Effect of salt types on salt precipitation and water transport in saline sandy soil

Salt precipitation on the surface of porous media significantly affects water transport processes. Most studies on salt precipitation mainly focused on single salts, but in nature, salt precipitation usually occurs as mixtures. Consequently, information on the crystallization of salt mixtures and its effect on water transport remains scarce. This study investigated the precipitation of mixtures (the mass ratios of NaCl:Na₂SO₄ were 3:7, 5:5, and 7:3, respectively) of NaCl (typical efflorescence) and Na₂SO₄ (typical subflorescence) in the initially saturated sandy soil columns and its effect on evaporation and compared it with the cases of the two salts individually. The results showed that salt mixtures exhibited a mixed pattern of crystals including both efflorescence and subflorescence, and the efflorescence showed granular aggregation, unlike the mono-salts. The crystallization coverage of the salt mixtures was smaller than that of NaCl mono-salt; high (7:3) and low (5:5 and 3:7) proportions of NaCl led to larger and smaller crystallization coverage than that of Na₂SO₄ mono-salt, respectively. While the salt mixtures had less crystallization coverage than the mono-salts, they showed lower evaporation because the salt mixtures formed a denser crystallization structure of efflorescence-subflorescence-soil layer, this crystallization structure exhibited greater inhibition of water vapour diffusion, thus reducing evaporation. In addition, the crystallization of the salt mixtures with higher NaCl proportion afforded greater resistance of evaporation. The mixed crystallization pattern formed by the salt mixtures significantly enhances the crystallization resistance to evaporation.     

无机盐改性对沸石覆盖技术控制底泥氮磷释放的影响研究

通过试验,考察了无机盐改性对沸石覆盖控制底泥氮磷释放效果的影响,并对沸石覆盖技术控制底泥氮磷释放的机理进行初步探讨,结果表明:①NaCl及CaCl2改性对沸石吸附氨氮的性能影响不大;CaCl2改性可以提高沸石Ca2 的交换量而降低Na 的交换量,NaCl改性则可以明显降低Ca2 的交换量和增加Na 的交换量.②NaCl及CaCl2改性对沸石覆盖技术控制底泥氨氮的释放影响不大,而对控制底泥磷的释放则影响较大,沸石覆盖控制底泥磷释放效率从大到小依次为CaCl2改性沸石＞天然沸石＞NaCl改性沸石.③沸石覆盖技术控制底泥氨氮释放的机理为沸石的物理吸附和阳离子交换作用,控制底泥磷释放的机理包括沸石的机械阻挡作用和沸石与铵所交换出来的Ca2 对磷酸盐的固定作用.     

Salt fretting in the valley cliff of the Asama volcano region,Japan

On the pumice flow deposits of the Asama volcano, Japan, many salts such as halite (NaCl), gypsum (CaSO₄·2H₂O), hexahydrite (MgSO₄·6H₂O) and mirabilite (Na₂SO₄·10H₂O) crystallize at the base of south-facing valley cliffs. The zone of salt efflorescence and of resulting polygonal rind correspond to the zones of notch formation and high water content. The main conditions for salt crystallization and polygonal rind formation are: (1) the existence of groundwater containing a high concentration of Cl^?, SO, Ca²⁺, Mg²⁺, and Na⁺; (2) a valley cliff material with a high capillary action and small tensile strength; and (3) low humidity and a high ground-surface temperature derived from the direct incidence of sunshine. Given the right conditions, salt weathering can occur not only in the arid regions but also in humid, temperate inland regions.     

