1 Fitting of ochrons a1 Vugrinovich (1981) Butler (1982), Rockand Duffy (1986), Ganguly and Ruiz (1986), Rock etal. (1987), Cavazzini (1988), Castorina and Riccardo (1989),Kostitsy (1989), Kalsbeek and Hansen (1989), Haack (i990), Kent etal 4990), Provost (1990), and Wendt (1093), Harmer and Eglington (1990) published a useful review of the statis tical principles used to fit straight lines to data points. Ludwig 1992) developed a program for fitting isochrans ‘on IBM PCs based on the equations of York (1966, 1969), Kullerud (1991) reconsidered the use of analytical er- rors to obiain weighting factors and emphasized the importance of determining these ertors accurately in sets of samples having a wide range of Rb and centrations. Additional shortcomings of the Rb-St isochron method of dating have been pointed out by Schleicher etal, (1983) and Lutz and Srogi (2986). Brooks etal, (1972) examined the different statistical procedures proposed by Mclatyee et al, (1966), York (4900, 1909), Brooks etal. (1968), and by Wendt (1969). Using simulated testeata,they demonstrated thatall four models of Mcintyre etal. (1966) yield identical results in those cases where the observed scatter of the data points can be accounted for solely on the basis of ran- dom analytical errors. in ses, the line detined by the data isa true izockron because the data satisfy the assumptions for dating. In cases where the seatter ex ceeds analytical error, the slope and intercept ofthe best fit ine (errorchron or seatterchron) vary depending on the statistical model that is used, and therefore may not be reliable, The dates and initial "'Sr/™Sr ratios derived from errocchrons may, nevertheless, convey gealogically useful informationsespecially in cases where additional facts or judgments support them, such as the results of dating by other All of the weighted by Brooks et al. (1972) make use of a statistical index to test the goodness of fit of the data points to the best steaight line. The index used by Metntyre et al.(966) is the mean square of weighted deviates (MSWD), The nu- merical value of MSWD for a set of analytical dita can be used to decide whether the scatter of data points is consistent with the magnitudes of the (Wendt and Carl ,g91), If the regression is based! on a very large number of data sets and if the analytical er r duplicates, then a value of unity or less for MSWD signi fies that the line is an isociran. However, when the number of data sets and duplicates is less than in the ideal case the limiting value of MSWD increases, The magnitudes of the limiting values of MSWD for ditter- ent numbers of data sets and duplicates are given in an F distribution tablein Appendix 3 of Brooks et al.(1972) For example, in case a regression is based on sets and five duplicates, the limiting value of MSWD is 51 at the 95% conlidence level. Limiting values of pic methods gression procedures reviewed s have been calculated from a very large nursber of data MSW for different numbers of duplicates and ata sets 19 MSI, 95% confidence Number of amples regressed Fig. 1.4. Limiting vaos of the mean square of wei’ asd duplicates used in the "leasLsquare eubic” regressing of Melmtytect al 1966) ine York (a6) Ihe SW caletated for 1 cata set equal to «(ess than the theoretial value he scatter i points is ennsient with the analytical errars 4 tm lie isan iushirone I the MAID is ges 3 p I vale, the regression line is an errorchra whose sone and intercept may be inaccurate and require confirmation by other evidence amrelated tothe regression (Sourer Hrooks eral. 19 npendix are presented in Fig 14 based on Appendix 9 of Brooks tal. ( The data in Fig. 1.4 indicate that the distinction be tweeen sechvons and errorchrons fora givea number of data sets depends on the number of duplicates used to evaluate analytical errors. For example, MSWD = 6. f ten samples and four duplicates indicates that the re gression line isan isochron, However if the number of duplicates is greater tham 4, MSWD = 8.0 indicates that the line is an errorchron and that geological error is present nother words, as analytic tolerance for scatter decreases and regression lines be come errarchrans or scatterchrons Geological errors may be associated