Monitoring of fluid–rock interaction and CO2 storage through produced fluid sampling at the Weyburn CO2-injection enhanced oil recovery site,Saskatchewan, Canada

The Weyburn Oil Field is a carbonate reservoir in south central Saskatchewan, Canada and is the site of a large CO₂ injection project for purposes of enhanced oil recovery. The Weyburn Field, in the Mississippian Midale Formation, was discovered in 1954 and was under primary production until secondary recovery by water flood began in 1964. The reservoir comprises two units, the Vuggy and the Marly, and primary and secondary recovery are thought to only have significantly depleted the Vuggy zone, leaving the Marly with higher oil saturations. In 2000, PanCanadian Resources (now EnCana), the operator of the field, began tertiary recovery by injection of CO₂ and water, primarily into the Marly. The advent of this project was an opportunity to study the potential for geological storage of CO₂.Using 43 Baseline samples collected in August 2000, before CO₂ injection at Weyburn, and 44 monitoring samples collected in March 2001, changes in the fluid chemistry and isotope composition have been tracked. The initial fluid distribution showed water from discovery through water flood in the Midale Formation with Cl ranging from 25,000 to 60,000 mg/L, from the NW to the SE across the Phase 1A area. By the time of Baseline sampling the produced water had been diluted to Cl of 25,000–50,000 mg/L as a result of the addition of make up water from the low TDS Blairmore Formation, but the pattern of distribution was still present. The Cl distribution is mimicked by the distribution of other dissolved ions and variables, with Ca (1250–1500 mg/L) and NH_{3 (aq)} increasing from NW to SE, and alkalinity (700–300 mg/L), resistivity, and H₂S (300–100 mg/L) decreasing. Based on chemical and isotopic data, the H₂S is interpreted to result from bacterial SO₄ reduction. After 6 months of injection of CO₂, the general patterns are changed very little, except that the pH has decreased by 0.5 units and alkalinity has increased, with values over 1400 mg/L in the NW, decreasing to 500 mg/L in the SE. Calcium has increased to range from 1250 to 1750 mg/L, but the pattern of NW–SE distribution is altered. Chemical and isotopic data suggest this change in distribution is caused by the dissolution of calcite due to water–rock reactions driven by CO₂. The Baseline samples varied from −22 to −12‰ δ¹³C (V-PDB) for CO₂ gas. The injected CO₂ has an isotope ratio of −20‰. The Monitor-1 samples of produced CO₂ ranged from −18 to −13‰, requiring a heavy source of C, most easily attributed to dissolution of carbonate minerals. Field measured pH had increased and alkalinity had decreased by the second monitoring trip (July 2001) to near Baseline values, suggesting continued reaction with reservoir minerals.Addition of CO₂ to water–rock mixtures comprising carbonate minerals causes dissolution of carbonates and production of alkalinity. Geochemical modeling suggests dissolution is taking place, however more detail on water–oil–gas ratios needs to be gathered to obtain more accurate estimates of pH at the formation level. Geological storage of CO₂ relies on the potential that, over the longer term, silicate minerals will buffer the pH, causing any added CO₂ to be precipitated as calcite. Some initial modeling of water–rock reactions suggests that silica sources are available to the water resident in the Midale Formation, and that clay minerals may well be capable of acting as pH buffers, allowing injected CO₂ to be stored as carbonate minerals. Further work is underway to document the mineralogy of the Midale Formation and associated units so as to define more accurately the potential for geological storage.     

Reactive transport simulation study of geochemical CO2 trapping on the Tokyo Bay model – With focus on the behavior of dawsonite

A long-term (up to 10 ka) geochemical change in saline aquifer CO₂ storage was studied using the TOUGHREACT simulator, on a 2-dimensional, 2-layered model representing the underground geologic and hydrogeologic conditions of the Tokyo Bay area that is one of the areas of the largest CO₂ emissions in the world. In the storage system characterized by low permeability of reservoir and cap rock, the dominant storage mechanism is found to be solubility trapping that includes the dissolution and dissociation of injected CO₂ in the aqueous phase followed by geochemical reactions to dissolve minerals in the rocks. The CO₂–water–rock interaction in the storage system (mainly in the reservoir) changes the properties of water in a mushroom-like CO₂ plume, which eventually leads to convective mixing driven by gravitational instability. The geochemically evolved aqueous phase precipitates carbonates in the plume front due to a local rise in pH with mixing of unaffected reservoir water. The carbonate precipitation occurs extensively within the plume after the end of its enlargement, fixing injected CO₂ in a long, geologic period.Dawsonite, a Na–Al carbonate, is initially formed throughout the plume from consumption of plagioclase in the reservoir rock, but is found to be a transient phase finally disappearing from most of the CO₂-affected part of the system. The mineral is unstable relative to more common types of carbonates in the geochemical evolution of the CO₂ storage system initially having formation water of relatively low salinity. The exception is the reservoir-cap rock boundary where CO₂ saturation remains very high throughout the simulation period.     