Na and HTO diffusion in compacted bentonite: Effect of surface chemistry and related texture

In underground repository concepts for radioactive waste, bentonite is studied as a reference swelling material to be used as an engineered barrier. Under the changing geochemical conditions prevailing within the barrier (saturation with the fluid coming from the host formation, diffusion of various chemical plumes caused by the degradation of some constituents of the barrier-system, etc.), the surface chemistry of the clay particles could evolve. This work aims to characterize the effects of these changes on (i) the microstructure of compacted bentonite samples and (ii) the diffusion properties of HTO and Na in these samples.For this purpose, bentonite sets were equilibrated with different solutions: NaCl, CaCl₂, CsCl solutions as well as an artificial clayey porewater solution. The microstructure of the different samples was characterized by HRTEM and XRD, in a water saturated state. In parallel, effective diffusion coefficients of both HTO and ²²Na were measured for the different samples. The density of the bentonite in the diffusion tests and in the HRTEM observations was set at 1.6 Mg m⁻³.From the microstructural observations and the results of diffusion tests, it is deduced that one key parameter is the occurrence of a gel phase in the material, which is found to depend strongly on the bentonite set: the gel phase dominates in Na-bentonite, while it is lacking in Cs-bentonite. The HTO diffusion coefficients are found to be lower in the samples with high gel phase content. Sodium diffusion does not follow the same trend: when compared with HTO, Na diffuses faster when the gel phase content is high. The latter result could indicate that the “accelerated diffusion mechanism” of cations, already mentioned in the literature, is enhanced in clayey materials that contain a gel phase.     

Interfacial tension between CO2 and brine (NaCl + CaCl2) at elevated pressures and temperatures: The additive effect of different salts

An extensive laboratory study was conducted to measure the interfacial tension (IFT) between CO₂ and brine consisting in equal molal concentrations of NaCl and CaCl₂. The experiments were repeated at various pressures, temperatures and salinities that are representative of conditions prevailing during CO₂ storage in deep saline aquifers. The dependence of CO₂/brine IFT on pressure and temperature is similar to that previously reported for the systems: CO₂/NaCl solution and CO₂/CaCl₂ solution. CO₂/brine IFT increases linearly with water salinity and the magnitude of this increase was found equal to the sum of the individual CO₂/NaCl solution and CO₂/CaCl₂ solution IFT increments, indicating a strong additive effect on IFT when the brine is composed of various salts.     

Untersuchung der Anwendungsmöglichkeiten von einigen komplexbildenden Ionenaustauschern zur Kupferabtrennung aus natürlichen Wässern und Abwässern

Application of Some Complexing Ion Exchangers for Copper Recovery from Natural Water and Wastewater The rational use of water resources is one of the urgent environmental control problems. These problems can be solved by the treatment of sewage. Removal of different non‐ferrous heavy metal ions from wastewater is of great importance. Besides, the selective complexing ion exchangers are of interest because of their good sorption properties. The present paper is devoted to the study of some complexing resins for copper recovery from natural water and sewage. The following carboxylic resins were studied: the cation exchangers KB‐2T, KB‐4 and the amphoteric ion exchangers ANKB 35, AMF‐2T, and AMF‐2S (manufacturer – “TOKEM” company, Kemerovo, Russia). The exchangers investigated differed from each other both by their functional groups and by their matrix physical structures. The copper recovery from CuCl₂‐, CuSO₄‐, and Cu(NO₃)₂‐solutions was studied in batch‐experiments (in presence of NaCl, Na₂SO₄, and NaNO₃). The initial copper concentration in the solutions was 0.0002...0.008 mol/L; pH values were 1.0...5.0. After equilibrium (24 h) the resins were separated from the solution. The copper concentration in the solutions after the sorption was determined by the photometrical method with pyridylazoresorcin (λ = 500 nm). On the basis of the experimental data distribution ratio, the separation factors, equilibrium constants, and stability constants of copper complexes in the exchanger phase were calculated. It was found out in this work that the amphoteric ion exchanger AMF‐2T of macroreticular structure is the most effective for the copper sorption from sewage.     

