Document 0gR3yy2K6qqro008nMbomLRjb

PRI Electric Power Research Institut 6 July 1983 Dr. Carl McMillin Monsanto Research Corp. 1515 Nicholas Road Dayton, OH 45418 Dear Carl: As per our telephone conversation, I am sending you a copy of E P R I 's statement of work for analysis of dioxins and furans in PCB and PCB contaminated oil. I anticipate that Monsanto would address Tasks 1, 2, 3 and 8. However, if you feel that you can contribute to any of the other tasks, then you may wish to respond there too. Your response should include completion of EPRI Form 112 for each task and another form for all tasks taken together. In addition, you should indicate whether you think Monsanto can accomplish the work as stated using state-of-the-art technology. If you feel some tasks cannot be done, please indicate the rationale for your position. Do provide budget and timetables for those tasks that you feel are achievable. Since EPRI is very anxious to begin this work, I would appre ciate a rapid response. Feel free to call me if you have any questions (415) 855-2018. Sincerely, Jacques Guertin Project Manager Environmental Physics and Chemistry JG sms Enclosures cc: Gil Addis 34i j ^ j illview Avenue. Post OMIce Box 10412. Palo Allo, CA 94303 Telephone (415) 855-2000 V NfcV 0 3 6 9 1 6 r|T j 1 * K?22)p522Q0* Ct : Jfit c J' EPRI - RFP2028 PCDP PROPOSED WORK STATEMENT 1. 1 1, STATEMENT OF WORK 11 Background Concorno about of Cueto of polychlorinated biphenyls (PCS) on human health end the anyironment led to * ban-, on production and to regulation of usd and disposal In the United States PCB, o ften blbhded with tri-a n d totrachiorobehsenes (T/TCB), were used as d ie le o trio flu id s in cap a cito rs, trails formers and other s le o tr ic a l equipment* Huyulation of PCU continues to have a vory d ire c t a ff e c t on owners or operators of th is equipment Work a t the E le c tric Power Rosearch I n s titu te (EPRI) 1b aimed a t aiding e le c t r i c u t i l i t i e s in complying with these regulations BPRI a l s o ,i s in v e stig a tin g axtaa which may a ffe c t the future perception of the hacards of PCI e r a l t e r . the requirements for compliance* Many of the e ffe c ts associated with PCB now appear to be a ttrib u ta b le . to e ith e r polychlorinated dibensofurans (PCDP) and/or dlbeniodiaxiM (PCDD) PCDF can be formed from PCB. PCD? and PCDD can be ferssd from T/TCU i t is possible then th a t PCD? and PCDD were introduced- J..,;* in to e le c tr ic a l apparatus as trace contaminants in PCB during n w i r ]<facture or in s ta lla tio n or th a t they may be formed during normal e r abnormal operation However, there i s l i t t l e hard inform ation on the occurrence i f any of PCDP and PCDD in e le c tr ic a l equipment and no basis for assessing th eir effects The purposes of the program are to id e n tify the le v e ls of PCDP and PCDD in operating e le c tr ic a l equipment end to a tts itp t to re la te these le v e ls to the conditions of serv ies of the equipment To accomplish these purposes, appropriate a n a ly tic a l techniques must be demon s tra te d end relev an t d ie le c tr ic liq u id samploa must be selected and analysed The re s u lts should have maximum r e l i a b i l i t y and c re d i b ili ty . Ihe overall program thus includes several p a rtic ip a n ts - the U niversity of Urns with C* Rapp# as co n su ltan t, the b a tta li* Manorial I n s titu te with Kuhlman Corporation as sub-contractor and thu New York S tate (NY8) Department of Health* Where d e sira b le , equipment t r i a l s w ill be staged in order to provide' p a rtic u la r PCU oxposure scona ri os which may not be read ily available from equipment in service* The fin a l rep o rt of .EPRI program RP1263-11 w ill be used as a lite r a tu r e base A Work Tasks 1 Task 1i P reparation of Samolas The purpose of th is task i s to provide samples of in su la ting liq u id s spiked with C13 lab eled PCDP and PCDD con- NEV 0 3 6 9 1 7 IU202U 2, geners. Carbon-13 containing congeners in measurable quan t i t i e s are ab sen t in normally o ccu rrin g m a te ria ls and are d e a r l y d i s t i n g u i s h a b l e from normal i s o t o p i c m a