JOURNAL OF GEOPHYSICAL RESEARCH, VOL. 105, NO.

E4, PAGES 9735-9739, APRIL 25, 2000

A thermal emission spectral library of rock-forming minerals

Philip R. Christensen,JoshuaL. Bandfield,Victoria E. Hamilton,
Douglas A. Howard,• Melissa D. Lane,• Jennifer L. Piatek,-•
Steven W. Ruff, and William L. Stefanov
Department of Geology,Arizona State University,Tempe

Abstract. A library of thermal infrared spectraof silicate,carbonate,sulfate,phosphate,

halide, and oxide mineralshas been prepared for comparisonto spectraobtained from
planetary and Earth-orbiting spacecraft,airborne instruments,and laboratory
measurements.The emphasisin developingthis library has been to obtain pure samplesof
specificminerals.All sampleswere hand processedand analyzedfor compositionand
purity. The majority are 710-1000/am particle size fractions,chosento minimize particle
size effects.Spectralacquisitionfollows a method describedpreviously,and emissivityis
determinedto within 2% in most cases.Each mineral spectrumis accompaniedby
descriptiveinformation in databaseform includingcompositionalinformation, sample
quality,and a commentsfield to describespecialcircumstances and unique conditions.
More than 150 sampleswere selectedto includethe commonrock-formingmineralswith
an emphasison igneousand sedimentaryminerals.This library is availablein digital form
and will be expandedas new, well-characterizedsamplesare acquired.

1. Introduction quenciesthat are directly related to the crystalstructureand

The Thermal EmissionSpectrometer(TES) instrumentar-
rived at Mars on September11, 1997,aboardthe Mars Global
Surveyorspacecraft.This instrumenthas obtainedspectraof
Martian surfacematerials[Christensen et al., thisissue(a), (b);
Smith et al., this issue] and is scheduledto map the entire
surfaceof Mars overits 3 year mission[Christensen et al., 1992].
Thisinstrument
willreturnover109high-resolution
IR spectra
of Martian surface materials. In addition, a broadband ther-
mal-IR imagerbeing developedfor the 2001 SurveyorOrbiter
will returnover10•ø100-mresolution,
nine-point
spectra
cov-
eringthe entireplanet.A TES instrumentwill alsobe flownon
the 2001 and 2003 Surveyorlander and rover missionsthat will
return high spectralresolutiondata. In this paper, we present
the laboratorymeasurementsacquiredin emissionat Arizona
StateUniversitythat are designedto supportthe interpretation
of the data returnedfrom Mars. In addition,the library can be
used to interpret data returned from the thermal infrared
multispectralscanner(TIMS) [PalluconiandMeeks,1985],the
AdvancedSpaceborneThermal Emissionand ReflectanceRa-
diometer(ASTER) that is scheduledfor launchon the Earth
ObservingSatellite(EOS) in 1999,and mineralogicalandpet-
rological laboratorystudies.The purposeof this paper is to
describe the method used to obtain a library of well-
characterized,high-purity mineral samplesand spectra that
may be usedfor mineralogicaldetermination.
Vibrational spectroscopy is basedon the principle that vi-
brational motionsoccurwithin a crystallattice at specificfre-
elemental composition(i.e., mineralogy)[e.g., Wilsonet al.,
1955;Farmer, 1974].The fundamentalfrequenciesof geologic
materialstypicallycorrespondto wavenumberslessthan 2000
cm-• (greaterthan-5/am) andprovidea diagnostic
toolfor
identifyingall minerals.An extensivesuite of studiesover the
past 35 yearshas demonstratedthe utility of vibrationalspec-
troscopyfor the quantitativedeterminationof mineralogyand
petrology[e.g.,Lyon, 1962;Lazerev,1972;Farmer,1974;Hunt
and Salisbury,1976; Salisburyet al., 1987, 1991; Salisburyand
Walter, 1989; Salisbury,1993; Lane and Christensen,1997b;
Hamilton et al., 1997]. The fundamentalvibrationswithin dif-
ferent aniongroupssuchas CO3, SO4,PO4, and $iO4 produce
unique, well-separatedspectralbands that allow carbonates,
sulfates,phosphates,silicates,oxides,and hydroxidesto be
readily identified. Additional stretchingand bending modes
involvingmajor cations,such as Mg, Fe, Ca, and Na, allow
further mineral identification, such as excellent discrimination
of mineralswithin the silicateand carbonategroups.
A variety of techniqueshave been developedthat measure
emitted, reflected, transmitted,or scatteredenergyas a func-
tion of wavelengthto detect absorptionfeaturesdue to the
fundamental vibrational modes. The emission spectroscopy
techniqueusedhere hasbeen appliedpreviouslyin the labo-
ratory [e.g.,Lyon, 1965;Low and Coleman,1966;Conel,1969;
Griffiths,1972;ChristensenandHarrison,1993;Ruff et al., 1997]
and acquiresspectrain a similar manner to remotely sensed
data. This similarityallowsfor direct, quantitativecomparison
of laboratoryspectrato remote sensingdata sets.