Salt weathering: influence of evaporation rate,supersaturation and crystallization pattern

Micro- and macroscale experiments which document the dynamics of salt damage to porous stone have yielded data which expose weaknesses in earlier interpretations. Previously unexplained differences are found in crystal morphology, crystallization patterns, kinetics and substrate damage when comparing the growth of mirabilite (Na₂SO₄. 10H₂O) and thenardite (Na₂SO₄) versus halite (NaCl). The crystallization pattern of sodium sulphate was strongly affected by relative humidity (RH), while a lesser RH effect was observed for sodium chloride. Macroscale experiments confirmed that mirabilite (crystallizing at RH > 50 per cent) and thenardite (crystallizing at RH < 50 per cent) tend to form subflorescence in highly localized areas under conditions of constant RH and temperature. This crystallization pattern was more damaging than that of halite, since halite tended to grow as efflorescence or by filling the smallest pores of the stone in a homogeneous fashion, a result which contradicts Wellman and Wilson's theoretical model of salt damage. Low RH promoted rapid evaporation of saline solutions and higher supersaturation levels, resulting in the greatest damage to the stone in the case of both sodium sulphate and sodium chloride crystallization. At any particular crystallization condition, sodium chloride tended to reach lower supersaturation levels (resulting in the crystallization of isometric crystals) and created negligible damage, while sodium sulphate reached higher supersaturation ratios (resulting in non-equilibrium crystal shapes), resulting in significant damage. ESEM showed no damage from sodium sulphate due to hydration. Instead, after water condensation on thenardite crystals, rapid dissolution followed by precipitation of mirabilite took place, resulting in stone damage by means of crystallization pressure generation. It is concluded that salt damage due to crystallization pressure appears to be largely a function of solution supersaturation ratio and location of crystallization. These key factors are related to solution properties and evaporation rates, which are constrained by solution composition, environmental conditions, substrate properties, and salt crystallization growth patterns. When combined with a critical review of salt damage literature, these experiments allow the development of a model which explains variations in damage related to combinations of different salts, substrates and environmental conditions. Copyright © 1999 John Wiley & Sons, Ltd.     

Effects of ultrafiltration on salt migration and isotopic composition of pore water in groundwater depression area in Hengshui,NCP

Clay aquitards are semipermeable membranes that allow groundwater flow while retarding solute migration has been researched extensively but also subjected to much debate. At present, there is no evidence of whether the physical and chemical properties of clay soil and the isotopic composition of pore water affect the semipermeable membrane effect. In this study, we collected clay samples from drilling cores (30–90 m) in the Hengshui area located in the North China Plain (NCP), then extracted pore water using a high-pressure squeezing device. Vertical hydrochemical and isotopic profile variation trends for the pore water were revealed using hydrochemical (Cl⁻, Na⁺, Ca²⁺, K⁺, Mg²⁺, and SO₄²⁻) and stable isotopic measurements of H, O and Cl. The results showed that the hydrochemical clay interlayer pore water of the saline aquifer is Cl/SO₄-Na/Mg type and the average total dissolved solids (TDS) are 10.17 g/L. However, the hydrochemical clay aquitard pore water is of the Cl/SO₄-Na/Ca type with an average TDS of 1.90 g/L. The hydrochemical clay interlayer pore water of aquifer II is of Cl-Na/Ca type with an average TDS of 1.10 g/L. Our results showed that the water quality of the aquifer II is not affected by the upper part of the saline aquifer, thus the clay aquitard acts as a significant barrier to salt movement. A polarization layer concentrated in ions was formed between the upper part of the saline aquifer and the clay aquitard. The concentration polarization layer increases the salt-inhibition effect. H, O and Cl isotopic composition results showed significant fractionation. The pore water of aquifer II lacked heavy isotopes (²H, ¹⁸O, ³⁷Cl), but had significant heavy isotope enrichment in the concentrated polarized layer (the δ²H value was −76‰, the δ¹⁸O value was −8.4‰, and the δ³⁷Cl value was 1.59‰). Hyperfiltration thus played a significant role in isotope fractionation.     

