Developments in quantitative luminescence technique

Greer, R. T.

Vand, V.

Weber, J. N.

White, E. W.

English

NASA Technical Reports Server

PRECEDING PAGE BLANK NOT FILMED.
IIAYMOND T. GRlllfll_ VI_ADIMIR YANDoJON _, WiIBIK_ oralEUGENE W. WlI|TN
MeNrlnla RulnrelJ l,_tloreforU and IJqN_tm_lt# O?Gl_hemle#_ll and MIM:'nlo#tl
5rhehnnel_lmn/n iltat_ UIItNPII|II
BevolopmomInIlmdltatlvotumlneswuTenhnlquu
i
In emQnnotionwith the 0anof lumlnmnunonfur the Idnntlflostlunot I,mnr mat_rl_ln,s
ImimloInborltoi'y ntndy Irondnmonntl_l_dthe fnMlblllty of obtnlnlflll llnefnlourrelntlonnof
minerallumlnmnnntphnnumnnn. _wn lnmmnhmm,ttOl_.phntomnltlpllernttnnhmentntn nn
eleotronml_ruprohelave burn dnvelOlPOdwhineimrmlt the ntndy of nlithmlnlnmlnc_m,00m,
honumnn_on s mivrnnannie. The isttnehmpnt4nlt_nd th_ ismdytlvidenpmbilltil_of ten
nntrllilslintslid taldlllAto| (I) r_urdlllll ut lilmlllPmmnunimeottlb(9} obtnininl(i,h. dlntrlh.-
lion of I_imln_auntphlmtmIn mlnr_lmulmonnandbalk llmnlmetln,(ll) evnhtntlnltnl_4rouOl_l-
InN the rd|atlunnhllmI_twenn iluormonn_ pntt_ nnd (nnventlonni X.rn? r_prmentntlnn
of nn Men nnnn_(4) lltnd)'il_@lrndlatlonInihlenCmon _,_inrmnenendeolsy,nnd (11)reistlnR
Inmhl_Io_nooinfirmity to eumpmltlonwithin _ phlmn, Thin I,tormntiun provldt_ it hub
mo_orelisoimblntime tlmt formed)' nm_ for Int_pmtlnll rnmmt obie_vstlunnof Itlnaf
inmlnmoenu0
INTRODUCTION eleotmn.mloroprnbe,IIt_hh-wlre5'mtJn8mono-
ohmmstc¢ assembly. Although other equip-
The use of lundnuoenoeto ohsmot_dae meetunitearo a_wdlshletom,ohaes_'l_lumlnm.
lune_-pud_e ms,minis wu prompted'by. oh- oenoeIflmnomens{rdn. 4 to 9), the mioroprobe
w_Slon8 of lun_ lumlnmomoereportedby sad us_hodolumlnmmnuedetmtorunitsoff.r ,_
Kopsl (re/. l), Rmdthsm (re/. 9), and (_mnomn oomprehendve snslytiad e3mt_s for det4Hed
_d Ollhmmy (rd. 9). An Inner, salon el lnvmdpdom.
kn_mSrislmlnm,_l,likelyto o_mr4n the Moon Some of the eleotrou-mdt_d lundnmomas +
hm demomtmt_d the fmudbiUtyof obt_nt_ Inlormst_on obt_dnod in thin ntudy m_r be
qu_titBtive me_urements of minend lundnN- ueed to pal Jot the ph3miosl, md to rome
oehoe, It hm sire lnE_ted eta4kin_va_dsdom at_n_ the obendmd,pmperflm of ndnende
o_rjpeemd emet_ dbtdbutiom sad udtstion which ms)' be prwmt on the lunsr nurfm sad'
dlidenoim within the individual epeeiinen whioh 5sve been exposed to retinue losses of +
itudnesad thu_ emphubed the ImlmrSlm_eof mdisbton, q_ds rosy then lead to the de-
s _ Iouliud lnvmUl_lon of s multiphue t_ninst_o_ of the 8pttlld dJlJtt_but_Oll.r
mmmh|q_e to provide en undmtsnding of the svdlsbtlity of specific indigenous lun_ or
bulk hminmmnt mpome d the material, phutetm_ourf_mmmnmL
In order to mhieve the level of preoblonImd R_ reported in t4_bpaper m epon-dlm)dminsUou neeesw_r for evalueflp_ the wrul by the Nttk)ntl A_on_utl m end Opm
int4mlst/o_ of'wsvelenl_ madintmu_,ky_4th _dndnbt_Uon. The suShomwleh So Shank
vlls4ouedement_,eompodtioM, etruetuMs, sad Dr, Brim Menu--n,CmSo_' of Meteo14te_
dqme of rem_t411hsdon, two equipment _hnKh_nisn ImUtution, for hb help in ueu_
modUie_tlomwee derdopedfor um withan ins sulmmplm of meteorite q_hnenL
deetron.miempmbeX.n_y mud_.e_. _work
hm dmm4bm the development end BXPRItlMBNTA/,
sppUm_donof two tale _thodoluminemuee
detector uniso: (1) ms eleotron-ndm'Oln'olm, l,amdaemeue _ lJ/Mem
hstwhmme filter sttaduamt; and (9) u The two udhodolumtnmoenoeunlm muNd
ur/
.... ,,. ,, ,. illilll I 151 I iliaD + ........ " imll ....... ., ,,u - JJJ
+ - +,;.,++_, ...... ._+" , _ ............
