Document dm0Dd4ggpj907OJb499rb5L0

.-i. PLAINTIFF'S EXHIBIT Identification of Minerals Associated UC-2243 with Asbestos by X-Ray Diffraction Patterns By M, S. BADOLLET* and J. P. McGOURTY {Annual General Meeting, Vancouver, April, 1958) (Traneactiont, Volume LXl, 1958, pp. 169-174) Introduction als which the chemical analyses in dicate to be present. - IT HAS I.ONG been customary Dr. Cooke was very co-operative for chemists to analyze samples in furnishing us with samples of of asbestos and their associated material identical to those he used rocks by routine chemical proce in his studies. We accepted his dures. Results of these investiga chemical analyses and his re-cast tions are usually reported in the minerals data and have applied the conventional wav, i.e., the percent X-ray technique for checking and ages of the various constituents identifying the minerals actually existing in the sample under investi present in the samples. The dual gation. Often an examination of the purpose of this investigation was, data shows that re grouping of the first, to explore the limits of the chemical analyses and re-calculation X-ray diffraction method for iden of the data in terms of minerals will tifying the minerals; and second, shed more light on the true com to develop a simplified technique position of the sample. for applying this information in The late Dr. H. C. Cooke in his G S.C. .Memoir 211 (1) presented an exhaustive study of analyses of asbestos and rocks taken from the Thetford. Disraeli, and eastern sample identification. Such a tech nique would be of great value to company geologists in searching for new asbestos deposits, as well as in the examination of drill cores. half of Warwick map-areas in the Province of Quebec. Also he dis cussed the composition of asbestos and other fibres of the Thetford district in a paper he presented to the Koval Society of Canada in 1985 (2). Both papers include a series of analyses of fibres from the chemical point of view. The an alyses are accompanied by a re cast of the data in terms of miners als in which Dr. Cooke sought to deduce the mineral composition of each sample. TW* presentation of data was well dope. It has been stimulating to the X-ray specialist who is interested in carrying the investigation further to confirm the predictions of the chemist, miner alogist, and geologist, and to make definite identification of the miner- Section Chief, I Research Engi neer, Johns-Manville Research-Cen ter, Manville, New Jersey, U.S.A. (1) Cooke. H. C., Mem. 211, Geol. Survey, Dept, of Mines and Re sources. Ottawa, 1937. (2) Cooke, H. C., Roy Soc. Can., Trans., Sec. IV, 3rd Series, Vol. XXXIX, 1935. X-Ray Technique Employed The X-ray pictures were taken by the Norelco X-ray diffraction unit with a Debye-Scherrer camera for a four-hour exposure, using cop per radiation with a nickel filter. All samples were carefully powd ered in an agate mortar before they were examined in the unit: The X-ray pictures accompany ing this paper carry the following identifications: A Line 5--Serpentine.......................... C--Chrysotile........................... A--Antigorite........................... B--Brucite............................... F--Iron oxide........................... G--Gramrnatite (tremolite) .. E--Epidote............................... 0--Quartz................................. 2.49 2.44 2.53 2.35 1.61 8.4 2.9 3.34 When doubt existed in identifica tions. it was necessary to adopt spectrographic and petrographic tech niques. DiscusstoN of Data Sample 1* Sample 1 represented a "normal red-weathering serpentine from a chromite pit in the northwest corn er of lot 19 N.W., Range X, Coler aine township". The chemical an alysis (Table I) revealed that it contained SiO?, MgO, and H-O, with small amounts of other metals. Re-casting into minerals by Dr. Cooke indicated that the sample was mainly serpentine rock. The reddish colour probably was due to weathering of the small amount