Experimental simulation of magma–carbonate interaction beneath Mt. Vesuvius, Italy

We simulated the process of magma–carbonate interaction beneath Mt. Vesuvius in short duration piston-cylinder experiments under controlled magmatic conditions (from 0 to 300 s at 0.5 GPa and 1,200 °C), using a Vesuvius shoshonite composition and upper crustal limestone and dolostone as starting materials. Backscattered electron images and chemical analysis (major and trace elements and Sr isotopes) of sequential experimental products allow us to identify the textural and chemical evolution of carbonated products during the assimilation process. We demonstrate that melt–carbonate interaction can be extremely fast (minutes), and results in dynamic contamination of the host melt with respect to Ca, Mg and ⁸⁷Sr/⁸⁶Sr, coupled with intense CO₂ vesiculation at the melt–carbonate interface. Binary mixing between carbonate and uncontaminated melt cannot explain the geochemical variations of the experimental charges in full and convection and diffusion likely also operated in the charges. Physical mixing and mingling driven by exsolving volatiles seems to be a key process to promote melt homogenisation. Our results reinforce hypotheses that magma–carbonate interaction is a relevant and ongoing process at Mt. Vesuvius and one that may operate not only on a geological, but on a human timescale.     

Sediment–well interaction during depressurization

Depressurization gives rise to complex sediment–well interactions that may cause the failure of wells. The situation is aggravated when high depressurization is imposed on sediments subjected to an initially low effective stress, such as in gas production from hydrate accumulations in marine sediments. Sediment–well interaction is examined using a nonlinear finite element simulator. The hydro-mechanically coupled model represents the sediment as a Cam-Clay material, uses a continuous function to capture compressibility from low to high effective stress, and recognizes the dependency of hydraulic conductivity on void ratio. Results highlight the critical effect of hydro-mechanical coupling as compared to constant permeability models: A compact sediment shell develops against the screen, the depressurization zone is significantly smaller than the volume anticipated assuming constant permeability, settlement decreases, and the axial load on the well decreases; in the case of hydrates, gas production will be a small fraction of the mass estimated using a constant permeability model. High compressive axial forces develop in the casing within the production horizon, and the peak force can exceed the yield capacity of the casing and cause its collapse. Also tensile axial forces may develop in the casing above the production horizon as the sediment compacts in the depressurized zone and pulls down from the well. Well engineering should consider: slip joints to accommodate extensional displacement above the production zone, soft telescopic/sliding screen design to minimize the buildup of compressive axial force within the production horizon, and enlarged gravel pack to extend the size of the depressurized zone.     

The time scales of magma mixing and mingling involving primitive melts and melt–mush interaction at mid-ocean ridges

We have studied the chemical zoning of plagioclase phenocrysts from the slow-spreading Mid-Atlantic Ridge and the intermediate-spreading rate Costa Rica Rift to obtain the time scales of magmatic processes beneath these ridges. The anorthite content, Mg, and Sr in plagioclase phenocrysts from the Mid-Atlantic Ridge can be interpreted as recording initial crystallisation from a primitive magma (~11 wt% MgO) in an open system. This was followed by crystal accumulation in a mush zone and later entrainment of crystals into the erupted magma. The initial magma crystallised plagioclase more anorthitic than those in equilibrium with any erupted basalt. Evidence that the crystals accumulated in a mush zone comes from both: (1) plagioclase rims that were in equilibrium with a Sr-poor melt requiring extreme differentiation; and (2) different crystals found in the same thin section having different histories. Diffusion modelling shows that crystal residence times in the mush were <140 years, whereas the interval between mush disaggregation and eruption was ≤1.5 years. Zoning of anorthite content and Mg in plagioclase phenocrysts from the Costa Rica Rift show that they partially or completely equilibrated with a MgO-rich melt (>11 wt%). Partial equilibration in some crystals can be modelled as starting <1 year prior to eruption but for others longer times are required for complete equilibration. This variety of times is most readily explained if the mixing occurred in a mush zone. None of the plagioclase phenocrysts from the Costa Rica Rift that we studied have Mg contents in equilibrium with their host basalt even at their rims, requiring mixing into a much more evolved magma within days of eruption. In combination these observations suggest that at both intermediate- and slow-spreading ridges: (1) the chemical environment to which crystals are exposed changes on annual to decadal time scales; (2) plagioclase crystals record the existence of melts unlike those erupted; and (3) disaggregation of crystal mush zones appears to precede eruption, providing an efficient mechanism by which evolved interstitial melt can be mixed into erupted basalts.     

