天然有机质和金属离子在矿物表面的共吸附

天然有机质(NOM)在土壤、沉积物和水体等环境中无处不在,其中富里酸和胡敏酸是主要形态。富里酸及胡敏酸活性高,易与天然矿物颗粒和金属离子发生相互作用,影响矿物的表面化学特性以及金属离子的形态与迁移性,进而在控制环境中金属离子的生物有效性和毒性等方面起重要作用。本文主要综述了富里酸和胡敏酸等NOM和金属离子在矿物表面共吸附特性与主要影响因素,归纳了表面络合模型和现代光谱技术在上述三元体系研究中的应用及其反应机制研究进展。NOM在较大程度上改变了金属离子在矿物表面的吸附特性和反应机制,并受体系pH、金属离子类型和浓度、NOM浓度、NOM和金属离子的添加顺序、矿物类型等因素的影响。低pH时,NOM通常促进矿物对金属离子的吸附。NOM和金属离子在矿物表面的共吸附机制包括:NOM和金属离子竞争吸附表面活性吸附位点;在溶液中形成NOM-金属离子络合物;形成金属离子桥接矿物表面位点与NOM的A型三元络合物(矿物-金属离子-NOM)或NOM联接矿物表面与金属离子的B型三元表面络合物(矿物-NOM-金属离子);静电作用改变表面电荷特征。最后展望了天然有机质等配体与金属离子在矿物表面共吸附有关的研究热点和方向。     

Chemical reactions of anions in the gas phase

Anions of many types, both organic and inorganic, farmiliar and exotic, can be generated in the gas phase by rational chemical synthesis in a flowing afterglow apparatus. Once formed, the rates, products, and mechanisms of their reactions with neutral species of all kinds can be studied, not only at room temperature but at higher energies in a drift field. These completely unsolvated ions undergo a large number of reactions that are analogous to those they undergo in solution, as well as some that are less familiar. New types of ions, for which there are no counterparts in solution, can be produced and their chemical reactions explored.     

Phototaxis and sensory transduction in Euglena

The accumulation of Euglena gracilis in an illuminated region is brought about by two main mechanisms: orientation and subsequent directed movement (positive phototaxis) toward light scattered from particles in the illuminated zone; and by the trapping of cells in this region because of shock reactions experienced upon the cells encountering a sudden decrease of light intensity at the light-dark boundary (inverse photophobic responses).Phototactic orientation is mediated by inverse photophobic reactions which occur when the shadow of the stigma periodically falls upon the photoreceptor proper. Euglena also exhibits shock reactions when an already high light intensity is increased further (direct photophobic responses). The expression of both types of phobic responses depends upon stimulus intensity and adaptation of the sensory system in a seemingly complex way. A definition of the minimum components of the stimulus transduction system and a systems analytical approach to the study of input-output relationships enables one to construct an electronic analog of the cell's signal processing system that converts the photoreceptor input to commands which activate or inhibit flagellar reorientation. Computer simulation studies show that this model has considerable predictive value. It is hoped that with the approach presented in this article, a generalized model has become available for dealing with the questions of sensory transduction in aneural systems. Certainly, at this point more questions have been raised than have been answered. Where is the processing device located? Are its kinetic properties determined by electrical processes or by the rates of chemical reactions? Is the processor, and thereby the behavior of the orgamism, modulated by natural environmental parameters, and can it be modified permanently through more drastic chemical treatment of the cell? Is the system capable of permanent or transitory modification through repeated response, that is, does it exhibit phenomena analogous to learning and memory in higher organisms? These are only a few of the problems that require study in the future.     

Reactivity of organic compounds in hot water: geochemical and technological implications

Understanding of the reactivity of organic molecules in hot water is developing from studies aimed at explaining how organic matter (kerogen) forms in natural environments and then breaks down into energy source materials. In natural systems where kerogens are depolymerized, hot water is ubiquitous and usually contains salt and minerals. Reactions such as ionic condensation, cleavage, and hydrolysis are facilitated by changes in the chemical and physical properties of water as temperature increases. These changes make the solvent properties of water at high temperature similar to those of polar organic solvents at room temperature, thus facilitating reactions with organic compounds. An understanding of aqueous organic chemistry may lead to potential applications in areas as diverse as the recycling of plastics, the synthesis of chemicals, and coal liquefaction.     

Nanominerals, mineral nanoparticles, and Earth systems

Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller, in at least one dimension, than a few nanometers, to perhaps as much as several tens of nanometers. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This recognition is broadening and enriching our view of how minerals influence the hydrosphere, pedosphere, biosphere, and atmosphere.     

State- and bond-selected unimolecular reactions

Unimolecular reactions are crucial chemical events that have been the focus of increasingly sophisticated investigation in the past decade. Unraveling their details is one fundamental goal of experimental and theoretical studies of chemical dynamics. New techniques are revealing the possibilities, and challenges, of eigenstate- and bondspecific unimolecular reactions. These experiments clearly demonstrate the intimate connection between intramolecular processes and unimolecular reaction dynamics and suggest means of exploiting molecular properties to study and control reactions at the level of individual quantum states.     

