Chemistry and Materials Research ISSN 2224- 3224 (Print) ISSN 222 - !" # ($nline) %ol.3 No.&!' 2!

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Lead Isotope Determinations by Mass Spectrometry and Its Application by Isotope Dilution Technique
()*+I+ .I. ),SS*IN -e.artment o/ Chemistry' College o/ 0d1cation-I2n *l-)aitham' ,ni3ersity o/ 4aghdad Abstract * method /or the determination o/ +ead isoto.e ratios 2y thermal ioni5ation mass s.ectrometry (6IMS). 6his method also descri2es the a..lication o/ isoto.e dil1tion mass s.ectrometry (I-MS) to the /ield o/ re/erence material (RM) characteri5ation /oc1sing on the a..roach. 0m.hasis is .laced on I-MS meas1rements o/ highest analytical 71ality. 4asic .rinci.les as well as the e71ation system are 2eing recalled. 6he e3a.oration and ioni5ation c1rrents are determined /or a meas1rement o/ isoto.ic ratios o/ head' em.loying do12le rheni1m /ilament assem2ly in the ion so1rce and 8araday c1. as the detector 1sing the .resently a3aila2le RM. Introduction +ead has /o1r nat1rally-occ1rring isoto.es9 2!4P2' 2!#P2' 2!:P2 and 2!;P2. 2!4P2 is not radiogenic. 6he isoto.ic com.osition o/ P2 is commonly e<.ressed as the ratios 2!;P2= 2!#P2 or 2!#P2= 2!:P2. 6he less a21ndant 2!4P2 is o/ten 1sed as a re/erence in geochronological st1dies 2eca1se it is sta2le and its a21ndance is constant >&?. 6he other three (2!#P2' 2!:P2 and 2!;P2) are the end .rod1cts o/ radioacti3e decay o/ 23;,' 23 , and 2326h' res.ecti3ely>2?. 6he 2!:P2= 2!#P2 and 2!;P2= 2!#P2 3al1es are commonly 1sed in com.aring en3ironmental sam.les since the total lead concentrations are o/ten low and the relati3e a21ndances o/ these three isoto.es is m1ch higher than that o/ 2!4P2. 6he relati3e a21ndances o/ these isoto.es 3ary with the ty.e and geological ages o/ the roc@s and ore de.osits at di//erent sites' and hence with geogra.hic locations >3?. 6hermal ioni5ation mass s.ectrometry (6IMS) is still regarded as the de/initi3e methodology /or lead isoto.e meas1rements. * de3elo.ment o/ sam.le loading techni71e 1sing silicagel drastically. Im.ro3ed the ioni5ation e//iciency o/ P2 in 6IMS' which allowed the P2 isoto.e analysis with signi/icantly smaller sam.le si5e com.ared to the electron im.act ioni5ation method with gaseo1s methyl P2 >4?. 6he origin o/ the isoto.e dil1tion .rinci.le is not @nown e<actly. -i//erent ass1m.tions can 2e /o1nd in the literat1re' where o most o/ them see the origin in 5oology > ?. 6he isoto.e dil1tion .rinci.le /irst was 1sed to co1nt the .o.1lation o/ rare 2irds on islands. M. 4ergl1nd /o1nd a clear re/erence that the isoto.e dil1tion .rinci.le has 2een a..lied in 5oology >#?. 6he .rinci.le o/ I-MS is s1r.risingly sim.le. * sam.le with @nown isoto.ic com.osition o/ the analyte element' 21t 1n@nown element content is mi<ed with a @nown amo1nt o/ s.i@e. 6his s.i@e contains the analyte element in a di//erent isoto.ic com.ositor. Ideally enriched in the rarest nat1ral isoto.e. */ter com.lete mi<ing o/ sam.le and s.i@e the so-called sam.le-s.i@e 2lend or isoto.e dil1ted sam.le gained a new isoto.e ratio 2eing 2etween the isoto.e ratio o/ the sam.le and that o/ the s.i@e >:?. *s I-MS only re71ires isoto.e ratio determination and mass meas1rements' the ad3antage com.ared to other methods 2ecome a..arent9 */ter e71ili2ration losses o/ analyte do not a//ect the acc1racy o/ the analytical res1lt' 2eca1se the meas1re and' the 2lend isoto.e ratio' is e71al in all s12-sam.les o/ the 2lend >;'"?. I-MS o//ers the .ossi2ility to determine maAor (B) to 1ltra-trace concentrations (C ng. (g) o/ elements' s.ecies and com.o1nds in 3ario1s matrices. 6he /actor that I-MS has the .otential to .rod1ce analytical res1lts o/ highest acc1racy and .recision' metrologically denoted to as smallest 1ncertainties' ma@es it most s1ita2le as re/erence method /or RM characteri5ation >&!?. In the last years the 1tility o/ ind1cti3ely co1.led .lasma mass s.ectrometry (ICP-MS) in P2 isoto.ic st1dies has 2een e<.lored and the de3elo.ment o/ sensiti3e and highly .recise analytical techni71es 2ased on ICP-MS has allowed the determination o/ isoto.ic relations o/ P2 in en3ironmental and geologic materials>&&-&3?. Experimental: Apparatus __ 6hermal ioni5ation mass s.ectrometer (M*6 2#&)' 8innigan Mat Co. (Dermany). 6he characteristics o/ this instr1ment are as /ollow __ Single /oc1sing. __ * m1lti.le /ilament assem2ly. __ %arying magnetic /ield. __ 6he ion c1rrent is meas1red 2y either a 8araday c1. or secondary electron m1lti.lier. __ *ngle o/ de/lection "! E . __ 4ac@gro1nd determination a/ter each scan. __ Ion accelerating 3oltage &! (%.