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foe tits Identllientlolt and dl,t.lnetlm, of plmme me,t replm._ the .r,lar tithe ,f tim optl_al
nuomblngmpfl,r the det_rminaLSm.f tim dl,- mle_mt,.Im .. th_ mi,,ropr.bp, 'fS_ hdpr.
t.rJbutl,ll ,| ronetl.m Im,lu,tn. ned f.r Lhe l.hallgonblePOlnlmtlentMere udtly Ivermutod
qultnl|tatlva i_vnluntl.n of the Imllinmi:ent m: i.hnt _,5eoperator sen perb_r;nn vt_d¢_ty,'if
pr.pertlea f.r npeeimone.f Inioro.eopl,_sine, eXlmrlmentnorlienthe Inll;rimt;npeJ|itile nt,rm#l
Tile tw,, lilll|n h.,llltnte the ntlid_ ,,f e_th.do, mnllller wlth.ut havlnll t,, rem,,vn tile _t_it_Jll.
lulllhlt_Wellt,0phellOlllellltoli a iillP,rl}ll selile of llleflt, Fro'visualitll(_r,,_POlDi_exftmillltL|ntl,the
the nlJeehnonwlth.liL dlnturldng the llOrlllltJ (Wtllilt In llinorLndhl the nttnt,hmonl,. Theft the
tunetloli ot the filler.lit.be, ]_ILherdetetblr npot'imenen,bevie_v_dthrough the monoel_r.-
Ullil, replne,m tile _e.ulnrtubi_ill| the nlloropt,ope illlt|or, hl _'hluh elil4e |.lle speeilllt_llis Reell 111 a
.f an ApplIed Ro_nreh l,nb.ral_rlm model j_Vell e.ol.rnd light, .r, nlterll/lllvely, the 11101110-
]{MX mioropr.lm, Moat nonmetnllle m,tleril, ehrollinh}r elm im IDbpllt4Me,l f,,l'l.l,mltl mlero-
,tln himlnmee in thevl_Ibleregi,n wlienborn- w,pl,, .bnervnlJoll, l)eihdnl_ .llt. h.r the
birded by relatively high OllorKy,.Im,tr.llS (/_t. llllllliwhrollllttor ,ire l..erll, d Ill llhii'p Ill the
_t) keY), _|nee the Jllf011nJi_ySlid nl,nUtrnldis- ,wuh|r, nnd tht_nIth.hmttllllllller lllht_ In llghl_.
frlbllLiOll t;f tile lulllllleaemluu i11tll Yfil'_ eYPll tlldil, hounlnp_nl*pnllppnd Olll.ll the littllPhlltelll.
with nlnitll (_liillKt_ lit lllllllli*Jt]?i'Ollti_ll_lthe h,r elei,trollh, deist,lion oJ'lJghl, Intellsltles,
hln,t.qen+ent_e,hnrneteri.tl¢,mKlve llillmrl,alll In. The lllOlllwhr(mlator within the attnqhm¢_f, '
h_rmljllon eolii.orninll the trat:eq,olllpuailim! mid in It ]jliuneh& Imlnb wodpppilit_ll_etelleefiller of :
liprowthqharneteristlqnof It Kiveu l)hnne, Wltb nnmm. liiili_wMth (;0 imnometetn(lllii)) nml
rheas det_tbm Ulllt_, qualltltnllvo llleMUse. 8_ p0reon5lransmlmlon, The llneardlnpemlon
men_ of the hllnlueeeelieOspentre are ,brained Is _,_ llmlinm With a UniDflllwa'..elenilthr_ol_e
without impeding theinherent useof the iniel_- .f 4(I0to ?O0 ilallOliiOtel_l, An odolnetorinused
probeu an analytical tool. ' to sendwavolencth direotly to the nearest1.0.
