NCD980602163_19970117_Warren County PCB Landfill_SERB C_Environmental Science & Technology - Long-Term Measurements of Atmospheric PCBs in the Vicinity of Superfund Dumps-OCR

F:on Hite s ID:812-85 5-1076 JAN 17'97 15:06 No.002 P.01
RONALD A. HTTES
School of Public & Environmental Affairs
Indiitna University
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Date: l / I 1 LCJ'l I 7
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F:on Hite s ID:812-855-1 076 JAi·~ 1 7 '97 15:06 No.002 P.02
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' &~rlo~lfrozri ENV1RONMENTAL SCIENCE & 'l'.KCHNOLOGY, Vol, Z3, Pa,e 1263, O~tober 1989
Copyright ® 1989 by the American Chemical Society and r(•prlnled by permle1lon or the copyright owner .
.... ~ -· .. . . .
Long-Term Measurements of Atmospheric Polychlorlnateci Blphenyls. In the
i •J . ' . .
Vicinity; of Superlund Dumps · ' 1 I • . • :-I • • , • • f
Mark H. H•rm~ntont end Ronald A. Httes•
;.
School or P~bllc'aiid .Envfrcinmei·ntai"A'fte~s and Department of Chemistry, Indiana University, Bloomington, lndla;na 47405 .. . . : '. . ·-.. •. . ,. .. '
•")~ ... .,. ,'f r.·• ~~••-..f!' .. :4-r1"':11J f-i_....._j,,~t•, ,,~ .... ~ 0:,~'f':,'
1,1/rQ-;.,ut~(,:.~ ·~·.. -· -, .' ,. : -~· • · .: · .'. .. · "~ ~ _,, ."(/ ..... _, .... ~-... -~, .l,,J_ ......... ,,I\! .. , ..... , .. 1
!~.a}ycblQfl,nt'ted biph~~lsJ(P,C13s).are.ubiqultoua con-
taminants jn Uie~Ero-.th's atint>&pher~dl-16), Previous .
atudies-~a~e-1lven '18'1·ome ,infdrmatfon on typical at~
mosphefjc ~ricenttatioh11,"geographical variability, and
vapor:-par~oulate: partitioning .• l!owever, there are two
problems with the,e data: 1 FirAl; bee&U.$e data reporting
eoli~Jbes·,ha"e ~volv~d ove~,1,l~e, the\'~ is a considera1;>Ie
variaUt>lfjnjthe.pl.lblish&d.data., For t1:wnple, some etud1es
have idetttifl.ed:t.he ro~erol4li>OB tnlxture (6-8, 10, 12);
ebme-&tudilis hive quantltet&d -ttotal·MB" as the sum of
·, ~~ ,_J \ -.l ·~•ti;f _.., ·1 .~ .. , ·1· __ ; 'r~ r1 :,'"" .•ft. 1.:-·;;·~ .i -1/::,:~ · .
·,,p.,fufu atiilrt1e~•l::eJte1 fotiGtlt·OO&i Studioa, University of
Wisconsin-?~Ulwaukee, Milwaukee, WI 68204.
• UI' ·. . .. ~1.
two (9, 13, 12) or thre6 (6; 10)' ooln'?nerblalnilxtut&s; 'en'd
somE! studies have ldentffled 1epteEl&UUt1ve i>CBi0<>11genel'A-
(J , :J, 11). Other studiee have reported PCB ooncentrations'
in both vapor a11d particulate ph8888 (1, JO, 13), while
otheri; have reported only a .. PCB"lVa1ue''(2!.;S;'1~9,:· Tfie
sec:ond problem relates to' aeuonil ·varlab1Uty>";1n ()\J,r
earlier studies 011 lele-·Royale in Lake ·superior ~!);:we
ohR6rvsd a large seasonal variation in -atmospheric PCB
hwel~. For example, th& PCB oonO&nU-atlona ·ht ·tHe ,um;:
mer were 5 times higher thin the'concentration11 in tha
winter. If there is a large &eoonal variatiol'l; thia•further:
complicatea the compariaonof the:data cited above'.' we;·,
therefore, thought it.-waa•importent•0to determ'itte the·
seasonal variability of PCB conoentration11 at one location.·
If it were possible to underat.and the funotional ·re'Iationahttf
bet.ween atmospheric concentration ind temperature, it
would then be pos11ible •to·,corteot ,future ·atmo1ph&rio;
measurements to a cori:ut1oh ·U1rdj)6tii\:.u~rfa·'°1de1' to ochiovc comparabillty;-1 ,,.-~. ,1··1··,:·t ··:·0·~ .... -. .,. , •• .,,..at: .. "·1•
_Ol~r study Ulled l?.~J:te~I~p~_g. ~t·ft\~ltlp~e•si.~81
w1t.h1n a local uea, em.plo>4e'd, quan'tlutiotH)r -AUai'ge,
number of PCB congener& in both<Yapor ~d-partioulate
phasos, and included tilmptiratuttei>bi"'litl~ ~t~.r•
cally, we sampled airborne vapor and piutic-ule.te•ad&broed
PCBs at three sites fo the Bloomington, IN', area from
Oct-Ober 1986 to Aug\18t 1,988 .. L?~•~rm wnp1ln8' ~~~led·
us t.o observe soasonal cliana-ee m 1nd1vlcl"ulll CiOngener and
rouil vapor and particulate --PcB·oon~ntratlona;changet·
in vapor-t<>-particulatt partltlorung,.fuid 'VariabUit5' of PCB;
concentrat.lon_s amo~g1the1'hr~·s{tea; In·1t\tld!_tJ9n; ~i~
i;tudy prOVldes baa~line attnbsph~rtci MB oorto&ntratlons·
for the Bloomington atM;'wh'gre)ti'traali~fuel&d ltlclhel'atof
is proposed for thermttl :dettruetton -0f -600000 mt of
F:on Hite::: ID:812-855-1076 JAi·~ 1 7 '97 15:07 No .002 P.03
,--··-, ~-· : ,✓.--· r l , ,: j I
--~ ..... .J ) "·~
D
I
.... i J lnt,rom ~torag, 1-tilit; •·:f"'-••··-·
J -81tch1lor. LJ o __ _
,nilt
I
., ... :•.·•
,iour•··,. e1oom1iieton1,· INOarei air' 'umpllng locations, Sup&rfund dump site&, prop011td lncl~~.tor site, Ind lntitrlm 1tor1ge tacllty Ille.
