X-ray spectromicroscopy is a powerful tool for addressing key questions in the environmental sciences due to its high spectral and spatial resolution. It has been used successfully for material research, biology and environmental studies, e.g. in the form of μ-X-ray fluorescence and spectromicroscopy with a spatial resolution of <100 nm. With the combination of high-resolution microscopy and spectroscopy it is possible to determine elemental composition as well as chemical speciation, and also identify trace elements to nm-resolution. Samples from soils and groundwater aquifers have been imaged to visualize the appearance of structures on the nm- and μm-scale. The effectof changing chemical conditions in an aqueous environment on the appearance of these structures has been imaged and evaluated. Clay dispersions, microhabitats and morphological effects of biologically-induced redox changes of humic substances have been imaged tomographically, conveying a detailed threedimensional presentation of the specimen structure. Using the spectromicroscopy potential, the distribution of organic and inorganic components, as well as different inorganic components, has been studied. Spectra were analysed for major chemical constituents and were used, for example, to assess differentsulphur species in an entire soil profile.

The kinetics and mechanisms of the transformation of 2-line ferrihydrite (FH) to hematite (HM), in the presence of Pb at elevated temperatures and high pH condition, were elucidated using synchrotron-based, in situ energy dispersive X-ray diffraction (EDXRD). The time-resolved diffraction data indicated that HM crystallization occurred via a two-stage process. Based on the EDXRD data, combined with high-resolution electron microscopic images, an aqueous-aided 2D growth mechanism is proposed for both HM crystallization stages.

In order to determine the links between geochemical parameters controlling the formation of silica sinter in hot springs and their associated microbial diversity, a detailed characterisation of the waters and of in situ-grown silica sinters was combined with molecular phylogenetic analyses of the bacterial communities in Icelandic geothermal environments. At all but one site, the microorganisms clearly affected, and in part controlled, the formation of the macroscopic textures and structures of silica sinter edifices. In addition, the class and genera level phylogenetic diversity and distribution appeared to be closely linked to variations in temperature, salinity and pH regimes.

The earthworm calciferous gland produces a concentrated suspension of calcium carbonate and in certain species precipitates as concretions of CaCO3, which then enter the soil. Here we investigated the initial stages of CaCO3 formation in the earthworm Lumbricus friendi by means of Fourier transform infrared and electron microscopy techniques (field-emission scanning electron microscopy, transmission electron microscopy, high resolution electron microscopy and selected area electron diffraction). In addition, comparisons between the IR spectra of the water-dissolved carbonic anhydrase (CA) and the glandular secretion (‘milky fluid’) were performed in order to investigate the mechanisms involved in CaCO3 precipitation. Our results strongly suggest that carbonation starts with the dissolved CO2, which is transformed via deprotonation to HCO3-, then to CO32- and finally to amorphous calcium carbonate (ACC). While ACC stabilization takes place under the biological control, further transformation stages leading to calcite concretions seem to be inorganically driven by an Ostwald ripening process.

Synchrotron-based XANES characterization of sulphated sulphur combined with atomic force microscopy and transmission electron microscopy (imaging and diffraction) allow insights into the crystallization of the calcareous units produced by invertebrates. As a result of a series of converging data, reticulate crystallization of the amorphous Ca-carbonate molecules conveyed to the micron-thick growth layer by the sumicrometric organo-mineral units seems a reasonable hypothesis, providing us with a method of explaining the multiple and taxonomy-linked ‘vital effects’ which have long been recognized among the calcareous biocrystals.

With their long geological history and stable low-Mg calcite shells, Rhynchonelliform brachiopods are attractive sources of environmental data such as past seawater temperature (Buening and Spero, 1996; Auclair et al., 2003; Brand et al., 2003; Parkinson et al., 2005). Concerns about the influence of vital effects on the stable isotope composition of brachiopod shells (Popp et al., 1986), led to isotope analyses of different parts of brachiopod shells in order to identify those parts of the shell that are influenced by any vital effect and those parts that may be suitable recorders of seawater temperature via stable oxygen isotope composition (Carpenter and Lohmann, 1995; Parkinson et al., 2005). Such detailed studies demonstrated that the outer primary layer of acicularcalcite is isotopically light in both δ18O and δ13C while the secondary layer, composed of calcite fibres, is in oxygen-isotope equilibrium with ambient seawater(Fig. 1) (Parkinson et al., 2005).

