River system recovery following the Novaţ-Roşu tailings dam failure, Maramureş County, Romania

The River Vişeu catchment in Maramureş County, northwestern Romania, has a long history of base and precious metal mining. Between 1994 and 2003 waste from mining activity at Baia Borşa was stored in the Novaţ-Roşu tailings pond in the upper Vişeu catchment. However, in March 2000, the tailings dam failed releasing approximately 100,000 m³ of contaminated water and 20,000 t of mineral-rich solid waste, which was routed downstream through the Rivers Novaţ, Vaser and Vişeu into the River Tisa. Following the accident metal (Cd, Cu, Pb, Zn) concentrations in river water and river channel sediment were assessed in samples collected annually (July 2000, 2001, 2002 and 2003) from 29 sites in the Vişeu catchment, downstream of the tailings pond. Additionally, the speciation of sediment-associated metals was established using a 4-stage sequential extraction procedure (SEP) and Pb isotope analysis (^206/204Pb and ^207/204Pb) was carried out to establish the provenance of contaminated sediments. Metal concentrations in river water were found to comply with EU directive ‘target’ values within four months of the failure. However, the impact of the spill upon river channel sediments was found to be much longer-lasting, with evidence of the delayed downstream remobilization of tailings stored within the narrow Novaţ valley following the dam failure, as well as continued inputs of contaminated sediment to the River Vişeu from the River Tisla, another mining-affected tributary. Comparison with data from other recent tailings dam failures, indicates that river system recovery rates depend upon local geomorphological conditions, hydrological regimes, and the nature and scale of post-spill clean-up operations.     

Heavy metal pollution of coastal river sediments, north-eastern New South Wales, Australia: lead isotope and chemical evidence

 Heavy metal and metalloid concentrations within stream-estuary sediments (<180-μm size fraction) in north-eastern New South Wales largely represent natural background values. However, element concentrations (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn) of Hunter River sediments within the heavily industrialized and urbanized Newcastle region exceed upstream background values by up to one order of magnitude. High element concentrations have been found within sediments of the Newcastle Harbour and Throsby Creek which drains into urbanized and light industry areas. Observed Pb enrichments and low ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios are likely caused by atmospheric deposition of Pb additives from petrol and subsequent Pb transport by road run-off waters into the local drainage system. Sediments of the Richmond River and lower Manning, Macleay, Clarence, Brunswick and Tweed River generally display no evidence for anthropogenic heavy metal and metalloid contamination (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn). However, the rivers and their tributaries possess localized sedimentary traps with elevated heavy metal concentrations (Cu, Pb, Zn). Lead isotope data indicate that anthropogenic Pb provides a detectable contribution to investigated sediments. Such contributions are evident at sample sites close to sewage outlets and in the vicinity of the Pacific Highway. In addition, As concentrations of Richmond River sediments gradually increase downstream. This geochemical trend may be the result of As mobilization from numerous cattle-dip sites within the region into the drainage system and subsequent accumulation of As in downstream river and estuary sediments. Received: 5 September 1997 · Accepted: 4 November 1997     

Lead in archaeological samples: an isotopic study by ICP-MS

Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration and isotopic composition of Pb in archaeological human and animal skeletal remains, soil from a village site of the Omaha tribe (U.S.A.) and cosmetic pigments.Lead concentrations in human bones from the Omaha tribe vary between 4.8 and 2570 μg/g, with younger people having the highest concentrations. Lead concentrations in animal bones from an Omaha village vary between 0.6 and 3.7 μg/g, and those of three soil samples range between 18 and 21 μg/g. Lead concentrations found in human bones from Anasazi (Utah, U.S.A.) and Alta (Peru) populations vary between 0.7 and 3.2 μg/g.Isotope ratios of a reagent grade Pb(NO₃)₂ solutions were measured by thermal ionization mass spectrometry (TIMS), as well as by ICP-MS to provide laboratory reference materials. The accuracy of the ICP-MS measurements relative to TIMS for the standard solution were found to be within 0.02–0.31% for²⁰⁶Pb/²⁰⁴Pb, 0.02–0.55% for²⁰⁷Pb/²⁰⁴Pb, and 0.16–0.56% for²⁰⁸Pb/²⁰⁴Pb. The precision of measurements on artifacts was 0.42–0.65% for²⁰⁶Pb/²⁰⁴Pb and 0.41–0.62% for²⁰⁷Pb/²⁰⁴Pb, whereas the precision for the same ratios for the bones was 0.85–1.8 and 0.82–1.67%, respectively. For the cosmetic lead-bearing pigments, a precision of 0.07–0.15% was found for both²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb ratios. Lead isotope ratios of artifacts give a radiogenic Pb signature, of which are close to signatures from PbZn mines of the central U.S. region. Lead isotope ratios of the pigments give non-radiogenic Pb signatures. Lead isotope ratios of the bones differ from those of the artifacts, and although similar in isotopic ratio to the pigments, they are more scattered, suggesting potential mixing of Pb from different regions.     