PCB-contaminated tnaterlaldronrtbree Superfund dump
•eites and from an ·interim POB etorage facility (see Figure
l " :.1).-:,· ·•·. h. ,·; ~-,·:~·-.-:~ ~: ,1/t-''" ·~_;I ,-;
•·• 1 ,• •: • · • I , , ... ~••r 1 • 1 • '• l •• 0 • ,
r·''l ~xpe~.i.ment'ill .Section . •:, ( ; I., .. ,,,.
i ija.i)lpllnr·Sltet,-We located~ wnplen on rooftops Jn the Blot>mh1gton atea to correspond to locations where
, · , -•the atmosphere,ts· expected·to •be affected most and least
by sta:ok eml.Asiona frorri' the proposed incinerator. These
, .. , . : areas.were idontitled hi .a riik;aaaeaament model (17). A
• -: · ... , :ilite . in · downtown ;Bloomington, ,an the Monroe County
. · · · :Courtho118e (1ee Figure 1), wu ·closeet to the Superfund
:., : ; , ,dwnPB, but it wae in the area &xpeoted to be affected least
.. J,: by .tb6 ~tack 'emission. Thebther sites, on the Batchelor
. , ir,. Middle School and on tho former Sandere School, were in
. ,, .. Afoia.ofleaa urbruHievelopment out nearer the proposed
') · -, 1incinerator,and in ,areaa of-troator estimated effect of the
, , · .,~taok,emwiono.• 'r.he&toheloralte v.aa also ~l km from
the interim 1tora,ge faclllty, ~lilob was being filled with
,,,,1 ,.PCB-oon~a,:,ed me.tomudurlni part of our sampling
,_ ~ · period {April to-Octobot .i987). · All Superfund sites, the
interim 1tor11ge facility, the prQpoeod incinerator site, and
-: ,o, ~Ul:-three 61UX1Plin~ locations "1or&iocated within an area
! ~,. of .128, Jkm8·("8"tnl ). -:··•·, ..... ~-:, 1
.. , .. , ~ SdlPle O.Ollo.otlon, We collected wnpleB with Hi-Vol
1 ··',': ,.1~,..-~plo~·($_ion-•1,Mfseo,1 Berkeley, CA; Model 650)
· , . ·· ·· -rno<iif\&d ior slniwtaneous-p:art(culate and vapor collection
. . •. usfu,ji iyetem ♦vA1ua.lei1 .by L'ewf,,et al. (18). Particles
· · ·-~ · Jar,er;thap 0.1 µmin di~et,rwe~e·eollected on a 20.3 cm
, ; . )< -~5.4 ~.af e-lasa fibet filtet (OFF) (Gelman Science, Ann
,-,:1 •• . ...Arbor'.-Ml);;the:flrat -traplnlilie.eampler aintream, The
' filtet1 we~ heated at 4!0 •C ·before aampling to clean
,. . ,ther:n:~·: PartloQ!ate ~PllnJ .ihcluded Jravimetric mea-
. 19 9
surement of to~ _11~pe11ded partlculato loadlnie (TSP).
Vapors were adsorb~dJri~. a 9,6 cm >< 10,-0:cm poly-
urethane foam plug.(PUF• cartridge behind ,tbe GFF lo
the sampler air. •tream ~ti). Betore iampllri&, ·the PUF
cartridges were cleaned t>y.eoxhlet eitta-ction ln •-ootono,
dichloromethane,·and pettoleum ·ether·(eacti-for:24 h).
Samplen were r.alibrated with a -venturi calibrator (Sier-
ra-Miaco: Model 1080) every 6 m·ontha or whenever &am·
piers were moved or repaired:' Flow was aeUo' a 'known
amount, approrlmatety ·o:5 m8 )nin~1• before the' oollection of each sample.•' r ·· ·,,.,. •• • .. _. · ·· .,_ · :·! •· · -
Our sample volume&·rant~.trotn 7,00 -m• ln'slllntner to
1500 m8 in winter.''Wo.eelectMtheie'vol~ ~(.ite they
pro .. ided ,ufficl~nt _a~dlf 1~jh~.' i>l)~~r$tl?.~ J~f. many congene?II at a 11grtal toblarik ratio of at ¥~a.at 6. Break-
through of di.' throujh' ·~tiiu:'lµpf,o '. ~~e~eif pi~ a po-
tential problem becauae the~ ,Mi;n.ol<>Jlf~~ t:o1.~t-P.er; make
up 94% of Aroclor 1242 (19), whioh wu prt188nt in the
Bloomington dumpa. Some dlchloro OQnge~!'°' IQ partic-
ular would be prone ,to hreak~rous'b'.,· a.e' <>"P.aerved by
Burdick and Bidleimtn (~O);:~u.se-of their hlgb~r vapor
preaaure11 (21). Wtl'~sted !ot brealc:tN'ougb ~Ollf timea
?uring the pro~&et. hr, cioll~ng i>qB_~ on::~. PU~ plug cut
into upper and'lo~er halvee. 'l'h~ hM~~~r.ueparateq
after &amp ling ana analyied for PC&.· The upetreakn half
ahould contain '?host' or .all of thtPCBIJ"it 1>ti!~oueh
has not occurrML Tliuk~~-u~~~ t6 lo~l!t tatlo would be
high if no breaktbrbulh·tw'o&uned,!:':A(ratl~ &qlial to or
less than 1 inl,ileitte 'btrMlU'6tigh. ··'ReaulU bf out ex-
periments show mouurable -quantities of only a few di· and
trichloro congenere ln the lower PUF pltJi. Upper to lower
ratios or less than 3 w~re'·f~\µld only'for· a few ~chloro
congeners. · , · '' · --· · ·· · -,.· ··
·,.
