Radioisotope dynamics - the origin and fate of nuclides in groundwater

The use of radionuclides as clocks for groundwater dating and as probes to investigate the geometry and spatial extent of the contact area between rocks and water is reviewed. Subsurface production rates for²²²Rn³⁷Ar,⁸⁵Kr,³⁹Ar,³⁶CI,³He,⁴He and⁴⁰Ar in various rock types are listed. Measured Rn fluxes from the surface of sandstone grains and from pieces of granite point to scale-dependent diffusion coefficients. The temporal evolution of subsurface-produced²²²Rn-,³⁷Ar-,⁸⁵Kr- and³⁹Ar-activities in groundwaters yields radionuclide escape factors between 0.1 % and 9% for the Stripa granite (Sweden) and between 1% and 4% for the Milk River sandstone (Canada). The combination of³H,⁸⁵Kr,³⁹Ar,¹⁴C,³⁶CI,⁴He in the UK Triassic sandstone aquifer allows groundwater dating up to 40 000 a. Very old groundwaters can be studied using Cl,³⁶Cl and⁴He evolution as demonstrated in the Milk River aquifer in Canada.     

Geochemistry,radiocarbon ages,and paleorecharge conditions along a transect in the central High Plains aquifer,southwestern Kansas,USA

Water samples from short-screen monitoring wells installed along a 90-km transect in southwestern Kansas were analyzed for major ions, trace elements, isotopes (H, B, C, N, O, S, Sr), and dissolved gases (He, Ne, N₂, Ar, O₂, CH₄) to evaluate the geochemistry, radiocarbon ages, and paleorecharge conditions in the unconfined central High Plains aquifer. The primary reactions controlling water chemistry were dedolomitization, cation exchange, feldspar weathering, and O₂ reduction and denitrification. Radiocarbon ages adjusted for C mass transfers ranged from <2.6 ka (¹⁴C) B.P. near the water table to 12.8 ± 0.9 ka (¹⁴C) B.P. at the base of the aquifer, indicating the unconfined central High Plains aquifer contained a stratified sequence of ground water spanning Holocene time. A cross-sectional model of steady-state ground-water flow, calibrated using radiocarbon ages, is consistent with recharge rates ranging from 0.8 mm/a in areas overlain by loess to 8 mm/a in areas overlain by dune sand. Paleorecharge temperatures ranged from an average of 15.2 ± 0.7 °C for the most recently recharged waters to 11.6 ± 0.4 °C for the oldest waters. The temperature difference between Early and Late Holocene recharge was estimated to be 2.4 ± 0.7 °C, after taking into account variable recharge elevations. Nitrogen isotope data indicate NO₃ in paleorecharge (average concentration=193 μM) was derived from a relatively uniform source such as soil N, whereas NO₃ in recent recharge (average concentration=885 μM) contained N from varying proportions of fertilizer, manure, and soil N. Deep water samples contained components of N₂ derived from atmospheric, denitrification, and deep natural gas sources. Denitrification rates in the aquifer were slow (5 ± 2× 10⁻³ μmol N L⁻¹ a⁻¹), indicating this process would require >10 ka to reduce the average NO₃ concentration in recent recharge to the Holocene background concentration.     

Fluorite (U–Th)/He thermochronology: Constraints on the low temperature history of Yucca Mountain,Nevada

Fluorite is one of the secondary minerals precipitated in pore spaces at the future nuclear waste repository site at Yucca Mountain, Nevada. The authors have conducted (U–Th)/He dating of this fluorite in an attempt to constrain the temperature and timing of paleo-fluid flux into the site. Repeated analysis of colourless fluorite yielded a weighted average age of 9.7 ± 0.15 Ma (2σ), younger than previously determined sanidine ⁴⁰Ar/³⁹ Ar ages (12.8 Ma) for deposition of the tuff.Laboratory He-diffusion experiments conducted on the Yucca fluorite yield a preliminary He closure temperature (T_c) of 90 ± 10 °C (cooling rate of 10 °C/Ma) and previous studies have determined that the fluorite precipitated from warm fluids (65–80 °C) at depths of <400 m. However, minerals can experience partial He loss at temperatures well below the T_c and therefore the (U–Th)/He age of 9.7 Ma is interpreted to be a cooling age. This result implies that the last period of elevated temperature fluid circulation through the Yucca site was approximately 9.7 Ma ago.It was observed that the purple coloured outer portion of the fluorite nodule yielded non-reproducible and invariably older ages than colourless fluorite. Several possible reasons are suggested.     

