Constraining recycled detritus in quartz‐rich sandstones: Insights from a multi‐proxy provenance study of the Mid‐Carboniferous,Clare Basin,western Ireland

Quartz‐rich sandstones can be produced through multiple sedimentary processes, potentially acting in combination, such as extensive sedimentary recycling or intense chemical weathering. Determining the provenance of such sedimentary rocks can be challenging due to low amounts of accessory minerals, the fact that the primary mineralogy may have been altered during transport, storage or burial and difficulties in the recognition of polycyclic components. This study uses zircon and apatite U‐Pb geochronology, apatite trace elements, zircon‐tourmaline‐rutile indices and petrographic observations to investigate the sedimentary history of mineralogically mature mid‐Carboniferous sandstones of the Tullig Cyclothem, Clare Basin, western Ireland. The provenance data show that the sandstones have been dominantly and ultimately sourced from three basement terranes: older Laurentian‐ associated rocks (ca. 900–2500 Ma) which lay to the north of the basin, peri‐Gondwanan terranes (ca. 500–700 Ma) to the south and igneous intrusive rocks associated with the Caledonian Orogenic Cycle (ca. 380–500 Ma). However, the multi‐proxy approach also helps constrain the sedimentary history and suggests that not all grain populations were derived directly from their original source. Grains with a Laurentian or a Caledonian affinity have likely been recycled through Devonian basins to the south. Grains with a peri‐Gondwanan affinity appear to be first cycle and are potentially derived from south/southwest of the basin. Taken as a whole, these data are consistent with input into the basin from the south and southwest, with the reworking of older sedimentary rocks, rather than intensive first‐cycle chemical weathering, likely explaining the compositional maturity of the sandstones. This study highlights the need for a multi‐proxy provenance approach to constrain sedimentary recycling, particularly in compositionally mature sandstones, as the use of zircon geochronology alone would have led to erroneous provenance interpretations. Zircon, together with U‐Pb geochronology from more labile phases such as apatite, can help distinguish first‐cycle versus polycyclic detritus.     

Automated statistical matching of multiple tephra records exemplified using five long maar sequences younger than 75 ka,Auckland, New Zealand

Detailed tephrochronologies are built to underpin probabilistic volcanic hazard forecasting, and to understand the dynamics and history of diverse geomorphic, climatic, soil-forming and environmental processes. Complicating factors include highly variable tephra distribution over time; difficulty in correlating tephras from site to site based on physical and chemical properties; and uncertain age determinations. Multiple sites permit construction of more accurate composite tephra records, but correctly merging individual site records by recognizing common events and site-specific gaps is complex. We present an automated procedure for matching tephra sequences between multiple deposition sites using stochastic local optimization techniques. If individual tephra age determinations are not significantly different between sites, they are matched and a more precise age is assigned. Known stratigraphy and mineralogical or geochemical compositions are used to constrain tephra matches. We apply this method to match tephra records from five long sediment cores (≤ 75 cal ka BP) in Auckland, New Zealand. Sediments at these sites preserve basaltic tephras from local eruptions of the Auckland Volcanic Field as well as distal rhyolitic and andesitic tephras from Okataina, Taupo, Egmont, Tongariro, and Tuhua (Mayor Island) volcanic centers. The new correlated record compiled is statistically more likely than previously published arrangements from this area.     

Suitability of Existing Numerical Model Codes and Thermodynamic Databases for the Prognosis of Calcite Dissolution Processes in Near-Surface Sediments Due to a CO2 Leakage Investigated by Column Experiments

