Gypsum Precipitation Research Articles

Phylogeny and functional diversity of halophilic microbial communities from a thalasso environment

The El-Rawda solar saltern, located in North Sinai, Egypt, is formed through the process of water evaporation from the Bradawil lagoon. This evaporation leads to the precipitation of gypsum, halite minerals, and salt flats, which subsequently cover the southern and eastern areas of the lagoon. This study employed the shotgun metagenomic approach, the illumine platform, and bioinformatic tools to investigate the taxonomic composition and functional diversity of halophilic microbial communities in solar saltern. The metagenomic reads obtained from the brine sample exhibited a greater count compared to those from the sediment sample. Notably, the brine sample was primarily characterized by an abundance of archaea, while the sediment sample displayed a dominant abundance of bacteria. Both samples exhibited a relatively low abundance of eukaryotes, while viruses were only found in the brine sample. Furthermore, the comparative analysis of functional pathways showed many important processes related to central metabolism and protein processing in brine and sediment samples. In brief, this research makes a valuable contribution to the understanding of very halophilic ecosystems in Egypt, providing insights into their microbial biodiversity and functional processes.

Design and Manufacture of Bone Cements Based on Calcium Sulfate Hemihydrate and Mg, Sr-Doped Bioactive Glass.

In the present study, a novel composite bone cement based on calcium sulfate hemihydrate (CSH) and Mg, Sr-containing bioactive glass (BG) as solid phase, and solution of chitosan as liquid phase were developed. The phase composition, morphology, setting time, injectability, viscosity, and cellular responses of the composites with various contents of BG (0, 10, 20, and 30 wt.%) were investigated. The pure calcium sulfate cement was set at approximately 180 min, whereas the setting time was drastically decreased to 6 min by replacing 30 wt.% glass powder for CSH in the cement solid phase. BG changed the microscopic morphology of the set cement and decreased the size and compaction of the precipitated gypsum phase. Replacing the CSH phase with BG increased injection force of the produced cement; however, all the cements were injected at a nearly constant force, lower than 20 N. The viscosity measurements in oscillatory mode determined the shear-thinning behavior of the pastes. Although the viscosity of the pastes increased with increasing BG content, it was influenced by the frequency extent. Pure calcium sulfate cement exhibited some transient cytotoxicity on human-derived bone mesenchymal stem cells and it was compensated by introducing BG phase. Moreover, BG improved the cell proliferation and mineralization of extracellular matrix as shown by calcein measurements. The results indicate the injectable composite cement comprising 70 wt.% CSH and 30 wt.% Mg, Sr-doped BG has better setting, mechanical and cellular behaviors and hence, is a potential candidate for bone repair, however more animal and human clinical evaluations are essential.

Fluid-mineral dynamics at the Rincón de la Vieja volcano—hydrothermal system (Costa Rica) inferred by the study of major, minor and rare earth elements in the hyperacid crater lake

Volcanic lakes are complex natural systems and their chemical composition is related to a myriad of processes. The chemical composition of major, minor, Rare Earth Elements (REE) and physico-chemical parameters at the hyperacid crater lake of Rincón de la Vieja volcano (Costa Rica) are here investigated during February 2013–August 2014. The study of the lake chemical composition allows to identify the main geochemical processes occurring in the lake and to track the changes in the volcanic activity, both important for active volcanoes monitoring. The total REE concentration (∑REE) dissolved in the crater lake varies from 2.7 to 3.6 mg kg−1 during the period of observation. REE in the water lake samples normalized to the average volcanic local rock (REEN-local rock) are depleted in light REE (LREE). On the contrary REEN-local rock in the solids precipitated (mainly gypsum/anhydrite), from lake water samples in laboratory at 22°C, are enriched in LREE. The low variability of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios (0.92–1.07 and 0.66–0.81, respectively) in crater lake waters is consistent with the low phreatic activity (less than 10 phreatic eruptions in 2 years) observed during the period of observation. This period of low activity precedes the unrest started in 2015, thus, it could be considered as a pre-unrest, characterized by infrequent phreatic eruptions. No clear changes in the REE chemistry are associated with the phreatic eruption occurred at mid-2013. The results obtained investigating water-rock interaction processes at the Rincón de la Vieja crater lake show that rock dissolution and mineral precipitation/dissolution are the main processes that control the variability of cations composition over time. In particular, precipitation and dissolution of gypsum and alunite are responsible for the variations of REE in the waters. Despite the low variations of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios, this study allows to suggest that REE can be used, together with major elements, as practical tracers of water-rock interaction processes and mineral precipitation/dissolution at active hyperacid crater lakes over time, also during periods of quiescence and low phreatic activity.

