CHAPTER 11 The Common-Lead Method kao is widely distributed throughout the Earth and occurs not only as the radiogenic daughter of U and Th but also forms its own minerals from which U and Th are excluded. Therefore, the isotopic composition of Pb in terrestrial rocks and minerals varies between wide limits from the highly radiogenic Pb in old U, ‘Th-bearing minerals (Chapter 10) to the common Pb in galena (PbS) and other minerals that have ow U/Pb and ThiPb ratios. The isotope composition of common Pb in galena is assumed to have evolved by decay of U and Th in reservoirs in the crust and lithospheric mantle of the Earth. The radiogenic isotopes of Pb subsequently mixed with the primeval Pb that was incorporated into these reservoirs at the time the Earth formed. Therefore, the Pb that was later withdrawn from the reservoirs is a mixture of the primeval Pb with varying additions of radiogenic Pb depending on the U/Pb and ‘ThPb ratios of a particular reservoir. This mixed Pb subsequently crystallized as galena during ore-fomming events in the history of the Earth ‘Therefore, the common Pb in galena and other Pb- rich but U,Th-poor minerals records the isotopic composition of its source within which it evolved for an interval of time ending with its removal from the reservoir and its crystallization as galena in the rocks of the continental crust, The common-Pb ‘method of dating, which was proposed by Holmes (1946) and Houtermans (1946), was later presented in books by Rankama (1954, 1963), Russell and 256 Farquhar (1960), Hamilton and Farquhar (1968), and Doe (1970). The isotope geochemistry of Pb in the oceans is discussed in Section 19.4 11.1 THE HOLMES-— HOUTERMANS MODEL The isotopic composition of common Pb in galena and other U,Th-poor minerals (e.., sulfide miner- als of other metals and K-feldspar in which Pb?* replaces K*) was originally determined by Aston (1927). At that time, the atomic weight of com- mon Pb was thought to be constant, which implied that its isotopic composition did not vary. How- ever, Nier (1938) and Nier et al. (1941) reported that, contrary to expectations, common Pb from dif- ferent sources has a range of isotopic compositions. The suggestion of Nier et al. (1941) that common Pb is a mixture of primeval and radiogenic Pb became the basis of a model for the isotopic evolution of common Pb proposed independently by Holmes (1946) and Houtermans (1946). This ‘model is based on certain assumptions 1. Originally the Earth was fluid and homogeneous, 2. At that time U, Th, and Pb were uniformly distributed. 3. The isotopic composition of primeval Pb was everywhere the same 4, Subsequently, the Earth became rigid and small regional differences arose in the U/Pb ratio.5. The U/Pb ratio in any given region changed only as a result of decay of U to Pb. 6. Ata later time, the Pb was separated from U and Th and its isotopic composition remained constant thereafter. LL.la Decay of U to Pb ‘The single-stage Pb evolution model described by these assumptions can be expressed by means of equations arising from the law of radioactivity (Chapter 4). The °Pb/*™*Pb), ratio of Pb that was removed from a U-bearing reservoir years ago and was crystallized as galena is equal to mm) () oe) (CE eee eG:) where @Pb/2™Pb), = value of this ratio of primeval Pb that was incorporated into the reservoir when it formed T years ago @%Pb/™Pb)r = value of this ratio that formed in the same reservoir by decay of 28U starting T' years ‘ago and extending to the present time C%Pb/2%Pb), = value of this ratio that formed in the same reservoir by decay of SAY starting + years ago and extending to the present (f <7). The value of the (*Pb/™Pb)r ratio of the reservoir at the present time can be calculated from the equation aay app (T—1y a12) where ?*U/™Pb is the present value of this ratio in the reservoir and 2 is the decay constant of ™8U The value of (*Pb/*™Pb), is expressed similarly pp) HU , (=e), spp" -D (113) The Holmes—Houtermans Model 257 Therefore, the ™*Pb?™Pb ratio of the Pb that was withdrawn from this reservoir at time 1 is obtained by substituting equations 11.2 and 11.3 {nto equation 11.1 pp (=) which reduces to (2) ( ) Bane 2p), ~ Pb), Pb ana) Similar equations can be written to represent the decay of ?5U to 2”Pb and ?"Th to 2*Pb; es? —e) (2) app Pb/s (11.5) (22) -(@) -Ber-e where 22 is the decay constant of 75U and Ay is the decay constant of 2°Th (Table 10.2). The present ?*UPPb ratio of the reservoir symbolized by the Greek letter |. (mu). Since the present 2U/5U ratio is a constant equal to 137.88 (Steiger and Jager, 1977), + aaapp uP SUPP UP Pb wm 137.88 Hence, By ipp ~ 137.88 ra In addition, *°°Th/**'Pb = w and *°Th/?U Equations 11.4 and 11.5 can be combined: C*P/*Pb), ~ C°PL/™PD) FP>FAPD), — EXPL PD), Let wim (Srae)258 II. The Common-Lead Method This equation can be used to calculate the age T of the Earth using the isotope composition of Pb in a specimen of galena of known age ¢ and the isotope composition of primeval Pb (Gerling, 1942; Moorbath, 1962), 11.1b Decay of Th to Pb ‘The C™*Pb/Pb), in equation 11.6 can be eom- bined with the ?™Pb?™Pb), ratio of equation 11.4 to link the decay of Th in the reservoir to the decay of "*U. The resulting equation is analogous to equation 11.8: Pb/°PD), — C*P/?*PD)p (Pb Pb), — C™P/*Pb)y SMe) ao where As is the decay constant of "Th (Table 10.2). The *? Tb? *U ratio is expressed in terms of wand @ as Th TPP @ Ba SUPP (1.10) The ™°Th?™U ratio in equation 11.9 refers to the present THU ratio of the reservoir in which Pb evolved that was later deposited as galena during the formation of an ore deposit at a known time 1 in the past. 11.1c Analytical Methods ‘The interpretation of the isotope ratios of com- ‘mon Pb by the Holmes-Houtermans model (or by other models) may be confounded by system- atic measurement errors (Catanzaro, 1967), For this reason, the analytical methods have been exten- sively improved in order to eliminate the effects of instrumental isotope fractionation and interlabora- tory discrepancies. The effects of isotope fraction- ation are significantly reduced by the use of double ‘or even triple spikes, which allow the isotope ratios of Pb to be comected fer isotope fractionation (Compston and Oversby, 1969; Dallwitz, 1970; Dodson, 1970; Gale, 1970; Ozard and Russell, 1970; Hofimann, 1971; Russell, 1971, 1975). The propagation of experimental errors in the double- spike methods was explained by Cumming (1973), whereas Richards (1981) wamed against systematic ‘errors of measurement caused by isotope fraction- ation in the mass spectrometer that may generate linear arrays of Pb isotope ratios of replicate anal- yses of the same sample. Such “pseudoisochrons” yield erroneous dates that confuse the geological interpretation of the isotopic data. ‘The subsequent application of Pb isotope geochemistry to the study of volcanic zocks (Chapter 17) has necessitated re-examination of the theory and practice of double spiking: Hamelin et al., 1985, Geochim. Cosmochim. Acta, 49:173~182. Woodhead et al., 1995, Analyst, 120:38-39, Todt et al., 1996, Am. Geophys. Union, Monograph 95:429-437. Woodhead and Hergt, 1997, Chem. Geol, 138:311-321. Galer and Abouchami, 1998, ‘Min, Mag., 62A:491~492. Powell et al., 1998, Chem. Geol, 148:95~104. Galer, 1999, Chem. Geol, 157-255-214. Thirlwall, 2000, Chem. Geol., 163:299-322. Another strategy t0 standardize isotope ratios of Pb is to define isotope standards that can be ana- lyzed by all laboratories where such measurements are made: Kollar et al., 1960, Nature, 187:754-756. Richards, 1962, J. Geophys. Res., 67:869-884, Delevaux, 1963, U.S. Geol. Surv. Prof. Paper, 475:B160-BI61. Catanzaro, 1968, Earth Planet, Sci. Lett, 3:343-346. Catan- zaro et al., 1968, J. Res. Natl. Bur, Stand. (Phys. Chem.), 72A:261~267. Cooper et al., 1969, Earth Planet, Sci, Lett, 6:467-478, Hor et al, 1997, Geostand. Newsletter, 12:191-203, Although isotope dilution has been the preferred method to determine the concentration of Pb in rocks and minerals, ICP-MS is coming into wide use. This technique, combined with laser ablation, can be used to measure the isotope ratios of Pb with g00d precision and accuracyLongerich et al, 1987, Spectrochim. Acta, 42B:39-48, Walder and Furata, 1993, Anal. Sci., 9:675~680. Fryer et al., 1995, Can, Mineral, 33:303~312. Hirata, 1996, Ana lyst, 121:1407-1411, Promits et al., 1998, Chem. Geol,, 144:137-149, Rehkimper and Halliday, 1998, Jat. J. Mass Spectrom lon Proc., 58:123-133. Belshaw et al., 1998, Int. J. Mass Spectrom lon Proc., 181:51~58. White et al., 2000, Chem Geol,, 167:257-270. Poitrasson et al., 2000, Geochim. Cosmochim. Acta, 64:3283-3297. In addition, ion microprobe mass spectrometers have been used to measure isotope ratios of Pb in galena (Cannon etal, 1963; Hart et al, 1981). 