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FILE NAME Talc TALC DATE 1976 DOC TALC017 DOCUMENT DESCRIPTION Journal Article - Consumer Talcums and Powders Mineral and Chemical Characterization  COPY COPY COPY COPY COPY COPY COPY COPY COPY COPY COPY COPY CONSUMER TALCUMS AND POWDERS CHEMICAL CHARACTERIZATION MINERAL AND A. N. Rohl A. M. Langer I. J. Selikoff A. Tordini R. Klimentidis Environmental Sciences Laboratory Mount Sinai School of Sciences Medicine ofthe City York New York York University of New York R. Bowes D. L. Skinner Department of Geology The University of Glasgow Glasgow Scotland Representative consumer talcums and powders including 20 oody powders baby powders facial calcums and also one pharmaceutical talc were analyzed to determine their mineralogical and chemical composition Where known all were formulated prior to 1973. Of the 20 products 10 contained detectable amounts of tremolite and anthophyllite principally asbestiform while some also contained fragmented forms of these minerals two contained The amounts ranged from tenths ofa percent detectable amounts of chrysotile usbestos fiber to over 14 by Eight contained weiant quartz seven ranging from 2 to % with one as nigh as 35 The analyses showed that the consumer products examinea were rarely the pure mineral taic out rather were mixtures of various minerals come samples consisted of three to five minerals only one of which .was 201C Other common mineral phases included chlorite platy serpentine pyropnyllite mica and carbonate minerals Kaolin additive was identified In wo products The single pharmaceutical talc examined contained only a trace amount of quartz The unmical composition of these products including both maior ovide and trace ement content correlated with their mineral components Four sumples contained Jostantial concentrations of nickel cobalt and chromium Juggesting lattice substitu- 1270 1270 the presence of trace mineral phases In aertained On the DUSIS of chemistry Geological provenance of Possible gaverse health the taics may effects from nrmittent use o these products especially those that contain usbestiform and Fragmented anthoonvilite and we re s. Innown and Innown Innown and C sR er Ei Oal tremonte oO. at at or or chrysotile quartz and trace metals are INTRODUCTION Consumer talcums and powders are considered by the public to genbeyratlhe product E 7 ossted 337 200 la Surances ~ Autona Autona . ~ - ' ao nanes gee ~ hy NOT . Joa ~ grant 10923 10923 com the 7 Nationa inst ute Scienus Scienus aesdt IS oe ~ ek 3 ... ... > A wos ' tly mo s ore 7) ars . 5 menta vas Dotst lt. 7, 256 N. ROHL ET AL mineralogically names and ingredients listed on the container labels However knowledge of the geological occurrence and mineralogical character of source materials suggests the nature of talc to be highly variable and complex Twenty consumer talcums and powders Table 1 were and chemically analyzed to determine whether these products are actually talc mineral Talc is a and physical MgSiO defined mineral entity based on specific chemical crystalline , properties Ford 1957 i0 s seldom observed The empirical chemical formula in nature as a result of cation substitution For nickel chromium example magnesium or manganese in the is frequently replaced by crystal structure Talc is a iron sheet silicate with a structural unit consisting of three layers a sheet of octahedrally coordinated magnesium hydroxide groups is sandwiched between two layers of tetrahedrally linked silica layers The Van der Waals bond between the talc sheets are of low energy accounting for the ease with which talc as well as other sheet silicate minerals micas clays cleave TABLE 1. Label Designation of Contents in Brand Name or Sample no Date of formulation Products designated as talcs 3 Not available 8 Not available 12 Approximately 1972 12 September 1972 17 17 Not available April 16 1973 May 1973 196 Not available Products designated as powders talc on label 4 December 1970 18 Not available 20 December 1970 5 February 1973 16 Not available Products 1 14 15 9 11 13 2 10 designated as powders or dust Between January 1968 and July October 3 1970 1970 Between October 1970 and March 1973 February or March 1973 July 1969 July 1970 Not available Approximately 1972 CONSUMER TALCUMS AND POWDERS GEOLOGICAL OCCURRENCE OF TALC Talc rocks including those commercially worked are formed by several complex geological processes reacting upon many possible chem- cally diverse preexisting rock types Hydrothermal alteration of magnesia- and silica ultramafic rocks under a range of moderate tempera- tures and pressures may produce talc Thermal metamorphism of silica- rich dolomite however also CaMg commonly will produce talc as well These processes result in the formation of a number of other Coexisting mineral phases predominantly hydrous magnesium silicates Some of these for example anthophyllite tremolite and serpentine minerals including chrysotile occur as microscopic intergrowths with taic taic as macroscopic nodules or even as discrete zones within or adjacent tale Table 2 Talc rock is therefore generally not monominerallic but s often a mixture of minerals that may vary widely with respect to kind and quantity Phlogopite a magnesium minerals related to the micas are also mica and commonly chlorite a group of associated with talc Some of these associated mineral phases are asbestiform amphiboles and chrysotile see discussion of the terms asbestos and asbestiform in Appendix A Converselv talc has been described as a common accessory ) mineral in commercial asbestos deposits Hurlbut and Williams 1935 Taic deposits may be zoned with different mineral assemblages nsically nsically changing in occurrence and proportions over extremely variable TABLE 2. Minerals that Commoniy Occur in Taic Deposits Mineral groUD Phase Formula Calcite CaCO Curbonates Curbonates Dolomite CaMg CO Magnesite MgCO 4 we t Amphiboles Amphiboles Tremonte i Anthophyllite O. OHI ; FeMg O. FeMg Serpentine Antigorite Chrysotile uncommon zargite uncommon Mg OH Mg 51. OH Mg OOH Others Others oniogopite Chlorite e.g penninite Pyrophylite Pyrophylite Pyrophyllite SIC K. Mg Fe Mg Al Fe 2. A SLO SLO SLO Sp MLa O y : SA 10 10 (OH), OH - brow and TONDO. forms forms Other ride mis mis often 258 258 A. ROHL ET AL distances ranging from centimeters to tens of meters Mineral phases in such deposits may include talc plates and fibers tremolite and anthophyllite fibers intergrowths of amphibole and talc serpentine minerals which may include chrysotile and free silica quartz Ross et al 1968 The fiber intergrowth is often such that even extensive beneficiation may not yield a pure product Thus where grained intergrowths of talc and tremolite occur the processed product will likely contain residual tremo- lite Further details concerning the crystal chemistry structure synthesis and geological occurrence of talc are found in Appendix B. INDUSTRIAL AND COSMETIC GRADE TALCS It is generally recognized that various commercial grades of talc are marketed in the United States Appendix C Hildick 1976 has stated that a talc suitable for pharmaceutical purposes used in cosmetic and toiletry products contains at least 90 talc mineral and no detectable asbestos Such stated compositional restrictions are not placed on industrial grade talcs One study demonstrated that a number of industrial talcs contained substantial quantities of tremolite up to 87 by weight of the sample Schulz and Williams 1942 In 1968 a study Cralley et al 1968 of 22 cosmetic talcum products demonstrated fiber contents ranging from 8 to 30 by count with an average of 19 The fibrous material was predominately talc but probably contained minor amounts of tremolite anthophyllite and chrysotile as these are often present in fibrous talc mineral deposits With the exception of 4 of the 22 cosmetic talcum products analyzed the levels of free silica cobalt nickel chromium and manganese were generally of a low magnitude and within a narrow range levels of silica chromium and nickel in these four products are sufficiently high however to be of concern in their potential to cause disease Thus as late as 1968 some consumer talcum products marketed in the United