MINERAL-AQUEOUS SOLUTION INTERFACES AND THEIR IMPACT ON THE ENVIRONMENT
MINERAL-AQUEOUS SOLUTION INTERFACES AND THEIR IMPACT ON THE ENVIRONMENT
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DOI：
10.7185/geochempersp.1.4
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发表时间：
2012-10-01
影响因子：
3.8
通讯作者：
Calas, Georges
中科院分区：
文献类型：
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作者：
Brown, Gordon E., Jr.;Calas, Georges
这个视角描述了地球化学的一个领域，涉及矿物，它们的表面，以及这些表面与水和水中存在的离子和分子的相互作用，其中一些，如砷，对生物体有很高的毒性。这些相互作用以及微生物与矿物表面之间的相互作用的重要性怎么估计都不为过，因为它们控制着我们自然环境的组成，并减轻了一些人为干扰，这些干扰正在以通常不可预测、有时甚至有害的方式改变我们的环境。以下概述我们的科学生涯迄今为止，包括我们以前和现在的学生和研究合作者的简历，我们强调了一些科学贡献的维克托Goldschmidt，欧文朗缪尔，莱纳斯鲍林，康拉德克劳斯科普夫，沃纳斯图姆，和其他直接或间接导致这一领域的发展，回顾个人互动与一些这些先驱。在所有科学领域，当新的实验方法、新的表征和计算工具以及新的理论出现时，就会取得进步。矿物-水界面地球化学领域也不例外，在过去的30-40年里，由于分子水平实验方法的巨大变化，特别是那些涉及被称为同步加速器的极强X射线源的实验方法，在数字计算机和分子水平理论中，矿物-水界面地球化学领域取得了显着进展。我们（GB和GC）提供我们的观点，同步辐射源的发展及其应用的矿物-水界面过程，根据我们的个人经验，在这些主要的用户设施的早期开始。由于矿物-水界面的复杂性，特别是在天然有机物和微生物起着重要作用的地表环境中，矿物-水界面的研究是一个复杂的过程。在我们寻求理解发生在大气中的化学过程时，我们采用还原论的方法，并考虑复杂性不断增加的简单模型系统。这些界面在分子水平上。我们开始讨论的酸碱化学的金属氧化物表面接触散装水和经验模型的双电层（EDL），被认为是发展在固体-水界面。然后，我们考虑的实验和理论研究的EDL，这表明，经典的Helmholtz-Gouy-Chapman-Stern-Grahame模型是定性正确的。下面的故事，一些新的，有争议的研究水的结构，我们讨论（1）实验和理论研究的水与金属氧化物表面的反应，（2）水合矿物表面的结构，（3）金属氧化物表面的阳离子和阴离子的吸收，（4）X射线吸收光谱研究的铅和砷吸附复合物在矿物-水界面，（5）有机分子在矿物-水界面的吸附，（6）有机和微生物生物膜涂层对矿物表面的反应性的影响，以及（7）粒度对纳米颗粒的结构和性质的影响，使用水铁矿作为天然纳米矿物的实例，使用银纳米颗粒作为工程纳米颗粒的实例。为了与地球化学观点的精神保持一致，我们穿插了我们参与这些研究领域的个人经验。为了把这些更基础的研究结果放在上下文中，我们最后讨论了矿物-水界面地球化学在环境和地球科学问题中的选定应用，包括（1）在受到非均匀扰动的真实的环境系统中的吸附反应，重点是美国和法国的铅污染区和南亚和法国的砷污染区，（2）硅酸盐矿物和锆石的溶解和风化机制，（3）铝与硅藻表面的相互作用，（4）钴与锰氧化物的相互作用，（5）矿物表面反应在同位素分馏中的作用，（6）矿物表面在矿物碳酸化反应中的作用，（7）与核废料玻璃蚀变有关的表面化学，最后，我们对过去30年来矿物-水界面过程的研究现状进行了总结，并对这一领域中等待下一代地球化学家的一些令人兴奋的研究机会提出了我们的看法。
This Perspective describes an area of geochemistry that involves minerals, their surfaces, and the interactions of these surfaces with water and the ions and molecules present in water, some of which, like arsenic, are highly toxic to organisms. The importance of these interactions, together with those between microorganisms and mineral surfaces, cannot be overestimated, for they control the composition of our natural environment and mitigate some of the anthropogenic perturbations that are changing our environment in ways that are often unpredictable and sometimes detrimental. Following overviews of our scientific careers to date, including acknowledgments of our former and current students and research collaborators, we highlight some of the scientific contributions of Victor Goldschmidt, Irving Langmuir, Linus Pauling, Konrad Krauskopf, Werner Stumm, and others that led directly or indirectly to the evolution of this field, recalling personal interactions with some of these pioneers. In all fields of science, advances are made when new experimental methods, new characterisation and computational tools, and new theories become available. The field of mineral-water interface geochemistry is no different and has advanced significantly over the past 30-40 years due to enormous changes in molecular-level experimental methods, particularly those involving the extremely intense X-ray sources known as synchrotrons, in digital computers, and in molecular-level theories. We (GB and GC) offer our perspectives on the development of synchrotron radiation sources and their applications to mineral-water interface processes, based on our personal experiences starting in the early days of these major user facilities. We discuss some of these new methods and theories and their applications to mineral-water interface processes through various examples.Because of the complexity of mineral-water interfaces, particularly in natural Earth surface environments, where natural organic matter and microorganisms play very important roles, we adopt a reductionist approach and consider simple model systems of increasing complexity in our quest to understand the chemical processes occurring at these interfaces at the molecular level. We start with a discussion of the acid-base chemistry of metal-oxide surfaces in contact with bulk water and empirical models of the electrical double layer (EDL) that is thought to develop at solid-water interfaces. We then consider experimental and theoretical studies of the EDL, which show that the classical Helmholtz-Gouy-Chapman-Stern-Grahame model is qualitatively correct. Following a story about some of the new, controversial research on the structure of water, we discuss (1) experimental and theoretical studies of the reaction of water with metal-oxide surfaces, (2) the structure of hydrated mineral surfaces, (3) the uptake of cations and anions on metal-oxide surfaces, (4) X-ray absorption spectroscopy studies of lead and arsenic adsorption complexes at mineral-water interfaces, (5) the adsorption of organic molecules at mineral-water interfaces, (6) the effect of organic and microbial biofilm coatings on the reactivity of mineral surfaces, and (7) the effect of particle size on the structure and properties of nanoparticles, using ferrihydrite as an example of a natural nanomineral and silver nanoparticles as an example of an engineered nanoparticle. In keeping with the spirit of Geochemical Perspectives, we interspersed personal experiences resulting from our involvement in most of these research areas.To put the results of this more basic research in context we end by discussing selected applications of mineral-water interface geochemistry to environmental and Earth science problems, including (1) sorption reactions in real environmental systems that were anthropogenically perturbed, focusing on lead-polluted sites in the USA and France and As-polluted areas in southern Asia and France, (2) dissolution and weathering mechanisms of silicate minerals and zircon, (3) the interaction of aluminum with diatom surfaces, (4) the interaction of cobalt with manganese oxides, (5) the role of mineral-surface reactions in isotope fractionation, (6) the role of mineral surfaces in mineral-carbonation reactions, and (7) the surface chemistry associated with alteration of nuclear waste glasses.We finish with our thoughts on what has and has not been learned about mineral-water interface processes over the past 30 years and offer our opinions about some of the exciting research opportunities in this field that await the next generation of geochemists.