111d Primeval Pb in Meteorites Meteorites are fragments of larger parent bodies that formed during the early history of the solar system, evolved rapidly by partial melting and chemical differentiation, and then solidified. Dur- ing this process, an Fe sulfide phase formed, known as troilite (FeS), that contains appreciable concen- trations of Pb but is virtually free of U and Th Therefore, the isotopic composition of Pb in troilite has remained very nearly constant since the time of crystallization of the parent bodies of the mete- orites and of the terrestrial planets that formed at the same time. For these reasons, the isotope ratios of Pb in troilite approach those of primeval Pb that was incorporated into the Earth at the time of its formation, The isotope composition of Pb in stony and iron meteorites varies widely depending on their concentrations of U, Th, and Pb summarized in Table 11.1 (Rogers and Adams, 1969a, b; Wede- pohl, 1974). The average U/Pb ratio of chondritic meteorites is U _ 133 x 107 a 0.012 Pb 110 A compilation of U and Pb concentrations of chondrite meteorites by Tilton (1973) yielded a similar average U/Pb ratio of 0.013. The Holmes-Houtermans Model 259 Table 11.1. Average Concentrations of U, Th, and Pb in Stony and Iron Meteorites U, x10 Th, x10 Pb, Type Pom ppm ppm Stony meteorites Chondrites 1.3321) 455.02) 1.10 (36) £014 £018 boas Achondrtes $9412) 358(16) 0.45 6) $35 £16 £013 Iron meteorites Metal <0.033 (6) 0.0010 (3) 0.136 (19) £0022 0.0005 + 004s Troilite (eS) <0.767 (6) — 5.91.13) + 0.300 + 3.08 Source: Rogers and Adams, 196, b; Wedepobl, 1974 Note: The number of determinations is indicated in parentheses ‘The average U/Pb ratio of rvilites in Table 11.1 is less than 0.0013 and, in some cases, reaches values as low as 0.0005. For example, troilite in the iron meteorite Canyon Diablo, whose impact is recorded by Meteor Crater near Winslow in north- ern Arizona, has U = 0.37 x 10? ppm (Goles and Anders, 1962) and Pb = 6.5 ppm (Wedepohl, 1974) giving it a low U/Pb ratio of 0.00057. ‘There- fore, twoilite of Canyon Diablo was chosen to determine the isotope composition of primeval Pb. The results reported by Tatsumoto et al. (1973) in Table 11.2 were later confirmed by Chen and Wasserburg (1983). These results are also in good agreement with the isotope composition of Pb in the Pb-rich chondrite Mezi-Madaras (Pb = 5.27 ppm, U = 0.0113 ppm, U/Pb = 0.002) ana- lyzed by Tilton (1973). Il.le The Age of Meteorites and the Earth The >Pb/™PD and *"PL/™PD ratios of stony meteorites have increased with time from their primeval values at rates that depend on the U/Pb ratios of the analyzed specimens in accordance with equation 11.8. When this equation is applied. to meteorites, 1= 0 because the decay of U has continued to the present time. Therefore260 11. The Common-Lead Method ‘Table 11.2. Isotope Ratios of Primeval Pb in Troilite of the Iron Meteorite Canyon Diablo and in the Pb-Rich Chondrite Mezi-Madaras Sample 26D 27pHP>*PH 28pH2%Pb References Canyon Diablo Troilite 9.307 10.294 29.476 Tatsumoto et al, 1973 9.3066 10293 29.475 Chen and Wasserburg, 1983 Mezi-Madaras Chondtrite 9.310 10.296 29.57" Tilton, 1973 “Estimated by assuming that 22Th/28U = 3.8 equation 11.8 reduces to Py oe ee Pb) — CPb/*Pb)» wal I (Pb /™Pb), = _ ot (erty ay BE ok a | ~ 3738 (ery ae Po wh ten ae where the subscripts m and p identify the iso- fe aereneee tope ratios of meteoritic and primeval Pb, respec- Qo tively, and T is the age of meteorites and hence the age of the Earth. The isotope ratios of Pb of all meteorites that have remained closed to U and Pb since their formation at time T and that originally contained only primeval Pb satisfy equation 11.11 and therefore plot on a straight line in coordinates of ?™Pb/**Pb (x) and "PPP (y). This line is @ Pb-Pb isochron whose slope m is net (1) * 737.88 VT AT This equation can be solved for T by interpolating in Table 10.3 in Chapter 10. Patterson (1956) used the isotope compositions of Pb in three stony and two iron meteorites to efine the Pb-Pb isochron in Figure 11.1 whose slope yielded a date of 4.55 + 0.07 Ga. The data array includes Pb in a sample of terrestrial marine sediment that fits the Pb-Pb meteorite isochron and thereby supports the theory that the Earth formed at the same time as the meteorites and that it originally contained primeval Pb. an.i2) 8pb/7™4Pb rnoune 111 Lead isochron for meteorites and modem ocean sediment. The slope of this isochron (Equation 11.12) indicates an age of T = 4,55 £0.07 x 10° y for meteorites, based on the decay constants used by Patterson (1956). Many other meteorites and their constituent minerals have been analyzed since Patterson's pioneering work: Huey and Kohman, 1973, J. Geophys Res., 78:3227~3244, Tatsumoto et al., 1976, Geochim. Cosmochim. Acta, 40:617-634. Chen and Tilton, 1976, Geochim. Cos- mochim. Acta, 40:635~643, Manhés and Allegre, 1978, Meteoritics, 13:543~S48, Gale, 1979, Geochim. J, 13:191. Gale et al. 1980, Earth Planet. Sci. Lett, 48:31 Unruh et al., 1977, Barth Planet. Sci, Lett, 37:1-12. Unruh et al., 1979, Proc. 10th LunarPlanet. Conf., Geochim. Cosmochim, Acta, ‘Suppl: 1011-1030. A reconsideration by Allegre et al. (1995) of the age of meteorites based on Pb-Pb systematics yielded the following results Refractory inclusions, 4568-4565 Ga Allende Phosphate, equilibrated 4.563-4.504 Ga chondrites Basaltic achondrites, 4.558-4.53 Ga ‘These results indicate that the parent bodies of stony meteorites crystallized and cooled during a period of about 64 million years between 4.50 and 4.57 Ga. Therefore, the re-examination of the data by Allegre et al. (1995) confirmed the date of 4.55 £0.07 Ga originally reported bby Patterson (1956) based on different decay con- stants than those recommended later by Steiger and Jager (1977), ‘The isotope analyses of Pb in meteorites also indicate that the U-Pb systematics of some mete- orites were disturbed after their initial crystal lization. For example, Hanan and Tilton (1985) reported a Pb-Pb date of 4.480 + 0.011 Ga for sep- arated phases and a whole-rock sample of Mezo- Madaras and a similar date of 4.472 + 0.005 Ga for the meteorite Sharps. The U-Pb data of both meteorites form discordia chords on the con- cordia diagram indicating that their U/Pb ratios were recently disturbed. Hanan and Tilton (1985) and Minster and Allégre (1979) reported that the Rb-Sr systematics of Sharps and Mez6-Madaras, were also disturbed. 11.2 DATING COMMON LEAD In the Holmes-Houtermans model, the Pb in galena and other Pb-rich but U.Th-poor minerals is assumed to be a mixture of primeval Pb with varying amounts of radiogenic Pb that formed by decay of ™°U, 5U, and *Th in the continental crust and lithospheric mantle. The Pb was separated from U and Th at some time () in the past and was deposited as galena (or some other Pb-rich and U-poor mineral), thereby preserving its isotopic Dating Common Lead 261 composition. The isotope ratios of Pb generated by this single-stage process are expressed by equations 11.4~11.6 and depend on the time of separation (f), the age of the Earth (7), and the U/Pb and ThiPb ratios of the reservoirs from which the Pb was extracted. 11.2a The Geochron ‘The time-dependent evolution of the p/P and ?”"Pb-™Pb ratios in reservoirs having different 28UP™Pb ratios (1) is illustrated in Figure 11.2 based on equations 11.4 and 11.5. In addition, the isotope composition of primeval Pb was assumed to be *Pb/2™Pb = 9,307.2" Pb/2*Pb = 10.294, and 2"*Pb/2™Pp = 29.476 (Tatsumoto et al., 1973), ‘and the age of the Earth (7) was taken to be 4.55 Ga (Patterson, 1956). The isotopic evolution lines of galena Pb of the Holmes-Houtermans model in Figure 11.2 form a set of curved trajectories that fan out from the point representing primeval Pb depending fon the jc-values of the reservoirs. Experience hhas shown that most samples of common Pb evolved in U-Pb systems having j.-values between 8 and 10. For example, point P in Figure 11.2 represents a sample of common Pb that evolved in a reservoir whose present j.-value is 10 and whose single-stage model date is 3.0 Ga. Therefore, the age of the mineral in which this sample of common Pb resides at the present time is 3.0 Ga or less In addition, Figure 11.2 contains a set of straight-line isochrons that are defined by the iso- tope ratios of single-stage leads that were separated at the specified dates from U-Pb reservoirs hav- ing different values of 1. One of these isochrons is called the geockrox because it is the locus of Pb samples that have reservoir-separation dates of 1 = 0 years. The Pb samples on the geochron have resided in their respective reservoirs for 4.55 x 10° years or were removed from these reservoirs only recently. The stony meteorites in Figure 11.1 lie oon the geochron because the Pb they contain is assumed to have evolved by the uninterrupted decay of U and Th in closed systems for 4.55 x 10” years. The slope of the geochron is calculated from262 II, The Common-Lead Method * 7p 4b pp ae Primeval teed Evolution of Single-Stage sah Lead 4 7 L 1 L L L 4 . 16 7 1 16 8 E a 2°5Pb/ 24 Ph Figure 112 Graphical representation of the Holmes—Houtermans model. The curved lines are Pb growth curves for U: Pb systems having present-day j.-values of 8, 9, and. 10. The straight lines are isochrons for selected values of #. For example, the coordinates of point P are the *”Pb/**Pb and Pby2”*Pb ratios of a galena Pb that was withdrawn 3.0 x 10° years ago from a source region whose present “*UP™Pb ratio (1) is 10.0. This diagram was constructed by solving equations 11.4 and 11.5 assuming that the age of the Earth is T = 55 x 10° y. equation 11.11: where 2) = 1.58125 x 1019 y-! 10° y"1, and T = 4.55 x 10° y 11.26 Dating Single-Stage Leads The reservoir-separation date of a sample of common Pb that satisties the Holmes-Houtermans ‘model can be calculated from its measured isotope ratios by means of equation 11.8. The procedure is to calculate the slope of the Pb-Pb isochron by means of the **Pb™Pb and 2"PBy2Pb ratios of the specimen of common Pb and of the primeval Pb (Table 11.2): Pb), — 2 Pb/*PD) 2 La3) Pb), = CPP), UP) The result is then used to calculate the reservoir separation date (1) from the equation OTe are) where T = 4.55 x 10° y. Equation 11.14 can be solved by interpolation in Table 17.3 or by numeri- cal iteration to any desired level of precision. After 1 has been determined in this way, the present 1 aa ( ais)Table 11.3. Slopes of Isochrons (m) and Corresponding Model Dates (¢) of Single-Stage Pb Based on Equation 11.14 Age. Age (, Ga Slope (m) | Ga__Slope (my 0 0.61761 24 0.98101 02 0.63705, 26 1.03410 o4 0.65509 28 1.09295 06 0.67624 3.0 1.15830 08 0.69923, 32 1.23100 10 072426 34 131205 12 0.75158 36 1.40257 14 078146 38 1.50387 16 os1415 40 1.61743 18 0.85005 42 1.74498 20 0.88952 44 1.88849 22 0.93300 46 2.05025 Note: hy = 1.59125 x 10° 9.8885 x 10- YT = 485% 10" y value of 1 of the U-Pb reservoir is calculated from equation 11.4: 206pp (Se ) ewer ae Pb/2™Pb), 206pp, 2*PD)y ais) The geological significance of the resulting values of t and jx depends on the extent to hich the single-stage model reproduces the actual geological history of the samples of common Pb that was analyzed, Experience has shown that ‘only a small number of ore deposits contain Pb that satisfies the assumptions of the single- stage model and are therefore referred to as “ordinary” leads. Ore deposits that contain single-stage Pb can be identified by the following criteria 1, All samples of common Pb in a particular ore deposit yield the same model date within analytical errors unless there is evidence for episodic mineralization spanning an interval of time Dating Common Lead 263 2. The model dates have positive numerical values. 