of iron present. During recent years the X-ray diffraction patterns of serpentine have been fairly well indexed and identifications have been made easier. The pattern of Sample 1 showed clearly the typical ring structure of serpentine with a con siderable amount of crystalline brucite. These two diffraction lines are identified in Figure 1. The chemical analysis showed an excess of MgO over the amount required to combine with SiO- to form serpentine, H<MgaSi20>; this excess of MgO crystallized in the form of brucite, Mg(OH)t, which is intimately associated mechan ically with the serpentine. The asbence of evidence in the dia gram of the presence of other minerals is due to the fact that any compounds formed by the minor constituents shown by the chemical analysis are not in suffi cient quantity to yield definite Xray diffraction patterns. The brucite is so closely associated with the serpentine that it could not be re moved by mechanical means but it could be dissolved out ehemicallv. The descriptions and chemical analyses of samples 1 to 21 are re produced from GjS.C. Memoir 211. by Dr. H. C. Cooke. Numbering- of the samples is the same as in that report. 44- UCC 004636 Sample 2 Sample 2 represented the same material as in Sample 1, but it ex hibited "material blackened over a zone a foot wide, and flanking a dyke about a foot wide''- Chemical analysis (Table 1) showed the presence of AlOa, Fe20,, and FeO in quantities that indicated other minerals than serpentine must he present as impurities. The X-ray diffraction patterns did not reveal the presence of brncite. thus confirming the chemical analysis, which showed sufficient SiOj to combine with all the MgO to form serpentine; hence, no ex cess MgO remained to form brucite or any other magnesia mineral. Al though the chemical analysis showed the presence of aluminum and iron compounds, they were not identified in the X-ray pattern be cause they are present only in very small amount. Sample 3 Sample 3, which represented "chrysotile asbestos taken from the King mine", is typical of the fibre from that area. The chemical an alysis (Table 1) disclosed a com position equivalent to that of chrysotile asbestos, with small traces of impurities. Dr. Cooke, in his re-calculation of the analysis, deduced the possible presence of minerals such as chlorite, talc, and perielase as impurities associated with the chrysotile asbestos. X-ray diffraction lines did not indicate the presence of brucite, but they did show a trace of quart*. Al though the chemical analysis, when re cast in terms of minerals, indi cated the presence of chlorite, tale" and perielase, lines for these miner als were not visible in the X-ray pattern. ' This sample jtgaabo analyzed quantitatively by emission spectro scopy* with known oxide mixes ss standards; the data obtained, on an ignited basis, showed the presence of Abo,, 0.10%; Fe20, 1.3%; and CaO, 0.11%. If the iron in the orig inal sample was in the form of be,0,. it would have been oxidized to Fe.Oj by the treatment pre ceding to the spectroscopic examin ation. The total amounts of Al.Oj, he,0,, and CaO by spectroscopic 4 Emission spectroscopy is not a means of identifying compounds bat can be used as a supplement to or dinary wet chemical analysis. Tabu I.--Analyses, Samples 1 to 4 JL ai02-.. AljOj 34.40 0.50 F20-" 0.82 FcO CaO*. * MgO * H20+<Mao-... T102 HnO .... C02 3.79 0.02 42.36 15.17 0.47 MU 0.94 0.38 CrjO.... 0.48 10------- --..P.-3?