Geochemistry of arsenic during low-temperature water–rock interaction

High arsenic water has been a global focus of both scientists and water supply managers because of its serious adverse impact on human health and wide distribution in the world. Processes of redox, sorption, precipitation, and dissolution release arsenic in both natural systems and in environments intensely modified by human activities. In natural systems, groundwater arsenic is controlled by lithologic geochemistry, sedimentation conditions, hydrogeologic setting and groundwater chemistry. However, in the intensely human-affected systems (such as mining and tilling areas), arsenic mobilization is dependent on the composition of the primary materials, treatment methods, storage design, and local climate. Well-designed experimental systems aid in characterizing sorption, precipitation, and redox processes associated with arsenic dynamics during water-rock interaction. Continued investigations of field sites will further refine understanding of the processes favoring arsenic mobility in the range of natural and man-made systems. The combination of field and experimental studies will lead to better understanding of arsenic cycling in all systems and sustainable management of water resources in arsenic-affected areas.     

H2O–CO2 solubility in mafic alkaline magma: applications to volatile sources and degassing behavior at Erebus volcano, Antarctica

We present new equilibrium mixed-volatile (H₂O–CO₂) solubility data for a phonotephrite from Erebus volcano, Antarctica. H₂O–CO₂-saturated experiments were conducted at 400–700 MPa, 1,190 °C, and ~NNO + 1 in non-end-loaded piston cylinders. Equilibrium H₂O–CO₂ fluid compositions were determined using low-temperature vacuum manometry, and the volatile and major element compositions of the glassy run products were determined by Fourier transform infrared spectroscopy and electron microprobe. Results show that the phonotephrite used in this study will dissolve ~0.8 wt% CO₂ at 700 MPa and a fluid composition of $ X_{{{\text{H}}_{ 2} {\text{O}}}} $ ~0.4, in agreement with previous experimental studies on mafic alkaline rocks. Furthermore, the dissolution of CO₂ at moderate to high $ X_{{{\text{H}}_{ 2} {\text{O}}}}^{\text{fluid}} $ in our experiments exceeds that predicted using lower-pressure experiments on similar melts from the literature, suggesting a departure from Henrian behavior of volatiles in the melt at pressures above 400 MPa. With these data, we place new constraints on the modeling of Erebus melt inclusion and gas emission data and thus the interpretation of its magma plumbing system and the contributions of primitive magmas to passive and explosive degassing from the Erebus phonolite lava lake.     

Interactions between basalts and oil source rocks in rift basins： CO2 generation

Basalts interbedded with oil source rocks are discovered frequently in rift basins of eastern China, where CO2 is found in reservoirs around or within basalts, for example in the Binnan reservoir of the Dongying Depression. In the reservoirs, CO2 with heavy carbon isotopic composition (δ13C>-10‰ PDB) is in most cases accounts for 40% of the total gas reserve, and is believed to have resulted from degassing of basaltic magma from the mantle. In their investigations of the Binnan reservoir, the authors suggested that the CO2 would result from interactions between the source rocks and basalts. As the source rocks around basalts are rich in carbonate minerals, volcanic minerals, transition metals and organic matter, during their burial history some of the transition metals were catalyzed on the thermal degradation of organic matter into hydrocarbons and on the decomposition of carbonate minerals into CO2, which was reproduced in thermal simulations of the source rocks with the transition metals (Ni and Co). This kind of CO2 accounts for 55%-85% of the total gas reserve generated in the process of thermal simulation, and its δ13C values range from -11‰- -7.2‰ PDB, which are very similar to those of CO2 found in the Binnan reservoir. The co-generation of CO2 and hydrocarbon gases makes it possible their accumulation together in one trap. In other words, if the CO2 resulted directly from degassing of basaltic magma or was derived from the mantle, it could not be accumulated with hydrocarbon gases because it came into the basin much earlier than hydrocarbon generation and much earlier than trap formation. Therefore, the source rocks around basalts generated hydrocarbons and CO2 simultaneously through catalysis of Co and Ni transition metals, which is useful for the explanation of co-accumulation of hydrocarbon gases and CO2 in rift basins in eastern China.     

