Document 5bgpMLvrNM1QRgy452xx2qgK4

VV " i'' June 1984 National Dioxin Study Tier 4 -- Combustion Sources Project Plan By Air Management Technology Branch DRAFT U.S. ENVIRONMENTAL PROTECTION AGENCY Office Of Air And Radiation Office Of Air Quality Planning And Standards Research Triangle Park, NC 27711 June 1984 This document is an OAQPS staff draft that is being circulated for technical review and comment. It has not been fully reviewed within EPA and does not represent Agency policy. / .r.- ^v II ACKNOWLEDGEMENTS work p l a n w a a p r e p a r e d by the ' A ir Managementr Technology" Branch^* M onitoring and Data A nalysis D iv isio n , O ffice o f A ir Q u a lity P lanning and S tan d ard s, O ffice of A ir and R adiation w ith s ig n if ic a n t in p u t and a s s is ta n c e from Mr* Andrew M iles and h i s s t a f f a t R adian C o rp o ra tio n * Many h e lp f u l rev iew comments on a p re lim in a ry d r a f t were provided by th e T ie r 4 N a tio n a l D ioxin Study Work Group composed o f r e p r e s e n t a t i v e s o f th e G. S* E n v iro n m e n tal P ro te c tio n Agency R egional O ffic e s , O ffice o f R esearch and Development,. O ffic e o f P e s tic id e s and Toxic S u b stan ces, O ffice o f Solid Waste and Emergency R esponse, O ffic e o f W ater _and others- A ll p a r t i c i p a n t s , and re v ie w e rs a re acknowledged g e n e ra lly and in d iv id u a lly fo r th e ir e f f o r ts In d ev eloping th is work p lan . l ill  ,',.;,i V.-? -. -'V "" -^. :v " '-'V / .. <v ; " i - ' 5 <;' ^ T~ " v ` :: ---O'V Table Of Contenta L i t o f T a b le s ....................... . . . . . . . . . . . . ............................................................ .................... v i i i L i s t o f F ig u r e s ............................................................................................... .......................... . . . v i i i Section 1 I n tr o d u c ti o n And Summary Of T i e r 4 Work P la n .......................... I I . 1 Introduction . . ***.. *. 1 1 .2 Background ..................................................................................................... I 1 .3 Management Of The N a tio n a l D ioxin S tr a te g y ........... 3 1 .4 Pro je c t Approach .............. "3 1 .5 B a sis F o r I n v e s t i g a t i o n Of C om bustion S o u rces ........................ 5 1 .6 Summary Of T i e r 4 Program P la n ......................................................... 6 1 .7 P o s s ib le R e s u lts Of The T i e r 4 S tu d y ........................................... 13 1 .3 Form at Of T h is R ep o rt .................. 14 Section 2 A lte r n a te S ttriy P la n s Which Were C o n sid ered ........................... . 15 2 .1 A lte rn a tiv e 1 - Focus The T ie r 4 E f f o r t P rim a rily On M u n icip al W aste I n c i n e r a t o r s ....................................................... 15 2 .2 A lte r n a tiv e 2 - I n v e s tig a te C o n d itio n s Which In c re a s e /D e c re a s e D io x in E m issio n s ................................................ 17 2 .3 A lte r n a tiv e 3 - Develop A M e c h a n istic Model To E s tim a te 2378-TCDD e m is sio n s ............................................................. 13 2 .4 A lte r n a tiv e 4 - C o lle c t Ash Samples From A L arge Number Of Source C a te g o rie s ............................................................... 19 2 .5 A lte rn a tiv e 5 - Analyze Samples For S p e c ific Isom ers And Homologues Of F u ran s ...................................................................... 20 v Table Of Contenta ; Page Section 3 The T i e r 4 Work P la n ................................................... . . ............. .. 21 3 .1 O verview .......................... 21 3 .2 L i t e r a t u r e Review AndE v a lu a tio n ....................................................... 21 3 .3 , Summary Of A v a ila b le D ata ................................ 21 3 .3 .1 PCDD In Feed .......................................................................... 23 3 .3 .2 P r e c u rs o rs I n Feed ............................................................. 25 3 .3 .3 C h lo rin e I n Feed ................................................................. 27 3 .3 .4 C om bustion C o n d itio n s ....................................................... 27 3 .4 I d e n t i f i c a t i o n Of Source C a te g o rie s W ith A P o t e n t i a l To Emit D ioxin .................................................................. 30 3 .5 Development Of C r i t e r i a F or P r i o r i t i z i n g The C a n d id ate Source L i s t ......................... ................... ...................... 31 3 .5 .1 Rank D Source C a te g o rie s ................................................ 34 3 .5 .2 Rank C S ource C a te g o rie s ................................................ 37 3 .5 .3 Rank B Source C a te g o rie s ............. 38 3 .5 .4 Rank A Source C a te g o rie s ................................................ 40 3 .6 S e le c tio n Of C e r ta in C an d id ate S ource C a te g o rie s ' r For S ta c k T e s tin g ................................................................................... .. 41 3 .7 Types Of Samples To Be C o lle c te d Under The S ta c k T e s tin g Program ........................................................................ 44 3 .8 Ash S c re e n in g Program ........................................ 48 vl ;*$*>n / Table Of Contents % % % ? ;* =T - ` ,,'Page Section 4 4*1 4.2 4.3 4 .4 4.5 4.6 4.7 4.8 4.9 Im p le m e n ta tio n Of The T ie r 4 F la n ............................... *............... 51 Overview ***' * .. 51 -'`S e le c tio n Of I n d iv i d u a l S ources F o r T estin g : :. . . . . . . 51 Ash Sam pling Program ................................................................................. 52 Source T e s tin g Program ............................................................................. 53 Q u a n tita tiv e E xposure And Risk. A ssessm ent ................................ ~54" Ambient A ir Q u a lity S tudy ...................................................................... 54 Management Of T i e r 4 ...................... . ............................................... 55 C o o rd in a tio n W ith The EPA R eg io n al O f f ic e s ................................ 55 A d d itio n a l In f o rm a tio n .................................................. R eferences ................................................................................. .............................................. 59 Appendix A ........................... ........................ ........................................................................... 64 v ll LIST OF TABLES 1-1 Com bustion S ource C a te g o rie s Where Ash Samples W ill L ik e ly Be C o lle c te d ............................................. *............... ............................... .................... 7 1-2 Sam pling And A nalyses M o d e l................ . . . . . ........................ . ............... ........... 10 1-3 Ranked Source C ateg o ry L i s t . . . . . ............................................ . . . . . ............. 11 v ' 3-1 :'"7 C om bustion S o u rces F o r Which TCDD T e s t D ata Are A v a ila b le . . 22->r*? 3 -2 C h a r a c t e r i s t i c s Of S ources T e sted F or D io x in s . . . . . . . ................. 24 3--3 C om bustion S o u rces .............................. 32 3 -4 C om bustion Source C a te g o rie s B eliev e d To Have The G r e a te s t P o t e n t i a l To Em it D io x in s ........................... ..................................................... 33 3 -5 Ranked Source C ateg o ry L i s t ..................... 36 3 -6 S ource T e s t P la n O p tio n s F or S ta c k E m issio n s ............................ 42 3-7 Summary Of D ra ft ASME P r o to c o l For Sample C o lle c tio n .......................... 45 3 -8 Sam pling And A n aly ses Model . . . . . . . . . . . .......................................................... 47 3 - 9 C om bustion Source C a te g o rie s Where Ash Samples W ill L ik e ly Be C o lle c te d ............................................................................................................. . . . .4 9 . 4 - 1 T i e r 4 Work Group .................................................................. 56 4-2 R eg io n al O ffic e C o n ta c ts - T i e r 4 ................................................................ 57 LIST OF FIGURES Number Fage 1-1 Schedule: N a tio n a l D ioxin Study - T ie r 4 - Combustion S ources ............................................................. ..................................... ................. 12 3-1 P r e lim in a r y S ource1L i s t (fro m T a b le 3 -4 ) ..................................................... 35 A -l D e te rm in a tio n Of Sample S iz e From M u n icip al W aste I n c i n e r a t o r s . 65 v ili > ' Section 1 1 I n tr o d u c ti o n And Summary Of T i e r 4 Work P la n --j- 1-1 In tro d u c tio n T h is r e p o r t p r e s e n ts th e U. S. E n v iro n m e n tal P r o te c tio n A gency's (E PA 's) plans fo r Id e n tify in g lik e ly sources and a sse ssin g the m agnitude o f dioxin* e m is s io n s from com bustion so u rc e s un d er T i e r ,,4 o f th e N a tio n a l D io x in S t r a t e g y .The r e p o r t d e s c r ib e s th e in fo r m a tio n EFA p la n s to c o l l e c t o v e r th e n e x t 18 months to Improve o u r c u r r e n t u n d e rs ta n d in g o f com b u stio n s o u rc e s w hich may e m it d io x in to th e am bient a i r . T his r e p o r t a lso d e s c rib e s the r a tio n a le used _ln_ d e s ig n in g th e s tu d ie s w hich make up th e p r o je c t p la n , a s w e ll a s a l t e r n a t i v e , approaches c o n sid e re d .. While source sam pling and a n a ly tic a l methods and proce^ dures to be used d u rin g the study a re id e n tif ie d , th is re p o rt i s n o t intended to d e s c rib e th e se proced u res in d e t a i l . R eferen ces a re made to o th e r documents where th e se methods and p ro ced u res a re more f u l l y d e s c r ib e d . " 1.2 Background There a re 75 d i f f e r e n t c h lo rin a te d d io x in Iso m e rs, d iv id e d In to e ig h t hom ologues, each w ith d i f f e r e n t p h y s ic a l and c h e m ic a l p r o p e r t i e s . 1 One o f th e 22 isom ers w ith fo u r c h lo rin e atoms is 2 ,3 ,7 ,8 -te tra c h lo ro d ib e n z o -p -d io x in (2373-TCDD). There a r e th r e e re a so n s why t h i s Isom er h as b een s e le c te d a s th e .p rin c ip a l focus of the N ational Dioxin S trateg y : 1. I t Is believed to be the most to x ic o f the c h lo rin a te d d io x in s , 2. I t is the isom er most o fte n a sso c ia te d w ith exposure and p o te n tia l h e a lth ris k s to humans, and Throughout th is work p la n , the terms d io x in and d io x in s a re used g e n e rlc a lly to i n d i c a t e c h lo r in a te d d io x in compounds as d i s t in g u is h e d from 2378-TCDD, th e s p e c ific Isomer o f m ajor concern. -1- 3. There is s u f f ic ie n t a sso ciated h e a lth and exposure inform ation ^w ^ ,-rw_. a v a i l a b l e to a llo w a ta rg e te d ^ study^ to be d ev elo p ed On December 1 5, 1983, EPA r e le a s e d a D ioxin S tr a te g y ^ which p ro v id e s ' a fram ew ork under w hich EPA w i l l : 1 . Study th e n a tu r e and e x te n t o f c o n ta m in a tio n o f 2378-TCDD and th e a s s o c ia te d r is k s to humans and th e environm ent; : 2^ Im plem ent "o r compel n e c e s s a ry c le a n u p a c tio n s a t c o n tam in ate d s i t e s ; and 3 . F u rth e r e v a lu a te re g u la to r y a l t e r n a t i v e s to p re v e n t f u tu r e conrtam ln atlo n , as w ell as d isp o sa l a lte rn a tiv e s to a lle v ia te c u rre n t problems To im plem ent th e s t r a t e g y , EFA has formed sev e n stu d y t i e r s , o rd e re d by th e d e c r e a s in g p o t e n t i a l f o r 2378-TCDD c o n ta m in a tio n : T ie r 1 - 2 ,4 ,5 -tric h lo fo p h e n o l (245-TCP) p ro d u ctio n s i t e s and asso ciated waste d isp o sal s ite s ; T ie r 2 - S ite s (and a s s o c ia te d w aste d is p o s a l s i t e s ) where 245-TCP was used a s a p re c u rs o r to make p e s t l c i d a l p ro d u c ts ; T ie r 3 - S ite s (and a s s o c ia te d w aste d is p o s a l s i t e s ) where 245-TCP and i t s d e riv a tiv e s were form ulated in to p e s tlc id a l p ro d u cts; T ie r 4 - Combustion so u rces; T ie r 5 - S ite s where p e s tic id e s d e riv e d from 245-TCP have been and are being used on a commercial b a sis; T ie r 6 - C e rta in organic chem ical and p e s tic id e m anufacturing f a c i l i t i e s where im proper q u a lity c o n tro l on c e r ta in p ro d u ctio n p ro c e s s e s could have r e s u lte d in the fo rm a tio n o f a 2378-TCDD contam in a te d product w aste stream ; and T i e r 7 - C o n tro l s i t e s where c o n ta m in a tio n from 2378-TCDD i s n o t suspected. 1 1 1.3 Management Of The N a tio n a l D ioxin S tra te g y O v e rall r e s p o n s ib ility fo r th e management of the S tra te g y has been assig n ed to the A s s is ta n t A d m in istra to r fo r the O ffice o f S olid Waste and Emergency R esponse (OSWER). OSWER I s a ls o m anaging th e i n v e s t i g a t i o n s f o r s i t e s In T i e r 1 and 2 o f th e study* The O ffic e o f W ater R e g u la tio n s and S ta n d a rd s (OWRS) I s man a g in g T ie r s 3 , 5 , 6 and 7 , w h ile th e O f f ic e o f A ir and R a d ia tio n (OAR) I s re s p o n - ..1Vs l b l e f o r T i e r 4* The O f f ic e o f R ese arch and D evelopm ent (ORD) I s r e s p o n s ib le f o r sam p lin g and a n a l y t i c a l gu id an ce* ORD I s a ls o r e s p o n s ib le f o r p ro v id in g a n a l y t i c a l s u p p o rt and p la n s to do so v ia an a rra n g em en t w ith th r e e EPA la b o r a t o r i e s (D u lu th ; Bay S t . L o u is; and R ese arch T r ia n g le P a r k ) , c o l l e c t i v e l y known, a s th e TROIKA* As d e s c rib e d l a t e r , EPA 's R eg io n al O ffic e s w i l l be r e s p o n s ib le fo r Im plementing v ario u s asp ects o f the N ational Dioxin S tra te g y , Including portions of T ier 4. 1.4 P ro je c t Approach C l e a r l y , th e r e a r e many d a ta gaps I n th e a v a i l a b l e In fo rm a tio n c o n ce rn in g em issions o f d io x in s from com bustion s o u rc e s ,3 and a number o f d if f e r e n t approaches could be taken to f i l l th ese d a ta gaps* A fter co n sid erin g v ario u s a lte r n a t iv e s , th e Agency has decided to focus the T ie r 4 e f f o r t on the c o lle c tio n o f d a ta from a number o f com bustion source c a te g o rie s which are b eliev ed to have some p o t e n t i a l to e m it 2378-TCDD. D e ta ile d s ta c k t e s t d a ta and ash sam ples w i l l be c o l l e c t e d and a n a ly z e d f o r 2378-TCDD a u i th e h ig h e r d io x in homologues ( l * e ., t e t r a , p e n ta, h ex a, h e p ta , and o c ta ) . Such e f f o r ts are needed to broaden our understanding o f em issions o f d io x in s from com bustion sources* The prim ary o b je c tiv e o f th e T ie r 4 p ro je c t th u s , i s one o f problem d e f in itio n what source c a te g o rie s em it d io x in and a t what c o n c e n tra tio n s? The In v e s tig a tio n s are not designed to answer what can be done to m inimize em issions. - 3- T his approach I s b e lie v ed n e ce ssa ry f o r a number o f re a so n s . Only a lim ited number o f com bustion source c a te g o rie s have p rev io u sly been te ste d to d e te rm in e I f th e y e m it d io x in s in c lu d in g 2378-TCDD to th e a m b ien t a i r . W hile th e se d io x in compounds have been found in the s ta c k em issions and f ly ash from some s o u rc e c a t e g o r i e s , th e y have n o t been d e te c te d a t a l l o f th e so u rc e c a t e . g o rle s which have been te s t e d . Ranges o f t e s t v a lu e s have been shown to be , v e ry broad ( o r d e r s o f m a g n itu d e s ) .- Some o f th e ra n g e s may be d u e r o f c o u r s e , to s o u rc e s u b c a te g o r iz a ti o n [ e . g . , mass burn v e r s u s r e f u s e d e riv e d f u e l (RDF) as^ s u b c a te g o r ie s o f m u n ic ip a l i n c i n e r a t o r s ; d ry p ro c e s s v e rs u s w et p ro c e s s as s u b c a te g o r ie s o f RDF, e t c . ] b u t d a t a a g a in a re I n s u f f i c i e n t to s u p p o rt su ch c o n c lu s io n s . Also t e s t methods have v a rie d c o n sid e ra b ly w ith in the d a ta base now a v a il a b le . These and o th e r f a c t o r s , n o t s u r p r is in g ly , have le d to c o n f l i c t in g th e o r ie s on how and when d io x in s a r e form ed. I n summary, c u r r e n t l y a v a i l a b l e d a ta do n o t c le a r ly d e fin e th e scope o f the problem , o r i f indeed th e re c le a r ly is one.^ The scope o f the T ie r 4 stu d y must be lim ite d , fo r s e v e ra l p r a c tic a l re a sons* While the T ie r 4 budget o f $1.4 m illio n is a c o n sid e ra b le sum, i t does n o t allo w th e Agency to im plem ent a com prehensive stu d y program d esig n e d to examine a l l a sp e c ts o f d io x in em issions from com bustion so u rc es. A key fa c to r i s the hig h c o st o f s ta c k sam pling which i s estim ated to c o s t ap p ro x im ately $90,000* fo r each source te s te d , not in clu d in g s im ila rly expensive a n a ly tic a l work. Because o f th ese high c o s ts and the lim ite d re so u rce s a v a ila b le , the scope of the study mustbe sh arp ly fo cu sed . *$90,000 Is an e stim ate based on a ty p ic a l source t e s t , and does n o t in c lu d e any la b o ra to ry a n a ly s is fo r d io x in s , homologues o r isom ers. A ctual c o s ts w ill v ary depending on source c o n fig u ra tio n , s p e c if ic a n a ly tic a l work d o n e ., e t c . Each work plan fo r In d iv id u a l s i t e s w ill have in d iv id u a l e stim a te s and c o sts w ill be optim ized.^ - 4- Also o f c o n sid e ra b le Im pact I s c o n sid e ra tio n fo r the f a c t th a t the N a tio n al D io x in S tr a te g y I s a two y e a r e f f o r t sch ed u led to end I n December 1985.2 At t h a t tim e , a re p o rt to Congress I s planned which w ill, summarize th e r e s u lts o f th e s tilly . T his schedule lim its the types o f a c t i v i t i e s which can be I n it ia te d and completed by th a t d a te . C ertain re sea rc h s tu d ie s, such a s , developing and v a li d a tin g a m e ch a n istic model o f d io x in form ation in com bustion so u rc e s , would l i k e l y tak e y e ars to d e sig n and c o m p lete, and would n o t be p r a c t i c a l t a c o n s id e r fo r th is study. However, because a l l a sp e c ts o f the d io x in Issu e cannot be c o n sid e re d , fo llo w up s t u d i e s may be n e ed e d . The. T ie r 4 r e s u l t s sh o u ld p ro v id e a more re a so n a b le b a s is fo r more s tu d ie s I f needed. 