# Candi date Conditional Method ZZ: Determination of Metal Concentration in CES’ Xact CEMS Stilling Chamber Using Filters and Solid Sorbents with X-Ray Fluorescence Analysis

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



### Revision 1.0 June, 2005

# Candidate Condition al Method ZZ: Determination of Metal Concentration in CES’ Xact CEMS Stilling Chamber Using Filters and Solid Sorbents with X-Ray Fluorescence Analysis

Draft June 23, 2005

Prepared for U. S. Environmental Protection Agency Research Triangle Park, NC

Prepared by: J.A. Cooper, B.E. Johnsen, K. Petterson, C. A. Yanca, M. Nakanishi, D. Barth, S. FryCooper Environmental Services, LLC 10180 SW Nimbus Blvd Suite J6 Portland, Oregon 97223

# Candidate Conditional Method ZZ: Determination of Metal Using Filters and Solid Sorbents with X-Ray Fluorescence Analysis

Prepared by:___________________________________ Date:_________ Douglas C. Barth, Environmental Scientist Prepared by: ___________________________________ Date:_________ Cay A. Yanca, Environmental Scientist Prepared by: ___________________________________ Date:_________ Krag Petterson, Environmental Scientist Reviewed by: ___________________________________ Date:_________ Bruce E. Johnsen, QA Manager Approved by: ___________________________________ Date:________ John A. Cooper, Director

### Executive Summary Eli Lilly and Com p any (Lilly ) opera tes a waste in cineration s y stem locate d at the T i pp ecanoe Laborato r ies in Laf a yette , Indiana. T h is inc i ner a tor system includes an X act m u lti-m e tals continuous em issions m o nitoring system (Xact-CEMS, m a nufactured by Cooper Environm ental Services, LLC) for demonstrat ing attainm e nt with the Hazardous W a ste Com bustor MACT f o r sem i -volatile m e tals, lo w-volatile m e tals, and m e rcury em issions. Lilly m u st conduct an in itial performance evaluation tes t as w e ll as quarterly and annu al audits to assure the accu racy of the reported resu lts from the CEMS. Lilly has proposed the use of a NIST-traceable refere nce aerosol generator for re lative accuracy and linearity determ inatio ns. In addition, Lilly is also pr opos in g the use of a new sam p l i ng and analysis reference m e thod for m e tals to assure the ac curacy of the spiked reference aerosol. This appendix describes this new sampling and analysis m e thod used in Method 301 tests described in the body of this report and propos ed for the above noted initial perform a nc e evaluation test and annu al audits of Lilly ’s X act-CEMS. This new m e thod is an X-ray Based Filte r Me tho d (XFM) tha t draws a r e presentative sam p le of inciner a tor emissions f r om the Xact-CEMS stilling cha m ber throug h a series of reac tive and non-rea c tiv e f ilter s . The f ilter deposits are non-destructively analyzed by X-Ray Fluorescence (XRF) to determ ine m e tal concentratio ns in the filter de posits. Metal concentrations in the em issions are calculated by dividing the volum e of s a m p led flue gas in to the m e tal m a ss m easured by XRF. This m e thod is applicable to the m easurem en t of chrom i um ( C r), arsenic (As), cadm i um (Cd), m e rcury (Hg), and lead (Pb)) in em issi ons from Lilly’s hazardous w a ste incinerator. Although the XFM is optim ized for these elem en ts, it is applicable to other elem ents including: vanadium (V), m a nganese (Mn), ir on (Fe), nickel (Ni), c opper (Cu), zinc (Zn), silver (Ag), antim ony (Sb), barium (Ba), thallium (Tl), tin (Sn), bism uth (Bi), cobalt (Co) and selenium (Se). The XFM can quantify flue ga s concentrations ranging from less than 0.2 to over 2000 μg/dscm

.