U-Pb and Ar/Ar geochronological constraints on the exhumation history of the North Qinling terrane, China

The amphibolite facies grade North Qinling metamorphic unit forms the centre of the Qinling orogenic belt. Results of LA-ICP-MS U-Pb zircon, ⁴⁰Ar/³⁹Ar amphibole and biotite dating reveal its Palaeozoic tectonic history. U-Pb zircon dating of migmatitic orthogneiss and granite dykes constrains the age of two possible stages of migmatization at 517 ± 14 Ma and 445 ± 4.6 Ma. A subsequent granite intrusion occurred at 417 ± 1.6 Ma. The ⁴⁰Ar/³⁹Ar plateau ages of amphibole ranging from 397 ± 33 Ma to 432 ± 3.4 Ma constrain the cooling of the Qinling complex below ca. 540 °C and biotite ⁴⁰Ar/³⁹Ar ages at about 330–368 Ma below ca. 300 °C. The ages are used to construct a cooling history with slow/non-exhumation during 517– 445 Ma, a time-integrated cooling at a rate < 2.5 °C/Ma during the period of 445–410 Ma, an acceleration of cooling at a rate of 8 °C/Ma from 397 Ma to 368 Ma, and subsequently slow/non-cooling from 368 to 330 Ma. The data show a significant delay in exhumation after peak metamorphic conditions and a long period of tectonic quiescence after the suturing of the North China and South China blocks along the Shangdan suture. These relationships exclude classical exhumation models of formation and exhumation of metamorphic cores in orogens, which all imply rapid cooling after peak conditions of metamorphism.     

Thermochronological record of Middle–Late Jurassic magmatic reheating to Eocene rift-related rapid cooling in the SE South China Block

We investigate the Mesozoic–Cenozoic thermal history of the Daxi region (central SE South China Block) to evaluate the influence of the subduction of the Paleo-Pacific oceanic plate beneath the SE South China Block along the block's southeast margin on the tectonothermal evolution of the upper plate. We apply a multi-chronological approach that includes U-Pb geochronology on zircon, ⁴⁰Ar/³⁹Ar dating on muscovite and biotite from granitic rocks as well as fission-track and (U-Th-Sm)/He analyses on zircon and apatite from granitic and sedimentary rocks. The Heping granite, located in the Daxi region, has a magmatic age of ca. 441 Ma. The biotite ⁴⁰Ar/³⁹Ar ages of ca. 193 Ma for the Early Jurassic Shibei granite and ca. 160 Ma for the Late Jurassic Fogang granite, respectively, reflect magmatic cooling. The Triassic Longyuanba granite yielded a muscovite ⁴⁰Ar/³⁹Ar age of ca. 167 Ma, recording heating to ≥ 350 °C induced by nearby intrusion of Middle Jurassic granites. Zircon fission-track and (U-Th-Sm)/He ages from Lower Carboniferous–Lower Jurassic sandstones (140–70 Ma) record continuous cooling during the Cretaceous that followed extensive Middle–Late Jurassic magmatism in the Daxi region. Cretaceous cooling is related to exhumation in an extensional tectonic setting, consistent with lithospheric rebound due to foundering and rollback of the subducted Paleo-Pacific oceanic plate. Apatite fission-track (53–42 Ma) and (U-Th-Sm)/He ages (43–36 Ma), and thermal modelling document rapid cooling in the Paleocene–Eocene, which temporally coincides with continental rifting in the SE South China Block in the leadup to the opening of the South China Sea.     

Refertilization of lithospheric mantle beneath the Yangtze craton in south-east China: Evidence from noble gases geochemistry

The Yangtze craton (YC), in eastern China, is one of the oldest cratons in the world and is characterized by a complex tectonic and geodynamic evolution. This evolution regards most of the eastern China craton, which since Mesozoic time has undergone significant thinning (> 200 km) of Archean lithosphere. This thinning favored the refertilization of the old refractory subcontinental lithospheric mantle (SCLM) by the upwelling of younger fertile asthenosphere. Whether this feature is localized only beneath certain areas of eastern China or is a more widespread characteristic of the mantle, including the YC, is a matter of debate.In order to constrain the history of the YC SCLM, we have measured the He- and Ar-isotopic compositions of fluid inclusions hosted in mantle xenoliths in the Lianshan area, which is part of the poorly investigated YC in south-east China. We also report new mineral chemistry and trace element compositions of clinopyroxenes from the same suite of samples, for comparison with noble gases. Two distinct types of xenoliths can be identified: Type 1, characterized by mantle-like He-isotopic (³He/⁴He) ratios (up to 9.1 Ra), represents fragments of a fertile lithospheric mantle; Type 2, showing ³He/⁴He values in the SCLM range (³He/⁴He < 7 Ra), represents shallow relicts of a refractory mantle. The patterns of rare-earth elements as well as the Y and Yb concentrations in the clinopyroxenes normalized to primitive mantle (Y_N and Yb_N, respectively) indicate that fractional partial melting might have affected the local mantle by < 3% in Type 1 and up to 20% in Type 2 xenoliths from Lianshan, respectively. The range of ⁴He/⁴⁰Ar* (⁴⁰Ar* is corrected for atmospheric contamination) ranges from 4.9 × 10^− 4 to 3.6 × 10^− 1, which is below the typical production ratio of the mantle (⁴He/⁴⁰Ar* = 1–5); this range is however compatible with this fractional partial melting. The variable ³He/⁴He and ⁴He/⁴⁰Ar* values in Lianshan xenoliths suggest that the local mantle source was also influenced by kinetic fractionation, possibly triggered by metasomatic melts. Metasomatism associated with carbonatitic melts, together with fluxing by CO₂-rich fluids, have permeated the mantle beneath Lianshan, generating the observed decoupling between noble gases and trace elements. The interpretative framework is also applicable for other mantle xenoliths from eastern China, indicating that the refertilization of the SCLM by ascending mantle-like melts is common also to YC, which can be identified using noble gases.     