Chemical effects of sulfur dioxide co-injection with carbon dioxide on the reservoir and caprock mineralogy and permeability in depleted gas fields

The most suitable candidates for subsurface storage of CO₂ are depleted gas fields. Their ability to retain CO₂ can however be influenced by the effect which impurities in the CO₂ stream (e.g. H₂S and SO₂) have on the mineralogy of reservoir and seal. In order to investigate the effects of SO₂ we carried out laboratory experiments on reservoir and cap rock core samples from gas fields in the northeast of the Netherlands. The rock samples were contained in reactor vessels for 30 days in contact with CO₂ and 100 ppm SO₂ under in-situ conditions (300 bar, 100 °C). The vessels also contained brine with the same composition as in the actual reservoir. Furthermore equilibrium modeling was carried out using PHREEQC software in order to model the experiments on caprock samples.After the experiments the permeability of the reservoir samples had increased by a factor of 1.2–2.2 as a result of dissolution of primary reservoir minerals. Analysis of the associated brine samples before and after the experiments showed that concentrations of K, Si and Al had increased, indicative of silicate mineral dissolution.In the caprock samples, composed of carbonate and anhydrite minerals, permeability changed by a factor of 0.79–23. The increase in permeability is proportional to the amount of carbonate in the caprock. With higher carbonate content in comparison with anhydrite the permeability increase is higher due to the additional carbonate dissolution. This dependency of permeability variations was verified by the modeling study. Hence, caprock with a higher anhydrite content in comparison with carbonate minerals has a lower risk of leakage after co-injection of 100 ppmv SO₂ with CO₂.     

Dawsonite formation in the Beier Sag,Hailar Basin,NE China tuff: A natural analog for mineral carbon storage

We determined the rock types, the authigenic minerals, the paragenetic sequence, and the origin of dawsonite in pyroclastic rocks from the Yimin Formation of Beier Sag in the Hailar Basin, China. Dawsonite, a diagenetic mineral, is thought to result from a large influx of CO₂ and, therefore, this system represents a natural analogue for in-situ mineral carbon storage. The studied host rocks are mainly tuffs/tuffaceous sandstones which now contain up to 70 vol% authigenic carbonates, including dawsonite, ankerite, and siderite. The initial alteration of the tuffs yielded minor siderite. Kaolinite, illite and mixed illite/smectite then formed as product phases. Dawsonite and quartz subsequently precipitated in response to CO₂ influx apparently coupled to feldspar and perhaps kaolinte dissolution. Dawsonite reaches a maximum 25 vol% of the bulk rock. Mass balance suggests that this CO₂ influx was coupled to the external import of sodium and export of SiO₂. Ankerite and additional siderite precipitated during the late-stage alkaline diagenesis. The carbon isotope values of the dawsonite are in the range −4.1‰ to −2.2‰, indicating the magmatic origin of the CO₂. Vitrinite reflectance and thermal gradient constraints suggest that the dawsonite at this location formed at a temperature of ∼75 °C.     

