天然沸石改性应用研究进展

分析了2001年～2007年期间国内发表的根据不同产地、不同类型天然沸石的改性方法及应用方面的论文.改性方法主要有离子交换改性、加热焙烧改性、矿物表面改性、载体改性等.介绍了上述几种方法的特点和功效.     

Characterization of a natural magnetite

Single crystals of a rock magnetite were separated from steatite cobbles collected in a geological site near the city of Serro (18° 36′ 47′′ S 43° 22′ 46′′ W), Minas Gerais, Brazil. A typically well-shaped magnetite single crystal was characterized by chemical analysis, ⁵⁷Fe Mössbauer spectrometry at 300, 77 and 4 K and under an applied magnetic field of 6 T at 10 K, magnetization measurements and electronic microprobe. From Mössbauer data, the sample is stoichiometric with a tetrahedral and octahedral site occupancy ratio of 1:2. Elemental chemical analysis and point-to-point electron microscope probing show some inclusions of lamellar ilmenite (≤ 1 mass%) randomly distributed throughout the magnetite matrix, and also that the magnetite matrix is constituted only by Fe²⁺ and Fe³⁺, with no isomorphic substitution. Results are discussed on the basis of the magnetization curve and of the temperature dependence of the AC magnetic susceptibility. The Verwey transition occurs in the temperature range of 100–115 K, observed by a sudden change in the temperature dependence of the magnetization.     

Infrared absorption and reflection spectroscopy on the natural zeolite harmotome

Infrared absorption spectra (400–4000 cm^?1) were measured on dehydrated and partially dehydrated powder of the zeolite harmotome Ba₂[(AlO₂)₄(SiO₂)₁₂]·12H₂O. Whereas the disappearance of the bending mode at ～1640 cm^?1 proved the absence of water molecules after dehydration, the O-H stretching mode at 3200 cm^?1 showed the presence of hydroxyl groups. The vibrational modes of the framework are only slightly influenced by dehydration.     

Mazzite,a new mineral,the natural counterpart of the synthetic zeolite Ω

Mont Semiol (also called Mont Semiouse), Montbrison, Loire, France, is the only place where the zeolite offrettite is known to occur. Now, a new mineral, Mazzite, has been found in the same locality. It occurs in the form of tiny needles, and its properties closely match those of the synthetic “molecular sieve” Ω. The chemical formula is Na_0.03K_1.91Ca_1.35Mg_1.99[Al_9.77Si_26.54O₇₂]·28.03 H₂O. Lattice dimensions are a=18.392 Å, c=7.646 Å, with P 6₃/mmc as most probable space group; D_calc.=2.108. Offrettite and mazzite occur in association with phillipsite, chabazite, calcite and siderite. The mineral has been so named in honour of Prof. Fiorenzo Mazzi.     

天然沸石的铵吸附容量研究

为了探讨天然沸石对NH4^＋的吸附规律,以江苏镇江的天然沸石为实验对象,测试其矿物组成与化学成分,通过静态摇床法实验研究其对铵离子的吸附特性及阳离子的交换特性,进行吸附等温线实验。结果表明,实验沸石对NH4^＋吸附等温线符合Langmuir公式。根据数学分析,确定沸石的铵吸附容量。     

Removal of chromate from aqueous solution using treated natural zeolite

This paper present the possible alternative removal options for the development of safe drinking water supply in the chromium-affected areas. The Cr (VI) state is of particular concern because of its toxicity. The mordenite has suitable mineralogical properties that enable them to be used for ion-exchange processes. This includes total cation exchange capacity. However, in the present work, the modified-natural zeolite was used as an adsorbent for the removal of Cr (VI) from aqueous solution. The ability of modified natural zeolite (mordenite) to remove inorganic anion was investigated. Laboratory experiments were conducted examining the effect of the sorption of cationic surfactants. On the basis of the results of this study, the HDTMA-HSO₄ modified zeolite appears suitable as a sorbent for hexavalent chromium whereas EHDDMA-modified zeolite were not removed with the same efficiency. The sorption of chromate on HDTMA-zeolite results from a combination of entropic, coulombic, hydrophobic effects, and HDTMA counterion.     