States contained asbestiform minerals free silica and trace metals HUMAN DISEASE ASSOCIATED WITH TALC EXPOSURE For nearly half a century a number of reports have shown that occupational exposure to talc dust is associated with a fine diffuse interstitial lung scarring known as talcosis Fibrous talcs appeared to be more pathogenic than platy talcs producing in addition to talcosis increased risk of malignant tumors in exposed workers Kleinfeld and CONSUMER TALCUMS AND POWDERS Messite 1960 Kleinfeld et al 1967 Studies concerning the biological consequences associated with talc dust exposure including cancer are referred to in Appendix D. OBJECTIVES OF THE PRESENT STUDY Twenty samples of consumer talcums and powders including baby powders body powders facial powders and a pharmaceutical talcum were obtained at retail stores in the New York City area These samples were acquired and studied during the period 1971-1975 Table ) The major purpose of the study was to determine the mineralogical and chemical composition with particular emphasis on the quantitative determination of tremolite anthophyllite serpentine minerals and quartz Another objective was to establish a base line for consumer talcums and powders based on a sampling of products available during the period 1971-1975 This base line provides an index for evaluating possible changes in subsequent formu- lations METHODOLOGY AND RESULTS OF MINERAL AND CHEMICAL CHARACTERIZATION The analytical techniques employed for mineral identification and quantification included optical microscopy transmission electron microscopy with selected area electron diffraction ray diffraction and scanning electron microscopy with ray analysis capabilities Chemical determinations bulk chemistry and trace metals were made with a number of standard instruments and geochemical techniques including spectrophotometry SiO TiO2 Al2O3 total Fe O3 by difference from FeO P2O5 atomic absorption MnO MgO CaO flame photo- metry Na K O wet chemical assay FeO weight loss volatiles H COO organics ray fluorescence was used for all trace metals Bowes and Langer 1974 Optical Microscopy Optical microscopy is a conventional technique for the identification of minerals and for the study of mineral relationships A microscope equipped with bright field illumination and polarized light optics was used to analyze the cosmetic powders Approximately 0.5 mg of powder was placed on a precleaned glass slide and immersed in index oils of known refractive indices These were checked on a refractometer The information obtained on particles with this method included most of the measurable optical properties including indices of refraction extinction angles of fibers general morphology and size characteristics of mineral phases Fig ) In grained powders fibers could be identified tremolite anthophyllite talc Two samples contained cornstarch easily recognized FIGURE 1. Optical photomicrographs of cosmetic talcums and powders grossly contaminated with asbestiform minerals Photos obtained in plane polarized light Fi and between crossed polars G Scale in A for all photos Fibers shown have optical properties consistent with tremolite Tr and anthophyllite An Quartz grains Ou and calcite fragments Ca are also shown Most tremolite fibers tend to possess smaller length ratios than anthophyllite Tremolite is observed as fragments C Photo obtained between crossed polars G also demonstrates the presence % of fibers in the matrix material Asbestiform length ratios measured up to 20 F eos 260 CONSUMER TALCUMS AND POWDERS by morphological and optical characteristics One product consisted entirel of cornstarch - most samples however the powders were too fine grained with particle dimensions significantly less than 10 10 ...mfor the technique to be usefu The limiting factor for determination of optical constants and nence for identification of particles is the resolving power of the microscope The presence of talc fibers which may have indices of refract on similar to amphibole tremolite anthophyllite anthophyllite fibers also confounds analysis Therefore although this technique is an excellent diagnostic instrument in some instances these restrictions limited its usefuusefulnles unseefulsnesss Other investigators have experienced similar difficulties For example study of the asbestos content of talc Stanley and Norwood 1973 dif iculty there was difficulty difficulty in applying optical microscopy to the problem The authors concluded that optical microscopy while it works works well on pure samples of fairly massive fiber ength from 3 to 5 electron microscopy microns our observations by transmission have shown that naturally occurring asbesti- form minerals often lie belowthethe working resolution capabilities of the light microscope and furthermore while massive fiber cundles can often be observed by either light or electron microscopy the observation of individual fibers smaller than 0.5 0.2 micrometers often will require the high resolution by capability of the transmission electron microscope emphasis added its further stated samples with large that light microscopy was helpful part.cles and high concentrations only in screening of objectionable diffraction By comparing numbers numbers numbers fibers fibers fibers theresults of optical microscopy with those of quantitadiffraction and electron microscopy we observed that large go undetected In addition to the restraints of resolution by drawback imposed light microscopy another maior relates to the or break along of tendency large planes weakness when they are crushed producing numbers of smallfibers fibers For example light of which which contains over microscopic examination % tremolite see Table a talc sample demonstrates the no presence demonstrates mineral fragments that Ever electron microscopic are primariiv not examination of the same toot many of the submicroscopic tremolite particles Fig 1C How- sample demonstrates demonstrates are ffiibrboruosus see see see Fig Fig 2200 The problem involving the determination of the relative proportions ach of these moronological rases 1+ the same sample ass milang new se distributo yous go ray Diffraction The application of ray diffraction analysis in scan mode for quantitative determination of asbestos in talc has been described in detail Rohl and Langer 1974 including the selection of talc and asbestos reference materials the preparation of standard dilutions of asbestos minerals in talc to ensure sensitivity and reproducibility the selection of characteristic ray reflections to be scanned and instrumental technique Selection of talc mineral standard Screening of various types of talcs for use as reference material was made by ray diffraction and transmission electron microscopic analysis A continuous scan was first made to identify the major mineral phases present Talcs that showed the presence of any serpentine mineral tremolite or anthophyllite were eliminated as reference materials The possibility of false negatives for these minerals was checked by step scanning the diagnostic reflections Table 3 Further verification of the absence of asbestiform minerals was made by trans- mission electron microscopy These techniques permitted the selection of a matrix talc that was completely free of asbestiform minerals Chlorite minerals are hydrous magnesium silicates frequently associated with talcs Their presence may interfere with the detection of serpentine minerals both platy antigorite and fibrous chrysotile This is particularly true if they are present in equal or larger amounts than these latter minerals Two intense basal reflections at 14.2 ^ 001 and 7.1 ^ 002 are characteristic of chlorite minerals The latter reflection occurs close to the 002 reflection of serpentine minerals 7.3 A The 3.66 ^ 004 reflection of serpentine was selected as diagnostic Table 3 since the lower intensity 004 reflection of chlorite 3.53 A in this region was found not to cause interference Selection of the asbestos standard Reference samples of pure asbestos minerals were obtained from various mineral collections and from the International Association for Research on Cancer ARC These were screened for purity and particularly for the