Calcite veins are a common product of hydrothermal fluid circulation. Clumped-isotope palaeothermometry is a promising technique for fingerprinting the temperature of hydrothermal fluids, but clumped-isotope systematics can be reset at temperatures of > ca. 100 °C. To model whether the reconstructed temperatures represent calcite precipitation or closed-system resetting, the precipitation age must be known. LA-ICP-MS U–Pb dating of calcite is a recently developed approach to direct dating of calcite and can provide precipitation ages for modelling clumped-isotope systematics in calcite veins. In this study, clumped-isotope and LA-ICP-MS U–Pb calcite analyses were combined in basalt-hosted calcite veins from three settings in Scotland. Samples from all three localities yielded precipitation temperatures of ca. 75–115 °C from clumped-isotope analysis, but veins from only two of the sites were dateable, yielding precipitation ages of 224 ± 8 Ma and 291 ± 33 Ma (2σ). Modelling from the dated samples enabled confident interpretation that no closed-system resetting had occurred in these samples. However, the lack of a precipitation age from the third location meant that a range of possible thermal histories had to be modelled meaning that confidence that resetting had not occurred was lower. This highlights the importance of coupling clumped-isotope thermometry and LA-ICP-MS U–Pb calcite dating in determining the temperature of hydrothermal fluids recorded in calcite veins. This paired approach is shown to be robust in constraining the timing and precipitation temperature of calcite formation, and thus for tracking hydrothermal processes.
10 March 2013 in Contributions to Mineralogy and Petrology
There is growing global concern that greenhouse gas (GHG) emissions from water bodies are increasing because of interactions between nutrient levels and climate warming. This paper investigates key land-cover, seasonal and hydrological controls of GHGs by comparison of the semi-natural, agricultural and urban environments in a detailed source-to-sea study of the River Clyde, Scotland. Riverine GHG concentrations were consistently oversaturated with respect to the atmosphere. High riverine concentrations of methane (CH4) were primarily associated with point source inflows from urban wastewater treatment, abandoned coal mines and lakes, with CH4-C concentrations between 0.1 - 44 µg l-1. Concentrations of carbon dioxide (CO2) and nitrous oxide (N2O) were mainly driven by nitrogen concentrations, dominated by diffuse agricultural inputs in the upper catchment and supplemented by point source inputs from urban wastewater in the lower urban catchment, with CO2-C concentrations between 0.1 - 2.6 mg l-1 and N2O-N concentrations between 0.3 - 3.4 µg l-1. A significant and disproportionate increase in all GHGs occurred in the lower urban riverine environment in the summer, compared to the semi-natural environment, where GHG concentrations were higher in winter. This increase and change in GHG seasonal patterns points to anthropogenic impacts on microbial communities. The loss of total dissolved carbon, to the estuary is approximately 48.4 ± 3.6 Gg C yr-1, with the annual inorganic carbon export approximately double that of organic carbon and four times that of CO2, with CH4 accounting for 0.03%, with the anthropogenic impact of disused coal mines accelerating DIC loss. The annual loss of total dissolved nitrogen to the estuary is approximately 4.03 ± 0.38 Gg N yr-1 of which N2O represents 0.06%. This study improves our understanding of riverine GHG generation and dynamics which can contribute to our knowledge of their release to the atmosphere. It identifies where action could support reductions in aquatic GHG generation and emission.
The relative depletion of high field strength elements (HFSE), such as Nb, Ta and Ti, on normalised trace-element plots is a geochemical proxy routinely used to fingerprint magmatic processes linked to Phanerozoic subduction. This proxy has increasingly been applied to ultramafic-mafic units in Archaean cratons, but as these assemblages have commonly been affected by high-grade metamorphism and hydrothermal alteration/metasomatism, the likelihood of element mobility is high relative to Phanerozoic examples. To assess the validity of HFSE anomalies as a reliable proxy for Archaean subduction, we here investigate their origin in ultramafic rocks from the Ben Strome Complex, which is a 7 km2 ultramafic-mafic complex in the Lewisian Gneiss Complex of NW Scotland. Recently interpreted as a deformed layered intrusion, the Ben Strome Complex has been subject to multiple phases of high-grade metamorphism, including separate granulite- and amphibolite-facies deformation events. Additional to bulk-rock geochemistry, we present detailed petrography, and major- and trace-element mineral chemistry for 35 ultramafic samples, of which 15 display negative HFSE anomalies. Our data indicate that the magnitude of HFSE anomalies in the Ben Strome Complex are correlated with light rare earth-element (LREE) enrichment likely generated during interaction with H2O and CO2-rich hydrothermal fluids associated with amphibolitisation, rather than primary magmatic (subduction-related) processes. Consequently, we consider bulk-rock HFSE anomalies alone to be an unreliable proxy for Archaean subduction in Archaean terranes that have experienced multiple phases of high-grade metamorphism, with a comprehensive assessment of element mobility and petrography a minimum requirement prior to assigning geodynamic interpretations to bulk-rock geochemical data.