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Chemistry and Materials Research ISSN 2224- 3224 (Print) ISSN 222 - !" # ($nline) %ol.3 No.&!' 2!&3
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Masses (No. 23' ( 3") are cali2rated to meas1re the intensities o/ +ead isoto.es.

__

Rea ents N4S ";& standard re/erence material' common lead isoto.ic standardF this standard was .1ri/ied to at least ""." G .ercent .1rity' and e<tr1ded into wire /orm.

*2sol1te *21ndance Ratio' 2!4P2=2!#P2 H !.! "!42 I !.!!!!3 *2sol1te *21ndance Ratio' 2!:P2=2!#P2 H !."&4#4 I !.!!!33 *2sol1te *21ndance Ratio' 2!;P2=2!#P2 H 2.&#;& I !.!!!; P2H &.42 P2H 24.&442 2!: P2H 22.!;33 2!; P2H 2.34:! __ N4S ";3' Radiogenic lead isoto.ic standard' this standard was .1ri/ied to at least ""." G .ercent .1rity and e<tr1ded into wire /orm' it has 2een em.loyed as a s.i@e standard.
2!# 2!4

*2sol1te *21ndance Ratio' 2!4P2=2!#P2 H !.!!!3:& I !.!!!!2 *2sol1te *21ndance Ratio' 2!:P2=2!#P2 H !.!:&2!& I !.!!!!4 *2sol1te *21ndance Ratio' 2!;P2=2!#P2 H !.!&3#&" I !.!!!!24
2!4 2!#

P2H !.!342 P2H "2.&4": 2!: P2H #. #&& 2!; P2H &.2 !
__ __

*nalytical reagent grade nitric acid (Carlo 0r2a' Milan' Italy' No. 4!;!& ). )ydrochloric acid /rom (Merc@' -armstadt' Dermany). __ MilliJJ Kwater (Milli.ore' 4ed/ord' M*' ,S*). __ +ead (II) car2onate (*ldrich Com.any' *CS reagent ""."" G B). 6he lead metals o/ N4S standard (";&F ";3) were dissol3ed in a mi<t1re o/ (3)Cl G& )N$3) /or o3ernight then were added e<cess o/ )N$3 to con3ert the lead chloride to lead nitrate. !rocedure o" IDMS In the I-MS' a series o/ lead mi<t1res were .re.ared 2y mi<ing a @nown ali71ot o/ s.i@e sol1tionF N4S ";3 with a certain .ortion o/ sam.le (1n@nown concentration o/ lead (II) car2onate) already .re.ared. 6he mi<t1res were chosen to re.resent a series o/ di//erent ratios o/ s.i@e to sam.le as shown in 6a2le 4. 8ig &' shows the I-MS .rinci.le /or lead. 8or .ro/o1nd disc1ssion on I-MS the schematic diagram (8ig. &) is not detailed eno1gh and it is necessary to ha3e a closer loo@ at the e71ation system. 8or the calc1lation o/ lead concentration in the sam.le (lead (II) car2onate ta@en as 1n@nown)' the /ollowing e71ation is 1sed /or I-MS >&4?.