New evidence of mantle heterogeneity beneath the Hyblean Plateau (southeast Sicily,Italy) as inferred from noble gases and geochemistry of ultramafic xenoliths

We analyzed major and trace elements, Sr and Nd isotopes in ultramafic xenoliths in Miocenic age Hyblean diatremes, along with noble gases of CO₂-rich fluid inclusions hosted in the same products. The xenoliths consist of peridotites and pyroxenites, which are considered to be derived from the upper mantle. Although the mineral assemblage of peridotites and their whole-rock abundance of major elements (e.g., Al₂O₃ = 0.8–1.5 wt.%, TiO₂ = 0.03–0.08 wt.%) suggest a residual character of the mantle, a moderate enrichment in some incompatible elements (e.g., La_N/Yb_N = 9–14) highlights the presence of cryptic metasomatic events. In this context a deep silicate liquid is considered the metasomatizing agent, which is consistent with the occurrence of pyroxenites as veins in peridotites. Both the Zr/Nb and ¹⁴³Nd/¹⁴⁴Nd ratios of the investigated samples reveal two distinct compositional groups: (1) peridotites with Zr/Nb ≈ 4 and ¹⁴³Nd/¹⁴⁴Nd ≈ 0.5129, and (2) pyroxenites with Zr/Nb ≈ 20 and ¹⁴³Nd/¹⁴⁴Nd ≈ 0.5130. The results of noble-gas analyses also highlight the difference between the peridotite and pyroxenite domains. Indeed, the ³He/⁴He and ⁴He/⁴⁰Ar* ratios measured in the fluid inclusions of peridotites (respectively 7.0–7.4 ± 0.1 Ra and 0.5–8.2, where Ra is the atmospheric ³He/⁴He ratio of 1.38 × 10^? 6) were on average lower than those for the pyroxenites (respectively 7.2–7.6 Ra and 0.62–15). This mantle heterogeneity is interpreted as resulting from a mixing between two end-members: (1) a peridotitic layer with ³He/⁴He ≈ 7 Ra and ⁴He/⁴⁰Ar* ≈ 0.4, which is lower than the typical mantle ratio (~ 1–4) probably due to melt extraction events, and (2) metasomatizing mafic silicate melts that gave rise to pyroxenites characterized by ³He/⁴He ≈ 7.6 Ra, with a variable ⁴He/⁴⁰Ar* due to degassing processes connected with the ascent of magma at different levels in the peridotite wall rock. The complete geochemical data set also suggests two distinct mantle sources for the xenolithic groups highlighted above: (1) a HIMU (high-μ)-type source for the peridotites and (2) a DM (depleted mantle)-type source for the pyroxenites.     

Age structure and recharge conditions of a coastal aquifer (northern Germany) investigated with 39Ar, 14C, 3H, He isotopes and Ne

A tide-influenced two-layer aquifer system in northern Germany was investigated using environmental dating tracers (³H, ³⁹Ar, ¹⁴C), the noble gas isotopes ³He, ⁴He and Ne. The study area is a marshland at the River Ems estuary, exposed to regular flooding until?AD 1000. The construction of dykes, artificial land drainage and groundwater abstraction define the hydraulic gradient. The aquifer depicts a pronounced age stratification with depth. Tritium concentrations above 0.03 TU are found only in the top 30?m. Two tritium-free samples between 20 and 30?m depth show ³⁹Ar ages of 130 and 250?years. Below a clay layer?Cabout 50?m below surface level (mbsl)?Call analysed samples are ³⁹Ar free and, thus, older than 900?years. The initial ¹⁴C activities were about 70 pmC. Resulting ¹⁴C ages increase with depth and increase up to 9,000?years, in agreement with minimal ³⁹Ar ages. Concentrations of radiogenic ⁴He correlate with ¹⁴C ages. Samples in a mid-depth range (20?C70 mbsl) show significant gas loss. The gas loss is assigned to recharge in a methane producing environment. Deduced ⁴He ages were used to assign this water to a infiltration period of about AD 1000.     

