Trace metal distribution and mobility in drill cuttings and produced waters from Marcellus Shale gas extraction: Uranium,arsenic, barium

Development of unconventional shale gas wells can generate significant quantities of drilling waste, including trace metal-rich black shale from the lateral portion of the drillhole. We carried out sequential extractions on 15 samples of dry-drilled cuttings and core material from the gas-producing Middle Devonian Marcellus Shale and surrounding units to identify the host phases and evaluate the mobility of selected trace elements during cuttings disposal. Maximum whole rock concentrations of uranium (U), arsenic (As), and barium (Ba) were 47, 90, and 3333 mg kg⁻¹, respectively. Sequential chemical extractions suggest that although silicate minerals are the primary host for U, as much as 20% can be present in carbonate minerals. Up to 74% of the Ba in shale was extracted from exchangeable sites in the shale, while As is primarily associated with organic matter and sulfide minerals that could be mobilized by oxidation. For comparison, U and As concentrations were also measured in 43 produced water samples returned from Marcellus Shale gas wells. Low U concentrations in produced water (<0.084–3.26 μg L⁻¹) are consistent with low-oxygen conditions in the wellbore, in which U would be in its reduced, immobile form. Arsenic was below detection in all produced water samples, which is also consistent with reducing conditions in the wellbore minimizing oxidation of As-bearing sulfide minerals.Geochemical modeling to determine mobility under surface storage and disposal conditions indicates that oxidation and/or dissolution of U-bearing minerals in drill cuttings would likely be followed by immobilization of U in secondary minerals such as schoepite, uranophane, and soddyite, or uraninite as conditions become more reducing. Oxidative dissolution of arsenic containing sulfides could release soluble As in arsenate form under oxic acidic conditions. The degree to which the As is subsequently immobilized depends on the redox conditions along the landfill flow path. The results suggest that proper management of drill cuttings can minimize mobilization of these metals by monitoring and controlling Eh, pH and dissolved constituents in landfill leachates.     

Reductive weathering of black shale and release of barium during hydraulic fracturing

Hydraulic fracturing is an important technological advance in the extraction of natural gas and petroleum from black shales, but water injected into shale formations in the fracturing process returns with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium, Ba. It is generally assumed that high TDS comes from the mixing of surface water (injected fluid) with Na–Ca–Cl formation brines containing elevated Ba, but the mechanisms by which such mixing might occur are disputed. Here we show that Ba in water co-produced with gas could originate from water-rock reactions, with Ba levels observed in produced waters reached on a time scale relevant to hydraulic fracturing operations. We examined samples from three drill cores from the Marcellus Shale in Pennsylvania and New York to determine the possible water-rock reactions that release barium during hydraulic fracturing. Two samples, one containing microcrystalline barite (BaSO₄) and one without barite, contain elevated concentrations of Ba relative to the crustal average for shale rocks. A third sample is slightly depleted in Ba relative to the crustal average. Micro-XRF measurements and SEM/EDS analysis combined with chemical sequential extraction methods reveal that a majority of the Ba in all samples (55–77 wt.%) is present in clays and can only be leached from the rock by dissolution in hydrofluoric acid. Thus, a majority of barium in our samples is relatively inaccessible to leaching under hydraulic fracturing conditions. However, the balance of Ba in the rocks is contained in phases that are potentially leachable during hydraulic fracturing (e.g., soluble salts, exchangeable sites on clays, carbonates, barite, organics).We next studied how shale reacts with water at elevated temperatures (80 °C), low Eh (−100 to −200 mV), and a range of ionic strengths (IS = 0.85–6.4) that emulate conditions prevalent at depth during hydraulic fracturing. Our experimental results indicate that the amount of Ba released from the bulk rock has a positive correlation with the ionic strength of the reacting fluid. Between 5 and 25% of the total Ba in the rock can be leached from shale under ionic strength conditions and leachate compositions typical of produced waters over a contact time of just 7 days. We suggest that reductive weathering of black shale occurs during hydraulic fracturing due to: 1) Ba²⁺ in clays exchanging with Na⁺ and Ca²⁺ ions that are present in high concentrations in produced water, and 2) increased solubility and dissolution kinetics of barite under high ionic strength conditions. At the low Eh conditions prevalent during hydraulic fracturing the sulfate deficient water allows Ba to be dissolved into the produced water. Based on Ba yields determined from laboratory leaching experiments of Marcellus Shale and a reasonable estimate of the water/rock mass ratio during hydraulic fracturing, we suggest that all of the Ba in produced water can be reconciled with leaching directly from the fractured rock.     