2. Method
Currentlyat Raytheon,Dallas,Texas.
Currentlyat NASAJohnson SpaceCenter,Houston,
Texas. Sampleswere preparedthrougha processof crushing,siev-
Currentlyat Departmentof GeologyandPlanetaryScience,
Uni- ing, and washing.Crushingwas done either by hand usinga
versi•tyof Pittsburgh,Pittsburgh,Pennsylvania.
rock hammer or through a jaw crusher.Sampleswere then
Copyright2000 by the American GeophysicalUnion. dry-sievedusing a Ro-tap mechanicalsieve shaker, and the
Paper number 1998JE000624. 710-1000/amsizefractionwasseparated.This sizefractionwas
0148-0227/00/1998JE000624 $09.00 used becausevolume scatteringeffects that are introduced
9735
9736 CHRISTENSEN ET AL: THERMAL IR SPECTRAL LIBRARY

Wavelength (/•m) globarsourceand the mirror closestto it. The samplechamber

7 8 9 10 12 15 20
is containedwithin a glove box external to the spectrometer,
and both the spectrometerand the glove box were continu-
Silicate ouslypurgedwith nitrogengasduring sampleanalysisto min-
(Wollastonite)
imize atmosphericH20 and CO2, which also have absorption
_

features
in the2000-400cm-• regionof thespectrum.
Partic-
ulate sampleswere placedon a heater elementto maintainan
-80øC temperatureduringspectralacquisitionand raisedinto
- (Calcite) a water-cooledsample chamberthat closelyapproximatesa
_

blackbodycavity. The temperature of the chamberis moni-

tored, allowingfor environmentalenergyreflectedoff the sam-
- Sulfate ple and into the spectrometerto be accountedfor and cali-
- (Gypsum) brated out of the resultant spectrum.Energy emitted from a
_

-1-cm spot of the sample in a 37ø cone is reflected off a

paraboloidmirror and directedinto the spectrometerthrough
i Oxidean emissionport.A totalof 270scansat 2 cm-• samplingare
_
_
• (Ilmenite)taken over a -7 min period and averagedtogether by the
spectrometer.In the case of a hand sample, active heating
duringmeasurementis not possible.Hand samplesare taken
• - Phosphate
directly from the oven and placed into the samplechamber,
- (Apatite) and 180 scansare taken over a period of -5 min to minimize
_

the effectsof samplecooling.

_ _

Halide
3. Calibration
(Fluorite)
The calibration method is a variation of method 1 of Chris-
1600 1400 1200 1000 80•
Wavenumber (cm-)
600 400 tensenand Harrison[1993],as describedin detailby Ruffet al.
[1997]. This one-temperaturemethod requires only a single
Figure 1. Exampleof library emissionspectra(normalized)
of several mineral classesdemonstratingthe wide variety in
absorptionband position and shape between each mineral Wavelength (/•m)
7 8 9 10 12 15 20
class.Librarysamplenumbersare (from top to bottom)ASU-
60, 91, 82, 35, 96, 59.

