Mineralogical Magazine, February 2003, Vol. 67(1), pp. 103–111
Raman spectroscopyof the mineralsbo le¨ite,cumenge¨ite, diabole¨ iteandphosgenite – implications forthe analysisof cosmetics of antiquity
1, 2 1 R. L. FROST *, P. A. WILLIAMS AND W. MARTENS 1 Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, GPOBox 2434, Brisbane, Queensland 4001, Australia 2 Centre for Industrial and Process Mineralogy, School of Science, Food and Horticulture, University of Western Sydney, Locked Bag 1797, Penrith South DC,NSW1797, Australia
ABSTRACT Theapplication of Raman spectroscopy to the study of the mixed cationic Pb-Cu and Pb-Cu-Ag minerals:bole ´ite,cumenge ´iteand diabole ´itehas enabled their molecular structures to be compared. Eachof these three minerals shows different hydroxyl-stretchin gvibrationalpatterns, but some similarityexists in the Raman spectra of thehydroxyl-deformatio nmodes.The low-wavenumber region ischaracterized by the bands assigned to the cation-chloride stretching and bending modes. Phosgenite isalso a mixedchloride-carbonate mineral and a comparisonis made with the molecular structure of theaforementioned minerals. Raman spectroscopy lends itself to thestudy of these types of mineralsin complexmineral systems of secondary mineral formation.
KEY WORDS: bole´ite,cumenge ´ite,diabole ´ite,lead, chloride, phosgenite, Raman spectroscopy.
Introduction authorssuch as Dioscorid esand Pline (1st CenturyB.C.): silver foam PbO iscrushed and INTEREST inthecompounds of Pb for pharmaceu- mixedwith rock salt and sometimes with natron ticaland cosmetic purposes of antiquity has been (Na2CO3)(Tsoucaris et al.,2001).It followsthat knownfor some considerable time (Lacroix, theEgyptians mastered this kind of chemical 1911;Lacroix and de Schulten, 1908). Indeed synthesisand technology very early, a factof recentchemical analyses have shown that the Pb greatimportance in the history of sciences. Fire- mineralssuch as crushed ore of galena (PbS) and basedtechnology was employed to manufacture cerussite(Pb CO 3)togetherwith lau rionite EgyptianBlue pigments in the third millennium (PbOHCl)and phosgenite (Pb 2Cl2CO3) were B.C. Itis now suggested that wet chemistry was usedas cosmetics in Egyptian times (Martinetto alreadyin existence some 4000 years ago. et al.,2001;Tsoucaris et al.,2001;Walter, 1999). Someof theseminerals also formed the basis of Itmust be noted that the latter two minerals are manypaint pigments (Bersani et al.,2001;Black rarein nature and therefore it isinferred that such andAllen, 1999; Brooker et al.,1983;Burgio et al., mineralswere synthesized. Ancient literature has 2001;Burgio et al.,1999;Burgio et al., 2000). providedinformati onon the pharmace utical Manyof these pigments were based upon lead preparationsof these minerals (Walter, 1999; dioxide(PbO 2).The Raman spectra of plattnerite Walter et al.,1999).Support for this statement [lead(IV)oxide, PbO 2]andof the lead pigments red comesfrom recipes of medicinal products to be lead (Pb3O4),leadmonoxide [PbO, litharge ``usedin ophthalmol. ’’ reportedby Greco-Roman (tetragonal)and massicot (orthorhombic)], lead white[basic lead carbonate, 2PbCO 3.Pb(OH)2] *E-mail: [email protected] andof their laser-induced degradation products DOI: 10.1180/0026461036710088 havebeen measured. The degradation of PbO 2 has
