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NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023
EXHIBIT 160
FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020
NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023
MASTER EXHIBIT 50
FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020
NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023
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J ~dentification and Quantitation of Asbestos in Talc
·b'y Arthur N. Rohl 0 and Arthur M. Langer 0
Theaum~~Dtl,y IUed 8JIII},pdca1 methodJlor ldutillcatloa, characterJaattoza ud quutltation at
ubet&oilfl.llw lu oouumer taleum Pl'Oduotl bacluda JOJarJr.ed JJPt anit;ruco.w, z-r., difrrao.
tin ual.Yiia, tnr11mlnloa electroD mJcrosoa.w wl&htelectecl area eJeatrvn dlfl'ractlon ud eJeo.
t.roD nilaroprvlle tecJmlquu.
U.ht mtcroaoope methocliJ lave avere HmltatioulmpoiNII) b1 &he ultllllate at. ruolatiGD of
the IJPH»tical ayatem. SmaJI putlclelao Wll'tllolvedr thoae ma.rPuaii1 N&OlYell.., PG~HJI
optfeal proPertiea dUrennt !rom tbOA ~-cited !a tbeUieNtareJ.IIlfttO~ Jll'CIJICII'&IH,
•·•·• buUeet of refl'aotloll, are dUilcul& to llleblln oa IID&ll putlclu, Ia adc11tloa to &lie• dit·
fleulUN, talc flbezw oftOJl poiiMI optlaal propert.iu cWfereat from thCIH ol bJo plate1, w&lch
rurtber OODiound ualJtll, U.Jd mllll'IIIIIIIJIY J1 t'eOIIDUileiUie tor Gill onb' at a ..,......lnrfna13't.ool
Oil Umited, lup.lliled, umplel, 'bnamt11t01l e1ectroa JD!crolllDP.f11 a pod t&a'lldard teclml·
que far YllaaUr.atiOil ol CCJiltamlnant ubeltol ft'b110. Topther with aeJectecl ua eleolm!. dit•
ftacttoa. We ft.'ben mi.J be eulb dUfereD.tiated lrolllamplal'bole ubettos tlben oa the Hilt ot
both morpholoctcalud atructunl aharaoterisatloD. CheytotUe llben ate _ . dlttlapbW
Oil W• bull aa well. The amphl'bole ........_, mlaeralt nqlllre chemlcal abuaoterlu.titm to
clUfercmtlate &mODI the dltfenlat fiber t.Ypea, Probe uaiytllla awsdator.Y for auoll fihert. The
major drawba.cb to electrOil beam lllltrumentatlo.alor the mllleralollcal characterlatloa of
taiCJUJD J~nducta are Ua• time ad etrGr& required 1or uta acqullltl& Tbu• lecludqlllll do aut
led themlel"Nt to routlae aN.c~.Y.
X·n.v dUrracUOil aub'all, uUilldD.a the atep.acu method, ofrert a ~ npld, lllWl•
t.l.tative tecJmlQue lor ~rou m. ~. Bated oa compuiaa with aw.4ardiiPICimaa the
11• OOilteut or ea1a1 mAl be flUIIJltltatlftl1 ~ It I• UJ~Dtlll to employ a apeo~mu
Pl'QU&tlOJl &ealm!que wldah 7leldl hoaaopneolUtY dltpenN partlelel. 'J'remoJ1tt IUJ be
detel'mllled at lnek ulow u D.lO'Fo b,y we.IJht, chl;vtottle 0.2115. ucliWll.ollllyWt.e at J.K b7
we!Pt OCIISurreace ID talc. Ta. 'l'aJ'1ulae oltllete nl\11111 diiPIIIldt upoa1UQ11ac&o;rt,lllclu4Jilll
Use mu• abaorptloa ooefllc.lllllt ol the llber liJpet •• CflllliiU'IICI to talc aacl aelaoW dlapottla
nl.lectiDDa uul their relative lo&en•ltlea.
Ballh ol the above tecblquea i• deJGl'lbed In detaiL A method tor to\lt.l.no aaab'tll of OODJumer
taleum producil it llllllllkld. . . .
Introduction common than fibers. The term "fibrous talc" im-
The mineral talc is a monoclinic, occasionally plies, mineralogically, talc occurring with a
triclinlc. hydrated magnesium sheet sUlcate fiber habit (form). As used in the medical
with the ideal formula: MgcSiiOao(OH)•. literature, fibrous talc is synonymous for tales
Although a magnesium silicate, It frequently containing any fiber, including asbestos.
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contains smaU amounts of iron and other trace Geologically, talc occurs in rock masses often
metals in the structure. It can occur in several coexisting with a. large number of other
hydrated magnesi~m silicate mineral species (8,
: ·:;. crystal habits from plates to fibers. (1, J). In
.,
·..J
inost talc deposits, plates tend to be far more /r). This latter observation is baserf on
mineralogical analysis of naturally occurring
'Environmenta!Selencea Laboratory, Mount Sinal School tale deposits and laboratory studies of tale
of Medicine or the City Uruveralty of New York, New crystallization. Frequently, these coexisting
'I
York, 10029. · mineral phases are asbestos (Table 1).
Decemb.er 1974 96
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Table 1. Talc and ita AUOclated ubeltoa miMraiJ,
Talc Tremollte Anthopb.ylltte · ~sotlle
Empirical formula Mg.SitO~t(OH}• caaMBJSlaOU(OH)a
Common chemi~:al FeforM!r ll'eforMg
llllbstitutiona Al!orSi MntorMg
NaforCa
Strueture and bablt Sheet aillcat.e; plates Ch.afn alll.e&te; fibers Cbairl tUicAte; flhera Sheet. aDI~te; curved
common; fibera com· common; oft.eu aa maa- common; columnar or aheeta form Iibera;
mon; forma mua!ve alve earegates; forma fibrous agpegataa; often u compaeted
foliated aggreptes; intergrowths ln some fDl'ma illtergrowthl in rmera in pnudo-platas
intersrowtha on sub- tales on nbmk:ron aome talca; fibers tend (foliated mueea), es-
micron scale; many talo IICA!e; Iibera tePd tQ tQ be lODg and thin; aile peclally in aerpentlne
fibere observed in platy short and stubby; alr.e ranpa from vlalble by roclc; forma lnterplanar
talca on nbmiaon ranges from visible by eye to aublfsht micro- (lnterlamlnar) eon~
acala eye to aubllght. micro- aeopic. - taanlnan~ ln talc platea;
acopl~ · flben ln tale tald to be
IUbllght micraacoplc in
alze
Cryatal ayatem Monoclintc; Monoclinic Orthorhombic Monoclinic
trlcllnlc ortborbomblo
Cleavage Parallel to plate; (001) Parallel and across Parallel and acroaa Parallel to fibar axla;
perfect; priam termf. fiber axia; (110} per- fiber axta; (110) parfect (001) for clino variety
nations feet
Optical properties
"::I 1.589-1.550 1.681-1.616 1.596-l.BM "1.582-1.649
"z 1.589-1.600 1.601-1.641 1.626-1.666 1.645-1.556 ..
Indicel hilther lor J'Jidlcea lower for low-
fibers iron ebeysotHea
Maaa absorption co- -1032 -1885 -11172 ..71'1
effidenta {CuKa •
1.64!)'