Geochronological and geochemical constraints on the intermediate-acid volcanic rocks along the Chiang Khong–Lampang–Tak igneous zone in NW Thailand and their tectonic implications

Volcanic rocks preserved in the Lampang–Den Chai area in NW Thailand are important components of the giant Paleotethyan igneous belt. Constraining their age and petrogenesis is critical for better understanding their temporal-spatial relationship with the Lancangjiang igneous zone and the Paleotethyan tectonic evolution in SE Asia. The volcanic suite is constituted by intermediate to acid rocks with zircon U–Pb ages of 240.4 ± 1.7 Ma and 240.6 ± 1.9 Ma for the representative andesitic and rhyolitic samples, respectively. Volcanic sequence is dominated by calc-alkaline andesites, dacites and rhyolites. The andesitic and dacitic samples are characterized by high Mg# (37–57) and TiO₂ (0.91–1.59 wt%), and can be classified as high-Mg series. They are enriched in LILEs and LREEs and depleted in HFSEs. Representative andesitic samples have ⁸⁷Sr/⁸⁶Sr (i) ratios of 0.70398–0.70567, ε_Nd (t) values of +3.6–+3.9, zircon ε_Hf (t) values of +2.8–+8.0 and δ¹⁸O values of 7.01–8.11‰, respectively. The rhyolitic samples are characterized by high Mg# (38–70) and low TiO₂ (0.25–0.61 wt%). They are enriched in LILEs and LREEs, along with ⁸⁷Sr/⁸⁶Sr (i) = 0.70468–0.70645, ε_Nd (t) = +2.0–+4.3 and zircon ε_Hf (t) = +5.7–+13.6. Geochemical signatures suggest that the andesitic and dacitic samples might originate from a newly modified mantle source by slab-derived fluids and recycled sediments, and rhyolitic samples were derived from juvenile mafic crust. It is proposed that the Middle Triassic high-Mg volcanic rocks in the Lampang–Den Chai area formed in response to slab roll-back during transition of tectonic regime from subduction to continental collision between the Sibumasu and Indochina blocks. These rocks constitute part of the Chiang Khong–Lampang–Tak igneous zone, and can northerly link with the Lancangjiang igneous zone and southerly extend to the Chanthaburi, Malaysia and Singapore areas.     

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems – 2: New experiments with supercritical CO2 and implications for carbon sequestration

In order to evaluate the extent of CO₂–water–rock interactions in geological formations for C sequestration, three batch experiments were conducted on alkali feldspars–CO₂–brine interactions at 150–200 °C and 300 bars. The elevated temperatures were necessary to accelerate the reactions to facilitate attainable laboratory measurements. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. SEM, TEM and XRD analysis of reaction products showed extensive dissolution features (etch pits, channels, kinks and steps) on feldspars and precipitation of secondary minerals (boehmite, kaolinite, muscovite and paragonite) on feldspar surfaces. Therefore, these experiments have generated both solution chemistry and secondary mineral identity. The experimental results show that partial equilibrium was not attained between secondary minerals and aqueous solutions for the feldspar hydrolysis batch systems. Evidence came from both solution chemistry (supersaturation of the secondary minerals during the entire experimental duration) and metastable co-existence of secondary minerals. The slow precipitation of secondary minerals results in a negative feedback in the dissolution–precipitation loop, reducing the overall feldspar dissolution rates by orders of magnitude. Furthermore, the experimental data indicate the form of rate laws greatly influence the steady state rates under which feldspar dissolution took place. Negligence of both the mitigating effects of secondary mineral precipitation and the sigmoidal shape of rate–ΔG_r relationship can overestimate the extent of feldspar dissolution during CO₂ storage. Finally, the literature on feldspar dissolution in CO₂-charged systems has been reviewed. The data available are insufficient and new experiments are urgently needed to establish a database on feldspar dissolution mechanism, rates and rate laws, as well as secondary mineral information at CO₂ storage conditions.     

Rock alteration in alkaline cement waters over 15 years and its relevance to the geological disposal of nuclear waste

The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO₃)₂ + 2OH⁻ → Mg(OH)₂ + CaCO₃ + CO₃²⁻_(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)₂ dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.     

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.     

Fluid metasomatic genesis of stratiform skarn in the Suoerkuduke Cu-Mo deposit,East Junggar,NW China

