Long-range vs. short-range ordering in synthetic Cr-substituted goethites

A series of Cr-substituted goethites with (Cr:Fe molar ratio up to 0.12) were prepared. Thermal analysis of the solids indicates the formation of cation-deficient compounds that are more stable towards the transformation to hematite as the Cr content increases. Powder X-ray diffraction (PXRD) and extended X-ray absorption fine structure (EXAFS) techniques were used to assess the structural characteristics of the whole series of the substituted solids. XRD patterns demonstrate that the order around Fe remains typical of a goethite-like structure. Rietveld refinement of X-ray diffraction data indicates that the incorporation of Cr causes a slight decrease in the cell volume with the c-cell parameter following the Vegard’s law. This decrease is accompanied by changes in opposite directions of the various Me-Me distances. EXAFS spectra at the Fe K-edge indicate that the local order around the Fe atom changes slightly upon Cr substitution: Measurements in the Cr K-edge show that the Cr environment remains unchanged in the whole series. All the observed trends in both average Rietveld and local EXAFS distances can be traced back to the differences in the coordination polyhedra around Cr and Fe. The polyhedron around Cr is more symmetric and can be described as Cr(OH_0.5)₆ as opposed to the polyhedron around Fe that contains two distinct sets of ligands, FeO₃(OH)₃. The effects caused by substitution are governed by this difference, rather than by the smaller size of Cr(III) as compared to Fe(III). Simultaneous use of XAS and Rietveld refinement of XRD data permits tracing the trends in the average long range ordering (Me-Me distances) to local changes in distances and angles when Cr³⁺ substitutes Fe³⁺ in goethite. Complex changes in the various interatomic distances and angles may result in deceivingly simple long-range trends. These trends are therefore of limited value as probes for the atomic scale changes. On the other hand, XAS provide direct information on the fundamental, atomic-scale changes.     

Geology of the platanares geothermal area, Departamento de Copán, Honduras

The Platanares geothermal area, Departamento de Copán, Honduras, is located within a graben that is complexly faulted. The graben is bounded on the north by a highland composed of Paleozoic (?) metamorphic rocks in contact with Cretaceous - Tertiary redbeds of unknown thickness. These are unconformably overlain by Tertiary andesitic lavas, rhyolitic ignimbrites, and associated sedimentary rocks. The volcanic rocks are mostly older than 14 Ma, and thus are too old to represent the surface expression of an active crustal magma body. Thermal fluids that discharge in the area are heated during deep circulation of meteoric water along faults in a region of somewhat elevated heat flow. Geothermometry based upon the chemical composition of thermal fluids from hot springs and from geothermal gradient coreholes suggests that the reservoir equilibrated at temperatures as high as 225 to 240°C, within the Cretaceous redbed sequence. Three continuously cored geothermal gradient holes have been drilled; fluids of about 165°C have been produced from two drilled along a NW-trending fault zone, from depths of 250 to 680 m. A conductive thermal gradient of 139°C/km, at a depth of 400 m, was determined from the third well, drilled 0.6 km west of that fault zone. These data indicate that the Platanares geothermal area holds considerable promise for electrical generation by moderate- to hightemperature geothermal fluids.     

The big picture of field hydrology studies in Brazil

ABSTRACT

In-situ

hydrological monitoring is essential for a proper decision-making process and modelling. Efforts have been made in Brazil to carry out field activities at the basin scale, but how complete and comprehensive are those studies? Where are they located? How long have they been carried out? What are the main findings? To answer these questions, an overview of experimental monitoring basins in Brazil is presented, listing their geographical locations, monitored variables, operational status, monitoring periods and main publications. We identified 60 monitored sites, spread across most Brazilian biomes, with an average monitoring period of 12 years. However, some publications from these monitoring studies are not fully accessible to the international community. Field hydrology activities in Brazil contribute to a better understanding of hydrological processes in humid and semi-arid regions and inform us about the impacts of land-use change on water quality and quantity.     

Antimony quartz and antimony–gold quartz veins from northern Portugal

Antimony- and Pb–Sb-quartz veins from the Bragança district, Portugal, are mainly hosted by Silurian phyllites. Antimony–Au-quartz veins from the Dúrico–Beirã region are mainly hosted by a Cambrian schist–metagraywacke complex, as well as Ordovician phyllites and quartzites. The deposits were mostly exploited in the late 19th Century. Mineralogical characteristics and chemical compositions of individual ore minerals are similar in the two areas. First and second generations of arsenopyrite precipitated at 390 and 300 °C, respectively. Berthierite and stibnite are the most abundant Sb-bearing minerals and precipitated between 225 and 128 °C, native antimony at < 200 °C. Drastic fluid cooling is the main cause of mineral precipitation. The Pb isotope compositions of stibnite suggest a homogeneous crustal source of lead, from the metasedimentary sequences, for Sb, Pb–Sb and Sb–Au deposits in both areas, which is consistent with the findings for comparable mineralizations elsewhere in Europe. Remobilization of Pb is related to Variscan metamorphism and deformation.     

