Selective Chiral Interactions between Hydrophilic/Hydrophobic Amino Acids and Growing Gypsum Crystals.

In nature, selective interactions between chiral amino acids and crystals are important for the formation of chiral biominerals and provide insight into the mysterious origin of homochirality. Here, we show that chiral amino acids with different hydrophilicities/hydrophobicities exhibit different chiral selectivity preferences in the dynamically growing gypsum [001] steps. Hydrophilic amino acids show a chiral selectivity preference for their d-isomers, whereas hydrophobic amino acids prefer their l-isomers. These differences in chiral recognition can be attributed to the different stereochemical matching between the hydrophilic and hydrophobic amino acids on the [001] steps of growing gypsum. These different chiral selectivities resulting from the amino acid hydrophilicity/hydrophobicity are confirmed by the experimental crystallization investigations from nano regulation on dynamic steps, to microscopic modification of gypsum morphology, and to macroscopic precipitation. Furthermore, as the hydrophilicity of amino acids increases, the disparity in chiral selection rises; conversely, the increase in the hydrophobicity of amino acids results in a decline in chiral selection. These insights improve our understanding of the interaction mechanism between amino acids and crystals and provide insights into the formation process of chiral biominerals and the origin of homochirality in nature.

Comparative analysis of cyanobacterial communities in gypsum outcrops: insights from sites in Israel and Poland.

Today, the biodiversity of endolithic microbial colonisations are only partly understood. In this study, we used a combination of molecular community metabarcoding using the 16S rRNA gene, light microscopy, CT-scan analysis, and Raman spectroscopy to describe gypsum endolithic communities in 2 sites-southern Poland and northern Israel. The obtained results have shown that despite different geographical areas, climatic conditions, and also physical features of colonized gypsum outcrops, both of these sites have remarkably similar microbial and pigment compositions. Cyanobacteria dominate both of the gypsum habitats, followed by Chloroflexi and Pseudomonadota. Among cyanobacteria, Thermosynechococcaceae were more abundant in Israel while Chroococcidiopsidaceae in Poland. Interestingly, no Gloeobacteraceae sequences have been found in Poland, only in Israel. Some of the obtained 16S rRNA gene sequences of cyanobacteria matched previously detected sequences from endolithic communities in various substrates and geographical regions, supporting the hypothesis of global metacommunity, but more data are still needed. Using Raman spectroscopy, cyanobacterial UV-screening pigments-scytonemin and gloeocapsin have been detected alongside carotenoids, chlorophyll a and melanin. These pigments can serve as potential biomarkers for basic taxonomic identification of cyanobacteria. Overall, this study provides more insight into the diversity of cyanobacterial endolithic colonisations in gypsum across different areas.

High-Performance Nanofiltration Membrane with Dual Resistance to Gypsum Scaling and Biofouling for Enhanced Water Purification.

Nanofiltration (NF) technology is pivotal for ensuring a sustainable and reliable supply of clean water. To address the critical need for advanced thin-film composite (TFC) polyamide (PA) membranes with exceptional permselectivity and fouling resistance for emerging contaminant purification, we introduce a novel high-performance NF membrane. This membrane features a selective polypiperazine (PIP) layer functionalized with amino-containing quaternary ammonium compounds (QACs) through an in situ interfacial polycondensation reaction. Our investigation demonstrated that precise QAC functionalization enabled the construction of the selective PA layer with increased surface area, enhanced microporosity, stronger electronegativity, and reduced thickness compared to the control PIP membrane. As a result, the QAC NF membrane exhibited an approximately 51% increase in water permeance compared to the control PIP membrane, while achieving superior retention capabilities for divalent salts (>99%) and emerging organic contaminants (>90%). Furthermore, the incorporation of QACs into the PIP selective layer was proved to be effective in mitigating mineral scaling by allowing selective passage of scale-forming cations, while simultaneously exhibiting strong antimicrobial properties to combat biofouling. The in situ QAC incorporation strategy presented in this study provides valuable guidelines for the fit-for-purpose design of the selective PA layer, which is crucial for the development of high-performance NF membranes for efficient water purification.

