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Mackerer et al analyzed 12 retail asphalt coatings and found significant potential mutagenicity with 11 out of the 12.
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Received:
.: 16th International Symposium on~olycyclicAromatic CompoundsNovember 4 - 7p 1997Charlotte, North Carolina, USA
Jan 15 2009 01:45Dm
Presentation Session: 11 Nov 7 0950-1010
MackererMutagenicity and PAC content of seal coatings for asphalt pavement
MUTAGENICITY AND PAC CONTENT OF SEAL COATINGS FOR ASPHALTPAVEl\.1ENT. C. R. MACKERER1• T. A. ROyl and G. R. BLACKBURN2
lproduct Stewardship and Toxicology, Mobil Bu.ciness Resources Corporation, Paulsboro,Nl 08066 and 2PetroLabs, Inc-
7IvYland, PA 18974
We have evaluated the mutagenicity and polycyclic aromatic compound (PAC) comem: of12 water emulsion products available to cOl1SUIIlers fOT the sealing of asphalt pavemtom.Small pails of product (5-6 gallons each) were pun:hased at local department storcs_According to the labels on the pails there were 11 coal tM emulsions (samples 1 - 10 and12) and one asphalt emulsion (sample 11). The emulsions were broken by cc:posing thepails to multiple freeze-thaw cycles~ and the ceDlIill portion of the solids fraction wassampled and blotted dry. Appro~matpjy 20 g of each product was~ for PACanalysis and testing in the modified Ames mutagenicity assay (ASTM E1687J9S). Forsamples 1 - l2, the level of solids (i.e. DCM insoluble mnerial) ranged from 56% to 91%(mean, 72.5%). The DCM soluble material was tested in ASTM E1681J95 where samples1 - 10 and 12 produced very high mutagenicity index (Ml) values (ranging from 275 to657 (mean, 445); sample 11 produced an MI of.only 0.6. The DCM soluble fractions ofsampiE3 1 - 10 and 12 contained similar amounts of 3-7 ring PAC ranging from 43% to57% (mean, 50.9%); sample 11 contained an estimated 3-7 ring PAC level of 2.6%_GeMS analysi~ indicated that samples 1 - 10 and 12 contained coal tar obtained from thesame source, but also, that sample 11 contained a low level of the same ~oal tar. In.addition., sample II did not comain pentane insoluble components such as asphaltenes thatwould indicate the presence of asphalt. The very high MI values seen fo[" samples 1 - 10and J2 suggest that individuals who may have prolonged and repeated dennal contact withproducts such as these may also have an elevated risk for skin cancer.
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CompDsition LabellnformationSample Product Name· Component CASNo. Toxicology First Aid
No.t Blacktop Driveway Relined coal tu 65996·90·9 May caUBe skin irritation.
Coating Clay 1312·58-7Silica 14808-60-1Water 7732-18-5
I 1 Polymer Fortified Asphalt 8052-42-4Driveway SealerlFiHer Clay 1332-58-7 No skin irritants.
-, - Silica J4808-60..7 Ecologically safe.Ethylene-vinyl 25067·10-0·Acetate copo~ymer
Water 7732-18-52 Dri\leway Sealer Premium- Contains no solvents May cause irritation. In case of skin contact
Rubberized Coa] ter based tinse with water.4 Driveway Contairts no solvents May cause irritation. In case of skin contact
Sealer/Resurfacer. Coal tar based rinse thoroughly withPolymer Fortified Sealer, water.Rubberized - Te.l(lurized ,
3 Rubberized Blacktop Contains coallar pit.ch May cause skin irritation. In case of contact withSealer Coal tar 8007-45-2 Harmful if swaJlowed. eyes or skrn, flush with
K.aolin clay 1332..58-7 water.Amorphous silica 7631 ..86-9
7 Driveway Sealer, Blacktop Contains coal tar pitch Eye and skin irritant. [n case ofcontact withTar Emulsion Coal t.3.r 8007-45-2 Harmfullfswallowed. eyes or skin. flush whh
Kaolin clay 1332-58-7 water.5 Drive\vay Sealer Filler. Latex, finely graded ... flusI1 with water [i.e.
Rubberized. Latex aggratales and mineral eyes and mouth] '.'formula. coal tar,
Refined coal tar 65996-90-9 --._.
Cla.y 1332-58-7Silica 14808-60-7'i\TaIer 7732-J 8-5
Page 1prd.doc
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'.
Composition Label InfonnationSamplf~ Product Name Component CAS No. Toxicology First Aid
No,B Coal Tar - Sealer Filler. Coal tar ... flush with water (Le.
