Limitations of the ferrozine method for quantitative assay of mineral systems for ferrous and total iron

The quantitative assay of clay minerals, soils, and sediments for Fe(II) and total Fe is fundamental to understanding biogeochemical cycles occurring therein. The commonly used ferrozine method was originally designed to assay extracted forms of Fe(II) from non-silicate aqueous systems. It is becoming, however, increasingly the method of choice to report the total reduced state of Fe in soils and sediments. Because Fe in soils and sediments commonly exists in the structural framework of silicates, extraction by HCl, as used in the ferrozine method, fails to dissolve all of the Fe. The phenanthroline (phen) method, on the other hand, was designed to assay silicate minerals for Fe(II) and total Fe and has been proven to be highly reliable. In the present study potential sources of error in the ferrozine method were evaluated by comparing its results to those obtained by the phen method. Both methods were used to analyze clay mineral and soil samples for Fe(II) and total Fe. Results revealed that the conventional ferrozine method under reports total Fe in samples containing Fe in silicates and gives erratic results for Fe(II). The sources of error in the ferrozine method are: (1) HCl fails to dissolve silicates and (2) if the analyte solution contains Fe³⁺, the analysis for Fe²⁺ will be photosensitive, and reported Fe(II) values will likely be greater than the actual amount in solution. Another difficulty with the ferrozine method is that it is tedious and much more labor intensive than the phen method. For these reasons, the phen method is preferred and recommended. Its procedure is simpler, takes less time, and avoids the errors found in the ferrozine method.     

Platiniferous gold–tourmaline aggregates in the gold–palladium belt of Minas Gerais,Brazil: implications for regional boron metasomatism

Mineralogy and Petrology - The platiniferous gold–palladium belt of Minas Gerais, Brazil, forms an approximately 240-km-long, roughly north–south-trending domain that includes numerous...     

Late Quaternary vegetation and climate dynamics in central-eastern Brazil: insights from a ~35k cal a bp peat record in the Cerrado biome

The late Quaternary evolution of central-eastern Brazil has been under-researched. Questions remain as to the origin of the Cerrado, a highly endangered biome, and other types of vegetation, such as the Capões – small vegetation islands of semi-deciduous and mountain forests. We investigated the factors that influenced the expansion and contraction of the Cerrado and Capões during the late Quaternary (last ~35 ka), using a multi-proxy approach: stable isotopes (δ¹³C, δ¹⁵N), geochemistry, pollen and multivariate statistics derived from a peat core (Pinheiro mire, Serra do Espinhaço Meridional). Five major shifts in precipitation, temperature, vegetation and landscape stability occurred at different timescales. Our study revealed that changes in the South Atlantic Convergence Zone (SACZ) seem to have been coeval with these shifts: from the Late Glacial Maximum to mid-Holocene the SACZ remained near (~29.6 to ~16.5k cal a bp ) and over (~16.5 to ~6.1 k cal a bp ) the study area, providing humidity to the region. This challenges previous research which suggested that climate was drier for this time period. At present, the Capões are likely to be a remnant of a more humid climate; meanwhile, the Cerrado biome seems to have stablished in the late Holocene, after ~3.1 k cal a bp .     

Experimental testing, numerical modelling and seismic strengthening of traditional stone masonry: comprehensive study of a real Azorian pier

Stone masonry is one of the oldest building techniques used worldwide and it is known to exhibit poor behaviour under seismic excitations. In this context, this work aims at assessing the in-plane behaviour of an existing double-leaf stone masonry pier by experimental testing. Additionally, a detailed 3D finite element numerical analysis based on micro-modelling of the original pier is presented (fully describing the geometry and division of each individual elements, namely infill, blocks and joints) aiming at simulating the experimental test results. This numerical strategy can be seen as an alternative way of analysing this type of constructions, particularly useful for laboratory studies, and suitable for the calibration of simplified numerical models. As part of a wider research activity, this work is further complemented with the presentation of an effective retrofit/strengthening technique (reinforced connected plaster) to achieve a significant improvement of its in-plane cyclic response which is experimentally verified in the results presented herein.     

Distribution and sources of aliphatic hydrocarbons in surface sediments of Sergipe River estuarine system

The assessment of aliphatic hydrocarbons was performed in the Sergipe River estuarine system, northeastern Brazil. Aliphatic hydrocarbons concentration ranged from 9.9 ug g?1 up to 30.8 ug g?1 of dry sediment. The carbon preference index (CPI, based on nC?? to nC?? range), indicated predominance of petrogenic input in two of the sites analyzed (P4 and P5). The unresolved complex mixture (UCM) was found to be present in seven of the nine sites sampled (except for P4 and P5). Overall, the results of this work suggest that there is a mix of organic matter sources to the sediment. Although the coast of Sergipe has an intense off shore petroleum exploration and the Sergipe River crosses the entire city of Aracaju, the capital city of Sergipe, non-significant anthropogenic fingerprint was assessed.     

