Lead isotopes of the carbonate-hosted Kabwe, Tsumeb, and Kipushi Pb-Zn-Cu sulphide deposits in relation to Pan African orogenesis in the Damaran-Lufilian Fold Belt of Central Africa

Lead isotope ratios of galena from the carbonate-hosted massive sulphide deposits of Kabwe (Pb-Zn) and Tsumeb (Pb-Zn-Cu) in Zambia and Namibia, respectively, have been measured and found to be homogeneous and characteristic of upper crustal source rocks. Kabwe galena has average isotope ratios of ^206/204Pb = 17.997 ± 0.007, ^207/204Pb = 15.713 ± 0.010 and ^208/204Pb = 38.410 ± 0.033. Tsumeb galena has slightly higher ^206/204Pb (18.112 ± 0.035) and slightly lower ^207/204Pb (15.674 ± 0.016) and ^208/204Pb (38.276 ± 0.073) ratios than Kabwe galena. The isotopic differences are attributed to local differences in the age and composition of the respective source rocks for Kabwe and Tsumeb. The homogeneity of the ore lead in the two epigenetic deposits suggests lead sources of uniform isotopic composition or, alternatively, thorough mixing of lead derived from sources with relatively similar isotopic compositions. Both deposits have relatively high ²³⁸U/²⁰⁴Pb ratios of 10.31 and 10.09 for Kabwe and Tsumeb galenas, respectively. These isotope ratios are considered to be typical of the upper continental crust in the Damaran-Lufilian orogenic belt, as also indicated by basement rocks and Cu-Co sulphides in stratiform Katangan metasediments which have a mean μ-value of 10.25 ± 0.12 in the Copperbelt region of Zambia and the Democratic Republic of Congo (formerly Zaire). The ²³²Th/²⁰⁴Pb isotope ratios of 43.08 and 40.42 for Kabwe and Tsumeb suggest Th-enriched source regions with ²³²Th/²³⁵U (κ-values) of 4.18 and 4.01, respectively. Model isotopic ages determined for the Kabwe (680 Ma) and Tsumeb (530 Ma) deposits indicate that the timing of the mineralisation was probably related to phases of orogenic activity associated with the Pan-African Lufilian and Damaran orogenies, respectively. Galena from the carbonate-hosted Kipushi Cu-Pb-Zn massive sulphide deposit in the Congo also has homogeneous lead isotope ratios, but its isotopic composition is comparable to that of the average global lead evolution curve for conformable massive sulphide deposits. The μ (9.84) and κ (3.69) values indicate a significant mantle component, and the isotopic age of the Kipushi deposit (456 Ma) suggests that the emplacement of the mineralisation was related to a post-tectonic phase of igneous activity in the Lufilian belt. The isotope ratios (^206/204Pb, ^207/204Pb, ^208/204Pb) of the three deposits are markedly different from the heterogeneous lead ratios of the Katangan Cu-Co stratiform mineralisation of the Copperbelt as well as those of the volcanogenic Nampundwe massive pyrite deposit in the Zambezi belt which typically define radiogenic linear trends on lead-lead plots. The host-rock dolomite of the Kabwe deposit also has homogeneous lead isotope ratios identical to the ore galena. This observation indicates contamination of the Kabwe Dolomite Formation with ore lead during mineralisation. Received: 8 September 1997 / Accepted: 21 August 1998     

Petrogenesis of isotopically unusual Pliocene olivine leucitites from Deep Springs Valley, California

High-K mafic alkalic lavas (5.4 to 3.2 wt% K₂O) from Deep Springs Valley, California define good correlations of increasing incompatible element (e.g., Sr, Zr, Ba, LREE) and compatible element contents (e.g., Ni, Cr) with increasing MgO. Strontium and Nd isotope compositions are also correlated with MgO; ⁸⁷Sr/⁸⁶Sr ratios decrease and ɛ_Nd values increase with decreasing MgO. The Sr and Nd isotope compositions of these lavas are extreme compared to most other continental and oceanic rocks; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7121 to 0.7105 and ɛ_Nd values range from −16.9 to −15.4. Lead isotope ratios are relatively constant, ²⁰⁶Pb/²⁰⁴Pb ∼17.2, ²⁰⁷Pb/²⁰⁴Pb ∼15.5, and ²⁰⁸Pb/²⁰⁴Pb ∼38.6. Depleted mantle model ages calculated using Sr and Nd isotopes imply that the reservoir these lavas were derived from has been distinct from the depleted mantle reservoir since the early Proterozoic. The Sr-Nd-Pb isotope variations of the Deep Springs Valley lavas are unique because they do not plot along either the EM I or EM II arrays. For example, most basalts that have low ɛ_Nd values and unradiogenic ²⁰⁶Pb/²⁰⁴Pb ratios have relatively low ⁸⁷Sr/⁸⁶Sr ratios (the EM I array), whereas basalts with low ɛ_Nd values and high ⁸⁷Sr/⁸⁶Sr ratios have radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios (the EM II array). High-K lavas from Deep Springs Valley have EM II-like Sr and Nd isotope compositions, but EM I-like Pb isotope compositions. A simple method for producing the range of isotopic and major- and trace-element variations in the Deep Springs Valley lavas is by two-component mixing between this unusual K-rich mantle source and a more typical depleted mantle basalt. We favor passage of MORB-like magmas that partially fused and were contaminated by potassic magmas derived from melting high-K mantle veins that were stored in the lithospheric mantle. The origin of the anomalously high ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios and low ɛ_Nd values and ²⁰⁶Pb/²⁰⁴Pb ratios requires addition of an old component with high Rb/Sr and Th/Pb ratios but low Sm/Nd and U/Pb ratios into the mantle source region from which these basalts were derived. This old component may be sediments that were introduced into the mantle, either during Proterozoic subduction, or by foundering of Proterozoic age crust into the mantle at some time prior to eruption of the lavas. Received: 28 February 1997 / Accepted: 9 July 1998     