Stratiform skarns associated with ore deposits are widespread in the north of East Junggar, particularly in the Suoerkuduke Cu-Mo deposit. The Suoerkuduke stratiform and stratoid skarns are hosted by Devonian intermediate-mafic volcanic and pyroclastic rocks, mainly andesite, andesitic porphyry and tuffaceous sandstone, without carbonate or calcareous rocks. The skarns consist of dominant andradite-grossular, epidote, diopside-hedenbergite and minor actinolite, quartz, magnetite and metallic sulfides. The garnet and epidote composition, especially Fe^3 + and Al contents, is largely a function of the bulk composition and physicochemical environment (particularly fO₂) during crystallization. Such mineralogy indicates a relatively oxidizing environment and medium acidity of solution during skarnization.The Suoerkuduke skarns are distinct from typical contact metasomatic skarn in wall rock, as no carbonate or calcareous rocks were found, and differ in the distribution patterns of skarn zonation in that gradually weakened skarn zones are not quite symmetrically distributed on both sides of the alteration center (a garnet skarn). Abundant remnants of andesite, andesitic porphyry and tuffaceous sandstone in the weakened skarn zone indicate that the protolith of the skarn is andesite, andesitic porphyry and tuffaceous sandstone. Magmatic water, meteoric and seawater are involved in skarn alteration. Moyite and granitic porphyry are not coeval with skarn, and their emplacement resulted in the hornfelization of wall rock instead of skarnization, and themselves keep away from skarn alteration. Therefore, there was probably a huge batholith supplying magmatic fluid for skarn formation. Mass balance estimates suggest that hydrothermal fluid must contribute a portion of Ca and Fe to ensure sufficient supply for skarn formation in the absence of local carbonate and calcareous rocks. In conclusion, the stratiform skarns in the Suoerkuduke are products of intermediate-mafic volcanic and pyroclastic rocks metasomatised by hydrothermal fluid that probably leached calcareous wall rock during ascent.     

Can the long-term potential for carbonatization and safe long-term CO2 storage in sedimentary formations be predicted?

A sedimentary formation perturbated by supercritical CO₂ reacts by dissolving primary minerals and forming new secondary phases. In this process CO₂ may be trapped in stable carbonate minerals and may thereby be immobilized for long time spans. The potential for mineral trapping can be estimated by solving kinetic expressions for the reservoir minerals and possible secondary phases. This is, however, not trivial as kinetic data are uncertain or even lacking for the minerals of interest. Here, the rate equations most commonly used for CO₂ storage simulations have been solved, and the rate parameters varied, to obtain sensitivity on the total amount of CO₂ stored as mineral carbonate. As various expressions are in use to estimate growth rates of secondary carbonates, three formulations were compared, including one taking into account mineral nucleation preceding growth. The sensitivity studies were done on two systems, the Utsira Sand being representative for a cold quartz-rich sand (37 °C, 100 bar CO₂), and the Gulf Coast Sediment, being representative for a medium temperature quartz–plagioclase-rich system (75 °C, 300 bar CO₂).The simulations showed that the total predicted CO₂ mineral storage is especially sensitive to the choice of growth rate model and the reactive surface area. The largest sensitivity was found on α, fraction of total surface area available for reactions, with a reduction of one order of magnitude for all reacting phases leading to 3–4 times lower predicted CO₂ mineral storage. Because the reactive surface area is highly uncertain for natural systems, the range in predicted results may be even larger. The short-term predictions (<100–1000 a), such as the onset of carbonate growth, were highly sensitive to nucleation and growth rates. Moreover, the type of carbonate minerals formed was shown to be model dependent, with the simplest model predicting an unlikely carbonate assemblage at low temperature (i.e., formation of dolomite at 37 °C). Therefore, to use kinetic models to upscale short-term (<months) laboratory experiments in time, to identify the past reactions and physical conditions of natural CO₂ storage analogues, and finally to predict the potential for CO₂ trapping in existing and future storage projects, more knowledge has to be collected, especially on the reactive surface area of CO₂ storage reservoirs, and on the rate of secondary carbonate nucleation and growth.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Analysis of parageneses of metapelite gneisses of the Okhotsk granulite complex by minimization of Gibbs thermodynamic potential

The problem of modeling of real parageneses has been solved by minimization of Gibbs thermodynamic potential for metapelites of the Okhotsk granulite complex. Model mineral assemblages completely reproduce the composition of minerals and their modal contents in the studied rocks. This fundamental fact directly verifies the solution of the problem, proving the validity of the principle of local equilibrium in the studied assemblages and the agreement of all thermodynamic data accepted on the modeling. The pressure and temperature during the metamorphism of granulites of the Okhotsk complex, estimated by modeling, are 5.2–7.0 kbar and 620–770 °C, which corresponds to the near-boundary conditions of the amphibolitic and granulitic facies. Model mineral assemblages similar to real parageneses in the composition of minerals and their modes can be successfully obtained with the Selektor software under conditions of both inert and moving water. The composition of the external metamorphic fluid and the approximate weight ratio of fluid to rock have been determined. The oxidation potential of this fluid is similar to the potential of oxygen at the buffer C–CO–CO₂ if the fluid/rock ratio is 0.03–0.30 and the low partial pressure of water varies from 1.80 to 0.35 kbar. The Okhotsk metamorphic complex is not an analog of the granulites of the southern Aldan Shield, because considerably higher pressure and temperature are typical of the latter.     

