Quartz Precipitation Research Articles

Geochemical modeling of diagenetic reactions between albitization of K-feldspar and plagioclase feldspar in sandstone reservoirs under the influence of CO2 partial pressure

Diagenetic albitization has been observed in sedimentary basins around the world. This process significantly changes the original composition of sandstones and the chemistry of the formation waters under the influence of partial pressure of CO2. The transformation of detrital feldspars into albite is considered a crucial diagenetic process in the Gulf Coast and North Sea reservoirs. Earlier studies suggest that plagioclase albitization typically happens before that of K-feldspar. In the Gulf Coast's Frio Sandstone, located in the Upper Oligocene at depths between 900 and 2400 m, detrital plagioclase is often dissolved and replaced by albite, while K-feldspar mostly dissolves without much substitution. Similarly, in the North Sea reservoirs, especially in the upper section of the Upper Triassic Lunde Formation at depths beyond 2900 m, plagioclase tends to undergo albitization, whereas K-feldspar remains largely unaffected or experiences minimal transformation. This research focuses on analyzing the differences in the albitization patterns of detrital and K-feldspar plagioclase through the KINDISP and Geochemist's Workbench (GWB) geochemical modeling tools, aiming to compare them. These diagenetic processes are crucial for reservoir geology, as they influence the concentration of silica in water, which, in turn, affects quartz cementation. This study aims to explore the variations in the albitization behavior of detrital and K-feldspar plagioclase using the KINDISP and Geochemist's Workbench (GWB) geochemical models and conduct a comparative analysis between them. Understanding these diagenetic reactions becomes relevant for reservoir geology analysis, as such phenomena control the aqueous silica concentration to some extent, which is consequently reflected in the quartz cementation. The dissolution of plagioclase and K-feldspar releases silica into the pore fluids. As the concentration of silica in the fluid increases, it leads to the precipitation of quartz as overgrowths on detrital quartz grains, a process known as quartz cementation. This was observed particularly in simulations involving temperature increases up to 150 °C, where the equilibrium between albite and anorthite was closely linked to the stability of quartz (Ben et al., 1993). The removal of feldspar through albitization reduces porosity and permeability but contributes silica to the system, which promotes quartz cementation. This, in turn, decreases the reservoir quality by filling pore spaces with secondary quartz, reducing the rock's ability to store and transmit fluids. Thus, the study highlights the importance of these diagenetic processes in reservoir evaluation, as the balance between feldspar dissolution and quartz cementation ultimately controls reservoir properties.

Corundum-quartz metastability: the role of silicon diffusion in corundum

The synthesis of the Al2SiO5 polymorphs kyanite, sillimanite and andalusite in a pure Al2O3–SiO2–H2O (ASH) system has long been known to be impeded. In order to decipher individual aspects of the reaction: corundum + SiO2aq, which repeatedly fails to produce thermodynamically stable Al2SiO5, we conducted experiments within the stability fields of kyanite and sillimanite (500–800 ℃; 0.2–1 GPa) with the aim of forming reaction coronas on corundum. Results showed that metastable corundum + quartz assemblages form persistently in pure ASH, even in Al2SiO5 seeded experiments, despite the presence of catalyzing fluid and evidence of fast reaction kinetics. Coronas on corundum spontaneously formed when additional components (Na, K, N, and Mg) were added to the experiment. In a similar experiment with baddeleyite (ZrO2) instead of corundum in silica saturated water, a zircon corona formed readily. This implies that nucleation and growth of Al2SiO5 is obstructed under conditions of Al and Si saturation in aqueous fluid, while both corundum and quartz saturated aqueous fluid are willing participants in other reactions towards stable corona formation. Instead of Al2SiO5 precipitation, an unexpected fluid-aided silica diffusion process into corundum was documented. The latter included the formation of nanometer wide hydrous silicate layers along the basal plane of the corundum host, which enhanced the silica diffusion rate drastically, leading to silica supersaturation in the host mineral, and ultimately to precipitation of quartz inside corundum. We conclude that the natural metastable assemblage of quartz and corundum is not necessarily the result of dry or fluid absent conditions, given that the aqueous fluid in experiments does not promote Al2SiO5 formation, but rather seems to support the formation and preservation of a metastable assemblage.

Formation of Topaz-Greisen by a Boiling Fluid: A Case Study from the Sn-W-Li Deposit, Zinnwald/Cínovec

Abstract Zinnwald/Cínovec is one of the largest Li-Sn-W greisen deposits in Europe. Greisens in general are important hosts for many major ore deposits of several high-tech elements—most prominently Sn, W, and Li. However, the mechanisms of greisenization in relationship to ore formation are still not well understood, especially for the important case of fluoride-rich greisen. Here, we investigate the sequence and formation mechanism of the topaz-greisen in the Zinnwald/Cínovec deposit. Based on the mineral abundances, the alteration profile can be divided into four distinct zones: (1) rhyolite, (2) albitite, (3) low-degree greisen, and (4) high-degree greisen. In the greisen zones, almost all the feldspar has been replaced by topaz (up to 12 vol %) + quartz (up to 78 vol %), and the abundance of mica gradually decreases from 11 to 3 vol % with increasing degree of greisenization. Mass balance calculations indicate a net influx of F and silica during greisenization. Our observations are best explained by a two-stage greisenization process involving phase separation by boiling in the pore space of the sample: first an acidic HF-rich phase, likely a vapor, reacted with feldspar to form topaz and quartz in a dissolution-precipitation reaction. This reaction created substantial transient porosity, which was subsequently sealed by the precipitation of quartz and fluorite from a boiling liquid. We interpret the vapor and liquid as emerging from a common supercritical aqueous parental fluid. The characteristic sequence of creation of pore space by a vapor and the subsequent reduction of porosity by precipitation from the associated boiling liquid constrain the conditions and time available for ore formation. This study evaluates the mechanism of topaz greisenization and the controls on porosity evolution, which are crucial to ore element redistribution.