Standard Operatin g Procedure f o r the CES XFM: V1.0 Page i of i

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

........................................................................................................................ iv List of Figures ............................................................................................................................v 1.0 Method Summary

.......................................................................................................... 1 1.1 Principle

................................................................................................................ 1 1.2 Applicability

......................................................................................................... 1 1.3 Cautions

................................................................................................................ 1 2.0 Definitions and Abbreviations

...................................................................................... 2 3.0 Safety

............................................................................................................................ 2 4.0 Apparatus

...................................................................................................................... 2 4.1 Overview

............................................................................................................... 2 4.2 Extrac tion a ssem b ly

.............................................................................................. 3 4.3 Extraction flow control module

............................................................................ 3 4.4 Dilution flow control m odule

................................................................................ 3 4.5 Sam p le f ilte r holder asse mbly

............................................................................... 3 4.6 Sa m p le flow control m o dule

................................................................................. 3 5.0 Reagents an d Standards

................................................................................................ 4 5.1 Filte r cas sette

........................................................................................................ 4 5.2 Desiccan t

............................................................................................................... 5 5.3 XRF standards

....................................................................................................... 5 6.0 Pre-sam p le Preparation

................................................................................................. 5 6.1 Test prep aration

.................................................................................................... 5 6.2 Pre-te st labo ratory p r epa r ation

.............................................................................. 5 6.3 Sam p le tra i n prepar ation

....................................................................................... 5 7.0 Sam p le Collection

......................................................................................................... 6 7.1 Filte r holde r leak che c k

......................................................................................... 6 7.2 Setting tota l f l ow needle valve

.............................................................................. 6 7.3 Filte r tem p eratur e rang e ........................................................................................ 6 7.4 Evaluation o f sam p le m e ter accuracy

................................................................... 6 7.5 Filte r cas sette installatio n ...................................................................................... 7 7.6 Sam p ling

............................................................................................................... 7

11/29/ 200 5 3:45 PM Page ii of v7.7 Sam p le reco very .................................................................................................... 7 7.8 Post-test Ch ecks

.................................................................................................... 7 8.0 Sa m p le Recovery, Handling and Preservation

.............................................................. 7 9.0 Elem ental Analysis

....................................................................................................... 8 9.1 Analysis

................................................................................................................. 8 9.2 Calibra tion

............................................................................................................. 8 10.0 Calculations

................................................................................................................... 8 10.1 Flow Correction Factor

......................................................................................... 8 10.2 XFM Measured Aerosol Concentration

................................................................ 9 11.0 Quality Con t rol

............................................................................................................. 9 11.1 Sam p ling

............................................................................................................... 9 11.2 Analysis

................................................................................................................. 9 12.0 Method Perf orm a nce ..................................................................................................... 9 12.1 Range

.................................................................................................................. 10 12.2 Detection Lim its

.................................................................................................. 10 13.0 Pollution Pr evention

.................................................................................................... 10 14.0 W a ste Managem e nt

..................................................................................................... 10 15.0 Tables and Figures

...................................................................................................... 10 16.0 References

................................................................................................................... 17

11/29/ 200 5 3:45 PM Page iii of v

### List of Symbols

e-XFM i C = Concentration of the i th analyte in th e em ission m easured by the XFM
PTFE i M = XRF-determined m a ss of the i th analy t e on the PT FE f ilter
7

− REO i M = XRF-determined m a ss of the i th analy t e on the rea c tive filter (REO-7)

XFM t V = Total volum e (em i ssion plus dilution) sam p led by the XFM
XFM d V = Volum e of dilution air dr awn through filters of the XFM

11/29/ 200 5 3:45 PM Page iv of v

### List of Figures Figure 1 Flow diagram of the sam p ling train used in Phase I and II XFM valida tion te sts.

.. 12 Figure 2: Sample train com ponents used in Phase I and II XFM validation tests.

................. 13 Figure 3: Exploded view of the extraction assembly.

............................................................. 14 Figure 4: Schem a tic diagram of th e extraction flow control module.

.................................... 14 Figure 5: Schem a tic diagram of the dilution flow control m odule.

........................................ 15 Figure 6: Ex ploded and a ssem b led view of the sample f ilter h o lder.

..................................... 15 Figure 7: Schem a tic diagram of the sam p ling flow control m odule.

