METASOMATIC CHANGES IN ROCKS OF SEDIMENTARY COMPLEXES IN THE CARPATHIAN OIL AND GAS PROVINCE AS AN INDICATOR OF CARBOHYDRATE MIGRATION

A field and laboratory investigation of sedimentary rocks in Carpathian oil and gas province was curried out. The theoretical and practical aspects of the peculiarities of the development of metasomatic process during the migration of fluids at the postsedimentation stage of rock formation were investigated. Based on detailed field researches, a consistent pattern of mineral aggregates’ and their crystalloid individuals developing was defined. The arguments for developing a new geochemical model of oil deposits indication in Carpathian oil and gas province were provided.

Improvement in pH and Total Iron Concentration of Acid Mine Drainage after Backfilling: A Case Study of an Underground Abandoned Mine in Japan

If the excavated underground veins are not backfilled, they may be a factor in the continued outflow of acid mine drainage (AMD). The flow rate of AMD can be reduced by backfilling underground drifts from abandoned mines. In addition, the quality of AMD may be improved as the flow rate of AMD reduces. In this paper, the quality of the AMD after backfilling was evaluated by a three-dimensional geochemical analysis model when the groundwater level was recovered after backfilling. The measured dissolved iron (Fe) and sulfate ion (SO42−) concentrations and pH before backfilling the drift were reproduced by the calibration of the simulation. Using the calibrated model, the pH at the outlet of the drift was changed from about pH 3 before backfilling to about pH 4 to 5 after backfilling. When calcite was contained in the filling materials of the drift, the pH approached neutral. However, when gypsum was formed, the neutralization was inhibited. The Fe concentration discharged from the drift was calculated at approximately 0.002 mol/L before backfilling. The total Fe concentration was calculated at 0.0004 mol/L or less after backfilling, and the dissolved Fe concentration decreased by several orders of magnitude after backfilling. A geochemical model quantitatively evaluated the improvement in water quality after backfilling the drifts. This method can be applied to the other abandoned mines with similar hydrogeological conditions.

Hydrochemical modeling of migration of dissolved oil products in groundwater

Изложена методика прогнозирования распространения нефтепродуктов группы BTEX (бензол, толуол, этилбензол, ксилолы) в подземных водах на основе гидрохимического моделирования с учетом изменения окислительно-восстановительных и кислотно-щелочных свойств раствора в процессе биодеградации нефтепродуктов. Представлена геохимическая модель биологического разложения нефтепродуктов комплекса BTEX на основе модифицированной кинетики Моно с учетом реакций между акцепторами, продуктами реакции биодеградации и неорганическими компонентами раствора. Приведены примеры геохимического моделирования, демонстрирующие важность учета процессов, связанных с изменением гидрогеохимической обстановки в подземных водах при разложении углеводородов. Разработанная модель может быть использована для выполнения геохимических прогнозов распространения легких нефтепродуктов в подземных водах, проведения работ в рамках оценки воздействия на природную среду, разработки систем инженерной защиты подземных вод от загрязнения нефтепродуктами. A method for predicting the spread of BTEX group oil products (benzene, toluene, ethylbenzene, xylenes) in groundwater based on hydrochemical modeling with account of changes in the redox, acidity or alkalinity of the solution during the biodegradation of oil products is stated. A geochemical model of the biological decomposition of oil products of BTEX group based on modified Mono kinetics with account of the reactions between acceptors, biodegradation products and inorganic components of the solution is presented. Examples of geochemical modeling are given that demonstrate the importance of taking into account the processes associated with the changes in the hydrogeochemical environment in groundwater during the decomposition of hydrocarbons. The developed model can be used to carry out geochemical predictions of the spread of light-end oil products in groundwater, to carry out works within the framework of estimating the environmental impact, and to develop systems for engineering protection of groundwater from oil pollution.

A Streamlined Workflow From Experimental Analyses to Dynamic Geochemical Modelling

Dynamic-geochemical model is a powerful instrument to evaluate the geochemical effects on CO2storage capacity, injectivity and long-term containment. The study objective is to apply an integrated multi-step workflow to a carbon capture and storage (CCS) candidate field (offshore), namely hereinafter H field. From experimental analyses, a comprehensive real data-tailored reactive transport model (RTM) has been built to capture the dynamics and the geochemical phenomena (e.g., water vaporization, CO2solubility, mineral alteration) occurring during and after the CO2injection in sedimentary formations. The proposed integrated workflow couples lab activities and numerical simulations and it is developed according to the following steps: Mineralogical-chemical characterization (XRD, XRF and SEM-EDX experimental techniques) of field core samples; Data elaboration and integration to define the conceptual geochemical model; Synthetic brine reconstruction by means of 0D geochemical models; Numerical geochemical modelling at different complexity levels. Field rocks chosen for CO2injection have been experimentally characterized, showing a high content of Fe in clayey, micaceous and carbonate mineralogical phases. New-defined, site-specific minerals have been characterized, starting from real XRD, XRF and SEM-EDX data and by calculation of their thermochemical parameters with a proprietary procedure. They are used to reconstruct synthetic formation water chemical composition (at equilibrium with both rock mineralogy and gas phase), subsequently used in RTM. CO2injection is simulated using 2D radial reactive transport model(s) built in a commercial compositional reservoir simulator. The simulations follow a step-increase in the complexity of the model by adding CO2solubility, water vaporization and geochemical reactions. Geochemical processes impact on CO2storage capacity and injectivity is quantitatively analyzed. The results show that neglecting the CO2solubility in formation water may underestimate the max CO2storage capacity in H field by around 1%, maintaining the same pressure build-up profile. Sensitivities on the impact of formation water salinity on the CO2solubility are presented. In a one thousand years’ time-scale, changes in reservoir porosity due to mineral alteration, triggered by CO2-brine-rock interactions, seem to be minimal in the near wellbore and far field. However, it has been seen that water vaporization with the associated halite precipitation inclusion in the simulation models is recommended, especially at high-level of formation brine salinity, for a reliable evaluation of CO2injectivity related risks. The proposed workflow provides a new perspective in geochemical application for CCS studies, which relies on novel labs techniques (analyses automation), data digitalization, unification and integration with a direct connection to the numerical models. The presented procedure can be followed to assess the geochemical short-and long-term risks in carbon storage projects.