Formation of a sulfide melt during Alpine metamorphism of the Lengenbach polymetallic sulfide mineralization,Binntal, Switzerland

Massive and well-crystallized Sulfides of Fe, Pb, As, Tl, Ag, Cu and Zn occur in the Lengenbach mineral deposit (Valais, Swiss Alps), located in a low- to medium-grade metamorphosed Triassic dolomite. Inclusions arranged along healed fractures in quartz consist of complex intergrowths of Tl-rich sartorite+tennantite+orpiment and are interpreted as relics of a sulfide melt generated during metamorphism and trapped in a similar way to associated aqueous fluid inclusions. Microprobe analyses of melt inclusions homogenized at 500°C demonstrate a strong enrichment of Tl in the melt phase, consistent with the observed late-stage Tl-enrichment in the deposit. The presence of a sulfide melt is compatible with Alpine metamorphism of the Lengenbach deposit under relatively closed conditions. The unique sulfide mineral assemblage of the Lengenbach deposit can be ascribed to fractional crystallization in a slowly cooling melt-aqueous fluid system during Alpine uplift.     

Transport of Pb and Sr in leaky aquifers of the Bufa del Diente contact metamorphic aureole, north-east Mexico

The Sr and Pb isotopes from the 31.6 ± 0.3 Ma (2σ) old Diente del Bufa alkali syenite, northeastern Mexico, and marbles of its contact aureole were used to trace the sources and the mobility of these metals during hydrothermal activity. Chert layers form aquifers within the marbles. The marbles represent aquitards. During fluid-wallrock reaction, the chert layers developed wollastonite rims. Early wollastonite rims have Sr and Pb isotopic compositions similar to those of their immediate host marbles, which indicates that the isotopic composition of Sr and Pb is initially buffered by the marble. Later wollastonite and other replacement minerals rimming the aquifer have Sr and Pb isotopic compositions that carry with time increasingly larger contributions from the high-salinity magmatic brine. The Sr and Pb contributions from the alkali syenite can be traced isotopically for more than 90 m away from the contact of the intrusion. In contrast, Sr and Pb originating from the alkali syenite are traceable within the marbles only for 3 to 5 cm from the aquifer-marble boundary. This distance is comparable to the spatial distribution of isotopic alterations of C and O implying that Sr and Pb were transported into the marbles through a fluid phase. The isotopic variation of Sr, Pb, C, and O across the aquifer-marble profiles reflects infiltration as a transport mechanism rather than diffusion. Because Sr and Pb are minor components in both the infiltrating fluid and the rock and because their concentrations are strongly affected by the distribution coefficients among the solid phases present, there is little correlation between the isotopic compositions of the trace elements Sr and Pb and those of C and O, which are major components in fluid and rock. Very thin meta-argillite rinds at the outer margin of the aquifer represent residual material after the dissolution of calcite. They are distinctly enriched in Rb, Sr, and U. The Rb and Sr are to some extent residual from the original limestone mineralogy, whereas U is dominantly derived from the magmatic fluid and leaked from the aquifer with the escaping immiscible CO₂-rich H₂O-CO₂ fluid that was produced by decarbonation. The ²³⁸U/²⁰⁴Pb values ranging from 100 to 250 and distinctly lowered Th/U in the meta-argillite rims (1) demonstrate that U was transported with the magmatic fluid along the aquifer and (2) imply that during unmixing of the highly saline magmatic fluid U fractionated into the CO₂-rich H₂O-CO₂ fluid from which it precipitated selectively in the meta-argillite band across the aquifer. Radioautographs demonstrate that the upper meta-argillite rim has 20 to 40 times more U than the lower rim, which implies that 20 to 40 times more CO₂-rich H₂O-CO₂ fluid has left through the upper aquifer contact. Received: 30 September 1997 / Accepted: 15 December 1997     

K-Ar ages and Pb,Sr isotopic characteristics of Cenozoic volcanic rocks in Shandong Province,China

28 samples of Cenozoic volcanic rocks collected from Shandong Province have been dated by K-Ar method. They are mainly Neogene with an age range of 4–19 m. y. The basalts from Linqu and Yishui in west Shandong Province are Miocene and those from Penglai and Qixia in east Shandong Province are Miocene and Pliocene in age. The basalts from Wudi in north Shandong Province are Middle-Early Pleistocene in age. In each area the duration of volcanic eruption was estimated at about 2–3 m. y. Pb and Sr isotopic compositions and U, Th, Pb, Rb, Sr, and major elements in most of the samples were determined. The isotopic compositions are:²⁰⁶Pb/²⁰⁴Pb—16.92-18.48,²⁰⁷Pb/²⁰⁴Pb—15.30-15.59,²⁰⁸Pb/²⁰⁴Pb—37.83-38.54, and (⁸⁷Sr/⁸⁶Sr)_i—0.70327-0.70632. There are some positive or negative linear correlations between²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb, Pb isotopes and Pb content, Pb isotopes and Sr isotopes, and Sr isotopes and other elements. The basaltic rocks from east and west Shandong Province have somewhat differences in isotopic composition and element content. The basalts probably are products of multi-stage evolution of the mantle. They have preserved the primary features of the source, although they were influenced, to some extent, by the contamination of crustal materials.     