...................................... 16

11/29/ 200 5 3:45 PM Page v of v

### 1.0 Method Summary 1.1 Principle A representative sam p le of flue gas is drawn from an Xact CEMS 1 stilling cham ber through a cassette con t aining PTFE and reac tive f ilter s . The elem ents in particula t e m a tter (PM) are deposited on the PTFE f ilte r while th e vapor phas e elem ents a r e tr apped o n the re activ e f ilte r. The elem ental m a ss in each filte r de posit is determ ined by X- Ray Fluores cence (XRF) using EPA IO Compendium Method 3.3 2 . Meta l conc entra tions in stilling chamber flue gas are calculated by dividing the volum e of the flue gas sam p led into the elem ental m a ss m e asured by XRF. 1.2 Applicability This m e thod is applicable to the m easurem ent of m e tal aerosol concentrations in the X actCEMS stilling cham ber. 1.2.1 Analytes This m e thod is applicable to Antim ony (Sb), Arsenic (As), C a dm ium (Cd), Chrom i um (Cr), Cobalt (Co), Lead (Pb), Manganese (Mn), Mercury (Hg), Nickel (Ni), and Selenium (Se) and is generally appropriate for elem ents with at om ic num b er from about 13 (Al) through 92 (U) as noted in IO Com p endium Method 3.3 . This sam p ling m e thod is also applicable to Beryllium ( B e), if m eas ured with IO Com p endium Method 3.4 3 after non-dest ructive XRF analys is. 1.2.2 Interferences There are no known flue gas com ponents in thei r typical concentrations that interfere with sam p le collection. Elemental interferences are addressed in IO Com p endium Method 3.3 2

. 1.2.3 Concentration Range The applicable concentration range of this m e t hod is from less than 0.2 μ g /dscm (Table 1) to over 2000 μg/dscm

. 1.3 Cautions This m e thod does not include all of the specifica tions essential to its perform a nce. Som e m a terial is incorporated by refere nce. Therefore, to obtain reli able results, persons using this m e thod should have a thorough knowle dge of at least EPA Methods 1 4 and 2 5 and EPA IO Com p endium Method 3.3 2

.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 1 of 17

### 2.0 Definitions and Abbreviations Accuracy: The agreem ent between an experim e ntally determ ined value and the true value. Aerosol : A suspension of solids and / or liquids in a gas. Analyte: A species (elem e nt, m e tal, etc.) of interest in an analytical m e thod. Detection Limit: The lo west concen tration of an elem en t that can reliably be distinguished from a zero concentratio n. Interferant: A substance other than the analy t e th at caus e s an undesired p o sitiv e or negative output. NIST: U. S. Departm e nt of Comm er ce, Nati onal Institute of Standards and Technology , Gaithersburg, MD 20899 Uncertainty : An indication of the degree of reli ability of a value usually expressed statistica lly (probability) as a m u ltiple of the stan dard deviation of a set of m e asurements. Unless othe r w ise sta t ed, the unce r ta inty in a m ean value of a serie s of m easurem ents will be the standard deviation. In the case of values based on calculations, th e uncertainty in the value is equ a l to the pro p agated uncertainty ba sed on the uncertainties in the param e ters used in the c a lcu l ations. 

### 3.0 Safety This m e thod involves the m easurem e n t of h azard ous m a terials and the op eration of equipm ent with the potential to cause bodily harm . This test m e thod does not address appropriate safety and health prac tices associated with its use. It is the responsibility of the user of this test m e thod to establish appropria te safety and health plans prior to perform i ng this m e thod. 

### 4.0 Apparatus 4.1 Overview The sam p le collection apparatus used for this m e thod is described in the following subsection. The equipment requ ired for the XRF an alys is of the filters is s p ecified in IO Com p endium Method 3.3 2

. The sam p le collection equipm ent consists of the following five m a jor components (Figure 1 and Figure 2):

• Extrac tion a ssem b ly

• Extraction flow control module

• Dilution flow control m odule

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 2 of 17• Sam p le f ilte r holder asse mbly

• Sa m p le flow control m o dule 4.2 Extraction assembly The extraction assem b ly (Figure 3) is used to draw flue gas from th e Xact stilling chamber through the extraction plate via the extraction flow control m odule (Subsection 4.3). A subsam p le of this flow is drawn from the ex traction assem b ly through the probe plate by the sam p le flow control m o dule (Subsection 4.6). A dilution plate is direc tly downstream of the probe plate and the stack gas sam p le is dilute d and m i xed with CDA pr ior to passing through the filter holder (Subsection 4.5). 4.3 Extraction flow control module This m odule (Figure 4) uses an eductor to dr aw flue gas through the extraction assembly. The flow rate is controlled by a standard i ndustrial pressure regul ator with gauge and powered by com p ressed CDA. The flue gas is th en filtered, d r ied, and d e nuded of corrosive m a terial before it is exhausted back into the stilling cham ber. 4.4 Dilution flow control module The dilution flow control m odule (Figure 5) drie s, cleans, controls, m easures and totalizes the flow of dilution gas. Clean, dry, compressed air is further dried in this module before it is used to dilute the sam p le flue gas. The diluti on gas flow and pressure are controlled with a regulator, pressure gauge and a needle valve. The flow rate is m easured by a m a ss fl ow m e ter (D-MFM). A dilution flow integrator (D FI) totalizes the output from the D-MFM and reports the total vo lum e of dilution a i r th at has been added to the gas stream