3. The single-stage Pb dates are in general agreement with isotopic dates of other minerals in the ore and in the surrounding country rock. However, exact agreement with dates determined bby other methods is not expected because the ‘model Pb dates of galena refer to a different event than the isotopic dates of associated silicate minerals, 11.2c Lead from Cobalt, Ontario ‘The isotope ratios of Pb in the ore deposits of the Cobalt-Noranda area of Ontario and Quebec (Kanasewich and Farquhar, 1965) were included by Doe and Stacey (1974) in a list of 13 ore deposits that appear to fit the Holmes Houtermans model. The ore deposits at Cobalt are hydrothermal veins that occur in the Early Pro- terozoic rocks of the Cobalt Group, which con- sists of conglomerate, tillite, graywacke, arkose, and sandstones (Thorpe, 1974), These metasedi- mentary rocks are unconformably underlain by intensely folded metavotcanic rocks of Archean age and by granitic batholiths that intrude the metavolcanics. The rocks of the Cobalt Group were themselves intruded by sills of the Nipissing Diabase to which the mineralization of the veins in the Cobalt area is genetically related (Hriske- vich, 1968), ‘The Nipissing Diabase was dated by the whole-rock Rb-Sr isochron method, which yielded a date of 2109 + 80 Ma (Van Schmus, 1965). In addition, Fairbaim et al. (1969) obtained a date of 2240 + 87 Ma for graywacke and argillite of the Cobalt Group by the same method. ‘The average isotope ratios of Pb in galena in the ore at Cobalt are (Doe and Stacey, 1974; Stacey and Kramers, 1975) 2p Py supp = 1487 supp = 15.16 20pp = 3444 Pb The slope of the Pb-Pb isochron in coor- dinates of ™Pb2*Pb and ~”Pb?™PD ratios264 II. The Common-Lead Method (equation 11.13) is 15.16 — 10.294 m= ey sospT = 087470 ‘The reservoir separation date ¢ obtained from the slope of the Pb-Pb isochron by interpolation in Table 11.3 is 0.2 « 0.02465 1a 18+ = 192 Ga The value of is then calculated from equation 11.15: 14,87 — 9.307 Moss = 1349 ‘The single-stage Pb-Pb date of the ore at Cobalt, Ontario, is Tower than the geological age of the Cobalt Series, which ranges ffom 2240 87 to 2109 + 80 Ma. The discrepancy is a signal that the Pb inthe ore at Cobalt, Ontario, des not quite satisfy the assumptions of the single-stage model. However, the 4. value of the source region from which the Pb was derived (y= 8.2) is well within the range of values of this ratio in other mineral deposits that contain common Pb. A date based on the two-stage model of Pb evolution is calculated in Section 11.2f. 11.2d Limitations of the Single-Stage Model Only a small number of ore deposits contain Pb that actually satisfies the single-stage model. Doe and Stacey (1974) listed 13 such deposits whose ages range from 3.2 Ga (Barberton, South Africa) 10.0 Ga (White Island, New Zealand). However, the single-stage model dates of these selected deposits in Figure 11.3 are up to 400 million years younger than dates determined by other methods, which means that ore deposits of Phanerozoic age, in some cases, yield negative Pb-Pb model dates. ry Primeval Pb e 10 2 Single-Stage Ore Leads 14 16 is 2 OR pp / py FIGURE 13, Isotopic evolution of common leads that meet the assumptions of the single-stage Holmes—Houtermans model for z = 8.1, T = 4.55 x 10? y, based on equations 11.4 and 11.5, The ore deposits are identified by number: 1. Barberton, South Africa; 2. Manitouwadge, Ontario; 3. Geneva Lake, Ontario; 4. Cobalt, Ontario; 5. Broken Hill, N.S.W., Australia; 6, Mount Isa, Queensland, Australia; 7. Balmat, New York; 8. Captain's Flat, N.S.W., Australia; 9, Hall's Peak, N.S.W., Australia; 10. White Island, New Zealand. Data from Doe and Stacey (1974) and Tatsumoto et al. (1973).To avoid this problem, Doe and Stacey (1974) reduced the value of T in equation 11.14 from 4.55 to 443Ga_ and tabulated the slopes of single-stage Pb-Pb isochrons based on this mod ification, However, the necessity for making this ad hoc alteration diminishes the validity of the Hotmes—Houtermans model. Another noteworthy feature of the ore deposits selected by Doe and Stacey (1974) is that their p-values vary only within narrow limits and have a mean of 8,100.24 for 10 deposits. This value was used to construct the Pb growth curve in Figure 11.3. The measured ™Pb/™Pb and 2” pb/™Pb ratios of all 13 deposits follow the growth curve closely, but only 10 are shown to avoid crowding the diagram. The points represent- ing Pb from Captain’s Flat (8), Hall's Peak (9), and White Island (10) lie to the right of the geochron in a part of the diagram representing the future. ‘These and other deposits (not shown) yield nega~ tive single-stage model Pb dates that invalidate the Holmes-Houtermans model The evidence that all of the deposits in Figure 11.3 have similar .-values indicates that the reservoirs from which they originated had similar U/Pb ratios even though the ore deposits formed on different continents during a time interval of about 3 billion years. This evidence therefore supports, the view that the reservoirs of common Pb on the Earth are homogeneous with respect to their U/Pb ratios. Alternatively, the evidence implies extensive isotopic homogenization of Pb during its removal from reservoirs that may have had a wide range of UP ratios, Stanton and Russell (1959) originally recog- nized that ore deposits containing apparent single- stage Pb occur in stratigraphic sequences of vol- canic and marine sedimentary rocks that were deposited in volcanic island ares. The ore deposits in these kinds of rocks are conformable with the structure of their host rocks and were emplaced as a result of voleanic activity without contamination by radiogenic Pb from the crust. Armstrong (1968) proposed that these single-stage leads originated from marine sediment of crustal origin, that the Pb ‘was removed from its source during subduction of the sediment and was deposited syngenetically by precipitation of galena and other sulfides from hot aqueous solutions on the sea floor along spreading Dating Common Lead 265 ridges, in subduction zones, and/or back-arc basins. ‘According to this scenario, single-stage leads were homogenized isotopically during removal from het- ‘erogenous sources. ‘The identification of single-stage leads and the fitting of their isotopic evolution line has been the subject of several papers: Ostie et al., 1967, Can. J. Earth Sci., 4:245— 269. Kanasewich, 1968, in Hamilton and Far- quhar (Eds.), Radiometric dating for Geolo- gists, pp. 147-223. Wiley, New York. Sinha and Tilton, 1973, Geochim. Cosmochim. Acta, 37:1823—-1849. Cumming and Richards, 1975, Earth Planet, Sci. Lett, 28:155~171. Allbaréde and Juteau, 1984, Geochim. Cosmochim. Acta, 48:207-212. The consensus is that single-stage leads could not have evolved continuously since the Earth formed at 4,55 Ga as postulated in the Holmes-Houtermans model. In addition, experience has shown that most samples of common Pb do not have single stage histories and are therefore classified as, being anomalous. 11.2e The Stacey—Kramers Model ‘The discrepancies between single-stage Pb dates of ‘many ore deposits and their geological ages require a refinement of the Holmes—Houtermans model for the isotopic evolution of common Pb (Richards, 1971; Oversby, 1974). The fact that the single- stage Pb dates of many ore deposits of late Precambrian and Phanerozoic age are younger than their geological ages suggests that the U/Pb ratios, of the Pb reservoirs in the Earth have increased either continuously or episodically with time. The reduction of the parameter T from 4.55 to 4.43, billion years proposed by Doe and Stacey (1974) is not a good solution to the problem because it violates the assumption that meteorites and the Earth have the same age (ie., 4.55 x 10° years) ‘The refinement of the Holmes—Houtermans model proposed by Stacey and Kramers (1975) is that Pb in ore deposits formed by a two-stage process. The resulting Pb isotope ratios in Table 11.4 were used to plot Figure 11.4. The first266 11. The Common-Lead Method Table 11.4, Isotopic Evolution of Pb in the ‘Two-Stage Model of Stacey and Kramers (1975) with the Decay Constants Later Adopted by Steiger and Jager (1977) 1Ga “PBF pp = PHAMpH PHAM, First Stage 457 9.307 10,294 29.487 4.30 9.906 11,391 30.036 400 10.544 12313, 30.637 3.70 11152 12.998 31.230 Second Stage 370 11.152 12.998 31.230 3.50 11,680 13.481 31.666 32512317 13.965 32.204 3.00 12.931 14.343 32.736 215 13,520 14.639 33.261 2.50 14.088 14.870 33.780 2.25 14.634 15.051 34.293 2.00 15.159 15.192 34.799 175 15.664 15,303 35.299 1.50 16.149 15,389 35.793 125 16.617 13.457 36.280 100 17.066 15.509 36.762 0.75 17.499 15.551 37.238 050 17.915 15,583 37.708 0.25 18315, 15,608 38.172 0.00 18.700 15.628 38.630 stage started at T = 4.57 x 10” y with primeval Pb in a reservoir having 4 = 7.192 and w = 32.208. ‘This stage ended at 7’ = 3.70 x 10° y when increased from 7.192 to 9.735 and w rose from 32.208 to 36.837. The isotope ratios of commen Pb at T’ = 3.70 x 10? y were During the second stage, the isotope ratios of Pb in the reservoir shown in Figure 11.4 increased by decay of U and Th from 1” = 3.70 x 10? y to the present time. The present isotope ratios of Pb in the ‘Stacey~Kramers model are (ER) ( Pb (sR). = 38.630 All common leads that evolved in this reservoir and were removed from it at some time ¢ in the past have isotope ratios that define a point on the growth curve in Figure 11.4. The reservoir-separation date of a sampie of common Pb that evolved by the two-stage process of the Stacey-Kramers model is derivable from the equation that describes the second stage: 2p) 7 a) _7 15608 Sipp aa a6) ap ‘3 “ . (1.17) and hence for the U-Pb decay CPP), 12.998 1 (et = @SPb/* Pb), — 11.152 137.88 eT = eb 118) where the subscript ¢ identifies the isotope ratios of Pb in galena. The Th-Pb system is defined by a similar equation: G)(===) «a1.i9) where 23 is the decay constant of 2TH (is 4.9475 x 107"! y~!), ‘The two-stage model of Stacey and Kramers (1975) is used to date ordinary Pb by means of equation 11.18, This equation is more flexible than equations 11.16 and 11.17 because it does not require that the second-stage reservoir of the Pb samples being dated had the j1-value (9.735) specified by the model. The slopes of the secondary Pb-Pb isochrons are used to solve equation 11.18 for ¢ by interpolating in Table 11.5 After 1 has been determined, the «o/s ratio of the @*Pb/?