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32 pages, 711 KB  
Review
Recent Advances in Particle Design for High-Concentration Protein Suspension Injectables
by Yijing Huang, Chanakya D. Patil, Kinnari Santosh Arte, Jiaying Liu, Haichen Nie, Qi Tony Zhou and Li Lily Qu
Pharmaceutics 2026, 18(4), 450; https://doi.org/10.3390/pharmaceutics18040450 - 7 Apr 2026
Cited by 1 | Viewed by 2911
Abstract
Subcutaneous administration has become an increasingly important route for delivering protein therapeutics, driven by patient convenience and the growing use of self-administration devices. However, conventional subcutaneous injection systems are typically limited to injection volumes of approximately 1–2 mL, posing significant formulation challenges for [...] Read more.
Subcutaneous administration has become an increasingly important route for delivering protein therapeutics, driven by patient convenience and the growing use of self-administration devices. However, conventional subcutaneous injection systems are typically limited to injection volumes of approximately 1–2 mL, posing significant formulation challenges for protein drugs requiring high therapeutic doses. Monoclonal antibodies (mAbs), for example, often require concentrations exceeding 100 mg/mL to enable subcutaneous delivery, which introduces challenges related to limited solubility, elevated viscosity, and an increased risk of physical and chemical instability. Therefore, high-concentration protein suspensions have emerged as a promising formulation strategy to overcome these limitations and enable subcutaneous administration of high-dose proteins. In such systems, therapeutic protein solid particles are suspended in vehicles in which they are insoluble, giving rise to unique considerations related to particle properties, protein stability, and suspension behaviors such as viscosity, injectability, and sedimentation. Accordingly, multiple particle production approaches have been explored to enable the development of ultra-high-concentration protein suspensions (>200 mg/mL). This review article aims to provide a comprehensive overview of particle formation techniques and the relationships between key particle properties and suspension performance attributes relevant to the development of high-concentration protein suspensions for injectable applications, as well as future directions in this field. Full article
(This article belongs to the Special Issue Recent Advances in Injectable Formulations)
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22 pages, 1916 KB  
Article
Freeze-Dried Probiotic Fermented Camel Milk Enriched with Ajwa Date Pulp: Evaluation of Functional Properties, Probiotic Viability, and In Vitro Antidiabetic and Anticancer Activities
by Sally S. Sakr and Hassan Barakat
Foods 2025, 14(15), 2698; https://doi.org/10.3390/foods14152698 - 31 Jul 2025
Cited by 7 | Viewed by 4051
Abstract
Noncommunicable diseases (NCDs) like diabetes and cancer drive demand for therapeutic functional foods. This study developed freeze-dried fermented camel milk (FCM) with Ajwa date pulp (ADP), evaluating its physical and functional properties, probiotic survival, and potential benefits for diabetes and cancer. To achieve [...] Read more.
Noncommunicable diseases (NCDs) like diabetes and cancer drive demand for therapeutic functional foods. This study developed freeze-dried fermented camel milk (FCM) with Ajwa date pulp (ADP), evaluating its physical and functional properties, probiotic survival, and potential benefits for diabetes and cancer. To achieve this target, six FCM formulations were prepared using ABT-5 starter culture (containing Lactobacillus acidophilus, Bifidobacterium bifidum, and Streptococcus thermophilus) with or without Lacticaseibacillus rhamnosus B-1937 and ADP (12% or 15%). The samples were freeze-dried, and their functional properties, such as water activity, dispersibility, water absorption capacity, water absorption index, water solubility index, insolubility index, and sedimentation, were assessed. Reconstitution properties such as density, flowability, air content, porosity, loose bulk density, packed bulk density, particle density, carrier index, Hausner ratio, porosity, and density were examined. In addition, color and probiotic survivability under simulated gastrointestinal conditions were analyzed. Also, antidiabetic potential was assessed via α-amylase and α-glucosidase inhibition assays, while cytotoxicity was evaluated using