humidity, and lhe weight of the solution. Document new readings for these parameters every 

l hour. Also record bags of ice added aod time as well as any necessary notes. 

9.6 Shut-down 

To tum the QAG off after testing, first close the manual ball valve on the nebuli:ring air line 

and sbut 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 SOlution uut of the droplet eener.uing 

chamber as pos~ible and tum off the peffitaltic pump, balance, and laptop. Finally, shut off 

tlte main flow. 

9.7 Post-Test Procedures 

9. 7. I Balance Check 

Check lhe balance 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 of the ambient pressure with a NIST-traceable pressure gauge. 

9. 7.4 Solrtlion Sample 

Collect and store an additional 50 ml sample of the anal)'le solllion for possible quality 

assurance checks ot a later time if necessary. 

10.0 Calculations 

10.1 Generated Aerosol CoiiCeJI/TDiion 

The following equation is used to calculate tbe generated aerosol concentration of the i"' 

element ( Ctt)AC) from the QAG's recorded parameters: 

cs·QAG 

C~-QAG- 1 (R - R ) ' F • .. ' E-quation 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 Page l~of23 

VES0091 
F, = Total flow, i.e., the combined flow of nebulizer air and drying air 

added within the aerosol generation system, determined by the 

flow meter located between the QAG and the t:"dnsport >Y>1em. 

R., ; Measured rate of reservoir mass loss, detennined as the slope of a 

linear least squares fit of the reservoir mass dma over the period of 

a test or series of tests. 

Rv = Rate of vapor loss is a calculated vatu" hased on the following 

equation: 

Equation 2 

Where: 

F, = Flow rate of the expanded nebulization air as measured by the flow 

meter on the nebulizing air line. 

M. = Mass of water vapor in a liter of saturated air at 32 •f. This value 

has been well defined and documented: 

M, (32°F) = 4.847 rug/liter 

Pe = Pressure of the expanded gas outside the nebulizer nozzle. Since 

tbe droplet generating chamber ond the droplet size selector are 

open to the atmosphere, P, is the atmospheric pressure recorded 

from the field barometer reading. 

P, = Absolute pressure of the compressed air upstream of the nebulizer 

nozzle. calculated by adding the atmospheric pressure to tbe gauge 

pressure. 

I 0. 2 Generated Aerosol Cottcemratiorr Urrcertainty. 

The uncertainty of the generated aerosol concentration ( u c~) is determined u.~ing standard 

propagafun of error techniques5 relevant to the parameters of Equation l. Tbe uncertainty 

values for the parameters arc those listed as certified uncertainties b)' the manufacrurers 

andfor NIST. This procedure is consistent tb those used at N!ST"7JI 

The uncertainty of the generated aerosol concentration ( C~" ) is calculated using the 

foUoY.i ng equation: 

_ c a- QAG 

I j 

Equation 3 

Psg~~ 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 Solution Conce/1/ration and Flow Rate Set Points 

To determine the required solution concentration and Oow rate set poi1ns for given lest run, 

select a desired concentration of the QAG's aerosol emissions ( c;-\1•'

0 ) . Use the expanded 

form of Equation I: 

c.•-(J,<(i = c;-!!A" [R -F M (1-f>. )] I F , Cf v p r < 

Plug in the desired concentration ( c,...e«; ), the estimated rate of mass loss (Rw. see also 

section 8.3), the mass of water vapor in a liter of saturated air at 32 °F (A/,. 32 op • 4.847 

mglliter), the pressure oft he expanded nebulization air (P,), and the absolute pressure of the 

compressed nebulizing air (Pc). Solve for an appropriate combination of solution 

concentration ( c;o..c ) and flow rates, bearing in mind that total flow (F,) equals the 

expanded flow of nebulizing air (F,; which must be between I 0 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 size oflbe salt panicles emitted by tl1e QAG: 

St!\.:ti-on 10.0 Coln1latious Page 17of23 

VES009902 
Equation 7 

Where: 

D,.1, The diameter of the salt in 1101. 

Duq = The diameter of the liqu1c1 c1roplets in 11m u~ specified by the 

nebulizer manufacturer in )l.nl. 

c;-Q•c = The concentration of the analyte standard in the NJST-tracenble 

solution in grams of analyte salt per gra~n of solution 

P.m c The density of the analyte salt in g/m3

• 

Pu. = The density oftbc liquid droplet in sfm'. 

11.0 Documentation ofQua.lity Control and Assurance 

11.1 Certificlltions 

Prepare a eheck list and con fum the certifications of NlST-traceable components. Assemble 

the certifications ofNIST traceability for each component. 

J 1.2 Field Data Rerords 

Create and use a data sheet for the calibrdtion the balance and flow meters in the field. 

12.0 Pollution Prevention 

The excess aerosol genemtcd by the QAG should be trapped in a filter and disposed of 

acconding to the appropriate regulations. The unused solution sbould tlso be disposed of 

according to regulation. 

13.0 Waste Management 

The soiUiion standards should be handled according to their Material Safety Dala Sheets. 

fruarumeattl M~ for a QAG: V 1.0 Secfiuu J 3.0 Waste Mnnagomenr Pa11e 18 of23 

VES009903 
14.0 Fig ures and Tables 

I \ 

""'""' 

,-

' -"""' I .. I '

--=:. -~ 1.:- 1'\'rlr.u."k -*. 

""''• ....... "'"' 'I # C'olliJbl 

So:oiii!JM -

'l = S!Ganl Sllttutloll ·-- I« Ba!ll 

c- au_~ ' I g 

A. B. 

Figure I : A. Schematic of flow through QAG components. B. 0 \'ervlew of the set-up of 

lbe CES QAG. 

\ 

Figure 2: Schematic of tbe CES QAG standard solullou control system, 

Page 19 of23 

VES009904 
·~.~ 1=r~= .... -r;-r:ltlf ~ f lfi 

J. !lt ---·· ;.J 

Coodmlot 

!O 

,. ' . ,. .. ,.,.,. ... t'iber 

Me"' Regu111(0t Unitt 

Figure 3: Schematic of the CES QAG nebulizer air control system. 

Nebuhm 

hng.fqoiltJnocins 

Cbllntber 

Nebulizer 

NolLie 

Figure 4: Schematic of the CES QAG nebulizer and droplet size control system. 

VES00990S 
~ 

Or>ina 

Chomber-1'- lieoter(•l 

Dr)-ing 

Chamber 

,--

• 

•lJc 

- ' . l.eJ 

~ I ~ 

[\ Dtyina Air P~~ure 

Tube Flow Meter R•gulacor 

Hcatc.1~S) 

t::: -- " 

--·- DTying 

Air Ring 

Figure 5: Scbcmadc of the CES QAG drying air aud drying chamber system. 

Page 21 of23 

VES009906 
Dala Sheet QAG 11~1 Tes1s 

Ojflliror: Soli. Cone Do~: 

loc<lloo: Sian illllll' .. 

~: SQOOT• 

lillol .... """ .... 

,_ "::." ,_ 

""""" IIY.II -: 

Rlo:rl 

ltYt Pres. i)(jj Jk 

I~ ,.FIDw Ailemp r.epcrt F1Dw Flor 11!111 '111111 c.s:a S!CII ffi m (sbol l'fl f,i\ 1001 1 ·•n •• llri m ~ 1\au(i 

