Quality assessment of replacement stones for the Cologne Cathedral: mineralogical and petrophysical requirements

Owing to its long building history, different types of building stones comprised the construction of the Cologne Cathedral. Severe damage is observed on the different stones, e.g., sandstones, carbonate, and volcanic rocks, especially when the different stone materials neighbor the medieval “Drachenfels trachyte” from the “Siebengebirge”. The question arises, “Is the insufficient compatibility of the implemented building materials causatively related to the strong decay of the Drachenfels trachyte?” The present investigations focus on the petrography and mineralogical composition of eight different stones from the Cologne Cathedral. Petrophysical data, i.e., phase content, moisture and thermal characteristics as well as strength properties are determined and discussed in correlation to each other, showing that not only in terms of lithology great differences exist, but also the petrophysical properties strongly diverge. The ascertained parameters are discussed in view of the deterioration behavior and decay mechanisms of the different stones. To evaluate the compatibility of original, replacement and modern building materials, the properties of the investigated stones are compared to those of Drachenfels trachyte by means of constraints given in the literature. Besides optical properties, petrophysical criteria are also defined as well as strength values. It could be shown that primarily moisture properties, i.e., capillary and sorptive water uptake, water saturation, drying processes and moisture dilatation can be addressed to the deterioration processes.     

Première approche pour l'étude des bassins hydrogéologiques profonds du Sud-Ouest tunisien

Due to their high cost, a small number of deep wells cannot give a satisfactory image of the architecture of deep geological formations and their continuity. However, it is very important at an early stage of research to recognize the relations that can exist between the different compartments of the underground formations. Generally speaking, we usually deduce that the hydrodynamic and geochemical parameters can be generated by geological discontinuity. In southwestern Tunisia, the seismic and diagraphic data make it possible to get a satisfactory insight into the underground layers so as to identify the hydrogeological basins and the extension of their parameters. To cite this article: M. Chalbaoui, C. R. Geoscience 337 (2005).     

Modelling the effect of temperature on unsaturated soil behaviour

A simple thermohydromechanical (THM) constitutive model for unsaturated soils is described. The effective stress concept is extended to unsaturated soils with the introduction of a capillary stress. This capillary stress is based on a microstructural model and calculated from attraction forces due to water menisci. The effect of desaturation and the thermal softening phenomenon are modelled with a minimal number of material parameters and based on existing models. THM process is qualitatively and quantitatively modelled by using experimental data and previous work to show the application of the model, including a drying path under mechanical stress with transition between saturated and unsaturated states, a heating path under constant suction and a deviatoric path with imposed suction and temperature. The results show that the present model can simulate the THM behaviour in unsaturated soils in a satisfactory way.     

Discrimination between primary magmatic biotites, reequilibrated biotites and neoformed biotites

The ternary diagram TiO₂–FeO*–MgO (FeO* = FeO + MnO) is proposed as a quantitative objective tool for distinguishing between primary magmatic biotites and those that are more or less reequilibrated, or possibly neoformed, by or within a hydrothermal fluid. The limit of the domains of the primary magmatic biotites, the reequilibrated biotites and the neoformed biotites were determined on the basis of optical, paragenetic and chemical criteria. To cite this article: H. Nachit et al., C. R. Geoscience 337 (2005).     

Formulation and characterization of an appropriate lime-based mortar for use with a porous limestone

Several studies have shown that the degradation of architectural monuments constructed using Tuffeau stones from Val de Loire region of France over a period of time are often related to use of mortars that are not compatible with the Tuffeau stones. For this reason, it is important to ensure physico-chemical compatibility between Tuffeau and the mortar. To alleviate differences in compatibility characteristics, a mortar is prepared from hydrated lime and aggregates obtained from the crushing of Tuffeau stone and used in this study. The key parameters that influence the strength and durability characteristics such as mechanical resistance, water transfer properties, and physico-chemical properties were identified and studied. Based on these studies, recommendations are offered for the preparation of a more compatible mortar that can be used in the construction and restoration of monuments using Tuffeau stone.     