Calcite and aragonite shell layers of the main classes of Molluscs are composed of monocrystalline units (prisms, tablets, laths or fibres). Scanning electron and atomic force microscopy studies show these units are composed of small round granules with a thin cortex (amorphous calcium carbonate and/or organic matrix). These granules are organo-mineral composites. A comparison of the size and shape of the granules in different taxa (Mollusca, Brachiopoda) suggests a possible relationship with taxonomy and/or phylogeny.

Elemental distribution maps by wavelength-dispersive electron microprobe of enamel and dentine in modern crocodile teeth illustrate variations in both minor and major elements. Mg has the largest difference between the enamel and dentine, being enriched in the dentine. Mg, Ca and P are not homogeneously distributed in the dentine, but their distribution reflects changes during growth of the teeth. These variations in compositional differences of teeth from modern samples potentially can assist in establishing growth rates in fossil teeth samples, and thereby provide information on the physiology of extant species.

Coccolithophores, among which Emiliania huxleyi is the most abundant and widespread species, are considered the most productive calcifying organism on earth. The export of organic carbon and calcification are the main drivers of the biological CO2 pump and are expected to change with oceanic acidification. Coccolithophores are further known to produce transparent exopolymer particles (TEP) that promote particle aggregation. As a result, the TEP and biogenic calcium carbonate (CaCO3) contribute to the export of carbon from the surface ocean to deep waters. In this context, we followed the development and the decline of E. huxleyi using batch experiments with monospecific cultures. We studied the link between different processes such as photosynthesis, calcification and the production of TEP. The onset of calcification was delayed in relation to photosynthesis. The timing and the general feature of the dynamics of calcification were closely related to the saturation state of seawater with respect to calcite, Ωcal. The production of TEP was enhanced after the decline of phytoplankton growth. After nutrient exhaustion, particulate organic carbon (POC) concentration increased linearly with increasing TEP concentration, suggesting that TEP contributes to the POC increase. The production of CaCO3 is also strongly correlated with that of TEP, suggesting that calcification may be considered as a source of TEP precursors.

Darwin (1881) was one of the first scientists to formally record that earthworms excrete calcium carbonate granules, with some up to 2 mm in diameter. However, since Darwin’s studies they have received relatively little attention. The function of the granules remains a mystery, but may be related to regulation of Ca, CO2, pH or some other as yet undiscovered metabolic process (Robertson, 1936; Piearce, 1972). There has recently been an increase in research activity focussed on earthworm calcium carbonate granules driven by the work of Canti (Canti, 1998, 2007; Cantian d Piearce, 2003) and largely relating to their potential use in archaeology.

The importance of silica in terrestrial land plants has been recognized since the middle of the 19th century with applications in agronomy and palaeovegetation reconstruction. In this presentation, we will review the latest advances in our understanding of phytolith formation and present a few examples of applications in the field of global environmental changes.

Inorganic calcite precipitation experiments were conducted to determine whether inducing specific orientations of calcite crystal growth can cause the enrichment of cations larger than Ca. Malonic acid (CH2(COOH)), a di-carboxylic acid, was used to poison growth on acute kink sites, promoting growth on obtuse kink sites, causing calcite crystals elongated along their c-axes to form in a mechanism similar to that seeninthe growth of E. huxleyi coccoliths. Calcite was precipitated with a range of malonic acid concentrations (0 to 10-1 M), and 9x10-5 M of either SrCl2 or MgCl2. The results show that calcite crystals precipitated in the presence of large malonic acid concentrations show significant elongation along the c axis, and suggest that increasing malonate concentrations corresponded with increasing DSr. Experiments with 10-1 M malonic acid caused elevated DSr comparable to that predicted for E. huxleyi coccolith calcite (Langer et al., 2006).

The influence of both sulphate ions and aspartic acid on directing the growth of baryte has been explored using computer simulation. Both species are found to significantly reduce the activation free-energy to growth under appropriate conditions, with the influence of sulphate being surface specific. This offers the potential for a new approach to morphology control without inhibition that may have implications for biomineralization.