Remediation of acid mine drainage and immobilization of rare earth elements: Comparison between natural and residual alkaline materials

Acid mine drainage (AMD) is a well-known source of toxic trace metals in freshwaters. Traditional passive treatment systems rely on AMD neutralization with limestone and removal of most common toxic transition metals such as Cu and Zn with little attention to rare earth elements (REE). Alkaline waste materials now receive increasing attention as low cost AMD treatment alternatives in the circular economy. This study was set up to identify the efficiency of alkaline waste materials remediating AMD and scavenging REE in addition to other toxic trace elements. An AMD sample was collected from a lixiviate coming from pyrite heaps in the Iberian Pyrite Belt (pH = 1.8, 30 μM ∑REY). The sample was treated with either blast furnace slag (BFS) generated during smelting of iron ore in a blast furnace or biomass ashes (BA) derived from combustion of biomass, thereby using analytical grade CaCO3, and NaOH as reference products. The batch alkalinization experiments were conducted by adding each alkaline material at an amount to obtain an equal pH to ≈6.5. The required amounts of the products were NaOH < CaCO3<BFS < BA in line with their acid neutralizing capacities. The largest removal of sulfate from water was obtained in the CaCO3 treatment suggesting gypsum precipitation which was lower with BA and BFS and virtually absent with NaOH, these trends were confirmed by SEM-EDX and XRD. Both BFS and BA removed more Fe than CaCO3 and NaOH. The REE elements were well removed by all treatments (>99%) and the remaining REE concentrations in the solutions were clearly lower than values for Cu and Zn. The Zn and Cu removals were not consistently high enough (except with NaOH) to meet environmental limits in the discharge waters. The largest efficiency for REE removals was obtained with CaCO3. Indirect evidence here suggests that gypsum is a better host for the trivalent REE than Fe(III) minerals in the precipitates. The ionic radii of trivalent REE are more similar to Ca2+ than to Fe3+, explaining the better potential of gypsum as REE host. This study showed also the potential of BFS as alkaline agent for the remediation of AMD in terms of its higher alkalinity generation potential as compared to BA, thus making BA less promising than BFS.

Changes in hydrocarbons and elemental distribution in peloids during maturation processes (Sečovlje Salina Nature Park Slovenia)

In Sečovlje Salina Nature Park, the therapeutic mud matured in the natural sedimentary environmental site. This work aimed to determine the influence of the peloid maturation process on the hydrocarbon and elemental distributions, as well as changes in morphology. For this purpose, the sample before and after maturation was examined using various methods.n-Alkanes were the most abundant among saturated hydrocarbons in both immature and mature peloid samples. The results showed that the maturation mainly influenced the change in distribution and concentration (from 378 to 1958 ppm) of n-alkanes. The organic matter (OM) of the immature peloid sample was characterized by a slight prevalence of long-chain and odd carbon-numbered n-alkanes, maximizing at n-C27. However, mature peloid's OM showed a similar share of short-, mid- and long-chain n-alkanes with a slight dominance of short-chain members, maximizing at n-C16. The origin of short-chain and even carbon-numbered n-alkanes was attributed to microbial precursors (e.g., Leptolyngbyaceae).Hopanes were considerably more dominant compared to steranes in both peloids. The hopane series of immature peloid was characterized by the dominance of 22,29,30-trinor-hop-5(6)-ene (C27 hopene), as well as the presence of C30-hop-22(29)-ene (diploptene), which are widespread in cyanobacterial species. The aromatic fraction of immature peloid pointed to the predominance of polycyclic aromatic hydrocarbons (PAHs). As peloid aging progressed, the sample was richer in methyl-branched alkanes, carboxylic acids, their methyl esters, and thermodynamically more stable hopanes and steranes.The presence of elements with toxicological relevance during maturation was reduced below the limits prescribed in most of the directives for cosmetic products. It specifically refers to: As, Ni and Se. A higher concentration of total sulfur in the mature peloid can be related to gypsum precipitation in the summer and/or more intensive microbial activity.