M. C< H Cs# ms # # m. Ms

)s ).

2!#

2!;

(&= %mi<.) J (&= %s) & J %. = %mi<.

C<H +ead conc. in the 1n@nown sam.le sol1tion (mg=ml). CsH +ead conc. in the s.i@e sol1tion (mg=ml). msH amo1nt o/ s.i@e sol1tion weight in mg. m.H amo1nt o/ 1n@nown sam.le sol1tion in mg. M.H mean atomic weight o/ lead in the 1n@nown sol1tion. MsH mean atomic weight o/ lead in the s.i@e sol1tion. )s2!#H atom B 2!#P2 in the s.i@e. ).2!;H atom B 2!;P2 in the sam.le. %mi<.H atomic ratio o/ 2!;P2= 2!#P2 in the mi<t1re. %s.H atomic ratio o/ 2!;P2= 2!#P2 in the s.i@e.

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%. H atomic ratio o/ 2!;P2= 2!#P2 in the sam.le. Sample Loadin : 6he /ilament 1sed /or loading is a single /ilament made o/ Rheni1m. 6he 71antity o/ lead load on the e3a.oration /ilament (!.3 Lg= ml) as a +ead Nitrate sol1tion /ollowed 2y a dro. o/ &!B N)4$) sol1tion to ins1re the /ormation o/ P2($))2 which ena2le the lead sam.le to stic@ on the /ilament d1ring e3a.oration .rocess >& ?. 6he /ilament which is in the loading .osition is connected a1tomatically 3ia s.ring contact to the .re.aration heating. 6his 1nit .ro3ides /acilities /or re.rod1ci2le' tem.erat1re .rogrammed heating 1. o/ the loaded /ilaments' ma@ing .ossi2le to concentrate the sam.le on a small area in the mid o/ the /ilament. Results and Discussion: In the analysis o/ N4S standard' ";& (common lead isoto.ic standard) and N4S' ";3 (Radiogenic lead isoto.ic standard). 6he ioni5ing /ilament c1rrent is set at & *m. and then the heating c1rrent /or ioni5ing /ilament is slowly increased (a2o1t !.2 *m. e3ery min1tes)' 1ntil the lead signal is detecta2le on the grid and then grow' as the higher tem.erat1re .hase 2egins to 2e ioni5ed. 6he 2est intensity o/ P2 (2!;' 2!#' 2!4' 2!:) signals re71ired c1rrent o/ (2.3J 2.# *m.)' /or the ioni5ing /ilament only at a tem.erat1re o/ (&&!!J & !! E C). * small amo1nt o/ isoto.ic /ractionation generally occ1rs d1ring on analysis' the 2!;P2= 2!#P2 ratio changes d1ring the data ta@ing .eriod o/ an analysis (2! mins.). 6o minimi5e the e//ect o/ this /ractionation' all analysis were in an identical manner. ,s1ally' the data were always ta@en thro1gh the same time inter3al >& ?. Mass discrimination e//ects ha3e 2een o2ser3ed in meas1rements o/ isoto.ic ratios 1sing 6IMS. Se3eral .rocess contri21te to this .henomenon. 6hese are mainly s.ace charge e//ects (Col1m2ic re.1lsions) in the s@immer cone region' which res1lts in .re/erential transmission o/ the hea3ier ions >&#?' and massJ de.endent sensiti3ity o/ the mass s.ectrometer. 6he e//ect o/ mass 2ias sho1ld 2e monitored' and i/ necessary corrected' 2y 1sing standard o/ @nown isoto.ic com.osition close to that o/ the 1n@nown. 6he standard sho1ld 2e analy5ed /re71ently d1ring an analytical r1n to monitor changes in mass 2ias with time. Mean ratio' standard deri3ation and the correction /actor. 8or the isoto.e ratios 2!;P2= 2!#P2 and 2!:P2= 2!