Leaching characteristics of ash from the May 18, 1980, eruption of Mount St. Helens volcano,Washington

Leaching of freshly erupted air-fall ash, unaffected by rain, from the May 18, 1980, eruption of Mount St. Helens volcano, Washington, shows that Ca²⁺, Na⁺, Mg²⁺, SO ₄ ^2? , and Cl^? are the predominant chemical species released on first exposure of the ash to water. Extremely high correlation of Ca with SO₄ and Na with Cl in water leachates suggests the presence of CaSO₄ and NaCl salts on the ash. The amount of water soluble material on ash increases with distance from source and with the weight fraction of small (less than 63 micrometers) ash particles of high-surface area. This suggests that surface reactions such as adsorption are responsible for concentrating the soluble material. CaSO₄, NaCl, and other salts are probably formed as microscopic crystals in the high-temperature core of the eruption column and are then adsorbed by silicate ash particles. The environmentally important elements Zn, Cu, Cd, F. Pb, and Ba are released by a water leach in concentrations which could pose short-term hazards to some forms of aquatic life. However, calculated concentrations are based on a water-to-ash ratio of 4:1 or less, which is probably an underestimation of the regionally operative ratio. A subsequent leach of ash by warm alkaline solution shows dramatic increases, in the amount of dissolved SiO₂, U, and V, which are probably caused by increased dissolution of the glassy component of ash. Glass dissolution by alkaline ground water is a mechanism for providing these three elements to sedimentary traps where they may coaccumulate as uraniferous silica or U-V minerals. Leaching characteristics of ash from Mount St. Helens are comparable to characteristics of ash of similar composition from volcanoes in Guatemala. Ashes from each locality show similar ions predominating for a given leachate and similar fractions of a particular element in the ash removed on contact with the leach solution.     

Malachite Green Adsorption onto Chitosan Coated Bentonite Beads: Isotherms,Kinetics and Mechanism

The removal of Malachite green (MG) from aqueous solutions by cross‐linked chitosan coated bentonite (CCB) beads was investigated and the CCB beads were characterized by Fourier Transform Infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS) and X‐ray diffraction (XRD) analysis. Solubility and swelling tests were performed in order to determine the stability of the CCB beads in acidic solution, basic solution and distilled water. The amount of MG adsorbed was shown to be influenced by the initial pH of the solution, contact time and the initial MG concentration. A kinetic study indicated that a pseudo‐second‐order model agreed well with the experimental data. From the Langmuir isotherm model, the maximum adsorption capacity of MG was found to be 435.0 mg g^–1. Desorption tests were carried out at different concentrations of EDTA, H₂SO₄ and NaOH. However, all desorbing solutions showed zero recovery of MG at all concentrations.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Laboratory simulation of salt weathering under moderate ageing conditions: Implications for the deterioration of sandstone heritage in temperate climates

Salt weathering is a significant process affecting the deterioration and conservation of stone-built heritage in many locations and environments. While much research has focused on the impact of salt weathering under arid or coastal conditions with characteristic climatic conditions and salt types, many sites found to be experiencing salt-induced deterioration, such as sandstone rock-hewn cave temples in Gansu Province, China and sandstone buildings in the northern UK, experience high humidities, moderate temperature ranges, and different salt types. To evaluate the impact of salt weathering on sandstone-built heritage under such mild humid environmental conditions, a lab simulation experiment was designed. The experiment was carried out on three types of sandstone (used in the northern UK and Gansu Province, China) and utilized a realistic diurnal humidity and temperature cycle (85% RH/16°C + 60% RH/22°C), and three widespread damaging salts, that is, Na₂SO₄, MgSO₄, and the mixture of Na₂SO₄–MgSO₄. The nature and extent of deterioration was monitored by photography, weight loss, and the changes in petrophysical properties measured using hardness, ultrasonic pulse velocity (P-wave velocity), water absorption coefficient by capillarity, open porosity, and apparent density. All three sandstones were found to be susceptible to MgSO₄ and the mixture of Na₂SO₄–MgSO₄, but weakly affected by Na₂SO₄ under mild humid environmental conditions.     