Spatial Geochemistry: A Characterisation of Heterogeneity in Reference Materials

Geochemical reference materials (RMs) for microbeam techniques are typically characterised by averages and dispersion statistics (e.g., standard deviation, variance) that are calculated for a number of measurements (beam shots). It is proposed that the mapping of RMs will add spatial information that better characterises the grouping and magnitudes of the heterogeneities and provides the information necessary to define a minimum analytical mass. A simple mathematical solution is proposed, which can be easily computed and understood. The analogous notions to sill and range from geostatistics are applied to the minimum analytical mass versus the relative standard deviation. To assess grouping and magnitudes of the heterogeneities, a ‘proximity number’ is computed for each average value ± ‘n’ standard deviations (magnitude). Different chemical anomalies have been simulated to demonstrate the behaviour of the proximity number. To further test the proposed spatial geochemistry concept, sulfide‐ and oxide‐bearing RMs have been selected because many are crippled with nugget effect. They have been mapped with a micro‐XRF apparatus, and results are presented for CHR‐Bkg, CHR‐Pt+, MASS‐1, MASS‐3, WMS‐1 and WMS‐1a. MASS‐1 and MASS‐3 are the most suitable RMs for microbeam techniques. Spatial geochemistry offers a new approach to better characterise reference materials.     

Growing mountain ranges and quenched river networks

River networks in mountain ranges owe their existence to the competing effects of tectonic uplift and climate-controlled erosion. However, paradoxically, the universal geometric properties of river networks are independent of both tectonics and climate. Currently, this paradox has still not been resolved. Here we propose a solution that consists in considering that the geometry of river networks is established on the lowland margins of incipient uplifts, and is quenched into the erosion zone as the mountain belts widen with time. In our model, the geometry of river networks simply reflects the downward coalescence of alluvial rivers on un-dissected surfaces outside of mountain belts, and is therefore independent of erosion processes. To cite this article: S. Castelltort, G. Simpson, C. R. Geoscience 338 (2006).     

Sources and extractibility of chromium and nickel in soil profiles developed on Czech serpentinites

Soil profiles developed on serpentinites from several localities in the Czech Republic were investigated by a combination of geochemical and mineralogical methods (selective extractions, XRD, SEM/EDS) to determine the partitioning and mobility of chromium (Cr) and nickel (Ni). Whereas Cr is released from pyroxenes, amphiboles and Cr-spinels present in the bedrock, Ni is primarily mobilized from olivines and small Fe-Ni sulphide inclusions. The results of extraction methods indicated significant differences in the availability and mobility of Cr and Ni in soils. Chromium is almost not phytoavailable, as indicated by the DTPA extractions. The selective extractions showed that Cr is tightly bound to well-crystallised Fe-oxides and primary rock-derived phases. In contrast, Ni is substantially more mobile in soil, being mainly controlled by Mn-oxides and amorphous/less crystallised Fe-oxides. The DTPA extraction indicated that up to 10% of total Ni might be phytoavailable.     

The Reliability of Assigned Values from the GeoPT Proficiency Testing Programme from an Evaluation of Data for Six Test Materials that have been Characterised as Certified Reference Materials

Assigned values derived from the GeoPT proficiency testing programme were compared with certified values for six certified reference materials that have been used as test materials in the GeoPT programme. Statistical analysis showed that there were few significant differences between these sets of data and that these differences had no significant impact on the GeoPT assessment when fitness‐for‐purpose criteria were taken into account.     

Thermal decay of carbonate dimension stones: fabric,physical and mechanical changes

This paper deals with the effects of thermal stresses on selected carbonate rocks used as dimension stones. They are Mesozoic calcareous and dolomitic rocks cropping out in Apulia (southern Italy) that, for their physico-mechanical and aesthetic properties, have always been finding a large application both as ornamental stones and as simple construction materials; their use is attested not only in Italy, in works of archaeological, historical and artistic interest too. The cause–effect relationships of thermal degradation were studied by means of an artificial accelerated ageing test, in order to provide a perspective about the decay of carbonate stones due to diurnal and seasonal temperature fluctuations, as well as thermal shocks during events of fire development. The stone samples were subjected to thermal cycles in a muffle furnace, ranging from 100 to 700 °C; after each cycle, several non-destructive and semi-destructive tests were carried out: mass and volume measurements, mercury intrusion porosimetry, sclerometer tests, ultrasonic tests, thin-section observations and determination of chromatic alterations through image analysis and Munsell charts method. In this way, the qualitative and quantitative modifications induced in fabric, physical and mechanical properties were discussed. The results highlight the fundamental role of depositional and diagenetic fabric that, together with mineralogical composition, represents the most significant discriminating factor in the response of the stone to thermal stresses.     

Calpionellid zonation of the Jurassic–Cretaceous transition in North-Atlasic Tunisia. Updated Upper Jurassic stratigraphy of the ‘Tunisian trough’ and regional correlations

The analysis of calpionellid associations from jebels Amar and Jédidi sections in North-Atlasic Tunisia provides, for the first time, a precise biozonation of the Jurassic–Cretaceous transition succession. In the light of the new data obtained and considering recently published results, the age of Upper Jurassic formations is clarified, allowing correlations with the Tunisian ‘Dorsale’ and the North–South Axis successions. Within the Maghrebides' range, sections from the external zones correlated to the Tunisian successions are quite distinctive from their equivalent in the internal zones. Both have evolved in different palaeogeographic domains related to the early structuration of the northwestern and southwestern Tethys margins. To cite this article: M. Boughdiri et al., C. R. Geoscience 338 (2006).     

