Research on the inhibitory properties and mechanism of carboxymethyl cellulose-modified sulfur quantum dots towards calcium sulfate and calcium carbonate.

An eco-friendly antimicrobial sulfur quantum dot scale inhibitor (CMC-SQDs) synthesized using carboxymethyl cellulose (CMC) showed strong inhibition of calcium sulfate (CaSO4) at a concentration just below 1 mg/L, with an inhibition efficiency exceeding 99 %. However, the precise interaction process between CMC-SQDs and CaSO4 remains unclear. This article investigates the effectiveness of SQDs in inhibiting the formation of CaSO4 and calcium carbonate (CaCO3) scales. Through static scale inhibition tests, molecular dynamics simulations, and quantum chemical calculations, the study aims to elucidate the different impacts of CMC-SQDs on CaSO4 and CaCO3 scale formation. The research focuses on understanding the relationship between the structural activity of CMC-SQDs and their scale-inhibiting performance and delving into the underlying mechanisms of scale inhibition. The findings describe the role of SQDs in a water-based solution, acting as persistent "nanodusts" that interact with calcium (Ca2+) ions and sulfate ions. CMC forms complexes with Ca2+ ions, and the presence of SQDs enhances the van der Waals force, indirectly increasing the resistance of associated ions and the binding energy on the surface of precipitated gypsum. Conversely, SQDs exhibit weak surface stability and have minimal binding energy when interacting with calcite, leading to limited occupation of available adsorption sites.

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.

Staged purification of phosphogypsum using pH-dependent separation process.

Phosphogypsum (PG) is an industrial by-product of the transformation of phosphate rocks. For decades, PG has been a source of environmental concern due to the massive amount produced thus far, i.e., 7 billion tons, with a current production rate of 200-280 million tons per year. Phosphate minerals contain various impurities that precipitate and concentrate within PG. These impurities hinder PG usability in various sectors. This paper aims to purify PG using an innovative process based on staged valorization of PG. Initially, PG dissociation by ethylenediaminetetraacetic acid (EDTA) was optimized. After screening of different parameters and monitoring the ionic conductivity of solutions, it was disclosed that a pH-dependent solubilization process in the presence of EDTA resulted in high solubility of PG, up to 11.82 g/100 mL at pH > 11. Subsequently, a recovery of the purified PG by selective precipitation of calcium sulfate dihydrate (CSD) from obtained filtrate through pH adjustment to 3.5 were investigated. An abatement of 99.34% Cr, 97.15% Cd, 95.73% P2O5, 92.75% Cu, 92.38% Al2O3, 91.16% Ni, 74.58% Zn, 72.75% F, 61.43% MgO, 58.8% Fe2O3, 56.97% K2O, and 55.41% Ba was achieved. The process relied on the variation of EDTA chelation properties towards monovalent, divalent, and trivalent cations at different pHs. According to the findings of this study, a staged purification process in the presence of EDTA is an effective method for removing impurities from the industrial PG.

Elution profiles of metronidazole from calcium sulfate beads.

BACKGROUND: Antibiotic beads are used to treat local bacterial infections by delivering high drug concentrations to infected tissue. OBJECTIVES: This study examined the elution characteristics of metronidazole from metronidazole-calcium sulfate (MCa) and metronidazole-calcium-potassium sulfate (MCaK) beads over 20 days and the antibacterial efficacy of the beads after storage. METHODS: The MCa and MCaK beads were prepared by mixing 250 mg of metronidazole and 10 g of calcium sulfate hemihydrate with water and a 3% potassium sulfate solution, respectively. The beads were placed in phosphate-buffered saline for the elution study. The metronidazole eluents were determined using high-performance liquid chromatography. The microstructures were examined by scanning electron microscopy (SEM), and the antimicrobial activity was evaluated by a microbioassay. RESULTS: For the 20-day study, the total amount of metronidazole released was greater in the MCa beads than in the MCaK beads by 6.61 ± 0.48 mg (89.11% ± 3.04%) and 4.65 ± 0.36 mg (73.11% ± 4.38%), respectively. The amounts of eluted drugs from the MCa and MCaK beads were higher than the minimum inhibitory concentration at 0.5 µg/mL against anaerobic bacteria at both 20 days and 14 days. SEM showed that calcium crystals on the outer surface had dissolved after elution, and thinner calcium crystals were prominent in the MCaK beads. The MCa and MCaK beads exhibited antibacterial activity after setting, followed by storage at room temperature or 4°C for 21 days. CONCLUSIONS: The MCa beads could release more drug than the MCaK beads, but all eluted metronidazole amounts were effective in controlling bacterial infections. Both metronidazole beads could be stored at ambient temperature or in a refrigerator.