with all of the samples in a set or with only one or two-of the samples. The former case may arise in dating voleanic rocks which ‘may have different initial “Sri"Sr ratios because the ‘magma from which they formed may have assimilated tstal rocks containing varying amounts of radiogenic Sn. only one or two specimens in a suite of samples deviate significantly trom the best-fit line, they can be excluded from the regression. The remaining samph may then yield an isochron irom which a reliable date cam be derived. The geological erro dleviant simples is a clue that they may have been af fected by geological events not reconded in the other samples, Therefore,samples baving geological error de the cause for their ecognized in the serve additional study to determin deviation from the isochron,2 __Cuarten 1 - Chemical Properties and Isotope Systematics 1.5. The Sm-Nd Methed of Dating ‘The sensitivity of Rb-Sr dates to altsration mandates that such rocks sheuld also be dated by the Sm-Nd method because i is less Vulnerable toalteration. Samarium (Sin) and neodymium (Na) ate both rate-earth elements and feccurin rock-torming minerals in low but easily meas terable concentrations (Faure 1980). ‘Samarium (Z = 62) hss seven stable and naturally ce curring isotopes whose abundances are: "Sm = 518s Sm 15,9855 #8 = 1h.29%5 "Sin = 13.8 Sm = 2. Sm = 26.7% 81S = 22.896, Samarinm-147 is radi active and decays by alpha emission ta stable Nd with a hall-life of 1.06.» 10" years (A =6.54 x10" yr"), Neodymium (Z.= 60} also has seven stable isotopes whose abundances ate: '#'Nd = srs “Nd = 12.243, agiots! Nd = 8.3% Nd = 173%!" 5.0%. The abundances of the Nd isotope 1cks and minerals change with time because ofthe for imation of radiogenic "Nd by alpha decay of '"”Sm. ‘The 'ONd/"Nd satios of rockssaind minctals are ve lated to the '"’smy!"'Nd ratios and to time by the equa. on a xd (193 This equation is-analogous to Eq. 1.12 for the Rb-Sr system and is the basis for the Sm-Nd isochron method, of dating, Sets of whole-rack samples having the same age (t) and the same initial "'Ne/"""Né ratio define the Sm-Nd isachron in coordinates of '*'Nd/'*!Nd and 'Sm/!"'N4. The stope (mn) of the isochron is related to the age of the rocks that define the isochron by: mae (0.20) 1 f= ting ty Insome cases, Sn hnole-rock isochron dates are older than the Rb-Sr Isochron dates of the same rock specimens because Sm and Nd tend to be less mobile during thermal or hydrothermal alteration, For this rea son, the Sm-Ni method is preferred for dating metavol canic rocks of Archean and Proterozoic age 1.6 The Epsilon Notation The epsilon notation was introduced by DePaolo and Wasserburg (1976a,b) in order to facilitate the interpre lation of measured '"'Nal'*Nd ratios of basaltic vol: canic rocks derived from magma sources ip the mantle ‘The epsilon parameter (Na) compares the measured '8Nd/""Nd ratio of a rock or mineral sample to the present '"Na/'"Nd ratio of a hypothetical Chondritic Uniform Reservoir called “CHUR’ and is defined by the equation: [UNAH NG 800) =| a [Pina Nake 108 (a0) where ( "na “Nd. J ‘The epsilon value can be recalculated so that it refersto a time in the post. The appropriate value ofthe "Ndi! *Nd ratio of CHUR is obtained from Eg, 1.12 | = 0.591847 oF 01512638 (clepending on the way the isotope fractionation cor rection isapplied) is the present value of this ratio in CHUR (DePaolo 1988), Joa | Na Nd tng (uaa) where 16m = value of this ratio at the present time 1967 (DePaolo 19885 Wasserburg etal1981) Na)! 4) cuux tio at the present time) Epsilon values referred to a time in the past are des ignated by &'(Na) where ris the specified age. The '*!Ndi*Nd ratio of the chondritic uniform ervoir is affected by the way in which the measured iso- Lope ratios of Nd ate corrected for isotope fractiona~ Hon. Most isctope geochemists base the isotope frac tonation correction of measured ''Nd/"*Ned ratios on g for the Nd/"Nd ratio, whereas oth: Na = 0.636151 as the reference ratio, value of 0.7: sonra Wasserburg et al, (1981) demonstrated the relation among the isotope ratios shown in Table 1.6. Both schemes yield identical ”(Nd) values provided that the 'ENG/!"Nd ratios of the rock samples were corrected