Driveway Sealer with Sand eyes and mouth]...Sand Added
12 Coal Tar Driveway Sealer Refined coal tar 55996·90..9 If substance gets in eyesClay 1332-58-7 or maut h, flush withSmca 14808..60-7 water...Water 7732.. 18-5
6 Rubberized Driveway Coal tar M~y cat:ne s,kin irritation, [f swallowed. do notSealer lnduce vomiting.
10 Rubberized Driveway Coal tar May cause skin irritatIon. If swallowed, do notSealer induce vomitjng.
9 Driveway Sealer) Latex Coal tar pilch 8007-45-1 Harmful or fatal if ,..if swallowed, induceRubber Formula (Pilch Refine.~ coal tar swallowed. E~e. skin, vomiting. In case of eyeBase) Clay 1332-58.. 7 respiratory irritant. contact ~ flush with
Water_..-
1732:-Y"8~- -p1enty1Jfwann-water.Sand 14808-60-1 Irregu~ or stopped
brealhing - administeroxygen, startresuscitation.
"Sources ofproducts: Hecltingerl Ox.ford Valley, PA; Sears Roebuck, TrenLon J NJ~ Channel Lumber. Lawren:JevilleJ NJ; andGros!;man, Lawrenceville) NJ.
Page 2prd.doG
I~odlfled Ames TestLiver
Mineral MelaboUztngall Ames Tester 5-9 Mixture
(Per Assay) BacterIa (Per Plate)
E Add 3 ml of Strain Prepare a-FoldQ.to TAgS"0:1'" Cyclohexane to (400 ~t/Plate) Arocior~
0 2. ml of all 1254 Induced. SyrianCD0
V Golden Hamster LIver~
~
L.n Mix 5-9.......c
Add 10 ~I DMSO(0~ V
V Add 2-Ford (B mM)MIx Every 5 Min. NADP Cofaclor
for 30 Min. VV Add Standard Amounts
Collect 5 ml Aliquot of Other Componentsof Lower DMSO L:ayer of S·9 Mlxtu reFree of C~IOhexane
Slore In Dark at4·C Until Assayed
"'C Combine Acpropriale VolumesI1l:> In uspenslonI1l0 VCl)
~
Incubate 20 Min. at 37w
CV
Pour Into Petri PlateV
Incubate 48 Hrs .. at 37·CV
Count Revertant Colonies 930354 7
2 x 2 Table for Tumor Incidence and MutagenicityIndices for 55 Oils'
< 2 MiceWith Tumors
~ Boiling Above 50[f FoCDooN
lC)...-c.(1:1.., > 2 Mice.-
With Tumors
\.
oMI < 1
I
13 I. ' f
......; -.~ :-".1'"1 "-.-.-~ .-••-_. ~ ~_&_. '_"J..-.&' ~_•• 'lI t~.'l· -., ~. J>I'J'..J ". ~ .. ~ ..~" :J 4""" .~.-••,..:. -"... ,. J'•• .fJ _·_l:~':..· .." ,)..•.! ).. &J.J:.-':~ #~~ 4~'''' .'. '.4 ~"h 'Y /.. "~~"'-''''' M ~•• ?>;,~ ~.rr- .~_ - "":1.-_-.- '.M" •. r-, ~. 4 ~._.J (A: ::.' l..., '.' ,~.,~ ."". .l.~•. ", u.",." _t_·.9 ._ _." "Jt..--" n~_~._ -_-.~~ -...,_.~- _ ......--.to '" ~ \"r'>. "" 11;.\ "~'••A..'~ I. IJ';' -•• ~..v ,J, -_ ,..~_-r,J.'. ~
Ml ~ 1 1 1 41~ ..
u <Itu...- ~ ~ ..-. A. ".-a·.- ".' ••".'l""<! ~ _,I 0..:1>4.1.. ';,--&.: '1 :--.& .~ ~. "-:"."- '''_'.1. ~.J.. 1.'.A6V' u , ~ ~••_• ..""., .'T,' #-7.10 &_ &.- -•• -._"'rI-" ".._a_ _':. a'a '.' '" '~".. ,!.., ••4." _•••~ 14'·.), -.. -.- ••~- • .-/:~ ~~ ~.. -.~~~~_.~&~_••_ ••~. '.":-". ,"••_._" V '!._.~"'. '~_."" .\_/, 'I.. ,'4. _••__ ' •• :'_':'__•_.: ,__•_-.: .1.-:.! .~••.__& •__& ".'.':. ".' J> : __,: ".~.\. ".__' ~ _ , ~ ,••_.4 ~ '.~,.114.' •••~•••_ • :4-;' U __ •.•~ ••~.J 4' ~_•••_~_
p= .0001
GC/FID Chromatogram of a High Percentage PAC PetroleumDistillate Extract With Overlay of PAH Standard Chromatogram
EQ
CD...q
.....0
CD00N
LO ..,....C.10..,
CDC G)CD C... G.'.c ......
~cCDtU (1)
C C CG) Q) CD-.r:: ....
~c. >.0- eD
P"-t a.ca 0.....,-c N NC1J:> r: cQ.l(.l (1) CDQ.l
cr. aJ ID
930354 23
Carcinogenicity vs. 3-7 Ring PAC Content (%)
EQ.