Containment of sulfate in leachate as gypsum (CaSO4·2H2O) mineral formation in bio-cemented sand via enzyme-induced carbonate precipitation

Enzymatically induced carbonate precipitation (EICP) using urea hydrolysis is a well-known bio-cementation process that not only promotes the precipitation of calcium carbonate (CaCO3) but can provide excess calcium cations for further reaction depending on the substrate constituents and reaction stage. This study presents the EICP recipe to contain sulfate ions in landfill leachate sufficiently using remaining calcium cations and a series of tests were conducted to validate its ability to retain sulfates. The reaction rate for 1 M CaCl2 and 1.5 M urea was identified by controlling the purified urease content and the curing time of the EICP process. The results showed that 0.3 g/L of purified urease produced 46% CaCO3 and reduced sulfate ions by 77% after 3 days of curing. The shear stiffness in EICP-treated sand was enhanced 13 times by CaCO3 precipitation followed by 1.12 times increment due to subsequent precipitation of gypsum (CaSO4·2H2O) crystals implying sulfate containment. A cost-efficient EICP treatment using soybean crude urease instead of lab-grade purified urease exhibited lower sulfate removal efficiency (i.e., 18%) with only nominal formation of gypsum in the EICP-treated sand. The addition of gypsum powder was effective in increasing sulfate removal by 40% when soybean crude urease was used for EICP.

Mechanism of CaO in Light-Burned Magnesia on the Formation Process, Mechanical Properties, and Water and Chloride Resistance of the 517 Phase

With the continuous exploitation of high-quality magnesite ores, a large number of low-grade magnesite ores with high calcium contents were abandoned, thereby occupying the land, polluting the environment, and causing substantial resource waste. Therefore, resource utilization of low-grade magnesite ores is urgently needed. These low-grade magnesite ores can be used by calcination to prepare raw materials of magnesium oxysulfate (MOS) cement, but CaO could be produced during calcination because dolomite is a dominant mineral. Therefore, this paper mainly studied how CaO affects the formation process, mechanical properties, and water and chloride resistance of the pure 517 phase. Light-burned dolomite (LBD) was used to offer CaO, replacing a certain amount of light-burned magnesia (LBM) in this work. It was found that CaO will react with Mg2+ and SO42− to form an amorphous phase that remains stable when curing in air but unstable when immersing in water. When immersed in water, Ca2+ would continue to react with SO42− to precipitate gypsum, thus destroying the original structure and reducing the stability of the pure 517 phase. Therefore, in the preparation of MOS cement, attention should be given to the content of CaO, and modifiers should be added to obtain a low solubility calcium compound to reduce the negative effects of CaO on MOS cement.

Effect of engineered water and scale inhibitor concentration on the adsorption performance of gypsum inhibitors on multi‐walled carbon nanotubes and crushed sandstone

AbstractEngineered waterflooding is an effective process for enhanced oil recovery, but it can lead to mineral scale deposition due to the incompatibility of brines. Previous studies on scale mitigation have mainly focused on high‐temperature baryte and anhydrite scales, neglecting gypsum precipitation and inhibitors adsorption at low temperatures. Additionally, earlier research has used simple brines that do not reflect the actual injection and formation water in reservoirs. In this study, the impact of temperature, various brine mixtures, and thermodynamic databases on saturation ratio and scale precipitation is explored using PHREEQC (pH‐REdox‐EQuilibrium‐C program). The study reveals that the copresence of calcium and magnesium ions improves the gypsum inhibition efficiency of scale inhibitors (SIs) at low concentrations to a maximum of 79%. However, this effect is reversed or neutral at higher SI concentrations. The study also shows that the presence of monovalent ions reduces the adsorption of SIs by multi‐walled carbon nanotubes (MWCNTs). Removing sodium ions from seawater while leaving calcium and magnesium ions intact increases MWCNTs' adsorption capability to 93%. This is because monovalent cations attach to the adsorbent surface and block the active sites, whereas divalent cations act as a bridge between MWCNT and SIs. The study establishes that the behaviour of SIs regarding adsorption on MWCNT and crushed sandstone depends on various factors, including molecule size, calcium toleration of the SIs, point of zero charge, and solution pH. Understanding these factors can improve the effectiveness of SIs, reduce chemical costs, and prolong the life of oil wells.