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).

Chromium removal from chromium gypsum through microwave hydrothermal crystal phase regulation.

Chromium gypsum (CG) is a common hazardous waste formed in chromium salt or electroplating industries. The trapped or lattice-doped CrO42- in gypsum crystals are difficult to be reduced or removed by traditional methods, which will be re-oxidized or slowly released during long-term hypaethral storage. In this study, microwave hydrothermal treatment was applied to remove chromium in CG. Under optimal conditions (solid-liquid ratio of 1:5, 0.1 M sulfuric acid as liquid media, and 110 °C), over 99% of the chromium in CG can be removed within 10 min. XRD spectra indicated that 59.8% gypsum was transformed to from dihydrate gypsum to hemihydrate gypsum. The toxicity leaching test shows that chromium in CG is 377.0 mg/L before detoxification and 0.55 mg/L after detoxification, which proves that chromium in CG lattice can be efficiently removed. This work enables to significantly advance the dehydration phase transformation process of gypsum and release the heavy metal impurities within it more quickly and provides new possibilities to treat similar solid waste containing gypsum or minerals with hydration water.

The self-regulating on cohesion properties of calcium phosphate/ calcium sulfate bone cement improved by citric acid/sodium alginate.

Calcium phosphate cement (CPC) has attracted extensive interest from surgeons and materials scientists. However, the collapsibility of calcium phosphate cement limits its clinical application. In this work, a gel network of SA-CA formed by the reaction of citric acid (CA) and sodium alginate (SA) was introduced into the α-TCP/α-CSH composite. Furthermore, a high proportion of α-CSH provided more calcium sources for the system to combine with SA forming a gel network to improve the cohesion property of the composite, which also played a regulating role in the conversion of materials to HA. The morphology, physicochemical properties, and cell compatibility of the composites were studied with SA-CA as curing solution. The results show that SA-CA plays an important role in the compressive strength and collapse resistance of bone cement, and its properties can be regulated by changing the content of CA. When CA is 10 wt%, the mechanical strength is the highest, reaching 12.49 ± 2.03 MPa, which is 265.80% higher than water as the solidifying liquid. In addition, the cell experiments showed that the samples were not toxic to MC3T3 cells. The results of ALP showed that when SA-CA were used as curing solution, the activity of ALP was higher than that of blank sample, indicating that the composite bone cement could be conducive to the differentiation of osteoblasts. In this work, the α-CSH/α-TCP based composite regulated by gel network of SA-CA can provide a promising strategy to improve the cohesion of bone cement.

Enhancing dissolved inorganic phosphorous capture by gypsum-incorporated biochar: Synergic performance and mechanisms.