presence of interfering contaminants according to the procedures previously described for talc Two different specimens of chrysotile were used as reference materials a triple jet milled sample from the Jeffrey Mine Quebec provided by the Manville Corp. and a specimen from Coalinga California provided by the Calidria Division Union Carbide Corp. Sample preparation Among the variables that strongly influence the precision and accuracy of quantitative ray diffractometry are particle size preferred orientation and surface flatness Variation due to particle size can be minimized by crushing and screening the asbestos and talc standards to ensure a uniform size distribution with an effective crystallite dimension on the order of 5 ...m or less The effect of preferred orientation is more difficult to control The tendency for preferred orientation is largely the function of mineral cleavage properties Both the talc and the asbestos minerals have excellent cleavages platy in talc and CONSUMER TALCUMS AND POWDERS TABLE 3 Catoration Catoration Curve Data for the Determination of Ascestitorn Minerais and Quartz ete NT ABN 55 Mineral phase Antrophy 9 Chrysotile 25 - Od-, j 1004 3.50 23 Quartz 21118 54 15 59 5-60.5 Fremonte 7:10 3.38 100 10.0-11.0 Percent mineral in tale and corresponding area of reflection Anthopavilite Anthopavilite Chrisotile ee a In Quartz ; in Tremolite % 1 _ Le fo 20 o S 0.92 7 22 ai 2 ne 0.25 05 1.0 2.0 SC 70 70 3.9 8.53.9 01 03 0.08 0.22 0.94 1.52 21 2:34 2:34 2:34 50 10.0 200 200 25.0 30 0 40.0 tod 2,75 75 7.11 9.30 13.20 16.90 Lod 01 0.13 a5 0.30 22 0.43 2.7 4.3 0.57 7 as 5 665 5 100 0 2.08 2.30 2.30 2.30 Detection limit 0 ' Anthoon lite = Area 201 =! AP Chrisotile Chrisotile = Area 004 004 004 Ht te 7a 1 '2 : Quartz YL emot 4 wd 0 28 28 ia) A o oO Chi; 7 0.50 0.50 0.50 - R 0 60 60 -0.04 -0.04 -0.04 -0.04 RP 0 | .98 0.96 0.96 0.96 1 098 098 098 2.0 % 0.7 % 110 110 10 loa mA scintillation counter 1450 VDC with level Continuous scan 1 Rnombonedral nex Repeated measurements o arcus under Jurves with a power planimeter indicated average 264 264 N. ROHL ET AL The reproducibility of reflection intensities was also greater than other preparation techniques tested Binary dilution standards of chrysotile anthophyllite and tremolite in talc were prepared gravimetrically Asbestos fiber concentrations were prepared initially at 5.0 4.0 2.0 1.0 0.5 0.2 and 0.1 Fifty milligrams of the asbestos mixtures were homogenized in 10 ml filtered water utilizing ultrasonic energy This slurry was poured into a 30 cc syringe and filtered through a 0.22 ...m pore size membrane filter To prevent stratification due to differential particle size and density effects the syringe is held in a horizontal filtration The residue forms a thickness on the membrane filter position rotated and shaken during flat cake of about 0.5 _ mm uniform When dried the sample is affixed to a glass slide for ray diffraction analysis Rohl and Langer 1974 Selection of ray reflections Because of crystal structure similarities in the minerals being studied i.e. tremolite and anthophyllite consider- able overlapping and interference of ray reflections occur The low symmetry and consequent complex ray diffractograms of such minerals as talc chlorite and mica as well as possible interferences from admixed phases such as kaolinite make it necessary to select a reflection or set of reflections for each mineral component that could be used as an index of the amount of that mineral in a mixture Such diagnostic reflections were selected by referring to standard ray powder diffraction data These diagnostic reflections were scanned at 0.02 2 theta in a fixed count mode 2 ^ 10 counts Precise positions and profiles of the diagnostic reflections were determined In the fixed count mode each of the angular intervals selected are scanned with equal accuracy Thus weak reflections can be determined with equal precision as high intensity reflections The statistical accuracy depends only on the total number of counts recorded and the counting rate selected gives a percentage probable error of about % Profiles of the diagnostic reflections plotted as a function of number of counts vs. 2 theta are measured with a compensating polar planimeter The intensity of a reflection is proportional to but not necessarily a linear function of its concentration Other factors that may influence reflection intensities include instrumental conditions particle size degree of pre- ferred orientation sample thickness and flatness and absorption character- istics Klug and Alexander 1954 Rohl and Langer 1974 Figure 2 shows calibration curves obtained for chrysotile anthophyl- lite tremolite and quartz using the scan technique Measured areas of diagnostic reflections are plotted against percent dilution in talc As indicated in Table 3 tremolite may be determined at levels as low as 0.10 by weight chrysotile from 0.25 to 0.50 and anthophyllite as low as % in talc It is important to note that the limits of detection given in Table 3 are higher and based on a best fit regression analysis For example regression analysis indicates that the detection limit for chrysotile is 0.7 whereas from 0.25 to 0.5 can be actually detected CONSUMER CONSUMER CONSUMER TALCUMS CONSUMER CONSUMER CONSUMER CONSUMER CONSUMER CONSUMER CONSUMER TALCUMS TALCUMS TALCUMSTTALCAUMSLCUMS ANADND AND POWDERS POWDEPROSWDERS POWDERSPOWDERS PPOOWDWEPRDSOEWRDSERS POWDERS 265265265 - < A a Soe - _e y Tremoute Tremoute TremoutTeremouteTremouTremouteteTremoute Tremoute 2- ' 20 20 ^ & Chrysoti Chrysoti Chrysoti Chrysoti Chrysoti ChrysotiChrysoti Chrysoti e in Quartz Quartz Quartz Quartz QuartQzuartz in Taan10 ArAeraea - 10 10 - 0 Q Anthophyl ite Anthophylite Anthophylite Anthophylite Anthophylite AnthopyliteAnthophyAnlthlopihtyleite UT O4 o ro oO a- 1 2 3 Percent Percent Percent Percent 4 5 7 6 8 aspestiaforsm pestiforaspmestiformaspestifasoperstimform aspestiform aspestiform aspestiform mineralmsinermianerlalss minerals minerals minerals 1100 talc- talc talc talc 5 1010 15 15 20 20 25 25 3030 3535 Percent Percent Percent Percent Percent Percent asbestiformasbestiasfboesrtimforamsbestiafsboesrtimfoarmsbestiforamsbestiform amphibole amphiboleamphibole amphibole amphiboleamphibampohibole leamphibole quartzquartz 45 45quartz in in taic taic in and FIGURE FIGURE 2 Canbration Canbration Canbration Canbration Canbration Canbration Canbration Canbration Canbration > asbestiform asbestiforasbmestiform asbestifoarsbmestiform asbestiform asbestiforamsbestiform- amphiboalmepshiboleasmphibolesamphiboles amphiboles amphiboles amphaimbphoilbeolses and quartzquartquzartz quartz in talc talc talc talc FIGURE pyr FIGURE The depending depending depending or particlpearticle particle particle particle size size degree degree degree degree of crystalinty crystalin crystalin crystalinty crystallinity , etc. etc. The TThehe changes changcheangses changes changes in depending depending ' of > depnding depending or lower particle end oof f degre degre curves arearecrystalinty crystalinty reflected axial reflected axial the the C58 at the lower lower end end the curves curves curves curves curves reflected reflected so so that that axial not abscisa endend of of the abscissa abscissa . step the sncanoothetr 0.25 absciaabestiform%Stanley asbestiformtremoliteasbetiform mineraltsalc 1 such suchsuch of levls levels of Chrysotle ChrysotleChrysotle Chrysotle and theminimum detcted mineralschclohrilteorite However However minimum minimum minmu However minum minimum minmu such such such of of low lowlow levs 0.5 % levels levels levs chrysotile chrysotile chrysotile chrysotile Chrysot le Chrysot leChrysotle Chrysotle step step step scan scan mode mode minum andand and minmu of 0.25 otherother otherother were Chrysotle werewere were not not detected detected detected detected Stanley Stanley StanleyStanley Stanley tremolite tremolite tremolite tremolite asbestiform asbestiform asbestiform asbestiform asbestiform detcted detected detected whenwhenwhen andand Nor-Nor- Nor- tremolite talc minerals minerals minerals chlorite chlorite chlorite chlorite Howevr as. present present present present . mixed containers Step scanningscanning scanning scanning The contents