Nd-Sr-Pb systematics and age of the Kings River ophiolite,California: implications for depleted mantle evolution

Sm-Nd whole-rock and mineral data for the Kings River ophiolite define two isochrons of 485±21 Ma and 285±45 Ma age with _Nd (483)= +10.7±0.5 and Nd (285)= +9.9±1.1, respectively. The 483 Ma isochron is defined by samples of the main igneous construct. Samples from crosscutting diabase dikes and flaser gabbro sheets within the peridotite unit yield the 285 Ma isochron. The 483 Ma data provide the first evidence of lower Paleozoic oceanic crust in the Sierran ophiolite belt. New U-Pb analyses of zircons from a plagiogranite lying on the 483 Ma Sm-Nd isochron yield upper and lower intercepts with the concordia of 430 _–60 ⁺²⁰⁰ and 183±15 Ma. Published zircon ages have underestimated the primary age of the ophiolite by 200–300 m.y. due to the effects of polymetamorphism. The 483 Ma samples have initial ⁸⁷Sr/⁸⁶Sr=0.7023–0.7030, ²⁰⁶Pb/²⁰⁴Pb=17.14–17.82, ²⁰⁷Pb/²⁰⁴Pb=15.37–15.52, ²⁰⁸Pb/²⁰⁴Pb=36.80–37.38. The 285 Ma samples have similar initial ⁸⁷Sr/⁸⁶Sr, but more radiogenic Pb. The range in Sr and Pb compositions is probably due to introduction of radiogenic Sr and Pb during multiple post-emplacement metamorphic events. The high _Nd, low ⁸⁷Sr/⁸⁶Sr, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, ²⁰⁸Pb/²⁰⁴Pb of the least disturbed samples are clearly diagnostic of a midocean ridge origin for the 483 Ma portion of the ophiolite. Igneous activity at 285 Ma is thought to have occurred in an arc or back-arc setting, or perhaps along a leaky transform. The initial _Nd (483)=+10.7 is indistinguishable from that of the similar age Trinity Peridotite (Jacobsen et al. 1984). This value is the highest yet reported for the Mesozoic or Paleozoic depleted mantle and requires either a mantle source that was depleted 850 m.y. earlier than average or a source more highly depleted than average. Alternatively, if such values were more typical of the early Paleozoic mantle than is currently thought, then there has been little evolution of the depleted mantle over the last 500 m.y. This requires that the modern mantle has been refluxed by material with low _Nd, such as continental crust.Division Contribution # 4302 (530)     

Pb and Nd isotope constraints on the origin of high Mg and tholeiitic amphibolites,Kolar Schist Belt,South India

The late Archean, north-south trending Kolar Schist Belt in south India, 4 km wide by 80 km long, is thought to be a suture between two gneiss terranes (Krogstad et al. 1989). Within this volcanics-dominated belt are recognized both tholeiitic and high Mg (komatiitic and picritic) amphibolites, which make up some 70% and 5% respectively of the exposed outcrops. A massive tholeiitic amphibolite separates the belt into western and eastern parts. A Pb-Pb whole-rock age of 2732±155 Ma on samples from a single outcrop of massive tholeiite is a minimum age for this rock. Samples of this rock have _Nd values at 2700 Ma that range between +3.8 and +6.8, ₁ (initial ²³⁸U/²⁰⁴Pb) of 7.5 and K ₁ (initial ²³²Th/²³⁸U) of about 4. Two different types of high-Mg amphibolites are recognized from the western part of the belt: a picritic or P-type, and a komatiitic or K-type. The P-type have highly variable Ce/Al ratios all greater than chondritic, Nd/Yb ratios greater than chondritic, _Nd at 2700 Ma of +1.5 to +8, and Pb isotope compositions variable in ²⁰⁷Pb/²⁰⁴Pb with ₁ of about 8.0 and k ₁ of about 4. The trace-element data suggest that the light-REE enrichment is a character of the mantle source and is not due to residual garnet. The K-type amphibolites have near chondritic Ce/Al and Nd/Yb ratios, _Nd at 2700 Ma of +1.5 to +8, and ₁ of about 8 and k ₁ of about 4. Although the P-type is light-REE enriched compared to the K-type, both types have similar Ce/Nd ratios as well as initial Pb and Nd isotopes. If the 2696±136 Ma age for the Sm-Nd isochron which includes both types of high-Mg amphibolite has any significance it dates the time of light-REE enrichment of the mantle source for the P-type komatiitic amphibolites. The high-Mg amphibolites in the eastern part of the belt are light-REE enriched, have Pb isotopic compositions that are variable in ²⁰⁷Pb/²⁰⁴Pb with a ₁ about 8.5 and _Nd at 2700 Ma of +1.8 to +4.5. Hydrothermal fluids associated with metamorphism and shearing prior to about 2400 Ma ago were responsible for the introduction of gold-quartz-carbonate veins into the Kolar Schist Belt. The Pb isotope composition of galena in these veins suggests that these fluids may have also introduced extraneous Pb from adjacent older granitoid gneisses into the amphibolites, which could be responsible for the variability in the ²⁰⁷Pb/²⁰⁴Pb ratios of the samples. This extraneous Pb probably is not responsible for the distinct Pb isotope character of each type of amphibolite.     