# 2003The Mineralogical Society R. L. FROSTETAL.
beenshown to follow the pathway PbO 2 ? Pb3O4 smartendurance single bounce diamond ATR ? PbO (litharge) ? PbO (massicot);the shorter cell.Spectra over the 4000 to 525 cm –1 range thewavelength of the excitation line, the greater its wereobtained by the co-addition of 64scanswith –1 power.The Raman spectrum of PbO 2 showedthree aresolutionof 4 cm anda mirrorvelocity of bands,at 653, 515 and 424 cm – 1,identied as 0.6329cm/ s. arisingfrom the B2g, A1g and Eg modesrespec- Spectroscopicmanipulation such as baseline tively,by analogy with the corresponding modes of adjustment,smoothing and normalization were – 1 isostructuralSnO 2 (776,634 and 475 cm ). What performedusing the Spectracalc software package isof particular importance is that the synthetic GRAMS (GalacticIndustries Corporation, New mineralssuch as laurionite and phosgenite, which Hampshire,USA). Bandcomponent analysis was wereused by the ancient Egyptians, have not been undertakenusing the Jandel ‘ Peakt’ software analysedby Raman spectroscopy. In fact few package,whichenabled the type of tting Ramanor infrared (IR) spectra of these two functionto be selected and allows speci c mineralshave been forthcoming. parametersto be xedor varied accordingly. Band ttingwas done using a Gauss-Lorentz cross-productfunction with the minimum number Experimental ofcomponent bands used for the ttingprocess. Minerals TheGauss-Lorentz ratio was maintained at values Theminerals used in thisstudy were supplied by >0.7and ttingwas undertaken until reproducible theAustralian Museum (ASM). The minerals resultswere obtained with squared correlations of havebeen characterized by bothX-ray diffraction r2 >0.995. (XRD) andby chemical analysis using ICP-AES techniques. Thefollowing samples were used: (a) sample Results anddiscuss ion ASM-D49056bole ´itefrom the Amelia Mine, Phosgeniteis an example of a mixedhalogen- SantaRosalia, Baja, California, Mexico; (b) carbonatespecies of formula (Pb 2CO3Cl2). This sampleASM-D 27575cumenge ´iteBeleo, Baja mineralis compositionally related to northupite, California,Mexico; (c) sample ASM D36845 parisiteand bastna ¨sitebut is structurally different, diabole´itefrom Mannoth mine, Tiger, Arizona, belongingto space group P4/mbm and factor USA; and(d) sample ASM D191881phosgenite group D4h.Thecarbonate ion lies on C2v sites and fromConsols mine, Broken Hill, South Australia. thisresults in considerablesymmetry reduction as maybe evidencedby thesplitting of the n3 and n4 bands.The mineral, which is in some ways Ramanm icroprobespectroscop y compositionallyrelated,isdiabole´ite Crystalsofthe minera lswere place dand (Pb2CuCl2(OH)4)(Abdul-Samad et al., 1981). In orientatedon a polishedmetal surface on the thismineral, stoichiometrically the carbonate has stageof anOlympusBHSM microscope,which is beenreplaced by hydroxyl units. This is a mixed equippedwith 10 6 and 506 objectives.The anionicand a mixedcationic species. The crystal microscopeis part of a Renishaw1000 Raman structureof diabole ´ite,Pb 2Cu(OH)4Cl2, is tetra- microscopesystem,which also includ esa gonal, P4mm, a = 5.880(1), c = 5.500(2) AÊ , V = monochromator,a ltersystem and a Charge 190.1 (1) AÊ 3, Z =1(Cooperand Hawthorne, CoupledDevice (CCD). Ramanspectra were 1995).There is one unique Cu 2+ position excitedby a Spectra-Physicsmodel 127 He-Ne coordinatedby four (OH – ) and two Cl – anions; laser(633 nm) at a resolutionof 2 cm – 1 in the the Cl – anionsoccupy the apical positions, and rangebetween 100 and 4000 cm – 1. Repeated theCu octahedron shows the [4+2] distortion acquisitionusing the highest magni cation was typicalof Cu 2+ oxidesand oxysalts. There is one accumulatedto improve the signal to noise ratio unique Pb2+ positioncoordinated by four (OH –) inthe spectra. Spectra were calibrated using the and four Cl – anions.All the OH – unitsform short 520.5 cm –1 lineof a siliconwafer. (0.246nm) bonds with Pb 2+,andlie to oneside of thecation, whereas the Cl – anionsall form long (0.322and 0.340 nm) bonds with Pb 2+, and are on IRspectroscop y theother side of the cation. Pb 2+ shows a one- Infrared(IR) spectrawere obtained using a sidedcoordination typical of stereoactive lone- NicoletNexus 870 FTIR spectrometerwith a pairbehavio ur.There are two unique Cl –