the MTT assay on Caco-2 cells. The results show that ADP supplementation significantly improved dispersibility (up to 72.73% in FCM15D+L). These improvements are attributed to changes in particle size distribution and increased carbohydrate and mineral content, which facilitate powder rehydration and reduce clumping. All FCM variants demonstrated low water activity (0.196–0.226), indicating good potential for shelf stability. The reconstitution properties revealed that FCM powders with ADP had higher bulk and packed densities but lower particle density and porosity than controls. Including ADP reduced interstitial air and increased occluded air within the powders, which may minimize oxidation risks and improve packaging efficiency. ADP incorporation resulted in a significant decrease in lightness (L*) and increases in redness (a*) and yellowness (b*), with greater pigment and phenolic content at higher ADP levels. These changes reflect the natural colorants and browning reactions associated with ADP, leading to a more intense and visually distinct product. Probiotic survivability was higher in ADP-fortified samples, with L. acidophilus and B. bifidum showing resilience in intestinal conditions. The FCM15D+L formulation exhibited potent antidiabetic effects, with IC50 values of 111.43 μg mL−1 for α-amylase and 77.21 μg mL−1 for α-glucosidase activities, though lower than control FCM (8.37 and 10.74 μg mL−1, respectively). Cytotoxicity against Caco-2 cells was most potent in non-ADP samples (IC50: 82.22 μg mL−1 for FCM), suggesting ADP and L. rhamnosus may reduce antiproliferative effects due to proteolytic activity. In conclusion, the study demonstrates that ADP-enriched FCM is a promising functional food with enhanced probiotic viability, antidiabetic potential, and desirable physical properties. This work highlights the potential of camel milk and date synergies in combating some NCDs in vitro, suggesting potential for functional food application. Full article
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20 pages, 4029 KB  
Article
Dynamic Migration Characteristics of Potassium During Agricultural Waste Combustion and the Mechanism of Combined Chlorine–Sulfur Action
by Jian Li, Yunlong Zhou, Guochao Zhao and Qixin Yuan
Molecules 2025, 30(12), 2495; https://doi.org/10.3390/molecules30122495 - 6 Jun 2025
Cited by 6 | Viewed by 1547
Abstract
Alkali metals in fuel seriously affect the normal operation of generator sets. Using agricultural waste (AW) from a corn field as raw material, the dynamic change of alkali metal K migration and transformation and the effect of competition between chlorine and sulfur on [...] Read more.
Alkali metals in fuel seriously affect the normal operation of generator sets. Using agricultural waste (AW) from a corn field as raw material, the dynamic change of alkali metal K migration and transformation and the effect of competition between chlorine and sulfur on the behavior of AW were studied systematically. The results showed that transformation between different forms of K, especially water-soluble K, occurred. At low temperatures, K remained in the ash in the form of inorganic salt, and high temperature precipitated K and formed insoluble alkali metal compounds. Via FactSage thermodynamic equilibrium calculations, it was confirmed that KCl reacted with SiO2 to form a K2O·nSiO2 molten mixture in combustion. K initially existed in the form of KCl (s) and K2SO4 (s), high temperature promoted its transformation and decomposition, and it was eventually released as KCl (g). During combustion, Cl was more volatile than K, while S reduced the release of K and Cl through sulfation reaction to reduce the sediment viscosity. Full article
(This article belongs to the Special Issue Renewable Energy, Fuels and Chemicals from Biomass, 2nd Edition)
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20 pages, 2586 KB  
Article
The Properties of Diesel Blends with Tire Pyrolysis Oil and Their Wear-Related Parameters
by Leszek Chybowski, Marcin Szczepanek, Tomasz Pusty, Piotr Brożek, Robert Pełech and Andrzej Wieczorek
Energies 2025, 18(5), 1057; https://doi.org/10.3390/en18051057 - 21 Feb 2025
Cited by 4 | Viewed by 2195
Abstract
This research presents the impact of diesel blends with tire pyrolysis oil (TPO) as an additive for minimizing the wear and tear of engine components. This study investigates the blends of normative diesel oil with TPO content ranging from 5% m/m to 20% [...] Read more.