Late Cenozoic basalt and gabbro in the subsurface in the Phetchabun Basin,Thailand: Implications for the Southeast Asian Volcanic Province

Fragments of basaltic and gabbroic rocks were obtained in cuttings from 15 exploration wells in the Na Sanun area of the Wichian Buri Sub-basin of the Phetchabun Basin in central Thailand. The samples represent flows and sills in lacustrine and fluvial sedimentary rocks of the Lower to mid-Miocene Wichian Buri Group. Mafic igneous units were identified in the sections based on their typically high-amplitude seismic reflections, confirmed by the examination of several hundred well cuttings and magnetic susceptibility measurements. Cross-sections of the sub-basin were constructed on the basis of previously published subsurface interpretations, seismic and well data, and petrological observations. Basaltic flows A, B, E, and F have ages of ca. 2 Ma, 16 Ma, 24 Ma and 18 Ma, based on inferred stratigraphic position. Gabbroic sill C and dioritic sill G are inferred to be correlative at ca. 11.6 Ma, and differ petrologically from ca. 12.8 Ma gabbroic sill D. Major minerals in both basaltic and gabbroic samples are plagioclase (ca. An₅₀), anorthoclase, and augite, with pervasive alteration to Na- and Ca- zeolite minerals and analcime. Leucodioritic sill G also contains amphibole and high Ti-phlogopite. Overall, the rocks show within-plate tholeiitic to alkalic characteristics, and show similarities to basaltic surface outcrops of similar ages in the Wichian Buri-Lop Buri area. No evidence was seen in the subsurface for the andesitic to rhyolitic rocks of similar ages that occur at surface, but their presence cannot be precluded based on our limited data.     

Long‐Term Reaction Characteristics of CO2–Water–Rock Interaction: Insight into the Potential Groundwater Contamination Risk from Underground CO2 Storage

CO₂ sequestration into saline aquifers is considered to be one of the most promising options for reducing industrial CO₂ emissions to the atmosphere. However, there are still many uncertainties regarding the storage of CO₂ in the subsurface because of a lack of knowledge about CO₂–water–rock interaction within CO₂ reservoirs and the potential risk of CO₂ leakage. In this study, we construct a semi‐open type experimental system that can reproduce the interactions under conditions close to those of actual CO₂ reservoirs. Using the system, we conduct CO₂–water–rock interaction experiments for 8 months to monitor the long‐term reaction and the mobilization of harmful metal elements. Altered tuffaceous rock is used in the experiment because these tuffaceous rock formations (called “Green Tuff”) are a potential candidate for CO₂ storage in Japan. The results show that the major‐element water composition will converge to the point where host rock dissolution and secondary mineral precipitation are balanced; then, the interaction will proceed under a certain groundwater composition. In addition, we found that groundwater contamination by some metal elements (Ni, Ba, and Mn) may reach unsafe levels for drinking water as a result of CO₂‐water–rock interaction.     

Segregation of magmatic fluids and their potential in the mobilization of platinum-group elements in the South Kawishiwi Intrusion,Duluth Complex,Minnesota — Evidence from petrography,apatite geochemistry and coexisting fluid and melt inclusions