Lead isotopic systematics of major river sediments: a new estimate of the Pb isotopic composition of the Upper Continental Crust

The lead isotopic composition of river sediments is reported in the present work for the Earth's major river basins, from old cratonic to young orogenic areas and from subarctic to tropical climates. Sediment samples from these large river basins provide a useful tool to calculate the average upper crustal composition because they are large-scale integrated samples of the weathering products of the present-day Upper Continental Crust (UCC). Two different and complementary calculations were done to estimate the average lead isotopic composition of the UCC. The first, based on the flux weighted average of particulate lead delivered by the rivers, gave values of 19.07, 15.74 and 39.35 for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. To avoid over-estimating the contribution of orogenic areas, which produces a bias (because the flux of particulate lead depends strongly on the physical erosion rate), a second calculation was done by averaging with drainage areas of each river basin. This gave values of 18.93, 15.71 and 39.03 for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios, respectively. These direct calculations of the lead isotopic composition of the UCC are similar and are in agreement with previous estimates made using an indirect approach.     

Pb isotopic variability in the modern-Pleistocene Indus River system measured by ion microprobe in detrital K-feldspar grains

The western Himalaya, Karakoram and Tibet are known to be heterogeneous with regard to Pb isotope compositions in K-feldspars, which allows this system to be used as a sediment provenance tool. We used secondary ion mass spectrometry to measure the isotopic character of silt and sand-sized grains from the modern Sutlej and Chenab Rivers, together with Thar Desert sands, in order to constrain their origin. The rivers show a clear Himalayan provenance, contrasting with grains from the Indus Suture Zone, but with overlap to known Karakoram compositions. The desert dunes commonly show ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb values that are much higher than those seen in the rivers, most consistent with erosion from Nanga Parbat. This implies at least some origin from the trunk Indus, probably reworked by summer monsoon winds from the SW, a hypothesis supported by bulk Nd and U-Pb zircon dating. Further data collected from Holocene and Pleistocene sands shows that filled and abandoned channels on the western edge of the Thar Desert were sourced from Himalayan rivers before and at 6-8 ka, but that after that time the proportion of high isotopic ratio grains rose, indicating increased contribution from the Thar Desert dunes prior to ∼4.5 ka when flow ceased entirely. This may be linked to climatic drying, northward expansion of the Thar Desert, or changes in drainage style including regional capture, channel abandonment, or active local Thar tributaries. Our data further show a Himalayan river channel east of the present Indus, close to the delta, in the Nara River valley during the middle Holocene. While this cannot be distinguished from the Indus it is not heavily contaminated by reworking from the desert. The Pb system shows some use as a provenance tool, but is not effective at demonstrating whether these Nara sediments represent a Ghaggar-Hakra stream independent from the Indus. Our study highlights an important role for eolian reworking of floodplain sediments in arid rivers such as the Indus.     

Lead isotopes as tracers of anthropogenic pollution in urban topsoils of Mexico City

A survey was performed to trace the main source of anthropogenic Pb pollution in Mexico City through Pb isotopic signatures (²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁷Pb, and ²⁰⁸Pb/²⁰⁷Pb) from 103 urban topsoil (0–5 cm) samples. Those were collected in the metropolitan area of Mexico City and compared with isotopic compositions of leaded gasoline (LG), domestic Pb ores (DLO) and parent rock (PR). The isotope ratios (IRs) of Pb were determined by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) and total Pb concentration analyzed by wavelength dispersive X-ray fluorescence (WDXRF). The range of Pb concentrations levels in urban topsoil samples was 15–473 mg/kg. The IR values obtained for these samples were 37.965–39.718 (²⁰⁸Pb/²⁰⁴Pb), 18.375–19.204 (²⁰⁶Pb/²⁰⁴Pb), 1.177–1.218 (²⁰⁶Pb/²⁰⁷Pb) and 2.443–2.496 (²⁰⁸Pb/²⁰⁷Pb). Analyzed topsoil samples with low Pb content (<50 mg/kg) displayed high dispersion in ²⁰⁸Pb/²⁰⁴Pb values, which are determined by different natural sources. Samples with 51–200 mg/kg Pb content, shown low dispersion that revealed the mixing between the natural Pb and anthropogenic Pb. The assessment of the IR values shown that, as Pb concentration increases, a trend toward gasoline IR data has been observed. The results obtained by this research suggest that although the use of leaded petrol had been banned in Mexico since 1997, the Pb pollution in the urban topsoils due to the historical use of Pb in petrol is still significant.     

