Preview
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
EXHIBIT 31
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
issued: 10-746
ASBESTIFORM AMPHIBOLE MINERALS IN COSMETIC TALC
Part 1: X-ray Diffraction Method
Part II: Optical Microscopy and Dispersion-Staining Method
Introduction
The method which has been adopted for the detection of amphibole minerals in cosmetic talc is the generally
accepted method of x-ray diffraction. Methods which appear in the literature for the detection of fibrous amphibole,
such as, transmission electron with selected area diffraction¹ and electron microprobe,2
microscopy have also
been considered since they are capable of a lower level of detection than by x-ray diffraction. However, they have
not hun edopted ppce suffer kom the drawbacks, that the amount of mateda! under examina'ion is quite
they
small (less than a microgram) and the time for analysis, expertise required, and expense of equipment eliminates
them as routine methods.
The methodology presented is the most practical available, based on current technology. The use of Transmission
Electron Microscopy with Selected Area Electron Diffraction offers greater sensitivity, but is not presented since it
is unsuitable for normal quality control application.
Enrichment or concentration techniques using flotation cells have been tried as a means of improving the detection
level; however, all efforts so far have been unsuccessful.
Principle
The x-ray diffraction method is based upon the principle that when a crystalline material is placed in an x-ray
beam, a portion of the x-rays are diffracted by each set of atomic planes within the crystal. The diffracted rays
strike a scintillation counter as the sample is scanned through a prescribed angle with the resulting development
8.85A°
of peaks corresponding to each interplanar distance (d). A peak with d value in the range of 8.04 to for a
sample talc is strong evidence for the presence of amphibole in that talc. The level of detection of amphibole by
this method is 0.5% and above. The variability of-detection is caused by such factors as age and manufacturer of
x-ray diffractometers, sample homogeneity, specific amphibole mineral present, morphology of amphibole, particle
size, preferred orientation, etc. For these reasons the level of detection should be reported for levels above 0.5%,
since below this level the data has been found to be not reproducible. If a statistically significant peak is found of
intensity equal to or greater than that obtained for the 0.5% standard in the d range for amphibole, described above,
then the sample must be put through the following confirming scheme:
(--
)
X-ray Diffractometry ) Optical Microscopy ) Stop (Amphibole absent)
(Acid Leach) and
Dispersion-Staining Color
, , s ( +)
(- )
Stop (Amphibole absent) Fibrous Morphology ) Stop (Asbestiform Amphibole absent)
( +)
Stop
(Asbestiform Amphibole present)
P
QE-CPC00001142
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-t
issued: 10475
Paget
Part 1: Amphibole Minerals by X-ray Diffractometry
Apparatus
1. X-ray diffractometer, employing nickel-filtered copper K-alpha radiation, horizontal or vertical goniometer
with variable scan speed capability, suitable talc pellet sample holder, variable speed recorder, electronic
panel including ratemeter and variable attenuation and time constant settings
2. Hydraulic press, capable of attaining a pressure of 15,000 3"
to 24,000 lb calculated on a ram
3. Mortar and pestle or grinding mill (Note 1)
Blendor,"
4. Waring or equivalent blender
Mixer/Mill,*
5. Spe x or equivalent mechanical mixer
6. Sieve, 325-mesh
7. Optical microscope (Note 2)
1¼"
8. pellet press
Reagents
1. Standard talc sample, containing no detectable amphibole minerals
2. Standard tremolite sample, at least 80% pure
Sample of tremolite standard be obtained from The Cosmetic and Fragrance Associa-
may by ordering Toiletry
tion, Inc., 1133 Fifteenth Street, N.W., Washington, D.C. 20005.
3. Denatured ethanol
4. Boric acid
Procedure
The procedure consists of slow-scanning, under previously determined conditions,
a compressed pellet of the sample taic in the 11.0 to 10.0°26 (8.85 to 8.04 A) region
for the presence of an amphibole peak. There are times when itis difficult to discrimi-
nate a possible peak for amphibole over the background noise level.