1.5 B asis For I n v e s tig a tio n Of Combustion Sources There a re se v e ra l unproven hypotheses concerning d io x in em issions from com bustion p r o c e s s e s . Dow C h e m ic a l's " C h e m is trie s o f F ir e " th e o ry p ro p o se s t h a t d io x in s a r e a n a t u r a l b y p ro d u c t o f f i r e and w i l l be formed a t some q u a n t i t i e s In a l l com bustion p ro c e ss e s .3 However, ex p erim en tal r e s u l t s by Buser and Rappe and an e v a lu a tio n of d a ta from the lite r a tu r e ^ su g g ests th a t d io x in s a re em itted o n ly under lim ite d c o n d itio n s . The m ost p re v a le n t th e o r ie s , In c lu d in g Espo s i t o 's form ation mechanism, Involve the Incom plete com bustion of p o ly c h lo rin a te d d lb e n zo d io x in (FCDD's) o r FCDD p r e c u r s o r s . A lthough th e r e I s some d is a g re e m e n t on th e d e f i n i t i o n o f p r e c u r s o r s , PCDD p re c u rs o r s a r e d e fin e d In t h i s work p la n a s c h lo r in a te d a ro m a tic s t h a t can produce FCDD's th ro u g h b lm o le c u la r r e a c t i o n s and therm al rearran g em en ts. Examples In clu d e c h lo rin a te d phenols and c h lo r i n a te d b e n z e n e s. When FCDD's a r e l a th e feed o f a co m b u stio n s o u r c e , th e y c an escape w ith the fin e p a r tic u la te when the therm al d e s tr u c tio n e f f ic ie n c y I s lo w .3 A d d itio n a lly , FCDD p r e c u r s o r s may be th e rm a lly re a rra n g e d d u rin g Inco m p lete com bustion to form PCDD's.3 -5- N e ith e r th e Dow h y p o th e s is o r th e p re c u rs o r h y p o th e s is have been con c l u s i v e l y su p p o rte d , o r r e f u t e d . ^ ^ . R ecen t s t u d i e s i n v o l v i n g p y r o ly s is o f wood w ith and w ithout c h lo rin a tio n , In conjunction w ith the stu d ie s of p y ro ly sis of ch lo rin ated c o a l, suggest th a t Inorganic chlorine a t high le v e ls w ith any organic m a t e r i a l may v e ry w e ll le a d to PCDD fo rm atio n * S in ce com b u stio n s o u rc e s a re u b iq u ito u s and a re f a i r l y co n cen trated In urban a re a s , I t Is conceivable ch at a la r g e p o r tio n o f th e U nited S ta te s p o p u la tio n may be exposed to d io x in s In c lu d in g 2378-TCDD i n th e am bient a i r . More d a ta a r e needed to d e te rm in e the m agnitude and e x te n t o f exposure to d io x in s from com bustion so u rc e s . While c u rre n t e v i dence does not suggest th a t an unreasonable ris k e x is ts , the Dioxin S trateg y p ro v id es an o p p o rtu n ity to perform a more o rd e rly and thorough in v e s tig a tio n o f th e is s u e * An a ss e ss m e n t o f r i s k from each so u rc e te s t e d w ith in f e r e n c e s to th e so u rce c a te g o ry w ill be produced a s a p a r t o f t h i s e f f o r t and be Included in the T ie r 4 re p o rt generated as In p u t to the s tu d y 's re p o rt to C ongress. 1 .6 Summary Of T i e r 4 Program P la n Two l e v e l s o f s o u rc e sam p lin g a re planned In T ie r 4 . F i r s t , r e l a t i v e l y Inexpensive ash samples (sc ree n in g ) w ill be c o lle c te d from com bustion source c a t e g o r i e s l i s t e d l a T a b le 1 -1 . As e x p la in e d l a t e r , th e s e so u rc e c a te g o r ie s a r e b eliev ed to have a reaso n ab le lik e lih o o d o f e m ittin g d io x in s . Samples a re a lso expected to be c o lle c te d from a lim ite d number o f a d d itio n a l source c a te g o rie s a s may be i d e n t i f i e d by EPA R eg io n al and S ta te O f f i c i a l s . Ash sam ples w i l l be c o lle c te d from three d if f e r e n t sources In each source category se le c te d - These sam ples w i l l g e n e r a lly c o n s i s t o f ho p p er a sh from c o n t r o l d e v ic e s , o r "bottom** a s h w here no c o n tr o l d e v ic e s a r e p r e s e n t . These sam ples w i l l be a n aly z e d to d e te rm in e th e t o t a l p o ly c h lo r in a te d d io x in s (PCDDs) p r e s e n t in th e a s h , a s w e ll a s 2373-TCDD and the h ig h e r d io x in hom ologues. These d a ta w i l l be used to provide a q u a lita tiv e In d ic a tio n of the lik e ly presence o f dioxins In the flu e S' T a b le 1 -1 . C om bustion S o u rce C a te g o r ie s Where Aah Sam ples W ill L ik e ly Be C o lle c te d - ' Source C ateg o ries;* Chemical Sludge In c in e ra to rs - y ^C arbon R e g e n e ra tio n U n it ( a t I n d u s t r i a l s o u r c e ) 1; V v t Charcoal M anufacturing Wire R eclam ation Wood S to v e s - Wood B o ile r s B urning PCF T re a te d Wood Spreader-Stoker Coal B oiler Hazardous Waste In c in e ra tio n Lime/Cement K lin Burning Hazardous W astes Forest Fires t*>3 ,# -*,1p-^p-S ^ t t~ * ' A partm ent House Flue Fed I n c in e r a to r s A g ric u ltu ra l Burning - ^ - ^ v '"r^wA.' ----- - "" *To be supplem ented by o th e r c a te g o r ie s I d e n tlf e d by S ta te and R eg io n al O f f i c i a l s v l t h re a s o n a b le U k llh o o d o f e m ittin g 2378-TCDD. 7- gas em issio n s. Because of the n a tu re o f these sam ples, they cannot be used to e s t i m a t e th e m a g n itu d e o f 2378-TCDD: e m is s io n s V n o r 'ca n th e y be used to d e te rm in e a b s o l u t e l y t h a t 2378-TCDD i s n o t p r e s e n t in th e e m is s io n s . I t i s e x p e c te d , how e v e r, th a t th ese d a ta w ill provide d a ta to examine fu r th e r the u sefu ln ess o f ash an aly ses as a v ia b le means to a sse ss r e la tiv e the magnitude o f d io x in em issions from* com bustion s o u r c e s . A lim ite d number o f . com bustion source c a te g o rie s have been s e le c te d f o r d e ta ile d source te s tin g based on a v a ila b le d a ta and in fo rm atio n . Because o f th e lim ite d b u d g et and th e c o s t In v o lv e d w ith s ta c k t e s t i n g , o n ly a b o u t 12 d i f f e r e n t so u rces can be te s te d . These s ta c k t e s t s w ill be perform ed u sin g EPA's m o d ified Method 5 and so u rce t e s t in g p ro c e d u res c o n s is te n t w ith th o se d e sc rib e d in the re c e n tly developed American S o c ie ty o f M echanical E ngineers (ASME) sam pling p r o to c o l f o r e n erg y re c o v e ry f a c i l i t i e s . Samples to be c o lle c te d d u rin g the s ta c k te s tin g program a re d iscu ssed in S e c tio n 3 and a re b r ie f ly summarized h e re . They In clu d e gaseous and p a r tic u la te s ta c k em ission samples (b o th befo re and a f t e r c o n tr o ls ) , ash samples from the c o n tro l d ev ice and fire b o x ash ho p p ers, sam ples o f the feed o r f u e l, and samples of nearby s o ils . Precom bustion a i r samples w ill also be c o lle c te d a t those sources where p recu rso rs are suspected to be p re se n t in s ig n ific a n t co n cen tra tio n in the a i r from o th e r nearby so u rces. S ta c k , a s h and p re c o m b u stlo n a i r sam ples w i l l be a n aly z e d f o r th e 2378-TCDD iso m er, t o t a l d io x in , and to ta ls fo r each o f the h ig h er homologues o f d io x in ( l . e . , t e t r a , p e n ta , hexa, h e p ta , and o c ta ) . Precom bustlon a i r and feed sam ples w ill a ls o be analyzed fo r s e le c te d su sp e c t d io x in p re c u rso rs. Feed and w aste w a te r sam ples w i l l a ls o be a n aly z e d f o r 2378-TCDO and t o t a l p o ly c h lo r in a te d d io x in s. S u ffic ie n t q u a n titie s o r d u p lic a te s o f a l l samples w ill be c o lle c te d In the event chat o th e r analyses are needed a t a la te r d a te . Furans, fo r example, - 8- w ill n o t be analyzed under th is program due to c o sts but a re o f se rio u s concern b u t s u f f i c i e n t sam ples w i l l be c o lle c te d and may be so a n aly z e d l a t e r . Sam ples w i l l be c o l l e c t e d p r im a r ily by~EPA c o n t r a c t o r s who w i l l s h ip th e them to th e d e s ig n a te d TROIKA l a b o r a to r y f o r a n a l y s i s . P ro c e d u re s f o r th e c o l le c tio n and sh ipping of sam ples, as w e ll as the a n a ly tic a l and q u a lity c o n tro l p ro ced u res to be f o lio w ed, a re d is c u s s e d e l s e w h e r e A summary o f th e sam ples to be c o lle c te d d u rin g s ta c k te s tin g and the an aly ses to be perform ed under T ie r 4 a re o u tlin e d in Table 1 -2 . Although n o t noted in the ta b le , an a d d itio n a l number of samples (approxim ately 20 p e rc en t) w ill be c o lle c te d and analyzed fo r q u a lity assurance/quality control purposes. The Agency has a lre a d y perform ed an a n a ly s is to id e n tif y those com bustion so u rc e c a te g o r ie s which have th e g r e a t e s t p o te n tia l to em it 2378-TCDD.3 These source c a te g o rie s are lis te d In Table 1 -3 . Source c a te g o rie s ra te d as "Rank A Sources'* w i l l be s ta c k te s te d as soon as p o s s ib le . T e stin g of so u rce c a te g o rie s ranked and w ill be d e fe rre d u n til th e r e s u lts of the ash screen in g program are a v a ila b le . These d a ta 'w i l l be used to re-exam ine the c u rre n t ranking of source c a te g o r ie s , so th e f in a l l i s t i n g o f B and C ranked source c a te g o rie s could change th e f i n a l s e l e c t i o n o f r e s i d u a l so u rc e t e s t s can be made a t t h a t tim e . Figure 1-1 p resen ts the a n tic ip a te d schedule fo r the T ier 4 p ro je c t. At th e co n clu sio n o f the T ie r 4 stu d y , th e Agency w ill have c o lle c te d e ith e r screen in g sam ples o r d e ta ile d sta c k samples from a number of com bustion source c a te g o r ie s . These d a ta w ill p ro v id e the Agency w ith a b e t t e r u n d erstan d in g of th e s o u rc e c a te g o r ie s w hich e m it 2378-TCDD to th e a tm o sp h e re . F u r th e r , th e d e ta ile d s ta c k t e s t d a ta w ill allo w th e Agency to determ in e the m agnitude o f the 2378-TCDD e m issio n s from th e s e s o u rc e s and c a l c u l a t e th e r i s k to which th e p eo p le a re expo s e d . -9- S u p la T ib io 1 - 2 . SAMPLING AMU ANALYSES HODfiL Method Sanplee A n a ly s e s T o ta l S aaplea* fo r A nalysis 'i v)i'vr'' In p u t* Fraconbuatloa A ir XAfr-2 (P U F f)b O - l* 2378-TCDD, PCD*, TOCL*, C1 -p h e n o ls , C l-b e o te n s * 1 & fa sd /fu a l O utputa Stack (b afora c o n tro l) Crabe MUTS D a lly CoMpoelte PCDO S can, C t-p h e n o la C l-b e o se u e a , fC B , TOCL 2 tra in * - la c k H a lf B a lly Compoolto -condanaer Blnaa -a dsorb ent B asin - f r o n t U a lf D a lly Coapoalta -c y c lo n e Catch -filte r -probe rlo a * 2378-TCDD, Uoaologuesb ( t n t r a - o c t a ) , PCDO 3 6 i. lk f t*} l i -.r tack ( a lta r c o n tro l) HUT 2 tra in * -la c k N a if D a lly Coapoalta 2378-TCDD, Uoaologuas ( t a t r a - a c t a ) , FCDD 3 % -condanaer B ine* -a d so rb e n t B asin J,;; - f r o n t U a lf D a lly Coapoalta j 0--I1 V\iS o tto o Aab Crab# - f i l t e r Catch -p robe B lass D a lly Coapoalta 2378-TCDD, Uoaologuas j: 3 ( t a t r a - o c t a ) , PCDO Aah Vroa C o n tro l Device Quaocb M ater E fflu e n t O ther S o la ( lo v lc lo lty ) Crabs Crabs o r lge D a lly Coapoalta D a lly Coapoalta 1 C oapoalta 2378-TCDD, Uoaologuas ( t a t r a - o c t a ) , PCDD 2378-TCDD, Uoaologuas ( t a t r a - o c t a ) , PCDO 2378-TCDD, Uoaologuas (ta tra - o c ta ), KDO .* 3 i V 1- 3 t 1 T o ta l 26* blAD-2 (P U ff) de note s t M o d ifie d b lg b voluae e l r e a a p le r w ith epee 1*1 a a a p lln g beed f o r u b la n t a rg s u lc copouadi * S * a p l* to be c o lle c te d I f th e re I * e s i g n i f i c a n t e o u rc * o f euepected p re c u re o re l a v l c l o l t y o f s a a p lio g e l t e . dpCOD " P o ly c fa to r lu lle d d Ib e a to d lo e la . TOCL - T o te l o rg a n ic c h lo r in e , fin e ly * !* by co n tra c to r. IHHST I * a M o d ifie d BFA "Method S ' t r a i n an d e fin e d In fb * ASHE p r o t o c o l. f bUonologuea Aoelyeea done on h ig h e r ( t e t r i th ro u g h o c t a l PCDO1* aa a t o t a l f o r each group o n ly . * tfc iltlp le analyaaa fo r each aaaple w i l l have a M u lt ip lie r e ff e c t on the a n a ly tic a l c o a t* a la o . T o ta l does oot In clu d e q u a lity aaauraoca aaaplea (a p p ro *. 2 0 1 ). I 1 ai tr/i h 'I o 1 \ T abla 1-3- Ranked Source C ategory L i s t Rank A Source C a te g o rie s: " Sewage Sludge In c in e r a to r s Black Liquor B oilers Commercial B o ile rs F irin g Fuels C ontaim lnated w ith C h lo rin ated O rganic Wastes Rank 8 Source C ateg o ries: PC? Sludge I n c i n e r a t o r s Carbon R egeneration (In d u s tria l) Charcoal M anufacturing Wire R eclam ation Rank C Source C a te g o rie s: Wood S to v es B o ile r s ( F ir in g PC? tr e a t e d Wood) Mobile Sources Small S preader-S toker Coal B o iler H azardous Waste In c in e ra to rs Lime/Cement K iln s C o -fired w ith C h lo rin ated O rganic Was te s Rank D Source C a te g o rie s: M u n icip al S o lid W aste (MSW) I n c i n e r a t i o n I n d u s tr ia l B o ile rs C o -flrln g W astes Rank A: Large source c a te g o rie s (g re a te r than I m illio n tons of fu e l and/or w aste burned annually) w ith elev ated d io x in p recu rso r contam ination of fe e d /fu e l. These c a te g o rie s a re judged to have the h ig h e st p o t e n t i a l to e m it TCDD. Rank B: Small source c a te g o rie s (le s s than 1 m illio n tons of fu e l and/or w aste burned an nually) o r source c a te g o rie s w ith lim ited d io x in p recu rso r contam ination o f fe e d /fu e l. These c a te g o rie s have a high p o t e n t i a l to e m it TCDD. Rank C: Source c a te g o r ie s l e s s l i k e l y to e m it TCDD. ^ Rank D: Source c a te g o r ie s w hich have a lr e a d y been te s t e d th r e e o r more tim e s . - 11- ItvX` ** - figure Schedule; N ational Dioxin Study - T ie r 4 - Conbustion Source \w7% i>Sf'i 1983 1984 198S 1986 A ctivities NDJFHANJJASONDJ FHAHJ JASONP. JFHAHJ Begin p ro je c t T ie r 4 Work Croup H eetlng* o Perform lit e r a tu r e .review Develop T ie r 4 work plan S elect sources for ash screening S elect individual sources --I f o r te s t i n g KI> Ash sam ples c o l le c tio n and a n a ly sis D raft P in a l o~---- -- o ' - '= t 'Vy &' :# II lift tt ;K `('I) Prepare individual source te s t plane: conduct source te s tin g and prepare source te s t reports A ll an a ly tica l re su lts a v a ila b le Prepare d ra ft fin a l T ier 4 report , * '' o > Q---- --- - - -- O YS '%ffi - V%V: S1^ -Sci * T ie r 4 Work Group w i l l Meet p e r io d i c a l ly th ro u g h o u t th e s tu d y p e r io d . N ote: T his schedule i s very s k e le t a l end w ill he f u r th e r d e fin e d w ith the in d iv id u a l t e s t e f f o r t s and su b p ro je c t work p la n . 1' ! t l "ft r i$ fi 11 AWii J-V*. *(.*>, The in fo rm a tio n c o lle c te d under T ie r 4 w i l l be summarized in a f i n a l r e p o r t . The re p o r t w ill a lso summarize th e s ta t e of knowledge o f d io x in ( p a r tic u la r ly 2378-TCDD) e m is s io n s a v a i l a b l e from co m bustion so u rces * ''T h e s t a t u s 'o f (ingoing s tu d ie s w ill be given and a v a ila b le r e s u lts of such s tu d ie s w ill be re p o rte d upon in the f in a l T ier 4 re p o rt. For example, the stack te s t d a ta being c o llected from v a r io u s com bustion s o u rc e s by New York S ta te -a n d o th e r s w i l l be in c lu le d , i f \ a v a i l a b l e . .Any p re lim in a ry r e s u l t s from th e th r e e m illio n d o l l a r th re e y e ar e f f o r t b e in g i n i t i a t e d by E nvironm ent Canada to exam ine th e s ig n if ic a n c e fc>f v a r ious o p e ra tin g c o n d itio n s on d io x in em issions from m unicipal In c in e ra to rs w ill be p a r t i c u l a r l y o f i n t e r e s t . An u p dated l i s t o f recom m endations f o r f u t u r e te s t in g and stu d y w ill be provided a t th a t tim e I f w a rra n te d . 1.7 P o s s ib le R esu lts Of The T ie r 4 Study While the previous paragraphs have b r ie f ly d e scrib ed the o b je c tiv e o f T i e r 4* i t i s w orth n o tin g w hat th e s tu d y may o r may n o t be a b ie to acco m p lish The prim ary o b je c tiv e o f th e T ie r 4 e f f o r t i s problem d e f i n i t i o n . The degree to which T ie r 4 can s a ti s f y th is o b je c tiv e depends In la rg e measure on th e : m ag nitude and p e rv a s iv e n e s s o f th e 2378-TCDD e m is s io n s found d u rin g th e stu d y . For exam ple, a p o s s ib le outcome of the stu d y Is th a t ash sam pling and a n a l y s i s may be v a l i d a t e d a s an e f f e c t i v e to o l to t e s t to v e r i f y t h a t 2- 78-TCDD I s n o t em itted from a source o r source c ate g o ry . A lso, the sta c k t e s t c a ta and s u b se q u e n t r i s k a s s e s s m e n ts may i n d i c a t e , a t l e a s t f o r th e s o u rc e s or so u rc e c a t e g o r i e s t e s t e d , t h a t 2378-TCDD e m issio n s do n o t l i k e l y r e s u l t in an u n reaso n a b le r i s k to the p u b lic Assuming th e se a re th e f in d i n g s , some g e n e ra l conclu sio n s about the scope o f the problem are expected to be drawn from the T ie r 4 stu d y . Such co n clu sio n s w ill obviously need to be s ta te d c a r e fu lly , acknowl e d g in g th e p o s s l b l l t y t h a t some u n te s te d s o u rc e s may e x i s t w hich may e m it e le v a te d l e v e l s o f 2378-TCDD. N e v e r th e le s s , th e T ie r 4 stu d y i s in te n d e d Co - 13- e p ro v id e in fo rm a tio n f o r the Agency to r e a l i s t i c a l l y d e fin e the scope and ' m agnitude o f the problem* A more l i k e l y outcom e I s t h a t th e a sh sam p lin g program w i l l i d e n t i f y a num b er o f source c a te g o rie s w ith a s u ffic ie n t p ro b a b ility o f having le v e ls o f 2378TCDDs p r e s e n t i n th e a sh w hich m e r it f u r t h e r c o n c e rn . As a r e s u l t , th e s e so u rc e " 'c a t e g o r i e s may w a rra n t f u r t h e r s ta c k t e s t i n g program s to o b ta in more d e f i n i t i v e r e s u l t s . S im ila rly , the s ta c k t e s t program which can be conducted under T ie r 4 may I d e n t i f y r e l a t i v e l y h ig h e m is sio n r a t e s from some o f th e s o u rc e s which a r e t e s t e d , th e re b y in d ic a tin g a need fo r a number o f o th e r which so u rces should be te ste d . Since th ere are Inadequate reso u rces a v a ila b le under T ier 4, fo r the la rg e amount o f te s tin g th is would r e q u ir e , such f u r th e r developm ents w i l l l i k e l y depend upon follow up s tu d ie s to d e fin e more f u l l y th e m agnitude o f such problem s. Ia summary, i t i s lik e ly th a t th e T ie r, 4 stu d y w ill b e tte r d e fin e the scope o f th e problem b u t may n o t p ro v id e s u f f i c i e n t d e f i n i t i o n to a d e q u a te ly d e fin e the magnitude o f the problem nor w ill i t develop any re g u la to ry program, t h a t m ig h t be n e e d . More d e t a i l e d s tu d y may be needed in 3uch c a s e s . 