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- KWJ . 5 UNITE D STATE S ENVIRONMENTA L PROTECTIO N AGENCY I AAl/ Z? WASHINGTON , D.C . 2046 0 , 

# jt-F-f 4-qo-i s

JU LI 8 199 0 OFFIC E O F AI R AN O RADIATIO N MEMORANDU

M SUBJECT : Repor t t o Directo r - Th e Effect s o f a Copper-Base d Fue l
FROM : Marily

n yj . McCall , Environmenta l Protectio n Specialis t Fuel s Sectio n THRU : Jame s W . Caldwell , Chie f ..,--: : ^' 1 v !

Fuel s Sectio n ^''k x %-\'-V ! 'X: V ? V-V-" - •'>'• . BarryNussbaum , Chie f * - ^ w , . Fiel d Operation s an d Complianc e PolicyBranc h' .?•'*' n-dXX v ". ; r.C\

- L TO : MaryT . Smith , Directo r

Fiel d Operation s an d Suppor t Divisio n -"• ' ('- V l r.

Us e o f Copper-Base d Fue l Additive s Fue l additive s containing organometalli c compound s ca nb e effectiv e whe n use d i n diesel-fuele d engine s i n tw o modes : 1 ) i n th e combustio n chambe r during th e combustio ncycle , and , 2 ) i n th e exhaus t systemafte r th e combustio n chamber . I t i s importan t no t t o confus e th e tw o conceptua l use s o f organometalli c additive s i n diesel-fuele d engines . Organ o compound s o f barium , calcium , manganes e an d iro n (an

d others ) hav e prove n effectiv e i nth e combustio nchambe r during combustio n i n suppressing smok e o r soo t particulates . Thes e compound s affec t engine-ou t exhaus t particulates.(1) * I hav e reporte d o n th e effect s o f thes e type s o f diese l fue l additive s previousl ysubmitte d t o yo u o n th e subjec t o f barium-base d diese l fue l additives.* *

* Number s i n parenthese s designat e reference s a t th e en d o f th e memo . * * McCall , Marilyn , Ai r Toxic s Repor t t o Directo r - Barium-Base d Fue l Additives , Jun e 26 , 1990 .P. 3

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- Additionally , us e o f a copper-containing additiv e i n a combinatio n wit ha particulat e trap t o reduc e particulate s ha s prove n effectiv e i n th e exhaus t system afte r th e combustio n chamber.(1 ) Whe n variou s metal s suc ha s copper , manganese , an d lea d ar e deposite d along wit hth e soo t i nth e trap , th e autoignitio n temperatur e o f th e mixtur e i s lowere d t o a leve l wher e exhaus t temperature s ca n ignit e an d allowcomplet e oxidatio n o f th e soo t t o occur . Thi s regenerate s th e filte r t o contro l bac k pressur e buildu

p i n th e trap„(1 )
Eve n thoughmetalli c additive s produc e particulate s vi a thei r product s o f combustion „ theyar e applie d t o fuel s t o giv e a ne t positiv e result o Consideratio n shoul d b e give n t o thei r potentia l long-ter

mengin e durabilit yan d healt heffects.(1 ) M yresearc hshow s tha t ther e i s n o industry-accepte d standard tes t metho d t o evaluat e fue l an d fue l additiv e effect s o n particulates . Man yinvestigators , however , ar e testing pe r procedure s an

d guideline s se t fort hb yth e EPA . EPAi s currentl y developing first-time testing requirement s fo r fuel s an d additives.(1 ) A s an asid e o nthi s subject , i n m yresearch , I ran acros s a n interesting documen t publishe d b yth e Nationa l Researc h Council' s Transportatio n Researc hBoard whic hgive s guideline s t o transi t operator s fo r evaluating fue l additives . Thi s bod y recommends , among othe r procedures , tha t additive s underg o severa l laborator