. 4.5 Sample filter holder assembly The sam p le f ilter ho lder assem b ly (Figure 6) is u s ed to trap p a rticula t e an d vapor phas e m e tals in the em ission sample. Two filters are co ntained with in a 37 mm polypropylene filter cassette insid e the filter ho lder. The first filter is non- reactiv e PTFE filter and is used to trap particulate phas e metals. The s econd filter is a reactiv e filter th at co llects vapo r p h ase m e tals 6 . Downstream of the filters, a therm o c ouple provides temperature in for m ation to ensure th at the filters rem a in within their optim al tem p erature range of 1 00° to 180° F. This assem b ly includes a quick disconne ct for use with leak checks. 4.6 Sample flow control module This m odule (Figure 7 ) controls the flow rate of diluted flue gas through th e filters and m easures the total sam p le flow. Afte r passi ng through the filters, the gas is dried and corrosive species rem o ved prior to determ ining the dry gas flow rate with a m a ss flow m e ter. 4.6.1 Desiccant D r yer Downstream of the filter holder, a d e s i ccan t drye r is used to re move m o isture prio r to f l ow m easurem ent. The XFM reports con centra tions as m a ss per dry standard volum e.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 3 of 174.6.2 Corrosive T r ap Following the desiccant dryer, the diluted flue g a s i s d r a w n t h r o u g h a c o r r o s i v e t r a p d e s i g n e to rem ove corrosive flue gas species. d

A si gnal which is read and totalized by the total f l ow integra t or (TFI ). The tota l sam p le volum e is calculated by subtracting the dilution v o l u m

e d i n t h e X F M during leak checks. Monitoring of this gauge during sam p le collec tion provides co ntinuing qu a lity assur a nc e of vacuum and f ilte r integ r

l y , little t o f t h e n e e d l e v a l v e is ne cessary af ter the in itial a d justm e nt to achieve the desired flow. 4.6.6 Two-way Valve

l e a k c h e c k s . T h i s v a l v e c a n a l s o b e u s ed as a course flow adjustm e nt to regulate the total flow passing th rough the filter. 4.6.7 Vacuum Pump

g a s s a m p le that p a sses through th e pum p is then return ed to the stack.

One 37 mm diam eter PTFE (Teflo 7 or equivalent) and one 37 mm dia m eter REO-7 8 f ilter f o r u i r e d b y t h i s m e thod for each run. T h e two filters s hould be pre-loaded into a labeled 37 mm dia m eter filter cas sette in a clean , dry t e s t run. Filter cassettes should be st ored in a labeled Petri dish before and after sam p ling. 4.6.3 Total Flow M F

M The total m a ss flow m e ter (T-M FM) m easures the total flow (1-2 dslpm ) passing through the filters. This flow m e ter produces a 4

- 20 m e f r om the tota l v o lum e . 4.6.4 Vacuum Gauge A vacuum gauge capable of reporting a vacuum b e t w e e n 0 a n d 2 9 i n . H g i s u s e d t o e n s u r that a v acuu m can be m a i n t a i n e ity. 4.6.5 Needle Valve A needle valve is used for fine control of the total flow rate during sa m p lin g . G e n e r a l adjustm e n

A m a nual two-way valve located just upstream of the vacuum pum p is used to perform presam p l e

A diaphragm vacuum pum p is used to pull th e em ission and dilution gas sam p le through the f i l t e r s . T h e f i l t e r e d , c l e a n e d a n d d r i e d


### 5.0 Materials, Reagents and Standards 5.1 Filter cassette trapping particulate and vapor phase m e t a l s a r e r e q environm e n t p r i o r t o t h e

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 4 of 175.2 Desiccant T h e X F M s a m p l e d r y e r r e q 9 u i r e s a n i n dicat ing des i ccant (Agilent Silica Gel Grade 40 or equivalent). A single dry e r ca rtr i dge m a y be used f o r m u ltiple runs as long as the des i c cant m o val capacity specified by the m a nufacturer.

r a t e t h e X R F p r i o r t o rem a i n s b e l o w t h e r e 5.3 XRF standards XRF thin-f ilm standards f o r m e tals of inte rest s h o u l d b e u s e d t o c a l i b operation according to IO Method 3.3 . Standards should have a known mass per area e r c e n t

.

t h a t , i n order to obtain reliable results, both testers and analysts m u st be trained and experienced with the test procedures, including source ; s a f e t y e q u i p m en t and procedures; analytical calculations; reporting; and the specific procedural descriptions throughout this m e thod.