Kinetics of Exchange-Adsorption Processes in the Formation of Mineral Sulfate Sodium Waters

The ion-exchange properties of terrigenous rocks have been studied, and physicochemical modeling has been used to study the formation of sulfate sodium water in the Volga–Ural Basin of the Russian Plate and the Kartalinskii Basin of the Caucasian hydrogeological folded area. Hydrogeochemical experiments have shown that the exchange-adsorption interaction between gypsum water and adsorbed Na⁺ of terrigenous rocks in the water–rock system involves many stages, resulting in the accumulation in solution of considerable amounts of Na₂SO₄ (up to 9–17 g/dm³).     

Fractionation of Ni,Cr and Cu from Soil by Sequential Extraction Procedure and Determination by Inductively Coupled Plasma Optical Emission Spectrometry

Five‐step sequential extractions were employed to fractionation of Ni, Cr and Cu in soil polluted by anthropogenic activities and determine the mobility of the metals. Twelve samples were collected on an agricultural area that was located near an airport and intercity roads in Elazig‐Turkey. Exchangeable, organically bounded, carbonate bounded, adsorbed species on Fe and Mn oxides and residual species (except silicates) of Ni, Cr and Cu were extracted into solution by using CaCl₂, Na₄P₂O₇, Na₂EDTA, NH₂OH–HCl and HNO₃–H₂O₂, respectively. Mobile metal concentrations in fractions and total recoverable in soils were determined by using inductively coupled plasma‐optical emission spectrometry (ICP‐OES). Total recoverable Ni, Cr and Cu concentrations were in the range of 40–119, 45–126 and 23–72 mg kg^?1, respectively. It was observed that total concentrations of metals in some of the samples were higher than the permitted values. The sum of the mobile percentages of metals was found to be lower than 50%. The Ni, Cr and Cu percentages for exchangeable species are in the ranges of 0.18–1.64, 0.03–0.59 and 0.42–2.53%, respectively.     

Adsorption of Cadmium Ions from Aqueous Solution Using Granular Activated Carbon and Activated Clay

The present study was aimed at removing cadmium ions from aqueous solution through batch studies using adsorbents, such as, granular activated carbon (GAC) and activated clay (A‐clay). GAC was of commercial grade where as the A‐clay was prepared by acid treatment of clay with 1 mol/L of H₂SO₄. Bulk densities of A‐clay and GAC were 1132 and 599 kg/m³, respectively. The surface areas were 358 m²/g for GAC and 90 m²/g for A‐clay. The adsorption studies were carried out to optimize the process parameters, such as, pH, adsorbent dosage, and contact time. The results obtained were analyzed for kinetics and adsorption isotherm studies. The pH value was optimized at pH 6 giving maximum Cd removal of 84 and 75.2% with GAC and A‐clay, respectively. The adsorbent dosage was optimized and was found to be 5 g/L for GAC and 10 g/L for A‐clay. Batch adsorption studies were carried out with initial adsorbate (Cd) concentration of 100 mg/L and adsorbent dosage of 10 g/L at pH 6. The optimum contact time was found to be 5 h for both the adsorbents. Kinetic studies showed Cd removal a pseudo second order process. The isotherm studies revealed Langmuir isotherm to better fit the data than Freundlich isotherm.     

Effective Removal of Microorganisms and Biostimulants of Wastewater by the Application of Various Electrolytes

