Showing papers on "Silicate minerals published in 2021"

Global silicate weathering flux overestimated because of sediment-water cation exchange.

Abstract: Rivers carry the dissolved and solid products of silicate mineral weathering, a process that removes [Formula: see text] from the atmosphere and provides a key negative climate feedback over geological timescales. Here we show that, in some river systems, a reactive exchange pool on river suspended particulate matter, bonded weakly to mineral surfaces, increases the mobile cation flux by 50%. The chemistry of both river waters and the exchange pool demonstrates exchange equilibrium, confirmed by Sr isotopes. Global silicate weathering fluxes are calculated based on riverine dissolved sodium (Na+) from silicate minerals. The large exchange pool supplies Na+ of nonsilicate origin to the dissolved load, especially in catchments with widespread marine sediments, or where rocks have equilibrated with saline basement fluids. We quantify this by comparing the riverine sediment exchange pool and river water chemistry. In some basins, cation exchange could account for the majority of sodium in the river water, significantly reducing estimates of silicate weathering. At a global scale, we demonstrate that silicate weathering fluxes are overestimated by 12 to 28%. This overestimation is greatest in regions of high erosion and high sediment loads where the negative climate feedback has a maximum sensitivity to chemical weathering reactions. In the context of other recent findings that reduce the net [Formula: see text] consumption through chemical weathering, the magnitude of the continental silicate weathering fluxes and its implications for solid Earth [Formula: see text] degassing fluxes need to be further investigated.

Contrasting water-rock interaction behaviors of antimony and arsenic in contaminated rivers around an antimony mine, Hunan Province, China

Abstract: Although antimony (Sb) and arsenic (As) exhibit similar geochemical behavior and toxicity in the environment, growing evidence suggests that their water–rock interaction behavior in contaminated rivers is quite different. Twenty-nine river water samples were collected between September and November 2018 from contaminated rivers around an antimony mine in Hunan Province, China. The concentrations of As and Sb were inversely proportional to the water flow distance. The rates and magnitudes of Sb decrease were more prominent than those of As. Silicate mineral dissolution from rocks such as silicified limestone increased the As and Sb concentration of in-mine-district (IMD) water. Dissolution of carbonate minerals, ion exchange, and competitive adsorption were the major water–rock interactions, resulting in rapidly decreasing As and Sb concentration in IMD direct impacted water and IMD indirect impacted water. The behaviors of As and Sb during water–rock interaction were dissimilar for areas dominated by carbonate and silicate minerals.

CO2 utilization in built environment via the PCO2 swing carbonation of alkaline solid wastes with different mineralogy

Abstract: Carbon mineralization to solid carbonates is one of the reaction pathways that can not only utilize captured CO2 but also potentially store it in the long term. In this study, the dissolution and carbonation behaviors of alkaline solid wastes (i.e., waste concrete) was investigated. Concrete is one of the main contributors to a large carbon emission in the built environment. Thus, the upcycling of waste concrete via CO2 utilization has multifaceted environmental benefits including CO2 emission reduction, waste management and reduced mining. Unlike natural silicate minerals such as olivine and serpentine, alkaline solid wastes including waste concrete are highly reactive, and thus, their dissolution and carbonation behaviors vary significantly. Here, both conventional acid (e.g., hydrochloric acid) and less studied carbonic acid (i.e., CO2 saturated water) solvent systems were explored to extract Ca from concrete. Non-stoichiometric dissolution behaviors between Ca and Si were confirmed under far-from-equilibrium conditions (0.1 wt% slurry density), and the re-precipitation of the extracted Si was observed at near-equilibrium conditions (5 wt% slurry density), when the Ca extraction was performed at a controlled pH of 3. These experiments, with a wide range of slurry densities, provided valuable insight into Si re-precipitation phenomena and its effect on the mass transfer limitation during concrete dissolution. Next, the use of the partial pressure of CO2 for the pH swing carbon mineralization process was investigated for concrete, and the results were compared to those of Mg-bearing silicate minerals. In the PCO2 swing process, the extraction of Ca was significantly limited by the precipitation of the carbonate phase (i.e., calcite), since CO2 bubbling could not provide a low enough pH condition for concrete–water–CO2 systems. Thus, this study showed that the two-step carbon mineralization via PCO2 swing, that has been developed for Mg-bearing silicate minerals, may not be viable for highly reactive Ca-bearing silicate materials (e.g., concrete). The precipitated calcium carbonate (PCC) derived from waste concrete via a pH swing process showed very promising results with a high CO2 utilization potential as an upcycled construction material.