Rb-Sr and U-Pb systematics of metasedimentary carbonate rocks: The Paleoproterozoic Kuetsjarvi Formation of the Pechenga Greenstone Belt, Kola Peninsula

The Rb-Sr and U-Pb systematics have been studied in the metasedimentary carbonate rocks from the Paleoproterozoic Kuetsjarvi Formation. Samples were taken from the borehole drilled in the northern zone of the Pechenga Greenstone Belt in the northwestern Kola Peninsula. The carbonate section of the formation is made up of three units (from the bottom to top): (I) dolomite (68 m), (II) calcareous-dolomite (9 m), and (III) clayey calcareous (1 m) ones. Dolomites (Mg/Ca = 0.55–0.61) from the lowermost unit I contain 70.3–111 ppm Sr. Initial ⁸⁷Sr/⁸⁶Sr ratio in them varies within 0.70560–0.70623 and characterizes the primary continental-lacustrine carbonate sediments. Calcareous dolomites (Mg/Ca = 0.39–0.59) and dolomitic limestones of units II and III (Mg/Ca = 0.02–0.36) are enriched in Sr (285–745 and 550–1750 ppm, respectively). Initial ⁸⁷Sr/⁸⁶Sr ratios in these rocks (0.70406–0.70486 and 0.70407–0.70431, respectively) fall within the range typical of the Jatulian seawater, which indicates that the carbonate sediments of two upper units were formed in an open marine basin. Study of dolomites from unit I showed that the Svecofennian metamorphism more significantly affected the U-Pb systems of carbonate rocks as compared to their Rb-Sr systems. In the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram, most data points corresponding to the carbonate constituent of dolomites define isochron with an age of 1900 ± 25 Ma (MSWD = 0.5). The same samples define a positive correlation in the ²⁰⁸Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb plot. Since sedimentary carbonates usually do not contain Th, this correlation points to secondary enrichment of the studied dolomites in Th or thorogenic ²⁰⁸Pb. Hence, the obtained Pb-Pb dating can be regarded as the age of the Svecofennian metamorphic event. Three samples from dolomites of unit I lack any disturbance of the initial U-Th-Pb systematics, but their trend in the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram deviates from the 1900 Ma isochron. Based on these samples, the model U-Pb premetamorphic age of the Kuetsjarvi carbonate sediments is 2075–2100 Ma. This interval is consistent with the age range of the Lomagundi-Jatulian event, which was responsible for the formation of carbonate sediments with high positive δ¹³C values.     

Contrasting Pb isotopes of Archaean and Palaeoproterozoic sulphide mineralisation, Disko Bugt, central West Greenland

Sulphide separates from mineralisation in Archaean and Palaeoproterozoic host rocks of the Disko Bugt area, central West Greenland, have been analysed for trace elements and Pb isotopes. Isotopic compositions of lead from sulphide separates of Archaean supracrustal rocks show wide variations. Archaean semi-massive sulphides and sulphides separated from felsic metavolcanites yield an errorchron age of 2821 +77/−82, with a model μ₁ value of 7.36; this is comparable to the estimated age of the supracrustal rocks. The two most prominent mineralised sites, the Andersen and Eqip prospects, have their own unique Pb isotope pattern; the Andersen prospect is considered to represent the result of an upper crust of Palaeoproterozoic process. The sulphide separates of Palaeoproterozoic epigenetic mineralisation hosted in shear and fault zones in the supracrustal rocks has a common origin, e.g. linked to a metamorphic peak and/or hydrothermal alteration. Gold-bearing samples indicate a local origin for associated sulphides; no regional processes seem to be involved in the formation of the gold occurrences. Received: 17 March 1997 / Accepted: 8 July 1997     

A Study of REE and Pb,Sr and Nd Isotopes in Garnet—Lherzolite Xenoliths from Mingxi,Fujian Province

The REE and Pb, Sr, Nd isotopes in three xenoliths from limburgite and scoria-breccias, including spinel-lherzolite, spinel-garnet-lherzolite and phlogopite-gamet-lherzolite, were analysed. The REE contents of the xenoliths are 1.3 to 3.3 times those of the chondrites with their REE patterns characterized by weak LREE depletion. The¹⁴³Nd/¹⁴⁴Nd values of whole rocks and minerals range from 0.51306 to 0.51345 with εNd=+ 8.2− +15.8,²⁰⁶Pb/²⁰⁴ Pb < 18.673, and²⁰⁷Pb/²⁰⁴Pb < 15.574. All this goes to show that the upper mantle in Mingxi at the depth of 67–82 km is a depleted mantle of MORB type, with⁸⁷Sr/⁸⁶ Sr ratios 0.70237–0.70390. In Nd-Sr diagram the data points of whole rocks are all out of the mantle array, implying that the xenoliths from Mingxi have more radiogenic Sr isotopes than those of the mantle array.     

Pb isotopic constraints on the formation of the Dikulushi Cu–Pb–Zn–Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

Base metal–Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu–Pb–Zn–Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E–W- and NE–SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.07–18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE–SW-oriented faults into a chalcocite-dominated Cu–Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram (²⁰⁶Pb/²⁰⁴Pb = 18.66–23.65; ²⁰⁷Pb/²⁰⁴Pb = 15.72–16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U–Th–Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu–Pb–Zn–Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the ²⁰⁸Pb/²⁰⁴Pb–²⁰⁶Pb/²⁰⁴Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu–Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.     