"RegisteredTrademark
AS\tFTtr init rTRY iNn rp tra t ver a conct tyrny rve . t i 22 c:c,,.-.t e.. ,. v w w. t :..... .. n c ,nnne
Q E-CPC00001143
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA MethodJ4-1
Issued: 10-7-76
Page3
"noise"
Should the presence of a small amphibole peak above the background be
in question, it will
be necessary to statistically evaluate the scan. A timer/scaler is
required on the electronic panel of the x-ray diffractometer. In order for a peak to be
statistically significant, the peak intensity must equal or exceed three standard
deviations (3Ã) above the average background intensity (N):
N + 3Ã = minimum peak intensity
N = average background count
Where:
"Peak"
' A" I
'"a"
10.3 10.7
10.0 10.2 10.4 10.6 10.8 11.0 °26
Figure 1.
Determine the region of the scan in question: in the Figure 1 scan, a peak appears to be present in the 10.40 to
10.60°26 region.
Slow scan with cumulative pulse counting through the peak region three separate times and average the number
of counts.
Determine a background count by scanning a region equal to ½ of the°26region covered by the peak, immediately
before and after the peak. The counting time for each of these background regions will equal ½ the total counting
time used for the peak. Count each background region three times. Then average each region and add the two
averages to obtain the background count (N).
AC\fFTI TATI FTRY AND FR a .RAN F ARRAFIATION TN . II11 Fiftoonth Stroot N W h0oton nr AAAC
QE-CPC00001144
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
issued: 10-7-76
Page4
Example:
In Figure 1.
Region (°2 4 Time (sec.)
Peak . ............. . ..... 10.40 to 10.60 120
Background
Region A . . . . . . . . ...... 10.30 to 10.40 60
Region 8 .. . . . . . . . . . . . . 10.60 to 10.70 60
Background
Peak Region A Region B
10.40 to 10.60 °2 6 10.30 to 10.40 °2 0 10.60 to 10.70 °2 0
time secs. counts time secs. counts time secs. counts
120 60,332 60 28,784 60 28,506
1 20 59,870 60 28,943 60 28,368
120 60,105 60 28,634 60 28,204
Average 60,102 28,787 28,359
N = 28,787
+ 28,359 = 57,146
g =_ V57,146 = 239 3Ã = 717
N + 3Ã = 57,146 + 717 = 57,863
The actual number of counts obtained for the integrated peak intensity was 60,102;
"suspect"
therefore, the peak is statistically present in the scan.
COSMETIC. TOILFTRY AND FRAC.RANCF ASSOCIATION INC " I133 Fifteenth Street N W Whinoran D C Inns
Q E-CPC00001145
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
issued: 10-7-76
PageS
Standard Preparation
Optimal instrument conditions must first be determined with the use of tremolite
standards: 1.0%, 0.75°Æ, 0.5% tremolite by weight, prepared in a standard talc
which is free of interfering peaks in the 11.0 to 10.0°20 region.
Weigh out appropriate amounts of standard talc and tremolite both of which have been ground to pass a 325-mesh
Blendor.*
sieve. Transfer to a Waring Add 100 mi of ethanol to the blender and blend at tow speed for 5 minutes.
Carefully transfer the contents of the blender, with repeated ethanol washings, into a large beaker. Evaporate the
ethanol on a steam bath.
Mixer/Mill*
Shake the sample in a plastic vial for 5 minutes on a Spex to remove clumps and caked sample resulting
from the evaporation of ethanol.