F:on Hite s ID:812-855-1076 J R t·•l 1 7 ' 9 7 15 :08 No .002 P .04
Table I. Total Vapor and Partloula~ PCB Concentrailonr. and Air Temperatures tor 'fhree Bloomln~on 8lte1
Courthousu Bat.ch&lor Bandera
Julian • ,apot, ni/rA'· ·
year day Court.ho~ .8a\che1.or Sanden
partic,
ng/m8
partk-,0
µg /r,
partic,
ng/m'
partlc1 pa.rtic,•
'tliim' 11o1/s
av
temp, •c
. ' --✓~ 86 800 •· • 0.47 • nm :· • nm 0.071.1 nm nm nm nm nm 16.1
86 816 Cl.40 , nm nm 0.053 nm nm nm nm nm -~.0
86 888 • nm , · 0.68 nm nm nm 0.043 · nm nm • nm 4.2
87 •· 15 • 0.81 nin• nm 0.000 nm nm nm nm nm · ..... 6.8
87 :28 • · nfu 0.83 nm nm nm 0.018 0.45 nm nm ,6.l
87 ,29 ,, · •nm · -· nm 0.88 nm nm nm nm ·· 0.oo.6 ·· 0.18 8.7
87 48 0,24 · ; mn nm 0.032 0.26 nm nm nm nm 6.8
. ·57__ ;70 0,71), . :, I? nm 0.15 2.1 run nm . ;, .;,run .· . -nm 6.Q , . •. 87.. .:12. -~ -~---~~ ·. :.:. '. ,, .-rwi ..... , O.fS nm llln nm .nm,, .. ,~ , .,..o.~ ... · .. · .-0-7~. " .. · , .u.~ .
· 87 aa,. .. suns·,. . 1,1 . , nm run mn 0.097 ·02._600:.:. :,,• 'on_i:r.l.·2.,, ; . ,. rnn . 18.8 ~ sf . 'i 1<5s , . .>· 1.s \l :,· . . o.~5 _ ... .-2.s 0.01s 1.6 0.001s .o:i. o.,s 1~.\'I',
·.87 1 , 138 ,• : , .5.( ;•.,. , -tl 1 ·;., 1.8 0.087 0.98 0.0047 0.08 0.Ol'i7 U 27.'5
87 . 166 6.8 ... . . U . 8.0 0.18 1.6 0.030 -0.16 0.11 0.67 82.4
87 194 6.9 1,7 2.8 0.0048 nm 0.0071 nm 0.41 nm 26.6 1 :;-: · ·lit·•--~ ~-::f-., , ..... ·i!~· .. ,· .. : ~a g:~~5 g:~i . g:g~: ·· ~:;i ~;,2 ~;9 ~::
· 8'7 ·• 287 .. 2.9 ' · ' ' 2:.C · 0.SOt 0.11 0.98 0.21 ·u · 0.083' 0.69 18.4
·•87 · ·220 ·· , o.a7 · : o.M, ·· · s.e o.oa2 o.n5 o.oas ·1.0 . o.069 2.0 19.6
, _67 .. • 848 .2.0 . . . . D,,24 .'. 0.32 0.063 nm 0.025 0.98 . ,_o
0
._
0
0
2
1&
7
. 0,45 4.2
88 25 0,30 , , I 0,036 · • 0,18 0,081 2.4 0.015 0.42 0.21 -7,9
. 86 ;63 · .Q.86 · 0121 . 0.28 0.071 0.79 0.039 0.15 0.0084 ·nm 12.~ -, as "· '76 --•-: • ''Mr'··· ·••·· 0.12 "•-o.oe 0.0~16 o.f!r. 0.0009 o.so o.oss· 1.3 1.6
' 68 .. ·. 110 ·' i .1 .. : . ,., nm '; ,: nm 0.0[,4 1.0 nm nm nm nin 11.7
88 111 U . : . '. ·0.60 0.28 . 0.052 0.72 0.064 -0.86 ·0.089 2.2 17.8
· 68 144 . 2.6e ' 1,1 1.1 o.029' 0.63 0.010 0.30 0.027 . MO 19.8
' 88 168 · , 8.4f 2.8 · · · 3.6 0.079' 1.6 0.029 0.74 0.41 9.6 21.8
,88 193 . 9.3 , . 1,7 . . 1.6 0.075 1.3 0.097 0.49 . . O.OM · ·. 0.4'7 · 24.4 ·
• ~;I ,: •• ;~5 i. 20 ,;.. 4;a s.o 0.11 o.s2 o.085 o.ss . o.088 o.76 a5.B.
' ·•POB·oonoentratlon,-peryram of toUI tuapended parlldo11 (TSP). bnm. not meuured becaUlle DO ~pie'waa tllk~n. "Duplioa~ ~~­olUNtnenu. · · ,; .:. , . :·. , :·,. -. .. · · · · · · · ..
· Sample Anllyaes,, After ~ing welghed for TSP, the
~lass iiber filten1 were extracted with ·benzene in a Soxhlet.
.iapparatua for -24 h. ,;p{JF Wii enraoted in petroleum ether
ifor ·24 h in a·tioxhletlapparatua built~apecially to ace om•
•modate I the ilarse ~rtridge: • ;k · known amount of
2,2'.8;414',5,'6;8'-octathloroblphenyl [IUPAC no. 204 (22);
·Ultra·:so1entific, Hope, Rl}'.wu idded to each GFI<' and
PUF betore sample extraction .to ~rve as a quantitation
. .et&ndard .. : . ,. · : ; . , . .. ...