te r ia ls by mass s p e c tro m e try . Spiking sample* with la b e le d congeners providos a unique in tern al standard for accurate analysis* S y n th e sis and sp ik in g w i l l be done by 7 _________________ v'. One grdm sifcet a l i q u o t s of . the spiked l i q u i d s w ill be s u p p lie d to 'th e round robin p a r tic ip a n ts - B a tte lle Memorial I n s t i tu t e , Nts and the U n iv e rs ity of Umea (C, Rappe) S im ila r a l i q u o t s w ill be r e ta in e d fo r use in t h i s program by the s p ik e r . This procedure minimises the risk of loss of these co stly and p o te n tia lly hasardous m a te ria ls . A re p re s e n ta tiv e of B S ttelle w ill p a r tic ip a te in the spiking procedure and the associated record keeping. The work in t h i s ta sk i s d iv id e d i n t o th re e p a r t s i V; a. Standard M aterials Six congeners of PCDr, p re p a red from C13 p r e c u r s o r s , 1 ; v i v i l i be pro v id ed to spike a p p ro x im a te ly n i n e t y (90) jS. *" 1 d ie ie o t r i o f l u i d samples of one gram e ls e a t a p p r e m i ^ F mately the 100 ppb l e v e l of each congener The ^ congehars w ill bei l.a.1 1.a .2 1.a,3 1 .a .4 1 1.a.51 1a 6^ 2,3,7,8-PCDP 1 . 2 . 3 . 7 . 8 - PCDF 2 . 3 . 4 . 7 . 8 - PCDF 1. 2 . 3 . 4 . 7 . 8 - PCOr 1 . 2 . 3 . 7 . 8 . 9 - PCDP 1 , 2 , 3 , 6 , 7 , 8-PCDP Does the use of any of these pose any separation problems with present state-of-the-art techniques? , (b ' B aseline Samples Samples of fiv e l i q u i d s w i l l be spiked w ith measured amounts (100 ppb) of each of the s i x PCDP and one PCDO congeners l i s t e d above ( 1 . a . 1 -1 . a . 7 ). The fiv e liq u id s w ill bet 1*b*1 ' 1.b.2 A roclor 1016 A roolor 1242 1 1 .a .4 , 1 .a .5 , and 1 .a .6 are prepared as a mixture in the r a tio of 1i1.3iO5. NE V 0 3 6 9 1 0 ** RP2Q28 3, 1. b.3 1.b.4 1*b* 5 A roclor 1260 Tri/tetrachlorobensene mixture (T/TCIi) Aged m ineral o i l c o n ta in in g 500 ppm PCB and 500 ppm T/TCB The f i r s t fo u r samples w ill approximate as c lo s e ly as p o s s ib le unused l i q u i d s fo rm erly employed i n the manu f a c tu r e of e l e c t r i c a l ap p aratu s* The o i l used in sumpio l . b . 5 w ill be o b tain ed from an aged tra n sfo rm e r and w ill be sp ik ed w ith A ro c lo r 1254 and T/TCB approx imating the condition of unused askarol* o. In-Service Samples Samples of up to twenty l i q u i d s s u p p lie d by B a t t e i i e from e l e c t r i c a l apparatus in se rv ic e (see Task 3 for a d iscu ssio n of the sample s e le c tio n and a c q u is itio n p ro c e s s ) w ill be spiked in the same way i t s a o |k le ft , 1.b* 1 - 1 * b .5 Spiking l e v e l w i l l be determ ined i f t t f , . . completion of Tasks 3a and 3b* Hie sp ik in g is boot * done fo r a l l samples in one, o r a t most, two ; b a tc h e s , This w ill maximise r e p r o d u c i b i l i t y and v e il a b i l i t y and minimise demand on an o u ts id e ex p ert* .* (A liquots of only ten samples w i l l be p ro v id e d .'% the U n iv e rs ity o f Umes ) . 'H 4* i 2. Task 2 S e le c tio n of Samples from In W rtpjM l a. Selection of Ganerlo Candidates The range of a p p l i c a t i o n s of equipm snt f i l l t d w ith a s k a re l or m in ersl o i l c o n ts ln ln g PCB w ill be surveyed ? and th e ir typioal and extreme conditions of s e r v ic e w i l l be d e lin e a te d * From t h i s , ap p ro x im a tsly twenty (20) generic equipment candidates for sampling and a n a ly s is of l i q u i d w ill be i d e n t i f i e d * Bopheeis i n the i d e n t i f i c a t i o n procese w i l l be on e q u ip a e n t operating under extreme condition* However, e broed enough range of samples should be planned to determ ine c o n d itio n s under which no PCDF w ill be found* A c h e r t of p e r t i n e n t h i s t o r y to be o b ta in e d on each sample w ill be developed to g e th e r w ith a l i s t i n g of d e s i r a b l e added o p tio n a l in fo r m a tio n to be re p o rte d as a v e i l a b le . The sample s e l e c t i o n prooees and the form at of the h i e t o r y c h a r t w i l l be confirmed by the SPAS p r o j e c t manager* A m ilestone r e p o r t on t h i s