P r i o r t o shipping, lo ad one upstream PTFE fi lter and one downstream REO-7 filter for each ru n into a a b e l e d Petri dish for transport. Prov ide one lo ad ed filter cassette for a QA fi eld blank.

n e r c e n t o f t h e r e a d i n g on the certified NIST traceable me t e r .

. 1 Sample flow rates and sample time p a y range from 0.5 to 1.0 slpm , but should not vary by m o re than ten percent during a test run. S a m p le tim e s hould be between 10 and 50 m i nutes. 6.3.2 Extraction a ssembly and dilution flo w module leak checks an d sampling rate

a ctCEMS sa m p ling port. To perform this leak ch eck, cap the port adaptor with a rubber stopper a n d i n e d air to the dilution plate port and cap the 3/8”ex tra c tion p l ate p o rt. Pres surize the a ssembly to ( μ g/cm 2 ) t o w i t h i n f i v e p 

### 6.0 Pre-sample Preparation 6.1 Test preparation The com p le xity of this m e t h o d i s s u c h

sam p l i n g ; s a m p l e h a n d l i n g
6.2 Pre-test laboratory preparation Check filters visually ag ainst ligh t for irregul arities, flaws, or pi nhole leak s . labeled filter cassette and p l a c e i n t o a l
Before each series of tests, the flow rates for both the to tal flo w and the dilution flow integrators should be checked against a certifie d NIST-traceable m e t e r . T h e f l o w r e a d i n g o the integrator should be within f i v e p
6.3 Sample train preparation 6

. 3 Sa m l e a n d d i l u t i o n f l o w r a t e s m

The extraction and dilution assem b ly m u st be leak checked prior to m o u n t i n g o n t h e X

s e r t t h e e x t r a c t i o n a s s e m b ly plug (Figur e 3). Connect the dilution line for com p r e s s 5 psi and close the dilution flow shut-off valv e. The gauge reading should be stable (±5%) for 30 seconds. Followin g a successf ul leak chec k, rem ove the stopper an d 3/8” cap n u t

. T h e

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 5 of 17extraction assem b ly and dilution line can now be mounted on the Xact-CEMS stilling cham ber sampling port. The flow from the Xact-CEMS stilling cham be r through the extraction assem b ly should be m a intained in the range of 15-30 slpm. The XF M extraction assem b ly tem p e r a t u r e s h o u above 220°F. l d b e

l d

e r l e a k c h eck b e p e rf orm e d af te r the f i lter c a ssette has b e en loaded in the eck, s eal th e f ilter holder as se mbly with th e f ilte r holde r cap F p and allow the vacuum to reach 15 in H g. Close the sam p le flow shut-off valve (Figure 4), turn off the pu mp, and reco rd the in itial pressure and the

ample and dilution) th at pas s es through the filte r is controlled by a ) . To determ ine the n eed le valve’s initial set point, place a load ed e r a n d l eak check as s t ated above. Install the filter holder onto the extraction assem b ly, which is at operating conditions. Open the sam p le shutd s

e

filter tem p erature b e m a intained at ab out 140°F before sam p ling begins an d should not s a m p l i n g .

lder contain i ng a filter casse tte, attach the NISTa t, turn on the sample pum p, open the ball valve and allow s t ack gas to p a ss through the filter, T-MFM and NIST-traceab le m e ter. Compare 

### 7.0 Sample Collection 7.1 F i l t e r h o A f ilter hold e r le ak chec k m u s t f ilter ho lder. To perf orm this ch n u t ( i g u r e 6 ) , t u r n o n t h e p u m pressure after 30 seconds. To pass this check, the change in pressure m u st be less than five percen t of the initia l pres sure. Diseng age the sampling train quick disconnect to release the vacuum (Figure 6). 7.2 Setting total flow needle valve T h e t o t a l f l o w r a t e ( s needle valve (Figure 7 blank filter cassette in t o t h e f i l t e r h o l d off valve fully and turn on the sam p le pum p. Se t the need le v a l v e s o t h a t t h e T