· il'ollowltli e,:tractlon,~both·thePUF and GFF extracts
·were·reduood in volume; they'were·then cleaned with a
1o-cm·oolumnof8% deactivated 1ill011 gel (100-200 mesh).
,The sample ~aa eluted wlthbexane, 10% dichloromethane
in heiatie, and dichlorolhethane. The hexane and 10%
tdiohlorotnethane fractions were oomblned and used for the
.anal)ii.sof~,0&;• Th~ required·volumee of these fractions
·were determined ·experimentally et :the beginning of the
·project when we ·spiked PUF 'with the internal standard
,tmd With an A?oolor-1242 atandard:-
, ·· Quandtatlonl',:We an8lyzed till .aamplea wlth a Hew-
·1ett-Poackard :68~A-1aa chromatograph equipped with an
:'SNi election :0aptute deteot.or.(ECD), a 80-m DB-5 ca-
piUaey co1umn·(J&W Sclil\tlfitl;Folsom, CA), and an HP
7671A aut.osampler. • ELich ivapor dmple wae analyzed in
triplloa~.-·Particulate •~lhplei w~e ·analyzed only once
·becauae --they were -inuch·ieaa conoe·ntrated than vapor
,samples:~. :1::, . · .! .. ,
· 'I'he Q0 temperatute-pr<>g"tam ·ua&d a 1-min hold at 70
°C, then a ramp t.o 180 11C at 80 4 C min-1, then at 1.5 °C
1nlin•l:to;260 Qe,,and·«t 10~C niinrlto 280 °0. We used
aplltlew{nject1on•t 226 ~.();;the ECD·wH held at. !'l2fi °C.
.Helium ~er ia& .flow wae l,9t:riL mtn-1 at 70 °C. A 95 %
:argon e.r1e ~o·:irn-eth~ fnlitur~·w!&'18ed for the makeup
~b.· ,'l'ota1'flow-w'aa 2l•mlr,mln"ll;·,;." ·
-· ,Tl)~ instrumt1rltt\Vas (lftill)ra_t.edrt~tlve to the quanti-
tatlon a~dard ~(PC~ '294}, f~M1ongener apecific mea-
Sllrement.8 with a mi.xtur~ of Aroolo~ 1282, 1248, and 1282
in a 25:18:18 ratio. The wide range of this mixture includee
most environmentally importani PCB oorigenerai. The
concentrations of the indMdual ·oongenets in thee& throo
Arodors has been previoualy determined {28).-·The call-
bration mixture wu ·analyr.oo filter each group of eample1
to verify that the inatl'tlnl&nt could r11produti6· the oall•
bration. Our sampl6e O'O'n1det6rttlyahowed 61of'the·oa1J-
brated GC peaks (78 congenert). '•: ,
Field blank11 were collected and analyzed with eac1ri&t
of samples and the ·amount of the:blank wae1Jubtracted
from the sample on a oongerier~by-oongener basl.8; •The ·stze
of this correction -wanrnill, tiwlilly ;.;.,&% of thnampte.
Occasionally, for particulate ,amples taken· ln th& winter,
the correction WQ8 a& lar,e' U 40%:--The_'.linear range-'Of
the inRtrument reel)Oneeietarted ·at,c);l•ng, whtoh was at
loost 10 times the in&trum&ntal -1.bnit of dlreotlon .. At• level
of 0.1 ng, the relative ttandatd·devlatlbn·was ·...,5%. · ·
·• I '~ •
Results and Discussion '
'!'he PCB conoon'trat!ons tn the vapor phase and 1n the
particulate phase (relative to both· the alr:voh:1me 4nd t.o
the particulate weight) ar6 -giv~~it1'Teb1e I alonk with the
average atmosphedc tem:perature during thcn111.nip1ing
period. Th18 table baa been aubdlvided·by the three &am•
pling sites. SampleB were tehn 28 tlmee durlngithe period
October 1986 to AugUAt l98ll. · : . . ~.: . :·
Overall Dlstrlbutloh:' Oono&11!'Atk,rtat>!the·\'a.p6t and
particulate samples w&re av&rag&d •t,ver :a11 loMtlori& ,~a
temperatures on a ·eongflneMpeciflc baJll. · lf ·airboma
PCBr. in Bloomington were derlv&d only' from 'the Aroolor
1242 present in the Sup&rtund dumpl;-theae' ,verqet
should correlate well with th"b' 60tt1f>b8ttto1'i"~f th18 ~tor
mixture. On a conganei'tiy-dongen~tbUl•1~6'0iloula~
a correlation coeffiolein <r) :i,f Q.~79 tfot'th~~e.por:-pha,~
and 0.672 for the particulate pha.se"(ses Figure -2).· For
F:o n Hite s ID:8 12-855-1076
•·· .. ,.
I I,,
....
;, j
!I
r,.01 \';1r,. • O.WI', ' ---
./ h H I . ~·-.....
• 0.IJl:.t ~,.
fl.001
-~.ed.':.·,·•·· ..
.ij ... ,.;.
1<,.ooo'-, . 0.11.1
I•
},'~~I I o.oo n.' -
~
fl.OOU I ·-• t /; .C,F:-o•, 7 .. ' ,, ,,., o:<ion.1..__...._.....__.....;............._ _____ ..___,!f.-~', ;.. ··; , n 11.1 :n., -, 0 .• 1 -1 .1 ,) 10 .io
111» Ar.oolor J 24• C!Ot1~. (511 ,,
Flgur•~~-Regreap~~:of the atm()spherk: oonoentretlons of 27 PCB
eonge~&r• In the vipi>r phate ~leb axil) •nd In the particulate phase
(rtght,4~~) ver•u1,~_;00noeqT(~lon of ~ae congeners Jn Aroclor
1242. i . ·•;; :, ... • r,: .1 ..