Diagenetic Impact on High-Pressure High-Temperature Reservoirs in Deep-Water Submarine Fan Sandstone of Qiongdongnan Basin, South China Sea

The diagenetic evolution of sandstone is very complicated under the conditions of high temperatures and pressures in deep-water, deep-buried regimes, which have great influence on reservoir quality. This study investigates the typical reservoir target of Neogene deep-water, submarine-fan sandstones under high-temperature, high-pressure regimes in the Qiongdongnan Basin, South China Sea. Utilizing a thin section, scanning electron microscope (SEM), mineral geochemistry combined with burial history evolution, complex diagenetic events, and main controlling factors of the sandstone in the Neogene Meishan Formation were determined. The results show that the evolution of sandstone reservoirs is initially controlled by depositional framework compositions and subsequently modified by eogenetic and mesogenetic alterations during progressive burial. Eogenetic alterations mainly include the following: (1) mechanical compaction; (2) dissolution of feldspar; (3) low-Fe calcite cementation. Mesogenetic events were identified as the following: (1) dissolution of feldspar; (2) ferroan calcite and ankerite formation; (3) precipitation of quartz and clay mineral. Mechanical compaction is greatly influenced by the original depositional framework composition, and sandstone samples enriched in high contents of detrital clay matrix always experienced extensive mechanical compaction. Different phases of carbonate cement during different diagenetic regimes lead to continuous destruction on reservoir porosity. The dissolution of unstable feldspar minerals during eogenetic and mesogenetic environments leads to the development of secondary porosities and would enhance the quality of the reservoir. Overpressure formation is pervasively developed owing to early disequilibrium compaction and subsequent natural gas charging. Only well-sorted sandstones with low contents of detrital clay matrix could resist early mechanical compaction, lead to ample residual original porosities, and then undergo extensive mineral dissolution to generate sufficient secondary porosities. Subsequently, these porosities would be effectively protected by overpressure formation. Poor-sorted sandstones with high contents of detrital clay matrix would experience strong mechanical compaction and extensive destruction of original porosities. Thus, these sandstones are difficult to have significant dissolution and are unable to be effectively protected by overpressure formation. Therefore, the interplay between the original framework composition and the corresponding diagenetic pathways coupled with overpressure formation would result in strong reservoir heterogeneity for the deep-buried sandstones during progressive burial.

Timing and Mechanism of Ore Precipitation in Porphyry Cu Systems: Insight from LA-ICP-MS Analysis of Fluid Inclusions and In Situ Oxygen Isotope Analysis of Hydrothermal Quartz at Zhunuo Porphyry Cu Deposit, China

Abstract The timing and mechanism of ore precipitation in porphyry copper systems are hot topics and remain controversial. The large Miocene collision-related Zhunuo porphyry Cu deposit in the Gangdese belt of southern Tibet, China, was produced by multistage quartz veining and hydrothermal alteration, accompanied by Cu sulfide precipitation. In this study, we have combined cathodoluminescence (CL) petrography with in situ oxygen isotope analysis and fluid inclusion microthermometry and laser ablation-inductively coupled plasma-mass spectrometer microanalysis to constrain the growth history of individual quartz veins, the source and evolution of the hydrothermal fluids, and the timing and mechanism of ore precipitation at Zhunuo. Early quartz A veins associated with potassic alteration are composed of quartz, K-feldspar, biotite, Cu-Fe sulfides, and pyrite. Quartz B veins are composed of quartz, Cu-Fe sulfides, molybdenite, and pyrite. CL imaging shows that quartz grains in the A and B veins consist of abundant early generation of bright-luminescent quartz (QA and QB) with volumetrically minor later generation of dull-luminescent quartz (QA-crack and QB-crack) occurring in the voids or at the margins of the QA and QB veins with embayed contacts. Cu-Fe sulfides are generally in contact with the dull-luminescent quartz and locally in contact with the bright-luminescent quartz and K-feldspar in the A and B veins or occur as disseminations in the potassic-altered porphyries that have been overprinted by chlorite ± muscovite alteration. QA and QB contain single-phase intermediate-density inclusions and abundant brine and vapor-rich inclusions. A boiling assemblage in QA has a homogenization temperature of ~560°C and trapping pressure of ~530 bar. Two boiling assemblages in QB have homogenization temperatures of ~440°C with trapping pressures of ~230 and ~250 bar, indicating a transition from lithostatic to hydrostatic conditions at a paleodepth of ~2.0 to 2.5 km. QA-crack and QB-crack contain aqueous inclusions with lower homogenization temperatures of 340° to 400°C and salinities of 6 to 12 wt % NaCl equiv. In situ oxygen isotopes indicate that QA and QB have δ18O values of 7.6 to 11.4‰, whereas QA-crack and QB-crack have δ18O values of –7.2 to 6.7‰. Combined with fluid inclusion compositions, we propose that condensation of vapors into brines and mixing with 25 to 60% meteoric water can produce the salinity and oxygen isotopes of fluids that caused the dissolution of the early bright-luminescent quartz and the precipitation of the later dull-luminescent quartz. Zhunuo Cu-Fe sulfides are in contact with the bright-luminescent quartz and cut the growth bands. The dull-luminescent quartz in contact with the Cu-Fe sulfides has oscillatory growth banding. In addition, Cu-Fe sulfides in the A and B veins or in the potassic-altered rocks coexist with chlorite ± muscovite alteration minerals. These geologic observations, together with evidence that there is an abrupt drop in the Cu/(Na + K) ratio by more than one order of magnitude in the aqueous fluids within the dull-luminescent quartz compared to the brines within the bright-luminescent quartz, indicate that precipitation of Cu-Fe sulfides occurred after the potassic alteration stage and during the chlorite ± muscovite alteration stage. Ore precipitation was associated with mixing of magmatic fluids (brines + vapors) with meteoric water, accompanied by fluid cooling, salinity decrease, and retrograde quartz solubility as the rocks transitioned from lithostatic to hydrostatic conditions. During continued cooling in the latest stage, the hydrothermal fluids precipitated D veins that contain abundant pyrite with minor quartz. Quartz in the D veins (QD) contains aqueous inclusions with much lower temperatures and Cu/(Na + K) ratios, indicating that most of the Cu-Fe sulfides have been precipitated during this stage.