A 2400-year record of trace metal loading in lake sediments of Lagoa Vermelha, southeastern Brazil

Sediments of the Lagoa Vermelha (Red Lake), situated in the Ribeira Valley, southeastern Brazil, are made of a homogeneous, organic-rich, black clay with no visible sedimentary structures. The inorganic geochemical record (Al, As, Ba, Br, Co,Cs, Cr, Fe, Mn, Ni, Rb, Sc, Sb, V, Zn, Hg and Pb) of the lake sediments was analyzed in a core spanning 2430 years. The largest temporal changes in trace metal contents occurred approximately within the last 180 years. Recent sediments were found to be enriched in Pb, Zn, Hg, Ni, Mn, Br and Sb (more than 2-fold increase with respect to the “natural background level”). The enhanced accumulation of Br, Sb, and Mn was attributed to biogeochemical processes and diagenesis. On the other hand, the anomalous concentrations of Pb, Zn, Hg and Ni were attributed to pollution. As Lagoa Vermelha is located in a relatively pristine area, far removed from direct contamination sources, the increased metal contents of surface sediments most likely resulted from atmospheric fallout. Stable Pb isotopes provided additional evidence for anthropogenic contamination. The shift of ²⁰⁶Pb/²⁰⁷Pb ratios toward decreasing values in the increasingly younger sediments is consistent with an increasing contribution of airborne anthropogenic lead. In the uppermost sediments (0-10 cm), the lowest values of the ²⁰⁶Pb/²⁰⁷Pb ratios may reflect the influence of the less radiogenic Pb from the Ribeira Valley District ores (²⁰⁶Pb/²⁰⁷Pb between 1.04 and 1.10), emitted during the last 50 years.     

The effect of allanite inclusions on U–Pb step-leaching ages and Sm–Nd isotope systematics of garnet from the Ogcheon metamorphic belt,South Korea

The Ogcheon metamorphic belt consists primarily of metasedimentary and metavolcanic rocks that have experienced polyphase tectonometamorphism since the Neoproterozoic. Peak metamorphism reaching up to lower-amphibolite facies produced ubiquitous garnet porphyroblasts in pelitic and mafic schists. To determine the timing of their formation, step-leaching experiments were undertaken for five garnet fractions separated from pelitic and quartz-hornblende-garnet schists. The U–Pb ages from three samples are identical within 2σ errors, ranging from 291 ± 41 Ma to 276 ± 29 Ma. The quasi-linearity of leachates in ²³⁸U–²⁰⁶Pb and ²⁰⁸Pb–²⁰⁶Pb diagrams suggests that U and Pb are released from a single mineral phase and that minor chemical fractionation between U and Pb may have occurred during the leaching experiment. Deviations of residues and bulk garnet fractions from the linear trend are attributed to partial dissolution of refractory inclusions of detrital zircon. Th/U ratios of leachates are in the range of 3.4–12, much higher than those of pure garnet, and suggest the contribution of allanite. Negative relationships in the Sm–Nd isochron diagram and similar ¹⁴⁷Sm/¹⁴⁴Nd ratios between whole rock and garnet corroborate the influence of light rare earth element (LREE)-rich allanite on the Sm–Nd isotopic system. Simple mass-balance calculations indicate that only a trace amount (0.35 modal%) of allanite inclusions should govern the U–Th–Pb systematics of garnet. Petrographic evidence together with the consistency in U–Pb ages suggests that allanite is a product of prograde metamorphism. Thus, peak metamorphism responsible for the growth of allanite-bearing garnet porphyroblasts in the Ogcheon metamorphic belt is best estimated to be Early Permian.     