Reactions between olivine and CO2-rich seawater at 300 °C: Implications for H2 generation and CO2 sequestration on the early Earth

To understand the influence of fluid CO₂ on ultramafic rock-hosted seafloor hydrothermal systems on the early Earth, we monitored the reaction between San Carlos olivine and a CO₂-rich NaCl fluid at 300 °C and 500 bars. During the experiments, the total carbonic acid concentration (ΣCO₂) in the fluid decreased from approximately 65 to 9 mmol/kg. Carbonate minerals, magnesite, and subordinate amount of dolomite were formed via the water-rock interaction. The H₂ concentration in the fluid reached approximately 39 mmol/kg within 2736 h, which is relatively lower than the concentration generated by the reaction between olivine and a CO₂-free NaCl solution at the same temperature. As seen in previous hydrothermal experiments using komatiite, ferrous iron incorporation into Mg-bearing carbonate minerals likely limited iron oxidation in the fluids and the resulting H₂ generation during the olivine alteration. Considering carbonate mineralogy over the temperature range of natural hydrothermal fields, H₂ generation is likely suppressed at temperatures below approximately 300 °C due to the formation of the Mg-bearing carbonates. Nevertheless, H₂ concentration in fluid at 300 °C could be still high due to the temperature dependency of magnetite stability in ultramafic systems. Moreover, the Mg-bearing carbonates may play a key role in the ocean-atmosphere system on the early Earth. Recent studies suggest that the subduction of carbonated ultramafic rocks may transport surface CO₂ species into the deep mantle. This process may have reduced the huge initial amount of CO₂ on the surface of the early Earth. Our approximate calculations demonstrate that the subduction of the Mg-bearing carbonates formed in komatiite likely played a crucial role as one of the CO₂ carriers from the surface to the deep mantle, even in hot subduction zones.     

Atmospheric CO2 sink: Silicate weathering or carbonate weathering?

It is widely accepted that chemical weathering of Ca–silicate rocks could potentially control long-term climate change by providing feedback interaction with atmospheric CO₂ drawdown by means of precipitation of carbonate, and that in contrast weathering of carbonate rocks has not an equivalent impact because all of the CO₂ consumed in the weathering process is returned to the atmosphere by the comparatively rapid precipitation of carbonates in the oceans. Here, it is shown that the rapid kinetics of carbonate dissolution and the importance of small amounts of carbonate minerals in controlling the dissolved inorganic C (DIC) of silicate watersheds, coupled with aquatic photosynthetic uptake of the weathering-related DIC and burial of some of the resulting organic C, suggest that the atmospheric CO₂ sink from carbonate weathering may previously have been underestimated by a factor of about 3, amounting to 0.477 Pg C/a. This indicates that the contribution of silicate weathering to the atmospheric CO₂ sink may be only 6%, while the other 94% is by carbonate weathering. Therefore, the atmospheric CO₂ sink by carbonate weathering might be significant in controlling both the short-term and long-term climate changes. This questions the traditional point of view that only chemical weathering of Ca–silicate rocks potentially controls long-term climate change.     

Soil–projectile interaction during penetration of a transparent clay simulant

Visualization of soil structure interaction during projectile penetration of clay is made possible by use of a surrogate composed of magnesium lithium phyllosilicate combined with high-speed photography and digital image correlation. A free-falling penetrator striking at 5.5 m/s simulated a projectile. Penetration resistance was constant within the resolution of the experiment; it was mainly due to the bearing resistance of the soil in contact with the nose, rather than skin friction. Bearing resistance in dynamic penetration for a hemispherical-nose rod was about 20% higher than quasi-static tests using a sphere. Bearing resistance was also about 20% higher for a hemispherical nose compared to a conical nose. Cavitation behind the nose is dependent on its shape with soils rebounding toward the projectile for conical noses but not hemispherical ones.