Variations in mineralogy of dust in an ice core obtained from northwestern Greenland over the past 100 years

Abstract: . Our study is the first to demonstrate a high-temporal-resolution record of mineral composition in a Greenland ice core over the past 100 years. To reconstruct past variations in the sources and transportation processes of mineral dust in northwestern Greenland, we analysed the morphology and mineralogical composition of dust in the SIGMA-D ice core from 1915 to 2013 using scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The results revealed that the ice core dust consisted mainly of silicate minerals and that the composition varied substantially on multi-decadal and inter-decadal scales, suggesting that the ice core minerals originated from different geological sources in different periods during the past 100 years. The multi-decadal variation trend differed among mineral types. Kaolinite, which generally formed in warm and humid climatic zones, was abundant in colder periods (1950–2004), whereas mica, chlorite, feldspars, mafic minerals, and quartz, which formed in arid, high-latitude, and local areas, were abundant in warmer periods (1915–1949 and 2005–2013). Comparison to Greenland surface temperature records indicates that multi-decadal variation in the relative abundance of these minerals was likely affected by local temperature changes in Greenland. Trajectory analysis shows that the minerals were transported mainly from the western coast of Greenland in the two warming periods, which was likely due to an increase in dust sourced from local ice-free areas as a result of shorter snow/ice cover duration in the Greenland coastal region during the melt season caused by recent warming. Meanwhile, ancient deposits in northern Canada, which were formed in past warmer climates, seem to be the best candidate during the colder period (1950–2004). Our results suggest that SEM–EDS analysis can detect variations in ice core dust sources during recent periods of low dust concentration.

Provenance of Fe in Chinese Deserts: Evidence from the geochemistry and mineralogy of soil particles

Abstract: Determining the categories and content of Fe containing silicate minerals in the desert soils and sediments of northern China is important for understanding the Fe cycle and for correctly interpreting the paleoenvironmental signals from the Loess Plateau downwind. Using a mineral liberation analyzer (MLA), we established the modal mineral abundances of a complete set of Fe containing mineral species in the fine sand to silt fractions of surface samples from Chinese deserts. Results show that the most common discrete particles containing Fe are the silicate phases (~15 wt%), while the weathering product (i.e., Fe oxides) phases are minor and their abundances vary greatly (0.38–4.15 wt%). The degree of weathering has a substantial particle size dependence. The fine fraction (5–20 µm) generally has a relatively low Fe/Si ratio, possibly due to weathering, while the Fe/Si ratio of the coarse fractions (20–45 µm, 45–63 µm, 63–75 µm, and >75 µm) are relatively invariant. Abundant Fe is contained within the coarse fractions, which are associated with the local geology. The strong relationship between the Fe and Mg bound within the silicate phases further supports the conclusion that the correlated deviations in the Fe/Si and Mg/Si ratios originate from the provenance bedrock (i.e., siliciclastic, low-grade metamorphic, and possibly high-grade metamorphic, rocks). Since Mg tends to be easily removed during weathering, the Fe/Mg ratios of silicate species largely reflect the weathering intensity. We used the regression equation for the relationship between the local precipitation amount and the Fe/Mg ratios of the soils to produce a novel precipitation proxy. Compared with classical provenance studies conducted using coarse sand and larger rock fragments, the MLA methodology is more applicable to the fine sand and silt fractions; thus, it contributes to the development of weathering and provenance indices based on geochemistry and mineralogy.