Determine by microscopy the homogeneity of the prepared standard previous to the x-ray diffraction analysis.
a1¼"
Press the homogeneous standard into pellet with a backing of boric acid. Transfer 2 (±0.2) g of standard to
the die-holder and evenly distribute on a polished, scratch-free die. Distribute 4 (±0.2) g of boric acid evenly on the
talc layer. Press the mixture into a pellet under conditions suitable for obtaining a smooth planar surface (for example,
3"
a pressure of 15,000 to 24,000 lb calculated on a ram has been found to produce suitable pellets). The resulting
pellet must have a talc face which is free of flaws; if not, the pellet must be discarded (Note 3). Prepare two acceptable
pellets from each standard.
"RegisteredTrademark
ActfrTI TATT CTDV 4 Un CD 4 D t V C 4 CCA I TIAN TN . 1111 C:fenonek Ce..ant N W Work;nntnn n 0000C
Q E-CPC00001146
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
Issued: 10-7-76
Page 6
Sample Preparation
Prepare two pellets from each sample in the manner described for the standard pellets. Make a qualitative scan
from 4 to 50°26 on one of these pellets to ascertain the presence of amphibole above the 2% level or the presence
of mineral impuritieshaving interfering peaks in the 11.0 to 10.0°26 (8.85 to 8.04A) region of the scan. The presence
of such interference will eliminate use of the x-ray diffraction method for the sample, and one will have to proceed
directly to the microscopical procedure.
instrumentation
Instrumental variables are optimized on the 1% standard. Lower standards are then
analyzed under the optimum conditions to determine the tower level of detection.
of major importance in obtaiñ|ñg mawmum la5trument seasitivity ars a slow dif-
fractometer speed combined with compatible recorder and high attenua-
speed,
tion combined with a statistically acceptable time constant on the ratemeter. Under
appropriate instrumental conditions the peak obtained for the 0.5% standard should
be detectable above background noise as shown in Figure 2.
Typical instrumental conditions employed for the Siemens Diffractometer (Model No. M386-X-A4), and Counter
and Recorder Unit (Type T) are:
Radiation: Cu with K filter at 40KV and 24 ma
1°
Divergence slit: Receiving slit: 0.2 mm
Goniometer speed: 1/so°26/minute
Recorder speed: 300 mm/hour
Attenuation: 1 × 103 impulses/second
Time constant: T (s) = 4
Statistical error of 1.1% under these conditions
Rise Time = 0.18
Attenuator = 20
COSMETIC TOILETRY AND FRAGRANCE ASSOCIATION. INC. " 1133 Fifteen th Street. N.W.. Washington. D.C. 20005
Q E-CPC00001147
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
issued: 10-7-76
Page 7
0.5% Tremolite
,,
in Talc
70-
20-
to-
*29
Figure 2
X-Ray Diffraction Scans
10.0°
Place the standard or sample pellet in a suitable holder slowly scan between
and 11.0 and 2 8. Then rotate the
90°
pellet with respect to its original position in the goniometer and rescan between 11.0 and 10.0°26 since pellet
orientation may affect peak intensity. The presence of a reproducible peak (or peaks) is due to the presence of
amphibole mineral (or minerals); the absence of peaks in this region indicates the absence of amphibole in the
sample, within the limit of detection of this technique.
detected" level," "X"
Report results as "None or as "Detected at approximately X% where equals the level detected.
AcurTT TATI FTpy Wn FRacD AN F ARCA TATION IN . 1111 Fifteenth Rtreat N w Washinoton n 700n5
Q E-CPC00001148
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
issued: 10-7-76
Page 8.
Part II: Asbestiform Amphibole Minerals by Optical
Microscopy and Dispersion-Stainihg
Apparatus
1. Polarizing microscope. Best results will be obtained if the instrument includes the following:
a. Individually centering objectives
b. Bertrand lens
c. High-intensity light source
d. Centering condenser/substage
2. Dispersion-staining device (Note 4)
3. Vacuum filtration equipment, including either a porcelain cone with glass fiber filter mat or a porous glass bottom
cup
Reagents
1. Hydrochloric acid, 10% v/v
nE5©
2. Cargille immersion liquid Series HD, = 1.605 (Note 5)
. .