Geochemical evaluation and environmental application of Yemeni natural zeolite as sorbent for Cd<Superscript>2+</Superscript> from solution: kinetic modeling,equilibrium studies,and statistical optimization

Yemeni natural zeolite was characterized by XRD, SEM, FTIR and XRF as well as its applicability as a sorbent material for Cd²⁺ ions in aqueous solutions. The zeolitic sample is clinoptilolite-K of heulandite group with intermediate Si/Al ratio. The removal% of Cd²⁺ by natural clinoptilolite was investigated as a function of contact time, zeolite dose, pH and initial concentration of Cd²⁺ ions. Kinetic experiments indicated that sorption of Cd²⁺ follows two steps: rapid ion exchange process on the outer surface is followed by slow adsorption process on the inner surface of clinoptilolite. The equilibrium was attained after 120 min, and the results were fitted well with pseudo-second order and Elovich kinetic models. The Cd²⁺ removal% is strongly dependent on pH value and increases with the increasing pH value. Equilibrium sorption isotherm of Cd²⁺ by clinoptilolite was described well using the Langmuir, Freundlich, and Temkin isotherms models. However, the data relatively well fitted with Freundlich model (R ² = 0.97) rather than by the other models. Response surface methodology in conjunction with central composite rotatable statistical design was used to optimize the sorption process. The model F-value indicated the high significance of second-order polynomial model to represent the interaction between the operating parameters. From the Design Expert’s optimization function, the predicted optimum conditions for maximum removal% of Cd²⁺ (80.77%) are 116 min contact time, 0.27 gm dose, and pH 7 at an initial Cd²⁺ concentration of 25 mg/L.     

Characterization of natural colloids from a river and spring in a karstic basin

 Colloids are known to transport contaminants over long distances in natural media. Despite this potentially harmful effect, very few studies have been undertaken in subsurface aquifers. This paper presents the first results of a study of natural colloids and particles in a karstic aquifer. The site was chosen for its coverage by clay layers and peat which deliver various and numerous particle types in water. The methodological part describes three methods used for size determination and sample fractionation of surface water and spring water. These methods have been adapted for the treatment of multiple samples due to the rapid discharge variation typical of karstic aquifers. The analysis of many particle size distributions (PSD) shows that they can be described by a Pareto law. The variation of the slope of the PSD at the spring is mainly dependent on discharge. This behavior is interpreted as a washing of the karstic drains during the first phase of high flow events. Fractionation of the samples allowed application of various characterization techniques to particle size classes. X-ray diffraction (XRD) patterns showed that most of the mineral particles originated from Quaternary deposits and limestones. However the use of scanning electron micrsocopy with energy-dispersive spectrometer (SEM-EDS) detailed the composition of individual particles and revealed particles not found by XRD. These techniques also showed the high complexity of the natural particles and the important place of coprecipitation in their formation. Consequences on the fluxes of particulate matter and its potential role as a carrier of contaminants are discussed. Received: 28 October 1996 · Accepted: 7 July 1997     

吉林省沸石的性质与应用

沸石是一种新近被综合利用的非金属矿产,本文通过对吉林省的沸石类型、矿物特征、化学组合、矿石的物理性质(热稳定性、比表面积)进行测定,从矿石的本质上说明其应用的可行性,通过对矿石在农业,建材方面的试验结果来证明矿石的可利用性。为沸石矿物综合利用提供一些试验数据,以便在应用中参考。     

Kinetics of formation of zeolite Na-A [LTA] from natural kaolinites

 The kinetics and mechanism of hydrothermal formation of zeolite A from natural kaolinites have been studied using as starting materials two international kaolinite standards (KGa-1 and KGa-2 from Georgia, USA) exhibiting a different degree of stacking disorder. Precursors utilized for the synthesis were prepared by heating the kaolinites at 800 °C. Metakaolinite was also prepared from KGa-1 by thermal activation at 600 °C. The hydrothermal syntheses were accomplished by heating the samples in NaOH solutions at temperatures between 70 and 110 °C. The kinetic experiments were performed by time-resolved synchrotron powder diffraction in isothermal mode using a transmission geometry and an Image Plate detector. The results of the kinetic analysis are interpreted in the light of the structural state of the starting kaolinite, and of the temperature of activation of the precursor material. For kaolinite activated at high temperature the nucleation and crystallization of zeolite A is essentially independent of the defect density of the original kaolinite, and the thermal history of the precursor seems to be the main controlling parameter. The formation process of zeolite A from metakaolinite materials obtained at lower activation temperatures shows significantly faster reaction rates and lower apparent activation energies. This is again interpreted in the light of the short range inhomogeneities present in metakaolinite. As the reaction proceeds metastable zeolite A transforms into hydroxy-sodalite. Received April 18, 1996 / Revised, accepted September 27, 1996     