This research presents the impact of diesel blends with tire pyrolysis oil (TPO) as an additive for minimizing the wear and tear of engine components. This study investigates the blends of normative diesel oil with TPO content ranging from 5% m/m to 20% m/m. Reference measurements are made for pure diesel oil (D100) and pure TPO. This investigation included an evaluation of the corrosion effect and the effect of the fuels tested on abrasive wear. For each fuel, the sulfur content, water content, lubricity (which is defined as the corrected average diameter of the wear trace during the high-frequency reciprocating rig (HFRR) test), and impurity content are determined. Impurities are assessed using indicators such as ash residue, coking residue from 10% distillation residue, determination of wear metals and contaminants, insoluble impurity content, and total sediment by hot filtration. All parameters are determined using recognized methods described in international standards. Approximation models are built for all the analyzed parameters, which can be used in future studies. At the same time, the individual values of the analyzed factors are compared with the threshold values specified in selected standards and regulations. Consequently, it is possible to assess the usefulness of individual fuels in terms of meeting the requirements for minimum wear of engine components. The results show the suitability of pyrolysis oil and the potential for its use as an additive to fossil fuels in terms of meeting most factors. Some of the fuels tested did not meet the standards for acceptable sulfur content. However, in terms of sulfur content, all of the analyzed fuels can be used to power watercraft and land-based power and thermal power plants equipped with flue gas desulphurization systems. A second indicator for not meeting the standards is the ash residue value, which indicates the high content of non-combustible, mainly metallic, substances in the pyrolysis oil used for the tests. Post-recycled oils must, therefore, undergo appropriate purification before being used as an additive to diesel fuels for internal combustion engines. Once the post-recycling oil has been subjected to desulfurization and advanced filtration, it can be used as a fuel additive for land vehicles, which fits in with closed-loop economies and sustainable development strategies. Full article
(This article belongs to the Special Issue Internal Combustion Engine Performance 2024)
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20 pages, 5914 KB  
Article
Numerical Simulation Study of the Optimization on Tubing-to-Sediment Surface Distance in Small-Spacing Dual-Well (SSDW) Salt Caverns
by Lei Wang, Zheng Chu, Jiang He, Yujia Zhai, Junming Huang and Haonan Yang
Processes 2025, 13(2), 322; https://doi.org/10.3390/pr13020322 - 24 Jan 2025
Cited by 1 | Viewed by 1346
Abstract
The small-spacing dual-well (SSDW) technique plays a crucial role in the establishment of underground salt cavern gas storage reservoirs. However, during the cavity dissolution and brine discharge processes, insoluble sediment is prone to being carried into the discharge tubing with the brine, leading [...] Read more.
The small-spacing dual-well (SSDW) technique plays a crucial role in the establishment of underground salt cavern gas storage reservoirs. However, during the cavity dissolution and brine discharge processes, insoluble sediment is prone to being carried into the discharge tubing with the brine, leading to tubing blockages or clogging, which disrupts injection and withdrawal operations and severely affects both project efficiency and the safety of the gas storage facility. This study systematically analyzes the influence of the gap between the injection and discharge tubing and the surface of the sediment-on-sediment movement, deposition, and tubing safety in SSDW salt caverns. Through numerical simulations, this study investigates the influence of tubing layout on the internal flow field distribution of the cavern and the suspension behavior of sediment, revealing the changing trend of the risk of sediment entering the tubing at different distances. The results show that a rational tubing distance can significantly lower the risk of sediment backflow and tubing entry, while maintaining high brine discharge efficiency. Based on the simulation results, an optimized tubing layout design suitable for SSDW salt caverns is proposed, offering technical direction to guarantee the safe and effective functioning of underground salt cavern gas storage sites. Full article
(This article belongs to the Special Issue Modeling, Control, and Optimization of Drilling Techniques)
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25 pages, 7600 KB  
Review
A Review of Enhanced Methods for Oil Recovery from Sediment Void Oil Storage in Underground Salt Caverns
by Xinxing Wei, Xilin Shi, Yinping Li, Peng Li, Mingnan Xu, Yashuai Huang and Yang Hong
Energies 2025, 18(2), 360; https://doi.org/10.3390/en18020360 - 16 Jan 2025
Cited by 15 | Viewed by 4283
Abstract
Salt caverns are recognized as an excellent medium for energy storage. However, due to the unique characteristics of China’s bedded salt formations, which contain numerous salt layers and a high concentration of insoluble impurities, significant accumulation at the bottom of salt caverns occurs, [...] Read more.
