Formation Of Chlorite Research Articles

Insights into the formation and growth of authigenic chlorite in sandstone: Analysis of mineralogical and geochemical characteristics from Shaximiao Formation, Sichuan Basin, SW China

Chlorite is a widely distributed clay mineral in sandstone reservoirs, attracting significant attention due to its complex physicochemical properties and unique reservoir significance. The Shaximiao Formation in the Sichuan Basin, SW China, features abundant diagenetic chlorite, offering valuable insights into chlorite growth theories. Petrographic observations and electron probe analyses reveal that the formation of authigenic chlorite resembles a continuous, staged growth process, akin to tree growth. This process encompasses stages from depositional smectite clay (seeding) to inner-layer chlorite formation (germination), outer-layer chlorite development (branching), and pore-filling chlorite precipitation (blooming). During the initial burial, depositional smectite (seeds) transforms into low-Fe, low-Mg inner-layer chlorite (germination) under the influence of Fe and Mg ions in the original formation water. In the early diagenetic stage, volcanic detritus and biotite alteration release substantial Fe2+ and Mg2+, fostering the growth of outer-layer chlorite (branching) on the inner-layer chlorite. In the middle diagenetic stage, volcanic detritus releases Ca2+, Fe2+, and Mg2+ under the influence of organic acids, leading to supersaturation of Si4+, Al3+, Fe2+, and Mg2+ in pore water, which directly crystallizes into highly euhedral pore-filling chlorite (blooming). The presence of precursor smectite is fundamental to this process, while sufficient Fe and Mg sources are crucial for chlorite formation.

Diagenesis and reservoir quality evolution of estuarine sandstones: Insights from the Cenomanian-Turonian Yolde Formation, northern Benue Trough, NE Nigeria

Estuarine sandstones often exhibit complex diagenetic pathways due to the interaction of fluvial and shallow marine processes, resulting in significant reservoir heterogeneities. The Yolde Formation is an important petroleum reservoir in the Northern Benue Trough, NE Nigeria. However, diagenetic and reservoir quality evolution of the formation are still poorly understood. This study utilizes thin-section petrography, XRD, SEM, and fluid inclusion microthermometry to analyse the composition, diagenesis, and reservoir quality of the sandstones. Results show that the sandstones are mainly arkose and subarkose in composition; they are generally well-sorted and vary in grain size from very fine-to coarse-grained. Three diagenetic stages are identified: early, middle, and late. The early stage includes feldspar dissolution, formation of kaolinite, development of clay coating, and mechanical compaction. The middle stage comprises the formation of authigenic chlorite and Fe-oxide cements. The late-stage diagenesis involves illitization of kaolinite, formation of dickite, albitization of K-feldspar, and precipitation of quartz overgrowths. The diagenetic evolution of the sandstones was strongly controlled by their compositional makeup. The feldspathic nature of the sandstones resulted in the formation of kaolinite, illite, and quartz overgrowths, through feldspar dissolution and silica supply. The inner and middle estuarine facies have inhibited the development of quartz overgrowths due to well-developed clay coatings, whereas the outer estuarine facies were well-cemented by quartz overgrowths due to lack of clay coatings. Illitic clay coatings were found to be effective in preventing quartz cementation. Fluid inclusion analysis reveals that the formation temperatures of the quartz overgrowths range from 98 °C to 135.5 °C, corresponding to burial depths ranging between 2.3 and 3.5 km. These findings would provide useful insights that would reduce the risks of exploration of the sandstones and also supplies potential input data for forward diagenetic modelling of their subsurface equivalents in similar depositional settings elsewhere.

Mineral chemistry of the Geyer SW tin skarn deposit: understanding variable fluid/rock ratios and metal fluxes