ytest s o f fue l propertie s i nth e evaluatio n process . Th e tes t procedure s ar e mainl ythos e se t dow n b yASTMprocedure s fo r testing variou s fue l propertie s suc ha s pou r point , col d filte r plugging temperature „ accelerate d stability , gravity , particulat e contamination , et c Th e accelerate d stabilit ytes t measure s th e tendencyo f th e fue l t o for minsolubl e deposit s resulting fro m exposur e t o oxyge n o r heat o Th e particulat e contaminatio ntes t i s a sensitiv e indicato r o f particle s tha t coul d plug fue l filter s o r caus e increase d injecto r an d pisto nring wear . I t wa s designe d fo r aviatio n fuel s bu t ca n b e usefu l fo r diese l fuels.(2 ) Thi s asid e i s include d her e becaus e I believ e tha t some mentio n o f evaluatio n o f fue l additive s mus t b e mad e a s animportan t aspec t o f th e investigatio n o f th e potentia l effect s o f an yfue l additive . Lubrizo l Compan

yha s develope d a ne wcopper-base d diese l fue l additive fo r us e i n a trap-base d diese l particulat e contro l system whic hheav

ydut yengin e an

d light-dut yvehicl e manufacturer s migh t wis ht o us e t o mee t future , mor e stringent , particulat e standards . Thi s additiv e mechanis mi s being looke d a t b yth e EPAa s a potentiall yviabl e mean s fo r some engine s t o mee t th e stringen t EPA standard s se t t o begi n i n 1994 . Lubrizo l ha s submitte d thei r researc ho n thi s coppe r additiv e systemi n a repor t entitle d "A n Analysi s o f Possibl e Healt hEffect s Du e t o th e Us e o f a Coppe r Diese l Fue l Additive, " date d May1990 .P. 4

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- Thei r technica l finding s o f thi s system ar e presente d i n a pape r entitle d "A

n Experimenta l Evaluatio n t o Determin e th e Effec t o f a n Organometalli c Fue l Additiv e o n Particulat e Trap Regeneration, " b y thei r Messrs . Levi n an d Koehler , (undated) . Lubrizo l gav e a presentatio n o n th e effect s o f thi s systemt o EPAo nMay7 , 1990 , a t Ann Arbor , Michigan . Th e contro l strateg ytha t Lubrizo l ha s develope d relie s o na trap system

whic hfilter s particulat e fro mth e exhaus t gas , accumulating particulat e unti l regeneratio ni s initiated . During accumulation , th e mas s o f particulat e increases , resulting i na proportiona l increas e i nbac k pressure . Regeneratio nmus t b e initiate d whe n a maximu mbac k pressur e i s reache d o r whe ncontinue d particulat e accumulatio n woul d b e expecte d t o resul t i na regeneratio n wit htemperatur e excursion s know nt o caus e excessiv e therma l stres s withi n th e filtratio nmedia . Regeneratio ni s typicall yinitiate d b yoperating th e engin e a t relativel yhigh speed/load modes , adding energ yt o th e tra

p vi a a nexterna l source , o r b yadding a catalys t t o reduc e particulat e activatio n energy . Coppe r act s a s th e catalys t becaus e o f it s superio r effec t i n reducing th e activatio n energ yo f particulat e combustion.(3 ) M y researc hshow s tha t i n othe r studie s involving us e o f additive s containing coppe r plu s nickel , an d additive s containing coppe r plu s ceriu mtha t ove r 95 % o f th e fue l additiv e wa s collecte d i nth e trap , releasing abou t 5 % o f th e compoun d int o th e atmosphere.(1 ) Lubrizo l believe s tha t thi s i s hardl ya dro p i nth e copper emission s bucket . I hav e read Lubrizol' s repor t o n th e possibl e healt heffect s o f using a coppe r diese l fue l additive . Thei r repor t strike s m e a s being verythorough . Thei r bibliograph yreveal s tha t w e (Lubrizo l an

d I ) consulte d i n common , severa l literatur e source s o n healt heffect s o f emission s o f copper . Adiscussio n o f m y finding s follows . Coppe r an