Monitoring Pedogenic Inorganic Carbon Accumulation Due to Weathering of Amended Silicate Minerals in Agricultural Soils

Abstract: The present study aims to demonstrate a systematic procedure for monitoring inorganic carbon induced by enhanced weathering of comminuted rocks in agricultural soils. To this end, the core soil samples taken at different depth (including 0-15 cm, 15-30 cm, and 30-60 cm profiles) are collected from an agriculture field, the topsoil of which has already been enriched with an alkaline earth metal silicate containing mineral (such as wollastonite). After transporting to the laboratory, the soil samples are air-dried and sieved. Then, the inorganic carbon content of the samples is determined by a volumetric method called calcimetry. The representative results presented herein showed five folded increments of inorganic carbon content in the soils amended with the Ca-silicate compared to control soils. This compositional change was accompanied by more than 1 unit of pH increase in the amended soils, implying high dissolution of the silicate. Mineralogical and morphological analyses, as well as elemental composition, further corroborate the increase in the inorganic carbon content of silicate-amended soils. The sampling and analysis methods presented in this study can be adopted by researchers and professionals looking to trace pedogenic inorganic carbon changes in soils and subsoils, including those amended with other suitable silicate rocks such as basalt and olivine. These methods can also be exploited as tools for verifying soil inorganic carbon sequestration by private and governmental entities to certify and award carbon credits.

Effect of Ti on crystal transition and solid solution characteristics of white Portland cement clinker

Abstract: Titanium (Ti) is a common trace element in white Portland cement clinker. Ti4+ generally replaces Si4+ to form a solid solution in silicate minerals, which has an important influence on the mineral...

Recommendations for offline combustion-based nitrogen isotopic analysis of silicate minerals and rocks

Abstract: Rationale Due to isotope fractionations during partial nitrogen release from minerals and rocks, the complete extraction of nitrogen for analysis is crucial to ensure high-quality nitrogen isotopic data. However, the appropriate nitrogen extraction conditions (e.g. temperature, duration) have not been established for most silicate minerals and rocks. Methods Nitrogen in a number of common minerals and rocks was extracted using the most robust sealed-tube offline combustion techniques, purified and quantified in a custom-made metal manifold, and carried by helium gas to an isotope ratio mass spectrometer for isotopic measurement at nanomolar nitrogen level. Each mineral or rock was combusted in a variety of temperature and duration conditions to compare the nitrogen yields and isotopic compositions. Results The nitrogen yields and isotopic compositions of minerals and rocks are strongly affected by combustion temperature and duration. The optimal combustion temperature is lowest for cyclosilicate minerals, followed by phyllosilicate, tectosilicate and inosilicate minerals. Preheating of samples can induce significant nitrogen loss and δ15 N shift. Heating of samples above their optimal temperatures may cause nitrogen re-assimilation by the residual mineral or rock. Conclusions Each mineral or rock has a characteristic optimal temperature and duration for complete nitrogen release. Preheating, under-heating or over-heating can cause nitrogen loss and isotopic shift. Therefore, we recommend using the offline combustion techniques and the optimal combustion conditions obtained in this study for nitrogen quantification and isotopic analysis of silicate minerals and rocks.

Mineral Characteristics of Low-Rank Coal and the Effects on the Micro- and Nanoscale Pore-Fractures: A Case Study from the Zhundong Coalfield, Northwest China.

Abstract: The mineral characteristics (occurrence, type, and content) of low-rank coal and their influence on coalbed methane (CBM) reservoirs are investigated at the micro- and nanoscales. Six coal samples of three representative coalmines were used to demonstrate the uniform tectonization from the Zhundong coalfield, NW China. Based on optical microscopy and scanning electron microscopyenergy dispersive spectrum (SEM-EDS) analysis, the mineral composition and occurrence characteristics were discussed. The micro- and nanoscale reservoir characteristics in low-rank coal (pore size distribution and adsorption capability) were studied by diverse methods, including lowtemperature N₂ adsorption/desorption, mercury intrusion porosimetry and CH₄ isotherm adsorption analysis. The coal reservoir nuclear magnetic T₂ spectra of porosity and movable fluid were obtained by combining low-field nuclear magnetic resonance (NMR) analysis, which has an advantage of determining pore fluid technology. The mineral content is highly variable (4˜16 vol.%) in the Xi Heishan prospecting area of the Qitai region. Kaolinite, goyazite, ankerite and anorthosite were microscopically observed to be filling in coal pores and microfractures, and the minerals are given priority to silicate minerals. There is a greater content of mesopores (100-1000 nm) and transition pores (10-100 nm), and they are well connected. The micropores (0-10 nm) are dominated by parallel plate, closed or wedge-shaped pores. Furthermore, the microfractures are mainly observed for types B (width ≥ 5 μm and length≤ 10 mm) and D (width<5 μm and length<300 μm). The results show that microfractures B and C (width< 5 μm and length ≥ 300 μm) are better connected, but the orientation and connectivity of type D are worse. The Langmuir volume and mesopore content decreased with increasing mineral content, which shows that the low-rank coal minerals filled some adsorption space; the reduced CBM adsorption capacity and cellular pore and intergranular pore filled with minerals affect the mesopore content. Therefore, mineral characterization significantly influences methane adsorption capacity and pore structure.

