for t he test are generated 

### as a result of s1ack op eration yo u m ust mea sure the co nc entration ofthe metals in the Stack using method 29 or 

### a s uitabl e alternative and comt>arc the values with those repo rted by your CEMS. We recommcod using dual refere n ce me th od train s to screen th e reference m e t

ho d for p rec i sion and bias. 2. Non.quantitative spi k i ng You may either spik e non- qua nti tati vely into th e stack or duct i tSe lf or into the transport system as c lo se as possible to the sample p robe. If yo u >-pike into th e sou r ce you must measure the concentrati on in the source using met!Jod "l. 'J or a s u itable alternutive . T his**cos urom~ot**  i s then c mnp1lretlto the resu lt of your CEMS. 

### If you choose to spike into the transport line yo u mus t m eas u re the concentration immed i ate l y do wnstre:un o f the s pik e point with a met!Jod 29 or 

### a s uitab l e alternative and compare th at me asure ment with th e co nc e ntrat io n reported 

### by yo u r CEMS . 3. QuantiLative Spiking You may s p ike a qu antitati ve aerosol d i rectly into the so urce or into the transport line as clo se as po ss ible to sam pl e prob e . E i ther way tl> e know n s piked concen tration is compared**\\~tb** that measured by t he CEMS . Opti o n B: Linea rity f or Sampling and 

## XRF Modules Only 

### In option 

### B only the samp ling and 

### XRF modu l es of your multi meta l s CEMS are chall eng ed with 

### a linearity test. Yo u must a lso comp lete 

### a tran sport effi ci enc y te s t along wi th the li n earity test The p rocedwe s for performing a tran spo rt effi c i enc y tes t are des cr ibed i o s ection 3.1.5 . Til e procedu res for option 

### B associated with each metals generation option 

### are li s ted be l o1v . 1 . Metal s ge nera te d as a result of stack oper a tio n
Spcdftt:a!.ioN (or XRF fbsfd M11 t1i.M cub Cf'.:- tS { P S.YY) P age 9 of30 

### VES00 992 6Ifme t als concentrations for the accuracy teSt are generated as a result of stack operation yo u must m eas ure the concentration of the metal s as close as possible to th e sampling module using method 

### 29 or a suitable ahernati' e a nd compare the valu es wi t h those reported by your CEMS . We recomme n d using dual reference method trains t o screen the referen a: method for prec ision a nd bias. 2 . Non-quantitative spiking You may ei t her spi k e non-q uanti tative l y into t h e stac k or duct I t Se lf or into the transpon system . Either way you mus t measure the concentrations of t he a na lytcs as close as po ss ible to t he samp l ing m odule an d co mpare that concentration with that reponed by your multi metal CEMS . J . Quantitative Spiking You must spike at a l ocation as close as possible to the sa mpllng m odul e and compare the known spiked concentration wi th th a t reponed by yo ur CEMS.

• R e l ati ve Bias Tt -s l R e q uire me n ts (Opti on s C a n d 0 }: There 

### are tWo relative b ias options available: one that challeng es the entire CE MS aud one that challenges the sampling and XRF modules separately from th e sample interface . Either op t i on requires at least 1 2 CEMS meusur:ments be made at a concentration l evel 80 to 120 percent ofthe emission limit for a meta l from each category of metals ana l yzed by your X RF mu lti metal C EMS . lfyou are not using quantitative spiking you mus t al . so hav e at l e ast 12 co rr espondio!l 

### runs of metho d 29 or a s u i table alternative at this conc entration level. We recommend usin g dual trains for the rofo:rence meth od to screen th e data for imprecisio n and bias. Additi onally , for at least one metal**me•~ured** :tt thP. e mission limit or fo r a surrogate metal that can be 

### measured by your CE MS (such 

### as iron} yo u mu s t test th e CEMS at t h ree different co n centration levels . These three lev e ls must in corp orate at l eas t 

### a tw o-fo ld change in conccutration and one of the levels mu st 

### be b e tween 

### 80 and 

### 1 20 percen t of the emission limit (the concentration of the emission limit for th e sur rogate metal is equal to tbat f or the metal measu red by your CEMS with the b.igbest emission limit }. You are required to o btain a t lea s t three measuremen ts at eac h concentration level and are required to h ave a total ofat least 1 2 measurements . You m ust report th e results ofa ll me asure ments . Th e relative bia s is an indicator of acCUI"liC)' and should be calculated using equation 

### 5 fo r eac h eleme n t. Als o , the percent relative standard deviation , which is an indicator ofprecision , shc • u ld be calculated for each metal lfyou challenge the entire CEMS system and you do not meet the te s t criteria you may ap p ly a correction factor to your CEMS data. Calcu l ate a correction fa c t or for eac h m etal in t be rel a ti v e bi as test acco rd ing to the equation found 

### in s e ct i o n4 .2.13 . If yo u challenge the sampling and XRF modules sepamtel y from t h e sample iote.rtace yo u may n ot ap p ly a correction fa ctor to t he data Paae 10 of30 

## VES009927

### from the relative bias test, you may, however , ap p ly a c .orrection fuc tot · to the res ull s of t he transport efficiency test. For the metal that was spiked over s everal concentrations you must p erform li near leas t squares regression analys is on the data. The correlation coefficient for this fit must be 

### better than 0.90. 

### This is to dc mon stmt e th a t the instrum e n t res pons e i s valid over its 

### app licab l e range. If the criteria for tbis test is met then the correction factors are assu med to be va li d ov er t h e range of the ins trument. Ooti on C 

### I n a ccuracy t est option C the entire CEMS is subjected to a relative bias test. T h e opt io n s fo r metals generatio n and the a ssoc iated spiking and ref e rence meth od requirements are the same as those for Option A under the LineMity**tes ~.**  

### Option D 

### In accuracy test option 

### D only the 

### XRF and sampling modu l es are subjected t o a 

### relative bias test. The 

### options fo r me tals gene ration and ctteir associated spiking and reference method requ irements 

### are the sa me 

### as t ho se lor Option 

### B . You 

### are also required to perform a transpon efficiency test 

### 3. U 

### Transport Efficiency Test You must pcrfonn**~** 

### transport efficiency t est if you**~ve** 

### on ly ch allenged th e**~amp** 

### ling and 

### XRF modules duri n g the accuracy teSts**(option.~** 

### B and 

### D). Any one of the four methods described below ore va lid way s ofdetenniniug perc e n t transpon fo r yo ur multi

- metal s CEMS . Pa nlc uJ ate M atter ( PM ): In thi s 

### approach pa rti c ul ate matt er i s mea sured conc urre n tly in two l ocations, ( I ) 

### in the stack effluent stream as c lose 

### as possible to 

### yo ur multi

- metals CEMS samp le interface, and (2) a t 

### a po i n t in th e transpon system 

### as close 

### as possible to the sampling module. You may 

### use any stand ard reference method to meas u re 

### PM including Metl•od 

### 5 , M ethod 

### Si, o r Metl1od 

### 17 ( 40 CFR 60, Appendix A)m , ;v,v. Particul at e matter mu s t be generated by operating th e 

### sou rce. You mu s t acquire at least 12 

### paired concentration measurements (each pair 

### consists of th e measurement made as 

### close as 

### p ossib le t o the samp le in t erface and 

### the measurement made as close as po ss ible to 

### the sampling module. The percent tran s mission is calculated fo r each pair using equation 6 and the overd!l percent**tr.~m111ission** 

### is determined by calculating th e average of all twelv e mn s. • E l e me n t of opp o rtu nity: Alternatively , transpon efficiency 

### can be determined using a 

### surrogate metal suc h as iro n or zi n c that is 

### co mroonl y p rese nt in s tack 

### effluent M ethod 

### 29 (40 CFR 60, Appendix A).; or a suitable alternati ve can 

### be used to**m~ ure**  

### t he meta l co n centration in 

### t he stack efflu e nt stream a s 

### c l os e a s 

### possible to the sample probe and 

### at a point in the transport 

### system 

### as c l ose as poss ib le to the samplin g m odule . Al so, if your XRF mult:i-metals CEMS i s**P<~ge** 1 1 

### of 30 

## VES009928

### capable of m easuring the element of interest, you may compare the measured concentration on the CEMS 

### with that measured in the stationary source 

### using th e reference method . Transport efficiency is calculated us i ng equation 6. You arc required to make at least twelve paired concentration measurements to 

### determine the mean tran s port efficiency. • Non -q u antit ative sptldn g: An aerosol containing 

### a surrogate metal or 

### a metal anulyte can be spiked non-quantitatively into the s tack or duct gas stream or into the transport system as cl ose as possible tu the sampling probe . 

### The concentrati on of the spiked metal is measured by n1eth od 29 (40 

### C FR 60, 

### Appendix A) 5 

### or a s uitable alternative as close as possible 10 

### the CEMS ' s ample probe and by another Mctl:tod 29 or 

### a suitable alternative 

### a s close 

### as possible to the sampling module. If 

### you spike directly into the tnutsp<>n tine 

### you must 

### make your up s tream concentration measurement as close 

### as possible to 

### the spike loc a tion and yo ur downstream measurement 

### as close as possible to the samp li ng module. 

### If your 

### XRF multi

- meta l s CEMS is capable of measuring t . he spiked metal, you may compare its reported concentration wi th the in source metals measurement or with the upslream in transpo1t line measurement to calculate transpon efficiency according 10 

### equation 

### 6. You are required to make at least t welve paired concentration measurements (l) 

### determine the mean transpon efficiency . Q uanti t ative 

### Spiki n g: An 

### aerosol containing a surrogate metal or a m etal analyte can be spiked quantitatively into the sta ck or duc t ga s stream or in to the tran s pon system**a~** 

### c lose 

### as po ssible to the sampling probt. The concentration may b e measured on the CEM S o r by using me t hod 29 ora suitable alternative as close as po ssible to the sampling module. Thi s 

### measurement i s then compared with 

### the known concentrdtion of the s piked aerosol to detemt i ne the percent transport. 3.1 . 6 Dual Tt-ain Requirements 

### If you use a reference melhod (eg . , method 29 or Si) during th e linearity , relative b i as, or transpo n effi cien cy tests it is recommended that you use dual trains to screen the reference method for bias and imprecision. 3.1.7 Crde Time Requiremems 

### The cycle time for your XRF multi-melals CEMS should be 

### n o greater than one-third of the averdging period for the applicable standard . During all phases of tbe performance specification test including the CEMS must use the same c ycle time as will be used d uri ng day to 

### day operation . 3.2 How do I rep ort the results qft h e initial peif ormafl ce specification test? 

### Summarize the**es ult~**  

### of the c a li b ration drift and accuracy tests in tabular form. Include a ll data sheets , calculations, and records ofCEMS measurements nece ss ary to substan tiate th e perfonnance of the CEMS a nd any other dev ice s or methods (e.g. , method 29) . The C EM S Pnge 12 of30 

## VES009929measuremc01s s hall be reporte d t o the agency in u nits of 11ghn ' on a dry basis, corrected to 

## 2o•c . 4.0 P e rf o

rman ce Criteria and Calc u l ation s 4.1 What 2Nllht! pPrfarmance criteria for my XRF multi

- metals CEMS? You must demonstrate that your 

### XRF multi-metal 

### CEMS has adequate stability , precision, accumcy, cycle tim e and data reporting capabilities to detennine if your facility is in compliance w ith metal emi ss ion standards or opemting permit I 

### units us specified in applicable regulations or permits. You wiU demonstrate this capacity by showing that your XRF mu lti -metal CEMS meets th e following performan ce criteria. 4.1. J 7-day Drift Check Criteria- Stability U

p scale Drift : The u pscale drift 

### us calculated 

### in sectio n 4. 2 .8 m ust 

### be le ss than 

### I 5% of the o ri ginal ca l ibration value ofthe upscale reference each day for seven consecutive days . Zer o Dr ift: Th e ze ro drift as calculated in Section 4.2.9 must be les s than 20% of the emis;ion limit each day for sev en consecutive days . Volume or Fl ow**Drift ~**  T he volume or flow dri ft as calculated in Section 4.2. 11 mu st be l ess t hen 20% ofthe full >Cale value of the flow or volume measurement device each day f or seven consecutive days. 4.1.1 X - Ray Fluorescence Calibration Dri}i Criteria For eac h metal measured by your multi·metal 

### CBMS tor compliaoce purp.,.;,es the xray ;luorescencc calibration drift must be les s than I 0% of the vdrue o f the standard. (N01c: you are n ot req u ired to cal cula te th e XRF calibration drift fo r tho se metals used during the bias and precision testing). 4.1.3 Relative Bia s Crite ria
- Accuracy and Precision The relative bias of the instrument must 

### be Jess than 15% and the relative percent s tandard devia t ion (RSD) must be I 0% or Je ss if you challenge t h

e 

### :A'RF an d sampling modules of your CEMS separately from your transport system . Ifyou challenge your entire CEMS and it do es n ot mecttb e above re lativ e bi as criteria you m u st apply a correction factor to the results reported by your CEMS. The cor.ection factor i s calcula t ed using the equation in section 1 4. 2. 13. Al so, the correl ation coefficient for 

### a least square s linear regression fit of the metal that was spiked at three diff ere nt co n centra ti o n l evel s mus t be g reater than 0 .90 . Thi s is to help assure that the correction factor 

### is applicable over the range of the inStrument.

Page 1 3 of 30 

## VES0099304 .1.4 Line arity Test C 1 i reria
- Acc11racy and Precision 

### If you choose to do linearity tests to determine the accuracy and precision of your XRF mulli

-met a l

s 

### CEM S tb e s l op e of the l east squares l inear fit sho uld be 

### between 

### 0. 85 and 

### 1.15. The correlation coefficient must be 

### 0. 90 or better 

### and the intercept s h oul d be 

### less than 200/o ofthe applicable em i ssion li mit. If you challenge on ly the XRF module and the sampling module of your CEMS you must 

### meet th e above criteria. lf yo u challenge 

### your entire CFMS 

### and you do no t meet the slope or intercept criteria you must adjus t the results reported by your 

### CEMS , yo u must h owever. S till m ee t th e correlation coefficient criteria. The correction facto r is 

### calculated according to the p

roce d ures 

### in section 4 .2.12. 4 . 1.5 Transport cfficil!llcy- Accurac y 

### ff the average tran s port efficiency is between 

### 90 and I I0 percent, 

### d1en no correc ti on for tr.lnsport efficiency needs to be applied to conc e ntrations repo rt ed by your XRF multi-metals CEMS. If, however, your average trdll spor t eflicienc y is le ss t han 

### 90 percent or more than 

### II 0 percent then you must 

### use a correction factor. You may use y our tran s miss i on eft l ciency t est data t o establ ish a correcti on factor that would change the r(J>Oned 

### CEMS concentrations for eac h metal to 

### a value that would reflect 

### I00% tra nsm i ssion efficiency . 4.1 . 6 Cycle lime

- Appropriate Reporting 

### TI1e cycle time for your 

### XRF multi-metals 

### CEMS must be 

### no greater t h

an on e-th ird 

### of the averaging period for the applicable standard . 4 . 2 Wh01 calclllations, eqllat/ons, and data analyses un : needed? 4.2.1 Arit hm etic Mean 

### Ca l culate tb e ari thmetic mean ofa data set as follows.

- 1 "\'**~- £...,** **,** n Where: x • 

### Aritlunetic mean 11 • 

### N u mber of data points 

### x

1**~** 

### Value ofeach data point Eqllati o n 1

P ag e t 4 nf30 

### VES 00993 1

### 4.2.2 Arithmetic Mean of Differen ce To ca l c ulate th e arithmetic mean of differenc e use the above equation substituted for 

### x. Where Equation 2 Where : 

# cfE"'s - The co nc enttation 

### of the i'h element 

### as reported by the CEMS R,

.. ,**~** The concentration of the 

### ; do element 

### as reportoo by the ref erence method or aresol 

### 4.2.3 Standllrd 

### Deviation (of differences)

. Equatio n 

### 3 W

he re: 

### SD; = The standard dev i ation 

### of differences for the 

## i"' element n = The number 

### of data points d

1**~** The difference between the concentratio n measured by the reference method or the conc entrati on of tlte reference aerosol and the concentration reported by the 

### CEMS. 4 . 2A Per ce 11t relative sta11dard 

### deviation 

### SD . PRSD , =:=l-><1 00 RIW



### • Where : E quation 

### 4 

## R:U'**~** The av erage of the reference method data se t or the reference aeroso l concentration for the i 'h element 

### PRSD, = The relative percent standartl devi atio n for the j'l' metal 

### 4.2 .5 Relative Bias 

# ld.l PRB . = =x !OO I Rlt.ll I Equatio n 5
Page 15 of"\0 

### VES009932Where 

## d 1 is th e mean difference, 

## R ,"' is the average of tbe reference m e t hod data set or the average aeroso l concentration for the itb element, and 

### PRB 1 is the re l at i ve bias for th e ith e l ement 4 .2. 6 Percent Transmission 

# c - PT,**xiO(I** 

# c

, Where: 

# c

t .. Concentration of the ilhel ement at the stack E quatio n 6 

## c:M**~** Ccncentration of the i"' element at the samplin g mod ul e or as reported by the XRF multi

-metals CEMS. 