     

Magma–magma interaction in the mantle recorded by megacrysts from Cenozoic basalts in eastern China

ABSTRACT

Recently, besides magma–rock and rock–rock reaction, magma–magma interaction at mantle depth has been proposed as an alternative mechanism to produce diverse compositions of mantle. Clinopyroxene and garnet megacrysts can be formed at this condition since this process is suggested to trigger the high-pressure crystallization of these minerals. Studying on this type of megacrysts provides us important information on the genesis of intraplate basalts and the chemical heterogeneity of mantle, which has not been reported before. Here we present major, trace elements and Sr isotopes of clinopyroxene and garnet megacrysts hosted by Cenozoic basalts from Penglai, Shandong province of eastern China. The megacrysts are suggested to be formed by crystallization from magma because of their moderate Mg^# (74.0–79.9 for clinopyroxene and 58.8–65.0 for garnet) and good correlations between Mg^# and other elements (e.g. CaO, TiO₂, Nd and Lu). The potential crystallized temperature and pressure are estimated to be ~1156°C at 2.6–3.2 GPa, which should occur at the top of asthenosphere or lithosphere–asthenosphere boundary based on the lithospheric thickness in this area (~60–70 km). Since the megacrysts show variable Sr isotopes, and their primary magmas show negative correlation between ⁸⁷Sr/⁸⁶Sr and Hf/Sm ratios, as well as positive correlation between Ba/Th and Nb/U for clinopyroxenes, it indicates a mixing origin. Cenozoic basalts from Shandong show a mixing trend, and high-pressure fractionation of clinopyroxene and garnet is suggested to occur during the mixing process because some basalts show significantly higher Sm/Yb and lower Ca/Al ratios than others, which again supports our interpretations. When compared to megacrysts and host basalts from other locations of eastern China, similar geochemical variations and a deviation trend relative to the mixing trend are also observed. It indicates that magma–magma interaction can be a common process for formation of intraplate basalts and basalt-borne megacrysts.     

Noble-metal ore genesis and mantle–crust interaction

The mineral and geochemical compositions of noble-metal (first of all, gold) deposits of the Fennoscandian, Siberian, and Northeast Asian orogenic belts are considered. These deposits are of several types: Au (disseminated Au–sulfide and Au–quartz), Au–Bi, Au–Ag, Au–Sb, Ag–Sb, Au–Sb–Hg, and Ag–Hg. They formed in different geodynamic settings as a result of the active motion of crustal tectonic blocks of different nature. Subduction processes (both at the front and at the rear of continent-marginal and island-arc magmatic arcs) resulted in Au–Ag, Ag–Sb, Ag–Hg, Au–Sb–Hg, and Au–Bi deposits. Collision events gave rise to Au and Au–Bi deposits. Intraplate continental rifting and formation of orogenic belts along the boundaries of block (plate) sliding led to the origin of Au and Au–Bi ores in association with Au–Ag, Au–Sb–Hg, and complex ores. In all cases, the formation of noble-metal mineralization was accompanied by magmatism of different types and metamorphism. Because of this diversity of ores, there is no single concept of the genesis of noble-metal mineralization. Several competing models of genesis exist: hydrothermal-metamorphic, pluton-metamorphic, plutonic, activity of mantle fluid flows, and multistage concentration during the crust–mantle interaction with the leading role of sedimentary complexes.     

Early to late Neoproterozoic magmatism and magma mixing–mingling in Sri Lanka: Implications for convergent margin processes during Gondwana assembly