Origin and regional significance of late Precambrian and early Palaeozoic granitoids in the Pan-African belt of Somalia

Granitoids within the Precambrian basement of north-eastern and southern Somalia are subdivided on the basis of geology, geochronology and petrology into three different assemblages. The post-kinematic assemblage in north-eastern Somalia ( 630 Ma) comprises granodiorites and granites which belong to a medium-K calc-alkaline suite. Average initial Sr, Nd and Pb isotopic ratios [Sr_i = 0.7048, _Nd = –1.8,²⁰⁶Pb/²⁰⁴Pb(i) = 17.704 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.611] indicate that these melts were derived from a mantle or juvenile crustal source with only slight involvement of pre-existing crust as a contaminant. Two different assemblages are found in southern Somalia. The older assemblage is composed of crustal anatectic, synkinematic, parautochthonous granites ( 600 Ma) related to amphibolite facies retrogression of an intensively reworked pre-Pan-African crust [Sr_i = 0.7100, _Nd = –8.4,²⁰⁶Pb/²⁰⁴Pb(i) = 15.403 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.259]. These monzo- and syenogranites are moderately potassic and peraluminous. The younger assemblage ( 470 Ma) consists of post-kinematic monzonites to syenogranites with A-type affinities. Initial Sr, Nd and Pb isotopic data for this metaluminous assemblage [Sr_i = 0.7114, _Nd = –13.1,²⁰⁷Pb/²⁰⁴Pb(i) = 16.913 and²⁰⁷Pb/²⁰⁴Pb(i) = 15.512] indicate a significant lower crustal component but, however, also a mantle signature. The late Proterozoic to early Palaeozoic granitoids in Somalia thus express contrasting regimes, characterized by strong juvenile input in the north, close to the Arabian-Nubian Shield, whereas intense crustal reworking with little addition of juvenile material prevailed in the south. Somalia was definitively not a cratonic area during the Pan-African, but a zone of high crustal mobility.     

Cell parameters of thermally treated anorthite. Al,Si configurations in the average structures of the high temperature calcic plagioclases

Thermal treatments of anorthite carried out at up to 1,547° C show that the unit cell parameter changes as a function of the treatment temperature. The best fit curve found by non-linear least squares analysis is: =91.419-(0.327·10^-6)T ²+(0.199·10^-12)T ⁴-(0.391·10)T ⁶. The results obtained support significant Al,Si disorder (Al0.10, where Al=t ₁(0)-1/3 [t ₁(m)+t ₂(0)+t ₂(m)], Ribbe 1975), in anorthite equilibrated near the melting point and confirm a high temperature series differentiated from the low temperature series for calcic plagioclases in the An₈₅–An₁₀₀ range also. In the plot vs. An-content the high and low temperature curves intersect at An₈₅ composition and progressively diverge in the An₈₅–An₁₀₀ range. The trends of the high and low temperature curves in this range are interpretable on the basis of the degree of Al, Si order in the average structures of calcic plagioclases.     

Trace-element and Sr,Nd, Pb,and O isotopic composition of Pliocene and Quaternary alkali basalts of the Patagonian Plateau lavas of southernmost South America

