Asymmetric measures of association, closed data, and multivariate analysis

The association between constant-sum variables X_i and X_j expressed as percentages can be calculated as a product-moment correlation between X_i and X_j/(100 – X_i ) and a correlation between X_j and X_i/(100 – X_j ). An asymmetric, square matrix may be formed from these coefficients, and multivariate analysis performed by two methods: singular value decomposition and canonical decomposition. Either analysis avoids problems in the interpretation of correlation coefficients determined from closed arrays, and provides information about dependencies among the variables beyond that obtained from the usual correlation coefficient between X_i and X_j.Two examples show the canonical decomposition to have the greater usefulness.     

Shock‐induced formation of wüstite and fayalite in a magnetite‐quartz target rock

Projectile–target interactions as a result of a large bolide impact are important issues, as abundant extraterrestrial material has been delivered to the Earth throughout its history. Here, we report results of shock‐recovery experiments with a magnetite‐quartz target rock positioned in an ARMCO iron container. Petrography, synchrotron‐assisted X‐ray powder diffraction, and micro‐chemical analysis confirm the appearance of wüstite, fayalite, and iron in targets subjected to 30 GPa. The newly formed mineral phases occur along shock veins and melt pockets within the magnetite‐quartz aggregates, as well as along intergranular fractures. We suggest that iron melt formed locally at the contact between ARMCO container and target, and intruded the sample causing melt corrosion at the rims of intensely fractured magnetite and quartz. The strongly reducing iron melt, in the form of μm‐sized droplets, caused mainly a diffusion rim of wüstite with minor melt corrosion around magnetite. In contact with quartz, iron reacted to form an iron‐enriched silicate melt, from which fayalite crystallized rapidly as dendritic grains. The temperatures required for these transformations are estimated between 1200 and 1600 °C, indicating extreme local temperature spikes during the 30 GPa shock pressure experiments.     

An integrative hierarchical monitoring approach applied at a natural analogue site to monitor CO2 degassing areas

This paper introduces an integrative hierarchical monitoring concept allowing for the detection and assessment of possible leakages from geological storage formations into the shallow subsurface or atmosphere. The concept introduced in this paper combines various investigation methods working at different scales and with varying resolutions. This approach will allow large spatial areas to be consistently covered, to enable efficient monitoring. Experience gained from the adoption of these tools for naturally occurring CO₂ deposits (analogue sites) is helpful for the evaluation and adoption of the methods to the requirements of storage projects.     

Available energy and energy balance closure at four coniferous forest sites across Europe

The available energy (AE), driving the turbulent fluxes of sensible heat and latent heat at the earth surface, was estimated at four partly complex coniferous forest sites across Europe (Tharandt, Germany; Ritten/Renon, Italy; Wetzstein, Germany; Norunda, Sweden). Existing data of net radiation were used as well as storage change rates calculated from temperature and humidity measurements to finally calculate the AE of all forest sites with uncertainty bounds. Data of the advection experiments MORE II (Tharandt) and ADVEX (Renon, Wetzstein, Norunda) served as the main basis. On-site data for referencing and cross-checking of the available energy were limited. Applied cross checks for net radiation (modelling, referencing to nearby stations and ratio of net radiation to global radiation) did not reveal relevant uncertainties. Heat storage of sensible heat J _H, latent heat J _E, heat storage of biomass J _veg and heat storage due to photosynthesis J _C were of minor importance during day but of some importance during night, where J _veg turned out to be the most important one. Comparisons of calculated storage terms (J _E, J _H) at different towers of one site showed good agreement indicating that storage change calculated at a single point is representative for the whole canopy at sites with moderate heterogeneity. The uncertainty in AE was assessed on the basis of literature values and the results of the applied cross checks for net radiation. The absolute mean uncertainty of AE was estimated to be between 41 and 52 W m^?2 (10–11 W m^?2 for the sum of the storage terms J and soil heat flux G) during mid-day (approximately 12% of AE). At night, the absolute mean uncertainty of AE varied from 20 to about 30 W m^?2 (approximately 6 W m^?2 for J plus G) resulting in large relative uncertainties as AE itself is small. An inspection of the energy balance showed an improvement of closure when storage terms were included and that the imbalance cannot be attributed to the uncertainties in AE alone.     