SO2-Induced Aging of Hematite- and Cinnabar-Based Tempera Paint Mock-Ups: Influence of Binder Type/Pigment Size and Composition

Hematite- and cinnabar-based paint mock-ups prepared with either rabbit glue or egg yolk binder were artificially aged in an SO2-rich atmosphere, as a model system for investigating the deterioration of tempera paints exposed to an industrial atmosphere. The overall research aim was to identify the type of degradation occurring in tempera paints and the different alteration mechanisms related to the physical, mineralogical and chemical characteristics of the paint. Tempera mock-ups were prepared by mixing binder (egg yolk or rabbit glue) and pigment (cinnabar of different particle sizes or hematite) and were then exposed to SO2 for 2 months in accelerated aging tests. The colour, gloss, reflectance, roughness and micro-texture of the surfaces of the mock-ups were determined before and after the tests. In addition, chemical and mineralogical changes were determined by X-ray Powder Diffraction (XRPD), Attenuated Total Reflection-Fourier Transform Infrared spectroscopy (ATR-FTIR) and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Colorimetric changes were confirmed, mainly in the cinnabar-based paints containing egg yolk, and in the hematite-based paints containing rabbit glue. Neoformed mineral phases have not been detected by XRPD, but precipitation of gypsum on the exposed surfaces has been confirmed by SEM. For cinnabar-based paints, the amount of sulfate-rich deposits was higher on egg yolk mock-ups than on rabbit glue samples, though the opposite was observed for the hematite-based paints. This confirmed the influence of the binder composition and pigment-binder tandem in the susceptibility to SO2 deposition. Pigment particle size did not have a clear influence on the physical and chemical changes in the tempera mock-ups during the ageing tests.

Ferric Hydroxide Recovery from Iron-Rich Acid Mine Water with Calcium Carbonate and a Gypsum Scale Inhibitor

The focus of this study was to improve the Reverse Osmosis Cooling (ROC) process by using CaCO3 for neutralization and selective recovery of Fe(OH)3 at pH 3.5. By using a specific inhibitor, ferric hydroxide was recovered separately from gypsum and other metals present in mine water. Ferric hydroxide was processed to pigment, a product that is imported and used as colorant in paints and tiles. In addition to pigment recovery, aluminum hydroxide and calcium carbonate can also be recovered from mine water. The following conclusions were made: (i) the rate of gypsum crystallization, in the absence of Fe3+, is influenced by the over saturation concentration in solution, the seed crystal concentration and temperature; (ii) gypsum crystallization from an over-saturated solution, in the presence of Fe(OH)3 sludge, required an inhibitor dosage of 100 mg/L to keep gypsum in solution for a period of 30 min; (iii) gypsum crystallization from an over-saturated solution, in the presence of both Fe(OH)3 sludge and CaCO3 reactant, required a higher inhibitor dosage than 100 mg/L to keep gypsum in solution for a period of 30 min. A dosage of 200 mg/L kept gypsum in solution for the total reaction period; (iv) when only Fe(OH)3 is present in the slurry, gypsum inhibition is more effective when Fe(OH)3 sludge is allowed to settle after the initial mixing; (v) when both Fe(OH)3 and CaCO3 are present in the slurry, gypsum inhibition is more effective when the inhibitor is added over a period of time (10 min) rather than applying the total dosage at time zero; (vi) Fe(OH)3 can be changed to yellow pigment (Goethite) by heating to 150 °C and to red pigment (Hematite) by heating to 800 °C. Pigment of nano particle size was produced; (vii) in the case of Na2CO3, the TDS increased from 12,660 mg/L in the feed to 13,684 mg/L due to the replacement of metal ions (Fe3+, Al3+, Fe2+, Mn2+ and Ca2+) with Na+ in solution. In the case where CaCO3 was used for the removal of Fe3+ and Al3+, Ca(OH)2 for the removal of Fe2+, Mn2+, and Na2CO3 for the removal of Ca2+, the TDS dropped from 12,661 mg/L to 2288 mg/L, due to gypsum precipitation. The alkali cost in the case of calcium alkalis amounted to ZAR29.43/m3 versus ZAR48.46/m3 in the case of Na2CO3.