- M F M r e a the des i red s a m p ling rate. Then close the s hut-off valve and tu rn off the pump. For each sam p le run, the shut-off valve will be used to start the sam p l i n g f l o w w h i l e t h e n e e d l e v a l v should be used to m a ke m i nor flow adjustm e nts as needed af ter the sam p ling has started. 7.3 Filter temperature range Since filter holder tem p erature can increase at the star t of the run, it is recomm e n d e d t h a t t h e exceed 180° F a t a n y t i m e d u r i n g 7.4 Evaluation of sample meter accuracy Prior to the f i rst run, th e accura c y o f t h e T

- M F M s h o u l d b e c h ecked using a NIST-traceable flow m e ter and stack gas

. Mount the filter ho trac e b l e f l o w m e ter to the sam p le f l o w o u t l e the T-MFM value to the NIST f l ow m e ter. The values should be within f i ve percen t. I f they differ by m o re than five percent, a correction should be m a de using the form ula in Section 10.1. Disconnect th e NIST flowm e ter and place a new filter cassette in the filter ho lder before starting the first sam p le run.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 6 of 177.5 Filter cassette ins t allatio n F o r e a c h r u n , fill out the XFM Field Data Sheet (Table 2), identifying the date, run, op erato r , XFM m odul e I.D. no., and filter I.D. num b ers, and date, time, and other data for the test run. r t h o ld er and conduct a filt er holder leak check.

a r t o f an Xact sam p le run, start the XFM sample pum p, op en the ball valve, a nd record the initial d s t a r t t i m e. Sa m p le for 10 to 50 m i nutes, recording temperatures, pressures, and volum es every five minutes. Use the dilution and tota l f l o w needle valves to

u n e n d

h e 7.7 Sample recovery

m b ly, disassem b le the filter holder and rem ove the f ilter ca s s ette. Retur n the f ilter c a ssette with f ilter s to th e origin al Petr i dish,

. D o not separa te the PTFE and reactiv e f ilters f r om the f ilter cassette. Do cum e nt any abnorm a lities on the filter and ship to the approp riate laboratory for

i n g c h e c k s n eed to be m a de after th e la st test run is com p lete and before packing the equipm ent for return shipm e nt. 7.8.1 Flow Agreement Check

m a ss flow meters should be checked f o llowing the sam e procedure as in subsection 7.3. 7.8.2 Extraction a ssembly and dilution flo w module assembly lea k checks

u t i o n f l o w m odul e leak check should be perform e d according to the sam e procedures found in subsection 6.3. 

### 8.0 Sample Recovery, Ha ndling and Preservation

n o t e t h e c o n d ition of the f ilter s . Car e f u lly rem ove the filters from the filte r cass e tte s and pla ce each filte r sam p ling side up in a s a t t e m p e r atures less than I n s e f ilter cassette into the f i l t e r 7.6 Sampling Prior to sampling, zero the total flow integrator . At a tim e c o n c u r r e n t w i t h t h e s t dilution volum e a n ensure th at the flow rates are cons tant and m onitor the filter tem p erature to ensure th at it rem a ins below 180°F. When sa m p ling is com p le te, close the shut-off valve, turn off the vacuum pump and immediately record the dilu tion volum e, total volum e and sam p l e r tim e on the worksheet. Note: It is recommended that a post-test sam p le f l o w l e a k c h e c k n o t b e c o n d u c t e d s i n c e t test m a y comprom i se th e sam p le collected on the f ilter.

After rem o ving the filter holder from the extrac t i o n a s s e

a n d s e a l t h e d i s h w i t h t a p e analysis. 7.8 Post-test Ch ecks T h e f o l l o w

Calibration of the dilution and t o t a l

The extraction assem b l y a n d d i l

Open the f ilter cass e ttes in a clean wo rk are a a n d separately labeled Petri slide. Filters should be stored in arch i v e

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 7 of 175°C. The f ilters rem a in in archiv es u n til th ey a r e scheduled f o r analys is. F o llowing XRF analys is the f ilter s m a y be retu rned to storage and analyzed ag ain at a la ter d a t e o r t h e be subm itted f o r analysis f o r beryllium (Be) acc ording to the procedur es outlin ed in Com p endium Method IO 3.4

. y m a y

9.1 Analysis ilar to those in Com p e ndium Method IO-3.3 2 “Stan d ard r e f o r t h e X

- R a y F l u o r e s c e n c e A n a l y s i s o f P M 2. 5 Deposits on Teflon Filters”. These m e thods address the applica tion of energy dispersiv e X-ray fluorescence r

is calibrated using thin film standards of a known y i n μg/cm 2 ). Potential m a nufacturers of thin film standards are listed in Com p endium Method IO-3.3 For each elem ent, a calibratio n se nsitivity factor is obtained by g / c m 2 )