### PT, "' The percent transport of the i d! eleme nt Report the average p ercent transpon ( PT) of aU measurements for each element that was tested (only one element is requ ired though more can b e te s ted). 4. 2. i B est 

### Fir Li11e for Li11eari ty T est Calculate th e linear correlation equ ation given below . 

## y .: b . + b , x Where: b. • The y intercept b o = The s lope The inte rcept is ca l c ul ated according to the following equation . 

### b

... Ji - b , x Where : I • 

### i= - 

# l: x , n ,_ ,

The slope ofthe line is calculated according to equation below . Eq ua tion 7

Equation 8

Pa

ae 16 of30 

### VES009933

## • 

# :L/x,

- x)(y, - ji) 

### b

, = J=LI

_ _ _ _ _ _



# i: rx,-xf Equa1ion 9

1-J Tbe linear correlation coetlicient is ca l culated according to the follow i ng equation .



### ,. = -;: :of'";<,'====== Equation 10

- t I! 

## :[< x, -XJ' I:( y,- Yl' 1• 1**~~** 4.2 . 8 Upscale 

### Drifi 

## I 

# L

- L • j UD, .. 1

- 1 

### xiOO 

# L

: Equa tion 11 Where : 

### UD , = The up s cale drift of the i'h element on your C EMS in p ercent.**~"** = The meas u red CEMS response t o the i " element in the up s cale s tandard 

## g = T be calibrated value of the ith element of th e upscale standard


### :1.2 . 9 Zero D rijl 

## [L;""'**~I** ZD ,= L 

### xiOO 

# c, Equ ati on 12 

### ZD; = The zero drift of th e i * element on your CEMS in percent 

# L

-:- = The m eas ured CEMS**re.~ponse** to the zero standard for the 

### i'b element**L~** The calibrated value oftlt e 

### i'" element on th r zero s tandard C

1 L The emi SSiO n limit Ofthe i t> element 4.2. 10 X-Ray Fluorescence Calibration A ccuracy

Page 17 of30 

## VES009934E quat ion 1 3
Where : 

### CA, c X-ray nuon:scence calibration accuracy 

## L-;- The vQlue of the st1111daro reported by your CEMS 

## L;"' e The kn own value of the s tandard 4.2. I I Daily Sampl e Volwne Ch eck 

# I V.- -V--1 VD= x iOO Equation 14 

### FS Where : VD m Volume drift 

### V" "" c Sample ga s vol ume (or now) measured by the CE MS volume check measurement device 

## v.. E Sample gas vol u me (or llow) reported by yo ur multi-metal CE MS 

### FS = Full seale value of the CEMS volume (or now) measurement dev i ce 4.2.12 Linearity 

### T cs 1 Correction Fa c tors (Appli c able on()' 

### whe.111he li n ea rity 

### les t r.hal/enges th e entire 

### C E

MS) I . Correctio n equation if CEMS does not meet either tbc slope or the intercept crit eria. C ( - y,- b,

I - 

### b , Equation IS Wbere:**C~** N corrected CEMS concentration for the i llo clemen t y, c CEMS reported concentration fo r the ill! element bo = the intercept ofthe least squares linea r regression line b 1 c t h

e slope of tb e least s qu ares l i ne a r regression line 2. Correction filctor i fCEMS meets intercept crit e ria , but d oe s no t meet the s l

ope criteria.**Po~e** 1 8 of30 

## VES009935c 

### Y· 

## c =__!..

, b I Equation 1 6 3. Correction factor if CEMS meets slope criteria but doe s not meet intercept criteria. Equation 1 7 

### 4 . 2. 1 J 

### Relati ve Bias Corr ec

tion Fac t or

s Equation 18

Where: 

## CF /"**~** The rclutive bias correction factor for the i"' el ement C,w• = The average reponed concentration of the C EMS for t . h

e i

tlo element 

## R

, "" Th e average ofthe reference method measure m ents for th e 

### i

'" metal



### 4 . 2.1 4 Per cent transport co r rection factor YT I 

### CF, == 

### PT, Equa tio n 19 Where 

### CF, " Correct ion factor fo r pe rcent transport for th e i 0 ' e l e ment PT , = Average p ercen t transport for the i 1 11 element

Pag e 19 of30 

## VES009936

### 5.0 Otbtr R equireme nts an d Information 5.1 What 1uality co ntro l measures are required ? 

### Qualit y control meas ure s for a n 

### XRF mul t i-metal 

### CEMS are a ddressed in procooure 

### Z "'Qua lity**A~sur.mce** 

### Requirements for X
- Ray Fl u orescence 

### Based Multi

- M etals Con ti n uous Em i ss io n Monitors ." 5.1 What calibratio n and standardization procedures must/ perform ? 

### Refer to 

### yoJr C E MS owner's manual and manufacture r to determine what calibration a nd s tandardization p roce d ures are requ ired f or yo ur m ulti -metal CEMS . 5.3 What JX)llution prewmriott procedures must/ follow ? {reserved] 5.4 What wasre management procedures mt<St I use? 

### AU chemica l s used to produce a ref er

ence aerosol or in 

### p erformi n g standard methods n eed to be disposed of proper l y. 5.5 Who : reference ta bles and figures ore relewmt to PS-YY?**Pa~e20** 

### of30 

## VES009937Ta b le l. 

# s lfi ti T d C" l nlhal P er o rman cc Specl 1 ca on ests an n te n a T est Test T es t Require m en ts T es t C ri teria Ca f i!I:OI"l ' Zero Drift Monitor UrO standlttd for 1 <**~** dnfl<very day COr sevm con secutivt days under nomual ClOOse.. "'Uri ve days ODenltine. coodi tio n s Seve n D a ! · Upscale Drift M oai10< ups<ale slandanl f« 7 <**15~** dril\ fNUY day for $-eYm consecutive days u nder n ormal coosecutivc days Stability oper• t ins. cooditloni Flow Drifi Moni i or now dnll lor 1**c:on~urlve** .... 20% dfin every day for**oo~n** days under nom101l opcming**~cloys** conditio n s X

- Ray Fluoresce.uce Te sraii&IOO a td fo r c11.ch elemen t < I 0% d rift f or every clcnk' n t Calibra ti on Cahbration Drill Cbeck l!le<I$UIOd for complianox by yoor 1UC&s-Jnd: for compliance by CEMS3 times ' vourCEMS Opt ion A • At**kt~ l**  o n e m ct11l fr om**~c h**  

### • Sl>po @ o. g

s to 1. 1 

### s ea 1 egoty 

## •**r~0.90** Perform a li oear try tc::st on • Keed at least 3 conc:en -rra !ion 

### • i.Jtcr«opc. < 2<M ofr:n'lission ea 1ire C EMS le ve ls wbic: h inc lu de a 2 fold lmi t cone . ('haltge and the em i nio n limit 

# . iftbt- above criteria are me. 

## • lfspiking. spike into SOW'\:(!, or- tbeu no «<trection

sp ik e i nto tran s p o rt line 1u1 close 

## • i f n o t met ap p l

y u. correcri oJ • as J>O<>ilil< . 10 1 bc probc (coo-elation critcriunust be o:<t) QptjonB • At**t** one m etal fro m t-ach UnotriN Crit e ria**cat~gory** 

## • Slope

- 0.&5 1 0 1.1 

### s • Perfonn a llneMry test 

### • Need ot lc 3St l concc:ntrLUion 

## • ra,0.90

<m !lam t >1i n g mod ule le vels whi ch i nc lu de a 2 fol d 

## • ilt erx:cp t < 2 0% o f e • ni ss1on snd XRF mnd ule oo l y cone. c:h&nge arw:l th e emiss io n liruil 

### • Otrenmne tranSpOr1 1imh 

## • de J.inQriry etheria IWSI be

efficiency separutdy • S pike or m ea sure**«~nccntna.tions** 

# .... w ith**refere~** meth od ftB c l ose as**)~ ~n!**  'f l :l!D:IQQ!l**Ctil~li !!**  po$Slble to ' he iac npting moduk 

## • SOSI'T S IIO 

### • Jr pen.'ettt t ran spon criteria Accu r acy are noC' 1001 app ly a cooe eno n fite 1 . or OQtion C • At kost ooe mcUI from each Perren• relallve BiM c.ue gocy <'If 80 to l 20 percent o f 1W ;£ L S Y. Perfonn a r dati vc**b~** t est emiss ion limh o/oRSD S 1 0% on enlft CE.:\fS • One olhe.-.neul ot 3 con< . le>'ds whic h mclude n 2 fo l d cone. •**90** for metal v.ith thTet c han ge a u d llt t> e.

mi.s$ion limn l O

id oonc c: h nnge 

### • If spiking. spit• into SO<Jr<e .,. 

## • " f CJit erla no t 1'0Cl apply a spike into mmsport li ne u do5e**torT"eC~ion** facwr (COI'Ydation as J'(lStnble 1 0 1bc prObe ooet licic n t entail must be me l) OptionD • At**k-a~** one ntd&J tfom each fgootl Rcb ti \' e 8j111 C riteria cateJOfY a t SO to l:W pnceut of RB!;IS% 

### • P erfo nn a re l.:uive b ia s cm iiiSkln timi t**RSD ~** **~/e~ c~**  on samplirtg • Oae o ther tl'lt'illliU 3 cone. "=veJs r := 0..90 fnr rt)dal 'il ' ith three: module and XRF ·which inclu& 1 2 fold cone. . modu le on. ly chan ge w 1 d the em i ssi on lin'i' fo ld cone . 

### mange • Dci..:mline n n q'IO!l 

### • Spike or measure conoentru. lions J )Q"Ct!!l fuuspnrt Criseri a c ffici<ocy**sq>~~Oidy** with n:fr:rmce method a_.;: close a..;; •**9D$PT ~J**  10 pMSib l c to the Jtu n p li ng module • If percent mnsport aiteria are

-00' met**apply~** co-l'fl'!Ct io n fac-tor Page- 2 1 of 30 

## VES009938

### Quantitative Spi kin g 

### Method s o f M etals Ge n erati on for A<:c ur acy T ests



### ' o nQuantitative 

### S p iking F ig u r e J: Types o f metal s generation available for acc u racy te$15. 

### Sta ck O p e ration

Pag" 22 of 30 

## VES0099 39Quut1 rarive**Spikht ~** 

C111ll**~lll~l:"l.!imlly** itlt() tflq 1 111ck or 11'1 1 0 !be**11111~1)(1 "** **t)1iiL1IIU~ill~tOthc** A!fFic P\)bc:'f



### v ..**ClloUo: ~at**  die tnti r t**bltl~ll li-~** **cmlt** Sy.: l('til , No**~~ .r**  ftllri!JM tft''lcicwy .

C'tn I Jf.Mfii i C"**~-·1+1•20%** c(**~** •rrdtiiO Rill ..., 11**C\'1~ ~**  ll'lt1lll rrom UCih elMS mch!.ln::d

.,. a:y C't..\G'!
Y

c•**Cllllg~:J~er~l(** ) fOC'ft!'!l .... '":'tk (-.)("..me ct'l'ltCfll frOM cad! cL.• of

mct1ol lil \d}'W rllCIIMl iCl d by my

C£\fS.
..**~(1M** kvtl**.~ tJ~**  2t»:.urtbo: ('fll h> 1ion 1 1 1\lh'l Can I Spllo.• t

nto the v ...**spot~** ll)'tk: U'I cklte**-~** 

# ..**..,.-.~1**

Y

e• \'ou**CMd!ll~ &heP~I'!ptlt-~** **llt:CI6ak-~h---~**

(lllniQnO ( )'OI !f b;irtCh M M CEl.t$ Jtfllh!lt!y f h : wu 4lw**~')'$liD.** t.o..· nu, )IOU "' · UI alto h3YC 110 llrb:rm!.t

t n.Mport**lll clttlcy** **,**



### "'" 

# ·-)

<Ofi:Wltr.l!ion k'fCU r .... til k ll i! (Wil tiiM I )"' C' Ul**foro~** that e:JO**~**



# ............. O:M S? N No

Yw**~~~: !!d**  10 1ry a l.f.ft'no.;Jtt li J'fll 'oodl,

Figure 2: Fl ow chart for using quantitaliv<' spiking during tbe accuracy tests. Pag e 2 3 of 3 0 

## VES009940c ..**,~.._,Y** ir'trl' ...**~** )lririM Ike**"riM~** i")'-lf l IUiooo:' "o1$ pCS.O I I) I

c t•lfut 1 /l.ll'(llotf)t'* ' !**01'11 ..-n~MI(tl,l** **__..-_i:I,..~UC".kor•llw** uaor.,_. •7'*""**~Y** .ftcr**W:tt~i'. iln~~.-** **ll**

Y

es**Cl" ~**  I I C en a i re bft l'- 11 M u -i.. M O

I IIkS)I\( \. 'I'n.**Nob'l~ l**  ,.

...

6wl f "tn11J611C" t'!liriMty.

v••

Ya 

### i 

# l 

# l No



# I i



## ..... . .**~**


## 't•-.**dl lc** **~** IN .u• ""'llll**)k~ U.** **~** tw!C'l po !l 11 !¥11 lll •lr.- o.:r flOI't \41 1! ol ' y O'llr N!C . h MM (,_ ' JiMS**~a ot)'**  froll'l t he**~TM'Kp!lf l**  f )'ll t,m ,**b~ .**  yo u. wi:l l .t.o tuwc to**~~("~ .** 

(Ill! I .,_,.) hi ¢CZd>AiotR k'\ltt•IOr**(IO'IC ~­** **n..~** ... 

### QMII- 

# ( .h.'II$Un:d <I ll die CI:.MS! No

N

Fi gure 3: Flow chart f o r u sing n o n -q uan tJtati ve spiklo . g d u ring th e a c cu racy t ests.

Page 24 of 30 

### VES009941M e u. l . s Ge n e r ated During Stac k Op e rati o n



### Ye s

Yes

Yes YQ u m ny usc ei l he r lin eari t y**inw** ot reln ti ve bio s, You oecd 10 usc a diff'e . mn m ethod to jlt.'Tlctat c m e hds .

Yo u mus1**u~e** relali vc bias,

Figur e 4: Fl o w c h a rt f01 · usin g stack operation to ge n e ra t e m e tal s c oncenlralioo s . Page 25 of30 

### VES009942f' M 

### Mea su rment Trans port 

### E ffi cienc y

Choose 

### Species

Elem e nt o f Oppo rtu nity Fi l,'llr e S: S peci es a vail able for tran s port t es t s 

### S p i ke

Page 26 of30 

## VES009943P M Meaounncnl**>--- -~** **----.**

y.,

Utt Mchod S, S i or I 7 10 r nu

.. wn PM cone . at tbc \wk atd • )'OtX C'DtS.**Ct~kuta;e** tron:;pon c-Olclc n cy .

Yt<**Na~~isacte$$U)'.** VOAJ 1\:• vc c.ompkted lllo**ll'll~n dt** **icil: ~**  test 

# " You nwn eslilblh h a contbtioa to**~~fo r**  tnlllspon cffic icnc)'
.



### Figure 6: 

### Procedure f or percent trans por t u sing Pl\1 .

Page27 of3 0 

### VE S0 09 9 44Yes Oft1)at0 CD'IC80llltion on or neN

the**I<S** vmh !he**oo nce~tatlon**  meowreo oo lhe KocJ<. Calc>J ia<e

tra.n**r~~tt~**

Yes No CO I 'I'CC(_ '(In f'accor IJ: lh."CCUO I )'. YOIIlr.\ ' c toq)I:Ck'd t lw**~** e!fi ci c oc

y tc6t. No

You m u:sl L-,tnb l i .\h 11 co mtatlon to comcl f« tran.spun**cffi o:k** **~~ey .** 

Fi

gure 7: Procedure f o r percent tra n spo rt det ernti n alio n u si ng a n element of opportunity.


### Paae 28 of 30 

### VES009945v ..



# ...

Ye o re 11\o**!)Otloet~rt!Xln** an m,.... '" ce.cs**~** .,.. c.n::EnlriiQ'!IIKli(iilftd

at the s t arJ., Celobtt t r ansport**~l'ic le** **l'lt')' .**  No!\• Q II : IIIIJIIlli \ -c Sp! I: C:**$¢ ~1**  l rm,pott l i 11 e- •**coo ~**  }lee:•" '' Sptd.':s**YC!UittC!o1l~e ~;.,.**  10 \IU(M:t rOJ • · , -np ort cofl ich!llcy.