Occurrence Geuerally preaent as Common eontamlnant Often • c:ontaminant Occaakmal contaminant
the m~or mineral In iD many talca (In iD ta1ca (In carbonate in tales (eapeclally in
commercial talc Clll"bonate rocb) and aerpeutlne rocb) .eerpent.lne.roc.ka)
Other minerala
' .
Carbonates (a.g., C"alcita); mlcaa (e.g., phlogoplte); ciaya {e.r., montmorfilonlteJ; chlorite;
commonly in talc: feldlpare (e.r., aodea!De); quarta; aerpantlne (e.g., .antigorite); eplnela (e.,c., magnetite) .
-• All coefflclenta calculated on the baai• of the empirical formula for each.
Tale rocks, those commercially worked for ore The metamorphism of siliceous dolomites
material, may form as the result of two major almost invariably results in tbe.formation of the
geological processes: hydro~hermal alteration of asqestos mineral tremolite (B).
preexisting mafic (Mg-Si.:..rieh) rocks and low- During geological alteration of rocks, new
grade hydrothermal metamorphism of siliceous mineral phases are frequently created from pre-
dolomite (sUica~bearlng, Mg-Ca-rieh) rocks. existing ones. Most commercial talc deposits are
These processes are geologically referred to as formed as the result of such processes. "ntese
steatitization and serpentinization. They involve deposits may consist of fine-grained, intimate
slightly different original bulk chemical com- mixtures of minerals, especially talc and
positions and end mineral products. Both may asbestos. In addition to the mineral complexities
produce significant amounts of asbestos· of talc deposits, these ore bodies are
often zoned.
minerals, chrysotile in serpentinization and That is, the mineral composition and
amphibole asbestos minerals in ateatitization. assemblage (reflecting changes in bulk
96 Env,lromnent(ll Health PeraiJectl
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cbeinistry) varies over short distances, several the 51 tales studied, none was 1009L tale (7). The
· · to several inches. This invariably means asbestos content Of these materials ranged from
the mined talc ore consists ot mineral mix· 0 to 87%. Studies of New York State tale
since mineral phase separation is difficult deposits an.d their asbestos contents have been
imJ:IOSS·ible tO achieve during mining. The carried out. Mineralogical analyses of. these
~~ca,znpilexi'ty of mineral deposits may be iJ. rna terials i'll'dlea·t:ed ··a'Jr ·aihnples:::were
1nAt:roat:4~f.l by a recent paper on the mineralogy predominantly asbesto& (8). ID another study, in
J mineral paragenesis of the New York State which 22 avaUable consumer talcum ~products
deposits in the Gouverneur district (S). were examined, it was found that fibrous con·
. I :• Beeause commercial talc deposits· consist of stitue~~ were present mall o! the samplea (BJ •
''"'ltturat admixtures of minerals. a number of
.Jllineralogically different materials have been
uaed as commercial talc. The mineral talc is Blolo,Eicat Consequences of Talc Dust Exposure
naturally soft and may be physically reduced fn EXPosure to talc dust, in intensity equivalent
siJe with little mechanical effort because of the to an occupational exposure, has beQn shown to
'weak bonding forces between adjacent unit be associated with· a diffuse interstitial lung
sheets. The material possesses a number of scarring which baa been termed talcosls
properties making · it useful in ·hundreds of (10.16), However, even in these studies, some
applications (6). Many of these applications, questions were raised as to the speclflc
bowevl!r, require small particle sfzea. high sur- pathogenic agent in the talc itself. For example,
face areas, apd good surface sorption asbestos bodies were.frequently observed in the
characteristics. Therefore, many of the talc lung tissues of individuals who died of taleoafs
. products must be fine-grained, but need not be (11, 13, 1'1'); clinical and radiological similarities
pure. The result ls a requirement for a talclike existed between the disease asbestosis and
rock rather than pure talc. Therefore, talc as talcosls (11, 18, 18); and "fibrous,. talc appeared
used in industry does not reler to the mineral to be more pathogenic than "platy" talc (19).
species talc, but rather to a property ('l). A Several investigators using· the individual
number o! materials have been used aa syn· mineral components of fibrous talc (made up of
onyms for talc: asbestine talc, steatite, mixtures of tremotite asbestos and platy talc)
aoa.Patont), tremolite talc, French talc, fibrous observed different biological responses to the
talc. All of these materials may contain quan· components in animals. They observed that the
tities of asbestos fiber. asbestos component induced a greater
I~''i978;:therew:ere·.88.major..talc.produ~.jn fibrogenic response in the anlmllls (SO). One in.;
theUnited·States; talc was mined in 10 states. vestigator has also reported an increased in·
The geological rock types from which these cidence of neoplasia amongst talc minera and
materials were mined covered the entire spec- millers exposed to asbestos-containing talc
trum of geological possibilities~o:r:Ql':exarilple, in dusts (S1). Lung tissues from workmen exposed
St. Lawrence County, New York State~ SO%.:or to talc dust have been analyzed in our
.:leaa<'o£ the.materlals :recovered. as: .~~cll.:is the laboratory. Both amphibole and chrysotile
U.~f:lf!.ineral .talc ·(5,6). ·In this deposit the asbestos fibers were observed in these tissues by
:W&~~h';r1t~!-ba~~~ll~~l~~ri:ffiitM~rJ~1~.·. ·.
electron microscopy (JS).
Several recent studies, involving experimen·
~~~ ~lileral· cbrysotile) occur throughout (5). tal animals and observations on human
./11i~~f#ei ·.the purity of ant commercially materials, have shown that exposure to asbestos
-.··available .talc in the United States is related to .. and talc may be associated with tumors of the
botldhe nature of the original tale deposit and ovary and cerVix (13, !4). In addition, the use of
the extent to which. the rock is upgraded to 'such talcum products as lubricants, drying
eliminate contaminant minerals. This latter agents, and excipients in a nu.mber of food and
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'., ~ ' process is often ~:eferred to as beneficiation. food packaging products may pose .a hazard fn
Some mineralogical analyses have been made terms of a.n fnereaseroslty of the specimen is comitant and
8u
0
353.i
that the specimen is tbiclt enough to diffract x-
rays with maximum intensity. ·
~ The powdered materials used In this study
and the filter-mounting technique of specimen
I Cl CHL 004
0
~ 0 Q qb 0 I I preparation were selected in order to fulfill
~~
~ o, 0 these basic requirements of quaptitative x-ray
I \ I
diffraction analyaia.