_ · (:lf1 ...----. ---, _ __.......,,__ ______ --, TJi1~r,r
• ,\, -•. I
:1, . · • .25 negr®A of fr~otn~ ,the a!.gruficance level i8 0.487 at the
--· .. , _;99VD ¾onl:i:>Cco~d6.t\C8, .. our~i'.alues.are, thus, highly
. .., ,. ,,correlated. 'Although-theteiunore-acatter than we would
... , . . lik,, it.ill cl~ar. that . .the ;atmo.apheric PCB composition is
''limilat to ·that -of 1Ar,bclot -1242, ·the major PCB mixture
..... , ePr~ent jn.:the d~pa ... No.te that.the particulate concen•
~L .. :_ ,,,tra.t1ous.(pgn't'-Xl& otF~.2) ad:afactor of 100 less than
11 . . --the va_por~phaae t,onoentrationa~left axis). Thus, the PCBs
· in Bloomington'e .atmo8pheH . .are..primeirily in the vapor
. '· :phaae! ,-.. 1 · ' · ·. •'.' , ·•·.;.,.; ,·
: ,. · .,_ .:,;. Se.iBQJll\llklld •Site1Compa.rllona. The effects of
: . r:.: · 1·changing·ll~JD1>n11 or.-in effect, ·chahging air temperaturo,
are apparent in•totaJ vapor .PCB concentrations at all three
, ,, sites, whe~.hiiher,concehtrations occur in warmer month~
... , ,, and l6Wef1n th~\Wlnter.,~-fo,faotrthe most concentrated
• , .. , , · iYa.J)or sample obeer\'ed during,the project we.s collected on
1,,,._, ., · · the wann88tday-atthe Cowthouse'elte. The sample taken
on the coldest tlay lrom the ,B.atchelor site showed the
lowest vapor concentration in thia etudy. A regression on
a congener-by-coniener bait& indicated that 56 out of 61
congeners were e!gnificantly oorrelated (5% level) with the
· • , ... · <Sverage.at.m.Ollph-.~mpetature. On the other hand, the
' .;:: , ; : .p~ioµlai,e o.onoentrat~na.did l\Ot exh.ibit a eeuon11l trend;
. . .only 18 congenen ,wer$. lignifi~tly correlated with at.-
·. . • 1+1osph.eric texnperilture. :· .. ·-:
.,-:._,,. -~-: To ;elmpl}' ,show thii efi'~. wt combined the vapor nnd
particulate concentrattonsof.,achJample into a t.otal PCB
M ;J •, -value ~n~;-lllgr:ened the logarithm of theee values versus
· ,s ,. ~-.. '._the,avoi:~e ait;t.e.1W)eratur41 • .:\r4la analysia showed that
o .;_: ·~h~P9.J3:gol'.\°tft)'.1tl'ltio~:V1C~~."?fth increasing air tem-·:->• ·)· • pei:at~re ~t1\ll•Qite,, .. 1tet ·(•ee figure 3). It ie apparent
·: • ... •:, -~aHtle Ol>urthbUlitite:b mote ooncentrated by a factor
._,.,i. ,,.. • -<,f ,tr 3ithft.tl ~t~or ~Uhe ,othet'two •ites. Closer proximity
!--:v: d ,;'.,pf the, ~µJ:lthouee•i~ .to th.~,;Buperfund aites may be a
,,~ .. :/.., :1.01J1.ce.l)f th11 dlffo~noe. !rnet6,may aleo be other, as yet
·· r-~· · ·"1Il~cQ!fni.zed,-9ouroet·near the-Oo'llrthouse site. It is also ··, . .. . .. .
. .
1 -~~! ·.1,~•-.-:F!l\'.lrqn;;S~. T.1Qhno1.~•\fol. 23;-Np; 10, 1989
~ . ...,
;:,.
1.000
.100
1()0
.\0
I()
J
0.J
JAi·~ 17'97 15:09 No.002 P.05
.. , .... , .... ,
---.-. ---'-.-~ ,..:.., .-. ..,..._ ,_.,..., •• -. _..,., ,.-....... ,,.,... •• -. r., ,~ •• -. ~..,.,.....,....,.---,_ (''l') ;_._ • Cl-l'l ........
nAII •
O. ~ .! J.J • 3.~ J.~ : .H, ;l.'i J.8 J 'l
.. w, 1000 1:{l\\'<i lt!mp)
··ti· I,, I, '·''
Figure ,. Regression of 1he loge~ of the ~-k>i)artleulate ratios
for PCB oonQen&l'8 99, 1-49, ana 180~ the Inver.., of-the average
absolute air tem~r~~ur• for all ot t~• Bloomln~on sltee; There are
five, six, and seven chlorlne atome In these ,three OOllgenera, re-
spectively. The corr~latlon ooefflc~:l\ts are 0.118, 0.874, and 0.782,
respectively. •· · •
,: . .' . ' \'' possible that thia site is aimply eJthibit!nr an elevated level
due to it.a relatively more urban charaoterlst!oa. The
Ratchelor eite a~~wed the t9~est totaf!vapor'.;fCB con•
centrations deapi~ the prtisenoe of tl?e interirp storage
facility ~ 1 km A.was (see 1ig\ire 1). , : t
Particulate PCB.conc:entr{'t-lons are v.ery low and are not
as eite specific as,wjipOre. Sanders and Courthouse values
were uaually the highest, as observed with :the vapor values,
but the differencea;between thf three site• weN111ometime& .