Fig u re 8 : Proced u re of perc e nt transport de t erminatio n using s piking.**$dtt~** Ill $mo(k Of**~NcwSrc:tlos ag~29nf3** **0** 

## VES0099465. 6 What r-eferences apply ra PS
- IT? 1 . United States . Enviro nmental Protecti on Agency [E.PA) . Technology Tmnsfer Network. Emissio n Measurement Center. Promulgated Methods. Medtod I: Sample and Velocity Traver ses tor Stationary Source s. Washington , D C: EPA; 2004. Available: http :// www.cpa.go\'lt1nlemc/ promgate/m

- OI . pd f via the Internet. Accessed May 

### 8, 2005 . ii U nited States. Environmental Protection Agency [EPA } . T echnology Transfer Network. Emission Meusuremcnt Center . P romulgated Methods. Method 2: Deter:niuation 

### of Stack 

### Gus Velocity and Volumetric Flow Rate . Washington , D . C: E PA; 2004. Available: http :/ fwww.e pa.gov / nn/ emc/promgar c/

m-02.pdf via the Internet Accessed May I 0, 200 5. iii. Uni t ed States. Environmental Protection Agency [EPA ). Technology Transfer Netwo rk . Emission Measurement Center. Promulga t ed Method s . Metbod 5: Detenninarion of Particulate Matter Emissions from Station ary So • Jrces . Washington , DC: EPA; 2004. Available: hnp: // www .epa.gov / nnlemc / promgate 1 m-05 . pdfvin the Internet. Acce ss ed May I 0, 2005. iv . United Stat es. Env ironmen tal Pro t ection Ag e ncy [EP A] . Technology Transfer Network . Emis s ion Measurement Center. Promulgated Method s. Method 5i: Determination of Low Level Particulate Matter Emissions from Stationary Sources. Washington, DC: EPA; 2004 . Avai l ab le: http: //www.epa.gov/ hwcmacl/frhwcS .p df via the Internet Accessed May I0, 2005. v. United States. Environmenta l Protect i on Agency [EPA] . Technology**'fran~** fer Network . Emission Measurement Center . Promulgated Me th ods. Metbod 1 7: Determinat ion o rP"rticulate Maner Emissions from Stationary Sources. WashingtOn, DC: EPA; 2004 . Available: http :ffwww.cp a.gov / ttn !e mc/promgate/m

- 17. pd fv ta the Internet . Accessed May I0, 2005. vi . Un ited S tates. Environm ental Protection Agency [EPA]. Techno logy Transf er Network. Emission Measurement Center . Promulgated Methods. Metbod 29. Detennination of Metal . s Emissions from Srationary Sources. Washington, D C: EPA; 2004. Available: http: //www.epa.gov / ttn/e m c/promgatc/ m - 29.pdf via the Internet Accessed May 

### 18, 2005 .

Sp.-orifitcioN for XRf**t-.hth ldU**  CEMS ( PS- Y Y) Pag e**~0** of30 

### VES009947

# VES009948
. pdf

## VES009948

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

Prep ared by: Coop er E n viron m ental Se r vices, LLC 

### 10180 SW Nimbus Blvd Suite Jb 

### Portland. Oregon 97223

Ju ne 9 , 2 005



## VES009949

## VES009950

# Procedure Z: Quality Ass urance R e quir e men ts for X-Ra y -Fluor es cence Bas e d Multi-.Metal s Continuou s E mi s sion M oni t oring Sys tems at Stationar y Sources

Pr e pa re d by: D a te:

_ _ _ Kr ag A . P ette rs o n , Env i r o n mental Sc i e n tis t R eviewe d by: 

### Dar e: __ _ Cay A . Ya n c a, En v i ro nm e nt al Scie n tist R e . vic we d b y: 

### Da re:

_ _ _ Br u c e 

### E . J oh n s o n , QA M a na ger A p prov ed b y: 

### Dare:

_ _ _ J oh n A . Cooper , D i r ecto r



## VES009951

### E x ec utiv e S umma ry Procedure Z outlines the contin u ing quali ty contr o l and q ua li ty ass u rance re qu irem eniS f or an x - ray fluorescence ba sed multi

- metal C E MS. Procedure Z requires daily c h ecks o f til e u pscale , zero a n d v olum e me as u re m e

n t d ri ft . 

### It a lso spec ifi es q u arterl y c he c k s of the x- ray fluorescence calibration and oft he volume measurement ca l ibratio n . F i na lly procedure Z requires that the entire XRF mu lt i metal CEMS acc u racy be verified on an annual basis.

Page i ofiv 

### VES009952

### b. b , = 

### CA 1 =

c 

# c, = 

# c cCOIS _

I -**~o r**  = 

## CF;PT = 

### CF,RI = 

# c,L = 

# c

,s = 

# c:- = d, 

## = d = 

## FS**L~** 

## c-

• =**L~ ·IU!J** **~-** 

# ' = L, "" = 

## c, = 11 

## = PT, = 

### Llst of Symb ol s They intercept of the best fit line TI1e slope of th e best fit line X -ray fluorescence calibration accuracy C

orrected CE MS concentrat ion for the i"' clement The concentration of th e i ' b c le ment as reported by th e CEMS The average reporte d concentration of the CEM S for the 

## i" element Co rrection factor for percent transport for th e i 11 ' 

### element The relative bias correction factor for the i' h element The em i ssion limit of the i"' element Conc entration of t he i<h e lement at th e stac k Concentration of the 

## f' element at the sampling module or as reported by the XRF multi-me t als C EM S. Difference b etween two pair e

d measurementS Arilhmetic mc-uu of differences 

### Full scale valu e of your CEMS volume (or flow) mea surement devi ce Tbe calibrated value of th e i 'h element on th e zer o s tandard The va lue of the 

### standa rd reporte d by your CEMS T he mea sured CEM S respou se to the zero standard for t h

e i' h element The measured CEMS response t o the i' h element in the ...,sca le stan dard The known value of the XRF calib rat i on c heck standard The valu e of the i' h 

### elem ent o f the up sca le sta nd ard Number of data points T be percent trunsport of the 

### i 1 b 

### element

Pas " ii o fiv 

### VES009953PT , PRB , 

## R "''

I

r SD; =**~**

= = Av erag e percent trdllSport for the i 'h e lem en t Perce n t relative 

### Bias of the i lh e lem e nt 

### The average of the refere nce m ethod measurements for the 

### i"' 

### metal The relative percent SI>Uldard deviation for the i'h metal Th e c orre l ati on coefficient 

### The s tand ar d d ev i ation ofdi ffere n ces 

### to r th e ilh c l ement 

### Va.., Sample gas vo lume (or flow) as measure d by the CEMS vo lum e check devi ce 

### VD 

# v., UD, X X; =

= =

= Volume d ri ft Volume (o r flow) reported by your mu lti -meta ls 

### C:EMS The upscale drift ofthe i'h element on yo ur CE MS in pe rcent. Arithmeti c mean Va lue of eac h da ta point CEMS reported ooncentmtio n for the ith element The zero dtift of t he i' " c l ement on your CEMS in percen!

Paee iii of iv 

## VE S009954

### Tabl e of Con te n t s Executive Summal)l .. .. . ......... .... .. . .. . .. ... .......... .. ...... . ... .. . . ........ ... ..... . ... ... ..... - ... ... ......... .... ... .. ... . .. i List of Symbo l s .. ... . . ........ . . . ... . ..... . . .. .... . .. .. . . .. ... . ... . . . . .... . . . . . . ... . .. . ... . . .. . .. . .. ..... . .. . .. . .. .. . .. . . ...... . . ... . . .. ii Table of Contents ................ . .. .... ..... ....... ........ .... ......... .... ....... .. ........... ... .... - .... .... .............. . ..... iv 1 . 0 I Js ing Pr oc edure Z .... . . .. .. . . . . . ... . ..... . . .... ....... ...... . . .... . . . . . .. . . ... . ... . . . . ... . .. ..... . . . . . . . .. .. . . . .. ... . . . .. .. . 1 

### 1 .1 What is the purpose a n d applicability of Procedure Z '! ...... ....... ...... ..... ....... ..... ........ I 

### 1 .2 Wh a t are th e basi c requ irem en ts of Procedu re 

### Z? . .. ... . . . ... . . . .. . .. .. . . .. .. . .... . .. .. . . ... . ... .. . . . . I 1 .3 Wh at s pec ial d e fini t ions apply to procedure 

### Z? ... . . .... ........ ..... ....... ........ ... .... .......... .. I 2. 0 I nterference s , Safet y, an d Eq ui pment R equ irem ents . ... .. .. . . ... . .. . ... . .. . .. . .. .. .... .. .... .. .... . ...... . 2 

### 2.1 W hat in t erference s are associated with procedure l '! ... .. .... ... .. ... ........ ..... ........... ... .. . 

### 2 2.2 W hat do I ne ed to know to ens u re**th ~**  sa f ety o f p ersons using Procedure Z ? . .. ... . ... . 2 

### 2.3 Wha t equi p m ent a n d s u pp lies do 

### I need? .. .. .. .... . . .. ....... ..... .. .. ...... .. ... ... ... .... .... . ... .. . ... . 

### 3 2 . 4 W hat reagents an d s tandards do I n eed? .... . . . ....... . ......... . . . .... . .... . .. . .... . ..... .. .... .. .. . .... ... 3 2. 5 Wha t sa mp l e co llect i on , preserv ati o n , storage, and transpon p rocedures a re relevan t to P rocedure Z '! ... .. . . ..... . ......... . .................. . ............. .. .. . .. ...... .. ... .. .. . ............ . . . ... .. ... . .... . .... 4 

### 3 .0 Quab t y Co n trol, Ca l ibration , a n d St.and urdizarion . .... ....... . . . . .. .. . .. .. .. .. .... ... .... .. ..... . ....... ... 

### 4 3.1 W hat q u a l ity contr o l me as u res are requ ired by thi s procedure for my m u lti

- metal CEMS ? .. . ... . .. ... .. .. ... . . .... . .. .... . ..... . ... ... .... .. ...... .. ... . .................. .. .. .... .... .. .... ...... .... ........ .... ... 4 32 What calib ration ch ec ks an d a udi t p roc edur es mu st I perf orm f or m y mu lt i

- m e tal CEt.IS ? .. ...... ....... .. .. .......... ... ........... ... ......... .... ....... ....... ....... ..... ......... .................... ... ....... 4 4 . 0 Ca lc

u l at i o ns . . ......... . . . ...... . .. . . ..... . . . .. ........ . . . .. . . . .... . . . ... ........ . . .... . .. . .. . . . .......... . . ..... .. .... .. .. .. ... . 7 4 . 1What calculations and data analysis must I perfomt ? ........... ... ...... ..... ...... ........ ...... .. 7 4. 2 Wh at w aste m anagement pr o cedures are re qui red f o r pro cedure Z ? .... .. . ..... ... . ... .... 1 3 

### 5.0 Other Requireme n ts and I nformation ......... .... ....... ................ . ... ....... ... ......... . ... ......... .. .. 

### 13 5 . 1 Wbat poll uti on p reve n ti on m eas u res mu st I ta k e w h en usin g proced ure Z ? ..... ... .. . 1 3 5.2 W'hat c riteria a re necessary fo r my XRF multi

- meta l CEMS to be in control and wbat d o I do if i t i s out of contr o l ? . .. . .. ..... .. . .. ... ..... .. .. . .... ... .. .... ... . . . . ... . . . . . ........ .. . . ... . ... .. . . 13 5. 3 What tab les, diagrams and flow chans are relevant to Procedure 

### Z? .............. ... .... . 16 5 .4 Wh at re fer e n ce s 

### are re l e van t to P roc edu r e Z? ... .. ..... . . . . . ... .. ..... . . . ..... . ....... ... ..... . . . . .. .. 18

P

a ge 

### iv of 

### i v 

### VES 009955

### 1.0 Using Proce du re Z I . I What is 

### tile pwpose and app/l cabilily 

### of Procedure Z ? The**purpo~e** o f Procedure . Z is to estab li sh the minimum requ irement s fo r qua lity control (QC) an d quality assu ranc e {QA) procedures for x-ro y tl uore sceoc e (XRF) based mu lti

metol< <:F.MS. These quality control and quality assurance procedures are in pl ace to ensure th e ac curacy 

### and validity of the data reponed by your multi-metal CEMS 

### tor errussio n comp lian ce purposes. You must m eet these mi n i mu m requirements if you p l an to use your multi

-metal CEMS for reponing purposes, however, we encourage you to develop 

### a more e xtensi ve QA progra m or to co n tinue with such pro grams where th ey a lr::ad y exist. Any 

### XRF multi-metals C EMS used to repo rt to us. tl1e state, or a l ocal enforcement agency must comply with procedure Z immediately after the completion of the initial performance spec ifica tion test outlined in Performance Specification YY'. I .2 What are 

### rhe basic requiremems 

### of Procedure Z? Procedure 

### Z requ ires you to per fo1111 several drift checks and audits wh ich e n s u re t he accuracy o :" the data reponed by your 

### XRF multi

-metals CEMS . You 

### are required 10 , on 

### a dai ly basi s, record and calclt la te zero drift. upscale drift , a nd, a sample 110 lume drift. On a quarte rl y bas is you are required to perfo m1 an XRF ca libratio n au dit (XfC A) and a s ample volume audit (SVA). On an annual basis you are required to exec ute either a linearity audit (LA) or a relative bias a u dit ( RBA) and, if applicab l e, 

### a transport efficiency audit (TEA). The criteria for passing th ese au dit s an d drift check s are outl i ned in procedure 

### Z. Proced-ure Z also swmmrizes the requirements for when and if your CEMS fu i ls an audit or drift te st FinaUy, Procedure Z also covers the requireme nts for an d time lines a ssoci ated with periods when your XRF multi-me tal s CEMS is ou t ofc ontrol. 

### 1.3 Wh((( specit1/ cle/illitiuns apply tu procedure Z ? Linearity Au di t: (LA) An assess me nt of the validity of the origina l linear corre lati on of yourCEMS . R efer ence material : A material of known value used to check the calibrotion drift ofyour 

### XRF mu l o- metal CEMS . R elatiVe Bias: The diffe.ence between a reference me thod or aerosol co ncentration an d the concentration recorded by your CEMS divided by the concentration ofthe reference measu reme nt. R elative Bias Audit: (RBA) An assessment of the bias in your C EM S. Sam p le Interface: The portion of th e CEMS used for one or m ore of the foll owi n g: samp l e acquisition from the**~1ack** or duct effiuent, sam ple transpon, sample conditioning, or protecti on of t h

e moni tor from th e effects of stack gas.
Page I of IR 

### VES009956Sam p le Module: The portion oftbe XRF multi -metal CEMS that !rapS t!e metals and d

e livers them to the x-ray fl uore scence modul e. Sta n da r d Yolume A udit: ( SVA) This is 

### an ev aluation of yo ur XRF multi-m etals CEMS sam ple vo lume measurement system. Thi s is required ifyour CEMS uses a vol ume meas u reme nt to re po rt metal concentrations an d is accomplished by co mparing the volume m eas ured by yo ur CEMS w i th the volume m eas ure d by 1 m independently ca librated de vice . T r ansport Efficien cy A u dit: (TEA) An assessment of the ll'ansport effiCiency of the sample interface of your m ul ti

- metal s CEMS. This a udit appli es to your XRF mllti-metals CB MS if ei th e r the R BA o r LA c hallenged o nl y the samp ling and XRF mo d ules . T r ansport System: Th e portion of the CEMS that trnnsports 

### a represe n tative samp le of source effluent from the sa mple p robe to t he s ample module. X
- Ra y Flu oresce nce C ali b ration A u di t : (XFCA) Thi s i s an e'' aluation of how weU th e xray fluore scence porti on ofyour m ulti-metal s CEMS h ilS maintained its original calibration. This is accomplished by challenging th e XRF module w i th a standard of kn own concentrat ion for each metal me asured b y your CEMS for co mpliance. 