X .oO
oo ·Specltll Foetor•: An important factor
0
'\ which affects the ability to detect small
amounts of material by x-ray dJffraetion
analysis is specimen x·ray absorption. This oc-
curs when two substances with different mass
absorption coefficients ~ mixed. The mass ab-
sorption coefficient (p./p) is a measure of' the
" . fraction of the energy in the incident x-ray beam
PlGllRB 6. SteJHICAII profile obtal11ed on a ataadard absorbed when a beam of .unit cross section
dllutioll or 1~ cheyiiOtile in a 90'1 tala maUix. traverses a unit mass of .materiaL It is useful
Note the COiltamination of talc with & trace of cblorite because it is characteristic of the chemical
(8.58 A reflection). Step-.scan obtained at o.osa 1'1
for 2000 counta. elements in the absorbing material and is essen-
tially independent of their chemical or physical
aggregate state. It· is a function only of the
of diffraction patterns of the constituent com· wavelength of the absorbed radiation and the
pounds (Fir. 4). The intensity of each eom· atOmic number of the abaorblng element. The
,.,,.,.,..~P•:'" . / pound's pattern is proportional to, but not sensitivity of detection of a component may
. necessarily a Hnear function of, its concentration vary considerably, depending on ,Up for the
~· ·, (!D). Aside from Instrumental factors (e.g., component relative to that of the matrix. The
·· change in x-ray output from target tube) which mass absorption coefficients of talc. chrysotile,
may influence the profiles of diffraction max- anthophyllite, and tremolite for the wavelength
ima, there are a number of other factors to be of copper x-radiatiOn .(1.542 A ) are given in
considered. ·These are related primarily to the Table 1. Chrysotile has the lowest p./p of the
material,. ihcluding sample homogeneity, four minerals, about 717, w.hicb is about 7/10
chemical makeup, particle size, preferred orien- that of talc, 1082. Thus, the sensitivity of deteo-
tation, sampl8. thickness and flatness, aJ,ld ab- tion of chrysotile in talc is greater than that of
sorption characteristics. the other two asbe5toa minerals, neglecting the
Geneml Focton: The components of a mix- effects of such variables as particle size and
ture and their relative amounts may be deter- degree of crystallinity which may have equal or
..
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mined by the intensity measurements of the dit· greater influences on the sensitivity of detec-
.. fraction patterns, if all these factors are con.. tion•
sidered: However, it is· neee.,sary that certain The precision (reproducibility) of intensity
conditions be satisfied. The component sought · measurements obtained in x-ray diffraction
<:·i., . must be homogeneously mixed in its matrix and analysis can be optimized by a suitable counting
....
.I . consist o! randomly oriented small particles to strategy. If an ~eeumulated . C()Unt of
December l974 103
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4Xl05-5X10' is obtained, the precision of the tural similarities between ·chrysotile and
relative intensity measurement 4ue to counting kaolinite, their x':'ray diffraction patterns~
statistics .alone .is N '". The determination is similar in many respects,· The first.order basal
also related to specimen preparation reproduc· reflection of kaolinite at .7..15 A may thus
ibility. With specimens having an average par· overlap or mask the chrysotile (Q02) reflection •t
ticle size .of 1-2pm, the range in intensity
measurements is from 0.1 to 0.5%. The overall
precision of quantitative x-ray analysis will
'1.24 A • Depending on the relative amounts of
these two minerals present, chryeotile may be
neither detectable nor quantitative}~ deter-
.....
probably lie in the range of 0.5 to 1.0% (Sr). · mined with precision by use of the 7.24 A reflec-
The accuracy of x-ray analysis depends in tion. It has been found that the 8.63 A (004)
large measure on the degree of preferred orien- reflection of chrysotile at 24.8° 29 is more useful
tation of particles in the sample. The materials than the (002) reflection for detecting the
used in this study, sheet silicates and fibers, can dilutions of that mineral in tale matrices. This
be expected to have a high degree of preferred chrysotlle reflection is better resolved from
orientation. This inescapable physical limitation reflections of associated minerals, particularly
is the main factor in controlling the level of ac- from the. 8.58 A (004) reflection of chlorite at
curacy. . 20.1° 28. The peak-to-background ratio of the
chrysotlle (004) line, which has an intensity of
Standard Dilutions about 8/10 of the (002) reflection, is thus used to
determine the minimum detectable amount of
ChryaotUe mTalc: The presence of chlorite ehrysotlle in talc standard . samples. The
in the talc standard used in preparation of samples are step-scanned at a rate of 0.02 per
chrysotile-talc dilutions may preclude the use of degree 28 from an angle of 28.0 to 27.0° 26m
the (002) reflection of chrysotile as a diagnostic order to achieve maximum peak and minimum
reflection. The chlorite reflection at about 12.6° background intensities in the same region of the
28 overlaps and masks the latter reflection. spectrum. A minimum of 0.25% by weight of
When the intensities of these two reflections are ebrysotile in standard talc has been detected
about the same, the peaks can be resolved with a consistently. Chrysotile at lower levels of dilu·
step.scanning rate of 0.01 1 per degree 28. Except tion cannot be detected. .
for this special condition, th~ peak-to· f'remoUie. ir.r. Tcllc: A few specimens, Ja..
background ratio of the chrysotile (002) does not beled as ~molite, .were .prepared for x·ray
pttrmit it to be measured with precision. If powder diffraction analysis .and continuously
chrysotile and chlorite are both present' in the scanned. ftoin 8° to 60° 28 at a rate of 1°/min~
sample, but ehrysotile predominates, then the When these spectra were indexed, it wa8 found
{002) peak of chrysotile can be used as an in· that only one tremolite sample was free of eon~
dicator of the relative amount of. cbrysotlle pre- taminants. That is, the positions and J:elative ln·
sent. tensities of all of its reflections compared exact-
Another mineral which may interfere with ly with the data given for an ASTM reference
the detection or quantitation of chrysotile is tremollte (American Society for Testing
kaolinite. This mineral Is the most common Materials standard powder diffra.etlon file, 113-
member of tlie kaolin group of hydrous 43'1). As indicated in Table 2, the 8.88 A reflec-
aluminum silicate clay minerals. Although tion of tremolite, which has a relative intensity
kaolinite has not been reported in talc or serpen· of 100, was selected as the diagnostic reflection
tine rock, particularly because the modes of for- for the tremollte-tale dilution series. The 8.12 A
mation and geochemical environment are quite tremolite reflection, which also has a relative in·
dissimilar, this fact does not preclude the tensity of 100, was not used ~use it overla:Ps
presence of kaolinite in industrial or consumer with the 8.12 A reflection of talc. Dilution levels
talcum by admixing. The mechanical and from 99.0% talc-1.0% tremolite through 99.95%
physical properties of kaolinite would be in har- talc-0.05% tremolite were prepared and step.
mony with those of talc. In fact, It has been scanned under constant instrumental con·
identified as a._component of some cosmetic ditions. The'G.iagnostic reflection of tremolite
talcum products. Because there a.re close struc- was detected at all levels of dilution up to, and
104 Environmental
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nd ·tne11uamg, the 99.9% talc-0.1% tremolite level. . Preparation and An.alysls of ChrysotUe- Talc Dilu· ·
tre 0.1% trem·olite was not detected above tfon Samples by Electron Microscopy . · ·,
1al bn.c.l®'jilunn. Replicate dilution mixtures at the
us ~-:,~··.. ·-· and 0.05% tremolite levels were prepared Aliquot portions of variouS chrysotile-ialc
at step-scanned to confirm these observations. dilution levels whiCh had been analyzed by x·ray
of results were consistent and reproducible. diffraction were prepared for transmission elee·
>e ~An.fh,oph.yUtte in Talc: The anthophyllite tron microscopy by a "rubou~ procedure (8B).
r- in preparing dilution mixtures of fiber in Standard weights (0.01 mg) of each of the dllu·
:- was from the UICC standard asbestos tion standards are dlspersed In a nitrocellulose
l) mineral collection. previously film and mounted on Formvar-coated electron
II ·fiA•.IInllll'&tlterlized (BB). A specimen of tbia material microscope grids. The dispersal is accomplished
e continuously scanned by x-ray diffraction by mounting the sample in a drop of
I 8° to 70° 2fJ at 1°/min. When the peaks on nitrocellulose-amyl acetate solution on a
I diffraction. pattern were assigned d microscope slide and grinding It with the edge of
~~tll,aeiJlgs. it w11.s found that the IUltbophylUte a clean watch glass to reduce the sample into
was contaminated by· talc. chlorite, and submicron-slzed particles. This procedtll'e breaks
:i>hlogopite. However, these intrinsic con- apart the fl.ber bundles of chrysotile, already
taminants do not preclude use of the material as greatly comminuted by triple air jet-milling and
dilution standard. A more serious limiting sonlfication, into unit fibrfls or into small fiber
condition pertains to the similarities between bundles. At the same time, large aggregates of
~he diffraction patterns of "puren antbophylUte talc particles are reduced in size and dispersed
·and talc (see Fig. 4). Among the most intense to allow all asbestos fibers to be seen and
reflections of anthophyllite are the 8.05 A counted. .