Excess nutrients, such as phosphorus (P), in watersheds jeopardize water quality and trigger harmful algal blooms. Using phosphorus sorption material (PSM) to capture P from wastewater and agricultural runoff can help recover nutrients and prevent their water pollution. In this study, a novel designer biochar was generated by pyrolyzing woody biomass pretreated with a flue gas desulfurization gypsum. The removal of dissolved inorganic phosphorus (DIP) by the gypsum-incorporated designer biochar was more efficient than the gypsum, suggesting the pretreatment of biomass with the gypsum results in a synergic effect on enhancing DIP capture. The maximum P adsorption capacity of the designer biochar was more than 200 mg g-1 , which is one order of magnitude greater than that of the gypsum. This result clearly showed that the designer biochar is a better PSM to capture DIP from nutrient-contaminated water compared to the gypsum. Post-sorption characterization indicated that the sorption of DIP by the gypsum-incorporated biochar involves multiple mechanisms. The precipitation reactions of calcium (Ca) cations and P anions to form CaHPO4 and Ca3 (PO4 )2 precipitates on the highly alkaline surface of the designer biochar were identified as a main mechanism. By contrast, CaHPO4 ·2H2 O is the only precipitated product for DIP sorption by the gypsum. In addition, the initial solution pH and the coexisting bicarbonate had less effects on the DIP removal by the designer biochar in comparison with the gypsum, which further confirms that the former is an excellent PSM to capture DIP from a variety of aquatic media.

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.

Study on the proportion of paste filling materials based on fluorogypsum.

A new type of paste filling material was created using fluorogypsum, a byproduct of hydrofluoric acid, as the raw material to address the issue of the filling material's high cost. The effects of five factors, including gangue, fly ash, fluorogypsum, lime content, and mass concentration on the physical and mechanical properties of filling material were also examined. In addition to analyzing slump and extension changes, the filler's mineral composition and microstructure were examined using SEM and XRD examinations. The results show that the best ratio of the developed filling material was 1000g coal gangue, 300g fly ash, 300g fluorogypsum, and 50g lime and mass concentration is 78%, and its compressive strength can reach 4-5MPa at 28 days. Raw materials such as gangue and fly ash will have a certain influence on the mechanical properties of the filling material. The hydration products of the developed filling material prepared by XRD and SEM were ettringite, calcium sulfate dihydrate, and calcium silicate hydrate gel. The new fluorogypsum-based paste filling material can be used to consolidate loose rock strata and fill goaf. It solves the problem of disposal of industrial waste fluoropgypsum and also solves the problem of coal mine gangue stacking, which has a far-reaching influence on ecological environment management.

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.

The study of self-regulating α-TCP based composite by micro/nano scaled silk fibroin and α-CSH on physicochemical and biological properties of bone cement.

A novel self-hardening α-tricalcium phosphate (α-TCP) bone cement complexed with different content of α-calcium sulfate hemihydrate (α-CSH) and micrometer hydroxyapatite mineralized silk fibroin (HA-SF) using micro/SF as curing liquid has been investigated in this work, which was capable of tunable setting time, degradation, mechanical property and ability to anti-washout. After addition 0 ∼ 25% α-CSH to the α-TCP cement with SFFs as curing liquid, it shortened the setting time of the modified composite to 10 ∼ 30 min. Furthermore, the addition of SFFs improved the compressive strength of the composite from 5.41 MPa to 9.44 MPa. The composites with both Na2HPO4 and SFFs as curing liquid showed good anti-collapse performance. The weight loss ratio of bone cement was -0.18 ∼ 12.08% in 4 weeks when the content of α-CSH in α-TCP/α-CSH was between 0 ∼ 25 wt%. During the degradation of α-CSH, the amorphous α-TCP were deposited as hydroxyapatite to formed a plate-like products on the surface of composite. Compared to the composite with Na2HPO4 solution as the curing liquid, alkaline phosphatase (ALP) activity of the composites using SFFs as curing liquid were maintained at high levels on the 14th day especially when the Ca/P ratio was 1.7. This study provides a theoretical basis for the regeneration of bone defects guided by bone cement materials.

Gypsum and carbon amendments influence carbon fractions in two soils in Ohio, USA.