The Sri Lankan fragment of Gondwana preserves the records of Neoproterozoic tectonothermal events associated with the final assembly of the supercontinent. Here we investigate a suite of magmatic rocks from the Wanni, Kadugannawa and Highland Complexes through geological, petrological, geochemical and zircon U–Pb and Lu–Hf isotopic techniques. The hornblende biotite gneiss, charnockites, metagabbro and metadiorites investigated in this study show geochemical features consistent with calc-alkaline affinity and subduction-related signature including LILE enrichment relative to HFSE coupled with distinct Nb–Ta depletion and weak negative Zr–Hf anomalies. The felsic suite falls in the volcanic arc granites (VAGs) field and the mafic suite shows island arc basalt affinity in tectonic discrimination plots, suggesting that the protoliths of the rocks were derived from arc-related magmas in a convergent margin setting. LA-ICPMS zircon U–Pb analyses show crystallization of charnockite and dioritic mafic magmatic enclave from the Highland Complex during ca. 565 and 576 Ma corresponding to bimodal magmatism. The diorite also contains metamorphic zircons of ca. 525 Ma. Hornblende–biotite gneiss from the Kadugannawa Complex shows protolith emplacement age at 973–980 Ma, followed by new zircon growth during repeated thermal events through late Neoproterozoic. The dioritic enclaves in these rocks are much younger, and form part of a deformed and metamorphosed dyke suite with emplacement ages of 559 Ma, broadly coeval with the bimodal magmatism in the Highland Complex at that time. The youngest group of zircons in this rock shows ages of 508 Ma, corresponding to the latest thermal event. A charnockite from this locality shows oldest group of zircons at 962 Ma, corresponding to emplacement age similar to that of the magmatic protolith of the hornblende biotite gneiss. This rock also shows zircon growth during repeated thermal events at 832 Ma, 780 Ma, 721 Ma and 661–605 Ma. The lower intercept age of 543 Ma marks the timing of collisional metamorphism. Charnockite from the Wanni Complex shows emplacement age at 1000 Ma, followed by thermal event at 570 Ma, the latter correlating with the bimodal magmatic event in the Highland Complex. The dioritic enclave within this charnockite shows an age of ca. 980 Ma, suggesting intrusion of mafic magma into the felsic magma chamber. Zircons in the diorite also record multiple zircon events during 950 to 750 Ma. Zircons in the Highland Complex charnockite possess negative εHf(t) values in the range − 6.7 to − 12.6 with T_DM^C of 2039–2306 Ma suggesting magma derivation through melting of Paleoproterozoic source. In contrast, the εHf(t) range of − 11.1 to 1.6 suggests a mixed source of both of older crustal and juvenile material. The εHf(t) values of − 4.5 to 4.5 and T_DM^C of 1546–1962 Ma for the hornblende biotite gneiss also shows magma derivation from mixed sources that included Paleoproterozoic components. The younger dioritic intrusive, however, has a more juvenile magma source as indicated by the mean εHf(t) value of 1.3. The associated charnockite shows a tight positive cluster of εHf(t) from 0.6 to 5.1, suggesting juvenile input. Charnockite from the Wanni Complex shows clearly positive εHf(t) values of up to 13.1, and T_DM^C in the range 937–1458 Ma suggesting much younger and depleted mantle source. The diorite enclave also has positive εHf(t) values with an average value of 8.5 and T_DM^C in the range of 709–1443 Ma clearly suggesting younger juvenile sources. The early and late Neoproterozoic bimodal suites are correlated to convergent margin magmatism associated with the assembly of Sri Lanka within the Gondwana supercontinent.     

An experimental study of focused magma transport and basalt–peridotite interactions beneath mid-ocean ridges: implications for the generation of primitive MORB compositions

We performed experiments in a piston-cylinder apparatus to determine the effects of focused magma transport into highly permeable channels beneath mid-ocean ridges on: (1) the chemical composition of the ascending basalt; and (2) the proportions and compositions of solid phases in the surrounding mantle. In our experiments, magma focusing was supposed to occur instantaneously at a pressure of 1.25 GPa. We first determined the equilibrium melt composition of a fertile mantle (FM) at 1.25 GPa-1,310°C; this composition was then synthesised as a gel and added in various proportions to peridotite FM to simulate focusing factors Ω equal to 3 and 6 (Ω = 3 means that the total mass of liquid in the system increased by a factor of 3 due to focusing). Peridotite FM and the two basalt-enriched compositions were equilibrated at 1 GPa-1,290°C; 0.75 GPa-1,270°C; 0.5 GPa-1,250°C, to monitor the evolution of phase proportions and compositions during adiabatic decompression melting. Our main results may be summarised as follows: (1) magma focusing induces major changes of the coefficients of the decompression melting reaction, in particular, a major increase of the rate of opx consumption, which lead to complete exhaustion of orthopyroxene (and clinopyroxene) and the formation of a dunitic residue. A focusing factor of ≈4—that is, a magma/rock ratios equal to ≈0.26—is sufficient to produce a dunite at 0.5 GPa. (2) Liquids in equilibrium with olivine (±spinel) at low pressure (0.5 GPa) have lower SiO₂ concentrations, and higher concentrations in MgO, FeO, and incompatible elements (Na₂O, K₂O, TiO₂) than liquids produced by decompression melting of the fertile mantle, and plot in the primitive MORB field in the olivine–silica–diopside–plagioclase tetrahedron. Our study confirms that there is a genetic relationship between focused magma transport, dunite bodies in the upper mantle, and the generation of primitive MORBs.     