Lead and strontium isotopic evidence for crustal interaction and compositional zonation in the source regions of Pleistocene basaltic and rhyolitic magmas of the Coso volcanic field,California

The isotopic compositions of Pb and Sr in Pleistocene basalt, high-silica rhyolite, and andesitic inclusions in rhyolite of the Coso volcanic field indicate that these rocks were derived from different levels of compositionally zoned magmatic systems. The 2 earliest rhyolites probably were tapped from short-lived silicic reservoirs, in contrast to the other 36 rhyolite domes and lava flows which the isotopic data suggest may have been leaked from the top of a single, long-lived magmatic system. Most Coso basalts show isotopic, geochemical, and mineralogic evidence of interaction with crustal rocks, but one analyzed flow has isotopic ratios that may represent mantle values (⁸⁷Sr/⁸⁶Sr=0.7036,²⁰⁶Pb/²⁰⁴Pb=19.05,²⁰⁷Pb/²⁰⁴Pb=15.62,²⁰⁸Pb/²⁰⁴Pb= 38.63). The (initial) isotopic composition of typical rhyolite (⁸⁷Sr/⁸⁶Sr=0.7053,²⁰⁶Pb/²⁰⁴Pb=19.29,²⁰⁷Pb/²⁰⁴Pb= 15.68,²⁰⁸Pb/²⁰⁴Pb=39.00) is representative of the middle or upper crust. Andesitic inclusions in the rhyolites are evidently samples of hybrid magmas from the silicic/mafic interface in vertically zoned magma reservoirs. Silicic end-member compositions inferred for these mixed magmas, however, are not those of erupted rhyolite but reflect the zonation within the silicic part of the magma reservoir. The compositional contrast at the interface between mafic and silicic parts of these systems apparently was greater for the earlier, smaller reservoirs.     

Assessment of geochemical anomalies for gold exploration using lead isotopes in west Hainan, China

Lead isotopic ratios and Pb contents have been measured along typical profiles across orebodies of the Baoban and Tuwaishan gold deposits on Hainan Island, China. These deposits are hosted by the middle to upper Proterozoic Baoban Group, which is composed of migmatite and extends for about 51 km on the hanging-wall side of the Gezhen Fault. The deposits have a common initial Pb isotopic ratio of ²⁰⁶Pb/²⁰⁴Pb = 18.683, but show distinctive variations within each deposit.The Pb isotopic ratios are more homogeneous in the orebodies and altered auriferous rocks than in the migmatite wall rocks. The richest orebody in the study area is known as the V1 orebody of the Baoban deposit; it has the lowest and most homogeneous ²⁰⁶Pb/²⁰⁴Pb ratio. This feature suggests that in this migmatitic area, it is possible to distinguish ores from barren wall rocks, and rich ore shoots from non-commercial mineralization, by their distinctive Pb isotopic ratios.A lower initial Pb isotopic ratio (²⁰⁶Pb/²⁰⁴Pb= 18.538) was measured in two other deposits, Beiniu and Erjia, which occur in the same migmatite and are controlled by the same fault as the Baoban and Tuwaishan deposits. Therefore, two metallogenic phases may have taken place, one at 85 Ma and the other at 170 Ma; these ages can be calculated using the Pb growth model of Cumming and Richards.The feasibility of evaluating geochemical anomalies through their Pb isotopic signatures was investigated by comparing the Pb isotopic ratios of B horizon soils from significant and non-significant anomalies with those obtained from the ores and alteration zone rocks. The results show that the Pb isotopic ratios in significant anomalies are consistent with those of the ores, whereas the signatures of non-significant anomalies are heterogeneous and rather different from those of the ores.Six unexplored anomalies have been evaluated using this criteria; five of them were found to be non-significant. One anomaly, however, presents the same signature as the Beiniu deposit, suggesting that it may be related to undiscovered ore close to the Gezhen Fault. Plans have been made to drill this target.     

Genesis of the South Zhuguang Uranium Ore Field,South China: Pb Isotopic Compositions and Mineralization Ages

U–Pb isotopic analyses indicate that ores from the South Zhuguang uranium ore field, south China, have high common (non‐radiogenic) Pb contents, with variable and relatively radiogenic initial Pb contents. The U–Pb isochron method was used to date these ores, with plots of ²⁰⁸Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb being used to identify sample suites with similar initial Pb isotopic ratios and to normalize variable initial Pb isotopic ratios. The resulting U–Pb isochrons indicate two substages of uranium mineralization at ~57 and 52 Ma, with a later hydrothermal reformation at ~49 Ma, which homogenized Pb isotopic compositions. Initial Pb isotopic systematics indicate that the ore‐forming fluid was characterized by high ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb ratios and low ²⁰⁸Pb/²⁰⁴Pb ratios, suggesting that the ore‐forming fluid was sourced from Cretaceous–Paleogene red‐bed basins, rather than from magma or the mantle, with consideration of mineralization ages.     