Carbon sequestration as influenced by management practices such as soil amendments is not yet fully understood. Gypsum and crop residues can improve soil properties, but few studies have focused on their combined effect on soil C fractions. The objective of this greenhouse study was to determine how treatments affected different forms of C, i.e., total C, permanganate oxidizable C (POXC), and inorganic C in 5 soil layers (0-2, 2-4, 4-10, 10-25, and 25-40 cm). Treatments were glucose (4.5 Mg ha-1), crop residues (13.4 Mg ha-1), gypsum (26.9 Mg ha-1) and an untreated control. Treatments were applied to two contrasting soil types in Ohio (USA)-Wooster silt loam and Hoytville clay loam. The C measurements were made one year after the treatment applications. Total C and POXC contents were significantly higher in Hoytville soil as compared to Wooster soil (P < 0.05). Across both Wooster and Hoytville soils, the addition of glucose increased total C significantly by 7.2% and 5.9% only in the top 2 cm and 4 cm layers of soil, respectively, compared to the control treatment, and residue additions increased total C from 6.3-9.0% in various soil layers to a depth of 25 cm. Gypsum addition did not affect total C concentrations significantly. Glucose addition resulted in a significant increase in calcium carbonate equivalent concentrations in the top 10 cm of Hoytville soil only, and gypsum addition significantly (P < 0.10) increased inorganic C, as calcium carbonate equivalent, in the lowest layer of the Hoytville soil by 32% compared to the control. The combination of glucose and gypsum increased inorganic C levels in Hoytville soils by creating sufficient amounts of CO2 that then reacted with Ca within the soil profile. This increase in inorganic C represents an additional way C can be sequestered in soil.

Effect of phosphate rock acid insoluble residue on hydration process and mechanical properties of α-hemihydrate gypsum.

The application of α-hemihydrate gypsum (α-HH) is limited by several factors, such as a rapid hydration rate, short setting time, poor water resistance, and high cost. Especially because of the high production cost, although α-HH has excellent mechanical strength, it is rarely used in the field of building materials. In this study, based on the composition characteristics of new industrial solid waste (phosphate-rock acid-insoluble residue, PAIR) and to meet the needs of resource utilization, gypsum matrix composites were prepared by adding PAIR to α-HH to solve the problems of short setting time and poor water resistance of gypsum matrix composites and improve the comprehensive properties of α-HH products. The results show that when the different types of pores formed during the hydration of α-HH were filled with inert substances, such as silicon dioxide, insoluble phosphate, and calcium fluoride from PAIR, the proportion of mesopores in the composite products increased, whereas that of harmful macropores decreased. The compressive and flexural softening coefficients of the PAIR/α-HH system with 23% PAIR were the highest at 57.25 and 60.125%, respectively, and the water resistance of the system was improved; when the content of PAIR reaches 35%, the strength of the composite products decreased from 58.125 to 43.8 MPa. The HPO42- in PAIR partially replaces the SO42- ion in the dihydrate gypsum (DH) lattice to form a Ca(SO4, HPO4)•2H2O double salt, leading to the production of eutectic phosphorus. Soluble F-, Al3+, Mg2+, and phosphorus-containing substances in PAIR form a variety of complex ions in PAIR/α-HH aqueous solution, which are adsorbed onto the surface of the new DH phase; the crystal morphology changed from thick, long columns to clusters, thin rods, and plates, inhibiting the nucleation and growth of DH and changing its crystal growth rate and crystallization behavior. Therefore, the setting time of gypsum is prolonged; when 35% PAIR was added, the induced nucleation period of the PAIR/α-HH system was prolonged from 40 to 265 min, and the final setting time was from 12 to 360 min. By mixing solid waste PAIR, while the setting time of α-HH is prolonged, its water resistance is improved, and its mechanical strength is not significantly reduced, reducing the cost. From the perspective of economy and environmental protection, this study is a way to α-HH is widely used in the field of building materials.

Bead size has a greater effect on in vitro elution from antimicrobial-impregnated calcium sulfate beads than drug concentration.