Mudstone diagenesis and sandstone provenance in an Upper Jurassic – Lower Cretaceous evolving half-graben system, Wollaston Forland, North-East Greenland

The influence of rifting on the composition of Kimmeridgian to Barremian mudstones from northern Wollaston Forland, North-East Greenland is investigated by petrographic and mineralogical analyses of the Brorson Halvø-1 and Rødryg­gen-1 cores, and provenance of analysis by zircon U-Pb age dating of nearby sandstones. Mudstone composition varies systematically as a function of the timing of rifting progression and position in the half-graben depositional system. Pyrite primarily precipitated in the early rift to rift climax phases. Euhedral pyrite overgrowths on framboids formed only during the rift climax phase (Lindemans Bugt Formation). Dolomite is the dominant carbonate cement, except for the sediments deposited in the early waning rift phase (Palnatokes Bjerg Formation) where calcite is dominant, and in the late waning rift phase (Stratumbjerg Formation) where siderite dominates. The highest-temperature reactions with precipitation of illite, quartz, ankerite and barite signify sediment burial depths of >2 km prior to exhumation. Uplift-induced fracturing occurred mainly in the early rift to rift acceleration succession (Bernbjerg Formation). Mudstones in the proximal part of the half-graben (Rødryggen-1) include more detrital kaolinite than the distal mudstones (Brorson Halvø-1), which contain more mixed-layer illite-smectite and illite. Vermiculite was deposited only in the proximal part of the basin in the rift climax and waning rift successions. Chlorite was deposited proximally and distally during the waning rift phase, though supply began earlier in the distal part. Fine-grained sediment in the distal part of the half-graben was therefore probably supplied by axial transport from Palaeoproterozoic crystalline rocks and Meso- to Neoproterozoic metamorphic rocks located to the north and north-west. This agrees with the zircon provenance signature from outcropping sand-rich facies, where zircon grains with U-Pb ages of 2.0–1.6 Ga are dominant, in addition to common 1.6–0.9 Ga ages, and fewer 2.8–2.6 Ga and 0.47–0.36 Ga ages.

Sustainable removal of nutrients (n and p) in a wastewater treatment plant, with eggshell (biocalcium)

Biological treatments have become insufficient to treat municipal wastewater with greater toxicity and excess nitrogen and phosphate species, thus affecting the organisms that consume the water. In this work, a process was implemented for the removal of nutrients through three stages: stage A, complete aeration (24 h, 43 months); stage B, decreased aeration (12 h, 17 months); and stage C, decreased aeration with biocalcium (12 h, 19 months). The addition of biocalcium from eggshell promoted the formation of flocks, which resulted in the removal of nitrites (61 %), nitrates (84 %), total nitrogen (57 %), total phosphorus (8.3 %), sedimentable solids (50 %), total suspended solids (69 %), BOD5 (76 %), helminth eggs (50 %) and fecal coliforms (54 %). The statistical analyses in the three stages indicated that there is a strong correlation between the concentration of fats and oils and the removal of sedimentable solids and total suspended solids, since these parameters were correlated by 97 and 89 %, respectively. Sedimentable solids were correlated with total suspended solids by 94 %, while nitrates and total nitrogen were correlated 92 %, which favors the removal of nutrients in wastewater. The increase in the concentration of nitrogen in the sludge in stage C generated a C:N ratio of 7.98. This ratio shows that the sludge is feasible for use as a mediator of soils and a biofertilizer because of the high contents of calcium, phosphorus and nitrogen. In addition, biocalcium promoted the precipitation of hydroxyapatite, struvite, calcite and quartz. In general, the three stages of the treatment contributed to the stabilization of the wastewater treatment plant (WWTP) in an efficient, economical, and safe way.