Metamorphic evolution of the Sesia-Lanzo Zone,Western Alps: time constraints from multi-system geochronology

 The Sesia-Lanzo Zone is a polymetamorphic unit containing Hercynian granulite relics overprinted by eclogite and greenschist facies metamorphism and deformation during the Alpine orogeny. Different parts of the unit record different stages on the P-T-deformation evolution, allowing multi-system isotopic studies to unravel the precise timing of the metamorphic history. New Rb–Sr white mica and U–Pb sphene data constrain the age of eclogite facies metamorphism and deformation to 60–70 Ma. This substantially alters the common view of early- to mid-Cretaceous eclogite facies metamorphism in this unit. The new results are more consistent with the established geotectonic framework for the Alpine orogeny, since they do not require a prolonged period of depressed geothermal gradient at a time when the region was in extension. It is also more concordant with recent studies of other units that demonstrate post-Cretaceous high-pressure metamorphism. Step-heated ⁴⁰Ar–³⁹Ar analysis of phengites yields good plateaux giving ages older than the corresponding Rb–Sr age. Such anomalously high ages indicate the presence of radiogenic argon-rich fluids in the grain boundary network under the fluid/pressure conditions acting during this high-pressure metamorphic event. The U–Pb sphene ages are variable in polymetamorphic rocks, and show inheritance of older Pb or sphene crystals into the high-pressure event. Two monometamorphic assemblages yield concordant ages at 66±1 Ma, reflecting crystallisation of the eclogite facies assemblage. The Gneiss Minuti Complex (GMC) lies structurally below the Eclogitic Micaschists, and its pervasive greenschist facies fabric yields tightly clustered Rb–Sr white mica ages at 38–39 Ma. This greenschist event did not affect the majority of the EMC. The ⁴⁰Ar–³⁹Ar ages of micas formed at this time were very disturbed, whereas micas surviving from an earlier higher pressure assemblage had their ⁴⁰Ar–³⁹Ar system reset. The greenschist event did not strongly affect U–Pb systematics in Hercynian age sphenes, suggesting that the GMC did not uniformly suffer an eclogite facies metamorphism during the Alpine cycle, but was juxtaposed against the EMC later in the orogeny. This model still requires that the locus of deformation and metamorphism (and possibly fluid flux) moved outboard with time, leaving the Sesia-Lanzo basement as a shear-bounded unreactive block within the orogenic wedge. Received: 12 October 1995/Accepted:25 June 1996     

The Proterozoic,albitite-hosted,Valhalla uranium deposit,Queensland, Australia: a description of the alteration assemblage associated with uranium mineralisation in diamond drill hole V39

The Valhalla uranium deposit, located 40 km north of Mount Isa, Queensland, Australia, is an albitite-hosted, Mesoproterozoic U deposit similar to albitite-hosted uranium deposits in the Ukraine, Sweden, Brazil and Guyana. Uranium mineralisation is hosted by a thick package of interbedded fine-grained sandstones, arkoses and gritty siltstones that are bound by metabasalts belonging to the ca. 1,780 Ma Eastern Creek Volcanics in the Western Succession of the Mount Isa basin. Alteration associated with U mineralisation can be divided into an early, main and late stage. The early stage is dominated by laminated and intensely altered rock comprising albite, reibeckite, calcite, (titano)magnetite ± brannerite. The main stage of mineralisation is dominated by brecciated and intensely altered rocks that comprise laminated and intensely altered rock cemented by brannerite, apatite, (uranoan)-zircon, uraninite, anatase, albite, reibeckite, calcite and hematite. The late stage of mineralisation comprises uraninite, red hematite, dolomite, calcite, chlorite, quartz and Pb-, Fe-, Cu-sulfides. Brannerite has U–Pb and Pb–Pb ages that indicate formation between 1,555 and 1,510 Ma, with significant Pb loss evident at ca. 1,200 Ma, coincident with the assemblage of Rodinia. The oldest ages of the brannerite overlap with ⁴⁰Ar/³⁹Ar ages of 1,533 ± 9 Ma and 1,551 ± 7 Ma from early and main-stage reibeckite and are interpreted to represent the timing of formation of the deposit. These ages coincide with the timing of peak metamorphism in the Mount Isa area during the Isan Orogeny. Lithogeochemical assessment of whole rock data that includes mineralised and unmineralised samples from the greater Mount Isa district reveals that mineralisation involved the removal of K, Ba and Si and the addition of Na, Ca, U, V, Zr, P, Sr, F and Y. U/Th ratios indicate that the ore-forming fluid was oxidised, whereas the crystal chemistry of apatite and reibeckite within the ore zone suggests that F⁻ and were important ore-transporting complexes. δ¹⁸O values of co-existing calcite and reibeckite indicate that mineralisation occurred between 340 and 380°C and involved a fluid having δ¹⁸O_fluid values between 6.5 and 8.6‰. Reibeckite δD values reveal that the ore fluid had a δD_fluid value between −98 and −54‰. The mineral assemblages associated with early and main stages of alteration, plus δ¹⁸O_fluid and δD_fluid values, and timing of the U mineralisation are all very similar to those associated with Na–Ca alteration in the Eastern Succession of the Mount Isa basin, where a magmatic fluid is favoured for this style of alteration. However, isotopic data from Valhalla is also consistent with that from the nearby Mount Isa Cu deposit where a basinal brine is proposed for the transport of metals to the deposit. Based on the evidence to hand, the source fluids could have been derived from either or both the metasediments that underlie the Eastern Creek Volcanics or magmatism that is manifest in the Mount Isa area as small pegmatite dykes that intruded during the Isan Orogeny.     