AbstractThe Geyer tin skarn in the Erzgebirge, Germany, comprises an early skarnoid stage (stage I, ~ 320 Ma) and a younger metasomatic stage (stage II, ~ 305 Ma), but yet, the source and distribution of Sn and the physicochemical conditions of skarn alteration were not constrained. Our results illustrate that contact metamorphic skarnoids of stage I contain only little Sn. REE patterns and elevated concentrations of HFSE indicate that garnet, titanite and vesuvianite of stage I formed under rock-buffered conditions (low fluid/rock ratios). Prograde assemblages of stage II, in contrast, contain two generations of stanniferous garnet, titanite-malayaite and vesuvianite. Oscillation between rock-buffered and fluid-buffered conditions are marked by variable concentrations of HFSE, W, In, and Sn in metasomatic garnet. Trace and REE element signatures of minerals formed under high fluid/rock ratios appear to mimic the signature of the magmatic-hydrothermal fluid which gave rise to metasomatic skarn alteration. Concomitantly with lower fluid-rock ratio, tin was remobilized from Sn-rich silicates and re-precipitated as malayaite. Ingress of meteoric water and decreasing temperatures towards the end of stage II led to the formation of cassiterite, low-Sn amphibole, chlorite, and sulfide minerals. Minor and trace element compositions of cassiterite do not show much variation, even if host rock and gangue minerals vary significantly, suggesting a predominance of a magmatic-hydrothermal fluid and high fluid/rock ratios. The mineral chemistry of major skarn-forming minerals, hence, records the change in the fluid/rock ratio, and the arrival, distribution, and remobilization of tin by magmatic fluids in polyphase tin skarn systems.

Genesis of high-Al chromitites from Xiaosuihe peridotite (Central Jilin Province, NE China): Implication for initial subduction of the Paleo-Asian ocean

This study presents whole-rock major- and trace-element data of serpentinites and mineral geochemistry of chromite/spinel from both serpentinites and associated podiform chromitites from the Xiaosuihe region in central Jilin Province, NE China, aimed to elucidate the genesis of serpentinites and podiform chromitites. The serpentinites exhibit low Al2O3/SiO2 ratios (0.01–0.02) and high Mg# (0.90–0.91), indicating their derivation from the fore-arc mantle wedge and protolith as harzburgite. Chromitite ores with semi-massive to disseminated textures occur as small pods. The chromite/spinel (Chr) present in both the podiform chromitite and serpentinite can be categorized into four distinct microstructural groups: (1) partially altered chromite, characterized by high-Al primary cores (Cr# = 0.44–0.49), surrounded by high-Cr porous rims; (2) porous chromite, featuring abundant pores enriched in Cr and Fe and depleted in Mg and Al, filled with chlorite; (3) zoned chromite consisting of high-Al cores surrounded by non-porous rims of Cr-magnetite (Cr-mag); and (4) homogeneous chromite, which is non-porous ferritchromite (Fe-Chr). The high-Al primary cores of the partly altered chromite are depleted in Cr but enriched in Mg, exhibiting MORB-like tholeiitic affinities. In contrast, the altered Chr displays low Mg# [Mg/(Mg + Fe2+)] along with elevated Cr# [Cr/(Cr + Al)] and Fe# [Fe3+/(Cr + Al + Fe3+)] values. Based on the above results, the high-Al cores of chromite within the chromitite originally formed through melt/fluid-rock interaction within the forearc mantle wedge. During the exhumation and post-magmatic processes, the reaction between high-Al Chr and olivine resulted in chlorite formation alongside secondary Chr enriched in Fe2+ and Cr content. Subsequently, the infiltration of hydrous fluid led to the development of Fe3+-rich Chr or Cr-mag along grain boundaries or fractures within the original chromite during the retrograde process. The Xiaosuihe serpentinized harzburgites, along with associated chromitites, represent the composition of peridotite in the forearc mantle wedge that could have formed during the initial subduction of an oceanic island arc abutting the northern North China Craton during the Cambrian. Subsequently, these rocks underwent retrograde metamorphism from amphibolite (eclogite) to greenschist facies during their exhumation.

Investigating the role of geochemistry and geotechnical properties in landslide characterization and triggering mechanisms: A case study from Dir Upper, Khyber Pakhtunkhwa Pakistan