### The analyzer response is compared with th e known concent.ration of d1e standard . X
- R ay F luo r escen ce M od o.lc: T h e portion of an XRF based multi

- metal CEMS which identifies and measure s metal m asses or co n centra t ion s using x - r•y fl u orescence . XRF Mu lti

- M etals C o nti nuous Emissio n M onitor (CEMS): All of the equipm ent req uired for determining metll l co ncentrations usin g x-ray fluore scence as an anal y

t icul tec h nique . Tbe system may cous is t of several major subsystems inc luding th e samp le interface, the x ray fluorescence module, the vo lume measurement module, diluent analyzer, data 

### recorder, and sampling m odul e. 

### 2 .0 Int er fere n ces, Sa f

ety , and Eq ujpm ent 

### Re quire m e n ts 2. I What i nt eife rences ar e a.w x; iated with procedur e Z? There may be interferences arising from the x-ray fl uorescence, the trappi n g media , or fro m co ndens ation in th e effluent gas. C h eck w ith your mu lti-meta l CEMS man u factur er to find out more a bout poten ti al i n terfere n ces. 2.2 What do I need to know to ensure the safety of persons using Procedure Z? l 'ersons us i ng procedur e Z may be exposed to hazardo u s material s, eq uipmen t , and operations. P roc edur e 

### Z does not purpor t to addr es s 

### all o ftbe safe t y ismes assoc iated with its use. It is your responsibility to establish appropriate safety and hea l m practices b efore u sing t hi s procedure. You may c.onsult wi th your CEMS manual and/o r manufac rurer for precautio ns SpL'Cifi c to yo ur multi-metal CEMS . If s tandard reference methods are used the n yo u may tlso co ns u lt the appropriate reference metbod s to addr ess sa fety co n ce rns .
Page 2 of 18 

## VES0099572.3 WhaJ equi'pment and supplies do I n eed? 

### [reserved] 2 .4 What reagent.• and s tand n r dv do T need? 

### Reference materials fo r the zero and up scale drifts along wi th a reference m easuremen t devi ce for t h

e samp le volume check . 2 .4.1 Ze ro drift referen ce 

### Every 

### XRF multi-metal s 

### C EMS must be equipped wi th a zero ref« ence that can be checked on a 

### dai ly basi s. This reference shou ld produce a 

### CEMS :e spons c indicat ing tJ1 e absence of metals. If 

### this is not**fea.~ib le**  

### lh i s st an dard s ho uld pro duce a val ue between zero and 

### 200/o of the emission lim it for at least two e l ements measured by yo u r 

### XRF multi-metals 

### CEMS whe n the instrument is operating appropriately. 2.4.2 Ups ca l e drift re ference 

### The teferenc e for the upscale drift check should generate 

### a response for at least one metal from each conditi o n us ed in 

### th e 

### XRF analy sis. This 

### r esponse must be at least 

### 80 percent of the emiss i on I 

### imit. 2 . 4.3 Sample vol ume 

### or flow check 

### If your 

### XRF multi

- meta l s 

### CEMS makes volume or flow mea s u rements it must be e quipped t o perfonn a daily sample volume check . 2.4.4 Sample volu me a11dit st andard 

### If your 

### XRF multi-meta l s 

### CE MS makes volume o r flow measurement s, period ic S

UUl d ard vo lume or flow a udi ts must 

### be perfo rm ed . An independent ly calibrated vo hrne o r flo w measur ement**de, ~ce**  

### or standard 

### such ns a 

### Dry**Cal ~**  is 

### required for these 

### auditS. The standard must be able to acq u i re 

### a volume or 

### flow mea surem en t a t s u

m

p

li ng rate s t ypical of your XRF multi-metal s CE MS. 

### 2. 4.**~** 

### X-ray Fluor esce n ce Calibrat io n Check 

### Standards You r XRF multi- metals CE MS must include a 

### means of c h ecki ng the x-ray fluorescen ce calibration against an external standard. NIST t raceable thin 

### film s tan dards are a n example of a s uitable x- ray fluor escence calibr.uion chec k stan dard . 2. 4 .6 R eagem s and stalldardsfo r th e Linea ri ty Audits and R elarife Bias Audits 

### You will n e ed other reagents and s tandards for th e 

### linearity audit or re l ative bias audit. 

### The regen ts a nd standards required 

### wi ll diffe r depending on how the se audits 

### are per fo rmed.
Page 3 

### of 18 

### VES 009 958

### 2.4. 7 Regents and standards for the Transport Efficiency Audit The regents and standards for tb.e transport efficiency audit also depend upon how the audit i s perfomled. 2.5 What 

### sample co llection. prese• ·va.tion, s torage. and transport pro ced ure.v are releva/11 to Pr <>eed ur

e Z? [r

eserved ] 

### 3.0 Q ual ity Co ntro l , C alibrati on , a nd S t a ndardi za tion 3. 1 What quality c ontml measur e

.v are required hy 

### this pro ce durefar "Y multi- metal CEMS? You must develop and implement a quality control program that, at a minimu m includes detailed written procedures for all ofthe follow i ng ac t ivities. I. Procedures for perfom1ing drift checks on a daily basis, including but not l im ited to , zero drift, upscale drift , and sample vo lum e measurement drift. 2. Procedures and methods of adjusting your multi-metal CEMS in response to tbe results of the drift checks . 3 . Preventative m ainte . nan cc ofyour XRF multi-metal s CEMS . 4. Data recording, calcula t ions, and reporting. 5. Procedures for required audits, including transport cfficienc) aud i ts (ifnecessary), lineari t y audits. and relativ e bias audits. 6. Procedures for adjusting your CEMS based on aud it results. 7. A program ofcorrective action and stack operation procedures in case ofa CEMS malfimction and nn out of control period. You arc required to keep written documentation of yo ur Q N QC procedure s on record a n d available for inspection for the lif e of the CEMS or until you arc no longer subject to the requirements of this procedure . If you fail tw o consecut i ve**aud~ s**  yo u mus t revi se yo ur QNQC procedures. 

### 3.2 What c alibration 

### checks and 

### audiJ pro ce dures mw,-t I perform far 

### my multi

- metal CEMS ? 

### 3.2 . 1 Daily drift 

### che c k procedures Your XRF multi-meUtls CEMS must have tbe ca pac ity to perfon11 each of the foll owing ch ecks on at least a daily bas is.**~ge** 4 of 18 

## VES009959

### • Ze ro drift: You m us t check the zero dri 

### Ato ensure the stability of your CEMS response to th e zero drift refere nce. The zero drift must be less th an plus or minus 20% of the emission limit each day . Follow your CEM S manufacturer's instructions for proper zero d rift c heck p roce d u r es. • Upscale d r i ft: You must check the up sca l e drift t o ensure the stab ility of y o

u r XRF multi-metal CEMS response to the upscale standard. The daily upscale d ri fi 

### m ust be less tha n 1 5% of the up sc al e referen ce value determined immediately a lter the x - ray fluore scen ce mod u le h M 

### bee n calibrated. FoUow 

### your CEMS manu facrurer's instructions for proper upscale drift check procedures. • D ally v olum e or flow c h eck: Y o u mu st c heck tl1 e 

### samp le vo lume or now mea su rement to verify the accurac y of the vo lume measurement on yo ur CEMS . Thi s vo l ume c hec k mu st 

### be don e at the n onnal sampling ra t e f o r the CEMS. Your CEMS is o ut o f contro l iftbe one day value exceeds 20% of th e full scale of t be volume or flow measurement de vice. Fo ll ow your CEMS manufacrurer's instructions for proper vo lum e or flow check procedures. 3.2.2 Audit procedures 

### Audit pro cedu res and criteria are li sred be l ow. These requirement> are als o summari z ed in Tab l e I in section 5.3. 1. 

### X- Ra y Flu oresce n ce Ca lib ration Audit (XFCA): You n11st perform an X

J'CA once eac h quarter. To perfonn an XFCA you mus t challenge the x-ray fluo rescen ce modul e ofy our multi

- metal CEMS with a standar d of known concentration for each m e tal measured by yo ur CEMS for compliance purpose s and compare the value reported by the CEM S with t he known va lue of t he <tandanl. Tfyou wi s h yo u m ay make on l y one meas urement of a standard for each elem ent. If your multi

- metal CEMS fails on the initi al measuremen t you may make two more measurements of each standard and average all t h ree me as urement s. If t he average CE M S response ov e r t he three measurements deviates by less th an I 0% fro m the kn own standa rd the CEMS has passe d th e XFCA. If the average exc eeds l 0% your CEMS h as failed the XFC A and is out-of-control. Y ou must fo ll ow the proc ed ure s outlined in Section 5 .2 . A n XFCA is required on ce per 

### q uart er . The minimum allowed t i me between each audit is two months and the maximum a ll owed time 

### is four months. 2. S amp le vol u me (or now ) audit ( S VA ): You must perform a sam ple vo l ume audit of your 

### XRF multi -m etals CEMS at least once per quarter and prior to any linearity or re lati ve accu rac y audit. To perform an SVA you must in

d e

pe n dent ly mea s ure the volume of s ampl e ga s extract ed from the s t ac k or du ct over th e s ampling peri od . You may make thi s measurement eith e r at t he inlet or o utl et of your CEMS. You must make volume measurements during three d i fferent s amplin g cy c le s and t he m e asurements mu >t 

### be able t o make correctio n s f o

r moismre c onten t if necessary.

Pag11**~** nf 18 

## VES009960If your CEMS measures flo w and totalizes that flow to determine volume you may per fonn 

### a flow a udit instead. You must make flow measurements duri ng three diO creut sampli ng cycles an d for eac h samplin g cy cle you mus t make at least 3 to 

### 5 simultaneous measurement s of fl ow on your CEMS an d on the independen t flow measurement devi ce. Yo u mlb't calcul ate the error from each set of mea s uremen ts according to equation 6 and th en calculate the average enor in th e flow during each sam p ling period. Fina lly you must calculate tb e av erag e error from all three sampling periods and this avettge must be Jess t h an l 00/o of th e indep endent flow or volume measurement device . A sample volume a u dit is required on a quarterly b as i s. The minim um required ti me between each SVA is at least two m o nths whi l e the maximum allowed time between audi ts is fo ur month s . Ac c uracy Audi ts : As outlined i n Pe rformun ce Spec ificatio n YY i t is acceptab l e durin g the initi al perfonnance s pecification test to a ssess the acc uracy and precision of the 

### XRF and sam pli ng modules o f your 

### XRF multi· me ta l C E MS separately from th e sampl e interfac e. You may also do this during the Linearity or Re l a t iv e Bias Audit s that ar c require d f o r Procedur e 

### Z. If yo u choose to challenge th e samp ling modul e and 

### XRF**~ystems** separate l y fro m th e $&mpling interface you mu st a l so perform a Transport Effici e ncy Audit (TEA). If you challenge th e entire X RF mu l ti-me tal ; CE MS during th e Lineru it

y and R e l ative Bias Audi ts you arc no t required to perf o rm an independent check of the CEMS tr.msport e fficien cy. For !be purpose!> of Procedure Z y ou arc required to perfonn e ither a linearity audit or a relative bi as audit, but not both . You nrc also not required to perfo nn t h

e sa me kind of te sts for the audi t as were performed durin g the i niti a l perf orm ance s pecifi ca tion test . For example, if 

### a linearity test was performed during the initial accuracy tests, e i t her a relative bi as au dit or 

### a linearity audit is acccptoblo. There arc four different options & \•a

ilabl e for the accuracy a ud i ts dependin g on w hethe r or not a linearity or relative b ias audit is perf o rmed and depending on whe t her or no t th e entire CEMS is cbnllcoged by the a udi t. The audit requirements are li s ted below. Linearity A u dits Option 

### A In this option a lin earity audit is perfonned on th e entire CEM S. The type s of metals generatio n and their a ssociated requirements 

### a re**i~ mi** **ca l**  to those f or Option 

### A in pe rform a nce specifi cation 

### YY s ectio n 

### 3. I 

### . 4 . 1 If yo u do oot meet Ute linearity criteria yo u mu s t app l y a co rrectio n ac cording to t b e procedu res outli n ed in perfomtance speci fica t ion 

### YY . 1 Option B 

### I n thi s optio n a l ineari ty audi t 

### i s performed o n 

### t h

e sampling and 

### XRF modu les of the CEMS separately from the sample interface. The types of metals generat i o n a nd t he ir associ at ed requ ireme n ts a re i dent ical to t hose fo r Option 

### B
P oge 

### ti of 18 

## VES009961in perfo nna nce specification YY section 3. 1 .4. 1 A transpo rt effi ciency aud it m ust a l so be completed. Rt!lati<oe Bias Audit Option C In t hi s option a relat i ve bias nud it i s perfonned on the entire CEMS. The types of metals ge neration and their associated requ irements a re identical to tho se for Optioo C in pcrfonnancc spccifirotion YY c ection 3. 1. 4 . 1 Ifyour CEMS fails to meet the criteria you must apply a correction fuctor acco!ding to the procedures i n perfonuance specific atio n YY . 1 Opt i on D In this option a relative bias audit is performed on the sampling and 

### XRF modules ofthe C EMS separately from the sample interface . The typeS of metals gene rat i o n an d their associated requirements are identical to th ose fo r Op t ion D i n pcrfonnance specification YY sect i on 3.1.4. 1 A tran sport efficiency audit 

### mus t also be co m pleted . An accuracy audit is required on an annual basis. The mi m mum time between successive accuracy audi ts is 9 mo nths while the maximum allowed time i s 15 months. 3. T ra.n sp ort Efflcie n cy Audit ( TEA ): Yo u are required to perform 

### a TEA only if you choose to c hallenge the samp l ing and 

### XRF modules ofyou r 

### XRF mu l ti · metals C EMS separat ely from the sampling interface. The procedures for perfo nnin g n TEA are the same as those for determini n g the transport efficiency during the in it ial performance spec ificati on t est and a re oudined in Perfonuance Speci ficati on YY. If the rnmsport efficienc)' of your CEMS is betw een 90 and 1 10 percent no correction 

### is necessary. Ifyour transport effi c iency is J ess 

### tl1an 90 pcr=ul uJ 8Jcalcr than 110 pcrocnt then y o u must establi s h a con-ecti o n foetor accordin g to the p rocedures outlined in section 3. 1 . 1 ofPerf onu auce Speci fication YY 1 • The minimum time betw ee n s u ccessive tra ns port efficiency te s ts is 9 mo nth s while the ma x.imwn all owed time i s 15 I T.O nths. 

### 4.0 Calcu l a ti ons 4.1 What 

### ca lc ulations and data**a11a~ vsis**  11m stl

### perform? 4.1. i 

### Arithmetic Mean Calculate t he arithmetic mean of 

### a data set 

### as follows

- l 

### x= - _Lx ; n Where: X n Ari thme tic mean Number of data points E q uati on l



### P•ee 7 nf I R 

### VES009962X t Value ofeach data 

### po int 4.1.2 Arithm e tic Mean af Differenc e To calculate th e arithmetic m ean of difference use the abov e eq uatio n substituted for 

### x . Then d t: :CI- _,Vi Equat io n 2 Where x and y are paired data poi nts from tlte CEMS and either th e reference aerosol or the reference 

### me th od. 4.1 . 3 Dai(y Ze r o Drift**~** 

# L ., ZD : ,.. , - I 1()() i L X 

# c, Equat ion 

### 3 Where : ZD, 

### The zero drift of the i 111 element on your 

### CEMS in percent 

### ! .!(""' The measured CE MS response to the zero standard fo r the i'h elemen t 

### _t, The cali brated value of the 

### i"' element on the zero standard C L The emission limit of the i' 1 ' ele m ent 

### • 4 . 1.4 Daily Upscale Drift

### ~" 

## - L 7

1 UD 

### = ' x JOO I L. I Equnllun 4 Where : UD 1 

### The upscale drift of the 

### ;m element on your 

### CE MS in 

### percent.**~** 

### The measured 

### CEMS response to 

### the ;m element in the upscale standard 

### L"

I = The cal ibrated val ue of the i ' h e lement of 

### the upsc• l e stan dard 4.1 . 5 Daily Sample Volume Check Equation 5 Where: P a g e 8 of**I~** 

## VES009963

### VD ; Vo lume drift 

## V,.,.,. ; Samp le 

### gas volume or flow measured by the 

### CEMS volume or flow c h eck 

### measureme n t d evice V., ; 

### Sample gas 

### vo lume or flow reported 

### by your multi

- metal CEMS 

### FS = 

### Full scal e va lue oft

### h e CEM S volume m ea s ur ement 

### d evic e 4.1 .6 Samplt: Volume Audit Accuracy 

# IV. - 

# V. l VA = xlOO 

## v

,. Equation 6 

### Where: VA = 

### Volume or flow measurement accuracy V , = 

### Sample gas volume or flow mea s ured by the 

### independent calibrated refere nc e device 

## v... ; Sample gas volume or flow reported by your mu lti-metal CEMS 4 . 1 . 7 

### X-Ra y F luore scence Calibrat ion Audit Calibrati o n 

## I ' "" - L ' o) 

# I CA 

# =**~"''** 1 x l OO I t.:IJ I Equation 7 

### Wh ere: CA, - X·ray fluorescence calibration accuntcy 

### L';"' =**·nu~** 

### value of th e 

### standa rd reporte d by yo u r CEM S 

## L

'/' • The known va l ue of the s t andard 

### 4.1 .8 Relative Bias Eq u atio n 8 Where 

## d , is the mean difference, 

## R , ...., is the average o f the reference metbod set or reference a erosol concent ration for the i"' 

### element. and PR 8 1 

### is the relative bias for the i'h element 

### 4.1 . 9 T ransp ort E.(!icicncy



## VES009964Equatio n 9 Where: 

# c• Coocentrution of the i"'element at the stac k



# ' C:"' Concen tration of the ilh element at the sam pli ng module or as reported by the 

### XRF multi

- metals CEMS . 