Reactive transport model of kinetically controlled celestite to barite replacement

Barite formation is of concern for many utilisations of the geological subsurface, ranging from oil and gas extraction to geothermal reservoirs. It also acts as a scavenger mineral for the retention of radium within nuclear waste repositories. The impact of its precipitation on flow properties has been shown to vary by many orders of magnitude, emphasising the need for robust prediction models. An experimental flow-through column setup on the laboratory scale investigating the replacement of celestite (SrSO4) with barite (BaSO4) for various input barium concentrations was taken as a basis for modelling. We provide here a comprehensive, geochemical modelling approach to simulate the experiments. Celestite dissolution kinetics, as well as subsequent barite nucleation and crystal growth were identified as the most relevant reactive processes, which were included explicitly in the coupling. A digital rock representation of the granular sample was used to derive the initial inner surface area. Medium (10 mM) and high (100 mM) barium input concentration resulted in a comparably strong initial surge of barite nuclei formation, followed by continuous grain overgrowth and finally passivation of celestite. At lower input concentrations (1 mM), nuclei formation was significantly less, resulting in fewer but larger barite crystals and a slow moving reaction front with complete mineral replacement. The modelled mole fractions of the solid phase and effluent chemistry match well with previous experimental results. The improvement compared to models using empirical relationships is that no a-priori knowledge on prevailing supersaturations in the system is needed. For subsurface applications utilising reservoirs or reactive barriers, where barite precipitation plays a role, the developed geochemical model is of great benefit as only solute concentrations are needed as input for quantified prediction of alterations.

Diversification of Archean tonalite-trondhjemite-granodiorite suites in a mushy middle crust

Tonalite-trondhjemite-granodiorite (TTG) suites are the dominant component of Earth’s first continents, but their origins are debated. The trace element concentrations of these rocks are conventionally linked to their source depths and inferred geodynamic settings with the implicit assumption that TTG compositions are source-controlled. Alternatively, their variable compositions may be caused by fractional crystallization in TTG plutons after emplacement and less clearly linked to source depth. Most TTGs in Archean mid-crustal exposures are the dominant component of igneous gray gneiss complexes; the processes that influence the evolution of TTG magmas in this setting are poorly understood. We present a petrological–geochemical model that explains the coexistence of TTGs in the middle crust with low-pressure and high-pressure geochemical trends, irrespective of tectonic setting or depth of the TTG source. We propose that mid-crustal TTGs were long-lived crystal mushes with compositions controlled by the separation of early-crystallizing plagioclase and melt. Using phase equilibrium modeling, we demonstrate that a suite of TTGs from the southern Superior Province in Canada represents variably plagioclase-rich and melt-rich fractions from a common parent magma. The behavior of plagioclase may have a strong influence on the geochemical trends of TTGs, including the degree of rare earth element fractionation. Our results suggest that trace element compositions of TTGs may not primarily reflect the depth of the source and cannot be used alone to infer Archean geodynamic settings.

GeoChemFoam: Direct Modelling of Multiphase Reactive Transport in Real Pore Geometries with Equilibrium Reactions

GeoChemFoam is an open-source OpenFOAM-based toolbox that includes a range of additional packages that solve various flow processes from multiphase transport with interface transfer, to single-phase flow in multiscale porous media, to reactive transport with mineral dissolution. In this paper, we present a novel multiphase reactive transport solver for simulations on complex pore geometries, including microfluidic devices and micro-CT images, and its implementation in GeoChemFoam. The geochemical model includes bulk and surface equilibrium reactions. Multiphase flow is solved using the Volume-Of-Fluid method, and the transport of species is solved using the continuous species transfer method. The reactive transport equations are solved using a sequential operator splitting method, with the transport step solved using GeoChemFoam, and the reaction step solved using Phreeqc, the US geological survey’s geochemical software. The model and its implementation are validated by comparison with analytical solutions in 1D and 2D geometries. We then simulate multiphase reactive transport in two test pore geometries: a 3D pore cavity and a 3D micro-CT image of Bentheimer sandstone. In each case, we show the pore-scale simulation results can be used to develop upscaled models that are significantly more accurate than standard macro-scale equilibrium models.