Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

Characterisation of primary and secondary carbonates in hypabyssal kimberlites: an integrated compositional and Sr-isotopic approach

Carbonates in fresh hypabyssal kimberlites worldwide have been studied to understand their origin [i.e. primary magmatic (high T) versus deuteric (‘low T’) versus hydrothermal/alteration (‘low T’)] and identify optimal strategies for petrogenetic studies of kimberlitic carbonates. The approach presented here integrates detailed textural characterisation, cathodoluminescence (CL) imaging, in situ major- and trace-element analysis, as well as in situ Sr-isotope analysis. The results reveal a wide textural diversity. Calcite occurs as fine-grained groundmass, larger laths, segregations, veins or as a late crystallising phase, replacing olivine or early carbonates. Different generations of carbonates commonly coexist in the same kimberlite, each one defined by a characteristic texture, CL response and composition (e.g., variable Sr and Ba concentrations). In situ Sr isotope analysis revealed a magmatic signature for most of the carbonates, based on comparable ⁸⁷Sr/⁸⁶Sr values between these carbonates and the coexisting perovskite, a robust magmatic phase. However, this study also shows that in situ Sr isotope analysis not always allow distinction between primary (i.e., magmatic) and texturally secondary carbonates within the same sample. Carbonates with a clear secondary origin (e.g., late-stage veins) occasionally show the same moderately depleted ⁸⁷Sr/⁸⁶Sr ratios of primary carbonates and coexisting perovskite (e.g., calcite laths-shaped crystals with ⁸⁷Sr/⁸⁶Sr values identical within uncertainty to those of vein calcite in the De Beers kimberlite). This complexity emphasises the necessity of integrating detailed petrography, geochemical and in situ Sr isotopic analyses for an accurate interpretation of carbonate petrogenesis in kimberlites. Therefore, the complex petrogenesis of carbonates demonstrated here not only highlights the compositional variability of kimberlites, but also raises concerns about the use of bulk-carbonate C-O isotope studies to characterise the parental melt compositions. Conversely, our integrated textural and in situ study successfully identifies the most appropriate (i.e. primary) carbonates for providing constraints on the isotopic parameters of parental kimberlite magmas.

     

Shape analysis and multispectral classification in geological remote sensing

This paper discusses the usage of mathematical morphology in image processing of remotely-sensed data for geologic interpretation. Particular attention is given to noise-reducing transformations of spectral bands before and after different methods of classification, and to the usage of textural context. The development of a viable processing strategy requires a multidisciplinary approach and expert knowledge in different areas: (a) geology, geomorphology, and vegetation in a study area, (b) properties of the sensor for imagery photointerpretation, (c) spectral/spatial properties of the digital data within an integrated dataset (remote sensing and ancillary data), and (d) data-processing tools including mathematical morphology theory. Examples of geometric characterization of Canadian LANDSAT scenes are described in which shape measurements are obtained using a PC-based hybrid image-processing and geographic information system, termed ILWIS, which was developed at ITC, in the Netherlands. Classes from supervised and unsupervised classification are compared to guide in geological mapping. Classes over individual occurrences of broad vegetation-landform units are studied to aid in environmental mapping. Field knowledge is the context necessary to construct expert procedures to drive sequences of data-processing steps toward a target result such as optimal classification, enhancement, or feature extraction. The interaction between expert rules and the image-processing steps can be based on synthetic measurements of shape to quantize the information either spatially or spectrally. Many useful geometrical transformations of spatially-distributed data are extensions or generalizations of spatial analysis functions typical of geographic information systems.     

Preboreal climatic oscillations recorded by pollen and foraminifera in the southern Adriatic Sea

Core SA03-1 from the southern Adriatic Sea (EC-Eurostrataform project) provides new information about climate changes and palaeocirculation in the Adriatic region during the last deglaciation. The results of an integrated study based on pollen and foraminifera records of the part of the core spanning the late Pleistocene–early Holocene transition (including the late Younger Dryas, the Preboreal and the beginning of the Boreal) are presented. The major vegetation changes and the short-term oscillations occurred during the early Holocene warming in the southern Adriatic basin on the basis of a high-resolution pollen record are documented. Vegetation changes are correlated to short-term oscillations detected in the foraminifera record during the same interval. The two independent terrestrial and marine proxies indicate at least three short-term cold and dry oscillations occurring at 11.2–11, 10.8–10.4 and 10 cal ka BP, according to the age–depth model adopted in this study. Finally, adopting an event-stratigraphy approach, the comparison of these results with two western Mediterranean records of Preboreal short-term oscillations suggest the occurrence of synchronous bio-events in the Mediterranean basin.     

Travertine deposition and faulting: the fault-related travertine fissure-ridge at Terme S. Giovanni,Rapolano Terme (Italy)

In this paper we describe an example of travertine fissure-ridge development along the trace of a normal fault with metre displacement, located in the eastern margin of the Neogene–Quaternary Siena Basin, in the Terme S. Giovanni area (Rapolano Terme, Italy). This morphotectonic feature, 250 m long, 30 m wide and 10 m high, formed from supersaturated hot waters (39.9°C) flowing from thermal springs aligned along the trace of the normal fault dissecting travertines not older than Late Pleistocene (24 ± 3 ka). A straight, continuous fissure with a maximum width of 20 cm occurs at the top of the ridge, along its crest. Hot fluids flow from cones mainly located at the extremities of the ridge, where travertine is depositing. The travertine fissure-ridge shows an asymmetrical profile since it buries the fault scarp. The difference in height of slopes corresponds to the vertical displacement of the normal fault. Fissuring of the recent travertine deposits along the strike of the crestal fissure, as well as recent hydrothermal circulation, lead us to believe that the Terme S. Giovanni normal fault may be currently active. On the whole, the Terme S. Giovanni fissure ridge can be defined as a travertine fault trace fissure-ridge, adding a helpful example for studying the relationship between faulting and travertine deposition.     