Feldspar
(Microcline)
_ _

with smallparticle sizesare minimized,it simulatesthe rough- _

nessof sandyand rocky surfaces,and grainsare ideally ran-

domly oriented to prevent preferential viewingof any crystal
axis.For severalsamples,suchasmica minerals,it wasimprac-
tical to achieve a random orientation, and these are noted in
_
Clay
_ (Kaolinire)
_ _

the database.The sampleswere washed repeatedly using _

deionizedwater, acetone,or ethanol as appropriateto remove

Amphi
clinging fines, and the purest grains were selectedby hand
under a magnifyinglens to ensurea high-qualitysample.The (Hornblende)
purity and compositionof each samplewas determinedby _

settingasidesomeof the final samplefor electronmicroprobe _

and/or X-ray diffraction analysis.In caseswhere there was

sufficientsamplequantity,bulk analysiswasalsoacquired.In
Pyroxene
the caseof hand samples(whichincludesmanyof the carbon- (Augire)
ate, sulfate, and phosphatesamples)and samplesdonated _ _

from the Hunt and SalisburyCollectionat the U.S. Geological _

,.

Survey(USGS), the standardsamplepreparationwasnot ap-

plied and grain sizeis not limited, but compositionalinforma- 01ivine
tion has been verified. (Forsterire)
The particulatesampleswere poured into coppercupswith _

a 3-cm internal diameterand 0.5-cmdepth and were heatedin

1600 1400 1200 1000 80• 600 400
an oven overnightat 80øCto increasethe signalto noiseratio. Wavenumber (cm-)
The sample was not leveled to avoid inducing preferential
Figure 2. Major silicate subclasslibrary emissionspectra
crystalorientations.Lab spectrawere acquiredusinga Matt- demonstratingdifferencesin both band shapeand positionas
son Cygnus100 interferometricspectrometerequippedwith a a resultof samplemineralogy.Tickson they axisare separated
KBr beam splitter and an uncooleddeuteratedtriglycinesul- by 0.05 emissivity,and eachspectrumhasa maximumemissiv-
fate (DTGS) detector. The spectrometerhas been adapted ity of 1. Library samplenumbersare (from top to bottom)
from transmissionto emission capabilities by removing the ASU-57, 178, 66, 54, 8.
 CHRISTENSEN lET AL: THERMAL IR SPECTRAL LIBRARY 9737

measurementof each sample and defines all of the possible Wavelength (/_•m)
? 8 9 10 12 15 20
energy contributionsto the spectrum in terms of radiance.
Blackbodymeasurementsat two temperaturesare needed to
derive detectortemperatureand an instrumentresponsefunc- Albite

tion. These blackbodymeasurementsare made only once dur-

ing a sessionof up to -15 sample measurements.Sample
temperatureis determined spectrallyat the wavelengthof the
highestbrightnesstemperature. Reflected environmental en- Oli•oclase
ergy is calculated and removed from the measuredradiance
with knowledgeof the controlledenvironmentenergyand the _

use of Kirchhoff'slaw, which relatesreflectivityand emissivity

(R = 1 - s) [Salisburye! al., 1994]. The resultingsample
radianceis dividedby a calculatedblackbodyradiancecurve at _

the temperature of the sample to obtain sample emissivity. _

This methodassumesthat the emissivityof the sampleis unity

at one point or more in the spectrum.Repeatabilitybetween
sessionsis better than 1% emissivity,and accuracyin most _
/••/•- Labrador _

casesis within 2% emissivity[Ruff et al, 1997]. _

4. Data and Documentation

The library is availableonline in digital form, currently at

•••//•/•
_

_
_
Bytowni
http://tes.la.asu.edu.This paper servesas a reference docu-
ment for the digital library, and usersare requestedto follow Anorthite