Strategies to characterize the geochemical interrelationship between coastal saline groundwater and seawater

Abstract: Groundwater contamination by the adjacent seawater has been a global problem. To address the process and evolution of salinity in groundwater, different procedures such as major ion ratios, standard plots, geophysical techniques, isotopic techniques, and modelling methods were adopted. It is difficult to distinguish the groundwaters’ with salinity, similar or greater than the seawater by adopting major ions. Saline to hypersaline conditions are reported in coastal groundwater of the arid regions. In order to address the sources of salinity, evolution and geochemical nature, groundwater samples were collected near the shore along with adjacent seawater. The ion-ratio and the Piper diagram did not show a clear demarcation between groundwater and seawater, but the fact that seawater values were within a narrow range than the groundwater. Whereas the Cl/Br and Br/Si ratios, thermodynamic stability plots of K-Silica system, Plagioclase stability and carbonate system with respect to logpCO2 reflected geochemical variation between the seawater and groundwater samples. Since the silica values of seawater samples were lesser, they proved to be a significant tracer to characterize the non-contaminated groundwater samples. The seawater–groundwater interaction was inferred from the study and probable locations of SGD were identified. The evolution mechanism of the brine composition with the present scenario was studied considering the saturation states of halite, silicates, carbonate and sulfate minerals. It was identified that the evolutionary pathway of brine from groundwater composition is governed by the Ca ion, which is a common ion for most of the carbonate and sulfate minerals. The groundwater chemistry indicates the Cl-SO4 brine evolution pathway leading to the formation of Mg-SO4 brine. Thus, the study proves that ratios of Cl/Br, Br/Si, thermodynamic stability plots with respect to silicate minerals and logpCO2 along with saturation states of minerals can serve as significant tool to characterize the hypersaline groundwater.

Iron isotope compositions of coexisting sulfide and silicate minerals in Sudbury-type ores from the Jinchuan Ni-Cu- sulfide deposit: A perspective on possible core-mantle iron isotope fractionation

Abstract: Many studies have shown that the average iron (Fe) isotope compositions of mantle-derived rocks, mantle peridotite and model mantle are close to those of chondrites. Therefore, it is considered that chondrite values represent the bulk Earth Fe isotope composition. However, this is a brave assumption because nearly 90% of Fe of the Earth is in the core, where its Fe isotope composition is unknown, but it is required to construct bulk Earth Fe isotope composition. We approach the problem by assuming that the Earth’s core separation can be approximated in terms of the Sudbury-type Ni-Cu sulfide mineralization, where sulfide-saturated mafic magmas segregate into immiscible sulfide liquid and silicate liquid. Their density/buoyancy controlled stratification and solidification produced net-textured ores above massive ores and below disseminated ores. The coexisting sulfide minerals (pyrrhotite (Po) > pentlandite (Pn) > chalcopyrite (Cp)) and silicate minerals (olivine (Ol) > orthopyroxene (Opx) > clinopyroxene (Cpx)) are expected to hold messages on Fe isotope fractionation between the two liquids before their solidification. We studied the net-textured ores of the Sudbury-type Jinchuan Ni-Cu sulfide deposit. The sulfide minerals show varying δ56Fe values (−1.37–−0.74‰ (Po) < 0.09–0.56‰ (Cp) < 0.53–1.05‰ (Pn)), but silicate minerals (Ol, Opx, and Cpx) have δ56Fe values close to chondrites (δ56Fe = −0.01 ± 0.01‰). The heavy δ56Fe value (0.52–0.60‰) of serpentines may reflect Fe isotopes exchange with the coexisting pyrrhotite with light δ56Fe. We obtained an equilibrium fractionation factor of Δ56Fesilicate-sulfide ≈ 0.51‰ between reconstructed silicate liquid (δ56Fe ≈ 0.21‰) and sulfide liquid (δ56Fe ≈ −0.30‰), or Δ56Fesilicate-sulfide ≈ 0.36‰ between the weighted mean bulk-silicate minerals (δ56Fe[0.70ol,0.25opx,0.05cpx] = 0.06‰) with weighted mean bulk-sulfide minerals (δ56Fe ≈ −0.30‰). Our study indicates that significant Fe isotope fractionation does take place between silicate and sulfide liquids during the Sudbury-type sulfide mineralization. We hypothesize that significant iron isotope fractionation must have taken place during core–mantle segregation, and the bulk Earth may have lighter Fe isotope composition than chondrites although Fe isotope analysis on experimental sulfide-silicate liquids produced under the varying mantle depth conditions is needed to test our results. We advocate the importance of further research on the subject. Given the close Fe-Ni association in the magmatic mineralization and the majority of the Earth’s Ni is also in the core, we infer that Ni isotope fractionation must also have taken place during the core separation that needs attention.