Source of quartz cement and its impact on reservoir quality in Jurassic Shaximiao Formation in central Sichuan Basin, China

Quartz cement is an essential authigenic mineral in the tight sandstones of the Shaximiao Formation in the Sichuan Basin, China. Accurately identifying its sources and investigating its impact on reservoir quality is important for understanding diagenetic fluid evolution and pore development in these reservoirs. To address this, we conducted a systematic analysis of the silicon sources in quartz cement employing mineralogical, fluid inclusion, and geochemical data. Quartz cement is characterized by two phases of quartz overgrowth and pore-filling authigenic quartz. Homogenization temperatures of fluid inclusions range from 60 to 150 °C, indicating that quartz cementation occurred from the early diagenetic phase (B stage) to the late mesodiagenetic phase. During the early diagenetic stage, volcanic material was dissolved by meteoric water, resulting in the formation of the earliest quartz cement and smectite. At temperatures of approximately 70–100 °C, smectite illitization, accompanied by K-feldspar consumption and SiO2 precipitation. In the mesodiagenetic stage (temperature approximately 100–130 °C), organic acids led to the dissolution of minerals like feldspar and laumontite, releasing SiO2. In the deep burial stage, clastic quartz grains experienced dissolution due to high stress, providing a limited source of SiO2. Smectite alteration and the dissolution of aluminosilicate minerals represent the primary sources of silicon for quartz cementation, while contributions from volcanic material hydrolysis and pressure solution are relatively minor. The presence of chlorite films inhibits the development of quartz overgrowths, and the limited precipitation of authigenic quartz within the primary porosity has a minimal impact on reservoir quality. Consequently, sandstones rich in chlorite films represent a favorable lithology for the development of high-quality reservoirs.

Evolution characteristics and exploration targets of Permian clastic rock reservoirs in Bohai Bay Basin, East China

Based on core observation, thin section examination, fluid inclusions analysis, carbon and oxygen isotopic composition analysis, and other approaches, the structural and burial evolution histories were investigated, and the diagenetic evolution process and genetic/development models were systematically discussed of the Upper Paleozoic Permian clastic rock reservoirs in the Bohai Bay Basin, East China. The Bohai Bay Basin underwent three stages of burial and two stages of uplifting in the Upper Paleozoic. Consequently, three stages of acid dissolution generated by the thermal evolution of kerogen, and two stages of meteoric freshwater leaching occurred. Dissolution in deeply buried, nearly closed diagenetic system was associated with the precipitation of authigenic clay and quartz, leading to a limited increase in storage space. Different structural uplifting–subsidence processes of tectonic zones resulted in varying diagenetic–reservoir-forming processes of the Permian clastic reservoirs. Three genetic models of reservoirs are recognized. The Model I reservoirs with pores formed in shallow strata and buried in shallow to medium strata underwent two stages of exposure to long-term open environment and two stages of meteoric freshwater leaching to enhance pores near the surface, and were shallowly buried in the late stage, exhibiting the dominance of secondary pores and the best physical properties. The Model II reservoirs with pores formed in shallow strata and preserved due to modification after deep burial experienced an early exposure-open to late burial-closed environment, where pore types were modified due to dissolution, exhibiting the dominance of numerous secondary solution pores in feldspar and the physical properties inferior to Model I. The Model III reservoirs with pores formed after being regulated after multiple periods of burial and dissolution experienced a dissolution of acidic fluids of organic origin under a near-closed to closed environment, exhibiting the dominance of intercrystalline micropores in kaolinite and the poorest physical properties. The target reservoirs lied in the waterflood area in the geological period of meteoric freshwater leaching, and are now the Model II deep reservoirs in the slope zone–depression zone. They are determined as favorable options for subsequent exploration.

Fluid evolution and related fluid–rock interactions of the Oligocene Zhuhai sandstones in the Baiyun Sag, northern margin of the South China Sea

Pore fluids control the diagenetic processes and storage spaces of deep clastic rock reservoirs and have become a major area of interest within the fields of sedimentology and petroleum geology. This paper aims to relate the diagenetic processes of the Oligocene Zhuhai sandstones in the Baiyun Sag to pore fluids varying with burial depth. The types and distribution patterns of authigenic minerals are investigated through analysis of petrographic, mineralogical, and geochemical features to illustrate the origin and flow patterns of pore fluids and their influences on reservoir diagenesis. Strong cementation of eogenetic carbonate cement near the sandstone–mudstone interface was a consequence of material migration from adjacent mudstones on a large scale. The pore fluids were mainly affected by microbial methanogenesis and carbonate mineral dissolution in adjacent mudstones during eogenesis. The pore fluids were diffusively transported in a relatively open geochemical system within a local range. Support for this model is provided by the heavier stable isotopic values present in eogenetic calcite and dolomite. Feldspar dissolution during early mesogenesis was spatially accompanied by the precipitation of authigenic quartz and ferroan carbonate cement. Pore fluids in this period were rich in organic acids and CO2, and their migration mechanism was diffusive transport. The obviously lighter carbon and oxygen isotopic compositions of the ferroan calcite support this inference. During late mesogenesis, the input of deep hydrothermal fluid might have been partly responsible for the precipitation of ankerite, barite and authigenic albite. Oil charging may have inhibited carbonate cementation and compaction, accordingly preserving porosity, and together with authigenic kaolinite, might have promoted the transition of the reservoir from water wet to oil wet to the benefit of oil entrapment. The findings reported here shed new light on the evaluation and prediction of sandstone reservoirs that have experienced multiple periods of fluid flow.

