Analysis of individual fluid inclusions using synchrotron X-ray fluorescence microprobe: progress toward calibration for trace elements

A critical problem for conducting quantitative analysis of individual fluid inclusions using Synchrotron X-Ray Fluorescence (SXRF) technique relates to the standardization and the calibration of the X-ray spectra. In this study, different approaches have been tested for calibration purposes: (a) the use of chlorine when Cl content can be estimated either from melting point depressions of undersaturated fluid inclusions or from saturation limits for halite-bearing fluid inclusions, (b) the use of calcium from synthetic fluid inclusions of known CaCl₂ content as an external standard. SXRF analysis was performed on individual fluid inclusions from the Chivor and Guali emerald deposits, Columbia. These well-known samples contain a single fluid inclusion population for which detailed crush-leach analyses are available, thus providing a relevant compositional reference frame. Concentration estimates were also compared to Particle Induced X-ray Emission (PIXE) analysis carried out independently on the same fluid inclusions.Results of the calibration tests indicate that major (Cl, K, Ca, Fe, Mn) and trace element (Cu, Zn, As, Br, Rb, Sr, Ba, Pb) concentration estimates can be performed without precise knowledge of the analytical volume and the inclusion’s 3D geometry. Although the standard deviation of the SXRF results can be relatively high depending on the calibration mode used, mean concentration estimates for most elements are in good agreement with PIXE and crush-leach analysis. Elemental distributions within single fluid inclusions were also established. Associated correlation diagrams argue for the homogeneous distribution of most elements in the fluid inclusion. In contrast, Br shows a bimodal distribution interpreted to reflect a significant enrichment of the vapor portion of the inclusion fluid.     

Estimation of tree water stress from stem and soil water monitoring with time‐domain reflectometry in two small forested basins in Spain

Soil‐tree water relationships were studied using time domain reflectometry (TDR) in two small forested basins in Spain. The stem water content of two Mediterranean Quercus species (Quercus pyrenaica and Quercus rotundifolia) was measured using previously constructed species‐specific equations. To monitor soil moisture, a TDR station network was used in both cases. Sixteen Q. pyrenaica and six Q. rotundifolia individuals were selected to install two TDR probes in their trunks (at 20 and 120 cm above the ground) to monitor stem water content. Stem and soil water contents were measured fortnightly. The stem water content of both species showed a similar temporal trend for the period studied. A spring maximum (0·654 cm³ cm^?3 for Q. pyrenaica and 0·568 cm³ cm^?3 for Q. rotundifolia) was found to be associated with high transpiration and no soil moisture deficit, and a late‐summer minimum (0·520 cm³ cm^?3 for Q. pyrenaica and 0·426 cm³ cm^?3 for Q. rotundifolia) was associated with the end of the dry season. This drop in stem water content occurs when the available water in the soil decreases. This seasonal difference presumably reflects water withdrawn from stem storage to support the transpirational demands of the tree. Since plant water stress results in reduced stem water content and since this drop can be measured by TDR, it may be concluded that this technology offers a suitable tool for detecting plant water stress. Copyright © 2007 John Wiley & Sons, Ltd.     

Palaeoenvironmental implications of ferruginous deposits related to a Middle–Upper Jurassic discontinuity (Prebetic Zone,Betic Cordillera,Southern Spain)