Among the risks of CO₂ storage is the potential of CO₂ leakage into overlaying formations and near-surface potable aquifers. Through a leakage, the CO₂ can intrude into protected groundwater resources, which can lead to groundwater acidification followed by potential mobilisation of heavy metals and other trace metals through mineral dissolution or ion exchange processes. The prediction of pH buffer reactions in the formations overlaying a CO₂ storage site is essential for assessing the impact of CO₂ leakages in terms of trace metal mobilisation. For buffering the pH-value, calcite dissolution is one of the most important mechanisms. Although calcite dissolution has been studied for decades, experiments conducted under elevated CO₂ partial pressures are rare. Here, the first study for column experiments is presented applying CO₂ partial pressures from 6 to 43 bars and realising a near-natural flow regime. Geochemical calculations of calcite dissolution kinetics were conducted using PHREEQC together with different thermodynamic databases. Applying calcite surface areas, which were previously acquired by N₂-BET or calculated based on grain diameters, respectively, to the rate laws according to Plummer et al. (Am J Sci 278:179–216, doi:10.2475/ajs.278.2.179, 1978) or Palandri and Kharaka (US Geol Surv Open file Rep 2004–1068:71, 2004) in the numerical simulations led to an overestimation of the calcite dissolution rate by up to three orders of magnitude compared to the results of the column experiments. Only reduction of the calcite surface area in the simulations as a fitting procedure allowed reproducing the experimental results. A reason may be that the diffusion boundary layer (DBL), which depends on the groundwater flow velocity and develops at the calcite grain surface separating it from the bulk of the solution, has to be regarded: The DBL leads to a decrease in the calcite dissolution rate under natural laminar flow conditions compared to turbulent mixing in traditional batch experiments. However, varying the rate constants by three orders of magnitudes in a field scale PHREEQC model simulating a CO₂ leakage produced minor variations in the pH buffering through calcite dissolution. This justifies the use of equilibrium models when calculating the calcite dissolution in CO₂ leakage scenarios for porous aquifers and slow or moderate groundwater flow velocities. However, the selection of the thermodynamic database has an impact on the dissolved calcium concentration, leading to an uncertainty in the simulation results. The resulting uncertainty, which applies also to the calculated propagation of an aquifer zone depleted in calcite through dissolution, seems negligible for shallow aquifers of approximately 60 m depth, but amounts to 35 % of the calcium concentration for aquifers at a depth of approximately 400 m.     

A geological database for parameterization in numerical modeling of subsurface storage in northern Germany

Underground land use can play a significant role in future concepts of energy and gas storage and requires an improved understanding of the parameters of potential storage formations (saline aquifers), for instance of porosity and permeability, and also of mineralogical and gas compositions. This study aims at providing data examples and calculating vertical spatial variations through variogram analyses of important North German geological reservoirs from Dogger, Rhaetian, Middle Buntsandstein, and Rotliegend (Sub)Groups and Formations, focusing on the western part of the North German Basin. Vertical correlation lengths of porosity and permeability data range between 0 and 30 m, while most results are calculated at approximately 2–4 m and do not show relevant differences among the evaluated formations. In the majority of the regarded formations, the Kozeny–Carman relationship between porosity and permeability is supported as long as low porosity and permeability values are excluded from the evaluation. Mineral percentages varied significantly among the evaluated sediments. Besides quartz, ankerite is the main compound in the Dogger Group, while feldspars and clay minerals were more frequent in the Rhaetian, Middle Buntsandstein, and Rotliegend sediments. Methane was the main gas compound in the reservoirs, followed by nitrogen, ethane, and carbon dioxide. This study serves as preparatory work to allow for the parameterization of geological models and a subsequent simulation of fluid transport to evaluate (long-term) safety and impacts of geothermal and gas storage projects.     

A cascade of magmatic events during the assembly and eruption of a super-sized magma body