The monoebsem.tor (inte_eseneeAlter)at,- The visiblesl)eeU'umis Mannedby useo( a t4yxa.
taebment eonsiste of a iIousinpba ,,l,mo- ehronoueIno_r drive on the monoeht'omator
ehrometor, an ooular tube, a neleetlon of with strtp-oh_t seeordlltg Of (,110milK111_,In :
intesehn_eeble slits, end Inter_h_leeble lilts-, this mann_ the complete vi,dble emimdon
tomultipll_, det_tm_. A dlalp'am of tills spee_rumof a lumlneseentim_ on the surface
iKtliehmen! IS showt_in ilituse 1. The attMh, of Sheample san be obt,_ined. The amplified
photomul_iplltn,ailmd eim idsobe displayedon
.,,,_, ,,_,,,,.._, . ._ .,_,.,, ,_: _,_,.,,,.. Chemeliloaeopein & way analogue to the eon-
_. -_ t..._,,u,. venllonal eleot_on-bsekeeatt_'im_e or X-rsy1,'_,:','_-2._'- f dlk
_.,:,,_._,..,_.,.__ ........ / (_u. im_ aed_b_ eturti_by Hdndeh(sefs,10
_"" i ' " _,_._,,,,, play _pabllitlee have been developed(seh. IS
____ te 11), how.., .th t" at.hm.t, Hgh,_ity dbpla_ ,i a pm'_euisr wa_lenl_h in
(_ _ __!2,.'.":'i_" the.blo ,poe.. e,m he photelpmpldeally
• A Ncondea¢_Iolumin_eeneed_on u_
, ba light-wise_'atinllmoaoohromator_mbly.
I I ....,,,,_,;_,,,_,,-, , TheIlilht,_mmCndby theNlionof theeleotxon
I _ _,x_._,,,, 5ira (typloally,S0 key end 0.03 mioro-
the oeulm' of the deetlron-mio_probe
"_ op_ _esmoo_ _th s fledble, _ehBauaeh& Lomb noneohesentHlfhl wire.
hov_ i._st_um_ lakn_wlllWr q_idealineidtmt _h_mth_ _i_ of
mtUmhment, the ll_l. opt]o rod b 60 j)eroo_ a_ the l_AIYIl_
00000003-TSA09
Q_ANTITA_SVtLuMm_m_INcB_ECHNWU_B 12t}
end,with a llght-$rannmlttlngefficiencyof por_lonofthempentrum(foremiatitep the host
/I percentabaorbanneIon per foot antia trann- crystal |umlne_en_oemtllion k In the blu_t
mlttance capabilityIn th_ visible nl_dnear- and the salivator.inducedlumlnemnenoemit.
Infrared mom_. A variety of signal r_ndoute, slon JeJn the rM, portiot_of _bempentrum),and
such ns Teletype printout,strip-short recording, at n variety of Mttlnl_ to obtain (m_lll_apidc
and oscillographicdisplay,are available, displaysof the lnminmoenoere:' nomparlaon
A Baurah & Lomb /100.mllllmeter4ouai- with eonvantionnlelentron-hnokmoattersod X.
lengthmonoohromatorwithtwo lnterahanKeable r_' lenin.
diffraction _tin_, one bla_ed at ?son A with All tim X.ray meMnreme_t_ were mode o_
iS00 I_ovm!mm aed one blazed at a000 _ an Applied ReaearohLaboratoriel mmlei J_MX
with 1900 _roovm/mm, p_rmJt_ n_rowband microprobe equipped with three deep.lye
spectra to be obtained whennecessary, channels, X.ray Intensitiesw0_e rend from
Hasher is-decode_alern or printedby a Tale,
BxlmlmantmlProcedure typnmn_hJnn.The I)rabe wM operatedwith
As one part of s n_temstin st_ldy of lmuinm- a l.mleron spot nine, The majority of the
canoe,! nnturai ma_dn|_ likely to occuron intenelti_ wore me_ured on n 4.lash LIF
Illnar and planetary n,rfa_, _ Variety of spectrometerusing a nsalM O,OOi-Jnehberyl.