Salt caverns are recognized as an excellent medium for energy storage. However, due to the unique characteristics of China’s bedded salt formations, which contain numerous salt layers and a high concentration of insoluble impurities, significant accumulation at the bottom of salt caverns occurs, leading to the formation of extensive sediment voids. These sediment voids offer a potential space for underground oil storage, referred to as sediment void oil storage (SVOS). Oil recovery process from these sediment voids is a critical process. This paper summarizes the oil recovery technologies for SVOS and identifies four key factors—geological evaluation, stability evaluation, tightness evaluation, and oil storage capacity—all of which influence enhance oil recovery from sediment voids. This paper also outlines the overall oil recovery process, presents oil recovery experiments, and discusses oil recovery methods for enhancing oil recovery from sediment void. Additionally, it addresses the challenges of oil recovery in SVOS and explores its potential advantages and applications. The findings suggest that salt cavern sediment voids, as a promising storage space, provide a new approach to realize oil recovery and can overcome the limitations associated with cavern construction in high-impurity salt mines. The oil recovery from the sediment void is feasible, and China has rich rock salt and other convenient conditions to develop SVOS technology. Full article
(This article belongs to the Special Issue Enhanced Oil Recovery: Numerical Simulation and Deep Machine Learning)
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16 pages, 3471 KB  
Article
Solidified Salt Melts of the NaCl–KCl–CeF3–EuF3 System as Promising Luminescent Materials
by Viktor Zinchenko, Ganna Volchak, Nataliia Chivireva, Pavlo Doga, Yaroslav Bobitski, Oleh Ieriomin, Serhii Smola, Anton Babenko and Małgorzata Sznajder
Materials 2024, 17(22), 5565; https://doi.org/10.3390/ma17225565 - 14 Nov 2024
Cited by 3 | Viewed by 1675
Abstract
This study presents the results of investigating the interaction between the CeF₃–EuF₃ system and the NaCl–KCl salt melt using spectroscopic methods. It was found that CeF₃ ions undergo no significant changes upon dissolution in the NaCl–KCl melt. In contrast, the dissolution of EuF₃, [...] Read more.
This study presents the results of investigating the interaction between the CeF₃–EuF₃ system and the NaCl–KCl salt melt using spectroscopic methods. It was found that CeF₃ ions undergo no significant changes upon dissolution in the NaCl–KCl melt. In contrast, the dissolution of EuF₃, both individually and within the CeF₃–EuF₃ system, is accompanied by redox reactions leading to the formation of Eu2⁺. The diffuse reflectance spectra of both the bottom (insoluble sediment) and upper parts of the solidified salt melt in the UV range indirectly indicate photoluminescence excitation from Ce3⁺ and Eu2⁺ ions. In addition, absorption bands in the near-IR region (1900–2300 cm⁻1) confirm the retention of some Eu3⁺ ions in the salt melt. The study explored the effects of various factors—including sample composition, excitation wavelength, prior and subsequent heat treatment, and medium composition—on the excitation and emission spectra of the samples. Intense 5d-4f luminescence of Ce3⁺ and Eu2⁺ ions (at 330 and 430 nm, respectively) was observed predominantly in the upper part of the salt melts, along with much weaker 4f-4f luminescence from Eu3⁺ ions. Certain parameters were optimized to reduce the luminescence contribution from Ce3⁺ and especially Eu3⁺ ions while enhancing the luminescence of Eu2⁺ ions. Solidified salt solution-melts of the NaCl–KCl–CeF₃–EuF₃ system show promise as materials for developing solar ultraviolet radiation detectors. Full article
(This article belongs to the Section Optical and Photonic Materials)
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19 pages, 2824 KB  
Article
Effect of Crop Protection Intensity and Nitrogen Fertilisation on the Quality Parameters of Spelt Wheat Grain cv. ‘Rokosz’ Grown in South-Eastern Poland
by Edyta Bernat, Sylwia Chojnacka, Marta Wesołowska-Trojanowska, Dorota Gawęda, Ewa Kwiecińska-Poppe and Małgorzata Haliniarz
Agriculture 2024, 14(10), 1815; https://doi.org/10.3390/agriculture14101815 - 15 Oct 2024
Cited by 2 | Viewed by 2072
Abstract
Spelt wheat is one of the oldest wheats cultivated by humans. It is characterised by high nutritional values and is sought after by consumers. Additionally, it does not have high habitat and fertilisation requirements and is resistant to diseases. The aim of this [...] Read more.