d it s Effect s i n th e Environmen t Th e concentratio n o f trac e metal s i n th e atmospher e hav e become a matte r o f considerabl e concern fo r man yreasons . Metal s i n ai r (a ) mayb e a healt hhazard t o huma n being s an d animals ; (b ) ca n ac t a s a catalys t i n atmospheri c reactions ? (c ) maypromot e th e corrosio n o f materials ; (d ) ma yinitiat e far-reaching change s i n th e receiving ecosystems ; an d (e ) i n associatio nwit hsuspende d particulat e matte r mayinduc e change s i nth e climate.(4 ) I wil l tr yt o limi t m

ydiscussio nt o (a ) only ; fo r t o discus s al l four concern s woul d requir e a verylength ytreatis e o nth e subject . Thre e principa l huma n source s o f pollutan t coppe r i nth e atmospher e ar e coppe r productio nan d handling (46 % o f tota l anthropogeni c emissions) , ironan d stee l productio n (10%) , an dP. 5

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- fossi l fue l combustio n (11%).(4 ) Severa l studie s hav e addresse d dispositio no f coppe r i nfly

as hsample s fro

mfossi l fue l combustio nsources . Th e mechanis mb y whic hth e fin e copper-ric haerosol s ar e forme d includ e (a ) condensatio n o f th e volatilize d coppe r o r it s compounds , (b ) preferentia l uptak e o f coppe r b ysome soli d o r molte n particles , an d (c ) chemica l reaction s wit hth e condensabl e gases , especiall y S0 2 an d th e nitroge n oxides . I nth e presenc e o f oxygen , particulat e coppe r oxide s maycatalyz e th e oxidatio no f S0 2 an d i n th e proces s become converte d t o coppe r sulfate . Th e result s obtaine d sho wtha t th e coppe r i s mostl yconcentrate d i nth e smalles t (respirable ) particles . Verylittl e i s currentl yknow n abou t th e chemica l compositio no f coppe r aerosol , however , severa l studie s sho wtha t a larg e fractio no f th e coppe r i n atmospheri c aerosol s occur s i n th e particl e size s tha t ar e th e mos t hazardou s t o huma n being s an d othe r organisms , i.e. , th e smaller-diamete r size.(4 ) Th e influenc e o f particl e siz e o nth e dispositio nan d retentio n o f particulate s i n th e respiratorysystemha s bee n investigate d (Morrow , 1964 ; Stuart , 1976 ; Ye he t al. , 1976) . Fo r cupreou s (copper-containing ) particle s o f abou t 1.0-/i mmas s media n diamete r (MMD) , approximatel y5 0 t o 60 % o f th e inhale d coppe r i s deposite d i n th e pulmonarycompartment , 2 0 t o 30 % i nth e nasopharyngea l compartment , an d <10 % i nth e tracheobronchia l compartment . Ahighproportio n (5 0 t o 80% ) o f th e <l-/n mparticle s retaine d i n th e respiratorysystemi s absorbe d i nth e bloodstream.(4 ) Lubrizol' s analyse s cite d some studie s tha t wer e don e late r tha n thos e mentione d abov e whic hshowe d sligh t variance s o f particulat e size s an d dispositio n efficiencies . N o studie s hav e specificall yaddresse d atmospheri c residenc e time s fo r cupreou s aerosols . B yanalog

ywit hwor k don e o ngenera l particulat e residenc e times , i t i s surmise d tha t th e residenc e time fo r cupreou s aerosol s i n unpollute d tropospher e i s 2 t o 1 0 days . I n urba n an

d pollute d area s th e residenc e time mayb e mor e tha n 4 day s fo r particle s o f smal l diameters.(4 ) Healt hAspect s o f Coppe r Unde r ordinarycircumstance s coppe r i s a benign agent , bu t whe n huma n being s an d othe r animal s ar e expose d t o excessiv e concentration s o f th e meta l i nan yo f it s form s ther e mayb e mil d t o seriou s o r eve n life-threatening consequences . Coppe r i s essentia l t o huma n lif e bu t i s als o potentiall ylethall ytoxic . Tw o distinc t an