104 PB-CU-AG MINERALSAND ANCIENTCOSMETICS
positions;one isstronglybonded to Cu 2+ and Pb2+ regularbiaugmented trigonal prism. There are two cations,whereas the other is primarily held in Cusites. The coordina tionpolyhedr ashare placeby a networkof hydrogenbonds emanating elementsto form prominent columns or rods of from the (OH – )groups.The Cu octahedra form polyhedraparallel to the c axisand centred on the corner-sharingchains along the c axis,and these 4-foldaxes of the unit cell. chainsare cross-linked by Pb 2+ cationsand by hydrogenbonding. Hydroxyl-stretchingbands Bole´iteoriginall ywrittenas Pb 26Ag9Cu24 Cl62(OH)47.H2Ohasbee nfoundto be of TheRaman spectra of the four minerals: (a) formula KPb26Ag9Cu24Cl62(OH)48 (Cooper and phosgenite,(b) bole ´ite,(c) diabole ´iteand (d) Hawthorne2000). The crysta lstructureis cumenge´itein the 3200 to 3700 cm –1 region are distortedcubic (Gossner, 1928; Gossner, 1930; shownin Fig. 1. The result softhe band Rouse,1973).Potass iumwasde tectedby componentanalysis of the separate regions are electron-microprobeanalysis, but the amount reportedin Table 1. Of co ursephosg enite determinedwas only 50% of the amount indicated containsnowater or hydroxy lgroupsand bysite-sc atteringrenement. However ,the Ramanspectroscopy clearly shows the absence renement results show K tobe disordered ofany hydroxyl- stretchingvibrations.X-ray withina largecage in the structure, and the crystallographycombined with the application electron-beambombardment probably induces ofIR spectroscopyto show the presence/ absence rapidmigration of K withinthe structure. The ofwater molecules, indicates that no water IRspectroscopyshowed that there is no H 2O moleculesare present in the formulae of bole ´ite, presentin the structure (Cooper and Hawthorne, diabole´iteand cumenge ´ite.Only hydroxyl units 2000).In some ways cumenge ´iteis composition- arepresent. For bole ´ite,three Raman bands are allyrelated to bole ´iteas it is a mixedcationic- observedat 3448, 3408 and 3371 cm –1. The anionicspecies (Humphreys et al., 1980). The bandsare broad with half widths of 71.0,21.0 and –1 crystalst ructureof cu menge´ite(Pb 21Cu20 164 cm .Onepossible interpretation of the rst Cl42(OH)40)istetragonal, with unit-cell para- twobands is that they are the antisymmetric and meters a = 15.065 and c = 24.436 AÊ ,spacegroup symmetricstretching vibrations of the OH units. I4/mmm, Z =2(Hawthorneand Groat, 1986). The Fordiabole ´ite,hydroxyl-stretchin gbandsare cumenge´itestructure shows a verydiverse range observedat 35 25,34 65,345 2,343 6and ofcationcoordinations. There are vedistinct Pb 3340 cm – 1.Theband component analysis of the siteswith the following coordination polyhedra: hydroxyl-stretchingregionfor this mineral is octahedron,square antiprism, augmented trigonal shownin Fig. 2 a.Infraredanalysis was attempted prism,distorted biaugmented trigonal prism, and usingthe diamond ATR cellbut was not
20000
15000 y t i s n
e (d) t n i
n 10000 a m
a (c) R
5000 (b)
(a) 0 3200 3250 3300 3350 3400 3450 3500 3550 3600 3650 3700 Wavenumber (cm – 1 )
FIG.1. Raman spectra of the hydroxyl-stretching region of (a) phosgenite, (b) bole´ite, (c) diabole´ite and (d) cumenge´ite.
105 R. L. FROSTETAL.
TABLE 1.Ramanspectroscopic results for the minerals: phosgenite, bole ´ite,diabole ´iteand cumenge ´ite.