Assessment of the oxygen reactivity in a gas storage facility by multiphase reactive transport modeling of field data for air injection into a sandstone reservoir in the Paris Basin, France

The first objective of this study is to present unique field data on a three-year pilot test during which air containing 8 mol% O2(g) was injected as a cushion gas into a natural gas reservoir, a carbonate-cemented sandstone aquifer located in the Paris Basin (France). 10-year system survey showed that: the oxygen was fully depleted several months after injection completion, meanwhile CO2(g) was detected around 2–6 mol%; the pH decreased from 8 to 6, while reducing conditions shifted to mildly oxidizing ones with increasing concentration of sulfates in equilibrium with gypsum. 3 years after injection completion, the pH gradually returned to its near initial state and sulfates were reduced by 2 to 3 times. The second objective is to develop a multiphase reactive transport model based on the field data. Simulations were constructed using the HYTEC reactive transport code, progressing from 0D-batch to 2D-reservoir configurations. The model reproduced the gas-water-rock reactive sequence: 1/ full depletion of the injected O2(g) due to pyrite oxidation, 2/ leading to acidity production and dissolved sulfates, 3/ acidity buffering by calcite dissolution, 4/ followed by gypsum precipitation and CO2(g) exsolution. The model demonstrated that pyrite kinetics was the most significant factor governing not only the amount of O2(g), CO2(g) and dissolved minerals, but also the spatial extent of these chemical reactions and, hence, the gas spread inside the reservoir. The formulated advective Damköhler number for oxygen consumption indicated advection- and reaction-dominant regimes explaining the gas composition and extension. The developed field-based model could be used as a workflow for other gas storage facilities, e.g. biomethane, compressed air, and CO2. For underground biomethane storage, the O2(g) contents recommended in Europe, i.e. the EASEE-gas specification 2005-001-02, should have a low impact on gas composition and reservoir geochemistry when the reservoir contains efficient pH-buffers such as calcite.

Experimental insight into the dissolution behavior and interaction of key components in shale-persulfate system

Shale-persulfate interaction is ubiquitous in hydraulic fracturing, but the underlying geochemical reaction and its impact on the shale matrix are still not well understood. In this study, key components, including pyrite, calcite, chlorite, and kerogen, were chosen to react with sodium persulfate (Na2S2O8) at reservoir temperature. Results showed the oxidation-dominated reaction in the pyrite-persulfate system turned to acidification in calcite/chlorite-persulfate. In the pyrite-rich kerogen (PRK), however, kerogen competed with pyrite for persulfate consumption. An increased concentration of Na2S2O8 enhanced the dissolution of pyrite, PRK, and chlorite but resulted in the mass increase of solid in the calcite-Na2S2O8 system because of gypsum precipitation. The concentration of dissolved cations significantly correlated with the mass change of the corresponding components during persulfate stimulation, demonstrating the feasibility of water chemistry for evaluating the potential matrix alteration. Reaction in the treatment of persulfate on a multi-component mixture further suggested a complex interaction. The higher amounts of PRK, calcite, and chlorite led to the enhanced dissolution of Fe, Ca, and Mg, respectively. Various chemical reactions also influenced the dissolution behavior of cations. At low pyrite dosage, chlorite was acidly etched and slightly contributed to the dissolution of Fe. The dissolution of calcite and precipitation of gypsum affected the behavior of Ca. Element Mg mainly came from chlorite, but persulfate hydrolysis and PRK oxidation also changed its dissolution. Based on the total mass change of the multi-component mixture after persulfate treatment, a binary model was established to predict the mass change and quantify the potential matrix alteration during shale-persulfate interaction. This model could be used for selecting a potential reservoir during the in situ application of persulfate stimulation for shale permeability enhancement.