The contents contents contents of ofof containers containers containers conctoantianienresrs containerscontaier containers were thorughly thorughly thoroughly thoroughlythoroughly thoroughly thoroughly mixed Aliquots Howevr samplseamplseample The contes avoicdontents straifctonthe straifcation efects efects thorughly Aliquots Step avoid samplesampsleamplsamplee souter souter souter soutter to avoid stratification stratification stratification stratification straifcton effects effects Aliquots Aliquots Aliquots of each were pread avoid using straifcton straifcationdentical efcts methodlgy methodlgy methodlgy described described the straifcation dentical described 50 ghing ghing y prepartion 50 wer dilution standards standards methodlogy mountmeodunted methodlgy described dentical ghing mg were mg preparation preparation preation the prepared ppreparredepared diluton diluton dilution prepared prepared using standards using using using standards standards standards dentical dentical dentical dentical dentical The filter methodology methodology methodology methodologymethodology described described mounted samples samples samples were the diluton the standrs filter intervals samples diagnostic for preparation dilution gonimetricstandrs intervals t siepsiep siep Scanned Scanned Scanned Over Over Over Over goniometric goniometric goniometricgonimetrc goniometric goniometric goniometric goniometric intervals diagnostic diagnostic diagnostic diagnostic diagnostic for for asbest and gonimetric Instrumenintervals intervals intervals diagnostic describesdcribedthe gonimetric intervals | asbest 3 13 asbest asbest form form minerals minerals minerals mminerialsnerals and and Instrument Instrument InstrumentInstrument Instrument operating operating operaopteriatningg conditions conditions condits Popa asbest with 17052 dilution diagnostic operating standrsstandrs minerals with dentica dentica cloted cloted cloted the Glugnostic dilution peak Poa, standards dentica with 17052 dilution dilution dilution dilution standards standrs alter t asbet measured measurd Glugnostic weight bercnts peak 3 ; cloted cloted clottedclotted for were were were measured the Glugnostic Glugnostic Glugnostic measured measured measured weight weight weight bercnts bercnts : teng : . 63 Glugnostic Is^es materials tl ae oO op s! a r + , materials . measured Is^es | : 4 m4 no oy \ d } at ? 5 2 5 Os -5 Ly ' i; , . , ny 7 ' reflection areas areas areas areas weight weight areas bercentsbercents peak bercents bercnts mee 3 Form materials materials FormForm materials , Form materials Form materials materials . 2s , to a nf : Boe 2 fe - - , TABLE 4. Summary of Mineralogical Composition of 21 Consumer Talcums and Powders Sample no 11 N2221 M N2 21 p 1337 N2 21 1337 N2 21 P 266 35.1 Anthophyllite 74 0.1 24 4.9 2.4 5 0.50 P M = majoi P = present Ir = trace bHigh K aOnd Na sOuggests that this phase is a mica muscovite POWDERS POWDERS POWDERS TALCUMS . ul . TTALCUMSALCUMS TALCUMS TALTCUMASLCUMSTALCUMS AND AAND ND POWDERS POWDERS POWDERS POWDERS POWDERS POWDERPS OWDERS i A c ging ginging with withging tromlite . ra} : was 3 DAD , with the the tromolite tromolite pore } , two two fe fication . ? . , fan 2 amounts amounts elctron amounts 1 , ta electron electron electron electron elctron ra cusiones oS elctron. Scaning 1 cusion cusion Scaning a cussion cusion cusion cusion - 2 ?Q 1 on . as 3 | as mk ne 1. 3 he ? y Enthophyllite expected butbutbut t on 6 es EnthopyliteEnhopylite TheEnthophylite a th th detectdioentection techniqutechnique his his his technique nat, > . , a use snown m6 . ny ay - snow oo mS ia snownsnown _ : ' ent ** ent ent ne ne amounts amounts amounts amounts tromlite comn offrom most mostmost amounts comn amounts comon common comonfromfrom the Tound tromlite the tromlie in amounts samples amounts amounts samples tromlite samples corespndig serpntie of corespondig corespondig fication samples amounts amounts amounts the serpentine serpentine the coresponding serpntie coresponding to to microSDV microSDVcorespondigcorespondig corespndig corespondig In other other other Scanig corespondig microSDVmicroSDV order order order crystaline crystaline ordercrystaline crystaline crystaline to study compnetscomponents at a scaning theatheta theta at proved satifactory thetaexpected was was genraly serpntie found it was was rate scanning scanning scanig scaning genraly genraly genraly proved proved proved general y satisfactory genraly generaly serpentine Enthopylie Enthopylie Enthophylite high noise noiseserpntie leve high high quanties serpntie .ow of detction quanties cuant tative on technique technique technique positvespositves indicated positives positives positives positve oror serpentsienrepentine serpentine noise leve leve leve quanties quantities quantities quanties for quanti es cuant cuant cuant as indicated positives , as as indcate indicated indicated ce for negative negative ce negative snown negative negative ce aditonaditon contiuos - aditon negative aditon Inminerals presncepresnce in presnce minerals minerals minerals minerals in the presence presence 2 tenths tenths tenths tenths " tenths the 21 and percnt anthophaynthopy anthophy anthopy " serpntie 21 mineral phase phaseanthophy live serpntie nearserpntie near the of at serpntie 1, the lowerchrysotle in onas LA the percent percent percent percent percent percent and and - over over over anthophy anthopy anthophy serpentine serpntie serpentine mineral mineral mineral mineral mineral phase phase phase live live was was was near the limitslimts limits limits of of limts in the the twG twG onasobserveodbserved observed observdchrysotle conetraions conetraionsconetracoinonestraions conetraiconsetraions conetraions twG observedobserved observed observed concentrations concentrations concentrations concentrations concentrations conetraions concentrations concentrations compnetscompnets the al minera.og- scaned minera.og-minera.og- scaned inera.og- componets thepresnce samples minera.og- minera.og- presence presence presence presence presence presence presence of all minera.og- minera.og- minera.og- components samples samples samples were scanned scaned compnets 17the theta identficaonsamplepseridentficaon forfor thethe theta theta theta theta identifcation identfcao to be incapble incapble to be found DeanDeanmierais background backgroundincapibnlceapble cases ofdetect minerais10 Dean - 4-6 background ratio the order order anlysi order As % result of of nigh andnoise analysis analysiansalysis contiuoscontiuos scanig noisewere by anlysi ampnibole ampnibole by step scaning scaning ampnibole ampnibole contiuoscontinuos scaning step genraly generaly genraly continuous chloritechloritechlorite scanig may kaolinte continuosof chlorite chlorite incapable except except background background background 4-6 4-6 contiuos continuous continuouscontinuous ampnibole by scanning scaning scan ing chlorite or incapableincapble incapable incapable of of in cases cases cases background % background result result detect detect detect detect ngng ng ratio , and nigh nigh aise aise aise noise noise noise continuous scanning scanning scanning scaning were were contius scanig scaning scaning scanning and scan ing maystep genr may notnot generaly general y generaly kaolinite kaolinite kaolinte kaolinte kaolinitkeaolinite Electron Electron ElectronElectron Electron Electron Electron MicroscopMicroyspy Microscopy Microscopy Microscopy Microscopy Microscopy Microscopy Microscopy and and and Electron Electron Electron Electron Electron Dif raction Dif raDcitfiofnraction Difraction DifDractioniffraction : ) transmi on transmistransmission ion transmission distrbution , : ) : transmion reduned size distribution H 4 size size size distribution { microscope electron For For Electron microscpe identifcation elctron microscpe microscope transmisontransmision reduned elctron electron electron electron microscope microscope ^ ber identification distribution elctron submicrospic submicroscopic identficaon distrbuion distribution distributiondistrbution of 1979 1979 - submicroscopic submicroscopicsubmicroscopic submicrospic has be r hashas beer shown shown shownshown to. possess possess poses thethe identifcation