The 83.5 km Chukyatan-Kumrat Upper Dir road plays a crucial role in transportation and tourism in North Pakistan. Despite its significance, the area faces frequent landslides due to hydrometeorological hazards, posing a threat to its stability. This study conducts the first extensive investigation of landslide susceptibility in the region, considering geological features, geotechnical properties, and rock weathering. The road traverses diverse rock formations, including meta-volcanics, andesites, meta-rhyolites, ignimbrites, volcanic ash, granodiorites, and spotted slates, overlain by residual soils. The presence of the Dir fault has led to significant accumulations of loose, weathered rock debris (>100 m deep). Exposed slopes exhibit polygonal stress fractures, joints, and fissures with steep inclinations (>40°), further enhancing instability. Geotechnical analysis reveals a low internal friction angle (28.5°–31.9°) and cohesion (4.1–5.9 kPa) of slope materials, indicating poor shear resistance compared to stable slopes. The unconfined compressive strength of bedrock (10.7–41.5 MPa) ranges from weak to moderate-strong, emphasizing the contribution of weaker rock formations to instability. Acidic soil pH (3.1–4.2) and clay minerals support the prevalence of weathering conditions promoting landslides. Thin section analysis and X-ray diffraction reveal hydrothermal alteration during low-grade metamorphism, leading to the formation of chlorite, smectite, montmorillonite, and zeolites. Additionally, physical weathering has increased quartz content, potentially impacting slope stability. The combined effect of factors such as steep slope geometry, low shear strength with strain-softening properties, rainfall, snowmelt, freeze-thaw activity, slope base cutting for road development, and massive loading from houses contributes to numerous landslides in the region. The study aids effective mitigation and preparedness in the Chukyatan-Kumrat area and offers insights for landslide susceptibility mapping in similar geological settings.

Al-Rich Titanites from Mont Blanc Alpine Fissures: Evidence of Ti-Nb-Y-REE Mobility during Water–Rock Interactions

Titanites can be excellent markers of element transfer in medium-temperature retrograde metamorphism. Euhedral titanites from several alpine fissures from Mont Blanc, particularly those of Périades and Courtes, crystallised at the end of the main quartz stage and are synchronous with the formation of green biotites and albite before chlorite formation. Micro-XRF, SEM, electron probe, and LA-ICP-MS analyses show that these titanites have a wide range of Al2O3 content from 1 to 8%, are dominated by -OH versus F, and have a wide range of Nb (up to 4500 ppm), Y (up to 3000 ppm), Zr (up to 1800 ppm), and Sn (up to 1400 ppm) concentrations. The allanite from the granite, partly destabilised into epidote, is the most likely source of Nb, Y, Zr, Sn, and REE. Titanites are enriched in HREE and show variations in LREE depending on the studied sites. Like quartz, they formed at around 400 ± 20 °C, which is compatible with the formation of green biotites after the destabilisation of granite Fe-Mg silicates. This early stage of fluid circulation, synchronous with the Mont Blanc massif uplift, is therefore marked by the titanite formation at the transition between the biotite and chlorite stability fields.

Origin of Grain-Coating Chlorite and Implications for Reservoir Quality in the Triassic Deep-Buried Volcaniclastic Sandstones, Central Junggar Basin, Northwestern China.

The occurrence and genesis of grain-coating chlorite were investigated in order to evaluate the impact of grain-coating chlorite on preserving porosity in the deep-buried Triassic Karamay volcaniclastic sandstones based on thin sections, scanning electron microscopy, and an electron probe. Grain-coating chlorite was formed during the eogenesis, originating from the precursor of smectite through the solid-state transformation (SST) mechanism. The hydration and dissolution of unstable, intermediately basic volcanic rock fragments provided essential Fe2+ and Mg2+ ions for the formation of grain-coating chlorite. Due to relatively high stability and low susceptibility to dissolution, acidic volcanic rock fragments could not promote chlorite formation but resulted in authigenic quartz and clays as pore-filling cements. This process would destroy reservoir properties. Under high hydraulic conditions, medium- to coarse-grained sandstone experienced saltation transport, creating significant velocity differentials and pressure differentials on grain surfaces. Subsequently, clay grains adhere to the surfaces, forming grain-coating chlorite during diagenesis with good continuity. In contrast, pebbly sandstone undergoes rolling transport, resulting in smaller velocity differentials on grain surfaces. This makes relatively ineffective clay adsorption and leads to discontinuous grain-coating chlorite in subsequent stages. Under weak hydraulic conditions, grains and clay particles in fine-grained sandstone undergo suspended transport, lacking mutual movement and velocity differentials. Clay particles cannot effectively cover particles but instead fill the pores between them. Therefore, continuous grain-coating chlorite is more commonly developed in the medium- to coarse-grained sandstones and is crucial for inhibiting quartz cementation with a coverage rate exceeding 80%. Inadequate coatings fail to inhibit quartz cementation effectively, while excessive coatings may block pore throats. Optimal protection of primary porosity could occur only when grain-coating chlorite is moderately developed.