Tuning the growth morphology of gypsum crystals by polymers

True control over the morphology of gypsum crystals formed via homogeneous precipitation from solution has rarely been reported in the literature. In this work, we have tested a large number of dissolved additives (polymers as well as small molecules) with respect to their ability to alter the typical microscopic appearance of precipitated gypsum powders, which is usually characterized by a mixture of single-crystalline needles and twinned plates. Among the many additives studied, a copolymer of vinylpyrrolidone and acrylic acid (PVP-co-PAA) was identified as powerful growth modifier for gypsum already at low concentrations. In both slow titration and rapid mixing experiments, unconventional blocky crystals with tilted stacking edges as well as pseudo-hexagonal plates could be synthesized reproducibly with the help of the copolymer. Systematic characterization revealed the dynamic mode of action of the newly identified growth modifier, which seems to stabilize a highly reactive face of gypsum and promote the formation of macrosteps. The degree of morphological control achieved in this way is unprecedented in the case of calcium sulfate and may devise entirely new concepts for additive design in the areas of plasters and cementitious materials, gypsum wallboard production and/or scale prevention.

Groundwater quality evaluation based on water quality indices (WQI) using GIS: Maadher plain of Hodna, Northern Algeria.

In a semi-arid region of Maadher, central Hodna (Algeria), groundwater is the main source for agricultural and domestic purposes. Anthropogenic activities and the presence of climate change's effects have a significant impact on the region's groundwater quality. This study's goals were to use water quality indices to evaluate the groundwater's quality and its suitability for drinking and irrigation, as well as to identify contaminated wells using a geographic information system (GIS) and the spatial interpolation techniques of ordinary kriging and inverse distance weighting (IDW). The results reveal that all water samples exceeded the World Health Organization's standards for nitrate ions and had alarming concentrations of calcium, chlorine, and sulfate (WHO). According to Piper's diagram, the groundwater hydrochemical facies is composed of the elements sulfate-chloride-nitrate-calcium (SO42--Cl-NO3--Ca2+ water type). The majority of samples fall into the poor water category, slightly more than 10% fall into the very poor water category, and less than 10% fall into the good to the excellent quality category, per the water quality indices, which classify samples in a similar manner. According to irrigation water indices, every sample is suitable for irrigation. Depending on the direction of groundwater flow, the spatial distributions of Ca2+, Na+, Mg2+, SO42-, and Cl- show that their concentrations are high north of the area and relatively low south of Maadher village (Fig.3). Nitrate concentrations are high in the majority of samples, particularly those close to the Bousaada wadi. In most samples, particularly those close to the Bousaada wadi, nitrate levels are high. Various water quality models were described, and GIS spatial distribution maps were created using standard kriging and inverse distance weighting (IDW) techniques through selected semi-variograms predicted against measurements. To determine the origin of mineralization and the chemical processes that take place in the aquifer-which include the precipitation and dissolution of dolomite, calcite, aragonite, gypsum, anhydrite, and halite-the groundwater saturation index was calculated.

A reactive transport model designed to predict the environmental footprint of an ‘in-situ recovery’ uranium exploitation

Worldwide, most uranium production relies on the ‘in situ recovery’ (ISR) extraction technique. This consists of dissolving the ore using a leaching solution (acid or alkaline) directly within the deposit through a series of injection and extraction wells. Due to the nature of the injected ISR solutions, the water quality of the aquifer could be affected. Reactive transport modeling is a powerful tool for predicting fluid flow and geochemical reactions in ISR reservoirs. In this study we present a coupled 3D environmental geochemical model (EGM) (based on the HYTEC reactive transport software), capable of predicting the physico-chemical conditions in an acid-leaching ISR uranium mine and its environmental footprint on the aquifer in the years following the closure of the production block. The model was validated at the KATCO mine (Kazakhstan) on two different and independent production blocks, over 10 years after their closure. The model shows that incorporating two main geochemical processes, (1) cationic sorption on clay surfaces (smectite-beidellite) and (2) precipitation of gypsum (CaSO4.2H2O), successfully reproduces the measured well data (pH, acidity and SO4) over short- and long-term time scales. Clay surface sites remain mostly saturated in protons during the production phase. Simulations show that sorbed protons on the clay surfaces maintains the acid conditions for a longer period of time. The environmental impact model was also compared to a pre-existing model specifically developed for production simulation purposes: differences are observed as expected for the uranium production, but also for the impact distances, due to differences in the considered reactive mineralogical paragenesis. Thus, the choice of geochemical model should be made with due regard for the desired objectives. This work will assist the mine operator by providing a tool capable of assessing both the short- and long-term environmental footprints of the ISR production operation conditions and of identifying the best remediation strategy.

