Natural speciation of Zn at the micrometer scale in a clayey soil using X-ray fluorescence, absorption, and diffraction

Combined use of synchrotron-based X-ray fluorescence (SXRF), diffraction (XRD), and absorption (EXAFS) with an X-ray spot size as small as five micrometers allows us to examine noninvasively heterogeneous soils and sediments. Specifically, the speciation of trace metals at low bulk concentrations and the nature of host minerals can be probed with a level of detail unattainable by other techniques. The potential of this novel analytical approach is demonstrated by determining the Zn species in the solid phases of a pristine horizon of a clayey acidic soil (pH 4.5-5.0) having a Zn concentration of 128 mg/kg. The sample presents a differentiated fabric under the optical microscope with traces of localized manganiferous, ferriferous and argillaceous accumulations. The high chemical and textural heterogeneity of this soil offers an opportunity to identify new Zn species and to confirm the existence of others proposed from published least-squares fits of bulk averaged EXAFS spectra. As many as five to six Zn species were observed: sphalerite (ZnS), zincochromite (ZnCr₂O₄), Zn-containing phyllosilicate and lithiophorite, and Zn-sorbed ferrihydrite or Zn-phosphate, the results being less definitive for these two last species. Bulk EXAFS spectroscopy applied to the powdered soil indicated that Zn is predominantly associated with phyllosilicates, all other species amounting to < ∼10 to 20% of total zinc. The role of lithiophorite in the sequestration of zinc in soils had been inferred previously, but the firm identification of lithiophorite in this study serves as an excellent demonstration of the capabilities of combined micro-SXRF/XRD/EXAFS measurements. The micro-EXAFS spectrum collected in an area containing only phyllosilicates could not be simulated assuming a single Zn structural environment. Two distinct octahedrally-coordinated crystallographic sites (i.e., two EXAFS components) were considered: one site located within the phyllosilicate structure (isomorphic cationic substitution in the octahedral sheet) and another in the interlayer region in the form of a Zn-sorbed hydroxy-Al interlayered species. This second subspecies is less certain and further investigation of the individual EXAFS spectrum of this component is needed to precise its exact nature and the uptake mechanism of zinc in it.     

Periodicity of Element Changes in the Upper Devonian Strata of Dachang Area,Southern China—A Case Study of Spectral Analysis

Power spectral analysis is discussed and an exmple of its application to a geochemical stratigraphic profile is presented.In the Dachang area,all major elements,as well as the maximal sedimentary trend factor(MSTF),demonstrate consistent change periodicity,but are out-of-step with cach other.This can be explained by sedimentogecochemical consideration.The results of power spectral analysis enable geochemists to group elements on the basis of the distribution of their changed periods,and to interpret some special geological and geochemical situations.     

L'extension à Madagascar du Néogène à l'Actuel: arguments structuraux et géophysiques

Field studies and observations from aerial photographs, remote sensing and numerical field models show that the Meso-Cenozoic and Recent sedimentary sequences of Madagascar are affected by normal faults. These faults, north-south, north-northeast-south-southwest and north-northwest-south-southwest trending, are responsible for the following morphological effects: scarps, block tilting and opening of faulted basins, the most important of which being the Lake Alaotra Basin. The general orientation of these brittle structures and some observations in the field show tha the horizontal maximum extension isroughly east-west directed. Other lines of evidence, seismic and gravimetric, confirm that Madagascar is presently submitted to a crustal and lithospheric extension, parallel to that in East Africa and the Mozambique Channel.     

Quantitative Control of Migration: A Geostatistical Attempt

This paper is devoted to a geostatistical attempt at modeling migration errors when localizing a reflector in the ground. Starting with a probabilistic velocity model and choosing the simple geometrical optics background for the wave propagation in such media, we give the expression of the errors. This may be quantified provided the covariance of the velocity field is known. Variance of arrival times at constant offset is related to the covariance of the velocity field at hand. A practical application is given in the same paragraph. After that we give a typical schema for migration and uncertainty modeling: starting with seismic data, we make the weak seismic inversion. We then obtain the covariance of the velocity field that we use for simulating migration errors. The main issues of this methodology are discussed in the last paragraph.     

Jurassic lagoonal environments and quasi-abiotic platy limestone accumulation: microbial interventions

Within the regressive sequence (eustatic sea-level fall) that characterizes the French Southern Jura carbonate platform during the Kimmeridgian, a succession of three facies (called here units 1–3) may be observed in a palaeolagoon near Orbagnoux. Unit 1 is a shallow-water, intensely burrowed, carbonate deposit; unit 2 (consisting of laminated, organic matter-rich carbonate) represents a shallow lagoonal environment, prone to stromatolite development and organic matter accumulation; unit 3 consists of platy limestones almost devoid of identifiable biota. Trace element distributions indicate that depositional and early diagenetic conditions must have been reducing during deposition of unit 1 and, especially, unit 2, whereas they were much less reducing during deposition of unit 3. However, the latter does not contain body or trace fossils, with the exception of structures interpreted as calcified bacteria. The reasons why the apparently normal marine environment of unit 3 did not allow a normal biota to develop are explored and lead us to propose that: (i) unit 2 may be a Jurassic counterpart of modern kopara deposits (stromatolites of French Polynesian atolls); and (ii) unit 3 may be the result of palaeokopara reworking. This model invokes the extensive intervention of microbes in the formation of these carbonate deposits.     