Crystal chemistry and formation of authigenic chlorite: Influence on tight sandstone reservoir in the Yanchang formation, Ordos Basin, China

Authigenic chlorite is a crucial diagenetic cement that significant impacts tight sandstone reservoirs. The occurrence, crystal chemistry, formation and influences on reservoirs of different authigenic chlorite types were studied in the Yanchang Formation tight sandstones from the Ordos Basin. This study identified two primary types of chlorites: alteration chlorite and autochthonous authigenic chlorite. The alteration chlorite, characterizing by high Fe, Mg, Ti and AlIV contents and low Si and AlVI contents, originated from biotite during diagenesis. The autochthonous authigenic chlorite can be further classified into grain-coating, pore-lining, and pore-filling chlorite. The grain-coating chlorite features thin layers and limited crystal form. During the syndiagenetic stage, Fe2+ and Mg2+ carried by water adsorbed onto the particle surfaces. Additionally, the grain-coating chlorite contains relatively high K content due to the hydrolysis of biotite during the eodiagenetic A stage. The pore-lining chlorite formed during the prolonged eodiagenetic B stage. The biotite and abundant intermediate-basic magmatic fragments released Fe2+ and Mg2+, contributing to the widespread development of euhedral pore-lining chlorite. Notably, the pore-lining chlorite displayed elemental composition variations from the grain edge to the pore center, with increased Fe, Mg and AlIV, and decreased K and AlVI. The pore-filling chlorite formed locally resulted from Fe2+ and Mg2+ crystallization due to the hydrolysis of intermediate-basic magmatic rocks and the dissolution early formed chlorite. The pore-filling chlorite contains the most Fe, Mg and Mn contents and the least K content. Overall, authigenic chlorite acts as a "double-edged sword" in tight sandstone reservoir. The grain-coating and grain-lining chlorite enhance the mechanical strength, resist compaction, and inhibit quartz overgrowth, while pore-filling chlorite trends to obstruct pore throats and break reservoir quality. This study provides valuable insights into the detailed control factors influencing reservoir quality and can serve as a reference for further research.

Impact of sediment provenance and depositional setting on chlorite content in Cretaceous turbiditic sandstones, Norway

AbstractChlorite minerals, mainly in the form of clay coats, play a critical role in determining the reservoir quality of siliciclastic rocks. They can positively influence reservoir quality by preserving porosity during deep burial, but they can also play a negative role by reducing permeability through pore filling. The main aim of this research is to determine the optimal conditions for chlorite growth in sedimentary basins. This study investigates the Lower Cretaceous turbidite sandstone of the Agat Formation in the North Sea. We used a source‐to‐sink approach to investigate the impact of sediment source composition, chemical weathering and depositional environment on chlorite formation. Understanding the interplay between these processes can help refine exploration and exploitation strategies, optimise hydrocarbon recovery, and reduce exploration risks. Representative samples from two hydrocarbon fields (the Duva and Agat fields) were investigated using petrography, geochemistry, heavy mineral identification and quantification, and U–Pb geochronology of detrital zircons. Our results show a strong heterogeneity in the sediment provenance between the two turbidite systems. In the Duva field, the sandstone is derived from a mixture of mafic and felsic sources, producing Fe‐rich sediments. Intense chemical weathering generates fine fraction materials rich in kaolinite, vermiculite, and hydroxy‐interlayered clays, which are transported into shallow marine settings. Subsequent interaction with seawater results in the formation of glauconitic materials, Fe‐illite, and phosphatic concretions. These Fe‐rich materials are remobilised into deep marine settings, providing precursors for the development of authigenic Fe‐clays such as berthierine and chlorite. Conversely, in the Agat field, the sandstone is predominantly sourced from felsic rocks that underwent low chemical weathering, producing sediment rich in quartz and feldspar with a low amount of clays. With few Fe‐rich materials transported into the basin, the development of chlorite in the Agat field was less pervasive. Basin configuration and depositional environment exerted additional control on chlorite distribution. In the confined turbidite system (e.g. Duva field), chlorite is typically found as coating, whereas in less confined turbidite systems (e.g. Agat field) chlorite shows complex distribution related to depositional environment and dewatering processes. Our findings demonstrate the importance of considering the entire sediment routing system, from source to sink, when predicting chlorite occurrence and its impact on reservoir quality in deep marine settings. This integrated approach can guide exploration and development efforts in deepwater clastic reservoirs.