Quartz types and origins of the Upper Permian Dalong Formation shale of the Sichuan Basin: Implications for pore preservation in deep shale reservoirs

Quartz is critical to reservoir properties (e.g., rock mechanical behavior and porosity) of organic mudstones, exerting an important effect on shale gas production. However, the types and origins of quartz in deeply-buried Upper Permian mudstones, a potential target of shale gas exploration in South China, remain poorly understood. A suite of deeply buried (5636–5645 m) mudstone samples of the Upper Permian Dalong Formation (DL) in the Sichuan Basin (South China) was selected to characterize quartz minerals using petrological and geochemical approaches, including SEM-CL observation. The studied mudstone samples are relatively enriched in organic matter (OM) (total organic carbon (TOC) = 1.88–18.46 wt%) and have been thermally over-matured. The DL organic mudstones accumulated in a failed rift basin, far removed from provenance areas, are chiefly composed of intrabasinal quartz and carbonate (mostly calcite). Quartz is represented by six major forms, including detrital quartz grains, siliceous skeletal fragments, silica nanospheres, microquartz aggregates, grain-replacive quartz, and matrix-dispersed microquartz, of which the latter five are of authigenic origin. Detrital quartz grains are not common in the DL mudstones. Silica reprecipitated as authigenic quartz was largely sourced from dissolved siliceous skeletal fragments (mostly radiolarians), and some silica appeared to have been released from the alteration of volcanic debris (mainly plagioclase) to form matrix-dispersed microquartz grains. Authigenic quartz influenced pore development and preservation of shale reservoirs in two ways. A rigid framework formed from numerous authigenic quartz grains (e.g., microquartz aggregates, silica nanospheres, and siliceous skeletal fragments) shields organic pores during mechanical compaction, whereas authigenic quartz precipitation (e.g., cavity-filling quartz, grain-replacive quartz) reduces porosity by filling voids. A moderate abundance of authigenic quartz (Sixs = ∼20%) is most favorable for development and preservation of pores (especially organic pores) in deep mudstone. Organic pores, widely developed in the studied DL deep mudstones, seem to be largely preserved in the samples with TOC values as much as 18.46 wt%. In summary, the DL mudstone deposits enriched in OM and contained moderate contents of authigenic quartz are especially favorable targets of deep shale gas exploration.

A Reevaluation of the Timing and Temperature of Copper and Molybdenum Precipitation in Porphyry Deposits

Abstract The timing and temperature at which copper-iron and molybdenum sulfide deposition occurs in porphyry deposits remain controversial. Petrologic estimates indicate that veins and wall-rock alteration zones containing copper-iron sulfides form in a wide temperature range from ~350° to 650°C. Most sulfides are hosted in potassium(K)-silicate–altered rock and quartz A veins or in early-halo alteration selvages formed above ~450°C. In contrast, cathodoluminescence (CL) imaging of A veins indicates that copper-iron sulfides are contained within a primary lucent (bright and gray)-CL quartz and are crosscut by microfractures filled with younger dull (dark and medium-gray)-CL quartz in direct contact with copper-iron sulfides. These observations have been interpreted as supporting late copper-iron sulfide introduction together with dull-CL quartz at moderate temperatures of ~300° to 450°C, based on fluid inclusion estimates. We provide new CL, QEMSCAN, and petrographic data and images of vein quartz as well as petrologic data of altered wall rock from Haquira East (Peru), Encuentro (Chile), and Batu Hijau (Indonesia) porphyry deposits, which were formed at conditions ranging from deep to shallow (~2–10 km). At all three deposits, dull-CL quartz in microfractures is ubiquitously observed crosscutting all generations of high-temperature lucent-CL quartz veins. Each lucent-CL vein type hosts distinct sulfide populations, crosscuts the others, and coexists in space within the copper and molybdenum ore zones. Within this ore zone, the dull-CL quartz only contains copper-iron sulfides where it transects old A veins and early halos, molybdenite where it transects young molybdenite-bearing quartz veins, and both copper-iron sulfides and molybdenite in younger B veins. Furthermore, where the dull-CL quartz crosscuts igneous or barren (deep) quartz veins, it typically lacks copper and molybdenum. Therefore, dull-CL quartz has no particular spatial or genetic affinity with copper-iron sulfides or molybdenite. We propose that copper was introduced and precipitated at high temperatures in stability with K-silicate alteration. In shallow porphyry deposits, most copper was introduced with lucent-CL quartz in A veins, likely formed via adiabatic decompression from magmatic lithostatic to hydrostatic conditions at ~450° to 600°C. In deep deposits, most copper is introduced with quartz-poor early halos, likely formed at a temperature range similar to that of A veins but during an early stage of retrograde silica solubility. The inferred timing and temperature of copper precipitation are consistent with available solubility experiments for copper-bearing solutions that suggest copper precipitation may start at a high temperature of ~600°C, and ~90% precipitates before it cools down to ~400°C. Much of the molybdenum is introduced and precipitated with discrete pulses of molybdenite-bearing quartz veins that crosscut and postdate copper-bearing A veins and early halos and, to a lesser degree, with B veins that may carry both copper and molybdenum. Whereas molybdenite-bearing and barren (deep) quartz veins form at relatively high temperatures of ~550° to 650°C, copper-molybdenum–bearing B veins likely form at lower temperatures near ~500°C. Copper precipitation and local copper remobilization from older veins and halos continued during the formation of copper-iron sulfide veinlets, named C veins, and during the precipitation of dull-CL quartz following K-silicate alteration. C veins and even younger pyrite-rich D veins may have chlorite or sericite selvages and are composed of dull-CL quartz that formed at ~450° and 300° to 450°C, respectively. Microfractures form through all lucent-CL quartz veins because of the thermal contraction of high-temperature quartz at the onset of sustained cooling after K-silicate alteration has ceased. The fluid that migrated through these microfractures was initially in retrograde silica solubility, which causes dissolution and corrosion of the older lucent-CL quartz. The formation of C veins may overlap in time with the initial stage. At a later stage and temperatures below <450°C, the fluid precipitates dull-CL quartz in microfractures and dissolution zones within older lucent-CL quartz. In copper-iron sulfide-bearing A and B veins and molybdenite-bearing quartz veins, corroded lucent-CL quartz and the younger dull-CL quartz infill can often be observed in contact with older sulfides because quartz sulfide grain boundaries are preexisting discontinuities, and they are preferentially opened during volume contraction. Collectively, these observations and estimates are consistent with silicate phase petrology and numerous observations that most copper-iron sulfides precipitate in K-silicate alteration zones or in early halos with K-feldspar-muscovite-biotite assemblages.