We use comprehensive geochemical and petrological records from whole-rock samples, crystals, matrix glasses and melt inclusions to derive an integrated picture of the generation, accumulation and evacuation of 530 km³ of crystal-poor rhyolite in the 25.4 ka Oruanui supereruption (New Zealand). New data from plagioclase, orthopyroxene, amphibole, quartz, Fe–Ti oxides, matrix glasses, and plagioclase- and quartz-hosted melt inclusions, in samples spanning different phases of the eruption, are integrated with existing data to build a history of the magma system prior to and during eruption. A thermally and compositionally zoned, parental crystal-rich (mush) body was developed during two periods of intensive crystallisation, 70 and 10–15 kyr before the eruption. The mush top was quartz-bearing and as shallow as ~3.5 km deep, and the roots quartz-free and extending to >10 km depth. Less than 600 year prior to the eruption, extraction of large volumes of ~840 °C low-silica rhyolite melt with some crystal cargo (between 1 and 10%), began from this mush to form a melt-dominant (eruptible) body that eventually extended from 3.5 to 6 km depth. Crystals from all levels of the mush were entrained into the eruptible magma, as seen in mineral zonation and amphibole model pressures. Rapid translation of crystals from the mush to the eruptible magma is reflected in textural and compositional diversity in crystal cores and melt inclusion compositions, versus uniformity in the outermost rims. Prior to eruption the assembled eruptible magma body was not thermally or compositionally zoned and at temperatures of ~790 °C, reflecting rapid cooling from the ~840 °C low-silica rhyolite feedstock magma. A subordinate but significant volume (3–5 km³) of contrasting tholeiitic and calc-alkaline mafic material was co-erupted with the dominant rhyolite. These mafic clasts host crystals with compositions which demonstrate that there was some limited pre-eruptive physical interaction of mafic magmas with the mush and melt-dominant body. However, the mafic magmas do not appear to have triggered the eruption or controlled magmatic temperatures in the erupted rhyolite. Integration of textural and compositional data from all available crystal types, across all dominant and subordinate magmatic components, allow the history of the Oruanui magma body to be reconstructed over a wide range of temporal scales using multiple techniques. This history spans the tens of millennia required to grow the parental magma system (U–Th disequilibrium dating in zircon), through the centuries and decades required to assemble the eruptible magma body (textural and diffusion modelling in orthopyroxene), to the months, days, hours and minutes over which individual phases of the eruption occurred, identified through field observations tied to diffusion modelling in magnetite, olivine, quartz and feldspar. Tectonic processes, rather than any inherent characteristics of the magmatic system, were a principal factor acting to drive the rapid accumulation of magma and control its release episodically during the eruption. This work highlights the richness of information that can be gained by integrating multiple lines of petrologic evidence into a holistic timeline of field-verifiable processes.     

Degradation of chlorinated ethylenes by Fe0: inhibition processes and mineral precipitation

. Granular zero-valent iron was used for the treatment of groundwater pollution caused by chlorinated ethylenes, mainly TCE, cis-DCE and VC at an industrial site. The rapidly decreasing rates of de-chlorination in the initial phase were attributed to the precipitation of carbonates and the development of hydrogen by anaerobic corrosion. After 70 pore volumes, sulphate was reduced by bacteria. From this point in time, the degradation of TCE was slightly accelerated whereas the de-chlorination rates of the other chlorinated ethylenes decreased only slowly. This relative improvement was assumed to be caused by the uptake of electron-transfer-blocking hydrogen by bacteria. Because the overall trend of the degradation rates is negative we conclude that the inhibitive effect of carbonate precipitation and hydrogen formation cannot be compensated for by the positive influence of the activity of sulphate-reducing bacteria.     

Zircon trace element chemistry at sub-micrometer resolution for Tarawera volcano,New Zealand,and implications for rhyolite magma evolution

Zoned crystals can be important recorders of magmatic processes in space and time. However, in most situations, the temporal dimension is difficult to quantify. Here, we have employed secondary ion mass spectrometry depth profiling to excavate parallel pits into non-polished crystal faces of zircon to obtain ~5 μm resolution U–Th disequilibrium ages (one pit) that can be correlated with trace element zoning at sub-μm resolution derived from a second pit. Data from 17 crystals representing each of the four rhyolite eruptions of Tarawera volcano, an intra-caldera edifice within the Okataina Volcanic Centre, reveal diverse zircon growth conditions over time. Most crystals display rimward depletions in Zr/Hf and Ti, broadly consistent with cooling and crystallization. However, a significant fraction of crystals lacks these patterns and displays rimward trace element variations consistent with isothermal or prograde crystallization. Oscillatory zonation patterns in Y, Th, and U are superimposed on the Zr/Hf and Ti trends. Despite the limited number of crystals analyzed in this way, the striking lack of ubiquitous trace element zoning patterns in crystals from the same hand sample implies that fractional crystallization upon cooling was punctuated by magma recharge and crystal mixing affecting different parts of the magma reservoir. By combining data from all crystals, a systematic change to more heterogeneous trace element abundances is revealed by zircon crystal domains <45 ka following the Rotoiti caldera-forming eruption. This contrasts with the more uniform conditions of zircon crystallization lasting >100 ka prior to caldera formation and is best explained by the post-caldera system consisting of small, isolated melt pockets that evolved independently. An important conclusion is that the zircon ‘cargo’ in volcanic rocks reflects thermally and compositionally divergent processes that act near simultaneously in a magma storage region and not exclusively the conditions in the eruptible magma.