'* .lddld let 

~~~t l&.gs 

'IUinlltlentaiMtbxl for 1 OAG: VIIJ Page 22 of23 

VES009907 
1 S.O References 

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 Mesures, International Electrote.chnical 

Commission, lntemntional Federation of Clinical Chemistry and Laborau>ry 

Medicine, lntcmarlooal Orgauaation for Stnodnrdizarion, International Union of Pure 

and Applied Chemistry International Union of Pure and Applied Physics, 

lnte:natiooal Organization ofLegal Metrology [BIPM, IEC, !FCC, ISO, IUPAC, 

IUPAP, OIML). International Vocabulary of Basic and GeneraJ Tenns in Metrology 

(VIM). Geneva, Switzerland: BIPM, rEC, JFCC, ISO, JUPAC, IUPAP, OlML; 1993. 

Available from: ISO, Geneva, Switzerland; ISBN 92-67-01075-1. 

3. Smithsonian Physical Tables, 9th Rev. Ed. Washington D.C.: Smithsonian Institution 

Press; 1954. 

4. Scace, G.E. and J.T. Hodges. Uncertainty of tbe NIST Low Frost-Point Humidity 

Genemtor. Gaithersburg, MD: National Institute ofSrondards and Technology; 2004. 

5. McClave, J.T .. F.H. Dietrich, Jl, and T. Sincicb. Statistics, 7th Ed. Upper Saddle 

RiYer. NJ: Prentice HaU; 1997. 

6. Taylor, B.N. and C.E. Kuyatl Guidelines for Evaluating and Expressing the 

Uncertainty of NIST Measurement Results. Gaithersburg, MD: Nationallnstirute of 

Standards and Technology (NJST]; 1994. Available from: NIST, Gaithersburg, MD; 

TN 1297. 

7. Al!lCrican National Standftfd< Tn~tituteJNatiooal Conference of Standards 

L<lbomtories (ANSIINCSL]. U.S. Guide to the Expression of Uncertainty in 

Measurement. Washington, D.C: ANSUNCSL; 1997. Available from: NCSL 

International, Washington, D.C; Z540-2-1996. 

8. May, K.R. The Collison nebulizer: description, performance and application. Aerosol 

Science 1973; 4: 253-243. 

IA..........,Mdhod for aQAO· Vl.O Page 23 of23 

VE$009908 
VES009909.pdf 
VES009909 
Performance Specification YY: 

Specifications and Test Procedures for X-Ray 

Fluorescence Based Multi-Metals Continuous 

Emission Monitoring Systems at Stationary Sources 

Prepared by: 

Cooper "Environmental Sen•lccs, LLC 

10180 SW Nimbus Blvd SuiteJ6 

Ponland, Oregon 97223 

Revision: 1.0 

June, 2005 

VES009910 
VES009911 
VES009912 
Performance Specification YY: 

Specifications and Test Procedures for X-Ray 

Fluorescence Based Multi-Metals Continuous 

Emission Monitoring Systems at Stationary Sources 

Prepared by: Date:, _ _ _ 

Krag A. Petterson, Environmen tal Scientist 

Reviewed by: Date: __ _ 

Cay A. Yanca, Environmental Scientist 

Reviewed by: Date: _ _ _ 

Bruce E. Johnson, QA M anager 

Approved by: Da t,e: __ _ 

John A. Cooper, Director 

VES00991 3 
Executive Summary 

Performance Specification YY details the performance requirements for • multi-metals 

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

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

stability, arul instrumental response laid out in this document. In addition, every XRF multi· 

metals CEMS must meet the instaUation requirements in PS-YY and the on-going quality 

control and quality assurance procedures set forth In pro~;c<lu c Z if it is used for emt~<inns 

compliance purposes. 

Page i of iv 

YES0099ll 
b. = 

bt 

CA1 c 

Cf 

c c£.1/S ~ I 

cc•.v I c 

CF."' I c 

CF.,.. I E 

C' a 

' 

cs 

I c 

List of Symbols 

They intercept oft he best tit line 

The slope of the best fit line 

X-rny fluorescence calibration accuracy 

Corrected CEMS concentration for the ;•• element 

The concentrntion of the i,. element as reported by the CEMS 

The avernge reported concentrJtion of the CEMS for the i" element 

Correction f.1ctor for percent transport for lhe i'b element 

The relative bias correction factor for the ith element 

The emission limit of the i

111 element 

Concentration of the i"' clement at the stack 

C'M 

1 • Concentration of the ilh element at the sampling module or as reported by the 

XRF multi-metals CEMS. 

dl 

d 

FS 

~ 

L"'" I 

c-I 

£'~~- I 

E/J 

J: ' 

ll 

PT, 

PT, 

PRB, 

a 

= 

= 

c 

~ 

-

= 

= 

c 

• 

• 

Difference between two paired measurements 

Arithmetic mean of differences 

Full scale value of your CEMS volwne (or flow) measwement device 

The vnlu" of the i"' element on the zero standard determ~ted immediately after 

calibration 

The value of the calibrntion ch..ck standard reported by your CEMS 

The measured CEMS response to the zero standard for the ido element 

The measured CEMS rest>Onse to the im element in the upscale standard 

n1e known value of the calibration cheek standard 

The calibrated value of the i'• element oftbe upscale standard 

Number of data points 

The percent transport of the i

111 element 

Average percent transport for the ;•b element 

Relative Bias of the i• element 

Page ii ofiv 

VES0099l5 
Rt.u ~ 

PRSD,= 

r = 

SD! ~ 

~ = 

VD = 

v .. ~ 

UD1 = 

X = 

Xt ~ 

Y1 

ZD; = 

The average of the reference method measurements for the i" tnctal 

The relative percem standard deviation for the i

1

• metal 

The correlation coefficient 

The standard deviation of differences for lhe i

1

b element 

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

Volume drift 

Volume (or flow) reponed by your multi-metals CEMS 

The upscale drift of the i'h element on your CEMS in percent. 

Arithmetic mean 

Value of each data point 

CEMS reponed concentration for the i

111 element 

The zero drift of the ilh element on your CEMS in percent 

l'age iii of iv 

VES009916 
Table of Contents 

1.0 Using PS-YY ................................................................................................................ I 

1.1 V.bat is the purpose and applicability of Performance Specification YY? .............. I 

1.2 What wiU be discussed in PS-YY? ........................................................................... I 

1.3 What arc the instaUation and pre-performance specification test requirements? ..... 2 

1.4 What special definitions apply toPS-YY? ................................ .............................. 3 

2.0 Interferences, Safety, and Equipment Requirements .................................................... 5 

2.1 Are there any potential interference ~ for my XRF multi-metal CEMS? .................. 5 

2.2 What do 1 need to know to ensure the safety of persons using PS-YY? .................. 5 

2.3 What equipment and supplies do I need? ................................................................. 5 

2.4 Wltat regents and standards do I need? ..................................................................... 6 

3.0 Performance Evaluation Procedures and Reporting .................................................... 6 

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

required to perform the tests? ............................................................................................... 6 

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

4.0 Petformance Criteria and Calculations ....................................................................... 13 

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

4.2 What calcnlations, equations, and data analyses are needed? ................................ 14 

5.0 Other Requirements and Information ......................................................................... 20 

5.1 What quality control measures are required? .......................................................... 20 

5.2 What calibration and standardization procedures must I perform? ........................ 20 

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

5.4 What waste management procedures must l use? ................................................... 20 

5.5 What reference tables and figures are relevant toPS-YY? ..................................... 20 

5.6 What references apply toPS-YY? .......................................................................... 30 

Page iv ofiv 

VES009917 
1.0 Using PS-YY 

1.1 What is the purpose and applicability of Performance Specification !1'? 

/././ Purpose 

The purpose of Performance Specification YY is to establish the perfonnance 

requirements that must be me.t by a multi-metals contmuous emission rnuuitoring 

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

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

data rnuy be achieved by foUowing tbc procedures defined in Proc dure Z-XRF 

Based Multi-Metal CEMS Quality Assurance Procedures. 

1.1.2 Application 

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

~'tablishing compliance with federal regulations for metal emissions from stationary 

sources. 

1.1.3 Measurement Capabilities 

A multi-metals CEM.S must be capable of measuring total concentrations of at least 

two metd!S in the units of the applicable standard or in units that em be converted to 

units of the applicable standard. 

I. I .4 Other Monitoring 

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

the units oftbe exi>~ n:gulotion no additional monitoring is necessary. if your 

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

mor.itoring (e.g., oxygen, tcmperarure, and pressure) are necessary to convert the units 

reported by your CEMS to the units of the standard. 

1.2 What will be discussed in PS-YY? 

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

the initial performance specification test. 

1.2.1 1nstrwnent Requirements 

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

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

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

anslyles of interest on a medium. The CEMS must bave a cycle time that is less than 

one third rhe period of the applicable standard. The range of tbe instrwncnt must be 

from l 0 percent to atleast400% of dte :opplicable regulation as determined by field or 

Page I of30 

VES009918 
laboralory tests. FinaJly. the instrument or operator must be able to perform daily 

upscale, blank, and flow quality assurance cbec.Jcs to ensure the accuracy, precision, 

and st1biliry oftl1e instrument and its data. 

1.2.2 In ilia/ Performance Specification Tests 

The purpose of the initial performance specification test is to establish the stability, 

•ccuracy, ""d precision of your XRF multi-metals CEMS. 11te perfomlWlce 

specitication test can be divided ittto two phases: (I) t11e stabiUty tt>t, and (2) the 

accnrncy test. 

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

and i1 done prior to the accuracy testing. For the uccuracy tests, three methods of 

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

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

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

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

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

1.3 What are the insrallatton and pre-peiformance specification tesr requirements? 

1.3.i lnstallalion Requirements 

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

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

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

stationary source. It is recommended that tl1e sampling location be at least two 

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

generation, bend, or other point at which a change i.n poUutant concentration or flow 

dismrbaoce may occur. Tbe sampling location is ulso recommended to be at lea<t two 

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

according 40 CFR Par160, Appendix A. Method I, Section 2.1;. 

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

should he no less than 1.0 meter from the stack or duct wall or Jccated over the 

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

ell'ective measurement path should 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 the path 

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

collect;on and instrumental analyzer portions of your XRF multi-metals CEMS may be 

located any distance from the sampling point provided the transmission efticiency 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 that the 

sampling probe for your multi-metal CEMS be located at point without stratification. 

You may test for stratification at the proposed CEMS sampliJ1g point by using either 

P~1 (as outlined in PS-ll). velocity tests as described in Method 2u. or metals 

concentrations using Method 29 or an acceptable alternative. 

Page 2 of30 

VES009919 
1.3.2 Sampling RequiremcniS 

Your multi-mew I CEMS should sample from the source at a flow rate which is within 

I 0 peteent of true isok.inetic. If your multi-metal CEMS does not maintain an 

isokinetic sampling rate you must use actual site-specific data or dzta from a similar 

installation to prove to us, tbe State, and/or local enJorcement agency that isokinetic 

sampijng is not necessary. 

1.3.3 Pro-Test Preparation Requirements ond Sltggestions 

Prior to the initial performance speeification test you need to eru;ure that your multimetal CE.MS data Jogger accurately records emissions levels as well as signals (flags) 

that indicate botlt nonnal and abnormal operation. Prior to start of the seven day 

stabi~ty test the daily drift measurements (upscale and zero values) should be 

monitored to ensure that the instrument is operating in an appropriate and stable 

manner. We recommend that you use your XRF multi-metal CBMS for a suft1cicnt 

length of rime. to become comfortable with its per~tion prior to the >'tart of the initial 

perf~nnance specification test. 

1.4 Wha1 special definitions apply fiJ PS· YY? 

Calibration Drift: The difference in the CEMS output readings from the established 

reference value ufter a stated period of operation during which no unscheduled maintenance 

or adjustment took place. 

Cycle Thae: The time between when the stack gas first comes in contact witb the 

concentrating media and when the concentration value for that sample is reported. 

Data Recorder: The portion oftlte CEMS that provides a record of analyzer output 

including metal concentrations, flags which indicate normal operotion, and flag• indir.llting 

abnonnal operation. The data recorder may record other pertinent data such as effiucot flow 

rates, and various instrument temperatures. 

Diluent module: The part of the CEMS in which any diluent is added and measured. 

Drift Calbration Standard: A standard containing a constant annoum of metal used to 

establish the drill in the x-ray fluorescence module response. 

Emis5ion Limit: The emission limit for a single metal is equal to the maximum amount 

aUowed under the applicable regulation for its category assuming all of the other metals in its 

category were not present. 

Elemen t or Opportunity: An element that is present in the stack effluent and can be used to 

establish transport efficiency. 

Instrumen t Mensurement Range: The range of metal concentrations the instrtJment can 

reliably measure from the lowest concentration to the highest. The instrument measurement 

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

Page3 of30 

VES009920 
more than four times tbe emission limit. the upper limit does not need to 'le definitively 

established. 

Patb Sampling CEMS: A CEMS that samples the source effluent along a path greater than 

10 percent oftbe equivalent diameter of the swck or duct cross section. 

Point Sampling CEMS: A CEMS that samples the source effluent at u single point. 

Non-Quantitutive Spiking: The process of introducing un unknown umounl ofmctnl or 

metals into the effluent or srunple stream. 

Quantitative Spiking: The process of introducing a known amount metal or metals into the 

effluent or sample s1ream. 

Percent Rei alive Bias: The difference between a reference value and the CEMS measured 

value divided by the reference value. 

Reference material: A material of known value used to check the calibration driH of your 

XRF multi-metal CEMS. 

Sample Tnterf3ce: The portion of the CEMS used for one or more of the following: sample 

acquisition, sample transport, sample conditioning. or protection of the monitor from the 

effects of nack gas. 

Sampling mod·ule: l'be portion of an x-ray lluorescence based multi-metal CEMS that traps 

the metals and delivers them to the XRF module. 

Spiking: The process of introducing metals into the effluent stream or the sampling stream. 

Tran~1>ort Efficiency: The pe~nt of me"' I that is transported from the sample probe 10 a 

point as close as possible to the sampling module. 

Upscale Drift: The upscale drifl is the difference in the reponed vahJe for the upscale 

reference from its value at the last calibration, divided by the value at the last calibration. It 

is used to monitor the stability of the x-ray fluorescence analysis. 

X-Ray Fluorescence (XRF) Module: The ponion of an XRF based multi-metal CEMS 

which identifies and measures metal mli$ses or concentrations using x-ray nuoresccnce. 

XRF Multi-Metals Continuous Emission Monitoring System (CEI\tS): AU of the 

equipment required for detennining metal concentrations using x-rdy fluorescence as an 

analytical technique. The system may consist of several major subsys;ems including but not 

limited to the foUowing the sample interface, the x-ray fluorescence module, diluent module, 

data recorder, sampling module lUld volume measurement module. 

Zero Drift: The zero drift is the difference in the CEMS readings for the zero reference from 

their values after the most recent calibration, divided by the emission limit for each element. 

Page 4 of30 

VES009921 
2.0 interferences, Safety, and Equipment Requirements 

2.1 Are tl:ere a11y potemia/ interfereucesfor my XRF multi-meral CEMS? 

There may be interferences arising from the x-ray fluorescence analysis, the trapping media, 

or from condensatioo in the effluent gas. Check with your multi-metal CEMS manufacturer 

to find out more about potential interferences. 

2.2 What do I need to know to <'11Sure the safety of persons using PS-YY? 

People usir.g PS-YY may be exposed to hazardous material, operational hazards. and 

bazatdous $ite conditions. PS-YY does not address all the safety issues associated with its 

use. It is yi>ur responsibility to ensure tl1e safety of persons using PS-YY. Some helpful 

references may include tile CEMS ma.nual, the CEMS manufacturer, other reference 

methods, and on-site safety regulations. 

2.3 Whal equipment and supplies do I need? 

2.3.1 Eqw'pmem for the CEMS 

I. Sample interface: Ths portion of the CEMS must present a sample of source 

efflucou to the sampling module that is directly representative or can be 

corrected so as to be representative of source. To accomplish this, the sample 

interface may contain, among other things, heaters or beating systems, and 

dilution air. 

2. Sampling module: The sampling module must collect and trap aU the analytcs 

of interest from~ representative sample of stack eftluent without significant 

loss. The trapped analytes then must be presented to the XRF module. 

3. XRF module: The XRF module uses x-ray fluorescence to determine tbe mass 

or concentration of metal captured by the sampling module. 

4. Volume measurement module: This portion of the CEMS measures the 

volume of source effiuent from which the metal analytes were captured in the 

sampling module. This volume along with the data from tbe XRF to determine 

concentration of source effluent. 

5. Ollucnt Module: Lfyour multi-metals CEMS uses a diluent such as air or 

nitrogen it is added to tbe effluent sample and me:JSured using the diluent 

module. 

6. Quality assurance and quallty control materials: Your multi-metal CEMS 

must possess tbe necessary equipment to perfonn daily ~sca e and zero 

checks. Your multi-metal CEMS must also possess the equipment to perform a 

daily check of the sample volume at normal sample Oow rates. 

7. Data recorder: Your XRF multi-metal CEMS must be2ble to recotd metal 

concentrations and instrument status signals (flags). 

Spcdftcadoo> (or XRF 8aM'd MtJto.r..,.\1tUis CllMS (PS·YYJ Page 5 of30 

VES009922 
2.3.2 Otlrer Equipment Needed for 1he Perfom•ance Specification Test 

PS-YY does not specify all the equipment and supplies necessary for lhe performance 

specificntion tests. Some oftbis information is included in the appiicable reference 

methods (e.g .• Method 29 or an acceptablealtemalive). 

2.4 What regenls and srandardr do I need? 

2.4.1 Zero Drifi Reference 

Yourmulti-mclals CEMS musl include a standard for the measurement of the daily 

zero drift. This reference should produce a CEMS response indicating the absence of 

metals. If this is not. feasible this standard should produce a value between zero and 

~/ooftbe emission limit for at least two elements measured by your XRF multimetals CEMS when lbe instrument is operating appropriasely. 

2.4.2 Upscale Drift Reference 

The reference for the upscale drift check should generale a response for at least one 

metal from each condition used in the XRF analysis. This response must be at least 80 

percent of the emission limit 

2.4.] Volume Drift measurement device 

During the initial perfbnnance specification test the volume measurement must be 

corr.pared on a daily basis against an internal volume or flow measurement device. 

Tni• volume or flow rneasuremenl device must be calibraled independently of the 

sample volume or flow mcnsuremont device and mu<t he as accurate or more accurate 

than the sample volume or How measurement device. 

2.4.4 X-ray Fluorescence Calibrariafl Check Standards 

Your XRF multi-metals GEMS must include u means of checking the :t-ray 

flu<>rescence calibration against an ex1emal standanl. NIST traceable thin film 

standards are an example of a suitable x-ray fluorescence calibrn:ion check slandard. 

3.0 Performance Evaluation Procedures and Reporting 

3.1 What is the purpose of the initio/ peiformancr specification tesLr ami whlll is required 

to perform rile rests? 

The purpose of the initial perfom1ance specification tests is to determine the bias, precision, 

stability, and cycle time of your multi-metal CEMS. 

Page 6 of30 

VES009923 
3.1.1 Pretest Preparatio" 

Prior to tbe srnrt of your initial perfomtaoce specifi.cation tests you must be sure that 

your CEMS is insmlled according to the specifications laid out in this document After 

installing your XRF multi-metals CEMS we recommend that you use the CEMS for a 

period of time to familiarize yourself with its operation. We also recommend that you 

conduct daily checks of the z.ero and upscale drift to verify that the instrument is 

functioning properly. When you are confident that tbe instrument is performing 

satisfactorily it is time to prepare for the initial performance specit cation tests. 

3. 1.2 X-ray Fluorescence Calihratirm Check 

If your CEMS measures more metals for compliance purposes than will be evaluated 

during the CEMS accuracy testing described later in this document you must perfonn a 

calibration check of the x-ray fluorescence module for these additional metals. During 

the ~libration check you must challenge the x-ray fluorescence trodule with a standard 

or ~tandards for e-•ch metal measured by your XRF multi-metal CEMS. Each metal 

must be measured at least three times and tbe error is calculated according to 

Equation 13 for each measurement The average error of the three measurements 

must be less than 10% of the calibration standard's value for each metal, if not your 

CEMS may not be properly calibrated. The x-ray fluorescence calibration check may 

occ~r at anytime during the initial perfmmancc specification tesL. 

3. U Stability - The 7-day CalibraJion. Driji Tests 

Prio: to the start of the accuracy test you must perfonn a calibrntion drift test for a 

pe.riod of at least seven days. The purpose of this test is to verify that the instrument 

operation is stable. During the calibration drift test period you mJSt determine the 

mOWJitude oftlte zero calibration drift (us calculated in Section 4 2.9), tlte upscale 

calibration drift (as calculated in Section 4.2.!1), and the volume (uo flow) drift 

(calculated using Equation 14) at least once each day. During the srnbility tests no 

adjustments or c.alibrations may be made to the CEMS. The results of the stability test 

mu..<t be reported along with tbe results ofthe accuracy tests. 

J./.4 CEMSAccuraC)J 

Theaccumcy of your XRf multi-metal CEMS may be detennin«< using one of the 