Differences in lead isotope composition in the stratiform McArthur zinc-lead-silver deposit

Lead isotopic composition and uranium and lead concentrations have been determined for galena, sphalerite, pyrite and acetic acid soluble material from the McArthur area in order to test the hypothesis of a dual sulphur source suggested by the sulphur isotope data of Smith and Croxford (Sulphur isotope ratios in the McArthur lead-zinc-silver deposit, Nature Phys. Sci. 245, 10–12 (1973)). Galena, sphalerite and the acetic acid washes from the McArthur deposit have uniform isotopic ratios (²⁰⁶Pb/²⁰⁴Pb, 16.07–16.15; ²⁰⁷Pb/²⁰⁴Pb, 15.37–15.47; ²⁰⁸Pb/²⁰⁴Pb, 35.57–35.89) consistent with other conformable ore deposits, whereas the ratios for pyrite are variable and quite radiogenic (²⁰⁶Pb/²⁰⁴Pb, 16.24–16.49; ²⁰⁷Pb/²⁰⁴Pb, 15.42–15.58; ²⁰⁸Pb/²⁰⁴Pb, 35.82–36.98). Acid washes where dolomite is a major dissolved phase are also radiogenic. The lead in the pyrite appears to have been derived from at least two sources: the less radiogenic lead coming from an exhalative source as for galena and sphalerite and the more radiogenic lead probably being leached from the country rocks. It is proposed that analysis of pyrite for isotopic composition and concentration of lead could be used as an indicator for similar types of deposits in this area.     

Lead isotope systematics of the giant massive sulphide deposits in the Iberian Pyrite Belt

Lead isotope analyses were performed on 26 polymetallic massive sulphide deposits of the Iberian Pyrite Belt, as well as on overlying gossans and associated volcanic rocks. All the massive sulphide deposits (except for Neves-Corvo), and nearly all the volcanic rocks show very similar isotopic compositions grouped around 18.183 (²⁰⁶Pb/²⁰⁴Pb), 15.622 (²⁰⁷Pb/²⁰⁴Pb) and 38.191 (²⁰⁸Pb/²⁰⁴Pb), indicating that most of the ore deposit lead was derived from the same continental crust environment as the associated volcanic rocks. The isotopic compositions are representative of the average south Iberian crust during the Devonian to Early Carboniferous (Dinantian), and their constancy implies a homogenization of the mineralizing fluids before the deposition of the massive sulphides from hydrothermal fluids circulating through interconnected regional fracture systems. This isotopic constancy is incompatible with multiple, small, independent hydrothermal cells of the East Pacific Rise type, and fits much better with a model of hydrothermal convections driven by “magmatic floor heating”. Neves-Corvo is the only south Iberian massive sulphide deposit to have a heterogeneous isotopic composition with, in particular, a highly radiogenic stanniferous ore (²⁰⁶Pb/²⁰⁴Pb of the cassiterite is >18.40). A model of lead mixing with three components is proposed to explain these variations: (1) one derived from the Devonian to Early Carboniferous (Dinantian) continental crust that generated all the other massive ores; (2) an Eohercynian stanniferous mineralization partly remobilized during the formation of the massive sulphides, but independent of them; and (3) a Precambrian continental crust component. The juxtaposition of three different sources places Neves-Corvo in a specific paleogeographic situation that could also explain its mineralogical specificity. The geodynamic context that best explains all the obtained isotopic results is one of an accretionary prism. The fact that lead isotope signatures of the gossans are almost identical to those of the underlying massive sulphides means that this technique could be a useful exploration tool for the Iberian Pyrite Belt.     

Archaeological reconstruction of medieval lead production: Implications for ancient metal provenance studies and paleopollution tracing by Pb isotopes