Enhanced solidification/stabilization (S/S) of fluoride in smelting solid waste-based phosphogypsum cemented paste backfill utilizing biochar: Mechanisms and performance assessment.

Phosphogypsum (PG) cemented paste backfill (CPB) is a primary non-hazardous method for treating PG. However, using traditional binders like cement increases global carbon emissions and mining operational costs while complicating the reduction of fluoride leaching risks. This study introduces a novel PG-based CPB treatment method using steel slag (SS) and ground granulated blast furnace slag (GGBFS) as binders, calcium oxide as an exciter, with biochar serving as a fluoride-fixing agent. We investigated the effect of biochar addition on the hydration and solidification/stabilization (S/S) of fluoride in SS and GGBFS-PG-based materials (SSPC). The results indicated that the optimal strength and performance for fluoride S/S were achieved with a biochar addition of 0.2 wt%. Compared to the control group without biochar, the strength increased by 54.3%, and F leaching decreased by 39.4% after 28 days of curing for SSPC. The addition of 0.2 wt% biochar facilitated heterogeneous nucleation and acted as a microfiller, enhancing SSPC's properties. However, excessive biochar reduced the compactness of SSPC. Additionally, the distribution of fluoride was strongly correlated with P, Ca, Fe, and Al, suggesting that fluoride S/S is linked to the formation of stable hydration products like fluorapatite, fluorite, and complexes such as [AlF6]3- and [FeF6]3-. These findings offer a promising approach for the safe treatment of PG and the beneficial reuse of solid waste from SS and GGBFS.

Vermicompost and flue gas desulfurization gypsum addition to saline-alkali soil decreases nitrogen losses and enhances nitrogen storage capacity by lowering sodium concentration and alkalinity.

Saline-alkali soils have poor N storage capacity, high N loss and inadequate nutrient supply potential, which are the main limiting factors for crop yields. Vermicompost can increase organic nutrient content, improve soil structure, and enhance microbial activity and function, and the Ca2+ in flue gas desulfurization (FGD) gypsum can replace Na+ and neutralize alkalinity in saline-alkali soils though chemical improvement. This study aimed to determine if vermicompost and FGD gypsum addition could improve the N storage capacity through decreasing NH3 volatilization and 15N/NO3- leaching from saline-alkali soils. The results indicate that the combined application of vermicompost and FGD gypsum led to the displacement and leaching Na+ in the upper soil layer (0-10 cm), as well as the neutralization of HCO3- by the reaction with Ca2+. This treatment also improved soil organic matter content and macroaggregate structure. Also, these amendments significantly increased the abundance of nifH and amoA genes, while concurrently decreasing the abundance of nirK gene. The structural improvements and the lowering of Na + concentration in and alkalinity decreased cumulative NH3 volatilization, and leaching of 15N and NO3- to the deep soil layer (20-30 cm). FGD gypsum increased the 15N stocks and inorganic N stocks of saline-alkali soil, whereas vermicompost not only increased the 15N and inorganic N stocks, but also increased the total N stocks, the combination of vermicompost and FGD gypsum can not only increase the available N storage capacity, but also enhance the potential for N supply. Therefore, vermicompost and FGD gypsum decrease N loss and increase N storage capacity through structural improvement, and lowering of Na+ concentration and alkalinity, which is crucial for improving the productivity of saline-alkali soil.

Highly efficient recovery of phosphate and fluoride from phosphogypsum leachate: Selective precipitation and adsorption.