The Lewisian Gneiss Complex of Northwest Scotland is a classic Precambrian basement gneiss complex. The Lewisian is divided into a number of terranes on the basis of structural, metamorphic and geochronological evidence. The most well-studied of these is the Assynt Terrane, which forms the central part of the Lewisian outcrop on the Scottish mainland. Field evidence shows that it has a complex tectonothermal history, the early stages of which remain poorly constrained. This paper sets out to better understand the chronology and thermal evolution of the Assynt Terrane through zircon U-Pb dating and Ti-in-zircon thermometry, the latter applied to the Lewisian for the first time. This is placed in context by integration with detailed field mapping, sample petrography, zircon cathodoluminescence (CL) imaging and rare earth element (REE) analysis.\ud \ud Zircons from six tonalite-trondhjemite-granodiorite (TTG) gneiss samples and two metasedimentary gneiss samples were analysed. The TTG gneisses were predominantly retrogressed to amphibolite-facies; zircons showed a range of CL zoning patterns and REE profiles were similar to those expected for magmatic zircon grains. Zircons from the metasedimentary gneisses also displayed a range of CL zoning patterns and are depleted relative to chondrite in heavy REEs due to the presence of garnet.\ud \ud Zircon analysis records a spread of concordant U-Pb ages from ∼2500 to 3000 Ma. There is no evident correlation of ages with location in the crystal or with CL zoning pattern. A weighted average of 207Pb/206Pb ages from the oldest igneous zircon cores from the TTG gneiss samples gives an age of 2958 ± 7 Ma, interpreted to be a magmatic protolith crystallisation age. A weighted average of 207Pb/206Pb ages of the youngest metamorphic rims yields an age of 2482 ± 6 Ma, interpreted to represent the last high-grade metamorphism to affect these rocks. Ti-in-zircon thermometry records minimum temperatures of 710–834 °C, interpreted to reflect magmatic crystallisation.\ud \ud REE profiling enabled the zircons in the metasedimentary rocks to be linked to the presence of metamorphic garnet, but resetting of U-Pb systematics precluded the determination of either protolith or metamorphic ages. Zircons from the metasedimentary gneisses generally record higher minimum temperatures (803–847 °C) than the TTG gneisses, interpreted to record zircon crystallisation in an unknown protolith.\u
1 November 2017 in Journal of Asian Earth Sciences
The Chingshui geothermal field, a moderate-temperature and water-dominated hydrothermal system, was the site of the first geothermal power plant in Taiwan. Many geological, geophysical and geochemical studies using more than 21 drilled wells have been performed since the 1960s. However, there are still controversies regarding the heat and fluid sources due to the tectonically complicated geological setting. To clarify the heat and fluid sources, we analyzed clumped isotopes with carbon and oxygen isotopic compositions of calcite scaling in geothermal wells and veins on outcrops and calculated the δ18O values of the source fluids. Two populations of δ18O values were calculated: −5.8 ± 0.8‰ VSMOW from scaling in the well and −1.0 ± 1.6‰ to 10.0 ± 1.3‰ VSMOW from outcropping calcite veins, indicative of meteoric and magmatic fluid sources, respectively. Meanwhile, two hydrothermal reservoirs at different depths have been identified by magnetotelluric (MT) imaging with micro-seismicity underneath this area. As a result, we propose a two-reservoir model: the shallow reservoir provides fluids from meteoric water for the scaling sampled from wells, whereas the deep reservoir provides magmatic fluids from deep marble decarbonization recorded in outcropping calcite veins