d specifi c geneti c regulatorymechanism s exis t i n norma l huma n beings . On e appear s t o facilitat e th e transmembranou s transfe r o f copper . Absenc e o f thi s mechanis m result s i n a hereditaryfor

mo f coppe r deficiencywhic hi s fata l despit eP 6

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- attempt s a t eithe r ora l o r parentera l treatmen t wit hcopper . A secon d mechanism , transmitte d a s an autosoma l recessive , seem s t o b e essentia l t o th e excretio n o f ceruloplasmi n coppe r fro mhepati c lysosomer s int o bile , an d mayb e responsibl e fo r th e maintenanc e o f th e norma l zer o balanc e o f copper . I npatient s i n whomthi s secon d typ e o f geneticall ytransmitte d mechanis mi s absent , Wilson' s diseas e o r humanchroni c coppe r toxicosis , ultimatel y develop s an

d i s fata l i f untreated.(5 ) Toxicosi s du e t o coppe r i s avoide d i ngeneticall ynorma l individual s bot hb

yth e actio no f thi s secon d mechanis man

d als o b yvirtu e o f th e fac t tha t th e essentialit yo f coppe r act s onl y throughspecifi c coppe r proteins . Suc ha meta l protei ncomple x reduce s th e concentratio n o f fre e coppe r ion s throughou t th e bod y an d thu s avoid s th e toxicit ytha t i s a s inheren t i ncoppe r ion s a s i t i s i n ion s o f suc hnonessentia l metal s a s lead an d mercury.(5 ) Acquire d deficiencyo f coppe r ca n b e effectivel ytreate d b y administratio n o f th e element . Acquire d o r inherite d toxicosi s o f thi s meta l ca n b e treate d b yus e o f a chelating agent , whic h promote s th e excretio n o f copper.(5 ) EPApropose d a criteri a documen t fo r coppe r i ndrinking wate r fo r th e EPAOffic e o f Drinking Wate r i nFebruary1987 . Coppe r ha s bee n identifie d b

ytha t Offic e a s a pollutan t i n drinking wate r an d theyar e presentl ysetting maximu mcontaminan t leve l goal s (MCLG ) fo r coppe r (an

d lead) . Thes e standard s wil l b e promulgate d i n Decembe r 1990 . Aphon e cal l t o tha t Offic e reveale d tha t th e MCL G fo r coppe r wil l b e 1. 3 mg/L . Coppe r compound s can b e absorbe d b yal l thre e environmenta l routes : dermal , ora l an d inhalation . Norma l dail yintake s o f coppe r ar e 2. 5 mg/day , mostl yfro mfood an

d water , wit ha sligh t contributio n fro

mair . Th e tota l bod yconten t o f norma l adul t human s i s ~ 70-12 0 mg o f copper , mos t o f whic hi s locate d i nth e liver.(6 ) EPAfoun

d tha t ther e wa s limite d informatio no nth e presenc e o f coppe r i n ambien t air . Informatio nwa s availabl e fro ma nationwid e stud

yo n coppe r concentration s i nambien t ai r fo r th e year s 1977-198 3 (U.S . EPA1984) . Concentratio nsample s analyze d range d fro

m0.00 3 - 7.3 2 p,q/m 3, wit ha rang e o f media n value s fo r differen t citie s an d year s o f 0.00 4 - 1.7 9 /ig/m 3 an d mea nvalue s o f 0.004 3 - 1.9 6 /Ag/ m . (6 ) Using th e highvalu e o f th e rang e o f media n level s an

d assuming a ventilatio nrat e o f 2 0 m 3 /dayfo r th e averag e adul t male , th e intak e o f coppe r fro mai r woul d b e 35. 8 /ag/day . (6 ) Acquire d chroni c toxicosi s i n human s i s mor e unusua l tha nth e acut e form.(5 ) Th e literatur e i s replet e wit hstudie s regarding th e nutritiona l essentialit yo f copper , bu t coppe r toxicit yfro mP. 7