™Pb), — 31.230 @Pb/>"Pb), — 11152p/p Dating Common Lead 267 ‘Two-Stage Evolution, ‘Stacey-Kramers Model =po/*ry riovar 114 Two-stage Pb model of Stacey and Kramers (1975) summarized in Table 11.4. In this model, Pb evolves from primeval isotope ratios between 4.57 and 3.70 Ga in a reservoir with 2*UP™Pb = 7.192. At point Q (¢ = 3.70 Ga) on the evolution line, the ?“U/°™Pb ratio of the reservoir changed by geochemical differentiation to 9.735. Lead evolution then continued undisturbed to point P. representing average crustal Pb, Straight lines connecting any point on the evolution line between 3.70 Ga and the present to Q are isochrons. The slopes of such isochrons are related by equation 11.18 to the time elapsed since a Pb sample was isolated from the reservoir. Plotted from data in Table 9 of Stacey and Kramers (1975), second reservoir is obtained from equation 11.19. The value of this ratio should be close to 3.78, as required by the Stacey—Kramers model (ie., eo] 4 = 36.837/9.135 = 3.78), ‘Table 11.5. Slopes of Isochrons (m) and Corresponding Model Dates (£) of the ‘Two-Stage Model of Stacey and Kramers (1975) Age (Ga Slope (m) ‘Age (1), Ga_ Slope (m) 0 0.34840 18 0.51781 02 0.36103, 20 0.54764 04 0.37482 22 0.58079 06 0.38991 24 0.61769 08 0.40645 26 0.65884 10 0.42460 28 0.70482, 12 0.44457 3.0 0.75630 14 0.46659 0.81404 16 0.49090 34 0.878: 11.2f Balmat, St Lawrence County, New York The Pb-Zn ore deposit at Balmat, New York, is composed of sulfide minerals hosted by Late Proterozoic (Grenville) marble whose age is about 1060 Ma (Doe, 1962a, b). The isotope ratios of Pb in this deposit approach the single-stage growth curve in Figure 11.3 (Doe and Stacey, 1974). The single-stage Pb-Pb isochron has a slope m = 0.68314, which yields a date of 0.66 Ga by interpolation in Table 11.2. This date significantly underestimates the age of the sulfide ore at Belmat ‘According to Doe and Stacey (1974), the isotope composition of Pb in the ore of Balmat is 20 Sapp = 15.505 16935 SpE 36.423268 11. The Common-Lead Method ‘The slope of the isochron relative to point Q in Figure 11.4 is 15.505 — 12.998 16.935 = 11.152 0.43351 Interpolating in Table 11.5 yields 0.2 x 0.00891 11.04 SX OORPE = 1.098 Ga The date derived from the Stacey~Kramers model differs only by about 30 million years from the age of the Balmat ore as determined by other isotopic methods. The Stacey-Kramers model also improves the concordance of the date derivable from the galena at Cobalt, Ontario (Section 11.2c). The slope of its Pb-Pb isochron relative to point Q in Figure 11.4 is, _ 15.16 — 12.998 © 7487-11152 m 0.58149 Interpolation in Table 11.5 yields 0.2 x 0,0007 0.0369 = 2.204 Ga This date exceeds the single-stage date (1 1.92 Ga) by about 280 million years. Although the two-stage model of Stacey and Kramers (1975) yields more accurate dates than the single-stage model, it is only applicable to a limited number of ore deposits. It does not ‘work for anomalous leads that formed by mixing of two-stage Pb with radiogenic Pb derived from granitic basement rocks prior to the deposition of galena, 11.3 DATING K-FELDSPAR Microctine or orthocase erytals in high-grade metamorphic and igneous rocks capture Pb** in place of Kons because ofthe similarity of thet radii Pb = 120 A: K* = 1.35 A), which gives Pb?* a charge-to-radius ratio of 1.67 compared to only 0.74 for K*. Consequently. Kefeldspars in Table 11.6 have elevated concenttations of Pb but Table 11.6. Concentrations of Pb, U, and Th in K-Feldspar (Concentration (pm) Source Pb vu References Ganies and B16) 00535) v mencs = F134 £0005, Pegmaties 20612) <0. = La £115 Marine 52016) 01216) O31) 2 sediment, E31. 00M 006, etal Veleanic pM - = 3 rocks £40 Piuonic 5121) 0G) O30) 3 rocks 9s Meumoric MIC 3 rocks m Miner, 52805-816. § Tow concentrations of U_and Th. As a result, the isotopic composition of Pb in feldspar is virtually invariant with time. However, since feldspars are sink for ambient Pb during metamorphism, the isotope composition of Pb in K-feldspar may be altered in some cases by the addition of varying amounts of radiogenic Pb. The isotopic composition of Pb in micro- cline of Precambrian pegmatites was determined by Catanzaro and Gast (1960), who also referenced the work of their predecessors. They reported that single-stage model dates calculated from the iso- tope ratios of Pb in feldspar are in good agreement with dates determined by other methods. However, 4 white microcline from a pegmatite (2600 Ma) ‘on the southem slope of the Bridger Mountains and about 20 km north of Bonneville, Wyoming, yielded an anomalously low date of 1350 Ma. After leaching the microctine with 50 percent HNOs for 15 min, the single-stage model date increased to 2550+ 100 Ma, which is indistinguishable from the “accepted” age of this pegmatite, The authors suggested that the feldspar of the Bonneville peg- matite had been contaminated after crystallization by the addition of ambient crustal Pb. Contamina tion of feldspar with crustal Pb was also detected by Doe et a. (1965), who reported that the isotopecomposition of Pb in the feldspar of Precambrian ‘gneisses near Baltimore, Maryland, was altered during Paleozoic regional metamorphism. Sinha and Tilton (1973) developed an open- system model for Pb evolution in which 4 increased linearly with time. However, to achieve agreement with dates based on other isotopic methods, the authors were forced to increase the value of T from 4.55 x 10° to 4.66 x 10° years. Neverthe- Jess, Sinha and Tilton (1973) compiled an inter- esting set of isotopic ratios of Pb in galena and feldspar from several regions after normalizing the isotope ratios of Pb to the same interlabora- tory standard. The galena samples from the Superior struc tural province of Canada in Table 11.7 yielded an average model date of 2951 +: 30 Ma, whereas five samples of K-feldspar from the same region aver- aged 2877 +75 Ma. However, age determinations by the K-Ar, Rb-Sr, and U-Pb methods reviewed by Sinha and Tilton (1973) indicate that magmatic activity and regional metamorphism in the Supe- rior Province occurred at about 2750+ 50 Ma Therefore, the model Pb dates of the galenas Dating K-Feldspar 269 ‘and K-feldspar are between 200 and 125 million years older, respectively, than the conventional isotopic dates. ‘The isotopic compositions of Pb in the Superior suctural province of Canada compiled by Sinha and Tilton (1973) were also evalu- ated by the two-stage Stacey-Kramers model in Table 11.7. The resulting average dates of the galenas (2796 + 39 Ma) and feldspars (2702+ 1€M Ma) are consistently lower than those cal- culated by Sinha and Tilton (1973) and are in better agreement with the age of igneous activity and regional metamorphism at 2750 50 Ma. ‘The feldspars in the pegmatites of the Bal- timore area analyzed by Doe et al. (1965) and included in the compilation of data by Sinha and Tilton (1973) yield a single-stage date of =220 Ma. The two-stage model date of this feldspar based on the Stacey-Kramers model (Table 11.5) is 414 Ma, which agrees with the date of 425 Ma reported by Wetherill et al. (1966) for the post-Glenarm pegmatites of the Maryland Piedmont ‘Table 11.7. Isotope Ratios of Pb and Corresponding Two-Stage Model Dates (Stacey and Kramers, 1975) of Galena and Feldspars from the Superior Structural Province of Canada (Sinha and Tilton, 1973) Locality or Model I Model It Number PPMP 2” PHP Slope* Date, Ma Date, Ma Galena Willroy Mine 1330 14.54 0.71787 2850 2980 Geco Mine 13.30 1451 0.70391 2796 2975 13.407 14.576 0.69977 278 2925 Lun Echo 13.404 14.565 0.69582 2760 2925 Average date of galenas 2796 + 39 2951 £30 Feldspar MG-19 13.69 14.65 0.65090 2561 2770 MG-1 1345, 1451 0.65796 2595 2850 MG-45 Bai 1463 0.72276 2869 2975 RNIT 13.28 13.53, 0.71992 2858 2950 KA-82 1347 146.54 0.66522 2627 2840 Average date of feldspars: 2702416 2877 £75 ‘Note: Model I: Stacey and Kramers (1975). Model I: Sinha and Tilton (1973), “Relative to point Q in Figure 11.4 whose coordinates are: "*Pb/*™Pb = 11.152; ™"Pb/2™Po = 12.998; *Pb/*™Pb = 31.230.270 ‘IL, The Common-Lead Method 11.4 ANOMALOUS LEADS IN GALENA Many ore deposits contain Pb whose isotopic com- position is anomalous because it is not consistent with the single- and two-stage models of Pb evo- lution (Farquhar and Russell, 1957; Stanton and Russell, 1959). These deposits may have negative ‘model Pb dates that represent the future rather than the past because they contain excess amounts of radiogenic Pb. Russell and Farquhar (1960) and Kanasewich (1968) devised mathematical procedures by means of which additional information can be extracted from suites of anomalous leads (Doe, 1970). These procedures take advantage of the fact that the isotope ratios of anomalous leads in a particular ore body or mining district, in many cases, form straight lines in coordinates of the **Pb?™P» 16] 15] 14] 13] 10 12 ¥4 (x) and >°"Pb/PD (y) ratios. These so-called anomalous Pb lines are attributable to mixing of ‘two-stage Pb with varying amounts of radiogenic Pb. This interpretation yields useful information about the history and origin of suites of anomalous, Pb derived from 1. the coordinates of the point of intersection of the anomalous Pb line and the growth curve of the Stacey-Kramers model and 2. the slope of the anomalous Pb line based either on the “instantaneous” or the “continuous decay of the U isotopes. 