Effect of oxalic acid pretreatment on the mechanical properties and microstructure of phosphogypsum

In China, the amount of phosphogypsum (PG) accumulated has been increasing rapidly with the development of the phosphate fertilizer industry. PG exists mainly in the form of dihydrate gypsum, which can replace natural gypsum to produce hemihydrate gypsum and is used in the building materials industry. However, it contains impurities, such as phosphate, fluoride, sulfate, and natural radioactive elements, which limit its application and seriously pollute the surrounding environment. To promote the application of PG, it is crucial to understand how pretreatment affects the properties of hemihydrate phosphogypsum (HPG). In this research, the mechanical properties and microstructure of HPG after pretreatment was investigated for improving the reuse of PG as a promising resource. The harmful phosphorus impurity in PG was efficiently removed with different concentrations of by H2C2O4. Then the hydration process and the hardening characteristics of HPG were studied in detail. The findings indicate that H2C2O4 alters the particle characteristics of HPG and has an impact on hemihydrate gypsum dissolution and dihydrate gypsum precipitation. According to studies, small amounts of H2C2O4 can remove impurities, promoting hydration and enhancing strength by opening the closed orifice of HPG, which would promote the dissolution of HPG and alter the morphology of gypsum from a tiny crystal to a thickened columnar structure. However, the addition of excessive H2C2O4 impacts the compression strength of HPG plaster and reduces the rehydration of HPG due to the formation of calcium oxalate on the gypsum crystal surface. These new findings may give insight into how H2C2O4 affects the performance of HPG. Therefore, to ensure the efficient utilization of PG, quality stabilization and improvement are crucial.

Geochemical Characteristics of Geothermal Fluids of a Deep Ancient Buried Hill in the Xiong’an New Area of China

The Xiong’an New Area is one of the areas with the richest geothermal resources in the east-central part of China. However, the genesis of the geothermal water in Jixianian carbonate reservoirs in this area is still unclear. This study conducted systematical geochemical and isotopic analyses of the geothermal water in the Jixianian carbonate reservoirs in the Rongcheng geothermal field and summed up the genetic mechanisms of geothermal fluids in deep geothermal reservoirs. The results are as follows: the geothermal water in the study area has a hydrochemical type of Cl·HCO3-Na and originates from meteoric water in the Taihang Mountains. The age of the geothermal water increases from 22 ka in the west to 45 ka in the east, and its transport rate is approximately 1.02 m/a. The Sr concentration and 87Sr/86Sr ratio of the geothermal fluids increase along their runoff direction and are related to the dissolution and filtration of minerals such as dolomite and gypsum and the decay of 87Rb in the Earth’s crust. The geothermal water is involved in deep circulation and occurs in a closed system. These results are consistent with those obtained using the PHREEQC inverse model. The reverse hydrogeochemical simulation results exhibited the precipitation of gypsum and halite, the dissolution of anorthite and quartz, and desulfurization. The geothermal reservoir temperatures were estimated to be 92–113 °C using a SiO2 geothermometer, and the thermal groundwater may have undergone deep circulation, with a prolonged retention time. Moreover, the groundwater occurs in a closed environment, strong water-rock interactions occur between the groundwater and related minerals, and the groundwater absorbs the heat from the deep heat source, thus forming geothermal water.

Insight into the Process and Mechanism of Water-Rock Interaction in Underground Coal Mine Reservoirs Based on Indoor Static Simulation Experiments.