Phosgenite Bole´ite Diabole´ite Cumenge´ite Raman Raman IR IR IRRaman Raman IR Raman Suggested (Rulmont, (this (Farmer, (Rulmont, assignement 1978) work) 1974) 1978)
3448 3525 3588 34083465 3466 3482 Hydroxyl stretching 3371 3452 3413 34363426 3366 3410 3358 3340
16721670 1660 Carbonate 1518 1608 1510 (n3) 1510 antisymmetric 13841417 1378 stretching 1327 1326 1350 (n3) 1346 1304 1293
1061 (n1) 1062 Carbonate 1058 (n1) symmetric stretching
833 834 838 838 (n2) 837 921 978 1023 760 760 (n4) 760 817 846 984 667 666 653 (n4) 650 757 781 794 891 731 672 673 830 696 632 797 594 715 563 676 538
500 478 468 465 455 437 386 376 309 361 365 347 300 294 307
282 282 234 227 271 252 215 243
186 175 192 182 182 149 154 176 178 161 130 155 152 152 145 146 129 115 128 107 91 80 61
successful.Spectra could have been obtained by onloan. This actually demonstrates the power of crushingor grindingthe samples but this was not Ramanspectroscopy, since the spectra can be possiblebecause the samples are unique and are measuredwithout harming the crystals in any
106 PB-CU-AG MINERALSAND ANCIENTCOSMETICS
0.0a
0.014
0.012 3452 y t
i 0.01 s n e
t 3465 n i
0.008 n a m
a 0.006
R 3436 3526
0.004 3405 3340 0.002
0 3200 3250 3300 3350 3400 3450 3500 3550 3600 3650 3700
Wavenumber (cm – 1 ) b
0.006 3482 3413 0.005
y 0.004 t i s n e t 3366 n i
0.003 n a m a
R 0.002 3588 0.001
0 3000 3100 3200 3300 3400 3500 3600 3700 Wavenumber (cm – 1 )
FIG.2. Band component analysis of the hydroxyl-stretching region of the Raman spectrum of (a) diabole´ite and (b) cumenge´ite.
way.In the crystal of diabole ´itethere are two asto the origin of the third set of bands (c). It cations.The Cu 2+ isbondedto four OH unitsin a mustbe remembered that Raman spectroscopy squareplane arrangement. The Pb 2+ is bonded to functionson a picosecondtimescale compared fourOH unitsand four Cl – units.The structure is withthe long-ti memeasurem entsof X-ray distorted.It is apparent that the two types of diffractionwhere a timeaverage structure is hydroxylunits, depending on whetherthe OHs are determined.It is possible that an interaction bondedto the Cu 2+ or the Pb2+,aredifferent. occursbetween the Cl anionand an adjacent Thereare apparent in the spectra three sets of hydroxylunit and forms a hydrogenbond of the bands:(a) 3465 and 3526 cm – 1,(b)3436 and type Cl –HObond.Hence the two bands observed 3452 cm – 1 and(c) 3340 and 3405 cm – 1 (very at3340 and 3405 cm – 1 areassociated with lowintensity). The rstpair of bands (a) is hydroxylunits, which are strongly hydrogen assignedto the symmetric and antisymmetric bonded.The Raman spectrum of cumenge ´ite stretchingvibrations of OH unitsassociated with (Fig. 2b)althoughof low signal to noise ratio, thePb cation. The second set of bands is likewise showsthree strong bands at 3482, 3413 and associatedwith the Cu cation. The question arises 3366 cm – 1.Low intensitybands are observed at