### PT,**~** Th e percent trnnsport of the i lh element Report the average percent transport ( 

### PT) of all measurementS for each e

lement that was t ested (only one element is required t hough more can 

### be tested). 4.1.1? Linearity Audit- Least Squar es Linear R egressio11 Calculate the linear corr elation equati o n g i ven below. 

### y=b, + b ,x 

### Where: = The y intercept 

### The s lope The inte r cept is ca l cu lated accordin g to t h e following equation.
Where: 1 • X =-

# L: xr n,.,

Tbe s lope of the line is calculated according to equation below . 

## I tx , -x){y , - 

## . v

J 

# .. b

, 

# i:, rx, - x )' I•

J Equa tio n 10

Equati on 11

Equatio n 12
The li near correlation coefficient is calculated according to tbe following equation. 

### Pa&c 10 ofl 8 

### VES009965

# I (x , - f) (y , - Y) r**~ f'** **-~ =-** **=** 

# :t<x;

- f) ' I(Y; - Y) ' 1- 1 ,.. 1
4 . 1 . 11 Standard U eviatmn (of differ e nces) ' I ( , , '£.d ; · - - 

### L.d ·J SD, a 11 n - 1 Where : Eq uatio n 13

E q u at ion 1 4 

### SD, The standard deviation of d i n·ercnces for the i 0 elem e nt 11**~** The number of data points d

, The difference between the conc entrat ion measur ed by the reference method o r the concentration of the reference aerosol and the CEMS repozted co n centration. 

### 4 . 1 . 12 Per c ent sumdard devialion 

### SD PRSD 1**~ ~**  x 100 

# R

/m Where : E q uat io n I S 

## R

/"' a The average of the reference metho d data set t or t b e i 'h element 

### PRSD , a T he relative percent stand ard deviation for the im metal 

### 4

. 1

. 13 Lin earity 

### T est Correction Fa c tors (Applicable onl y when the linearity 

### test**ht~lltmges** 

### tlze e mire CEMS) I.**Corre~1 n**  equation ifCEMS does n o t meet e ithe r the slope o r t he in t erc ep t criteria. Eq u ation 1 6 Where :

Paie II ofl8 

### VES009966

# cc Comected CEMS concentration f or the i 'h element l y ; = 

### CEMS reported concentration for the i'' element b

o = 

### The i n tercep t of the least sq uares linear regression lin e b 1 

### The s lope ofthe least squares linear regression line 2. 

### Correction factor if CEMS meets intercept c r iteria, but does not meet t he slope criteria. Equation 1 7 3. 

### Correc t ion factor ifCEMS meets slope criteria but does mt me et intercept criteria. 4.1.14 Relative Bia s Correction Factors**CF,RD -~~** 

d I+ __:_ Where: 

# R"·" I 

### Equation 

### 18 Equation 19



### CF.RB The re l ati ve bias correction factor for the 

### i '" element 

# ' C

;':<M = 

### The average reported concentra tion ofthe CEMS for the 

### i'b element R;•"' = The 

### average of the r efe r ence method measurements for the i ll> metal 4.1./ J Percent trans pori correction factor
PT [ 

### CF, = = 

### PT, Where 

### E quation 20



### CF/ '' = 

### Correction f actor for percent transport for the 

### l'" element Average per c ent transport for the i 111 

### e lement

()ual il\' A sstltL!Ince fOf X R F & sed Mvhi· ll<kt:ll $CEM S (Ptoce dure Z) Page 12 

### of 18 

### VES009967

### 4.2 What waste managemelll procedur es are required for procedure Z? All chemica ls used to produce 

### a reference nerosol or i n perfonning**tand ~rd**  met hods need to be disposed of properly. l'le-dse consult the appropriate rcfereuce method s. 

### 5.0 Oth e r Requ i r e m e nt s and Inf o rmation 5.1 What pollution prevention measure s must/take when usingprocedur e Z? [reserved) 

### 5.2 What crill!ria are necessary for my XRF multi-melD/ CEMS robe 

### ig comrol and what do I 

### t'.o 

## if it is out of control? 5.2. 1 Required Corrective Action fo r Drift Ch ecks a n

d Audits • Daily 

### Zero Dr if

t: If the one day drift 

### exceeds 20"A. you 

### are required to rerun your zero drift reference. 

### If the 

### XRF multi-metal 

### CEMS n-.eets the criteria during the second test you may continue to operate. Ifthe 

### CEMS fails to meet the zero drift criteria again then it is out of co n trol. It is recommended that you exami n e the 

### zero d rift standard tor defect s . After repairs to the 

### CEMS are completed you are required to perlorm at least five successful zero dri ft checks within a 24 hour period. After the five checks have been successfully completed the n you 

### CEMS is in control. If the repairs were made to the 

### XRF mod ul e of the multi

- metals CEMS you are also required to complete an x-ray fluorescence calibratio n audit (XFCA) to verify the accuracy of your x- rdy fluorescence calibra tion . Dail y U p sc ulc Drift : If the one day drift exceeds 15% you arc required to retest the upscale drift reference. Lf the 

### XRF multi -metals CEMS meets the criteria during the second test you may continue to operate , howew:r, if the C£.'15 fails the second upscale drift c h eck it i s out ofcontrol. It is recommended that you examine 

### the up sca le drift standard for defects. After repai:s to the 

### CEMS are completed you are req uired to perform at least five s ucc essful up" ale drift checks within n 24 hour period. After the five drift checks are successfully completed the 

### CEMS is back 

### in control. Again , if repairs were m ade to the 

### XRF module of the multi-metal 

### CEMS you are also required to successfully comp l ete an x-ray fluore.o;cence calibration audit (XFCA) t o verify the accura cy of the calibration. Dall y Sa mpl e Volu me**he~k :**  If yo ur sample volume or Dow drift exceeds 20% i t has failed the daily volume check and you mus t perform another daily vo lume check. Ifthe 

### CEMS passes the second check you may co ntinue to operate. If your CEMS fail s the seco nd test it i s out ofcontrol and your 

### CEMS must be repaired. After repairs have been made the CEMS must sucecssfolly complet e live sample volu me checks within u 24 ho ur per i od. Upon successful co m pletion ofthe five checks your 

### CEMS is back i n control. 

### If the repait·s Page 13 of 18 

## VES009968were made to 

### a vo l ume o r 

### flow measurement dev i ce you are a lso required to successfully complete a sample volume audit { SVA) . • Quar terly Sam p le Volume Audit (SVA): Your 

### XRF multi me tals CE MS is out of control if vo l u m e (or now ) measured by your CE MS diff ers ti·om that measured by the independent standard by more than 1 0% percent. A fa ilur e of this audit may indicate that repairs need to be made to !he volume measurement syst em. Upon completion of these repa irs you must perfonn and pass another SVA. • Quart e r l y X
- Ray Fluoresce n ce Calibration A u dit (XFC A ): The response of your XRF multi

- metals CEM S mus t be within 10% of !he StSDdard's value for each meta l measu red for compl ianc e purposes by your CEMS. 

### l f yo ur CEMS fai ls th e XFCA ini t iully , rerun euch standard t wo more ti mes and take the average oflhe three meas urem ents. Tfthe average CEMS response m eets the XFCA criteria you may continue to operate. however, iftltc CEMS fails to meet th e criteria th eo it is out ofcontrol. After the CEMS has been repaired yo u must co mp lete another XFCA. Upo n successful com p l etio n ofthe XFCA th e CEMS is back in control. • Annual CEM S Acc ur acy Tests Linenri(J ' Audit Opti o n A ( Lin earity au dit of the entir e CEMS). If you challenge the entire CEMS system (including sampling interface 

### and the sam 1 > li ng an d 

### XRF mod u les) wi th 

### a linearity au dit you 

### do not need to apply 

### a correction factor to your CEM S data if i t meets the following criteria : J. a s l ope between 

### 0.85 and 1.15 2. the corre lat ion coefficient equal to 

### 0.90 or more 3. an inter cep t ot'less than 

### 20 percent o f the emjssion 

### limit Ifyour CEMS does not meet th e s l ope or intercep t criteria you mus t app ly a correction factor according to the procedures descn'bed in Performance S p ecifica tion YY Section 4.2.1 2. 1 Yo ur CEMS, however , mus t still meet the correlation criteria . Ifyour C EMS fails the linearity test it i s out of control. After the necessary repairs are made it must pass 

### a linearity or relative bias test to be considered back in control. Opt io n 

### B ( Linearity audit of th e samp lin g module and 

### XRF mo dul e o nly followed by a TEA) If you cha lleng e the s amplin g and XRF modules separately 

### from the s ample interface , your XRF multi-m e ta l CE MS is out ofcontrol if the l inear lea s t squ ares regression ana l ys is of your aud i t data does not meet the following criteria for each ofthe metals measured by your CEMS tbr compliance purp oses:

Paee 14 of 18 

## VES0099691. a slope between 0.85 and 1.15 2. the correlation coeffi cient equal to 

### 0. 90 or more 3. an intercept of l ess than 20 perc ent of tbe emission limit If yo ur 

### XRF mu lti -metals CE MS fa i ls 

### a linearity audi t yo u 

### mUS1 make the n

ecessary repairs to yo ur CEMS and successf ully comp l ete either a relativ e bias u

u d i t or 

### a linearity au dit before it is considered to be back i n co ntr o l. You m ust also complete a transport etlic • cncy audit (TEA) along with your linea rity a ud it. Rc/aJil•e Bi as A11dit O pti on C (Rel ative bias test of !he e n tire CEMS) lfyour CEMS meets th e fo llow ing criteria it has pas sed th e relative b i as audit and you do not need to a pply 

### a co rr ection fac tor to yo ur CEMS. 1 . t he percen t re lative bias 

### (PRB) exceeds 

### 15% 2. the percent re l ativ e standard devia t ion ( PRSD) exceeds 

### I 0% 3 . the correlation coefficient (r) for linearity portion of !he relative bias audit is l ess than 

### 0. 90 Ify ou r XRf multi -metals CEMS fails to m eet tlte re l ative bia s c rit eria you may apply a correction factor according tlte procedures described in performance specification YY Soctio n 4 . 2.13 . H owever, if your CEMS fail s to meet either the percent re lativ e s tandard d evi ation cri teria or th e co rrelation coe ffi cient c riteria it is out of co ntrol. 

### If yo ur 

### XRF mu lti-metal 

### CEM S fails a re lat i ve bias audit it must successfully compete another linearity or relative bias audit to be co nsidered in control. Option D ( Perform a relative bius le s t on tile s amplin g an d XRF modu les) Your XRF multi-metals CEMS is out ofcontrol i f : 1. t h

e p erce nt r elative bias (PRB) exceeds 

### 15% 2. t he percent rela ti ve standard d evi ati on(PRSD ) exceeds 

### 1 0% 3 . the correlation coefficien t (r ) for linearity portion ofthe relative bias audit is less than 

### 0.90 Yo u mu st succ es sfully comp l e te anotlter IillA or a li nearity a udit before you r CEMS is considered to be in control. You must also successfully comple1e 

### a transport effi ciency aud it alon g wi th the re l ative bias a udit. Transport Effic i e n cy Aud i t ( T EA) : A T EA is onl y required i 

## r yo u challenge your sampling XRf modules separately 

### from your sample interface (Options B a nd 

### D). lftbe percent tra nsp ort is betw een 

### 90 and 

### 1 10 percent no correctio n factor i s neceSSllry, h o wever , if th e percent transp ort is l ess than 

### 90 percen t or gre ater th an 

### II0 

### percent then yo u 

### must apply 

### a correct ion factor to 

### the resu lt s reponed by your multi metal CEMS. 

### Tile proced u res for applying a correction factor using the equation in Section 4.1. 1 5. Page 15 of 18 

## VES0099705.2.2 Gen era l out of control guideline s • Out of co ntrol period: The out of control period begin s inmediately after th e failed drift test or audit and is over immcdiotcly following the successful completion ofrequired proc edures associa ted with th e failure of the au dit test. During the out of contro l period yo u m ay not use the data generated by your 

### XRF multi-me ta l 

### CEMS for complian ce purposes . • R e p onlog gutd cll n •o: You must i n clude in your report to us , the stole, o r**loc~l** enforcement agency the results of the failed audit or drift check, th e c orrective action that was taken, and the results of the successful audi t or drift check. • Rul es govern ing auditing tim e periods: The X-Ray F luorescence C alibration Audit (XFCA) and the Sample Volume Audi t (SV A} ore requi red once a quatter. Two months must pas s between successive quarte rly audits an d n o more than four months may pass.. The Linea rit y Audit (LA) and the Relative Bias Audit (RBA) are required on an annual basis. Successive LAs a nd RBAs must be separated by at least nine months and no more t ha n 15 months . 5.3 What tables, diagrams and flow charts are relevam 10 Pro cedure 

# z?

Page 16 of 18 

### VES009971T abl e 1: Co ntinu in . ll. QA P rocedures for XRF M u lti

- Met als CEMS Tes t T est Tes t Procedur es P assi ng C r iteria Fr equ cncv Zero Drift C bcd> Z n'O**M~td** 3lld**ul r.u** **11 ~**  dti ft < 2£)% dri fl encb day Dail )'**UDSo~ l<**  Orin Otttlt**ups~»k** te aodard a nd c:olleu l a l t dr in < IS% d rift c nc: b d ay Volume or flow Drift C"hcdt flow drift .00**e~kull!i1e** dri R < 2)% drift deb dlty X-Ray Fluores<:ence Tc.st**a~ for~**  c:kmtulllliCI:SURlll b •**<l~ditr~bevny**

Ca

l ib rarioo Aud il cow-IJiian!!:C by )'OUr CEMS ( I lir. 1 c ptr ckmmt**~!lu red**  "' stoo d c.rd) comp l j anc:(' by )'atlr**CE~S** • If**criteri!l~W~C** i nitial l y me • you 1nay 1ak. e 'he •Vtl ' agt of 3**~** Sample Vo lu me**~** < It%**ddf~** hom iDe J[Uidltd (o r Flow) Audit • C omp.1 ro CE MS \AOi umo 118tainst a !lltl!nd!lrd Qu art e rl y dU'I'II\& l**:ut. ~ing**  c:)'Ciell 

### •**Vffi~Ce** flfl three 

### am. • 3 10**$now~** wtdts:md&td

<Uid CEM-5 "" SOJq>lo qdo 

### •**Me~~.** ..un: i n 3 ('EMS SII.IT(t lc 'ycks • Ca l c u

l n

te aver:ag c d i ffc: rtn c:(l becwecn CE. M S 1uwJ Shlocb.rds over ab tbi:ISUCtmt:ns 

### Option A 

### • Atl.!:t:Jt 011e DI!CCaJ (tom ext. cacpy • Slop< .. 

### a.as 10 1 . 1 

### s 

## • Need Itt l eas• l conc:c:ntMit:tOn l evc: l::i winch •**r~0.90** P

e •

ioon a l h tcarity te!U 01t i no:: l u ck al f'o W¢00.:,**chan~ ~md**  1 he • lntcrcep 1 < l0%o feru isi i oo e n

tin: CEMS**~lo l\** **li t**  l i mi1 

### • I f ipll::.illc. J.pikt- into SOWTe, or spike i!l. 1 o • rfa btwecril«ill!lrDNihenr.o**~liM** at' clo!;e .. Jw.N"'Wt to the CC)m(liM 

# - •**;(nntmrta~yac(ll't'edM'III** 

### Option B 

### • AI**!.co~** one mctd from t!Kh calcgocy Lhswjly Cri!(lia 

### •**~lit** l o:Alll 3 ccnc e i'M l ti oo**e~-e~** which • Slupe• 0,8 S t u I ,IS 

### • Pelfonn a line arity cc.-st inrfullr a 2 fol d Ol'lftt
.**dlan~,;e** tnd the •**t~0. 90**  on qmplingand Xl!F onisdoellmn • ima¢ep( <**2'0%of~** modu l es aoly • Spike C!ll'**~** coeeftltmJoos w i :ill 

# , .... • lktermine transp ort**R":fum~ ct**  method as**el~»e** It P<mible to 1ht •**r~~** .. Jm...uil)• c nttcia 11" .4.19 biiC mec etT

w.:k: n cy ae(»>ratcly**J~aqllillJJnlQC!I.I)e Ill**  I!:!cl nlQ:Ll C lil!llda • 90<-_PT $.1 1 0 • If**~** traMJ)()ft c:dcnt are Annually ..-.:. met 

## .,..,.y • comctioo 

# - OptionC • At**s~** unc md 1d from t il t h**e~~t cgory**  a. 80 • Pc«en!**~ldiv~** D i u to 1 20 pen:enl ofe: m i .t!\

i on limil • RB ;SU% Perform a relative biat r est • Olle**01ht~** mel.l1 at 3 oonc k\'(.1$ which •**%RSD~** !0% on Mtire CEMS ioeb.<lo • 2101d .._ .._ ond ... • t**~** 0.90 for metal wi:tb Wee :mmioolmil 

## • If sptk [ na,.**kc** imo 10\ltCC Of**pike** into**lold«>n<.~ w~**  li M as close as poJS i bie to \be • If Cri1er i a not met t! ppl y o. p<ob e oorr««tO" &..:c ar ( c(Jf'lt l ation e oeffi ci etll c r i l tr;ia • nus.t be:**m~** 

### Ootion D • Al leaRGM:neul**fiumad!~ea<ttYin** 80**P:tttt~t** Rd !!Cn·r Hlr: Critsrj1 lO 120**~of**tmi:s:sicn limit •**RB~** IS'K 

### • Pcr fonn a re l -ative**bi~s** 

## • Otlt 

# '"'* tD:tll**~t** 3**~:GfiC .**  Ients whi;b •**MSO~IO%** test on sam p lin g a

n d i • ,elu<k 112 J O i d cone . c: bnngc ond the • r**~** 0 . 90 for l'nl:tlll w ith thr oe:: X R F mo dules o oly cmh ak>n Umil fo l d wnc.**h~~r~ge** Dccennlne**uanspo~1** 

### • Spike or Metiurt eoncmtl'l:llotl$ w i ftl l=m Ima5JUid (dteri a 

### • A"ft'rcnce uxthod as**d~** t); pos.sibk: to 1M

<ffockncy scpanrt<ly

### ~- • 90$PTSIIO • l fpcnxMinrlqlOft cril.:ria 1W\:

no t met eno l · a COI'n!ctio n
P ag e 17 of 18 

### VES0099725. 4 What references are rclevam 

## w Procedure Z ? 

### i. l'erfommnce Specification YY: Specificatio ns an d Test Proced u res fo r Batch Multi-Metals Corttinuous Emission Monitoring Systems at Stationary Sources. 2005 .