_ X 40.42 2.2k 2.11 4.26 0.29 39.44 11.11 0.10 J 42.05 eu 0.96 0.39 0.05 43.30 12.52 0.75 Total* 99.68 99.97 100.02 + 43.48 1.41 0,60 2,36 0.12 39.50 12.69 0.45 100.61 FSgur 1. S--serpentine line; B--brucite line. Figure 2. S--serpentine line. Figure J. C--Chrysotile line; Q--quartz line. Figure 4. C--chrysotile line; F--iron line* t 1 >i k tile- fibre which war; ifg&s p.......... *11 .. brittle apparel blackened*;;: zone close tar ' chemical analysis (Tsblei.j) ihdk-'' cated chrysotile aabestos, w>th AItO, and FeO and an,, excess of SiO, present. The data, when. re cast into minerals,' showed! the pos sible presence of chlorite, brucite, and silica. . ' - ' The X-ray diagram did nodi show brneite, silica as quart*/or<dilorite. .. The chemical analysis, hqwerer, dicatcd an excess of SiO, oret amount1 required bf th&.MgQ form asbestos: ThinSiG, ihaj hare';" been In thnv form: oft. amorphous SiO,, which would/not show in the X-ray diagram asit'may barrVbeeis in combination wttbrjth& m&or qqn-'' stituento shown' . analysis, and tilt tdnpoudr din formed are not in suffidfcttt qtun- . ., .... ......... .. . tity to produce an X-ray dhqpnnn ' *>;/. i * '*'***** & The X-ray film did indicate iron as '. ; ___ Is?: FeaO, or Fe,0:' " v.y^T^ik-.-y., Emission speetnweopjp ^ql .tldniij sample, showed ths/ pTSatjwd A1,0,, 0.26% i Ft.O^ djfeand^#1 CaO, 0.08%.- Ili6s<r-^*ttn^(^a^&: data did pot agree witit^tf' ical analysis, again ^__ __ _ difficnlty of Ifsfc-rfo; minerals present. Am. ''slSk - .-Wa' ".. S>i >` 'JsS'i? . cTr?il; .!.-' Sample 7 represented^! " high-grade chry. taken from chemical minor minum, presence re-cast data.cite, and pei 1 The X-ray lines for brnettty claBe; although sis indicated a it was not identified diagram. Iron- in the X-ray dfagtyaUr EnMsMuS^/y spectroscopy showed the.ptttenen'Sf/;.;' A1,0,, 0.12% s-'PeJfcj^r^V^St'V CaO, 0.08%. ;y>; i-- Km -V-S SofHjfe at'*/'/ oSample 8 represented a "highgrade chrysotile asbestos taken UCC 004638 I%iirw lOt ' ' " C--chrysotile line; F--iron line. -46* from Deloro township, Province of Ontario". The chemical analysis (Table II) showed the presence of impurities. The re-cast data indi cated the possible presence of chlorite, talc, and periciase. The X-ray diagram did not show chlorite, talc, brucite, or periciase. If these minerals were present, the quantities were insufficient to pro duce an X-ray diffraction pattern. Emission spectroscopy demonstrated the presence of A1203, 0.07%; FejOj, 1.0%; and CaO, 0.02%; amounts which differ from the chemical analysis. Sample 9 Sample 9 is a chrysotile fibre from the "British Canadian mine at Black Lake". The fibre is further identified as a semi-harsh type, i.e., not actually brittle, but not soft and silky. The chemical analysis (Table It) showed small amounts of AUO,, Fe.O,, and CaO, and almost 2 per cent FeO. Calculated in terms of minerals, the presence of chlor ite, talc, and periciase was indi cated. The X-ray diagram did not re veal the presence of brucite, chlorite, or periciase, but it did show small amounts of FeiO*. Emission spectroscopy showed tile presence of Al2Oa, 0.16%; Fc.Ot, 4.0%; and CaO, 0.02%. If Fe^O, were present originally it was probably oxidized to Fe2Oi by the ignition process in preparing tlie fibre for this test. Sample 10 Sample 10 is an extrardinary chrysotile asbestos fibre of harsh texture bordering upon a brittle nature. It is from the "Vimy Ridge mine in Coleraine township". The chemical analysis (Table II) indi cated a low MgO-SiOj ratio, a low combined water content, as well as a high percentage of Fe203. Re cast in terms of minerals, the pres ence of chlorite, talc, and periciase was indicated. The X-ray pattern did not show lines for brucite, talc, periciase, or chlorite. If these minerals were present they must have been in very small quantities, not detectable by the X-ray technique. Emission spectroscopy showed Al,0-,, 0.52%; Fe.Oj, 3.0%; and CaO, 0.03% ; amonnts which do not agree with the chemical data. . Table II.--Analyses, Samples 7 to 10 3102... Al20g ra ... f5 -.. co - X*D . . HaOf.. H20------- 7 41.13 0.90 1.01 0.58 0.03 43.24 12.74 0.45 Totals- 99.98 42.40 0.14 0.97 0.19 0.14 43-09 12.60 0.45 99.98 41.90 0.64 0.80 1.89 0.14 42.18 12.07 0.20 99.72 to 42.95 111 2.08 0.84 0.19 41.60 10.26 1.61 99.53 Figure 11. C--chrysotile line. Figure 12. B--brucite line; C--chrysotile line (barely visible). Figure 13. B--brucite line. Figure 14. C--chrysotile line; A--antigorite line. -- 47 -- UCC 004639 Figure 15. C--chrysotile line. ntStmr feys--- iwdos; inhfirintir' of biiieraliiy. '*4;' peridase were The X-ray diagram^ showed no trace of brteite, ` . perfctiise,., of chlorite; however, the diffraction lines for chrysotile and iron are clearly defined. A.