for detrminatondetrminato detrminato detrmidnaetorminatideotnrmination identification and for determinationdetrminato detrmination of determination submicrospicidentifcation particlesandand particles Langer Langer and Porevdetrminato submicroscopic particles particles particles particles Langer Langer Langer Langer Langer and andand Poorev Po rev PoorePv oorePvoorev ut technique technique that samples dispers disperse particlesprepared in elctron drop drop , Sanh's by glas second particles for drop GioseGiose Giose GioseGiose solution solution drawndrawn shoe second leavingglas film and pot yO and : - and mende to minzeare lightly aprtaprt particle leavinlgeaving distribu . ) ,, D Giose Tim mounted elctron electron microscopemicroscope microscopeaprt microspe grids and and size distrbu scaned distribu oo Tim - pe,6 is 20,0 ' tons tons ? by tons relogical 20, 0 relogical relogical . . relogical relogical relogica relogical minerals Both amphibole introe introniteintronite introniteintronite genral tremoli quite are areare rectdismilar linear linearlinearlinear sate S sate sate Both na tremolitetremolitequent tremolite tremolit : . ae o. mcnipole pers Stop eavge elctioenlction tremoli with , : a toe fone his den and rok OL an tne tend Langer ~ ; . ~ 7. Sy trast gures Langer 1 Of cS. eG Langer Brgy ter ry 1, n . an Langer an : tO, Sys Contesmya, nenote pe, a rs , , quo's quo's me = quo's quo's quo's by Sanah'ss talcum of talcum of technique techniquetechnique technique technique technique solutionsolution on on glass shoeshoe TWC mended mended mended mountedmounted 20,m00o0unt2e0d,0 02,0 . , amphibole amphibole minerals minerals minerals minerals are are drawn drawn minze minimize minimizmeinimize minimize the the electron mounted on electron electron 20,0 0 amphibole amphibole amphibole oth introniteintronite intronite ne _ Stop Stop eavage eavage were samplessamples samples were were prepared prepared prepared prepared prepared that disper second lightly lightly particles particles particles particles secosndecond particles glass slide apart apart leaving leaving leaving alteration alteration microscope microscope of microscope microscope microscope microscope particle grids grids grids grids general generall general general quite are na na tremolite tremolite ' eavage quent electron for for electron electron a slide placed placed aa sizesize size and and scannedscan ed drop or This distribu scanned dissimilar from dismilar rect rect linear pers pers pers ae tend tend ) atter ater a c ns 2y ~ : co. Dy 8G a 7 8 , L . . 2 (hoe re Fy ie am 7) . lo election his i trast go trasttd x .24 dense electionelction dense and denden den or Langer gures gures Langer Langer tO FY rc ~ be 2 4 poe to- 7 . , i 4 ~ Out Out Out Out Out : a7 . a a. bbe . : ; ie 1936 2 1936 19361936 19361936 1936 he , ; ' , - be , . . : ) ; : : ; Tum FIGURE 3. Transmission electron micrographs showing range in morphological characteristics of asbestiform tremolite and anthophyllite in talc The entire range of morphological variations observed for these minerals is observed in the asbestos standards rectilinear fibers with paralle ends and edges A cleavage ends B unit fibrils protruding from fiber body C curvilinear fiber with amphibole cleavage end D high length ratio fibers E fibers protruding from interiors of described in talc plates F All of these morphological variations and forms A have been anthophyllite and tremolite asebestos samples The amphibole structure was confirmed in all cases by selected area electron diffraction characterization Scale as marked Micrographs obtained on a JEOL JEM 120 U with an accelerating voltage at 120 KV 268 CONSUMER TALCUMS AND POWDERS 4 FIGURE vem a) 1 B Transmission electron micrograpns of cosmetic taic samples composed primarily or an occasional large tar fiber B C taic with many tale fibers Di Scale is the same in and n C and D All selected area electron diffraction patterns obtained on fibers 151162 Consistent oe 1 Slates see see Fig 5 A and wc containing samples 25 " clectron YN 131 grains tended to range from to 2 m in greatest Micrograon obtained or s EOL EOL IEM .20 U with an Coltage : kV the 10 samples shown to be moo Shatook amounts amounts amounts that that aan 4 os ot ary pet ey FIGURE 5. Transmission electron micrographs and accompanying selected area electron diffraction SAED patterns for cosmetic tale samples The talc plate TP in A shows typical polygonal cleavage and diffraction contrast contours displays the characteristic reciprocal ab directions indicated on A Measurement for the mineral species The accompanying SAED plane pseudohexagonal symmetry symmetry for tale Talc * of pattern indicates 5 3 A repeat along " and pattern and b 9.1 repeat for * measured at 1110 Talc fther TF in B displays incgular ends and nonrectilinear edges The SAED pattern is also pseudohexagonal but some reflection intensities e.g. the 060 0.12.0 are more pronounced This may be due to both orientation and structural effects The curled talc plate CT in C displays an incipient Scheire ring pattern the effects or both folding over of talc and small associated grains The amphibole fiber D was distracted only on one of the protruding unit mors The . axis is shown sith upata upata upata 5.3 A. Areas where diffraction patterns were obtained are indicated by location uncles particles were photo- graphed at the SAED magnification 26,500 Scale is the same in C scule in D as marked Micrographs obtained on a EOL JEM 120U with an accelerating voltage at 120 K 270 ee sgt Sion electron electron , , ... most nominent and cry Covert . ey cosmetic taic other than inc ON electron markers A and B fiber bungles appear found na ample 272 272 272 A. ROHL ET AL comparison with known dilution levels of chrysotile in talc observed by electron microscopy the levels of contamination of chrysotile in the two samples correspond to about 0.25-0.5 chrysotile which was suggested by the ray diffraction results The chrysotile fibers were all shorter than 2 ...m and the diameters less than 0.2 ...mexplaining why they were not visible by optical microscopy Chemistry of Consumer Talcums and Powders The bulk chemistry Table 5 and mineral contents Table 4 of the talcums and powders complement each other in that one data set implies limits for the other For example analysis of sample 1 shows the presence of FeO and CaO Table 5 Recalculation of these oxides into values for the empirical formulas for tremolite and anthophyllite indicates that sufficient quantities are present to account for the presence of these minerals Table 4 An appreciable decrease in SiO2 which should normally occur was not observed because of the occurrence of over % quartz content The Al2O3 Na and K aOre reflected by the presence of chlorite probably the penninite phase Variations in oxides were also observed in the other samples that contain amphibole minerals 6-8 11 12 15-17 and 21 In these samples a number of other factors account for the wide variations in oxide percentages in 6 the presence of chlorite TABLE 5. Major Oxide Content of 21 Consumer Talcum and Powders Sample no Major oxide 1 20 30 4 5 6 7 8 9 10 11 Sio TiO Al O F-- O FeO MnO MgO CaO Na KO P O Volatiles Total 61.99 0.10 0.82 0.00 1.51 0.00 29.60 0.40 0.07 0.02 0.01 5.36 99.88 0.00 0.00 1.