OBJECTIVE: To compare the elution characteristics of amikacin-impregnated calcium sulfate (CaSO4) beads based on different drug concentrations and bead size configurations. SAMPLE: Six groups of amikacin-impregnated CaSO4 beads and one negative control group. PROCEDURES: Amikacin-impregnated CaSO4 beads were formed with either 500 mg (low-concentration) or 1 g (high-concentration) of amikacin per 15 g CaSO4 hemihydrate powder. The number of beads necessary to approximate 150 mg of amikacin for each of the 3 bead sizes (3 mm, 5 mm, and 7 mm) at both low and high concentrations were placed in 6 mL of phosphate-buffered saline. The saline was sampled at 14 time points over 28 days. Amikacin concentrations were determined using liquid chromatography-mass spectrometry. RESULTS: Smaller beads reached higher mean peak concentrations than larger beads (P < .0006). Peak concentrations for the low- and high-concentration groups were 20.5 mg/mL and 27.4 mg/mL, 13.1 mg/mL and 14.0 mg/mL, and 8.85 mg/mL and 6.75 mg/mL for the 3 mm, 5 mm, and 7 mm beads, respectively. Bead size also affected the length of therapeutic duration, lasting 6 days for the 3 mm and 5 mm beads and 9 days for the 7 mm beads. However, this was only statistically evident among the high-concentration beads (P < .044). Antimicrobial concentration within the same bead sizes did not affect elution. CLINICAL RELEVANCE: Amikacin-impregnated CaSO4 beads achieved extreme supratherapeutic eluent concentrations. While additional studies are needed, bead size significantly affected elution with smaller beads reaching higher peak concentrations and 7 mm, high-concentration beads demonstrating a longer therapeutic duration than smaller beads.

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.

Scytonin in gypsum endolithic colonisation: First Raman spectroscopic detection of a new spectral biosignature for terrestrial astrobiological analogues and for exobiological mission database extension.

Microbial colonisations of gypsum from Eastern Poland (Badenian, Middle Miocene age) were investigated by Raman microspectrometry with a rarely used excitation 445 nm excitation. Zones of microbial colonisation in selenitic gypsum endolithic outcrops comprise algae and cyanobacteria, which commonly contain the photosynthetic and protective pigments carotenoids, scytonemin and gloeocapsin. Diagnostic bands differing from those of scytonemin have been identified in black colonies in gypsum outcrops at Chotel Czierwony (Poland). Raman spectral signatures of scytonin are reported here for the first time in two endolithic specimens identified by the band wavenumbers predicted from DFT calculations. The strong or medium strong intensity Raman bands observed at 1603, 1585, 1559, 1435, and 1424 cm-1. Other weaker bands were located at 1676 (sh), 1660 (sh), 1649, 1399, 1362, 1342, 1320, 1294, 1272, 1259, and 1052 cm-1. The first observation of the Raman spectrum of scytonin in the cyanobacterial colonisation of gypsum facilitates the inclusion of this new biomolecular signature in the library of unique Raman spectra of biological pigments invaluable for detection of traces of life in frame of the planetary missions.

Mitigating soil salinity stress with titanium gypsum and biochar composite materials: Improvement effects and mechanism.

Titanium gypsum and biochar are considered effective amendments for mitigating soil salinity stress. However, the knowledge is inadequate regarding their efficiency and application as an improvement. In this study, TG-B composite was prepared by using industrial by-products titanium gypsum and biochar as raw materials and then modified by ball milling method, to characterize its microscopic characteristics and explore the improvement effect on saline-alkali soil and plant growth. Besides, we explored the mechanism of TG-B in improving saline-alkali soil and the dynamic balance of the solution reaction process. Our results showed that the CaSO4·2H2O particles in TG-B were finer, dispersed evenly, and contacted fully with soil gelatinous particles, which was more conducive to the improvement of saline-alkali soil. The results of TG-B with different ball milling ratios and different materials dosages indicated that the application rate of TG-B was 5%, and the optimum ratio of TG-B was TG: B (mass ratio) = 10:1, with the best soil improvement effect. The pot experiment proved that the indicators of indicating soil salinity such as pH, EC, SAR, and soluble Na+ decreased by 20.74%, 77.24%, 68.77%, and 44.70%, respectively, thus playing a good role in improving saline-alkali soil. In addition, pot experiments demonstrated that compared with the control group, the soil porosity and soil moisture content in the TG-B group increased by 15.95% and 38.71%, respectively, and further improve the structure and diversity of soil bacterial community when compared with titanium gypsum and biochar alone. Finally, the application of TG-B promoted the germination and growth of rice significantly through the synergistic effects of composite material components. These results all suggested that the application of TG-B was an effective strategy to improve soil salinity and promote plant growth. Therefore, it might provide new insights into the utilization of solid waste resources to improve saline-alkali lands.