The Pliocene and Quaternary Patagonian alkali basalts of southernmost South America can be divided into two groups. The cratonic basalts erupted in areas of Cenozoic plateau volcanism and continental sedimentation and show considerable variation in ⁸⁷Sr/⁸⁶Sr (0.70316 to 0.70512), ¹⁴³Nd/¹⁴⁴Nd (_Nd) and ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios (18.26 to 19.38, 15.53 to 15.68, and 38.30 to 39.23, respectively). These isotopic values are within the range of oceanic island basalts, as are the Ba/La, Ba/Nb, La/Nb, K/Rb, and Cs/Rb ratios of the cratonic basalts. In contrast, the transitional basalts, erupted along the western edge of the outcrop belt of the Pliocene and Quaternary plateau lavas in areas that were the locus of earlier Cenozoic Andean orogenic arc colcanism, have a much more restricted range of isotopic composition which can be approximated by ⁸⁷Sr/⁸⁶Sr=0.7039±0.0004, _Nd, ²⁰⁶Pb/²⁰⁴Pb=18.60±0.08, ²⁰⁷Pb/²⁰⁴Pb=15.60±0.01, and ²⁰⁸Pb/²⁰⁴Pb=38.50±0.10. These isotopic values are similar to those of Andean orogenic are basalts and, compared to the cratonic basalts, are displaced to higher ⁸⁷Sr/⁸⁶Sr at a given ¹⁴³Nd/¹⁴⁴Nd and to higher ²⁰⁷Pb/²⁰⁴Pb at a given ²⁰⁸Pb/²⁰⁴Pb. The transitional basalts also have Ba/La, Ba/Nb, La/Nb, and Cs/Rb ratios higher than the cratonic and oceanic island basalts, although not as high as Andean orogenic are basalts. In contrast to the radiogenic isotopes, ¹⁸O values for both groups of the Patagonian alkali basalts are indistinguishable and are more restricted than the range reported for Andean orogenic are basalts. Whole rock ¹⁸O values calculated from mineral separates for both groups range from 5.3 to 6.5, while measured whole rock ¹⁸O values range from 5.1 to 7.8. The trace element and isotopic data suggest that decreasing degrees of partial melting in association with lessened significance of subducted slabderived components are fundamental factors in the west to east transition from arc to back-arc volcanism in southern South America. The cratonic basalts do not contain the slab-derived components that impart the higher Ba/La, Ba/Nb, La/Nb, Cs/Rb, ⁸⁷Sr/⁸⁶Sr at a given ¹⁴³Nd/¹⁴⁴Nd, ²⁰⁷Pb/²⁰⁴Pb at a given ²⁰⁸Pb/²⁰⁴Pb, and ¹⁸O to Andean orogenic arc basalts. Instead, these basalts are formed by relatively low degrees of partial melting of heterogeneous lower continental lithosphere and/or asthenosphere, probably due to thermal and mechanical pertubation of the mantle in response to subduction of oceanic lithosphere below the western margin of the continent. The transitional basalts do contain components added to their source region by either (1) active input of slab-derived components in amounts smaller than the contribution to the mantle below the arc and/or with lower Ba/La, Ba/Nb, La/Nb, and Cs/Rb ratios than below the arc due to progressive downdip dehydration of the subducted slab; or (2) subarc source region contamination processes which affected the mantle source of the transitional basalts earlier in the Cenozoic.     

Sm−Nd and Pb isotopic study of mafic rocks associated with early Proterozoic continental rifting: the Peröpohja schist belt in northern Finland

The Peräpohja schist belt in northern Finland rests unconformably on Archaean granitoids, and marks the early stages of Proterozoic crustal evolution in the Fennoscandian (Baltic) shield. 2440 Ma old layered mafic intrusions predate the supracrustal , and ca. 2200 Ma old sills of the gabbro-wehrlite association intrude the lowest quartzites and volcanics (Runkaus) of the sequence. The Sm-Nd mineral isochron of the Penikat layered intrusion gives an age of 2410±64 Ma. The initial _Nd-values of the Penikat intrusion (_Nd(2440) = –1.6) and the Runkausvaara sill (_Nd(2200) 0) suggest that these mafic magmas were contaminated by older crustal material. The Sm-Nd and Pb isotopic results on the 2.44–2.2 Ga old Runkaus volcanics indicate mobility of Pb, fractionation of Sm/Nd during late greenschist facies metamorphism, and crustal contamination. The Pb-Pb data provide an age of 1972±80 Ma with a high initial ²⁰⁷Pb/²⁰⁴Pb ratio (₁ = 8.49), while scattered Sm-Nd data result in an imprecise age of 2330±180 Ma, with an initial _Nd-value of about zero. Secondary titanite gives an U-Pb age of ca. 2250 Ma. The Jouttiaapa basalts, in contrast, ascended from the mantle without interaction with older crust. These LREE depleted tholeiites mark a break in continental sedimentation, and yield a Sm-Nd age of 2090±70 Ma. Their initial _Nd = + 4.2 ±0.5 implies that the subcontinental early Proterozoic mantle had been depleted in LREE for a long period of time. The first lava flows are strongly depleted in LREE, suggesting that their source was significantly more depleted than the source of mid-ocean ridge basalts today.     

H,O, Sr,Nd, and Pb isotope geochemistry of the Latir volcanic field and cogenetic intrusions,New Mexico,and relations between evolution of a continental magmatic center and modifications of the lithosphere