Spelt wheat is one of the oldest wheats cultivated by humans. It is characterised by high nutritional values and is sought after by consumers. Additionally, it does not have high habitat and fertilisation requirements and is resistant to diseases. The aim of this study was to determine the effect of different levels of nitrogen fertilisation and the intensification of fungicide protection on the grain quality characteristics of spelt cv. ‘Rokosz’ grown under south-eastern Polish conditions. The present research showed that the intensification of fungicide crop protection and increasing the nitrogen dose from 70 to 130 kg ha−1 had a positive effect on the quality features of spelt grains. The highest protein, gluten and starch contents were found after four fungicide treatments. These parameters increased their values under the influence of fungicides. After the application of 130 kg ha−1, spelt wheat grain had the most favourable chemical composition, containing the most protein, gluten, soluble dietary fibre, insoluble dietary fibre and fat. It also had a positive effect on the Zeleny sedimentation index and the amino acid content of the grain. Due to the favourable response of the spelt cv. ‘Rokosz’ to intensified fungicide protection and nitrogen fertilisation, it should be recommended for cultivation in integrated technology. Full article
(This article belongs to the Section Crop Protection, Diseases, Pests and Weeds)
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11 pages, 1031 KB  
Article
Waste Zinc–Carbon Battery Recycling: Focus on Total Material Recovery
by Anatoliy Ranskiy, Olga Gordienko and Vitalii Ishchenko
Recycling 2024, 9(5), 83; https://doi.org/10.3390/recycling9050083 - 21 Sep 2024
Cited by 7 | Viewed by 7751
Abstract
Currently, less attention is paid to zinc–carbon batteries, although they are still widely used and are among the major types of batteries collected and recycled. The recycling technologies currently in use do not allow the complete recovery of resources, are not self-sufficient and [...] Read more.
Currently, less attention is paid to zinc–carbon batteries, although they are still widely used and are among the major types of batteries collected and recycled. The recycling technologies currently in use do not allow the complete recovery of resources, are not self-sufficient and require additional financing. Therefore, this paper aims to study the possibility of complete recycling of waste zinc–carbon batteries and to suggest the practical use of the final products generated in the recycling process. The possibility of complex processing of spent zinc–carbon batteries using mechanical separation and processing of the battery’s components (steel case, zinc electrode, graphite electrode, polypropylene and paper insulators) is justified. The separation of spent electrolytes from other components of batteries with hydrochloric acid was studied. It was shown that the extraction of Zn2+ and NH4+ cations takes place following the addition of an equivalent amount of Na3PO4 solution and water-insoluble NH4ZnPO4 salt sedimentation. Waste agglomerate (mixture of MnO2, MnO(OH), and graphite) was regenerated to its initial composition (MnO2, graphite) at a temperature of 300–325 °C; manganese (III) hydroxide was oxidized to manganese (IV) dioxide. Thermal destruction of polypropylene and paper insulators with additional introduction of polyethylene into the primary mixture produced pyrolysis liquid, pyrocarbon and pyrolysis gas as products. The practical use of the products obtained and compliance with the environmental requirements of the suggested method of waste batteries recycling were shown. Full article
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19 pages, 2045 KB  
Review
Mediterranean Marine Mammals: Possible Future Trends and Threats Due to Mercury Contamination and Interaction with Other Environmental Stressors
by Roberto Bargagli and Emilia Rota
Animals 2024, 14(16), 2386; https://doi.org/10.3390/ani14162386 - 17 Aug 2024
Cited by 7 | Viewed by 4225
Abstract
Despite decreasing anthropogenic mercury (Hg) emissions in Europe and the banning and restriction of many persistent organic pollutants (POPs) under the Stockholm Convention, Mediterranean marine mammals still have one of the highest body burdens of persistent pollutants in the world. Moreover, the Mediterranean [...] Read more.