Cathodoluminescence as a tracing technique for quartz precipitation in low velocity shear experiments

Two simulated gouges (a pure quartz and a quartz-muscovite mixture) were experimentally deformed in a ring shear apparatus at a constant low velocity under hydrothermal conditions favourable for dissolution–precipitation processes. Microstructural analysis using scanning electron microscope cathodoluminescence imaging and cathodoluminescence spectroscopy combined with chemical analysis showed that quartz dissolution and precipitation occurred in both experiments. The starting materials and deformation conditions were chosen so that dissolution–precipitation microstructures could be unambiguously identified from their cathodoluminescence signal. Precipitated quartz was observed as blue luminescent fracture fills and overgrowths with increased Al content relative to the original quartz. In the pure quartz gouge, most of the shear deformation was localized on a boundary-parallel slip surface. Sealing of fractures in a pulverized zone directly adjacent to the slip surface may have helped keeping the deformation localized. In the quartz-muscovite mixture, some evidence was observed of shear-accommodating precipitation of quartz in strain shadows, but predominantly in fractures, elongating the original grains. Precipitation of quartz in fractures implies that the length scale of diffusive mass transfer in frictional-viscous flow is shorter than the length of the quartz domains. Additionally, fracturing might play a more important role than generally assumed. Our results show that cathodoluminescence, especially combined with chemical analysis, is a powerful tool in microstructural analyses of experimentally deformed quartz-bearing material and visualizing quartz precipitation.

Effects of Quartz Precipitation on the Abundance and Preservation of Organic Matter Pores in Cambrian Marine Shale in South China

To evaluate the effects of quartz precipitation on the abundance and preservation of organic matter pores in marine shale reservoirs, the type of authigenic quartz and the source of silica, as well as the corresponding relation of the Lower Cambrian Shuijingtuo Formation shale in South China were investigated. Quartz in the Shuijingtuo shale occurs as four different types: detrital quartz, replacement of biosiliceous debris, euhedral quartz filled in interparticle pores, and microquartz dispersed in a clay matrix. Euhedral quartz (1–5 μm) and matrix-dispersed microquartz (100–400 nm) are found to be the dominant forms of authigenic quartz. The euhedral quartz accumulates along the interparticle pores, and the porous organic matter fills the interior of the space. Microquartz is mainly wrapped in porous organic matter. Two silica sources were revealed: biogenic silica and clay-derived silica. Biogenic Si is most likely the major source for authigenic quartz in the organic-rich (total organic carbon (TOC) > 2.55 wt.%) samples, which accounts for 23–57 wt.% (average 35 wt.%) of the total Si. Based on petrographic observations, we posit that the precipitation of large-sized euhedral quartz in the interparticle pores most likely originated from biogenic silica in the early stage of diagenesis and that the silica for the clay matrix-dispersed microquartz is provided by biogenic silica and clay-derived silica. The observation of SEM images indicates that the precipitation of early diagenetic euhedral quartz in the interparticle pores enhances rock stiffness, and the buttressing effect can protect the organic matter pores from compaction during the late-stage burial diagenesis. In contrast, the precipitation of late diagenetic microquartz in the clay matrix can lead to a reduction in the capacity of the accommodation space to host retained petroleum, consequently leading to a reduction in the development of organic matter pores and the generation of shale gas.

Diagenesis and reservoir quality of Neoproterozoic dolomitized microbialites following multi-stage diagenetic fluid activity: a case study of the Sinian Dengying Formation, China

Neoproterozoic marine microbialites have been targets for exploration and hydrocarbon reservoir development. The original depositional fabric and diagenesis control the pore systems of microbialites, leading to the complicated origin of microbialite reservoirs. This study aimed to reveal the origin of microbialite reservoirs following multi-stage diagenetic fluid activity in the fourth Member of the Dengying Formation in the central Sichuan Basin in southwestern China. The fourth Member of the Sinian Dengying Formation developed dolomitized microbialites, mainly including stromatolites, laminates, and thrombolites. Based on the background of tectonic movement, petrology and geochemistry examinations were executed to analyze the origin of the microbialite reservoir. Based on the cathodoluminescence and the homogenization temperature of the brine inclusions, it is credible that there were four stages of diagenetic fluid activities in the burial diagenesis. In the first stage, the microbialite reservoir was charged by oil in the Silurian period, with evidence from residual asphalt around the pores. In the second stage, dolomite precipitated to incompletely fill the pore spaces. In the third stage, the silica-rich diagenetic fluid with high temperature resulted in the precipitation of authigenic quartz. In the last stage, the oil charged again during the Triassic period, followed by siliceous filling, with residual asphalt filling the pore spaces. There were two stages of subaerial emergence, which occurred in two episodes of the Sinian-Early Cambrian Tongwan movement. The evidence for the two tectonic events includes two phases of dolomites with meteoric water origin, two cycles of V, Sr, and Na element profiles, two instances of negative excursion δ18O isotope, and two cavity layers. By comparison, the karstification of reservoirs in the Tongwan III episode could generate a higher quality of reservoir than that in the Tongwan II episode. As a result, the quality of the microbialite reservoir from the fourth Member of the Dengying Formation was mainly improved by the subaerial exposure in the Tongwan III episode and then was partly destroyed by the siliceous filling. The identification of multi-staged diagenetic fluid charging can illustrate the evolution of the reservoir quality of Neoproterozoic microbialites.