meteoflte speclmennwere exa;uined ul_der Ih;m-windnwarllondotaeto_(a_on 19xatron);
eleet_onbombardment.Detailedexamination slllom¢lVltennlLJeaworememwM udnga 4.t_oh
of what _t fist appeared to be h.m_eneo,n ADP (ammordumdlhydrogonphosphate) span.
material, free from obvious lnchmlon_ of trometerwitha0.004-mm-thlck_oarb_n-ooated,
extraneous phmm (I,e,, metals_ mJlfld_ and nomupported, Mylu window and a flow pro.
dllcates other than enstat|t_), revealedetflkln¢ Imrtionaicounter with P-10 pe at atmaJphedo
vsrlati,,n In fluorm_nee and cheesiest @spa- premure.
titian between selenites, In order to chars. The procedure for ma_lng X-ray laterally
terke the extent of erichvariation, an eleetron measurements was t_ eelee_a iq_n using
microprobe was utdll_ed to examine ensta_ite reflectedlight optics and _lmuJl_neouelyremml
(Millet) grains deriwd from the followi_tg the inndne_m(m Jlgiml from the inset the
meteorite epeelmene: (1) enit_tite ahonddtee: _eet_on beam impinged Ohthe epeeimen and
Abee, Adhl Kot, Atlanta, Bllthfleld, Khairpur, the X_r_y sJszids, )'or _ndtvJdud Irmine de-
JaJh deh Eo_ I,ai.u.,and Hvitt_; and (9) dyed from the lalller ssmplee_ Iron (_e),
emt_tite Mhonddtee. Bkhopvllle, Cumberland man_anme (Ms), ehromim (Cr)j #skium (Ca),
Falb, Kbor Tendld, Pmyanoe, and _Jhallo. and dikes (el) were determined. The in.
water. Itzdividualgods, 10 to S00 micros in tendty of the _iK_ Xmsy emimdonline dgnsi
diameter, were relented for analyeb, and there was utilked to monitor the pbeea (in tide ame,
umtplee were embeddedIn ll-ineh.diameter emt_lto, MilliOn), The Fe_CII, andCr were
plmtio rode. Polkhinl_ wu done by the monitored_ ee to determine their infJueneeon
_que_tiai u_e of 6-, _, ud l-micron dimaond the optical fluoreNem responseof the enstat.ito
pazte and K-mimes Osmol polbhinl_oumpan- host crystal. The Mn wee montto_ to deter
zion. The munpleewere murbonnested to a mine Its _ontribution to the utivjto_ndueed
thieknme of about SO()to 400 _ to provide a red lumineeeenee bud for an enetottte host.
eonduetlng path for absorbed eleot_m _md Although group IVB ozidm _n Immme the
warepIMedin _ b,,_u hold_ in the ndm.oprobe h_t luminemnm (in the blue), thqr w_m not
chamber for aMly_b, monitoreddone their preeeneein there meteor.
lntemity of luminaeenee wm reeordedon a lte ipmlm b weU below the 1 wdl;ht.pet_nt
dud-pan 8_p reamim.. The wavelenl_ _ nameery to enhaneetheestate blue embdo_
from 400 to fO0nanometre wm lnvee_ted in band. The LLPmpeet_o_et_ w_ uNd to mm
two ways: At monoehromator eetthqp to for the K, X-rq embdon lime of the demeate
monitor and oompmt_the blue and the red Ca, l_e, Ms, and C_I the ADP epeetrometm,
I_ _a .... i_ I . I - ' ............................. -........................ "ll .. IllI II
• _ ,. _ ,'_, .- , , ._ ._ _ ...... _ .. ._. ,,, ,. -
00000003-TSA10
180 ZXTRAT_RH_S_X_nE_R_U
wee ujed to identify the K, X_ay eminion the red, and eonnquently _heoselllol_'Jphie
J|netfor Sl, displa_ dearly mhowthe lobationof eeeh,
OperRtionait4_hnlquewna amfollowm:(1) _uoreueeneeb)mostinte_0neln theredportion
obtain the lumlnenoeneeintermlt¥ meMure- of the mpentrum,Almost all of the mtz_ng
me_tm; (D) reoord five replleatloM at each lumlne_,entnampleseontainvery little )_eor
ai¢,_tantodometermetringand at the husk- @a, and the Mhonddte cauterizemp_lmenm
f_ound odometer jetting for that element, for lumine..ee etronger than do the ehondrltes
a terien of point_within a grnJ. or graina (tel, throttghout the visible speet_m,
1O); and (a) photograph lumtm_eenee osetllo. The elinoenstatlte speelmen_luminmee with
_ephJe dlmplaymand the eonventional eathode- relatively low An_len_y and primarily in the
ray-tube eleetfon.baekeoatter image and X.ray blue, and the orthorhombieenstatite speeimenm
lmqm, lumJneaeewith relutlvely hJ_er emelene¥ both
ia the blue and in the red part of the visible
Procedure for Anellde of I_#perlmen_l Data npeetrum, Ire r_odJlys0zh_titutmfor MK ilJ
• enmtetiteand dlr4_ldeand t4AnInrpr eoneentra-
Multivariate s_tistieai snaiytleal teehniqmn tionM in the _Alnoenst*tlt* _peelmens, The
(rds, I? and 18) were ntlllned to proem the prmeneeof Fa quenehe, luminmnee and ainu
data, From this informationit wMposdble to ean effe_tlve|y reduee the Mn inmlneteent
determine to what extent illtoreeeenee_pjetra eml_lon eontribution to red en:.belon, (Man.