Procedure
Acid Treatment
Because of the interference caused
by some carbonates (e.g. calcite) in the detec-
tion of asbestiform amphiboles in talc by optical microscopy/dispersion-staining, it
is necessary to first remove these carbonates by a simple acid leaching procedure:
Q E-CPC00001149
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
. CTFA Method J 4-1
Issued: 10-7-76
Page 9
Weigh out 2 g of the talc into a 100 mi beaker. Add 25 mi of 10% v/v HC1 slowly (to prevent excessive evolution of gas
if carbonates are present) and heat, with occasional stirring on a steam bath for 30 minutes.
Filter with vacuum filtration equipment, and wash several times with hot water. Dry the talc.
Optical Microscopy and Dispersion-Staining
disperse 0.1 mg of talc in one drop of Cargille HD liquid, = 1.605, and cover with a clean cover slip.
Carefully r¶
Examine the sample in the dispersion-staining centrai stop mode. The substage diaphragm should be almost com-
pletely closed, the field diaphragm may be partially closed to enhance color contrast, and ine polarizer should be in
position.
Tremolite, actinolite and presumably other under these condi-
amphibole
minerals,
tions, will show the following dispersion-staining colors: yellow changing to blue
with rotation of the sample relative to the polarizer or yellow changing to orange
with rotation. The variation of the color change is due to the fact that the tremolite
may lie in one of two positions relative to its principal optical orientation.
Examine the sample for asbestiform fibrous amphibole minerals.
in order for an amphibole mineral to be considered asbestiform fibrous it must meet the following OSHA definition
(Reference 4).
1. Particles must appear to be fibrous.rather than as crystals or slivers.
2. The maximum diameter of a fiber to be counted in 3 microns.
3. The maximum length of a fiber to be counted is 30 microns.
4. The length to width ratio must be 5 or more to 1, that is, 5 times or more longer than wide.
sticks"
5. The separate or individual fibers must contain fibrils or the "bundle of effect, unless they are at a
nondivisible stage. A fibril cannot be subdivided and would be counted, if it meets the other criteria. The
length to width ratio of 5 or more to 1 is not meant to imply tnat other particles are not hazardous.
QE-CPC00001150
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023
NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023
CTFA Method J 4-1
Issued: 10-7-70
Page 10
Present" Absent."
Report results as "Asbestiform Amphibole or as "Asbestiform Amphibole
It is imperative that both dispersion-staining color and fibrous morphology criteria
be satisfied before a particle as asbestiform amphibole, since other sub-
identifying
stances may show colors similar to those described.
Notes
1. Tales to be analyzod and the tremolite used to preparo standard samples must be finer than 325 mcch (maxi-
mum particle size of 44 microns). The Tekmar Analytical Mill (Model A-10) is recommended. It is available from:
Tekmar Company
P.O. Box 37202
Cincinnati, Ohio 45222
2. It is important that the homogeneity of the prepared talc-tremolite standard samples be verified by optical
microscopy.
3. This requirement is critical since excessive surface scatter will cause abnormally high background counts.
4. The only commercially available dispersion-staining device is sold by:
Walter C. Mc Crone Associates, Inc.
2820 South Michigan Avenue
Chicago, Illinois 60616
5. Available from:
R. P. Cargille Laboratories, Inc
Cedar Grove, New Jersey 07009
-or from laboratory suppliers.
References
1. Rohl, A. N., Langer, A. M.,Environmental Health Perspectives 9, 95 (1974)
2. Rubin, I. B., Maggiore, C. J.,Environmental Health Perspectives 9, 81 (1974)
3. L. S. Birks,
X-Ray Spectrochemical Analysis, pages 54-55, interscience Publishers (1959)
Talc." informa-
4. "Tremolite and U.S. Department of Labor, Occupational Safety and Health Administration, Field
tion Memorandum # 74-92, November 21, 1974.