Sanidinite facies metamorphism at Nagarahal Village of Bilgi taluk, Bagalkot district, Karnataka, India


 
 
 Nagarahal village in the Bilgi taluk of Bagalkot district in Karnataka state shows the contact between the younger Bilgi granites and the Deccan basalts. The thermal impact that has happened on the pre-existing granites by the basalts has been studied by identifying the field occurrence of the contact zone of granites and basalts. The unaffected portion of the granites and the basalts that are far away from the contact are studied as well. The petrographic studies of the contact rocks between the granites and basalts show the polygonal recrystallized quartz with the triple point contact with other grains indicating the decussate texture indicating the high-temperature conditions, crushed quartz grains having contact with each grain appear as sugary crystals from the granoblastic texture, the irregular oriented mafic and felsic crystals show the hornfelsic texture and micrographic, and intergrowth textures showing the effect of thermal metamorphism near to the contact between the granite and basalt. The post-hydrothermal solution activity is at the peripheral region of the contact between granite and basalt which is seen by the formation of tourmaline. The mineral assemblages that are identified by the petrographic studies are muscovite, quartz, orthoclase, sanidine, sillimanite, chlorite, and Fe-Ti oxide minerals. The mineral chemistry data shows the high potash K-feldspar that consists of Or from 84% to 97.97%, Ab2%- 4.26%, and An0.09%-1.34% was identified as sanidine variety of K-feldspar, the plagioclase feldspar shows the dominant composition of Ab ranging from 84.92% to 97.10%, An content in plagioclase was found to be ranging from 0.87% to 14.02%, and the Or content is ranging from 1.06%-7.41%. indicating the presence of the albite variety of plagioclase, the Fe2+ dominating chlorite, and the presence of tourmaline indicates the hydrothermal effects at the periphery of the contact. The two feldspar thermometry indicates the formation temperature was 750°C at the contact and the chlorite formation temperature calculated is found to be 313°C which shows a decrease in the temperature away from the contact of the basalt and the granitic rocks. Whereas the granite and the basalts that are far away from the contact do not show any changes. The mineral assemblages, mineral chemistry data, and thermometric results indicate the high temperature and low-pressure sanidine facies of contact metamorphism in the studied area.
 
 

CHLORITE AUTHIGENESIS AND ITS EFFECTS ON RESERVOIR POROSITY IN THE EARLY CRETACEOUS BIMA SANDSTONE, YOLA SUB-BASIN, NORTHERN BENUE TROUGH, NIGERIA

The effects of chlorite on sandstone reservoirs have received more attention recently. Deeply buried sandstone reservoirs are prone to diagenetic alterations due to the presence of clays thereby affecting their reservoir quality (porosity). The effects of chlorite authigenesis on reservoir porosity are yet to be fully understood, and these create uncertainties in reservoir exploration of the fluvial reservoir in the basin. The Early Cretaceous Bima Sandstone which is divided into the Lower and Upper Members was deposited in a braided river to alluvial fan settings. An integrated approach, including thin-section petrography, Scanning Electron Microscopy (SEM) and X-ray diffraction (XRD) analyses was employed in the study with the aim of determining the effects of different chlorite occurrences on reservoir quality (porosity). Sandstone reservoir quality depends on both depositional parameters like grain size, sorting and matrix content as well as diagenetic alterations. Chlorite formation involves the availability of precursor clays like smectite, kaolinite and berthierine as the material base and dissolution of detrital grains to provide Fe and Mg ions. Two types of authigenic chlorite occurrences were observed in this research; the grain-coating chlorite and the pore-filling chlorite. The study shows that chlorite sourced from smectite-dominant clays occurs as grain-coating thereby inhibiting quartz overgrowth, whereas chlorite formed from kaolinite are found as pore-fillings which leads to deterioration of reservoir porosity.

Evolution of Upper Carboniferous tight sandstone reservoirs in the Ruhr and Lower Saxony basins (NW Germany) of the Central European Variscan foreland