Page 18 

## or 18 

### VES009973

# VES009974
. pdf

# •**~~~**

STACK &omplo 

### ....!:l:m. Amb lem 

# l



# - 0< Sample V alve Box

RG«;m 10 Stack

H E 

# " T E R Sample Shut -<>If Vrjve**~** 

### 1 

## G4- 

# J HEATeR 

# -I

FIGURE 2. SIG RIST PARTI CU LATE MA TIER CE MS 

## I 

# I
H E A T E R

# ~e~ Photo m eter 

# v SAMP L E BUILD I NG**o~** 

## I UL FIG2 

### _l 020:lOS 

### VES00 9974

# VES0099 7 5.pdf

### ECOCHEM PLC S I GRIST CONTROLLER

DAS

H I STORIAN

FIGURE 3 . T149 CE MS DATA EXCHAN GE 

### XACT CONTROLLER



## VES009975

# VES009976.pdf

# ~

# ~**~ ~** 

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# VES0099 7 8 . pdf

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### T LILF I G6 

### _l 020005 

### YES009978

# VES0099 7 9 . pdfL.O PIU iCJSlON AND BIA S Z .l PA IRED SAMP LIN G T RAIN PRE CISION Z . l.l What I s ?reci sion and Why Is It I mportan t? Preci sion**i~** a 111 easure of the agreement betwee n two or more i n depe n dent observa tions of the s ame phy s ical q uan tity ob ta ined under th e same condition s . Wh e n paired samp lin g trains are u s ed, assess ing the p recisio n o f the tw o data points collected f o r a give n tes t run i s important i n identifying possible prob lelll!> with the sampling train or sample collec tion method . Although t he PM concentrations measured 

### by the two sampling trains should be the same for a test run, there in variably are differe n ce s in the two meas u rements. Typically, the d illerc n ces in emissions between the two sampling trains are insi gnifi C(Ult. I n som e cases . i t is uncl ear wh e ther t he two data points a re in relat iv e ag reement or i f th ere are significant diff e r

e n

ces , which co uld indica t e a problem with the sampling in s truments , collection methods , or a nalytical proced u res. Z.l.2 Doe s PS-1 1 Reou jrc Me To E valuate th e Preci sjop of Paired Sa mpl jpg Tmjn Da ta? Eval ua tin g t he pre c isi on of paired s ampling train data is n ot req u ired under P S

- 11. However, i n Section 

### 8.6{ I)(i) ofPS

- 11, it is recommendoo t hat you use paired samp ling t rdi n .s 

### and screen the data for pr ecision w hen conducting a correlation tes t or an R CA L ilc ew ise , thl\ Jlrncedure s described here for evaluating paired sampling train precision are recommendations and not requirement s. Section 8.6(3) of PS

- 11 specifie s that wilen conducting a correlation test, you may reject th e**res ult** **~** of up to fiv e test runs w i thout exp lanation; additio nal te st nms ca n be rejected under certai n condit ions. The same pr ovi si on s a pp l y to R CAs. T h e p roc edure s described in th e follow ing paragraphs ca n help in deciding which l es t ru n s, if a n y , you shoul d co ns ider rejecti n g. Z.l.3 What Methods Can I Use To Determine the Precision of Paired Sampli ng Tmjp Data ? This secti on d . i scusse s tw o m e

th ods f or eva l uati ng th e precision ofpa ired samp ling train da ta . Section Z . l.4 descn l>es a m e thod tha t i s based on the determinnt ion of the relative s tandard dev i atio n (RSD). Sect ion Z. l .5 presents an a lte rn ative method , wh ic h i n volve s ca lcul ating th e regression res iduals for th e data se t and comparing them 

### with the standardized residuals for th e test run. Section Z. l.6 compares the tw o methods and pre sentS reco mmendations on which procedure to U3e and how lO use th e res ult s of eval uat ions of d a ta precisio n for i ni tial correlation te sts and R CAs.



## VES009979

### Z.L4 H ow [)o 

### I Evalu at e P recjsio g Usiue the 

### Relati v e Stapdard De vi ation ? Determinin g the RSD is a re lati vely simple and s traightfot wa rd procedure for evaluating the precision of paired sampling d a ta . lbis proccdut·e, whic h wa s inclu ded in earlier proposals of PS- 1 1, cutTen tl y appears i n Sectio n 12.2 of M e th od 5i. The RSD presented in this discussion and in Met h

od 5i is not the true RSD but is actually a measure of t h e >tand ardized halfrange. For two data points , th e s tandardized h a lf range 

### diff ers from the true 

### RSD 

### by a 

### factor of(llf2) o r 

### 0. 707; t h

at is , th e 

### R SD (as 

### presented here) 

### equals the true 

### RSD • 

### 0. 707. Evaluating tl1e 

### ?recision of paired sampling ll"llin data usin g the RSD entails the following steps : !. 

### C alculate the RSD fo r each t est run ; 

### 2. D e t ermine the a verage 

### PM co nce n tra tion for e ach run ; 

### 3 . Determine the recommended maximum RSD for each run, 

### based on the average 

### PM concentration for the run: and 4 . 

### Com pare dte 

### calcul at ed RSD wi th the recommended maximum RSD for each 

### run a nd fl ag those t est r un s for which the ca lc ulated RSD exceeds t be recommended ma>. imum RSD value . T

h e following ?aragrap h s descri be each oft.hcsc steps in m ore detail.**Exruq~ e**  

### ca lculations are also presen ted . Steo I; 

### C ale ylat e RSD The RSD is calculated for each test run using equation Z 1- 1 :

where RSD 

# c. c . J C

, ·

C.I (Equation Z . l- 1)

relativ e s t an dard deviation , percentage : co n centrati on measured u s ing Train A, 

### u ni ts of concentration concenrrat 'i on mea s ured using Tra in B , same u nits as C, = 

### absolute value ofthe difference b etween 

## c . a nd 

### C, same units of concentration. T h e concentrat io n uni ts for the var iables 

### C, and 

### Cb do n ot matter , provided the same units are used for both concentratio ns (e .g ., both co nce ntrations could be in u nit s ofmwd scm or both could b e i n units ofmwacm) . Z - 2 

## VES009980I n t h

e fo ll owing exa m p

le cal cu l atio n , ass u me the c onc entration fo r Train A w as 9.2 mglacm, and the concentra t ion fo r Train B d uri n g t he wme test run wa s 7.6 m g/acm. 

### k 92

- 7 . 6) 1 1.6 

### RSD = 100" /o x 

### = - x 100 = 

### 95% ( 9 . 2 

### + 7.6 ) 16.8 Sten 2: Oetennjne Average PM Conccntmtjon The recommended maxim u m RSD (RSD, ) is based on the average PM concentration (C., .) for t h

e tes t n on . For the pre vi ou s exa m p l e, the average PM co n cen tratio n for the ru n is 

## c 

## = 

## c . +c . - 9 .2 

### + 7 .6
- 8 .4

... 2 2 Step 3: Detennjne Recommended Maximum RSD The recommended maximum RSD i s 

### a function of t h

e average PM concentration for the two data points , as follows: • For average PM co n ce nt ratio ns t11 a t a re a t leas t 10 mg/dscro (o r at l eas t 1 0 mg/acm). the r ecommended max imum RSD is 10 perc e n t; • For average P M co n ce

n tration s that are l ess t h an or equa l to 1.0 mgfdsc m (or less th a n or equal to 1.0 m g/

acm), the recommended maximum RSD t S 2 5 percent ; and • Fo r average PM concentrations between 1.0 and 10 m g! dscm ( or between 1.0 and 

### I0 mg/acm) , the recommended maximum RSD i s determined using Equation Z . l-2, whio h is s imp l y a linenr interpo l ation betw een I 0 arul 2 5 pe rcent · 

### R

SD , . • (26 . 67
- 1.6 7 C,.,) (Equ ation Z.l-2) w h ere RSD , s recommendtd maximum RSD for average PM concentrations between I .0 and 10 , percent C.,., E average PM concentrati on for the two sampling trains. units of concenll8tion. For the above example, the average PM c oncentr.Uion is greater t han 1.0 m!Vdscm ant! l ess t h an I 0 mgldscm ; t h

erefore, E qu ation Z . l

-2 i s used to d etermine the recommended maximu m RSD as follows: 

### RSD, = 26.67- 1.67 X 

# c . .. = 26 . 67
- 1. 67 X 

### 8 . 4

- 1 2.6 %

Z-3 

### VES0099 8 1Step 4: Compare Calc ula ted RSD to Recommended Maxi mum RSD Th e calculated RSD is 9.5 percent, which i s less than the recommende d m aximum RSD o f 12.6 percent. Therefore, the test run satis fi es the criterion for RSD . Ex •mple Prob l em: H ow D o 1 Evaluate the Precision of P ai r ed Sn mp liag Trai n DMta Us in g the RS D ? Fo r the ini tial correlation test ofa PM C E MS , 20 test runs are conduc ted us i ng paired sam pling trains. The results of the test are summari zed io Table Z . l

- 1. The table also show s f o r each test run the average PM concentration, the RSD calculated using Equation Z .l -1 , and the recommen ded maxim um RSD . Finally, the tab le indicates whether each**te~1** run met th e RSD cri t erion. Table Z..l- 1. Exam ple R S D Ca l culat ion s - Result s of Ini tial Cor r elation Te st P M C once ntration , mg/dsem RMOmmeoded D oes tb e test r un C alculated mulmumRS D, satisfy t he RSD Run TrainA Train B Average RSD ,% % criterion?

I 2.6 4. 2 3 .4 23.5 2 1 

### No 2 3.9 4 .4 4 .2 6 19.7 Yes 3 4.2 2.8 3.5 20 20.8 Yes 4 8. 6 10 .3 9.5 9 10 . 9 Yes 5 15 .1 1 4 .5 14 .8 2 10 y .. 6 1 8.3 19.7 19.0 3.7 1 0 Ye s 7 22.4 21.3 21. 9 2.5 1 0**Ye ~**  8 24 . 5 20.2 22 .4 9.6 10 Yes 9 24 . 3 36.9 30.6 20 . 6 10 

### No 10 32.9 32.2 32 .6 1.1 10 Ye s II 6 . 4 7.4 6.9 7.2 15 . 1 Y es 12 9.5 1 4 .2 11.9 19.8 1 0 

### r 

### N o 13 12.4 15.1 13.8 9.8 1 0 Ye s 1 4 14. 2 1 1.2 12.7 1 1.8 1 0 

### No 15 7.8 7.1 7.5 4 .7 1 4 .2 Yes 16 21.3 18 .3 1 9.8 7 . 6 1 0 Yes 1 7 4 .6 13 .5 9.1 49.2 11.6 

### No 1 8 28 .7 24 .2 26.5 8 .5 10 Yes 19 12.6 14 . 8 13 .7 8 10 Ye s 2 0 10.5 1 1. 3 10.9 3.7 10 Ye s

Z-4 

## VES009982As show n in the table, Run s I , 9 , 12 . 14. a nd 17 did not mee t the prec i s ion c ri terio n for RSD . For Run 1, th e average PM co ncenlrati on was 3.4 percent, and the RSD w as 23.5 pereent. Since the average PM concentration is between 1.0 and 10 mgfdscm, Equation Z.1·2 is used to detennine th e recommended maximum RSD for this run. Using !hat eq ua ti oo, the recommended maximum RSD for Run I is calculat ed to be 2 L percent (26.67- 1. 67 x 3.4 = 21.0). For Run 9, tb e RSD ( 20.6 percent ) exceeded th e recommen ded maximum RSD of LO percent. For Run s 12 and 1 4. th e RSD s wer e 19 . 8 per cent and 1 1.8 percent, respecti ve l y, both of which exceed the re commended maxi mum of 10 percent. Fina lly, the RSD for R u n 1 7 w as 49.2 pereent , which exceeds the rerommended maximum RSD of 1 1 .6 percent f o r that 

### run , as determined by Equation Z . l- 2. Sect ion 8.5(3) ofPS-1 1 req u ires 

### a minimum of 1 5 test 

### run s for the initial correlation te st, a nd paragraph 8 . 5(3) ( iii) allows up to 5 tes t ru ns to be discarded with ou t exp l an ati on. In th e :tbove exam ple, the f ac i lity might consider discardin g the 5 test 

### nms for wh ic h the RSD exceeded the reco mme nd ed maximum RSD; if it di d so , th ere still would be 

### a s ufficient numb er of te st runs to deve l op the initia l corre l a t

i on. Ho wever, the facili t y wou l d not be required to reject a n y of the data; it could decide to 

### keep the results of any or all of the te st runs that did n o t meet the RSD criter iotL Z. l.5 How Do I Evalu a te the Precision of Pa j red Sa mpli ng Traj u Da ta Us i ng Residua l s? A residual is defined as the difference between an observed val u e and th e fitted vall1e th a t is de te nuined ushg 

### a regre ssi on equation . Using residua l s to eva luat e th e precis i on ofpaired sam pli ng trai n data i s a n iterati ve proces s, whi ch consists ofth e fo ll owing steps: I . Deenni nc the 

### linear regre ss ion equation for the data ; 2. Calc u late . tb e residual and standardized residual for each te s t 

### run : 3. E limi nate any run for whi ch th e abso lute value of U1 e s t a ndardized re si dual exceeds 3.0 ; 4. Recalculate th e residuals and standardized residual s fo r each test run; and 

### 5. Repeat S teps 3 and 4 u n ti l the ab so lute value of th e st andardize d res i dual f o r each nm is Jess than or equal to 3 .0. The followin g paragraphs des c tibe th ese ste p s in more d etail . An examp l e problem to illustrate all ofthe calcul ations for eva lua t ing paired sampling data precision using residuals also is presented . Step 1 : Determine**Rc~essio n**  EQu ation B e l ore the residu a l s can be ca lc ula t ed , t he rc gTess io n equation mu st be determined. For paired sampling train data, a linear regression model is us ed . The proc ed u re for d ete rmini ng th e linea r regression equation is identical to that specified in Section 12 .3(1) of PS-I! for dev e loping a li

near co rrelation model. The data from either sampling train can be used for the dependem 

### Z-5 

## VES0099 83variable (y) or independent variable (x). For this discuss ion, the data from T r ain B represent th e depend ent vari able , and the data from 'T'min A represent the independent variable. The regression equation i s 

### of the form pre se n ted in Eq uation Z.l -3: (Equation Z.l-3) where 

### y • predicted (fitted) PM co ncentration for Train B b 0 = i n tercep t of th e regre ssion line , as calculated u s in g Equation Z . l-4 b 1 • slope of the regress ion l ine:, as calculated using Equation Z .l

- 6 x = PM concentration mea s tu-ed by T rain A. T hey int e r cept (b 0 ) 

### of the regres s ion lin e is detennined using Equation Z .l -d :

where

w here l1**~** mean of the Train A data, as ca lc ulated using Equat i o n Z. l

- 5 

### y 

## = mean of the Train B data , as calcul ated us ing Equation Z.l-5.

x , c PM concentration measured using Train A for ru n i y 1 - rM concentratio n m easu red using 'Tra i n B for run i n = number of data pairs . The s lope (b, ) of the regression line i s d e termined using Equ ation Z.l

- 6:

where 

# s ... , S , 1 = as calculated us ing Equation Z . l-7:



# . ' S = 

## "'(x 

## -x ) K.: L ; . ;-I 

## s ., 

## = 

# f (x ,- x )(

y, - 

## .Y) ;-I where
x ., 

## x. y . 

### and y = as defined above for Equa tions Z.l-4 and Z.l

- 5. 