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- chroni c exposur e ha s no t bee n wel l investigated.(6 ) Unde r ordinarycircumstances , i t seem s almos t impossibl e t o overwhel mth e body° s defens e agains t coppe r toxicosi s b yora l ingestio n o f th e element ° Chilean coppe r miner s ea t thei r lunc h fo r a s long a s 2 0 years , i nanatmospher e cloud ywit h2 % coppe r or e dust . Analyse s o f th e coppe r content s o f live r an d bloo d i na smal l numbe r o f thes e miner s hav e bee n normal.(5 ) Vineyar d worker s wlh o spra ygrape s wit hcoppe r arsenat e hav e show n some toxi c effects , bu t thes e ar e no t clearl yrelate d t o copper.(5 ) Villa r (1974 ) reporte d observing copper-containing granuloma s i n th e lung , live r an d kidneyo f a decease d patien t wh o had bee n occupationall yexpose d t o Bordeauxmixtur e (a n aqueou s solutio n o f lime an d 1-2 % coppe r sulfate ) during th e spraying o f vineyards . Pimenta l an d Menze s (1975 ) reporte d finding copper containing live r granuloma s i nthre e patient s wit ha historyo f using Bordeau

xmixtur e involve d i nvineyar d spraying.(6 ) I foun d man yreference s t o variou s studie s o f vineyar d worker s being expose d occupationall yt o thi s "Bordeaux " mixture . Lubrizol' s repor t refer s t o studie s b ysevera l investigator s (Pimenta l an d Marques , 1969 ; Villar , 1974 ; Pimenta l an d Menzes , 1975 ; Plamena c e t al . 1985 ) an

d thei r report s o f a syndrome know na s "vineyard sprayer' s lung, " whic hmayinvolve symptom s suc ha s lesion s i nth e lungs , dyspnea , decrease d appetite , weigh t loss , an d genera l weakness . Lubrizo l dismisse s thes e studie s a s no t conclusiv e becaus e non e o f th e report s gav e estimate s o f th e level s o f exposure . Als o theystat e tha t vineyar d worker s mayals o b e expose d t o othe r agent s sucha s arseni c compound s i n additio nt o Bordeau xmixtur e an

d i t i s no t clea r i n th e studie s tha t coppe r compound s wer e th e sol e cafstafe l agent s i n th e incidence s o f th e illness.(3 ) Gleaso n (1968 ) reporte d symptom s o f meta l fume feve r (genera l discomfort , fever , sensation s o f chill s o r warmt hand stuffines s o f th e head ) i n thre e worker s expose d t o fin e coppe r dus t a t concentration s o f ®o® 3 - ©„1 2 mg/m3

. (6 ) (Th e Federa l standar d fo r coppe r fume i s 0, 1 mg/ur 1 ; fo r coppe r dust s an d mists , i t i s 1 mg/m 3

. (9) ) Meta l fum e feve r symptom s wer e absen t i nthes e worker s afte r th e installatio n o f loca l exhaus t ventilation , whic hreduce d th e airborn e coppe r concentratio n t o <0.00 8 mg/m 3

. (6 ) Th e potentia l fo r acut e poisoning fro mingestio n o f coppe r compound s ha s long bee nrecognized . Th e unwitting ingestio no f man ytype s o f food an

d nonfoo d items containing coppe r ha s produce d symptom s o f coppe r poisoning ranging fro m G l disturbances , headache , dizziness , metalli c taste , t o death . I ngenera l instances , th e exposur e i s t o coppe r sulfat e leading t o th e theory tha t some o f th e toxicit ymayb e du e t o th e sulfat e compound . Studie s o f case s o f coppe r poisoning i nchildre n indicat e tha t childre n mayb e mor e susceptibl e t o coppe r toxicosis.(6 )P. 8