Over 200 H, O, Sr, Nd, and Pb isotope analyses, in addition to geologic and petrologic constraints, document the magmatic evolution of the 28.5–19 Ma Latir volcanic field and associated intrusive rocks, which includes multiple stages of crustal assimilation, magma mixing, protracted crystallization, and open- and closed-system evolution in the upper crust. In contrast to data from younger volcanic centers in northern New Mexico, relatively low and restricted primary ¹⁸O values (+6.4 to +7.4) rule out assimilation of supracrustal rocks enriched in ¹⁸O. Initial ⁸⁷Sr/⁸⁶Sr ratios (0.705 to 0.708), ¹⁸O values (-2 to-7), and ²⁰⁶Pb/²⁰⁴Pb ratios (17.5 to 18.4) of metaluminous precaldera volcanic rocks and postcaldera plutonic rocks suggest that most Latir rocks were generated by fractional crystallization of substantial volumes of mantle-derived basaltic magma that had near-chondritic Nd isotope ratios, accompanied by assimilation of crustal material in two main stages: 1) assimilation of non-radiogenic lower crust, followed by 2) assimilation of middle and upper crust by inter-mediate-composition magmas that had been contaminated during the first stage. Magmatic evolution in the upper crust peaked with eruption of the peralkaline Amalia Tuff (26 Ma), which evolved from metaluminous parental magmas. A third stage of late, roofward assimilation of Proterozoic rocks in the Amalia Tuff magma is indicated by trends in initial ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb ratios from 0.7057 to 0.7098 and 19.5 to 18.8, respectively, toward the top of the pre-eruptive magma chamber. Highly evolved postcaldera plutons are generally fine grained and are zoned in initial ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb ratios, varying from 0.705 to 0.709 and 17.8 to 18.6, respectively. In contrast, the coarser-grained Cabresto Lake (25 Ma) and Rio Hondo (21 Ma) plutons have relatively homogeneous initial ⁸⁷Sr/⁸⁶Sr and ²⁰⁶Pb/²⁰⁴Pb ratios of approximately 0.7053 and 17.94 and 17.55, respectively. ¹⁸O values for all the postcaldera plutons overlap those of the precaldera rocks and Amalia Tuff, except for those for two late-stage rhyolite dikes associated with the Rio Hondo pluton that have ¹⁸O values of-8.6 and-9.5; these dikes are the only Latir rocks which may be largely crustal melts.Chemical and isotopic data from the Latir field suggest that large fluxes of mantle-derived basaltic magma are necessary for developing and sustaining large-volume volcanic centers. Development of a detailed model suggests that 6–15 km of new crust may have been added beneath the volcanic center; such an addition may result in significant changes in the chemical and Sr and Nd isotopic compositions of the crust, although Pb isotope ratios will remain relatively unchanged. If accompanied by assimilation, crystallization of pooled basaltic magma near the MOHO may produce substantial cumulates beneath the MOHO that generate large changes in the isotopic composition of the upper mantle. The Latir field may be similar to other large-volume, long-lived intracratonal volcanic fields that fundamentally owe their origins to extensive injection of basaltic magma into the lower parts of their magmatic systems. Such fields may overlie areas of significant crustal growth and hybridization.     

Lead isotope study of Zn-Pb ore deposits associated with the Basque-Cantabrian basin and Paleozoic basement, Northern Spain

A total of forty-three galena samples from syngenetic and epigenetic Pb-Zn mineralizations emplaced in the Lower Cretaceous Basque-Cantabrian basin and Paleozoic basement of the Cinco Villas massif in the western Pyrenees, have been analyzed for Pb-isotopic composition. Galena from sedex mineralizations hosted in Carboniferous clastic rocks in the Cinco Villas massif display an homogeneous lead isotopic signature (²⁰⁶Pb/²⁰⁴4Pb 18.43, ²⁰⁷Pb/²⁰⁴Pb 15.66, ²⁰⁸Pb/ ²⁰⁴Pb 38.69) suggesting a single lead reservoir. These values are slightly more radiogenic than lead from other European Hercynian deposits, possibly reflecting the influence of a more evolved upper crustal source. Underlying Paleozoic sediments are proposed as lead source for the Cinco Villas massif ores. Analyses from twenty-six galena samples from the four strata-bound ore districts hosted in Mesozoic rocks reveal the existence of two populations regarding their lead isotopic composition. Galena from the western Santander districts (e.g., Reocin) is characterized by more radiogenic isotope values (²⁰⁶Pb/²⁰⁴Pb 18.74, ²⁰⁷Pb/²⁰⁴Pb 15.67, ²⁰⁸Pb/ ²⁰⁴Pb 38.73) than those from the central and eastern districts (Troya-Legorreta, Central and Western Vizcaya, ²⁰⁶Pb/²⁰⁴Pb 18.59, ²⁰⁷Pb/²⁰⁴Pb 15.66, ²⁰⁸Pb/ ²⁰⁴Pb 38.73). In all districts, the most likely source for these mineralizations was the thick sequence of Lower Cretaceous clastic sediments. The existence of two separate lead isotopic populations could be the result of regional difference in the composition of the basement rocks and the clastic sediments derived of it or different evolution histories. In both sub-basins, isotopic ratios indicate an increase in crustal influence as the age of the ores decreases.     

Latest precambrian (Cadomian) zircon ages,Nd isotopic systematics and P-T evolution of granitoid orthogneisses of the Erzgebirge,Saxony and Czech Republic

