macla nº16. junio ‘12 182 revista de la sociedad española de mineralogía ;on<destructive Analytical Methodologies for the Mineralogical CharacteriCation of Mine Materials / NAIARA GOIENAGA-ELIAS (*), JOSE-ANTONIO CARRERO-HERNÁNDEZ, MAITANE OLIVARES-ZABALANDIKOETXEA, LUIS-ÁNGEL FERNÁNDEZ-CUADRADO, JUAN-MANUEL MADARIAGA-MOTA DTepArtment of AnAlyticAl Chemistry. University of the BAsque Country. P.O. Box 644, 48080 Bilbao (SpAin) INTRODUCTION hardness etc. often in com@ination ! nia aman confocal microscope y with detailed Dnowledge of the regional enishaw 6Ienishaw8 loucester Determination of the actual chemical geological history a first identification shire UK euipped with ecitation composition and crystalline structure of of many rocforming minerals is lasers of nm 1 nm and 2 a mineral is difficult without the proper possi@le. nm. analytical euipment Dyar and unter ! A porta@le CnnoIamTM Iaman 200. Whilst most of the traditional t ecomes more difficult to identify the spectrometer 6B^WTEKC_C. ewar analytical methodologies are useful in more rare minerals mostly present in EEUU provided with a YT nm estalishing the identification of only minor amounts and often as small ecitation laser. relatively common minerals8 including crystals. their chemical composition they are not PortAble Micro-Energy Dispersive X-RAy very helpful for species which are As an attempt to etter characterie the Fluorescence Spectroscopy ([-ED-XRF): compleB or when they are polymorphs. mineralogy of the impacted area for the identification of elemental several Dind of samples were collected: composition. The portale ArtTa `FMIE n an outline of the main identification ntec currently Bruer AS Berlin methods developed during the last fifty ! olling stones outside and inside the ermany was employed in laoratory years in an ongoing effort to mae mines<. analysis. minerals show some of their secrets ! IocDs of the galleries walls 6inside<. several hyphenated analytical ! Soils 6outside and inside<. Handheld Energy Dispersive X-Ray techni5ues have @een developed. ! Efflorescences8 newly formed powderF Fluorescence Spectrometer (ED-XRF): Eurthermore8 in a period in which type reprecipitations inside. for the identification of elemental analysis ased on nondestructive and ! Particulate matter deposited on composition. A portale analyer MF direct techniues for their further vegetation in the runoff outside. MET100 Oford nstruments UK application in many fields art allowed in situ elemental analysis. environment8 etc.< are in vogue8 science AnAlyticAl Equipment is asDing also not only for in situ ScAnning Electron Microscope-Energy measurements8 @ut also for the RAmAn Spectroscopy: for the molecular Dispersive X-RAy Spectroscopy (SEM- application of a green chemical characteriation. EDS): for elemental characteriation approaches 6i.e.8 without the use of and sample imaging. An E[Oc\0 chemicals or minimiGing their volume<. An interesting nondestructive Scanning Electron Microscope Carl Therefore the present wor ets on complementary alternative to the ay eiss TS mH ermany provides the nondestructive techniues such as diffraction is the aman microscopy. electron image acuisitions. An Ma aman Spectroscopy S Scanning Etensive and growing dataases of Energy Dispersive MFIay Spectrometer Electron MicroscopeEnergy Dispersive reference spectra give S the potential Oford nstruments Aingdon ay Spectroscopy SEMEDS and the to @ecome a widely used tool for routine Ofordshire UK is connected to the Energy Dispersive MFIay Eluorescence mineral identification 67asharova8 SEM to perform the determination of ED for the mineralogical 200. Despite its potential advantages the elemental composition. characteriation of minepolluted areas. e.g. little or no sample preparation multiFmicronFscale single grain analysis8 RESULTS AND DISCUSSION MATERIALS AND METHODS molecular analysis insitu analysis< it has not yet een widely employed y We have studied a numer of spectra of The results here eBplained were the geosciences community Hope . A. various minerals 6Ta@le 1 summariGes otained in 2 a@andoned mining areas: et al. 2001. some all with crystals not larger than a a nP mine located in Western Biscay few millimeters. This will demonstrate north of Spain and a CuEe mine ! A portale dispersive aman the strength of the S techniue as it placed at Easterner Biscay. micropro@e Ienishaw IA100 shows that each spectrum is uni5ue and spectrometer 6Ienishaw loucester can @e used as a sort of fingerprint for The identification of minerals generally shire UK with a nm ecitation the identification of the mineral when a starts in the field y visual eamination. diode. large enough data@ase of mineral Based on properties such as colour spectra is availa@le. pAlAbrAs clAve: Espectroscopia Iaman8 Muestras key words: aman Spectroscopy Environmental samples onF medioam@ientales8 _o destructivo8 Andlisis in situ. destructive8 Cn situ analysis. resumen