Foreland basins have been extensively explored for hydrocarbon resources, geothermal, and gas storage applications, and multidisciplinarily studied to reconstruct orogenic processes. In fact, in the case of the Late Carboniferous Central European Variscan foreland basin, numerous drill cores have been recovered by the hard coal industry and comprehensive geological data sets have been made available by research. These cores and data sets provide a continuous record of the tectono-sedimentary and reservoir evolution over time. For this purpose, we have compiled petrophysical and petrographic literature data of >450 mostly tight (porosity <10%, permeability <1 mD) siliciclastic rock samples from Variscan foreland (Ruhr and Lower Saxony basin, NW Germany) and intramontane basins (Saar-Nahe basin, SW Germany) covering the complete Late Carboniferous stratigraphy. As a result, increases in mean grain size, sorting, detrital quartz, and proportion of metamorphic to sedimentary rock fragment contents, and decreases in detrital feldspar contents along the Westphalian B–C boundary are interpreted as a response to sedimentary recycling and unroofing of the Variscan hinterland due to tectonic uplift in the course of the northwestward propagating Variscan front. Thus, tectonics have a greater influence on sandstone petrography and porosity than the depositional environment. Porosity is mainly controlled by grain size and dissolution porosity. Basin-specific paleogeothermal gradients affect authigenic quartz (up to 25.0%) and chlorite (up to 7.7%) formation. Moreover, quartz cement contents <5% may stabilize the granular framework against mechanical compaction preserving porosity. With increasing quartz cement contents >5%, however, pore space is progressively clogged and the porosity preserving effect diminishes.

Redistribution of incompatible elements during hydrothermal alteration of pegmatite from the Djurkovo Pb-Zn deposit, Central Rhodopes

Mineralogical and geochemical study was done on weakly deformed, relatively thin pegmatites that intruded the marbles of the Rhodope metamorphic complex in the Djurkovo Pb-Zn deposit, Central Rhodopes. The pegmatites consist mainly of K-feldspar and quartz and contain minor garnet; the pegmatites lack clear zonation except for the preferable crystallization of the garnet in the central parts. The main accessory minerals are ishikawaite, zircon, monazite-(Ce), apatite, and titanite. The textural relationships indicate later hydrothermal alteration of pegmatites which led to the formation of albite, epidote, sericite, chlorite, carbonate, quartz and leucoxene. The (REE+Y, ACT, Nb, Ta, Ti)-bearing pegmatite minerals (oxides, silicates and phosphates) are partly leached and/or replaced by secondary ones. The newly-formed phases precipitated as anhedral grains along fractures and dissolved zones onto/or close to the primary minerals due to the limited mobility of the incompatible elements in fluids conditioned by pH, ligand activity and temperature.

Analysis and mathematical modeling of chlorite formation and content in water treated with chlorine dioxide in the drinking water supply system

Today, at the present time, a study of methods of introduction of uncontaminated drinking water, which are characterized by high bactericidal ability and do not lead to the detection of toxic substances in drinking water in unsafe quantities, has been carried out. With the help of such methods, it is necessary to treat drinking water with chlorine dioxide. Through the use of this reagent in water treatment, toxic chlorites become the priority raw materials for drinking water. I have to conduct an analysis and apply mathematical modeling of the solution and amount of chlorites in water, which are developed from the water environment of the Dnieper at water supply stations with traditional technology of water purification by treatment with chlorine dioxide, to determine the optimal technological parameters for carrying out the technological process with the advantages of Ukrainian and European legislation. The developed mathematical models show the possibility of transferring the process of treatment of Dnieper water with chlorine dioxide and deeper purification at water supply stations, performing processes using the method of determining the characteristics of drinking water, as well as conveniently optimizing the process of preparing drinking water.

Accelerated degradation of micro-pollutant by combined UV and chlorine dioxide: Unexpected inhibition of chlorite formation

UV/chlorine dioxide (ClO2) process can be intentionally or accidently conducted and is potentially effective in micro-pollutants degradation. UV irradiation can promote ClO2 decay and subsequently result in the formation of reactive radicals. Hence, the co-exposure of ClO2 and UV exhibited a synergetic effect on metribuzin (MET) degradation. The MET degradation was promoted by UV/ClO2 with a rate of 0.089 min−1 at pH 7.5, which was around 2.4 folds the total of rates caused by single ClO2 (0.004 min−1) and single UV (0.033 min−1). Reactive radicals mainly HO• and reactive chlorine species were involved in the acceleration effect, and contributed to 59%–67% of the total degradation rate of MET during UV/ClO2 under pHs 5.5–7.5. Among them, HO• was the predominant contributor and the contribution rate gradually rose under higher pH. Chlorite (ClO2−) and chlorate (ClO3−) formation has been the major concern of ClO2 oxidation. However, a comparison of their formation during UV/ClO2 and ClO2 oxidation is rarely reported. Herein, during MET degradation by ClO2, only ClO2− was identified with the highest amount of 1.17 mg L−1. Conversely, during MET degradation by UV/ClO2, only ClO3− was identified with the highest amount of 0.68 mg L−1, showing an upward trend with prolonging treatment time. Furthermore, organic halogenated DBPs formation after 24 h post-chlorination with UV/ClO2 and ClO2 pre-treatments was comparatively evaluated. Organic DBPs formation after post-chlorination was higher with UV/ClO2 pre-treatment compared to ClO2 pre-treatment. The overall concentration of DBPs produced with 30 min UV/ClO2 pre-treatment was about 4.5 times that with 1min UV/ClO2 pre-treatment. This study provided useful reference for the application of UV/ClO2 in micro-pollutants degradation.