Nature of the crust in Maine,USA: evidence from the Sebago batholith

 Neodymium and lead isotope and elemental data are presented for the Sebago batholith (293±2 Ma), the largest exposed granite in New England. The batholith is lithologically homogeneous, yet internally heterogeneous with respect to rare earth elements (REE) and Nd isotopic composition. Two-mica granites in the southern/central portion of the batholith (group 1) are characterized by REE patterns with uniform shapes [Ce_N/Yb_N (chondrite normalized) = 9.4–19 and Eu/Eu* (Eu anomaly) = 0.27–0.42] and ɛ _Nd(t) = −3.1 to −2.1. Peripheral two-mica granites (group 2), spatially associated with stromatic and schlieric migmatites, have a wider range of total REE contents and patterns with variable shapes (Ce_N/Yb_N = 6.1–67, Eu/Eu* = 0.20–0.46) and ɛ _Nd(t) = −5.6 to −2.8. The heterogeneous REE character of the group 2 granites records the effects of magmatic differentiation that involved monazite. Coarse-grained leucogranites and aplites have kinked REE patterns and low total REE, but have Nd isotope systematics similar to group 2 granites with ɛ _Nd(t) = −5.5 to −4.7. Rare biotite granites have steep REE patterns (Ce_N/Yb_N = 51–61, Eu/Eu* = 0.32–0.84) and ɛ _Nd(t) = −4.6 to −3.8. The two-mica granites have a restricted range in initial Pb isotopic composition (²⁰⁶Pb/²⁰⁴Pb = 18.41–18.75; ²⁰⁷Pb/²⁰⁴Pb = 15.60–15.68; ²⁰⁸Pb/²⁰⁴Pb = 38.21–38.55), requiring and old, high U/Pb (but not Th/U) source component. The Nd isotope data are consistent with magma derivation from two sources: Avalon-like crust (ɛ _Nd>−3), and Central Maine Belt metasedimentary rocks (ɛ _Nd<−4), without material input from the mantle. The variations in isotope systematics and REE patterns are inconsistent with models of disequilibrium melting which involved monazite. Received: 8 December 1995 / Accepted: 29 April 1996     

S,Pb, C and O isotopic compositions and ore genesis of the strata-bound polymetallic sulfide deposits in central Inner Mongolia,China

The strata-bound Cu−Pb−Zn polymetallic sulfide deposits occur in metamorphic rocks of greenschist phase of the middle-upper Proterozoic Langshan Group in central Inner Mongolia. δ³⁴S values for sulfides range from −3.1‰ to +37.3‰, and an apparent difference is noticed between vein sulfides and those in bedded rocks. For example, δ³⁴S values for bedded pyrite range from +10.6‰ to +20.0‰, while those for vein pyrite vary from −3.1‰ to +14.1‰. δ³⁴S of bedded pyrrhotite is in the range +7.9‰–+23.5‰ in comparison with +6.5‰–+17.1‰ for vein pyrrhotite. The wide scatter of δ³⁴S and the enrichment of heavier sulfur indicate that sulfur may have been derived from H₂S as a result of bacterial reduction of sulfates in the sea water. Sulfur isotopic composition also differs from deposit to deposit in this area because of the difference in environment in which they were formed. The mobilization of bedded sulfides in response to regional metamorphism and magmatic intrusion led to the formation of vein sulfides. δ¹⁸O and δ¹³C of ore-bearing rocks and wall rocks are within the range typical of ordinary marine facies, with the exception of lower values for ore-bearing marble at Huogeqi probably due to diopsidization and tremalitization of carbonate rocks. Pb isotopic composition is relatively stable and characterized by lower radio-genetic lead. The age of basement rocks was calculated to be about 23.9 Ma and ore-forming age 7.8 Ma.²⁰⁷Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb plots indicate that Pb may probably be derived from the lower crust or upper mantle. It is believed that the deposits in this region are related to submarine volcanic exhalation superimposed by later regional metamorphism and magmatic intrusion.     

Generation of voluminous silicic magmas and formation of mid-Cenozoic crust beneath north-central Mexico: evidence from ignimbrites,associated lavas,deep crustal granulites,and mantle pyroxenites