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 98.70 62.68 0.14 0.37 0.08 0.32 0.00 29.83 0.04 0.03 0.02 0.03 4.66 58.72 0.04 0.24 0.04 3.03 0.00 28.25 0.10 0.03 0.02 0.03 5.38 61.94 0.03 0.45 0.03 0.51 0.01 30.19 0.04 0.05 0.02 0.01 5.51 52.95 0.17 1.16 0.02 0.86 0.00 29.02 3.46 0.00 0.05 0.13 10.32 59.67 1.40 0.87 0.18 0.84 0.00 29.23 0.90 0.05 0.05 0.14 5.64 100.00 98.20 95.88 98.79 98.14 98.97 71.93 0.19 15.73 0.10 0.34 0.00 2.95 2.37 0.48 1.37 0.05 5.25 100.76 58.68 0.08 0.58 0.12 3.12 0.00 29.23 0.17 0.00 0.00 0.00 5.34 51.65 0.71 1.45 0.09 0.34 0.00 27.90 4.75 0.03 0.00 0.05 9.72 49.48 0.22 2.32 1.23 0.07 0.00 25.67 1.61 0.42 0.19 0.01 10.41 97.32 96.69 91.63 Weight percent recalculated as oxides following standard petrochemical procedures The bulk analysis of the powders reflects the combined mineral content after additives were extracted using water dilute HCI acetone benzene and ether b Analysis of 2 98.7 = starch + organics and volatiles 1.3 = Al aluminum chlorhydrate Standard talc used as matrix for fiber standard dilutions CONSUMER TALCUMS AND POWDERS 273 273 273 sharply reduces the SiO2 content and elevates the Al2O3 content The presence of the carbonate mineral calcite increases the expected CaO and volatile contents the latter includes CO in 7 the high TiO2 is reflected by the presence of the mineral rutile TiO in 11 the high CaO moderately high Al2O3 and low SiO contents reflect the presence of calcite chlorite and tremolite Several of the above samples numbers 8 12 and 15 require special evaluation Sample 8 is extremely high in SiO2 Al2O3 Na and K and extremely low in MgO content The chemistry indicates that this material was not derived from a talc rock but rather from one rich in alumina and silica The mineralogy reflects this as do the trace metals see trace metal section The amphibole minerals in sample 8 are associated with both pyrophyllite A14 and quartz both present in substantial quantities The mica phase is not phlogopite but muscovite accounting for the presence of substantial quantities of K O and Na A plagioclase feldspar was also detected in the mineral phase Sample 12 is very high in A2but extremely low in SiO2 apparently the result of high chlorite content as well as substantial amounts of pyrophyllite Sample 15 is low in SiO and extremely high in volatile content reflecting the presence of both carbonate phases and organic additives The trace element analyses Table 6 show distributions that are in accordance with the known behavior of trace elements in minerals With TABLE 5 continued Major Oxide Content of 21 Consumer Talcum and Powders 12 13 14 15 Sample no 16 17 18 19 20 21 Ad Be 47.32 53.83 57.47 44.83 62.26 54.45 59.93 58.54 62.19 0.18 0.11 0.11 0.07 0.06 0.10 0.10 0.18 0.08 1.65 0.69 0.45 0.79 1.11 0.69 0.05 0.03 0.02 0.00 0.18 0.04 0.00 0.00 0.00 0.70 0.65 0.62 0.84 1.38 0.81 0.00 0.00 0.00 0.00 0.00 0.01 29.83 27.14 26.98 23.88 30.00 30.79 30.40 29.83 30.19 0.69 3.67 1.13 0.50 1.13 0.43 0.03 0.07 0.05 0.09 0.09 0.09 0.07 0.05 0.00 0.02 0.07 0.05 0.02 0.02 0.00 0.00 0.21 0.14 0.13 0.10 0.04 0.13 0.00 0.13 10.26 10.31 10.41 21.34 5.92 7.54 5.65 5.94 5.14 99.18 100.06 98.01 95.62 100.19 99.87 98.45 98.21 99.73 56.34 0.12 1.35 0.02 1.39 0.00 27.90 1.53 0.07 0.00 0.02 9.99 98.73 57.34 0.21 2.30 0.1 1.05 0.00 27.44 1.69 0.10 0.10 0.70 8.03 98.20 61.49 0.01 1.20 0.38 1.07 0.00 30.54 0.46 = = = 5.00 100 Average of 20 talc samples 2 Average Average of 8 taic analyses in Volatiles Volatiles are lost on ignition Deer et al 1962 CO total H.O CO organics and other volatiles TABLE 6. Trace Element Content of 21 Consumer Talcum and Powders" Sample no Trace metals 12345 12345 12345 12345 12345 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Ba 10 - 10 10 10 10 10 50 10 990 10 10 10 10 10 10 10 10 10 10 < 10 Ce 10 - 10 10 10 10 10 10 10 0 10 10 10 10 10 10 10 10 10 10 10 10 CI 210 - 130 135 185 200 140 130 115 125 115 120 430 435 410 165 140 130 110 120 130 Co 35 = < 85 <<<< 88 < < < < < < 21 < 4<3 < Ci 310 = 28 600 16 23 24 15 820 25 18 24 38 49 41 340 32 30 28 25 42 Cu < - < < 8<< 9 < <<< S 8 10 13 6 7 6 6 13 Ga 274 274 La Nb < 4< 10 -- 10 10 7 8 8 < 1< 10 10 10 11 7 9 20 < 1 3 13 2 1 40 10 10 10 10 10 10 14 S 7 6 18 7 7 2 2 7 30 10 10 5 5 9 3 2 3< 10 10 10 10 8 9 9 7 Ni 710 11 11 12 12 13 13 < 2210 34 4 11 10 17 10 460 19 20 20 19 12 Pb 8 11 11 12 12 <5 13 19 7 <5 17 5 7 12 18 19 19 20 20 19 16 Rb S = 11 12 12 <5 13 19 <5 <5 <5 <5 <5 5 18 19 19 20 20 19 <5 S 235 ~ 130 120 2230 440 150 305 155 425 110 280 485 595 535 320 140 160 105 155 1070 Si 10 - 10 10 10 20 30 160 8 10 25 100 10 15 20 20 10 15 10 10 10 15 Th <<< <<< 6 <<<<< < 5 <<<<< < Zn 2 ~~ 85 37 18 4 12 20 37 > >>>> 35 } 20 21 81 3 >> /,, 10 - 10 10 10 90 10 190 10 10 10 30 10 10 10 10 50 10 10 10 10 : Values in parts per million The symbol < indicates the limit of detection of the analytical method The symbol > indicates concentrations of 7n are greater greater than 1,000 ppm CONSUMER TALCUMS AND POWDERS 275 275 275 the crystal lattice of a mineral acting as a sorting mechanism for cations the cations can enter a crystal structure providing they have appropriate and charge These phenomena apply to major as well as minor Thus barium is present in large amounts in sample 8 which has K.O content content 137 Since barium and potassium have similar onic radii barium is easily admitted into potassium minerals such as and feldspars both found in 8 Rubidium and strontium are orioned in sample 8 since these metals also easily substitute potassium Gallium is found in large amounts in samples 8 12 and also for 17 These samples are also very high in charge and radius as aluminum and Al_03 in fact Gallium has the same ionic is found only in aluminum- bearing minerals in four samples 1 concentrations of cobalt 4 9 and chromium 16 and there nickel are significantly higher than found in the other samples These association of four sampies also have high contents of these four transition metals has been FeO Table 5 The observed before in certain geochemical environments particularly in ultramafic rocks Since derived from the metamorphism of serpentines and derived peridotites ultramafic rocks are considerably enriched in FeO Deer et al 1962 it brucite Skely Skely that the divalent cations are substituting for iron in the laver of the taic Muix DISCUSSION AND CONCLUSIONS Talc used in the United States represents a wide range of mineralogical Industrial grade talcs are obtained from different rock types of variable mineral mineral composition with the result that the mineral talc grav ma actually be a minor constituent However it has been stated that consumer talcum products should contain at least 90 of the mineral of the same name and no asbestos fiber Hildick 1976 Review of the terature cosmetic Talc suggests that at least until 1968 materials that were marketed as talcum products did not necessarily conform to these criteria mineral may occur in a platy form or in a fibrous form Tale ~ per may occur as a small proportion of the mineral desposit or as a Intergrowths ma constituent common These phases Intergrowths of talc with other mineral phases are may be simply macroscopic zones adjoining talc mineral or may occur as microscopic intergrowths within the talc Of the man minerals that may coexist with talc a number of asbestiform phases Summon Qentified occur tremonte anthophyllite free deposits In addition frfreee e and silica silica chrysotile ( quartz quartz is is have been metal contert may include elevated evels of romium and cobalt genral cement content of the the mineral composition and onsumedicum onsumedicum products products the the 276 276 276 A. ROHL ET AL basis of mineral and chemical contents the type of geological provenance | may be ascertained Methodology has been developed for quantitative ray diffraction determination of anthophyllite tremolite serpentine and quartz in consumer talcums and powders Important factors in the calibration standard development include selection of talc and reference minerals and the selection of diagnostic ray reflections The sample preparation technique is sensitive and reproducible Dilution standards are step scanned over diagnostic reflection areas peak areas are measured and a set of standard calibration curves is developed by regression analysis Samples of consumer talcums and powders are prepared and analyzed under identical conditions and compared with the calibration curves permitting quantitative analysis of these minerals ray diffraction alone cannot distinguish between asbestiform and fragmented forms of anthophyllite and tremolite nor between asbestiform and platy serpentine varieties Electron microscopic analysis was used to distinguish between these forms Mineralogical characterization of 21 consumer talcums and powders showed that 10 contained measurable concentrations of asbestiform tremo- lite and anthophyllite and some also contained fragmented forms of these minerals Two samples contained trace quantities of chrysotile 0.25-0.5 These observations were confirmed by transmission electron microscopy The amphibole phases present in these talcum products ranged