Isotope and dissolved gas evidence for nitrogen attenuation in landfill leachate dispersing into a chalk aquifer

The authors present data for the chemical, stable isotope (¹³C/¹²C, ¹⁵N/¹⁴N and ³⁴S/³²S), and dissolved gas (N₂, Ar, O₂ and CH₄) composition of groundwaters sampled in and around a landfill site in Cambridgeshire, England. Decomposition of 3 × 10⁶ m³ of largely domestic waste, placed in unlined quarries, has given rise to the formation of an NH₄-rich leachate dispersing as a plume into the surrounding Middle Chalk aquifer. In addition to identifying zones of methanogenesis and SO₄ reduction, the data indicate processes of NH₄ transformation by either assimilation or oxidation, and losses by formation of N₂. Depending on the mixing ratio between leachate and background water, it may be possible to account for all NH₄ loss by combined nitrification + denitrification in a system where there are abrupt temporal and spatial changes in redox conditions.     

Geochronology of the initiation and displacement of the Altyn Strike-Slip Fault,western China

⁴⁰Ar/³⁹Ar dating studies have been carried out along the Dangjin Pass transect across the Altyn Strike-Slip Fault (ASSF). The samples gave ages of 445.2–454.3 Ma in the Northern Belt, 164.3–178.4 Ma in the Mesozoic Shear Zone and 26.3–36.4 Ma in the Cenozoic Shear Zone. Using the piercing point of the Bashikaogong Fault and the Cangma-Heihe Fault an offset of 350–400 km along the ASSF has been estimated. The ⁴⁰Ar/³⁹Ar dating of the syntectonic-growth or syntectonic-resetting minerals from the samples within the ASSF belt, and offset estimations from different age piercing points suggest that the ASSF should be initiated in the Middle Jurassic (178.4–160 Ma). Combined with previously reported ages, our studies show that the ASSF is characterized by multi-phase re-activation during 85–100, 25-40 and 8–10 Ma following its initiation in the Middle Jurassic in the regional tectonic setting of convergence between the Indian and Eurasian continents.     

Geology,geochemistry and age of the Hukeng tungsten deposit,Southern China

The Hukeng tungsten deposit, located in the Wugongshan area in central part of Jiangxi province, South China, is a large-scale quartz-vein wolframite deposit. It is hosted in the Hukeng granitic intrusion. Based on the mineral assemblage and crosscutting relationship of the veins, three mineralization stages are identified, including: (1) quartz–wolframite stage, (2) quartz–fluorite–wolframite stage, and (3) quartz–pyrite–sphalerite–wolframite stage.The homogenization temperatures of fluid inclusions in vein quartz vary from 220 to 320 °C, and the salinities are from 0 to 10 wt.% NaCl equiv.; corresponding densities range from 0.7 to 1 g/cm³. These features indicated that the ore-forming fluids in the Hukeng tungsten deposit have medium temperature, low density and low salinity.The δ¹⁸OSMOW values of quartz range from 10.8‰ to 14.4‰, with corresponding δ¹⁸O_fluid values of 3.7‰ to 7.7‰, and δD values of fluid inclusions of between ? 70‰ and ? 55‰. The combined isotopic data indicate that the ore-forming fluids of the Hukeng tungsten deposit were mainly derived from magmatic water, with some minor input from meteoric water.We have carried out molybdenite Re–Os and muscovite ⁴⁰Ar/³⁹Ar dating to constrain the timing of mineralization. Re–Os dating of six molybdenite samples yielded model ages ranging from 149.1 ± 2.0 to 150.7 ± 3.7 Ma, with an average of 150.0 Ma. The Re–Os analyses give a well-defined ¹⁸⁷Re/¹⁸⁷Os isochron with an age of 150.2 ± 2.2 Ma (MSWD = 0.60). Hydrothermal muscovite yields a plateau ⁴⁰Ar/³⁹Ar age of 147.2 ± 1.4 Ma. ⁴⁰Ar/³⁹Ar age is in good agreement with the Re–Os age. These ages show that the timing of tungsten mineralization occurred at about 150 Ma. Our new data, when combined with published geochronological results from the other major deposits in this region, suggest that widespread W mineralization occurred in the Late Jurassic throughout South China.     