C�CO�CH�CS fluids and granitic magma: how S partitions and modifies CO2 concentrations of fluid-saturated felsic melt at 200?MPa

Hydrothermal volatile-solubility and partitioning experiments were conducted with fluid-saturated haplogranitic melt, H₂O, CO₂, and S in an internally heated pressure vessel at 900°C and 200?MPa; three additional experiments were conducted with iron-bearing melt. The run-product glasses were analyzed by electron microprobe, FTIR, and SIMS; and they contain ??0.12 wt% S, ??0.097 wt% CO₂, and ??6.4 wt% H₂O. Apparent values of log f _O2 for the experiments at run conditions were computed from the [(S⁶⁺)/(S⁶⁺+S^2?)] ratio of the glasses, and they range from NNO ?0.4 to NNO?+?1.4. The C?CO?CH?CS fluid compositions at run conditions were computed by mass balance, and they contained 22?C99?mol% H₂O, 0?C78?mol% CO₂, 0?C12?mol% S, and <3 wt% alkalis. Eight S-free experiments were conducted to determine the H₂O and CO₂ concentrations of melt and fluid compositions and to compare them with prior experimental results for C?CO?CH fluid-saturated rhyolite melt, and the agreement is excellent. Sulfur partitions very strongly in favor of fluid in all experiments, and the presence of S modifies the fluid compositions, and hence, the CO₂ solubilities in coexisting felsic melt. The square of the mole fraction of H₂O in melt increases in a linear fashion, from 0.05 to 0.25, with the H₂O concentration of the fluid. The mole fraction of CO₂ in melt increases linearly, from 0.0003 to 0.0045, with the CO₂ concentration of C?CO?CH?CS fluids. Interestingly, the CO₂ concentration in melts, involving relatively reduced runs (log f _O2????NNO?+?0.3) that contain 2.5?C7?mol% S in the fluid, decreases significantly with increasing S in the system. This response to the changing fluid composition causes the H₂O and CO₂ solubility curve for C?CO?CH?CS fluid-saturated haplogranitic melts at 200?MPa to shift to values near that modeled for C?CO?CH fluid-saturated, S-free rhyolite melt at 150?MPa. The concentration of S in haplogranitic melt increases in a linear fashion with increasing S in C?CO?CH?CS fluids, but these data show significant dispersion that likely reflects the strong influence of f _O2 on S speciation in melt and fluid. Importantly, the partitioning of S between fluid and melt does not vary with the (H₂O/H₂O?+?CO₂) ratio of the fluid. The fluid-melt partition coefficients for H₂O, CO₂, and S and the atomic (C/S) ratios of the run-product fluids are virtually identical to thermodynamic constraints on volatile partitioning and the H, S, and C contents of pre-eruptive magmatic fluids and volcanic gases for subduction-related magmatic systems thus confirming our experiments are relevant to natural eruptive systems.     

An analytical model of soil–structure interaction with swelling soils during droughts

Lightly loaded structures constructed on expansive soils may develop structural damage as a result of changes in the soil’s moisture content. This study investigated an analytical model of soil–structure interaction to assess the settlement of dwellings built on swelling soils when droughts occur. The building behavior was investigated with the Euler–Bernoulli beam theory, and the ground behavior was investigated with a Winkler-derived model based on the state surface approach. The analytical model results were compared to those of a finite element analysis using the Barcelona Expansive Model (BExM) performed with Code_Bright.The analytical model was then used to assess the settlement transmission ratio for a typology of clayey soils and different parameters of building. The results indicated that the final deflection of the building increased with the building length and soil suction. The building deflection due to the suction variations was inversely proportional to the load, the rigidity of the building and the embedding depth of the foundation. Increasing these parameters made the building less vulnerable to shrinkage and swelling action.     

Experimental identification of CO2–oil–brine–rock interactions: Implications for CO2 sequestration after termination of a CO2-EOR project

Carbon dioxide enhanced oil recovery (CO₂-EOR) has been widely applied to the process of carbon capture, utilization, and storage (CCUS). Here, we investigate CO₂–oil–water–rock interactions under reservoir conditions (100 °C and 24 MPa) in order to understand the fluid–rock interactions following termination of a CO₂-EOR project. Our experimental results show that CO₂-rich fluid remained the active fluid controlling the dissolution–precipitation processes in an oil-undersaturated sandstone reservoir; e.g., the dissolution of feldspar and calcite, and the precipitation of kaolinite as well as solid phases comprising O, Si, Al, Na, C, and Ti. Mineral dissolution rates were reduced in the case that mineral surfaces were coated by oil. Mineral wettability and composition, and oil saturation were the main controls on the exposed surface area of grains, and mineral wettability in particular led to selective dissolution. In addition, the permeability of the reservoir decreased substantially due to the precipitation of kaolinite and solid-phase particles, and due to the clogging of less soluble mineral particles released by the dissolution of K-feldspar and carbonate cement, whereas porosity increased. The results provide insight into potential formation damage resulting from CO₂-EOR projects.     