Phosphogypsum, a typical by-product in the phosphorus chemical industry, could generate a large amount of leachate containing phosphate and fluoride in the process of rainfall and long-term stacking, which not only causes serious environmental pollution, but also leads to a waste of resources. In this study, a united treatment of calcium hydroxide precipitation and lanthanum zeolite (La-ZFA) adsorption was proposed to achieve the recovery of phosphate and fluoride from phosphogypsum leachate. In phosphogypsum, most phosphorus could be leached except P in the residual occurrence form, while for fluoride, only water-soluble F could be effectively leached. The optimum leaching amounts of phosphate and fluoride were 22.59 and 4.64 mg/g, respectively, at liquid-solid ratio of 400:1, leaching time of 120 min, pH of 6.0, particle size of >200 mesh (<0.075 mm), and leaching temperature of 25°C. Using Ca(OH)2 as the precipitant, the phosphate could be precipitated selectively from phosphogypsum leachate by controlling pH and time, and the concentrations of it decreased significantly to 0.29 mg/L at pH 10.0, with a removal efficiency of 99.48%. XRD, SEM and Visual MINTEQ software analysis proved that the main component of the precipitate was hydroxyapatite (Ca5(PO4)3(OH)). After P precipitation, a series of sorbents for fluoride were investigated, and La-ZFA sorbent was chosen and utilized to recover the fluoride from the leachate through a cyclic fixed-bed column. The efficiency of La-ZFA was basically not affected by the high concentration sulfate, and it can selectively adsorb fluoride from phosphogypsum leachate, leading to a final fluoride concentration of 0.29 mg/L in the effluent. The characterization demonstrated that fluoride might be adsorbed onto the La-ZFA via ligand exchange with hydroxy groups. The proposed method in this study is expected to sequentially recover phosphate and fluorine from the leachate of phosphogypsum, and it has great guiding significance for resource utilization and management of phosphogypsum.

Synergistic effects of Co-pyrolysis on the immobilization and transformation of lead (Pb), chromium (Cr), nickel (Ni), and fluorine (F) in phosphogypsum-biomass mixtures.

Co-pyrolysis of biomass with phosphogypsum (PG) presents an effective strategy for facilitating the recycling of PG resources. However, it is crucial to note the environmental threats arising from the presence of Pb, Cr, Ni, and F in PG. This study investigated the effect of immobilization and transformation of four elements during co-pyrolysis with biomass and its components. The co-pyrolysis experiments were carried out in a tube furnace with a mixture of PG and corn stover (CS), cellulose (C), lignin (L), glucose (G). Co-pyrolysis occurred at varying temperatures (600 °C, 700 °C, 800 °C, and 900 °C) and different addition ratios (10%, 15%, and 20%). The results indicated that an increase in co-pyrolysis temperature was more conducive to the immobilization and transformation of harmful elements in PG, demonstrating significant efficacy in controlling F. Additionally, the addition of biomass components exerts a significant impact on inhibiting product toxicity, with small molecules such as glucose playing a prominent role in this process. The mechanism underlying the control of harmful elements during co-pyrolysis of PG and biomass was characterized by three main aspects. Firstly, biomass components have the potential to melt-encapsulate the harmful elements in PG, leading to precipitation. Secondly, the pyrolysis gas produced during the co-pyrolysis process contributes to the formation of a rich pore structure in the product. Finally, this process aids in transforming hazardous substances into less harmful forms and stabilizing these elements. The findings of this study are instrumental in optimizing the biomass and PG blend to mitigate the environmental impact of their co-pyrolysis products.

Environmental assessment of phosphogypsum: A comprehensive geochemical modeling and leaching behavior study.

