First evidence of the production of Ginalski E5 button spurs from copper alloy in Central Europe

Ginalski-type E5 button spurs made from a Cu alloy are a characteristic attribute of the Middle Roman period in barbarian Europe. The find of part of a mould made of non-ferrous metal at the Luleč site in the district of Vyškov, Czech Republic, provided key evidence for explaining the issue of their production. The discovery of this unique artefact showed that based on current knowledge, the spurs made from a Cu alloy were also produced in the Middle Danube region and not only in Northeast Europe as had previously been thought.     

Mineral precipitation associated with vertical fault zones: the interaction of solute advection,diffusion and chemical kinetics

This article is concerned with chemical reactions that occur between two interacting parallel fluid flows using mixing in vertical faults as an example. Mineral precipitation associated with fluid flow in permeable fault zones results in mineralization and chemical reaction (alteration) patterns, which in turn are strongly dependent on interactions between solute advection (controlled by fluid flow rates), solute diffusion/dispersion and chemical kinetics. These interactions can be understood by simultaneously considering two dimensionless numbers, the Damköhler number and the Z‐number. The Damköhler number expresses the interaction between solute advection (flow rate) and chemical kinetics, while the Z‐number expresses the interaction between solute diffusion/dispersion and chemical kinetics. Based on the Damköhler and Z‐numbers, two chemical equilibrium length‐scales are defined, dominated by either solute advection or by solute diffusion/dispersion. For a permeable vertical fault zone and for a given solute diffusion/dispersion coefficient, there exist three possible types of chemical reaction patterns, depending on both the flow rate and the chemical reaction rate. These three types are: (i) those dominated by solute diffusion and dispersion resulting in precipitation at the lower tip of a vertical fault and as a thin sliver within the fault, (ii) those dominated by solute advection resulting in precipitation at or above the upper tip of the fault, and (iii) those in which advection and diffusion/dispersion play similar roles resulting in wide mineralization within the fault. Theoretical analysis indicates that there exists both an optimal flow rate and an optimal chemical reaction rate, such that chemical equilibrium following focusing and mixing of two fluids may be attained within the fault zone (i.e. type 3). However, for rapid and parallel flows, such as those resulting from a lithostatic pressure gradient, it is difficult for a chemical reaction to reach equilibrium within the fault zone, if the two fluids are not well mixed before entering the fault zone. Numerical examples are given to illustrate the three possible types of chemical reaction patterns.     

Revealing the Monastic Kitchen: Chemical Analysis of the Soil Inside the Monastery of Cornellana (North‐West Spain)

The residues deposited on the floor of the kitchen of the monastery of Cornellana (Asturias, Spain), while it was still in use in the 18th century, have been analysed using different techniques, including the Kjeldahl method, phenol – sulphuric acid assay, FT–IR, SEM–EDX and LOI. This has allowed us to determine the areas of concentration of proteins, carbohydrates, fatty acids, phosphorus and carbonates, and thus approach the interpretation of the layout of the different areas of activity related to the treatment and cooking of foodstuffs in the kitchen. In any case, and regardless of the fact that this is the first time that these techniques have been applied to study a monastic kitchen in the Iberian Peninsula, the aim of this research is to demonstrate their applicability to other case studies of this integrated set of analytical techniques, some of which are not used very often in the analysis of concentrations of residues and analysis of areas of activity on archaeological soils.     

Organic–inorganic rock–fluid interactions in stylolitic micro‐environments of carbonate rocks: a FIB‐TEM study combined with a hydrogeochemical modelling approach

Stylolites and the interfaces to the host limestone have been investigated by means of a multidisciplinary analytical approach (thin section microscopy, FIB‐TEM, organic geochemistry and petrography). Carbonate dissolution assuming different boundary conditions was simulated by applying a generic hydrogeochemical modelling approach. It is the conceptual approach to characterize and quantify traceable organic–inorganic interactions in stylolites dependent on organic matter type and its thermal maturity, and to follow stylolite formation in carbonates as result of organic matter reactivity rather than pressure solution as a main control. The investigated stylolite samples are of Upper Permian (Lopingian, Zechstein), Middle Triassic (Muschelkalk) and Late Cretaceous (Maastrichtian) age and always contain marine organic matter. The thermal maturity of the organic matter ranges from the pre‐oil generation zone (0.4–0.5% R_r) to the stage of dry gas generation (>1.3% R_r). The results of the generic hydrogeochemical modelling indicate a sharp increase of calcite dissolution and the beginning of stylolite formation at approximately 40°C, which is equivalent to a depth of less than 800 m under hydrostatic conditions considering a geothermal gradient of 30°C and a surface mean temperature of 20°C. This temperature corresponds to the pre‐oil window when kerogens release an aqueous fluid enriched in carbon dioxide and organic acids. This aqueous fluid may change the existing pore water pH or alkalinity and causes dissolution of carbonate, feldspar and quartz, and clay mineral precipitation along the stylolite. Dissolution of limestone and dolostone leads to reprecipitation of calcite or dolomite opposite of the dissolution side, which indicates only localized mass redistribution. All these integrated hydrogeochemical processes are coupled to the generation of water during organic matter maturation. In all of the calculated hydrogeochemical scenarios, H₂O is a reaction product and its formation supports the suggested hypothesis.     

