Abstract Focused gallium ion beam devices were developed simultaneously at the University of Chicago and at the Oregon Graduate Institute in the mid-1970s. Micron-sized structures were milled from integrated circuits applying a high-current-density focused ion beam from a liquid metal ion source (LMIS) (Puretz et al. , 1984). Previously, focused ion beam (FIB) was used preferentially in the semiconductor industry. Typical applications are quality control, wafer repair and microelectronic failure analysis. In the late 1980s and the early 1990s transmission electron microscope (TEM) foil preparation with FIB was introduced. The great success of that technique was the unique ability of FIB to prepare site-specific TEM foils (Kirk et al. , 1989; Young et al. , 1990; Basile et al. , 1992; Overwijk et al. , 1993). The publications listed describe the procedure: how to remove the foil from the excavation site, the ex situ lift-out technique, which later was improved by Giannuzzi et al. (1997). a summary of the FIB technique was presented by Orloff et al. (2003), and by Giannuzzi and Stevie (2005). Application of FIB in the geosciences began in the early 2000s (Wirth, 2000, 2001; Dobrzhinetskaya et al. , 2001; Dobrzhinetskaya & Green, 2001; Heaney et al. , 2001; Dobrzhinetskaya et al. , 2002; Wirth, 2002; Lee et al. , 2003; Dobrzhinetskaya et al. , 2003; Wirth, 2003; Graham et al. , 2004; Wirth, 2004, 2005; Smith et al. , 2006). at present, the major application of FIB in geosciences is site-specific TEM foil pre paration, though the technique is being used increasingly for other purposes such as micro machining of diamonds, specimen preparation for infrared (IR) spectroscopy and 3D cross-sectioning. The hardness contrast in multiphase materials, a major problem with conventional argon ion milling, is overcome with FIB. Interfaces are thinned preferentially by conventional argon ion milling because the interface region deviates in chemical composition and bonding from the bulk crystal structure. Interfaces are not thinned preferentially by the FIB method (Wirth, 2004; heinemann et al. , 2005; Seydoux-Guillaume et al. , 2003).

Abstract Though it may sound like a contradiction to obtain detailed information about large-scale processes such as mountain building, plate tectonics, global recycling or even the origin and formation of our solar system from investigations at the nanoscopic to atomic scale, the step from the micro- to the nanoscale is indeed the most important one. This is not just analysis with greater magnification, but the study of matter at a fundamental level. To better understand geodynamic processes such as subduction, continent–continent collision or exhumation of oceanic or continental crust, it is essential to quantify the evolution of each component in as much detail as possible. records of all of these processes are kept in the microstructures. In addition to the widely used geothermobarometric methods based on element partitioning between minerals, microstructures provide a variety of systems to determine temperature-time histories ( e.g. Buseck & Iijima, 1975 ; Buseck et al. , 1980 ; Robinson et al. , 1971 , 1977 ; Schröpfer et al. , 1990 ; Skrotzki et al. , 1991 ; Skrotzki, 1992 ; Schumacher et al. , 1994 ; Klein et al. , 1996 ; Joanny et al. , 1991 ; Carpenter, 1981b ; Müller, 1991 ; Müller et al. , 1995 ; Veblen, 1991 ; Weinbruch & Müller, 1995 ).

Abstract Iron, the fourth most abundant element in the Earth, commonly occurs in two valence states, Fe 2+ and Fe 3+ , even within a single mineral. Determination of Fe 3+ /EFe ratios in minerals at sub-micrometre scale has been a long-standing objective in geosciences. One of the most important characteristics of iron is that the charge on the metal is extremely sensitive to its surrounding reduction-oxidation (redox) conditions, which often results in changes in iron valence state reflecting these conditions. The quantification of ferrous/ferric ratios in minerals can therefore provide great insights into physico-chemical conditions of rock formation such as temperature and oxygen fugacity, and allows the determination of redox states for mineral crystallization and the interpretation of geological and geochemical processes. The high spatial resolution available on a (scanning) transmission electron microscope ((S)TEM) combined with the benefits of electron energy-loss spectroscopy (EElS) allows detailed analysis of multivalent element ratios ( e.g. Fe 2+ and Fe 3+ ) on the scale of nanometres. Electron energy-loss spectroscopy is a powerful technique for analyzing the interactions of fast probe electrons with matter, and the energy transferred for a certain excitation process can be measured as an energy loss of the incident electron which reduces its kinetic energy. The probability of inelastic scattering over energy loss is called energy-loss spectrum which results from the excitation of inner-shell, valence or conduction electrons. Excitations are only possible from occupied states below the Fermi level to allowed unoccupied states beyond it. Maxima in the energy loss spectrum correspond to strong electron-specimen interactions. apart from the qualitative and quantitative determination of elements, it is also possible to determine quantitative concentration ratios of