铁氧化物-硅酸盐复合物的形成、性质及其对砷的固定

铁氧化物与硅酸盐矿物是土壤中最重要、最活跃的固相组分,它们之间的交互作用直接影响土壤物理化学特性,可有效地调控土壤(类)重金属的迁移、转化。本文以铁氧化物和硅酸盐矿物胶结过程中的一些表观特征变化为出发点,从宏观、表观到微观综述了二者交互作用的界面特性和机理、交互作用前后对土壤砷的固定与释放机制等内容。本文阐明层状硅酸盐与铁氧化物通过多种化学作用而发生表面复合,其中静电作用是作用力之一,带负电荷的硅酸盐与带正电荷的铁氧化物在静电引力的作用下迅速结合,在胶体表面双电层上形成二元团聚体;形成的二元团聚体可改变土壤矿物的表面积和孔性结构、表面电化学特性和物理性质。同时,铁氧化物-硅酸盐复合物表面的活性基团可以通过内层络合共氧的方式将土壤中AsO_4~(2-)络合,形成单核或双核表面络合物而固定砷。复合物对AsO_4~(2-)的吸附能力介于铁氧化物和硅酸盐矿物之间,并更接近铁氧化物的表面吸附特性。本文旨在为土壤砷的原位固定提供理论支撑。     

Venus: chemical weathering of igneous rocks and buffering of atmospheric composition

Data from the Pioneer Venus radar mapper, combined with measurements of wind velocity and atmospheric composition, suggest that surface erosion on Venus varies with altitude. Calcium- and magnesium-rich weathering products are produced at high altitudes by gas-solid reactions with igneous minerals, then removed into the hotter lowlands by surface winds. These fine-grained weathering products may then rereact with the lower atmosphere and buffer the composition of the observed gases carbon dioxide, water vapor, sulfur dioxide, and hydrogen fluoride in some regions of the surface. This process is a plausible mechanism for the establishment in the lowlands of a calcium-rich mineral assemblage, which had previously been found necessary for the buffering of these species.     

Molecular beam studies of elementary chemical processes

The experimental investigation of elementary chemical reactions is presently in a very exciting period. The advance in modern microscopic experimental methods, especially crossed molecular beams and laser technology, has made it possible to explore the dynamics and mechanisms of important elementary chemical reactions in great detail. Through the continued accumulation of detailed and reliable knowledge about elementary reactions, we will be in a better position to understand, predict, and control many time-dependent macroscopic chemical processes that are important in nature or to human society. In addition, because of recent improvements in the accuracy of theoretical predictions based on large-scale ab initio quantum mechanical calculations, meaningful comparisons between theoretical and experimental findings have become possible. In the remaining years of the 20th century, there is no doubt that the experimental investigation of the dynamics and mechanisms of elementary chemical reactions will play a very important role in bridging the gap between the basic laws of mechanics and the real world of chemistry.     

粘土矿物修复重金属污染土壤的研究进展

粘土矿物修复重金属污染土壤是一种原位修复技术，该技术通过向污染土壤中添加粘土矿物，利用粘土矿物对重金属的吸附、配合、共沉淀等作用降低重金属的移动性和生物有效性，减少重金属向水体和植物及其它环境单元的迁移，从而实现了重金属污染土壤的化学修复。由于粘土矿物资源丰富、修复过程操作简单、修复效果迅速，使其在重金属污染土壤的治理过程中有着不可替代的作用。本文对粘土矿物修复重金属污染土壤的机理进行了探讨，总结了粘土矿物对重金属污染土壤的应用效果，介绍了该技术研究的实验方法和评价方法，最后指出了粘土矿物的应用前景以及目前存在的问题，对以后工作应侧重的一些方面提出了建议     

Focal points in mass spectrometry

Mass spectrometry has advanced with the renaissance of time-of-flight mass analysis, the use of ion traps as analyzers and reactors, the application of tandem mass spectrometers to problems in ionic reaction mechanisms and chemical analysis, and the development of new desorption ionization techniques. These developments have allowed determination of the molecular weight distributions for polymers through the 10,000-dalton range, as well as the molecular weight and partial sequence of biopolymers of similar size. Surfaces can be characterized by use of the mass, energy, and angle distributions of particles ejected by sputtering or by laser-induced desorption. Mass spectrometry has yielded new information on the kinetics of catalytic surface reactions and on the reactivity of metal clusters.     

The chemistry of self-splicing RNA and RNA enzymes

Proteins are not the only catalysts of cellular reactions; there is a growing list of RNA molecules that catalyze RNA cleavage and joining reactions. The chemical mechanisms of RNA-catalyzed reactions are discussed with emphasis on the self-splicing ribosomal RNA precursor of Tetrahymena and the enzymatic activities of its intervening sequence RNA. Wherever appropriate, catalysis by RNA is compared to catalysis by protein enzymes.     