### Z-6 (Equation Z . l

- 4 )

(Equation Z. l -5)

(Equation Z . l-6 )

(Equa tion Z . l

- 7 )



## VES009984for the dnta listed in Table Z.l- 1, the cn lculated values are 

### ns follows: I 2 0 

# x = 20

### ~ (2 . 6+ 3.9+ .. . 

### + 10 . 5) = 14.24



### - I 

### zo y 

### = 20

### ~ (42 

### + 4.4+ .... 

### + 113) = 15.18 

# "' s

"' = 

# L: ((2.6

- 14 .24;' 

### + (3.9

- 14.24/ 

### + ... + (1 0.5

- 1 4 . 24/) 

## = 1.5 11 f = i 20 S ., • 

# L ((2.6-14.24){4.2-15.18)+ ... + { I 0.5-14.24)(11 .3- 1 5.1 

### 8)) 

## = 1.348 i : l h

- 1,348

- 1- ) ,5))- 0.892 h 0 

## = 15 . 18

- 

### (0.892x 1424)= 2.47 The regression equation is then expressed as 

## y = 2.47 

### + 0 .892x Sten 2: Ca l cy!a t e Residua l s and Stnndurdjzed Re s jd ua l s For a paired sa:npling train test run, the residual is simp l y the difference bet•.veen the concentration 

### (y) measured by one of the trains (e.g_, Train B) and the concentration detennined using the regrwioo equation 

### (Y), as shown in Equation Z . J- 8: 

### e=y -f (Equation Z.l

- 8) 

### where e = residual y = concentration measured by Sampling Train 

### B 

### y • predicted ( fitted ) concentration for Sampling Trnin 

### B calculat ed using the regression equation . The s tandardi ud residual for a test run i s a function of the residual for the run an d the residual varianc e, as cal cu lated using Equation Z . l -9 : e . 

### e - '



## s-**~Var(e)** (Equ a t ion Z.l-9)



### Z-7 

## VES009985where 

### e, standardized residual 

### c; = residual for Run i Var(e} = residual vari an c e, as detennined usi ng Equation Z .l

- 10.

where n 

# l: e,' Var(e) 

## = _,. _ , _ · (n - 1 )
Var(e} , e i, and n = as defined previously. (Equation Z. l -10)

Based on the da t a presented in Table Z.l -1 , the fitted y values for Runs I and 2 are 

### Run I: 

# y = 

### 2.47 + (0.892 x 

### 2 . 6) 

### = 4.79 Rtm2: 

### y=2.47 +(0.892 x 

### 3.9) -= 5.95 From Equation Z .l-8, the residuals fo r Runs I and 2 are 

### Ru11l: 

### e 1 = 

### 4.2

- 4.79 

### = - 0.59 

### Run2 : 

# ez = 4.4- 5 .9 5 

# = - 1.55 From Equation Z .l -10 , the residual variance for the data in Table Z.l- 1 is 

# "' 

# L ( - 059 2 + ( - L55 2 ) + ...+(-Q54 2 ) Var(e) = 1 " 1 = 1 6.19 

## (20

- 1) FromEquationZ. I -9, the standardized residual for Run I is



### - 0.59 

### e - r=



### ' vl6.19 - 0 .147 For this ru n, th e abwlute value of the standardized residual is 0.147, which is less than 3.0. Therefore, Run I meets the criterion for precision b ased on the residuals .

Z-8 

## VES009986Ex amp l e Prob lem : How Do I Evaluat e the Precis io n o f 

### Pa ired S a mpli ng 

### Train Data Using Residuals? This example uses th e same initial correl ation tes t data presented in Table Z.l-1. A totdl o f 20 test rutlS wer e co n ducted using paired sampling trains. The first step is to perform a linear regression using the data from sampling Train 

### A 

### as the independent variable(x values ) and the data for Tra in Bas the dependent vari ab le (y values). Ta b le Z.l

- 2 summarizes the res u lts of the regression analysis. The re - sulting regress i on equation is 

### f = 2.473 

### + 0 . 892 

### y. T a b l e Z. l-2 . Summary of R egr ess i o n Ca l cul a tion s Va riable Calculated va l u e E q u ation no. X 14.24 Z.l

- 5

- - ·· 

## ·--·-- ·· ····· -- 'J 15 . 1 8 Z.l·5 n 20 Z.l-5 s:c .

• 1. 511 Z.l

- 7

## -··-**,.,** 1 348 Z.l

- 7



### - -· -- · .. 

## -- b. 2.473 Z.l

-4 

### b, 0.892 

# ' ' Z. l

- 6 The residual s a re calcul ated using Equation Z . l -8, and the standardized r esiduals are calculated using Equations Z .J -9 and Z.l

- 1 0. Table Z . l-3 sh ows th e predicted (fitted) y valu e, the residua . !, a nd the standardized r esidual fo r each test run . As shown in the table, all runs meet the precision criterion except R un 9. For that ru n, th e absolute value of the stand ardized residual is 3.167. which exceeds 3.0. 

### Tab le Z.l-3. S umma r y of R esidu al s fo r 

### Exam pl e P ro blem - Firs t 

### Iteration P

M c oncflltratlon , m gl d sc m P r edicted PM Standardized Run Train A Tr a in B e oncentratlon(9) Res i d u al (e .) r esidu a l (e,) I 2.6 4.2 4.7 9
- 0.593 ..0.147 2 3.9 4.4 5.95 -1.553

- 0.386 3 4 . 2 2.8 6. 22 -3.421 -0.850 4 8.6 10.3 10.15 0.153 0.038 

### --· . 

# - 5 1 5 .1 14.5 1 5.95 -1.447
- 0.360 6 1 8.3 19.7 1 8.80 0.89 7 0.223 7 22 .4 21.3 22.46 - 1.161

- 0.289 8 24.5

### 20.~**--- ·-·**  24.34 -4.135 -1. 0 2 8

. .. 

# . (co!llillued) 

### Z

- 9 

## VES009987Tabl e Z.l-3. ( continued ) 1'M c oncenrrallon , mgf d

scm Predicted PM Stan dardiz e d Run Train A Trni n 8**conce ntratio** **~)** R esi dual (t 1 ) residua l (e,) 9 2 4.3 36.9 2 4 . 16 12 .7 43 3 .1 67 10 32.9 32.2 31.8 3 0 . 36? 0 . 092 II 6.4 7 .4 8. 18 -0 .78 4

-0 . 195 12 9.5 1 4 .2 10.95 3.25 0 0 . 808 13 12.4 15. 1 1 3.54 1.5 62 0 . 388 1 4 14 .2 1 1. 2 15 .1 4 - 3.944

- 0.980 15 7.8 7.1 9.43

- 2.333 ..0 . 580 16 21.3 1 8.3 21.48 - 3. 180 ..0 . 790 17 4.6 13.5 6.58 6 . 922 1 . 720 1 8 28 .7 2 4 . 2 28 . 08 - 3.883

-0 .965 19 12 . 6 1 4 .8 13.72 1. 083 0 . 269 20 10 .5 1 1. 3 11.84 -0 . 543 -0 .1 35 The next step is to re mo ve Ru n 9 from th e data s et and recalcul ate the regress i on equation and standa rdized re;iduals to determi ne if any of th e data 

### points exceed 3.0 afte r th e outlier (Run 9) has been removed . Ta ble Z . l -4 s urruna rizes the regress ion param eters. Table Z. l -4. S u m mary o f R egression C al c ul ations for E xam ple Prob lem " it b Run 9 R emove d**ariob~** Calcul ated value lt 1 3. 71 

### y 1 4.04


# - n 19**s~~** 1404 

## s

.,. I I 1 8 b

, 3. 12



## -- b , 0. 796 The residnals and standard residuals are recalculated. The revised cn l cularions, s ummarized 

### in Ta ble Z.l

- 5, 

### show that the absolute value o ftbe standardized residual is les s th an 3.0 for all runs . Therefore, the ev aluation i s co mpl ete wi th only one outlier (Run 9) identified. The fa cility can d ecide to re j ed that run, but it is no t required to do so. Z - 10 

## VES009988T atle Z. l

- S. Re•ised C alculatio n of Resid u als after Remo v al of Run 

### 9 PM wncentration , m3 l dsem Predicted PM S ta n dard ize d Rgn Train A T rain U c o nren tradon (9) Residual (e.) r esidua l (e .) 

# -· 1 2. 6 4 . 2 5. 19 -0 . 99 -0 .37 8 2 3.9 4 . 4 6 . 23 - 1.8 25 -0 . 6 9 6 3 4.2 2.8 6 . 46 -3.664 -1.39 8 4 8 .6 10 . 3 9 . 97 0 .332 0.1 2 7 5 1 5 .1 1 4 .5 15.1 4 ..().643 ..() . 2 45 6 1 8.3 19 . 7 17.69 2 . 009 0 . 766 7 22.4 21.3 20.96 • 0.344 0. 131 8 24 . 5 20.2 22 . 63

- 2 . 4 28 -0.926 IQ 32.9 32.2 29 . 32 2 . 884 1.1 I I 6.4 7 .4 8.22 ..().8 1 6 -0.3 11 12 9 5 14 .2 10 .6 8 3.5 1 6 1. 3 41 13 1 2.4 15. 1 12 .99 2 .107 0 . 804 1 4 1 4 .2 I 1. 2 1 4.4 3 -3 . 22 7 • 1.23 1 15 7. 8 7. 1 9. 33 · 2.23 1 · 0 . 85 1 16 21.3 1 8.3 2 0 .0 8 I

- 1. 7 8 0 · 0 .679 17 4 . 6 13.5 6.7 8 6.717 2.563 1 8 28.7 2-4 . 2 25.97 -1.772 ·0.676 19 12.6 1 4 . 8 1 3.15 1.647 0.629



## -- 20 10. 5 1 1.3 1 1.41! ; ..() . 180 -0.069
Z. l.6 Which Procedure Shou ld I Use fo r Evaluati ng P a ire<l S am pling T raj n Da ta P recjs jon ? The methods jnSen ted in Sec tio n s Z. l.3 an d Z .l.4 fo r e v a l uating prec is i o n d iffe r i n terms of s implic i ty a n d results . The m e th o d b as ed on re s iduals analysis i s a relati v e ly c o m ple x , i terati v e procedu re . The RSD m ethod i s m u c h s impler a nd r equires a single round of ca l c ulations . Howev er , as ir. dicated b y th e resu lt s of th e e xamp l e probl em, the RSD me th od is mor e s trin g ent in t e rms of**ide ~tify** **in g**  o utlier s. In the exam ple probl em , the resul ts of five l eSt run s were id enti fi ed as possibl e outl ie r s based o n R S D , but th e re si dual s a n al ys is of th e s a me data s et i d en tifi ed only o ne tes t run as n potential o utlier. Altho u gh either meth od can b e used to evaluate paired samp ling train prec is i on, a r ecommended pro cedur e i s to use th e RS D m eth od ini t ially to evaluate data prec isio n. I f the RS D analysis shows that the data for all test runs are withi n the rerommended maximum RSD , n o further assess m ent ofdata preeision shoul d be necessary bee2use th e RS D method is the more string ent ofthe two methO<h presented here. If the RSD v al u es f o r o n e or m ore t es t n m s i n d icat es that the d ata set conlllinso ut.liers . an anal ysis of the res idual s is r e c omme n ded. 

### Z. ll 

## VES009989Regardless of whic h meth od is u se d , any potential o utliers should be i n vestigated to de termine possib le causes for th e J ack of precision. U problems are identified in h ow the samp les were collec t ed or analyze d, the suspect data pairs sho uld be discarded . 

### lf n o prob l ems 

### cao be identi fied, it**m~y** be that the app are nt lack ofprecis ion is simply evidence of the na tural variations in the data . Jn a n y case, th e faci l i ty has the option ofdi scard in g the res ult s of up to five test runs w i tho u t explana t io n, provided the re remains a minimum nu mber 

### of t es t ntns to satisfy PS- I I (i. e ., IS ru n s for developing a correlation or 12 run s for an R C A). The re sults of addi tional test rons can be reject e d iflbe basis for re j ec ting the run s is specified in PS

- 11, the test med10d, o r the qual i ty assura n ce plan for tbe facility. As sta t ed above, 

### a mmm1um of t 5 te st runs 

### is needed io deve lop a corre l ati on , an d a minimum of 12 te st runs i s required fo r an RC A. Z . 2 PAiRED 

### SAMPLING TR AJN BIAS Z .2.1 What Js Bj as and Wbv Is II lmoonaot ? Bias is 

### a sys t ematic error in d ata. Bias 

### can arise from diff erences in parameter measurement m ethods, data collection meth ods, o r data reduction methods. I n paired samp li ng tra ins, bias can occ ur when the ins truments used t o measu r e emiss i ons differ from one 

### troin t o tb e other, o r when th e test crew operat e s the two sam pling trains differently. For examp l e , i f two sampling trains include heated filters, an d th e litter temperatur es are s ignificantly di fferen t, mo re 

### PM cau condense on the filter with th e l ower t emperature , res ul ting in bia s ed data. B eca u se i t may no t be a pparent that there are diff ere n ces b e twe e n th e s ampling train s or data collec ti o n methods , it is important to evaluat e the da ta f o r bias. When develop i ng th e correla tion equa ti o n for P S-1 1 , bias 

### can introduce more sca tt

e r in the data, skew the correla tion eq uati on, or resu l t in fa i l ure to meet the con-el ati on accepta n ce cri t eria s p ecified in Section 1 3.2 ofPS

- 11 . Z .2 .2 How Do 

### I D ereanjpe Bias j n 

### Paired Sampling Train Dat a ? lbn"""' severn I rncthcxb tlu>t can be used to identify bi3S in p3ired sam plins train data. The meth od described in tbe following**paragr~ bs**  consis t s ofthree steps: I. Determine the linea r regress ion equation for the data; 2. Calculate the confide n ce inl erval for the slope of r h e re gression li ne ; a nd 

### 3. Cakulate th e confi de n ce i n t erval for the in t ercep t of the reg r ess i on line. 

### TI1e following paragraph s d escribe th ese s t eps in more detail. Ste o l: Deteonjne Regres s ion Ea u a t jon The procedure for dete rmi ning th e l i n ear r egressi on equation is th e same as is d escribed in Section Z .l .2 .1 for eval u atin g residual s for precis ion. The data fTom either oft h e pa i red sampling trains can be used for th e depe n dent variab le or th e independent v ariable. and the res u lting 

### line:u regression equat io n has the form indicated by Equati on Z .1-l. 

## y = b 0 t 

### b,x

Z-1 2 

## V E S009990Steo 2: Petennine Confide n ce lnteryal for Slone The next step is to determine the 95 percen t confidence interval for the s l ope of tbe regression line 

### (b 1 ). The criterion for the s l ope of 

### the regression l ine is that the value 

### 1 .0 [ails within the confidence in t erval. The 95 percent cont1de nce i n terv al for the slope is ca l c ul ated u sing Equation Z.2-l. 