Strontium isotopic evidence on the chemical evolution of pore waters in the Milk River Aquifer,Alberta, Canada

Strontium isotope ratios were measured on 13 rock, 18 leachate and 28 pore-water samples from the Milk River aquifer, the confining argillaceous formations, and the glacial till mantling the recharge area. Strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) of pore waters from the aquifer, confining units, and the glacial till ranged from 0.7069 to 0.7082. The ⁸⁷Sr/⁸⁶Sr ratios in aquifer pore waters decrease with increasing distance from the aquifer recharge area, and this is interpreted to be the result of mixing and water–rock interaction within the aquifer.The solute composition of the recharging groundwater is modified by the local lithology, causing distinct geochemical patterns along different flow paths within the aquifer. Whole-rock ⁸⁷Sr/⁸⁶Sr ratios indicate that the shales and till are generally more radiogenic than the aquifer sandstone. The authigenic carbonate cements and rock-forming minerals comprising the major lithologic units had little apparent influence on the pore-water Sr chemistry. Carbonate cement leachates from the till and the aquifer sandstone are more radiogenic than those from the confining shale formations. Feldspar separates from the aquifer sandstone have relatively radiogenic Sr isotope ratios, whereas bentonites from the Milk River and Colorado Shale Formations have whole-rock and leachate Sr isotope ratios that are relatively unradiogenic. Ratios of most Milk River aquifer pore waters are lower than those of any leachates or whole rocks analyzed, except the bentonites.The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the bentonites are similar to ratios found in the more evolved pore waters. Simple rock–water interaction models calculated for the whole-rock, leachate, and exchangeable-ion/pore-water pairs indicate that ion exchange with bentonite clays within the Milk River and Colorado Shale Formations appears to influence the isotopic evolution of the pore-water Sr in each of these units.     

黑色页岩与土壤重金属污染

本文利用ICP—MS等技术分析了湘中地区黑色页岩及其相应土壤的重金属含量,在对分析结果进行统计分析的基础上,探讨了黑色页岩与土壤重金属污染的关系。研究表明,黑色页岩是富集多种重金属元素的特殊岩石。以黑色页岩岩系为母岩的土壤,不仅明显富集Cu、Cd、Cr、Co、Pb、Zn、Mo、Ni、V、U、Sn、Sb、T1、Th等多种重金属元素,而且受到Mo、Sb、Cd、U、Tl、Cu、V、Sn、Th等重金属的污染,其中以Mo、Cd、Sb、U、Tl等的污染尤为严重。黑色页岩土壤重金属污染在一些地方已产生明显的负面环境效应,值得关注。     

The Zhaxikang Vein‐type Pb‐Zn‐Ag‐Sb Deposit in Himalayan Orogen,Tibet: Product by Overprinting and Remobilization Processes during Post‐collisional Period