Understanding the variations in the geochemical composition of phosphogypsum (PG) destined for storage or valorization is crucial for assessing the safety and operational efficacy of waste management. The present study aimed to investigate the environmental behavior of PG using different leaching tests and to evaluate its geochemical behavior using geochemical modeling. Regarding the chemical characterization, the PG samples were predominantly composed of Ca (23.03-23.35 wt%), S (17.65-17.71 wt%), and Si (0.75-0.82 wt%). Mineralogically, the PG samples were primarily composed of gypsum (94.2-95.9 wt%) and quartz (1.67-1.76 wt%). Moreover, the automated mineralogy revealed the presence of apatite, fluorine and malladrite phases. The overall findings of the leaching tests showed that PG could be considered as non-hazardous material according to US Environmental Protection Agency limitations. However, a high leachability of elements at a L/S of 2 under acidic conditions ([Ca] = 166.52-199.87 mg/L, [S] = 207.9-233.59 mg/L, [F] = 248.62-286.65 mg/L) is observed. The weathering cell test revealed a considerable cumulative concentration over 90 days indicating potential adverse effects on the nearby environment (S: 8000 mg/kg, F: 3000 mg/kg, P: 700 mg/kg). Based on these results, it could be estimated that the surface storage of PG could have a serious impact on the environment. In this context, a simulation model was developed based on weathering cell results showed encouraging results for treating PG leachate using CaO before its disposal. Additionally, PHREEQC was used to analyze the speciation of major elements and calculate mineral phase saturation indices in PG leaching solutions. The findings revealed pH-dependent speciation for Ca, S, P, and F. The study identified gypsum, anhydrite, and bassanite as the key phases governing the dissolution of these elements.

A Comparative Evaluation of Three Methods of Disinfection of Gypsum Casts and the Changes in Surface Roughness and Dimensional Accuracy after Disinfection-An Ex Vivo Study.

BACKGROUND: One of the major problems of everyday dental practice is cross-contamination. It can place office personnel, dentists, and patients at risk of acquiring serious illness. Disinfection helps in controlling this cross-contamination to an extent. The evaluation was done to find the efficient disinfection method on gypsum casts. AIMS: The aim of this study is to evaluate and compare the efficacy of three methods of disinfection of gypsum casts, namely, chemical disinfection by immersion, spray method, and microwave method, and also to evaluate and compare changes in surface roughness and dimensional accuracy between the three methods after disinfection. MATERIALS AND METHODS: Ex vivo and experimental study. Thirty participants were selected, and impressions of the maxillary arch were made using polyvinyl siloxane impression material. Ninety type IV die stone gypsum casts were poured. It was divided into three groups and was subjected to chemical disinfection by immersion and spray methods, and microwave method. The disinfected casts were evaluated for microbial growth, surface roughness, and dimensional accuracy. It was performed by using the one-way analysis of variance test and paired t-test followed by the Kruskal - Wallis test and Wilcoxon signed rank test (α = 0.05). RESULTS: Microwave disinfection was more effective than both immersion and spray chemical disinfection methods (P < 0.010 and <0.001). The surface roughness of the microwave-irradiated casts had significantly increased after disinfection. However, there were no significant dimensional changes by any of the methods of disinfection. CONCLUSION: Within the limitations of the study, the microwave method of disinfection is more effective in eradicating microorganisms when compared to chemical methods of disinfection by immersion and spray methods.

Irrigation water quality, gypsum, and city waste compost addition affect P dynamics in saline-sodic soils.

The amendments used for sodicity reclamation also profoundly influence P dynamics and leaching losses. This study characterized the effect of irrigation water quality on P dynamics and leaching from saline-sodic soil during reclamation utilizing gypsum alone or in combination with manure and city compost. Changes in properties of unleached and leached soils were fitted with labile P pools using redundancy analysis. The relation between leachate properties and P loss was explained by means of monitoring leachate properties up to ten pore volumes. During incubation, the water-extractable P (PH2O) concentration was greater than Olsen's P (PNaHCO3) in all treatments. The PNaHCO3 decreased in proportion to the amount of gypsum applied. Applying the organics with gypsum increased the PNaHCO3, PH2O, and organic P concentration compared to gypsum alone. The labile P pools in soil were positively correlated with HCO3- content (r = 0.39-0.77; P < 0.05) of leached and unleached soils. Adding gypsum and compost caused a 10-14% decrease in cumulative P leaching. The cumulative P leaching were greater with rainwater compared to saline water of SAR (sodium adsorption ratio) 5 and 15. The CO32-, HCO3-, pH, and SO42-content of the leachate explained about 71% variability in total P leaching (adj. R2 = 0.71; P < 0.001). This study concludes that low electrolyte water had a greater risk of P leaching and associated environmental pollution. Leaching of the saline-sodic soil amended with gypsum and city waste compost with low SAR saline water can reduce P leaching compared to good quality rainwater.