 Isotopic and trace element data from mantle and granulite xenoliths are used to estimate the relative contributions of mantle and crustal components to a large ignimbrite, referred to as the upper ignimbrite, that is representative of the voluminous mid-Cenozoic rhyolites of northwestern Mexico. The study also uses data from the volcanic rocks to identify deep crustal xenoliths that are samples of new crust created by the Tertiary magmatism. The isotopic composition of the mantle component is defined by mantle-derived pyroxenites that are interpreted to have precipitated from mid-Cenozoic basaltic magmas. This component has ɛ_Nd≈+1.5, ⁸⁷Sr/⁸⁶Sr≈0.7043 and ²⁰⁶Pb/²⁰⁴Pb≈18.6. Within the upper ignimbrite and associated andesitic and dacitic lavas, initial ⁸⁷Sr/⁸⁶Sr is positively correlated with SiO₂, reaching 0.7164 in the ignimbrite. Initial ²⁰⁶Pb/²⁰⁴Pb ratios also show a positive correlation with silica, whereas ɛ_Nd values have a crude negative correlation, reaching values as low as −2. Of the four isotopically distinct crustal components identified from studies of granulite xenoliths, only the sedimentary protolith of the paragneiss xenoliths can be responsible for the high initial ⁸⁷Sr/⁸⁶Sr of the upper ignimbrite. The Nd, Sr, and Pb isotopic compositions of the upper ignimbrite can be modeled with relatively modest assimilation (≤20%) of the sedimentary component ± Proterozoic granulite. Gabbroic composition granulite xenoliths have distinctive Nd, Sr, and Pb isotope ratios that cluster closely within the range of compositions found in the andesitic and dacitic lavas. These mafic granulites are cumulates, and their protoliths are interpreted to have precipitated from the intermediate to silicic magmas at 32–31 Ma. These mafic cumulate rocks are probably representative of much of the deep crust that formed during mid-Cenozoic magmatism in Mexico. Worldwide xenolith studies suggest that the relatively great depth (≤20 km) at which assimilation-fractional crystallization took place in the intermediate to silicic magma systems of the La Olivina region is the rule rather than the exception. Oligocene ignimbrites of the southwestern United States (SWUS) have substantially lower ɛ_Nd values (e.g. <−6) than the upper ignimbrite and other rhyolites from Mexico. This difference appears to reflect a greater crustal contribution to ignimbrites of the SWUS, perhaps due to a higher temperature of the lower crust prior to the emplacement of the Oligocene basaltic magmas. Received: 16 December 1994 / Accepted: 13 September 1995     

The Paleoproterozoic carbonate-hosted Pering Zn–Pb deposit, South Africa. II: fluid inclusion, fluid chemistry and stable isotope constraints

The Pering deposit is the prime example of Zn–Pb mineralisation hosted by stromatolitic dolostones of the Neoarchean to Paleoproterozoic Transvaal Supergroup. The hydrothermal deposit centers on subvertical breccia pipes that crosscut stromatolitic dolostones of the Reivilo Formation, the lowermost portion of the Campbellrand Subgroup. Four distinct stages of hydrothermal mineralisation are recognised. Early pyritic rock matrix brecciation is followed by collomorphous sphalerite mineralisation with replacive character, which, in turn, is succeeded by coarse grained open-space-infill of sphalerite, galena, sparry dolomite, and quartz. Together, the latter two stages account for ore-grade Zn–Pb mineralisation. The fourth and final paragenetic stage is characterised by open-space-infill by coarse sparry calcite. The present study documents the results of a detailed geochemical study of the Pering deposit, including fluid inclusion microthermometry, fluid chemistry and stable isotope geochemistry of sulphides (δ³⁴S) and carbonate gangue (δ¹³C and δ¹⁸O). Microthermometric fluid inclusion studies carried out on a series of coarsely grained crystalline quartz and sphalerite samples of the latter, open-space-infill stage of the main mineralisation event reveal the presence of three major fluid types: (1) a halite–saturated aqueous fluid H₂O–NaCl–CaCl₂ (>33 wt% NaCl equivalent) brine, (2) low-salinity meteoric fluid (<7 wt% NaCl) and (3) a carbonic CH₄–CO₂–HS⁻ fluid that may be derived from organic material present within the host dolostone. Mixing of these fluids have given rise to variable mixtures (H₂O–CaCl₂–NaCl ±(CH₄–CO₂–HS⁻), 2 to 25 wt% NaCl+CaCl₂). Heterogeneous trapping of the aqueous and carbonic fluids occurred under conditions of immiscibility. Fluid temperature and pressure conditions during mineralisation are determined to be 200–210°C and 1.1–1.4 kbar, corresponding to a depth of mineralisation of 4.1–5.2 km. Chemical analyses of the brine inclusions show them to be dominated by Na and Cl with lesser amounts of Ca, K and SO₄. Fluid ratios of Cl/Br indicate that they originated as halite saturated seawater brines that mixed with lower salinity fluids. Analyses of individual brine inclusions document high concentrations of Zn and Pb (∼1,500 and ∼200 ppm respectively) and identify the brine as responsible for the introduction of base metals. Stable isotope data were acquired for host rock and hydrothermal carbonates (dolomite, calcite) and sulphides (pyrite, sphalerite, galena and chalcopyrite). The ore-forming sulphides show a trend to ³⁴S enrichment from pyrite nodules in the pyritic rock matrix breccia (δ³⁴S = −9.9 to +3.7‰) to paragenetically late chalcopyrite of the main mineralisation event (δ³⁴S = +30.0‰). The observed trend is attributed to Rayleigh fractionation during the complete reduction of sulphate in a restricted reservoir by thermochemical sulphate reduction, and incremental precipitation of the generated sulphide. The initial sulphate reservoir is expected to have had an isotopic signature around 0‰, and may well represent magmatic sulphur, oxidised and leached by the metal-bearing brine. The δ¹⁸O values of successive generations of dolomite, from host dolostone to paragenetically late saddle dolomite follow a consistent trend that yields convincing evidence for extensive water rock interaction at variable fluid–rock ratios. Values of δ¹³C remain virtually unchanged and similar to the host dolostone, thus suggesting insignificant influx of CO₂ during the early and main stages of mineralisation. On the other hand, δ¹³C and δ¹⁸O of post-ore calcite define two distinct clusters that may be attributed to changes in the relative abundance in CH₄ and CO₂ during waning stages of hydrothermal fluid flow.     