Did changes in terrigenous components of deep-sea cherts across the end-Triassic extinction relate to Central Atlantic magmatic province volcanism?

The end-Triassic mass extinction event (ETE) is considered to be linked with the emplacement of the Central Atlantic magmatic province (CAMP), yet their temporal relation and underlying nature of global environmental and biotic changes remain controversial. A drastic radiolarian faunal turnover was associated with deep-sea acidification and changes in the chemical composition of pelagic terrigenous components, which were interpreted as the results of increased CAMP-derived materials, such as Fe2O3/Al2O3, MgO/Al2O3, and SiO2/Al2O3, without statistical tests. Here, we re-examined these CAMP-like signatures in terms of changes in the chemical composition of the Triassic–Jurassic pelagic deep-sea chert succession in Japan. Our newly compiled dataset suggests that changes in Fe2O3/Al2O3 and MgO/Al2O3 across the ETE were not significant, and thus, they may not be appropriate proxies for CAMP-derived material, potentially due to the dissolution of iron by ocean acidification and the formation of chlorite during diagenesis, respectively. Decreased SiO2/Al2O3 was also considered to have been reflected in increased CAMP-related dust flux and/or decreased biosiliceous productivity, but a slight increase in the Al2O3/TiO2 ratio (a biosiliceous productivity proxy) and an increase in shale bed thickness (dust flux proxy) across the radiolarian ETE imply increased eolian dust flux rather than decreased productivity. Furthermore, statistically significant Na enrichment at the radiolarian ETE level might be related to CAMP volcanism and/or associated changes in the source areas of eolian dust.

Evolution of the Hydrothermal System Associated with the ABM Replacement-Style Volcanogenic Massive Sulfide Deposit, Finlayson Lake District, Yukon, Canada

Abstract The ABM deposit, Finlayson Lake district, Yukon, Canada, is a bimodal-felsic, replacement-style volcanogenic massive sulfide (VMS) deposit (19.1 Mt @ 6.6 wt % Zn, 0.9 wt % Cu, 2.0 wt % Pb, 1.4 g/t Au, and 148 g/t Ag) hosted by Late Devonian continental back-arc–related volcanosedimentary rocks of the Kudz Ze Kayah formation. The VMS-related hydrothermal alteration associated with the deposit extends &amp;gt;1 km beyond the mineralization. Zones of pervasive sericite and chlorite alteration occur proximal to the massive sulfide lenses (&amp;lt;50 m) both in the hanging wall and the footwall, and zones of pervasive sericite and moderate sericite ± chlorite alteration extend laterally from the mineralization and into the hanging wall and footwall for hundreds to thousands of meters. Geochemical data and petrographic observations indicate that feldspar destruction and formation of white mica and chlorite were the main alteration processes. In both the hanging wall and footwall to the mineralization, base (e.g., Zn, Cu, Pb) and trace metals (e.g., Sb, Tl, Mo) form halos with elevated values up to 100 and 200 m, respectively. The paragenesis and the formation conditions of the hydrothermal alteration were determined through petrography of hydrothermal alteration assemblages and their crosscutting relationships, electron microprobe analyses of the compositions of white mica, chlorite, and carbonate, and illite-chlorite geothermometry. These data suggest that the sericite ± chlorite assemblage was the earliest and most extensive phase of the hydrothermal alteration that formed at temperatures around 215° ± 30°C. Overprinting the sericite-chlorite assemblage is the pervasive sericite assemblage that formed at temperatures around 250° ± 15°C. The pervasive chlorite assemblage formed at temperatures around 320° ± 10°C and overprints the preceding sericite-rich assemblages. Microprobe analyses of white mica and chlorite generally show that Mg-rich varieties are more common proximal to mineralization and formed earlier in the deposit paragenesis than Fe-rich varieties. Mineralogy derived from short-wave infrared data for mica and chlorite, however, shows no clear spatial trends across the deposit due to complex overprinting relationships between alteration minerals.