Fe-Mg interdiffusion in (Mg,Fe)SiO3 Perovskite and lower mantle reequilibration

Fe-Mg interdiffusion coefficients for (Mg,Fe)SiO3 perovskite have been measured at pressures of 22 to 26 gigapascals and temperatures between 1973 and 2273 kelvin. Perovskite Fe-Mg interdiffusion is as slow as Si self-diffusion and is orders of magnitude slower than Fe-Mg diffusion in other mantle minerals. Length scales over which chemical heterogeneities can homogenize, throughout the depth range of the lower mantle, are limited to a few meters even on time scales equivalent to the age of Earth. Heterogeneities can therefore only equilibrate chemically when they are stretched and thinned by intense deformation.     

Simulations of Gas-Phase Chemical Reactions: Applications to SN2 Nucleophilic Substitution

Computer simulations and animations of the motion of atoms as a chemical reaction proceeds give a detailed picture of how the reaction occurs at a microscopic level. This information is particularly useful for testing the accuracy of statistical models, which are used to calculate various attributes of chemical reactions. Such simulations and animations, in concert with experimental and ab initio studies, have begun to provide a microscopic picture of the intimate details of a particular class of gas-phase ion-molecule bimolecular reactions known as S(N)2 nucleophilic substitution. In these reactions, a nucleophile is displaced from a molecule by another nucleophile. The dynamical model of S(N)2 reactions that emerges from the computer studies, and its relation to statistical theories, is discussed here.     

Distinguishing the direct and indirect products of a gas-surface reaction

It has long been postulated that gas-surface chemical reactions can occur by means of two distinct mechanisms: direct reaction on a single gas-surface encounter or reaction between two adsorbed species. It is shown here that these mechanisms have distinct dynamical signatures, as illustrated by the reaction of hydrogen with chlorine on gold(111). The direct reaction product leaves the surface with a high kinetic energy in a narrow angular distribution that displays a "memory" of the direction and energy of the incident hydrogen atom. The indirect reaction product has a near-thermal energy distribution and an angular distribution that is close to that of a cosine function.     

Linked reactivity at mineral-water interfaces through bulk crystal conduction

The semiconducting properties of a wide range of minerals are often ignored in the study of their interfacial geochemical behavior. We show that surface-specific charge density accumulation reactions combined with bulk charge carrier diffusivity create conditions under which interfacial electron transfer reactions at one surface couple with those at another via current flow through the crystal bulk. Specifically, we observed that a chemically induced surface potential gradient across hematite (alpha-Fe2O3) crystals is sufficiently high and the bulk electrical resistivity sufficiently low that dissolution of edge surfaces is linked to simultaneous growth of the crystallographically distinct (001) basal plane. The apparent importance of bulk crystal conduction is likely to be generalizable to a host of naturally abundant semiconducting minerals playing varied key roles in soils, sediments, and the atmosphere.     

土壤矿物与生物炭可溶性组分的交互作用及机制

为探究生物炭可溶性组分与土壤矿物的交互作用,进而从矿物角度揭示生物炭在土壤中的稳定机制,以水稻秸秆为生物质原料制备不同炭化温度的生物炭(RS300、RS500和RS700),选用高岭石、蒙脱石和伊利石3种土壤矿物,开展土壤矿物与生物炭可溶性组分的吸附结合实验。结果表明:随生物炭可溶性组分碳浓度的升高,土壤矿物对其吸附量逐渐增加,3种土壤矿物的吸附量顺序总体为蒙脱石>伊利石>高岭石,这与土壤矿物的自身结构直接相关。高岭石、蒙脱石对生物炭可溶性组分的结合机制以范德华力为主,其贡献比例分别为3.4%~87.0%和32.0%~82.0%;而伊利石与RS300可溶性组分的吸附结合作用以Ca²⁺架桥为主(贡献比例为60.4%~70.6%),与RS500和RS700可溶性组分的结合以范德华力为主(贡献比例分别为18.7%~65.0%和53.0%~67.6%)。经综合对比分析,RS500通过与蒙脱石的交互结合,最大程度上抑制了可溶性组分的溶解,有利于更好地发挥生物炭的固碳减排优势。     

铁锰氧化矿物添加对土壤镉有效态及生物效应的影响

利用铁锰氧化矿物对土壤中镉的吸附特性,研究了镉污染的土壤中施加铁锰氧化矿物后对土壤中镉的有效态及植物有效性的影响.结果表明:在土壤中添加铁锰氧化矿物后,土壤中镉的有效态含量明显降低;铁锰氧化矿物对土壤中镉的吸附在十天左右达到平衡;在相同的加入量,软锰矿比针铁矿的吸附效果好;利用数量化理论预测法,建立了氧化矿物加入量和土壤中镉含量及理化性质之间关系的预测模型,预测精度较好;通过温室土培试验,几种植物添加铁锰氧化矿物后镉的总量明显降低,证明添加铁锰氧化矿物可以明显降低土壤中镉的生物有效性.     

Thermochemical decomposition of water based on reactions of chromium and barium compounds

A potentially useful thermochemical cycle developed for the production of hydrogen and oxygen from water consists of three chemical reactions that take place in the temperature range from 400 degrees to 1200 degrees K. The oxidation and reduction of chromium compounds by barium hydroxide and the hydrolytic disproportionation of barium chromate(IV) and barium chromate(V), the reactions which constitute the proposed cycle, have been demonstrated.