Comparison of Two Sample Preparation Methods for X‐Ray Fluorescence Spectrometry in the Determination of Ni and Cr

Pressed powder pellets and fused beads or glass disks are routinely used in X‐ray fluorescence spectrometry for the determination of major and trace elements, respectively, in geological materials. In order to evaluate the performance of these two sample preparation methods, we determined Ni and Cr concentrations of fourteen RMs from Japan, France and South Africa, and eighty‐five igneous and three sedimentary rock samples from Mexico in both powder pellets and glass beads. We also computed new values of statistical parameters for RMs from an outlier‐based multiple‐test method and compared them with the literature mean and confidence limit values. The results showed that the multiple‐test method provided more reliable central tendency and dispersion parameters for RMs than those obtained previously from the two or three standard deviation method, or from robust methods. The powder pellet and fused bead sample preparation methods provided consistent results for Ni and Cr at concentration levels > 50 μg g^?1 in this application; for lower concentration levels, however, these methods showed somewhat greater differences. For quantitative comparisons, both ordinary and weighted least‐squares linear regression models were used to show that the two sample preparation methods provided generally unbiased results.     

The effect of mineralogical and cationic heterogeneities on rheological properties of suspensions with Li-smectites, extracted from Volclay MX-80

The rheological study of colloidal suspensions contributes to the understanding of the aggregation phenomena of colloidal particles within a suspended fluid. The infra-2-μm (equivalent diameter) fraction of a bulk material, Volclay MX-80 bentonite was intensively analysed in order to understand the relative rheological data scattering observed with Li-smectite suspensions, prepared with the usual saturation procedure. A good mineralogical characterisation, especially for secondary minerals, coupled to a verification of cation exchanges on clayey fraction allowed us to propose a new way for investigating the observed differences of the bentonites rheological behaviour. Indeed, for a well Li-saturated smectite obtained from the purified infra-2-μm fraction, rheological data proved to be very accurate and perfectly reproducible. This emphasises the role of other minerals as well as the commonly observed discrepancy between the rheological behaviours of natural and industrial bentonites.     

A spectrophotometric measurement of soil cation exchange capacity based on cobaltihexamine chloride absorbance

Among numerous methods for cation exchange capacity (CEC) determination for soils and sediments, the cobaltihexamine chloride method is frequently used due to its ability to measure CEC at soil pH. After exchange with Co(NH₃)₆³⁺ ions, CEC is estimated via the measurement of the Co remaining in solution. The modified method proposed allows a more rapid determination of CEC based on the measurement of the absorbance at 472 nm of the cobaltihexamine chloride solution before and after exchange. This method has been applied to various soil's horizons from four sites, selected to cover a wide range of CEC and pH values. The model obtained allows one to calculate CEC from absorbance at 472 nm with 95% confidence intervals. As CEC is of relevant meaning in agronomical and environmental purposes, and more recently in ecotoxicological studies, this modified method can be proposed as a rapid test for CEC evaluation.     

Ni-Co sulphide segregation in the Mamb pyroxenite intrusion, Cameroon

The amphibole metapyroxenite intrusion from Mamb (Cameroon) consists of enstatite, diopside-augite, edenite, and traces of plagioclase, biotite and rutile. It contains notable amounts of sulphides (pyrrhotite, pentlandite, chalcopyrite, pyrite and Co-rich violarite). The sulphide phase segregated during magma crystallization as immiscible droplets (≤ 1 mm) included in growing ferromagnesian minerals or aggregated in the silicate crystal mush to form an interstitial phase. However, observed sulphide assemblages are likely to result from low-T (≤ 300 °C) re-equilibration of high-T monosulphide solid solutions, more particularly during the Pan-African metamorphic event. The Mamb amphibole pyroxenite intrusion is tentatively considered as a potential source for Ni and Co mineralization.     