(obscured by the supe~oaition of the talc 8.12 After dispersing the sample, a drop of amyl
=
A.Ill• 40); the 4.60 A (obscured by the 4.53 acetate is placed on a second clean side. The two
A. lilt =12 and the 4.56 A, lilt ... 45 both of slides are placed in contact and the ground
talc) and the 3.23 A (obscured by the 8.33 A residue and nitrocellulose solution is further
mica eon taminan t of talc, Ilia = 100). Since the dispersed. The residue is typically spread over
peak·to-background ratio of the most intense the ali~e for a length of 5 crit. 'rhe two sUdes are
·reflections o! the powder pattern is the most im· then pulled apart, leaving two films with the
portant single factor in determining the powder uniformly distributed in them. The
minimum detectable amount of a substance, the films quickly chy: The edges of the sllde with at-
interference between similarly spaced strong tached film are scraped wlth a scalpel blade;
reflections of talc and anthophyllite significant· then by dipping the slide into water, the film
ly diminishes the possibility of detecting minute can be floated onto the surface of the water.
amounts of anthophyllite asbestos in talc. The Electron microscope grids are placed on top of
8.26 A reflection of anthophyllite, with the segments of the film and covered with a strip of
relative intensity of 55, was selected as the most filter paper. The grid is retrieved by lifting the
useful diagnostic reflection for the filter paper out of the water. After drying, the
anthophyllite-talc dilution series. DDiition grids can be picked off the filter paper and
mixtures ranging from 95.0% talc-5.0% mounted in the electron microscope for scan·
antbophylllte through 99.5% talc-0.5% ning. .
anthophyllite were prepared. When step- Typically. three grids are prepared for each
scanned under constant co~ditions. dilution level of chrysotne-talc and six squares
anthophyllite was not detected at concen· of each grid are scanned at about lO,OOOX
tratlons below 2.0% in repeated samples. With magnification to obtain a number of represen·
continuous scanning, anthophyllite was . not tative fields for study. A large number of fields
detected at or below the 4.0% dilution level when are photographed and enlarged prints are then
the 8.26 A reflection was used as an index (see made. From the photographic enlargements the
Fig. 4). . .
.
·:
.•
number of long unit fibrils per field are counted
• t .•
J
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I.
J)eoember 1974 105
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•,
and the resultS are tabulated. When multiple Application of Transmission Electron Microscopy
fibril bundles are encountered, the number of Methods (Including Selected Area Electron Dlf·
unit fibrils in the bundles is estimated by fraction) in Detection of Asbestos in Consamer
counting the number of visible central Tales ·
capillaries and by judgblg the optical denslty of Consumer tales have been prepared and
the fiber bundle. The electron mfcroscopie fiber examined by means of transmission electron
counts show a fairly good correlation with levels microscopy. Representative sample aliquots
of ehrysotile dilution. For example, the average were sonically dispersed in filtered water and
number of chrysotile fibrils per field, scanned a.t plpetted onto Formvar-carbon 200·mesh
7100X magnification was counted at the follow- copper electron microscope grids. After these
ing dilution levels: 5% cbrysotile-95% talc, 92 preparations were dry they were again carbon
fibrils per field ::l; 10%; 1% chrysotile-99% talc coated t9 insure a therm~y and electrically
22 fibrils per field :1: 10%; 0.5% stable preparation. Samples were scanned at
chrysotile-99.5% talc 8 fibrils per field :1: 10%; magnification in excess of 20,000 and examined
0.25% cbrysotJle-99.75% talc 6 fibrils per field for their fiber content. A representative platy
:1: 10%. It is evident that there are considerable and fibrous talc is shown in Figure .6. The
numbers of chrysotile fibers present in talc even asbestos content of tale may be directly es-
at very low dilution levels. By using the fiber timated utilizing transmission electron
count data for the various dilution levels' it is microscopy. Each fiber type may be identified.
possible to calculate the number of fibrils con- For example, ehrysotile asbestos is
tained In a unit weight of sample. morphologically unique. Its internal capillary,
The area of the nitrocellulose fUm is known, fibril dimensions, susceptibility to electron
as is the magnification factor. From these and a beam damage, and unique electron diffraction
measurement of the area of the photographs, a pattern, aU make the fiber easily recognizable
conversion factor is calculated. Allowing for an (38).
error as large as one magnitude the calculations Fibers which are electron-dense and which
show that there are 2N X 10' fibrils/mg of sam· possess the morphological eharacteristlcs of
ple, the value N being the average number of amphiboles, were examined by selected area
fibrils per field. Thue, in a 1% dilution of electron diffraction for confirmation. We have
chrysotile in talc, tbere would be about 4 X 10' done this on many particles ln numerous
fibrUs/mg. At the lowest level of detection of samples and are able to differentiate fibrous
ehrysotlle by x-ray diffraction, i.e., 0.25%, there talc £rom fibers of asbestos quite easily (Fig. 7)
would be about a 1()1' fibrils/mg. (88). However, this method is not sufficiently
It is clear that in issuing regulations specify. sensitive to distinguish among the amphiboles.
ing the absence or absolute limits of asbestos in Here, microchemical characterization is
tale, close attention must be paid to the necessary (8.4). Electron. microscopy is an ex·
capabilities of the analytical technique used for cellent qualitative tool for determining the
determining whether, or how much, asbestos is presenc!e or absence of asbestos fibers in. talc.
present. X-ray diffraction can provide positive
answera to these questions only at the 0.25% lev· Microchemical Analysis by Eledron Microprobe
el for ehrysotile which has been shown to be a Analysis · ·
crude and inaeeurate measure of the potential By means of microchemical analysis, it is
contamination and possible hazard involved. In possible to differentiate among the amphibole
addition, as mueh as 2.0% of anthophyllite in asbestos fiber types. We have examined talc
talc may not be detected by this method. On samples obtained from a mill in which
the other ha.nd, electron microscopic analysis anthophyllite and tremolite fibers oceurred
can be a sensitive tool for detecting extremely within the talc. These samples were examined
minute amounts of chrysotile and other on an ARL electron microprobe analyzer
asbestos minerals in talc. equipped 'Yi~b crrstal spectometers. The instru·
106 Environmental Health Perspectives
FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020
NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023
Utd
ron
ots
.nd
sh
ISS
:m
Jy
at
td
'¥
.e
I• 7.
:..... 1. .
l
....
.~ ~:·~
~-...·~).
~··.r
:.· ,-~-y~
............