#P2 are gi3en in 6a2le & and 2 /or the two standard re/erence materials ";& and ";3. 6he res1lts are shown in 8ig. 2 and 3' 6he 6IMS was o.timi5ed to ma<imi5e P2 signal intensity in the meas1rements o/ SRM ";& and ";3 P2 sol1tion. 6he res1ltants a3erage 3al1es o/ SRM ";& and ";3 are 2!;P2= 2!# P2 H 2.!#;2!24 and !.!&3424 res.ecti3ely. 6he correction /actors to the certi/ied 3al1e /or SRM ";& and ";3 are 2!;P2= 2!#P2 H &.!4;3!2 and &.!&4 2#' which shows an e<cellent re.rod1ci2ility o/ o1r analysis. 8ig. (4)' P2 isoto.e com.osition o/ SRM ";&' re.orted in literat1res com.ared with o1r data. 6he relati3e di//erences o2tained 2y 6IMS data seem to 2e de3iated /rom the e<.ected straight linear mass de.endent /ractionation trends d1e to anomalo1s 2eha3ior o/ P2 as .ointed o1t .re3io1sly >& ' &:' &;?. 6a2le 3' shows the res1lts o/ analysis o/ P2 isoto.e ratios' standard de3iation and correction /actor o/ the mean ratios' determined 2y 6IMS /or lead car2onate. 8rom these analyses the sta2ility o/ .ea@ intensity /or lead car2onate has the longer time o/ the ion c1rrent d1e to isoto.e /ractionation occ1rred in the ionic emission .rocess. I/ the signal starts to decay' the r1n sho1ld 2e reAected. -ecaying singles generally show signi/icant change in the o2ser3ed ratio with time >&"?. Per/orming I-MS with 6IMS re71ires an analyte isolation ste.' as e3a.oration' ioni5ation and th1s /ractionation in 6IMS dramatically change with matri<. 4eca1se analyte isolation in mandatory /or 6IMS and th1s an intrinsic com.onent' the meas1rement .roced1re M6IMSM is largely 1na//ected 2y matri< >;?. I-MS has the .otential to .rod1ce analytical res1lts o/ highest acc1racy and .recision. 6he I-MS e71ation system is not disc1ssed anymore as it seems well-@nown. 41t /or a 2etter 1nderstanding o/ all details and /or /ollowing the com.arison o/ di//erent I-MS a..roaches it is hel./1l to reca.it1late the I-MS e71ation system' which descri2ed in e<.erimental. -ata /or the meas1rements o/ lead concentration 2y I-MS is gi3en in 6a2le 4' which shows the mi<ing ratios o/ 2!;P2 and 2!#P2 /or the isoto.ic dil1tion analysis o/ 2!#P2. It is seen /rom this ta2le that the ratio &9 gi3es 2etter res1lts in com.arison with the other ratios (&9& and &92). 6his co1ld 2e attri21ted to the di//erence in the .ea@ height o/ these isoto.es. 6otal error in the I-MS o/ +ead sam.les 2y isoto.ic dil1tion *nalysis consists o/ the /ollowing errors >2!-2&?9 A$ 6he error o/ weighing (21oyancy' electrostatic charge' moist1re content' sta2ility). %$ Isoto.e ratio determination (inter/erences' mass discrimination or /ractionation e//ects' dead time e//ect' cali2ration e//ect' contamination' a21ndance sensiti3ity). &$ 6he error o/ sam.le .re.aration (incom.lete digestion' incom.lete isoto.ic mi<t1re = e<change). &onclusions 6he e<.erimental res1lts re.orted in this wor@ s1ggest that good .recision and acc1racy may 2e achie3ed 2y 1sing