Despite decreasing anthropogenic mercury (Hg) emissions in Europe and the banning and restriction of many persistent organic pollutants (POPs) under the Stockholm Convention, Mediterranean marine mammals still have one of the highest body burdens of persistent pollutants in the world. Moreover, the Mediterranean basin is one of the most sensitive to climate change, with likely changes in the biogeochemical cycle and bioavailability of Hg, primary productivity, and the length and composition of pelagic food webs. The availability of food resources for marine mammals is also affected by widespread overfishing and the increasing number of alien species colonizing the basin. After reporting the most recent findings on the biogeochemical cycle of Hg in the Mediterranean Sea and the physico-chemical and bio-ecological factors determining its exceptional bioaccumulation in odontocetes, this review discusses possible future changes in the bioavailability of the metal. Recent ocean–atmosphere–land models predict that in mid-latitude seas, water warming (which in the Mediterranean is 20% faster than the global average) is likely to decrease the solubility of Hg and favor the escape of the metal to the atmosphere. However, the basin has been affected for thousands of years by natural and anthropogenic inputs of metals and climate change with sea level rise (3.6 ± 0.3 mm year−1 in the last two decades), and the frequency of extreme weather events will likely remobilize a large amount of legacy Hg from soils, riverine, and coastal sediments. Moreover, possible changes in pelagic food webs and food availability could determine dietary shifts and lower growth rates in Mediterranean cetaceans, increasing their Hg body burden. Although, in adulthood, many marine mammals have evolved the ability to detoxify monomethylmercury (MMHg) and store the metal in the liver and other organs as insoluble HgSe crystals, in Mediterranean populations more exposed to the metal, this process can deplete the biological pool of Se, increasing their susceptibility to infectious diseases and autoimmune disorders. Mediterranean mammals are also among the most exposed in the world to legacy POPs, micro- and nanoplastics, and contaminants of emerging interest. Concomitant exposure to these synthetic chemicals may pose a much more serious threat than the Se depletion. Unfortunately, as shown by the literature data summarized in this review, the most exposed populations are those living in the NW basin, the main feeding and reproductive area for most Mediterranean cetaceans, declared a sanctuary for their protection since 2002. Thus, while emphasizing the adoption of all available approaches to mitigate anthropogenic pressure with fishing and maritime traffic, it is recommended to direct future research efforts towards the assessment of possible biological effects, at the individual and population levels, of chronic and simultaneous exposure to Hg, legacy POPs, contaminants of emerging interest, and microplastics. Full article
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14 pages, 5358 KB  
Article
Research on the Influencing Factors of the Void Volume of Insoluble Sediment in Salt Cavern Gas Storage
by Xiangrui Sun, Guosheng Ding, Kang Li, Chuanqi Xin, Zhide Wu, Yanxia Gou, Li’na Ran, Haitao Li, Song Bai and Jia’nan Wu
Processes 2024, 12(4), 636; https://doi.org/10.3390/pr12040636 - 22 Mar 2024
Cited by 6 | Viewed by 1874
Abstract
Utilizing voids of insoluble sediment (IS) to store gas is an effective way to improve the efficiency of salt cavern gas storage (SCGS) in China. In this study, a suitable method for predicting the void volume of insoluble sediments (VVISs) is established. This [...] Read more.
Utilizing voids of insoluble sediment (IS) to store gas is an effective way to improve the efficiency of salt cavern gas storage (SCGS) in China. In this study, a suitable method for predicting the void volume of insoluble sediments (VVISs) is established. This study explores three key factors affecting the VVISs through laboratory experiments. Firstly, in order to make the experimental results more in line with production realities, an analysis of the characteristics of IS in X SCGS was conducted to provide a basis for setting parameters for subsequent experiments. Secondly, experimental setups and methods for measuring the VVISs were designed. Finally, the experimental results were used to predict the VVISs in on-site cavity wells. The results indicate that the higher the proportion of quartz, illite, and large-grain particles in IS, the larger the VVISs. Under different parameters, the VVISs can account for approximately 10–40% of the IS accumulation volume. Different particle sizes can cause a variation of approximately 5–30% in the VVISs, while different mineral compositions can result in a difference of 6–23% in the VVISs. With increasing compaction pressure, the VVISs can decrease by around 5–80%. The prediction of the VVISs in on-site cavity wells shows a high degree of fit with empirical algorithms. This study can provide a reference basis for the utilization of the void space of IS in SCGS. Full article
(This article belongs to the Section Chemical Processes and Systems)
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15 pages, 2827 KB  
Article
Interactions of Perrhenate (Re(VII)O4) with Fe(II)-Bearing Minerals
by Anthony W. N. Kilber, Maxim I. Boyanov, Kenneth M. Kemner and Edward J. O’Loughlin
Minerals 2024, 14(2), 181; https://doi.org/10.3390/min14020181 - 7 Feb 2024
Cited by 3 | Viewed by 2949
Abstract
Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which [...] Read more.