~v·
.~, ....::... ·.. .. ::.. .
riJ!', . . . . •,:
···~ :~
FIGUR!l: 7. Selected area electron diffraction patternJ
obtained on (A) a talc plate and (marked TF in B)
a tale fiber. 'l'alc fibere are not con1'uled with amphl-
bolea. 'l'hey are often cun!llnear, poueu Irregular
.dlftracti
Preview
FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 EXHIBIT 160 FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 MASTER EXHIBIT 50 FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 >e .. ,· f J ~dentification and Quantitation of Asbestos in Talc ·b'y Arthur N. Rohl 0 and Arthur M. Langer 0 Theaum~~Dtl,y IUed 8JIII},pdca1 methodJlor ldutillcatloa, characterJaattoza ud quutltation at ubet&oilfl.llw lu oouumer taleum Pl'Oduotl bacluda JOJarJr.ed JJPt anit;ruco.w, z-r., difrrao. tin ual.Yiia, tnr11mlnloa electroD mJcrosoa.w wl&htelectecl area eJeatrvn dlfl'ractlon ud eJeo. t.roD nilaroprvlle tecJmlquu. U.ht mtcroaoope methocliJ lave avere HmltatioulmpoiNII) b1 &he ultllllate at. ruolatiGD of the IJPH»tical ayatem. SmaJI putlclelao Wll'tllolvedr thoae ma.rPuaii1 N&OlYell.., PG~HJI optfeal proPertiea dUrennt !rom tbOA ~-cited !a tbeUieNtareJ.IIlfttO~ Jll'CIJICII'&IH, •·•·• buUeet of refl'aotloll, are dUilcul& to llleblln oa IID&ll putlclu, Ia adc11tloa to &lie• dit· fleulUN, talc flbezw oftOJl poiiMI optlaal propert.iu cWfereat from thCIH ol bJo plate1, w&lch rurtber OODiound ualJtll, U.Jd mllll'IIIIIIIJIY J1 t'eOIIDUileiUie tor Gill onb' at a ..,......lnrfna13't.ool Oil Umited, lup.lliled, umplel, 'bnamt11t01l e1ectroa JD!crolllDP.f11 a pod t&a'lldard teclml· que far YllaaUr.atiOil ol CCJiltamlnant ubeltol ft'b110. Topther with aeJectecl ua eleolm!. dit• ftacttoa. We ft.'ben mi.J be eulb dUfereD.tiated lrolllamplal'bole ubettos tlben oa the Hilt ot both morpholoctcalud atructunl aharaoterisatloD. CheytotUe llben ate _ . dlttlapbW Oil W• bull aa well. The amphl'bole ........_, mlaeralt nqlllre chemlcal abuaoterlu.titm to clUfercmtlate &mODI the dltfenlat fiber t.Ypea, Probe uaiytllla awsdator.Y for auoll fihert. The major drawba.cb to electrOil beam lllltrumentatlo.alor the mllleralollcal characterlatloa of taiCJUJD J~nducta are Ua• time ad etrGr& required 1or uta acqullltl& Tbu• lecludqlllll do aut led themlel"Nt to routlae aN.c~.Y. X·n.v dUrracUOil aub'all, uUilldD.a the atep.acu method, ofrert a ~ npld, lllWl• t.l.tative tecJmlQue lor ~rou m. ~. Bated oa compuiaa with aw.4ardiiPICimaa the 11• OOilteut or ea1a1 mAl be flUIIJltltatlftl1 ~ It I• UJ~Dtlll to employ a apeo~mu Pl'QU&tlOJl &ealm!que wldah 7leldl hoaaopneolUtY dltpenN partlelel. 'J'remoJ1tt IUJ be detel'mllled at lnek ulow u D.lO'Fo b,y we.IJht, chl;vtottle 0.2115. ucliWll.ollllyWt.e at J.K b7 we!Pt OCIISurreace ID talc. Ta. 'l'aJ'1ulae oltllete nl\11111 diiPIIIldt upoa1UQ11ac&o;rt,lllclu4Jilll Use mu• abaorptloa ooefllc.lllllt ol the llber liJpet •• CflllliiU'IICI to talc aacl aelaoW dlapottla nl.lectiDDa uul their relative lo&en•ltlea. Ballh ol the above tecblquea i• deJGl'lbed In detaiL A method tor to\lt.l.no aaab'tll of OODJumer taleum producil it llllllllkld. . . . Introduction common than fibers. The term "fibrous talc" im- The mineral talc is a monoclinic, occasionally plies, mineralogically, talc occurring with a triclinlc. hydrated magnesium sheet sUlcate fiber habit (form). As used in the medical with the ideal formula: MgcSiiOao(OH)•. literature, fibrous talc is synonymous for tales Although a magnesium silicate, It frequently containing any fiber, including asbestos. - .. ~ contains smaU amounts of iron and other trace Geologically, talc occurs in rock masses often metals in the structure. It can occur in several coexisting with a. large number of other hydrated magnesi~m silicate mineral species (8, : ·:;. crystal habits from plates to fibers. (1, J). In ., ·..J inost talc deposits, plates tend to be far more /r). This latter observation is baserf on mineralogical analysis of naturally occurring 'Environmenta!Selencea Laboratory, Mount Sinal School tale deposits and laboratory studies of tale of Medicine or the City Uruveralty of New York, New crystallization. Frequently, these coexisting 'I York, 10029. · mineral phases are asbestos (Table 1). Decemb.er 1974 96 FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 Table 1. Talc and ita AUOclated ubeltoa miMraiJ, Talc Tremollte Anthopb.ylltte · ~sotlle Empirical formula Mg.SitO~t(OH}• caaMBJSlaOU(OH)a Common chemi~:al FeforM!r ll'eforMg llllbstitutiona Al!orSi MntorMg NaforCa Strueture and bablt Sheet aillcat.e; plates Ch.afn alll.e&te; fibers Cbairl tUicAte; flhera Sheet. aDI~te; curved common; fibera com· common; oft.eu aa maa- common; columnar or aheeta form Iibera; mon; forma mua!ve alve earegates; forma fibrous agpegataa; often u compaeted foliated aggreptes; intergrowths ln some fDl'ma illtergrowthl in rmera in pnudo-platas intersrowtha on sub- tales on nbmk:ron aome talca; fibers tend (foliated mueea), es- micron scale; many talo IICA!e; Iibera tePd tQ tQ be lODg and thin; aile peclally in aerpentlne fibere observed in platy short and stubby; alr.e ranpa from vlalble by roclc; forma lnterplanar talca on nbmiaon ranges from visible by eye to aublfsht micro- (lnterlamlnar) eon~ acala eye to aubllght. micro- aeopic. - taanlnan~ ln talc platea; acopl~ · flben ln tale tald to be IUbllght micraacoplc in alze Cryatal ayatem Monoclintc; Monoclinic Orthorhombic Monoclinic trlcllnlc ortborbomblo Cleavage Parallel to plate; (001) Parallel and across Parallel and acroaa Parallel to fibar axla; perfect; priam termf. fiber axia; (110} per- fiber axta; (110) parfect (001) for clino variety nations feet Optical properties "::I 1.589-1.550 1.681-1.616 1.596-l.BM "1.582-1.649 "z 1.589-1.600 1.601-1.641 1.626-1.666 1.645-1.556 .. Indicel hilther lor J'Jidlcea lower for low- fibers iron ebeysotHea Maaa absorption co- -1032 -1885 -11172 ..71'1 effidenta {CuKa • 1.64!)' Occurrence Geuerally preaent as Common eontamlnant Often • c:ontaminant Occaakmal contaminant the m~or mineral In iD many talca (In iD ta1ca (In carbonate in tales (eapeclally in commercial talc Clll"bonate rocb) and aerpeutlne rocb) .eerpent.lne.roc.ka) Other minerala ' . Carbonates (a.g., C"alcita); mlcaa (e.g., phlogoplte); ciaya {e.r., montmorfilonlteJ; chlorite; commonly in talc: feldlpare (e.r., aodea!De); quarta; aerpantlne (e.g., .antigorite); eplnela (e.,c., magnetite) . -• All coefflclenta calculated on the baai• of the empirical formula for each. Tale rocks, those commercially worked for ore The metamorphism of siliceous dolomites material, may form as the result of two major almost invariably results in tbe.formation of the geological processes: hydro~hermal alteration of asqestos mineral tremolite (B). preexisting mafic (Mg-Si.:..rieh) rocks and low- During geological alteration of rocks, new grade hydrothermal metamorphism of siliceous mineral phases are frequently created from pre- dolomite (sUica~bearlng, Mg-Ca-rieh) rocks. existing ones. Most commercial talc deposits are These processes are geologically referred to as formed as the result of such processes. "ntese steatitization and serpentinization. They involve deposits may consist of fine-grained, intimate slightly different original bulk chemical com- mixtures of minerals, especially talc and positions and end mineral products. Both may asbestos. In addition to the mineral complexities produce significant amounts of asbestos· of talc deposits, these ore