Isopropylxanthate ions uptake by modified natural zeolite and removal by dissolved air flotation

This work describes a laboratory study concerning the adsorption of isopropylxanthate ions onto modified zeolites particles. The separation of the loaded carrier and their removal, from aqueous solutions, was conducted by flocculation followed by dissolved air flotation, DAF. The zeolite employed was a natural sample (approximately 48% clinoptilolite and 30% mordenite) which was previously treated with sodium ions (activation) and modified with copper ions (Cu–Z) before the xanthate ions uptake. Adsorption capacities (q_m) for Cu–Z were 0.34 meq g^− 1 for the powdered form, and 1.12 meq g^− 1 for the floc form. The adsorption capacity for the floc form appears to involve an enhanced electrostatic adsorption due to the positive sites on the floc surface. In all cases, the isopropylxanthate concentration in the treated water was found to be negligible (< 0.04 mg L^{− 1}). The flotation technique showed to be a fast process, requires a low recycle ratio (20%) in air saturated water, and the treated water ended up with a very low residual turbidity (6.8 NTU). It is believed that this adsorption–flotation technique, here named adsorptive particulate flotation, using activated and modified natural zeolite has a high potential as an alternative for pollutants removal (copper and isopropylxanthate ions) from waste mining effluents.     

河北围场天然沸石的矿物学特征及吸附性研究

河北承德围场地区含有储量丰富的天然沸石资源,然而目前关于该地区天然沸石的研究较少。本文利用X射线衍射仪、X射线荧光光谱仪、红外光谱仪、比表面积及孔隙度分析仪和扫描电镜及能谱分析仪等对围场天然沸石的矿物学特征进行了研究,并分析了围场天然沸石对苯、甲苯和水蒸气等的吸附性。结果发现,该地区天然沸石主要含斜发沸石和石英,硅铝比为5. 3,样品中含有少量微孔和大量介孔,具有相对较高的比表面积;样品对苯、甲苯和水蒸气均具有良好的吸附效果。     

Geological and environmental factors involved in natural gas accidents

Variability in soil mineralogy, texture, and pavement cover are involved in events leading to undetected gas leaks and subsequent explosions in Bowie, Md. and Washington, D.C. These geologic parameters are involved in selectively removing the gas odorant additive t-butyl merceptan as the gas came into contact with the soil near the pipeline breaks. This removal resulted in an accumulation of combustable natural gas without detectable odor. Soil samples from drill holes and near surface sites were utilized to map soil type, texture, and mineralogy. Residual methane content of the samples was also measured. The data from two dissimilar sites indicates that finegrained soil enriched in montmorillonite preferentially removes the odorant.     

Characterization of calcium isotopes in natural and synthetic barite

The mineral barite (BaSO₄) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (δ^44/40Ca = −2.01 ± 0.15‰) but are different from hydrothermal and cold seep barite samples (δ^44/40Ca = −4.13 to −2.72‰). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, Δ^44/40Ca = −3.42 to −2.40‰. Temperature, saturation state, , and aCa²⁺/aBa²⁺ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower ⁴⁴Ca/⁴⁰Ca than calcite, by −9‰ at 0 °C and −8‰ at 25 °C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower δ^44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca²⁺ substitution for Ba²⁺ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca²⁺ and other elements in inorganic and biogenic minerals.     

Characterization of natural pyrolusite by electron microscopy

A manganese-bearing mineral characterized by a black hair-like surface crystal growth, and somewhat unique to the Socorro County, New Mexico Area, has been referred to as psilomelane or pseudo-pyrolusite. X-ray diffraction measurements indicated the structure to be the tetragonal (a=4.42 Å, c=2.87Å) MnO₂ (pyrolusite) structure; with α-Mn enrichment. Detailed examinations of the mineral specimens made in the scanning and transmission electron microscopes showed the fiber crystals to be pseudo-fluted as a result of an apparent stacking of long needles to form continuous single-crystral bundles oriented along the x-axis These crystals were shown by selected-area electron diffraction to be composed of extended superstructure cells, and these to be commposed of as many as 10 MnO₂ unit cells stacked along the x-axis; interrupted by a stacking fault shear of the basic MnO₂ lattice resulting in stacking faults. Individual whisker crystals were observed to be terminated by crystallographic facets which is indicative of solution growth expected on considering their geological and mineralogical environment.     