Pegmatitic and other felsic rock pockets and dike-like intrusions are abundant in the South Kawishiwi Intrusion of the Duluth Complex, including the basal, Cu–Ni–PGE mineralized units. These occurrences are found as pockets, pods or as veins and contain abundant accessory apatite and quartz. Quartz hosts primary fluid inclusions as well as silicate melt inclusions. Combined microthermometry and Raman spectroscopy helped to determine the bulk composition of primary fluid inclusions that are CO₂-rich (95 mol%) and contain small amounts of H₂O (4.5 mol%), CH₄ (0.4 mol%) and trace N₂, respectively. This combined technique also made it possible to measure total homogenization temperatures of the inclusions (Th_tot = ~ 225 ± 10 °C), otherwise not detectable during microthermometry. Silicate melt inclusions have been quenched to produce homogeneous glasses corresponding to the original melt. Composition of the entrapped melt is granitoid, peraluminous and is very poor in mafic components. We interpret the melt as a product of partial melting of the footwall rocks due to the contact effect of the South Kawishiwi Intrusion. The presence of CO₂ in the vapor bubbles of the quenched melt inclusions and petrographic evidence suggest that the fluid and melt inclusion assemblages are coeval. The composition of the fluid and melt phase implies that the fluid originates from the mafic magma of the South Kawishiwi Intrusion and the fluid and melt phases coexisted as a heterogeneous melt–fluid system until entrapment of the inclusions.Coexistence of primary fluid and melt inclusions makes it possible to calculate a minimum entrapment pressure (~ 1.7 kbar) and thus estimate formation depth (~ 5.8 km) for the inclusions. Chlorine is suggested to behave compatibly in the silicate melt phase in the fluid–melt system represented by the inclusions, indicated by the high (up to 0.3%) Cl-concentrations of the silicate melt and CO₂-rich nature of the fluid.Apatite halogen-contents provide further details on the behavior of Cl. Apatite in pegmatitic pockets often has elevated Cl-concentrations compared to troctolitic rocks, suggesting enrichment of Cl with progressive crystallization. Systematic trends of Cl-loss at some differentiated melt pockets suggest that in some places Cl exsolved into a fluid phase and migrated away from its source. The segregation of Cl from the melt is probably inhibited by the presence of CO₂-rich fluids until the last stages of crystallization, increasing the potential for the development of late-stage saline brines.Platinum-group minerals are often present in microcracks in silicate minerals, in late-stage differentiated sulfide veinlets and in association with chlorapatite, indicating the potential role of Cl-bearing fluids in the final distribution of PGEs.     

Assessing the potential consequences of CO2 leakage to freshwater resources: A batch-reaction experiment towards an isotopic tracing tool

The assessment of the environmental impacts of CO₂ geological storage requires the investigation of potential CO₂ leakages into fresh groundwater, particularly with respect to protected groundwater resources. The geochemical processes and perturbations associated with a CO₂ leak into fresh groundwater could alter groundwater quality: indeed, some of the reacting minerals may contain hazardous constituents, which might be released into groundwater. Since the geochemical reactions may occult direct evidence of intruding CO₂, it is necessary to characterize these processes and identify possible indirect indicators for monitoring CO₂ intrusion. The present study focuses on open questions: Can changes in water quality provide evidence of CO₂ leakage? Which parameters can be used to assess impact on freshwater aquifers? What is the time scale of water chemistry degradation in the presence of CO₂? The results of an experimental approach allow selecting pertinent isotope tracers as possible indirect indicators of CO₂ presence, opening the way to devise an isotopic tracing tool.The study area is located in the Paris Basin (France), which contains deep saline formations identified as targets by French national programs for CO₂ geological storage. The study focuses on the multi-layered Albian fresh water aquifer, confined in the central part of the Paris Basin a major strategic potable groundwater overlying the potential CO₂ storage formations. An experimental approach (batch reactors) was carried out in order to better understand the rock–water–CO₂ interactions with two main objectives. The first was to assess the evolution of the formation water chemistry and mineralogy of the solid phase over time during the interaction. The second concerned the design of an isotopic monitoring program for freshwater resources potentially affected by CO₂ leakage. The main focus was to select suitable environmental isotope tracers to track water rock interaction associated with small quantities of CO₂ leaking into freshwater aquifers.In order to improve knowledge on the Albian aquifer, and to provide representative samples for the experiments, solid and fluid sampling campaigns were performed throughout the Paris Basin. Albian groundwater is anoxic with high concentrations of Fe, a pH around 7 and a mineral content of 0.3 g L⁻¹. Macroscopic and microscopic solid analyses showed a quartz-rich sand with the presence of illite/smectite, microcline, apatite and glauconite. A water–mineral–CO₂ interaction batch experiment was used to investigate the geochemical evolution of the groundwater and the potential release of hazardous trace elements. It was complemented by a multi-isotope approach including δ¹³C_DIC and ⁸⁷Sr/⁸⁶Sr. Here the evolution of the concentrations of major and trace elements and isotopic ratios over batch durations from 1 day to 1 month are discussed. Three types of ion behavior are observed: Type I features Ca, SiO₂, HCO₃, F, PO₄, Na, Al, B, Co, K, Li, Mg, Mn, Ni, Pb, Sr, Zn which increased after initial CO₂ influx. Type II comprises Be and Fe declining at the start of CO₂ injection. Then, type III groups element with no variation during the experiments like Cl and SO₄. The results of the multi-isotope approach show significant changes in isotopic ratios with time. The contribution of isotope and chemical data helps in understanding geochemical processes involved in the system. The isotopic systems used in this study are potential indirect indicators of CO₂–water–rock interaction and could serve as monitoring tools of CO₂ leakage into an aquifer overlying deep saline formations used for C sequestration and storage.     