1 .8 Form at Of T h is R eport T h is s e c tio n has provided a b r ie f overview o f the scope and purpose o f the T ie r 4 program under the N ational Dioxin S tra te g y . S ectio n 2 d iscu sses v ario u s a lte r n a tiv e s which were considered in the d esig n o f the stu d y . S ectio n 3 pro v id e s f u r t h e r d e t a i l on how th e so u rc e c a t e g o r i e s to be te s t e d un d er T i e r 4 were i d e n t i f i e d , the number and types o f sam ples to be c o lle c te d and the v a rio u s a n a ly s e s p la n n e d . S e c tio n 4 d e s c r ib e s Im p le m e n ta tio n I s s u e s , such a s how th e i n d i v i d u a l s o u rc e s w i l l be s e le c te d f o r t e s t i n g and how th e v a r io u s sam ples w i l l be c o lle c te d . - 14- Section 2 > . - A lte r n a tiv e Study P la n s Which Were C o n sid ered ~^ ^ i:'r l | i The previous s e c tio n p resen ted a b r ie f overview o f the scope and purpose o f the T ie r 4 stu d y . In d esig n in g o f th e stu d y , the Agency co n sid ered v a rio u s 1 a lte r n a tiv e s The m ost fre q u e n tly recommended a lte r n a t iv e s a re d e sc rib e d below , "T / .' I a lo n g w ith th e re a s o n s why th e y were n o t In c lu d e d In th e f i n a l T i e r 4 p la n . 2 .1 A lte rn a tiv e 1 : Focus The T ie r 4 E f f o r t P rim a rily on M unicipal Waste In c in e ra to rs ^ The m ost fr e q u e n tly su g g ested a lte r n a t iv e was to focus th T ie r 4 s tu d y , In whole o r in p a r t, on determ ing the m agnitude o f d io x in em issions from v a rio u s m unicipal waste In c in e ra to rs . There were se v e ra l reasons fo r th is . F i r s t , o f the com bustion source c a te g o rie s which have been te s te d , d io x in e m issio n s a re much g r e a t e r f o r t h i s so u rce c a te g o ry th an f o r o t h e r s . T h is so u rce c a te g o ry I s , t h e r e f o r e , viewed w ith much I n t e r e s t and c o n c e rn . Second, a number o f urban a re a s a re p r e s e n tly c o n s id e rin g th e p e rm ittin g o f new m u n ic ip a l In c in e ra to rs , p rim arily as resource recovery u n its , due to the lim ita tio n s asso ciated w ith land d is p o s a l. S olid w aste program re p re s e n ta tiv e s and o th e r government o f f i c i a l s , re p re s e n ta tiv e s o f In d u s try , and the p u b lic a re concerned about the p o te n tia l exposure and r i s k from d io x in em issions from th ese proposed f a c i l i t i e s . As a r e s u l t , I t h as been recommended t h a t a number o f m u n ic ip a l w aste In c in e ra to rs be tested In o rd er to g ain a b e tte r understanding of the m agnltixle o f the d io x in problem from th is source c ateg o ry . A fte r c a r e f u l c o n s id e ra tio n , th e Agency has d ecid ed to focus th e T ie r 4 e f f o r t p rim arily on combustion source c a te g o rie s o th e r than m unicipal w aste in c in e r a to r s . While the Agency p lan s to t e s t one m unicipal In c in e r a to r under - 15- T ier 4 , a broader study of m unicipal in c in e ra to rs has not been included fo r the follow ing reasons: '.A-V -- IT- (1 ) S ix of the approxim ately 40 la rg e co n v en tio n al (non-m odular) m unicipal w aste In c in e ra to rs in the United S ta te s have been te s te d .3 As s u c h , t h i s so u rc e c a te g o ry i s by f a r th e m ost te s te d o f a l l combustion source c a te g o rie s . (2 ) Based on th e r e s u l t s o f th e se p rev io u s t e s t s , the Agency h as con cluded th a t the em issions from w ell operated f a c i l i t i e s do not pose a pu b lic h e a lth problem to those persons liv in g in the v ic in ity o f th ese s o u rc e s . T his p o s itio n was i n i t i a l l y c o n ta in e d in a r e p o r t e n t i t l e d " I n te r im E v a lu a tio n Of H e a lth R isk s A sso c ia te d W ith E m issio n s Of T e tr a c h lo rin a te d D ioxin From M u n icip al Waste R esource Recovery F a c il i t i e s ,"8 and was r e c e n tly re a ffirm e d by th e Agency in December 1983.9 (3 ) I t i s p o s s ib le t h a t o t h e r so u rc e c a te g o r ie s may e m it s i m i l a r o r l a r g e r q u a n t i t i e s o f 2378-TCDD o r have a g r e a t e r ex p o su re and r i s k a s s o c ia te d w ith them th an m u n ic ip a l w aste in c in e r a to r s . T his can n o t be determ ined unless reso u rces a re devoted to te s tin g o th e r source c a te g o rie s , and (4) There appears to be considerable lo c al in te re s t in te stin g s p e c if ic m unicipal w aste in c in e r a to r s , so th a t re so u rce s e x te rn a l to th is study w ill lik e ly be a v a ila b le to t e s t these f a c i l i t i e s , even I f m unicipal waste in c in e ra to rs are not te sted under T ie r 4. At p re se n t, approxim ately ten m unicipal w aste in c in e ra to rs are under co n sid eratio n fo r te s tin g , p rim a rily by Region I I I , in d iv id u a l S ta te s , o th e r ag en cies and by Environm ent Canada. For th e se re a so n s , the Agency has d ecid ed n o t to focus the T ie r 4 e f f o r t on m unicipal In c in e ra to rs . At th is tim e, the Agency, te n ta tiv e ly plans to t e s t o n ly one i n c i n e r a t o r (H em pstead, New Y o rk ,) a s p a r t o f T ie r 4 to f u l f i l l a -16 p re v io u s com m ittm ent. However, Che d a ta c o lle c te d from th e v a r io u s o th e r t e s t s o f m unicipal in c in e ra to rs by o th e r agencies w ill be o b ta in e d , and Included In the f in a l T ier 4 re p o rt. 2 .2 A lte r n a tiv e 2 : I n v e s tig a te C o n d itio n s Which In c re a s e /D e c re a se Dioxin Em issions A nother a lte r n a t iv e co nsidered was to in clu d e a stu d y in the T ie r 4 program designed to examine the s ig n ific a n c e o f v a rio u s combustion, d ev ice o p e ra tin g pa* ram eters on the m agnitude of d io x in em issio n s. Under th is o p tio n , d e ta ile d sta c k sam pling would be perform ed a t one o r two f a c i l i t i e s . O p e ra tin g c o n d itio n s su ch a s p e rc e n t load and p e rc e n t e x cess would be c a r e f u lly m onitored over a range -and em issions measured fo r c o rre la tio n . I t i s re c o g n iz e d t h a t such work i s u s e f u l and n e c e s s a ry to u n d e rs ta n d how d ioxin em issions can be m inim ized, however, such a study has not been Included in T ier 4 . Again, the prim ary reason Is lim ited p ro je c t re so u rce s. There are c le a r ly i n s u f f i c i e n t funds a v a ila b le to c h a r a c te r iz e b o th a broad number o f com b u s tio n so u rce c a te g o r ie s and to perform th e type o f s ta c k t e s t in g which would be needed to determ ine q u a n tita tiv e ly the s ig n ific a n c e o f v ario u s o p e ra tin g param eters on em ission ra te s . F u rth e r, o th e r ag en cies a lre a d y have p ro je c ts underway which a re designed to address th is s p e c ific is su e . Environment Canada, fo r example, has re c e n tly i n i t i a t e d a th r e e y e a r , $3 m illi o n s tu d y d e sig n e d to i n v e s t i g a t e th e s i g n i f i can ce o f changes o f v a r io u s o p e r a tin g c o n d itio n s upon e m issio n s o f 2378-TCDD a t th r e e m u n ic ip a l w aste i n c i n e r a t o r s . A ls o , th e ASME p la n s a s e r i e s o f t e s t s a t a United S ta te s In c in e ra to r designed to provide d a ta to develop a re la tio n s h ip betw een v a r io u s o p e r a tin g p a ra m e te rs and 2378-TCDD e m is s io n s . F or th e s e re a sons, T ie r 4 stu d ie s a re not d esired to c o lle c t a d d itio n a l fie ld d a ta s p e c if i c a lly to c h a ra c te riz e the s ig n ific a n c e of o p e ra tin g param eters. R ath er, T ie r 4 w ill o b ta in the r e s u lts o f o th e r s tu d ie s th a t are underway and as p re v io u sly - 17- conducted and summarize th e ir fin d in g s In the f in a l T ie r 4 r e p o r t. O perating -io d a ta from a l l sources tested , under T ie r 4 .w ill h o w e v e rb e c a r e f u lly m onitored and documented so they can be Included In the d a ta base fo r g e n e ra lly analy zin g th e e f f e c t s on e m issio n s o f 2378-TCDD. 2 .3 A lte r n a tiv e 3 : D evelop A M e c h a n istic Model To E s tim a te 2378-TCDD E m issio n s S in ce re so u ce s to conduct d e ta ile d s ta c k t e s t s f o r each c a n d id a te combus tio n source c a te g o ry would n o t be w ith in reason I t has been suggested th a t an e m p iric a l o r m e ch a n istic model be developed which could be used to e stim a te e m is s io n s o f 2378-TCDD from so u rc e c a te g o r ie s w hich co u ld n o t be a d e q u a te ly te s te d * W hile such m odels may be o f v a lu e In e s tim a tin g e m is s io n s , t h i s a l t e r n a tiv e was n o t In cluded In th e f i n a l T ie r 4 p lan fo r th e fo llo w in g re a so n s : (1) The d esig n of a m ech an istic o r e m p iric a l model p rio r to any d a ta c o l l e c t i o n e f f o r t may r e q u i r e a s u b s t a n t i a l amount o f time* Given th e c u rre n t schedule o f the N atio n al Dioxin S tra te g y , I t I s c le a r th a t ' th e re Is not s u f f ic ie n t time to (a) d esig n such a m odel, (b) c o lle c t th e source te s t d a ta , (c) v a lid a te the model, and (d) e stim ate d io x in e m is sio n s f o r many s o u rc e c a te g o r ie s ; (2) I t Is n o t e n tire ly c le a r , a t th is tim e, I f a sin g le model could be developed which would be a p p lic a b le to a l l com bustion source c a te g o r ie s , o r w hether a number o f models would need to be developed fo r v ario u s types o r groups o f com bustion source c ateg o ries* I f th e l a t e r c a s e I s t r u e , c o n s id e r a b le funds may be needed f o r d ev elo p m en t and v a l i d a t i o n . C e r ta in t h e o r e t i c a l m odels now e x i s t , b u t th e p ra c t i c a l f ie ld a p p lic a tio n o f th ese models la b eliev ed lim ite d a t th is tim e ; and (3 ) The d ev elo p m en t and v a l i d a t i o n o f su ch m odels may n o t be p o s s ib l _ o r su cc e ssfu l* given the lim ite d amount o f t e s t d a ta which can be _ collected under T ier 4. F or th e se re a so n s, th e Agency h as d ecided n o t to in c lu d e the developm ent o f m ech an istic o r e m p iric a l models as p a rt o f the T ie r 4 program However, I t is a n tic ip a te d th a t a p ro je c t to fu r th e r examine the f e a s i b i l i t y o f developing a " p r a c tic a l e m p iric a l o r m echanistic m odel(s) w ill be; lik e ly la te r Such e f f o r ts could use the d a ta c o lle c te d under T ier 4 and o th e r p ro je c ts as a framework to d e sig n such a a model developm ent and v a lid a tio n program- 2 .4 A lte r n a tiv e 4 : C o lle c t Ash Samples From A L arge Number Of Source C ategories I n o r d e r to a d d re s s w hich so u rc e c a te g o r ie s e m it 2378-TCDD, i t h as been suggested th a t ash sam ples be c o lle c te d from a la rg e number of com bustion so u rce c a te g o r ie s . Under th is a l t e r n a t i v e , ash sam pling would become the p r i mary a c t i v i t y o f T ie r 4 . While the I n i t i a l T ie r 4 program has been m odified as a r e s u l t o f th is comment to in c lu d e more e x te n s iv e ash sam pling th a n o r ig i n a lly planned*a t o t a l l y com prehensive ash sam pling program was n o t In c lu d e d In T ie r 4 because ash sam ples have a lim ite d v a lu e In I d e n tif y in g s o u rc e s w hich may e m it 2378-TCDD. ^ l a a few c a s e s where 2378--TCDD h as b een m easured In th e f l u e g a s , I t was n o t m easured I n th e a s h . F u r th e r , c o n c e n tr a tio n s o f 2378-TCDD from a v a ila b le d a ta do n o t c o r r e la te s u f f i c i e n t l y w ith e m issio n s d a ta to allo w them to be used to e s tim a te 2378-TCDD c o n c e n tr a tio n s In th e f l u e g a s . T here a r e a ls o c a s e s where 2378-TCDD was n o t d e te c te d I n th e a sh b u t was m easured i n th e s ta c k g a sse s. A lthough the d a ta a v a ila b le tend to su g g est a "trend,** ash sam pling has lim ite d v a lu e , even to a d d re s s which s o u rc e s e m it 2378-TCDD. I t i s e x p e c te d th a t the a d d itio n a l d ata co lle cte d a t the stac k sam pling s ite s for T ier 4 w ill provide the b a sis fo r re v a lu a tio n o f th is c o rre la tio n a t the end of the stu d y . - 19- f- The T ie r 4 s tu d y h as been d e sig n e d ln such t h a t a sh sam pling w i l l comi p lim e n t th e s ta c k , t e s t i n g program * The a sh sam p les. w i l l be- u sed w ith o th e r* In fo rm atio n to p r io r itiz e the source c a te g o rie s b eliev ed to have the g re a te s t p o t e n t i a l to e m ir 2378-TCDD f o r s ta c k t e s t i n g . S u g g e s tio n s a r e , n e v e r th e le s s , s o lic ite d from th e R egional O ffic e s and o th e r rev iew ers o f th is document on w hether o th e r source c a te g o rie s which have a reaso n ab le llk llh o o d o f e m ittin g . 2378-TCDD sh o u ld be In c lu d e d u n d e r th e ash sam pling program* 2 .5 A l t e r n a t i v e 5 : A nalyze Samples F or S p e c if ic Isom ers And Homologues Of F rans I t has been suggested th a t the samples c o lle c te d under T ier 4 be analyzed f o r f u r a n s , a s w e ll a s 2378-TCOD and h ig h e r d io x in hom ologues. W hile th e r e I s g e n e ra l agreem ent th a t In fo rm a tio n on fu ra n s would be b e n e f ic ia l, th e se a n a ly s e s have n o t been Included In th e work p la n , p rim a rily because o f reso u rce and tim e c o n stra in ts* I f fu ran analyses are Included, fewer dio x in analyses are p o ssib le . The D io x in S tr a t e g y h a s b e en d e s ig n e d to fo c u s on 2378-TCDD* A lthough I t reco g n izes- the p o ssib le im portance o f o th e r d io x in isom ers and "dioxin-like** compounds and has I n it ia te d a program to a sse ss what should be done concerning the o th e r Isomer is s u e , the S trateg y fu rth e r recognizes th a t Im plem entation of any^other Isom er program I s co n tin g en t upon a v a ila b ility o f adequate re so u rc e s. At t h i s tim e , T ie r 4 has been a llo c a te d approxim ately 700 an aly ses from the TROIKA. T hese a l l o c a t e d a n a ly s e s a r e c u r r e n t l y planned f o r 2378-TCDD o r d io x in hom ologues. I f fu ran an aly ses were Inclu d ed , only about h a lf of the planned d io x in an aly ses could be complete* For th is re a so n , fu ran s have n o t been Included In T ie r 4 . However, s u f f i c i e n t samples w ill be c o lle c te d and s p l i t s o r o r e x tr a c ts scored fo r p o ssib le follow up a n a ly s is . -20- Section 3 The T i e r 4 Work P la n - 3.1 Overview T h is s e c tio n d e s c rib e s th e p ro cess which was used to I d e n tif y those com bustion source c a te g o rie s which a re lik e ly to have the g r e a te s t p o te n tia l, to em it d io x in to the am bient a i r . These source c a te g o rie s are can d id ates fo r source sam pling under T ie r 4 . The p ro cess i n i t i a l l y Involved a l i t e r a t u r e review o f in fo rm a tio n re la te d to d io x in em issions from com bustion s o u rc e s .3 The in fo rm a tio n was review ed to d eterm in e (a ) which com bustion so u rce c a te g o rie s had a lre a d y been te ste d fo r d io x in and (b ) which fa c to rs appear to be most im p o rtan t w ith re s p e c t to d io x in being em itted from com bustion so u rc es. C r ite r ia were then applied to p r io r itiz e those source c a te g o rie s b eliev ed to have the g re a te s t p o te n tia l to em it d io x in . 3 .2 L i t e r a t u r e Review And E v a lu a tio n An i n i t i a l l i t e r a t u r e s e a rc h f o r d io x in e m is s io n in fo r m a tio n was made in 1983 f o r 0AR/EFA.10 T his s e a rc h was used as th e s t a r t i n g p o in t f o r a more s p e c ific search concerning d io x in em issions from com bustion so u rc es. C ontacts w ere made to i d e n t i f y r e c e n t l y perform ed o r o n g o in g s tu d ie s w hich co u ld be used co su p p lem en t th e d a ta b a s e . W hile th e f u l l r e s u l t s o f th e l i t e r a t u r e re v ie w a re re p o rte d e lse w h e re , th e fo llo w in g p a ra g rap h s p ro v id e a summary o f th e key findings of the sea rc h .3 3 .3 Summary Of A v a ila b le D ata A review o f the l i te r a tu r e ^ has id e n tif ie d 12 com bustion source c a te g o rie s which have been te ste d fo r d io x in s and fo r which d a ta a re a v a ila b le . T able 3-1 l i s t s th ese source c a te g o rie s and the c o n c e n tra tio n s which have been m easured. -21- Sourca Catagory TABLE 1 - 1 . ummiSTUffl SOUKCES KUH UIUCH l-CliU TEST BATA AWE AVAILABLE ttu aber 01 fa c ilitie s Taetad S taple Heap TCUD* Baoga 237B-TCDD* Hean Bang# Sel e r a n e a t K i n l c l p e l Ueata Coaba (o re e USA o Buropaan 4 Stack 3.3 ng/a3 H0-240 n g /a 3 3.3 ng/a3 0.30 - 9.1 a g /a3 I I - IS 13 S ta c k 23.6 ng /a ) NO-120 n g /a 3 -b 14 - 20 Uasardoua lla a ta lo c la a ra to ra o lo c ln a ra to r Ib lp o Land Baaad la c lM c a t o r a 2 10(7)4 S ta c k S ta c k ND 0.34 ng/a3 NO NO-2.3 n g /a 3 NO ee 2 1 , 22 23 - 26 fiavega Bludga lo e t u r a to ra 1 Stack 1 l - 27 U t illt y Coal B o lla ra G oaaerclal B o lla ra (lla a ta T ira d ) 7 (O * S ta c k S ta c k 1HO S ND - - 1 2 , 13 2* lo d u a trla l B o lla ra (llaa ta T ira d ) 4(1 } * 8 te ck 10.13 u g /n3 NO-40.3 n g /a3 IS ,000 p p t* NO-33,000 p p t S , 29 - 31 A c tlv a te d Carbn B egeaaratioe l Stack 0.013 ppt H0 -0 .0 3 0 p p t 0.019 ppt ND-0.0B3 p p t 32 to 33i B a o ld a n tla l Conbusclon* 4 S crapings 329 p p t NO-777 p p t 242 p p t 26-400 p p t to I M ablla Sourcaai 9(4>d Babauat 4.0 ppt ND-20 p p t 3.0 ppt a J. * U lra la c le a a tlo a In c is a ra to re Llna/C aaant K lla a (Ueata T ira d ) 1 1(1)4 S craplnga S ta c k 234 p p t S 31-410 pp t a - - .. 33 36 A ccid e n ta l S Ie c tric e 1 Iq u lpaen t T ire s* 2 H a ll Sulpee 44 ppa* NO-193 ppa 0.039 ppa a 37, 3 TCDD T t n c h lo r a d ib a t o - 'f * d t n iio . ^0b " Mo d i t i > CMP " None d i u c t * 4 ( d e te c tio n U n i t s v a r y ) . Nuabar o i te s ta which have b u n p e rfq m a d , b u t f o t w hich cha ra a u ltq baya n o t baaa o l i l c l a l l y r a p x u d i * - Ona d c t i a , no yanga a v a lla b ia . ffCDD acan o n ly . TCDO c o n c e n tr a tio n s rengad f r a 4S3 n g /a 1 Co 1 ,1 4 0 n g /a 3 w it h a aaaa o f 739 a g /a 3 . iK a a u lta have o a t y a t baaa o f f i c i a l l y cayosta d . hppt " T a rta par t r l l l l o o by m ig h t. *T u a ls loe luda wood, m o d /o ll n ls tu r s , and n a tu ra l gaa. Vuela In c luda d ie s e l, unloaded and laadod g a a o lln a . In ona ta a t a a rla a aabauac s c ra p in g s u r n a n a ly s e d . In the o th e r a a rla a . H it a r m d lia Iro n aabauac saaplea. k In c lu d e s K l t ca n e lo r o a r a aod c a p a c ito r b e t C o rle a . 