Tectonic and eustatic control on a mixed siliciclastic–carbonate platform during the Late Oxfordian–Kimmeridgian (La Rochelle platform,western France)

Boreal and Tethyan realms of Western Europe present significant sedimentological, paleontological, and stratigraphic differences. The purpose of this study is to constrain regional versus global controls on the dynamics of a sedimentary system located at the interface of these two realms in order to better understand the origin of their differences. Detailed sedimentological, palynofacies and calcareous nannofossil analyses were performed on two sections from the La Rochelle platform (western France). The Pas section includes part of the Late Oxfordian and Early Kimmeridgian, and the Rocher d'Yves section is assigned to the Late Kimmeridgian. They correspond to monotonous marl–argillaceous limestone alternations. Limestones are essentially mudstones with echinoderms, bivalves and foraminifera that suggest low-energy, open-marine conditions. Highly bioclastic and/or peloidal deposits occur commonly, and show wackestones to wacke-pack-grainstones textures. These deposits indicate frequent high-energy events, and are interpreted as storm deposits. Marls dominate in the most proximal depositional environments, while calcareous deposits are more important in more distal environments. The Rocher d'Yves section is globally more marly than the Pas section, suggesting a more proximal setting. Palynofacies are dominated by woody particles, suggesting shallow-water, proximal depositional environments. Calcareous nannofossils are ascidian spicules, coccoliths, and schizospheres. Watznaueria britannica dominate calcareous nannofossil assemblages in the Pas section. The Rocher d'Yves assemblages are quasi-exclusively composed of Cyclagelosphaera margerelii, and indicate more proximal paleoenvironments than those of the Pas section. Different orders of depositional sequences are defined, with sequence boundaries corresponding to the most rapid relative sea-level falls. They are hierarchically stacked, and correlate, on the basis of ammonite zones, with the sequences of contemporaneous sections from Tethyan and boreal realms. The stacking pattern of these sequences suggests an orbital control on sedimentation. Small-, medium- and large-scale sequences correspond to precession (20 ky) cycles and to 100 ky and 400 ky eccentricity cycles, respectively. The elementary sequences have durations shorter than 20 ky. The Kimmeridgian was a period of global sea-level rise that ended in the Late Kimmeridgian. More proximal depositional environments in the Rocher d'Yves section (Late Kimmeridgian) than in the Pas section (Early Kimmeridgian) imply a progradation of the La Rochelle platform during the Kimmeridgian. This progradation resulted from a slowdown of the subsidence in the Aquitaine Basin during the Kimmeridgian, corresponding to the first steps of Atlantic Ocean opening. High-frequency cycles on the La Rochelle platform formed in sync with Milankovitch orbital cycles, while tectonics controlled the formation of the low-frequency cycles.     

Long-term spatio-temporal hydrochemical and 222Rn tracing to investigate groundwater flow and water–rock interaction in the Gran Sasso (central Italy) carbonate aquifer

In the Gran Sasso fissured carbonate aquifer (central Italy), a long-term (2001–2007) spatio-temporal hydrochemical and ²²²Rn tracing survey was performed with the goal to investigate groundwater flow and water–rock interaction. Analyses of the physico-chemical parameters, and comparisons of multichemical and characteristic ratios in space and time, and subsequent statistical analyses, permitted a characterisation of the hydrogeology. At the regional scale, groundwater flows from recharge areas to the springs located at the aquifer boundaries, with a gradual increase of mineralisation and temperature along its flowpaths. However, the parameters of each group of springs may significantly deviate from the regional trend owing to fast flows and to the geological setting of the discharge spring areas, as corroborated by statistical data. Along regional flowpaths, the effects of seasonal recharge and lowering of the water table clearly cause changes in ion concentrations over time. This conceptual model was validated by an analysis of the ²²²Rn content in groundwater. ²²²Rn content, for which temporal variability depends on seasonal fluctuations of the water table, local lithology and the fracture network at the spring discharge areas, was considered as a tracer of the final stages of groundwater flowpaths.