work w i l l be w r i t t e n . by b* Acguisl tioii' of Sample a B a t t e i i e w ith the h e lp of the EPRI p r o j e o t manager, i f needed, w ill arrange to acquire liq u id sample re p re s e n ta tiv e of the candidate type* Id e n tif ie d above in 3t>9 19 RP2028 o rd e r to su pply the samples t o ? -CRD f o r s p ik in g * Taak 1c* 3 Task 3i Gas Chromatography/Mass Spectroaoopy Analysis (GC/MS) V The purpose of t h i s ta s k i s to an aly ze d i e l e c t r i c f l u i d s c o n ta in in g PCU f o r PCOt' and RCQD co n g en ers, s p e c i f i c a l l y those lis te d in Task It 7__ B a tte lle , and NY8 [and, under s u b c o n tr a c t, the U n iv e rs ity o f Uuua (C, RuppuHt w ill uuo the b e i t - s e p a r a t i o n and GC/MS te c h n iq u e s a t t h e i r d is p o s a l and w ill Implement any improvoinantB in methodology appearing during t h i s work* The work i n t h i s tusk i s d iv id e d i n t o fo u r s e c tio n s a, PC/MS Cross Check the U nivorsity of. Umet, B s tte lle , and NY8 w ill 'analyze the fiv e samples provided under Task 1b fo r PCDF and tCDD* At a ml1nun, the samples w ill be analysed f o r t h # Six 2 ,3 ,7 t 8,X-FC&r congensrs . lis te d in Task- 1a and fo r 2 ,3 ,7,8-PCDD, The i n i t i a l *' goal fo r the lower U n i t of d etectio n w ill be 1 ppb> | Actual detection lim its for each of the sig n ific a n t V compounds w ill be estim ated Control samples w ill be ? evaluated as necessary* (If ntoessary, rep licate analyse! w ill be performed on se le c te d samples as requested by EPRI - a t an ad d itio n al oost of 13000 per samplet) Other compound, p a rtic u la rly BCD? and PCDD congeners w ill be determined whsn feasible* Any s ig n ific a n t unknown or indeterm inate peaks found in the gas chromatogram or mass apeotrogram w ill be noted* b* Assessment of Methodology ?___(and, via subcontract, C* Rappe), B a tte lle , and NYS w ill p articip ate in the preparation of a milestone report summarising the re su lts of the an alytical cross-chock, the sources of any i n i t i a l d iffe re n c e s, the reso lu tio n of these d iffen ces and any remaining unrosolved problems with suggestions for future reso lution* The re p o rt w ill be prepared in order to provide a common working b asis for the l a t e r round robin (Task 3o) and to provide recommendations to EFRI to e ith e r continue the program as planned i n i t i a l l y or to d iv ert funds for additional v e rifica tio n of analy tic a l methodology* Contaminated aged transform er o il w ill receive p a rtic u la r atten tio n here because i ts chemical complexity may n o t allcer a n aly sis of con geners a t the ppb or even tans of ppb level* Such a finding could a ffe c t the sample se lec tio n process (Task 2)* ttiia re p o rt i s not intended fo r pu b licatio n NEV 0 3 6 9 2 0 0. i RP2Q28 5, and would not bo d is trib u te d boyond BPR1 and i t s reviewers and tho p a rtic ip a n t# in th is task* o. Round Robin Analysis ? fia tte ll / and NVS w ill analyze a minimum of twenty (20) sample# (U niversity of Urnsa 10 samples) from Task 1o for the six 2 ,3 ,7 ,Q,X-PCDF congeners l is te d in Task la and for 2 ,3 ,7 ,8,-PCDD and, by standard methods, for PCBs* Other compounds w ill be determined when agreed upon between each contraotor and-EPRI Any-additional costs fo r a d d itio n al an aly sis w ill be agreed on before hand D etection lim its sought w ill be speoifled based on re s u lts in Tasks 3a and 3b* 4 Task 4i Equipment T ria ls The purpose of th is task i# to in v e stig a te the conditions under which PCODs and FCDPs might be forrad in u t i l i t y operations B stte ll# w ill have primary re s p o n s ib ility fo r supervising th is task* Their subcontractor (Kuhlman) w ill run a t l e a s t ten t r i a l # using 10 kVa single-phase teens* * formers operating under a v a rie ty of condition Contact-* i notod mineral o il o r a sk arels 'from the t e s t equipment w ill' bs sampled and analysed by the GC/K0 technique v alid ated in i Task 3 to evaluate fa c to rs which can lead to PCDF and PCUO ' form ation' Experimental v ariablee w ill include such fac to rs as arcin g , corona, high temperature aging, and v aria tio n s in ask arel and contaminated o il composition ?