Constraints of C–O–S–Pb isotope compositions and Rb–Sr isotopic age on the origin of the Tianqiao carbonate-hosted Pb–Zn deposit,SW China

The Tianqiao Pb–Zn deposit in the western Yangtze Block, southwest China, is part of the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province. Ore bodies are hosted in Devonian and Carboniferous carbonate rocks, structurally controlled by a thrust fault and anticline, and carried about 0.38 million tons Pb and Zn metals grading > 15% Pb + Zn. Both massive and disseminated Pb–Zn ores occur either as veinlets or disseminations in dolomitic rocks. They are composed of ore minerals, pyrite, sphalerite and galena, and gangue minerals, calcite and dolomite. δ³⁴S values of sulfide minerals range from + 8.4 to + 14.4‰ and display a decreasing trend from pyrite, sphalerite to galena (δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena). We interpret that reduced sulfur derived from sedimentary sulfate (gypsum and barite) of the host Devonian to Carboniferous carbonate rocks by thermal–chemical sulfate reduction (TSR). δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite range from –5.3 to –3.4‰ and + 14.9 to + 19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid was a mixture origin of mantle, marine carbonate rocks and sedimentary organic matter. Sulfide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.378 to 18.601, ²⁰⁷Pb/²⁰⁴Pb = 15.519 to 15.811 and ²⁰⁸Pb/²⁰⁴Pb = 38.666 to 39.571) that are plotted in the upper crust Pb evolution curve and overlap with that of Devonian to Carboniferous carbonate rocks and Proterozoic basement rocks in the SYG province. Pb isotope compositions suggest derivation of Pb metal from mixed sources. Sulfide minerals have ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7125 to 0.7167, higher than Sinian to Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than basement rocks. Again, Sr isotope compositions are supportive of a mixture origin of Sr. They have an Rb–Sr isotopic age of 191.9 ± 6.9Ma, possibly reflecting the timing of Pb–Zn mineralization. C–O–S–Pb–Sr isotope compositions of the Tianqiao Pb–Zn deposit indicate a mixed origin of ore-forming fluids, which have Pb–Sr isotope homogenized before the mineralization. The Permian flood basalts acted as an impermeable layer for the Pb–Zn mineralization hosted in the Devonian–Carboniferous carbonate rocks.     

An experimental study of lake water-sediment interaction rates

Dissolution rates of sediments obtained from the Oued Cherf reservoir were measured in closed-system batch reactors at 25 °C in fluids sampled concurrently from the same locations as the sediments. The BET surface areas of the sediments ranged from 16 to 45 m²/g and consisted primarily of quartz, calcite, and clay minerals. After a brief initial period, release rates of Si, Mg, Ca, Cl, SO₄, and NO₃ from these sediments are approximately linear with time over the course of the experiments, which lasted from 3 to 5 months. BET surface area normalized Si release rates ranged from 10^–17.4 to 10^–18.4 mol/cm²/s. These release rates match closely Si release rates from quartz and clay minerals determined from laboratory dissolution rates reported in the literature. This coherence suggests that laboratory measured silicate dissolution rates can be used with confidence to predict the dissolution behavior of sediments in natural surface waters.     