The Zhaxikang Pb-Zn-Ag-Sb deposit, the largest polymetallic deposit known in the Himalayan Orogen of southern Tibet, is characterized by vein-type mineralization that hosts multiple mineral assemblages and complicated metal associations. The deposit consists of at least six steeply dipping veintype orebodies that are hosted by Early Jurassic black carbonaceous slates and are controlled by a Cenozoic N–S-striking normal fault system. This deposit records multiple stages of mineralization that include an early period(A) of massive coarse-grained galena–sphalerite deposition and a later period(B) of Sb-bearing vein-type mineralization. Period A is only associated with galena–sphalerite mineralization, whereas period B can be subdivided into ferrous rhodochrosite–sphalerite–pyrite, quartz–sulfosalt–sphalerite, calcite–pyrite, quartz–stibnite, and quartz-only stages of mineralization. The formation of brecciated galena and sphalerite ores during period A implies reworking of pre-existing Pb–Zn sulfides by Cenozoic tectonic deformation, whereas period B mineralization records extensive openspace filling during ore formation. Fluid inclusion microthermometric data indicate that both periods A and B were associated with low–medium temperature(187–267°C) and low salinity(4.00–10.18% wt. Na Cl equivalent) ore-forming fluids, although variations in the physical–chemical nature of the period B fluids suggest that this phase of mineralization was characterized by variable water/rock ratios. Microprobe analyses indicate that Fe concentrations in sphalerite decrease from period A to period B, and can be divided into three groups with Fe S concentrations of 8.999–9.577, 7.125–9.109, 5.438–1.460 mol.%. The concentrations of Zn, Sb, Pb, and Ag within orebodies in the study area are normally distributed in both lateral and vertical directions, and Pb, Sb, and/or Ag concentrations are positive correlation within the central part of these orebodies, but negatively correlate in the margins. Sulfide S isotope compositions are highly variable(4‰–13‰), varying from 4‰ to 11‰ in period A and 10‰ to 13‰ in period B. The Pb isotope within these samples is highly radiogenic and defines linear trends in 206 Pb/204 Pb vs. 207 Pb/204 Pb and 206 Pb/204 Pb vs. 208 Pb/204 Pb diagrams, respectively. The S and Pb isotopic characteristics indicate that the period B orebodies formed by mixing of Pb–Zn sulfides and regional Sbbearing fluids. These features are indicative of overprinting and remobilization of pre-existing Pb–Zn sulfides by Sb-bearing ore-forming fluids during a post-collisional period of the Himalayan Orogeny. The presence of similar ore types in the north Rhenish Massif that formed after the Variscan Orogeny suggests that Zhaxikang-style mineralization may be present in other orogenic belts, suggesting that this deposit may guide Pb–Zn exploration in these areas.     

Rare earth elements, yttrium and H, O, C, Sr, Nd and Pb isotope studies in mineral waters and corresponding rocks from NW-Bohemia, Czech Republic

The sparkling waters from the area of Kyselka near Karlovy Vary at the western slope of the Doupovske hory, Bohemia (Czech Republic), and CO₂-poor waters from two underground boreholes at Jachymov, Krusne hory, Bohemia, have been studied with the aim of characterizing the distribution of rare earth elements, yttrium, and H, O, C, Sr, Nd, Pb isotopes during the low-temperature alteration processes of the host rocks. Additionally, leaching experiments were performed at pH 3 on the granitic and basaltic host rocks from Kyselka and the granite of Jachymov. All REE patterns of the granite- and the basalt-derived waters from the Kyselka area are different from those of their source rocks and the leachates of the latter. This elucidates the inhomogeneous distribution of REE and Y among the solid phases in the altered magmatic rocks. The Eu and Ce anomalies in granite-derived waters are inherited, the Y anomaly is achieved by fluid migration. Yttrium is always preferentially leached by mineral waters, whereas Y/Ho ratios of rocks and their leachates are very similar. The REE abundances in waters from the wells in Jachymov are derived from rocks intensely leached and depleted in easily soluble REE-bearing minerals, whereas the granites and basalts from Kyselka still contain soluble, REE-bearing minerals. A comparison of REE/Ca patterns of the experimental leachates with those of the mineral waters elucidate the high retention of REE in rocks during water–rock interaction. In strongly altered rocks Sr isotope ratios of mineral waters and rocks differ widely, whereas the corresponding Nd isotope ratios are very similar. ²⁰⁷Pb/²⁰⁸Pb, ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in mineral waters are independent from U/Th ratios in the rocks. ²⁰⁶Pb/²⁰⁸Pb and ²⁰⁶Pb/²⁰⁷Pb are lower in mineral waters than in their source rocks and their leachates, which indicates that Pb is primarily derived from solid phases that do not contain significant contents of leachable U and Th. Thus, mineral waters, although CO₂ rich, only interact with surface films on minerals and not with the bulk of the minerals as in the leaching experiments.Calculation of mixing ratios of waters from the granitic and basaltic sources of the waters from the Kyselka area yield about 40% of water from the underlying granite in water recovered from the basalt, whereas the granite-derived water is mixed with only about 5% of the water from the basalt.     