The identification of metal provenance is often based on chemical and Pb isotope analyses of materials from the operating chain, mainly ores and metallic artefacts. Such analyses, however, have their limits. Some studies are unable to trace metallic artefacts or ingots to their ore sources, even in well-constrained archaeological contexts. Possible reasons for this difficulty are to be found among a variety of limiting factors: (i) problems of ore signatures, (ii) mixing of different ores (alloys), (iii) the use of additives during the metallurgical process, (iv) metal recycling and (v) possible Pb isotopic fractionation during metal production. This paper focuses on the issue of Pb isotope fractionation during smelting to address the issue of metal provenance. Through an experimental reconstruction of argentiferous Pb production in the medieval period, an attempt was made to better understand and interpret the Pb isotopic composition of ore smelting products. It is shown that the measured differences (outside the total external uncertainties of 0.005 (2*sd) for ²⁰⁶Pb/²⁰⁴Pb ratios) in Pb signatures measured between ores, slag and smoke are not due to Pb mass fractionation processes, but to (1) ore heterogeneity (Δ²⁰⁶Pb/²⁰⁴Pb_slag-ores = 0.066) and (2) the use of additives during the metallurgical process (Δ²⁰⁶Pb/²⁰⁴Pb_slag-ores = 0.083). Even if these differences are due to causes (1) and/or (2), smoke from the ore reduction appears to reflect the ore mining area without a significant disturbance of its Pb signature for all the isotopic ratios (Δ²⁰⁶Pb/²⁰⁴Pb_smokes-ores = 0.026). Thus, because the isotopic heterogeneity of the mining district and additives is averaged in slags, slag appears as the most relevant product to identify ancient metal provenance. Whereas aiming at identifying a given mine seems beyond the possibilities provided by the method, searching for the mining district through analysis of the smelting workshop materials should provide a more appropriate approach in cases where no archaeological evidence of ancient mining is available. Furthermore, smoke Pb isotopic composition does not seem to be significantly affected by the metallurgical process. Paleopollution recorded in peat deposits could help to detect ancient mining production and workshops. Integrated collaboration between mining archaeologists and geochemists appears crucial to achieve this goal.     

Ore-forming material sources of the Jurassic Cu–Pb–Zn mineralization in the Qin–Hang ore belt,South China: Constraints from S–Pb isotopes

The Qin–Hang ore belt in South China, which serves as the boundary between the Yangtze and Cathaysia blocks, is marked by extensive Jurassic porphyry-skarn-metasomatic Cu–Pb–Zn polymetallic mineralization. In this contribution, S and Pb isotopic compositions of the Baoshan Cu–Pb–Zn deposit in the western portion of the Qin–Hang ore belt were analyzed to determine the ore-forming material sources in the area. This is coupled by the first systematic collection, compilation and interpretation of previously published S and Pb isotopic data of multiple sulfide minerals to reveal the metal origin and accumulation mechanism of the Cu–Pb–Zn mineralization from the significant deposits in the region (i.e., Dexing, Qibaoshan, Shuikoushan, Baoshan, Huangshaping, Tongshanling and Dabaoshan). The results show that Cu mineralization is characterized by low and narrow δ³⁴S (‰) range of values (–5 to 6) and Pb isotopic ratios (²⁰⁸Pb/²⁰⁴Pb = 38.0–39.0, ²⁰⁷Pb/²⁰⁴Pb = 15.4–15.8, and ²⁰⁶Pb/²⁰⁴Pb = 17.7–18.7), which are consistent with those of local porphyries. In contrast, the Pb–Zn mineralization reveals higher and more variable δ³⁴S (‰) values (–4 to 18) and Pb isotopic ratios (²⁰⁸Pb/²⁰⁴Pb = 38.0–39.5, ²⁰⁷Pb/²⁰⁴Pb = 15.3–16.0, and ²⁰⁶Pb/²⁰⁴Pb = 18.0–19.0) that correspond to wall-rock and basement rock compositions in the region. This indicates that the sulfur and lead that formed the Cu mineralization in the Qin–Hang ore belt was mainly sourced from regional magmatism with mantle contributions, whereas the sulfur and lead for the Pb–Zn mineralization was likely derived from the host sedimentary rocks and Proterozoic metamorphic basement rocks, respectively. The S and Pb isotopic data, combined with the geochemical signatures of mineralization-related porphyries, suggest that the Cu was sourced from the deeper levels along with mantle-derived magmas. In contrast, the Pb–Zn probably originated from the crust, with partial melting of the crystalline basement in the Cathaysia Block. Consequently, a three-stage genetic model is proposed to explain the ore-forming processes of the Qin–Hang Cu-polymetallic belt in South China.     

Provenance ages and alteration histories of shales from the Middle Archean Buhwa greenstone belt, Zimbabwe: Nd and Pb isotopic evidence