CDvT"""oenooN
~c:l'tl..,
3·7 Ring PAC·< 10/0
3-7 Ring PAC~ 1%
P =.02
< 2.Mice .Wit'h Tumors
2---------
2
~ 2 MiceWith rumors
o
23
C:arcinogenicity of Petroleum Oil is Dep'endenl Upon theP~resence and Concentration of PAC
930354 33
Correlation Between 3·7 Ring Polycyclic Aromatic Compounds(PAC) and Mutagenicity In the Modified Ames Test for 104Petroleum-Derived Oils
E
180...... •<q
T""" 170
en . MI =0.778 x• .0760
160N
Ll")
15T"""
l:(0
14~
131211 • •
F\~ I •10 •98 "7 r =0.9206 &
5 •"'C4)
4~4)
u
3lU0:
2
2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1·7 18 19
% 3·7 R!ng PNA930354 10
Received: Jan 15 2009 01:47pm
Fractionation ofDrivevlay Sealer Emulsions
120g of samliliiJ DeM extractidD
determine wtOA. DeMsolubles
determine wtOA. '''nonas haltcnes" (solubles
reconstitute incyclohexane
"--~-~~---r
extract DMSO soluble
determine wt%DMSO soillbles/g
DCM solubles'
assayDMSOsoIubles etC-Fill
detennine wt%1-7 ring aromatics/g
DCM solubles
determine wtO/o solids
determine wt%entane-asphalteneslg
DeM solubles
. assayDMSOsolubles by GC-MS
dnray.doc
DCM Extractable Materllt In 12 Driveway SI.ler.
Sa[·np(~ No.
Fractlonatton of the OeM So'ub1e Components
B S8mple11
p,P'Jlin.fnsoJubit
99....-------Pol.,
p."fllnHtphrhtm/tFrI~flon
PentaneExtraction
DMSOExtraction
Modlned Ames Test Results for 12 Driveway Sea1ers
BOO .
E0. 675CD
vor-
" 'I~
CD~
~ IN600 ..
I.l"Jor- 557c::
"'...,518-i-liC
V421~
.E Jg7
.~ 400U'c~g~
200
""CGJ:>.-GJ(,JQJ
I:X:
0,6
0 ----l ---l ---l
2 :3 .{ 5 6 1 tl 9 '0 11 t2
Sample No.
1 - 7 Ring Aromatics Present in the DMSO Fraction of Samples 1 - 12(Expressed as % of Total)
Totaf Polycyclic Aromatie Compounds
SAMPLE 11
8. Polycyclic Aromatics
SAMPLES 1-10 1 12
1
Aromatics Found ~n Ring Groups
A. AU Aromatics
SAMPLES 1 ·12
35 33.1"O.B
30
~ 25t'1E
~ 20~
15
10
5 1,32:1:.51
01 2 3 4 5 6
Received:Jan 15 2009 01:49pm
Comparison ofGC-MS Results for Coal Tar Based Driveway Sealers
COALTAII1
1.. '220.96J].6611 .. 501.1.~G
g~42
«.47
Area ,Gaoui' IGROUP IIGROUP 'II%GROUP NGROUP VGROUP VIGROUP VIJ:
GC Rt!~ult.:
t'eak Na.aMI
-19COA1."'I'.I\B1
58-,.~ GC a••ults:
Peak NIIIDII' Area ,48alOOf I Q.S~GN)OP IX 11..1.039GROUP 1:I1 31.1ZGROtn'IV 11.26
29 GROUP V lL.'.-GROUP VX 10.18
,.....
tra GIWUP 'ILl: 5.24
COAL"1'A.Jl12
S8raY
.a
30
21
161
9
-liQ UI 21 38
PllfI.I.... ,
ClOUp I. GRQQ'P 'II:
GROUP XIXGlU)UlI rIGRQOP VGRQOP VIGRCOl' Vl:X
1 .. 9·19 .. 932.811 .. E12.:1lO .. Et. i
Comparison of GC-MS Results for Products 11 and 12EQ
c:n~
Com par eRe p 0 r t .,
COALTARll EK C e> lnJ 1 Ch 115
mV10
5 ,
In..J 1 Ch 1
ol.-ti~l.b.W.-w:;~~~~#~LtJJ~~.&.b~~~~~!::=::::~::::::::~-£:::L.
COALTARJ2 EX ( 0)2513"
2ae158
lee-5e~~...uu.~~JA/0..4.~~~~644L~~NJ.!.I~~~~~~~~~.........
o 10Mtnutes
mV
t.
Mutagenicity MI of AsphaJt and Coal Tar Pitch
'"0QJ:>
QJulU
a::
1100--
1000-
900··
BOO-
700--
600-:i
500-'
400-1,5
300-
200-
100-
C
Coal Tar RoofingPitch Asphala1
(Type I) Type Inl.
RoofingAsphaltTypelU
,
r-F 0,5