Gypsum (CaSO4·2H2O) and brushite (CaHPO4·2H2O) are minerals with similar structures, despite not being isostructural. They both belong to the monoclinic system, but crystallize in different space groups. It is known that, to some extent, phosphate and sulphate groups can substitute for each other within the structure of these minerals. In the present work, the dehydration behaviour of experimentally produced Ca(SO4,HPO4)·2H2O solid solutions is assessed from thermogravimetrical (TG and DTG) and differential scanning calorimetry (DSC) analyses. For the applied experimental conditions it was not possible to obtain homogenous precipitates with compositions within 0.27 < XBr < 0.53, where XBr is the brushite mole fraction. The results reveal that the dehydration behaviour of solid solutions with compositions within the 0 < XBr < 0.27 interval tend to approach the dehydration process of pure gypsum. On the other hand, solid solutions with compositions within 0.53 < XBr < 1 involve higher dehydration temperatures than the brushite end-member, in a two-step process.

A reproducible and simple protocol to synthesize and stabilize the metastable CaCO3·nH2O phase termed amorphous calcium carbonate (ACC) was developed in order to allow the characterization of its structure at the nanoscale using high-resolution microscopy combined with Raman spectroscopy and X-ray diffraction. ‘Stable’ ACC consists of relatively smooth spherical particles, 50—200 nm in size, that have XRD and Raman patterns with no intense peaks or sharp bands, as expected from amorphous material. Furthermore, high-resolution imaging also supports this finding but in addition, beam-damage induced crystallization and the concomitant formation of locally ordered domains in the ACC spheres are discussed.

The nucleation and growth of silica nanoparticles in supersaturated geothermal waters was simulated using a flow-through geothermal simulator system. The effect of silica concentration ([SiO2]), ionic strength (IS), temperature (T) and organic additives on the size and polydispersity of the forming silica nanoparticles was quantified. A decrease in temperature (58 to 33°C) and the addition of glucose restricted particle growth to sizes <20 nm, while varying [SiO2] or ISdid not affect the size (30—35 nm) and polydispersity (±9 nm) observed at 58°C. Conversely, the addition of xanthan gum induced the development of thin films that enhanced silica aggregation.

Biologically influenced mineralization either on the surfaces of, or in close proximity to bacterial cells may produce minerals that display distinct mineralogical or morphological features as a consequence of the microbial influence on the precipitation process. Characterizing such distinguishing features could potentially facilitate identification of early life in the geological record.

The development of a palaeothermometer for ancient oceans has been a prime goal of stable isotope geochemistry since its inception in the middle of the last century. Following the calibration of the calcite oxygen isotope palaeothermometer by Epstein et al. (1953), and expanding on the seminal papers by Cesare Emiliani, the technique blossomed into a widely applied tool of palaeoceanography. These studies resulted in major advances in our understanding of Quaternary, and to some extent Tertiary oceans, but for older time periods the effort is mired by controversy and is at a standstill. In part this is due to the dearth of well-characterized carrier phases for the temperature signal, such as foraminifera shells, in the pre-Tertiary strata, but an intractable disagreement among practitioners as to the oxygen isotopic composition of ancient seawater is probably a more important stumbling block.

Organic molecules control calcite growth byadsorbing preferentiallyonto particular surfaces of the crystal. Adsorption of a monosaccharide (-galactose) on various calcite surfaces has been simulated with molecular dynamics. The calculations of Z-density, mean square displacement (MSD) and adsorption energyindicate that the adsorption of monosaccharide on the acute-stepped calcite (31.8) surface is more favourable than that on the obtuse-stepped (31.16) surface, which suggests that monosaccharides maybe able to selectivelycover some surfaces, inhibit crystal growth on these surfaces, and as a result shape the calcite crystals as seen in biominerals, e.g. coccoliths.

The sensitivity of the global river-borne flux of Ca2+ to atmospheric pCO2 was obtained from model simulations under the assumption of saturation of CaCO3. The response was subdivided into contributions from changes in runoff, temperature and partial CO2 pressure and these were then used to parameterize the different direct and indirect effects of a changing climate on carbonate weathering and equilibria. The parameterizations are comparable/compatible to those of Walker et al. (1981) for silicate weathering, but are taken directly from models demonstrating the potential of this approach in weathering studies.