of the meteorite vary from eample to s_mple ganeaein Mg_lO0produemnew emi_ion honda
end to eorrelate the Intensity nnd wavelength at the exp_nseof the originalbands of the host
of fluormeenee with ehemleai eomposltion, eryst*l; the Mn activator would normally be
8inee some aero yaluee for the elemmtte were responsible for rise loug.wavelength embaton
prment (sow?pending. to the probe analysb band in this ease,) _nnttmerotmmea_urement_
dettetion limit for the element), the data trees- the Mn and Ye indicated s significant positive ,I,
fonmatiot_log (X+I) wa_ appropriate for the eorrelation, nnd thin emulation usually de- _
s_tieal e_al3mb, erem_ the red eontributionto the lumlnement
rmpone4for the epeeimene, In _ldltiou, the
RIWUL'I_AND DISCL_31ON ohm.red deermm in luminmeent _dBeleneyin
going from an orthorhomble enst*tite to a
When the temples were obaewed micro- monoelinJeeMt*tite speeimenis eonsistent with
tsoldo_lly during elw'_en bombardment, laslle the er_tel-fidd-thee_ explanation concerning
dtfferenem in beth , intendty and wave- the environment of the atom when the lattiee
lonf_th of the multh,g lumineMenee wore apMinff is altered sad else when there is a
evident. Different portions of a eingla minerel reduetionin dee eymmetry.
munpleemitted at wavelengt_ raall_q_gto beth An musminatlonof Nlaot_dndnetal Ip_dnsby
limits of the visible spsofa_tm. Within am the e_eotron mieroprobe revealed that the
individual mpeeimantho yaztatton in intensity dbpenion of eoneentustionsof Fe, Mn, Gr, and
and/or wavdength of flu_ee appea_ to Ca in them samples is also Imp. Thin vari-
be Moounted for by eorrmpondingvm4stion in ability indieat_ why a variety of intensity end
ehemied sompoaition, llillher soneelUstions wavelengthre_ponNemay be pomlblawithin s
of Ire,Ca, and(3_ tend to _ fl_ee, opeeimen. Them ebemisal peeulisdtise effee-
In m_y emm, ejeolutton phenomena(rob. 19 tively define the two peups (enst*tit* short-
and 90) repruentintraro_ of high Ca and low dritee and eftst*tit* Mhondrttee) (rda. |1 to
Oa pyroxeae are thmply sonttwted by moni. at), u well as tend to ddineate the east.tit,
aeries the opted fluormeent eadedon lntem_ty polymorph ptemnt, The eMt.tite ehondrltm
with the moneehmmstor eet in the red portion areeharaet*Hsedby a htl_ desteo of reduction,
of the vbllde _peotrem. Both the hil0t mdi The prineipal mineral is pure el' needy pure
Iow(_tl_Tmxenelundnmosintheblue;however, MBSIO0as rhombioshot.tit,, or elinoenst.tit*
the k_llh(_a quenehu mt_z_ luminemenet Jn in last. 8ome ehoadritmthow wdl-devdoped
00000003-TSA11
00000003-TSA12
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Developments in quantitative luminescence techniques

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