Predicting landscape-scale erosion rates using digital elevation models

Functional relationships between erosion rates and topography are central to understanding controls on global sediment flux and interactions among tectonics, climate, and erosion in shaping topography. Based on such relations digital elevation models (DEMs) allow predicting landscape-scale erosion rates to the degree that process models can be calibrated and to the extent that such processes reflect elevation, drainage area, and aspect, or their derivatives such as slope and curvature. Digital elevation models allow investigating the influence of erosional processes on landscape form and evolution through generalized quantitative expressions often referred to as ‘erosion laws’. The analytical forms of such expressions are derived from physical principles, but only limited data are available to guide calibration to particular landscapes. In addition, few studies have addressed how different transport laws interact to set landscape-scale erosion rates in different environments. Conventionally, landscape-scale sediment flux is considered to be linearly related to slope or relief, but recent analyses point toward non-linear relations for steep terrain in which changes in the frequency of landsliding accommodate increased rates of rock uplift. In such situations, landscape-scale erosion rates are more closely tied to erosion potential predicted by models of bedrock river incision. Consequently, I propose that using DEMs to predict absolute or relative erosion rates at the landscape-scale counter-intuitively involves the rate of fluvial processes as governing the sediment flux from steep landscapes, and rates of hillslope processes as governing sediment flux from low-gradient landscapes. To cite this article: D.R. Montgomery, C. R. Geoscience 335 (2003).     

Multi-technique monitoring of ocean tide loading in northern France

We have organised afield study of ocean tide loading in the northwestern part of France, where tidal amplitudes are known to be among the highest in the world. GPS and gravimetric techniques have already proved their capability to measure such weak and high-frequency signals. In this study, these classical observations are complemented with less usual techniques, such as tiltmeter and Satellite Laser Ranging (SLR) measurements. We present here the preliminary results for a common period of observations spanning from 12–19 May 2004. Additional measurements from the French Transportable Laser Ranging Station (FTLRS) were available during September and October 2004. Observation residuals are computed as the difference between the observed and the predicted time signals. We obtain small RMS residuals for GPS measurements (2.5/3.1/4.5 mm for the eastward, northward and upward components), for absolute and relative gravimetry (9 nm/s² and 13 nm/s²) and for tiltmeters (0.05 μrad for EW component). We also fit the amplitude of the main M2 tidal constituent to FTLRS observations and we find a value of 3.731 cm, which is comparable to the theoretical value.     

A Late Hauterivian short-lived anoxic event in the Mediterranean Tethys: the ‘Faraoni Event’

A Late Hauterivian interval (127.5 Ma), called the ‘Faraoni Event’, which is characterised by the deposition of deep-marine black shales in the Mediterranean Tethys, is demonstrably of sufficient geological brevity to be qualified as an anoxic event. This event lies within the Pseudothurmannia catulloi ammonite subzone, coincides with the extinction of the calcareous nannofossil species Lithraphidites bollii, and records an increase in a globular planktonic foraminifer. High quantities of marine organic matter were preserved in pelagic successions from northern and central Italy, Switzerland, southeastern France, southern Spain and probably elsewhere in the Mediterranean Tethys and Atlantic Ocean. Carbon-isotope stratigraphy from Tethyan and Atlantic sections shows a minor positive excursion in the uppermost part of the Hauterivian and Lowermost Barremian, suggesting accelerated extraction of organic carbon from the ocean reservoir just after the ‘Faraoni Event’. The duration of this short event is less than 100 ka according to cyclostratigraphy and coincides with a third-order sea-level rise. It is likely that similar forcing mechanisms responsible for global OAEs operated during this short time interval. To cite this article: F. Baudin, C. R. Geoscience 337 (2005).     

Quality Control and Reference Sample Data Bases*

A critical aspect of any quality control program is the definition of criteria for “satisfactory’ performance of analytical methods. These criteria should address both expected accuracy and expected precision of the methods, as well as any variation in these figures of merit from one sample type to another. Development of appropriate criteria and their application to analytical programs for the characterization of new reference samples is presented.     

Development of sustainability evaluation model for implementing product service systems

A new business model, product service systems, is proposed to promote a shift in focus from selling purely products to selling functions. This is achieved through a mix of products and services that fulfill the same consumer demands, while eliciting less environmental impact. Development of product service systems has become an increasingly important strategy in achieving social, economic, and environmental sustainability because product service systems advocates reducing resource consumption, while delivering better and more widely available goods and services. This paper proposes an evaluation framework of sustainable performance to implement product service systems. A literature review discusses 32 criteria categorized into two aspects: product and organization. The fuzzy Delphi method is then applied to identify the consistency of criteria. The relative weights of the selected criteria are determined using Fuzzy analytic hierarchy process. Results indicate that the top three criteria in product aspect are maintenance system (weight?=?0.172), use time or frequency (weight?=?0.145), and price of the product (weight?=?0.132). For the organization aspect, the top three criteria are integrated service plan (weight?=?0.197), product development and design (weight?=?0.144) and optimized transportation network (weight?=?0.089). The demand for implementing product service systems is completely different from selling traditional goods because product service systems must consider the issue of sustainability. The proposed evaluation framework can help companies identify the potential products suitable in implementing product service systems.