Recovery of zinc and extraction of calcium and sulfur from zinc-rich gypsum residue by selective reduction roasting combined with hydrolysis.

A novel process that includes selective reduction roasting followed by hydrolysis was proposed in this work to recover zinc, and efficiently extract calcium and sulfur from hazardous zinc-rich gypsum residue (ZGR) waste for high-purity of CaCO3 and sulfur production. The selective reduction behaviors of ZGR during the reduction roasting were investigated in detail based on thermodynamic analysis and roasting experiments. The effect of roasting temperature, carbon dosage and time on the selective reduction of ZGR was comprehensively investigated, and the results indicated that ZnO and CaSO4 in the ZGR can be selectively reduced to Zn(g) and CaS, respectively. The volatile Zn(g) was oxidized to ZnO and enriched in the dust, which can be used as a secondary zinc resource. Moreover, the hydrolysis behaviors and leaching kinetic of CaS during hydrolysis were studied intensively. Results depicted that in the H2S-H2O system, the CaS in the roasted product can be selectively and efficiently dissolved into the leachate. Furthermore, the kinetic analysis revealed that the hydrolysis of CaS conformed to the internal diffusion reaction control model in the shrinking core model and the apparent activation energy Ea = -12.02 kJ/mol. The obtained hydrolysate with low impurities could be used to capture CO2 for the production of high-purity sulfur and CaCO3. Iron and other impurities in the roasted product were concentrated into the leaching slag in the form of metallic iron and akermanite. The whole process realized the recovery of zinc, and the selective and effective extraction of calcium and sulfur, which could provide an alternative process for the large-scale treatment of these hazardous wastes.

Enhancing bauxite residue properties for plant growth: Gypsum and organic amendment effects on chemical properties of soil and leachate.

Here, we assess the effects of gypsum and local organic waste as amendments to non-weathered, filter-pressed bauxite residue (BR) to improve its properties and support plant growth. In addition, we monitored the leachate quality of the amended BR under progressive leaching that simulated precipitation conditions in Northern Brazil. Free-draining column tests consisting of BR amended with gypsum and organic waste, at 5% and 10% w/w, respectively, were leached for 8 weeks to assess the effects on the chemical composition of BR and the leachates. Adding gypsum to BR reduced the exchangeable sodium (Na) percentage (ESP) from approximately 79%-48%, whereas adding only organic waste had smaller effects on ESP (from ∼79% to âˆ¼ 70%). The mean leachate pH ranged from 8.7 to 9.4 for the gypsum, and organic waste amended BR, while this was 10.3 in the leachate of the unamended BR. The treatments had similar trends of electrical conductivity throughout the experiments and were below 2 dS/cm after 8 weeks, when ∼1.700 mm simulated precipitation had leached. Aluminium (Al), Arsenic (As), and Vanadium (V) concentrations in leachates of BR with gypsum, either alone or in combination with organic waste, were significantly lowered than in leachate of non-amended BR. By contrast, metal concentrations increased if organic waste was added to BR. We conclude that amending BR with gypsum, in combination with organic waste, significantly improves the chemical properties of the solid phase and achieved rehabilitation goals for SAR and EC of the leachates after 8 weeks of leaching. However, despite high leaching rates, rehabilitation goals for pH and ESP were not achieved with gypsum either alone or combined with organic waste.

Examination of the environmental behavior of phosphogypsum with the application of lab-scale experiment.

