Clumped isotope values (Δ47) of carbonates forming in high pH conditions do not correspond to mineral precipitation temperatures due to certain effects including kinetic isotope fractionation and dissolved inorganic carbon (DIC) endmember mixing. Field-based archives of these carbonate environments are needed to evaluate and quantify these effects accurately. In this study, we measure the clumped isotope values of anthropogenic carbonates for the first time. Tufa layers were analyzed from samples precipitating in a high pH (>10) stream that drains a major slag heap in north east England. Δ47 values are 0.044‰–0.183‰ higher than expected equilibrium values. Non-linear distribution of clumped isotope data is diagnostic of DIC endmember mixing, rather than partial equilibration of DIC. Episodic dilution of hydroxide-rich stream waters by equilibrated rainfall surface runoff provides the mechanism by which mixing occurs. Δ47 values are ~0.010‰–0.145‰ higher than linear clumped isotope mixing profiles, suggesting that the majority of Δ47 increase results from a combination of endmember non-linear mixing effects and an atmosphere-hydroxide sourcing of DIC. The diagnostic trends and variation in clumped isotope values present in these results demonstrates the potential of anthropogenic carbonate systems as a useful archive for studying and quantifying kinetic effects in clumped isotopes.
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.
Application of geochemical proxies to vein minerals - particularly calcite - can fingerprint the source of fluids controlling various important geological processes from seismicity to geothermal systems. Determining fluid source, e.g. meteoric, marine, magmatic or metamorphic waters, can be challenging when using only trace elements and stable isotopes as different fluids can have overlapping geochemical characteristics, such as δ18O. In this contribution we show that by combining the recently developed LA-ICP-MS U-Pb calcite geochronometer with stable isotopes (including clumped isotope palaeothermometry) and trace element analysis, the fluid source of veins can be more readily determined. Calcite veins hosted in the Devonian Montrose Volcanic Formation at Lunan Bay in the Midland Valley Terrane of Central Scotland were used as a case study. δD values of fluid inclusions in the calcite, and parent fluid δ18O values reconstructed from clumped isotope palaeothermometry, gave values which could represent a range of fluid sources: metamorphic or magmatic fluids, or surface waters which had undergone much fluid-rock interaction. Trace elements showed no distinctive patterns and shed no further light on fluid source. LA-ICP-MS U-Pb dating determined the vein calcite precipitation age – 318±30 Ma – which rule out metamorphic or magmatic fluid sources as no metamorphic or magmatic activity was occurring in the area at this time. The vein fluid source was therefore a surface water (meteoric based on paleogeographic reconstruction) which had undergone significant water-rock interaction. This study highlights the importance of combining the recently developed LA-ICP-MS U-Pb calcite geochronometer with stable isotopes and trace elements to help determine fluid sources of veins, and indeed any geological feature where calcite precipitated from a fluid that may have resided in the crust for a period of time (e.g. fault precipitates or cements).
Clumped isotopes geothermometry was applied to two dolomitic hydrocarbon reservoirs. Results indicate that late burial dolomitization occurred at ∼110 °C in the Albian Pinda dolostone (offshore Angola) and ∼90 °C in the Mano-Meillon dolostone (Aquitaine Basin, France), and did not continue on during subsequent burial/thermal evolution to present-day conditions (150-160 °C). This study illustrates the great potential of the clumped isotopes approach to help unravel dolomitization processes in hydrocarbon reservoirs.
Abstract Iron and steel slags have a long history of both disposal and beneficial use in the coastal zone. Despite the large volumes of slag deposited, comprehensive assessments of potential risks associated with metal(loid) leaching from iron and steel by-products are rare for coastal systems. This study provides a national-scale overview of the 14 known slag deposits in the coastal environment of Great Britain (those within 100 m of the mean high-water mark), comprising geochemical characterisation and leaching test data (using both low and high ionic strength waters) to assess potential leaching risks. The seaward facing length of slag deposits totalled at least 76 km, and are predominantly composed of blast furnace (iron-making) slags from the early to mid-20th Century. Some of these form tidal barriers and formal coastal defence structures, but larger deposits are associated with historical coastal disposal in many former areas of iron and steel production, notably the Cumbrian coast of England. Slag deposits are dominated by melilite phases (e.g. gehlenite), with evidence of secondary mineral formation (e.g. gypsum, calcite) indicative of weathering. Leaching tests typically show lower element (e.g. Ba, V, Cr, Fe) release under seawater leaching scenarios compared to deionised water, largely ascribable to the pH buffering provided by the former. Only Mn and Mo showed elevated leaching concentrations in seawater treatments, though at modest levels (<3 mg/L and 0.01 mg/L, respectively). No significant leaching of potentially ecotoxic elements such as Cr and V (mean leachate concentrations <0.006 mg/L for both) were apparent in seawater, which micro-X-Ray Absorption Near Edge Structure (μXANES) analysis show are both present in slags in low valence (and low toxicity) forms. Although there may be physical hazards posed by extensive erosion of deposits in high-energy coastlines, the data suggest seawater leaching of coastal iron and steel slags in the UK is likely to pose minimal environmental risk.
The iron and steel industry has a long tradition of bulk reuse of slags for a range of construction applications. Growing interest in recent years has seen slag resource recovery options extend to critical raw material recovery and atmospheric carbon capture. Full scale deployment of such technologies is currently limited in part by absent or partial inventories of slag deposit locations, data on composition, and volume estimates in many jurisdictions. This paper integrates a range of spatial information to compile a database of iron and steel slag deposits in mainland United Kingdom (UK) for the first time and evaluate the associated resource potential. Over 190 million tonnes of legacy iron and steel slag are present across current and former iron and steel working regions of the UK, with particular concentrations in the north west and north east of England, and central Scotland. While significant potential stockpiles of blast furnace and basic oxygen furnace slag could provide up to 0.9 million tonnes of vanadium and a cumulative carbon dioxide capture potential of 57–138 million tonnes, major management challenges for resource recovery are apparent. Over one third are located in close proximity to designated conservation areas which may limit resource recovery. Furthermore, land use analyses show that many of the sites have already been redeveloped for housing (nearly 30% urban cover). Deposits from recent decades in current or recently closed steel-working areas may have the greatest potential for resource recovery where such ambitions could be coupled with site restoration and regeneration efforts.
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