3Pf " T a rta par a illlo a by m ig h t. ii! I' h. % Xi;, V 1 : G en eral o p e r a tin g c h a r a c t e r i s t i c s o f th e s o u rc e s which w ere te s te d a r e sum m arized in T able 3-2 and a re used below to id e n tify com bustion re la te d para m e te rs w hich may a f f e c t th e l i k e l y p re s e n c e and m agnitude o f d io x in e m is sio n s from com bustion so u rces. Dow C h e m ic a l's " C h e m is trie s o f F ir e " h y p o th e s is p ro p o se s t h a t p o ly c h lo r i n a te d d ib e n z o d io x in s (PCDD's) a re a common and n a t u r a l b y p ro d u c t o f f i r e . 5 However, an e v a lu a tio n o f d a ta from th e l i t e r a t u r e s u g g e s ts t h a t PCDD's a r e ^ em itted during the Incom plete com bustion o f e ith e r (a) d io x in s o r (b) d io x in p re c u rso rs. Although u n c e rta in ty rem ains, d io x in p recu rso rs are d efin ed fo r p u rp o se s o f t h i s work p la n a s c h l o r i n a t e d a ro m a tic s w hich can produce d i o x in s ----through b lm o lecu lar re a c tio n s and therm al rearran g em en ts. Examples in c lin e c h lo rin a te d phenols and c h lo rin a te d benzenes. Based on the l i t e r a t u r e re v ie w ,3 the follow ing appear to a f f e c t d io x in em issions: PCDD I n f e e d , P recu rso rs in feed, "C h lo rin e In fe e d , (1 . e . , c h lo rin a te d compounds can n o t be formed w ithout chlorine present); 0Com bustion te m p e r a tu r e , 'R esidence tim e, "Oxygen a v a i l a b i l i t y , "Feed p r o c e s s in g , "Supplem ental f u e l. 3 .3 .1 PCDD I n Feed3 2378-TCDD i s an Im p u rity t h a t can r e s u l t from th e m a n u fa ctu re o f tr l c h lo r o p h e n o l, which i s used to make th e h e rb ic id e 2 ,4 ,5 -tr ic h lo ro p h e n o x y a ce t i c a c id (2 4 5 -T ). P e n tra c h lo ro p h e n o l (POP) p ro d u c tio n can a ls o r e s u l t i n a PCDD c o n ta m in a n t, p r im a r ily o c ta c h lo r o d ib e n z o - p - d lo x ln (OCDD). The p rim ary end u se - 23- Source 'fV, Table 3 -2 . C h a r a c te r is tic s Of S ources T ested For D ioxins ^ \ P re cu rso rs Furnace Type T em perature A vailable Air i' 4 t i k'- H uniclpal H aste Combustors o Conventional o Refuse Derived Fuel B o ilers C l-aram attes C l-arom atlca U aterw all S p re ad e r-S to k er Hazardous H aste In c in e ra to rs o Land Based o In c in e ra to r Ships PCBa, PCPe PCB. PCPs Rotary K iln Dual Chamber Sewage Sludge I n c in e ra to r s U tility Coal B oilers PCBa, C l-a ro m a tic a C oal, low C hlorine M ultiple H earth 1 Pulverized Coal Commercial B o ilers (w aste-fired) TCP Small F ire Tube In d u strial B oilers (w asto-fired) J4 , PCP, C l-a ro m a tic s Liquid In je c tio n /S to k e r A ctivated Carbon R egeneration PCBa F lu id iz e d Bed R e s id e n tia l Hood C onbustlon Low C h lo rin e Hood S to v e /F lr e p la c e Mobile Sources Low C h lo rIn e In te r n a l Combustion Engine H ire Reclamation In c in e ra to rs PCBa, PVCs Ba tch/G onveyor Line/Cement K ilns (w aate-flred) C l-organlcs Rotary K iln A ccidental Transform er Fire fCBs, Cl-bepzenes U n c o n tro lle d PCB O il F ire 11 E x ce ss: High a l r / f u e l r a t i o w lth e f f l c i e n t a l x ln g . Low: High a l r / f u e l r a ti o w ith in e f f ic ie n t m ixing. L im ited ; Designed fo r low a l r / f u e l r a t i o . b HA: Hot A v a ila b le , S00-1000*c .i 1000`C . 4 vf 1200*C V' 160*C 450-950*C 1200 *c 1000`C M 1300*C 'V , 7 5 0 - 1 0 0 0 *C \ <500*C 1800-2500*C j } 500*C ' I * 1400*C ,,v NA>* ; ] ; Low Excess Excess Excess Low Excess Excess Excess L im ited Low Excess Limi ted Excess HA A. ' ! [ . i-s . M '- r \ - # .t - 4 XV' 'll.* i # M h t 'At' 'c ,. ' ' l'j "Lff 4 v' 1 # 4-~ ^ Lvt ;i A f 1 p fft. f o r PC? I s a s a wood p r e s e r v a tiv e * I t I s a n t i c i p a t e d t h a t U n i t e d d io x in contam in a tio n w ill also occur during the m anufacturing o f o th e r sim ila r ch lo rin ated aro m atics, p a rtic u la rly i f the m anufacturing process Is In e ffic ie n t o r n o t v e il c o n tro lle d * T h e re fo re , d io x in s a re expected to e n te r th e environm ent a s a contam inant o f com m erlcal p ro d u c ts, such as rood, p re s e rv a tiv e s and p e stic id e s * The w idespread use o f th ese products In c re a s e s th e p o s s ib il ity o f 'f i n d i n g d io x in s in th e fe e d o f a com b u stio n p ro c e s s * F o r ex am p le, PCP t r e a t e d _ wood may be used to f i r e b o ile r s * R unoff may c a r r y p e s t i c i d e s c o n ta in in g d io x in s to w ater tre a ta e n t f a c i l i t i e s where the organics are in co rp o rated In to a sludge. The slu d g e may th e n be in c in e r a te d * L ik e w is e , c o n ta m in a te d w aste s tre a m s from-- m a n u fa c tu rin g p ro c e s s e s may be I n c in e r a te d a s an e n e rg y re c o v e ry p ro c e d u re . Two exam ples a re PCP slu d g e I n c i n e r a t o r s used a t wood p r e s e r v in g f a c i l i t i e s and black liq u o r recovery b o ile rs used a t paper m ills* B o iler stu d ie s discussed in the lite r a tu r e review^ dem onstrate th a t I f PCDD's have been d e te c te d in co m b u stio n so u rc e e m is s io n s w ith PCDD's In th e feed o f an I n e f f ic ie n t o r poorly c o n tro lle d com bustion p ro cess, I t Is very ;1 lik e ly th a t they w ill be released to the atm osphere. 3 .3 .2 P recursors In Feed Most o f the experim ents reviewed focused on the form ation o f d io x in s and fu ran a from precursors* E sposito e t a l . presented d e ta ile d d e s c rip tio n s o f the fo rm atio n mechanisms o f c h lo rin a te d d io x in s from p r e c u r s o r s .39 T his work organizes dioxin precursors into three classes: C lass I - Polyhalogenated phenols, p rim arily w ith a halogen ortho to the hydroxyl group, w ith a high p ro b a b ility of d io x in form ation; C lass I I - O rtho-halo phenols and o rth o -h a lo phenyl e s te r s where th e s u b s titu te d groups a re a m ixture of halogens and nonhalogens; and C lass I I I - O ther chem icals having the p o s s ib ility , but le s s l i k e l i hood, o f d io x in fo rm atio n , In clu d in g c h lo rin a te d arom atic compounds. - 25- The m a jo rity o f e x p erim en tal work to d a te has cen tered on th re e c la s s e s o f p r e c u r s o r s : c h lo r in a te d , phenols,,,. c h lo rin a te d : b e n z e n e s y a n d PCBTs - - D io x in form ation from the com bustion of c h lo rin a te d phenols has been te ste d e x te n siv e ly by Happe40 Jansson^1 , and A hling*2>43B D e ch lo rin atio n o f h ig h ly c h lo rin a te d hom ologues can r e s u l t In fo rm a tio n o f th e more to x ic 2378-TCDD is o m e r. C h lo r i n a te d p h e n o ls a r e used a s wood p r e s e r v a t i v e s , h e r b ic id e s ,, and f o r sap s t a i n c o n t r o l . Wood o r v e g e ta tio n sp ra y ed w ith c h lo ro p h e n o ls may be d is p o s e d o f by In c in e ra tio n o r used as a supplem ental fu e l In b o ile rs . In a d d itio n , ch lo ro - phenol w astes are o fte n disposed o f In sludge In c in e ra to rs and I n d u s tr ia l b o i l e r s . The id e n tif ie d re fe re n c e s above provide a rea so n a b le b a s is f o r con s id e rin g th ese combustion sources as can d id ates fo r the T ie r 4 te s tin g program. B user I n v e s tig a t e d th e fo rm a tio n o f PCDD's and PCDF's from th e p y ro ly s is o f c h lo ro b e n z e n e s .^ The fo rm atio n mechanism included a ch lo ro p h en o l and a p o ly c h lo r in a te d d ip h e n y l' e s t e r (FCDFE) I n te r m e d ia te . C h lo ro b en zen es a r e used in s o lv e n ts , d y e s, p h a rm a ce u tic a ls, and rubber production^ Such products make up much o f th e o rg a n ic c h lo r in e found In m u n ic ip a l w aste I n c in e r a to r f e e d . The a s s o c ia te d w aste p ro d u c ts may a ls o be d is p o s e d o f in o th e r I n c i n e r a t o r s o r b o ilers. B user a ls o I n v e s tig a te d th e fo rm atio n o f PCDF's from th e p y ro ly s is o f P C B 's .4 5 ,47 fj0 e x p e rim e n ta l w r k has been I d e n t i f i e d o n PCDD fo rm a tio n from PC B 's. However, s e v e r a l s t u d i e s have been I d e n t i f i e d t h a t found PCDD's e m itte d from PCB f i r e s . 2 3 , 3 7 ,3 8 a d d itio n , PCB's a re f r e q u e n tly in s o lu tio n w ith h ex - ach lo ro b en z e n es which have been shown to form PCDD's. PCB's have used a s d i e l e c t r i c f lu i d s , In tran sfo rm ers and c a p a c ito rs h y d ra u lic f lu id s , p la s t ic iz e r s , and d y e s . The I n c i n e r a t i o n o f PCB's a t w a ste d i s p o s a l f a c i l i t i e s o r In b o i l e r s may r e s u l t In PCDD and PCDF e m is s io n s . -26- 3 .3 ,3 C hlorine In Feed The ch lo rin e concent of fu e l la obviously an Im portant param eter a f f e c t i n g th e fo rm a tio n o f PCDD's o r PC D F's. S h lh e t a l . d ev elo p ed a ranked p r io r ity l i s t o f conventional combustion system s e m ittin g p o ly cy clic organic m a tte r in c lu d in g PCDD's and PCDF's-^ The r a t i o n a l e p re s e n te d f o r so u rc e ran k in g i s based on f u e l c h a r a c te r is tic s and com bustion c o n d itio n s- S h lh 's work p laces g r e a t em phasis on both the c h lo rin e c o n te n t o f th e feed and the , co n cen tratio n o f arom atics in the feed- Other authors have demonstrated the e ffe c t of chlorine on dioxin e m is s io n s - Mahle e t a l . d e m o n stra te d t h a t PCDD's w ere e m itte d from c o a l combuar_ t l o n o n ly when c h lo r in e was added .50 T ie r nan e t a l . found PCDD fo rm a tio n d u rin g th e co m b u stio n o f p in e In th e p re se n c e o f HC1, b u t no PCDD's w ere d e te c te d d u rin g th e com bustion o f p in e a l o n e .^1 L i b e r t i s tu d ie d th e co m b u stio n o f v e g e t a b l e s . ^ When In o r g a n ic c h lo r in e o r PVC I s ad d ed , PCDD's and PCDF's were d e te c te d I n th e fe e d - W hile th e r e I s g e n e r a l a c c e p ta n c e t h a t some c h lo r in a te d compounds a r e con c lu siv e to d io x in fo rm a tio n ,'th e s e In o rg an ic c h lo rin e stu d ie s dem onstrate th a t th e s p e c i f i c mechanisms in v o lv e d in PCDD fo rm a tio n a r e com plex and n o t w e ll un d ersto o d . However, i t can be g e n e ra lly s ta te d th a t c h lo rin e must be p re se n t f o r the fo rm a tio n o f PCDD, and g e n e r a l tre n d s s u g g e s t t h a t In c re a s e d c h lo r in e c o n c e n tr a tio n s In th e fe e d may Improve th e p o s s i b i l i t i e s o f PCDD e m is s io n s - 3 -3-4 Combustion C onditions The re m a in in g f a c t o r s t h a t a f f e c t PCDD e m is s io n s a r e co m b u stio n c o n d itio n s- These are combustion tem perature, resid en ce tim e, m ixing, use of su p p lem en tal f u e l , and fu e l p ro c e ss in g . The com bustion e f f ic ie n c y I s a fu n c tio n o f a l l o f th e s e f a c t o r s . I n o r d e r to d e s tr o y PCDD's o r p re v e n t t h e i r f o r m a tio n , th e com bustion e f f ic ie n c y must be h ig h - T his r e q u ir e s a co m b in atio n o f h ig h tem p e ra tu re s , a v a ila b le oxygen, high h e a t c o n ten t f u e l, and long resid en ce tim es. Each fa c to r Is d iscu ssed se p a ra te ly below. - 27- 3 .3 .4 .1 Combustion Tem perature v. E x p e rim e n ta l e v id e n c e s u g g e s ts t h a t te m p e ra tu re s o f 500-800C p ro m o te J.. PCDD fo r m a tio n , w h ile te m p e ra tu re s g r e a t e r th a n 800C d e s tr o y PCDDrs.543#47 B user e t a l . showed t h a t PCB p y r o ly s is a t 550-650*C form s P C D F .^ However, p y r o ly s is a t te m p e ra tu re g r e a t e r th a n 700*0 c a u se 99 p e rc e n t d e s t r u c t i o n o f PCB's and no PCDF f o r m a tio n .38 A hling e t a l . produced s i m i l a r r e s u l t s f o r b o th PCDD's and PCDF's d u rin g th e co m b u stio n o f c h lo ro p h e n o ls .^ 2 C om bustion te m p e ra tu re i s a f u n c tio n o f th e BTU ( B r i t i s h Therm al U n it) c o n te n t o f the fu e l o r supplem ental f u e l, the a v a ila b le a i r , and the degree of f u e l p ro c e ssin g . M unicipal w aste In c in e ra to rs a re co n sid ered a s ig n if ic a n t comr b u s tio u s o u rc e o f P C D D 's .^ " * These la r g e mass b u rn u n i t s a re c h a r a c te r iz e d by / low co m b u stio n te m p e ra tu re s , due i n p a r t , to th e h ig h m o is tu r e , low BTU f u e l ; poor a ir /f e e d mixing due to the la c k o f feed p ro cessin g ; and la ck o f supplemen t a l f u e l . In co m p ariso n , many h azard o u s w aste in c in e r a t o r s and h ig h e f f ic ie n c y b o i l e r s a r e d e sig n e d f o r v e ry e f f i c i e n t c o m b u stio n . These u n i t s b u rn h ig h BTU f u e l s a n d /o r add h ig h BTU s u p p le m e n ta l f u e l s ; a n d , even i f th e a l r / f u e l r a t i o i s low , th e a l r / f u e l m ixing i s e f f i c i e n t . The f u e ls a re p ro cessed to d e c re a s e m o situ re and improve m ixing. In many c a s e s , high tem perature a fte r b u r n e r s a re used f o r the combustion of o ffg a s e s . S everal stu d ie s have been id e n tifie d th a t d e m o n s tra te th e e f f e c t s o f h ig h co m b u stio n te m p e ra tu re s on PCDD's and PCDD p re c u r s o r s .2 2 ,2 3 ,2 6 F or exam ple, no PCDD's w ere d e te c te d in th e e m is s io n s o f th e V ulcanus i n c i n e r a t o r s h ip d u r in g th e co m b u stio n o f PCDD c o n tam in ated H e rb ic id e O r a n g e . 22 The c o m b u stio n te m p e ra tu re d u r in g t h i s p r o j e c t was 1600C. 3 .3 .4 .2 R esidence Time The r e s id e n c e tim e n e c e s s a r y to d e s tr o y PCDD's and th e co m b u stio n tem p eratu re a re in v e r s e ly r e l a t e d . The h ig h e r th e com bustion te m p e ra tu re , th e s h o r t e r th e r e q u ir e d r e s id e n c e tim e f o r PCDD d e s t r u c t i o n . L ik e w is e , a low te m p e ra tu re s o u rc e w i l l r e q u ir e a lo n g r e s id e n c e tim e f o r d e s t r u c t i o n o f PCDD' s . -28- Sachdev e t a l . showed th a t an in cre ase in both tem perature and residence time d e c re a s e d th e fo rm a tio n o f FCDD's from c h lo ro p h e n o l c o m b u s tio n .^ S im ila r r e s u lts have been found a t hazardous w aste in c in e ra to rs th a t run w ith 1.5?-2.0 second re s id e n c e tim e s. Combustion so u rces w ith lo n g e r re s id e n c e tim es and high tem peratures are le s s lik e ly to form products o f Incom plete com bustion, such as d io x in s. 3 .3 .4 .3 Oxygen A v a ila b ility rV'' v Oxygen* a v a i l a b i l i t y i s a f u n c tio n o f b o th th e a i r / f u e l r a t i o and a i r / f u e l m ixing e f f ic ie n c y , b o th o f which a re o f concern when burning s o lid f u e l s . S olid fu e ls and high v is c o s ity liq u id fu e ls (w aste ta r s , e t c .) burn as p a r tic u la te s o r la rg e d r o p le ts , and th e re fo re p o rtio n s o f the f u e l a re burned In low oxygen o r p y ro ly sis c o n d itio n s . A low a l r / f u e l r a tio o r poor a l r / f u e l m ixing w i l l promote poor com bustion c o n d itio n s and th e fo rm a tio n o f PCDD's. Ja n s son d e m o n stra te s t h a t an I n s u f f i c i e n t a i r su p p ly I n c r e a s e s FCDD e m is s io n s from chlorophenol com bustion.^- -M undpal w aste combustors are u su ally fire d w ith excess a i r . However, la rg e mass burn u n its have poor a l r / f u e l m ixing due to the la c k o f fu e l processing* A ctivated carbon re g e n e ra tio n and w ire re c lam a tio n in c in e r a to r s a re both d esigned w ith lim ite d a i r (some w ire re c la m a tio n I s d o n e, In p o o rly designed n e a rly open chambers which a re conduclves to low tem p eratu res and m ix in g ). A ll of th e se c a se s have been shown to em it d io x in s . 1 ^,3 2 ,3 5 a b le oxygen w ill be co n sid ered d u rin g the source ra n k in g . Sources w ith a low a l r / f u e l r a tio o r poor a l r / f u e l m ixing w ill be co n sid ered p o te n tia l so u rc es o f FCDD e m is s io n s . 3 .3 .4 .4 Feed P ro cessin g The feed m a te r ia l f o r a co m b u stio n s o u rc e may be a l i q u i d , a s o l i d , o r a g as. Both liq u id and gaseous f u e ls can be e a s ily mixed w ith a i r r e s u ltin g In a h ig h com bustion e f f i c i e n c y ; s o l i d fe e d s u s u a lly r e q u ir e some p ro c e s s in g to - 29- improve com bustion. O ften so lid feeds re q u ire d ry in g , sh red d in g , o r se p a ra tio n to Improve com bustion. S im ila rly ,, hig h v is c o s ity f u e ls , fo r example w aste t a r s , r e q u ir e some p re p a ra tio n s in c lu d in g p re h e a tin g and a to m iz a tio n p r io r to com buscion. Feed p ro cessin g w ill d e term in e , in p a r t, bo th oxygen a v a i l a b i l i t y and re sid e n c e tim e. F in e, homogeneous feed p a r tic le s w ill Improve a l r / f u e l m ixing and com bustion* L a rg e r p a r t i c l e s w i l l r e q u i r e lo n g e r r e s id e n c e tim es and may r e s u l t in lo c a l oxygen d e fic ie n c ie s due to poor m ixing. High m o istu re w ill a lso d e crea se com bustion e f f ic ie n c y . T h e re fo re , h ig h ly processed homogeneous feed s a r e l e s s l i k e l y to em it p ro d u c ts o f in c o m p le te c o m b u stio n , su ch as PCDD's v 3 .3 .4 .5 Supplem ental Fuel When b u rn in g a low BTU f u e l , th e a d d itio n o f s u p p le m e n ta l f u e l w i l l in c re a s e the com bustion tem perature and improve com bustion. H alle e t a l . t e s t e d a b o i l e r c o f i r i n g RDF w ith c o a l . ^2 The b o i l e r te m p e ra tu re was 1200C, and no PCDD's w ere d e t e c t e d . Dow C hem ical te s t e d an i n d u s t r i a l i n c i n e r a t o r burning w aste ta rs w ith o u t supplem ental fu e l and found p a rts per b il l i o n (ppb) l e v e l s o f TCDD's in Che f l y a s h .^ A fte r th e a d d itio n o f a su p p le m e n ta l f u e l , no TCDD's were d e t e c t e d . When s e l e c t i n g s o u rc e s f o r th e T ie r 4 t e s t i n g program , s o u rc e s f i r e d w ith h ig h BTU su p p le m e n ta l f u e l a r e c o n s id e re d l e s s l i k e l y Co e m it PCDD's. S o u rce s b u rn in g low BTU w a ste s w ith o u t su p p le m e n ta l f u e l s a r e h ig h c a n d id a te s for testin g . 