Treatment of high fluoride concentration wastewater by layered double hydroxides： Mechanism studies

An appropriate concentration of fluoride in drinking water is required to prevent dental cavities, but long-term ingestion of water that contains more than a suitable level of fluoride can cause bone disease and mottling of the teeth. Fluoride ions can be found in wastewater from the fluoride chemical industry, as well as the semiconductor, metal processing, fertilizer, and glass-manufacturing industries. The discharge standard for fluoride in industrial wastewater in China is 10 mg/L. Efficient treatment of fluoride-containing wastewater is therefore of major concern in China, following the rapid development of the fluoride chemical industry. Several methods have been used to remove fluoride from water, such as adsorption, chemical precipitation, electrodialysis, ion exchange and electrochemical processes. Layered double hydroxides （LDHs） are anionic clays with high anion exchange capacities which are effective adsorbents for removal of a variety of anionic pollutants. LDHs have been studied as potential adsorbents for removing toxic anionic species such as CrO4^2-, TcO4^-, SeO3^2-, pesticides, and anionic surfactants from aqueous systems. One of the main attractions of using LDHs for fluoride removal, is that unlike other chemical treatment methods, no chemical sludge should be produced. In the present study, an attempt was made to investigate the mechanism of fluoride removal by LDHs under different conditions using batch methods. In addition, the release of fluoride adsorbed on LDHs by treatment with an aqueous solution of Na2CO3 was studied. The residual fluoride was found to be 10 mg/L in a solution with an initial concentration of 1000 mg/L, which meets the discharge standard for fluoride in industrial wastewater in China.     

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides （LDHs）, is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/AI-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of （Mg, Al）-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like （Mg, Al）-oxide is transformed into a composite with periclase （MgO） and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.     

氢氧化物族矿物的氧同位素分馏

应用增量方法计算了氢氧化物族矿物的氧同位素分馏,得到常见氢氧化物的18O富集顺序为：褐铁矿＞三水铝石＞针铁矿＞水镁石＞硬水铝石。氢氧化物与其对应的氧化物相比显著地富集18O。三价阳离子的氢氧化物和氧化物的18O富集顺序为：M（OH）3＞MO（OH）＞M2O3。Al（OH）3同质多象变体之间也存在一定的分馏。对于石英-氢氧化物、方解石-氢氧化物和氢氧化物-水体系,本文计算提供了在0-1200℃温度范围内三组内部一致的分馏系数方程。这些理论校准与合成实验结果和／或地表温度下的天然样品相吻合,特别针铁矿、勃姆石和硬水铝石与水之间的氧同位素分馏关系能够满足地质测温的要求。因此,对氢氧化物-水体系的氧同位素分析可望提供表生环境下可靠的地质温度计。     

Influence of high-pressure processing on the structure and memory effect of synthetic layered double hydroxides

We investigate the structural evolution of synthetic layered double hydroxides (LDH) samples, processed at room temperature and high-pressure (up to 7.7 GPa) in a toroidal chamber with two pressure-transmitting media, lead and graphite, using X-ray diffraction, thermogravimetry and N₂-adsorption isotherms techniques. The X-ray patterns of compacted samples show a decrease in the peak intensities. For both pressure-transmitting media, our samples revealed a reduction of the basal d-spacing for the (003) plane when processed at 7.7 GPa. The expected high-pressure-induced amorphization was not observed. Surprisingly, we find high-pressure processing to have a strong influence on the memory effect of the LDH, due essentially to the reduction of the surface area and pore closing. Even when immersed in water, our samples did not recover the LDH structure, when either calcined at 450°C and compacted at 7.7 GPa, or calcined at 700°C and immediately compacted at 2.5 and 7.7 GPa.     

Spheroidal weathering of granite porphyry with well‐developed columnar joints by oxidation,iron precipitation,and rindlet exfoliation

Spheroidal weathering, one of the important rock weathering styles, has been attributed to chemical weathering by the water from joint surfaces, and mechanical aspects of the weathering have not been well addressed. We made an investigation on spheroidal weathering of Miocene granite porphyry with well‐developed columnar joints and found that this spheroidal weathering proceeds through chemical processes and accompanying mechanical processes. The investigation of the textures, physical properties, mineralogy, and chemistry of the porphyry revealed the presence of a brown band on the surface margins of corestones, representing the oxidation of pyrite and chlorite, and the precipitation of iron hydroxides, and the consequent generation of micro‐cracks within the band. During weathering, oxidation progresses inwards from joints that surround the rindlets, including both high‐angle columnar and low‐angle planar joints, and causes rounding of the unweathered interior portion of the rock. Microscopic observations of the brown band embedded with fluorescent resin show that pores are first filled with iron hydroxides, and that micro‐cracks then form parallel to the oxidation front in the outer portion of the brown band. Iron hydroxide precipitation increases the P‐wave velocity in the brown band, while micro‐crack formation decreases the tensile strength of the rock. Where the brown band has thickened to ~6 cm, the micro‐cracks are connected to one another to create continuous cracks, which separate the rindlets from the corestone. Micro‐crack formation parallel to the corestone surface may be attributed to compressive stresses generated by small amounts of volumetric expansion due to the precipitation of iron hydroxides in the brown band. Earth surface is under oxidizing environments so that precipitation of iron hydroxides commonly occurs; the spheroidal weathering in this paper is a typical example of the combination of chemical and mechanical processes under such environments. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation of Mg/Al Layered Double Hydroxides by Buffer Solution Method and Cr（Ⅵ） Adsorption Characteristics