Abstract The aim of this chapter is to impart an understanding of the physical principles behind unusual SIMS applications and to do so in terms of conveying mental pictures of processes rather than dwelling upon mathematics. Several texts are recommended for further reading: McPhail (2006) , Stephan (2001) , Vickerman & Briggs (2001) and Benninghoven et al. (1987) . Secondary Ion Mass Spectrometry relies upon the impact of an energetic ion into a surface, transferring enough energy to atoms in the surface to allow them escape and be ionized (creating the secondary ion). The process is complex to model but some simple pictures can give insight into the process. As we are interested here in nanoscale analytical techniques, we concentrate on secondary ionization with high spatial resolution (here nanoscale refers to sub-micrometer). To obtain this spatial resolution, primary ions are focused to a small spot size onto the sample. How this can be achieved will be discussed in section 1.1.3 below. The ions have high energy relative to the surface, typically >10 keV, and collide with atoms and molecules on the surface. Quantum mechanical treatment of this process is not appropriate for this chapter; a quick qualitative picture is all that is desired. The energetic ion colliding with species on the surface is envisaged. Most collisions will transfer 100s of eV to the surface species and these in turn will collide with their neighbours (Fig. 1 ). The volume will become rapidly thermalized and indeed the spectrum of ions leaving the surface matches a high-temperature plasma quite closely. a con sequence is that ions are ejected with a large range of energies (Fig. 2 ).

Abstract An ion microprobe is an instrument that uses a finely focused primary ion beam to erode, or ‘sputter’ a solid sample and to collect secondary ions ejected during that process into a mass spectrometer generating a spatially resolved mass spectrum. The underlying technique, Secondary Ion Mass Spectrometry (SIMS), has become a standard tool for the in-situ study of trace-element concentrations and isotope ratios in the fields of geochemistry, geochronology, biogeochemistry and cosmochemistry. an overview of the most recent developments in SIMS is given by Chabala et al. (1995) , Ireland (1995) , Mac Rae (1995) , Becker (2005) , Betti (2005) , Deloule & Wiedenbeck (2005) , Deloule (2006) and McPhail (2006) . Secondary ion mass spectrometry offers parts per million (ppm) or better detection limits for almost all elements, imaging capabilities, periodic table coverage (h–U), and isotope analyses of major and trace elements. The following three examples illustrate the unique power of the SIMS technique in measuring and imaging isotope ratios and trace element distributions. Firstly, the lateral distribution of elements of interest and isotope ratios can be measured. Figure 1 demonstrates the lateral resolution of SIMS imaging with the Cameca NanoSIMS 50. a spatial resolution of 50 nm is possible, even for biological samples. Scans of a cell culture were taken at appropriate mass number to recognize bacterial cells (CN − , major molecular ion image) on a nucleopore polycarbonate filter, to identify photosynthetic active cells by their incorporation of 13 C-labelled bicarbonate ( 13 C/ 12 C ratio, isotope ratio image), and to recognize species with the help of a halogen marker ( 19 F − , trace element ion image) that binds to the ribosome of the cell.