Magma mixing and gold mineralization in the Maevatanana gold deposit,Madagascar

The Maevatanana gold deposit in Madagascar is hosted by Archean metamorphic rocks in quartz–sulfide veins that are structurally controlled by NNW–SSE trending shear zones. Fluid inclusion data show that the trapping conditions in quartz range from 0.87 to 2.58 kbar at temperatures of 269–362 °C. Laser Raman spectroscopy confirms that these inclusions consist of CO₂, SO₂, and H₂O. The δ³⁴S values of the pyrites range from 1.7‰ to 3.6‰, with an average of 2.25‰, supporting a magmatic origin. Noble gases (He, Ne, Ar, Ke, Xe) are chemically inert, thus will not be involved in chemical reactions during geological processes. Also due to the low concentration of He in the atmosphere and the low solubility of He in aqueous fluids, the atmosphere-derived He is unlikely to significantly affect He abundances and isotopic ratios of crustal fluids, ensures that He production should have the typical crust ³He/⁴He ratios. The ³He/⁴He ratios of fluid inclusions in pyrite from the deposit range from 0.06 to 0.12 Ra, while the ⁴⁰Ar/³⁶Ar ratios range from 6631 to 11441. We infer that the ore-forming fluids could have been exsolved from a granitic magma. The oxygen and hydrogen isotope compositions of the ore-forming fluids (1.5‰ ≤ δ¹⁸O_H2O ≤ 7.8‰; –72‰ ≤ δD ≤ –117‰) indicate they were derived from a granitic magma. Four pyrite samples from the gold deposit yield a precise Re–Os isochron age of 534 ± 13 Ma. Given that the post-collisional granites in northern and central Madagascar were derived by melting of sub-continental lithospheric mantle and formed between 537 and 522 Ma, we can state that the gold metallogenesis was coeval with the crystallization age of these parental magmas. These data could be accounted for the formation of the Maevatanana gold deposit. First, the shear zones hosting the deposit formed around 2.5 Ga, when the Madagascan micro-continental blocks collided with other continental blocks, triggering large-scale tectono-magmatic activity and forming NNW–SSE trending shear zones. The gold mineralization at Maevatanana is coeval with the crystallization age of the Cambrian post-collisional A-type granitoid plutons in northern and central Madagascar, implying that this deposit is associated with extensional collapse of the East African Orogen. This extension in turn induced asthenospheric upwelling, melting of sub-continental lithospheric mantle. These magmas underplated the lower crust, generating voluminous granitic magmas by partial melting of the lower crust. The mixing magma during tectono-thermal reactivation of the East African Orogen produced large volumes of volatiles that extracted gold from the granitic magma and produced Au–S complexes (e.g., Au(HSO₃)²⁻). The shear zones, which were then placed under extensional collapse of the East African Orogen in the Cambrian, formed favorable pathways for the magmatic ore-forming fluids. These fluids then precipitated gold-sulfides that form the Maevatanana gold deposit.     

Fluid inclusion geochemistry and Ar–Ar geochronology of the Cenozoic Bangbu orogenic gold deposit,southern Tibet,China

Located along the southern part of the Yarlung Zangbo suture zone in southern Tibet, Bangbu is one of the largest gold deposits in Tibet. Auriferous sulfide-bearing quartz veins are controlled by second- or third-order brittle fractures associated with the regional Qusong–Cuogu–Zhemulang brittle-ductile shear zone. Fluid inclusion studies show that the auriferous quartz contains aqueous inclusions, two-phase and three-phase CO₂-bearing inclusions, and pure gaseous hydrocarbon inclusions. The CO₂-bearing inclusions have salinities of 2.2–9.5% NaCl_eq, and homogenization temperatures (Th) of 167–336 °C. The δD, δ¹⁸O, and δ¹³C compositions of the Bangbu ore-forming fluids are − 105.5 to − 44.4‰, 4.7 to 9.0‰ and − 5.1 to − 2.2‰, respectively, indicating that the ore-forming fluid is mainly of metamorphic origin, with also a mantle-derived contribution. The ³He/⁴He ratio of the ore-forming fluids is 0.174 to 1.010 R_a, and ⁴⁰Ar/³⁶Ar ranges from 311.9 to 1724.9. Calculations indicate that the percentage of mantle-derived He in fluid inclusions from Bangbu is 2.7–16.7%. These geochemical features are similar to those of most orogenic gold deposits. Dating by ⁴⁰Ar/³⁹Ar of hydrothermal sericite collected from auriferous quartz veins at Bangbu yielded a plateau age of 44.8 ± 1.0 Ma, with normal and inverse isochronal ages of 43.6 ± 3.2 Ma and 44 ± 3 Ma, respectively. This indicates that the gold mineralization was contemporaneous with the main collisional stage between India and Eurasia along the Yarlung Zangbo suture, which resulted in the development of near-vertical lithospheric shear zones. A deep metamorphic fluid was channeled upward along the shear zone, mixing with a mantle fluid. The mixed fluids migrated into the brittle structures along the shear zone and precipitated gold, sulfides, and quartz because of declining temperature and pressure or fluid immiscibility. The Bangbu is a large-scale Cenozoic syn-collisional orogenic gold deposit     

Assessing the solubility controls on vanadium in groundwater,northeastern San Joaquin Valley,CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H₂VO₄⁻. Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V⁵⁺ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH)₃⁺]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH)₃ molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V³⁺- or mixed V³⁺/Fe³⁺-oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions.Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO₃) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO₃ extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.     