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6IMS to determine lead isoto.ic ratios /or N4S-";&' N4S-";3 and lead car2onate. *lso the mean ratios o/ the lead isoto.e are corrected. 6he I-MS .rocess is well 1nderstood and all so1rces o/ errors are @nown in .rinci.le. 6he identi/ied errors or 2ias can 2e a3oided or corrected 2y sim.le mathematics or additional meas1rements leading to the highest acc1racy and .recision in elemental analysis com.ared to other techni71es. 6he I-MS has 2een together with I6MS' this com2ination esta2lished as international acce.ted re/erence method /or elemental analysis. I-MS o//ers s1//icient de3elo.ment .otential to /ollow /1t1re needs in analytical chemistry and re/erence material characteri5ation. Re"erences >&? M. 6. Rodrig1e5J Sala5ar' $. Morton 4ermea' 0. )ernande5J *l3are5' M. 0. DarciaJ *rreola' M. 6. $rt1noJ *r5ate' 2!&!' -e3elo.ment and %alidation o/ on analytical method /or the determination o/ lead isoto.ic com.osition 1sing ICPJ KMS' Deo/isica Internacional 4"(3)' &&3J &&:. >2? C. -. N1dd and (. Swami' 2!&!' ICPJ MS determination o/ lead isoto.e ratios in legal and co1nter/eit cigarette to2acco sam.les' Isoto.es in 0n3ironmental and )ealth St1dies %ol. 4#' No.4' 4;4J 4"4. >3? *. -ic@en' &"" ' Radiogenic Isoto.e Deology' Cam2ridge ,ni3ersity Press' Cam2ridge. >4? M. 6animi51 and 6. Ishi@awa' 2!!#' -e3elo.ment o/ ra.id and .recise P2 isoto.e analytical techni71e 1sing MCJ ICPJ MS and new res1lts /or DSN roc@ re/erence sam.les' Deochemical No1rnal' %ol. 4!' &2&J&33. > ? 0. Roth' &"":' Critical 03al1ation o/ the 1se and *nalysis o/ sta2le Isoto.es' P1re *..l. Chem.' #"' &:3 J &;2;. >#? M. 4ergl1nd' 2!!4' Introd1ction to Isoto.e -il1tion Mass S.ectrometry (I-MS) in P. -e Droot (ed.)' )and2oo@ o/ Sta2le Isoto.e *nalytical 6echni71e' &' ;2!J ;34. >:? N. %ogel and O. Prit5@ow' 2!&!' Isoto.e -il1tion Mass S.ectrometryJ * Primary method o/ meas1rement and its role /or RM Certi/ication' No1rnal o/ Metrology Society o/ India' %ol. 2 ' No. 3' &3 J &#4. >;? N. -iemer' C. R. K1etel and P.-.P. 6aylor' 2!!2' com.arison o/ Per/ormance o/ -i//erent ICPJMS Instr1ments on the Meas1rement o/ C1 in a water Sam.le 2y ICPJ I-MS' N. *nal. *t. S.ectrom.' &:' &&3:J &&42. >"? 8. Oom2cher' M. Reh@am.er' Me5er and C. M1n@er' 2!!3' Sta2le Isoto.e Com.osition o/ Cadmi1m in Deological Materials and Meteorites -etermined 2y M1lti.leJ Collector ICPJ MS' Deochim. Cosmochim. *cta.' #:' 4#3"J 4# 4. >&!? ). Oei' P. Qiao' *. S1n' C. Rhang and S. +i' 2!!4' 0//ecti3e elimination o/ iso2aric ions inter/erence and .recise thermal ioni5ation mass s.ectrometer analysis /or 2oron isoto.e' Int. N. Mass S.ectrometry. 23 (2)' &;:S&" . >&&? N. D. 8armer' +. N. 0ades' *. 4. Mac@en5ie' *. (iri@a and 6. 0. 4aileyJ Oatts' &""#'Sta2le +ead Isoto.e Record o/ +ead Poll1tion in +och +omond Sediments' 0n3iron. Sci. 6echnol. 3!' 33;!J 3!3;. >&2? 8. Monna' A. +ancelot' I. O. Cro1dace' *. 4. C1ndy and N. 6. +ewis' &"":' P2 Isoto.ic Com.osition o/ *ir2orne Practical Material /rom 8rance and the So1thern ,nited (ingdom9 Im.lications /or P2 Poll1tion So1rce in ,r2an *reas. 0n3iron. Sci. 6echnol. 3&' 22::J 22;#. >&3? ). C. Moor' 6. Schaller and M. St1rm' &""#' Recent changes in sta2le +ead Isoto.e Ratios in Sediments o/ +a@e R1g' Swit5erland' 0n3iron. Sci. 6echno. 3!' 2"2;J 2"33. >&4? *. )enrion' &""4' Red1ction o/ SystematicJ 0rrors in K1antitati3eJ *nalysis 2y Isoto.eJ -il1tion MassJ S.ectrometry (I-MS). N. *nal. Chem.' 3 !' # :J .# ;. >& ? 0. N. Caton5aro' 6. N. M1r.hy' O. R. Shieids' and 0. +. )arner' &"#;' N. o/ Research o/ the National 41rea1 o/ Standards' Physic and Chemistry' :2*' No. 3' 2#&J 2#:. >&#? I. 6. Plat5ner' &"":' Modern isoto.e ratio mass s.ectrometry' Chemical *nalysis' %ol. &4 ' &;:J &;". >&:? O. 6odt' R. *. Cli//' *. )anserand' *. O. )o/mann' &""#' 03al1ation o/ 2!2P2J 2! P2 do12le s.i@e /or highJ .recision lead isoto.e analysis' 0arth Processing9 Reading the Isoto.e Code' Deo.hysical monogra.h " . >&;? M. 8. 6hirlwall' 2!!!' InterJ la2oratory and other errors in P2 isoto.e analysis in3estigated 1sing 2!:P2J 2!4P2 do12le s.i@e.' Chem. Deol.' &#3' 2""J322. >&"? O. R. Shields' &"##' *nalytical mass s.ectrometry section' Instr1mentation and .roced1res /or Isoto.ic *nalysis' N4SJ 2::. >2!? (. D. (ehl' (. Oeira1ch' S. O1nderli and %. R. Meyer' 2!!!' 6he In/l1ence o/ %ariations in *tmos.heric Press1re on the ,ncertainly 41dget o/ Oeighing Res1lts' *nalyst' &2 ' " "J "#2. >2&? *. Reichm1th' S. O1nderli' M. Oe2er and %. R. Meyer' 2!!4' 6he ,ncertainly o/ Oeighing -ata $2tained with 0lectronic *nalytical 4alances' Microchim. *cta.' &4;' &33J&4&.