the guidelinespostedon the Web site for referencingsamples

donatedby externalsources(e.g.,NationalMuseumof Natural
History and Hunt and Salisbury).Attachedto eachspectrum
are databasefieldsthat describethe sample.In somecases,the
mineral hasbeen renamedas a resultof chemicalanalysis,but
the original mineral name, source,and samplenumber have
been retained in separate databasefields. A sample quality
field hasbeen includedto providea quickassessment of sam-
ple purity. This field containsthree degreesof samplepurity:
(1) the mineraland spectraare of highpurity and quality;(2)
there are minor impurities,but overallqualityis still good;(3)
the samplecontainssignificantimpuritieswhich may signifi-
cantly influenceits spectrum.Also includedwith the database
is a comment field that is used to describespecial circum-
stances,uniqueconditions,and individualcaveats.Other fields
includedare visual inspectionresults,donor history,bulk ox-
ides,microprobeoxides,X-ray diffractionanalysisresults,and
particle size.
Samplesof the library spectra are shown in Figures 1-3.
Mineral classesare easilydistinguishedon the basisof major
absorptions presentin differentwavelengthregions(Figure 1).
Smaller compositionaland structural variations also have a
significantinfluenceon band position and shape,as demon-
stratedwith the silicatesubclasses shownin Figure 2. Figure 3
shows the fine compositional and structural variation that
causesdistinctspectraldifferenceswithin a mineralogicalsub-
tlass.The presenceof distinctspectralfeaturesin a wide vari-
ety of mineralsallowsfor laboratoryand remote sensingmin-
eralogicaldeterminationsusingthis data set.
Probablythe best known and mostcommonlycited thermal
infrared spectrallibrarypublishedto date is that of Salisburyet
al. [1991]. This library was publishedin order to provide re-
flection rather than transmission measurements and to include
spectralinformationto shorterwavelengths(2 •m) than was
available in existing reflection/emissionworks. Reflectance
spectrain the Salisburyet al. librarywere acquiredvia biconi-
cal reflectancemeasurements,and five sampleshave hemi-
sphericalreflectancespectraavailableaswell. AlthoughKirch-
hoff'slaw (R = I - s) [Nicodemus, 1965] is commonlyused
1600 1400 1200 1000 80•) 600 400
Wavenumber (cm-)
Figure 3. Library emissivityspectraof the plagioclasefelds-
par series.This figure demonstratesa high degreeof discrim-
inabilitybetweenmineralswithin a singlesubclass.Tickson the
y axisare separatedby 0.05 emissivity,and eachspectrumhas
a maximumemissivity of 1. Librarysamplenumbersare (from
top to bottom) ASU-174, 22, 175, 176, 177, 178.
to predict spectralemissivityfrom reflectancemeasurements,
Salisburye! al. [1991]demonstratedthat this conversionis not
applicableto biconicalreflectancemeasurementsin a quanti-
tative sense.Instead, hemisphericalreflectancespectramust
be usedif an accuraterelationshipto emissionmeasurements
is needed(Figure 4). The directionalnature of the radiation
measuredby the biconicalmethoddoesnot adequatelyrepre-
sent the infrared radiation scattered in all directions as do the
emissionand hemisphericalreflectance measurements.Be-
causeboth the Arizona State Universityand Salisburyet al.
librariescontainsamplesacquiredfrom the National Museum
of Natural History, it was possibleto comparea few samples
commonto both libraries (Figure 5). As in the caseof the
quartz shownin Figure 4, the biconicalreflectancespectrum
displaysanomalousspectralfeatures,especiallyat shortwave-
lengthsnear the Christiansenfrequency.This disparityis prob-
lematic if quantitative analysisof thermal emissionmeasure-
mentsis desired,suchas in the caseof multimineralic(rock)
spectra;in suchcases,biconicalspectrashouldbe avoided,and
hemisphericalor emissionspectrausedinstead.
5. Conclusion
The library currently consistsof more than 150 mineral
samplesand is continuallyexpanding.The library is not com-
prehensive,as collectionand characterizationof many of the
library samplesis driven by individual researchinterests,in-
cludingseveralsystematic mineralogicalstudiessuchaspyrox-
9738 CHRISTENSEN ET AL: THERMAL IR SPECTRAL LIBRARY

Wavelength (/•m) Acknowledgments. The authors wish to thank Paul Barbera and
7 8 9 10 12 15 20
100
Don Andersonfor their help with samplecharacterizationand library
organization,the National Museum of Natural History and Roger
Clark for donatingor providingaccessto severalof the librarysamples,
and Brett McClellan, StephenHolloway,Nathan Glondys,and Teresa
Longazofor their helpwith samplepreparation.We wishto thankTed
080 Roush and Jeff Moersch for reviewsthat substantiallyimproved this
manuscript.

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