40Ar/39Ar dating of the Jiehe gold deposit in the Jiaodong Peninsula,eastern North China Craton: Implications for regional gold metallogeny

The Jiehe gold deposit, containing a confirmed gold reserve of 34 tonnes (t), is a Jiaojia-type (disseminated/stockwork-style) gold deposit in Jiaodong Peninsula. Orebodies are hosted in the contact zone between the Jurassic Moshan biotite granite and the Cretaceous Shangzhuang porphyritic granodiorite, and are structurally controlled by the NNE- to NE-striking Wangershan-Hedong Fault. Sulphide minerals are composed predominantly of pyrite with lesser amounts of chalcopyrite, galena, and sphalerite. Hydrothermal alteration is strictly controlled by fracture zones, in which disseminated sulfides and native gold are spatially associated with pervasive sericitic alteration. Mineralogical, textural, and field relationships indicate four stages of alteration and mineralization, including pyrite-bearing milky and massive quartz (stage 1), light-gray granular quartz–pyrite (stage 2), quartz–polysulfide (stage 3) and quartz–carbonate (stage 4) stages. Economic gold is precipitated in stages 2 and 3.The Jiehe deposit was previously considered to form during the Eocene (46.5 ± 2.3 Ma), based on Rb-Sr dating of sericite. However, ⁴⁰Ar/³⁹Ar dating of sericite in this study yields well-defined, reproducible plateau ages between 118.8 ± 0.7 Ma and 120.7 ± 0.8 Ma. These ⁴⁰Ar/³⁹Ar ages are consistent with geochronological data from other gold deposits in the region, indicating that all gold deposits in Jiaodong formed in a short-term period around 120 Ma. The giant gold mineralization event has a tight relationship with the extensional tectonic regime, and is a shallow crustal metallogenic response of paleo-Pacific slab subduction and lithospheric destruction in the eastern NCC.     

Early Paleoproterozoic–Archean dykes and gneisses in Russian Karelia of the Fennoscandian Shield—New paleomagnetic,isotope age and geochemical investigations

We present here new palaeomagnetic, isotopic age and geochemical data from Archean and Early Palaeoproterozoic rocks in the eastern Fennoscandian Shield. We have studied NE–SW trending gabbronorite dyke sets and their host Archean basement rocks in the Vodlozero block near the 2449 Ma Burakovka layered intrusion in southern Russian Karelia. Both dyke sets are genetically related to the Burakovka intrusion. The other, ca. 25 km long Avdeev dyke, locating a few kilometers south from the Burakovka intrusion, yields a stable single component remanence direction that is in agreement with the direction previously obtained from the Burakovka intrusion. Another NE–SW trending dyke, 0.8 m wide Shalskiy diabase dyke, about 30 km south of the Burakovka intrusion yields a similar remanence direction as the Avdeev dyke. The overall mean remanence direction has a palaeopole at Plat = −12.3°N, Plong = 243.5°E (A95 = 15.4°, 4 sites, 28 samples). The thin Shalskiy diabase dyke transects a similarly NE–SW trending 500 m wide coarse grained gabbronorite dyke which has now been dated by Sm–Nd method as 2608 ± 56 Ma. Geochemically all the dykes are quite similar showing slight calc-alkaline affinity and low TiO₂ and high SiO₂ with moderate MgO and low Cr and Ni. Furthermore, the dykes are geochemically identical to the 2.45 Ga dyke swarm in the northern Karelian Province.The remanence direction of the thin Shalskiy diabase dyke differs significantly from the high temperature and high coercivity remanence component of the unbaked Archean gabbronorite dyke which yields a palaeopole at Plat = 22.7°N, Plong = 222.1°E (dp = 8.2°, dm = 16.2°, five samples). On the basis of different remanence directions of the diabase dyke and the unbaked Archean gabbronorite dyke, the baked contact test for the diabase dyke is positive. In addition to the high temperature and high coercivity component of the baked and unbaked Archean gabbronorite dyke, in low temperatures and coercivities we isolated a similar component as in the diabase dyke. A comparable remanence component was also obtained from the Archean basement at ca. 8 km from the dykes. We propose that in the studied area, the Archean basement and the Archaean dyke were partly remagnetized due to emplacement and subsequent uplift and cooling of the large Burakovka layered intrusion and related dykes at about 2.40 Ga ago.This interpretation lends support from a new ⁴⁰Ar/³⁹Ar dating of hornblende from another area, Lake Paajarvi area, in northern Karelia. There, a negative baked contact test was previously obtained for the remanence of the dated ca. 2.45 Ga dyke rocks related to the ca. 2.45 Ga Oulanka layered intrusion. The ⁴⁰Ar/³⁹Ar dating of the unbaked Archean basement which yields the same remanence component as the dykes, shows a plateau age of ca. 2.6 Ga, but in addition, it also shows resetting of the basement at ca. 2.4 Ga ago. The dating thus supports reactivation and partial remagnetization of the Archean basement at ca. 2.4 Ga ago.Our new palaeomagnetic results from the Burakovka dykes and the new ⁴⁰Ar/³⁹Ar dating from the Lake Paajarvi area give support to our previous interpretation that at Lake Paajarvi area the remanence component suggested to be 2.4 Ga, despite to negative baked contact test, is indeed of this age. Therefore, it is implied that the results can be used for continental reconstructions.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Metallogenesis at the Carris W–Mo–Sn deposit (Gerês,Portugal): Constraints from fluid inclusions,mineral geochemistry,Re–Os and He–Ar isotopes