in amounts from several tenths of a percent to over 14 by weight Quartz was present in eight consumer talcs in amounts ranging from 1.6 to 35.1 by weight Consumer talcum products are for the most part complex mineral assemblages which confer ray sorbing and fluorescing effects that are not equivalent to and are usually greater than those of the binary systems used in preparing the dilution standards In consumer talcum products minerals such as talc micas chlorite calcite dolomite and others tend to diminish reflection intensities of asbestiform minerals by sorbing rays or by contributing to background noise Also repeat runs on some selected specimens have demonstrated greater peak areas due to slight modifications in instrumental settings e.g. increase in receiving slit width Therefore the values for weight percent concentrations given in this report are conservative Examination of the same consumer talcum products by both optical and transmission electron microscopy indicates that not all of the materials fall within the definition of fiber or asbestiform For example one consumer talcum product that contained more than % tremolite was observed to contain both fragmented tremolite grains by optical microscopy and asbestiform fiber with 3 or greater length ratio by transmission electron microscopy Optical microscopy may provide useful information However more complete characterization can be obtained by electron microscopy and selected area electron diffraction Using electron A 1i POWDERS TALCOMS TALCOMS TALCOMS TALCOMS TALCOMS TALCOMS TALCOMS AND AND AND AND POWDERS POWDERS POWDERS POWDERSPPOWDERSOWDEPORWDESRS POWDERS POWDERS - ... wn . - pow ; Jobween J ty roe ' : yo ao ' oO roy 250 250 250 250 poy. \ ty * 54 ' - ns ofof consucmeronsumer consumer on,ye aa Jobwen Jobwen or chorite plates plates plates chorite chorite numerous Jobwen small Luis small smal amphibole chorite chorite amphaibmolpe hiboleamphibole amphiboleamphibole plates platesplates examinton examination chorite go Luis 7 examination chorite examination examination examination of the thethe sestramptones sestramptones Jobwen Jobwen examinto techniqtuechnique examination demonstraed demonstraed demonstrateddemonstraed No technique and technique technique fibers encounterdencounterd encouterd encounterd and Real and technique technique Real Real Real has fibers fibers demonstrated demonstrated demonstrated demonstrated encountered encountered eencoutrdncountered encountered encountered encountered 5, Qucts iS one) SZ - ascesuiform asceuiform of the mineralogical mineralogical mineralogical mineralogical mineralogic mineralogimcinaerallogical mineralogical formulated formulated mineralogical formulated a formulated formulated formulated prio prior not prior CalCal formulated waswas not not usued sed usedused ascesuiform asceuiform arthopylite ascesuiform ascesuiform arthophyllite arthophylite arthophylite arthophylite fibers fibers fibers and and and June exclusively and tremolite were werewerweere sestramptones indivdual individual individual ^' } chemical chemicalJune exclusively exclusively tremolite fromfrom from from visblevisible visible visible indviualindivdual indivdual individual IARCIARC chemial chemical 197319731973 1973 The tremolite , chrysotile arthophylite athopylite asceuiform ne dned need for arthopylite regulatorryegulatoryarthopylite rgulaoy regulatory the for cognizat complexites standard complexites Shondthe nature cognizant cognizant Shond monitrg We alssohouldalso asociated complexittshat posibploesibleposible posible monitoringmonitorinbg ehealth also bonpossible be nature nature monitoring health cognizant cognizat cognizant cognizant cognizant and and should should monitoring We We health healt healht ealth razararsazaras razaras razaras regulatoreygulatory regulatory standard standard standard standard of talc provide provide for adequate that recomendrecomend recommend recommend recommend recommend asociated with asociatedassociaatsoecidated asociated asociated with with tremolite for complexities adequate adequateadequate that evaluation evaluationevaluation the the use use consumer talcum talcum talcum talcum products products products grains aprently productsinter- in talc talctalctalc grains aprently visible , ap arentalpyparently grainsgrains and aprently aapparpentlpy arently and in inter- inter- an electron sestramptones by setramptones fiberfiberfibefriber fiber chemistry chemistry chemistry chemistry elctronelctron is StandardsStandards Standards Asbestos Asbestos Asbestos Asbestos AsbestoAssbestos Standards StandSardts andards characterization characterization charcterization characterizationcharacterization characterization characterization of we conclude conclude conclude we conlude conlude conludeconlude presence presencepresence chrysotile chrysotile chrysotile chrysotichlrysoetile chrysotile , and and chrysotile talc cosmetic cosmeticcosmetic talc talc mineralogicalmineralogical mineralogical mineralogical protcis mineralogical analytical analytical mineralogical analytical analytical and evaluationevaluation evalution be be evalution made made use of evalu tion thesethese thesethese products products conlude that that that these quartzquartz quartz ThisThis and protocis protcis made products products products products AAPEPNDIPX ENDIX APENDIX AP ENDIX APPENDIX AAPENDIXPPENDIX APPENDIXAPENDIX APENDIX , DEFINITIONS DEFINTIONS DEFINIDTEIOFNISNITIONSDEFINTOS DEFINTIONSDEFINITIONS DEFIDNTOSEFINITIONS DEFINITIONS OOF FOF TERMS TERMS TERMS TERMSTERMSTERMS of naturly fibrous reise 4 ba 4 5 ap lied name applied ot namneame name name applied applied applied aplied aplied applied to to 4 group group of naturally natural y naturallynaturally naturaly naturally naturally fibrous fibrousfibrous fibrousfibrous fibrous mineraisminerais minerais minerais minerais minerais minerais minerais Whittaker Whittaker Whittaker term term posible possible posible possible possible including including attapulgite ori ori ori 278 SON ROH ET AL a B's = technique Amosite may be considered as an aggregate of unoriertua 2 discrete grunerite crystals with only the c axis in in common alignment - Comminution of such aggregates produces fibers with character- istics identical to those of single crystals of grunierite that have been Similarly pulverized Some workers have suggested that mechanical size reduction of amosite yields fibers with crystal growth surfaces rather than cleavage surfaces Since amphibole cleavage tends to paralie prominent crystal face planes such distinctions on the submicroscopIC level may disappear This appears to be the case for tremolite anc anthophyllite as well However because no methods exist to distin- guish between possible differences in fiber surface we do not refer to anthophyllite and tremolite fibers in these talcums as asbestos Insteac they are referred to as asbestiform It should be stressed however that evidence does not exist that would indicate that fibers with crystal crystal growth surfaces or cleavage surfaces possess lesser or greater biolog.cal potential than fibers from commercial asbestos deposits Asbestiform Formed like or resembling asbestos fibrous Bureau of Mines 1968 The term is used herein for amphiboles anthophyllite and tremolite seen on both which resemble comminuted light and asbestos submicroscopic examination varieties on the basis of morphology Essentially when these fibers are derived from commercial deposits we term them asbestos and when analytically identical fibers are found as noncommercial intrusions with the mineral talc we term them asbestiform The use of two terms does not imply differences that can be analytically determined Fiber The smallest single strand of asbestos or other fibrous materials Bureau of Mines 1968 We use this term in < broader sense For example chrysotile fibers are called fibrils possessing unit diameters of about 200-400 ^ Coherent bundles of fibrils are also called fibers Fiber in the present text is used to denote any elongated single mineral unit visible on the light or electron microscopic leve The Occupational Safety and Health Administration has applied a 3 1 length ratio to distinguish fiber from mineral fragment APPENDIX