Local structural heterogeneity,mixing behaviour and saturation effects in the grossular–spessartine solid solution

Local structural heterogeneities in crystals of the binary grossular–spessartine solid solution have been analyzed using powder IR absorption spectroscopy. Wavenumber shifts of the highest energy Si–O stretching mode in spectra collected at room temperature are consistent with variations in Si–O bond length from structural data. They show a smaller positive deviation from linearity across the join than is seen for the grossular–pyrope and grossular–almandine binaries. The effective line widths, corr, of three selected wavenumber regions all deviate positively from linear behaviour. An empirical calibration of this excess spectroscopic property, obtained by comparison with calorimetric enthalpy of mixing data, gives an estimate for the symmetric Margules parameter of W^H_spec = 14.4(7) kJ mol^–1 in H^mix = W^H_specX_GrX_Sp. W^H_spec values derived on the same basis for four aluminosilicate garnet solid solutions analyzed by IR spectroscopy vary with V², where V represents the difference in molar volume between the end members of each binary system. Measurements of lattice parameters and IR spectra were made over a range of temperatures for seven samples with different compositions. Positive excess molar volumes of mixing at low temperature (30 K) may be larger than the excess molar volumes at room temperature. The saturation temperatures of the molar volumes show no correlation with composition, however, in contrast with what had been expected on the basis of data for the grossular–pyrope binary. Saturation temperatures for spectroscopic parameters and lattice parameters of samples with compositions Gr15Sp85 and Gr60Sp40 seem to be outliers in all experiments. It is concluded that the data hint at systematic changes in saturation temperatures across the solid solution, with implications for both the excess entropy of mixing and the excess volume of mixing, but more precise data or further sample characterization are needed to prove that this composition dependence is real in garnet solid solutions.     

The development of forest damage — control and prognosis on the basis of remote sensing data

Forest damage can be caused by three types of stress which exercise their influence by predisposing, causative and contributory factors. Predisposing factors, above all permanent immision stress, cause the general diminishing of the trees' vitality. Causative fators such as long and extreme periods of dryness cause a fast and evident deterioration of the forest stand, contributory factors as eg pest attacks cause their mortification. When using remote sensing data to monitor the development of forest damage it is necessary therefore not only to pay attention to spectral signatures characterizing the degree of green space and thus the information of the canopy but also to spectral signs showing the water supply of the stands. This has not been done so far though nowadays the necessary multispectral satellite data are on regular offer. For this reason it may be suggested that the existing possibilities to predict the development of forest damage on the basis of remote sensing data have not yet been fully used.In order to examine these possibilities, in the environs of Berlin, ie in the east and south of the Land of Brandenburg both the vegetation index which has been known from literature for a long time and an index for the difference in remission identifying the water bands in the short-wave infrared have been calculated on the basis of Landsat-TM data. A multi-temporal comparison shows that despite the bad conditions of the forest in 1991 on the test site located north-east of Berlin due to a relatively good water supply in that year the pine forest damage had not progressed in 1992. This allows to draw the conclusion that at least in the pine forests of the East German interior lowland the development of forest damage is essentially determined by dryness stress. In this way on the basis of 1992 Landsat-TM data there was not only an inventory made of the actual condition of the forest on the east and south-east of the Land of Brandenburg but also trends of damage progress shown. The damage classification of pine stands be completed by a prognosis as to the development of damage.     

A generalized principal components model in petrology

Principal components analysis of elemental distributions among minerals elucidate chemical, thermal, and equilibrium effects. Previous approaches in applying this multivariate statistical method to petrologic data are united into a single model, so-called three-mode principal components analysis. The major advantage of the model lies in the separate analysis of each of the three modes: element, mineral, and sample. The three sets of principal components are related through a “core matrix”. The model accommodates the ordination of pair-wise combination of the modes, such as samples and minerals in visualization of multidimensional tie-lines. Because of its generality, the model permits great flexibility in the study of petrologic data.