COSMETIC, TOILETRY AND FRAGRANCE ASSOCIATION. INC. " I133 Fifteenth Street, N.W., Washington. D.C. 20005
QE-CPC00001151
Preview
FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 EXHIBIT 31 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 issued: 10-746 ASBESTIFORM AMPHIBOLE MINERALS IN COSMETIC TALC Part 1: X-ray Diffraction Method Part II: Optical Microscopy and Dispersion-Staining Method Introduction The method which has been adopted for the detection of amphibole minerals in cosmetic talc is the generally accepted method of x-ray diffraction. Methods which appear in the literature for the detection of fibrous amphibole, such as, transmission electron with selected area diffraction¹ and electron microprobe,2 microscopy have also been considered since they are capable of a lower level of detection than by x-ray diffraction. However, they have not hun edopted ppce suffer kom the drawbacks, that the amount of mateda! under examina'ion is quite they small (less than a microgram) and the time for analysis, expertise required, and expense of equipment eliminates them as routine methods. The methodology presented is the most practical available, based on current technology. The use of Transmission Electron Microscopy with Selected Area Electron Diffraction offers greater sensitivity, but is not presented since it is unsuitable for normal quality control application. Enrichment or concentration techniques using flotation cells have been tried as a means of improving the detection level; however, all efforts so far have been unsuccessful. Principle The x-ray diffraction method is based upon the principle that when a crystalline material is placed in an x-ray beam, a portion of the x-rays are diffracted by each set of atomic planes within the crystal. The diffracted rays strike a scintillation counter as the sample is scanned through a prescribed angle with the resulting development 8.85A° of peaks corresponding to each interplanar distance (d). A peak with d value in the range of 8.04 to for a sample talc is strong evidence for the presence of amphibole in that talc. The level of detection of amphibole by this method is 0.5% and above. The variability of-detection is caused by such factors as age and manufacturer of x-ray diffractometers, sample homogeneity, specific amphibole mineral present, morphology of amphibole, particle size, preferred orientation, etc. For these reasons the level of detection should be reported for levels above 0.5%, since below this level the data has been found to be not reproducible. If a statistically significant peak is found of intensity equal to or greater than that obtained for the 0.5% standard in the d range for amphibole, described above, then the sample must be put through the following confirming scheme: (-- ) X-ray Diffractometry ) Optical Microscopy ) Stop (Amphibole absent) (Acid Leach) and Dispersion-Staining Color , , s ( +) (- ) Stop (Amphibole absent) Fibrous Morphology ) Stop (Asbestiform Amphibole absent) ( +) Stop (Asbestiform Amphibole present) P QE-CPC00001142 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-t issued: 10475 Paget Part 1: Amphibole Minerals by X-ray Diffractometry Apparatus 1. X-ray diffractometer, employing nickel-filtered copper K-alpha radiation, horizontal or vertical goniometer with variable scan speed capability, suitable talc pellet sample holder, variable speed recorder, electronic panel including ratemeter and variable attenuation and time constant settings 2. Hydraulic press, capable of attaining a pressure of 15,000 3" to 24,000 lb calculated on a ram 3. Mortar and pestle or grinding mill (Note 1) Blendor," 4. Waring or equivalent blender Mixer/Mill,* 5. Spe x or equivalent mechanical mixer 6. Sieve, 325-mesh 7. Optical microscope (Note 2) 1¼" 8. pellet press Reagents 1. Standard talc sample, containing no detectable amphibole minerals 2. Standard tremolite sample, at least 80% pure Sample of tremolite standard be obtained from The Cosmetic and Fragrance Associa- may by ordering Toiletry tion, Inc., 1133 Fifteenth Street, N.W., Washington, D.C. 20005. 