During the storage of underground water reservoirs in coal mines, water–rock interaction occurred between mine water and collapsed rocks, resulting in improved mine water quality, but the water–rock process and mechanism have not been clarified. In this study, six sets of simulated experiments were designed to investigate the water–rock interaction between two types of roof collapse rocks and different water samples in the Daliuta coal mine. The ion ratio method and multivariate statistics are used to reveal the process and mechanism of water–rock interaction during the experimental process from the perspective of input and output water chemical characteristics and rock properties, respectively. The results show that the ion concentration of the effluent water is controlled by water–rock interaction, and the water–rock process mainly involves the dissolution of halite, silicate, pyrite, calcite, dolomite, magnesia chlorite, and gypsum precipitation and is accompanied by ion exchange. Mineral dissolution and precipitation are the most important factors affecting the ion abundance in the effluent. There are differences in the reaction rate, degree of reaction, and dissolution process during the experimental process of fine sandstone and mudstone. Fine sandstone is more reactive than mudstone in terms of reaction rate and degree of reaction, and fine sandstone is dissolved from surface pores to inside and around, while mudstone is generated in new dissolved pores. We found that rock type, ion concentration in the input water, and rock reaction period influence the water–rock interaction during the experiment. The results provide a reference for clarifying the water–rock interaction during the storage of underground water reservoirs in coal mines and predicting the water quality of the effluent.

Preservation and modification of the isotopic composition (18O/16O and 2H/1H) of structurally-bound hydration water of gypsum (CaSO4·2H2O) in aqueous solution

Early investigations on stable isotopes (δ18O and δD) of structurally-bound gypsum (CaSO4·2H2O) hydration water (GHW) suggested that soon after gypsum precipitation, its primary isotopic composition could be altered via gypsum re-crystallization or by isotope exchange by diffusion of water into the intact crystals. If this occurs, the use of stable isotopes of GHW as a paleoclimate proxy is compromised. Here we investigated the long-term (up to 6 years) stability of GHW in contact with aqueous solution by conducting isotopic exchange experiments at different temperatures and using varying gypsum grain size. We placed gypsum with known hydration water isotopic composition in 18O/D-enriched and 18O/D-depleted aqueous solutions and monitored any change in the stable isotopes of GHW with time. At low temperature (25 °C) and when the solution is in chemical equilibrium with the mineral, GHW preserves its primary isotopic composition after 2 years. In contrast, when the gypsum-solution system is out of chemical equilibrium, the δ18OGHW and δDGHW values are altered, first via gypsum re-crystallization from the solution and later by isotope exchange via diffusion. Importantly, δ18OGHW and δDGHW stabilized after 2 years to values that represent only an 8 % change relative to the original GHW and remain constant during the subsequent 4 years. Our results suggest that at low temperature the effect of isotope exchange on GHW is limited. At higher temperature (65 °C), chemical equilibrium is not attained after 2 years for fine-grained synthetic gypsum (<250 μm) and its isotopic values continues to change. In contrast, the δ18OGHW and δDGHW in experiments using fine-grained natural gypsum at 45 °C stabilized after 1 year and values changed less than 3 % with respect to initial conditions. Experiments with coarser-grained natural gypsum (1–2 mm) at 45 °C did not show measurable isotopic changes of the GHW, indicating the lack of gypsum dissolution/re-crystallization or diffusion isotopic exchange. We conclude that microcrystalline gypsum crystals (<250 μm) are more readily affected by diagenesis resulting from changes in the gypsum saturation state of the solution, whereas larger gypsum crystals are more likely to preserve their original isotopic compositions. Our results indicate that under certain conditions, GHW can preserve the isotopic composition of its parent fluid and provide valuable information about paleoclimate and paleo-hydrologic conditions.

Influence of Sulfates on Formation of Ettringite during Early C3A Hydration.

The hydration of C3A-gypsum systems was studied in the presence of various types of sulfates such as gypsum, hemihydrate and Na2SO4 in the first hour. The BET method combined with a DSC analysis enabled us to quantitatively characterize the amount of precipitated ettringite and its specific surface area along the hydration. It was found that sulfates not only affected the formation rate of ettringite, but also had a significant impact on the morphology of ettringite. For all the C3A-gypsum systems, a large part of the ettringite precipitated within the first 20 min and the specific surface area of the hydrated sample strongly increased within the first 5 min, whereas the specific surface area of ettringite gradually decreased along the C3A hydration reaction. Incorporating a small amount of Na2SO4 in the C3A-gypsum system could greatly promote the formation rate of ettringite in the first 20 min, and significantly decrease the specific surface area of ettringite. As hemihydrate was added to the C3A-gypsum system, two processes of ettringite precipitation and gypsum precipitation occurred. The nucleation and growth process of ettringite and gypsum resulted in the complex changes in the specific surface area of the hydrated sample, which first increased at the very beginning, then decreased and, finally, increased.