Phosphogypsum (PG) is a reject of the phosphoric acid production process in phosphate fertilizer industries. The process results in the production of relatively large quantities of PG that it might cause serious environmental and human health concerns. The data of a laboratory investigation of PG are presented here. Lab-scale experiments with lysimeters were conducted in order to simulate and examine the environmental characteristics and the temporal behavior of PG leachates in terms of physicochemical characteristics and chemical composition. Based on the results, leachates from already deposited for many years PG or its mixture with marble powder, seemed to have better pH and conductivity values and lower elemental concentrations compared to leachates from freshly disposed PG. However, the leachates characteristics improve and stabilize in both cases after four days of irrigation or of 1080-1240 mm of rain. Most major elements were found to have minimal leachability, and the material satisfied the environmental limits for its disposal at landfills for inert and non-hazardous wastes.

Interactions between flue gas desulfurization gypsum and biochar on water infiltration characteristics and physicochemical properties of saline-alkaline soil.

The application of flue gas desulfurization gypsum (FGDG) improves the soil structure, reduces soil pH, and accelerates soil salt leaching. Biochar amendment to soil can affect the soil infiltration rate, increase soil porosity, decrease soil bulk density, and enhance the water retention capacity. This study investigated the interactive effect of FGDG and biochar on water infiltration characteristics and physicochemical properties as well as determined the optimal amendment rate as a saline-alkaline soil conditioner. Seven experimental schemes were designed, and the newly reclaimed cultivated soil from Pingtan Comprehensive Experimental Zone in Fujian Province, China, was used in an indoor soil column experiment to simulate soil infiltration. Five models were employed to describe the infiltration process. The power function was used to represent the dynamic process of the wetting front. The conclusions of this study are as follows: (1) there was a reduction in the infiltration capacity of saline-alkaline soil (sandy soil) in each treatment, and the application of FGDG alone had the highest inhibition effect compared to the control (CK). The Kostiakov model provides the best fit for the experimental data of soil cumulative infiltration. (2) All treatments increased the total porosity and water content of saline-alkali soil, with the combined application of FGDG and biochar found to be more effective. (3) The application of FGDG alone or in combination with biochar decreased the pH and increased the electrical conductivity of the saline-alkali soil significantly, with the combined application having the most significant effect. In contrast, soil amended with biochar alone had minimal effect on the pH and EC of the soil. (4) The best improvement ratio was achieved with the F1B2 combination (75 g/kg FGDG + 30 g/kg biochar).

Evaluation of correlated studies using liquid cell and cryo-transmission electron microscopy: Hydration of calcium sulphate and the phase transformation pathways of bassanite to gypsum.

Insight into the nucleation, growth and phase transformations of calcium sulphate could improve the performance of construction materials, reduce scaling in industrial processes and aid understanding of its formation in the natural environment. Recent studies have suggested that the calcium sulphate pseudo polymorph, gypsum (CaSO4 ·2H2 O) can form in aqueous solution via a bassanite (CaSO4 ·0.5H2 O) intermediate. Some in situ experimental work has also suggested that the transformation of bassanite to gypsum can occur through an oriented assembly mechanism. In this work, we have exploited liquid cell transmission electron microscopy (LCTEM) to study the transformation of bassanite to gypsum in an undersaturated aqueous solution of calcium sulphate. This was benchmarked against cryogenic TEM (cryo-TEM) studies to validate internally the data obtained from the two microscopy techniques. When coupled with Raman spectroscopy, the real-time data generated by LCTEM, and structural data obtained from cryo-TEM show that bassanite can transform to gypsum via more than one pathway, the predominant one being dissolution/reprecipitation. Comparisons between LCTEM and cryo-TEM also show that the transformation is slower within the confined region of the liquid cell as compared to a bulk solution. This work highlights the important role of a correlated microscopy approach for the study of dynamic processes such as crystallisation from solution if we are to extract true mechanistic understanding.

Material characteristics of historic scagliola interiors in Vienna: A view through the microscope.