SEM/SEA 2012 e corresponding author: naiara.goyenagafehu.es macla nº16. junio ‘12 revista de la sociedad española de mineralogía 183 ELEMENT MINERALS it has also een suitale for single crystals as small as a few hundred LeAd Litharge, massicot, plattnerite, minium, galena, cerussite, Anglesite micrometers. Zinc Zincite, sphalerite, rosasite, smithsonite, leiteite, hemimorphite Iron HemAtite, goethite, lepidochrocite, pyrite, siderite, sArcopside At the molecular level the information provided for the a@ove mentioned Copper Tenorite, villAmAninite, delAfossite, libethenite, tsumebite, olivenite techni5ues seemed to @e also helpful TAble 1. Some minerAls identified by meAns of RS. not only for the identification of the presence of impurities ut also for a As shown in ig. 1 some spectra information. Eor instance8 the particle semiuantitative analysis of the otained can e found to e a miture siGe given @y SEM 6Eig. ]< provides environmental samples studied. Since i.e. two or more minerals present in etter nowledge of the health ris occasionally etter results are needed the same spot<8 which is not a pro@lem assessment associated to the the sample collection may @e re5uired for S which can gather spectra on aandoned mine studied as far as the for their la analysis i.e. y ED8 individual grains. atmospheric particulate matter 6PM< nia aman or A100. The results elow 10 `m is considered to e otained thereof may e clearer and harmful i.e. cancer. urthermore the more detailed. Anyway freuently the elemental composition of such PM field measurements are good enough 6mainly derived from the erosion of the for a good characteriation of the tailing wastes do also inform aout the minerals present in environmental possi@le risDs associated to the metals samples. present i.e. P@ n S in each type of particle siGe. Even if these analytical tools are suitale for the research lined to the geological field8 the est identification fig 1. A minerAl mixture identified by RS. of any mineral8 however8 will @e that in which converge the results of all the Once having assigned the S to a availale techniues D S MIE8 concrete mineral8 its elemental EDS8 etc. composition may @e analyGed more in depth. Eor instance8 the molecular ACKNOWLEDGEMENTS formula of the minerals itself do also give a clue of the oidation state of the This wor has een financially elements that constitutes it. t is fig 3. A SEM imAge of A re-precipitAted sAmple After supported y the Basue overnment worldwide now that the redo state of run-off phenomena. through the Berrilur project ef. the elements is directly lined to oth E0022. oienaga acnowledges the environmental and the human Since a huge amount of minerals may her predoctoral fellowship from the health ris of such components. Thus present impurities an advanced UP/EHU. Technical and human the risD associated can @e deduced8 and elemental analysis of the samples is support provided y the IamanFLASPEA conseuently the needed control re5uired. To achieve this goal8 several Laoratory of the Ser 6UP/EHU actions taen. analytical techniues such as ED MCCC__8 7[/Ej8 EIDE and ESE< is also EDFMIE or EDS may @e applied. Eor gratefully acDnowledged. With regard to the mineral structure8 the instance ig. shows the elemental possiilities are different. n some composition of a solid sample studied REFERENCES cases8 as seen in Eig. 28 the camera of y EDS. the S microscope at 0 or 100 can Dyar D & Gunter M. (2009): MinerAlogy and give a good image of the studied grains. Optical MinerAlogy. MinerAlogicAl Society of America, 708 p. Gasharova, B. (2008): RAman, conventional infrAred And synchrotron infrAred spectroscopy in Mineralogy and Geochemistry: bAsics And ApplicAtions. in: ”InstrumentAl Techniques Applied to Mineralogy And Geochemistry” I. Subias & B. BAuluz, eds. Seminarios SEM, 5, 57-81 fig 4. An EDS spectrum with the identificAtion of several elements present in a efflorescence Hope G.A., Woods, R., Munce, C.G. (2001): sAmple. RAmAn microprobe minerAl identificAtion. Min. Eng., 14, DOI: 1565-1577. fig 2. PrismAtic structures of A sieved (ab250 [m) soil sAmple seen in A RS cAmerA. CONCLUSIONS 10.1016/S0892-6875(01)00175-3, Goienaga N., Arrieta N., Carrero J.A., Olivares or a more in depth tetural analysis M., Sarmiento A., Martinez-Arkarazo I., This worD eBplains the application of Fernkndez L.A., MadariagA J.M. (2011): however8 SEM turns to @e a more nondestructive in situ techniues for Micro-RAmAn spectroscopic identificAtion suitale tool due to the fact that the the identification of minerals. n the of nAturAl minerAl phAses And their magnifications are higher. At this point present research S has een weAthering products inside An AbAndoned further study of the results otained successfully used for the identification zinc/leAd mine. Spectrochim. Act. A, 80, may provide other ind of helpful of minerals oienaga et al. 2011 and 66-74. DOI: 10.1016/j.saa.2011.01.032. .