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Table '# Mass Spectrometric Analysis o" Lead isotopes standard (%S )*'# +run Mean ratio Mean ratio Mean ratio ,-* ,-1 ,-2 (o# !b.,-/!b St# de0 !b.,-/!b St# de0 !b.,-/!b -3 -3 2.!#&"!4 2.; < &! !.;3433# &.2 < &! !.! !:" ' 2.!#"43# ." < &!-3 !.;3 &# 2.& < &!-3 !.! 22: , 2.!#"!3# 2.; < &!-4 !.;333:& 2.3 < &!-4 !.! 22# 3 2.!#" #4 &.; < &!-3 !.;34:"& &.3 < &!-3 !.! 4:&; 2 2.!:!!2; 2.2 < &!-3 !.;34;&! 2.# < &!-3 !.! 4"#; 4 2.!#"#&: 4.2 < &!-3 !.;34: 4 2.2 < &!-3 !.! 2:" / 2.!#"3!; 3.& < &!-3 !.;34 2" &.& < &!-3 !.! !"! 1 +each one is a mean o/ /i3e meas1rements. Mean ratio Mean ratio Mean ratio 2!; 2!: 2!4 P2=2!#P2 H 2.!#"442 P2=2!#P2 H 2.!#"442 P2=2!#P2 H 2.!#"442
2!;

St# de0 ;.: < &!& < &!-4 &.2 < &!-4 &.: < &!-4 3.& < &!-4 3.; < &!-4 "." < &!-

P2 = 2!#P2 H

2.&#;& H &.!4:#:4 2.!#"442

Correction /actor.

2!:

P2 = 2!#P2 H

!."&4#4 H &.!" "!3 !.;34 "" !.! "!42 !.! !;4

H &.!:&; 4

Correction /actor.

2!4

P2 = 2!#P2 H

Correction /actor.

Table ,# Mass Spectrometric Analysis o" Lead isotopes standard (%S )*3# +run Mean ratio Mean ratio Mean ratio ,-* ,-1 ,-2 (o# !b.,-/!b St# de0 !b.,-/!b St# de0 !b.,-/!b -4 -4 !.!&343 &.! < &! !.! 3"&" &.; < &! !.!!!#!2 ' !.!&32:4 3.# < &!!.! & & 4.4 < &!-4 !.!!! 3 , !.!&332: 4.; < &!!.! & 22 &.: < &!-4 !.!!! " 3 !.!&343& 4.# < &!!.! 44&3 &.# < &!-4 !.!!!#!: 2 !.!&3 :" &.2 < &!-4 !.! 4332 3.; < &!-4 !.!!! 42 4 !.!&34"; 2.3 < &!!.! 2&!" &.# < &!-3 !.!!! 3& / +each one is a mean o/ /i3e meas1rements. Mean ratio Mean ratio Mean ratio 2!; 2!: 2!4 P2=2!#P2 H !.!&3424 P2=2!#P2 H !.! 2"#; P2=2!#P2 H !.!!! #2
2!;