Composition and microstructure of four Viennese scagliola samples, originating from the early 18th to early 20th centuries, were analysed by different methods of microscopy. Results indicate a similar composition in all samples; only minor differences could be observed in the porosity and grain-size-distribution. While, the calcium sulphate raw material was fired at low temperatures (<200°C), the presumable presence of anhydrite II in two samples may indicate hot spots (200-300°C) during the calcination. To achieve 'marble-like' patterns mineral pigments were used to dye the ground mass. The first results show that scagliola surfaces of this study were produced by using the same or very similar technology between the 18th and early 20th centuries. The present study focuses on scagliola interiors in Vienna, Austria from different stylistic periods between the early 18th and early 20th centuries. Scagliola, also called stucco marble, imitates natural stone. It is produced by a mixture of gypsum (CaSO4 ·2H2 O), different pigments, animal glue and water. In the history of interior design, the material played an important role in the 18th and 19th centuries in Central Europe. The aim of the research was a detailed investigation of four selected samples in order to identify the raw materials and manufacturing technology of the stucco marbles used over time in Vienna. As a first step thin sections (i.e. polished, transparent samples with a thickness of 0.03 mm) were prepared from the samples and analysed by different microscopic techniques. All samples showed similarities in their bulk properties, but detailed investigations revealed also some differences in their mineralogical composition. The gypsum binders contained typical air voids and so-called secondary pores which were formed by dissolving larger binder-related particles during the preparation of the mixture. The macroporosity (i.e. the amount of the pores in the samples which are larger than 0.01 mm) measured on microscopic images varied in a narrow range between 14.1% and 19.3%. The raw materials of all samples were fired at relatively low temperatures (i.e. below 200°C), but in two samples we could also determine a few anhydrite (CaSO4 ) crystals that normally form at higher temperatures in the kiln. This indicates that the distribution of temperature in the kiln was heterogeneous during the firing process. The amount and appearance of some minor mineral constituents such as dolomite (CaMg[CO3 ]2 ) and celestine (SrSO4 ) suggest that they were naturally occurred in the raw material and not deliberately added to the binder as a filling material. To achieve different colour hues and imitate natural stone surfaces, fine-grained mineral pigments and charcoal powder were used. Although we have no distinct information about the gypsum sources of these stucco marbles, several small historical gypsum quarries existed southwest of Vienna. Some of them were already in operation in the 16th century, thus a local gypsum occurrence used as a raw material is very probable. Due to the fact that the main features of the analysed samples were very similar, we assume that the scagliola surfaces of this study were produced by using the same or very similar technology between the 18th and early 20th centuries.

Electron Paramagnetic Resonance and Synchrotron X-ray Absorption Spectroscopy for Highly Sensitive Characterization of Calcium Arsenates.

Calcium arsenates such as pharmacolite (CaHAsO4·2H2O), haidingerite (CaHAsO4·H2O), and weilite (CaHAsO4) are important sinks for arsenic in mine tailings as well as other natural and contaminated sites and are useful for reducing the mobility and bioavailability of this toxic metalloid in the environment. However, calcium arsenates usually occur in trace amounts dominated by other phases, making their detection, identification, and quantification challenging. In this contribution, pharmacolite, haidingerite, and weilite are shown to exhibit subtle but distinct postedge differences in As K-edge X-ray absorption near-edge structure (XANES) spectra and feature characteristic [AsO3]2-, [AsO4]2-, and [AsO4]4- radicals, all derived from the diamagnetic [HAsO4]2- precursor during γ-ray irradiation, in electron paramagnetic resonance (EPR) spectra. In particular, the 75As (nuclear spin I = 3/2 and natural isotope abundance = 100%) hyperfine coupling constants of the [AsO3]2- radicals in pharmacolite and haidingerite as well as other minerals (e.g., calcite and gypsum) are clearly distinct, allowing the unambiguous identification of calcium arsenates by the EPR technique readily at ∼0.1 wt %. Similarly, linear combination fittings of As K-edge XANES spectra demonstrate that pharmacolite and haidingerite at ∼0.1 wt % each in gypsum-rich mixtures can be detected and quantified as well. Therefore, a combination of the EPR and XANES techniques is a powerful approach for the highly sensitive characterization of calcium arsenates in the quest for the safe management and remediation of arsenic contamination. This work demonstrates the highly sensitive characterization of calcium arsenates by integrated electron paramagnetic resonance and synchrotron X-ray absorption spectroscopy.