Stable lead isotope ratios and metals in freshwater mussels from a uranium mining environment in Australia’s wet-dry tropics

Concentrations of Fe, Mn, Cu, Zn, U and Pb, and stable Pb isotopes ²⁰⁶Pb, ²⁰⁷Pb and ²⁰⁸Pb were measured via inductively coupled plasma mass spectrometry in sediments, water and freshwater mussels (Velesunio angasi) from two catchments in the Alligator Rivers Region, Australia. Sediment U and Pb concentrations were higher in Magela Creek downstream than upstream of the Ranger U mine due to the mineralised nature of the catchment and potential local input of sediment from the mine site. Water metal concentrations were highest in Georgetown Creek, which is a tributary of Magela Creek and part drains the Ranger mine site, but there was little difference in concentrations between the Magela Creek upstream and downstream sites. Metal concentrations in mussels collected immediately upstream and downstream of the mine site also showed little difference, whereas Pb isotope ratios displayed a very distinct pattern. The ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁷Pb isotope ratios were more uranogenic downstream than upstream of the site and also more uranogenic than ratios measured in Sandy Billabong, a reference billabong in a catchment not influenced by U mineralisation. Isotope ratios were also more uranogenic in younger mussels, potentially due to the increasing footprint of the mine site over the past decade. The most uranogenic ratios were found in mussels from Georgetown Creek and at a site approximately 2 km downstream. At Mudginberri Billabong, approximately 12 km downstream of the Ranger mine, the relative contribution of uranogenic Pb to the total Pb concentration in mussels was small and overwhelmed by the input of industrial Pb with a Broken Hill type Pb signature. Whereas metal uptake by and thus concentrations in mussel flesh are influenced by water chemistry, mussel condition and metabolic rates, Pb isotope ratios are independent of these factors and provide a powerful means of source apportionment of contaminants in mussels and waterways, in particular in an U mining environment.     

Origin of zircon in jadeitite from the Nishisonogi metamorphic rocks,Kyushu, Japan

On the basis of internal structures, laser ablation U–Pb ages and trace element compositions, the origin of zircon in jadeitite in the Nishisonogi metamorphic rocks was examined. The zircon comprises euhedral zoned cores overgrown by euhedral rims. The cores contain inclusions of muscovite, quartz, albite and possibly K‐feldspar, yield ²³⁸U–²⁰⁶Pb ages of 126 ± 6 Ma (±2 SD, n = 45, MSWD = 1.0), and have Th/U ratios of 0.48–1.64. The rims contain inclusions of jadeite, yield ²³⁸U–²⁰⁶Pb ages of 84 ± 6 Ma (±2 SD, n = 14, MSWD = 1.1), and have Th/U ratios of <0.06. The cores are richer in Y, Th, Ti and rare earth elements (REEs), but the rims are richer in Hf and U. Chondrite‐normalized REE patterns of the cores indicate higher Sm_N/La_N ratios, lower Yb_N/Gd_N ratios and larger positive Ce anomalies compared with those of the rims. Thus, the cores and rims have different ²³⁸U–²⁰⁶Pb ages and trace element compositions, suggesting two stages of zircon growth. Although the ²³⁸U–²⁰⁶Pb ages of the rims are consistent with the reported ⁴⁰Ar/³⁹Ar spot‐fusion ages of matrix muscovite in the jadeitite, the ²³⁸U–²⁰⁶Pb ages of the cores are older. The mineral inclusions and high Th/U ratios in the cores are best explained by crystallization from felsic magma. Therefore, the cores are considered relicts from igneous precursor rocks. The rims surrounding the inherited cores possibly precipitated from aqueous fluids during jadeitite formation. The elevated U concentrations in the rims suggest that infiltration of external fluids was responsible for the precipitation. This study provides an example of jadeitite formation by metasomatic replacement of a protolith.     