.

s t a b l i s h e d d u r i n g c a l i b r a t i o n . T h i s thin film to spot ratio is determ ined em pirically by using

10.1 Flow Correction Factor for both the to tal integration and the dilution a i n s t a certifie d N I ST-traceab le m e ter. The flow readin g on the in tegra t o r ( F ) should be within five percent of the reading on the certified NIST 

### 9.0 Elemental Analysis

The analytical procedures are sim Operating P r o c e d u spectrom e tr y (EDXRF) to the de ter m ination of elem ental co mposition of particulate m a t t e deposits on f ilters. 9.2 Calibration The X-ray fluorescence analyzer concentratio n ( u s u a l l dividing the x-ray intensity (coun ts/sec./m A ) by the concentration o f t h e s t a n d a r d ( μ Generally th ese stand a rd s are larger than the area of the exciting X-ra y beam while the XFM deposition spot is sm aller than the beam . For this reason, a thin film to spot ratio m u st be e a single standard of a known con centration with the sam e area as the XF M deposition spot. This ratio is determ ined for each an alysis condi tio n and is app l ied to each elem ent in th at analysis condition. 

### 10.0 Calculati o ns

Before each series of tests, the flow rates integ r ato r sh o u l d b e c h e c k e d a g
FI trac eable m e ter ( Nist F ) and recorded in th e fiel d notes. If they are not within f i v e p e r c e n t, the noted difference m u st be used to calculate a correction factor ( F CF ) as defined below:

FI Nist F F F CF = Equation 1

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 8 of 1710.2 XFM Measured Aerosol Concentration The XFM-determ ined c oncentr ation of the f i ve MACT m e tals in th e sam p led f l ue gas is based on a m easurem ent of the m e tal m a ss de posited on the XFM f ilters and the sam p le volum e that passed through the filters. The XR F analys is res u lts yield th e m e tal m a sses in μg of each reported m e tal per filter. The tota l sample volume is determ ined by subtracting the dilution volum e f r om the tota l v o lum e . Th e s e param e ters are used in Equation 2 to calcu late the concentration of each analyte as sh own below:

XFM d XFM t REO i PTFE i XFM e i V V M M C

− + = −

− 7 Equation 2
Where:

= Concentration of the i e-XFM i C th analyte in th e em ission m easured by the XFM (μg/dscm )

= XRF-determined m a ss of the i PTFE i M th analy t e on the PT FE f ilter (μg )

= XRF-determined m a ss of the i 7

− REO i M th analy t e on the reactive filter (REO-7; μg)

= Total volum e (em i ssion plus dilution) sam p led by the XFM (dscm ) XFM t V

= Volum e of dilution air drawn through filters of the XFM (dscm )

XFM d V 

### 11.0 Quality Control 11.1 Sampling The sam p ling quality control re quirem e nts include perform i ng all necessary leak checks and checking the flow readin gs agains t a NIST tracea ble standard. The following is a lis t o f all necessary sampling quality control procedures. 1. Extraction assem b ly leak check (See subsection 6.3) 2. Dilution assem b ly leak check (See subection 6.3) 3. Sam p le f ilte r holder asse mbly leak c h eck (See su bsection 7.1 ) 4. Flow calibration check (See subsection 7.3) 11.2 Analysis Quality con t rol and as surance proc ed ures are perf orm e d in accordance with Com p endium IO-3.3

. 

### 12.0 Method Performan ce

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 9 of 1712.1 Range The applicable concentration range is from less than 0.2 μg/dscm to over 2000 μg/dscm. 12.2 Detection Limits The interference free de tection lim its at the 95% confidence level Error! Bookm a r k not de fine d. are given in Table 1 assum i ng a sam p ling rate of 0.7 slpm and a sampling tim e of 30 m i nutes. Actual m e thod detection lim its are based on actual source sampling and an alytical results. If required, the m e thod in-stack de tection lim its can be im proved over those shown in Table 1 by either increasing the stack gas volum e sam p le d, the sam p le tim e, or XRF analytic a l tim e. Increasing the volum e sam p led by a factor of two results in a corresponding two fold incre a se in the detec tion lim its. XRF detec ti on lim its i m prove with the square root of the analysis time. 

### 13.0 Pollution Prevention The exhaust from the sample flow module is ve nted to the atmosphere after passing through the sam p ling f ilter s , dry e r and co rro sive gas den uder. There are no r eage n t solutions generated in this m e thod. 