B STRUCTURE OF TALC CRYSTAL CHEMISTRY CRYSTAL AND GEOLOGICAL OCCURRENCE Chemistry of Talc The empirical chemical formula of talc is Mg3 OH out ferrous and ferric oxides alumina titania soda lime and oxices of manganese have been reported in quantities up to several percents byby ns ME TALCUMS AND POWDERS sy Lx and manges ac commodated accommodated in Lo fla, : Stemple and Brindley 19601. One major talc deposit in States contains substantial amounts of nickel as much minor cocomponments ponents tail is essentially by structraly structurally bound water structure comprises a sheet of octahedrally brucite laver sandwiched between between SIO_ groups sifica layers Apical oxvgens directed toward the orucite laver and in part re- Weel o avaroxyl groups which form a portion of ence balance is accomplishacomplisheded within the the 7 to charge on juxtaposed unitunit unit lavers lavers lavers lavers lavers at at the the the the inner structura -ooee 1934 Hendricks 1938 lot were te tale only recently to be triclinic resolved Ravner and single ray now Brown 1966 Ross et al 1968 complexities talc occurs with devdeveelopmentlopment Ford 1957 The fiber nabits Ford 1957 The pate and fiber nabits of the fibrous fibrous the development form with an elongated crystallographic axis may be a mani- (oe se ofonic ofonic substitution since its refractive index is higher than platy 1944 Tale that contains pe and pressure parameters are defined defined within extremely restrict- pressure parameters 280 A. ROHL ET AL Nature of Talc Plates Electron microscopic examination of talc minerals demonstrates that single talc grains consist of contiguous single crystals mosaics of disoriented crystallites and intergrowths with other mineral phases particu- larly tremolite Kleinfeld et al 1973 Stemple and Brindley 1960 Wright 1960 Selected area electron diffraction patterns obtained on these objects display in order single crystal arrays Scherrer rings and superimposed complex patterns characteristic of intergrown single crystal phases Talc and Mineral Intergrowths Tremolite is one common intergrowth in talc and it requires relatively little energy thermodynamically to occur Replacement of magnesium by calcium in the brucite layer may lead to structural as well as chemical modification Bragg and Claringbull 1965 Rotation of unit tetrahedra in talc forms double chains from sheets readily accomplished by substitution of OH by OH The bulk chemistry is thereby changed from Mg6 O20 to OH The final structural array is remarkably similar in both materials the crystallographic axis of talc is approximately 5.26 ^ which corresponds with the crystallographic axis of tremolite approximately 5.24 A the axis for talc is approximately 9.10 ^ which is equal to the axis of tremolite the axis of talc approximately 18.8 ^ is about equal to twice the dimension of tremolite approximately 18.2 ^ The monoclinic stacking angles the angle are within a few degrees of each other Intergrowths may form in which amphibole formation is not complete so that a mixed phase exists referred to mineralogically as talcboles These are not as rare as once believed and may even be common in the more complex talc deposits APPENDIX C INDUSTRIAL AND COSMETIC GRADE TALCS Studies have demonstrated that industrial talc often consists of a variety of minerals the utilization of which is based on physical properties rather than mineral composition Hogue and Mallette 1949 Schulz and Williams 1942 Thompson 1974 Wells 1965 Early analyses of cosmetic talc also showed a wide range in mineral composition Of six such products examined in one study only 6-47 by weight of the inorganic material that constituted the product was the mineral talc 14-51 serpentine minerals 5-77 carbonate minerals trace quartz trace tremolite 3-12 other minerals Schulz and Williams 1942 NSUMER TALCUMS AND POWDERS 281 APPENDIX D BIOLOGICAL HAZARDSASSOCIATED WITH ALC EXPOSURE oe =. occu O diffuse diffuse bilateral progressive was fibrosis millers of tremolite talc n GeorgiaDreessen Dreessen Valle 1935. Siegal et al 1943 1943 studied observed among 1933. Dreessen a population of So miring ina milling tremolite and arthophyllite bearing tal sot. oe New York state In addition to the bilateral fibrosis pleural milar to those encountered in asbestos workers were observed study oy. postmortem material in this findings indicated that asbestos , _ o5es C7 present vere vere vere present present present present present in lung lung tisue tissue tissue tissue tissue lung Severe pneumoconiosis in These These These These findings findings findings ffinidinngdsings were also reported in tremolice millers by Davmon 1946 > Porro and Levine 1946 So 737 1947 11947 reported that ce nodular fibrosis in workers exposure to cosmetic No quartz was detected in talc prothe dust ~s -.. Author concluded that talc itself was capable of producing scarring eservation was supported in studies by Reichman 1944 and by e's 1949 and in a study of taic miners and millers in Italy where pure produced a 10 incidence of pneumoconiosis in Parmeggiani 1948 Excess deaths attributed to pneumoconiosis 2 ceen reported among among workers in northern Italy mining talc con- asbestiform Tibers Rubino et al 1976 have held that fibrous talcs not differentiated as sample platv are biologically more hazardous than a review of the literature by Porro et al talcs 1942 e and Gardner are referred to as considering that the clinical (sc ogical mia and pathological There are several disease reports states of the of asbestosis and talcosis are occurrence of asbestos bodies Soe ing tissue of Keinfeld et al exposed workers to taic Davmon 1946 Hobbs 1973 McLaughlin et al 1949. Porro et al 19421 Several Several studies suggest --) Included asbestos that fibrous tales are fiber For example more dangerous as a result McLaughlin et al 1949 ebers fibers ebers in tale with the proportion of fibers recovered from the larger concentration of fibers was the raw calc Talc pneumocoNIOSIS > rearformed rearformed by and Messite 1960 in their study of tthhee New demonstrated was demonstrated that taic of almost deaths the talc Elmucuriosis Elmucuriosis Elmucuriosis accounted for almost % excess among rs and millers due to the complication of mucuriosis mucuriosis % of the 91 deaths recorded up lL) malignant fibrosarcoma and peritoneal meso 282 N. ROHL ET AL these data indicated that a 3- to fold excess of cancers existed in this group as compared to a matched control population The biological activity of both tremolite and anthophyllite fibers has been known for some time and both have been cited as asbestos minerals by Merewether 1930 and Noro 1946 Asbestos disease among workers and others exposed to anthophyllite and tremolite has been reported Burilkov and Badajov 1970 Kiviluoto 1960 Meurman 1968 Meurman et al 1974 Schepers 1965 Wegelius 1947 Weiss and Boettner 1967 Recent experimental data also indicate that tremolite fibers are biologically active Graham and Graham 1967 Some investigators have suggested that inorganic fiber fibrogenicity and carcinogenicity is limited only by its ability to reach the alveolar space Holt et al 1965 Pott and Friedrichs 1972 Pott et al 1974 Robock and Klosterk^tter 1976 Stanton and Wrench 1972 Wagner et al 1975 reported lung scarring in Wistar rats with pure talc exposed by inhalation The severity and extent of the lung scarring was comparable to that produced by chrysotile asbestos under identical experimental conditions In addition to lung scarring ingestion of talc was reported to be associated with leiomyosarcoma of the stomach as well as one adenoma and several sarcomas of the uterus However the exposure levels were high and the numbers of observed tumors small so that statistical validation of the carcinogenic potential of pure talc and its relevance to human exposures were not achieved There are also extensive data concerning hazards associated with exposure to silica or trace metals particularly nickel and chromium National Research Council 1975 Analytical data are presented here that suggest possible disease potential and the need for investigation in these areas REFERENCES Bowen N. 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