A variety of electrolytes FeCl₃, CaCl₂, CuSO₄, Al₂(SO₄)₃, and LaCl₃ was investigated for their efficiency in removing biostimulants (phosphorous and nitrogen) to improve the water quality. Results show that the removal of PO₄^3– was achieved below the detection limit (BDL) by two electrolytes, CuSO₄ and Al₂(SO₄)₃, and up to 1.0 ± 0.0 mg/L by LaCl₃ from a value of 15.0 mg/L, of the concentration of PO₄^3– in amended water. The turbidity was found to be removed significantly by FeCl₃, CuSO₄, and Al₂(SO₄)₃ by about 5.8 ± 2.6, 9.7 ± 1.0, and 5.4 ± 1.1 nephalometric turbidity unit (NTU), respectively. The removal of the members of Enterobacteriaceae viz., Escherichia coli, Enterobacter spp. Pseudomonas fluorescence, and Pseudomonas spp. was found almost in all the chemical precipitants but their removal was more significant in the water samples treated with CuSO₄, Al₂(SO₄)₃, and LaCl₃. To achieve a complete removal and to sustain the after effects of precipitation, such as recurrence of algal growth, the combination of CuSO₄ and Al₂(SO₄)₃ was investigated. Reduction in the turbidity from 30.83 to <2 NTU, phosphate ion from a value of 1.28 mg/L to BDL and ammonia ion from a value of 44.71 to 36.48 mg/L of natural pond water were observed after the treatment with CuSO₄ and Al₂(SO₄)₃ in combination.     

Evidence for influence of mineral weathering on stream water sulphate in Vermont and New Hampshire (USA)

Mass balance studies in forested catchments in the northeastern USA show that S losses via streamwater SO₄^2? exceed measured atmospheric S inputs. Possible sources of the excess S loss include underestimated dry deposition, mineralization of organic S in soils, desorption of soil sulphate, oxidation of recently formed sulphides and mineral weathering. Evaluating the relative contribution of these sources and processes to SO₄^2? export is important to our understanding of S cycling as well as to policy makers in their evaluation of the efficacy of S emission controls. In order to evaluate the potential for mineral weathering contributions to SO₄^2? export, we measured concentration and isotopic composition (δ³⁴S and δ¹⁸O) of SO₄^2? in stream water, and concentration and δ³⁴S values of four S fractions in bedrock and soil parent material in catchments of varying geological composition. Geological substrates with low S concentrations were represented by catchments underlain by quartzite and granite, whereas geological substrates with high S concentrations were represented by catchments underlain by sulphidic slate, schist and metavolcanic rocks. Catchments with S‐poor bedrock had stream‐water SO₄^2? concentrations <100 µeq L^?1 and isotopic values consistent with those of atmospheric SO₄^2? that had been cycled through the organic soil pool. Catchments with S‐rich bedrock had stream‐water SO₄^2? concentrations ranging from 56 to 229 µeq L^?1. Isotopic values deviated from those of SO₄^2? in atmospheric deposition, clearly indicating a mineral weathering source in some cases, whereas in others spatial variability of mineral δ³⁴S values precluded the isotopic detection of a weathering contribution. These results, along with evidence suggesting formation of secondary sulphate minerals in bedrock weathering rinds, indicate that mineral weathering may be an important source of S in the surface waters of some forested catchments in the northeastern USA. Copyright © 2004 John Wiley & Sons, Ltd.     

Oxysulfates of copper, sodium, and potassium in the lava flows of the 2012–2013 Tolbachik Fissure Eruption