107 R. L. FROSTETAL.
3588and around 3180 cm – 1.Thestructure of the Fig.3 mustbe due to the hydroxyl deformation hydroxylsin cumenge´iteis complex.One possible modes.Sometimes these hydroxyl deformation attributionof the bands is that the 3413 and bandsare more de nitive than the hydroxyl 3482 cm – 1 isthe symmetric and antisymmetric stretchingvibrations because of band overlap of OH-stretchingvibrations. The band at 3366 cm –1 thelatter. For bole ´ite,bands attributed to the maybe attributed to the strong OH bondformed hydroxyldeformation modes are observed at 921, throughthe transient migration of the Cl anion. 817,757, 731 and 696 cm – 1.Inthe most recent structureof bole ´ite(KPb 26Ag9Cu24Cl62(OH)48) (Cooperand Hawthorne, 2000), there are 48 Hydroxyldeformationmodes of bole ¨ ite,diabole ¨ ite and hydroxylspresent. In the hydroxyl-stre tching cumenge¨ ite regionthere were six bands observed. Thus one TheRaman spectra of the three lead chloride- wouldexpect six hydroxyl deformation modes. hydroxycompounds are shown in Fig. 3. The Weobserve vebands, although the band at resultsof the band component analysis are 817 cm – 1 isbroad and could be resolved into a reportedin Table 1. In the low-wavenumber secondcomponent. Thus the analysis of the regionfrom 100 to 1000 cm –1,twotypes of hydroxyldeformation region is in agreement bandswill be observed: (a) those ascribed to the withthat for the hydroxyl-stretching region of hydroxyldeformati onmodes, and (b) those bole´ite. assignedto the PbCl and CuCl vibrations. The Incontrast, two hydroxyl deformation modes authorshave shown in previous publications that areobserved for diabole ´ite(Pb 2CuCl2(OH)4). For thecation-C lstretchingvibratio nsoccur at diabole´ite,six hydroxyl -stretchingvibratio ns positions<550 cm – 1;thereforethe bands in wereobserved at 3526, 3465, 3452, 3436, 3405 and 3340 cm – 1 andtwo hydroxyl deformation modesat 781and 672 cm – 1 areobserved. A low- 5 676 (c) 984 0.035 1061 797 1023 715 830
0.03 891
0.025 0.025
(b)
y 781 y t i
0.02 t s i s
n 672 e
n 0.02 t e n t i
n i n
a
978 n m a
a 0.015 m R a 0.015 R
833 0.01 1327 731 0.01 (a) 696 1518 757 0.005 817 0.005 1672 921 1304 1384
0 0 600700 800 900 1000 750 950 1150 1350 1550 1750 –1 Wavenumber (cm ) Wavenumber (cm – 1 ) –1 FIG.3. Raman spectra of the 600 –1000 cm region of FIG.4. Raman spectra of the carbonate region of (a) bole´ite, (b) diabole´ite and (c) cumenge´ite. phosgenite.
108 PB-CU-AG MINERALSAND ANCIENTCOSMETICS
–1 –1 intensityband at 978cm isalsoobserved. One of 8.0 cm .Thisband is of A1g symmetry possibilityis that the band may be due to (Rulmont,1978). The bands at 1384, 1327 and – 1 isomorphicsubstitution by sulphate. If this is the 1304 cm areassigned to the n3 modes. The casethen the bands at 781 and 672 cm – 1 are the observationof severalbands in thisposition is an hydroxyldeformation modes. X-ray diffraction indicationof the loss of site symmetry of the determinesa time-averagedstructure and low carbonateanion in the phosgenite structure. The – 1 concentrationsof sulphatemay not be detected by bandsat 760and 666 cm areassigned to the n4 XRDwhereasRamanspectr oscopyreadil y bendingmodes. The bands are in goodagreement detectsvery small concentrations of sulphate. withthose published by Farmer (1974). Suchcomments are also true for the cumenge ´ite sample.Two bandsare observed at 984 and Low-wavenumberre gion 1023 cm – 1,whichare assigned to the symmetric andantisymmetric stretching modes of sulphate. TheRaman spectrum of phosgenite, bole ´ite, Therehas been some isomorphic replacement of diabole´iteand cumenge ´itein the