Single zircons from two orthogneiss complexes, the Grey Gneiss and Red Gneiss, the lowermost tectonic units in the Erzgebirge, were dated. The grey Freiberg Gneiss is of igneous origin and has a ²⁰⁷Pb/²⁰⁶Pb emplacement age of 550±7 Ma. A quartz monzonite from Lauenstein contains idiomorphic zircons with a mean ²⁰⁷Pb/²⁰⁶Pb age of 555±7 Ma as well as xenocrysts ranging in age between 850 and 1910 Ma. Red gneisses from the central Erzgebirge contain complex zircon populations, including numerous xenocrysts up to 2464 Ma in age. The youngest, idiomorphic, zircons in all samples yielded uniform ²⁰⁷Pb/²⁰⁶Pb ages between 550±9 and 554±10 Ma. Nd isotopic data support the interpretation of crustal anatexis for the origin of both units. _Nd(t) values for the grey gneisses are –7.5 and –6.0 respectively, (mean crustal residence ages of 1.7–1.8 Ga). The red gneisses have a wider range in _Nd(t) values from –7.7 to –2.8 (T _DM ages of 1.4–1.8 Ga). The zircon ages document a distinct late Proterozoic phase of granitoid magmatism, similar in age to granitoids in the Lusatian block farther north-east. However, Palaeozoic deformation as well as medium pressure metamorphism ( 8 kbar/600–650° C) are identical in both gneiss units and distinguish these rocks from the Lusatian granitoids. The grey and red gneisses were overthrust by units with abundant high-pressure relicts and a contrasting P-T evolution. Zircon xenocryst and Nd model ages in the range 1000–1700 Ma are similar to those in granitoid rocks of Lusatia and the West-Sudetes, and document a pre-Cadomian basement in parts of east-central Europe that, chronologically, has similarities with the Sveconorwegian domain in the Baltic Shield.     

U-Pb and Pb-Pb zircon dating of the older orthogneiss suite in the Silvretta nappe,eastern Alps: Cadomian magmatism in the upper Austro-Alpine realm

Two orthogneiss suites dominate the Silvretta nappe. Primary crystallization of the larger suite (younger orthogneisses) is assumed to be Ordovician in age. The second, adjacent magmatic suite consists of older, alkaline to calc-alkaline, ultrabasic, basic to intermediate and granitic rocks known as older orthogneisses. U-Pb data of multigrain zircon fractions, as well as single zircon stepwise evaporation ²⁰⁷Pb/²⁰⁶Pb results suggest a latest Proterozoic to early Cambrian intrusion age for the protoliths of the older orthogneisses as both dating methods yield early Cambrian crystallization ages of 526±7 and 519±7 Ma for an alkaline granite gneiss; similar results were obtained for two neighbouring calc-alkaline orthogneisses (²⁰⁷Pb/²⁰⁶Pb ages of 533 ± 4 and 568 ± 6 Ma, respectively). The crystal habitus corresponds to P5, S19 and S9 zircons of magmatic origin. Whole-rock initial Sr isotope ratios indicate a primitive source. The igneous protoliths of these older orthogneisses represent a fragment of a Cadomian (Pan-African) crust found in places within the basement of the European Hercynides.     

Unilateral ARMA processes on a square net by the herringbone method

Because multidimensional ARMA processes have great potential for the simulation of geological parameters such as aquifer permeability, it was important to resolve which of two proposed alternative methods should be used for determining the two-dimensional weighting parameter, , for a unilateral ARMA (1, 0) process on a square net. Practical simulations demonstrates that the correct formulation is: =₁₀/(1+ ₁₀ ² where _r,s is the correlation between lattice points at lagsr and s. When the simulations are performed with correlations of 0.8 or more a residual bias was detected which was found to be caused by a difference in the variance between the one- and two-dimensional models. This can be rectified by modifying the two- dimensional model as follows: z_ij=(z_{i–1, j} + z_{i, j–1}) + a_ij where ²=1/(1 + ₁₀ ² ).     

Sargipali galenas: Unusual lead-isotope data from eastern India

The Sargipali sulphide deposit, hosted by a sequence of metasediments of the Precambrian Gangpur Series, represents the stratiform and stratabound Pb-Cu mineralization. Lead-isotope analyses obtained from six galena samples of different forms and stratigraphical levels, yielded a model Pb age of 1665 Ma, which predates the episodes of deformation and metamorphism ( 850 Ma) as well as syn-to late-tectonic magmatism. The model Pb age, on the contrary, shows a relationship to the closing phase of the Gangpur sedimentation (1700 Ma) in a shallow-water marine environment. The notable paucity of the interlayered volcanic rock in the deposit and its Pb-rich nature possibly point to its being the sedimentary exhalative (SEDEX) type. Documentary evidence for the Pb component from the geological environment of the upper continental crust is revealed by an exceptionally high (= ²³⁸U/²⁰⁴Pb) and the slightly above average W(= ²³²Th/²³⁸U) values. These indicate that the source rock was initially rich in U-Th-Pb concentration. For the Sargipali ore Pb, the parent is assumed to be late Archean-lower Proterozoic soda granite.     