Synthesis by microbes or chemists? Pharmaceutical research and manufacturing in the antibiotic era

This article presents a case study of the rise of Pfizer as a leading pharmaceutical company, with a focus on changing relationships between manufacturing technology and R&D between the mid 1940s and the mid 1960s. Pfizer first moved into pharmaceuticals through participation in the US government's penicillin effort during World War II. The company had expertise in deep tank, biological fermentation for the production of chemicals that it adapted to the manufacture of penicillin. Having greatly expanded its biological manufacturing capacity to meet state needs, Pfizer adopted an R&D program to find new microbial antibiotics suited to its manufacturing technology after the war ended. Pfizer's successes in this antibiotic era established the firm as a major pharmaceutical company. In looking to larger commercial markets for drugs, Pfizer, like its competitors, pursued medicines for chronic diseases rather than acute infections. For this pursuit, in the 1950s and 1960s, Pfizer transformed itself into a chemistry‐orientated pharmaceutical firm by reorienting its R&D toward chemistry. This led to a growing divergence between R&D and manufacturing and the eventual replacement of biological manufacturing with chemical manufacturing. The article explores the changing trajectories of R&D and manufacturing at Pfizer, their shifting positions within the firm, and the consequences of these changes and shifts for the firm's strategy and organization.     

Apatite grain boundary morphology and its response to low-temperature fluid infiltration in crystalline basement

Apatite grain boundaries on fractured rock surfaces have been examined in an amphibolite facies regional metamorphic granite gneiss from the central Swiss Alps. The morphology of apatite has been characterized using a scanning electron microscope and matched to surface textures in adjoining silicates. Apatites show a wide variety of different surface features ranging from planar crystal faces, to small-scale ridges and dimples, to extensive irregular pitting. Many of these features form in response to the periodic infiltration of fluids along open grain boundaries during the cooling history of the gneiss. Apatite shows evidence of both dissolution and re-precipitation that is controlled by the nature of the grain boundary, the structure of the adjoining silicate phase and the alteration of the host rock. Fracturing occurs in a range of retrograde conditions and is common both within the apatite and along grain boundaries. This coupled to the evidence of fluid interaction with mineral surfaces suggests that extensive permeable networks may be typical of cooling crystalline basement rocks. Grain boundary textures have the potential to reveal a unique record of fluid infiltration in the crust that would be very difficult to decipher using traditional petrographic methods.     

On modeling of chemical stimulation of an enhanced geothermal system using a high pH solution with chelating agent

Dissolution of silica and calcite in the presence of a chelating agent (NTA) at a high pH was successfully demonstrated in laboratory experiments using a high-temperature flow reactor. (Note that the term 'silica' used here includes amorphous silica, quartz, and silicate glass bead.) The mineral dissolution and associated porosity enhancement in the experiments were reproduced by reactive transport modeling using TOUGHREACT. The chemical stimulation method was applied by numerical modeling to a field geothermal injection well system to investigate its effectiveness. Parameters applicable to the quartz monzodiorite unit at the Enhanced Geothermal Systems site at Desert Peak (Nevada) were used. Results indicate that the injection of a high pH chelating solution results in dissolution of both calcite and plagioclase, while avoiding precipitation of calcite at high temperature conditions. Consequently, reservoir porosity and permeability can be enhanced especially near the injection well. Injection at a lower temperature of 120°C (temperature is over 160°C in the base-case) results in a porosity increase that is smaller close to the injection point, but extends to a larger radial distance. A slower kinetic rate results in less aggressive mineral dissolution close to the injection point and larger extent along the flow path, which is favorable for chemical stimulation.     

一批中国古代镶嵌玻璃珠化学成分的检测报告

结合外束质子激发X荧光（proton induced X-ray emission,PIXE）和能量色散X射线荧光（energy dispersive X-ray emission,EDXRF）分析技术,对中国新疆、湖北、四川、广东出土的古代镶嵌玻璃珠的化学成分进行了检测.结果表明：新疆拜城克孜尔墓地出土的西周-春秋时期镶嵌玻璃珠为CaO-MgO-SiO2玻璃,战国时期中国境内的PbO-BaO-SiO2和Na2O-CaO-SiO2镶嵌玻璃珠是同时存在的.本文亦对相关问题进行了一些讨论,并提出了部分今后的工作建议.     

The Diffusion of Voluntary International Management Standards: Responsible Care,ISO 9000, and ISO 14001 in the Chemical Industry

This article analyzes the factors that explain the international diffusion of voluntary international management standards. We argue that international management standards should not be analyzed in isolation but in conjunction with other standards and their institutional environment. We present two opposite views explaining how the previous diffusion of management standards facilitates or hampers the adoption of new management standards. We test a comprehensive model of diffusion of international environmental management standards within the chemical industry using a panel of 113 different countries during the period 2000 to 2003. Our results show that the previous experience of businesses in voluntary standards such as the Chemical Industry's Responsible Care Program or ISO 9000, government commitment toward Environmental Management Systems Standards, and the level of activity of international nongovernmental organizations in the country of adoption, impact positively on the adoption of ISO 14001 by chemical firms. Unlike previous studies that focused mostly on cross industry analyses, we do not find trade‐related factors significant while explaining adoption in the chemical industry. Our results differ, therefore, from previous research and highlight the need to isolate industry effects to understand the diffusion of international standards.     

安徽繁昌窑青白瓷釉初步研究

本文利用扫描电镜、X射线衍射仪与电子探针能谱仪对安徽繁昌窑青白瓷釉的显微结构、物相和化学组成进行了分析,并与同时期的湖北青山窑和江西景德镇窑青白瓷釉进行了对比研究,认为繁昌窑青白瓷釉属于钙系釉中钙釉类型,其瓷釉配方工艺与青山窑与湖田窑相似,应由一种“釉石”加入石灰石及草木灰制成。