low-wave- thechloride by sulphate anions in thecumenge ´ite numberregionareshowni nFig.5.For structure.Just as X-ray crystallography suggests, phosgenite,the spectrum is dominated by two thestructure as shownby Ramanspectroscopy of veryintense Raman bands at 182 and 152 cm –1. cumenge´iteis complex. This complexi tyis Thesebands have been assigned to the A1g and Eg reected in the number of hydroxyl deformation modesof phosgeniteand are attributed to ClPbCl modesobserved. Bands are observed at 830,797, bendingmodes (Rulmont, 1978). Two low- 715and 676 cm – 1.Sincebole ´iteand cumenge ´ite intensityba ndsareobservedat664and arecompositi onallyrelated, some similarit y betweenthe Raman spectra of thesetwo minerals inthe hydroxyl deformation region is observed. 140000 Phosgenitecarbonate structure (d) Thechemistry of the mineral phosgenite has been 120000 studiedfor a longtime (Ferraris, 1907; Mugge, 1914;Sillen and Petterson, 1944; Sillen and Pettersson,1946). The Raman spectrum of phosgeniteshows an extremely intense band at 100000 1061 cm – 1 (Fig.4). The band is assigned to the (c) carbonate (n1)symmetricstretching vibration. A y t
verylow-intensit ybandis also observed at 80000i – 1 s n
1058 cm .Thisband may be attributed to the e t n
COstretchingvibration of the isotopic CO of i
n (b)
carbonate.The bandwidth (as FWHM) ofthe a 60000
– 1 –1 m
1061 cm bandis 4.8cm .Theposition of this a symmetricstretching vibration is in excellent R agreementwiththat publish edby Rulmont (Rulmont,1978). The band is not observed in 40000 theIR spectraeither in this work or in published results.The second most intense band is that – 1 observedat 833 cm .Thisband is assigned to 20000 the n2 OCO bendingmode. A bandin this position (a) wasreported for the Raman spectrum of synthetic phosgenite(Rulmont, 1978). The bandwidth is 4.0 cm – 1,showingan extremely sharp Raman 0 band.Figure 4 alsoshows bands at 1672, 1518, 100 200 300 400 500 –1 1384,1327 and 1304 cm – 1.Thepositions of Wavenumber (cm ) –1 thesebands are in excellent agreement with FIG.5. Raman spectra of the 100 –500 cm region of publishedresults(Rulmont,1978).The (a) phosgenite, (b) bole´ite, (c) diabole´ite and 1670 cm – 1 bandis also sharp with a bandwidth (d) cumenge´ite.
109 R. L. FROSTETAL.
649 cm – 1.Onepossibility is that these bands are cumenge´ite,the most intense Raman band is –1 of A1g symmetryand are attributed to the CuCl observedat 154cm witha secondintense band stretchingmodes. It is not understood why the at 192 cm –1.Otherbands of quite low intensity bandsare of such low intensity. Very low- areobserved at 465, 376, 347, 307, 271 and intensitybands are also observed at 282 and 243 cm – 1.Theband at 154 cm – 1 isassigned to 252 cm – 1 inagreement with the published data of the ClMCl bendingmode. Rulmont(1978). Since the Raman spectrum of phosgenitewill not have any carbonate bands below 400 cm – 1,thenany bands below this Conclusions positionmay be attributed to PbCl vibrational Someminerals are of signi cance in the study of modes.This then allows a comparisonto bemade compoundsused in pharmaceutical and cosmetic withthe low-wavenumbe rregionof bole ´ite, applicationsin antiquity.Among these minerals is diabole´iteand cumenge ´ite. phosgenite.Related to this Pb mineral are the TheRaman spectra of the low-wavenumber naturallyoccurring Pb-Cu minerals formed during regioncan be used to easily distinguish between thecomplexcrystallization of secondary minerals. thefour minerals studied. The Raman spectrum of Includedin these minerals are bole ´ite,diabole ´ite bole´iteshows Raman bands at 478,455 and 