The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

Impact of drilling mud on chemistry and microbiology of an Upper Triassic groundwater after drilling and testing an exploration well for aquifer thermal energy storage in Berlin (Germany)

After completion of an exploration well, sandstones of the Exter Formation were hydraulically tested to determine the hydraulic properties and to evaluate chemical and microbial processes caused by drilling and water production. The aim was to determine the suitability of the formation as a reservoir for aquifer thermal energy storage. The tests revealed a hydraulic conductivity of 1–2 E-5 m/s of the reservoir, resulting in a productivity index of 0.6–1 m³/h/bar. A hydraulic connection of the Exter Formation to the overlaying, artesian “Rupelbasissand” cannot be excluded. Water samples were collected for chemical and microbiological analyses. The water was similarly composed as sea water with a maximum salinity of 24.9 g/L, dominated by NaCl (15.6 g/L Cl and 7.8 g/L Na). Until the end of the tests, the water was affected by drilling mud as indicated by the high pH (8.9) and high bicarbonate concentration (359 mg/L) that both resulted from the impact of sodium carbonate (Na₂CO₃) additives. The high amount of dissolved organic matter (>?58 mg/L) and its molecular-weight distribution pattern indicated that residues of cellulose, an ingredient of the drilling mud, were still present at the end of the tests. Clear evidence of this contamination gave the measured uranine that was added as a tracer into the drilling mud. During fluid production, the microbial community structure and abundance changed and correlated with the content of drilling mud. Eight taxa of sulfate-reducing bacteria, key organisms in processes like bio-corrosion and bio-clogging, were identified. It can be assumed that their activity will be affected during usage of the reservoir.     

Origin of complex zoning in olivine from diverse,diamondiferous kimberlites and tectonic settings: Ekati (Canada), Alto Paranaiba (Brazil) and Kaalvallei (South Africa)

Olivine in kimberlites can provide unique insights into magma petrogenesis, because it is the most abundant xenocrystic phase and a stable magmatic product over most of the liquid line of descent. In this study we examined the petrography and chemistry of olivine in kimberlites from different tectonic settings, including the Slave craton, Canada (Ekati: Grizzly, Koala), the Brasilia mobile belt (Limpeza-18, Tres Ranchos-04), and the Kaapvaal craton, South Africa (Kaalvallei: Samada, New Robinson). Olivine cores display a wide range of compositions (e.g., Mg# = 78–95). The similarity in olivine composition, resorption of core zones and inclusions of mantle-derived phases, indicates that most olivine cores originated from the disaggregation of mantle peridotites, including kimberlite-metasomatised lithologies (i.e. sheared lherzolites and megacrysts). Olivine rims typically show a restricted range of Mg#, with decreasing Ni and increasing Mn and Ca contents, a characteristic of kimberlitic olivine worldwide. The rims host inclusions of groundmass minerals, which implies crystallisation just before and/or during emplacement. There is a direct correlation between olivine rim composition and groundmass mineralogy, whereby high Mg/Fe rims are associated with carbonate-rich kimberlites, and lower Mg/Fe rims are correlated with increased phlogopite and Fe-bearing oxide mineral abundances. There are no differences in olivine composition between explosive (Grizzly) and hypabyssal (Koala) kimberlites. Olivine in kimberlites also displays transitional zones and less common internal zones, between cores and rims. The diffuse transitional zones exhibit intermediate compositions between cores and rims, attributed to partial re-equilibration of xenocrystic cores with the ascending kimberlite melt. In contrast, internal zones form discrete layers with resorbed margins and restricted Mg# values, but variable Ni, Mn and Ca concentrations, which indicates a discrete crystallization event from precursor kimberlite melts at mantle depths. Overall, olivine exhibits broadly analogous zoning in kimberlites worldwide. Variable compositions for individual zones relate to different parental melt compositions rather than variations in tectonic setting or emplacement mechanism.

     

A record of Lateglacial/Holocene environmental change from a high‐elevation site in the Intermountain West,USA

Records of past vegetation and fire history can be complicated by changes in the depositional environment of a sampling location. However, these changes can alternatively be used as a measure of climate variability. Our study site, ca. 18.0 cal. ka BP record from Little Brooklyn Lake, Wyoming, located near the crest of the Snowy Range, records three moisture states. Initially, the lake was likely a glacier‐fed pond indicated by the presence of Pediastrum algae colonies. Around 13.0 cal. ka BP this pond transitioned to a meadow environment, suggested by the loss of Pediastrum algae colonies and slow sedimentation rates. Meadow conditions were maintained until ca. 5.0 cal. ka BP when Pediastrum algae colony abundance increased,indicating the formation of a shallow lake. From 18.0 to ca. 5.0 cal. ka BP, the pollen record is suggestive of alpine vegetation conditions with relatively high spruce and herbaceous taxa. Low charcoal influx also characterizes the period between 18.0 and 5.0 cal. ka BP. After 5.0 cal. ka BP, the coincidence of the formation of shallow lake and pollen data, indicating a shift to a spruce and fir forest, suggests an increase in effective moisture. Fire remained rare in this basin over the entire record, however, once the lake established sedimentation rates and charcoal influx increased. Copyright © 2013 John Wiley & Sons, Ltd.