St# de0 3.2 < &!&.3 < &!&.# < &!2.& < &!2." < &!&.2 < &!-

P2 = 2!#P2 H

!.!&3#&" H &.!&4 2# !.!&3424

!.!:&2!& H &.34422# !.! 2"#; !.!!!3:& !.!!! #2

Correction /actor.

2!:

P2 = 2!#P2 H

Correction /actor.

2!4

P2 = 2!#P2 H

H !.##!&42

Correction /actor.

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Table 3# Results o" the determination o" lead isotope ratios "or Lead 5II6 &arbonate by TIMS# +run Mean ratio Mean ratio Mean ratio ,-* ,-1 ,-2 (o# !b.,-/!b St# de0 !b.,-/!b St# de0 !b.,-/!b St# de0 -3 -3 2.!#"3&" .4 < &! !.;3 ::; 2. < &! !.! 4: " &.: < &!-4 ' 2.!:!3&2 3.: < &!-3 !.;3 34! &.2 < &!-3 !.! 444 &.# < &!-4 , -3 -3 2.!:32 4 2.: < &! !.;3#&"# 2.! < &! !.! 4;:" &.2 < &!-4 3 -3 -3 2.!#:"&: 2.! < &! !.;3#2:& 2.& < &! !.! !:: &.# < &!-4 2 -3 -4 2.!#;""# &." < &! !.;3 ;;3 ;.& < &! !.! 4" # ". < &!4 -3 -4 2.!:&43! 2.; < &! !.;3 ;4 ".& < &! !.! 4#3: &.: < &!-4 / -3 -4 2.!:3;& 2.: < &! !.;3 2"# :.4 < &! !.! 4 ;: ".: < &!1 -3 -4 2.!:3&": &.# < &! !.;3#&!& 4.; < &! !.! 4 ;: &.3 < &!-4 * -3 -4 2.!:&!": 3.! < &! !.;3 4:; &.3 < &! !.! &44 2.; < &!-4 ) +each one is a mean o/ /i3e meas1rements. Mean ratio Mean ratio Mean ratio 2!; 2!: 2!4 P2=2!#P2 H 2.!:&!3" P2=2!#P2 H !.;3 :#" P2=2!#P2 H !.! 4: 3 */ter corection (*C) 2.&#"::4
2!;

*C !."& "22

*C !.! ;#;:

P2 H 2.3 4 P2 H 22.&!!3 P2 H 24.&2"!

2!:

2!#

2!4

P2 H &.4&#& Mixture (o# ' , 3 Table 2# Lead concentration measurements o" the Lead &arbonate by IDMS Spi7e Sample 5Lead Mixin Lead conc# Lead conc# 5m #6 &arbonate6 5m #6 Ratio ta7en 5m .ml6 "ound 5m .ml6 spi7e: sample &.!:!# &.!"": &9& #2. &&2 #2.&! & !. 2"; &.!"## &92 #2. &&2 #2.2"&3 !. 2 ; 2.:!43 &9 #2. &&2 #2.4;33

Chemistry and Materials Research ISSN 2224- 3224 (Print) ISSN 222 - !" # ($nline) %ol.3 No.&!' 2!&3

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8no9n quantities:$ J Sam.le mass or s.i@e mass. J Isoto.ic com.osition.

m=5 :i # ' Schematic IDMS principle demonstrated "or !b 9hen ,#1-23 m # o" sample mixed 9ith -#4,4* m # o" spi7e

4#

Chemistry and Materials Research ISSN 2224- 3224 (Print) ISSN 222 - !" # ($nline) %ol.3 No.&!' 2!&3

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:i # 3 Result o" repeated analysis o" a -#3 ; .ml SRM )*' !b solution< each result o" ,-*!b. ,-/ !b and run (o# is a mean o" "i0e measurements#

:i # 2 !b isotope composition o" (%S )*' reported in literates by TIMS compared 9ith our data#

4:

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