386, andcumenge ´ite.Raman spectroscopy has been 361,300, 234, 215, 160 146 and 128 cm – 1. The usedto determine the molecular structure of the mostintense band is thatat 160cm – 1. This band latterthree minerals for the rsttime and a iscomplexand may be deconvolutedinto at least comparisonis made to that of phosgenite. The twobands at 160and 146 cm – 1.Thesetwo bands hydroxylstretching and deformation vibrations of areassigned to the Cl MCl bendingmodes where bole´ite,diabole ´iteand cumenge ´itecharacterize M =Pb,Cu or Ag. The two bands at 455 and theseminerals. Hydroxyl deformation modes are 361 cm – 1 maybe due to the MCl-stretching characterizedby themixed cationic species of the vibrations.The bands at 234 and 215 are mineral.Low-wavenumber regions of theRaman attributedto hydrogen bonding (OH –O) type spectradisplay bands which may be assigned to vibrationsin the structure. thecation-chloride stretching and bending vibra- Insome resp ectsthe reis a reasonable tions.Raman spectroscopy has been used to comparisonbetween the low-wavenumber spec- determinethe molecul arstructu reof these trumof diabole ´iteand bole ´ite.Compositionally mineralsandthe three basic mixed cation thetwo minerals are related. Bole ´itehas Ag in the mineralscan be readily distinguished by their structureand both minerals are the mixed cationic Ramanspectra, thus making their identi cation in basicchloride minerals of Pband Cu. The Raman complexmineral systems easier. spectrumof diabole ´iteshows bands at 468, 437, 365and294cm – 1.Furtherbandsbelow Acknowledgements 300 cm – 1 areobserved at 227, 175, 149 and 130 cm – 1.Themost intense band is observed at The nancialand infrastructure support of the 227 cm – 1 andthis band has previously been QueenslandUniversity of Technology Inorganic assignedtoth eOH –Ohydrogenbon ding MaterialsRe searchPr ogramisgra tefully vibrations.The second most intense band is that acknowledged.The Australian Research Council at 174 cm –1.Thisband may be compared with (ARC) isthanked for funding. Mr Ross Pogson, themost intense band in the Raman spectrum of Scientic Ofce r,Coll ectionMa nagerfor bole´iteat 161cm – 1 andis assignedto the Cl MCl Mineralogyand Pe trology,The Austra lian bendingmode where for diabole ´ite M = Pb or Cu. Museum,is sincerely thanked for the loan of the Theionic radii of Cu 2+ and Pb4+ are0.072 and mineralsused in this research and for helpful 0.084nm, respectively, whereas the ionic radius advice. of Ag+ is0.126 nm. The ionic radii of Cu 2+ and Pb4+ aresuf ciently close that the Cl MCl band is References thesame for both minerals. In the case of bole´ite, twobands are observed at 161and 46 cm – 1. This Abdul-Samad, F.A., Humphries, D.A., Thomas, J.H. and latterband is probablythe ClAgCl bending mode. Williams, P.A.(1981) Chemical studies on the Asfor bole ´ite,the bands in the positions at 468, stabilitiesofbole´iteandpseudobole´ite. 437and 365 cm – 1 maybe attributed to the MCl Mineralogical Magazine , 44, 101 –104. stretchingvibrations. In the Raman spectrum of Bersani, D., Antonioli, G., Lottici, P.P.,Fornari, L.and
110 PB-CU-AG MINERALSAND ANCIENTCOSMETICS