Pb-Sr-Nd isotopic compositions and trace element geochemistry of megacrysts and melilitites from the Tertiary Urach volcanic field: source composition of small volume melts under SW Germany

 The Urach volcanic field is unique within the Tertiary–Quaternary European volcanic province (EVP) due to more than 350 tuffaceous diatremes and only sixteen localities with extremely undersaturated olivine melilitite. We report representative Pb-Sr-Nd isotopic compositions and incompatible trace element data for twenty-two pristine augite, Cr-diopside, hornblende, and phlogopite megacryst samples from the diatremes, and seven melilitite whole rocks. The Pb isotopic compositions for melilitites and comagmatic megacrysts have very radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios of 19.4 to 19.9 and plot on the northern hemisphere mantle reference line (NHRL). The data indicate absence of an old crustal component as reflected in the high ²⁰⁷Pb/²⁰⁴Pb ratios of many basalts from the EVP. This inference is supported by ²⁰⁶Pb/²⁰⁴Pb ratios of ∼17.6 to 18.3 and ɛ_Nd of ∼−7.8 to +1.6 for five phlogopite xenocryst samples reflecting a distinct and variably rejuvenated lower Hercynian basement. The ⁸⁷Sr/⁸⁶Sr ratios of 0.7033 to 0.7035 in the comagmatic megacrysts are low relative to their moderately radiogenic Nd isotopic compositions (ɛ_Nd +2.2 to +5.1) and consistent with a long-term source evolution with a low Rb/Sr ratio and depletion in light rare-earth elements (LREE). The melilitite whole-rock data show a similar range in Nd isotopic ratios as determined for the megacrysts but their Sr isotopic compositions are often much more radiogenic due to surface alteration. The REE patterns and incompatible trace element ratios of the melilitites (e.g. Nb/Th, Nb/U, Sr/Nd, P/Nd, Ba/Th, Zr/Hf) are similar to those in ocean island basalts (OIB); negative anomalies for normalized K and Rb concentrations support a concept of melt evolution in the lithospheric mantle. Highly variable Ce/Pb ratios of 29 to 66 are positively correlated with La/Lu, La/K₂O, and Ba/Nd and interpreted to reflect melting in the presence of residual amphibole and phlogopite. The data suggest an origin of the melilitites from a chemical boundary layer very recently enriched by melts from old OIB sources. We suggest that the OIB-like mantle domains represent low-temperature melting heterogeneities in an upwelling asthenosphere under western Europe. Received: 9 March 1995/Accepted: 24 July 1995     

Initial Pb–Sr(–Nd) isotopic heterogeneity in a single allanite–epidote crystal: implications of reaction history for the dating of minerals with low parent-to-daughter ratios

We analyzed 17 fragments from a zoned allanite–epidote crystal (ca 2.2 mm × 4.0 mm), which had formed during different prograde and retrograde stages of ultra high pressure (UHP) and amphibolite facies metamorphism (240–230 Ma, Sulu Belt, E China), for the isotopic composition of Pb, Nd, and Sr and contents of Pb, U, and Th, Sr and Rb, and Nd and Sm. Since most fragments had ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb values less than 1, corrections for in situ Pb growth are small and uncertainties in the recalculation of the Pb isotopic compositions to 240 Ma are insignificant. The recalculated Pb falls on a linear trend in the ²⁰⁶Pb/²⁰⁴Pb vs ²⁰⁷Pb/²⁰⁴Pb diagram with the allanite defining the low–²⁰⁶Pb/²⁰⁴Pb end (17.07) of this trend and the epidote defining its high–²⁰⁶Pb/²⁰⁴Pb end (17.56). The recalculated data scatter in the ²⁰⁶Pb/²⁰⁴Pb vs ²⁰⁸Pb/²⁰⁴Pb diagram, which implies that the initial Pb isotopic variation reflects the involvement of at least three different Pb sources. The low ⁸⁷Rb/⁸⁶Sr values account for a change in ⁸⁷Sr/⁸⁶Sr by in situ ⁸⁷Sr growth of less than 0.0007, which implies that the isotopic heterogeneity of ⁸⁷Sr/⁸⁶Sr (0.70601–0.7200) is a primary feature. The Pb and Sr isotope data unequivocally demonstrate that contributions from different precursor minerals result in initial isotopic heterogeneity in the metamorphic reaction product. It is likely that such an initial isotopic heterogeneity also exists for Nd, but it could not be resolved in the present study. Initially heterogeneous Pb and Sr isotope compositions imply that age differences between core and rim of large crystals may result in the determination of highly arbitrary geological rates, especially for minerals with relatively low parent-to-daughter ratios.     

Arsenic, antimony and other toxic elements in the drinking water of Eastern Thessaly in Greece and its possible effects on human health