Hydrothermal vent fluid-seawater mixing and the origins of Archean iron formation

Precambrian iron formation provides valuable windows onto ancient marine environments, but exactly how these Fe- and Si-rich chemical sedimentary rocks formed have remained a matter of debate. Traditional models envisage Fe(III)-oxide formation through chemical and/or biological oxidation of soluble Fe2+, but sedimentological and textural data show that, throughout much of Archean stratigraphy, the finest-grained Fe(III)-oxides, previously interpreted to reflect primary components, were largely derived through the oxidation of the Fe(II)-silicate mineral greenalite. These observations have formed the basis for an alternative model where Fe2+ and SiO2(aq) combined to precipitate greenalite upon the mixing of hydrothermal fluids with ambient seawater. All models for iron formation genesis invoke hydrothermal alteration of seafloor basalt as the principal source of soluble Fe2+, and its subsequent transport in an anoxic deep ocean. However, the processes and products associated with the venting of near-axis hydrothermal fluids into Precambrian seawater, and implications for Archean iron formation, have not been investigated.In order to test models for Archean iron formation genesis, we used reaction path models to investigate the interactions between ancient hydrothermal vent fluids and anoxic seawater. We assembled available thermodynamic data and executed reaction path models to examine: (1) the equilibration between anoxic SO4-free seawater and basalt/gabbro at subseafloor hydrothermal conditions (400oC and 400-500 bar), (2) the cooling and decompression of these fluids during their ascent through the oceanic crust, and (3) their subsequent mixing with anoxic SO4-free seawater. Our results confirm previous suggestions that the effective lack of SO4 in Archean seawater would have allowed fayalite-magnetite-pyrrhotite-quartz equilibria to buffer fluid chemistry, in turn leading to reaction zone fluids characterised by high Fe/H2S ratios. Cooling and decompression of these reducing fluids upon ascent, and further reaction with mafic wall rock, leads to significant Fe-chlorite and quartz precipitation with little to no sulfide precipitation. As these vent fluids mix with cold seawater directly, or with conductively-heated seawater, mineral assemblages are dominated by pyrite, greenalite, and/or siderite. These results were obtained with no constraints imposed by Archean iron formation, aside from the exclusion of minnesotaite, a demonstrably secondary mineral.The quantity of hydrothermally-derived Fe2+ partitioned into Fe(II)-bearing minerals upon mixing (96-99% of total aqueous Fe), the relative proportion of greenalite precipitated, and its further concentration via plume-driven transport (by virtue of its low density), together imply that the mixing between hydrothermal vent fluids and anoxic seawater may have served as a principal mechanism for generating a large proportion of the mineral mass now preserved as Archean iron formation. These results reconcile long-standing sedimentological and geochemical observations indicating that Archean banded iron formations record a strong hydrothermal influence, and suggest that these unique deposits have the potential to constrain the nature of seafloor-hosted hydrothermal systems on the ancient Earth, and their chemical interactions with seawater.

The genesis of hydrothermal veins in the Aukam valley SW Namibia– A far field consequence of Pangean rifting?

High purity fluorite veins (acid grade > 97 % CaF2) are generally rare in a global context. The fluorite-(±quartz-calcite) veins in the Aukam Valley mining district in SW Namibia have not previously been studied but due to their excellent exposure they are an ideal natural laboratory to study such mineralization. These veins cross-cut Mesoproterozoic high-grade gneisses and granites (Namaqua-Natal Metamorphic Province) close to the unconformity with the overlying late-Neoproterozoic Nama Group sedimentary rock cover. Based on the regional context, their genesis has been assumed to be related to nearby fluorite-bearing pegmatites. However, the present contribution provides new microthermometry data from vein fluorite (with 25.0–25.6 wt% NaCl and Th of 270–300 °C) that indicate precipitation from a mixed fluid with two chemically contrasting end-members for the early paragenetic fluorite stage. However, it was not possible to identify the chemical composition of the endmembers. Based on the chemical composition of the fluid mixture and the regional geological context, we propose that these end-members are F-rich brines sourced from the Namaqua basement and Ca-rich limestone-derived formation fluids of the Nama Group. A fluorite-overgrowing quartz precipitation is likely the effect of post-mixing fluid cooling as the fluid inclusions hosted in quartz show lower homogenization temperatures (Th 230–260 °C) with similar salinity. Locally, late-stage calcite is recognized with fluid inclusion compositions (0.2–2.7 wt% NaCl and Th of 60–92 °C) different from those observed in the fluorite and quartz. With significantly lower homogenization temperatures, they likely represent precipitates formed during the shutdown and collapse of the hydrothermal system. The fluorite veins are hosted in post-Cambrian N-trending brittle structures that probably formed during the opening of the South Atlantic in late Mesozoic times. Interestingly, similar massive fluorite mineralization on both sides of the Atlantic Ocean is also likely associated with Pangea rifting and known from numerous mining districts operating on unconformity-related hydrothermal veins in Central and North America, northern Africa and Europe.