11.4a_ Two-Stage Model Dates A hypothetical example of anomalous leads in Figure 11.5 illustrates the effect of mixing of Hypothetical Example of 1 ‘Anamoslous Leads Aromas | fendine ot 16 78 20 pp / Pb Hypothetical examples of anomalous Pb (solid circles) that formed by the addition of varying amounts of radiogenic Pb to common Pb at point P on the second stage of the Stacey Kramers growth curve. The slope of the anomalous Pb line is R = 0.160. The growth curve was plotted from a tabulation by Stacey and Kramers (1975),two-stage Pb with a component of radiogenic Pb ‘The resulting anomalous leads define a straight line of slope R that intersects the Pb growth curve of the Stacey~Kramers model at point P. ‘The two-stage model date of the Pb represented by P is calculated from the slope of the Pb-Pb isochron relative to point Q on the Stacey-Kramers ‘growth curve in Figure 11.4, In this example, the coordinates of point P are “°Pb/*™Pb = 15.879 and *""Pb/*Pb = 15.335. Therefore, the slope m of the line PQ and the comesponding two-stage model date ¢ from Table 11.5 are 15,335 — 12.998 15.879 — 11.152 0.2(0.49439 — 0.49090) 0.51781 — 0.49090 0.49439 1.63 Ga This date is the time in the past when the Pb was withdrawn from the second Stacey-Kramers reservoir and was thereby separated from U and Th. Subsequently, this Pb was mixed with radiogenic Pb and the resulting mixtures were then deposited in the form of galena. 11.4b Instantaneous Growth of Radiogenic Pb The slope of the anomalous Pb line is the 207pp/2%Pb ratio of the radiogenic Pb that was added to the Pb, represented by point Pin Figure 11.5. The time in the past when radiogenic Pb was formed having the *""Pb/?°Pb ratio equal to the slope R of the anomalous Pb line is 5U Ar R= soa, (11.20) where 7U, and “SU, are the abundances of the U isotopes at any time ¢ in the past. The past abundances of the U isotopes are related to their present abundances (°U, and 7U,) by the law of radioactivity and hence for both U and 5U Bey, = ™U,e 8, = By, eh Anomalous Leads in Galena 271 Substitution into equation 11.20 yields do) Upe" [in eA w= (52) suse = (2) Saree 09 Solving for ¢ yields 1 oa ( 22880 2—M (11.22) In the case under consideration, the slope of the anomalous Pb line is 199 *= (aR) = Acconingly. the instant in i in the as when he decay of **U and *U produced radiogenic Pb and *"Pb having the ™”"Pb/"*Pb ratio of 0.160 is, calculated from equation 11.22: 160 In 3.47482 = 150 Ga 520735 x 10-9 Evidently, the radiogenic Pb originated from rocks oor minerals of Precambrian age that predate the origin of the ore deposit. 11.4c Continuous Growth of Radiogenic Pb The radiogenic Pb could also have accumulated during an extended interval of time. In this case, the isotopic evolution of the radiogenic Pb is expressed by an equation of the form see (“2) =! ere (aay) = ara 1 = present age of the basement rocks in which the radiogenic Pb evolved 1 = time in the past when the radiogenic Pb was removed from the basement rocks Gest =272 ‘11. The Common-Lead Method Equation 11.23 can be solved for 1 based on the measured slope R of the anomalous Pb line provided that the age of the basement rocks (t,) is known. If t, = 2.0 x 10? y, interpolation in a table (not shown) of selected values of 1 indicates that R= 0.160 corresponds to t = 0.883 Ga. Therefore, the radiogenic Pb component could have accumulated in Precambrian basement rocks between f, = 2.0 and t = 0.88 Ga during an interval of about 1.12 billion years Alternatively, if the age 1 of the ore deposit is known from dating by other methods, equation 11.23 can be solved for f,, which is an overestimate of the present age of the basement rocks in which the radiogenic component of Pb accumulated. These interpretations have provided the fol- lowing information about the hypothetical ore deposits in which the anomalous Pb occurs: 1. The two-stage Pb originated from the second stage of the Stacey—Kramers model (se = 9.735) at 1.63 Ga. The Pb was subsequently contaminated with radiogenic Pb that was produced by decay of U isotopes at 1.50 Ga (instantaneous model) 3. Altematively. the radiogenic contaminant could have accumulated between t, = 2.0 Ga and 1 = 0.88 Ga (continuous model) in the basement rocks underlying the ore deposit 4, The age of the ore deposit in question is probably less than 0.88 Ga, as indicated by the instantaneous model, However, all of the dates derivable from the suite of anomalous leads are strongly model dependent. 114d Pb-Pb Isochrons A special case arises in the calculation of the C™Pb/*SPb)* ratio from equation 11.23 when ¢ is set equal to zero, The resulting equation, es “4 (“ 1) ans iepp) ~ 137.88 (ee 7 oa is identical to equation 10.18 in Section 10.1 1a. In other words, the straight line defined by a suite of anomalous galena leads is the Pb-Pb isochron of the rocks in which the radiogenic component formed by decay of 7U and "SU, The value of t obtained from equation 11.24 is the present age of these basement rocks. In the hypothetical example under consider ation, the slope of the anomalous Pb line (R 0.160) is used to solve equation 11.24 by interpo- lation in Table 10.3: 0.2 x 0.00518 24+ Orgs =245Ga This date is older than the age of tie basement rocks assumed in Section 11.4¢ (+, = 2.0 Ga) because t, is a maximum for any specified value of the C°PbPSPb)* ratio when t = 0 in equation 11.24. The basie reason for this relationship is that the radiogenic *”Ph/*Pb ratio, which is generated by decay of the U isotopes in Table 10.3, has decreased with time and has reached its lowest value of 0.04604 at the present time (t = 0). Consequently, ¢, must rise to a maximum when = 0 in order to generate a particular value of the @”Pb?™Pb)* ratio. For the same reason, t, decreases when 1 increase until ultimately 1, becomes equal to f. In that case, equation 11.23 converts to equation 11.21 for the instantaneous formation of the (2”Pb/?™°Pb)* ratio, 11.4e Thorogenic Lead Anomalous leads in ore deposits also gener- ate straight lines in coordinates of *Pb/°*Pb (x) and *8PB?%Pb (y). Such anomalous Pb lines. may intersect the Pb growth curve of the Stacey-Kramers model at a point P’ in Figure 11.6. The equation of the line P’-@ is PPMP) y (PPP) y CPb/2Pb)o C™PDP™PD)g = isotope ratios of Pb at these points in Figure 11.6 fy = 3.70 x 10" years (1.28) where P’,‘Two-stage Evolution, Thorogenic Lead | 29 L ay nb i b @ wb prinevatens 2590 (1p riGuRE 11¢ Two-stage Stacey-Kramers model for the evolution of thorogenic Pb. The point Q at 3.7 Ga marks the transition from the first stage to the second stage when the *°Th/™Pb ratio () changed from 32.208 to 36.837 and the =*U/™Pb ratio (1) changed from 7.192 to 9.735, Time in the past is expressed in billion years. Point P’ is not shown, date that corresponds to any point P’ on the Pb growth present value ofthis ratio in the second stage of Stacey~Kramers model is = decay constant of 2?Th (4.9475 x 107! y~!) decay constant of =U. (155125 x 10" y-}) ‘The TWU ratio of the second stage of the Stacey~Kramers model has a value of 3.78, from which it follows that PAM "Th _ 3.78 x 238.0289 x 100 _ 5 BB ~ 732.0381 x 99.2743 ~ ‘The coordinates of a point P’ in Figure 11.6 can be used to caleulate a date; from equation 11.25 Anomalous Leads in Galena 273 based on the 2 Th/*U ratio of the Pb growth curve, The result should be concordant with the date calculated from the *"Pb/™Pb and **Pb/™Pb coordinates of point P in Figure 11.5. The slope R’ of the anomalous Pb line is the 2°8Pb/™Pb ratio of the radiogenic Pb that contaminated the two-stage Pb at a point P’ in Figure 11.6. The equation for the instantaneously generated C™PB/%Pb)* ratio is analogous to equation 11.21 28PB\* da (THY ees ay -(@ay-2 C2), (11.26) where Th/*U), is the present value of this Similarly, the (°*Pb/*°°Pb)* ratio can be generated by continuous decay during an interval apy? (2) (2 <2) my This equation can be used to calculate the @ MPU), ratio based on values of t, and # determined from equation 11.23. Alternatively, the equation can be used to set limits on f, and by substituting the value of the @Th*U), ratio obtained from equation 11.26. However, the uncer- tainties of the dates derived from anomalous Pb lines are compounded when such dates are used to calculate the Th/U ratios of the rocks that produced the component of radiogenic Pb. R 11.4f Unresolved Issues The two-stage model dates of common Pb whose isotope ratios fit the Stacey~Kramers Pb growth curve are in good agreement with dates determined by other methods. However, only a relatively small number of Pb deposits fit this model. In addition, the reason for the increase of the value of at 3.70 Ga remains unexplained. In reality, the evolution of the isotope composition of Pb in the crust of the Earth is controlled by geological processes that homogenize Pb having a wide range274 IL, The Common-Lead Method of isotopic compositions and thereby create the illusion that the Pb evolved in a closed system. The straight lines defined by anomalous Pb may be the result of mixing of common Pb with varying amounts of radiogenic Pb. In es where the anomalous Pb line intersects the Stacey—Kramers growth curve, the coordinates of the point of intersection define the isotope com- position of the component of two-stage Pb and yield its model date. This date exceeds the age Of the Pb deposit but may not, in all cases, cor respond to a recognizable event in the geological history of the region. Likewise, the dates derivable from the slopes of anomalous Pb lines by either the instantaneous or the continuous model do not record specific geological events or processes and may be fictitious, The decay of **°Th to ®°*Pb plays a significant role in the isotopic evolution of Pb in ore deposits and generates growth curves in coordinates of Pb/™ Pb (x) and PPh (>). The equation relating the decay products of 7U and Th can be used to calculate either the TI/U ratio of the Pb growth reservoir or the time of separation of the Pb from that reservoir, but not both. If the Pb fits the Stacey~Kramers model, the Th/U ratio of the reservoir is fixed by that model. If the Pb does not fit the U-Pb or Th-Pb growth curves, the reliability of the model date is questionable and so is the Th/U ratio calculated by use of that date, Ore deposits containing Pb whose isotope ‘composition is anomalous have been reported by many investigators: Tilton and Steiger, 1969, J. Geophys. Res. 74:2118-2132, Zartman and Stacey, 1971, Fcon. Geol., 66:849-860. Rye etal, 1974, Econ. Geol., 69:814~822. Kuo and Folinsbee, 1974, Econ. Geol., 69:806-813. Tugarinov etal., 1975, Geokhimiya, 8:1156~1163. Sato et al, 1981, Geochem. J, 15:135~140, Godwin etal, 1972, Econ. Geol., 77:82-94, Fletcher and Farquhar, 1982, Econ. Geol, 77:464-$73, Kish and Feiss, 1982, Econ. Geol.,77:352~363 LeHuray, 1982, Econ. Geol., 77:335~351. LeHuray, 1984, Econ. Geol., 79:1561~1573 Sundblad and Stephens, 1983, Econ. Geol., 78:1090-1107. Large et al., 1983, Mineral Deposita, 18:235~244. Gulson ct al, 1988, Appl. Geochem., 3;243-254 In addition, Zartman (1984) discussed the isotope composition of Pb in ore deposits of the Rocky ‘Mountains of the United States. 