Shales of the ca. 3.0 Ga Buhwa Greenstone Belt, Zimbabwe, were derived from a compositionally diverse provenance whose ages, determined by ion probe analyses of detrital zircons in interbedded sandstones, range from 3.8 to 3.1 Ga. Geochemical data for the shales were previously interpreted to indicate that sediments had been derived from an intensely weathered source. REE concentrations in the shales were interpreted to suggest that the provenance was compositionally mixed, with components of felsic (tonalite and alkalic granitoid) and mafic rocks. Sm/Nd and Nd isotopic compositions of these rocks can be used to model initial Nd isotopic ratios at the time of sedimentation (ε_Ndsed), as well as model crustal formation ages (T_DM). The former, at the age of sedimentation, range from +0.6 to −10.8, consistent with a range of provenance ages. The latter range from 4.46 Ga to 2.99 Ga. The oldest crustal formation ages, up to 0.7 Ga older than known detrital components, are interpreted here to indicate that the Sm-Nd system of the sediments experienced open system behavior. The implied alteration would have included an increase in Sm/Nd by about 20-25 percent, probably in the form of preferential loss of Nd with respect to Sm. The Pb isotopic compositions of whole rock samples are quite radiogenic, with a range of ²⁰⁶Pb/²⁰⁴Pb from 25.5 to 154. An array of ten samples lies scattered about a line with a ²⁰⁷Pb/²⁰⁴Pb -²⁰⁶Pb/²⁰⁴Pb slope age of about 2.73 Ga. Five individual samples were sequentially leached to further test the timing and characteristics of this U-Th-Pb alteration event. These arrays of a whole rock, three leach steps, and a residue also form linear Pb-Pb arrays (one is more scattered) with ages ranging from 2260 ± 360 Ma to 2824 ± 170 Ma, suggesting that all samples experienced a latest Archean to earliest Proterozoic enrichment in U/Pb. This age range also may be the approximate age of Sm/Nd enrichment for the shales. All samples, both whole rocks and leached samples, lie grouped on a ²⁰⁸Pb/²⁰⁴Pb - ²⁰⁶Pb/²⁰⁴Pb diagram around a line with ²³²Th/²³⁸U = 3.5 (2.9 to 3.9). Because of the lack of large differences in the Th/U of the samples through large ranges of U/Pb, we interpret this consistency in Th/U to mean that the shales of the Buhwa belt experienced Pb loss, rather than U and Th gain. Circumstances that may be responsible for Pb loss in a sedimentary basin include loss of saline fluids during basin dewatering. Such an event would likely have been related to folding associated with the thrusting and magmatic intrusion of the adjacent Limpopo Belt, suggesting that uplift, dewatering, and geochemical and isotopic alteration can be genetically related.     

Geology and Lead-Isotope Study of the Baiyinnuoer Zn-Pb-Ag Deposit, South Segment of the Da Hinggan Mountains, Northeastern China

The Baiyinnuoer deposit (32.74 Mt ore with grades of 5.44% Zn, 2.02% Pb and 31.36 g t^?1 Ag), the largest Zn‐Pb‐Ag deposit in northern China, is hosted by crystalline limestone and slate of the Early Permian Huanggangliang Formation. Detailed cross‐section mapping indicates stratigraphic and fold structural controls on the mineralization. The Zn‐Pb‐Ag mineralization is hosted predominantly by skarn, which occurs as bedding‐parallel lens that pinch out at the margins of the main economic zone. Three skarn stages are identified at the deposit: (i) garnet‐clinopyroxene; (ii) sulfides; and (iii) carbonate‐epidote. Lead isotopic compositions were determined for galena and sphalerite of the ores, whole rock samples of the Yanshanian granite and granodiorite, Permian marble and tuff, and Jurassic volcanic and subvolcanic rocks in and around the Baiyinnuoer area in order to discuss the sources of ore‐forming materials and the relationship between the ore formation and these whole rocks. Galena and sphalerite of the Baiyinnuoer ore have uniform isotopic ratios (²⁰⁶Pb/²⁰⁴Pb, 18.267–18.369; ²⁰⁷Pb/²⁰⁴Pb, 15.506–15.624; ²⁰⁸Pb/²⁰⁴Pb, 38.078–38.394) consistent with the granite and granodiorite (²⁰⁶Pb/²⁰⁴Pb, 18.252–18.346; ²⁰⁷Pb/²⁰⁴Pb, 15.504–15.560; ²⁰⁸Pb/²⁰⁴Pb, 38.141–38.320), whereas the ratios for Jurassic volcanic and subvolcanic rocks are variable and radiogenic (²⁰⁶Pb/²⁰⁴Pb, 18.468–18.614; ²⁰⁷Pb/²⁰⁴Pb, 15.521–15.557; ²⁰⁸Pb/²⁰⁴Pb, 38.304–38.375). These results indicate that the mineralization was not related to the Jurassic volcanism, but to the Yanshanian magmatism. The Permian strata may have a slight contribution to the mineralization. All features show that the Baiyinnuoer deposit is related to the Yanshanian granitic magmatism, and can be classified as a zinc‐lead‐silver skarn deposit.     