3. Denatured ethanol 4. Boric acid Procedure The procedure consists of slow-scanning, under previously determined conditions, a compressed pellet of the sample taic in the 11.0 to 10.0°26 (8.85 to 8.04 A) region for the presence of an amphibole peak. There are times when itis difficult to discrimi- nate a possible peak for amphibole over the background noise level. "RegisteredTrademark AS\tFTtr init rTRY iNn rp tra t ver a conct tyrny rve . t i 22 c:c,,.-.t e.. ,. v w w. t :..... .. n c ,nnne Q E-CPC00001143 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA MethodJ4-1 Issued: 10-7-76 Page3 "noise" Should the presence of a small amphibole peak above the background be in question, it will be necessary to statistically evaluate the scan. A timer/scaler is required on the electronic panel of the x-ray diffractometer. In order for a peak to be statistically significant, the peak intensity must equal or exceed three standard deviations (3Ã) above the average background intensity (N): N + 3Ã = minimum peak intensity N = average background count Where: "Peak" ' A" I '"a" 10.3 10.7 10.0 10.2 10.4 10.6 10.8 11.0 °26 Figure 1. Determine the region of the scan in question: in the Figure 1 scan, a peak appears to be present in the 10.40 to 10.60°26 region. Slow scan with cumulative pulse counting through the peak region three separate times and average the number of counts. Determine a background count by scanning a region equal to ½ of the°26region covered by the peak, immediately before and after the peak. The counting time for each of these background regions will equal ½ the total counting time used for the peak. Count each background region three times. Then average each region and add the two averages to obtain the background count (N). AC\fFTI TATI FTRY AND FR a .RAN F ARRAFIATION TN . II11 Fiftoonth Stroot N W h0oton nr AAAC QE-CPC00001144 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 issued: 10-7-76 Page4 Example: In Figure 1. Region (°2 4 Time (sec.) Peak . ............. . ..... 10.40 to 10.60 120 Background Region A . . . . . . . . ...... 10.30 to 10.40 60 Region 8 .. . . . . . . . . . . . . 10.60 to 10.70 60 Background Peak Region A Region B 10.40 to 10.60 °2 6 10.30 to 10.40 °2 0 10.60 to 10.70 °2 0 time secs. counts time secs. counts time secs. counts 120 60,332 60 28,784 60 28,506 1 20 59,870 60 28,943 60 28,368 120 60,105 60 28,634 60 28,204 Average 60,102 28,787 28,359 N = 28,787 + 28,359 = 57,146 g =_ V57,146 = 239 3Ã = 717 N + 3Ã = 57,146 + 717 = 57,863 The actual number of counts obtained for the integrated peak intensity was 60,102; "suspect" therefore, the peak is statistically present in the scan. COSMETIC. TOILFTRY AND FRAC.RANCF ASSOCIATION INC " I133 Fifteenth Street N W Whinoran D C Inns Q E-CPC00001145 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 issued: 10-7-76 PageS Standard Preparation Optimal instrument conditions must first be determined with the use of tremolite standards: 1.0%, 0.75°Æ, 0.5% tremolite by weight, prepared in a standard talc which is free of interfering peaks in the 11.0 to 10.0°20 region. Weigh out appropriate amounts of standard talc and tremolite both of which have been ground to pass a 325-mesh Blendor.* sieve. Transfer to a Waring Add 100 mi of ethanol to the blender and blend at tow speed for 5 minutes. Carefully transfer the contents of the blender, with repeated ethanol washings, into a large beaker. Evaporate the ethanol on a steam bath. Mixer/Mill* Shake the sample in a plastic vial for 5 minutes on a Spex to remove clumps and caked sample resulting from the evaporation of ethanol. Determine by microscopy the homogeneity of the prepared standard previous to the x-ray diffraction analysis. a1¼" Press the homogeneous standard into pellet with a backing of boric acid. Transfer 2 (±0.2) g of standard to the die-holder and evenly distribute on a polished, scratch-free die. Distribute 4 (±0.2) g of boric acid evenly on the talc layer. Press the mixture into a pellet under conditions suitable for obtaining a smooth planar surface (for example, 3" a pressure of 15,000 to 24,000 lb calculated on a ram has been found to produce suitable pellets). The resulting pellet must have a talc face which is free of flaws; if not, the pellet must be discarded (Note 3). Prepare two acceptable pellets from each standard. "RegisteredTrademark ActfrTI TATT CTDV 4 Un CD 4 D t V C 4 CCA I TIAN TN . 