The Carris orebody consists of two partially exploited W–Mo–Sn quartz veins formed during successive shear stages and multipulse fluid fillings. They cut the Variscan post-D3 Gerês I-type granite. The most important ore minerals are wolframite, scheelite, molybdenite and cassiterite. There are two generations of wolframite. The earlier generation of wolframite is rare and has the highest WO₄Mn content (91 mol%) and the most common wolframite contains 26–57 mol% WO₄Mn. Re–Os dating of molybdenite from the ore quartz veins and surrounding granite yields ages of 279 ± 1.2 Ma and 280.3 ± 1.2 Ma, respectively which are in very good agreement with the previous ID-TIMS U–Pb zircon age for the Carris granite (280 ± 5 Ma).³He/⁴He ratio of pyrite ranging between 0.73 and 2.71 Ra (1 Ra = 1.39 × 10^− 6) and high ³He/³⁶Ar (0.8–5 × 10^− 3) indicate a mixture of a crustal radiogenic helium fluid with a mantle derived-fluid.The fluid inclusion studies on quartz intergrown with wolframite and scheelite, beryl and fluorite reveal that two distinct fluid types were involved in the genesis of this deposit. The first was a low to medium salinity aqueous carbonic fluid (CO₂ between 4 and 14 mol%) with less than 1.95 mol% N₂, which was only found in quartz associated with wolframite. The other was a low salinity aqueous fluid found in all the four minerals. The homogenization temperatures indicate minimum entrapment temperatures of 226–310 °C (average 280 °C) for the H₂O–CO₂–N₂–NaCl fluid and average temperatures of 266 °C for scheelite and 242 °C, 190 °C and 160 °C for the last generations of beryl, fluorite and quartz, respectively. It was estimated that wolframite was deposited ~ 7 km depth, assuming a lithostatic pressure, probably due to strong pressure fluctuation caused by seismic events triggered by brittle tectonics during the exhumation event. Precipitation of scheelite and sulphides took place later, at the same depth, but under a hydrostatic or suprahydrostatic pressure regime, and probably caused by mixing between the magmatic–hydrothermal fluid and meteoric waters that deeply penetrated the basement during post-Variscan decompression.     

Behaviour of boron and strontium isotopes in groundwater–aquifer interactions in the Cornia Plain (Tuscany,Italy)

The Cornia Plain alluvial aquifer, in Tuscany, is exploited intensely to meet the demand for domestic, irrigation and industrial water supplies. The B concentration of groundwater, however, is often above the European limit of 1 mg L⁻¹, with the result that exploitation of these water resources requires careful management. Boron and Sr isotopes have been used as part of a study on the origin and distribution of B dissolved in groundwater, and indirectly as a contribution to the development of appropriate water management strategies.The geochemistry of the Cornia Plain groundwater changes from a HCO₃ facies in the inland areas to a Cl facies along the coastal belt, where seawater intrusion takes place. The B concentration of groundwater increases towards the coastal areas, while the ¹¹B/¹⁰B ratio decreases. This indicates that there is an increasing interaction between dissolved B and the sediments forming the aquifer matrix, whose B content is in the order of 100 mg kg⁻¹. Adsorption–desorption exchanges take place between water and the sediment fine fraction rich in clay minerals, with a net release of B from the matrix into the groundwater, and a consequent δ¹¹B shift from positive to negative values. The aquifer matrix sediments therefore seem to be the major source of B dissolved in the groundwater.The groundwater–matrix interactions triggered by the ionic strength increase caused by seawater intrusion can also be detected in the Ca–Na ion exchanges. Dissolved Sr follows a trend similar to that of Ca, while the ⁸⁷Sr/⁸⁶Sr ratio is equal to that of the exchangeable Sr of the aquifer matrix and therefore does not change significantly.These results have helped to define a new strategy for groundwater exploitation, with the final objective of reducing B concentration in the water extracted from the aquifer.     