Electrical conductivity,thermopower and <Superscript>57</Superscript>Fe Mössbauer spectroscopy of aegirine (NaFeSi<Subscript>2</Subscript>O<Subscript>6</Subscript>)

DC and AC electrical conductivities were measured on samples of two different crystals of the mineral aegirine (NaFeSi₂O₆) parallel () and perpendicular () to the [001] direction of the clinopyroxene structure between 200 and 600 K. Impedance spectroscopy was applied (20 Hz–1 MHz) and the bulk DC conductivity _DC was determined by extrapolating AC data to zero frequency. In both directions, the log _DC – 1/T curves bend slightly. In the high- and low-temperature limits, differential activation energies were derived for measurements [001] of E_A 0.45 and 0.35 eV, respectively, and the numbers [001] are very similar. The value of _DC [001] with _DC(300 K) 2.0 × 10^{–6 –1}cm^–1 is by a factor of 2–10 above that measured [001], depending on temperature, which means anisotropic charge transport. Below 350 K, the AC conductivity () (/2=frequency) is enhanced relative to _DC for both directions with an increasing difference for rising frequencies on lowering the temperature. An approximate power law for () is noted at higher frequencies and low temperatures with () ^s, which is frequently observed on amorphous and disordered semiconductors. Scaling of () data is possible with reference to _DC, which results in a quasi-universal curve for different temperatures. An attempt was made to discuss DC and AC results in the light of theoretical models of hopping charge transport and of a possible Fe²⁺ Fe³⁺ electron hopping mechanism. The thermopower (Seebeck effect) in the temperature range 360 K < T <770 K is negative in both directions. There is a linear – 1/T relationship above 400 K with activation energy E 0.030 eV [001] and 0.070 eV [001]. ⁵⁷Fe Mössbauer spectroscopy was applied to detect Fe²⁺ in addition to the dominating concentration of Fe³⁺.     

U-Pb age and lead isotopic characterization of Au-bearing skarn related to the Andorra granite (central Pyrenees,Spain)

Auriferous skarns are associated with post- and late-kinematic Hercynian granites that intruded into Cambro-Ordovician to Devonian sediments of the central Pyrenees. We determined the age of the Andorra granite and the associated skarn at 305 ± 3 Ma by U-Pb dating titanite from the endo-skarn. The sulfur isotopic composition from sulfides in the skarn (Cardellach et al. 1992) shows a significant variation with isotopically light sulfur (³⁴S +3) in the barren skarns and heavy sulfur (³⁴S +11) in the gold-bearing skarns. Outwards, it increasingly resembles sulfur from arsenopyrite disseminations in the Cambro-Ordovician sediments. The lead isotopic composition from sulfides of the skarns is very homogeneous (²⁰⁶Pb/²⁰⁴Pb = 18.410, ²⁰⁷Pb/²⁰⁴Pb = 15.699, ²⁰⁸Pb/²⁰⁴Pb = 38.574) in contrast to the one in gold-bearing arsenopyrite veins and in arsenopyrite disseminations in the sediments (e.g. ²⁰⁶Pb/²⁰⁴Pb varies from 18.54 to 30.36). Combined, sulfur and lead isotope data indicate that the lead in the skarn is dominantly derived from the granite, whereas the sulfur is derived at variable portions from both the granite and the sediments.     

Changes in stable isotope ratios of metapelites and marbles during regional metamorphism,Mount Lofty Ranges,South Australia: implications for crustal scale fluid flow

The Mount Lofty Ranges comprises interlayered marbles, metapsammites, and metapelites that underwent regional metamorphism during the Delamarian Orogeny at 470–515 Ma. Peak metamorphic conditions increased from lowermost biotite grade (350–400°C) to migmatite grade (700°C) over 50–55 km parallel to the lithological strike of the rocks. With increasing metamorphic grade, ¹⁸O values of normal metapelites decrease from 14–16 to as low as 9.0, while ¹⁸O values of calcite in normal marbles decrease from 22–24 to as low as 13.2 These isotopic changes are far greater than can be accounted for by devolatilisation, implying widespread fluid-rock interaction. Contact metamorphism appears not to have affected the terrain, suggesting that fluid flow occurred during regional metamorphism. Down-temperature fluid flow from synmetamorphic granite plutons (¹⁸O=8.4–8.6) that occur at the highest metamorphic grades is unlikely to explain the resetting of oxygen isotopes because: (a) there is a paucity of skarns at granite-metasediment contacts; (b) the marbles generally do not contain low-XCO₂ mineral assemblages; (c) there is insufficient granite to provide the required volumes of water; (d) the marbles and metapelites retain a several permil difference in ¹⁸O values, even at high metamorphic grades. The oxygen isotope resetting may be accounted for by along-strike up-temperature fluid flow during regional metamorphism with time-integrated fluid fluxes of up to 5x10⁹ moles/m² (10⁵ m³/m²). If fluid flow occurred over 10⁵–10⁶ years, estimated intrinsic permeabilities are 10^-20 to 10^-16m². Variations in ¹⁸O at individual outcrops suggest that time-integrated fluid fluxes and intrinsic permeabilities may locally have varied by at least an order of magnitude. A general increase in XCO₂ values of marble assemblages with metamorphic grade is also consistent with the up-temperature fluid-flow model. Fluids in the metapelites may have been derived from these rocks by devolatilisation at low metamorphic grades; however, fluids in the marbles were probably derived in part from the surrounding siliceous rocks. The marble-metapelite boundaries preserve steep gradients in both ¹⁸O and XCO₂ values, suggesting that across-strike fluid fluxes were much lower than those parallel to strike. Up-temperature fluid flow may also have formed orthoamphibole rocks and caused melting of the metapelites at high grades.This paper is a contribution to IGCP Project 304 Lower Crustal Processes     

