1.2» otope Systematics of band Se > ose Boo 04200 Miions of years (Ma) 0 100 Presint Fig. 1.2, Time-dependent evolution ofthe iserape compesition of Selnsyotowes having diferent Rb/se ratios The diagrant iustrates the increas: of the "SHSr ratios of speciroens of comagimatic fogs that erystllized at 0 milo years | neous magma whose "Set ratio was. 0.700, The ‘ting tnd RhySr ratiosaf these rock specimens can be se termine the coordinates af the peiat of convergence. lathe sim ple ese under consideration, the coordinates ate the "89S of the St in the magmn finitial "/SrSe) and the time elapsed since ‘rymallizstion of the magna Le.the age of the rocks (Based on Ege) trate the time-dependent increase of the "Sr/"Sr ratio of different systems having Rb/Sr ratios of 2.0.1.0, and 0.4, However, Eq, 1.12 should be used whenever accurate results are required 1.2.3 Isotope Fractionation In order to measure the isotope composition of Sx, a small amount of Sr salt extracted from the sample is deposited ona metal filament (Ta. Re, or W) in the source of a mass spectrometer, Afier the source housing has been evacuated, the filament is heated electrically in order to form Sr” fons representing all of the isotopes of Srin the sample, However, the relative abundances of the Sr isotopes in the fon beam are notthe sameas those in the sample because of i evaporation and thermal jonization, Consequeatly, the measured ’Sr/"Sr ratios differ from the true value and commonly vary with time during the measurement which may take several hours. Under these condition the average*’St/"S¢ ratio recorded at the end of the "run! may have been changed by isotope fractionation rela- tive to the true value in the simple Several different procedures and measurem ope fractionation during strat egies have been tried 1o reduce the fractionation during the isotope analysis oF Sr, These have included the de sign of the ion source (single, double, or triple filaments), Re, or W), the the choice of metal for the lament (Ta composition of the Sr salt (chloride, nitrate, phosphate, oxalate), and the use of various additives (phosphoric acid silica gel, Ta-oxide powder); but none of these meas= tures has succeeded in completely eliminating isotope fractionation. Therefore, some analysis have standard ized all of the paramesers that affect fractionation and have adopted a rigorous schedule during the run,thereby hoping to improve the reproducibility of the results, However, the fraction: tion of Sr isotopes in the mass spectrometer may also be affected by the presence of impurities (A, Fe, Mg, Na, and others) that are not re moved with constant efficiency during the chemical separation of Sr from the same rock powder. Conse quently, standardizing the timing of different steps in the operation of the mass spectrometer does not always prodice the same result inthe analysis of replicate analy- ses of the same sample In order to eliminate the effects of both natural and instrumental fractionation of Sr isotopes, Herzog eta (1958) proposed that a correction could be applied to measured "'Sr/*Sr ratios derived from the value of the measured “Sr/'*Sr ratio, The correction is b assumption that all samples of terrestrial and extrater- restrial Sr have the same *Sr/*Sr ratio and that isotope fractionation is proportional to the mass differences be. ‘oxeen the isotopes of an element, The value ofthe ®Sr/*Sr ratio originally reported by Nier (1938) was 0.1194 therefore this value is used as the reference (Steiger and Jiger 1977). Since the mass difference between "Sr and "Sr is only about one half the mass difference between Sr and “Sr, the correction factor (f) is calculated dividin ratio (M) by a number that les half-way between 0.11940 and At Jed on the and Faure (1961) and Faure and Hurley (1963) adopted this method of correcting measured "'Sr/#Sr ratios for the effects of isotope fractionation and demonstrated a significant improvement in the reproducibility of rep- licate determinations of this ratio, The procedure was explained again by Faure and Powell (1972) and has tbeen used by all analysts measuring ® This correction also eliminates the effects of fraction ation of Sr isotopes in natere, although the actual oc currence of Sr-isotope fractionation has never b demonstrated unequivocally (Morse 1983). The fraction- ation correction described above is based on an assumed linear relation hetween fractionation of two isotopes and the difference in their masses. Hart and Zindler (19894) considered an “exponential” (ractianation lav, but the near" Fractionation correction in Eq, 1.7 issill widely used.