The Middle–Upper Jurassic boundary in the westernmost Tethyan basins is marked by a discontinuity. A thin iron crust with ferruginous ooids and pisoids and an overlying ferruginous oolitic limestone lithofacies occur in a genetic relationship to this discontinuity with a reduced thickness (< 50 cm) and very local distribution in the Prebetic Zone (Betic Cordillera).The ferruginous coated grains are subdivided into two types. Type A ooids are characterised by thin, regular lamination in concentric layers enclosing a nucleus; they are dominant in the top of the iron crust (100% of the ferruginous ooids) and in the ferruginous oolitic limestone (82%). Type B ooids typically have thick, irregular lamination in a few discontinuous concentric layers enclosing a variable nucleus including bioclasts and foraminifera; they are exclusive to the ferruginous oolitic limestone (18% of the ferruginous ooids). The bulk chemical composition varies between 80% Fe₂O₃ by weight in the iron crust and 67% by weight in the coated grains. In the ferruginous ooids, the contents in SiO₂ (5.4%), Al₂O₃ (6.5%), P₂O₅ (3.6%), and CaO (4.7%) are higher than in the crust. Trace elements (V, Cr, Co, Ni, Zn, Y, Mo, and Pb) in both the crust and ooids show enriched values compared with the bulk composition of the upper continental crust. The mineral composition of the iron crust and ooids is primarily goethite, with small amounts of Al-hydroxide (bohemite) and apatite, whereas hematite is identified only in the iron crust.The Type A ooids are interpreted as having an origin related to the iron crust. Since there is no evidence to support a marine genesis for the iron crust, the possibility of a subaerial origin is presented here. The crust has characteristics (chemical and mineralogical composition) similar to those of ferruginous pisolitic plinthite (highly weathered redoximorphic soil), and goethite shows an Al-substitution range (5–10 mol%) that indicates pedogenic conditions. Soil processes under periodic hydrous conditions are suggested; groundwater soils with hydrous conditions are congruent with the formation of the Type A ferruginous ooids and pisoids. In this situation, a coastal plain with periodically flooded soils would be the likeliest scenario. Callovian shallow carbonate shelf was possibly emerged and weathered, followed by marine sedimentation during the Middle Oxfordian, associated with major flooding of the Prebetic shelf and the erosion of ferruginous pisolitic plinthite. The first marine deposit was ferruginous oolitic limestones. Fragments of iron crust and Type A ferruginous ooids were reworked and incorporated into the marine sediments. A second phase of ferruginous ooids (Type B) with clear marine features developed, benefiting from iron-rich microenvironments due to the redistribution from iron crust fragments and Type A ferruginous ooids.     

Sedimentary processes in a submarine canyon excavated into a temperate‐carbonate ramp (Granada Basin,southern Spain)

During the Late Tortonian, shallow‐water temperate carbonates were deposited in a small bay on a gentle ramp linked to a small island (Alhama de Granada area, Granada Basin, southern Spain). A submarine canyon (the ‘Alhama Submarine Canyon’) developed close to the shoreline, cross‐cutting the temperate‐carbonate ramp. The Alhama Submarine Canyon had an irregular profile and steep slopes (10° to 30°). It was excavated in two phases reflected by two major erosion surfaces, the lowermost of which was incised at least 50 m into the ramp. Wedge‐shaped and trough‐shaped, concave‐up beds of calcareous (terrigenous) deposits overlie these erosional surfaces and filled the canyon. A combination of processes connected to sea‐level changes is proposed to explain the evolution of the Alhama Submarine Canyon. During sea‐level fall, part of the carbonate ramp became exposed and a river valley was excavated. As sea‐level rose, river flows continued along the submerged, former river‐channel, eroding and deepening the valley and creating a submarine canyon. At this stage, only some of the transported conglomerates were deposited locally. As sea‐level continued to rise, the river mouth became detached from the canyon head; littoral sediments, transported by longshore and storm currents, were now captured inside the canyon, generating erosive flows that contributed to its excavation. Most of the canyon infilling took place later, during sea‐level highstand. Longshore‐transported well‐sorted calcarenites/fine‐grained calcirudites derived from longshore‐drift sandwaves poured into and fed the canyon from the south. Coarse‐grained, bioclastic calcirudites derived from a poorly sorted, bioclastic ‘factory facies’ cascaded into the canyon from the north during storms.     

Aeolian sand sea development along the mid‐Cretaceous western Tethyan margin (Spain): erg sedimentology and palaeoclimate implications

The existence of a mid‐Cretaceous erg system along the western Tethyan margin (Iberian Basin, Spain) was recently demonstrated based on the occurrence of wind‐blown desert sands in coeval shallow marine deposits. Here, the first direct evidence of this mid‐Cretaceous erg in Europe is presented and the palaeoclimate and palaeoceanographic implications are discussed. The aeolian sand sea extended over an area of 4600 km². Compound crescentic dunes, linear draa and complex aeolian dunes, sand sheets, wet, dry and evaporitic interdunes, sabkha deposits and coeval extradune lagoonal deposits form the main architectural elements of this desert system that was located in a sub‐tropical arid belt along the western Tethyan margin. Sub‐critically climbing translatent strata, grain flow and grain fall deposits, pin‐stripe lamination, lee side dune wind ripples, soft‐sediment deformations, vertebrate tracks, biogenic traces, tubes and wood fragments are some of the small‐scale structures and components observed in the aeolian dune sandstones. At the boundary between the aeolian sand sea and the marine realm, intertonguing of aeolian deposits and marine facies occurs. Massive sandstone units were laid down by mass flow events that reworked aeolian dune sands during flooding events. The cyclic occurrence of soft sediment deformation is ascribed to intermittent (marine) flooding of aeolian dunes and associated rise in the water table. The aeolian erg system developed in an active extensional tectonic setting that favoured its preservation. Because of the close proximity of the marine realm, the water table was high and contributed to the preservation of the aeolian facies. A sand‐drift surface marks the onset of aeolian dune construction and accumulation, whereby aeolian deposits cover an earlier succession of coastal coal deposits formed in a more humid period. A prominent aeolian super‐surface forms an angular unconformity that divides the aeolian succession into two erg sequences. This super‐surface formed in response to a major tectonic reactivation in the basin, and also marks the change in style of aeolian sedimentation from compound climbing crescentic dunes to aeolian draas. The location of the mid‐Cretaceous palaeoerg fits well to both the global distribution of other known Cretaceous erg systems and with current palaeoclimate data that suggest a global cooling period and a sea‐level lowstand during early mid‐Cretaceous times. The occurrence of a sub‐tropical coastal erg in the mid‐Cretaceous of Spain correlates with the exposure of carbonate platforms on the Arabian platform during much of the Late Aptian to Middle Albian, and is related to this eustatic sea‐level lowstand.     