40Ar/39Ar and U–Pb dating of the Fish Canyon magmatic system,San Juan Volcanic field,Colorado: Evidence for an extended crystallization history

The ∼ 5000 km³ Fish Canyon Tuff (FCT) is an important unit for the geochronological community because its sanidine, zircon and apatite are widely used as standards for the ⁴⁰Ar/³⁹Ar and fission track dating techniques. The recognition, more than 10 years ago [Oberli, F., Fischer, H. and Meier, M., 1990. High-resolution ²³⁸U–²⁰⁶Pb zircon dating of Tertiary bentonites and Fish Canyon Tuff; a test for age “concordance” by single-crystal analysis. Seventh International Conference on Geochronology, Cosmochronology and Isotope Geology. Geological Society of Australia Special Publication Canberra, 27:74], of a ≥ 0.4 Ma age difference between the U–Pb zircon ages and ⁴⁰Ar/³⁹Ar sanidine ages has, therefore, motivated efforts to resolve the origin of this discrepancy. To address this controversial issue, we initially performed 37 U–Pb analyses on mainly air-abraded zircons at ETH Zurich and nearly 200 ⁴⁰Ar/³⁹Ar measurements on hornblende, biotite, plagioclase and sanidine obtained at the University of Geneva, using samples keyed to a refined eruptive stratigraphy of the FCT magmatic system.Disequilibrium-corrected ²⁰⁶Pb/²³⁸U ages obtained for 29 single-crystal and three multi-grain analyses span an interval of ∼ 28.67–28.03 Ma and yield a weighted mean age of 28.37 ± 0.05 Ma (95% confidence level), with MSWD = 8.4. The individual dates resolve a range of ages in excess of analytical precision, covering ∼ 600 ka. In order to independently confirm the observed spread in zircon ages, 12 additional analyses were carried out at the Berkeley Geochronology Center (BGC) on individual zircons from a single lithological unit, part of them pre-treated by the “chemical abrasion” (CA) technique [Mattinson, J.M., 2005. Zircon U–Pb chemical abrasion (“CA-TIMS”) method: Combined annealing and multi-step partial dissolution analysis for improved precision and accuracy of zircon ages. Chemical Geology, 220(1–2): 47–66]. Whereas the bulk of the BGC results displays a spread overlapping that obtained at ETH, the group of CA treated zircons yield a considerably narrower range with a mean age of 28.61 ± 0.08 Ma (MSWD = 1.0). Both mean zircon ages determined at ETH and BGC are older than the ∼ 28.0 Ma ⁴⁰Ar/³⁹Ar eruption age of FCT – even when considering the possibility that the latter may be low by as much as ∼ 1% due to a miscalibration of the ⁴⁰K decay constants – and is thus indicative of a substantial time gap between magma crystallization and extrusion. The CA technique further reveals that younger FCT zircon ages are likely to be associated with chemically unstable U-enriched domains, which may be linked to crystallization during extended magma residence or may have been affected by pre-eruptive and/or post-eruptive secondary loss of radiogenic lead. Due to their complex crystallization history and/or age bias due to Pb loss, the FCT zircon ages are deemed unsuitable for an accurate age calibration of FCT sandine as a fluence monitor for the ⁴⁰Ar/³⁹Ar method.Even though data statistics preclude unambiguous conclusions, ⁴⁰Ar/³⁹Ar dating of sanidine, plagioclase, biotite, and hornblende from the same sample of vitrophyric Fish Canyon Tuff supports the idea of a protracted crystallization history. Sanidine, thought to be the mineral with the lowest closure temperature, yielded the youngest age (28.04 ± 0.18 Ma at 95% c.l., using Taylor Creek Rhyolite [Renne, P.R. et al., 1998. Intercalibration of standards, absolute ages and uncertainties in ⁴⁰Ar/³⁹Ar dating. Chemical Geology, 145: 117–152.] as the fluence monitor), whereas more retentive biotite, hornblende and plagioclase gave slightly older nominal ages (by 0.2–0.3 Ma). In addition, a laser step-heating experiment on a 2-cm diameter feldspar megacryst produced a “staircase” argon release spectrum (older ages at higher laser power), suggestive of traces of inherited argon in the system. Thermal and water budgets for the Fish Canyon magma indicate that the body remained above its solidus (∼ 700 °C) for an extended period of time (> 10⁵ years). At these temperatures, argon volume diffusion is thought to be fast enough to prevent accumulation of radiogenic Ar. If this statement were true, an existing isotopic record should have been completely reset within a few hundred years, regardless of the phase and initial age of the phenocryst. As these minerals are unlikely to be xenocrysts that were incorporated within such a short time span prior to eruption, we suggest that a fraction of radiogenic Ar can be retained > 10⁵ years, even at T ∼ 700 °C.