Rhenium (Re) is an extremely rare element, with a crustal abundance of approximately 0.4 parts per billion (ppb) and a sea water concentration of 8.3 parts per trillion (ppt). However, Re concentrations in anoxic marine sediments range from 2 to 184 ppb, which is attributed to reduction of the highly soluble perrhenate ion (Re(VII)O4) to insoluble Re(IV) species. Anoxic sediments typically contain Fe(II) and sulfide species, which could potentially reduce Re(VII) to Re(IV). In this study, we examined the interactions of KReO4 with magnetite (Fe3O4), siderite (FeCO3), vivianite (Fe3(PO4)2•8H2O), green rust (mixed Fe(II)/Fe(III) layered double hydroxide), mackinawite (FeS), and chemically reduced nontronite (NAu-1) using X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy to determine the valence state and speciation of Re. Uptake of Re by green rust was rapid, with ~50% associated with the solids within 2 days. In contrast, there was <10% uptake by the other Fe(II) phases over 48 days. Reduction of Re(VII) to Re(IV) was only observed in the presence of green rust, producing clusters of bidentate-coordinated Re(IV)O6 octahedra.. These results suggest that except for green rust, the potential for other Fe(II)-bearing minerals to act as reductants for ReO4 in sedimentary environments requires further investigation. Full article
(This article belongs to the Special Issue Redox Reactivity of Iron Minerals in the Geosphere, 2nd Edition)
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11 pages, 1354 KB  
Article
The Chemical Nature of Mercury and Copper Sulfides and Its Implication for Bioavailability Assessments in Sediments
by Yuch-Ping Hsieh
Water 2024, 16(1), 70; https://doi.org/10.3390/w16010070 - 24 Dec 2023
Cited by 1 | Viewed by 3135
Abstract
Sulfur chemistry plays an important role in regulating the bioavailability of heavy metals (HMs) because HM sulfides are extremely insoluble in sediments. However, quantifying HM sulfides in sediments has been difficult because they are considered acid-extractable (AE). Previous studies also found that Hg [...] Read more.
Sulfur chemistry plays an important role in regulating the bioavailability of heavy metals (HMs) because HM sulfides are extremely insoluble in sediments. However, quantifying HM sulfides in sediments has been difficult because they are considered acid-extractable (AE). Previous studies also found that Hg and Cu behaved differently from other HMs in sediments. This study investigated the chemical nature of Hg and Cu sulfides and the causes of Hg and Cu anomalies in sediments. The results indicated that Hg and Cu sulfides are not mono-sulfides (HS or S=) but bi-sulfides (S2=), which are non-acid-extractable (NAE) under nitrogen. These results explain the Hg and Cu anomalies compared to other HMs and facilitate a procedure to quantify Hg and Cu sulfides in sediments. We analyzed the AE and NAE fractions of Hg, Cu, and Zn under nitrogen in the sediments of Apalachicola Bay, North Florida. Zn was included for comparison because Zn sulfide is mono-sulfide. The NAE Hg and Cu were, on average, 97.9 ± 2.7% and 84.6%, respectively, of the total, much higher than that of Zn (24.3% of the total) in the sediments, as expected. The NAE fractions of Hg and Cu were sulfides and thus could be excluded from the bioavailability assessments. Full article
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26 pages, 6285 KB  
Article
Semiarid Lakes of Southwestern Siberia as Sentinels of On-Going Climate Change: Hydrochemistry, the Carbon Cycle, and Modern Carbonate Mineral Formation
by Andrey Novoselov, Alexandr Konstantinov, Elizaveta Konstantinova, Yulia Simakova, Artem Lim, Alina Kurasova, Sergey Loiko and Oleg S. Pokrovsky
Atmosphere 2023, 14(11), 1624; https://doi.org/10.3390/atmos14111624 - 29 Oct 2023
Cited by 4 | Viewed by 2897
Abstract
Towards a better understanding of factors controlling carbon (C) exchange between inland waters and atmosphere, we addressed the inorganic carbon cycle in semiarid lakes of Central Eurasia, subjected to the strong impact of on-going climate change. As such, we assessed the hydrochemical variability [...] Read more.