Geochemical and mineralogical characterization of phosphogypsum and leaching tests for the prediction of the mobility of trace elements.

Phosphoric acid manufacturing generates large amounts of phosphogypsum (PG); a by-product generally disposed in the surface or evacuated in the seawater without any pretreatment. Phosphogypsum may host non-negligible amounts of valuable elements such as rare earth elements (REEs), which are critical elements on the global market. Surface disposal of PG may be a sustainable option to allow further processing in order to recover valuable elements. However, surface disposal exposes PG to atmospheric conditions (e.g., water, oxygen) which may increase their reactivity and accelerate the release rate of chemical species. This study aims to evaluate the trace element release rate from PG at atmospheric conditions. The studied PG samples were collected from a Moroccan phosphate treatment plant. The samples were characterized for their (i) chemical composition using inductively coupled plasma optical emission spectrometry (ICP-OES) for major elements and inductively coupled plasma mass spectrometry (ICP-MS) for trace elements; (ii) mineralogical composition by X-ray diffraction (XRD), scanning electron microscope equipped with energy-dispersive spectrometer (SEM-EDS), laser-induced breakdown spectroscopy (LIBS), and the mineral chemical composition was analyzed by electron probe microanalyzer (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS); and (iii) chemical species release rate using leaching tests over 24 h at 25 and 60 °C. Chemically, the PG samples were mainly composed of Ca (23.03-23.35 wt.%), S (17.65-17.71 wt.%), and Si (0.75-0.82 wt.%), and non-negligible amounts of trace elements: REE (344-349 ppm), Cd (3.5-7.4 ppm), U (9.3-27.4 ppm). Mineralogically, the PGs are mainly formed by gypsum (94.2-95.9 wt.%) and quartz (1.67-1.76 wt.%). In terms of chemical species release, the PGs showed a higher reactivity at 60 °C compared to room temperature with a higher release rate at the beginning of the leaching tests. Quantitatively, the PG samples released 3.57-4.11 µg/L/day of REE, 3.18-17.29 µg/L/day of U, and 1.67-5.49 µg/L/day of Cd. Based on the leaching results, we concluded that the trace elements (e.g., U, Cd, REE) are incorporated in PG crystal lattice, which may explain their low concentrations in the leachates. Consequently, total digestion of PG matrix is required to solubilize REE.

Mechanisms shaping the gypsum stromatolite-like structures in the Salar de Llamara (Atacama Desert, Chile).

The explanation of the origin of microbialites and specifically stromatolitic structures is a problem of high relevance for decoding past sedimentary environments and deciphering the biogenicity of the oldest plausible remnants of life. We have investigated the morphogenesis of gypsum stromatolite-like structures currently growing in shallow ponds (puquíos) in the Salar de Llamara (Atacama Desert, Northern Chile). The crystal size, aspect ratio, and orientation distributions of gypsum crystals within the structures have been quantified and show indications for episodic nucleation and competitive growth of millimetric to centimetric selenite crystals into a radial, branched, and loosely cemented aggregate. The morphogenetical process is explained by the existence of a stable vertical salinity gradient in the ponds. Due to the non-linear dependency of gypsum solubility as a function of sodium chloride concentration, the salinity gradient produces undersaturated solutions, which dissolve gypsum crystals. This dissolution happens at a certain depth, narrowing the lower part of the structures, and producing their stromatolite-like morphology. We have tested this novel mechanism experimentally, simulating the effective dissolution of gypsum crystals in stratified ponds, thus providing a purely abiotic mechanism for these stromatolite-like structures.