follawing four options. 

L Option A: Linearity test of the entire CEMS 

2. Option B: Linearity test of the XRF and sampling modules separately from the 

sample interface. 

3. Option C: Relative bias test of the entire CEMS. 

4. Option D: Relative bias test of the XRF and sampliog modules separately 

from the sample interface. 

Page 7 of30 

VES009924 
There are also several options for generating the metals that will be analyzed by your 

multi-metal CEMS including, metals that arc generated as a by-pro:luct of nonnal stack 

operation, quantitative spiking, and non-quantitative spiking .. Regardless of the 

generation option you choose you must be able to produce concentrations for some of 

the analytes of interest at 80 to 120 percent of the emission limiL All oftheCEMS and 

reference method measurements must be conducted while sampling nue gas. 

You do not need to test every metal that your CEMS measures, however, you must 

generate at least one metal from each category of metals measured by your Cl:lMS for 

the accuracy tests. For instance, if your XRF multi-metals CEMS measures semivolatile, low volatile. and high volatile metals you must test at least on~ metal from 

each of those categories. (Low volatile metals may also be used to verify the capture 

efficiency and detection of non-enumerated metals). You must also prove thnt the 

XRF module is properly calibrated to measure the elements that are not being 

measured during tbe accuracy test by following the procedures described in Section 

3 .1.2. The test requirements for each option are explained below and summarized in 

Table I. 

Unearity Test Requlreme.nts (Options A and B): The b1as and precision of 

your XRF multi-metals CEMS may be detennined by checking the linearity of 

the instrument response over a series of concentrations. If quantitative spiking 

is used. then 01e concentration of the aerosol is pa ired with a reponed CEMS 

concentration acquired at the same time. Each data point is then plotted with 

the spiked concentration oo the X axis and the reported CEMS concentration on 

theY axis. If either non-quantitative spiking or stack by product is used, then 

the reported CEMS concentration is plotted on the Y axis versus the 

concentration reported by method 29 or a suitable alternative. 

Linear least squares regression analysis is then used to fit the data points to a 

line. If you challenge only the XRF module and the sampling module the slope 

of this line, which is an indication of the accuracy of your XRF multi-metal 

CEMS. is required to be between 0.&5 and 1. 15 for each metal. The coefficient 

of correlation must be greater than 0.90 and is an indication of the precision of 

your multi-metal CEMS. Finally, the intercept of this best fit line must be less 

than 200/o oftbe applicable emission limit. If you challenge the entire CEMS 

system and do not meet the slope or intercept criteria you must apply a 

correction factor according to the procedures in Section 4.2.12. You arc, 

however, still required to have a correlation coefficient or0.90 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 of metals (high volatile, low 

volatile and semi-volatile) measured by your CEMS. The three levels must 

incorporate at least a two fold concentration cbange and one level must be 

between 80 and I 20 percent of the emission limit. You may acquire a blank 

sample if you wisl1, 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$009925 
least three measurements are required at each concentration level and a total of 

IS measurements are required overall. You may make additional 

measurements, however, you must report all the results. If you are not using 

quantitative spiki ng you must make IS corresponding measurements using 

method 29 or a suitable alternative. We recommend using duel trains for the 

reference method measurement to identify and screen the reference method data 

for imprecision and bias. 

Additional requit-cments for each of the twu linearity test options are outlined 

below. You may also want to refer to figures I through 8 for guidance on 

which option to choose. 

Option A: Total CEMS Linearltv 

fn option A the entire CEMS system is challenged during the linearity tests. 

Any one of the three meLhods of melals generation may be used during the test. 

Some of the testing requirements associated with metals generation are outlined 

below 

1. Metals generated as a result of stack operation 

If meta ls for the test are generated as a result of s1ack operation you must 

measure the concentration of the metals in the Stack using method 29 or a 

suitable alternative and comt>arc the values with those reported by your 

CEMS. We recommcod using dual reference method trains to screen the 

reference method for precision and bias. 

2. Non.quantitative spiking 

You may either spike non-quantitatively into the stack or duct itSelf or into 

the transport system as close as possible to the sample probe. If you >-pike 

into the source you must measure the concentration in the source using 

met!Jod "l.'J or a suitable alternutive. This cosurom~ot is then cmnp1lretlto 

the result of your CEMS. If you choose to spike into the transport line you 

must measure the concentration immediately downstre:un of the spike point 

with a met!Jod 29 or a suitable alternative and compare that measurement 

with the concentration reported by your CEMS. 

3. QuantiLative Spiking 

You may spike a quantitative aerosol directly into the source or into the 

transport line as close as possible to sample probe. Either way tl>e known 

spiked concentration is compared \\~tb that measured by the CEMS. 

Option B: Linea rity for Sampling and XRF Modules Only 

In option B only the sampling and XRF modules of your multi metals CEMS 

are challenged with a linearity test. You must also complete a transport 

efficiency test along with the linearity test The procedwes for performing a 

transport efficiency test are described io section 3.1.5. Tile procedures for 

option B associated with each metals generation option are listed belo1v. 

1. Metals generated as a result of stack operation 

Spcdftt:a!.ioN (orXRF fbsfd M11t1i.Mcub Cf'.:-tS {PS.YY) Page 9 of30 

VES009926 
If metals concentrations for the accuracy teSt are generated as a result of 

stack operation you must measure the concentration of the metals as close as 

possible to the sampling module using method 29 or a suitable ahernati' e 

and compare the values with those reported by your CEMS. We recommend 

using dual reference method trains to screen the referena: method for 

precision and bias. 

2. Non-quantitative spiking 

You may either spike non-quantitatively into the stack or duct ItSelf or into 

the transpon system. Either way you must measure the concentrations of the 

analytcs as close as possible to the sampling module and compare that 

concentration with that reponed by your multi metal CEMS. 

J. Quantitative Spiking 

You must spike at a location as close as possible to the sampllng module and 

compare the known spiked concentration with that reponed by your CEMS. 

• Relative Bias Tt-sl Requirements (Options C and 0 }: There are tWo relative 

bias options available: one that challenges the entire CEMS aud one that 

challenges the sampling and XRF modules separately from the sample 

interface. Either option requires at least 12 CEMS meusur:ments be made at a 

concentration level 80 to 120 percent of the emission limit for a metal from 

each category of metals analyzed by your XRF multi metal CEMS. lfyou are 

not using quantitative spiking you must al.so have at least 12 correspondio!l runs 

of method 29 or a suitable alternative at this concentration level. We 

recommend using dual trains for the rofo:rence method to screen the data for 

imprecision and bias. 

Additionally, for at least one metal me•~ured :tt thP. emission limit or for a 

surrogate metal that can be measured by your CEMS (such as iron} you must 

test the CEMS at three different concentration levels. These three levels must 

incorporate at least a two-fold change in conccutration and one of the levels 

must be between 80 and 120 percent of the emission limit (the concentration of 

the emission limit for the surrogate metal is equal to tbat for the metal measured 

by your CEMS with the b.igbest emission limit}. You are required to obtain at 

least three measurements at each concentration level and are required to have a 

total of at least 12 measurements. You must report the results of all 

measurements. The relative bias is an indicator of acCUI"liC)' and should be 

calculated using equation 5 for each element. Also, the percent relative 

standard deviation, which is an indicator of precision, shc•uld be calculated for 

each metal 

lfyou challenge the entire CEMS system and you do not meet the test criteria 

you may apply a correction factor to your CEMS data. Calculate a correction 

factor for each metal in tbe relative bias test according to the equation found in 

section4.2.13. If you challenge the sampling and XRF modules sepamtely 

from the sample iote.rtace you may not apply a correction factor to the data 

Paae 10 of30 

VES009927 
from the relative bias test, you may, however, apply a c.orrection fuctot· to the 

resulls of the transport efficiency test. For the metal that was spiked over 

several concentrations you must perform linear least squares regression analysis 

on the data. The correlation coefficient for this fit must be better than 0.90. 

This is to dcmonstmte that the instrument response is valid over its applicable 

range. If the criteria for tbis test is met then the correction factors are assumed 

to be valid over the range of the instrument. 

Ootion C 

In accuracy test option C the entire CEMS is subjected to a relative bias test. 

The options for metals generation and the associated spiking and reference 

method requirements are the same as those for Option A under the LineMity 

tes ~. 

Option D 

In accuracy test option D only the XRF and sampling modules are subjected to 

a relative bias test. The options for metals generation and ctteir associated 

spiking and reference method requirements are the same as those lor Option B. 

You are also required to perform a transpon efficiency test 

3. U Transport Efficiency Test 

You must pcrfonn ~ transport efficiency test if you ~ve only challenged the ~amp ling 

and XRF modules during the accuracy teSts (option.~ B and D). Any one of the four 

methods described below ore valid ways of detenniniug percent transpon for your 

multi-metals CEMS. 

PanlcuJate Matter (PM): In this approach particulate matter is measured 

concurrently in two locations, (I) in the stack effluent stream as close as 

possible to your multi-metals CEMS sample interface, and (2) at a point in the 

transpon system as close as possible to the sampling module. You may use any 

standard reference method to measure PM including Metl•od 5, Method Si, or 

Metl1od 17 (40 CFR 60, Appendix A)m,;v,v. Particulate matter must be 

generated by operating the source. You must acquire at least 12 paired 

concentration measurements (each pair consists of the measurement made as 

close as possible to the sample interface and the measurement made as close as 

possible to the sampling module. The percent transmission is calculated for 

each pair using equation 6 and the overd!l percent tr.~m111ission is determined 

by calculating the average of all twelve mns. 

• Element of opportu nity: Alternatively, transpon efficiency can be determined 

using a surrogate metal such as iron or zinc that is comroonly present in stack 

effluent Method 29 (40 CFR 60, Appendix A).; or a suitable alternative can be 

used to m~ ure the metal concentration in the stack effluent stream as close as 

possible to the sample probe and at a point in the transport system as close as 

possible to the sampling module. Also, if your XRF mult:i-metals CEMS is 

P<~ge 11 of 30 

VES009928 
capable of measuring the element of interest, you may compare the measured 

concentration on the CEMS with that measured in the stationary source using 

the reference method. Transport efficiency is calculated using equation 6. You 

arc required to make at least twelve paired concentration measurements to 

determine the mean transport efficiency. 

• Non-quantitative sptldng: An aerosol containing a surrogate metal or a metal 

anulyte can be spiked non-quantitatively into the stack or duct gas stream or 

into the transport system as close as possible tu the sampling probe. The 

concentration of the spiked metal is measured by n1ethod 29 (40 CFR 60, 

Appendix A)5 or a suitable alternative as close as possible 10 the CEMS' sample 

probe and by another Mctl:tod 29 or a suitable alternative as close as possible to 

the sampling module. If you spike directly into the tnutsp<>n tine you must 

make your upstream concentration measurement as close as possible to the 

spike location and your downstream measurement as close as possible to the 

sampling module. If your XRF multi-metals CEMS is capable of measuring t.he 

spiked metal, you may compare its reported concentration with 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 twelve paired concentration measurements (l) determine the mean 

transpon efficiency. 

Quantit ative Spiking: An aerosol containing a surrogate metal or a metal 

analyte can be spiked quantitatively into the stack or duct gas stream or into the 

transpon system a~ close as possible to the sampling probt. The concentration 

may be measured on the CEMS or by using method 29 ora suitable alternative 

as close as possible to the sampling module. This measurement is then 

compared with the known concentrdtion of the spiked aerosol to detemtine the 

percent transport. 

3.1.6 Dual Tt-ain Requirements 

If you use a reference melhod (eg., method 29 or Si) during the linearity, relative bias, 

or transpon efficiency 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 no 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 cycle time as 

will be used during day to day operation. 

3.2 How do I report the results qfthe initial peiformaflce specification test? 

Summarize the esult~ of the calibration drift and accuracy tests in tabular form. Include all 

data sheets, calculations, and records of CEMS measurements necessary to substantiate the 

perfonnance of the CEMS and any other devices or methods (e.g., method 29). The CEMS 

Pnge 12 of30 

VES009929 
measuremc01s shall be reported to the agency in units of 11ghn' on a dry basis, corrected to 

2o•c. 

4.0 Performance Criteria and Calculations 

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 time and data reporting capabilities to detennine if your facility is in 

compliance with metal emission standards or opemting permit I units us specified in 

applicable regulations or permits. You wiU demonstrate this capacity by showing that your 

XRF multi-metal CEMS meets the following performance criteria. 

4.1. J 7-day Drift Check Criteria- Stability 

Upscale Drift: The upscale drift us calculated in section 4.2.8 must be less than I 5% of 

the original calibration value of the upscale reference each day for seven consecutive 

days. 

Zero Drift: The zero drift as calculated in Section 4.2.9 must be less than 20% of the 

emis;ion limit each day for seven consecutive days. 

Volume or Flow Drift~ The volume or flow drift as calculated in Section 4.2.11 must 

be less then 20% ofthe full >Cale value of the flow or volume measurement device each 

day for seven consecutive days. 

4.1.1 X-Ray Fluorescence Calibration Dri}i Criteria 

For each metal measured by your multi·metal CBMS tor compliaoce purp.,.;,es the xray ;luorescencc calibration drift must be less than I 0% of the vdrue of the standard. 

(N01c: you are not required to calculate the XRF calibration drift for those metals used 

during the bias and precision testing). 

4.1.3 Relative Bias Criteria - Accuracy and Precision 

The relative bias of the instrument must be Jess than 15% and the relative percent 

standard deviation (RSD) must be I 0% or Jess if you challenge the :A'RF and sampling 

modules of your CEMS separately from your transport system. If you challenge your 

entire CEMS and it does not mecttbe above relative bias criteria you must apply a 

correction factor to the results reported by your CEMS. The cor.ection factor is 

calculated using the equation in section 14.2. 13. Also, the correlation coefficient for a 

least squares linear regression fit of the metal that was spiked at three different 

concentration levels must be greater than 0.90. This is to help assure that the 

correction factor is applicable over the range of the inStrument. 

Page 13 of30 

VES009930 
4.1.4 Linearity Test C1ireria - Acc11racy and Precision 

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

mulli-metals CEMS tbe slope of the least squares linear fit should be between 0.85 and 

1.15. The correlation coefficient must be 0. 90 or better and the intercept should be less 

than 200/o ofthe applicable emission limit. If you challenge only the XRF module and 

the sampling module of your CEMS you must meet the above criteria. lfyou 

challenge your entire CFMS and you do not meet the slope or intercept criteria you 

must adjust the results reported by your CEMS, you must however. Still meet the 

correlation coefficient criteria. The correction factor is calculated according to the 

procedures in section 4.2.12. 

4.1.5 Transport cfficil!llcy- Accuracy 

ff the average transport efficiency is between 90 and I I 0 percent, d1en no correction 

for tr.lnsport efficiency needs to be applied to concentrations reported by your XRF 

multi-metals CEMS. If, however, your average trdllsport efliciency is less than 90 

percent or more than II 0 percent then you must use a correction factor. You may use 

your transmission eftlciency test data to establish a correction factor that would change 

the r(J>Oned CEMS concentrations for each metal to a value that would reflect I 00% 

transmission efficiency. 

4.1. 6 Cycle lime - Appropriate Reporting 

TI1e cycle time for your XRF multi-metals CEMS must be no greater than one-third of 

the averaging period for the applicable standard. 

4.2 Wh01 calclllations, eqllat/ons, and data analyses un: needed? 

4.2.1 Arithmetic Mean 

Calculate tbe arithmetic mean of a data set as follows. 

- 1 "\' ~- £..., , 

n 

Where: 

x • Aritlunetic mean 

11 • Number of data points 

x1 ~ Value of each data point 

Eqllation 1 

Page t4 nf30 

VES009931 
4.2.2 Arithmetic Mean of Difference 

To calculate the arithmetic mean of difference use the above equation substituted for x. 

Where 

Equation 2 

Where: 

cfE"'s - The concenttation of the i'h element as reported by the CEMS 

R, .. , ~ The concentration of the ;do element as reportoo by the reference 

method or aresol 

4.2.3 Standllrd Deviation (of differences) 

.Equation 3 

Where: 

SD; = The standard deviation of differences for the i"' element 

n = The number of data points 

d1 ~ The difference between the concentration measured by the 

reference method or the concentration of tlte reference aerosol and the 

concentration reported by the CEMS. 

4.2A Perce11t relative sta11dard deviation 

SD. PRSD, =:=l-><100 

RIW 

• 

Where: 

Equation 4 

R:U' ~ The average of the reference method data set or the reference 

aerosol concentration for the i'h element 

PRSD, = The relative percent standartl deviation for the j'l' metal 

4.2.5 Relative Bias 

ld.l PRB.==x!OO I Rlt.ll 

I 

Equation 5 

Page 15 of"\0 

VES009932 
Where d1 is the mean difference, R,"' is the average of tbe reference method 

data set or the average aerosol concentration for the itb element, and PRB1 is 

the relative bias for the ith e lement 

4.2. 6 Percent Transmission 

c- PT, xiO(I 

c, 

Where: 

ct .. Concentration of the ilhelement at the stack 

Equation 6 

c:M ~ Ccncentration of the i"' element at the sampling module or as 

reported by the XRF multi-metals CEMS. 

PT, "' The percent transport of the id! element 

Report the average percent transpon ( PT) of aU measurements for each 

element that was tested (only one element is required though more can be 

tested). 

4.2. i Best Fir Li11e for Li11earity Test 

Calculate the linear correlation equation given below. 

y .:b. + b,x 

Where: 

b. • The y intercept 

bo = The slope 

The intercept is calculated according to the following equation. 

b ... Ji - b,x 

Where: 

I • i= - l:x, n ,_, 

The slope of the line is calculated according to equation below. 

Equation 7 

Equation 8 

Paae 16 of30 

VES009933 
• :L/x, - x)(y, - ji) b, = J=LI _ _ _ _ _ _ 

i:rx,-xf 

Equa1ion 9 

1-J 

Tbe linear correlation coetlicient is ca lculated according to the following 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: 

Equation 11 

Where: 

UD, = The upscale drift of the i'h element on your CEMS in percent. 

~" = The measured CEMS response to the i" element in the upscale 

standard 

g = Tbe calibrated value of the ith element of the upscale standard 

:1.2. 9 Zero Drijl 

[L;""' ~I ZD,= L xiOO 

c, 

Equation 12 

ZD; = The zero drift of the i* element on your CEMS in percent 

L-:- = The measured CEMS re.~ponse to the zero standard for the i'b 

element 

L~ The calibrated value oftlte i'" element on thr zero standard 

C1

L The emiSSiOn limit Of the it> element 

4.2. 10 X-Ray Fluorescence Calibration Accuracy 

Page 17 of30 

VES009934 
Equation 13 

Where: 

CA, c X-ray nuon:scence calibration accuracy 

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

L;"' e The known value of the standard 

4.2. I I Daily Sample Volwne Check 

IV.--V--1 VD= x iOO Equation 14 

FS 

Where: 

VD m Volume drift 

V""" c Sample gas volume (or now) measured by the CEMS volume 

check measurement device 

v.. E Sample gas volume (or llow) reported by your multi-metal CEMS 

FS = Full seale value of the CEMS volume (or now) measurement 

device 

4.2.12 Linearity Tcs1 Correction Factors (Applicable on()' whe.111he linearity lest 

r.hal/enges the entire CEMS) 

I. Correction equation if CEMS does not meet either tbc slope or the intercept 

criteria. 

C( - y,-b, I -

b, Equation IS 

Wbere: 

C~ N corrected CEMS concentration for the illo clement 

y, c CEMS reported concentration for the ill! element 

bo = the intercept of the least squares linear regression line 

b1 c the slope of tbe least squares linear regression line 

2. Correction filctor ifCEMS meets intercept criteria, but does not meet the 

slope criteria. 

Po~e 18 of30 

VES009935 
c Y· c =__!.. , b 

I 

Equation 16 

3. Correction factor ifCEMS meets slope criteria but does not meet intercept 

criteria. 

Equation 17 

4.2. 1 J Relative Bias Correction Factors 

Equation 18 

Where: 

CF/" ~ The rclutive bias correction factor for the i"' element 

C,w• = The average reponed concentration of the CEMS for t.he itlo 

element 

R,"" The average of the reference method measurements for the i'" 

metal 

4.2.14 Percent transport correction factor 

YT I CF, == 

PT, 

Equation 19 

Where 

CF," Correction factor for percent transport for the i

0

' element 

PT, = Average percent transport for the i

111 element 

Page 19 of30 

VES009936 
5.0 Otbtr Requirements and Information 

5.1 What 1uality control measures are required? 

Quality control measures for an XRF multi-metal CEMS are addressed in procooure Z 

"'Quality A~sur.mce Requirements for X-Ray Fluorescence Based Multi-Metals Continuous 

Emission Monitors." 

5.1 What calibration and standardization procedures must/ perform? 

Refer to yoJr CEMS owner's manual and manufacturer to determine what calibration and 

standardization procedures are required for your multi-metal CEMS. 

5.3 What JX)llution prewmriott procedures must/ follow? {reserved] 

5.4 What wasre management procedures mt<St I use? 

AU chemicals used to produce a reference aerosol or in performing standard methods need to 

be disposed of properly. 

5.5 Who: reference tables and figures ore relewmt to PS-YY? 

Pa~e20 of30 

VES009937 
Ta b le l. l nlhal Per ormancc s Specl lfi 1ca ti on T ests an d C" n ten a 

Test Test Test Requirements Test Criteria 

Cafi!I:OI"l' 

Zero Drift Monitor UrO standlttd for 1 < ~ dnfl<very day COr sevm 