Geochemical history of a Lower Miocene lake,the Cypris Formation,Sokolov Basin,Czech Republic

The intracontinental Lower Miocene Cypris paleo-lake originated during progressive subsidence in the Sokolov Basin, part of the Cenozoic Oh?e Rift, after the deposition of coal seams. The Cypris Fm. consists almost entirely of lacustrine clays with variable mineral composition and organic matter, where this succession is 70–120 m thick. The main objective of this study was to interpret the geochemical history of the Lower Miocene Cypris Fm. using high-resolution, down-core geochemical records and study of the organic matter. This work revealed that the lower part of the lacustrine sediment sequence was deposited in a freshwater lake, in an open hydrological system. An increase in the K/Zr and K/Ti ratios towards the upper part of the Cypris Fm. indicates a gradual increase in the pelitic fraction of the local sediments and/or a decline in input of volcanic material. Simultaneously, increasing Ca/K and Sr/K ratios indicate the precipitation of carbonates, predominantly dolomite and siderite. In the upper part of the Cypris Fm., there is a significant increase in Na/K, Na/Zr, and Na/Ti ratios, suggesting increasing salinity (alkalinity) of the paleoenvironment in a closed hydrological system. Reaction between the Na-rich water and clastic components of the sediment in an alkaline medium gave rise to the formation of zeolites, mixed-layer clay minerals and smectite. Abundant remains of aquatic organisms, especially algae, increased with greater salinity in the upper part of the Cypris Fm. This is reflected in the greater hydrogen index (HI_{Rock Eval}), and the growing proportion of liptinite group macerals of aquatic origin in the bulk organic matter. During the entire history of sedimentation in the Miocene lake, repetitive changes in the sediment geochemistry occurred at both micro- and macroscales, and fluctuations of K/Ti, K/Zr, and Sr/Ca ratios over meters to tens of meters are observed. These changes probably reflect either long-term climate fluctuations during the Lower Miocene or oscillations caused by changes in the rate of subsidence of the basin floor. Variations in the elemental composition of sediments can be used to correlate individual boreholes across the entire sedimentary basin.     

Fusion of airborne LiDAR and multispectral sensors reveals synergic capabilities in forest structure characterization

Forest stand structure is an important concept for ecology and planning in sustainable forest management. In this article, we consider that the incorporation of complementary multispectral information from optical sensors to Light Detection and Ranging (LiDAR) may be advantageous, especially through data fusion by back-projecting the LiDAR points onto the multispectral image. A multivariate data set of both LiDAR and multispectral metrics was related with a multivariate data set of stand structural variables measured in a Scots pine forest through canonical correlation analysis (CCA). Four statistically significant pairs of canonical variables were found, which explained 83.0% accumulated variance. The first pair of canonical variables related indicators of stand development, i.e. height and volume, with LiDAR height metrics. CCA also found attributes describing stand density to be related to LiDAR and spectral variables determining canopy coverage. Other canonical variables pertained to Lorenz curve-derived attributes, which are measures of within-stand tree size variability and heterogeneity, able to discriminate even-sized from uneven-sized stands. The most relevant result was to find that metrics derived from the multispectral sensor showed significant explanatory potential for the prediction of these structural attributes. Therefore, we concluded that metrics derived from the optical sensor have potential for complementing the information from the LiDAR sensor in describing structural properties of forest stands. We recommend the use of back-projecting for jointly exploiting the synergies of both sensors using similar types of metrics as they are customary in forestry applications of LiDAR.