Historical lead pollution in the central region of Guizhou province,China: A record of lead stable isotopes of lake sediments

Economic reform in China since 1978 has accelerated economic development nationwide hugely, but has also brought about some environmental pollution. In order to identify the primary Pb source to the atmosphere in the central Guizhou region, Pb isotopic ratios in the acid soluble fraction of sediment from Hongfeng Lake were investigated. Lead isotopes in the lake sediments record the history of regional atmospheric Pb pollution. Before the economic reform in 1978, the ²⁰⁸Pb/²⁰⁶Pb and ²⁰⁶Pb/²⁰⁷Pb ratios in the leachates of lake sediments were constant, with a range of 2.0060 to 2.0117 and of 1.2314 to 1.2355, respectively. In the early period of economic reform (1978 to 1988), with the rapid industrial growth in Guizhou province, the acid soluble Pb isotope ratios in the lake sediments changed sharply: the ²⁰⁸Pb/²⁰⁶Pb ratios increased from 2.0212 to about 2.05, while the ²⁰⁶Pb/²⁰⁷Pb ratios decreased from 1.2251 to 1.2060. Emissions from Pb-ore-related industries are suggested to be the major pollution source of Pb in this period. Due to output from a local power plant since 1988, the isotope ratios of the acid soluble Pb in sediments in 1990s are characterized by a little higher radiogenic Pb (²⁰⁸Pb/²⁰⁶Pb = 2.0340–2.0400; ²⁰⁶Pb/²⁰⁷Pb = 1.2122–1.2158) than for the 1980s.     

Influence of anthropogenic activity on the lead isotope signature of Thau Lake sediments (southern France): origin and temporal evolution

Lead concentrations and isotopic compositions were determined on both bulk sediments deposited in the Thau lake in southern France during the last 200 years, and leachates derived from a series of sequential leachings of the sediments, making it possible to identify the sources, natural (i.e. indigenous lithologic) or anthropogenic, and to quantify the different inputs of Pb.Two distinct inputs of Pb could be distinguished. One of these corresponds to the terrigenous material entering the basin, representative of the local natural Pb ‘background’. Its supply remained steady most of the time with ²⁰⁶Pb/²⁰⁷Pb ratios of 1.200±0.003, except at the time of heavy storms producing voluminous and sudden depositions, such as that of September 1875. This Pb supply is mainly hosted by the detrital silicate fraction of the sediments. The second Pb input is a direct consequence of anthropogenic activities of various industrial and domestic emissions in the region, particularly due to the city of Sète and, to a lesser extent, to the villages in the watershed. The ²⁰⁶Pb/²⁰⁷Pb ratios of this input are of 1.142–1.162. The Pb added to gasoline could also be identified in the uppermost sediments, because of its specific ²⁰⁶Pb/²⁰⁷Pb ratios of 1.069–1.094. The leaching experiments also showed that the anthropogenic Pb is mainly hosted by the oxi-hydroxides of the sediments and to a lesser extent by the carbonates. It may also be adsorbed on particle surfaces, while only limited amounts are bound to organic matter.     

Water-rock-tailings interactions and sources of sulfur and metals in the subtropical mining region of Taxco,Guerrero (southern Mexico): A multi-isotopic approach

Multi-isotope (H, O, S, Sr, Pb) systems coupled with conventional (major and trace element) hydrogeochemical analysis were applied to determine the origin of water, to model water-rock-tailings interactions and for source apportionment of sulfur and associated toxic metals in the mining region of Taxco, Guerrero in southern Mexico. Oxygen and H isotopes indicate that meteoric water in the zone is rainwater undergoing varying degrees of isotopic fractionation by atmospheric evaporation whereas Sr isotopes trace the interaction of pristine water from volcanics of the regional recharge zone and subsequently flowing through sandstone and shale to spring points. Leachates form from two distinctive sources (spring water and surface water) having differential interactions with bedrocks prior to entering the tailings. Compared to pristine water, leachates are enriched in sulfate, metals (e.g. Fe, Mn, Pb and Zn) and metalloids (e.g. As). The sulfur isotopic composition of ore-sulfides, leachates, secondary precipitates, regional surface water and hypogenic sulfates is described in terms of a two-component mixing model with shale of Mexcala and limestone of Morelos formations representing the light and heavy end-members, respectively, whereas Sr isotopic composition is bracketed combining three lithogenic (Mexcala/Morelos, Tilzapotla and Taxco Schist) sources. Finally, leachates have a mixture of lead from ore-sulfides and Taxco Schist Formation (Family I) or from ore-sulfides alone (Family II). The application of multiple environmental isotopic techniques is an outstanding tool for elucidating complex interactions of water with bedrocks and tailings and for determining the source of sulfur and toxic metal from mining and other metal polluted environments.     