1111 C:fenonek Ce..ant N W Work;nntnn n 0000C Q E-CPC00001146 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 Issued: 10-7-76 Page 6 Sample Preparation Prepare two pellets from each sample in the manner described for the standard pellets. Make a qualitative scan from 4 to 50°26 on one of these pellets to ascertain the presence of amphibole above the 2% level or the presence of mineral impuritieshaving interfering peaks in the 11.0 to 10.0°26 (8.85 to 8.04A) region of the scan. The presence of such interference will eliminate use of the x-ray diffraction method for the sample, and one will have to proceed directly to the microscopical procedure. instrumentation Instrumental variables are optimized on the 1% standard. Lower standards are then analyzed under the optimum conditions to determine the tower level of detection. of major importance in obtaiñ|ñg mawmum la5trument seasitivity ars a slow dif- fractometer speed combined with compatible recorder and high attenua- speed, tion combined with a statistically acceptable time constant on the ratemeter. Under appropriate instrumental conditions the peak obtained for the 0.5% standard should be detectable above background noise as shown in Figure 2. Typical instrumental conditions employed for the Siemens Diffractometer (Model No. M386-X-A4), and Counter and Recorder Unit (Type T) are: Radiation: Cu with K filter at 40KV and 24 ma 1° Divergence slit: Receiving slit: 0.2 mm Goniometer speed: 1/so°26/minute Recorder speed: 300 mm/hour Attenuation: 1 × 103 impulses/second Time constant: T (s) = 4 Statistical error of 1.1% under these conditions Rise Time = 0.18 Attenuator = 20 COSMETIC TOILETRY AND FRAGRANCE ASSOCIATION. INC. " 1133 Fifteen th Street. N.W.. Washington. D.C. 20005 Q E-CPC00001147 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 issued: 10-7-76 Page 7 0.5% Tremolite ,, in Talc 70- 20- to- *29 Figure 2 X-Ray Diffraction Scans 10.0° Place the standard or sample pellet in a suitable holder slowly scan between and 11.0 and 2 8. Then rotate the 90° pellet with respect to its original position in the goniometer and rescan between 11.0 and 10.0°26 since pellet orientation may affect peak intensity. The presence of a reproducible peak (or peaks) is due to the presence of amphibole mineral (or minerals); the absence of peaks in this region indicates the absence of amphibole in the sample, within the limit of detection of this technique. detected" level," "X" Report results as "None or as "Detected at approximately X% where equals the level detected. AcurTT TATI FTpy Wn FRacD AN F ARCA TATION IN . 1111 Fifteenth Rtreat N w Washinoton n 700n5 Q E-CPC00001148 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 issued: 10-7-76 Page 8. Part II: Asbestiform Amphibole Minerals by Optical Microscopy and Dispersion-Stainihg Apparatus 1. Polarizing microscope. Best results will be obtained if the instrument includes the following: a. Individually centering objectives b. Bertrand lens c. High-intensity light source d. Centering condenser/substage 2. Dispersion-staining device (Note 4) 3. Vacuum filtration equipment, including either a porcelain cone with glass fiber filter mat or a porous glass bottom cup Reagents 1. Hydrochloric acid, 10% v/v nE5© 2. Cargille immersion liquid Series HD, = 1.605 (Note 5) . . Procedure Acid Treatment Because of the interference caused by some carbonates (e.g. calcite) in the detec- tion of asbestiform amphiboles