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- Othe r effect s o f coppe r sulfat e acut e poisoning includ e hemolyti c anemia , Glucose-6-Phosphat e Dehydrogenas e (G-6-PD ) deficiency , rena l failure , hematuri a an d deat h(Wals he t al. , 1977 ; Roberts , 1956 ; Chughe t al. , 1975) . Thes e effect s wer e reporte d t o occu r a t dose s betwee n 3 an d 60 0 g o f coppe r sulfat e (0.7 6 - 152. 4 g CU).(6 ) I t ha s bee nsuggeste d tha t person s wit hWilson' s disease , deficiencie s i n G-6-P D activity , an d thos e having occupationa l exposur e t o coppe r mayb e a t ris k fro mth e toxi c effect s o f coppe r (U . S . EPA , 1980).(6 ) EPAconclude s tha t inadequat e dat a preclud e calculatio n o f a Referenc e Dos e a s ther e ar e n o dat a indicating tha t huma nexposur e t o coppe r result s i n chroni c toxi c effect s t o norma l individuals . Base d o n th e availabl e data , EPAcanno t classif ycoppe r a s a huma n carcinoge n o r mutagen.(6 ) Conclusion s Consideratio n shoul d b e give nb yEPAo n th e us e o f metallic

base d fue l additive s a s theyar e use d i n diesel-engine d vehicle s an d th e potentia l long-ter m effect s o f thes e additive s o nhealt h an d engin e durability . Th e ai mo f thi s pape r i s t o presen t m y finding s o n th e potentia l impac t o f th e us e o f a copper-base d fue l additive . M

yfinding s indicat e tha t ther e ar e a lo t o f unknown s o f th e long-ter

meffect s o f suc ha fue l additive . Thi s office' s role , a s I se e it , shoul d continu e t o b e on e o f monito r o f suc h use , especiall yi f ther e i s a n increas e i nth e us e o f metallic

base d fue l additives .P. 9

Reference s 1 . Tupa , R . C. , C . J . Doren , Th e Lubrizo l Corp. , "Gasolin e an d Diese l Fue l Additive s fo r Performance/Distributio nQualit y- II, " SAE Pape r 861179 , 1986 . 2 . Nationa l Researc hCouncil , Transportatio nResearc hBoard , Washington , D . C. , "Diese l Fue l Qualit yan d Effect s o f Fue l Additives, " 1984 . 3 . Levin , Dr . M . D . an d D . E . Koehler , "Lubrizo l Diese l Particulat e Filte r Developmen t - An Update " EPA- Lubrizo l Meeting Agenda , Ann Arbor , MI , May7 , 1990 . 4 . Nriagu , Jerome 0. , Ed. , Coppe r i nth e Environment . Vol . I , Canada Cente r fo r Inlan d Waters , JohnWile yand Sons , Inc. , Ne wYork , 1979 . 5 . Nriagu , Jerome 0. , Ed. , Huma nHealt hEffect s o f Copper . Vol . II , Canada Cente r fo r Inlan d Waters , JohnWile yan d Sons , Inc. , Ne wYork , 1979 . 6 . U . S . EPAEnvironmenta l Criteri a and Assessmen t Office , "Drinking Wate r Criteri a Documen t fo r Copper, " Cincinnati , OH , February1987 . 7 . Rot hAssociates , Rockville , MD , Prepare d fo r Lubrizo l Busines s Developmen t Company , "A nAnalysi s o f Possibl e Healt hEffect s Du e t o th e Us e o f a Coppe r Diese l Fue l Additive, " May1990 . 8 . McCall , Marilyn , "Ai r Toxic s Repor t t o Directo r - Barium-Base d Fue l Additives, " Jun e 26 , 1990 . 9 . Sitting , Marshall , Hazardou s an d Toxi c Effect s o f Industria l Chemicals . Noye s Dat a Corporation , Park Ridge , NJ , 1979 . 10 . RAO , V . D. , e t al. , "Advance d Technique s fo r Therma l an d Catalyti c Diese l Particulat e Trap Regeneration, " SAE Pape r 850014 , 1985 .