Abstract Synchrotron radiation (SR) is generated when highly relativistic charged particles (typically electrons or positrons) are forced to follow a curved trajectory in strong magnetic fields. as a result of the radial acceleration of these high-velocity charged particles, orbiting at speeds ( v ) of nearly the speed of light ( c ), electromagnetic radiation is generated which covers a wide wavelength (energy) range and has unique properties for spec-troscopic studies. Synchrotron radiation is emitted tangentially to the electron path, in the form of a narrow cone of intense electromagnetic beam (Fig. 1 ). This type of radiation is generated in so-called electron (or positron) storage rings, which consist of an evacuated, quasi-circular vacuum chamber coupled with a lattice of magnets, in which electrons/positrons can circulate freely in a closed orbit (Fig. 2 ). The path of the charged particles within the storage ring is determined by the magnetic lattice within the ring, which both focuses and bends the beam of charged particles, keeping it in a closed trajectory. The so-called first generation synchrotron storage rings were built for particle physics experiments, high-energy particle accelerators, in which the synchrotron radiation generated was considered to be an unwanted by-product, resulting in an energy-loss for the accelerated particles. In the 1960s, scientists began to use synchrotron radiation from several of these first generation accelerators in a ‘parasitic mode’, realizing that the synchrotron radiation emitted has very advantageous properties for many types of spec-troscopic applications.

Abstract Natural sciences have experienced important developments when the insights into both matter and its interaction with the environment advanced to the next scale in space and time – irrespective whether the direction was towards larger or smaller scales. A landmark advance took place at the end of the 19th century when the understanding of matter as composed of atoms eventually outranged the perception of matter as an energetic continuum. Although physical and mathematical discontinuities always pose serious problems, the atomistic perception of matter had the advantage of providing a valuable microscopic aside to thermodynamics, a new perspective to study the interaction between matter and radiation, and a better understanding of numerous properties of solids and liquids. Additionally, the concept of atoms has been proven to be a key to understand and quantify the kinetics of chemical reactions. The atomic age had begun. However, the advances derived from the idea of atoms not only led to new insights into matter, they also made it necessary to develop new models for the reactions of a solid composed of atoms ( i.e. composed discontinuously) with a liquid phase composed of the same or a different component ( i.e. melt or solvent). Among the reactions that can occur between a solid and a liquid, growth and dissolution are ubiquitous and very important to understand. Growth can be described as the formation of a (crystalline) solid from a liquid phase whereas dissolution can be perceived as the decomposition of a solid and the transfer of its constituents into a liquid phase.

Abstract Nanoscale phenomena dominate many of the important processes near the surface of the Earth. Therefore these phenomena are of special importance to the environment and human health. As nanoscale processes are intrinsically molecular, there is an immediate synergy between the study of nanoscale particles in natural systems and the disciplines of mineralogy, chemistry, physics and materials science. Since nanoparticulates have unique properties as isolated entities ( e.g. Gilbert et al. , 2004 ), it is tempting to focus on the nanoparticle in isolation. however, for nanoparticles in the environment in particular, it is important to analyse their properties in relation to their immediate atomic-scale environment, e.g. the nanoparticle-host interface. Often, certain types of nanoparticles are associated with specific host phases such as noble metal nanoparticles in sulphides, carbonate nuclei on organic templates, arsenic sulphides on Fe sulphides or oxides, or atmospheric nanoparticles on or in dust particles. In many cases, the nanoparticle structure, stability, chemistry, charge, electronic and magnetic properties, and finally, reactivity, are based on these interface properties. Thus, it is essential to develop an understanding of these interface properties at the atomic level. In order to capture the specific details of these interface properties, it is necessary to apply a combination of approaches in nanoscale characterization. These methods include a wide variety of microbeam and spectroscopic techniques, the synthesis of nanoparticles under controlled conditions ( e.g. utilizing ion implantation), the study of surface and interface clusters, and the use of quantum-mechanical and molecular-dynamics simulations to understand the observed processes. In addition, as a number of structural and electronic properties of nanoparticles and their interfaces are still difficult to determine experimentally, molecular simulations can further our understanding of nanoscale phenomena.

Abstract The properties of matter at extreme length scales and the respective processes can differ markedly from the properties and processes at length scales directly accessible to human observation. This scale-dependent behaviour is possible in both directions; towards very large and very small scales. Scientists explore the frontiers of these extreme length scales in an effort to gain insight into yet unknown properties and processes. While the exploration of larger scales has been established since the Renaissance era, a comprehensive investigation of small scales was impeded by the limitations of optical microscopy. These imitations were overcome in the 20th century. Since then, a continuous series of developments in analytical power has taken place. Today these developments allow studies of properties and processes even at the molecular or atomic scale (often referred to as nanoscience). These modern nanoscientific possibilities have triggered new innovative projects in geosciences, providing fascinating insights into small scales. Therefore, nanogeoscience has become a very important geoscientific subdiscipline.