Castrichini,M.(2001)Restorationofa mendipite, diabole´ite, chloroxiphite, and cumen- Parmigianino’s fresco: amicro-Raman investigation ge´ite, and their relationships to other secondary of the pictorial surface. Proceedings of SPIE-The lead(II) minerals. Mineralogical Magazine , 43, International Society for Optical Engineering , 4402, 901 –904. 221 –226. Lacroix, A.(1911) Minerals formed by the action of sea Black, L.and Allen, G.C.(1999) Nature of lead water on metallic objects. Comptes rendus de patination. British Corrosion Journal , 34, 192 –197. l’Academie de Paris , 151, 276 –279. Brooker, M.H., Sunder, S.,Taylor, P.and Lopata, V.J. Lacroix, A.and de Schulten, A.(1908) Note on the lead (1983) Infrared and Raman spectra and X-ray minerals of the Athenian slags of Laurium. Bulletin diffraction studies of solid lead(II) carbonates. Societe´franc¸aiseMineralogieetde Canadian Journal of Chemistry , 61, 494 –502. Cristallographie , 31, 79 –90. Burgio, L.,Clark, R.J.H. and Firth, S.(2001) Raman Martinetto, P., Anne, M., Dooryhee, E.,Drakopoulos, spectroscopy as ameans for the identication of M., Dubus, M., Salomon, J., Simionovici, A.and plattnerite (PbO ),of lead pigments and of their 2 Walter, P.(2001) Synchrotron X-ray micro-beam degradation products. Analyst, 126, 222 –227. studies of ancient Egyptian make-up. Nuclear Burgio, L.,Clark, R.J.H. and Gibbs, P.J. (1999) Pigment Instruments &Methods in Physics Research, identication studies in situ of Javanese, Thai, Section B:Beam Interactions with Materials and Korean, Chinese and Uighur manuscriptsby Ramanspectroscopy. JournalofRaman Atoms, 181, 744 –748. Spectroscopy , 30, 181 –184. Mugge, O.(1914) Translation in phosgenite and galena. Burgio, L.,Clark, R.J.H., Stratoudaki, T.,Doulgeridis, Neues Jahrbuch fu¨rMineralogie und Geologische , M.and Anglos, D.(2000) Pigment identication in 43 –51. painted artworks: adual analytical approach employ- Rouse, R.C.(1973) Crystal structure of bole´ite. Mineral ing laser-induced breakdown spectroscopy and containing silver atom clusters. Journal of Solid Raman microscopy. Applied Spectroscopy , 54, State Chemistry , 6, 86 –92. 463 –469. Rulmont, A.(1978) Vibrational properties of lead Cooper, M.A. and Hawthorne, F.C.(1995) Diabole´ite, carbonate-leadchloride,andbromide. Pb2Cu(OH)4Cl2,adefect perovskite structure with Spectrochimica Acta, 34A, 1117 –1125. stereoactive lone-pair behavior of Pb 2+. The Sillen, L.G.and Petterson, R.(1944) The crystal Canadian Mineralogist , 33, 1125 –1129. structure ofPb 2Cl 2CO3 (phosgenite)and Cooper, M.A. and Hawthorne, F.C.(2000) Bole´ite: Pb2Br2CO3. Naturwissenschaften , 32, 41. resolution of the formula, KPb 26Ag9Cu24Cl62(OH)48. Sillen, L.G.and Pettersson, R.(1946) The crystal The Canadian Mineralogist , 38, 801 –808. structure ofPb 2Cl 2CO3 (phosgenite)and Farmer, V.C.(1974) The Infrared Spectra of Minerals . Pb2Br2CO3. Arkiv for Kemi, Mineralogioch Monograph 4,Mineralogical Society, London, 539 Geologi, 21A, 9 pp. pp. Tsoucaris, G.,Martinetto, P.,Walter, P.and Leveque, Ferraris, E.(1907) Phosgenite and Cinnabar at J.L. (2001) Chemistry and cosmetic materials in Monteponi. Rassegna Mineraria, Metallurgica e ancient civilizations. Annales Pharmaceutiques Chimica, 26, 71. Franc¸aises , 59, 415 –422. Gossner, B.(1928) The crystal form of bole´ite. Walter, P.(1999) Chemistry of ancient Egyptian American Mineralogist , 13, 580 –582. cosmetics. Actualite´ Chimique, 134 –136. Gossner, B.(1930) Bole´ite, pseudobole´ite and cumen- Walter, P., Martinetto, P., Tsoucaris, G., Breniaux, R., ge´ite. Zeitschrift fu¨rKristallographie , 75, 365 –367. Lefebvre, M.A.,Richard, G.,Talabot, J.and Hawthorne, F.C.and Groat, L.A.(1986) The crystal Dooryhee, E.(1999) Making make-up in ancient structure and chemical composition of cumenge´ite. Egypt. Nature, 397, 483 –484. Mineralogical Magazine , 50, 157 –162. Humphreys, D.A., Thomas, J.H., Williams, P.A.and [Manuscript received 16 June 2002: Symes, R.F.(1980) The chemical stability of revised 19 December 2002 ]
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