11.5 LEAD-ZINC DEPOSITS, SOUTHEASTERN MISSOURI The most celebrated example of anomalous Pb ‘occurs in the Pb~Zn deposits of Missouri, Kansas, and Oklahoma, known as the Tri-State Dis- teict (Section 10.126). The literature on these and other Mississippi Valley Po-Zn deposits cited by Goldhaber et al, (1995) includes contributions conceming the isotope compositions of Pb, S, and Sr of ore and gangue minerals: Brown, 1967, Econ. Geol. Monogr., 3:410- 425. Richards et al., 1972, Mineral, Deposita, 7:285-201, Hart et al., 1981, Econ Geol, 76:1873—1878. Kessen et al, 1981, Econ. Geol, 76:913-920. Deloule et al.. 1986, Econ. Geol., 81:1307-1321. Crocetti et al., 1988, Econ. Geol., 83:355~376. Crocetti and Holland, 1989, Econ. Geol, 84:2196~-2216. Goldhaber and Mosier, 1989. U.S. Geol. Surv Cireular 1043:8-9. Other aspects concerning these deposits include: Age of the Ore: Bickford et al., 1981, Geol. Soc, Am, Bull., 92:323-341. Hearn and Sut- ter, 1985, Science, 228:1529-1531. Brannon et al,, 1992, Nanure, 356:509-511. Aleinikoff et al,, 1993, Geology, 21:73-76. Transport of Pb by Saline Groundwa- ter: Sverjensky, 1984, Econ. Geol., 79:23~37. Sverjensky, 1987, Econ. Geol., 82:1130-1141 Sverjensky, 1989, Geol. Assoc. Can. Spec. Pa- per 36:127-134, Clendenin and Duane, 1990, Geology, 18:116-119, Bethke and Marshak, 1990, Annu. Rey. Earth Sci., 18:287~315. Bran- non et al., 1991, Geochim. Cosmochim. Acta,55:1407-1419. Garven et al., 1993, Am. J. Sci., 293:497-568, Origin of the Ore Deposits: Sverjensky, 1981, Econ. Geot., 76:1848-1872. Diehl et al, 1992, U.S. Geol. Surv. Bull. 2012:A1—A13; Diehl and Goldhaber, 1993, U.S. Geol. Surv Bull, 1989:F1-P17 The sulfide minerals of the Tri-State District consist primarily of sphalerite, galena, and chal- copyrite. These ore minerals and the associated pyrite and calcite were deposited by replacement and cavity filling in the marine carbonate rocks of Late Cambrian to Early Ordovician age. Informa- tion presented in Section 10.13b indicates that the ‘ore and gangue minerals were deposited episod- ically between about 250 and 40 Ma from fot brines, remnants of which have been preserved in fluid inclusion in the calcite. The ore deposits of southeastern Missouri ‘occur in the dolomites of the Bonneterre Formation and in the underlying sandstones of the Lamotte Formation, both of which are Eariy Cambrian in age and were deposited on Precambrian basement rocks that crop out in the St. Francois Mountains in the center of the mining district. The ore deposits of southeastern Missouri have been subdivided into the Old Lead Belt, the Viburmum Trend, the Indian Creek, and several smaller districts (Goldhaber et al., 1995), 11.Sa Lead in the Ore Minerals The isotope compositions of Pb in the mines of soutkeastem Missouri were first determined by Nier et al. (1941) and subsequently by Doe and Delevaux (1972), Richards et al. (1972), Heyl etal. (1974), and Sverjensky et al. (1979). A. comprehensive study by Goldhaber et al. (1995) provided nearly 150 new isotope analyses of Pb in the ore minerals and pyrite from the principal mines of this region as well as of Pb in the host rocks The isotope ratios of galena and chalcopyrite in the mines of the Viburum Trend define an elongated area in Figure 11.7 that is displaced from, the zero-age isochron and the growth curve of Pb LeadZinc Deposits, Southeastern Missouri 275 in the Stacey-Kramers model. Therefore, the Pb in the galena and chalcopyrite of the Viburnum Trend contains excess radiogenic Pb. In fact, the anomalous Pb here and elsewhere in the world is referred to as J-type lead after the town of Joplin, Missouri The 36 isotope ratios of Pb in galena and chalcopyrite of the Vibumum Trend in Figure 11.7 define a poorly constrained anomalous-Pb line with a correlation coefficient of 0.586 27pp spp 0s( This line intersects the growth curve of the Stacey--Kramers model in Figure 11.8 at point P. whose coordinates are ™*Pb/?Pb = 13.10 and 2"Pb/?'Pb = 14.45. The slope m of the Pb-Pb isochron (P-Q) is 14.45 — 12.998 ™= F310 = 11.152 = 0.74537 Interpolation in Table 11.5 yields This is the date when the two-stage Pb was withdrawn from the second-stage reservoir of the Stacey-Kramers model and was subsequently mixed with varying amounts of radiogenic Pb. The age of the component of radiogenic Pd is derivable from the slope of the anomalous Pb line (R = 0.17505) by the “instantaneous” and “continuous” models. The instantaneous model represented by equation 11.22, “(e) yields a date of In 3.80167 : 8.29725 x 10° 161 Ga This date is the time in the past when the 20'pp/*%Pb ratio of the radiogenic Pb was equal to 0.17508.276 11. The Common-Lead Method Tri-State District ‘Viburnum, SE Missour (galena and chalcopyrite) stacey-Kramers model kame wd / 7 i 1 2 % 2 B 205 / Pp icuRE 117 Isotope ratios of Pb in galena and chalcopyrite in the ore bodies of the Viburnum Trend in southeastern Missouri. These anomalous leads define a straight line whose slope (0.17505) was determined by least-squares regression of 36 data sets. The Pb growth curve represents the two-stage model of Stacey and Kramers (1975). Data from Goldhaber et al. (1995). Anomalous - Lead Line (galena) Viburnum Trend wah 2 18S 2086 2205 ouke 11s Intersection at point P of the anomalous Pb line defined by galena and chalcopyrite of the Viburnum Trend in Figure 11.7 with the growth curve of the Stacey~Kramers model. Data from Stacey and Kramers (1975) and Goldhaber et al. (1995).The slope of the anomsious Pb line in Figure 11.7 can also be interpreted in accor- dance with the continuous model expressed by equation 11.23 Lo (ene where t, is the age of the source rocks in which the radiogenic Pb accumulated and ¢ is the date when the radiogenic Pb was separated from U and Th in these source rocks. According to independent evidence presented in Section 10.13b, the deposition of calcite gangue in the Bonneterre Formation started at 0.25 Ga, which therefore provides a lower limit for the value of r. ‘The date f,, when the component of radio- genic Pb began to accumulate, was determined from equation 11.23 by interpolation assuming that 1 = 0.25 x 10° y and R= 0.17505: 0.2 x 0.01026 0.02022 =250Ga = 24t This date is an overestimate of the age of the reservoir in which the radiogenic Pb evolved because fin equation 11.23 is probably greater than 0.25 x 10° years. AA literal interpretation of these dates implies that the two-stage Pb in the mines of the Vibur- num Trend stopped evolving isotopically in Late Archean time (2.96 Ga) and that it was mixed more than 1350 million years later with radio- genic Pb that formed by decay of U isotopes at 1.61 Ga (instantaneous model). Altematively, the radiogenic component evolved continuously from 2.50 to 0.25 Ga and then mixed with the two-stage Pb just prior to or during the deposition of galena in the Bonneterre Formation. The dates derived above gain validity in case the two-stage Pb resided in K-feldspar in the Precambrian basement rocks of the midcontinent region. These rocks also contain zircon and other ‘minerals within which the radiogenic Pb evolved by decay of the isotopes of U and Th. The wo components of Pb were ultimately leached from the ‘basement rocks by warm brines that transported the Ph into the overlying Paleozoic carbonate rocks and sandstones and mixed them isotopically. Lead~Zinc Deposits, Southeastern Missouri 277 11.5b Lead in Pyrite Trace amounts of pyrite occur widely in the Bonneterre and Lamotte Formations of southeastern, Missouri (Goldhaber et al. 1995). The isotope ratios of Pb in the pyrite of the Bonneterre Formation also define an anomalous Pb line whose ‘equation is app 2064 pp ops (2B) «2008 Tipp with a correlation ccefficient of 0.906 for 25 sets of data, Pyrite in the Lamotte Formation defines a similar anomalous Pb line: 2p 204 oat which hs a oiton cocci of 973 fr 2 tomas Kramers growth line in Figure 11.9 at point P, whose approximate coordinates are **Pb/?™Pb = 18.150 and *”Pb/?™Pb = 15.598. The slope m of tc PP oon P-0 anl corpenng 15,598 ~ 12.998 ‘18.150 — 11.152 0.2 x 0.0105 0.01379 ‘This result indicates that the two-stage Pb of pyrite in the Bonneterre Formation was removed from the Stacey-Kramers reservoir much more recently than the two-stage Pb in the galena of the Vibumum Trend in Figure i1.7. ‘The age of the radiogenic component is derivable from the slope R of the anomalous Pb line by means of equation 11.22 (instantaneous model) 1 (2 ssh) 1 n( 0.37153 02 = 035 Ga __In2.02908) ~ §29725 x 10-7 85 Ga Evidently, the Pb in the pyrite of the Bonneterre Formation is a mixture of two-stage Pb (which278 11. The Common-Lead Method , Pyrite, Bonneterre =p | pp ss62 1958 + 7 ie ie 20 Zipp / pp HOURE 19 Anomalous Pb line of disseminated pyrite in the Bonneterre Formation (Early Cambrian) in southeastern Missouti. The Pb growth curve is based on the Stacey~Kramers model and the dates marked along i are in units of billion years. The coordinates of point P specify the isotope ratios of the two-stage Pb component. Data from Stacey and Kramers (1975) and Goldhaber et al.