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.     

Lead in sediments and suspended particulate matter of the German Bight: natural versus anthropogenic origin

Sediments (568) and suspended particulate matter (SPM, 302 samples) of the southern German Bight and the adjacent tidal flat areas were analysed for selected major elements (Al, Fe, K), trace metals (Mn, Pb), and ²⁰⁶Pb/²⁰⁷Pb ratios using XRF, ICP–OES, ICP–MS. For selected samples a leaching procedure with 1 M HCl was used to estimate the Pb fraction associated with labile phases (e.g. Mn/Fe-oxihydroxide coatings) in contrast to the resistant mineral matrix. Enrichment factors versus average shale (EFS) reveal elevated Pb contents for all investigated sediments and SPM in the following order: Holocene tidal flat sediments (HTF, human-unaffected) <recent tidal flat sediments (RTF) <Helgoland Island mud hole sediments (MH) <nearshore SPM (SPM concentration>5 mg l⁻¹) < offhore SPM (<5 mg l⁻¹). Besides pollution, RTF contain elevated amounts of natural Pb-rich materials (K-feldspars and heavy minerals) due to a man-made high-energy environment (dike building) in comparison to HTF. ²⁰⁶Pb/²⁰⁷Pb ratios of RTF (1.192±0.019) are similar to the local geogenic background, determined from HTF (1.207±0.008). In contrast, Pb isotope ratios of nearshore SPM (1.172±0.007) and offshore SPM (1.166±0.012) show a distinct shift towards the anthropogenic/atmospheric signal of 1.11–1.14. This difference between RTF and SPM supports the assumption of low deposition rates of fine material in the intertidal systems. As the ²⁰⁶Pb/²⁰⁷Pb ratios of SPM do not reach the pure anthropogenic signal, the adsorbed Pb fraction was examined (leaching). However, the leachates also contained large amounts of geogenic Pb (SPM ≈40%, recent sediments ≈60%). The authors assume that the uptake of natural Pb occurs in nearshore waters, presumably in the turbid intertidal systems. Possible sources for dissolved Pb are mobilisation during weathering (geogenic signal) and dissolution of oxihydroxide coatings with subsequent release from porewaters, and unspecific riverine input. Comparatively small parts of SPM leave the coastal water mass and reach the open North Sea. This process therefore leads to a decontamination of the tidal flat sediments. Due to more pronounced atmospheric input, the offshore SPM becomes enriched in anthropogenic Pb as indicated by decreasing ²⁰⁶Pb/²⁰⁷Pb ratios with increasing distance from the coast.     

Sulfur, Carbon and Lead Isotope Studies of the Dajing Polymetallic Deposit in Linxi County, Inner Mongolia, China – Implication for Metallogenic Elements from Hypomagmatic Source

Abstract: The Dajing Cu‐polymetallic ore deposit in Linxi county, Inner Mongolia Autonomous Region, China, is economically a valuable Cu–Sn–Ag–Zn–Pb deposit in the southern section of the Da Hinggan metallogenic province. For the analyzed 23 samples of sulfide minerals, including chalcopyrite, pyrite, sphalerite and galena, the δ³⁴S values range from –1.8 to +3.8 % with an average of +0.65 %. The narrow distributions of the δ³⁴S values with +1 % peak value, including the published data, and the δ¹³C values around –5 % indicate that the sulfur and carbon of the hydrothermal fluids are derived from a hypomagmatic source, and exclude the possibility that the hosted strata, i.e., the Upper Permian Linxi Formation, provided certain amounts of sulfur and carbon. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of sulfide ores range respectively within 18.257‐18.368, 15.476‐15.609, and 37.916‐38.355 with the model ages of 122–209 Ma. The black shale, however, contains higher radiogenic lead with the ²⁰⁶Pb/²⁰⁴Pb ratios of 18.473‐20.156, differing from the ores. However, the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of the ore, basaltic porphyrite and feldspar leads are similar, and lie on the same lines in the diagrams of ²⁰⁸Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb. The fact that these mixing lines are composed of the two end members, the mantle and orogenic belt, strongly supports that all the metallogenic elements were carried by the hypomagma mixing the matters of the mantle and orogenic belt prior to the Mesozoic. Therefore, the Dajing ore deposit is a typical mag–matic–hydrothermal vein type ore deposit associated with subvolcanic rocks.     