in talc by optical microscopy/dispersion-staining, it is necessary to first remove these carbonates by a simple acid leaching procedure: Q E-CPC00001149 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 . CTFA Method J 4-1 Issued: 10-7-76 Page 9 Weigh out 2 g of the talc into a 100 mi beaker. Add 25 mi of 10% v/v HC1 slowly (to prevent excessive evolution of gas if carbonates are present) and heat, with occasional stirring on a steam bath for 30 minutes. Filter with vacuum filtration equipment, and wash several times with hot water. Dry the talc. Optical Microscopy and Dispersion-Staining disperse 0.1 mg of talc in one drop of Cargille HD liquid, = 1.605, and cover with a clean cover slip. Carefully r¶ Examine the sample in the dispersion-staining centrai stop mode. The substage diaphragm should be almost com- pletely closed, the field diaphragm may be partially closed to enhance color contrast, and ine polarizer should be in position. Tremolite, actinolite and presumably other under these condi- amphibole minerals, tions, will show the following dispersion-staining colors: yellow changing to blue with rotation of the sample relative to the polarizer or yellow changing to orange with rotation. The variation of the color change is due to the fact that the tremolite may lie in one of two positions relative to its principal optical orientation. Examine the sample for asbestiform fibrous amphibole minerals. in order for an amphibole mineral to be considered asbestiform fibrous it must meet the following OSHA definition (Reference 4). 1. Particles must appear to be fibrous.rather than as crystals or slivers. 2. The maximum diameter of a fiber to be counted in 3 microns. 3. The maximum length of a fiber to be counted is 30 microns. 4. The length to width ratio must be 5 or more to 1, that is, 5 times or more longer than wide. sticks" 5. The separate or individual fibers must contain fibrils or the "bundle of effect, unless they are at a nondivisible stage. A fibril cannot be subdivided and would be counted, if it meets the other criteria. The length to width ratio of 5 or more to 1 is not meant to imply tnat other particles are not hazardous. QE-CPC00001150 FILED: NEW YORK COUNTY CLERK 07/10/2023 10:29 PM INDEX NO. 190002/2023 NYSCEF DOC. NO. 116 RECEIVED NYSCEF: 07/10/2023 CTFA Method J 4-1 Issued: 10-7-70 Page 10 Present" Absent." Report results as "Asbestiform Amphibole or as "Asbestiform Amphibole It is imperative that both dispersion-staining color and fibrous morphology criteria be satisfied before a particle as asbestiform amphibole, since other sub- identifying stances may show colors similar to those described. Notes 1. Tales to be analyzod and the tremolite used to preparo standard samples must be finer than 325 mcch (maxi- mum particle size of 44 microns). The Tekmar Analytical Mill (Model A-10) is recommended. It is available from: Tekmar Company P.O. Box 37202 Cincinnati, Ohio 45222 2. It is important that the homogeneity of the prepared talc-tremolite standard samples be verified by optical microscopy. 3. This requirement is critical since excessive surface scatter will cause abnormally high background counts. 4. The only commercially available dispersion-staining device is sold by: Walter C. Mc Crone Associates, Inc. 2820 South Michigan Avenue Chicago, Illinois 60616 5. Available from: R. P. Cargille Laboratories, Inc Cedar Grove, New Jersey 07009 -or from laboratory suppliers. References 1. Rohl, A. N., Langer, A. M.,Environmental Health Perspectives 9, 95 (1974) 2. Rubin, I. B., Maggiore, C. J.,Environmental Health Perspectives 9, 81 (1974) 3. L. S. Birks, X-Ray Spectrochemical Analysis, pages 54-55, interscience Publishers (1959) Talc." informa- 4. "Tremolite and U.S. Department of Labor, Occupational Safety and Health Administration, Field tion Memorandum # 74-92, November 21, 1974. COSMETIC, TOILETRY AND FRAGRANCE ASSOCIATION. INC. " I133 Fifteenth Street, N.W., Washington. D.C. 20005 QE-CPC00001151