3 .4 I d e n t i f i c a t i o n Of S ource C a te g o rie s W ith A P o t e n t i a l To Em it D io x in The p rev io u s p arag rap h s have I d e n tif ie d a number of param eters which a re lik e ly to a f f e c t e ith e r the presence an d /o r m agnitude o f d io x in s em itted from com bustion so u rc es. In the a n a ly sis described below, combustion source c a te g o rie s a re review ed to determ ine which e x h ib it c h a r a c te r is tic s more c lo s e ly - 30- a sso ciated w ith these param eters. Source c a te g o rie s so id e n tifie d are higher p r io r ity candidates fo r source sam pling under T ier 4. _ .. A broad l i s t of com bustion source c a te g o rie s is provided In Table 3-3 . These source c a te g o rie s were examined in a somewhat judgm ental manner w ith the com bustion re la te d param eters prev io u sly d e sc rib e d . This process re su lte d in a l i s t i n g o f com bustion source c a te g o rie s (see Table 3 -4 ) which are considered to -be asso ciated w ith th ese param eters* This lis tin g also id e n tifie s those source c a te g o rie s where d io x in has p re v io u sly been found to be e m itte d . Source c a te - g o rle s in T able 3-4 re p re s e n t the com bustion source c a te g o rie s which are candidates fo r source sam pling under T ie r 4. 1 A number o f th e so u rc e c a te g o r ie s i n i t i a l l y l i s t e d in T ab le 3t>3 do n o t appear in Table 3 -4. For example, f o s s il fu e l-fire d b o ile r s , process h e a te rs , and gas tu rb in e s have been excluded due to th e ir use o f f u e l w ith low c h lo rin e c o n ten t* For th e same re a s o n , i n d u s t r i a l p ro c e sses u sin g low c h lo rin e f o s s i l f u e ls , such as the p ro d u ctio n o f carbon b lack and co al g a s if ic a tio n , have not been in cluded. Sources burning a low annual tonnage o f f u e ls , such as c o ffee r o a s tin g , p a th o lo g ic a l i n c i n e r a t o r s , m eat smoke houses o r open b u rn in g , a ls o have n o t been included in Table 3-4. S im ila rly , in te rm itte n t sources, such as s tru c tu ra l f i r e s have been e x c lu d e d . W hile some o f th e s e s o u rc e s may p o s s ib ly e m it 2 378- TCDO, th e s e so u rc e c a te g o r ie s a r e n o t e x p ec te d to pose a s g r e a t an e x p o su re problem as would be expected from la rg e so u rces which o p e ra te c o n tin u o u sly . 3.5 Development Of C r ite r ia For P r io r itiz in g The C andidate Source L is t I t w ill n o t be p o s sib le to s ta c k t e s t each o f the c a n d id a te com bustion so u rce c a te g o rie s lis t e d In Table 3-4 T ie r 4 . T h e re fo re , a method fo r p r io r i t i z i n g th e c a n d id a te so u rc e c a te g o r ie s by groups was d e v e lo p e d . The p ro c e ss - 31- Table 3-3. Combustion Sources F o ssil Fuel B oilers, Process H eaters, o r Engines B oilers ---- c o a l - f i r e d ----- o i l - f i r e d ----- n a t u r a l g a s - f i r e d - - -- liq u e fie d petroleum gas -----wood Process H eaters ----- o i l ----- n a t u r a l gas ----- r e f i n e r y gas T u rb in es -----o i l -- n atu ral gas I n te r n a l Combustion Engines ----- s t a t i o n a r y ----- m obile Home H e a tin g -----o i l ----- n a t u r a l gas -- coal wood s t o v e s / f i r e p l a c e s In d u stria l Processes C a ta ly tic Cracking Charcoal M anufacturing Carbon Black M anufacturing Coke M anufacturing Coal G a sificatio n A sphalt M anufacturing Coffee R oasting M eat Smoke Houses Black L iquor B o ilers (paper m ills) -32- Waste D isp o sal O p eratio n s Bagasse B o ilers Wood Waste B u rn e rs Refuse Derived Fuel B o ilers M unicipal Waste In c in e ra to r s Hazardous Waste In c in e ra to rs ----- lan d based -- in c in e ra to r ship Sewage Sludge I n c in e r a to r s Waste O il B o ile rs Cement/Llme K iln s (W aste F ire d ) Wire R eclam ation In c in e r a to r s Carbon R ea c tiv a tio n Pathological In cin erato rs Black Liquor B o ilers Open Burning A g ric u ltu ra l Burning A ccidental F ires E le c tric a l Transform ers S tructural Fires Forest F ires T ab le 3 -4 . Com bustion S ource C a te g o rie s B e lie v e d To Have The G r e a te s t P o t e n t i a l To Em it D io x in s Source R ationale H azardous Waste In c in e ra to rs M unicipal Waste In c in e ra to rs RDpZ B o ile r s Commercial Waste O il B o ile rs I n d u s tr ia l B o ile rs C o -flrln g Wastes Wire R eclam ation In c in e ra to rs A ctivated Carbon R egeneration PCF^ S ludge I n c i n e r a t o r s Sewage Sludge I n c in e r a to r s Mobile Sources Wood S to v e s /F lr e p la c e s Wood/Bark B o ile rs C harcoal M anufacturing Black Liquor B o ilers Cement/Lime K iln s C o -flrln g W astes Small S preader-S toker Coal B o ilers TCDD^- D etected TCDD D etec te d TCDD D e tec te d TCDD D etected TCDD D etected TCDD D etected TCDD D etected TCDD D etected PCDD4 D etected TCDD D e tec te d TCDD D etected E x p e rim e n ta l r e s u l t s w ith PCP tr e a t e d wood E x p e rim e n ta l r e s u l t s w ith PC? t r e a t e d wood, com bustion c o n d itio n s PCB's^ In e f f l u e n t , POPs In feed Precursors present Favorable com bustion co n d itio n s fo r dioxin form ation lTCDD r e f e r s to th e t e t r a homologues a s a g ro u p . A v a ila b le a n a ly s e s a r e m ix ed , w ith some r e s e a r c h e s r e p o r tin g " t o t a l t e t r a s " and o th e r s r e p o r tin g 2378-TCDD o r b o th . The p re se n c e o f TCDD's g e n e r a lly I n d ic a te s some lik e lih o o d o f 2378-TCDD b e in g p re s e n t. 2rdf * R efu se D erived F u e l. 3pCP - P e n ta c h lo ro p h e n o l. ^PCDD * T o ta l o f a l l d io x in hom olgues o r P o ly c h lo r in a te d d lb en zo d i o x i n s . W hile d e c tl o n o f PCDD's d o e s n o t n e c e s s a r i l y I n d ic a te p re se n c e o f TCDD o r 2378-TCDD, th ere are s u f f ic ie n t d a ta to In fe r such in th is c ase . 5pcB P o ly c h lo rin a te d b ip h e n y ls. - 33- used was s u b je c tiv e , s ia c e no r e a l i s t i c assignm ent o f w eig h tin g f a c to r s could be made f o r th e ra n k in g c r i t e r i a . C r i t e r i a and th e " d e c is io n t r e e " used to p rio r itiz e the candidate source categ o ries are Illu s tra te d in Figure 3-1. Based on th e se c r i t e r i a , can d id ate source c a te g o rie s were placed In to one o f the fo u r groups lis te d in Table 3 -5 . Table 3-5 a lso p re sen ts the grouped so u rce c a te g o ry l i s t . The so urce c a te g o rie s w ith in a p a r tic u la r group a re n o t l i s t e d In any p a r t i c u l a r o r d e r . The Rank A group I s ex pected to be the most l i k e l y to e m it 2378-TCDD and have th e g r e a t e s t p o t e n t i a l f o r human e x p o su re . Rank B and C gro u p s a ls o have a f a i r l y h ig h lik e lih o o d o f e m ittin g 2378-TCDD b u t a re h y p o th esized to p re s e n t le s s o f an exposure problem . Rank D source" c a te g o rie s have been te s te d th re e o r more tim es.* 4 3 .5 .1 Rank D Source C ateg o ries Rank D source c a te g o rie s in c lu d e m unicipal w aste In c in e ra to rs and In d u s tria l b o ile rs c o -flrln g w astes. Six m unicipal waste In c in e ra to rs have been te s te d in the U nited S t a t e s , H " 15 S e v e ra l f l y ash and s ta c k t e s t s have a lso been co n d u cted I n Canada and E u ro p e. 16"20 a. t o t a l o f s i x , w a s t e f l r e d , I n d u s t r i a l b o ile r t e s t s w ill be a v a ila b le a f t e r re -a n a ly z ln g arch iv ed sam ples from Indus t r i a l b o i l e r t e s t s . B ecause more th an th re e s ta c k t e s t s have been conducted f o r each of th ese source c a te g o rie s , they were not considered fo r a d d itio n a l te s tin g under T ie r 4 , beyond th a t re q u ire d to f u l f i l l p revious commitments o f the agency. *As d e s c r ib e d i n A ppendix A, I t I s b e lie v e d t h a t d a t a from th r e e d i f f e r e n t sources provides a reaso n ab le amount o f d a ta to c h a ra c te riz e a p a rtic u la r source c a te g o ry fo r th is e f f o r t . Appendix A a lso dem onstrates th a t i t w ill n o t be p o ssib le to o b ta in s t a t i s t i c a l l y s ig n if ic a n t r e s u lts under T ier 4 , sin ce I t Is not p o ssib le to t e s t enough sources under th is program to o b tain a rig o ro u sly re p re s e n ta tiv e sample to be ab le to develop m eaningful confidence lim its and a c c o u n t f o r v a r i a b i l i t i e s t h a t e x i s t among s o u rc e s . - 34- P re lim in a ry Source L is t (From T able 3 -4 ) Rank D M unicipal Waste I n c in e r a tio n I n d u s tr ia l Waste B o ile rs Rank C Mobile Sources Wood S to v e s ----- Wood F ire d B o ile r Spreader Stoker Coal Hazardous Waste I n c in e r a tio n Lime/Cement K iln s Rank B PC? Sludge I n c i n e r a t i o n Carbon R egeneration Charcoal M anufacture Wire R eclam ation Rank A Sewage Sludge I n c in e r a tio n Black Liquor B o ilers Commercial Waste O il B o ile rs Some r e s e a r c h e r s have r e p o r te d o n ly th e t o t a l f o r th e t e t r a hom ologue. The p re s e n c e o f TCDD i s assumed f o r t h i s ra n k in g p ro c e d u re to be a d e q u a te to in d ic a te the p o t e n t i a l to em it 2373-TCDD. 2"Size" o f categ o ry tak es in to c o n sid e ra tio n the number of so u rc es, th e ir em issio n volume and g e n e ra l lo c a tio n w ith re s p e c t to exposed p o p u la tio n s . F igure 3-1: Ranking C r ite r ia and D ecision Tree -3 5 - Table 3-5. Ranked* Source Category Lit Rank A Source C ateg o ries: Sewage Sludge In c in e r a to r s Black Liquor B oilers Commercial B o ile rs F irin g Fuels C ontalm lnated w ith C hlorinated O rganic Wastes Rank B Source C ateg o ries: FCP Sludge I n c i n e r a t o r s Carbon R egeneration (In d u s tria l) Charcoal M anufacturing Wire R eclam ation Rank C Source C ateg o ries: Wood S to v es Wood B o ile r s ( F ir in g PCP tr e a t e d wood) M obile Sources Sm all Spreader-Stoker Coal B o iler C h lo rin ated O rganic Waste In c in e ra to rs Llme/Cement K iln s C o -fired w ith C h lo rin ated O rganic W astes Rank D Source C ateg o ries: M u n icip al S o lid Waste (MSW) I n c i n e r a t i o n I n d u s tr ia l B o ile rs C o -firin g Wastes* *Ranklng I s by group, n o t by so u rces w ith in a group. Rank A: Large source c ate g o rie s (g re a te r than 1 m illio n tons of fu e l an d /o r w aste burned annually) w ith elev ated d io x in p recu rso r contam ination o r f e e d / f u e l . These c a te g o r ie s have a h ig h p o t e n t i a l to e m it TCDD and p o p u la tio n exposure i s expected to be h ig h . Rank B: Small source c a te g o rie s (le s s than 1 m illio n tons o f fu e l an d /o r w aste burned annually) o r source c ate g o rie s w ith lim ited d io x in precursor contam ination of fe e d /fu e l. These c a te g o rie s have a high p o te n tia l to e m it TCDD b u t p o p u la tio n e x p o su re s a r e e x p e c te d to be low . Rank C: Source c a te g o r ie s l e s s l i k e l y to em it 2378-TCDD. Rank D: S ource c a te g o r ie s w hich have been te s t e d th r e e o r more tim e s . -36- 3 .5 .2 Rank C Source C ateg o ries Rank C s o u rc e c a te g o r ie s a r e chose w hich have been judged. Co be l e s s l i k e l y co e m it 2378-7000, when compared Co Che o c h e r c a n d id a te so u rc e c a t e g o r i e s . T h is I s based on th e fo llo w in g f a c t o r s : (a ) Che l e v e l o f 2378-TCDD d e te c te d In p re v io u s t e s t s , (b ) Che a n t i c i p a t e d l e v e l o f p r e c u r s o r s In th e f u e l / f e e d , and (c ) the lik e lih o o d o f c o n d itio n s fa v o ra b le to Incom plete com bustion. Rank C s o u rc e c a te g o r ie s in c lu d e m ob ile s o u r c e s , wood s t o v e s , wood b o i l e r s , s m a ll sp re a d e r-s to k e r c o al b o ile r s , hazardous w aste in c in e r a to r s , and lim e/cem ent k iln s. M obile s o u rc e s have been te s t e d In two e a r l i e r s t u iie s .5 3 4 I n b o th c a s e s , 2378-TCDD was d e te c te d a t th e p a r t p er t r i l l i o n ( p p t) l e v e l In p a r t i c u l a t e m a tte r scraped from exhaust system s o r In f i l t e r e d exhaust sam ples. C hlorine c o n te n t o f the g a s o lin e and d i e s e l fu e ls a re a lso low (0-100 ppm). Based on th o se e a r l i e r t e s t s and c h lo rin e c o n te n t, m obile so u rces have been ranked C. Wood s to v e s have been te s te d by Dow C h e m ic a l.^33 2378-TCDD was d e te c te d In chimney s c r a p in g s up to 100 p p t. The c h lo r in e c o n te n t o f wood I s l e s s th a n 100 ppm. A lthough th e com b u stio n c o n d itio n s found In wood s to v e s fa v o r the fo rm atio n o f d io x in s , the low c h lo rin e c o n c e n tra tio n s and the low l e v e l s o f d io x in s d e te c te d in e a r l i e r s tu d ie s I n d ic a te t h a t t h i s c a te g o ry may n o t e m it h ig h l e v e l s o f 2378-TCDD. N e v e r th e le s s , 48 m illi o n to n s o f wood a r e burned a n n u a lly , so th e p o te n tia l exposure could be c o n sid e ra b le . W ood-fired b o ile r (b u rn in g u n tre a te d wood) a re more e f f i c i e n t com bustion system s and a re also ranked C. Sm all, sp re ad e r-sto k e r coal b o ile rs have also been placed in the Rank C c a te g o ry . T his so u rce c ate g o ry was ranked in th i s manner because o f com bustion c o n d itio n s w hich f a v o r d io x in fo rm a tio n ( e . g . , r e l a t i v e l y low com b u stio n tem peratures and poor a lr /f u e l mixing due to la rg e feed s iz e ) . I t - 37- should be noted chat te s ts on high tem p eratu re, c o a l-fire d u t i l i t y b o ile rs have not d etected d io x in s In sta c k em issions* Both hazardous w aste In c in e ra to rs and llm e/cem ent k iln s c o - f ir in g w astes have been ranked C. Elevated le v e ls o f ch lo rin ated d io x in precursors can be expected in the feed of th ese source c a te g o rie s* However, previous t e s t s have shown t h a t r e l a t i v e l y low le v e ls o f d io x in a re e m itte d .23-26,36 T his i s due to com bustion co n d itio n s which are not fav o rab le to d io x in form ation* G en erally , com bustion tem peratures fo r these sources are g re a te r than 1000C, and the r e s i dence tim e fo r f u e l ra n g e s from one to two s e c o n d s. The use o f h ig h BTU s u p p le m ental fu e l and a fte rb u rn e rs a lso d e c re a se s the lik e lih o o d of d io x in em issio n s" from th ese sources* 3 .5 .3 Rank B Source C ateg o ries Sources w ith h ig h p o te n tia l to em it a re ranked A o r B. Rank B source c a te g o rie s are sm aller source c a te g o rie s (le s s than one m illio n tons of fu e l burned per year) o r are c a te g o rie s w ith lower co n cen tratio n s of p recu rso rs in th e f e e d . These in c lu d e PCB slu d g e I n c i n e r a t i o n , c arb o n r e g e n e r a tio n , charcoal m anufacturing, and w ire reclam atio n . PC? w a ste i n c i n e r a t i o n h a s b een e v a lu a te d in two 50*54s t u d i e s . i n b o th c a s e s , PCDDs w ere d e te c te d in f l y a sh sam p les. Through e x p e rim e n ta l s t u d i e s , PCPs have been shown to form o c ta c h lo ro d lb e n z o -p -d lo x ln s (OCDD) d u rin g c o m b u stio n . ^ D e c h lo r in a tio n o f OCDD can r e s u l t In TCDD's and th u s 2378-TCD D .^ A n n u a lly , 1 9 ,0 0 0 to n s o f PCP a r e used to p re s e rv e wood.55 Only a sm a ll p e r c e n t age o f th is Is Inco rp o rated In sludge which must be d isp o sed . T y p ic a lly , the slu d g e I s I n c in e r a te d a t t th e wood p r e s e r v in g p l a n t , a lo n g w ith s c ra p wood* The la ck o f feed p rocessing and the high m oisture co n ten t o f the sludge can r e s u lt in poor co m b u stio n c o n d i t i o n s . T h e re fo re , PCP 3 lu d g e i n c i n e r a t i o n I s a p o t e n t i a l source of dioxin. -38- A c tiv a te d carb o n r e g e n e r a tio n was a ls o been ranked B. In o rd e r to prevent the com bustion o f the carbon during the carbon reg en eratio n p ro cess, th e a l r / f u e l r a t i o and the com bustion tem p eratu re (800C) a re k ep t low.56 These c o n d itio n s a re conducive to incom plete com bustion. The therm al regen e ra tio n o f a c tiv a te d carbon has been stu d ie d a t one so u rc e, where the sp en t c arb o n had been used to t r e a t a w a te r su p p ly s y s te m .52 pp t l e v e l s o f TCDDs were d e te c te d In the f ly a s h . P re c u rso r le v e ls in the carbon a re low In com parison to w hat may be e x p ec te d I n c arb o n used to t r e a t an I n d u s t r i a l w aste s tre a m . Charcoal m anufacturing Is a source category w ith combustion co n d itio n s which fa v o r d io x in fo rm atio n . Furnace tem p eratu res a re k ep t low (500C ), and both a l r / f u e l r a tio and a l r / f u e l m ixing a re p o o r.57 Source c a te g o ry surveys I n d ic a te t h a t c h a r c o a l m a n u fa c tu re rs a r e now h e a v ily u s in g s c r a p wood from saw m i l l s * 57 Much o f t h i s wood may have been tr e a te d w ith PCP p ro d u c ts f o r sap s t a i n c o n t r o l . The com bustion c o n d i t i o n s , a lo n g w ith th e p o t e n t i a l use o f PCP tr e a t e d wood, In d ic a te th a t th is source categ o ry has a high p o te n tia l to em it d io x in sA p proxim ately th re e to fo u r m illio n to n s o f wood a re used a n n u a lly In th e produc t i o n o f c h a r c o a l .5^ However, n o t a l l o f t h i s wood I s PCP t r e a t e d . I n a d d i t i o n , the m ajo rity of charcoal m anufacturing f a c i l i t i e s are located In ru ra l s e ttin g s . For th e s e re a s o n s , t h i s so u rce c a te g o ry was placed In th e Rank B c a te g o ry . The f i n a l Sank B so u rce c a te g o ry I s w ire re c la m a tio n I n c in e r a to r s . In p re v io u s t e s t s , p p t l e v e l s o f TCDDs were d e te c te d in f l y a sh s a m p le s .55 As w ith carbon re g e n e ra tio n and c h arco a l m an u factu rin g , both the com bustion tem perature and a v a ila b le oxygen a re kep t low In th is process .56 w ire In s u la tio n In c in e ra te d d u rin g th e p ro c e ss o f te n c o n ta in s PCBs and p o ly v in y l c h l o r i d e . -39- f 3 .5 .4 Rank A Source C ateg o ries The re m a in in g so u rc e c a t e g o r i e s were ra n k e d A These a r e sewage sludge I n c in e r a to r s , b lack liq u o r b o ile r s , and commercial b o ile rs c o - f ir in g chlorinated w astes. A pproxim ately 1.5 m illio n tons of sewage sludge are In c in e ra te d a n n u a l l y . ^ The hig h m o istu re c o n te n t o f the feed can r e s u l t In poor com bustion c o n d i t i o n s . In a d d i t i o n , sewage from an I n d u s t r i a l a r e a may c o n ta in e le v a te d l e v e l s o f FCBs and o th e r c h lo r in a te d a r o m a tic s . In an e a r l i e r C anadian s t i ^ y , PCDDs w ere d e te c te d in s ta c k e m is s io n s .