Calcium Carbonate Growth with the Ring Structure of Stalactite-Type Minerals in a Tuff Breccia

Abstract: Microbially induced carbonate precipitation (MICP) has attracted worldwide attention as an environmentally friendly ground restoration technology in response to geohazards. This study describes the relationship between calcium carbonate growth within stalactite-type minerals formed around fractures in tuff breccia and microorganisms. Scanning electron microscopy revealed that calcium carbonate was precipitated in the interstices of rings formed in stalactite-type minerals, as if the carbonate minerals enhanced the strength of the silicate minerals. In addition, X-ray powder diffraction analysis detected that the calcium carbonates were calcite and vaterite. Moreover, microorganisms, such as diatoms and green algae, inhabited the interstices and, consequently, MICP by these microorganisms could play a role in the stability of outcrops. The stable isotope ratios of δ13C and δ15N and the mass spectral signals of the demineralized samples also encouraged diatoms and green algae to be involved in the formation of minerals.

The syenite-carbonatite complex of Ihouhaouene (Western Hoggar, Algeria): interplay between alkaline magma differentiation and hybridization of cumulus crystal mushes

Abstract: The 2 Ga-old Ihouhaouene alkaline complex (Western Hoggar, Algeria) is among the oldest known carbonatite occurrences on Earth. The carbonatites are calciocarbonatites hosted by syenites, the predominant rock type in the complex. Both rock types are characterized by medium-grained to pegmatitic textures and contain clinopyroxene, apatite, and wollastonite, associated with K-feldspar in syenites and a groundmass of calcite in carbonatites. The rock suite shows a continuous range of compositions from 57–65 wt.% SiO 2 and 0.1–0.4 wt.% CO 2 in red syenites to 52–58 wt.% SiO 2 and 0.1–6.5 wt.% CO 2 in white syenites, 20–35 wt.% SiO 2 and 11–24 wt.% CO 2 in Si-rich carbonatites (>10% silicate minerals), and 50), whereas clinopyroxene was precipitated from silicate liquids characterized by lower LREE/HREE (Ce/Lu = 49–234) and variable Nb/Ta ratios (Nb/Ta = 2–30). The Si-poor carbonatites resemble the Si-rich carbonatites and the white syenites with elevated REE contents in apatite equilibrium melts compared to clinopyroxene. However, apatite equilibrium melt in Si-poor carbonatite shows a majority of subchondritic values (Nb/Ta<10) and clinopyroxene has chondritic-to-superchondritic values (Nb/Ta = 15–50). Although paradoxical at first sight, this Nb-Ta signature may simply reflect the segregation of the carbonatite from highly evolved silicate melts characterized by extremely low Nb/Ta values. Altogether, our results suggest an evolutionary scheme whereby slow cooling of a silico-carbonated mantle melt resulted in the segregation of both cumulus minerals and immiscible silicate and carbonate melt fractions, resulting in the overall differentiation of the complex. This process was however counterbalanced by intermingling of partially crystallized melt fractions, which resulted in the formation of hybrid alkaline cumulates composed of disequilibrium cumulus phases and variable proportions of carbonate or K-feldspar.