consecutivt days under nomual ClOOse.."'Urive days 

ODenltine. cooditions 

Seven Da!· Upscale Drift Moai10< ups<ale slandanl f« 7 < 15~ dril\ fNUY day for $-eYm 

consecutive days under normal coosecuti vc days Stability oper•tins. cooditloni 

Flow Drifi Moniior now dnll lor 1 c:on~urlve .... 20% dfin every day for oo~n 

days under nom101l opcming ~cloys 

conditions 

X-Ray Fluoresce.uce Tesraii&IOOatd for c11.ch element < I 0% drift for every clcnk'nt 

Calibration Cahbration Drill Cbeck l!le<I$UIOd for complianox by yoor 1UC&s-Jnd: for compliance by 

CEMS3 times ' vourCEMS 

Option A • At kt~l one mct11l from ~ch • Sl>po@ o.gs to 1.1 s ea1egoty • r~0.90 Perform a lioeartry tc::st on • Keed at least 3 conc:en-rra!ion • i.Jtcr«opc. < 2<M of r:n'lission ea1ire CEMS levels wbic:h include a 2 fold lmit cone. ('haltge and the em inion 

limit . iftbt- above criteria are me. 

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

spike into transport line 1u1 close • if not met apply u. correcrioJ• as J>O<>ilil<. 10 1bc probc (coo-elation critcriunust be 

o:<t) 

QptjonB • At t one metal from t-ach UnotriN Criteria 

cat~gory • Slope - 0.&5 10 1.1 s 

• Perfonn a llneMry test • Need ot lc3St l concc:ntrLUion • ra,0.90 

<m !lamt>1ing module levels which include a 2 fold • ilterx:cpt < 20% of e•niss1on 

snd XRF mndule ooly cone. c:h&nge arw:l the emission liruil 

• Otrenmne tranSpOr1 1imh • de J.inQriry etheria IWSI be 

efficiency separutdy • Spike or measure «~nccntna.tions .... with refere~ method ftB close as )~~n! 'fl:l!D:IQQ!l Ctil~li!! po$Slble to ' he iacnpting moduk • SOSI'TSIIO 

• Jr pen.'ettt transpon criteria 

Accur acy are noC' 1001 apply a 

cooeenon fite1.or 

OQtion C • At kost ooe mcUI from each Perren• relallve BiM 

c.uegocy <'If 80 to l 20 percent of 1W;£ LSY. 

Perfonn a rdativc b~ test emission limh o/oRSD S 10% 

on enlft CE.:\fS • One olhe.-.neul ot 3 con<. le>'ds 

which mclude n 2 fold cone. • 90 for metal v.ith thTet 

change aud lltt> e.mi.s$ion limn lOid oonc c:hnnge 

• If spiking. spit• into SO<Jr<e .,. • "f CJiterla not 1'0Cl apply a 

spike into mmsport line u do5e torT"eC~ion facwr (COI'Ydation 

as J'(lStnble 10 1bc prObe ooetlicicnt entail must be 

mel) 

OptionD • At k-a~ one ntd&J tfom each fgootl Rcbti\'e 8j111 Criteria 

cateJOfY at SO to l:W pnceut of RB!;IS% 

• Perfonn a rel.:uive bias cmiiiSkln timit RSD ~ ~/e~ 

c~ on samplirtg • Oae other tl'lt'illliU 3 cone. "=veJs 

module r := 0..90 fnr rt)dal 'il'ith three: and XRF ·which inclu& 1 2 fold cone.. module on.ly change w1d the emission lin'i' fold cone. mange 

• Dci..:mline n nq'IO!l • Spike or measure conoentru.lions J)Q"Ct!!l fuuspnrt Criseria 

cffici<ocy sq>~~Oidy with n:fr:rmce method a_.;: close a..;; • 9D$PT~J 10 

pMSiblc to the Jtunpling module • If percent mnsport aiteria 

are-00' met apply~ 

co-l'fl'!Ction fac-tor 

Page- 21 of 30 

VES009938 
Quantitative 

Spiking 

Methods of Metals 

Generation for 

A<:curacy Tests 

'onQuantitative 

Spiking 

Figur e J: Types of metals generation available for accuracy te$15. 

Stack Operation 

Pag" 22 of 30 

VES009939 
Quut1rarive 

Spikht~ 

C111ll ~lll~l:"l.!imlly 

itlt() tflq 1111ck or 11'110 !be 11111~1)(1" 

t)1iiL1IIU~ill~tOthc 

A!fFic P\)bc:'f 

v .. 

ClloUo: ~at die tntirt bltl~ll 

li-~ cmlt Sy.:l('til, No 

~~.r 

ftllri!JM tft''lcicwy. 

C'tn I Jf.Mfiii C" 

~-·1+1•20% 

c( ~ •rrdtiiO Rill ..., 

11 C\'1~ ~ ll'lt1lll rrom UCih 

elMS mch!.ln::d .,. a:y C't..\G'! 

Yc• 

Cllllg~:J~er~l( 

) fOC'ft!'!l .... '":'tk 

(-.)("..me ct'l'ltCfll frOM cad! cL.• 

of mct1ol lil\d}'W rllCIIMliCld by my 

C£\fS. .. ~(1M kvtl .~ 

tJ~ 2t»:.urtbo: 

('fllh>1ion 111\lh'l 

Can I Spllo.•tnto 

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

-~ .. ..,.-.~1 

Ye• 

\'ou CMd!ll~ &heP~I'!ptlt-~ 

llt:CI6ak-~h---~ 

(lllniQnO( )'OI!f b;irtCh M M 

CEl.t$ Jtfllh!lt!y fh:wu 4lw 

~')'$liD. t.o..·nu, )IOU 

"'·UI alto h3YC 110 llrb:rm!.t tn.Mport lllclttlcy , 

"'" <Ofi:Wltr.l!ion ·-) k'fCU r .... til k lli! (WiltiiMI)"'C' Ul 

foro~ that e:JO ~ 

............. O:MS? 

N 

No 

Yw ~~~:!!d 10 1ry a l.f.ft'no.;Jtt 

liJ'fll'oodl, 

Figure 2: Flow chart for using quantitaliv<' spiking during tbe accuracy tests. 

Page 23 of 30 

VES009940 
c .. ,~.._,Y 

ir'trl' ... ~ )lririM Ike "riM~ 

i")'-lfl IUiooo:' "o1$ pCS.OII)Ic 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 

Yes 

Cl" ~ IIC enaire bftl'-11 Mu-i.. 

M OIIIkS)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!l11!¥11 lll•lr.-o.:r 

flOI't\411! ol' yO'llr N!C.h MM (,_'JiMS 

~a ot)' froll'l the ~TM'Kp!lfl f )'llt,m, 

b~. you. wi:ll .t.o tuwc to 

~~("~. 

(Ill! 

I .,_,.) 

hi ¢CZd>AiotR k'\ltt•IOr 

(IO'IC ~­ n..~ ... QMII-

( 

.h.'II$Un:d <Ill die 

CI:.MS! 

No 

N 

Figure 3: Flow chart for using non-quantJtative spiklo.g d uring the accuracy tests. 

Page 24 of 30 

VES009941 
Meu.l.s Generated During 

Stack Operation 

Yes 

Yes 

Yes 

YQu mny usc eilher linearity 

inw ot relntive bios, 

You oecd 10 usc a diff'e.mn 

method to jlt.'Tlctatc mehds. 

You mus1 u~e relalivc bias, 

Figure 4: Flow chart f01· using stack operation to generate metals concenlralioos. 

Page 25 of30 

VES009942 
f'M 

Measurment 

Transport 

Efficiency 

Choose 

Species 

Element of 

Opportunity 

Fil,'llr e S: Species available for transport tests 

Spike 

Page 26 of30 

VES009943 
PM Meaounncnl 

>----~----. 

y., 

Utt Mchod S, Si or I 7 10 

rnu ..wn PM cone. at tbc 

\wk atd • )'OtX C'DtS. Ct~kuta;e tron:;pon 

c-Olclcncy. 

Yt< 

Na~~isacte$$U)'. 

VOAJ 1\:•vc c.ompkted lllo ll'll~n 

dticil: ~ test 

" You nwn eslilblhh a contbtioa to 

~~for tnlllspon cfficicnc)'. 

Figure 6: Procedure for percent transport using Pl\1. 

Page27 of30 

VES009944 
Yes 

Oft1)at0 

CD'IC80llltion on or neN 

the I<S vmh !he 

oonce~tatlon meowreo 

oo lhe KocJ<. Calc>Jia<e 

tra.n r~~tt~ 

Yes 

No COI'I'CC(_'(In f'accor IJ: lh."CCUOI)'. 

YOIIlr.\'c toq)I:Ck'dtlw ~ 

e!ficicocy tc6t. 

No 

You mu:sl L-,tnbli.\h 11 comtatlon to 

comcl f« tran.spun cffio:k ~~ey. 

Figure 7: Procedure for percent transport deterntinalion using an element of 

opportunity. 

Paae 28 of 30 

VES009945 
v .. 

... 

Ye 

ore 11\o !)Otloet~rt!Xln 

an m,.... '" ce.cs ~ .,.. c.n::EnlriiQ'!IIKli(iilftd 

at the starJ., Celobtt transport ~l'iclel'lt')'. 

No!\•QII:IIIIJIIlli\-c 

Sp!I:C: 

$¢ ~1 lrm,pott li11e-• 

coo~ }lee:•"'' Sptd.':s 

YC!UittC!o1l~e 

~;.,. 10 \IU(M:t rOJ •·,-nport coflich!llcy. 

Figure 8: Procedure of percent transport determination using spiking. 

$dtt~ Ill $mo(k Of 

~NcwSrc:tlos 

ag~29nf30 

VES009946 
5. 6 What r-eferences apply ra PS-IT? 

1. United States. Environmental Protection Agency [E.PA). Technology Tmnsfer 

Network. Emission Measurement Center. Promulgated Methods. Medtod I: Sample 

and Velocity Traverses tor Stationary Sources. Washington, DC: EPA; 2004. 

Available: http://www.cpa.go\'lt1nlemc/promgate/m-OI .pdf via the Internet. Accessed 

May 8, 2005. 

ii United States. Environmental Protection Agency [EPA}. Technology Transfer 

Network. Emission Meusuremcnt Center. Promulgated Methods. Method 2: 

Deter:niuation of Stack Gus Velocity and Volumetric Flow Rate. Washington, D.C: 

EPA; 2004. Available: http:/fwww.epa.gov/nn/emc/promgarc/m-02.pdf via the 

Internet Accessed May I 0, 2005. 

iii. United States. Environmental Protection Agency [EPA). Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Metbod 5: 

Detenninarion of Particulate Matter Emissions from Stationary So•Jrces. Washington, 

DC: EPA; 2004. Available: hnp://www.epa.gov/nnlemc/promgate1m-05.pdfvin the 

Internet. Accessed May I 0, 2005. 

iv. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Method 5i: 

Determination of Low Level Particulate Matter Emissions from Stationary Sources. 

Washington, DC: EPA; 2004. Available: http://www.epa.gov/hwcmacl/frhwcS.pdf via 

the Internet Accessed May I 0, 2005. 

v. United States. Environmental Protection Agency [EPA]. Technology 'fran~ fer 

Network. Emission Measurement Center. Promulgated Methods. Metbod 17: 

Determination orP"rticulate Maner Emissions from Stationary Sources. WashingtOn, 

DC: EPA; 2004. Available: http:ffwww.cpa.gov/ttn!emc/promgate/m-17.pdfvta the 

Internet. Accessed May I 0, 2005. 

vi. United States. Environmental Protection Agency [EPA]. Technology Transfer 

Network. Emission Measurement Center. Promulgated Methods. Metbod 29. 

Detennination of Metal.s Emissions from Srationary Sources. Washington, DC: EPA; 

2004. Available: http://www.epa.gov/ttn/emc/promgatc/m-29.pdf via the Internet 

Accessed May 18, 2005. 

Sp.-orifitcioN for XRf t-.hth ldU CEMS (PS-YY) Page ~0 of30 

VES009947 
VES009948.pdf 
VES009948 
Procedure Z: Quality Assurance Requirements for 

X-Ray-Fluorescence Based Multi-Metals 

Continuous Emission Monitoring Systems at 

Stationary Sources 

Prepared by: 

Cooper Environmental Services, LLC 

10180 SW Nimbus Blvd Suite Jb 

Portland. Oregon 97223 

June 9, 2005 

VES009949 
VES009950 
Procedure Z: Quality Assurance Requirements for 

X-Ray-Fluorescence Based Multi-.Metals 

Continuous Emission Monitoring Systems at 

Stationary Sources 

Pr epared by: Date: _ _ _ 

Kr ag A. Petterson, Envir onmental Scientist 

Reviewed by: Dare: __ _ 

Cay A. Yanca, Environment al Scientist 

Re.vicwed by: Dare: _ _ _ 

Br uce E. J ohnson, QA Manager 

Approved by: Dare: _ _ _ 

J ohn A. Cooper, Director 

VES009951 
Executive Summary 

Procedure Z outlines the continuing quality control and quality assurance 

requiremeniS for an x-ray fluorescence based multi-metal CEMS. Procedure Z requires daily 

checks of tile upscale, zero and volume measurement drift. It also specifies quarterly checks 

of the x-ray fluorescence calibration and of the volume measurement calibration. Finally 

procedure Z requires that the entire XRF multi metal CEMS accuracy be verified on an 

annual basis. 

Page i ofiv 

VES009952 
b. 

b, = 

CA1 = 

c c, = 

ccCOIS _ I -

~or = 

CF;PT = 

CF,RI = 

c,L = 

c,s = 

c:- = 

d, = 

d = 

FS 

L~ 

c-• = 

L~ ·IU!J 

~-' = 

L,"" = 

c, = 

11 = 

PT, = 

Llst of Symbols 

They intercept of the best fit line 

TI1e slope of the best fit line 

X-ray fluorescence calibration accuracy 

Corrected CEMS concentration for the i"' clement 

The concentration of the i'b clement as reported by the CEMS 

The average reported concentration of the CEMS for the i" element 

Correction factor for percent transport for the i

11

' element 

The relative bias correction factor for the i'h element 

The emission limit of the i"' element 

Concentration of the i<h element at the stack 

Concentration of the f' element at the sampling module or as reported by the 

XRF multi-metals CEMS. 

Difference between two paired measurementS 

Arilhmetic mc-uu of differences 

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

Tbe calibrated value of the i'h element on the zero standard 

The value of the standard reported by your CEMS 

The measured CEMS respouse to the zero standard for the i'h element 

The measured CEMS response to the i'h element in the ...,scale standard 

The known value of the XRF calibration check standard 

The value of the i'h element of the upscale standard 

Number of data points 

Tbe percent trunsport of the i

1

b element 

Pas" ii ofiv 

VES009953 
PT, 

PRB, 

R"'' I 

r 

SD; 

= 

~ 

= 

= 

Average percent trdllSport for the i'h element 

Percent relative Bias of the ilh element 

The average of the reference method measurements for the i"' metal 

The relative percent SI>Uldard deviation for the i'h metal 

The correlation coefficient 

The standard deviation of differences tor the ilh clement 

Va.., Sample gas volume (or flow) as measured by the CEMS volume check device 

VD 

v., 

UD, 

X 

X; 

= 

= 

= 

= 

Volume drift 

Volume (or flow) reported by your multi-metals C:EMS 

The upscale drift of the i'h element on your CEMS in percent. 

Arithmetic mean 

Value of each data point 

CEMS reported ooncentmtion for the ith element 

The zero dtift of the i'" clement on your CEMS in percen! 

Paee iii of iv 

VES009954 
Table of Contents 

Executive Summal)l ................................................................................... -.............................. i 

List of Symbols ......................................................................................................................... ii 

Table of Contents ....................................................................................... -............................ iv 

1.0 I Jsing Procedure Z ........................................................................................................... 1 

1.1 What is the purpose and applicability of Procedure Z'! ............................................ I 

1.2 What are the basic requirements of Procedure Z? ..................................................... I 

1.3 What special definitions apply to procedure Z? ........................................................ I 

2.0 Interferences, Safety, and Equipment Requirements ....................................................... 2 

2.1 What interferences are associated with procedure l '! ............................................... 2 

2.2 What do I need to know to ensure th ~ safety of persons using Procedure Z? ........... 2 

2.3 What equipment and supplies do I need? .................................................................. 3 

2.4 What reagents and standards do I need? .................................................................... 3 

2.5 What sample collection, preservation, storage, and transpon procedures are relevant 

to Procedure Z'! ............................................................................................................... 4 

3.0 Quabty Control, Calibration, and St.andurdizarion .......................................................... 4 

3.1 What quality control measures are required by this procedure for my multi-metal 

CEMS? ............................................................................................................................ 4 

32 What calibration checks and audit procedures must I perform for my multi-metal 

CEt.IS? ............................................................................................................................ 4 

4.0 Calculations ..................................................................................................................... 7 

4.1 What calculations and data analysis must I perfomt? ............................................... 7 

4.2 What waste management procedures are required for procedure Z? ....................... 13 

5.0 Other Requirements and Information ............................................................................ 13 

5.1 Wbat pollution prevention measures must I take when using procedure Z? ........... 13 

5.2 W'hat criteria are necessary for my XRF multi-metal CEMS to be in control and 

wbat do I do if it is out of control? ................................................................................ 13 

5.3 What tables, diagrams and flow chans are relevant to Procedure Z? ...................... 16 

5.4 What references are relevant to Procedure Z? ......................................................... 18 

Page iv of iv 

VES009955 
1.0 Using Procedure Z 

I . I What is tile pwpose and app/lcabilily of Procedure Z? 

The purpo~e of Procedure. Z is to establish the minimum requirements for quality control 

(QC) and quality assurance {QA) procedures for x-roy tluoresceoce (XRF) based multimetol< <:F.MS. These quality control and quality assurance procedures are in place to ensure 

the accuracy and validity of the data reponed by your multi-metal CEMS tor errussion 

compliance purposes. You must meet these minimum requirements if you plan to use your 

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

extensive QA program or to continue with such programs where they alr::ady exist. Any 

XRF multi-metals CEMS used to report to us. tl1e state, or a local enforcement agency must 

comply with procedure Z immediately after the completion of the initial performance 

specification test outlined in Performance Specification YY'. 

I .2 What are rhe basic requiremems of Procedure Z? 

Procedure Z requires you to perfo1111 several drift checks and audits which ensure the 

accuracy o:" the data reponed by your XRF multi-metals CEMS. You are required 10, on a 

daily basis, record and calcltlate zero drift. upscale drift, and, a sample 110lume drift. On a 

quarterl y basis you are required to perfom1 an XRF calibration audit (XfCA) and a sample 

volume audit (SVA). On an annual basis you are required to execute either a linearity audit 

(LA) or a relative bias audit (RBA) and, if applicable, a transport efficiency audit (TEA). 

The criteria for passing these audits and drift checks are outlined in procedure Z. Proced-ure 

Z also swmmrizes the requirements for when and if your CEMS fuils an audit or drift test 

FinaUy, Procedure Z also covers the requirements for and time lines associated with periods 

when your XRF multi-metals CEMS is out of control. 

1.3 Wh((( specit1/ cle/illitiuns apply tu procedure Z? 

Linearity Audit: (LA) An assessment of the validity of the original linear correlation of 

yourCEMS. 

Reference material: A material of known value used to check the calibrotion drift of your 

XRF mulo-metal CEMS. 

RelatiVe Bias: The diffe.ence between a reference method or aerosol concentration and the 

concentration recorded by your CEMS divided by the concentration of the reference 

measurement. 

Relative Bias Audit: (RBA) An assessment of the bias in your CEMS. 

Sample Interface: The portion of the CEMS used for one or more of the following: sample 

acquisition from the ~1ack or duct effiuent, sample transpon, sample conditioning, or 

protection of the monitor from the effects of stack gas. 

Page I of IR 

VES009956 
Sample Module: The portion oftbe XRF multi-metal CEMS that !rapS t!e metals and 

delivers them to the x-ray fluorescence module. 

Standard Yolume Audit: (SVA) This is an evaluation of your XRF multi-metals CEMS 

sample volume measurement system. This is required if your CEMS uses a volume 

measurement to report metal concentrations and is accomplished by comparing the volume 

measured by your CEMS with the volume measured by 1m independently calibrated device. 

Tr ansport Efficiency Audit: (TEA) An assessment of the ll'ansport effiCiency of the sample 

interface of your multi-metals CEMS. This audit applies to your XRF mllti-metals CBMS if 

either the RBA or LA challenged only the sampling and XRF modules. 

Tr ansport System: The portion of the CEMS that trnnsports a representative sample of 

source effluent from the sample probe to the sample module. 

X-Ray Fluorescence Calibration Audit: (XFCA) This is an e''aluation of how weU the xray fluorescence portion of your multi-metals CEMS hilS maintained its original calibration. 

This is accomplished by challenging the XRF module with a standard of known 

concentration for each metal measured by your CEMS for compliance. The analyzer 

response is compared with the known concent.ration of d1e standard. 

X-Ray Fluor escence Modo.lc: The portion of an XRF based multi-metal CEMS which 

identifies and measures metal masses or concentrations using x-r•y fluorescence. 

XRF Multi-Metals Continuous Emission Monitor (CEMS): All of the equipment required 

for determining metlll concentrations using x-ray fluorescence as an analyticul technique. 

Tbe system may cousist of several major subsystems including the sample interface, the xray fluorescence module, the volume measurement module, diluent analyzer, data recorder, 

and sampling module. 

2.0 Interferences, Safety, and Equjpment Requirements 

2. I What inteiferences are a.wx;iated with procedure Z? 

There may be interferences arising from the x-ray fluorescence, the trapping media, or from 

condensation in the effluent gas. Check with your multi-metal CEMS manufacturer to find 

out more about potential interferences. 

2.2 What do I need to know to ensure the safety of persons using Procedure Z? 

l'ersons using procedure Z may be exposed to hazardous materials, equipment, and 

operations. Procedure Z does not purport to address all oftbe safety ismes associated with 

its use. It is your responsibility to establish appropriate safety and healm practices before 

using this procedure. You may c.onsult with your CEMS manual and/or manufacrurer for 

precautions SpL'Cific to your multi-metal CEMS. If standard reference methods are used then 

you may tlso consult the appropriate reference metbods to address safety concerns. 

Page 2 of 18 

VES009957 
2.3 WhaJ equi'pment and supplies do I need? 

[reserved] 

2.4 What reagent.• and standnrdv do T need? 

Reference materials for the zero and upscale drifts along with a reference measurement 

device for the sample volume check. 

2.4.1 Zero drift reference 

Every XRF multi-metals CEMS must be equipped with a zero ref«ence that can be 

checked on a daily basis. This reference should produce a CEMS :esponsc indicating 

tJ1e absence of metals. If this is not fea.~ib le lhis standard should produce a value 

between zero and 200/o of the emission limit for at least two elements measured by your 

XRF multi-metals CEMS when the instrument is operating appropriately. 

2.4.2 Upscale drift reference 

The teference for the upscale drift check should generate a response for at least one 

metal from each condition used in the XRF analysis. This response must be at least 80 

percent of the emission I imit. 

2.4.3 Sample volume or flow check 

If your XRF multi-metals CEMS makes volume or flow measurements it must be 

equipped to perfonn a daily sample volume check. 

2.4.4 Sample volume a11dit standard 

If your XRF multi-metals CEMS makes volume or flow measurements, periodic 

SUUldard volume or flow audits must be performed. An independently calibrated 

vohrne or flow measurement de,~ce or standard such ns a Dry Cal~ is required for 

these auditS. The standard must be able to acquire a volume or flow measurement at 

sump ling rates typical of your XRF multi-metals CEMS. 

2. 4. ~ X-ray Fluorescence Calibration Check Standards 

Your XRF multi-metals CEMS must include a means of checking the x-ray 

fluorescence calibration against an external standard. NIST traceable thin film 

standards are an example of a suitable x-ray fluorescence calibr.uion check standard. 

2.4.6 Reagems and stalldardsfor the Linearity Audits and Relarife Bias Audits 

You will need other reagents and standards for the linearity audit or relative bias audit. 

The regents and standards required will differ depending on how these audits are 

performed. 

Page 3 of 18 

VES009958 
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 is perfomled. 

2.5 What sample collection. prese•·va.tion, storage. and transport procedure.v are releva/11 

to Pr<>eedure Z? 

[reserved] 

3.0 Quality Control, Calibration, and Standardization 

3.1 What quality contml measure.v are required hy this procedure far "Y multi-metal 

CEMS? 

You must develop and implement a quality control program that, at a minimum includes 

detailed written procedures for all ofthe following activities. 

I. Procedures for perfom1ing drift checks on a daily basis, including but not limited 

to, zero drift, upscale drift, and sample volume measurement drift. 

2. Procedures and methods of adjusting your multi-metal CEMS in response to tbe 

results of the drift checks. 

3. Preventative mainte.nancc of your XRF multi-metals CEMS. 

4. Data recording, calculations, and reporting. 

5. Procedures for required audits, including transport cfficienc) audits (if necessary), 

linearity audits. and relative bias audits. 

6. Procedures for adjusting your CEMS based on audit results. 

7. A program of corrective action and stack operation procedures in case of a CEMS 

malfimction and nn out of control period. 

You arc required to keep written documentation of your QN QC procedures on record 

and available for inspection for the life of the CEMS or until you arc no longer subject to 

the requirements of this procedure. If you fail two consecutive aud~s you must revise 

your QNQC procedures. 

3.2 What calibration checks and audiJ procedures mw,-t I perform far my multi-metal 

CEMS? 