Quartzose–mafic spectral feature space model: A methodology for extracting felsic rocks with ASTER thermal infrared radiance data

The original spectral features of felsic rocks are often intermingled with other surface objects, which results in difficulty of detecting felsic rocks using remote sensing techniques. Few felsic rock indices were proposed and visual interpretation with RGB false color composition is widely used to detect felsic rocks. This paper aims to construct a two-dimensional spectral feature space model to extract felsic rocks using ASTER thermal infrared radiance data. The study area is located in northern Qinghai Province, western China with average altitude of approximately 4200 m. A large number of training pixels of mafic–ultramafic rock, quartz-rich rock, felsic rock, carbonate rock and vegetation were selected from the ASTER images as samples of these surface objects. Then we used a quartz-rich rock index (QI, QI = band14 − 0.844 × band12 − 1.897) and a mafic–ultramafic rock index (MI, MI = 0.915 × band10 − band13 + 1.437) to generate a two-dimensional scatter plot. The plot was named after quartzose–mafic spectral feature space (QMFS). The samples show an approximate triangular shape in the QMFS. Mafic–ultramafic rock, quartz-rich rock and carbonate rock are located in separate locations in the three vertex regions, respectively, while felsic rock is located in the central region of the triangle. Next, we calculated a linear belt of silicate rocks in which silicate rocks vary regularly by using a linear regression analysis in the QMFS. Statistical characteristics of the felsic rock samples are analyzed. Afterwards, a polygon which delineates the distribution of felsic rock samples was constructed from the linear belt of silicate rocks. Then we generated a system of inequalities based on the equations of the edges of the polygon. The application of the inequalities to the ASER images shows a good performance of the QMFS for extracting felsic rocks.     

Geochemistry and geochronology of the volcanic rocks associated with the Dong'an adularia–sericite epithermal gold deposit,Lesser Hinggan Range,Heilongjiang province,NE China: Constraints on the metallogenesis

Late Mesozoic volcanism is widespread throughout NE China. On the basis of lithological associations and spatial relationships, the volcanic rocks in the Lesser Hinggan Range can be divided into two formations, i.e., felsic-dominant Fuminghe Formation and overlying mafic-dominant Ganhe Formation. The Dong'an gold deposit, a typical adularia–sericite epithermal system, is spatially closely associated with rhyolitic porphyry, which is a subvolcanic intrusion of the Fuminghe Formation. Total measured, indicated, and inferred resources for the Dong'an deposit are 70 tonnes (2.25 Moz) of gold with the grade of 5.04 g/t Au, making it one of the largest epithermal gold deposits in China.SHRIMP U–Pb zircon and ⁴⁰Ar/³⁹Ar geochronology applied to one rhyolitic porphyry sample and sericite separated from auriferous quartz veins of the main mineralization stage were carried out to constrain magmatic and hydrothermal events. The results suggest that the mineralization age of 107.2 ± 0.6 Ma overlaps with the age of the rhyolitic porphyry 108.1 ± 2.4 Ma. Our new age data indicate that there was a previously unrecognized mineralization event in NE China at 107–108 Ma.Systematic geochemical investigations on the volcanic rocks in the Lesser Hinggan Range show that both Fuminghe and Ganhe Formations are characterized by significant large ion lithophile elements (LILE) and light rare earth elements (LREE) enrichment coupled with high field strength elements (HFSE) depletion, but they have distinct Sr and Nd isotopic compositions. The Fuminghe Formation has relative high ⁸⁷Sr/⁸⁶Sr ratios of 0.707253 to 0.707373, and negative ε_Nd(t) values of ?2.78 to ?3.05 (t = 108 Ma), whereas the Ganhe Formation displays slightly lower ⁸⁷Sr/⁸⁶Sr range of 0.705434–0.705763 and positive ε_Nd(t) values of + 0.76 to +1.83. These geochemical data suggest that the rhyolitic magmas of the Fuminghe Formation probably represent the final differentiates of parental andesitic magmas, resulted from the partial melting of mafic lower crust, whereas the volcanic rocks of the Ganhe Formation were produced by fractionation of basaltic magmas generated from partial melting of a mixture of an incompatible element depleted anhydrous lherzolite asthenospheric mantle source and a hydrous enriched lithospheric mantle source in an extensional tectonic setting, in response to upwelling of asthenospheric mantle. The rhyolite porphyries of the Fuminghe Formation are inferred to have supplied heat that drove the convective hydrothermal system at Dong'an deposit, but also provided some of the fluid sources responsible for the development of the Dong'an epithermal system.