-i* -- VMl .' aw r m* * U' W-'W: : a io ' ftJfc. Ate *.w - TTMj:.s.fc. io....--3W_ MO.OO 100,40 100.75 *' *:4, 4/; ,-3fc - ----- *>,. &Mipfe 18 Sample 18 is another specimen of "slip serpentine taken frora^ a fault-soue in drtffrMMX of the Ktajpl mine, Thetford"; ' lie '*;- analyst (Table* III)-showed that the- SiO was slightly low, .and the MgO rath- er high, fr serpentine. Minor com stitnents were AljOs, Fe,0, FeO> ` and CO,. The data, re-cast as min erals, suggest the presence of chlorite, brncite, and hydromagne- site. - ji The X-ray diagram. ahowed.-n*r, trace- of brncite, chlorite,, or bydri-1 magnesite. It did:' show, however, chrysotile, and iron as F?,0,. Sample 17 . ; -P**'- Sample 17 represented, a stringy fibre from a = fanlt, drifts? C502E, near D 505X, King, mlne^_ Thetford''. Chemical analysis (XeM&j,. III) showed: substantial amotmt*v of Fe,0* and FeO. Ke-cast of the-; ] analysis in terms of minerals ih^r , cated the presence of chlorib^ fcrij^: : cite, and pcriclase. The X-ray diagram; trace of chlorite, brdcife,. clase, but the chrysoH$Qilfii l defined. >V\? - r-i^\ (*,1 -CT-V'V m& '. figius e Hae> B^-hrteito ffiiae" ^ V\L5| M i,-; gflhHmatihs tins; --eyidote line. ;S -^F`eitL'- dfiigra -I;*?. * i; 'sttooat^lwfe' in ' ahoot proportion .fe form serpentin^/ hot . tba presence of' relative^ - large "fibre tak-.atrTbet- ruGSTJr-. amonnt: amotmta of Fe^ and FeO snggjmfcr, ed an adraiitnre of othfeir minerahb. Be-calcvdated*' da'ta indicated. presence f ddbrite, taje, penrdhse, r'*;and hydromagnesite, ;... _THm-;X-rajr. dtag^on-. showed! of * ..... bfi ehiy^otf^ and^anti-- , ^-'*r'`^4J^ Pr; PP gositfci^.mrid Sample 18 ORbi asbestos fibre.; King mine, further identi a fanlt fibre. (Table III) showed 21 ta|Jent>: : JSatejdf 2tf^war deaenbed aa smr. -with k;pn*h*ae, "semi-fihrons pireofite fifilng- vete,: amounts of Al,Ot, Fe,Oi, ald noun.; - ^v_ mine at'. Thetferd^- 'C^Miaieal ,an- indicating considerable contamiifcj- tion. SiO was extremely low, H,ft rTM speeiaSm was- - shnwed that - "affMO s&bwtd^ fTahla tbit ' " ' alt contained' appnxiabla aittomda very hi^i, and MgO mranalhf indicating a peculiar fibre cflmjWa^'v pawned,,gf^wwiKrmtncatata..-. than.... tion. Be-calenlated data indicafad' that the minerals present mi^it bej Kid-?; KTS^:-- .. - plcrofite.Bsfeaat <df4bn-0naly^crhrdtealed tiU^tfamsh n^th he chlprttO - brncite, chlorite, and pcriclase, with ' brncite comprising 17.61 pet ..cent of the sample. This is an interest ing sample for further investigation*.'' The X-ray diagram showed a very high percentage of brncite. Samples bi(-n fwm a fanhr ptiteo at tS!''M)6;ft>ot level in the King mine in Thetford". Chemical analysis showed ((Table -Thn-K-aa/' diagfim did not shew Tines for brncite,: chlhrite, talc, or " pcriclase, hot it did show the dif fraction line for- chrysotile. UCC 004640 -- 48> .i ' '4'W'- ?ji - - <' A-' j',y^{drHuajtr^a-15 '.? S ` .*V-V` - Sample 50 'was described as a "tough string? fibre forming crossfibre veins at-60CX in the ; King ininey Tfcetwj^It was more specifically (iti nfjjfei' as a softcbrysotile fibs*. Clfejincal analysis (Table IV) shewed the presence of AljOi, FesO,, FeO, and CaO, as well as a small amount of XaaO and K,0. Re-cast by Dr. Cooke in terms of mineral composition the analysis indicates that chlorite 8.01%, and brncite 9.19%, may be associated with the chrysotile in this sample. The X-ray diagram disclosed the presence of chrysotile and brncite, but no chlorite. Sample 68* Sample 68, described as "pseudoasbestos ", represented fibrous veins in the footwall of the Federal pit near Robertsonville, Quebec. The analysis is given in Table IV. This specimen was an interesting sam ple for X-ray