The crystal structure of trigonite,Pb3Mn(AsO3)2(AsO2OH)

Summary The mineral trigonite crystallizes in the monoclinic space groupPn–C _s ² witha ₀=7.26,b ₀=6.78,c ₀=11.09Å; =91.5°,Z=2. The structure was determined from 1250 X-ray intensities collected on an automatic two circle Weissenberg-type diffractometer. The final residual isR=6.5% using anisotropic temperature factors for Pb, Mn and As, and isotropic temperature factors for O.The structure consists of MnO₆ octahedra, sharing all six oxygens with arsenite groups to form a framework. The Pb atoms are attached to this framework with Pb–O distances2.23Å. One oxygen, bound only to an As atom, is interpreted as the donor for a hydrogen bond of 2.75Å.

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Die Kristallstruktur des Trigonits, Pb₃Mn(AsO₃)₂(AsO₂OH)

Zusammenfassung Das Mineral Trigonit kristallisiert monoklin, RaumgruppePn–C _s ² ,a ₀=7,26,b ₀=6,78,c ₀=11,09Å; =91,5°;Z=2. Die Strukturermittlung erfolgte anhand von 1250 Röntgenintensitäten, die auf einem automatischen Zweikreis-Weissenbergdiffraktometer gesammelt wurden. Mit anisotropen Temperaturfaktoren für Pb, Mn und As sowie isotropen für die O-Atome ergibt sich einR-Wert von 6,5%.Die MnO₆-Oktaeder werden über die sechs Sauerstoffe mit Arsenitgruppen zu einem dreidimensionalen Gerüst verknüpft. Über Pb-O-Abstände2,23 Å sind die Pb-Atome in dieses Gerüst eingebaut. Ein Sauerstoff, nur an ein As-Atom gebunden, wird als Donator einer H-Brücke von 2,75 Å interpretiert.

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With 2 Figures     

Pilbara galenas: Precise isotopic assay of the oldest Australian leads; model ages and growth-curve implications

Precise Pb isotopic data are reported for 19 galenas and 2 other minerals from the Archaean Pilbara District of Western Australia. Repeated measurements on the Broken Hill Standard Ore show good agreement with published calibrations from two other laboratories, and an overall 95 percent confidence level within ±0.05 percent per mass unit, whether fractionation correction is by the double-spike procedure or by use of a simple mass-dependent factor. Two stratiform deposits yield the most primitive ratios (²⁰⁶Pb/²⁰⁴Pb=11.89; ²⁰⁷Pb/²⁰⁴Pb=13.69; ²⁰⁸Pb/²⁰⁴Pb=31.79) and model ages in good agreement with the 3.45 Ga age on zircons from volcanics correlatable with the host-rocks. Other minor galena occurrences, with quartz-vein association, appear to be younger, with position along the growth curve surprisingly consistent with the age sequence predicted from field observation. The data also extend the time-range of previously-reported trends in apparent U/Pb of the conceptual Pb source, and reveal new features of the corresponding Th/U systematics: a generally-observable trend in the Archaean of Australia, Southern Africa and West Greenland is that the source Th/U seems significantly higher than is allowed for in any of the current Pb-growth models. In detail, the sample-sample variations in indicated source parameters are in many cases correlatable with the nature of the neighbouring rocks and emphasise that, whereas Pb isotope rations in the galenas of huge deposits may well serve as a convenient sampler of overall trends in the Earth's crust, subeconomic occurrences such as these may reveal valuable information about local variations in U-Th-Pb distribution.     

Non-monotonic chemical and O,Sr, Nd,and Pb isotope zonations and heterogeneity in the mafic- to silicic-composition magma chamber of the Grizzly Peak Tuff,Colorado