生物标志的环境含义及其应用

生物标志,包括生物的壳体构造、生态特征、地球化学和群落组合等,在地球科学研究中具有十分重要的理论意义和实用价值。本文首先论述了影响生物生存的环境因素,包括地球因素和宇宙因素。并根据西南地区晚古生代地层中主要生物门类,特别是微体古生物的古生态,论证生物标志的环境含义。在此基础上,指出生物标志在地学研究中的应用,包括划分和对比地层、判断沉积相、分析古气候变化、划分生物地理区、推断海（湖）平面变化、指示地质找矿和阐释宇宙演变。最后,探讨生物标志的研究方法,包括分类统计学方法、形态构造学方法、地球化学方法和沉积埋藏学方法。     

Isolation and application of a wild strain photosynthetic bacterium to environmental waste management

A new photosynthetic bacterium isolate was morphologically identified as a non-motile rod-shape gram-negative bacterium. It produced a dark red culture under phototrophic condition, reproduced by budding and formed a lamellar intracytoplasmic membrane system parallel to cytoplasmic membrane, which contained bacteriochlorophyll a and caratenoids. It’s physiological and nutrient requirement tests gave indication that the isolate thrived and multiplied in varied environmental conditions. It was consequently named Z08 and identified as Rhodobacter sphaeroides by 16SrDNA. Adaptation of Z08 to biodegradation of two environmentally concerned wastewaters, i.e. soybean and pharmaceutical wastewaters, attested its potential in wastewater bioremediation. Z08 adaptation in a suspended batch photobioreactor treating pharmaceutical wastewater at 3500lx radiation recorded best result after wastewater dilution of 1:4 with concomitant chemical oxygen demand reduction, biomass yield and specific growth of 50 %, 780 mg/L and 0.015/h, respectively at the lowest hydraulic retention time of three days. Furthermore, gas chromatography mass spectra analyses of treated and raw pharmaceutical wastewater indicated that high molecular weight recalcitrant compounds found in the pharmaceutical wastewater were transformed to less toxic and acceptable lower molecular weight substances through biodegradation. Whilst Z08 treatment of soybean wastewater under natural light intensity radiation recorded 80 % reduction, 1540 mg/L and 0.025/h for chemical oxygen demand, biomass and specific growth rate respectively regardless of the food to microorganism ratio. This preliminary investigation showed that isolate Z08 has some toxic tolerance level which could detoxify refractory substances with great potential for cell protein recovery in high organic strength wastewater. Therefore, strain Z08 could be employed in biodegradation of contaminated wastewater streams.     

Physical-chemical and electrochemical characterization of Fe-exchanged natural zeolite applied for obtaining of hydrogen peroxide amperometric sensors

This work demonstrates that a Fe-exchanged zeolitic volcanic tuff from Cepari (Fe/CV) (Bistrita-Nasaud County, Romania) is suitable for the amperometric detection of H₂O₂, using new modified carbon paste electrodes based on this material (Fe/CV-CPEs). The physical-chemical characterization of natural (CV) and modified (Fe/CV) forms was realized using chemical analysis, optical microscopy, scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transformed infrared (FTIR) spectroscopy. The resulting electrodes (Fe/CV-CPEs) were investigated using cyclic voltammetry and chronoamperometry measurements. The new electrodes showed good electrocatalytic activity toward H₂O₂ reduction. The calibration curve for H₂O₂ determination was linear up to 0.1 mM, with a detection limit (signal to noise ratio of 3) of 20 μM.     

From natural hazard to environmental catastrophe: Past and present

The number of environmental catastrophes is rising, mostly owing to an increase in hydrometeorological hazards. The number of disasters is escalating as the world population grows and people settle in marginal areas. In order to improve preparedness, the geological and archaeological records must be investigated as they hold a wider range of possible events than the much shorter instrumental record. Catastrophes will gain amplitude with rapid onset, long duration, larger affected area, inflexible society and, of course, convergence of threats. Too often, it seems that today's societies resist learning from the past and therefore tend to repeat errors. A new field of science is emerging: the science of environmental catastrophes, which requires not only robust chronologies to firmly link cause and effect, but also bridges the crossing between the geosciences and social sciences.