Compilation of radiogenic isotope data in Mexico and their petrogenetic implications

Seven hundred and twenty-five Sr, two hundred and forty-three Nd and one hundred and fifty-one Pb isotopic ratios from seven different Mexican magmatic provinces were compiled in an extensive geochemical database. Data were arranged according to the Mexican geological provinces, indicating for each province total number of analyses, range and mean of values and two times standard deviation (2σ). Data from seven provinces were included in the database: Mexican Volcanic Belt (MVB), Sierra Madre Occidental (SMO), Baja California (BC), Pacific Ocean (PacOc), Altiplano (AP), Sierra Madre del Sur (SMS), and Sierra Madre Oriental (SMOr). Isotopic values from upper mantle and lower crustal xenoliths, basement outcrops and sediments from the Cocos Plate were also compiled. In the MVB the isotopic ratios range as follows:⁸⁷Sr/⁸⁶Sr 0.703003-0.70841;¹⁴³Nd/¹⁴⁴Nd 0.512496-0.513098;²⁰⁶Pb/²⁰⁴Pb 18.567-19.580;²⁰⁷Pb/²⁰⁴Pb 15.466-15.647;²⁰⁸Pb/²⁰⁴Pb 38.065-38.632. The SMO shows a large variation in⁸⁷Sr/⁸⁶Sr ranging from ∼0.7033 to 0.71387.¹⁴³Nd/¹⁴⁴Nd ratios are relatively less variable with values from 0.51191 to 0.51286. Pb isotope ratios in the SMO are as follows:²⁰⁶Pb/²⁰⁴Pb 18.060-18.860;²⁰⁷Pb/²⁰⁴Pb 15.558-15.636;²⁰⁸Pb/²⁰⁴Pb 37.945-38.625. PacOc rocks show the most depleted Sr and Nd isotopic ratios (0.70232-0.70567 for Sr and 0.512631-0.513261 for Nd). Pb isotopes for PacOc show the following range:²⁰⁶Pb/²⁰⁴Pb 18.049-19.910;²⁰⁷Pb/²⁰⁴⁷Pb 15.425-15.734;²⁰⁸Pb/²⁰⁴Pb 37.449-39.404. The isotopic ratios of the AP rocks seem to be within the range of those from the PacOc. Most samples with reported Sr and Nd isotopic data are spread within and around the “mantle array”. The SMO seems to have been formed by a mixing process between mantle derived magmas and continental crust. The MVB appears to have a larger mantle component, with AFC as the dominant petrogenetic process for the evolved rocks. There is still a need for Pb isotopic data in all Mexican magmatic provinces and of Nd isotopes in BC, AP, SMS, and SMOr.     

Ore lead and sulphur isotope pattern from the low-temperature veins of the Catalonian Coastal Ranges (NE Spain)

The lead isotopic composition of galenas from low-temperature veins of the Catalonian Coastal Ranges (NE Spain) displays a small but distinct range of values: 18.318 ≤²⁰⁶Pb/²⁰⁴Pb ≤ 18.678; 15.678 ≤²⁰⁷Pb/²⁰⁴Pb ≤ 15.767 and 38.534 ≤ ²⁰⁸Pb/²⁰⁴Pb ≤ 39.189. The data define a linear trend in the ²⁰⁸Pb/²⁰⁴Pb versus ²⁰⁶Pb/²⁰⁴Pb diagram that can be interpreted in terms of mixing of lead from different reservoirs. The lead appears to be derived from a solution that preferentially leached granites of Late-Hercynian age. Sulphur isotopic compositions of the galenas range from −8.5 to + 7.3‰ but variations in a single deposit are small (1–2‰), pointing to different sources of sulphur. In a δ³⁴S versus ²⁰⁶Pb/²⁰⁴Pb plot no clear correlation trends appear. Lead isotope data from deposits of similar characteristics situated within the Hercynian orogenic belt as the Linares-La Carolina district (S Spain) and the Inglesiente-Sulcis area (Sardinia) show slight differences indicating a source area of similar lead isotopic composition. In the CCR and Linares-La Carolina districts, the main source of lead is related to the Hercynian granites of each area, although small contributions from metasediments cannot be ruled out. The contribution of lead from metasedimentary rocks is particularly seen in the Sardinian (Hercynian vein-type) ores. Received: 8 August 1996 / Accepted: 5 December 1996     

Trace-element characteristics of east–west mantle geochemical hemispheres

Recent statistical analyses on the isotopic compositions of oceanic, arc, and continental basalts have revealed that the Earth's mantle is broadly divided into eastern and western hemispheres. The present study aimed to characterize the isotopically defined east–west geochemical hemispheres using trace-element concentrations. Basalt data with Rb, Sr, Nd, Sm, Pb, Th, and U in addition to the isotopic ratios ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb were selected mostly from the GEOROC and PetDB databases. A total of 4787 samples were used to investigate the global geochemical variations. The results show that the wide trace-element variations are broadly explained by the melting of melt-metasomatized and fluid-metasomatized mantle sources. The larger amount of the fluid component derived from subducted plates in the eastern hemisphere than that in the western hemisphere is inferred from the basalts. These characteristics support the hypothesis that focused subduction towards the supercontinent created the mantle geochemical hemispheres.     