^ ? Many new er u n i t s a re o p e ra te d on a fu e l e f f ic ie n t system . In o rd er to save energy, both the combustion tem perature and the a v a ila b le oxygen are held low. B lack liq u o r reco v ery b o ile r s a re a lso Rank A s o u rc e s . A pproxim ately 13 p e rc e n t o f a l l f u e l used in la rg e I n d u s t r i a l b o ile r s I s p u lp in g l i q u o r . ^ Some 42 m illi o n to n s o f p u lp in g liq u o r a r e re c o v e re d by b u rn in g I n b o i l e r s o f .w hich b la c k l i q u o r b o i l e r s a r e a s u b c a t e g o r y D u e to wood tre a tm e n t a t saw - m ills and b io cid es used in the pulping o p e ra tio n , the p o te n tia l fo r chlorophenol contam ination is high. In o rd er to prevent sm elt o x id a tio n , the tem perature is k e p t r e l a t i v e l y low1In th e se b o i l e r s . In a d d itio n , e a r l i e r s tu d ie s have d e te c te d FCBs in th e e m is sio n s from th e s e b o i l e r s The f in a l Rank A source cate g o ry i s com m ercial b o ile rs c o - f ir in g w a ste s. A pproxim ately 20 m illio n tons o f Resource C onservation and Recovery Act (RCSA) w a s te s a r e d is p o s e d o f In b o i l e r s a n n u a l l y . ^ Many o f th e s e w a ste s a r e c h lo rin a te d a ro m a tic s. Commerlcal s iz e b o ile rs a re e stim ate d to acco u n t fo r about o n e -th ird of th is waste d isp o sa l. These b o ile rs are le s s e f f ic ie n t than the la r g e r I n d u s tr ia l b o ile r s , and a re more lik e ly to produce p ro d u cts o f Incom p le te com bustion, such as d io x in s . They are a lso g e n e ra lly urban o rie n te d so u rces w ith low s ta c k s . - 40- The ra n k in g p ro c e d u re d e s c rib e d above l a h ig h ly s u b j e c t i v e . As d isc u sse d l a t e r , ash s c re e n in g t e s t s w ill be conducted on Rank B and C source c a te g o r ie s I n o r d e r to h e lp f u r t h e r d e f l n l t l z e a ranked so u rc e l i s t * As a r e s u l t , th e f i n a l ra n k in g o f B and C so u rc e c a te g o r ie s may ch an g e, d ep en d in g on the re s u lts of the screening te sts* 3 .6 S e le c tio n Of C e rta in C andidate Source C ateg o ries F or S tack T e stin g Since T ie r 4 funds a re on ly adequate to t e s t about 12 so u rc e s, s e v e ra l o p tio n s were considered fo r s e le c tin g the source c a te g o rie s fo r sta c k te s tin g from the p r io r itiz e d l i s t . Three o f the o p tio n s which were considered are illu s tr a te d In Table 3-6. These Include: O ption 1: Reasonable coverage (th re e sources te ste d ) fo r each o f the so u rc e c a te g o r ie s ranked A, B, and C. O ption 2: Minimal coverage (1 source te ste d ) fo r each o f the source c a te g o r ie s ranked A, B, and C. O ption 3; Reasonable coverage (th re e sources te ste d ) fo r source c ateg o ries ran k ed A, w ith th e re m a in in g so u rc e t e s t s to be re s e rv e d u n t i l th e r e s u l t s o f the ash screening program are a v a ila b le fo r r e - p r io r itlz ln g source c a te g o rie s c u rre n tly ranked B and C. O ption 1, which p ro v id es the most com prehensive t e s t p la n , cannot be s e le c te d due to th e lim ite d re s o u r c e s a v a il a b le f o r t e s t i n g . As p re v io u s ly men tio n e d , T i e r 4 can o n ly fund a b o u t 12 s ta c k t e s t s - n o t th e 32 o r more needed to Implement t h i s o p tio n . O ption 2 p ro v id es a more econom ical t e s t p la n , b u t i t p ro v id e s o n ly a s in g le s t a c k t e s t f o r each o f 12 d i f f e r e n t so u rc e c a t e g o r i e s . More r e l i a b l e r e s u l t s would be o b ta in e d I f th r e e so u rc e s w ith in each so u rc e categ o ry were te s te d . O ption 3 , although not providing the broad coverage of source c a te g o rie s , attem p ts to c o lle c t a reasonable amount o f d a ta ( l . e . , th ree - 41- TABLE 3 -6 . SORCE TEST PLAN OPTIONS FOR STACK EMISSIONS Number o f Recommended T e s ts Source O ption 1 O ption 2 O ption 3 Rank A Sources Sewage Sludge I n c in e r a to r Black Liquor B o ilers ......... Commercial B o ile rs Rank B Sources FCP S ludge I n c i n e r a t o r Carbon R egeneration (I n d u s tr ia l) C harcoal M anufacturing Wire R eclam ation Rank C Sources Mobile Sources* Wood S to v es Wood B o ile r s (PC? T re a te d ) Small S preader-S toker Coal B o iler Hazardous Waste In c in e ra tio n Lime/Cement K iln s (w /C hlorinated Organic W astes) Rank D Sources f t i n l c l p a l S o lid Waste (MSW) I n d u s tr ia l B o ile rs C o -firin g W astes . TOTAL 2 -3 3 2 2 3 2 2 3 3 3 1 2 1 0 32 1 ,1 .... 1 2 .3 2 1 ___ 1 1 11 14 I' 1 1 11 0 0 11 00 12 12 O ption 1: O ption 2: O ption 3: T h ree-test coverage of p o te n tia l source c ate g o rie s. Single-source coverage of p o te n tia l source c ate g o rie s. Recommended s ta c k t e s t p la n ; fo cu sed on s o u rc e c a te g o r ie s w ith greatest potential. *$10k a llo c a te d to EPA's E nvironm ental S cien ces R esearch L a b o ra to ry , R esearch T rian g le P ark, North C aro lin a, fo r supplem ental em issions te s tin g . - 42- sources te s te d ) fo r a lim ite d number of source c a te g o rie s . O ption 3 has been s e le c te d by th e Agency fo r Im plem entation under T ie r 4. S ta c k t e s t i n g under th e program w i l l be p h a se d . SPA p la n s to i n i t i a t e d e ta ile d s ta c k t e s t s In FY-84 o f sewage slu d g e I n c in e r a to r s , b la c k liq u o r recovery b o ile r s , and sm all commercial b o ile rs which c o - f ir e c h lo rin a te d org an ic w a ste . Three b la c k li q u o r b o i l e r s w i l l be t e s t e d , w h ile two sewage slu d g e i n c i n e r a t o r s and com m ercial b o i l e r s c o - f i r i n g w a ste s w i l l be t e s t e d . Two s o u rc e s In these la tte r source categ o ries w ill be te ste d , since a th ird source In both source c a te g o rie s Is being te ste d by o th e r groups. S e le c tio n c r ite r ia are under developm ent which w i l l a llo w o p tim iz a tio n o f c h a r a c t e r i s t i c s o f s o u rc e s to _be_ tested . EPA p la n s to b e g in the p ro c e ss o f lo c a t in g s p e c i f i c s o u rc e s f o r t e s t i n g In eac h s o u rc e c a te g o ry by J u ly 1984. As e x p la in e d in S e c tio n 4 , th e p ro c e ss o f l o c a t in g s p e c i f i c s o u rc e s f o r t e s t i n g w i l l be c o o rd in a te d w ith th e EPA R eg io n al O ffic e s , as w ell as the a p p ro p ria te S ta te and lo c a l a g e n c ie s. T e s tin g o f th e Rank A s o u rc e c a te g o r ie s w i l l use sev en o f th e a v a i l a b l e 12 so u rc e t e s t s . F ive* o th e r so u rc e t e s t s c an be p e rfo rm ed . At t h i s tim e , EPA plans to postpone f in a l s e le c tio n of source c a te g o rie s fo r these fiv e te s t s , u n til the r e s u lts o f the f i r s t phase o f the ash sam pling program are a v a ila b le . The in fo rm a tio n from th e ash program w ill be used to re -e v a lu a te the o rd e r o f the 3 and C ranked source c a te g o rie s . I t i s a n tic ip a te d th a t a f in a l s e le c tio n o f so u rc e c a te g o r ie s f o r th e s e f iv e t e s t s w i l l be made by th e b e g in n in g o f th e 1985 c a le n d a r y e a r. T his s e le c tio n w ill a lso take in to account o th e r s ta c k t e s t s underway o r planned by o th e rs e x te rn a l to T ie r 4. *One o f th e s e so u rc e t e s t s I s c u r r e n t l y re s e rv e d f o r t e s t i n g th e H em pstead, Hew Y ork, I n c i n e r a t o r . T his f a c i l i t y I s c u r r e n t l y s h u t down and may reo p en d u rin g the course of the T ie r 4 s tu d y . I f n o t, the source t e s t w ill be re a ssig n e d to a n o th e r so u rc e c a te g o ry . A d e c is io n on p o s s ib le re a ssig n m e n t w ill be made by December 1984. - 43- 3 .7 Types Of Samples To Be C o lle c te d Under The S ta c k T e s tin g Program The s ta c k te s t in g program i s d esig n ed to o b ta in a q u a n tita tiv e m easure o f th e 2378-TCDD e m issio n s d is c h a rg e d to th e atm o sp h ere from a g iv e n s o u rc e . Gaseous and p a r tic u la te m a tte r s ta c k samples w ill be c o lle c te d , both b efo re and a f t e r e x is tin g c o n tro l d e v ice s In m ost c a s e s . S tack em issions w ill be sampled u s in g m ethods s i m i l a r to th o se d e s c rib e d in th e newly d ev elo p ed ASMS sam p lin g p r o to c o l. 64 t h i s p r o to c o l I s based on use o f an EPA m o d ified Method 5 t r a i n w ith an XAD-2 s o r b e n t. A. summary o f the s ta c k t e s t i n g re q u ire m e n ts c o n ta in e d in th e d r a f t p r o to c o l I s o u tlin e d In T able 3 -7 . Three In d ep en d en t sam pling runs w ill be made a t each s i t e over a period of about one week. Sample c atc h e s from both the f r o n t and back halv es of the sampling tra in w ill be analyzed se p a ra te ly fo r each o f the sam pling ru n s . The an aly se s o f s ta c k sam ples w ill in c lu d e the t e t r a and h ig h e r d io x in hooologues ( l . e . , p e n ta , h e x a , h e p t a , and o c t a ) , a s w e ll a s 2378-TCDD, and t o t a l d io x in s (PCDD's). Samples w i l l be analyzed to th e low p p t le v e l o f d e te c t i o n ( 25 p p t ) . S u f f i c i e n t sam ples w i l l be ta k e n to a llo w a r c h iv in g a p o r tio n o f the sam ples fo r p o s s ib le follow up a n a ly s is , p rim a rily i f re so u rc e s become a v a ila b le to do a d d itio n a l Isom er s p e c if ic a n d /o r fu ran a n a ly s is . In a d d itio n to sta c k sam ples, a sh , w ater, s o i l , and. precom bustion a i r sam ples w i l l be c o l l e c t e d . Ash sam ples w i l l tie p e r i o d i c a l l y c o lle c te d d u rin g each o f th e s ta c k t e s t ru n s and com posited d a i l y . As d e s c rib e d l a t e r , com p ariso n s o f the magnitude of d io x in in the ash w ith th a t In the flu e gas are planned. A nalysis of ash samples w ill id e n tify any p o te n tia l d isp o sa l problem , w hich may e x i s t I f h ig h le v e l s o f 2378-TCDD e x i s t I n th e a s h . P ro c e d u re s f o r c o lle c tio n of ash samples are described In Standard S ite Flan fo r C hlorinated D ioxin Sampling a t Combustion Sources. ^ L im ite d s o i l b o rin g s w i l l tie c o l l e c t e d a t each o f th e s o u rc e s , p r im a r ily around ash handling a re a s . S o il sam ples w ill be c o lle c te d using stan d a rd iz e d - 44- T a b le 3 -7 . Summary Of D r a f t ASME P r o to c o l* F o r Sample C o lle c ti o n o Sam pling p ro c e d u re s w i l l be based on th e d r a f t ASME p r o to c o l re q u ire m e n ts . - Three separate te s t runs. - Sample q u a n titie s w ill allow f o r I n i t i a l a n a ly s is and a rch iv ed sam ples - Each source w ill be te ste d and In clu d es the follow ing sam ples: -- T o ta l Gasous and P a rtic u la te M atter S tack Em issions -- I n le t/O u tle t of C ontrol Devices -- Grab Samples o f F eed/F uel -- Bottom Ash Grab Samples -- Ash o r S lu r ry from C o n tro l D evices -- Precom bustlon A ir -- Quench W ater E fflu e n t -- Soil a S ta n d a rd EFA Method 5 t r a i n , m o d ified to I n c o r p o r a te a s o r b e n t module c o n ta in in g XAD-2. o Em issions C h arac te riz atio n : - S tack Temperattire - M oisture Content - C02, CO - 0 2 , N0X, THC, S0X, O p a c ity - T otal P articu lates ) ) ) ) Continuous M onitoring *D ata re q u ire m e n ts s e t f o r t h In th e ASME p r o to c o l w i l l be c o lle c te d a s a minimum. In many c a s e s , o th e r d a ta w i l l be c o lle c te d . For example T o ta l V o la tile Compounds, S C I, T o ta l C h lo rin e and o th e r a n a ly s e s may be g e n e r a te d a t some s i t e s . O p e ra tin g p a ra m e te rs and c o n d itio n s w i l l be c l o s e l y m o n ito red and docum ented. - 45- sam pling procedures d e sc rib e d In Sampling Guidance Manual fo r the N a tio n al D ioxin S t u d y . Composite s o i l sam ples from the v a rio u s s ite s w ill be analyzed f o r 2378-TCDD and d io x in hom ologues. I f s ta c k a n a ly s e s and r i s k a s s e ss m e n ts I n d ic a te re a so n fo r s e r io u s c o n c e rn , f u r t h e r sam pling o f s o i l s downwind w i l l be c o n sid e re d . Precom bustion a i r w ill be sampled a t any source where s ig n if ic a n t d io x in p recu rso rs a re suspected to be in the a i r as a r e s u lt of s i t e contam ination. Some h e a v ily I n d u s t r i a l i z e d a r e a s f o r exam ple, co u ld have r e l a t i v e l y h ig h (ppb to ppm l e v e l s ) c o n c e n tr a tio n s o f p r e c u r s o r s o f d io x in In th e am b ien t a i r . The d e c is io n to t e s t p re c o m b u stio n a i r w i l l be made on a s o u rc e -b y -s o u rc e b a s is du rin g the p re te s t su rv ey . Steps w ill be id e n tifie d in the p re te s t survey pro to co l described In Section 4 as c r ite r ia fo r th is d e c isio n . Precom bustion a ir sam ples w ill be c o lle c te d by the am bient sam pler ( e . g . , m odified high volume am bient sam p ler w ith an XAI>-2 c o l l e c t i o n r e s i n ) d e s c rib e d In g u id an ce f o r d io x in m o n ito r in g .65 Down wash from th e s ta c k sam pled w i l l be a v o id e d . These sam ples w i l l be a n a ly z e d f o r 2378-TCDD, th e h ig h e r d io x in hom ologues, PCBs, ch lo rin a te d phenols, c h lo rin a te d benzenes, and to ta l organic c h lo rin e . During the sta c k t e s t , fu e l/fe e d samples w ill be p e rio d ic a lly c o lle c te d and c o m p o sited . The f u e l / f e e d sam ples w i l l be a n aly z e d f o r t o t a l PGDDs, PCBs, t o t a l c h lo r in e , c h lo rin a te d p h e n o ls, and c h lo rin a te d b en zen es, s in c e th e s e compounds may be p r e c u r s o r s o f d i o x i n . I f 2378-TCDD i s d e te c te d i n th e s ta c k e m is s io n s , th e f u e l sam ples w i l l a ls o be a n aly z e d f o r 2378-TCDD and th e h ig h e r hom ologues. The TROIKA w i l l p erfo rm a n a ly s e s f o r th e d io x in compounds and the sam pling c o n tra c to r w ill analyze fo r the o th e r compounds. Thus, the e x te n t o f n o n -d lo x ln a n a ly se s w ill a f f e c t the c o s t o f each sample c o lle c te d and c o n s e q u e n tly T i e r 4 Ts b u d g e t. T ab le 3 -8 sum m arizes th e a n a ly s e s to be perform ed on each sample c o lle c te d during the sta c k t e s t . In a d d itio n to the number of -46- S a a p la T ab le 3-B . SAHPUtIC AND ANALYSES MODEL Method Saaplea Analyaee T o ta l Saaplea* fo r A nalyaie In p u ta Pracoabuatloa A ir 1AD-2 (PUPP)k O -l c 2370-TCDD, PCOHd, TOCL, C l-p h a o o la , Cl-baoaanaa 1= P a a d /P u a l Grebe D a lly Coapoelce PCDO Sean, C l-p h e o o le C i-b a n a a o a a , F C t, TOCL 1* O utputa Stack (h a fo ra c o o tro l) WST* 2 tra ln a -ke ck H a lf D a lly Coapoalte -condenser Ulnae -a d so rb e n t Bealn -F ro n t H a lf D a lly Coapoalte -c y c lo n e Catch -filte r -probe rlnaa 2370-TCDD. Hoaologueab ( t e t r a - o c t a ) , fCOO Stack ( a lt a r c o n tro l) l o t to a Aak MIST Graba 2 tra ln a -Sack H a lf D a ily Coapoalte -condanaar Blnaa -a dsorb ent ba sin -F ro n t H a lf D a lly Coapoalte - f i l t e r Catch -p robe Sloes D a lly Coapoalte 237S-TCOO, U oaaloguaa ( t e t r a - o c ta ) PCDD t 237S-TCDO, Nonologuea ( t e t r a - o c ta ) PCDD f 3 Aak Proa C o n tro l Device Graba D a ily Coapoalte 2370-TCDD. Hoaologuee ( t e t r a - o c t a ) , PCDD 3 Quench H a te r I f f l u a o t Ocher S ola ( la v ic in ity ) Graba a rin g a D a lly Coapoalte 1 C oapoalU 237S-TCOO, tloaologuea ( t e t r a - o c t a ) , PCDO 237S-TCDO, H oaologuea ( t e t r a - o c t a ) , FCOD 3 l T o ta l 26* alaaed on 3 a a a p lln g d a ys. i : b XAD-2 ( f U i r ) d i o o u i a a o d l l l i d h ig h v o lu a e a i r e a a p le r w it h a a p e c la l a a a p lln g bead l o r a a b le n c o r g a n ic coapounde* c S ta p le to ba c o lle c te d 11 th e re l a a a l g n l l l c a a t ao u rca o ( euapeccad p re c u re o ra In v i c i n i t y o f e a a p lio g a l t a . dpCDD P o ly c h lo r in a te d d lb a n to d l o i l n . TOCL " T o ta l o r g a n ic c h lo r in e . 1A aalyala by c o n tra c to r. (1ST l a a a n d Ilia d SPA "Method 1 " t r a i n aa d e fin e d In the ASHE p r o t o c o l. HHoaologuee * Analyeaa dona on h ig h e r ( l e t r a th ro u g h o c ta ) FCDD'e aa a t o t a l f o r each g ro u p o n ly . iH u ltlp la aaalyaaa fo r each eaaple w i l l have a M u lt ip lie r a ff a c t on the a n a ly tic a l coata e la o . T o ta l doea n o t Inclu de f u a llt y aaaurance eaaplea (a p p ro . 1 0 1 ). i I sam ples l i s t e d In th e t a b l e , an e s tim a te d a d d itio n a l 20 p e rc e n t w i l l be re q u ire d fo r q u a lity a ssu ra n ce /q u a lity co n tro l purposes (blanks, d u p lic a te s, blinds e tc ) 3-8 Ash S c re e n in g Program The T ie r 4 plan in clu d es a program to c o lle c t ash screen in g samples from s e v e ra l com bustion source c a te g o rie s which a re lis te d In T able 3 -9 . T his l i s t i n g in c lu d e s eac h o f th e s o u rc e c a te g o r ie s ranked B o r C, a s w e ll a s a few o th e r com b u s tio n s o u rc e c a te g o r ie s w hich have been recommended fo r t e s t i n g by EPA R e g io n a l O ffic e s and o th e r s . For exam ple, te s tin g ^ o f a g r i c u l t u r a l burn a re a s was reconrmended by EPA*s R egion X o f f i c e , w h ile f o r e s t f i r e r e s id u e s w ere recommended by an advisory group to T ier 4 . A dditio n al source c a te g o rie s th a t have a reasonable l i k llh o o d o f e m ittin g 2378-TCDD may be added to th e s c r e e n in g l i s t , based upon recom m endations from th e EPA R e g io n a l O f f ic e s and o t h e r s . The r a t i o n a l e f o r p e r forming. the ash sam pling program i s based p rim arily on the need to re fin e the re s u lts of the ad m ittedly su b jec tiv e stack te stin g p rio r itiz a tio n procedure. The ash sam pling program i s r e l a t i v e l y in ex p en siv e and w ill p rovide d io x in re la te d Inform ation fo r se v e ra l combustion sources. U n fo rtu n a te ly , th e re i s no r e l i a b l e s c re e n in g te ch n iq u e a v a ila b le to p ro v id e c o n c lu s iv e e s ti m a te s o f 2378-TCDD e m issio n s from com b u stio n s o u r c e s . 