3.2.1 Daily drift check procedures 

Your XRF multi-meUtls CEMS must have tbe capacity to perfon11 each of the following 

checks on at least a daily basis. 

~ge 4 of 18 

VES009959 
• Zero drift: You must check the zero dri A to ensure the stability of your CEMS 

response to the zero drift reference. The zero drift must be less than plus or 

minus 20% of the emission limit each day. Follow your CEMS manufacturer's 

instructions for proper zero drift check procedures. 

• Upscale drift: You must check the upscale drift to ensure the stability of your 

XRF multi-metal CEMS response to the upscale standard. The daily upscale 

dri fi must be less than 15% of the upscale reference value determined 

immediately alter the x-ray fluorescence module hM been calibrated. FoUow 

your CEMS manufacrurer's instructions for proper upscale drift check 

procedures. 

• Dally volume or flow check: You must check tl1e sample volume or now 

measurement to verify the accuracy of the volume measurement on your 

CEMS. This volume check must be done at the nonnal sampling rate for the 

CEMS. Your CEMS is out of control iftbe one day value exceeds 20% of the 

full scale of tbe volume or flow measurement device. Follow your CEMS 

manufacrurer's instructions for proper volume or flow check procedures. 

3.2.2 Audit procedures 

Audit procedures and criteria are lisred below. These requirement> are also 

summarized in Table I in section 5.3. 

1. X-Ray Fluorescence Calibration Audit (XFCA): You n11st perform an 

XJ'CA once each quarter. To perfonn an XFCA you must challenge the x-ray 

fluorescence module of your multi-metal CEMS with a standard of known 

concentration for each metal measured by your CEMS for compliance purposes 

and compare the value reported by the CEMS with the known value of the 

<tandanl. Tfyou wish you may make only one measurement of a standard for 

each element. If your multi-metal CEMS fails on the initial measurement you 

may make two more measurements of each standard and average all three 

measurements. If the average CEMS response over the three measurements 

deviates by less than I 0% from the known standard the CEMS has passed the 

XFCA. If the average exceeds l 0% your CEMS has failed the XFCA and is 

out-of-control. You must follow the procedures outlined in Section 5.2. An 

XFCA is required once per quarter. The minimum allowed time between each 

audit is two months and the maximum allowed time is four months. 

2. Sample volume (or now) audit (SVA): You must perform a sample volume 

audit of your XRF multi-metals CEMS at least once per quarter and prior to any 

linearity or relative accuracy audit. To perform an SVA you must 

independently measure the volume of sample gas extracted from the stack or 

duct over the sampling period. You may make this measurement either at the 

inlet or outlet of your CEMS. You must make volume measurements during 

three different sampling cycles and the measurements mu>t be able to make 

corrections for moismre content if necessary. 

Pag11 ~ nf 18 

VES009960 
If your CEMS measures flow and totalizes that flow to determine volume you 

may perfonn a flow audit instead. You must make flow measurements during 

three diOcreut sampling cycles and for each sampling cycle you must make at 

least 3 to 5 simultaneous measurements of flow on your CEMS and on the 

independent flow measurement device. You mlb't calculate the error from each 

set of measurements according to equation 6 and then calculate the average 

enor in the flow during each sampling period. Finally you must calculate tbe 

average error from all three sampling periods and this avettge must be Jess than 

l 00/o of the independent flow or volume measurement device. 

A sample volume audit is required on a quarterly basis. The minimum required 

time between each SVA is at least two months while the maximum allowed 

time between audits is four months. 

Accuracy Audits: As outlined in Performunce Specification YY it is 

acceptable during the initial perfonnance specification test to assess the 

accuracy and precision of the XRF and sampling modules of your XRF multi· 

metal CEMS separately from the sample interface. You may also do this 

during the Linearity or Relative Bias Audits that arc required for Procedure Z. 

If you choose to challenge the sampling module and XRF ~ystems separately 

from the $&mpling interface you must also perform a Transport Efficiency 

Audit (TEA). If you challenge the entire XRF multi-metal; CEMS during the 

Lineruity and Relative Bias Audits you arc not required to perform an 

independent check of the CEMS tr.msport efficiency. For !be purpose!> of 

Procedure Z you arc required to perfonn either a linearity audit or a relative 

bias audit, but not both. You nrc also not required to perfonn the same kind of 

tests for the audit as were performed during the initial performance 

specification test. For example, if a linearity test was performed during the 

initial accuracy tests, either a relative bias audit or a linearity audit is 

acccptoblo. 

There arc four different options &\•ailable for the accuracy audits depending on 

whether or not a linearity or relative bias audit is performed and depending on 

whether or not the entire CEMS is cbnllcoged by the audit. The audit 

requirements are listed below. 

Linearity Audits 

Option A 

In this option a linearity audit is perfonned on the entire CEMS. The types of 

metals generation and their associated requirements are i~mical to those for 

Option A in performance specification YY section 3. I .4.

1 If you do oot meet 

Ute linearity criteria you must apply a correction according to tbe procedures 

outlined in perfomtance specification YY .

1 

Option B 

In this option a linearity audit is performed on the sampling and XRF modules 

of the CEMS separately from the sample interface. The types of metals 

generation and their associated requirements are identical to those for Option B 

Poge ti of 18 

VES009961 
in perfonnance specification YY section 3. 1.4.1 A transport efficiency audit 

must also be completed. 

Rt!lati<oe Bias Audit 

Option C 

In this option a relative bias nudit is perfonned on the entire CEMS. The types 

of metals generation and their associated requirements are identical to those for 

Optioo C in pcrfonnancc spccifirotion YY cection 3.1.4.

1 If your CEMS fails 

to meet the criteria you must apply a correction fuctor acco!ding to the 

procedures in perfonuance specification YY.

1 

Option D 

In this option a relative bias audit is performed on the sampling and XRF 

modules of the CEMS separately from the sample interface. The typeS of 

metals generation and their associated requirements are identical to those for 

Option D in pcrfonnance specification YY section 3.1.4.1 A transport 

efficiency audit must also be completed. 

An accuracy audit is required on an annual basis. The mimmum time between 

successive accuracy audits is 9 months while the maximum allowed time is 15 

months. 

3. Tra.nsport Efflciency Audit (TEA): You are required to perform a TEA only 

if you choose to challenge the sampling and XRF modules of your XRF multi· 

metals CEMS separately from the sampling interface. The procedures for 

perfonning n TEA are the same as those for determining the transport efficiency 

during the initial performance specification test and are oudined in Perfonuance 

Specification YY. If the rnmsport efficienc)' of your CEMS is between 90 and 

110 percent no correction is necessary. If your transport efficiency is Jess tl1an 

90 pcr=ul uJ 8Jcalcr than 110 pcrocnt then you must establish a con-ection 

foetor according to the procedures outlined in section 3. 1.1 ofPerfonuauce 

Specification YY1

• The minimum time between successive transport efficiency 

tests is 9 months while the max.imwn allowed time is 15 IT.Onths. 

4.0 Calculations 

4.1 What calculations and data a11a~vsis 11mstl perform? 

4.1. i Arithmetic Mean 

Calculate the arithmetic mean of a data set as follows 

- l x= - _Lx; 

n 

Where: 

X 

n 

Arithmetic mean 

Number of data points 

Equation l 

P•ee 7 nf I R 

VES009962 
Xt Value of each data point 

4.1.2 Arithmetic Mean af Difference 

To calculate the arithmetic mean of difference use the above equation substituted for x. 

Then 

dt: :CI- _,Vi Equation 2 

Where x and y are paired data points from tlte CEMS and either the reference 

aerosol or the reference method. 

4.1.3 Dai(y Zero Drift 

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

Equation 3 

Where: 

ZD, The zero drift of the i

111 element on your CEMS in percent 

!.!(""' The measured CEMS response to the zero standard for the i'h element 

_t, The calibrated value of the i"' element on the zero standard 

CL The emission limit of the i'1

' element • 

4.1.4 Daily Upscale Drift 

~" - L71 

UD = ' x JOO I L. 

I 

Equnllun 4 

Where: 

UD1 The upscale drift of the ;m element on your CEMS in percent. 

~ The measured CEMS response to the ;m element in the upscale 

standard 

L" I = The calibrated value of the i'h element of the upsc•le standard 

4.1.5 Daily Sample Volume Check 

Equation 5 

Where: 

Page 8 of I~ 

VES009963 
VD ; Volume drift 

V,.,.,. ; Sample gas volume or flow measured by the CEMS volume or 

flow check measurement device 

V., ; Sample gas volume or flow reported by your multi-metal CEMS 

FS = Full scale value oft he CEMS volume measurement device 

4.1.6 Samplt: Volume Audit Accuracy 

I

V. - V.l 

VA = xlOO 

v ,. 

Equation 6 

Where: 

VA = Volume or flow measurement accuracy 

V, = Sample gas volume or flow measured by the independent 

calibrated reference device 

v... ; Sample gas volume or flow reported by your multi-metal 

CEMS 

4.1. 7 X-Ray Fluorescence Calibration Audit Calibration 

I'"" - L'o) I 

CA = ~"'' 1 x lOO I t.:IJ 

I 

Equation 7 

Where: 

CA, - X·ray fluorescence calibration accuntcy 

L';"' = ·nu~ value of the standard reported by your CEMS 

L'/' • The known value of the standard 

4.1.8 Relative Bias 

Equation 8 

Where d, is the mean difference, R,...., is the average of the reference metbod 

set or reference aerosol concentration for the i"' element. and PR 81 is the 

relative bias for the i'h element 

4.1.9 Transport E.(!icicncy 

VES009964 
Equation 9 

Where: 

c• Coocentrution of the i"'element at the stack ' 

C:"' Concentration of the ilh element at the sampling module or as 

reported by the XRF multi-metals CEMS. 

PT, ~ The percent trnnsport of the ilh element 

Report the average percent transport ( PT) of all measurementS for each 

element that was tested (only one element is required though more can be 

tested). 

4.1.1? Linearity Audit- Least Squares Linear Regressio11 

Calculate the linear correlation equation given below. 

y=b, + b,x 

Where: 

= The y intercept 

The slope 

The intercept is calculated according to the following equation. 

Where: 

1 • 

X=-L:xr n,., 

Tbe slope of the line is calculated according to equation below. 

I tx,-x){y,- .v J .. b, i:,rx, - x)' I•J 

Equation 10 

Equation 11 

Equation 12 

The linear 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 Ueviatmn (of differences) 

' I ( ,, '£.d;· - - L.d·J 

SD, a 11 

n - 1 

Where: 

Equation 13 

Equation 14 

SD, The standard deviation of di n·ercnces for the i

0 element 

11 ~ The number of data points 

d, The difference between the concentration measured by the 

reference method or the concentration of the reference aerosol and the CEMS 

repozted concentration. 

4.1.12 Percent sumdard devialion 

SD PRSD1 ~ ~ x 100 R/m 

Where: 

Eq uation IS 

R/"' a The average of the reference method data set tor tbe i'h element 

PRSD, a The relative percent standard deviation for the im metal 

4.1 .13 Linearity Test Correction Factors (Applicable only when the linearity test 

ht~lltmges tlze emire CEMS) 

I. Corre~1 n equation ifCEMS does not meet either the slope or the intercept 

criteria. 

Equation 16 

Where: 

Paie II ofl8 

VES009966 
cc Comected CEMS concentration for the i'h element l 

y ; = CEMS reported concentration for the i'' element 

bo = The intercept of the least squares linear regression line 

b 1 The slope of the least squares linear regression line 

2. Correction factor if CEMS meets intercept criteria, but does not meet the 

slope criteria. 

Equation 17 

3. Correction factor ifCEMS meets slope criteria but does mt meet intercept 

criteria. 

4.1.14 Relative Bias Correction Factors 

CF,RD -~~ 

d I+ __:_ 

Where: 

R"·" I 

Equation 18 

Equation 19 

CF.RB The relative bias correction factor for the i'" element ' 

C;':<M = The average reported concentration of the CEMS for the i'b 

element 

R;•"' = The average of the reference method measurements for the ill> 

metal 

4.1./ J Percent trans pori correction factor 

PT [ CF, = = 

PT, 

Where 

Equation 20 

CF/'' = Correction factor for percent transport for the l'" element 

Average percent transport for the i

111 element 

()ualil\' AsstltL!Ince fOf XRF &sed Mvhi·ll<kt:ll$ CEMS (Ptocedure Z) Page 12 of 18 

VES009967 
4.2 What waste managemelll procedures are required for procedure Z? 

All chemicals used to produce a reference nerosol or in perfonning tand~rd methods need to 

be disposed of properly. l'le-dse consult the appropriate rcfereuce methods. 

5.0 Other Requirements and Information 

5.1 What pollution prevention measures must/take when using procedure 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 for Drift Checks and Audits 

• Daily Zero Drift: 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. If the CEMS fails to meet 

the zero drift criteria again then it is out of control. It is recommended that you 

examine the zero drift standard tor defects. After repairs to the CEMS are 

completed you are required to perlorm at least five successful zero drift checks 

within a 24 hour period. After the five checks have been successfully 

completed then you CEMS is in control. If the repairs were made to the XRF 

module of the multi-metals CEMS you are also required to complete an x-ray 

fluorescence calibration audit (XFCA) to verify the accuracy of your x-rdy 

fluorescence calibration. 

Daily Upsculc 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 check it is out of control. It is recommended that you 

examine the upscale drift standard for defects. After repai:s to the CEMS are 

completed you are required to perform at least five successful 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 made to the 

XRF module of the multi-metal CEMS you are also required to successfully 

complete an x-ray fluore.o;cence calibration audit (XFCA) to verify the accuracy 

of the calibration. 

Dally Sample Volume he~k: If your sample volume or Dow drift exceeds 

20% it has failed the daily volume check and you must perform another daily 

volume check. If the CEMS passes the second check you may continue to 

operate. If your CEMS fails the second test it is out of control and your CEMS 

must be repaired. After repairs have been made the CEMS must sucecssfolly 

complete live sample volume checks within u 24 hour period. Upon successful 

completion of the five checks your CEMS is back in control. If the repait·s 

Page 13 of 18 

VES009968 
were made to a volume or flow measurement device you are also required to 

successfully complete a sample volume audit {SVA). 

• Quarterly Samp le Volume Audit (SVA): Your XRF multi metals CEMS is 

out of control if volume (or now) measured by your CEMS differs ti·om that 

measured by the independent standard by more than 1 0% percent. A failure of 

this audit may indicate that repairs need to be made to !he volume measurement 

system. Upon completion of these repairs you must perfonn and pass another 

SVA. 

• Quarterly X-Ray Fluorescence Calibration Audit (XFCA): The response of 

your XRF multi-metals CEMS must be within 10% of !he StSDdard's value for 

each metal measured for compliance purposes by your CEMS. lf your CEMS 

fai ls the XFCA initiully, rerun euch standard two more times and take the 

average oflhe three measurements. Tfthe average CEMS response meets the 

XFCA criteria you may continue to operate. however, iftltc CEMS fails to meet 

the criteria theo it is out of control. After the CEMS has been repaired you 

must complete another XFCA. Upon successful completion of the XFCA the 

CEMS is back in control. 

• Annual CEMS Accuracy Tests 

Linenri(J' Audit 

Option A (Linearity audit of the entire CEMS). 

If you challenge the entire CEMS system (including sampling interface and the 

sam1>ling and XRF modules) with a linearity audit you do not need to apply a 

correction factor to your CEMS data if it meets the following criteria: 

J. a slope between 0.85 and 1.15 

2. the correlation coefficient equal to 0.90 or more 

3. an intercept ot'less than 20 percent of the emjssion limit 

If your CEMS does not meet the slope or intercept criteria you must apply a 

correction factor according to the procedures descn'bed in Performance 

Specification YY Section 4.2.12. 1 Your CEMS, however, must still meet the 

correlation criteria. 

If your CEMS fails the linearity test it is out of control. After the necessary 

repairs are made it must pass a linearity or relative bias test to be considered 

back in control. 

Option B (Linearity audit of the sampling module and XRF module only 

followed by a TEA) 

If you challenge the sampling and XRF modules separately from the sample 

interface, your XRF multi-metal CEMS is out of control if the linear least 

squares regression analysis of your audit data does not meet the following 

criteria for each of the metals measured by your CEMS tbr compliance 

purposes: 

Paee 14 of 18 

VES009969 
1. a slope between 0.85 and 1.15 

2. the correlation coefficient equal to 0.90 or more 

3. an intercept of less than 20 percent of tbe emission limit 

If your XRF multi-metals CEMS fails a linearity audit you mUS1 make the 

necessary repairs to your CEMS and successfully complete either a relative bias 

uudit or a linearity audit before it is considered to be back in control. 

You must also complete a transport etlic•cncy audit (TEA) along with your 

linearity audit. 

Rc/aJil•e Bias A11dit 

Option C (Relative bias test of !he entire CEMS) 

lfyour CEMS meets the following criteria it has passed the relative bias audit 

and you do not need to apply a correction factor to your CEMS. 

1. the percent relative bias (PRB) exceeds 15% 

2. the percent relative standard deviation(PRSD) exceeds I 0% 

3. the correlation coefficient (r) for linearity portion of !he relative bias audit is 

less than 0. 90 

If your XRf multi-metals CEMS fails to meet tlte relative bias criteria you may 

apply a correction factor according tlte procedures described in performance 

specification YY Soction 4.2.13. However, if your CEMS fails to meet either 

the percent relative standard deviation criteria or the correlation coefficient 

criteria it is out of control. If your XRF mu lti-metal CEMS fails a relative bias 

audit it must successfully compete another linearity or relative bias audit to be 

considered in control. 

Option D (Perform a relative bius lest on tile sampling and XRF modules) 

Your XRF multi-metals CEMS is out of control if: 

1. the percent relative bias (PRB) exceeds 15% 

2. the percent relative standard deviation(PRSD) exceeds 10% 

3. the correlation coefficient (r) for linearity portion of the relative bias audit is 

less than 0.90 

You must successfully complete anotlter IillA or a linearity audit before your 

CEMS is considered to be in control. You must also successfully comple1e a 

transport efficiency audit along with the relative bias audit. 

Transport Efficiency Audit (TEA): A TEA is only required i r you challenge 

your sampling XRf modules separately from your sample interface (Options B 

and D). lftbe percent transport is between 90 and 110 percent no correction 

factor is neceSSllry, however, if the percent transport is less than 90 percent or 

greater than II 0 percent then you must apply a correction factor to the results 

reponed by your multi metal CEMS. Tile procedures for applying a correction 

factor using the equation in Section 4.1. 1 5. 

Page 15 of 18 

VES009970 
5.2.2 General out of control guidelines 

• Out of control period: The out of control period begins inmediately after the 

failed drift test or audit and is over immcdiotcly following the successful 

completion of required procedures associated with the failure of the audit test. 

During the out of control period you may not use the data generated by your 

XRF multi-metal CEMS for compliance purposes . 

• Reponlog gutdclln•o: You must include in your report to us, the stole, or loc~l 

enforcement agency the results of the failed audit or drift check, the corrective 

action that was taken, and the results of the successful audit or drift check. 

• Rules governing auditing time periods: The X-Ray Fluorescence Calibration 

Audit (XFCA) and the Sample Volume Audit (SV A} ore required once a 

quatter. Two months must pass between successive quarterly audits and no 

more than four months may pass.. The Linearity Audit (LA) and the Relative 

Bias Audit (RBA) are required on an annual basis. Successive LAs and RBAs 

must be separated by at least nine months and no more than 15 months. 

5.3 What tables, diagrams and flow charts are relevam 10 Procedure z? 

Page 16 of 18 

VES009971 
Table 1: Continuin.ll. QA Procedures for XRF Multi-Metals CEMS 

Test Test Test Procedur es Passing Criteria 

Frequcncv 

Zero Drift Cbcd> Zn'O M~td 3lld ulr.u 11 ~ dtift < 2£)% drifl encb day 

Dail)' UDSo~ l< Orin Otttlt ups~»k teaodard and c:olleulalt drin < IS% drift cnc:b day 

Volume or flow Drift C"hcdt flow drift .00 e~kull!i1e driR < 2)% drift deb dlty 

X-Ray Fluores<:ence Tc.st a~ for~ c:kmtulllliCI:SURlll b • <l~ditr~bevny 

Calibrarioo Audil cow-IJiian!!:C by )'OUr CEMS ( I lir.1c ptr ckmmt ~!lured "' stoodc.rd) compljanc:(' by )'atlr CE~S 

• If criteri!l~W~C initially me• you 

1nay 

~ 

1ak.e 'he •Vtl'agt of 3 

Sample Volume ~ <It% ddf~ hom iDe J[Uidltd 

(or Flow) Audit • Comp.1ro CEMS \AOiumo 118tainst a !lltl!nd!lrd 

Quarterly 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: in 3 ('EMS SII.IT(tlc 'ycks 

• Calculnte aver:agc diffc:rtnc:(l becwecn 

CE.MS 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 leas• l conc:c:ntMit:tOn levc:l::i winch • r~0.90 

Pe•ioon a lhtcarity te!U 01t ino::luck al f'oW ¢00.:, chan~ ~md 1he • lntcrcep1 < l0%oferuisiioo 

entin:CEMS ~lol\ li t limi1 

• If ipll::.illc. J.pikt- into SOWTe, or spike i!l.1o • rfabtwecril«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 lo:Alll 3 ccncei'Mltioo e~-e~ which • Slupe• 0,8S tu I,IS 

• Pelfonn a linearity cc.-st inrfullr a 2 fold Ol'lftt. dlan~,;e tnd the • t~0.90 

on qmplingand Xl!F onisdoellmn • ima¢ep( < 2'0%of~ 

modules aoly • Spike C!ll' ~ coeeftltmJoos wi:ill , .... • lktermine transport R":fum~ct method as el~»e It P<mible to 1ht • r~~ .. Jm...uil)• cnttcia 11".4.19 biiC mec 

etTw.:k:ncy ae(»>ratcly J~aqllillJJnlQC!I.I)e Ill I!:!clnlQ:Ll Clil!llda 

• 90<-_PT$.1 10 

• If ~ traMJ)()ft c:dcnt are 

Annually ..-.:. met .,..,.y • comctioo 

OptionC • At s~ unc md1d from tilth e~~tcgory a. 80 • -

Pc«en! ~ldiv~ Diu 

to 120 pen:enl ofe:mi.t!\ion limil • RB;SU% 

Perform a relative biat rest • 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~ liM as close as poJSibie to \be • If Cri1eria not met t!pply o. 

p<obe oorr««tO" &..:car ( c(Jf'ltlation 

eoefficietll criltr;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 

• Pcrfonn a rel-ative bi~s • Otlt '"'* tD:tll ~t 3 ~:GfiC. Ients whi;b • MSO~IO% 

test on sampling and i•,elu<k 112 JOid cone. c:bnngc ond the • r ~ 0. 90 for l'nl:tlll with throe:: 

XRF modules ooly 

cmhak>n Umil fold wnc. h~~r~ge 

Dccennlne uanspo~1 • Spike or Metiurt eoncmtl'l:llotl$ w iftl l=m Ima5JUid (dteria • A"ft'rcnce uxthod as d~ t); pos.sibk: to 1M 

<ffockncy scpanrt<ly 

~-

• 90$PTSIIO 

• lfpcnxMinrlqlOft cril.:ria 1W\: 

not met enol · a COI'n!ction 

Page 17 of 18 

VES009972 
5.4 What references are rclevam w Procedure Z? 

i. l'erfommnce Specification YY: Specifications and Test Procedures for Batch Multi-Metals 

Corttinuous Emission Monitoring Systems at Stationary Sources. 2005. 

Page 18 or 18 

VES009973 
VES009974.pdf 
• 