small. We present particula~ concent~ations'ln Table I
in two forms (in ·ng m•S and'ln µg g-1 '.I"SP). \Vhile tem-
poral difference~ ~n the former co~centrarJo~B vary over
2 orders of magnitude In th& e:i.trem.e cases, the 'l:'SP-based
numbers are more .con.ail.tent .. This indicllteHhltt" change11
in total atmospheric partic\llate oonc~ntt:ation,_ contribute
LO the' scatter obs~rved in -ihe voltune-ba§ed '9bt1centrations,
Vapor-to-Partfoula~'.U.tlos.i The obseH>alion of low
particulate PCB 1.16't1~ntratfbhs.~6riip!ri-~ ~t'Jf b&ampled
vapors in atmospheri"c-aamples ~e.de ·here ~d by others
( J, 2, I 1) suggests that' ~e 'v~por~ro-p~!_cware,_ {Y / FJ rati08
in our 88.mples would 1>e high,, )n facti •W~ C)baerved widely
scatt.ered, but high (>.WO), Y./ P -ratioe &Speclally for the lower chlorinated f6tl)rerte\'s. ,. .. ,,.,,., " ,_. .... :_" ",
The functional relationship between the· V/;P ratio and
atmospheric t.einperatuf-e lias been. ~viewed by Bidleman
(24); he telle ua that the-¼oprithm ~f the·· Vf P fotio is a
linear fun_ction of thh. ti~·dp~o~ _6f the attribaph'~ri~ tem-
perature (m degrees Kelvin),: I~ most CM68, th6 .f>articulaw
concentrations in•thkr~la~?ns~'ip at~ ~xp~e,~etf·rela~ive
to the TSP. In our't4l&e, however,·.we uw only 'a abght
improvement mtha ·~~-•oh! if'l'SP'vYas'~c\ilded; thWI,
for simplicity, wl!l ·regt"l!U-ec;l thtfldgai'lt~ ijf the-V / p ratio
versus the reciprocal of the average te~~ere..ti.lie. The
correlation coefficient& between thee~ two·par~ew_ rs were
significant (9:t theSo/o 1ev-e1) i6t ~ cong~n~l.'I $?Ul of 61. AB
exnmples, F1g1:1:e·4 ahowa plot.a Of log -~y /r) ,vr~~us 1/T
for congenere w_1th·I{!P,\t:_n:~~~~1.'149, ,nd_ls,Q,.one each
from the pent.a•, h&xa•i'llh'dh&pt«ohlorolhomol9gµe cla886a.
All three congeners ahowecf similar itren'd! witli'. tempera-
ture. Congener 180 edubited V / P ratios 6 time& 1~11 than
the others, some of th'erl\"felling below'l. 'Ntitethat our
regre88ion analysis revealed no differencell''b'e1ween the
three sampling elte!J; ·tnrtteatbil."tliat 'the CV'./J> ratio is
consistent at &1 given 't(me/'?' ;; . 1 • ... ·; :_ • • '. j .~.
Comparlso~ to Oihor 'Sites . .'1rhe'~tmo~pheric PCB
~once~tratione·from•tht~ -sfot!f 4tid,f'.ton:rs~~r.'1 .othe~a,
mcludmg cont&.ttl1naled 'afU:t rel'ho~ iltea, 'are1wen m
Table II. Given t:irtf1ttfe~ft'~'t'ths.t'tefil~'e¥atlite aeems
to have on the atmo1p1"Jrie'~'tl~ettttb.ll~fiij hl}a.ttven the
(largely unknown) dltfe~n~jj in· aatripling temperatures
represented by·thlH1afaln ~~1~ tl/thdalfflcult\o com-
F:o n Hite::: ID:812-855-1076
Tabl,.JJ~ {.)o~pa.-l,o~ P~.M~~a»berlo :pee Co Doon tra Lion a
• iJt. ~}:n..,") -~►--1'..:. ,•h~•,:\.,r· i. , • ..._,~ .. _.., •• .. •~.:.:, • ' •
l.ocat.lon "" ' '. . . v4por
Bloomington, IN•· · :·.·•:• ... , · · ,. ,.;,-,,,
Monroe County Courthou1e
,ummer
winter
Batchelor Middle School
,ummer
winter
Sanden School
8.8
0.68
1.7
0.27
tummer 1.9
winter 0.88
Neal's Landfill (a PCB dump)~
upwind 86
hot.spot 8660
downwind 1800
after cleanup
upwind 225
hottpot 8900
downwind 925
Ontario, Canada
PCB dump during .cleanup
work11lte 128
6111 from aouree 92
.. 6£99 m from'11our~ 17
>100 m from aouroe 4
Milwaukee, WI•
winter 2.25
Madison, WI•
partie•
ulate ref
0.049 g
0.06
0.021
0.027
0.074
0.018
8
117 13
51
23
8
0.37 JO
summer
'Mlnntiapolla, MN
Chicago, IL
7.49 0.2 JO
9
5
Lake M!ehlgatt'
tummer
Lake Superior
8-year m6&11 summer
I11le Royalt1, Ml0
eummet
wln~r
Gulf of Mexico
m&an of five off-ahore eli.
mean of thrM on-ahore alt.es
Antarctica
mean of four off-ahore alt.ee
Indian, Ooean__
30--70° eouth latitude
7.54
5.6•
0.87 0.13
9
2.8 0.06 1
0.59 0.025
0.11' 4
0.086-' 4
• Repor'.ted u i•ometrlc mean of eeveral ob11ervat!onH.
biu,portd.aa Aroclor 1242. -'Sum of .three Aroclo!'ll. "Combined
vapor and particulate conoentration11. •Vapot-to-partlcuh:itc, per-
titionlnr not reported. IVapor oonoentretlona only. 'Thi& 11tudy.