2378-TCDD I s h y p o th e s iz e d to be t y p i c a l l y e m itte d e i t h e r a s a p a r t i c u l a t e , a gas o r absorbed upon the f in e p a r tic u la te . I f th is i s tr u e , I t would g e n e ra lly n o t be co n cen trated In the ash of a p a rtic u la te c o n tro l d ev ice. Data are a v a il a b le which In d ic a te th e re Is lik e ly to be s e le c tiv e p a r titio n in g of homologues between those in the flu e gas and those In the f ly a s h . ^ These d a ta imply th a t, TCDD c o n c e n tr a te s In th e f l u e g a s , w h ile th e h ig h e r d io x in homologues c o n c e n tr a te I n th e a s h . As a r e s u l t , a s h sam ples can o n ly p ro v id e a g e n e r a l I n d ic a tio n o f th e p re s e n c e o f d io x in a t a s o u rc e . For exam ple, I f 2378-TCDD I s found in th e - 48- i T able 3 -9 . Combustion S ource C a te g o rie s Where Ash Samples W ill L ik e ly Be C o lle c te d * Source C a te g o rie s!* Chemical Sludge In c in e ra to rs Carbon R egeneration U nit ( a t in d u s tria l source) Charcoal M anufacturing Wire R eclam ation Wood S to v es Wood B o ile rs B urning PCP T re a te d Wood Spreader-Stoker Coal B oiler Hazardous Waste In c in e ra tio n Llme/Cement K iln Burning Hazardous W astes Forest Fires Apartm ent House Flue Fed In c in e ra to rs A g ric u ltu ra l Burning *To be supplem ented by o th e r c a te g o r ie s i d e n t i f i e d by S ta te and R eg io n al o f f i c i a l s w ith re a s o n a b le lik e lih o o d o f e m ittin g 2378-TCDD. -49- a s h , I t can o n ly be assumed t h a t 2378-TCDD was p ro b a b ly e m itte d In th e f l u e g a s . When 2378-TCDD I s n o t found In th e a s h , I t c a n n o t be assumed t h a t 2378-TCDD I s n o t em lted In the flu e g a s. At le a s t a t one so u rc e, where both s ta c k and ash d a ta were c o l l e c t e d from th e same s o u rc e , TCDD was found in th e f lu e g a s , even though no PCDD o r TCDD was found In th e f l y a s h ,17 b u t th e m ethodology and q u a l i t y c o n t r o l p ro c e d u re s used have n o t been th o ro u g h ly exam ined. Ash sam ples c a n p ro b a b ly now b e s t be used a s a s c r e e n in g to o l to I d e n t i f y th o s e s o u rc e c a t e g o rie s which have a lik e lih o o d of e m ittin g d io x in and which probably should be stack tested . D espite the lim ita tio n s asso ciated ' w ith these sam ples, ash sampling Is expected to be u s e fu l in p roviding d a ta to supplem ent th e ranking pro cess d e s c r ib e d in th e p re v io u s s e c t i o n . Ash and s ta c k sam ple d a t a c o lle c te d by T i e r 4 and from o th e r s tu d ie s b e in g co n d u cted by o t h e r s may p ro v id e a d d i t i o n a l d a ta to e v a lu a te c o r r e la tio n s . A more thorough exam ination o f d a ta r e la tio n sh ip s between homologues, source c h a r a c te r is tic s , e t c . , w ill be req u ired b efore a hypoth esis o r fu rth e r re sea rc h plan can be developed, however. - 50- Section 4 Im plem entation Of The T ie r 4 P lan 4.1 Overview The prev io u s s e c tio n Id e n tifie d th e s p e c if ic source c a te g o rie s to be sam pled u n d er T i e r 4 . T h is s e c tio n fo c u s e s on how in d iv id u a l s o u rc e s w i l l be s e le c te d f o r t e s t i n g and who w i l l be r e s p o n s ib le f o r v a rio u s a c t i v i t i e s under T ie r 4. This s e c tio n a lso d isc u sse s th e management and c o o rd in a tio n a sp e c ts o f T ier 4. 4.2 S electio n Of In d iv id u al Sources For T esting G e n e ra lly , ash a n d /o r s ta c k sam ples w ill be c o lle c te d from th re e sources w ith in each o f the so u rce c a te g o rie s w hich has been s e le c te d f o r te s t i n g . The process of sele c tin g Individual sources fo r te stin g w ithin each of the source c a te g o rie s w ill begin by T ie r 4 id e n tify in g s e v e ra l sources o r source c ate g o ry "models" which a re b elieved to be re p re s e n ta tiv e o r ty p ic a l o f each source c a te g o ry t a r g e t e d . The EPA R eg io n al s t a f f w i l l th e n be asked to recommend c e r t a i n so u rces from amongst th ese so u rces o r m eeting the model c r i t e r i a fo r screen in g o r s ta c k t e s t in g . In s e le c tin g th e se s i t e s , the Regions and T ie r 4 management w ill need to co n sid er a number o f p r a c tic a l c o n s tr a in ts . For exam ple, a c c e s s ib ility to a s i t e w ill be an Im portant f a c to r . While S e c tio n 114 A u th o rity o f th e C lean A ir A ct may be used to g a in a c c e ss to a p a r tic u la r f a c i l i t y , i f n e c e s sa ry , I t would be mare p r a c tic a l to s e le c t s i t e s where a c c e s s i b i l i t y i s n o t a problem . The p o te n tia l su p p o rt and c o o p e ra tio n o f S ta te /lo c a l agencies should also be co n sid ered , sin ce the ash sampling pro gram i s planned to be conducted by EFA R eg io n al O ffic e s f o r s o u rc e s lo c a te d w ith in th e ir ju r is d ic tio n . S e le c tin g s i t e s in those S ta te s which w ill provide a s s is ta n c e and c o o p e ra tio n would be b e n e f ic ia l. -51- 4 -3 Ash Sam pling Program Once I n d iv id u a l s i c e s have been approved f o r Che a sh sam p lin g program , th e a p p r o p r ia te R e g io n a l O f f l c e ( s ) v i l i be asked Co d e v e lo p s ic e p la n s f o r th e c o lle c tio n o f th e ash sam ples. The purpose o f th e p la n s Is to d e s c rib e the s p e c i f i c s o f how th e a s h sam ples and o th e r In fo rm a tio n w i l l be c o lle c te d a t the s ite ( s ) In accordance w ith g u id e lin e s to be fu rn ish ed by T ier 4. S p e c ific guidance on the types o f Info rm atio n to be c o lle c te d and hov the ash samples are to be c o lle c te d Is c u rre n tly under developm ent. B rie fly , I t i s planned th a t R egional (o r S ta te /lo c a l) personnel w ill o b tain the ash samples from a p a r tic u la r s i t e . Samples should be c o lle c te d from p a rtic u la te m a tte r c o n t r o l d e v ic e s , o r from th e a sh p i t , I n the e v e n t no c o n t r o l d e v ic e I s u s e d . Samples w ill need to be c o lle c te d In such a manner th a t they are In d ic a tiv e of lo n g term o p e r a tio n s w hich may r e q u i r e c o l l e c t i o n o f m u ltip l e sam p les. Samples c o lle c te d w ill be combined in to a s in g le com posite. A p o rtio n o f th is com posite sample w ill be sto red fo r p o ssib le fo llo w u p a n a ly se s. Equipment and d e ta ile d procedures needed to c o lle c t, package and sh ip sam ples to th e TROIKA f o r a n a ly s is w i l l be p ro v id ed by T ie r 4 . Each sam ple w i l l be a ssig n e d a unique sample i d e n t i f i c a t i o n number by th e Sample C o n tro l C en ter w hich h a s been e s ta b lis h e d to manage th e I n f lu x o f sam ples to th e TROIKA u n d er th e N a tio n a l D ioxin S tu d y . Once sam ples a re a n a ly z e d , th e r e s u l t s w i l l be v a lid a te d by th e la b o ra to ry b e fo re being re le a se d to T ie r 4 and recorded In STORET.* T i e r 4 w i l l a u th o r iz e th e v a lid a te d d a ta to be made a v a il a b le to th e Regional O ffice. *STORET I s a p a ra m e tric d a ta s to r a g e and h a n d lin g sy stem o p e ra te d by th e O ffic e o f W ater. This system has been adopted by the N a tio n a l D ioxin Study management as the c e n tra l re p o sito ry fo r a l l d a ta generated. -52- 4 4.4 Source T estin g Program S im ila r p rocedures 111 be used to Id e n tif y In d iv id u a l so u rc es f o r the d e t a i l e d s ta c k t e s t i n g program . I n i t i a l l y , OAR w i l l I d e n t i f y g e n e r a l d e s c r i p tio n s o r s p e c ific candidate sources b eliev ed to be re p re se n ta tiv e o f the source c ate g o ry . T his l i s t i n g along 1th s e le c tio n c r i t e r i a and guidance 111 gen e r a l l y be s e n t to th e SPA R e g io n s, vho 111 be asked to recommend s p e c i f i c so u rc es f o r t e s t i n g . Once s e le c te d , th e Regions w ill be asked to I n i t i a t e th e process o f c o o rd in a tin g w ith the S ta te /lo c a l agencies and g ain in g a c c e ss to the p a r t i c u l a r s o u rc e s w ith in th e R eg io n . Some t e s t s may be added to e x i s t i n g t e s t program s b ein g conducted by IERL. A fte r a c c e ss to a s i t e has been ag reed upon, an EPA c o n t r a c t o r 111 v i s i t th e so u rc e to make a p r e t e s t s u rv e y to o b ta in th e n ecessary background Inform ation needed to plan the source t e s t . A plan w ill be p re p a re d by th e c o n t r a c t o r and su b m itte d to OAR th e R eg io n , S t a t e , and th e source to be te ste d p rio r to the a c tu a l te s tin g . This plan w ill Inclu d e: (a) re fe re n ce to d e s c rip tio n s o f the sam pling procedures equipment to be used; (b) the number of In d iv id u a l source te s ts to be perform ed; (c) the number and types o f samples ( e . g . , b efo re o r a f t e r c o n tro ls , fe e d /fu e l, a sh , s o il) which 111 be c o lle c te d ; (d) the lo c a tio n a t the source o f where each sample w ill be c o lle c te d ; (e ) In fo rm a tio n on the v a rio u s o p e ra tin g p aram eters w hich w i l l be recorded during source te stin g ; ( f ) p ro ced u res to be follow ed concerning the la b e lin g , s to ra g e and sh ip m en t o f th e sam ples to th e TROIKA fo r la b o r a to r y a n a l y s i s ; and (g) a Q uality A ssurance/Q uallty C ontrol plan fo r the source te stin g program . - 53- Once Che plan la agreed upon, Che concracCor w ill make arrangemencs Co proceed wich Che sta c k t e a t . . EPA personnel w ill oversee most o the s ta c k sam pling, which Includes th ree sep arate t e s t ru n s, which may l a s t 5-10 days. A fte r the sta c k te s t has been com pleted, a re p o rt w ill be prepared fo r each source te s te d . A guidance m anual, In clu d in g an example T ie r 4 source te s t r e p o r t, i s c u r r e n tly being developed which w ill be used to a ssu re c o n siste n c y and c o m p a ra b ility among th e r e p o r ts assem bled under T ie r 4 4 .5 Q u a n tita tiv e E xposure And R isk A ssessm ent I n th e e v e n t t h a t 2378-TCDX) i s d e te c te d In th e s ta c k e m is sio n s a t any o f th e - so u rces te s t e d , a q u a n tita tiv e exposure and r i s k assessm ent w ill be perform ed fo r t h a t s i t e . E v a lu a tio n o f ln f e r r e n c e s t h a t can be made to o th e r so u rc es w ith in t h i s so u rc e c a te g o ry w i l l a ls o be p e rfo rm ed . An r e v is e d ex p o su re and r i s k meth odology i s c u rre n tly under developm ent by the S tra te g ie s and A ir Standards D iv is io n (SASD), OAQPS who w i l l perfo rm t h i s e x p o su re and r i s k a n a l y s i s . 4 .6 Ambient A ir Q u a lity Study At one o f th e s o u rc e s where h ig h le v e l s 2378-TCDD I s m easured ( I f Indeed such a case occurs) In the flu e g a s, a follow -up ambient a i r q u a lity study is p lan n ed . The purpose of th is stu d y w ill be to m easure m blent a i r q u a lity le v e ls o f 2378-TCDD i n th e v i c i n i t y o f th e s o u rc e . The stu d y w i l l be one to two months in d u ra tio n d u rin g the spring/sum m er o f 1985. A pproxim ately th re e to fiv e ambi e n t m o n ito rs w i l l be lo c a te d a t v a ry in g d is ta n c e s downwind from the s o u rc e . Ambient sam ples w ill be c o lle c te d on an a lte r n a te day schedule a t each o f the m o n ito rin g s i t e s . Each sam ple c o l l e c t e d w i l l be I n i t i a l l y sc ree n ed f o r PCDDs. In th e e v e n t PCDDs a r e d e t e c t e d , th e am bient sam ples w i l l be f u r t h e r an aly z e d f o r 2378-TCDD. A lthough I n s u f f i c i e n t d a ta w i l l be c o lle c te d to " v a l i d a t e 1* e x p o su re m odel p r e d ic tio n s o f 2378-TCDD c o n c e n tr a tio n s , th e m easured d a ta w i l l - 54- be compared to th e model e s tim a te s and some g e n e r a l o b s e r v a tio n s made. A d e c i s i o n on th e l o c a t i o n o f th e am b ien t a i r q u a l i t y s tu d y sh o u ld be made by March 1985. 4.7 Management Of T ie r 4 The r e s p o n s ib ility fo r managing T ier 4 has been assigned to the O ffice of A ir and R a d ia tio n (OAR). W ith in OAR, th e T ie r 4 program m anager I s Edward J . L i l l i s , C h ie f , A ir Management Technology Branch (AMTB). AMTB i s p a r t o f OAR's O ffic e o f A ir Q u a lity P la n n in g and S ta n d a rd s (OAQFS), M o n ito rin g and B ata A n a ly s is D iv is io n (MDAD), R ese arch T r ia n g le P a rk , N o rth C a r o lin a . The T ie r 4 program s t a f f c o n s i s t s o f James H. S o u th e rla n d , W illiam H. Lamaso a , W illiam B. Kuykendal and Edward Hanks w ith in the A ir Management Technology B ranch. An a d v is o r y T i e r 4 Work G roup, com prised o f r e p r e s e n t a t i v e s o f v a r io u s EPA program o f f ic e s (T able 4 - 1 ) , has been formed to : ( a ) a s s i s t OAR In th e d e s ig n and Im p lem e n ta tio n o f T ie r 4 ; ( b ) . se e k te c h n i c a l e x p e r t i s e and g u id an ce from o th e r EPA r e p r e s e n t a tiv e s on is su e s which a r is e d u rin g the p ro je c t; ( c ) p ro v id e s u g g e s tio n s on how to acco m p lish th e s tu d y o b j e c t i v e s ; (d) rev iew and comment on th e adequacy o f p r o to c o ls , sam pling s t r a t e g i e s , s o u rc e t e s t r e p o r t s , and o th e r m a t e r i a l w hich may be p re pared ; and (e ) keep o t h e r EPA o f f i c i a l s a p p ra is e d o f th e s t a t u s o f th e p r o j e c t . 4 .8 C o o rd in a tio n W ith The EPA R e g io n a l O ffic e s EFA's R egional O ffic e s a re expected to play a key r o le in the Im plem ent a tio n o f the T ie r 4 program. R egional co n tacts have been Id e n tifie d In each of the Region, to e s ta b lis h and m aintain lin e s of communication. A c u rre n t l i s t of R egional Office c o n ta c ts i s provided In Table 4 -2 . B rie fly , th e ir ro le i s to : - 55- o- Name Table 4-1 V ,, T i e r 4 Work Group - r. , ' - - V - _ " O rganization M all Code or Room Number Telephone Number (PTS) Edward J . L i l l i s James H* S o u th e rla n d OAQPS - RTF, NC f vv OAQPS - RTP, NC ' MD-14 MD-14 629-5586 629-5575 W illiam Lamason OAQPS - RTF, NC MD-14 629-5575 Jim Cummings D ioxin Management C o o rd in atio n S t a f f - W ashington, DC W-439 382-4686 Hike Slimak OWRS/OW - W ash in g to n , X E-829 382-7051 Don B arnes C h lo rin a te d D io x in Work Group - W ashington, X E-635 382-2897 Bob O lexsey IERL - C in c in n a ti , OH 684-7696 Dave Sussman OSW/OSWER - W ash in g to n , X WSM-S2811 382-7927 Paul des R osiers ORD - W ashington, X W-621 382-2722 Boniface Thayil A ir And R a d ia tio n - R egion V 886-6054 G a rre tt Smith S o lid Waste - Region I I 264-3407 Mike D e lia rc o ORD - W ash in g to n , X M-3100 382-5794 Jack McGinnity OAQPS - RTP, NC MD-14 629-5504 I s r a e l M ilner (In terim ) A ir Programs - Region I I I 3AMI2 597-9090 - 56- Table 4*2 R egional O ffice C ontacts - T ier 4 Region I II III IV V VI VII V ili IX X Name O rganization FTS Number M arg aret McDonough A ir Program s B ranch (RM 2313) 223-4870 G a rre tt Smith S o lid W aste B ranch (2AWM-SW) 264-3407 I s r a e l M iln e r ( I n te r im ) A ir B ranch (3AM12) 597-9090 B rian Beals A ir Management Branch 257-3454 Boniface T hayll . A ir and R ad iatio n Branch 886-6054 Doug Holy A ir Branch (6AWAT) 729-2825 B ill F airless S u r v e illa n c e and A n a ly sis (KC Lab) 926-3884 Norm Huey A ir Programs Branch 327-3763 K ath leen Shlmmln F ield O perations Branch 454-7466 Dana D avoli A ir Programs Branch (532) 399-1495 -57- (a ) co o rd in ate w ith T ie r 4 on R egional and S ta te plans fo r d io x in sam pling o f combustion- so u rces; (b ) recommend com b u stio n s o u rc e c a te g o r ie s f o r d io x in sam p lin g ; (c ) id e n tify p o te n tia l sam pling s ite s fo r combustion source c a te g o rie s ; (d) o b ta in access to s ite s se le c te d fo r ash and sta c k sam pling (e) c o lle c t ash samples a t screening s ite s ; ( f ) a p p ra ise o th e r R egional O ffic e s t a f f on the scope, o b je c tiv e s and s ta tu s o f T ie r 4; and (g) c o o rd in ate w ith o th e r R egional O ffice d io x in s t a f f and the d e sig n a te d p u b lic a f f a i r s lla s o n on community r e la tio n s is s u e s o f T ier 4. 4.9 A dditional Inform ation For a d d itio n a l in fo rm atio n on T ier 4, p lease c o n ta c t James Southerland o r W illia m Lamason a t FTS 629-5575* -58- R eferences* I . D ioxins, EPA-600/2-80-197, S. Environm ental P ro te c tio n Agency, C in c in n a ti , OH, November 1980 2 D ioxin S t r a t e g y , O ffic e Of W ater R e g u la tio n s And S ta n d a rd s and th e O ffic e Of S o lid W aste And Emergency R esp o n se, U. S. E n v iro n m e n tal P r o te c tio n Agency, W ashington, DC, November 2 8 , 1983. 3 . Review And E v a lu a tio n Of A v a ila b le D io x in E m issio n D ata And T e s tin g O p tio n s F o r Com bustion S o u rce s ( D r a f t ) , EPA C o n tra c t Number 6 8 -0 2 -3 5 1 3 , R adian C o rp o ra tio n , R esearch T r ia n g le P a rk , NC, Ju n e 1984. 4 . "D io x in T e s t C o s ts '*, Memorandum from Bob P a rk s , R ad ian C o r p ., R ese a rc h T r ia n g le P a rk , NC, to B i l l Lamason, O ffic e Of A ir Q u a lity P la n n in g And S ta n d a rd s , U. S. E n v iro n m e n tal P r o t e c t i o n Agency, R esearch T r ia n g le P a rk , NC, A p r il 3 , 1984. 5 . The T race C h e m is trie s Of F i r e - A S o u rce Of And R outes F or The E n try Of C h lo rin a te d D ioxins In to The Environm ent, C h lo rin ated D ioxin Task F o rce, M ichigan D iv is io n o f Dow C h em ical, U. S. A ., M id lan d , MI, 1978. 6 . Environm ental S tandards Workshop, American S o c ie ty o f M echanical E n g in e e rs , McLean, VA, J a n u a ry 2 3 -2 5 , 1984. 7 . A n a ly tic a l P ro c e d u re s And Q u a lity A ssu ran ce P la n F o r The N a tio n a l D io x in Study ( D r a f t ) , O ffic e Of R ese arch And D evelopm ent, U. S. E n v iro n m e n tal P r o te c tio n Agency, W ashin g to n , DC, J a n u a ry 1984. 8 " In te rim E v a lu a tio n Of H e a lth R isk s A ss o c ia te d W ith E m issio n s Of T e tr a c h lo r ln a te d D io x in s From M u n icip al W aste R ecovery F a c i l i t i e s " , EPA Environm ental News, 0 . S. E nvironm ental P ro te c tio n Agency, W ashington, DC, November 19, 1981. 9 . "TCDD E m issio n s From t t m l c l p a l W aste C om bustors", Memorandum from M ichael B. Cook, U. S. E n v iro n m e n ta l P r o te c tio n Agency, W ashington, DC, to D ivision D ire c to rs, Regions I-X , 0. S. Environm ental P ro te c tio n Agency, December 16, 1983. 