(1995), evolved until its separation from the Stacey- Kramers reservoir during the Paleozoic Era) with radiogenic Pb that was generated in the Late Proterozoic Era ‘The anomalous Pb line of pyrites in the Lamotte Formation does not intersect the Stacey-Kramers growth curve but plots above it. The two-stage Pb of pyrite in this formation therefore appears to have evolved in rocks having a j-value greater than that of the Stacey—Kramers model 11.5e Synthesis The ore deposits in southeastem Missouri and elsewhere in the Tri-State District of North America were deposited by warm brines that flowed in aquifers within the Paleozoic carbonate rocks and sandstones of the Mississippi Valley region between about 250 and 40Ma, The Pb in these ore deposits originated from the Precambrian base- ment rocks and from the Lamotte Sandstone, which not only was @ source of Pb but also acted as a conduit that channeled the flow of the brines (Goldhaber et al, 1995). The two-stage Pb resided primarily in K-feldspar of the local Pre- cambrian basement rocks (Section 11.3), wherea the radiogenic component originated in U-rich accessory minerals and occurred in grain bound- aries and in microfractures in minerals of these basement rocks. Davis and Krogh (2000) recently demonstrated experimentally that damage to the lattice of zircon erystals by a-partcle recoil pro- motes dissolution of "U (a daughter of **U) and of radiogenic "Pb, Therefore, mixing of the two-stage Pb and the radiogenic Pb could have occurred during leaching from the source rocks and during subsequent transport of the Pb by the brines, The deposition of the metals Pb, Zn, and Cu as sulfide minerals required the presence of hydrogen sulfide and the availablity of open cavities in the host rocks. The hydrogen sulfide (H:S) could have been generated by the reduction of sulfate ions by bacteria (Desulfovibrio) feeding on petroleum in the host rocks. Bacterial reduction of sulfate enriches the resulting Hx in °S and depletes it in ¥S relative to the isotope composition of S in the sulfate (Chapter 29). Goldhaber et al (1995) reported that the 4S values of galena and chalcopyrite in the ore of the Viburnum Trend range from +1.40 to +3.2%e, These values imply strong enrichment in "S compared. to 85'S ~ 4+30fbc in marine sulfate of Cambrian age. Therefore, the isotope composition of S in the ore is consistent with a bacteriogenic origin of the sulfide. The process outlined above was activated by the movement of saline groundwater on a regional scale in response to hydraulic gradients and geothermal heat. Such conditions have occurred in many places in the geological past, which accounts for the economic importance and wide distribution of the so-called Mississippi Valley Pb-Zn deposits11.6 MULTISTAGE LEADS The enrichment of Pb in radiogenic isotopes may ‘occur not only by mixing but also by multistage isotope evolution caused by the Pb passing through ‘two of more stages characterized by different values of . For example, the present isotope composition of a three-stage Pb is governed by equations of the form (=) ) eet en) ste = 1) (11.28) age of the Earth age of geological events that cause 4) 10 change to yz and jez to 113, respectively where CP b/?™Pb), = primeval value of this ratio CPD /2Pb),20 = present value of this ratio Similar equations canbe formulated for the =™PHF™Pb and **Pb/™Pb ratios. The number of stages and their j-values may be varied without limit. However, the resulting equations cannot be solved forty, fo... OF fy, Has + The only known, parameters are the age of the Earth (7), the isotope ratios of primeval Pb (Section 1!.1c), and the mea- sured isotope ratios of Pb and the j.-value of the rocks in which the Pb resides at the present time. Equation 11.28 can be simplified by setting ae — Hence, a) FY itt Multistage Leads 279 ‘The sum of the °*Pb/™Pb ratios is the initial ratio of the Pb that was incorporated into the rocks in which it presently resides. Therefore, (2) - GB) +( =) =p), and equation 11.28 becomes pp mp = ple — 1) (11.2 (sr) _=( ) me 129) SpE where the subscripts of jz and r have been omitted because they are no longer relevant. In cases where j. has a range of values but C°PB/™Pb), and f have the same values for all. specimens in a suite of igneous or metamorphic rocks, the measured °Pb/*Pb ratios have a range of values determined by equation 11.29. A similar development applies to the measured 2”'Pb/*PD ratios of a suite of rocks: (11.30) Equations 11.29 and 11.30 can be combined to yield the °Pb/*Pb ratio of the radiogenic Pb that hhas accumulated in the rocks since the time of their formation + years ago: 2 Pv\* __CPb/?™Pb),.0 — CPb/**Pb), aire) (5P5 7 PB), oa — CPP), 1 = =in(S ) a3ty Equation 11.31 represents a family of straight lines all of which pass through a common point whose coordinates are C™Pb*™PD), and CPbE*Pb), and whose slopes are the radiogenic S™PD/Pb ratios. Equation 11.31 is identical to equation 10.17 for Pb-Pb isochrons of U-bearing igneous and metamonphic rocks and sedimentary carbonate rocks. The beauty of these equations arises from the fact that Pb-Pb isochron dates are based entirely on280 11. The Common-Lead Method the measured isotope composition of Pb and do not require knowledge of the concentrations of U and Pb and its prior history extending back in time to primeval Pb. ‘The point to be made here is that the isotope compositions of multistage leads can vary widely and therefore deviate from the narrowly defined single- or two-stage Pb growth models. In addition, multistage leads may contain excess radiogenic Pb relative to the Stacey-Kramers model and thus could be classified as being anomalous. In other words, not all anomalous leads formed by mixing of two components because some may have acquired their isotope compositions as a result of multistage histories. 11.7 $ MMARY The isotopic composition of common Pb in min- erals that contain no U or Th can be accounted for by evolutionary models of varying complexity Tn the simplest case, represented by the single- stage Holmes-Houtermans model, Pb evolved in a homogeneous reservoir having characteristic U/P and ThvPb ratios until was withdrawn from that reservoir and was sequestered in a Pb mineral such as galena, The equations describing Pb evolution in this model require knowledge of the isotope ratios of primeval Pb and of the age of the Earth, both of which were determined from analyses of Pb in stony and iron meteorites ‘The single-stage model was found to apply only to a small number of conformable ore deposits associated with sequences of volcanic and sedimentary rocks deposited near island arcs and subduction zones. However, even for conformable ore deposits the dates calculated from the single- stage model do not agree well with the geological ages of the associated rocks. Moreover, the Pb in most other metallic ore deposits yields single-stage ‘model dates that are highly discrepant and, in some cases, even negative (i... associated with the future rather than with the past). ‘The two-stage model of Stacey and Kramers is based on a selected data set and proposes that ore leads evolved in two reservoirs having different U/Pb and Th/Pb ratios. The change in these ratios took place at 3.7 Ga and was caused by the geochemical differentiation of the Earth. ‘The mantle of the Earth may have been the first reservoir but, ater 3.7 Ga, Pb evolution occurred in frequently mixed continental sediment from which Pb was extracted during subduction into the mantle. The two-stage model yields dates for Pb in galena and in K-feldspar that agree much better with their geological ages than dates derived from the single stage model. The isotope ratios of so-called anomalous leads that do not fit the single- or two-stage model form linear arrays in the Pb evolution diagram. Such anomalous-Pb lines may be caused by the addition of varying amounts of radiogenic Pb to ordinary single- or two-stage Pb. If that is true, the slope of the anomalous Pb line can be used t0 derive information about the age and THU ratio of the source rocks that provided the radiogenic lead. In addition, the time of withdrawal of the single- or two-stage Pb from its reservoir can bbe estimated, However, anomalous-Pb lines may also result from mixing of two common leads of differing isotope compositions. In this case, the slope of an anomalous-Pb line does not convey information about the age of such Pb. Al of the dates that are derivable from the isotope composition of common Pb are model dependent and therefore are not as accurate or as, precise as U,Th-Pb dates derivable from zircon and other U.Th-bearing minerals The Pb in gelena and other sulfide minerals in Mississippi Valley-type Pb-Zn deposits originated from the granitic gneisses of the Precambrian basement rocks that underlie the carbonate host rocks. The so-called two-stage Pb resided in K- feldspar of the basement rocks, which crystallized at the date indicated by the point of intersection of the anomalous Pb fine with the two-stage growth curve, That date also records the start of the accumulation of radiogenic Pb in U-bearing (and ‘Th-bearing) minerals of the same basement rocks (€@. rircon, monazite) Eventually, both types of Pb were leached from the basement rocks (or their clastic derivatives) by geothermally heated groundwater (warm brines) whose movement was energized by hydraulic, gradients and density differences. The two isotopic components of Pb were mixed in varying proportions during leaching and transport until the Pb and theReferences for Primeval Pb in Meteorites and the Earth (Sections 11.Jd~ I1.Je) 281 associated metals (Zn and Cu) were deposited in the overlying sedimentary host rocks by cavity filling and replacement. REFERENCES FOR THE HOLMES-HOUTERMANS MODEL (INTRODUCTION, SECTIONS 11.1- 11.1a) ‘Aston, F. W., 1927. The constitution of ordinary lead, Nature, 120-224, Doe, B. R., 1970. Lead Isotopes. Springer-Verlag, Hei- elberg, Gerling, E.K., 1942. Age of the Earth according to radioactivity data. Compt. Rend. (Doklady) Acad. Sci USSR. 34, 9:259-261 Hamilton, E. 1, and R. M. Farquhar, 1968, Radiometric Dating for Geologists. Imerscience, London. Holmes, A., 1946, An estimate of