pare these values, Neverthele8.8, it la interesting to not.e
that the atm01pheric PCB valuee in Bloomington are lower
than in some other cl ties atO'Wld the Midwest. This is true
de11pit:8 the wideapread PCB contamination in Blooming-
ton. The highest mean Bloomington vapor value is similar
to those from Madison, Mlnneapolia, Chicago, and the
relatively remote Isle Royale, Thia suggests that there is
little differenoe in etmospheric PCB concentrations as a
function ·of location .. In fact, the Batchelor and Sanders
al~ in Bloomington show lower vapor concentrations than
at Iele .Royale, but those tlt&e ehow comparable values lo
another 0"9ervation on Lake Superior. Lake Michigan and
ahoreline $.rea.B arowid the Oulfof Melico show vapor PCB
concentrations eomewhat lower than the Batchelor and
Sanders sites, but thls may not be significant. Bloom-
ington pa..rticulat.t! valuea, although widely 1cattered, t1re
eimllar to ale Royale, but much less than &ummer values
reporU,d for Lake Mich.lgan and Milwaukee and Madison,
WI. The:poncentratlons ln the vichilty of Neal's Landfill
ere much higher than the ('.()noentratlon at the Courthouse,
16 km to ~he ea.at. ·'rhla may isuggeet that the atmosphere
JRH 17'97 15:11 Ho .002 P.06
is effectively diluting vapot~pha$e .PCBs emitt.d from this
and other Superf und aj~. · · · · · ·
Major differenOOll a.leo i.ppea.r·ln·Table 11.:'Wi~ter eon•
~ntratione for Mil;w~~~ ~.,ll fa~~-ot~lO,j~~~e.r ~
wmter concentrations an .. Bloomlnst,on. 1'ha vapor con-
centrations from the Ontario oleanup rdte and ita 1ur•
roundiugs are less than observed at Neal's Landfill. The
pnrticulat.e values at thl& Ontario site, however, are un-
ui::uaHy high in comparison with vapor conoentrationa.
High concentration& of airborne particulate& during
c!Mnup of contaminated soil may have influenced thl&
re,mlt. Other major dtfferencc,s are the conoontratione
roported for the moet remot.e aiuis in Table II: Antarctlca
and the Indian Ooean. Theae concentrations are an order
of magnitude lower than the sit.ea in Bloomington; This
may be fill indication of PCB stratification between the
Northern and Southern hemiepheres,
Acknowledgments
We are grateful to I. Basu for t.echnical auistanoe
throughout the project. We are indebt.ed to Monroe
County, IN, the Monroe County Community School Corp.,
and Mr. Jerry Chasteen for allowing us to looate and op-
crnto our air aamplere on their ·properties. '
Regl1u•y No. Arochlor 1242, 68469·21-9,
Literature Cited
(l) SwackhamQr, D. 1,.; McVeoty,B. D.; Hi~, R. A. Environ.
Sci. Ter.hnol. 1988, 2j, 664-672.
(2) Giam, C. S.; Atlas, E.; Ch.an, H. S.: Neff, 0. S. Atmo,.
Environ. 1980, 14, 6H9.
(3) Jan, J.: Trat.nik, M. Chemosphere 1988, 17, 809-818.
(4) Tanabe, S.; Hidaka, H.: Tat.eukawa, R. Chemosphere 1983,
12, 277-288.
(5) Murphy, T. J.; Formanaki, L. J.; Brownawell, B.: Meyer,
J. A. Environ. Sci. Technol. 1985, 19, 942-{!46.
(6) Hollod, G. J. Thaa!a, Univen.lty of Minnesota, Minneapolia,
MN, 1979.
(7) Lewis, R. G.: Martin, B. E.; Sgont.z, D. L.; Howea, J. E.
Environ. Sci. Teehnol. 1985, 19, 986-991.
(8) S,:onti, D. L.; Howe,, J. E, Ambient Monitoring for PCB
After Remedial Cleanup of Two LandfUla Jn the Bloom-
ington, Indiana Area. U.S. ·En\'ironment.l Protection
Ageney Report, EPA/600/4-86/018 (NTIS No. PB86·
177632); 1986.
(9) Eisenreich, S. J.; Looney, B. B.; Hollod, G. J. In Phy1lcal
Behcl)ior of PCB in the Great Lok&; Mackay, D., PaUereon,
S., Eiaenrflich, S. J., Simmons, M. 8., Eds.; Ann Arbor
Science: Ann Arbor, MI, 1988; Chapter 7.
(10) Doskey, P. V.: Andren, A. W. J. Great Ldkes Res. 1981, 7,
HH20.
(11) Wittlinger, R.; Balltchmltter, K. Chemoaphere 1987, 16,
2497-2513.
(12) BidlE,man, T. F.; Olney, C. E. Bull. Environ. Contam.
'l'oxicol. 197(, 11, 442-460.
(13) Hoeein, H. R.; Gray, L.; MoGuirt, J. J. Air Pollut. Control
Assoc. 1987, S7, 176-178.
04) Locating 1md Elltimatlng Air Emi&sions from Source, of
Polychlorlnated Biphenyl, (PCB), U.S. Environment.al
Prowction Agency Report., EPA-,60/ 4-84-007n (NTJS No.
PB87•209640); 1987.
(15) Murphy, T. J.; Rt:ea:i:utko, C. P. J. Great Lake, Res.1977,
.~. 306-312.
(16) St.achan, W. M. J.; Huneault, H.J. Great Lakes Res. 1979,
5, 61~8.
(17) Application for an Air Quality Permit to Conat.ruot e
Propoeed Bloon:un,ton Incinerator Facility. Weetingho'U8(!
Electric Corp., 1986.
(18) Lewie, R. G.; Brown, A. R,; Jacbon, M. D. Anal. Chem.
1977,49, 1668-1672.
(19) Albro, P. W.; Parker, C. E. J. Chromatog. 1979, 169,
161--166.