Twenty-six groundwater samples were collected from the Eastern Thessaly region and analysed by ICP-ES for these elements: Al, As, P, Pb, Zn, Mn, Fe, Cr, Sb, Cu, Na, Br, Cl, Si, Mg, Ag, Be, Bi, Dy, Er, Eu, Au, Ge, Ho, In, Ir, Os, Pt, Re, Rh, Ru, Lu, Hf, Hg, Tm, Zr and Nb. The objectives of the study were to assess the level of water contamination with respect to the EC and the USEPA health-based drinking water criteria. The geology of the studied area includes schists, amphibolites, marbles of Palaeozoic age, ophiolites, limestones of Triassic and Cretaceous age, Neogene and Quaternary deposits. The element ranges for groundwater samples are: Al 7–56 μg l⁻¹, As 1–125 μg l⁻¹, Br 6–60 μg l⁻¹, Cl 500–25,000 μg l⁻¹, Cr 1–6 μg l⁻¹, Cu 1–15 μg l⁻¹, Fe 10–352 μg l⁻¹, Mg 2,940–40,100 μg l⁻¹, Mn 0–8 μg l⁻¹, Na 3,650–13,740 μg l⁻¹, P 20–48 μg l⁻¹, Pb 0–7 μg l⁻¹, Sb 0–21 μg l⁻¹, Si 3,310–13,240 μg l⁻¹ and Zn 7–994 μg l⁻¹. The results of groundwater analyses from the region of Eastern Thessaly showed elevated concentrations of As and Sb. Factor analysis explained 77.8% of the total variance of the data through five factors. Concentration of Br, Cl, Mg, Na and Si is directly related to the presence of saltwater in the aquifer, so grouping of these variables in factor 1 probably reflects the seawater intrusion. Al, As and Sb are known to form complexes in the environment, so grouping of these elements in factor 2 indicates their similar geochemical behaviour in the environment. The high negative loading of Mn in factor 2 indicates the presence of manganese oxides–hydroxides in the study area. Pb and Zn are associated together in sulphide mineralisation; so grouping of these elements in factor 3 reflects the sulphide mineralization paragenesis in the Melivoia area. P and Cu are associated together in phosphate fertilizers; so grouping of these variables in factor 4 could be related to agricultural practices. Cr, Fe, Mn and Mg are associated together in iron and manganese oxides–hydroxides and the weathering products of the olivine of the ultrabasic rocks; so grouping of these elements in factor 5 reflects the lithology of the area. There is a natural contamination of groundwaters with elevated concentrations of As and Sb due to the presence of the arsenopyrite and stibnite mineralisation in the Melivoia, Sotiritsa and Ano Polydendri areas. Contamination over the health-based drinking water guidelines given by EC and EPA has been investigated from nine sampling sites out of 26 of Eastern Thessaly region.     

Nd, Pb, and Sr isotope composition of juvenile magmatism in the Mesozoic large magmatic province of northern Chile (18–27°S): indications for a uniform subarc mantle

The Jurassic to Early Cretaceous magmatic arc of the Andes in northern Chile was a site of major additions of juvenile magmas from the subarc mantle to the continental crust. The combined effect of extension and a near stationary position of the Jurassic to lower Cretaceous arc favoured the emplacement and preservation of juvenile magmatic rocks on a large vertical and horizontal scale. Chemical and Sr, Nd, and Pb isotopic compositions of mainly mafic to intermediate volcanic and intrusive rock units coherently indicate the generation of the magmas in a subduction regime and the dominance of a depleted subarc mantle source over contributions of the ambient Palaeozoic crust. The isotopic composition of the Jurassic (²⁰⁶Pb/²⁰⁴Pb: ∼ 18.2; ²⁰⁷Pb/²⁰⁴Pb: ∼ 15.55; ¹⁴³Nd/¹⁴⁴Nd: ∼ 0.51277; ⁸⁷Sr/⁸⁶Sr: ∼ 0.703–0.704) and Present (²⁰⁶Pb/²⁰⁴Pb: ∼ 18.5; ²⁰⁷Pb/²⁰⁴Pb: ∼ 15.57; 143Nd/144Nd: ∼ 0.51288; ⁸⁷Sr/⁸⁶Sr: ∼ 0.703–0.704) depleted subarc mantle beneath the Central and Southern Andes (18°–40°S) was likely uniform over the entire region. Small differences of isotope ratios between Jurassic and Cenozoic to Recent of subarc mantle-derived could be explained by radiogenic growth in a still uniform mantle source.Electronic Supplementary Material Supplementary material is available to authorised users in the online version of this article at .     

Groundwater in the Broken Hill region,Australia: recognising interaction with bedrock and mineralisation using S,Sr and Pb isotopes

The supergiant Pb–Zn–Ag Broken Hill orebody and numerous other minor mineral deposits occur within the limited outcrop of the Proterozoic Curnamona Province of Australia. The vast majority of this Province is concealed by up to 200 m of transported regolith, hampering conventional exploration strategies. Approximately 300 groundwater samples were collected over the southern Curnamona Province to test whether this medium could be helpful in the search for hidden mineral deposits. Sulphur, Sr and Pb isotope composition of the groundwaters were determined and S excess (S_XS), i.e., the amount of S that can be ascribed neither to evaporation nor to mixing, was calculated. Many samples were recognised to have undergone an addition of ³⁴S-depleted S, which can be attributed to oxidation of sulfides with a Broken Hill type δ³⁴S signature (average ∼0‰ V-CDT). Furthermore, Sr isotopes identify the broad types of bedrock that the groundwater has been interacting with, from the less radiogenic Adelaidean rocks (and minerals) in the west (groundwater ⁸⁷Sr/⁸⁶Sr ratio as low as 0.708) to the highly radiogenic Willyama Supergroup in the east (⁸⁷Sr/⁸⁶Sr ratio up to 0.737). The groundwaters have ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios comparable to, or intermediate between, various mineralisation types recognised in the area (Broken Hill, Rupee, Thackaringa, etc., types). The few samples taken in the vicinity of known mineralisation yield positive indicators (positive S_XS, low δ³⁴S, ⁸⁷Sr/⁸⁶Sr signature of bedrock type and Pb isotope fingerprinting of mineralisation type). This study also highlights several new locations under sedimentary cover where these indicators suggest interaction with mineralisation.