Lead and uranium isotopic behavior in diagenetic and epigenetic manganese nodules, Timna Basin, Israel, determined by MC-ICP-MS

Isotope ratios of U and Pb were measured in two types of Mn nodules from the Cambrian Timna Formation, Israel. Type A nodules are mainly composed of pyrolusite and hollandite, with Mn, Ba, Pb and U concentrations of 30–60%, 0.2–2.5%, 0.2–1.0% and 500–3500 ppm, respectively, whereas type B nodules were formed by alteration of the former, and contain mainly coronadite, with Mn, Ba, Pb and U concentrations of 7–48%, 0.2–7%, 0.6–5% and 10–160 ppm, respectively. The isotopic composition of U and Pb was measured by MC-ICP-MS on Mn-rich solutions (up to 100 mg/L) without and with chromatographic separation. The values for the 207/206 and 208/206 ratios have been determined with precisions of up to 50 ppm and those of 206/204, 207/204 and 208/204 – up to 200 ppm. The values for the 234/238 ratios have been determined with precisions of 0.4–1%. The results of the separated and unseparated solutions were shown to be equal within the error. Thus there is no significant matrix effect while measuring U and Pb in Mn rich solution using the MC-ICP-MS.The isotopic composition of Pb and U support the distinction between the two types of Mn nodules. Type A nodules have a wide range of ²⁰⁶Pb/²⁰⁴Pb ratios (18.278–19.776), and an almost constant ratio of ²⁰⁸Pb/²⁰⁴Pb. In contrast, type B nodules have almost constant ²⁰⁶Pb/²⁰⁴Pb ratios and a wide range of ²⁰⁸Pb/²⁰⁴Pb ratios (37.986–38.079). Type A nodules form a linear array on a ²⁰⁷Pb/²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb diagram, while type B nodules form a tight group characterized by lower Pb isotope ratios that slightly deviate from the type A array. The ²³⁴U/²³⁸U ratio differs between the two types of nodules; type A nodules exhibit a uniform and close to equilibrium ²³⁴U/²³⁸U ratio while type B nodules show a wide range of ²³⁴U/²³⁸U ratios above and below the equilibrium value. The isotopic composition of Pb in type A nodules might reflect Pb contributions from plutonic rock weathering, exposed at the time of deposition or later, to the Cambrian sea. These nodules have remained unaffected by processes that occurred since the Cambrian. The higher ²⁰⁸Pb/²⁰⁴Pb values of type B indicate that these nodules were formed from a Th-enriched solution probably during epigenetic processes which occurred also during the last 1 Ma.Thus the two isotopic systems of U and Pb can record formation, leaching and redeposition of Mn ores.     

Sr,Nd and Pb Isotopic Systematics of the Cenozoic Basalts of the Korean Peninsula and Their Implications for the Permo-Triassic Continental Collision Boundary

Sr, Nd and Pb isotopic compositions of the Cenozoic basalts were analyzed from Baengnyeongdo Island, Jeongok, Ganseong, and Jejudo Island of Korea. They reveal relatively enriched Sr and Nd isotopic compositions (⁸⁷Sr/⁸⁶Sr = 0.70330∼0.70555, ¹⁴³Nd/¹⁴⁴Nd = 0.51298∼0.51256) compared with MORB.²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values of all the analyzed Korean basalts lie above the Northern Hemisphere Reference Line (NHRL) defined by Hart (1984). Pb isotopic compositions of basalts from Jejudo Islands (²⁰⁶Pb/²⁰⁴Pb = 18.61∼19.12, ²⁰⁷Pb/²⁰⁴Pb = 15.54∼15.69, ²⁰⁸Pb/²⁰⁴Pb = 38.98∼39.72) are significantly more radiogenic than the rest (²⁰⁶Pb/²⁰⁴Pb = 17.72∼18.03, ²⁰⁷Pb/²⁰⁴Pb = 15.44∼15.58, ²⁰⁸Pb/²⁰⁴Pb = 37.77∼38.64). The Cenozoic Korean basalts thus can be divided into two groups based on their Sr, Nd and Pb isotopic compositions. The north group reveals mixing between DMM and EM1 while the south group displays DMM-EM2 mixing. Such a distribution is the same as Chinese Cenozoic basalts and it can be interpreted that the subcontinental lithospheric mantle under Korea represents simple lateral continuation of the South and North China Blocks. We suggest that Korean continental collision zone cross the Korean Peninsula through the region between the north and south basalt groups of Korea.