analysis since it showed a high percentage of A1203, Fe,0, FeO, and CaO, with MgO exceedingly low. The X-ray diagram showed lines corresponding to grammatite (tremolite) and epidote. Conclusions Chemical analyses of chrysotile, picrolite, and other varieties of ser pentine invariably, or almost invari ably, show that, in addition to the MgO, SiOj, and H,0 necessary to form chrysotile of theoretical com position H4MgjSi,0,, they contain The descriptions and chamical analyses of samples SO and 6S are reproduced from the paper by-Dr. H. C. Cooke in Vohuna XXIX, 1935, of the Transactiona-af the Royal So- , ciety of r unuli TTwibenliili of the samples is the satgr'ga~>(n that paper. ViC Table IV.--Analyses, Samples SO ani> 63* Sample 50 SiOj.............. AljO............ Fed)............ FeO.............. CaO.............. MgO............. HjO+.......... H.O-.......... TiO.............. MnO............ NiO.............. Na.O............ K.O.............. 37.44 0.58 1X3 0.54 0.20 43.49 14.60 1.71 -- -- -- 0X8 0.05 100.12 Sample 63 46.36 11.39 9.30 3.18 18.47 8.94 1.87 0.12 0.05 0.61 0.15 -- -- 100.44 also a small, or in some specimens a very appreciable, percentage of AljOa, Fe,Oj, FeO, etc. By re-cast ing the analyses in terms of miner als these may be assigned to various minerals such as brucite, chlorite, periclase, and hydromagnesite, which may or may not actually be present admixed with the chrysotile. Except when in very small amount, definite verification of the presence of one or more of these minerals can be made by application of Xray diffraction, emission spectro scopy, or petrograpbical methods of examination. These methods, and in particular the X-ray diffraction method, have been used in the pres ent investigation of specimens of serpentine from a number of asbes tos mines in the Eastern Townships of Quebec, and of one from Deloro township, Ontario,. A critical study of chemical, and re-cast mineral, analyses of the specimens had been made earlier by Dr. H. C. Cooke, who very, kindly supplied the writ ers with the materia] used in their investigation. For some specimens, the X-ray diffraction patterns confirmed the mineral composition as derived by Dr. Cooke in his mineral re-cast of the chemical analysis; for some '-- ........................- - - others, in which the extraneons min eral or minerals were in very small amount, diffraction lines for these did not appear. Clearly, with a sam ple containing two or more minerals, only those present in sufficient quan tity to give diffraction tines can be. definitely identified as being pres ent. Samples of the latter type were analyzed by emission spectroscopy and in a general way, though not quantitatively, the results were in agreement with those derived by Dr. Cooke from his study of the chemical analyses. Petrographic ex aminations under the microscope were also helpful in cases where doubt existed. This investigation has indicated that no one method is adequate in itself for complete and positive identification of all the minerals present , in a sample. For this it is necessary to resort to a combination of several methods. For complete identification of all the minerals present in samples obtained in pros pecting or in drill cores of asbes tos bodies, not only chemical' an alyses but also the results of X ray diffraction, spectrographic, and pe trographic studies are necessary. Acknowledgments Chemical data used in this paper were taken from GJ3.C. Memoir 211, by the late Dr, H. C. Cooke, and from a paper by him in the Transactions of the Royal Society of Canada, Volume XXIX, 1988. This investigation was initiated six years ago after a discussion with Dr. Cooke, in Ottawa, on the use of X-ray technique for identification of minerals. Dr. Cooke supplied all samples used in the investigation. The assistance of Mr. Charles Whinfrey, formerly of the J'ohnsManville Research Centre, who made the preliminary X-ray studies, is appreciated. -- 49 -- UCC'004641