Development of a rain‐on‐snow detection algorithm using passive microwave radiometry

Currently observed climate warming in the Arctic has numerous consequences. Of particular relevance, the precipitation regime is modified where mixed and liquid precipitation can occur during the winter season leading to rain‐on‐snow (ROS) events. This phenomenon is responsible for ice crust formation, which has a significant impact on ecosystems (such as biological, hydrological, ecological and physical processes). The spatially and temporally sporadic nature of ROS events makes the phenomenon difficult to monitor using meteorological observations. This paper focuses on the detection of ROS events using passive microwave (PMW) data from a modified brightness temperature (T_B) gradient approach at 19 and 37 GHz. The approach presented here was developed empirically for observed ROS events with coincident ground‐based PMW measurements in Sherbrooke, Quebec, Canada. It was then tested in Nunavik, Quebec, with the Advanced Microwave Scanning Radiometer for the Earth Observing System (AMSR‐E). We obtained a detection accuracy of 57, 71 and 89% for ROS detection for three AMSR‐E grid cells with a maximum error of 7% when considering all omissions and commissions with regard to the total number of AMSR‐E passes throughout the winter period. Copyright © 2016 John Wiley & Sons, Ltd.     

A methodology for regionalizing 3‐D effective porosity at watershed scale in crystalline aquifers

An innovative approach for regionalizing the 3‐D effective porosity field is presented and applied to two large, overexploited, and deeply weathered crystalline aquifers located in southern India. The method derives from earlier work on regionalizing a 2‐D effective porosity field in that part of an aquifer where the water table fluctuates, which is now extended over the entire aquifer using a 3‐D approach. A method based on geological and geophysical surveys has also been developed for mapping the weathering profile layers (saprolite and fractured layers). The method for regionalizing 3‐D effective porosity combines water table fluctuation and groundwater budget techniques at various cell sizes with the use of satellite‐based data (for groundwater abstraction), the structure of the weathering profile, and geostatistical techniques. The approach is presented in detail for the Kudaliar watershed (983 km²) and tested on the 730 km² Anantapur watershed. At watershed scale, the effective porosity of the aquifer ranges from 0.5% to 2% in Kudaliar and between 0.3% and 1% in Anantapur, which agrees with earlier works. Results show that (a) depending on the geology and on the structure of the weathering profile, the vertical distribution of effective porosity can be very different and that the fractured layers in crystalline aquifers are not necessarily characterized by a rapid decrease in effective porosity and (b) that the lateral variations in effective porosity can be larger than the vertical ones. These variations suggest that within a same weathering profile, the density of open fractures and/or degree of weathering in the fractured zone may significantly vary from a place to another. The proposed method provides information on the spatial distribution of effective porosity that is of prime interest in terms of flux and contaminant transport in crystalline aquifers. Implications for mapping groundwater storage and scarcity are also discussed, which should help in improving groundwater resource management strategies.     

Estimating River Conductance from Prior Information to Improve Surface‐Subsurface Model Calibration

Most groundwater models simulate stream‐aquifer interactions with a head‐dependent flux boundary condition based on a river conductance (CRIV). CRIV is usually calibrated with other parameters by history matching. However, the inverse problem of groundwater models is often ill‐posed and individual model parameters are likely to be poorly constrained. Ill‐posedness can be addressed by Tikhonov regularization with prior knowledge on parameter values. The difficulty with a lumped parameter like CRIV, which cannot be measured in the field, is to find suitable initial and regularization values. Several formulations have been proposed for the estimation of CRIV from physical parameters. However, these methods are either too simple to provide a reliable estimate of CRIV, or too complex to be easily implemented by groundwater modelers. This paper addresses the issue with a flexible and operational tool based on a 2D numerical model in a local vertical cross section, where the river conductance is computed from selected geometric and hydrodynamic parameters. Contrary to other approaches, the grid size of the regional model and the anisotropy of the aquifer hydraulic conductivity are also taken into account. A global sensitivity analysis indicates the strong sensitivity of CRIV to these parameters. This enhancement for the prior estimation of CRIV is a step forward for the calibration and uncertainty analysis of surface‐subsurface models. It is especially useful for modeling objectives that require CRIV to be well known such as conjunctive surface water‐groundwater use.     

Design of Inclined Covers with Capillary Barrier Effect

A design procedure is proposed to minimize water infiltration into landfills by optimizing the water diversion length of inclined covers with capillary barrier effect (CCBE). This design procedure is based on a conceptual, mathematical and numerical approach and aims at selecting materials and optimizing layer thickness. Selection among candidate materials is made based on their hydraulic conductivity functions and on a threshold infiltration rate imposed on the designer. The capillary break layer (CBL; bottom layer) is characterized by a weak capillarity, while the moisture retention layer (MRL; upper layer) is characterized by a compromise between strong capillarity and high hydraulic conductivity. The thickness of the CBL corresponds to the height where suction reaches its maximum value for a given infiltration rate. This height can be calculated using the Kisch [Géotechnique 9 (1959)] model. The optimal thickness of the MRL is determined by applying an adaptation of the Ross [Water Resources Research 26 (1990)] model. The results obtained using the proposed design procedure were compared to those obtained from numerical simulations performed using a finite element unsaturated seepage software. The procedure was applied for two cover systems; one where deinking by-products (DBP) were used as MRL and sand as CBL and another where sand was used as MRL and gravel as CBL. Using this procedure, it has been shown that an infiltration control system composed of thin layers of sand over gravel is highly efficient in terms of diversion length and that its efficiency can be enhanced by placing a hydraulic barrier – such as a layer of DBP – above the MRL.