Copper sulfates, phosphates, and arsenates as pollution containers and vectors

铜的主要来源是原生硫化物矿物。它们的氧化导致在过去开采铜矿或目前正在开采铜矿的地点形成次生和第三代铜矿。这些矿物质是铜的硫酸盐、磷酸盐、砷酸盐或碳酸盐。它们也可以在被铜污染的土壤中发现，这种元素是作为廉价杀真菌剂的一种成分引入的，它们是由人造铜结构（例如雕像）降解而形成的。在这些环境中，次生和第三系铜矿物的形成过程受其热力学性质的控制。在这里，我建议研究一些铜的硫酸盐，磷酸盐和砷酸盐的热力学性质。在研究中，我们将分别通过酸溶液和低温准绝热量热法确定这些相的形成熵（AH°f）和标准熵（S°）。本研究的材料将在我们的实验室中完全合成、制备和彻底表征。这项研究的一个组成部分将是在Lubietova（德国Libethen）地区的二级和三级铜矿物的研究，那里发现了丰富的硫酸铜，磷酸铜和砷酸铜。我们将通过透射电子显微镜研究特别是贫结晶的第三纪矿物，考虑到两个问题：（1）在这里的条件下，控制Cu沉淀的初始相是什么？（2）微生物是否帮助或协助沉淀过程？使用测量的AH°f和S°值，我们将计算每个研究相的吉布斯自由能，并构建与环境条件相关的相图。相图将适用于组合确定在lubietova，在网站上污染的铜一般，包括污染的土壤和降解铜结构。建议的工作的最终目标是提出一个可靠的和一致的热力学数据库的铜矿适用于任何污染的网站，这些数据可能需要。

The principal source of copper are primary sulfide minerals. Their oxidation leads to the formation of secondary and tertiary copper minerals at sites where copper ores were mined in the past or are being mined currently. These minerals are sulfates, phosphates, arsenates, or carbonates of copper. They can be also found in soils polluted by copper where this element was introduced as a component of cheap fungicides and they form by degradation of man-made copper structures, for example, statues. In all these environments, formation processes of the secondary and tertiary Cu minerals are controlled by their thermodynamic properties. Here I propose to study the thermodynamic properties of a number of copper sulfates, phosphates, and arsenates. Within the study, we will determine the formation enthalpies (AH°f) and standard entropies (S°) of these phases by acid-solution and low-temperature quasi-adiabatic calorimetry, respectively. Material for this study will be exclusively synthetic, prepared and thoroughly characterized in our laboratory. An integral part of this study will be the research of secondary and tertiary copper minerals at the locality Lubietova (Libethen in German) where copper sulfates, phosphates, and arsenates are found in abundance. We will investigate especially the pooriy crystalline tertiary minerals by the means of transmission electron microscopy, with two questions in mind: (1) What are the initial phases that control precipitation of Cu under the conditions present here, and (2) Do microorganisms aid or assist the precipitation processes? Using the measured AH°f and S° values, we will calculate Gibbs free energy for each studied phase and construct phase diagrams relevant to environmental conditions. The phase diagrams will be applied to the assemblages determined at lubietova, at sites polluted by Cu in general, including the polluted soils and degrading copper structures. The ultimate goal of the proposed work is to present a reliable and consistent thermodynamic database for the copper minerals applicable to any polluted site where such data may be needed.