利用氨水-氯化铵体系在pH 9～10时具有缓冲能力的特点,以其作为沉淀剂成功合成了镁铝水滑石（Mg3Al-Cl-LDHs）,采用XRD、FT-IR、TG-DTA等手段对材料结构进行表征,并测试了合成Mg3Al-Cl-LDHs样品对溶液中Cr（Ⅵ）的吸附性能。研究结果表明,缓冲溶液法制备的Mg3Al-Cl-LDHs材料晶相单一,晶面生长的有序程度较高,结晶度较好。晶胞参数a=0.3106 nm,c=2.367 nm,粒子尺寸约为36.44 nm。其热分解过程包括水滑石层间结构水脱除和层板羟基脱水、氯离子分解两个步骤。Mg3Al-Cl-LDHs对Cr（Ⅵ）的吸附主要发生在0～1 h内,随着时间的增长吸附量先增加后趋于平缓;温度对Cr（Ⅵ）吸附量影响不大,在常温下即可进行;随着pH值的减小,饱和吸附量先增大后减小,在pH 6时吸附效果较好;2价与3价竞争阴离子比1价阴离子对吸附性能的影响更大。在最佳吸附条件下,Mg3Al-Cl-LDHs对Cr（Ⅵ）的饱和吸附量可达58.73 mg/g,有望应用于实际Cr（Ⅵ）废水处理。     

富马酸根插层镁—铝类水滑石的共沉淀法制备及性质表征

富马酸根插层类水滑石(LDHs)是一种具有较好聚合物相容性和热稳定性等潜在应用价值的多功能复合材料.本文通过密度泛函理论对富马酸根离子静电势和离子尺寸的分析,预测了富马酸根插入LDHs的离子尺寸约为0.802 nm,并从热力学角度说明了富马酸根离子与乙烯、氢自由基加成反应的可能性;以低成本氯化物为原料,采用一步共沉淀法...     

谷氨酸插层镁铝水滑石微观结构与性能:实验与理论研究

采用共沉淀法合成了谷氨酸插层镁铝水滑石(LDHs-Glu),并使用XRD表征技术以及分子动力学模拟方法对其微观结构与性能进行了研究。结果表明随着LDHs-Glu中水分子数量增加,层间距d003逐渐增大。XRD表征得到其层间距为1.328 nm,与理论模拟得到的当水分子数Nw=7时的水滑石层间距d003=1.323 nm相近。随着层间水分子数量增加,水合能逐渐增大,最终趋于流体水的特征值(-41.8 kJ/mol)。水合过程中,水滑石层板与阴离子间的氢键逐渐减少,而层板与水分子间的氢键逐渐增多,说明水分子与层板间的亲和力更强。实验表征与理论模拟相结合的研究方法,有望成为插层复合材料微观结构研究的重要手段。     

Spectral characterization of weathering products of elemental iron in a Martian atmosphere: Implications for Mars hyperspectral studies

Visible and near-infrared spectroscopic properties have been measured on elemental iron experimentally weathered in simulated Martian atmosphere and correlated to mineralogical compositions determined by X-ray diffraction. Two main features are observed in the reflectance spectra, corresponding to two deep bands located at 0.9 and 3.1 μm, respectively the iron band and the hydration band. In early weathering stages both Fe²⁺ and Fe³⁺ bands are identified. In addition, whereas the water band position does not change with time, the Fe²⁺ band disappears, and the Fe³⁺ band shifts towards longer wavelength (from 0.88 to 0.92 μm) because of transition from Fe²⁺ phases (siderite) to Fe³⁺ phases (ferrihydrite and goethite). Apart from these spectral signatures, other bands more specific of each phase are not clearly evidenced, especially for siderite. This is due to relatively low abundance of siderite (<20 wt%), but also to the very small grain size of secondary phase as well as surface coatings of iron (oxy)hydroxides. Therefore, our results suggest that carbonates, even if not detected, could be present in the form of very small grains in the surface of Mars.