A fluid inclusion and stable-isotope study of hydrothermal vein mineralization, Schwarzwald district, Germany

A combined fluid inclusion and stable isotope study has been carried out on over 180 individual samples from 89 post-Variscan hydrothermal veins (Pb-Zn-Cu-bearing fluorite-barite-quartz veins, Co-Ni-Ag-Bi-U-bearing barite-fluorite-quartz veins and barren barite-fluorite-quartz veins) from the Schwarzwald district, Germany. The salinities of fluid inclusions in post-Variscan primary fluorite, calcite, barite and quartz are in the range of 22–25 wt.% equivalent (eqv.) NaCl, and the eutectic temperatures range between –57 and –45°C, indicating the presence of H2O-NaCl-CaCl2 fluids. Homogenization temperatures vary from 130 to 180°C. A low-salinity fluid (0 to 15 wt.% eqv. NaCl) was observed in some late stage fluorite, calcite and quartz samples, which were trapped similar temperature, range of high salinity fluids.
 Raman microprobe analyses show that the only detectable volatile in the vapour is CO2. Almost all δ18O (n=86) measurements of quartz from the fluorite-bearing post-Variscan veins range between +11.1 and +20.9 ‰. The calculated δ18OH2O values are between –11.0 and +4.4 ‰, using known quartz-water fractionation and fluid inclusion homogenization temperatures. The δ18OH2O values of directly extracted fluid inclusion water of fluorites range from –11.6 to +1.1 ‰, very consistent with the calculated values. The δD values of fluid inclusion water in calcites (extracted from primary and late calcite samples) lie in a narrower range between –26 and –15 ‰. The extracted fluid inclusion water from quartz samples has significantly more variable δD values between –63 and +9 ‰. The δ13C and δ18O values of fluid inclusion gas (CO2) range between –21.4 and –6.7 ‰ and between –16.3 to –7.1 ‰, respectively.
 Calculations for fluorite-barite-quartz veins combining oxygen isotope equilibria with microthermometric data result in quartz precipitation temperatures of 120–170°C at pressures between 0.3 to 0.5 kbar. The δ18OH2O and δD data, particularly the observed wide range in hydrogen isotopic compositions, indicate that the hydrothermal mineralization formed through large-scale mixing of a basement-derived saline NaCl-CaCl2 brine with meteoric water.

Low volumes of quartz cement in deeply buried Fulmar Formation sandstones explained by a low effective stress burial history

Upper Jurassic Fulmar Formation sandstones from the Fulmar Field in the Central North Sea are buried to 3.2 km and 128 °C but contain only 3.7 ± 1.7% (1σ) quartz cement, substantially less than volumes predicted by models based on temperature-related quartz precipitation kinetics. Oxygen isotope microanalysis of quartz overgrowths suggests that only limited cementation occurred at temperatures above 110 °C. We suggest that the anomalously low volumes of quartz cement are most readily explained by the effective stress history of the Fulmar Formation. Regional pore pressure analysis strongly suggests that pore fluid pressures in the Fulmar Formation decreased substantially in the last <0.5 Ma as a result of lateral seal failure, increasing effective stress from ca. 10 MPa to the current 31 MPa. A recent increase in effective stress is supported by the common occurrence of grains that are both fractured and unhealed by quartz cement. Intergranular pressure dissolution can account for around one third of the observed quartz cement, with the remainder from deep burial feldspar dissolution. We argue that the continuous history of low effective stress, until the very recent geological past, limited the rate of silica supply by intergranular pressure dissolution, and thus the rate of quartz cementation. Effective stress histories should be incorporated into predictive models of quartz cementation of sandstones.

Chert oxygen isotope ratios are driven by Earth's thermal evolution

The 18O/16O ratio of cherts (δ18Ochert) increases nearly monotonically by ~15‰ from the Archean to present. Two end-member explanations have emerged: cooling seawater temperature (TSW) and increasing seawater δ18O (δ18Osw). Yet despite decades of work, there is no consensus, leading some to view the δ18Ochert record as pervasively altered. Here, we demonstrate that cherts are a robust archive of diagenetic temperatures, despite metamorphism and exposure to meteoric fluids, and show that the timing and temperature of quartz precipitation and thus δ18Ochert are determined by the kinetics of silica diagenesis. A diagenetic model shows that δ18Ochert is influenced by heat flow through the sediment column. Heat flow has decreased over time as planetary heat is dissipated, and reasonable Archean-modern heat flow changes account for ~5‰ of the increase in δ18Ochert, obviating the need for extreme TSW or δ18Osw reconstructions. The seawater oxygen isotope budget is also influenced by solid Earth cooling, with a recent reconstruction placing Archean δ18OSW 5 to 10‰ lower than today. Together, this provides an internally consistent view of the δ18Ochert record as driven by solid Earth cooling over billion-year timescales that is compatible with Precambrian glaciations and biological constraints and satisfyingly accounts for the monotonic nature of the δ18Ochert trend.