Utilization path of bulk industrial solid waste: A review on the multi-directional resource utilization path of phosphogypsum.

Phosphogypsum is one of the hottest issues in the field of environmental solid waste treatment, with complex and changeable composition. Meanwhile, phosphogypsum contains a large number of impurities, thus leading to the low resource utilization rate, and it can only be stockpiled in large quantities. Phosphogypsum occupies a lot of land and poses a serious pollution threat to the ecological environment. This paper mainly summarizes the existing pretreatment and resource utilization technology of phosphogypsum. The pretreatment mainly includes dry method and wet method. The resource utilization technology mainly includes building materials, chemical raw materials, agriculture, environmental functional materials, filling materials, carbon sequestration and rare and precious extraction. Although there are many aspects of resource utilization of phosphogypsum, the existing technology is far from being able to consume a large amount of accumulated and generated phosphogypsum. Through the analysis, the comparison and mechanism analysis of the existing multifaceted and multi-level resource treatment technologies of phosphogypsum, the four promising resource utilization directions of phosphogypsum are put forward, mainly including prefabricated building materials, eco-friendly materials and soil materials, and new green functional materials and chemical fillers. Moreover, this paper summarizes the research basis of multi field and all-round treatment and disposal of phosphogypsum, which reduces repeated researches and development, as well as the treatment cost of phosphogypsum. This paper could provide a feasible research direction for the resource treatment technology of phosphogypsum in the future, so as to improve the consumption of phosphogypsum and reduce environmental risks.

Flotation purification of waste high-silica phosphogypsum.

High-silica phosphogypsum (PG) is a kind of industrial by-product with great utilization potential. However, it is difficult to reuse PG directly due to the related gangue minerals (e.g., SiO2), and thus efficient purification is required to allow its further applications. Herein, a typical high-silica phosphogypsum waste was purified by a new "reverse-direct flotation" method. The organic matters and fine slimes were removed by reverse flotation, and then, the silica impurity was removed by direct flotation. Via the closed-circuit flotation process, the whiteness of the PG concentrate is improved from 33.23 to 63.42, and the purity of gypsum in the PG concentrate increases from 83.90% to 96.70%, with a gypsum recovery of 85%. Additionally, the content of SiO2 is significantly reduced from 11.11% to 0.07%. In-depth investigations suggest that the difference in the floatability of gypsum and quartz is prominently intensified by flotation reagents at pH = 2-2.5, and thus leads to good desilication performance. Further characteristics of the PG concentrate prove that impurities have been well removed, and the PG concentrate meets the requirement of related standards for gypsum building materials. The flotation method reported here paves the way for the purification of high-silica phosphogypsum, which can be extended to the purification and value-added reutilization of other industrial solid wastes.

Potential uses of phosphogypsum: A review.

Phosphogypsum (PG) is a by-product of the phosphate fertilizer industry that is produced during the phosphoric acid production process. Annual global PG production ranges between 100 to 300 Mt, with only 15% of that utilized while the rest is usually placed on large dumps with potential serious human and environmental impacts. The aim of this study is to give an overview and to evaluate the existing and potential uses of PG that extend from soil stabilization to cement and chemical industry and for agricultural to geotechnical, human impacts, and environmental applications. More specifically, PG can be used as a substitute in the cement industry, in building materials and in road construction, as a fertilizer for soil improvement, as a raw material for the production of some chemicals, and as a backfilling material for the rehabilitation of abandoned mines and quarries, while the recovery of gypsum and the extraction of rare earth elements signifies the potential importance of PG to cyclic economy. The paper offers an extensive overview of existing and potential uses of PG, discusses their adequacy, and reveals that PG can be widely used under certain conditions, rather than disposed as waste in stockpiles.