‘Gusith | + Chemical Properties and \sotope Systematics ———— ee ——— eee 0 EOE EOE wee eee 1.24 Interlaboratory Sr-isotope Standards Although the fractionation correction improves the ee producibility (precision) of measured *'Sr/™S¢ ratios, systematic differences in the isotope ratios obiained in uifferent laboratories persist, In order to reduce these interlaboratory differences. most analysts report their results for certain standard samples that are analyzed repeatedly in the course of a particular investigation, The twointerlaboratory standards used most frequently are a Sr carbonate reagent formerly marketed by the Eimerand Amend Co, (Lot Number 492327)and NBS 987 distributed by the U.S. National Bureau of Standards, Uhe Fimer ane Amend 57 carbonate (ESA) was origi nally analyzed by Aldrich etal (1953) and by Herzog etal. (2953) in the course of a study to measure the isotope composition of Sr from different sources. They chase this Sr compound partly because A. 0. Nier, with whom 1. Aldrich had worked at the University of Minnesota, had originally used metallicSr obtained from Fier and ‘Amend fo measure the isotope composition of Sr (Nier 1938). Subsequent, the same Sr reagent was used in the laboratory of P.M. Hurley at M.LT.to prepare a stand- ard Sr solution for calibration of Sr-spike solutions by isotope dilution (Hergog and Hurley 1955). This solu- tion was analyzed periodically by Faure (1961) in order to determine the reproducibility of measured "S1i"S¢ ratios, and.a summary of the results was later published by Faure and Hurley (1963). The E&A Sr carbonate was distributed informallyin the 1960s to isotope laboratories and has been widely used as an interlaboratory standard by isotope geo- chemists studying the isatope composition of Sr in vol «anic rocks, marine carbonates, water on the continents, and i’ many other projects that rely on measurements of the absolute values of "Se!™Sr ratios, Most well-ad. justed mass spectrometers yield "SrSr ratios close to 0.70800 and this value has been adopted as the refer- nice value. Accordingly,measured "Sif"*Sr ratiosare ade justed tobe compatible withan "Sr/*Sr ratio of 0.70800, for E&A The EKA Sr carbonate continues to be used almost half a century after it was originally adopted. However, because the isotope composition of Sr in this compound has never been properly certified and because the sup- ply is limited. the National Bureau of Standards of the USA undertook to prepare a more appropriate inter- laboratory Sr-isotope standard. The compound was ab- tained by the National Bureau of Standards from Spex Industries, Inc. in Metuchen, New Jersey. According to the Certificate of Analysis issued on November 8, 1971, its "SrlSe ratio is 0.71014 +0.00020 after correcting it for isotope fractionation to "Sr/"*Sr= 0.1194. The cer tificate also reporied a value of 0.70794 for the ’S4/"*Sr ratio of the E&A Sr carbonate. However, more recent measurements indicate that the *'Sr/"Sr ratios of the two standards are + BBA: I 0.70800 S 987i ort035 when both are corrected for isotope fractionation to Sgy/6, = 0.11940. 1.3 The Rb-Sr Method of Dating The decay of Rband growth of Sr expressed by Eqs, 112 and 16 is used todate certain selected igneousand high- stade metamorphic rocks and some of their constitu. ent minerals. The method is based on measurements of the isotope composition of Sr and of the concentrations of Rb and Sr from which the PRO/ ‘ulated (Dodson i970; Birck 1986; Pin etal, 1994; Ludwig 1997)-The value ofthe initial "Se/**Srratio is determined hy analyring two or more specimens of comagmatic ig- hheous rocks or minerals that can be assumed to have the same age. Alternatively: Rb-rich minerals with large “'sr/%S ratios, such as muscovite and biotite, can be dated by assuming a value of the initial Sr!*Sr ratio provided that the numerical value of the date calculated From Eqs, 1.12 and 1.16 is not sensitive to the choice of initial "Sr?™Sr ratios, ‘The validity of age determinations of rocks and minerals by the Rb-Sr method depends on the fallow ing assumptions i ratio can be cal- The rocks or minerals to be dated did not gain or lose Rb or Sr after their original erystallization When a suite of rocks or minerals is dated as a set, each specimen must have had the same initial ”Sr/®°Se rato, Similarly each rock or mineral being dated in a set must have crystallized at the same time. The value of the decay constant (or hatf-tife) of "Rb is known accurately The measured values of the Sr/*S¢ ratios and con- centrations of Rb and Sr are free of systematic ana- lytical errors: ‘The frst three assumptions specify a simple model for the origin and subsequent geologic history of the rocks to be cated. This model is applicable to suites of differentiated igneous rocks (plutonic and volcanic) and to high-grade metamorphic rocks (schists and gneisses) (e.g. Burton and O'Nions 1990), However, conformance to this simple model cannot be taken for granted, but must be verified in each case by appropriate miners: logical and petrographic examination of the specimens to be dated and by using other complementary isotope geochronometers. Consequently, dating of igneous and