Samples from the surface of lava flows discharged by the 2012–2013 Tolbachik Fissure Eruption were found to contain oxysulfates of copper, sodium, and potassium: K₂Cu₃O(SO₄)₂ (fedotovite), NaKCu₂O(SO₄)₂, and Na₃K₅Cu₈O₄(SO₄)₈. The last two phases have no naturally occurring or synthetic analogues that we are aware of. They form flattened crystals of prismatic to long-prismatic habits. The crystals of Na₃K₅Cu₈O₄(SO₄)₈ have a chemical composition corresponding to the empirical formula Na_2.22K_5.47Cu_8.02S_8.05O₃₆. An X-ray analysis of this compound showed that it has a monoclinic symmetry, P2/c, a = 13.909(4), b = 4.977(1), c = 23.525(6) Å, β = 90.021(5)°, V = 1628.3(7) ų. The crystal structure was determined by direct techniques and refined to yield R ₁ for 3955 reflexes//web// with F ² > 4σF. The compound NaKCu₂O(SO₄)₂ also belongs to the monoclinic system, P2/c, a = 14.111(4), b = 4.946(1), c = 23.673(6) Å, β = 92.052(6)°, V = 1651.1(8) ų. The structure was determined by direct techniques to yield a tentative structural model that has been refined up to R ₁ = 0.135 for 4088 reflexes with F ² > 4σF. The crystal structure of Na₃K₅Cu₈O₄(SO₄)₈ is based on chains of [O₂Cu₄]⁴⁺ consisting of rib-coupled oxy-centered tetrahedrons of (OCu₄)⁶⁺. The chains are surrounded by sulfate radicals, resulting in columns of {[O₂Cu₄](SO₄)₄}^4? aligned along the b axis. The interchain space contains completely ordered positions of Na⁺ and K⁺ cations. The principle underlying the connection of NaKCu₂O(SO₄)₂ columns in the crystal structure of {[O₂Cu₄](SO₄)₄}^4? is different, in view of the relation Na:K = 1 as contrasted with 3:5 for the compound Na₃K₅Cu₈O₄(SO₄)₈. The presence of oxy-centered tetrahedrons in the structure of these new compounds furnishes an indirect hint at the importance of polynuclear copper-oxygen radicals with centering oxygen atoms as forms of transport of copper by volcanic gases.     

Preparation and evaluation of polyaluminum chloride sulfate (PACS) as a coagulant to remove natural organic matter from water

A series of polyaluminum chloride sulfate (PACS) coagulants, which have different SO₄^2–/Al³⁺ and OH/Al (γ) mole ratio, has been successfully developed using AlCl₃·6H₂O, Al₂(SO₄)₃·18H₂O and Na₂CO₃ as raw materials. The coagulation performance of PACS for removing natural organic matter (NOM) from surface water was evaluated, and the effect of SO₄^2–/Al³⁺ mole ratio and γ value in coagulants PACS on DOC and UV₂₅₄ removal was determined. Furthermore, the influence of pH and dosage of the selected PACS with a SO₄^2–/Al³⁺ ratio of 0.0664 and a γ value of 2.0, which achieved the best coagulation performance for the removal of DOC and UV₂₅₄ of all PACS coagulants, on the removal of DOC and UV₂₅₄ and residual aluminum concentration in treated water was investigated. The results were compared with the ones of polyaluminum chloride (PAC) with γ value of 2.0. The experimental data show that the performance of PACS as a coagulant was highly dependent on SO₄^2–/Al³⁺ mole ratio and γ value. Both for the selected PACS and for PAC, the best DOC and UV₂₅₄ removal results were obtained in the range of pH from 5.0 to 8.2 and at the coagulation dose of 5.0 mg/L as Al. Under the optimum coagulation conditions, the selected PACS gave higher DOC and UV₂₅₄ removal efficiencies, and lower residual aluminum concentrations in the treated water than PAC. The maximum removal of DOC and UV₂₅₄ for PACS was approximately 88.0% and 93.0%, respectively. At the optimum coagulant dose and pH 6.5, the concentration of residual aluminum in treated water by both selected PACS and PAC can comply with the regulated limits. The major mechanisms of NOM removal by PACS and PAC coagulation involve complexation‐charge‐neutralization‐precipitation.     

CO2/CaCl2 solution interfacial tensions under CO2 geological storage conditions: Influence of cation valence on interfacial tension

The effectiveness of CO₂ storage in deep saline aquifers and hydrocarbon reservoirs is governed, among other factors, by the interfacial tension between the injected CO₂ and formation water (brine). Experimental data on CO₂/water and CO₂/NaCl solution have revealed that the interfacial tension depends on the pressure, temperature and water salinity. However, there is still a lack of data for other salts (such as MgCl₂ and CaCl₂) which are also present in aquifers and carbonate reservoirs.