### CJ .. = 

### b, ± 

# t., .,. X 

### SE(b,) (Equation Z.2- l) where

SE(b , ) 95 percent confidence interval for the slope slope of the regression line t(n-2 , 0.975) is the 100(1-0 . 00512) percentage point of 

### a Student ' s I· distribution with n - 2 degrees of freedom (see Appendix A } = standard 

### error of the slope . The standard error of t he slope 

### is calculated using Equarion Z.2-2: 

# s SE(

# b , ) = 

## r== ="=' = 

# I (x, - :X}' (Equation Z.2

- 2) 1-l where 

### x, and 

# x as defined above for Equat i ons Z.l-4 and Z.l-5 S = root 

### mean square error . The root mean square error ( S) is calculated u sing Equat ion Z.2-3: (Equation Z . 2-3)
where 

### y , , 

## Y; , Md n =as defined above for Equations Z.l-3 through Z. l -5. For 

### the data presented in Table Z. I · I , the regression equation was previously detennined to be j = 2 . 47 

### + 0.892x. U sing that equati o n and 

### the Train 

### B data from Table Z . l·l. 

### the root 

### mean square 

### error is calculated using Equation Z .2 · 3 as follows:

Z-13 

### VES0099912() 

# I (4.2

- 4.79) ' +(4 .4

- s.95) 2 

### + . .. + (11.3

- tt.84) ' (20- 

## 2) /• l 

# = 4.13 S = The mean x value was previously determined to be 14.24. When the value for Sand the data for Train A from Table Z . l -1 are inserted in Equation 2.2-2, the standard error of tl1e slope is calculated as follow5: 

### ( ) 4.13 

### SE b , 

### =**--;::::::=== =~** **== ===**  

### 0.106 l O 2 

### l; ((2.6

- 1424) + (3.9

- 14.24) 2 

### + . .. + ( 1 0 .5

- 14.24) 2 i• l For 18 degrees of freedom (n • 2 

## =2 0

- 2 

## = 18), the va lue for the t statistic (refer to Ap p e nd i x A) i s 2.10 I. Insert i ng that value and the results of the above calcu l ations for root mean square error and t he standard erro r of the slope i nto Equation 2.2

- 1, the confidence inter,a l for the slope 

### is as follows: 

### CI h i = 

### 0.892 ± 

### (2.1 0 I X 

### 0.1 06) = 

### 0 . 89 2± 0 . 223 This can a l so 

### l>e written 

### as 0.669**~b ,**  :d.ll6 with 

### 95% confidence Since tl1is interval i ncludes the value 1.0, the data satisfy tl1e bias c ri terion for slope. S tep 3; Determine Co nfidence Interval for loterceot The final s tep i; to determine the 

### 95 percent confidenc e inte rval for the intercept of the regression line (b 0 ). 

### If the value 0.0 falls 

### within the confi de n ce int erval for the intercept, the d ata satisfy the bias criterion and are acceptable . The 9 5 p ercent confidence interval for the in t ercept is calcu lat ed using E q uation 2.2

-4 :

where CI, 0 = 

### 95 percent confidence interval fo r th e i ntercept b 0 = interc ep t of the regression l ine t, $% = 

### as defmed above fo r Equ ation 2.2-1 SE(bo) = >tandard error of the intercept.

Z-14 (Equation 2.2-4 )



### VE$009992The standard error of the intercept is calc ulated us ing Equat i on Z.2

- 5: 

# t.x: SE(b ) 

## = S '"'

- 

# . .. (Equation Z.2-5) 

# nL(x ,- ;) ; 

## .. 

# , where all variab l es are as defined above in Equations 

### Z. l -3 to Z.l-5 and Z .2 -4 . For the data pre se nted in Table Z . l-1, the parameter SE(b.), which is de t ermined f rom Equat ion Z.2-5. i s as follows: 

# L (2.6 z + 3.9 2 

### + . .. +1 0.5 2 ) 

### SE(b ) = 

### 4.13 ; 

### 1.774 0 

### 20L; ((2.6

- 14 . 24)+(3 . 9
- 14.24)+ ... +(10.5

- 14 . 24)) Substituting into Equation Z.2-4, the confidence interval for the intercept is as follow s: 

### C/, 0 

### = 2.47± (2 .1 0x 

### 1.77) 

# = 2.47± 

### 3.73 Thi s can also be v.ntten as

- 1.25**~** b 0 ,; 6 . 20 with 95 percent confidence Since t his inter" 

### a! inc l ude-s t h

e valu e 0 . 0 , t he data satisfY the bias criterion 

### for intercept. Example Pro blem A: How Do I t:va lu ate Paired S ampling T ra in Uata lor Bias ? 

### In this exa mple, 1 5 test runs were perfomJed using paired sampling trains. Table Z . 2-l summari zes 

### the data 

### for the two sampling trai ns .

Z-15 

## V ES009993Table Z. 2-1. 

### Example A

- S u mma r y of Test R es ult s PM Co ncent ra tion Run Tra in A (x) T rai n B (y) I 2.3 2.5 2 3.9 4.4 3 4.2 4.1 4 8 .6 10 .3 5 1 4 .2 13 .1 6 I 5. 1 1 4 . 5 7 18.3 19 8 22.4 21.3 9 2 4 .5 22.8 10 2 8.1 2 8.2 I I I 32.9 32.2 12 6.4 6.9



## - - - ... 13 7.2 6.9 14 12.6 1 2. 4 1 5 10.5 11.3 Table 2.2

- 2 summarizes the results of the regression calculations. Table Z.2-2. 

### S ummary o f Regression Ca l c ulation s Vari abl e Ca lc u. J ated vaJue Equation No. ii 14 . 08 Z . l-5 

### y 13.99 Z.l · 5 n 15 : Z.l

-5 

## s, 1239 

## i Z.l-7 

## s, , 1182 Z. l

- 7 b. 0.556 Z. l -4 b , 0 .954 Z. 1. · 6 

## s 0.793 Z .2- 3**t~~** 2.16**....,,.,~ --** **A~£~~dixA** SB(b , ) 0.0225 Z.2-2 SE(b 0 ) 0.378 Z.2

-5 Cl, 0.906< b, < 1.003 Z.2·1**~** -0.260

### <~< 1.372 Z.2-4

Z-16 

## VES009994The resulting regression equation is 

# y = 0.556 + 0 . 954x The confi d ence interval for the s l ope is determined from Equation Z.2-l to be 0.906 

### < b, < 1.003. Because the confidence interval inc l udes the value 1 . 0 , the data are cons i dered to be unbiased with respect to regressio n line slope. The confid en ce in terval for the intercept i s d e termined fron > Equation Z.2-4 to be
- 0 . 2 60 < b 0 < l . 3n .**R~r.ause** the cor fide nee interval includes the val ue 

### 0.0 , the data are considered to be unbiased wi th respect to regression l. ine intercep t. Therefore , the data are co n sidere.d to be u nbiased . Exam ple Proble m B : Ho w Do I E\ · al nat e Pa ire d S a m p ling Tr a in D ata for Bias? 

### ln this example, 1 8 tes t runs were performed using paired sampling tr ains . Table Z.2-3 sununarizes the data for the two sampling train s . Tab l e Z.2-3. Exa m p l e B
- S um m a r y o f Te st Resu lts P M C o n centration R un Tra i.n A (x ) T ral o B ( y) 1 2.3 2 . 5

. 2 3.9 4.4 3 4 .2 4 . 8

. 

# - . 4 8.6 10.3 5 14.2 1 4 .1 

## -·- - 6 I 5. 1 16 . 2 7 1 8.3 19.0 8 22.4 22.5 9 24. 5 26.8 10 28. 1 28.2 II 5.2 7 . 7 12 6.4 6.9 13 ; 7.2 8.5 14 12.6 13 . 9 15 10.5 11.3 16 22.4 2 4 .3



## -- - . " 1 7 29.3 29.1 18 26 . 9 26 . 1

Z-1 7 

## V ES009995

### The resulting regression equation is 

## y**~** Ll8+ 0.974x 

### Table 

### Z. 2 -4 summari z es the resu lts of the regression calc u lations. 

### The confidence interval for the slope is determined a s 0.924 < 

### b , < I . 024 . 

### Beca us e the confidence inten al includes the value I .0 , 

### the data are considered to be unbiased with respect to regressio n li n

e slope. T he co n fidence interval for t h

e inte rce p t is calculated to be 

### 0.325 < 

### b 0 < 

### 2.036 . In this case , the co nfi dence interval doe s not inc lude the val u e 0.0. 

### Conseq ue ntly , t h e data are 

### considered to be 

### biased . 

### A closer look at 

### the data shows that the 

### PM concentrat i on measured by Train 

### B was higher than the 

### PM concentration for th e same ru n measured by T rai n 

### A i n 

### 15 of th e 

### 18 test runs. T h e test does not r eveal which samp ling train provided the more accurate meas u rements , so both trains s h ould be checked for possible sources ofbias. If t h e**~ou ce**  

### of the bi as 

### can be de termined, only the data f rom t he tra i n that provided the unbiased results shou l d be 

### used to develop t he c o rr

e l atio n equation. If 

### the source of the bias cannot be de t ermined, t he owner or operator can decide to use t h

e data or repeat the correlat i on test . However , if paired sampling data are requi red by regulat i on, the emission te s t s h ould be repea t ed. Table Z . 2-4 . S umm ary of R egr ess ion C al c ul a tion s

Va riabl e C alc ul ated valu e 

## ! Equation No . 

### x 1 4 .56 I 

### ' Z.2

- 3 

### 'J 15.37 Z . 2

- 3 

## s ., 1425 Z . 2

-5 

## s., 1388 Z . 2

-5 b

o 1.18 Z .2

- 2

-- - -·· ·· b , 0.974 Z.2

-4 

## s 0.893 Z . 2

- 8 

# ""' 2. 12 Appendix. A SE(b 1 ) 0.0 2 36 Z . 2

-7 SE(b,) 0.404 Z.2

- IO

C

l " 0 . 924 < b , < 1.024 Z. 2

- 6 Cl 0.325 < b < 2.036 Z. 2 . -9 

### Z.2.5 Us in g tl1e Bias Check Spreadsheet This section provid es instructions f or using the Bias Ch eck Spread s he et. The spreadsheet can be used to c h ec k paired samplin g train data for b i as us ing the procedure described in t b

e previous sections. The spread sh eet inclu d es tlu-ee work sheets. The worksheets ap pea r as tabs at the bottom of the scree n. You can move from one worksheet to another by clicking on the appropriate workshe e t Z-18 

## VE S 009996tab . The i nitial worksheet (Tes t Data) i s used for data entry. The Calcu l a ti ons worksheet s hows t he intemledia t e calc ul a t ions tha t are n eeded fo r ch e cking bi as. Th e S u mma ry of R esults works h eet prese n ts the resul ts ofthe bias check The Calc ulati on s a n d S u mmary worksheets are complet e ly locked, which mean s that tl1e user can open t h e work s heet and view t he results of the calc u lations b u t canno t modi f y any of t he cells i n the wotksheet. The Test Data worksheet i s partially locked . The us er e n ters the test data for one sampli ng t rai n ( Train A ) i n cells A6 t hrough A65 and the data for t he other s a m pli n g train (Train 

### B) i n ce ll s 

### B6 10 

### B6 5 . I t makes no d ifference in the analysis wh:ch train is consid ered Train 

### A and which is consid e re d Train 

### B. Cell s 

### F3 to 

### F 6 are us ed to enter the facility name, location, emissio n unit, and tes t dat es. All other cells i n the Test Data worksheet are locked. F igure Z2· 1 s hows the Test Data work sheet fo r Examp l e Problem A described previous ly.

I!!) I!> I"' 

# ... 

# - 

# - !"* 

# ,... 

# - ""' D**Iii** d 'ti <i !A**~** 

# ' ""' ·::**~** l: . S" l**~** 

## A! ., .,.**;< X'El--** **fG .**  cil 

# ...**~** {01 

# - . 

## " 

## • J u

### ~··**fil** 

# "" 

# .**~: !~**  tie;: 

## - . 

# "' ' IB D + I 

# ,-- I 

### - .:.. 

### .. 0 1 

# . 

# '

A 

# • 0 0 f r 

# • H I 

## ' K L N 

## " I f!A I !I!:fP UMf!t..ji.JVTBAUI DSJ DW 

## ' 

# ' f1<1 ¢o nunti/J ll ll f ,) C IIIy.**#~t ..-** **Eital k**  Pow • C M I! I Ii ll lf 

## ' TUUII A**~** lK" *- J.tf)'I..., • US A 

# ' ""' ' & -• "' IIMI Utlll: 8 ..... ""-l 

## ' ' 23 2**"*****~~:** Mmdo e ..**lil 1**  7 

## . 

## • ' 

## • ' · ' 

# • 

# ... I •• ' " '

..



## " t2 

## ' ,. , 

## , . 

# , " 

## '**u** m 

## • 

# •• • 

### ' 

## { 

# .. " II 

# ,. ' " 

# ,, I 

# •• " ' · ' ' ·' ! n 

## • • 

# .. 

# . 

# ! l " "' " ••• IU 

# "' l • 7l 

## • 

## •**~** 

## ! • 

# ,. • 

# ,. ' ' • 

### • a 3**~ ~**  v 

### , , ...,",.... e ....... .. ........_ ... r'd> _ 

# .. "' 

# ., 31 

# ,. 

# .. "**~** "• •**>~ ftortO.to** **.( ~ti:reJ..** **~o1R !S!J** **!S I,"I/** **E4W./** 

# · - F ig ure Z . 2

- J . Exa mpl e ofT es t Data works h eet for Bias C h ec k Spreadsh eet (Exam ple Problem A).

Z-19 • - If I(

0 

### c=:! -

1 • 1 • 1



## VES009997The Calculatio n s worksheet consists of several co lu mns that display the resul ts of the various calculations needed for the linear regression. All cells are locked in thi s worksheet. Figure 

### Z.2

- 2 shows the Calculat io ns worksheet for Example Problem 

### A.

!H) Ek Cdc. !h hot**~** 10$**~ ~**  a$**lil '!!<!Pill.** **:;<· ~,.lll!** **l!ll<l** •r · t l l l**"'~ ""** **'ii'?' l(i)** **.**

... <I> 3 ..,! Arill .z o - o r D**•••~** s"',**:.::t:s ft'~**  _ . J:!:oo . IBD+I 1 - _ 1 - A. · -**ll'r.** li lliloCO"f>ll(; · fc:luc:**......,.~** C n n!f.'•WIY lO C

,JII (U A l f)(O ' III._ l6A

. 

### ' 

## •**&111 --** **""' :** **~·b )**  hU (NIIH: M:M ct 1 6tlt 1 5.l ....

Figure Z .2

- 2 . Example o f Ca lculation s worksheet for Bias C heck S preadsb eet (Examp l e Proble m A) . T h e Summary of Results worksheet incl u des the information about the facility, emission unit , an d the emission tes t date that were en tered o n the Data Entry worksheet, fo:Iowed by a table displayi n g the ''al u es for the statistical paramet ers that m u st be calculated to eval uate the data for bias . Finally , the summary of th e results is displayed. This summary inclu d es the u pp er and lower bounds for the confidence intervals for the slope and intercept oft he regression li ne . T he spread sheet a lso i n dicates whet h er the data satisfy the bi as cr i teria for slope ii n d inte r cept Figure 

### Z.2-3 shows tbe Summary of Res ul t s worksheet for Exampl e Problem A.

Z- 20 

## VES009998**~** 6k idt**~** O"oK\**~** !.?$**~ ~** **~** 

### o .-.. teJ dJ !:'1 e; 11 -:,"' '(**~ m~** **..;:** 

## . , . "'-' r .**~. ~**  

### u 

## o 4 1**~** •**~** ..,**~** 

### v e .

.. <.:> 3 .,.; INI**lo -o** **a;a• sx** **~:2 ~!!~!r_** **.e-** mo+l , -

_ 1 - A. · .



## '"""' W.'lli- (""'"""- U. .il: 

## , .... 

## , .... .-:**,. ~dokf'o**  .. c •**<:~** J!o¥o .. .**~,.** l'loA! o .._S M

mllU01 S.NN**tt:~.e.ctdClt M1** **10oldll lt**  ... ooolPS · U**(.UI&"fl(~ f>o** **-""' ltloll** **fiii'IIIP ·** **IOI!II ('"".\** **(Il..,** l;lwd..•U-• .... ,. ' • H\ r f\tQm ..{**~I:Q >..** **s-.orx of** **~l'l e.so** **/** 1 · 1 ·1 1 

# -

Figure Z.Z-3. 

### Example of Summ ary of Results worksheet fo r Bin s C h eck Spread s heet (E xample Pro blem A). Z . 2 .6 Using Excel Data Analysis Tools t o Evaluate Bias The data analys i s tools included in Microsoft Ex cel also ca n b e used to perfonn the bias check. • Key in the data fo r the two sampling trains in separate columns . • Uncer the Tools menu, select Data Analysis. • Scroll down tl1e 

### li st of options to 

### Regression, then c lick OK. • Click on the ico n in t h

e Input Y Range cell, then block o ff the dam for sampling Train B and press enter. • Clic k on th e icon in 

### the Input X Range ceU, then block off the data for sampling Train A and press enter.
Z-21 

## VES009999