Strong compositional zonation of the 34 Ma Grizzly Peak Tuff in west-central Colorado is attended by non-monotonic trends in O, Sr, Nd, and Pb isotope ratios. Fiamme from the tuff cluster in chemical compositions and petrographic characteristics, indicating the magma chamber was not continuously zoned but consisted of at least seven compositional layers. The most mafic magma erupted (57 wt% SiO₂, fiamme group 7) had ¹⁸O= +8.5, initial ⁸⁷Sr/⁸⁶Sr=0.7099, _Nd, and ²⁰⁶Pb/²⁰⁴Pb=17.80, suggesting that the magma was produced by 50% fractional crystallization of basaltic magma that assimilated 20 to 40 wt% Proterozoic crust. Isotopic compositions of more evolved parts of the chamber (up to 77 wt% SiO₂, fiamme group 1) depart from the mafic base-level composition of fiamme group 7, and reflect late-stage assimilation that occurred largely after compositional layering was established. ¹⁸O values decrease by as much as 1.5 from fiamme groups 7 through 4, indicating assimilation of hydrothermally altered roof rocks. ¹⁸O values abruptly inerease by up to 1.5 between fiamme groups 4 and 3. This discontinuity is interpreted to reflect evolution in an asymmetric chamber that had a split-level roof, allowing assimilation of wall rocks that varied vertically in degree of hydrothermal alteration. This chamber geometry is also supported by collapse structures in the caldera. Late-stage assimilation of heterogeneous wall rocks is also indicated by variations in Sr, Nd, and Pb isotope ratios. Large Sr isotope disequilibrium exists between some phenocrysts and whole-rock fiamme, and initial ⁸⁷Sr/⁸⁶Sr ratios in phenocrysts are as high as 0.7170. values regularly increase from-13.0 in fiamme group 7 to-11.3 in fiamme group 3, and then decrease to-12.2 in fiamme group 1. ²⁰⁶Pb/²⁰⁴Pb ratios generally increase from 17.80 to 17.94 for fiamme groups 7 through 1. The rhyolitic parts of the Grizzly Peak Tuff have isotopic compositions that could be attributed to a purely crustal melt. It is unlikely, however, that the mafic parts of the tuff were generated by crustal melting, and the compositional and isotopic variations across the entire zonation of the tuff are best explained by fractional crystallization of mantle-derived magmas, accompanied by extensive assimilation of Proterozoic crust.     

Possible non-equilibrium oxygen isotope effects in mantle nodules,an alternative to the Kyser-O'Neil-Carmichael18O/16O geothermometer

Kyser, O'Neil, and Carmichael (1981, 1982) measured the ¹⁸O values of coexisting minerals from peridotite nodules in alkali basalts and kimberlites, interpreting the nodules as equilibrium assemblages. Using Ca-Mg-Fe element-partition geothermometric data, they proposed an empirical¹⁸O/¹⁶O geothermometer: T(°C)=1,151–173–68 ², where is the per mil pyroxene-olivine fractionation. However, this geothermometer has an unusual crossover at 1,150 °C, and in contrast to what might be expected during closed-system equilibrium exchange, the most abundant mineral in the nodules (olivine) shows a much greater range in ¹⁸O (+4.4 to +7.5) than the much less abundant pyroxene (all 50 pyroxene analyses from spinel peridotites lie within the interval +5.3 to +6.5). On ¹⁸O-olivinevs. ¹⁸O-pyroxene diagrams, the mantle nodules exhibit data arrays that cut across the ¹⁸O=zero line. These arrays strongly resemble the non-equilibrium quartzfeldspar and feldspar-pyroxene ¹⁸O arrays that we now know are diagnostic of hydrothermally altered plutonic igneous rocks. Thus, we have re-interpreted the Kyser et al. data as non-equilibrium phenomena, casting doubt on their empirical geothermometer. The peridotite nodules appear to have been open systems that underwent metasomatic exchange with an external, oxygen-bearing fluid (CO₂, magma, H₂O, etc.); during this event, the relatively inert pyroxenes exchanged at a much slower rate than did the coexisting olivines and spinels, in agreement with available exchange-rate and diffusion measurements on these minerals. This accounts for the correlation between ¹⁸O pyroxene-olivine and the whole-rock ¹⁸O of the peridotites, which is a major difficulty with the equilibrium interpretation.Contribution No. 3978, Publications of the Division of Geological and Planetary Sciences, California Institute of Technology     

Whole-grain evaporation for 207Pb/206Pb-age-investigations on single zircons using a double-filament thermal ion source

A technique has been developed and tested to analyse ²⁰⁷Pb/²⁰⁶Pb apparent ages by thermal evaporation of radiogenic lead directly from untreated whole zircon grains (0.3 mm). The evaporation analyses are performed in the double-filament arrangement of a thermal ion mass spectrometer (ThIMS). The method is a powerful tool to distinguish between different lead components occurring in the same grain because differing activation energies of the competing lead components cause their sequential evaporation from the zircons. The evaporation of test samples results in ²⁰⁷Pb/²⁰⁶Pb apparent ages in good agreement with U/Pb ages known from literature: single zircons from a granite of the Marble Mountains/California yield an age of crystallization of 1,410±30 Ma; Ceylon zircons from heavy-mineral bearing gravels yield 560± 40 Ma as age of crystallization of the pegmatitic gravel sources; individuals from a heterogeneous zircon population of a diatexite from the Southern Schwarzwald/SW-Germany indicate metamorphic zircon formation around 500 Ma and the existence of Middle-Proterozoic relics (1.95±0.05 Ga).The evaporation analyses revealed closed-system U/Pb evolution of the crystalline domains of all investigated zircons irrespective of discordancy-trends documented by U/Pb analyses on related zircon concentrates. Therefore the majority of discordia-lines derived from U/Pb isotope distributions of zircon samples are supposed to be due to phase mixing. Lead components from the crystalline domains are concordant end members of the mixing arrays. Open-system behaviour and U/Pb fractionation should be attributed only to phases with low Pb activation energies eg. metamict zircon domains or intergrown non-zircon minerals.