Towards a better understanding of factors controlling carbon (C) exchange between inland waters and atmosphere, we addressed the inorganic carbon cycle in semiarid lakes of Central Eurasia, subjected to the strong impact of on-going climate change. As such, we assessed the hydrochemical variability and quantified its control on the formation of authigenic carbonate minerals, occurring within the upper layer of sediments in 43 semiarid lakes located in the southwest of Western Siberia (Central Eurasia). Based on measurements of pH, total dissolved solids (TDS), cationic and anionic composition, dissolved organic and inorganic C, as well as textural and mineralogical characterization of bottom sediments using X-ray diffraction and scanning electron microscopy, we demonstrate that lake water pH and TDS are primarily controlled by both the lithological and climatic context of the lake watershed. We have not revealed any direct relationships between lake morphology and water chemistry. The most common authigenic carbonates scavenging atmospheric CO2 in the form of insoluble minerals in lake sediments were calcite, aragonite, Mg-calcite, dolomite and hydromagnesite. The calcite was the most common component, aragonite mainly appears in lakes with sediments enriched in gastropod shells or artemia cysts, while hydromagnesite was most common in lakes with high Mg/Ca molar ratios, as well as at high DIC concentrations. The relationships between mineral formation and water chemistry established in this study can be generalized to a wide suite of arid and semiarid lakes in order to characterize the current status of the inorganic C cycle and predict its possible modification under on-going climate warming such as a rise water temperature and a change in hydrological connectivity, primary productivity and nutrient regime. Full article
(This article belongs to the Special Issue The Impact of Climate Change on Water Resources)
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16 pages, 3178 KB  
Article
The Flow Law of Brine and Sediment Particles in Gas-Driven Brine Drainage in the Sediments of Salt Cavern Gas Storage
by Yi Zhang, Jun Lu, Jun Li, Yan Liu and Erdong Yao
Sustainability 2023, 15(16), 12613; https://doi.org/10.3390/su151612613 - 21 Aug 2023
Cited by 5 | Viewed by 2138
Abstract
The geological resources of salt cavern gas storage in China are mostly complex layered salt beds with many thin inter-layers and high insoluble matter content. In the process of cavity-building by water-solution method, the insoluble matters in salt layers and inter-layers are peeled [...] Read more.
The geological resources of salt cavern gas storage in China are mostly complex layered salt beds with many thin inter-layers and high insoluble matter content. In the process of cavity-building by water-solution method, the insoluble matters in salt layers and inter-layers are peeled off and deposited at the bottom of salt cavern, occupying more than one-third of the whole cavity volume. These sediments have a large pore volume and strong compressibility, and they are filled with brine; as a result, they have great potential for gas storage. The research on the flow law of brine and sediment particles in gas-driven brine drainage in the sediments of salt caverns is the basis of utilizing the void space of sediments for gas storage. In this paper, salt cores of salt cavern gas storage wells in the Jintan District were selected, and the physical characteristics of insoluble sediments of the salt cores were analyzed. Then, a laboratory simulation device and experimental method of the gas-driven brine drainage were presented. Using artificial composite sediments in the experimental device, the following was tested: (i) the flow rates of brine and particles in the vicinity of the brine drain pipe in the sediments under different nitrogen displacement pressures, (ii) the relationship between the sand extraction amount and nitrogen displacement pressure of different brine drain pipes, (iii) the sand extraction amount of different sizes of particles with brine drain time, (iv) the cumulative sand extraction amount of different brine drain pipes, and (v) the effect of brine flow rate on the sand extraction amount. The results show that quartz, plagioclase, and ankerite account for 45–94% and clay accounts for 3.3–14.4% of the insoluble minerals of the salt cores from the Jintan District. The particle size distribution of the sediments ranges from 0.04 mm to 6 mm and can be divided into four ranges: <0.5 mm, 0.5 mm~2 mm, 2 mm~4 mm, and >4 mm. The mass percentage of each range is 37.9%, 36.5%, 17%, and 8.6%, respectively. There is a threshold pressure of the gas-driven brine drainage, where the larger the diameter of the sieve hole, the lower the threshold pressure, and the easier the pipe is to sand out. The diameter of the sieve hole has a great influence on the flow rate of the sediment particles near the brine drain pipe. The increase in nitrogen displacement pressure has a positive correlation with the flow rate of sediments near the pipe with 5 mm diameter sieve holes, but has little effect on the flow rate of sediments near pipes with 1.5 mm or 0.5 mm diameter sieve holes. The sand extraction amount is affected by factors such as the nitrogen displacement pressure, diameter of sieve hole, brine drain time, and brine flow rate in the process of gas-driven brine drainage. A higher nitrogen displacement pressure and brine flow rate lead to more sand extraction. A screen pipe with 1 mm diameter sieve holes is suggested to be used for sand control, the sieve holes are recommended to be machined in the shape of a trumpet with a small inlet section (i.e., 1 mm) and a large outlet end (i.e., 1.5 mm), and the brine flow rate is suggested to be about 30 m3/h when the brine removal is carried out in the sediments of salt cavern, which depends on the actual operation on site. Full article
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