~~~ 

STACK 

&omplo 

....!:l:m. 

Amblem 

l 

-Sample 0< 

Valve Box 

RG«;m 10 Stack 

H 

E 

" T 

E 

R 

Sample 

Shut -<>If 

Vrjve 

~ 

1 G4-

J HEATeR -I 

FIGURE 2. SIGRIST PARTICULATE MATIER CEMS 

I 

I 

H 

E 

A 

T 

E 

R 

~e~ 

Photometer 

v 

SAMPLE BUILDING 

o~ I ULFIG2 _l 020:lOS 

VES009974 
VES009975.pdf 
ECOCHEM 

PLC 

SIGRIST 

CONTROLLER 

DAS 

HISTORIAN 

FIGURE 3 . T149 CEMS DATA EXCHANGE 

XACT 

CONTROLLER 

VES009975 
VES009976.pdf 
~ 

~ ~ ~ 

STAGK 

Sample 

Probo 

I 

J. 

Motalo DYnamic 

Splko<J.-

Relurn to St.x*_ 

OAG 

Ambient 

I 

AmbienV UssVal~ 

..-<---

H 

E 

A 

T 

E 

R 

L..,-

Sample 

~hllt.ntl 

Volvo 

1c:H. 

J HEATER -I 

FIGURE 4. MULTI- METALS CEMS (XACT) 

I 

J 

H 

E 

" T 

E 

R 

~ 

XACT 

SAMPLE BUILDING 

STILLING 

CHAMBER 

I 09123105 I ULFIG4 I 020305 

VES009976 
VES009977 .pdf 
r-

• 

STAO< 

Sample 

Prolle -tedFl t•r 

Box to Probo 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

I 

--. 