bodies are often zoned. minerals, chrysotile in serpentinization and That is, the mineral composition and amphibole asbestos minerals in ateatitization. assemblage (reflecting changes in bulk 96 Env,lromnent(ll Health PeraiJectl . .. ' .. ve.s . FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 cbeinistry) varies over short distances, several the 51 tales studied, none was 1009L tale (7). The · · to several inches. This invariably means asbestos content Of these materials ranged from the mined talc ore consists ot mineral mix· 0 to 87%. Studies of New York State tale since mineral phase separation is difficult deposits an.d their asbestos contents have been imJ:IOSS·ible tO achieve during mining. The carried out. Mineralogical analyses of. these ~~ca,znpilexi'ty of mineral deposits may be iJ. rna terials i'll'dlea·t:ed ··a'Jr ·aihnples:::were 1nAt:roat:4~f.l by a recent paper on the mineralogy predominantly asbesto& (8). ID another study, in J mineral paragenesis of the New York State which 22 avaUable consumer talcum ~products deposits in the Gouverneur district (S). were examined, it was found that fibrous con· . I :• Beeause commercial talc deposits· consist of stitue~~ were present mall o! the samplea (BJ • ''"'ltturat admixtures of minerals. a number of .Jllineralogically different materials have been uaed as commercial talc. The mineral talc is Blolo,Eicat Consequences of Talc Dust Exposure naturally soft and may be physically reduced fn EXPosure to talc dust, in intensity equivalent siJe with little mechanical effort because of the to an occupational exposure, has beQn shown to 'weak bonding forces between adjacent unit be associated with· a diffuse interstitial lung sheets. The material possesses a number of scarring which baa been termed talcosls properties making · it useful in ·hundreds of (10.16), However, even in these studies, some applications (6). Many of these applications, questions were raised as to the speclflc bowevl!r, require small particle sfzea. high sur- pathogenic agent in the talc itself. For example, face areas, apd good surface sorption asbestos bodies were.frequently observed in the characteristics. Therefore, many of the talc lung tissues of individuals who died of taleoafs . products must be fine-grained, but need not be (11, 13, 1'1'); clinical and radiological similarities pure. The result ls a requirement for a talclike existed between the disease asbestosis and rock rather than pure talc. Therefore, talc as talcosls (11, 18, 18); and "fibrous,. talc appeared used in industry does not reler to the mineral to be more pathogenic than "platy" talc (19). species talc, but rather to a property ('l). A Several investigators using· the individual number o! materials have been used aa syn· mineral components of fibrous talc (made up of onyms for talc: asbestine talc, steatite, mixtures of tremotite asbestos and platy talc) aoa.Patont), tremolite talc, French talc, fibrous observed different biological responses to the talc. All of these materials may contain quan· components in animals. They observed that the tities of asbestos fiber. asbestos component induced a greater I~''i978;:therew:ere·.88.major..talc.produ~.jn fibrogenic response in the anlmllls (SO). One in.; theUnited·States; talc was mined in 10 states. vestigator has also reported an increased in· The geological rock types from which these cidence of neoplasia amongst talc minera and materials were mined covered the entire spec- millers exposed to asbestos-containing talc trum of geological possibilities~o:r:Ql':exarilple, in dusts (S1). Lung tissues from workmen exposed St. Lawrence County, New York State~ SO%.:or to talc dust have been analyzed in our .:leaa<'o£ the.materlals :recovered. as: .~~cll.:is the laboratory. Both amphibole and chrysotile U.~f:lf!.ineral .talc ·(5,6). ·In this deposit the asbestos fibers were observed in these tissues by :W&~~h';r1t~!-ba~~~ll~~l~~ri:ffiitM~rJ~1~.·. ·. electron microscopy (JS). Several recent studies, involving experimen· ~~~ ~lileral· cbrysotile) occur throughout (5). tal animals and observations on human ./11i~~f#ei ·.the purity of ant commercially materials, have shown that exposure to asbestos -.··available .talc in the United States is related to .. and talc may be associated with tumors of the botldhe nature of the original tale deposit and ovary and cerVix (13, !4). In addition, the use of the extent to which. the rock is upgraded to 'such talcum products as lubricants, drying eliminate contaminant minerals. This latter agents, and excipients in a nu.mber of food and ...'. . '., ~ ' process is often ~:eferred to as beneficiation. food packaging products may pose .a hazard fn Some mineralogical analyses have been made terms of a.n fnereaseroslty of the specimen is comitant and 8u 0 353.i that the specimen is tbiclt enough to diffract x- rays with maximum intensity. · ~ The powdered materials used In this study and the filter-mounting technique of specimen I Cl CHL 004 0 ~ 0 Q qb 0 I I preparation were selected in order to fulfill ~~ ~ o, 0 these basic requirements of quaptitative x-ray I \ I diffraction analyaia. X .oO oo ·Specltll Foetor•: An important factor 0 '\ which affects the ability to detect small amounts of material by x-ray dJffraetion analysis is specimen x·ray absorption. This oc- curs when two substances with different mass absorption coefficients ~ mixed. The mass ab- sorption coefficient (p./p) is a measure of' the " . fraction of the energy in the incident x-ray beam PlGllRB 6. SteJHICAII profile obtal11ed on a ataadard absorbed when a beam of .unit cross section dllutioll or 1~ cheyiiOtile in a 90'1 tala maUix. traverses a unit mass of .materiaL It is useful Note the COiltamination of talc with & trace of cblorite because it is characteristic of the chemical (8.58 A reflection). Step-.scan obtained at o.osa 1'1 for 2000 counta. elements in the absorbing material and is essen- tially independent of their chemical or physical aggregate state. It· is a function only of the of diffraction patterns of the constituent com· wavelength of the absorbed radiation and the pounds (Fir. 4). The intensity of each eom· atOmic number of the abaorblng element. The ,.,,.,.,..~P•:'" . / pound's pattern is proportional to, but not sensitivity of detection of a component may . necessarily a Hnear function of, its concentration vary considerably, depending on ,Up for the ~· ·, (!D). Aside from Instrumental factors (e.g., component relative to that of the matrix. The ·· change in x-ray output from target tube) which mass absorption coefficients of talc. chrysotile, may influence the profiles of diffraction max- anthophyllite, and tremolite for the wavelength ima, there are a number of other factors to be of copper x-radiatiOn .