Optimization of BiVO4 coatings for high yield photoelectrochemical production of reactive chlorine species

Photoelectrochemical (PEC) synthesis of valuable chemicals, such as hydrogen and oxidants, is widely studied as a potential alternative to replace conventional synthesis processes with high carbon footprint. In the present study two different approaches were used to improve photoelectrochemical activity of BiVO4 coatings, i.e. doping with molybdenum and heterostructuring with BiOCl. Crystalline structure, chemical composition and morphology of the coatings were characterized using X-ray diffraction, energy-dispersive spectroscopy and scanning electron microscopy techniques. Performance of the photoelectrodes was tested in the solutions of Na2SO4 and NaCl. PEC activity was found to increase in the sequence BiVO4 < Mo_BiVO4 < Mo_BiVO4/BiOCl and the enhancement was much more pronounced in chloride medium. Mo doping was found to double incident photon to current conversion efficiency (from 5% to 10%) as well as Faradaic efficiency of photoinduced generation of reactive chlorine species (RCS) (from an average of 36% to 78%). Formation of hypochlorite and chlorite (ClO− and ClO2−) was determined experimentally. Construction of heterojunction between Mo_BiVO4 and BiOCl promoted separation of photogenerated electrons and holes and led to significant enhancement of photocurrent. Moreover, presence of BiOCl layer was found to catalyze photooxidation of ClO− to ClO2−. Findings of the study demonstrate the potential of BiVO4-based coatings for photoelectrochemical production of RCS via saline water splitting.

Diagenetic signatures in the deltaic and fluvial-estuarine Messinian sandstone reservoirs in the Nile Delta as a tool for high-resolution stratigraphic correlations

The current study utilizes a range of diagenetic fingerprints to differentiate between sandstone facies deposited in the Nile Delta before and during the Messinian salinity crisis (MSC), which is normally a challenging task considering the complex bio- and lithostratigraphic subdivisions of Messinian rock units. Subaerial exposure of the pre-MSC (Qawasim deltaic sandstone), during drawdown of the Mediterranean Sea at the time of the MSC, triggered pervasive dissolution of unstable rock fragments, kaolinization of feldspar, and meteoric dolomitization of carbonate. This was followed by mesogenetic calcite cementation and kaolinite transformation into dickite in deeply buried Qawasim sandstone. Comparatively, the Abu Madi estuarine facies, deposited during transgression after drawdown related to the MSC, is characterized by eogenetic iron (Fe)-calcite, glauconite, and pyrite (averages of 14.5%, 6%, and 2%, respectively). This facies transition is marked by abundance of mature glauconite (with potassium oxide (K2O) at about 8%) whose content abates upward from the transgression surface. Moreover, the compositional variability of the Abu Madi sandstone gave rise to multiple diagenetic trajectories that resulted in chlorite formation presumably following smectite and kaolinite. Listed diagenetic variations in the studied Messinian sandstone resulted from a complex interplay between rocks’ compositional, depositional, and burial attributes, ultimately serving as a basis for high-resolution stratigraphic correlation in continental and marginal marine settings with poor biostratigraphic controls.

Simultaneous removal of chlorite and coexisting emerging organic contaminants by sulfite: Kinetics and mechanisms

The inevitable formation of chlorite (ClO2–) and the ineffective degradation of some emerging organic contaminants (EOCs) during chlorine dioxide disinfection have aroused increasing concern about their adverse effects on human health. In this study, the kinetics and mechanisms of simultaneous removal of ClO2– and coexisting EOCs by sulfite (S(IV)) were investigated. Under aerobic conditions, ClO2– and coexisting EOCs could be effectively removed by S(IV) at pH 6.5–7.5, and their removal rates decreased as pH increased. ClO3– was generated in this process but its amount decreased with increasing pH. Many lines of evidence verified that the reaction of ClO2– with HSO3– and H+ generated SO3•− and ClO•, and the generated ClO• was rapidly quenched by S(IV) to form OCl– and SO3•−. Subsequently, SO3•− quickly reacted with O2 to form SO5•−, which was further transformed into SO4•−. SO4•− was the dominant reactive oxidant contributing to the degradation of coexisting EOCs and the formation of ClO3–. Using S(IV) to simultaneously control ClO2– and coexisting EOCs in water treatment is a promising approach because its performance was slightly affected by the water matrix.