I 

I 

\-Hoated Umbillical 

I 

t 

• Heated ~e Regtation 

[_ ___ ::~; -----~ ~ 1~-

L ---------1 

I 

I 

I 

CALI!AAnON MANIFOLD 

AAJ,A 

~ L-J L__j LCali.bration Gases 

FIGURE 5. ECOCHEM CEMS (HCI) 

SAMPLE BUILDING 

Oullo Stack 

I 09123105 1 LILFIG5 I 020305 

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• 

STACK 

Sample 

Pmbo I Hoetod Filte< 

___, 8oJ< 10-

I 

' 

MASSF\.OW 

CONTROl. 

j)._ 

HCI 

REFEREN<;t;, 

CYLINDER . 

-, 

I 

I 

}-Heated Uml>l1 

T 

• He~:ned Pt&4e:LI'e RegulaUon 

• Lomhw Flow Element 

SAMPLE BUILDING 

l_ _________ Ef----- ~ ECOOiEM I ~~1 I Re~~~:e ~ 

FIGURE 6. ECOCHEM DYNAMIC SPIKING OVERVIEW T LILFIG6 _l 020005 

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L.O PIUiCJSlON AND BIAS 

Z.l PAIRED SAMPLING TRAIN PRECISION 

Z.l.l What Is ?recision and Why Is It Important? 

Precision i~ a 111easure of the agreement between two or more independent observations of the 

same physical quantity obtained under the same conditions. When paired sampling trains are 

used, assessing the precision of the two data points collected for a given test run is important in 

identifying possible problelll!> with the sampling train or sample collection method. Although 

the PM concentrations measured by the two sampling trains should be the same for a test run, 

there invariably are differences in the two measurements. Typically, the dillercnces in emissions 

between the two sampling trains are insignifiC(Ult. In some cases. it is unclear whether the two 

data points are in relative agreement or if there are significant differences, which could indicate a 

problem with the sampling instruments, collection methods, or analytical procedures. 

Z.l.2 Does PS-1 1 Reoujrc Me To Evaluate the Precisjop of Paired Sampljpg Tmjn Data? 

Evaluating the precision of paired sampling train data is not required under PS-11. However, in 

Section 8.6{ I )(i) ofPS-11, it is recommendoo that you use paired sampling trdin.s and screen the 

data for precision when conducting a correlation test or an RCA Lilcewise, thl\ Jlrncedures 

described here for evaluating paired sampling train precision are recommendations and not 

requirements. Section 8.6(3) of PS-11 specifies that wilen conducting a correlation test, you may 

reject the res ult~ of up to five test runs without explanation; additional test nms can be rejected 

under certain conditions. The same provisions apply to RCAs. The procedures described in the 

following paragraphs can help in deciding which lest runs, if any, you should consider rejecting. 

Z.l.3 What Methods Can I Use To Determine the Precision of Paired Sampling Tmjp Data? 

This section d.iscusses two methods for evaluating the precision of paired sampling train data. 

Section Z. l.4 descnl>es a method that is based on the determinntion of the relative standard 

deviation (RSD). Section Z. l.5 presents an alternative method, which involves calculating the 

regression residuals for the data set and comparing them with the standardized residuals for the 

test run. Section Z. l.6 compares the two methods and presentS recommendations on which 

procedure to U3e and how lO use the results of evaluations of data precision for initial correlation 

tests and R CAs. 

VES009979 
Z.L4 How [)o I Evaluate Precjsiog Usiue the Relative Stapdard Deviation? 

Determining the RSD is a relatively simple and straightfotward procedure for evaluating the 

precision of paired sampling data. lbis proccdut·e, which was included in earlier proposals of 

PS-11, cutTently appears in Section 12.2 of Method 5i. 

The RSD presented in this discussion and in Method 5i is not the true RSD but is actually a 

measure of the >tandardized half range. For two data points, the standardized half range differs 

from the true RSD by a factor of(llf2) or 0. 707; that is, the RSD (as presented here) equals the 

true RSD • 0. 707. 

Evaluating tl1e ?recision of paired sampling ll"llin data using the RSD entails the following steps: 

!. Calculate the RSD for each test run; 

2. Determine the average PM concentration for each run; 

3. Determine the recommended maximum RSD for each run, based on the average PM 

concentration for the run: and 

4. Compare dte calculated RSD with the recommended maximum RSD for each run and 

flag those test runs for which the calculated RSD exceeds tbe recommended 

ma>.imum RSD value. 

The following ?aragraphs describe each oft.hcsc steps in more detail. Exruq~ e calculations are 

also presented. 

Steo I; Caley late RSD 

The RSD is calculated for each test run using equation Z 1-1: 

where 

RSD 

c. 

c. JC,·C.I 

(Equation Z. l-1) 

relative standard deviation, percentage 

: concentration measured using Train A, units of concentration 

concenrrat'ion measured using Train B, same units as C, 

= absolute value of the difference between c. and C, same units of 

concentration. 

The concentration units for the variables C, and Cb do not matter, provided the same units are 

used for both concentrations (e.g., both concentrations could be in units ofmwdscm or both 

could be in units ofmwacm). 

Z-2 

VES009980 
In the following example calculation, assume the concentration for Train A was 9.2 mglacm, and 

the concentration for Train B during the wme test run was 7.6 mg/acm. 

k92 - 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 maximum RSD (RSD,) is based on the average PM concentration (C.,.) for 

the test non. For the previous example, the average PM concentration for the run is 

c = c. +c. - 9.2 + 7.6 - 8.4 ... 2 2 

Step 3: Detennjne Recommended Maximum RSD 

The recommended maximum RSD is a function of the average PM concentration for the two 

data points, as follows: 

• For average PM concentrations t11at are at least 10 mg/dscro (or at least 10 mg/acm). 

the recommended maximum RSD is 10 percent; 

• For average PM concentrations that are less than or equal to 1.0 mgfdscm (or less 

than or equal to 1.0 mg/acm), the recommended maximum RSD tS 25 percent; and 

• For average PM concentrations between 1.0 and 10 mg!dscm (or between 1.0 and 

I 0 mg/acm), the recommended maximum RSD is determined using Equation Z.l-2, 

whioh is simply a linenr interpolation between I 0 arul 25 percent· 

RSD,. • (26.67 - 1.67C,.,) (Equation Z.l-2) 

where 

RSD, s recommendtd maximum RSD for average PM concentrations between I .0 and 

10, percent 

C.,., E average PM concentration for the two sampling trains. units of concenll8tion. 

For the above example, the average PM concentr.Uion is greater than 1.0 m!Vdscm ant! less than 

I 0 mgldscm; therefore, Equation Z. l-2 is used to determine the recommended maximum RSD as 

follows: 

RSD, = 26.67- 1.67 X c ... = 26.67 - 1.67 X 8.4 - 12.6% 

Z-3 

VES009981 
Step 4: Compare Calculated RSD to Recommended Maximum RSD 

The calculated RSD is 9.5 percent, which is less than the recommended maximum RSD of 12.6 

percent. Therefore, the test run satisfies the criterion for RSD. 

Ex•mple Problem: How Do 1 Evaluate the Precision of Paired Snmpliag Train DMta 

Using the RSD? 

For the initial correlation test of a PM CEMS, 20 test runs are conducted using paired sampling 

trains. The results of the test are summarized io Table Z.l-1. The table also shows for each test 

run the average PM concentration, the RSD calculated using Equation Z.l-1, and the 

recommended maximum RSD. Finally, the table indicates whether each te~1 run met the RSD 

criterion. 

Table Z..l-1. Example RSD Calculations - Results of Initial Correlation Test 

PM Concentration, mg/dsem RMOmmeoded Does tbe test run 

Calculated mulmumRSD, satisfy the RSD 

Run TrainA Train B Average RSD,% % criterion? 

I 2.6 4.2 3.4 23.5 21 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 14.5 14.8 2 10 y .. 

6 18.3 19.7 19.0 3.7 10 Yes 

7 22.4 21.3 21.9 2.5 10 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 Yes 

II 6.4 7.4 6.9 7.2 15.1 Yes 

12 9.5 14.2 11.9 19.8 10 r No 

13 12.4 15.1 13.8 9.8 10 Yes 

14 14.2 11.2 12.7 11.8 10 No 

15 7.8 7.1 7.5 4.7 14.2 Yes 

16 21.3 18.3 19.8 7.6 10 Yes 

17 4.6 13.5 9.1 49.2 11.6 No 

18 28.7 24.2 26.5 8.5 10 Yes 

19 12.6 14.8 13.7 8 10 Yes 

20 10.5 11.3 10.9 3.7 10 Yes 

Z-4 

VES009982 
As shown in the table, Runs I, 9, 12. 14. and 17 did not meet the precision criterion for RSD. 

For Run 1, the average PM concenlration was 3.4 percent, and the RSD was 23.5 pereent. Since 

the average PM concentration is between 1.0 and 10 mgfdscm, Equation Z.1·2 is used to 

detennine the recommended maximum RSD for this run. Using !hat equatioo, the recommended 

maximum RSD for Run I is calculated to be 2 L percent (26.67- 1.67 x 3.4 = 21.0). For Run 9, 

tbe RSD (20.6 percent) exceeded the recommended maximum RSD of LO percent. For Runs 12 

and 14. the RSDs were 19.8 percent and 11.8 percent, respectively, both of which exceed the 

recommended maximum of 10 percent. Finally, the RSD for Run 17 was 49.2 pereent, which 

exceeds the rerommended maximum RSD of 11.6 percent for that run, as determined by 

Equation Z. l-2. 

Section 8.5(3) ofPS-1 1 requires a minimum of 15 test runs for the initial correlation test, and 

paragraph 8.5(3)(iii) allows up to 5 test runs to be discarded without explanation. In the :tbove 

example, the facility might consider discarding the 5 test nms for which the RSD exceeded the 

recommended maximum RSD; if it did so, there still would be a sufficient number of test runs to 

develop the initial correlation. However, the facility would not be required to reject any of the 

data; it could decide to keep the results of any or all of the test runs that did not meet the RSD 

criteriotL 

Z. l.5 How Do I Evaluate the Precision of Pajred Sampling Traju Data Using Residuals? 

A residual is defined as the difference between an observed value and the fitted vall1e that is 

detenuined ushg a regression equation. Using residuals to eva luate the precision of paired 

sampling train data is an iterative process, which consists of the following steps: 

I. Deenninc the linear regression equation for the data; 

2. Calculate. tbe residual and standardized residual for each test run: 

3. Eliminate any run for which the absolute value of U1e standardized residual exceeds 

3.0; 

4. Recalculate the residuals and standardized residuals for each test run; and 

5. Repeat Steps 3 and 4 until the absolute value of the standardized residual for each nm 

is Jess than or equal to 3.0. 

The following paragraphs desctibe these steps in more detail. An example problem to 

illustrate all of the calculations for evaluating paired sampling data precision using residuals also 

is presented. 

Step 1: Determine Rc~ession EQuation 

Belore the residuals can be calculated, the rcgTession equation must be determined. For paired 

sampling train data, a linear regression model is used. The procedure for determining the linear 

regression equation is identical to that specified in Section 12.3(1) of PS-I! for developing a 

linear correlation model. The data from either sampling train can be used for the dependem 

Z-5 

VES009983 
variable (y) or independent variable (x). For this discussion, the data from Train B represent the 

dependent variable, and the data from 'T'min A represent the independent variable. The 

regression equation is of the form presented in Equation Z.l-3: 

(Equation Z.l-3) 

where 

y • predicted (fitted) PM concentration for Train B 

b0 = in tercept of the regression line, as calculated using Equation Z.l-4 

b1 • slope of the regression line:, as calculated using Equation Z.l-6 

x = PM concentration meastu-ed by Train A. 

They intercept (b0) of the regression line is detennined using Equation Z.l-d: 

where 

where 

l1 ~ mean of the Train A data, as calculated using Equation Z.l-5 

y = mean of the Train B data, as calculated using Equation Z.l-5. 

x, c PM concentration measured using Train A for run i 

y1 - rM concentration measured using 'Train B for run i 

n = number of data pairs. 

The slope (b,) of the regression line is determined using Equation Z.l-6: 

where 

s ... , S,

1 = as calculated using Equation Z.l-7: 

. ' S K.: = "'(x L ; . -x) 

;-I 

s., = f (x,- x)(y, - .Y) 

;-I 

where 

x., x. y. and y = as defined above for Equations Z.l-4 and Z.l-5. 

Z-6 

(Equation Z.l-4) 

(Equation Z. l-5) 

(Equation Z.l-6) 

(Equation Z. l-7) 

VES009984 
for the dnta listed in Table Z.l-1, the cnlculated values are ns follows: 

I 20 

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 - 14.24/) = 1.5 11 f =i 

20 

S., • L ((2.6-14.24){4.2-15.18)+ ... +{I 0.5-14.24)(11.3-15.1 8)) = 1.348 i : l 

h - 1,348 - 1- ),5))- 0.892 

h0 = 15.18 - (0.892x 1424)= 2.47 

The regression equation is then expressed as 

y = 2.47 + 0.892x 

Sten 2: Calcy!ate Residuals and Stnndurdjzed Resjduals 

For a paired sa:npling train test run, the residual is simply 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 calculated using the 

regression equation. 

The standardiud residual for a test run is a function of the residual for the run and the residual 

variance, as calculated using Equation Z. l-9: 

e. e - ' 

s- ~Var(e) (Equation Z.l-9) 

Z-7 

VES009985 
where 

e, standardized residual 

c; = residual for Run i 

Var(e} = residual variance, as detennined using Equation Z.l -10. 

where 

n 

l: e,' Var(e) = _,._,_ · (n - 1) 

Var(e}, ei, and n = as defined previously. 

(Equation Z. l-10) 

Based on the data 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 for Runs I and 2 are 

Ru11l: e1 = 4.2 - 4.79 = - 0.59 

Run2: ez = 4.4- 5.95 = - 1.55 

From Equation Z.l-10, the residual variance for the data in Table Z.l-1 is 

L "' (- 0592 + (- L552)+ ... +(-Q542

) 

Var(e) = 1

"

1 = 16.19 (20- 1) 

FromEquationZ.I-9, the standardized residual for Run I is 

- 0.59 

e - r= 

' vl6.19 - 0.147 

For this run, the abwlute value of the standardized residual is 0.147, which is less than 3.0. 

Therefore, Run I meets the criterion for precision based on the residuals. 

Z-8 

VES009986 
Example Problem: How Do I Evaluate the Precision of Paired Sampling Train Data 

Using Residuals? 

This example uses the same initial correlation test data presented in Table Z.l-1. A totdl of 

20 test rutlS were conducted 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 Train Bas the dependent variable (y values). Table Z.l-2 summarizes the results of the 

regression analysis. The re-sulting regression equation is f = 2.473 + 0.892 y. 

Table Z.l-2. Summary of Regr ession Calculations 

Variable Calculated value Equation no. 

X 14.24 Z.l-5 - - ·· ·--·--·· ·····--

'J 15.18 Z.l·5 

n 20 Z.l-5 

s:c.• 1.511 Z.l-7 

-··- ,., 1348 Z.l-7 --· --· .. -- b. 2.473 Z.l-4 

b, 0.892 ' ' Z. l-6 

The residuals are calculated using Equation Z.l-8, and the standardized residuals are calculated 

using Equations Z.J-9 and Z.l- 1 0. Table Z. l-3 shows the predicted (fitted) y value, the 

residua.!, and the standardized residual for each test run. As shown in the table, all runs meet the 

precision criterion except Run 9. For that run, the absolute value of the standardized residual is 

3.167. which exceeds 3.0. 

Table Z.l-3. Summary of Residuals for Example Problem - First Iteration 

PM concflltratlon, mgldscm Predicted PM Standardized 

Run Train A Tra in B eoncentratlon(9) Residual (e.) residual (e,) 

I 2.6 4.2 4.79 -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 15.1 14.5 15.95 -1.447 -0.360 

6 18.3 19.7 18.80 0.897 0.223 

7 22.4 21.3 22.46 - 1.161 -0.289 

8 24.5 20.~ ---·-· 24.34 -4.135 -1.028 . .. . 

(co!llillued) 

Z-9 

VES009987 
Table Z.l-3. (continued) 

1'M concenrrallon, mgfdscm Predicted PM Standardized 

Run Train A Trnin 8 concentratio ~) Residual (t1

) residual (e,) 

9 24.3 36.9 24.16 12.743 3.1 67 

10 32.9 32.2 31.83 0.36? 0.092 

II 6.4 7.4 8.18 -0.784 -0.195 

12 9.5 14.2 10.95 3.250 0.808 

13 12.4 15.1 13.54 1.562 0.388 

14 14.2 11.2 15.1 4 -3.944 -0.980 

15 7.8 7.1 9.43 -2.333 ..0.580 

16 21.3 18.3 21.48 -3.180 ..0.790 

17 4.6 13.5 6.58 6.922 1.720 

18 28.7 24.2 28.08 -3.883 -0.965 

19 12.6 14.8 13.72 1.083 0.269 

20 10.5 11.3 11.84 -0.543 -0.1 35 

The next step is to remove Run 9 from the data set and recalculate the regression equation and 

standardized re;iduals to determine if any of the data points exceed 3.0 after the outlier (Run 9) 

has been removed. Table Z.l-4 surrunarizes the regression parameters. 