### 14.0 Waste Management Sa m p le filters are arch iv ed for one year a nd then disposed as non-hazardo u s waste.


### 15.0 Tables and Figures Table 1: XFM Detectio n Limits E r r o r ! Book m a r k not defined. E l e m e n t S y m b o l Analy t ical (ng/spo t) In-stack (μg/dscm ) A n t i m o n y S b 2 3

. 0 2

. 2 0

Arse n i c A s 1

. 3 0

. 1 2 Cadmi u m C d 1 3

. 0 1

. 2 C h r o m i u m C r 1

. 3 0

. 1 2

Cob a l t C o 1

. 3 0

. 1 2 L e a d P b 1

. 7 0

. 1 6 Manga ne se M n 1

. 3 0

. 1 2

M e r c u r y H g 2

. 1 0

. 2 0

N i c k e l N i 0

. 8 0

. 0 8 S e l e n i u m S e 1

. 3 0

. 1 2

S i l v e r A g 8

. 4 0

. 8 0

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 10 of 17Table 2. XFM Field Da ta Sheet

Ex t Temp. Filte r Temp. Sa mp. Fl o w D il. Flow Flow Va c. Di l. Flow Pres. Ex t
. Flo w V ac. Ex t
. Flo w Pres
. Dr ie r Pr e s . °F °F li ter s li ter s i n . H g i n . H g in . H g in . H g in . H g

NOTES: F ) Tot a l Tes t Vol. ( E -D ) G) Net Sample Vol. ( F

- C ) E ) Fi n a l T o ta l V o l

. D) I n i t i a l T o t a l V o l. C ) Di l. Ai r f o r Te st ( B -A) B ) Fi n a l T o t. V o l. (D il. A i r) A) In it . T o t

. Vol. (Dil. Air) Sta r t T i me Sto p Time Op er ator( s ) :

L eak Check Post- t est Fil t er Ev

. P r e- test Fi l t er Ev al. Date Run No.

XFM Mo d u le N o
. PTF E F i l t e r N o
. REO-7 Fi lte r N o
.

Time 

## XFM FIELD D A TA SHEET

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 11 of 17Figure 1 Flow diagram of the sampling trai n used in Phase I and II XFM validation tests.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 12 of 17Figure 2: S a mple train components used in Phase I and II XFM validation tests.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 13 of 17Figure 3: E x ploded view of the extraction assembly.

Figure 4: S c hematic diagram of th e extraction flow control module.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 14 of 17Figure 5: S c hematic diagram of th e dilution flow control module.

Figure 6: E x ploded and assembled view of the sample filter holder.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 15 of 17Figure 7: S c hematic diagram of th e sampling flow control module.

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 16 of 17

### 16.0 Referen ces

1 Xact-CEMS. X-ray Based Continuous Em i ssions Monitoring System for Multi-Metals. Manufactured by Cooper Environm e n tal Services, LLC. Portland, OR. www.coope renvironm ental.com

. 2 EPA Compe ndium of M e thods for the De term ination of Inorganic Com p ounds in Am bient Air. June, 1999. Com p endium Met hod IO-3.3 Determ ination of Metals in Am bient Particulate Matter Using X-Ray Fluorescence (XRF) Spectroscopy. EPA/625/R96/010a. 3 EPA Compe ndium of M e thods for the De term ination of Inorganic Com p ounds in Am bient Air. June, 1999. Com p endium Met hod IO-3.4 Determ ination of Metals in Am bient Particulate Matter Using Inductiv ely Coupled Plasm a (ICP) Spectroscopy. EPA/625/R-96/010a. 4 EPA Method 1. Sa m p le and Velocity Traverses for Stationary Sources. 5 EPA Method 2. Determ ination of Stack Veloci ty and Volum e tric Flow Rate (Type S P itot Tube). 6 NIST. National Institute of Sta ndards and Technology. Gaithersburg, Md. www. NIST. gov. 7 Teflo Filter. 2003. Manufactured by Pall Li fe Sciences Laboratory Filtration and Separation Catalog. pp.30-31. 8 REO-7. Manufactured by Cooper Envi ronm ental Services, LL C. Portland, OR. www.coope renvironm ental.com

. 9 Agilent Dryer. Manufacturered by A g ilent technologie. Found on the web at: http://www.chem .agilent.com

11/29/ 200 5 XFM for Xact- C E M S SOP V1 Page 17 of 17