(1.542 A ) are given in considered. ·These are related primarily to the Table 1. Chrysotile has the lowest p./p of the material,. ihcluding sample homogeneity, four minerals, about 717, w.hicb is about 7/10 chemical makeup, particle size, preferred orien- that of talc, 1082. Thus, the sensitivity of deteo- tation, sampl8. thickness and flatness, aJ,ld ab- tion of chrysotile in talc is greater than that of sorption characteristics. the other two asbe5toa minerals, neglecting the Geneml Focton: The components of a mix- effects of such variables as particle size and ture and their relative amounts may be deter- degree of crystallinity which may have equal or .. .. .. mined by the intensity measurements of the dit· greater influences on the sensitivity of detec- .. fraction patterns, if all these factors are con.. tion• sidered: However, it is· neee.,sary that certain The precision (reproducibility) of intensity conditions be satisfied. The component sought · measurements obtained in x-ray diffraction <:·i., . must be homogeneously mixed in its matrix and analysis can be optimized by a suitable counting .... .I . consist o! randomly oriented small particles to strategy. If an ~eeumulated . C()Unt of December l974 103 .... I FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 4Xl05-5X10' is obtained, the precision of the tural similarities between ·chrysotile and relative intensity measurement 4ue to counting kaolinite, their x':'ray diffraction patterns~ statistics .alone .is N '". The determination is similar in many respects,· The first.order basal also related to specimen preparation reproduc· reflection of kaolinite at .7..15 A may thus ibility. With specimens having an average par· overlap or mask the chrysotile (Q02) reflection •t ticle size .of 1-2pm, the range in intensity measurements is from 0.1 to 0.5%. The overall precision of quantitative x-ray analysis will '1.24 A • Depending on the relative amounts of these two minerals present, chryeotile may be neither detectable nor quantitative}~ deter- ..... probably lie in the range of 0.5 to 1.0% (Sr). · mined with precision by use of the 7.24 A reflec- The accuracy of x-ray analysis depends in tion. It has been found that the 8.63 A (004) large measure on the degree of preferred orien- reflection of chrysotile at 24.8° 29 is more useful tation of particles in the sample. The materials than the (002) reflection for detecting the used in this study, sheet silicates and fibers, can dilutions of that mineral in tale matrices. This be expected to have a high degree of preferred chrysotlle reflection is better resolved from orientation. This inescapable physical limitation reflections of associated minerals, particularly is the main factor in controlling the level of ac- from the. 8.58 A (004) reflection of chlorite at curacy. . 20.1° 28. The peak-to-background ratio of the chrysotlle (004) line, which has an intensity of Standard Dilutions about 8/10 of the (002) reflection, is thus used to determine the minimum detectable amount of ChryaotUe mTalc: The presence of chlorite ehrysotlle in talc standard . samples. The in the talc standard used in preparation of samples are step-scanned at a rate of 0.02 per chrysotile-talc dilutions may preclude the use of degree 28 from an angle of 28.0 to 27.0° 26m the (002) reflection of chrysotile as a diagnostic order to achieve maximum peak and minimum reflection. The chlorite reflection at about 12.6° background intensities in the same region of the 28 overlaps and masks the latter reflection. spectrum. A minimum of 0.25% by weight of When the intensities of these two reflections are ebrysotile in standard talc has been detected about the same, the peaks can be resolved with a consistently. Chrysotile at lower levels of dilu· step.scanning rate of 0.01 1 per degree 28. Except tion cannot be detected. . for this special condition, th~ peak-to· f'remoUie. ir.r. Tcllc: A few specimens, Ja.. background ratio of the chrysotile (002) does not beled as ~molite, .were .prepared for x·ray pttrmit it to be measured with precision. If powder diffraction analysis .and continuously chrysotile and chlorite are both present' in the scanned. ftoin 8° to 60° 28 at a rate of 1°/min~ sample, but ehrysotile predominates, then the When these spectra were indexed, it wa8 found {002) peak of chrysotile can be used as an in· that only one tremolite sample was free of eon~ dicator of the relative amount of. cbrysotlle pre- taminants. That is, the positions and J:elative ln· sent. tensities of all of its reflections compared exact- Another mineral which may interfere with ly with the data given for an ASTM reference the detection or quantitation of chrysotile is tremollte (American Society for Testing kaolinite. This mineral Is the most common Materials standard powder diffra.etlon file, 113- member of tlie kaolin group of hydrous 43'1). As indicated in Table 2, the 8.88 A reflec- aluminum silicate clay minerals. Although tion of tremolite, which has a relative intensity kaolinite has not been reported in talc or serpen· of 100, was selected as the diagnostic reflection tine rock, particularly because the modes of for- for the tremollte-tale dilution series. The 8.12 A mation and geochemical environment are quite tremolite reflection, which also has a relative in· dissimilar, this fact does not preclude the tensity of 100, was not used ~use it overla:Ps presence of kaolinite in industrial or consumer with the 8.12 A reflection of talc. Dilution levels talcum by admixing. The mechanical and from 99.0% talc-1.0% tremolite through 99.95% physical properties of kaolinite would be in har- talc-0.05% tremolite were prepared and step. mony with those of talc. In fact, It has been scanned under constant instrumental con· identified as a._component of some cosmetic ditions. The'G.iagnostic reflection of tremolite talcum products. Because there a.re close struc- was detected at all levels of dilution up to, and 104 Environmental . Health ·. ' Pcn-spectives . FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 nd ·tne11uamg, the 99.9% talc-0.1% tremolite level. . Preparation and An.alysls of ChrysotUe- Talc Dilu· · tre 0.1% trem·olite was not detected above tfon Samples by Electron Microscopy . · ·, 1al bn.c.l®'jilunn. Replicate dilution mixtures at the us ~-:,~··.. ·-· and 0.05% tremolite levels were prepared Aliquot portions of variouS chrysotile-ialc at step-scanned to confirm these observations. dilution levels whiCh had been analyzed by x·ray of results were consistent and reproducible. diffraction were prepared for transmission elee· >e ~An.fh,oph.yUtte in Talc: The anthophyllite tron microscopy by a "rubou~ procedure (8B). r- in preparing dilution mixtures of fiber in Standard weights (0.01 mg) of each of the dllu· :- was from the UICC standard asbestos tion standards are dlspersed In a nitrocellulose l) mineral collection. previously film and mounted on Formvar-coated electron II ·fiA•.IInllll'&tlterlized (BB). A specimen of tbia material microscope grids. The dispersal is accomplished e continuously scanned by x-ray diffraction by mounting the sample in a drop of I 8° to 70° 2fJ at 1°/min. When the peaks on nitrocellulose-amyl acetate solution on a I diffraction. pattern were assigned d microscope slide and grinding It with the edge of ~~tll,aeiJlgs. it w11.s found that the IUltbophylUte a clean watch glass to reduce the sample into was contaminated by· talc. chlorite, and submicron-slzed particles. This procedtll'e breaks :i>hlogopite. However, these intrinsic con- apart the fl.ber bundles of chrysotile, already taminants do not preclude use of the material as greatly comminuted by triple air jet-milling and dilution standard. A more serious limiting sonlfication, into unit fibrfls or into small fiber condition pertains to the similarities between bundles. At the same time, large aggregates of ~he diffraction patterns of "puren antbophylUte talc particles are reduced in size and dispersed ·and talc (see Fig. 4). Among the most intense to allow all asbestos fibers to be seen and reflections of anthophyllite are the 8.05 A counted. . (obscured by the supe~oaition of the talc 8.12 After dispersing the sample, a drop of amyl = A.Ill• 40); the 4.60 A (obscured by the 4.53 acetate is placed on a second clean side. The two A. lilt =12 and the 4.56 A, lilt ... 