the age of the earth, Nature, 157:680-684. Houtermans, F. G., 1946, Die Isotopenhiufigkeiten im natirlichen Blei und das Alter des Urans. Narurwis senschafien, 33:185-186, 291 Moorbath, S., 1962. Lead isotope abundance studies fon mineral occurrences in the British Isles and their geologic significance. Philos. Trans. Roy. Soc:, 254205 -360. Nier, A.O., 1938. Variations in the relative abundances ‘of the isotopes of common lead from various sources. J. Am. Chem. Soe., 6015711576. Niet, A. O.,R. W. Thompson, and B. F, Murphey, 1941. ‘The isotopic constitution of lead and the measurement of geologic time. 111 Phys. Rev., 60:112-116. Rankama, K., 1954, Isotope Geology. Pergamon, London, Rankama, K., 1963, Progress in Isotope Geology. Inter science, London. Russell, R.D., and R.M. Farquhar, 1960. Lead Isotopes in Geology. Interscience, New York Steiger, RH. and E. Jiger, 1977. Subcommission on ‘geochronology: Convention on the use of decay constants in geo- and cosmochronology. Earth Planet. Sci, Lett, 36:359-362, REFERENCES FOR ANALYTICAL M (SECTION 11.1c) HODS Cannon, R.S., Jr, AP. Pieree, and M.H. Delevaux, 1963. Lead isotope variation with growth zoning in & sgalena crystal. Science, 142:574~576, Catanzaro, E, J., 1967. Triple-filament method for solid sample lead isotope analysis. J. Geophys. Res 72413251327. Compston, W., and V.M. Oversby, 1969. Lead isotope analyses using a double spike. J. Geophys. Res 7443384348, Cumming, G.L., 1973. Propagation of experimental errors in lead isotope-ratio measurements using & double spike method, Chem, Geol, 11:187=165, allwitz, M. J, 1970. Fractionation correction in lead isotopic analysis. Chem. Geol, 6311-314. Dodson, M. H., 1970. Simplified equations for double spike isotopic analyses. Geochim. Cosmochim. Acta, 34:1241-1244, Gale, N. H., 1970. A solution in closed form for lead isotopic analysis using a double spike. Chem. Geol., 6:305-310. Han, $.R., N. Shimizu, and D. A. Sverjensky, 1981 Lead isotope zoning in gulena: An ion microprobe study of a galena crystal from the Buick Mine, southeast Missouri. Econ. Geol, 716:1873~ 1878 Hofmann, A. W., 1971. Fractionation corrections for rixed-isotope spikes of Sr, K, and P. Earth Planet, Sei, Lert, 10:397-402, Ozard, J. M., and R.D. Russell, 1970. Discrimination in solid-source lead isotope abundance measurement. Earth Planet, Sci. Let, 8:331~336. Richards, J. 1981. Some thoughts on the time- ependence of lead isotope ratios. Geochem. Int. 1981:17-36. Russell, R. D., 1971. The systematics of double spiking, J. Geophys, Res., 16:4949-4955, Russell, R, D., 1975, Mass discrimination inthe measure: ‘ment of lead isotope reference samples. Geochem. J 9347-50. REFERENCES FOR PRIMEVAL Pb IN METEORITES AND THE EARTH (SECTIONS 11.1D~ 11.1¢) Allegre, C.J.,G. Manhes, and C. Gopel, 1995. The age of the Earth. Geochim. Cosmochim. Acta, 59:1445-1456, Chen, J. H., and G. J. Wasserburg, 1983. The least radio- genic Pb in iron meteorites. Paper presented at the Fourteenth Lunar and Planetary Science Conference, Abstracts, Part 1, Lunar and Planetary Institute, Hous- ton, Texas, pp. 103-108. Goles, G. G., and E. Anders, 1962. Abundance of iodine, tellurium, and uranium in meteorites. Geochim. Cos- ‘mochim. Acta, 26:723,282 11. The Common-Lead Method ‘Hanan, B.B., and G.R Tilton, 1985. Early planetary ‘metamorphism in chondkitic meteorites. Earth Planet Sci, Let, 74:209-219. ‘Minster, J... and C. J Allbgre, 1979, Rb"Sr dating of L’ chondrites: Effects of shock and breeciation Meteorites, 14235, ‘Pattersos, C. C., 1956, Age of meteorites and the earth Geochim. Cosmochim, Acta, 10:230~237. Rogers, J.J. W., and J. AS, Adams, 1969a, Abun- darce ‘of uranium in meteorites ‘and tektites. In KH. Wedepohl (Ed), Handbook of Geochemistrs Bp 92C-1-92C-4. Springer-Verlag, Heidelberg ‘Rogers. J.J. W., and J. A. S. Adams, 19696, Abundance of thorium in meteorites, tektites, and lunar materials. In K. H, Wedepohl (Ed), Handbook of Geochemistry, pp. 90C-1-90C-6. Springer-Verlag, Heidelberg Steiger, R-H., and E. Jiger, 1977. Subcommission on Geochronology: Convention on the use of decay constants in geo~ and cosmochronology. Earth Planer Sci, Lert, 36:359-362 ‘Tatsumoto, M,, R. J. Knight, and C.J. Allegre, 1973. ‘Time differences in the formation of meteorites as determined from the ratio of lead-207 to lead-206. Science, 180:1279~1283, Tilton, G.R, 1973. Isotopic lead ages of chondritic meteorites. Earth Planet, Sci. Let, 19:321~329. Wedepohl, KH, 1974. Abundance (of lead) in the ‘cosmos, meteorites, tektites, and lunar samples. In K. H, Wedepohl, ed. Handbook of Geochemistry, I-5 p. 82C-O. Springer-Verlag, Heidelberg, REFERENCES FOR DATING COMMON LEAD (SECTION 11.2) Armstrong R. L,, 1968. A model for the evoluticn of strontium and lead in a dynamic earth. Rev. Geophys., 6:175=199. Doe, B.R., 19628. Distribution and composiion of sulfide minerals at Balmat, New York. Geol. Soc. Am. Bull, 73:833-854 Doe, B.R., 1962b. Relationship of Tead isotopes among _granites, pegmatites, and sulfide ores near Balmat, New York, J: Geophys, Res., 67:2895-2906, Doe, B.R., and J.S, Stacey, 1974, The application ‘of lead isotopes to the problems of ore genesis and ore prospect evaluation: A review. Econ, Geol., 69:757-776, Fairbaim, H. W., P.M. Hurley, K.D.Card, and C.J. Knight, 1969. Comelation of radiometric ages of Nipissing diabase and Huronian metasediments with Proterozoic orogenic events in Ontario. Can. J. Earth Sei, 6489-497, Hriskevich, M.E,, 1968. Petrology of the Nipissing diabase sill of the Cobalt area, Ontario, Canada, Geol Soc. Arm. Bull, 79:1387~1404, Kanasewich, E.R and R, M. Farquhar, 1965, Lead iso- tope ratios from the Cobalt-Noranda area, Canada, Can, J. Earth Sei, 2:361-384. Overby, VM, 1974. A new look at the lead isotope ‘prowth curve, Nature, 248:132. Patterson, C.C., 1956. Age of meteorites and the earth Geochim. Cosmochim, Acta, 10:230-237. Richards, JR, 1971. Major lead orebodies—Mantle ‘origin? Econ. Geol, 66:425-434 Stacey, J. S., and J. D, Kramers, 1975. Approximation of ‘erresvial lead isotope evolution by a two-stage model, Earth Planet. Sci Let, 26:207-221 Stanton, R. L.,and RD. Russell, 1959, Anomalous leads ‘and the emplacement of lead sulfide ores. Econ. Geol, 545588-607. Steiger, R. H. and E, Figer, 1977. Subcommission on ‘geochronology: Convention on the use of decay onstants in geo- and cosmochronology, Earth Planet Sci Lett, 36:359~362. Tatsumoto, M., R. J. Knight, and C.J. Allggre, 1973 ‘Time differences in the formation of meteorites as determined from the ratio of lead-207 to lead-206. Science, 180:1279~1283. ‘Thorpe, R., 1974. Lead isotope evidence on the genesis of silverarsenide vein deposits of the Cobalt and Great Bear Lake areas, Canada. Econ, Geol, 69:777-791, ‘Van Schmus, R., 1969. The geochronology of the Blind River-Bruce Mines area, Ontario, Canada. J. Geol, 73:755-780. REFERENCES FOR DATING K-FELDSPAR (SECTION 11.3) Catanzaro, E.J., and R. W. Gast, 1960. Isotopic compo- sition of lead in pegmatite feldspar. Geochim. Cos Imochim. Acta, 19:113~126, Doe, BR, G.R. Tilton, and C. A. Hopson, 1965. Lead ‘isotopes. in feldspars from selected granitic rocks associated with regional metamorphism. J. Geophys. Res., 10:1947-1968. Sinha, A.K., and G.R.Tilton, 1973. Isotopic evolu tion of common lead. Geockim. Cosmochim. Acta, 37:1823~1849, ‘Stacey, J. S.,and J. D. Kramers, 1975. Approximation of terrestrial lead isotope evolution by a two-stage model. Farth Planet. Sci. Ler, 26:207~221 ‘Wetherill, G. W., G.R. Tilton, G. L. Davis, S. R. Hart, and C. A. Hopson, 1966. Age measurements in the ‘Maryland Piedmont. J. Geophys. Res., 72:2139-2155,References for Lead-Zine Deposits, Southeastern Missouri (Section 11.5} 283 REFERENCES FOR ANOMALOUS PB IN ORE DEPOSITS (SECTION 11.4) Doe, B. R., 1970. Lead isotopes. Springer-Verlag, Berlin Farquhar, R.M., and RD. Russell, 1997, Anomalous Teads from the upper Great Lakes region of Ontario, Trans. Am. Geophys. Union, 38:552-556. Kanasewich, E. R., 1968, The interpretation of lead iso topes and their geological significance. In E. 1. Hamil ton and R. M, Farguhar (Eds), Radiometric Dating for Geologists, pp. 147-223, Wiley-Interscience, New York Russell, R. D., and R. M. Farquhar, 1960. Lead Isotopes in Geology. Wiley-Interscience, New York. Stanton, R-L., and R. D. Russell, 1959, Anomalous leads tnd the emplacement of lead sulfide ores. Econ. Geol, 54:588-607, Zartman, RE, 1974, Lead isotopic provinces in the Cordillera of the western United States and their geologic significance. Econ. Geol, 69:792~80S. REFERENCES FOR LEAD-ZINC DEPOSITS, SOUTHEASTERN MISSOURI (SECTION 11.5) Davis, D. W., and T. E. Krogh, 2000. Preferential dis. 'U and radiogenic Pb from a-recoil- solution of damaged latice sites in zircon: Implications for thermal histories and Pb isotopic fracionation in the near sur- face environment, Chem Geol., 172:41 58 Doe, B.R., and M. H, Delevaux, 1972. Source of lead in southeast Missouri galena ores. Econ. Geol., 67409 ~438, Goldhaber, M. B., $. E. Church, BR. Doe, J. N. Aleini= koff,J. C. Brannon, F. A. Podosek, E. L. Mosier, C. D. Taylor, and C. A. Gent, 1995. Lead and sulfur isotope investigation of Paleozoic sedimentary rocks from the southern midcontinent ofthe United States: Implications for paleohydrology and ore genesis of the southeast Missouri lead belt, Econ. Geol, 90:1875-1910. Heyl, A. V., G.P. Landis, and RD. Zartman, 1974, Isotopic evidence of the origin of Mississippi-Valley type mineral deposits: A review. Econ. Geol, 69:992— 1006. Nir, A. ©., R. W. Thompson, and B. F. Murphy, 1941 ‘The isotopic constitution of lead and the measurement of geologic time, IT. Phys, Rev, 60:112-116, Richards, JR, AK. Yonk, and C. W. Keigin, 1972. Upper Mississippi Valley lead isotopes. reexamined Mineral. Deposit, 7:285~21. Stacey, J.S. and J. D. Kramers, 1975. Approximation of terrestrial lead isotope evolution by a two-stage model. Earth Planet, Sei. Lee, 26:207-221, Sverjensky, D. A, D. M. Rye, and B. R. Doe, 1979. The lead and sulfur isotopic composition of galena from a Mississippi Valley-type deposit in the New Lead Belt, southeastern Missouri. Econ. Geol, 74:149-153