Evaluation of anthropogenic and biogenic inputs into the western Mediterranean using molecular markers

Aliphatic hydrocarbons (AHs), sterols (ST), and lipid classes were determined in suspended particles collected in the Catalan Sea, northwestern Mediterranean. Principal Component Analysis of the data set revealed a clustering of samples depending on the sources of organic matter, i.e., coastal influenced, open sea and frontal zone. Terrestrial inputs were recognized in particles collected in the surface waters, at the vicinities of river outflow (i.e., Rhône and Ebro), by a predominance of C₂₉ and C₃₁ n-alkanes, 24-ethylcholest-5-en-3β-ol (S12), and the anthropogenic 5β(H)-cholestan-3β-ol, coprostanol (S1). Phytoplanktonic molecular markers (n-C₁₇, 27-nor-24-methylcholesta-5,22E-dien-3β-ol, cholesta-5,22-dien-3β-ol and 24-methylcholest-5-en-3β-ol) were widespread but relatively more apparent in the open sea and frontal zones. A similar distribution was observed for lipid classes, with higher concentrations of phospholipids, and an enrichment in free fatty acids in the areas influenced by river discharges. Total sterol, the unresolved complex mixture of hydrocarbons and the pristane–phytane ratio were highest at a persistent frontal zone, possibly reflecting the combination of a higher primary productivity and fossil hydrocarbon absorption on to suspended particles. Moreover, vertical profiles exhibited a subsurface concentration maximum at 20–30 m water depth, concurrently with the chlorophyll.     

The international at-sea intercomparison of fCO2 systems during the R/V Meteor Cruise 36/1 in the North Atlantic Ocean

The ‘International Intercomparison Exercise of fCO₂ Systems’ was carried out in 1996 during the R/V Meteor Cruise 36/1 from Bermuda/UK to Gran Canaria/Spain. Nine groups from six countries (Australia, Denmark, France, Germany, Japan, USA) participated in this exercise, bringing together 15 participants with seven underway fugacity of carbon dioxide (fCO₂) systems, one discrete fCO₂ system, and two underway pH systems, as well as systems for discrete measurement of total alkalinity and total dissolved inorganic carbon. Here, we compare surface seawater fCO₂ measured synchronously by all participating instruments. A common infrastructure (seawater and calibration gas supply), different quality checks (performance of calibration procedures for CO₂, temperature measurements) and a common procedure for calculation of final fCO₂ were provided to reduce the largest possible amount of controllable sources of error. The results show that under such conditions underway measurements of the fCO₂ in surface seawater and overlying air can be made to a high degree of agreement (±1 μatm) with a variety of possible equilibrator and system designs. Also, discrete fCO₂ measurements can be made in good agreement (±3 μatm) with underway fCO₂ data sets. However, even well-designed systems, which are operated without any obvious sign of malfunction, can show significant differences of the order of 10 μatm. Based on our results, no “best choice” for the type of the equilibrator nor specifics on its dimensions and flow rates of seawater and air can be made in regard to the achievable accuracy of the fCO₂ system. Measurements of equilibrator temperature do not seem to be made with the required accuracy resulting in significant errors in fCO₂ results. Calculation of fCO₂ from high-quality total dissolved inorganic carbon (C_T) and total alkalinity (A_T) measurements does not yield results comparable in accuracy and precision to fCO₂ measurements.     

Investigating crater lake warming using ASTER thermal imagery: Case studies at Ruapehu,Poás,Kawah Ijen,and Copahué Volcanoes

A two-channel or split-window algorithm designed to correct for atmospheric conditions was applied to thermal images taken by the Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) of Lake Yugama on Kusatsu–Shirane volcano in Japan in order to measure the temperature of its crater lake. These temperature calculations were validated using lake water temperatures that were collected on the ground. Overall, the agreement between the temperatures calculated using the split-window method and ground truth is quite good, typically ± 1.5 °C for cloud-free images. Data from fieldwork undertaken in the summer of 2004 at Kusatsu–Shirane allow a comparison of ground-truth data with the radiant temperatures measured using ASTER imagery. Further images were analyzed of Ruapehu, Poás, Kawah Ijen, and Copahué volcanoes to acquire time-series of lake temperatures. A total of 64 images of these 4 volcanoes covering a wide range of geographical locations and climates were analyzed. Results of the split-window algorithm applied to ASTER images are reliable for monitoring thermal changes in active volcanic lakes. These temperature data, when considered in conjunction with traditional volcano monitoring techniques, lead to a better understanding of whether and how thermal changes in crater lakes aid in eruption forecasting.     

Particle transport in gravel-bed rivers: Revisiting passive tracer data

Data from tracer experiments were compiled and analysed in order to explore the role of geomorphological, hydrological and sedimentological constraints on fluvial gravel transport in gravel-bed rivers. A large data set from 217 transport episodes of tagged stones were compiled from 33 scientific papers. Our analyses showed that while magnitude of peak discharge is a major control on gravel transport and mobility, tracer travel distances show some scale dependence on the morphological configuration of the channel. Our results also highlight differences in the way tracers are displaced between step–pool and riffle and pool channels. The riffle–pool sequence seems to be a more efficient trap for travelling gravels than the step–pool pair. In addition, in step–pool channels there are clear differences in tracer transport between observations of first displacements after tracer seeding (unconstrained-stone conditions), and second and subsequent observations of tracer displacements (constrained-stone conditions). The comparison between tracer experiments under constrained conditions and those under unconstrained conditions also highlights the importance of bed state and structures in gravel mobility. The results of this study confirm that sediment transport in gravel-bed rivers is a complex process, whereby sedimentological and geomorphological controls are superimposed on the hydraulic forcing. © 2018 John Wiley & Sons, Ltd.