F:o n Hite~:
: .,., ·v
I
ID:812-E:5 5-1076
.. fi l\ -: I·• I j rl -, .. ~-•. -r !, \J , ,1 ::'. •
,;
I
' ·.j,,; 11'
,r, -,··
l,_4•: t,
, l -,I 1
... ,., .. , ~-.•·
\,'
~1 • n ,·. ~!
' ~-.. ., ~ ~'
•! ,, '. ~ ,,l : •f• I(; I '( j :, .1·.'
: f ~. _. .., .. : :i,-
1· . .-·•···:,1• , .• ,
'•·· '
.'. " I
,:,·1.1.
...
.,..,, 1 ··•· • ••·'
..... 1,.
:..J•• .-. -·~ .· ,4
.. ,.·r ,.•
)••I
, .... -1 ,1,,..,, .... _, .;.
·,.
........ i ,. .. ,. I\•,• •, • •. •-,l
...
JR H 17'97 15 1° No.00 2 P.07
Received for review Noveml>er 16, 1988. Accepted April 25, 1989.
This work was supported by th~. P.nvironmental Technology
Division of the WeBt~,..,,~!?!-!8~.El~~tric Corp. :,
••:
fl•"t•
I .
.,. •·• : .. : ,.,
j ., .. , ..
.,
l -.,
6-04.-1 996 1 : 0 8At-1
Jaouary 3, 1997 .................................................................................. byFAX
To: Technical Committee and full Working Group
From: Joel Hirschhorn
TI1rough: Doris --for immediate distribution
Subject: Response to state's Air Sampling Plan
Today, at 12:30 PM I received that attached cover letter and Plan. Note that the Plan is dated
December 18 and that testing is scheduled to begin this Monday, January 6. I find the state's
behavior in providing the Plan for revie"v at this late time both discourteous and disrespectful
I reject the entire Plan and advise the Working Group to r~ject the study for the following
reasons:
TI.1e key stated premise of the Plan is "it is n.ot believed that there are uncontrolled PCB
emissions." And the stated objective of the study "is to test this premise by determining if there
are uncontrolled PCB emissions." In other words, the "scientific" position of the state is that
there are uo emissions and their study will prove this. In fact, tb.e Plan states t11at "Generally the
vapor pressure of PCBs under normal conditions in the PCB landfill in Wanen County is too low
for volatilization and cannot be emitted directly into the air surrounding the landfill." If this
position was scientifically correct, then why did EPA conduct its study to measure PCB emissions
and why did EPA actua1ly measure PCB emissions? The Working Group and concerned citizens
should reject this biased state study from the outset. There is absolutely no reason to trust the
study.
With this kind of bias the public should not accept a state agency au.d state personnel conducting
the sampling and the laboratory testing. An independent contractor and au iudependeut
laboratory should be used, and the Science Ad,isors should be given adequate time to fully
examine and review the details of the sampling an.d testing methods.
Technically: I do not believe that the planned sampling methods are acceptable~ nor do they fully
conform with the recommendations of the EPA study.
It seems as if the state is committed to use any tactic to attack the previous work on PCB air
emissions in the past. Even if sound sampling and testing found no PCB emissions today, it
would not in any logical or scientific sense prove that there were no significant PCB air emissions
in the past.
Tile planned study is to include a risk assessment, but this too should not be considered objective
or reliab.le by the public. ·-.
P. I
From:
To:
Subject:
Ron,
BOB-DR LEWIS
intemet."[e-mail]"
N. C. PCB Landfill
Post-It"' brand fax transmittal memo 7671 ,, of pages ► /
Co. Co.
Dept. Phone ;,
Fax# 6 / -J ,) Z /
I was sorry to hear that you are unable to help us refute the criticisms lodged against me and the EPA in
connec:ion with the PCB monitoring we did at the Warren County landfill. Perhaps the package that the State sent
to you was a bit overwhelming, especially at this time of the year.
In brief, we monitored the landfill shortly after it was closed in 1983 using low-volume PUF air samplers and
GC/ECD both for within vent measurements and ambient air measurements. We found only very low PCB
concentrations in the vents, except for the main vent, where we found 120 ug/m3 of Aroclor 1242 and 2 ug/m3 of
Aroclor 1242. Over two days of monitoring, all ambient air samples were found to be negative for 1242 (LOO 6
ng/m3) and below or near the limits of detection for 1260 (10 ng/m3), except for 4 of 39 samples, including two at 50
and 70 ng/m3 at the fence line (98 m from the main vent) and two {11 and 12 ng/m3) near the main vent (one
upwind).
We published this data, along with results from the Bloomington landfill in ES&T in 1985 {19. 986-991). In
the paper I stated that these measurements did not appear to correlate with proximity to the main vent. {Note: In
Table II of the paper, we erroneously listed one of the measurements near the vent as being at a nearby house.
Location A-7 for the main vent was adjacent to A-8 for the house on the data·-sheet. In fact, nothing was ever
detected at the house, 1000 m away.) We concluded that emissions of PCB from a well-designed chemical waste
landfill were found to be negligible.
Dr. Hirshhom has harshly criticized our conclusions, and somehow equated what we found in Warren
County to the high emissions we found in Bloomington. In my rebuttals, pointed out that since the PCB detected in
ambient air did not correlate with proximity to the main vent (and main source), i.e., concentrations were higher at 98
m than 1 m, ao_g since the more volatile PCB mixture (1242) was the dominant component in the vent as contrasted
with 1260 being the only component detected in air, the ambient air detects may have been false positives. Given
that we were using ECO and pattern recognition, this likelihood is high.
Do you agree that (1) based on our results, PCB emissions from the landfill appear to have been negligible,
(2) little or nothing was found in ambient air, (3) the ambient air results were likely false positives, and (4) the main
vent was not likely the source of the PCB found in air even if the air measurements were real?
If you could respond to these questions in a brief letter to William Meyer, I would be grateful. You might
also add that you know of my work and have confidence in the quality of my interpretations.
Bob