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 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.     

A Critical Evaluation of U–Pb Calibration Schemes Used in SIMS Zircon Geochronology

Precision and accuracy in SIMS zircon geochronology strongly depend on the method of determination of the interelement ion ratios (e.g., ²⁰⁶Pb/²³⁸U) from the measured secondary ion ratios (²⁰⁶Pb⁺/²³⁸U⁺). Six possible U–Pb calibrations (Pb/U–UO₂/U, Pb/U–UO/U, Pb/U–UO₂/UO, Pb/UO–UO₂/U, Pb/UO–UO/U, Pb/UO–UO₂/UO) based on simple power law relationships, and Pb/UO₂‐related one‐ and two‐ (a power law) dimensional ones were compared using data acquired on the 91500 zircon reference material from one hundred measurement sessions, to determine the most statistically reliable scheme. Taking advantage of U oxide species (UO and UO₂) over atomic U, due to their similar energy distribution to Pb and higher intensities, the data calibrated with Pb/UO–UO₂/UO showed the smallest mean uncertainties and dispersions, and provided the best‐fit calibration curve consistently. Although it was demonstrated with Temora 2 that the unknown zircon age was not changed significantly by different calibrations, its precision could be improved using the Pb/UO–UO₂/UO calibration in zircon geochronology.     

Determination of U–Pb Ages for Young Zircons using Laser Ablation‐ICP‐Mass Spectrometry Coupled with an Ion Detection Attenuator Device

We have developed new analytical procedures to measure precise and accurate ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for young (~ 1 Ma) zircons using laser ablation‐ICP‐mass spectrometry. For young zircons, both careful correction for the background counts and analysis of very small Pb/U ratios (i.e., ²⁰⁶Pb/²³⁸U < 0.00016 and ²⁰⁷Pb/²³⁵U < 0.0001 for 1 Ma zircons) are highly desired. For the correction of the background, the contribution of the background signal intensities for the analytes, especially for the residual signal intensities for ²⁰⁶Pb and ²⁰⁷Pb, was defined through laser ablation of synthesised zircons (ablation blank) containing negligible Pb. The measured signal intensities for ²⁰²Hg, ²⁰⁶Pb and ²⁰⁷Pb signals obtained by the ablation blank were slightly higher than those obtained by data acquisition without laser ablation (gas blank). For the wider dynamic range measurements on Pb/U ratios, an attenuator device for the ion detection system was employed to extend the capability to monitor high‐intensity signals (i.e., > 3 Mcps). Through the attenuator device, the ion currents were reduced to 1/450 of the signal intensity without the attenuator. Because the switching time for the attenuator was shorter than 1 ms, signal intensities for only specific isotopes could be reduced. With attenuation of the ²³⁸U signal, counting statistics on ²⁰⁶Pb and ²⁰⁷Pb isotopes could be improved and counting loss on the ²³⁸U signal could be minimised. To demonstrate the reliability of this new analytical technique, ²³⁸U–²⁰⁶Pb and ²³⁵U–²⁰⁷Pb ages for three young zircon samples (collected from Osaka Group Pink Volcanic Ash, Kirigamine and Bishop Tuff) were measured. The data presented here demonstrate clearly that the present technique could become a major analytical tool for in situ U–Pb age determination of young zircons (~ 1 Ma).