45 both of slides are placed in contact and the ground talc) and the 3.23 A (obscured by the 8.33 A residue and nitrocellulose solution is further mica eon taminan t of talc, Ilia = 100). Since the dispersed. The residue is typically spread over peak·to-background ratio of the most intense the ali~e for a length of 5 crit. 'rhe two sUdes are ·reflections o! the powder pattern is the most im· then pulled apart, leaving two films with the portant single factor in determining the powder uniformly distributed in them. The minimum detectable amount of a substance, the films quickly chy: The edges of the sllde with at- interference between similarly spaced strong tached film are scraped wlth a scalpel blade; reflections of talc and anthophyllite significant· then by dipping the slide into water, the film ly diminishes the possibility of detecting minute can be floated onto the surface of the water. amounts of anthophyllite asbestos in talc. The Electron microscope grids are placed on top of 8.26 A reflection of anthophyllite, with the segments of the film and covered with a strip of relative intensity of 55, was selected as the most filter paper. The grid is retrieved by lifting the useful diagnostic reflection for the filter paper out of the water. After drying, the anthophyllite-talc dilution series. DDiition grids can be picked off the filter paper and mixtures ranging from 95.0% talc-5.0% mounted in the electron microscope for scan· antbophylllte through 99.5% talc-0.5% ning. . anthophyllite were prepared. When step- Typically. three grids are prepared for each scanned under constant co~ditions. dilution level of chrysotne-talc and six squares anthophyllite was not detected at concen· of each grid are scanned at about lO,OOOX tratlons below 2.0% in repeated samples. With magnification to obtain a number of represen· continuous scanning, anthophyllite was . not tative fields for study. A large number of fields detected at or below the 4.0% dilution level when are photographed and enlarged prints are then the 8.26 A reflection was used as an index (see made. From the photographic enlargements the Fig. 4). . . . ·: .• number of long unit fibrils per field are counted • t .• J .I I. J)eoember 1974 105 ,. FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 •, and the resultS are tabulated. When multiple Application of Transmission Electron Microscopy fibril bundles are encountered, the number of Methods (Including Selected Area Electron Dlf· unit fibrils in the bundles is estimated by fraction) in Detection of Asbestos in Consamer counting the number of visible central Tales · capillaries and by judgblg the optical denslty of Consumer tales have been prepared and the fiber bundle. The electron mfcroscopie fiber examined by means of transmission electron counts show a fairly good correlation with levels microscopy. Representative sample aliquots of ehrysotile dilution. For example, the average were sonically dispersed in filtered water and number of chrysotile fibrils per field, scanned a.t plpetted onto Formvar-carbon 200·mesh 7100X magnification was counted at the follow- copper electron microscope grids. After these ing dilution levels: 5% cbrysotile-95% talc, 92 preparations were dry they were again carbon fibrils per field ::l; 10%; 1% chrysotile-99% talc coated t9 insure a therm~y and electrically 22 fibrils per field :1: 10%; 0.5% stable preparation. Samples were scanned at chrysotile-99.5% talc 8 fibrils per field :1: 10%; magnification in excess of 20,000 and examined 0.25% cbrysotJle-99.75% talc 6 fibrils per field for their fiber content. A representative platy :1: 10%. It is evident that there are considerable and fibrous talc is shown in Figure .6. The numbers of chrysotile fibers present in talc even asbestos content of tale may be directly es- at very low dilution levels. By using the fiber timated utilizing transmission electron count data for the various dilution levels' it is microscopy. Each fiber type may be identified. possible to calculate the number of fibrils con- For example, ehrysotile asbestos is tained In a unit weight of sample. morphologically unique. Its internal capillary, The area of the nitrocellulose fUm is known, fibril dimensions, susceptibility to electron as is the magnification factor. From these and a beam damage, and unique electron diffraction measurement of the area of the photographs, a pattern, aU make the fiber easily recognizable conversion factor is calculated. Allowing for an (38). error as large as one magnitude the calculations Fibers which are electron-dense and which show that there are 2N X 10' fibrils/mg of sam· possess the morphological eharacteristlcs of ple, the value N being the average number of amphiboles, were examined by selected area fibrils per field. Thue, in a 1% dilution of electron diffraction for confirmation. We have chrysotile in talc, tbere would be about 4 X 10' done this on many particles ln numerous fibrUs/mg. At the lowest level of detection of samples and are able to differentiate fibrous ehrysotlle by x-ray diffraction, i.e., 0.25%, there talc £rom fibers of asbestos quite easily (Fig. 7) would be about a 1()1' fibrils/mg. (88). However, this method is not sufficiently It is clear that in issuing regulations specify. sensitive to distinguish among the amphiboles. ing the absence or absolute limits of asbestos in Here, microchemical characterization is tale, close attention must be paid to the necessary (8.4). Electron. microscopy is an ex· capabilities of the analytical technique used for cellent qualitative tool for determining the determining whether, or how much, asbestos is presenc!e or absence of asbestos fibers in. talc. present. X-ray diffraction can provide positive answera to these questions only at the 0.25% lev· Microchemical Analysis by Eledron Microprobe el for ehrysotile which has been shown to be a Analysis · · crude and inaeeurate measure of the potential By means of microchemical analysis, it is contamination and possible hazard involved. In possible to differentiate among the amphibole addition, as mueh as 2.0% of anthophyllite in asbestos fiber types. We have examined talc talc may not be detected by this method. On samples obtained from a mill in which the other ha.nd, electron microscopic analysis anthophyllite and tremolite fibers oceurred can be a sensitive tool for detecting extremely within the talc. These samples were examined minute amounts of chrysotile and other on an ARL electron microprobe analyzer asbestos minerals in talc. equipped 'Yi~b crrstal spectometers. The instru· 106 Environmental Health Perspectives FILED: ERIE COUNTY CLERK 03/17/2023 09:06 PM INDEX NO. 815818/2020 NYSCEF DOC. NO. 329 RECEIVED NYSCEF: 03/17/2023 Utd ron ots .nd sh ISS :m Jy at td '¥ .e I• 7. :..... 1. . l .... .~ ~:·~ ~-...·~). ~··.r :.· ,-~-y~ ............ ~v· .~, ....::... ·.. .. ::.. . riJ!', . . . . •,: ···~ :~ FIGUR!l: 7. Selected area electron diffraction patternJ obtained on (A) a talc plate and (marked TF in B) a tale fiber. 'l'alc fibere are not con1'uled with amphl- bolea. 'l'hey are often cun!llnear, poueu Irregular .dlftracti