Table Z.l-4. Summary of Regression Calculations 

for Example Problem " itb Run 9 Removed 

ariob~ Calculated value 

lt 13.71 

y 14.04 

- n 19 

s~~ 1404 

s.,. I I 18 

b, 3.12 -- b, 0.796 

The residnals and standard residuals are recalculated. The revised cnlcularions, summarized in 

Table Z.l-5, show that the absolute value oftbe standardized residual is less than 3.0 for all runs. 

Therefore, the evaluation is complete with only one outlier (Run 9) identified. The facility can 

decide to rejed that run, but it is not required to do so. 

Z- 10 

VES009988 
Tatle Z.l -S. Re•ised Calculation of Residuals after Removal of Run 9 

PM wncentration, m3ldsem Predicted PM Standardized 

Rgn Train A Train U conrentradon(9) Residual (e.) residual (e.) 

-· 

1 2.6 4.2 5.19 -0.99 -0.378 

2 3.9 4.4 6.23 -1.825 -0.696 

3 4.2 2.8 6.46 -3.664 -1.398 

4 8.6 10.3 9.97 0.332 0.1 27 

5 15.1 14.5 15.14 ..().643 ..().245 

6 18.3 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 -2.428 -0.926 

IQ 32.9 32.2 29.32 2.884 1.1 

I I 6.4 7.4 8.22 ..().8 16 -0.311 

12 95 14.2 10.68 3.5 16 1.341 

13 12.4 15. 1 12.99 2.107 0.804 

14 14.2 I 1.2 14.43 -3.227 • 1.231 

15 7.8 7. 1 9.33 ·2.231 ·0.85 1 

16 21.3 18.3 20.08 I 

-1.780 ·0.679 

17 4.6 13.5 6.78 6.717 2.563 

18 28.7 2-4.2 25.97 -1.772 ·0.676 

19 12.6 14.8 13.15 1.647 0.629 --

20 10.5 11.3 1 1.41! ; ..().180 -0.069 

Z.l.6 Which Procedure Should I Use for Evaluating Paire<l Sampling Trajn Data Precjsjon? 

The methods jnSented in Sections Z.l.3 and Z.l.4 for e valuating prec ision differ in terms of 

simplicity and results. The method based on residuals analysis is a relatively complex, iterative 

procedure. The RSD method is much simpler and requires a single round of ca lculations. 

However, as ir.dicated by the results of the example problem, the RSD method is more stringent 

in terms of ide~tifying outliers. In the example problem, the results of five leSt runs were 

identified as possible outliers based on RSD, but the residuals analysis of the same data set 

identified only one test run as n potential outlier. Although either method can be used to 

evaluate paired sampling train precision, a recommended procedure is to use the RSD method 

initially to evaluate data precision. If the RSD analysis shows that the data for all test runs are 

within the rerommended maximum RSD, no further assessment of data preeision should be 

necessary bee2use the RSD method is the more stringent of the two methO<h presented here. If 

the RSD values for one or more test nms indicates that the data set conlllinsout.liers. an analysis 

of the residuals is recommended. 

Z.ll 

VES009989 
Regardless of which method is used, any potential outliers should be investigated to determine 

possible causes for the Jack of precision. U problems are identified in how the samples were 

collected or analyzed, the suspect data pairs should be discarded. lf no problems cao be 

identified, it m~y be that the apparent lack of precision is simply evidence of the natural 

variations in the data. Jn any case, the facility has the option of discarding the results of up to 

five test runs without explanation, provided there remains a minimum number of test ntns to 

satisfy PS-I I (i.e., IS runs for developing a correlation or 12 runs for an RCA). The results of 

additional test rons can be rejected iflbe basis for rejecting the runs is specified in PS-11, the test 

med10d, or the quality assurance plan for tbe facility. As stated above, a mmm1um of t5 test 

runs is needed io develop a correlation, and a minimum of 12 test runs is required for an RCA. 

Z.2 PAiRED SAMPLING TRAJN BIAS 

Z.2.1 What Js Bjas and Wbv Is II lmoonaot? 

Bias is a systematic error in data. Bias can arise from differences in parameter measurement 

methods, data collection methods, or data reduction methods. In paired sampling trains, bias can 

occur when the instruments used to measure emissions differ from one troin to tbe other, or when 

the test crew operates the two sampling trains differently. For example, if two sampling trains 

include heated filters, and the litter temperatures are significantly different, more PM cau 

condense on the filter with the lower temperature, resulting in biased data. Because it may not 

be apparent that there are differences between the sampling trains or data collection methods, it 

is important to evaluate the data for bias. When developing the correlation equation for PS-1 1, 

bias can introduce more scatter in the data, skew the correlation equation, or result in failure to 

meet the con-elation acceptance criteria specified in Section 13.2 ofPS-11. 

Z.2.2 How Do I Dereanjpe Bias jn Paired Sampling Train Data? 

lbn"""' severn I rncthcxb tlu>t can be used to identify bi3S in p3ired samplins train data. The 

method described in tbe following paragr~ bs consists of three steps: 

I. Determine the linear regression equation for the data; 

2. Calculate the confidence inlerval for the slope ofrhe regression line; and 

3. Cakulate the confidence interval for the intercept of the regression line. 

TI1e following paragraphs describe these steps in more detail. 

Steo l: Deteonjne Regression Eauatjon 

The procedure for determining the linear regression equation is the same as is described in 

Section Z.l.2.1 for evaluating residuals for precision. The data fTom either of the paired 

sampling trains can be used for the dependent variable or the independent variable. and the 

resulting line:u regression equation has the form indicated by Equation Z.1-l. 

y = b0 t b,x 

Z-1 2 

VES009990 
Steo 2: Petennine Confidence lnteryal for Slone 

The next step is to determine the 95 percent confidence interval for the slope of tbe regression 

line (b1

). The criterion for the slope of the regression line is that the value 1.0 [ails within the 

confidence interval. The 95 percent cont1dence interval for the slope is calculated using 

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 the 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 Equations Z.l-4 and Z.l-5 

S = root mean square error. 

The root mean square error (S) is calculated using Equation 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. Using that equation 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 

VES009991 
2() I (4.2 - 4.79)' +(4.4 - s.95)2 + ... +(11.3- tt.84)' 

(20- 2) 

/•l S= = 4.13 

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

+ ... +(10.5 - 14.24) 2 

i•l 

For 18 degrees of freedom (n • 2 = 20 - 2 = 18), the value for the t statistic (refer to Append ix A) 

is 2.10 I. Inserting that value and the results of the above calculations for root mean square error 

and the standard error of the slope into Equation 2.2- 1, the confidence inter,al for the slope is as 

follows: 

CI hi = 0.892 ± (2.1 0 I X 0.1 06) = 0.892± 0.223 

This can also l>e written as 

0.669 ~b, :d.ll6 with 95% confidence 

Since tl1is interval includes the value 1.0, the data satisfy tl1e bias criterion for slope. 

Step 3; Determine Confidence Interval for loterceot 

The final step i; to determine the 95 percent confidence interval for the intercept of the 

regression line (b0). If the value 0.0 falls within the confidence interval for the intercept, the data 

satisfy the bias criterion and are acceptable. The 95 percent confidence interval for the intercept 

is calculated using Equation 2.2-4: 

where 

CI,0 = 95 percent confidence interval for the intercept 

b0 = intercept of the regression line 

t,$% = as defmed above for Equation 2.2-1 

SE(bo) = >tandard error of the intercept. 

Z-14 

(Equation 2.2-4) 

VE$009992 
The standard error of the intercept is calculated using Equation Z.2-5: 

t.x: 

SE(b . ) = S .. '"' - (Equation Z.2-5) 

nL(x,-;) ; .. , 

where all variables are as defined above in Equations Z.l-3 to Z.l-5 and Z.2-4. 

For the data presented in Table Z.l-1, the parameter SE(b.), which is determined from 

Equation Z.2-5. is as follows: 

L (2.6z + 3.92+ . .. +10.52

) 

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 follows: 

C/,0 = 2.47± (2.1 0x 1.77) = 2.47± 3.73 

This can also be v.ntten as 

-1.25 ~ b0 ,; 6.20 with 95 percent confidence 

Since this inter" a! include-s the value 0.0, the data satisfY the bias criterion for intercept. 

Example Problem A: How Do I t:valuate Paired Sampling Train Uata lor Bias? 

In this example, 15 test runs were perfomJed using paired sampling trains. Table Z.2-l 

summarizes the data for the two sampling trains. 

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Table Z.2-1. Example A - Summary of Test Results 

PM Concentration 

Run Train A (x) Train B (y) 

I 2.3 2.5 

2 3.9 4.4 

3 4.2 4.1 

4 8.6 10.3 

5 14.2 13.1 

6 I 5.1 14.5 

7 18.3 19 

8 22.4 21.3 

9 24.5 22.8 

10 28.1 28.2 

II I 32.9 32.2 

12 6.4 6.9 - -- ... 

13 7.2 6.9 

14 12.6 12.4 

15 10.5 11.3 

Table 2.2-2 summarizes the results of the regression calculations. 

Table Z.2-2. Summary of Regression Calculations 

Variable Calc u.Jated 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(b0) 0.378 Z.2-5 

Cl, 0.906< b, < 1.003 Z.2·1 

~ -0.260 <~< 1.372 Z.2-4 

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The resulting regression equation is 

y= 0.556+ 0.954x 

The confidence interval for the slope is determined from Equation Z.2-l to be 0.906 < b, 

< 1.003. Because the confidence interval includes the value 1.0, the data are considered to be 

unbiased with respect to regression line slope. The confidence interval for the intercept is 

determined fron> Equation Z.2-4 to be - 0.260 < b0 < l .3n. R~r.ause the cor fide nee interval 

includes the value 0.0, the data are considered to be unbiased with respect to regression l.ine 

intercept. Therefore, the data are considere.d to be unbiased. 

Example Problem B: How Do I E\·alnate Paired Samp ling Tra in Data for Bias? 

ln this example, 18 test runs were performed using paired sampling trains. Table Z.2-3 

sununarizes the data for the two sampling trains. 

Table Z.2-3. Examp le B - Summary of Test Results 

PM Concentration 

Run Trai.n A (x) T ralo 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 14.1 -·-- 6 I 5.1 16.2 

7 18.3 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 24.3 --- . " 

17 29.3 29.1 

18 26.9 26.1 

Z-17 

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The resulting regression equation is 

y ~ Ll8+ 0.974x 

Table Z.2-4 summarizes the results of the regression calculations. The confidence interval for 

the slope is determined as 0.924 < b, < I .024. Because the confidence intenal includes the 

value I .0, the data are considered to be unbiased with respect to regression line slope. The 

confidence interval for the intercept is calculated to be 0.325 < b0 < 2.036. In this case, the 

confidence interval does not include the value 0.0. Consequently, the data are considered to be 

biased. A closer look at the data shows that the PM concentration measured by Train B was 

higher than the PM concentration for the same run measured by Train A in 15 of the 18 test runs. 

The test does not reveal which sampling train provided the more accurate measurements, so both 

trains should be checked for possible sources of bias. If the ~ou ce of the bias can be 

determined, only the data from the train that provided the unbiased results should be used to 

develop the correlation equation. If the source of the bias cannot be determined, the owner or 

operator can decide to use the data or repeat the correlation test. However, if paired sampling 

data are required by regulation, the emission test should be repeated. 

Table Z.2-4. Summary of Regression Calculations 

Variable Calculated value ! Equation No. 

x 14.56 I 

' Z.2-3 

'J 15.37 Z.2-3 

s., 1425 Z.2-5 

s., 1388 Z.2-5 

bo 1.18 Z.2-2 --- -···· b, 0.974 Z.2-4 

s 0.893 Z.2-8 

""' 2.12 Appendix. A 

SE(b1) 0.0236 Z.2-7 

SE(b,) 0.404 Z.2-IO 

Cl" 0.924 < b, < 1.024 Z.2-6 

Cl 0.325 < b < 2.036 Z.2.-9 

Z.2.5 Using tl1e Bias Check Spreadsheet 

This section provides instructions for using the Bias Check Spreadsheet. The spreadsheet can be 

used to check paired sampling train data for bias using the procedure described in tbe previous 

sections. 

The spreadsheet includes tlu-ee worksheets. The worksheets appear as tabs at the bottom of the 

screen. You can move from one worksheet to another by clicking on the appropriate worksheet 

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tab. The initial worksheet (Test Data) is used for data entry. The Calculations worksheet shows 

the intemlediate calculations that are needed for checking bias. The Summary of Results 

worksheet presents the results of the bias check 

The Calculations and Summary worksheets are completely locked, which means that tl1e user 

can open the worksheet and view the results of the calculations but cannot modify any of the 

cells in the wotksheet. The Test Data worksheet is partially locked. The user enters the test data 

for one sampling train (Train A) in cells A6 through A65 and the data for the other sampling 

train (Train B) in cells B6 10 B65. It makes no difference in the analysis wh:ch train is 

considered Train A and which is considered Train B. Cells F3 to F6 are used to enter the facility 

name, location, emission unit, and test dates. All other cells in the Test Data worksheet are 

locked. Figure Z2·1 shows the Test Data worksheet for Example Problem A described 

previously. 

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!AI!I!:fP UMf!t..ji.JVTBAUI DSJ DW " 

' ' f1<1 ¢onunti/Jllll f ,)CIIIy. #~t..- Eitalk Pow• CMI!IIilllf 

' TUUIIA ~ lK"*- J.tf)'I...,• USA 

' ""' ' & -•"'IIMIUtlll: 8 ..... ""-l 

' ' 23 2 "* ~~: Mmdoe .. 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./ 

·- Figure Z.2-J. Example of Test Data worksheet for Bias Check Spreadsheet 

(Example Problem A). 

Z-19 

• - If I( 

0 c=:! -

1•1•1 

VES009997 
The Calculations worksheet consists of several columns that display the results of the various 

calculations needed for the linear regression. All cells are locked in this worksheet. 

Figure Z.2-2 shows the Calculations worksheet for Example Problem A. 

!H) Ek Cdc. !h hot ~ 10$ ~ ~ a$ 

lil '!!<!Pill. :;<· ~,.lll! l!ll<l •r· tl l l "'~ "" 'ii'?'l(i) . 

... <I> 3 ..,! 

Arill .zo - o r D •••~ s"', :.::t:s ft'~ _ . J:!:oo . IBD+I 1 - _ 1 - A. · -

ll'r. lilliloCO"f>ll(;·fc:luc: ......,.~ Cnn!f.'•WIY 

lOC,JII(U Alf)(OIII._ ' l6A 

. ' • 

&111 --""': ~·b ) 

hU(NIIH: M:Mct16tlt15.l .... 

Figure Z.2-2. Example of Calculations worksheet for Bias Check Spreads beet 

(Example Problem A). 

The Summary of Results worksheet includes the information about the facility, emission unit, 

and the emission test date that were entered on the Data Entry worksheet, fo:Iowed by a table 

displaying the ''alues for the statistical parameters that must be calculated to evaluate the data for 

bias. Finally, the summary of the results is displayed. This summary includes the upper and 

lower bounds for the confidence intervals for the slope and intercept of the regression line. The 

spreadsheet also indicates whether the data satisfy the bias criteria for slope iind intercept 

Figure Z.2-3 shows tbe Summary of Results worksheet for Example Problem A. 

Z-20 

VES009998 
~ 6k idt ~ O"oK\ ~ !.?$ ~ ~ ~ 

o .-.. teJ dJ !:'1 e; 11 -:,"' '( ~ m~ ..;: ., . "'-' r . ~. ~ u o 41 ~ • ~ .., ~ 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 

MmllU01S.NN 

tt:~.e.ctdClt M110oldll lt ... ooolPS· U (.UI&"fl(~ f>o -""'ltlollfiii'IIIP · IOI!II ('"".\ (Il.., l;lwd..•U-• .... ,. 

' • H\ rf\tQm ..{ ~I:Q >..s-.orx of ~l'l e.so / 1·1·11 

-

Figure Z.Z-3. Example of Summary of Results worksheet for Bins Check Spreadsheet 

(Example Problem A). 

Z.2.6 Using Excel Data Analysis Tools to Evaluate Bias 

The data analysis tools included in Microsoft Excel also can be used to perfonn the bias check. 

• Key in the data for the two sampling trains in separate columns. 

• Uncer the Tools menu, select Data Analysis. 

• Scroll down tl1e list of options to Regression, then click OK. 

• Click on the icon in the Input Y Range cell, then block off the dam for sampling Train 

B and press enter. 

• Click on the icon in the Input X Range ceU, then block off the data for sampling Train 

A and press enter. 

Z-21 

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