___ w ill provide co n su ltatio n on th is task S, Task Si Pyrolysis of Aroolors 1016, 1342 1354, and T/TCB Throe Aroclora w ill be pyrolyeed by NY8 using l i t e r a t u r e based procedures to explore th e ir re la tiv e tendencies to form FCDPe and re la te d m aterials I t has been suggested th a t 1016 and 1242 may form much lower amounts of b io lo g io a lly a ctiv e isomers than the Aroolors which have already been studied* This hypothesis w ill bo tostod using a n a ly tic a l procedures developed in Task 3 ?_ w ill provide c o n su ltatio n on th is task Task 6i Combustion of Aroolors 1016, 1242, 1254, and T/TCB V" -- Three Aroclors w ill be burned in CL&R's (NVS) model in o in e ra to r to explore th e ir re la tiv e propensity to form toxic PCDFs These experiments may shed l i g h t on the hazard posed in the combustion of Aroolors 1016 and 1242, 7__w ill provide ^ co n su lte d on on th is task* NEV 036921 RP202B rl 0 7* Task 7 Development and V alidation of a Rapid MS/MS Based Scfartin g Technique NY8 w ill develop a chem ically based screening technique to - provide a rapid, economical complement to tra d itio n a l v rigorous a n a ly tic a l procedures* The a v a ila b ility of the angles and ex trao te discussed in Tasks 3 .a , 3*o, 5 and 6 provide an unusual opportunity to v alid ate a HS/HS-baeed screening procedure rap id ly and economically* Xt may be desirable to involve an independent consultant agreeable to both NYS.and epri fo r tech n ical guidance* U. Task Ui UoportB a* P r e p a ra tio n of Monthly Itep o r ts Informal monthly l e t t e r f p o r t s summarising technical prog f e e w ill be prepared during the oourst of th is project* '1if-.? ' . b. aaaw ^ sflL .w .w aw tePt ftw rw / ?$; Kile atone rep o rts w ill be prepared on completion of i. bi* Task 2 a ? ________________ bii* Task 2b(B a tte lle ) b ill* . Task 3b(A ll) c. Preparation of Pinal Reports Final rep o rts including a l l work f p o r te d in previously mentioned milestone rep o rts w ill be prepared in publishable form by saoh of the co t m otor*. d* Sumpary Report "PCOF and PCDD in E le c tric a l Equipment" - Each con tracto r w ill p articip ate in preparation of a report summarising the FCDF and PCDD content found in .the / *fK, equipment sampled* The re p o rt would include any conclusions p o ssib le about the sources of any FCDF and PCDD found* I t would a lso include any e x tra p o la tio n s possible about the FCDF and PCDD oontont of e le c tr ic a l equipment in general* This rep o rt as w ell as ths milestone re p o rt on Task 3 may be b e st coordinated by an indepen dent consultant who i s not a p a rtic ip a n t In the a n aly sis of samples* Each co n tra cto r w ill contribute N6V 036922 rw* s a i a w r 7, ' > hi xparti# in th# ohwical an aly sis of d i o i a c t r i c f l u i d , i n th ohit r y of PCB, PCD? and PCDD and in th bahavior of lo c tr io a l quipnwnt# > NV 39 3 The University ofDayton October 3, 1985 Dr. John H. Craddock Product and Environmental Safety Director Monsanto Company 800 North Lindbergh Boulevard St. L o u i s , MO 63167 0C1 8 ^ Dear Dr. Craddock: Enclosed is an interim report of progress on the project entitled "Thermal Decomposition and Product Analysis of Selected Chlorinated Compounds and Dielectric Fluid Additives." This is only a draft and I would welcome any comments you have in regard to the content on organization of the report. As you know, at this point we have not detected the formation of any TCDFs in laboratory testing related to this project. However, our understanding of the thermal decomposition of 1,2,4trichlorobenzene has advanced considerably and I am confident that this new information will lead to future experimental success. It's my understanding that Barry Dellinger will be meeting with you at the EPRI conference in Seattle to discuss the direction of future work. If I may be of any assistance or can answer any questions regarding this report, please contact me. Sincerely, mab Enclosure Dc ,, L. Hall Environmental Chemist RESEARCH INSTITUTE 300 C ollege Park D a yto n, O h io 45469-0001 NEV 0 3 6 9 4 7