Cretaceous evolution of the Andean margin between 36°S and 40°S latitude through a multi‐proxy provenance analysis of Neuquén Basin strata (Argentina)

During the Cretaceous, the Neuquén Basin transitioned from an extensional back‐arc to a retroarc foreland basin. We present a multi‐proxy provenance study of Aptian to Santonian (125–84 Ma) continental sedimentary rocks preserved in the Neuquén Basin used to resolve changes of sediment drainage pattern in response to the change in tectonic regime. Sandstone petrology and U–Pb detrital zircon geochronology constrain the source units delivering detritus to the basin; apatite U–Pb and fission track dating further resolve provenance and determine the age and patterns of exhumation of the source rocks. Sandstone provenance records a sharp change from a mixed orogenic source during Aptian time (ca. 125 Ma), to a magmatic arc provenance in the Cenomanian (ca. 100 Ma). We interpret this provenance change as the result of the drainage pattern reorganisation from divergent to convergent caused by tectonic basin inversion. During this inversion and early stages of contraction, a transient phase of uplift and basin erosion, possibly due to continental buckling, caused the pre‐Cenomanian unconformity dividing the Lower from Upper Cretaceous strata in the Neuquén Basin. This phase was followed by the development of a retroarc foreland basin characterised by a volcanic arc sediment provenance progressively shifting to a mixed continental basement provenance during Turonian‐Santonian (90–84). According to multi‐proxy provenance data and lag times derived from apatite fission track analysis, this trend is the result of a rapidly exhuming source within the Cordillera to the west, in response to active compressional tectonics along the western margin of South America, coupled with the increasing contribution of material from the stable craton to the east; this contribution is thought to be the result of the weak uplift and exhumation of the foreland due to eastward migration of the forebulge.     

Application of a new computer program for tectonic discrimination of Cambrian to Holocene clastic sediments

TecSand is a new Java software that is used for deciphering the tectonic setting of clastic sediments and sedimentary rocks through two new multidimensional discrimination diagrams. For each sample, TecSand calculates four complex discriminant functions: DF1_m1 and DF2_m1 for the high-silica diagram and DF1_m2 and DF2_m2 for the low-silica diagram, each representing linear combinations of log-ratios of all major elements. These functions determine the position of each sample within island or continental arc, continental rift, and collision/convergent settings. The program also calculates the probability values for the three tectonic fields. TecSand provides a “ready for publication” report for each locality, including the adjusted major elements, log-transformed variables, DF1 and DF2 results, and probability values for individual samples. Validations from samples of known tectonic settings, evaluation of chemical changes, and applications to Precambrian clastic sediments have previously been demonstrated in the literature. Therefore, we illustrate the use of TecSand in 10 case studies covering ages from the Early Cambrian to the Holocene. The results obtained from these two diagrams were not only mutually consistent but also with other geological constraints. As an innovation, TecSand provides an overall synthesis of the two diagrams as total percent probability values. Comparison of the results of this study with the previously published tectonic discrimination diagrams reveals that two recent multidimensional discrimination diagrams are more efficient in discriminating tectonic settings. Although TecSand does provide graphics, which can be imported and modified in commercial software, plotting of the sample diagram is no longer required.     

Quality control in geochemistry from a comparison of four central tendency and five dispersion estimators and example of a geochemical reference material

Data quality control in geochemistry constitutes a fundamental problem that is still to be solved from the application of statistics and computation. We used refined Monte Carlo simulations of 10,000 replications and 190 independent experiments for sample sizes of 5 to 100. Statistical contaminations of 1 to 4 observations were used to compare 9 statistical parameters (4 central tendency—mean, median, trimean, and Gastwirth mean, and 5 dispersion estimates—standard deviation, median absolute deviation, S _n , Q _n , and \( {\widehat{\sigma}}_n \)). The presence of discordant observations in the data arrays rendered the outlier-based and robust parameters to disagree with each other. However, when the mean and standard deviation (outlier-based parameters) were estimated from censored data arrays obtained after the identification and separation of outlying observations, they generally provided a better estimate of the population than the robust estimates obtained from the original data arrays. This inference is contrary to the general belief, and therefore, reasons for the better performance of the outlier-based methods as compared to the robust methods are suggested. However, when all parameters were estimated from censored arrays and appropriate precise and accurate correction factors put forth in this work were applied, all of them became fully consistent, i.e., the mean agreed with the median, trimean and Gastwirth mean, and the standard deviation with the median absolute deviation, S _n , Q _n , and \( {\widehat{\sigma}}_n \). An example of inter-laboratory chemical data for a Hawaiian reference material BHVO-1 included sample sizes from 5 to 100, which showed that small samples of up to 20 provide inconsistent estimates, whereas larger samples of 20–100, especially >40, were more appropriate for estimating statistical parameters through robust or outlier-based methods. Although all statistical estimators provided consistent results, our simulation study shows that it is better to use the censored sample mean and population standard deviation as the best estimates.