1 0 . Summary Of A L i t e r a t u r e S e a rc h To D evelop In f o rm a tio n On S o u rces Of C h lo rin a te d D ioxin And F u ran A ir E m issio n s ( D r a f t ) , EPA C o n tra c t Number 6 8 -0 2 -3 5 1 3 , R adian C o rp o ra tio n , R e s e a rc h T r ia n g le P a rk , NC, Septem ber 1983. I I . C. L. H a lle , e t a l . , A ssessm ent Of E m issio n s Of S p e c if ic Compounds From A R eso u rce R ecovery M u n icip al R efu se I n c i n e r a t o r , EPA C o n tra c t Number 68-015915, M idwest R ese arch I n s t i t u t e , K ansas C i t y , MO, November 1983. Some o f th e s e re f e r e n c e c i t a t i o n s a r e In c o m p le te and w i l l be amended o r c o rre c te d in the f i n a l work p lan . - 59- * 1 2 . C om prehensive A ssessm ent Of The S p e c if ic Compounds P r e s e n t l a C om bustion P r o c e s s e s , Volume 1 , P i l o t Study o f C om bustion E m issio n s V a r i a b i l i t y , -.EPA--5 6 0 /5 -8 3 -0 0 4 , O f f ic e Of T o x ic S u b s ta n c e s , U. S . E n v iro n m e n ta l P r o t e c t i o n Agency, W ashington, DC, Ju n e 1983. 1 3 . C om prehensive A ssessm ent Of The S p e c if ic Compounds P r e s e n t I n Com bustion P r o c e s s e s , Volume 3 , N a tio n a l S u rv ey Of O rg an ic E m issio n s From C oal F ir e d U t i l i t y B o ile r P l a n t s , E P A -5 60/5-83-006, O ffic e Of T o x ic Sub s t a n c e s , U. S. E n v iro n m e n tal P r o te c tio n Agency, W ashington, DC, September 1983. 1 4 . G. H. H ig g in s , An E v a lu a tio n Of T race O rg an ic E m issio n s From R efu se Therm al P r o c e s s in g F a c i l i t i e s , EPA C o n tra c t Number 6 8 -0 1 -6 0 7 1 , S y s te c h C o rp o ra tio n , X e n ia , OH, J u ly 1982. 1 5 . T. 0 . T ie rn a n , e t a l . , " C h a ra c te riz a tio n Of Toxic Components In The E f f lu e n t From A R e f u s e - f ir e d I n c i n e r a t o r " , R eso u rces And C o n s e rv a tio n , 2} 343-354, 1982. 16. A. C a v a lla r o , e t a l . , "S am p lin g , O ccu rren ce And E v a lu a tio n Of PCDDs And PCDFs From I n c in e r a te d S o lid Urban W aste", C hem osphere, 9 ( 1 0 ) : 6 l l - 6 2 1 , 1980. 17. A. C a v a lla r o , e t a l . , "Summary Of R e s u lts Of PCDD A n aly ses From In c in e ra to r E fflu e n ts " , Chemosphere, 1 1 (9 ):859-868, 1982. 18. F . G iz z i, e t a l . , " P o ly c h lo rin a te d D ib e n z o -p -d io x in s (PCDD) And P o ly c h lo r in a te d D lb e n zo fu ran s (PCDF) In E m issio n s From An Urban I n c i n e r a t o r 1, A verage And Peak V a lu e s " , C hem osphere, 1 1 (6 ):5 7 7 -5 8 3 , 1982. 1 9 . J . J a n s s e n s , e t a l . , " Q u a lita tiv e And Q u a n tita tiv e A n a ly sis Of E m issio n s Of A M u n icip al I n c i n e r a t i o n I n s t a l l a t i o n " , p re s e n te d a t CEC P h y sic o c h e m ic a l B eh a v io r Of A tm ospheric P o l l u t a n t s , 2nd Symposium, V a re s e , I t a l y , Septem ber 29 - O cto b er 1 ,1 9 8 1 . 2 0 . K. O lie e t a l . , " P o ly c h lo r in a te d D ib e n z o -p -d io x in s And R e la te d Compounds In I n c i n e r a t o r E f f l u e n t s " , Pergamon S e r ie s On E n v iro n m e n tal S c ie n c e . 2 1 . D. G. Ackerman, e t a l . , A t-s e a I n c i n e r a t i o n Of PCB C o n ta in in g W astesOnboard The "M/T V u lc an u s" , E P A -600/7-83-024, U. S. E n v iro n m e n tal P r o t e c t i o n Agency, R ese arch T r ia n g le P a rk , NC, A p r il 1983. 2 2 . D. G. Ackerman, D e s tr u c tio n E f f i c i e n c i e s F o r TCDD D uring A t-s e a I n c i n e r a t i o n Of H e rb ic id e O ran g e, EPA C o n tra c t Number 6 8 -0 2 -2 6 6 0 , R adian C o rp o ra tio n , R ese arch T r ia n g le P a rk , NC, March 1979. 2 3 . PCB D is p o s a l By T herm al D e s tr u c tio n , PB82-24186G, N a tio n a l T e c h n ic a l In fo rm a tio n S e r v ic e , S p r i n g f i e l d , VA, R ese arch T r ia n g le P a rk , NC, June 1981. 24. H. 0 . R ghei and G. A. E lcem an, "A d so rp tio n And Therm al R e a c tio n s Of 1 , 2 , 3 ,4 - T e tr a c h lo r o d ib e n z o - p - d lo x in On F ly Ash From A M u n icip al In c in e ra to r" , Chemosphere, 1 1 (6 ):569-676, 1982. - 60- 25. " R e s u lts o f S ilv e x T e s t Burn DREs", l e t t e r from K. E. J o n e s , P hD ., Roy F . W eston A s s c o d a t e s , W e s tc h e s te r, PA, to M o rris H unt, R o llin s E nvi ro n m e n ta l S e r v ic e s ,. I n c . ,. B r id g e p o r t, N J, Septem ber 9 , 1983. 2 6 . Perform ance E v a lu a tio n Of F u ll S cale Hazardous Waste In c in e ra to rs (D ra ft F in a l R e p o rt) , p rep ared f o r I n c in e r a tio n R esearch D iv is io n , U. S. E n v iro n m e n tal P r o te c tio n Agency, C in c in n a ti , OH, NC J a n u a ry 1984. 27. Sewage Sludge Task Force R e p o rt, O ffice of W ater, U .S. E nvironm ental P r o te c tio n Agency, W ashington, DC. U n p u b lish ed . 28. P . F. F e n n e lly , e t a l . , E nvironm ental C h a ra c te riz a tio n Of D isp o sal Of W aste O ils I n S m all C om bustors ( D r a f t ) , EPA C o n tra c t Number 6 8 -0 2 -3 1 6 8 , GCA T ech nology, B ed fo rd , MA, A ugust 1983. 29. C. C a s ta ld in i, e t a l . , E m issions T e stin g Of I n d u s tr ia l B o ile rs C o -firin g H azardous W astes - S i t e s A, D, E, G, EPA C o n tra c t Number 6 8 -0 2 -3 1 7 6 , A curex C o rp o ra tio n , M ountain View, CA, 1983. -- 3 0 . B. DaRos, e t a l . , M easured M u lti-m e d ia E m issio n s From The Wood P r e s e r v in g I n d u s t r y , EPA C o n tra c t Number 6 8 -0 3 -2 5 6 7 , Acurex C o rp o ra tio n , M ountain View, CA, March 1981. 3 1 . J . H a l l , e t a l . , E v a lu a tio n Of PCB D e s tr u c tio n E f f ic ie n c y I n An In d u s t r i a l B o i l e r , GCA-TR-81-82-G, GCA C o rp o ra tio n , B ed fo rd , MA, A p ril 1981. 32. J . E. Howes, e t a l . , D eterm ination Of D ioxin L evels In Carbon R eactiv a t i o n P ro c e s s E f f l u e n t S tre a m s , EPA C o n tra c t Number 6 8 -0 2 -3 4 8 7 , B a t t e l l e , Columbus, OH. 3 3 . T. J . N e s t r i c k , e t a l . , M ethodology And P r e lim in a r y R e s u lts F o r The I s o m e r - s p e c if ic D e te rm in a tio n Of TCDDs And H ig h er C h lo rin a te d D ib en zo p * dioxins In Chimney P a r tic u la te s From W ood-fueled Domestic F urnaces L o cated I n E a s te r n , C e n tr a l And W estern R egions Of The U n ited S t a t e s , p re s e n te d a t th e I n t e r n a t i o n a l Symposium On C h lo rin a te d D io x in s And R e la te d Compounds, A r lin g to n , VA, O cto b er 2 5 -2 9 , 1981. 3 4 . D io x in s I n M obile S o u rces P a r t i c l e s , memorandum from Jo h n E. S ig s b y , C h ie f, to K arl H. H eilm an, C o n tro l Technology and A p p lic a tio n B ranch, U. S . E n v iro n m e n tal P r o t e c t i o n Agency, Ann A rb o r, MI, F e b ru a ry 2 3 , 1982. 3 5 . D. 0 . H ry h o rczu k , e t a l . , "A W ire R eclam atio n I n c i n e r a t o r As A Source Of E n v iro n m e n tal C o n ta m in atio n W ith T e tr a c h lo ro d lb e n z o -p -d lo x ln s And T e tra c h lo ro d ib e n z o fu ra n s" , A rchives Of E nvironm ental H e a lth , 3 6 (5 ): 228-234, 1981. 3 6 . J . A. P e te r s , E v a lu a tio n Of H azardous Waste I n c in e r a tio n I n Cement K iln s At San J u a n Cement Company, Monsanto R esearch C o rp o ra tio n , EPA C o n tra c t Number 6 8 -0 3 -3 0 2 5 , D ayton, OH, Ja n u a ry 1983. 3 7 . R. L . H a r l e s s , H igh R e s o lu tio n Mass S p e c tro m e try M ethods Of A n a ly sis F o r C h lo rin a te d D ib e n z o -p -d lo x in s And D ib e n z o fu ra n s , Human And E n v iro n m e n tal R isk s Of C h lo rin a te d D io x in s And R e la te d Compounds, 1983. -61-  38. P o ly c h lo rin ate d B iphenyls (PCBa); M anufacture, P ro c e ssin g , D is tr i- b u tio n i n Commerce and Use P r o h i b i t i o n s ; Use in E l e c t r i c a l T ra n sfo rm e rs 49 FR 11070,. March 2 3 , 1984. . --- 3 9 . M. P . E s p o s ito , e t a l . , D io x in s: Volume I - S o u rc e s . E x p o su re, T r a n s p o r t, And C o n tr o l, E P A -600/2-80-156, tl. S. E n v iro n m e n tal P r o te c tio n A gency, C i n c i n n a t i , OH, June L980. 4 0 . C. B appe, e t a l . , "F o rm atio n Of P o ly c h lo r in a te d D ib e n z o -p -d io x in s (PCDDs) And D lb e n zo fu ran s (PCDF) By B urning Or H e atin g C h lo ro p h e n a te s " , Chemosp h ere , 7_(3):269-281, 1978. *r . T 4 1 . B. J a n s so n , e t a l . , "F o rm atio n Of P o ly c h lo r in a te d D ib e n z o -p -d lo x in s D uring Com bustion Of C h lo ro p h en o l F o r m u la tio n s " , The S c ie n ce Of The T o t a l E nvironm ent, 10^(3): 209-217, 1978. 4 2 . B. A hllng and A. L ln d sk o g , "E m issio n Of C h lo rin a te d O rg an ic S u b sta n c e s From C om bustion", Pergamon S e r ie s on E n v iro n m e n tal S c ie n c e , 1982, p p . ----215-225. 4 3 . , B. A h lln g , e t a l . , "F o rm atio n Of P o ly c h lo r in a te d D ib e n z o -p -d lo x in s And D lb e n zo fu ran s D uring Com bustion Of A 2 ,4 ,5 -T F o rm u latio n '* . C hem osphere, 6(8):461-468, 1977. 4 4 . H. R. B u se r, "F o rm atio n Of P o ly c h lo r in a te d D lb e n z o -p -d lo x ln s (PCDDs) And D lb e n zo fu ran s (PCDFs) From The P y r o ly s is o f C h lo ro b e n z e n e s" , Chemosphere, 8(6):415-424, 1979. 4 5 . 3 . R. B u se r, e t a l . , " I d e n t i f i c a t i o n Of P o ly c h lo r in a te d D lb e n zo fu ran Iso m ers In F ly Ash And PCB P y r o ly s e s " , C hem osphere, 7 (5 ):4 1 9 -4 2 9 , 1978. 4 6 . H. R. B u se r, e t a l . , "F o rm atio n Of P o ly c h lo r in a te d D lb en zo fu ran s (PCDFs) From The P y r o ly s is Of PCBs", C hem osphere, 7 (1 ):1 0 9 -1 1 9 , 1978. 4 7 . H. R. B user and C. R appe, "F o rm atio n Of P o ly c h lo r in a te d D lb en zo fu ran s From The P y r o ly s is Of I n d iv id u a l PCB Is o m e rs " , C hem osphere, 8 (3 ) :1 5 7 -1 7 4 , 1979. 4 8 . C . R appe, e t a l . , " P o ly c h lo r in a te d D io x in s , D lb e n z o fu ra n s , And O th e r P o ly n u c le a r A rom atics Formed D uring PCB F i r e s " , Chemica S c r i p t s , 20:56-61, 1982. 4 9 . C. S h ih , e t a l . , POM E m issio n s From S ta tio n a r y C o n v e n tio n a l Com bustion P r o c e s s e s , W ith Em phasis On P o ly c h lo r in a te d Compounds Of D ib en zo -p d io x ln (PCDDs), B ip h en y l (PC B s), And D lb en zo fu ran (PCDFs), EPA C o n tra c t Number 6 8 -0 2 -3 1 3 8 , R adian C o rp o ra tio n , R esearch T r ia n g le Parle, NC, September 1979. 5 0 . N. Mahle and L. W h itin g , "The F o rm atio n Of C h lo ro d lb e n z o -p -d lo x ln s By A ir O x id a tio n And C h lo r in a tio n Of B itum inous C o a l" , C hem osphere, 9 (1 1 ) : 693-699, 1980. 5 1 . M. L. T le m a n , e t a l . , " C h lo ro d ib e n z o d io x in s , Ohio rod lb en zo f u r a n s , And R e la te d Compounds In The E f f lu e n t From C om bustion P r o c e s s e s " , C hem osphere, 12(4/5):565-606, 1983. - 62- r 5 2 . A. L i b e r t i , e t a l . , "PCDD And PCDF F o rm atio n In The Com bustion Of V e g e ta b le W a s te s" , C hem osphere, 12 ( 4 /5 ) ;6 6 1 - 6 6 3 , 1983. 5 3 - A K . S ach d ev , T herm al D e s tr u c tio n Of C h lo ro p h e n o l R e s id u e s , P r o j e c t Number KE 1 1 1 -1 -0 0 0 8 , D earborn E n v iro n m e n tal S e r v ic e s , M is s is s a u g a , O ntario, Canada, July 1983. 5 4 . C. Rappe and S. M arklund, "Therm al D e g ra d a tio n Of P e s t i c i d e s And X e n o b lo tlc s : F o rm atio n Of P o ly c h lo r in a te d D io x in s And D lb e n z o fu ra n s , , P e s t i c i d e C h em istry : Human W elfare And E n v lro m e n t", P ro c e d u re s Of The 5 th I n t e r n a t i o n a l C ongress On P e s t i c i d e C h e m is try , 3_: 3 1 7 -3 2 2 , 1 9 8 3 . 5 5 . SC. R. Rao ( e d i t o r ) , P e n ta c h lo ro p h e n o l: C h e m istry , P h arm aco lo g y , And E n v iro n m e n tal T o x ic o lo g y , Plenum P r e s s , New Y ork, 1978* 5 6 . S . K u lk a rn i, " P o l l u t i o n A sp ects Of The Therm al R e g e n e ra tio n Of S p en t A c tiv a te d C arb o n ", R adian C o rp o ra tio n , R ese arch T r ia n g le P a rk , NC, 1983. U npublished. 5 7 . P . B. Hillman, e t a l . , S c re e n in g S tu d y On F e a s i b i l i t y Of S ta n d a rd s Of P erfo rm an ce F o r Wood C h a rc o a l M a n u fa c tu rin g , EPA C o n tra c t Number 6 8 0 2 -2 6 0 8 , R ad ian C o rp o ra tio n , R ese arch T r ia n g le P a rk , NC, A ugust 1978. 5 8 . B. 6 . L ip ta k , E n v iro n m e n ta l E n g in e e rs Handbook', Volume 3 , C h ilto n Book Company, O n ta rio , Canada, 1974, p . 283. 5 9 . R. M. Dykes, A Review Of S ta n d a rd s Of P erfo rm an ce F o r New S t a t i o n a r y S ources - Sewage S ludge I n c i n e r a t o r s , EPA C o n tra c t Number 6 8 -0 2 -3 8 1 6 , R adian C o rp o ra tio n , R ese arch T r ia n g le P a rk , NC, J a n u a ry 1984. 60. R e p o rt On The 1980 M an u fac tu rin g I n d u s t r i e s E nergy C onsum ption S tu d y And S urvey Of L arge C om busto rs, D 0E/EIA I-0358, U. S. D epartm ent o f E n e rg y . W ashington, DC, Ja n u a ry 1983. 61. K r a f t P u lp in g : C o n tro l Of TRS E m issio n s From E x i s tin g M i l l s , EPA -450/278-003b , U. S. E n v iro n m e n tal P r o te c tio n Agency, R ese arch T r ia n g le P a rk , NC, March 1979. 6 2 . A p p lic a tio n Of C om bustion M o d ific a tio n s To I n d u s t r i a l C om bustion E quip m e n t, EPA -600/7-79--0 1 5 a , U. S. E n v iro n m e n tal P r o t e c t i o n Agency, R esearch T r ia n g le P a rk , NC, J a n u a ry 1979. 6 3 . Im pact Of B u rning H azardous Waste I n B o i l e r s , SCA C hem ical S e r v ic e s , I n c . , B o sto n , MA, A ugust 1982. 64. Standard S ite P lan For C h lo rin ated D ioxin Sampling At Combustion Sources ( D r a f t ) , EPA C o n tra c t Number 6 8 -0 2 -3 5 1 3 , R adian C o rp o ra tio n , R ese arch T r ia n g le P a rk , NC, Ju n e 1984. 6 5 . Sam pling G uidance Manual F or The N a tio n a l D io x in S tu d y , O ffic e Of W ater R eg u latio n s and S ta n d a rd s, U. S. E nvironm ental P r o te c tio n Agency, W ashington, DC, May 1984. -63 i - - t -y Appendix A O'r.:- 4 Number Of S o u rce s To Be T e s te d I n A S o u rce C ateg o ry The number of In d iv id u a l sources to be te ste d w ith in each source categ o ry depends upon s e v e ra l f a c to r s , In clu d in g the purpose o f the te s tin g , the number o f so u rc e s in th e so u rc e c a te g o ry w hich have been te s te d p re v io u s ly ,, and the- `""" i - ' > V ' ' " V . ^ - rW '- - - . t - ,v "" - '' a v a ila b le re so u rc e s* C a lc u la tio n s have been made to e s tim a te th e number o f sources w ith in a p a rtic u la r categ o ry which should be te ste d In o rd e r to c h a ra c te riz e s t a t i s t i c a l l y the em issions from the source c ateg o ry . In o rd e r to determ ine the number of te s ts needed, Inform ation concerning the v a r i a b ility o f em issions from the source c a te g o rie s Is needed. Since emis s io n d a ta a re n o t a v a ila b le f o r many so u rc e c a te g o r ie s , th e m u n ic ip a l w aste I n c i n e r a t o r s o u rc e c a te g o ry was ch o sen a s an exam ple In F ig u re A-L to e s tim a te the number o f sources w ith in th is categ o ry which should be te s te d . Based on these d a ta , I t has been determ ined th a t to c h a ra c te riz e th is source category in a - s t a t i s t i c a l l y s i g n i f i c a n t manner ( l . e . , a t a 95 p e rc e n t c o n fid e n c e ), betw een 14-39 t e s t s would be re q u ire d (s e e a t t a c h e d ) . More s p e c i f i c a l l y , 39 t e s t s would be required I f the re s u lts of each o f the six previous te s ts are used In the a n a ly s is . F o u rteen t e s t s would be re q u ire d i f c e r ta in so u rce t e s t s b e lie v e d to be n o n re p re se n ta tiv e a re n o t co n sid ered In the a n a ly s is . Assuming a c o s t o f $90,000 per source te s t (In clu d in g non-dioxin a n a ly se s), I t Is c le a r th a t the e n tir e T ie r 4 budget could be sp en t te s tin g em issions from only one source category fo r s ta tis tic a lly rep resen tativ e re s u lts . W hile i t w ill n o t be p o ssib le under T ie r 4 to sample enough so u rces to o b ta in rig o ro u s and s t a t i s t i c a l l y s ig n if ic a n t r e s u l t s , a reaso n ab le number of s ta c k t e s t and ash sam plings should be perform ed In each so urce c a te g o ry . The -6 4 - r- F ig u re A - l. D eterm in atio n of Sample S ize From M unicipal Waste I n c in e ra to rs :t ' ^PROBLEM* D eterm ine number o f m u n ic ip a l w aste1 c o m b u s to r s - th a t's h o u ld b e t e s t e d ^ l a o rd e r to e stim a te th e .a v e ra g e d io x in em issio n r a te w ith in a 5 ng/m2 I n te r v a l w ith 95 p e rc e n t confidence* M unicipal Waste Combustors: T o ta l p o p u la tio n 3 40 S ite TCDD (n g /m ?) A v^.V \ . `,-2 4 0 : .' c ; 6.3 D -'3.15 E 1.2 F ND Assume: Sam pling from a f i n i t e p o p u la tio n w ith o u t rep lacem ent N z2 SD2 d2 (N -l) + Z2 SD2 n sample size N p o p u latio n s iz e 40 Z * r e l i a b i l i t y c o e ff 2 (95Z co n fid en ce) SD * s ta n d a rd d e v ia t io n d c o n fid en ce i n t e r v a l * 5 ng/m2 Case X: ( a l l s i t e s l i s t e d ) x 46.7 SD - 8 7 .0 a " 40 (2 )2 (87)2 - 39 52 (4 0 -1 ) + (87)2 Case l i t (d ro p s i t e s w ith h i g h e s t and lo w e st a v erag e TCDD l e v e l s ) ;x 10.1 SD - 11.46 n - 40 (2 )2 (1 1 .4 6 )2 - 14 ' ii - 52 (40-1) + 22 (1 1 .4 6 )2 SOLUTION: In o r d e r to e s tim a te av erag e d io x in e m is s io n r a t e f o r m u n ic ip a l w a ste c o m b u stio n s, 14-39 s o u rc e s sh o u ld be t e s t e d . Based on 95Z c o n fid e n c e , r e s u l t s would be w ith in 5 ng/m2 o f tru e mean. - 65- f confidence In te rv a ls around these mean em issions should be f a i r l y n arro v to allow com parison among so u rc e c a te g o rie s * The c o n fid e n c e i n t e r v a l around a mean I s given by: r + tg s Vn~ The s iz e o f th e co n fid e n ce i n t e r v a l , th e r e f o r e , v a r ie s w ith th e s iz e o f th e sample (n ) and the value o f the t s t a t i s t i c . The s iz e o f the t value v a rie s w ith the d eg rees o f freedom (number o f sam ples minus one) and the confidence . c h o se n . Some exam ple v a lu e s o f th e t s t a t i s t i c a re shown below Number o f Samples 2 3 4 5 95% C . I . 12.706 4.303 * "'3 .1 8 2 2.776 t S tatistic 90% C . I . 6.314 2.920 2.353 2.132 - e.05/V n8.99 2.48 1.59 1.24 In s p e c tio n o f the above shows t h a t , beyond th re e sam ples, th e re a re d im in ish in g r e t u r n s . S i m i l a r l y , th e e f f e c t s o f 1 /n d im in is h beyond na 3*. For t h i s r e a s o n , and fo r p r a c tic a l c o n sid e ra tio n s ( l . e . , re s o u rc e s ), a sample siz e o f th re e te s ts w ill be co n sid ered o p tim a l f o r th e purposes of th is stu d y . T his approach a p p lie s to the number o f so u rces where a sh sam ples o r s ta c k sam ples would be c o lle c te d . -66-