Natural Arsenic Attenuation via Metal Arsenate Precipitation in Soils Contaminated with Metallurgical Wastes: I. Wet Chemical and Thermodynamic Evidences

Arsenic from natural and anthropogenic sources is a worldwide contaminant of aqueous environments, such as groundwater and soils. The present investigation was performed on Mexican soils contaminated with residues from metallurgical processes that have shown a natural As attenuation. Experimental aqueous arsenic extractions in these were successfully simulated for almost half of the soil samples using a database updated for all known metal arsenate formation constants, revealing the predominance of solubility-controlled As mobility via Pb, mixed Pb–Cu, and Ca arsenate solid formation. The relatively low total Fe/As ratios (2–13 w/w) present in the soils studied, together with the high and equivalent contents of As, Pb, and Cu in these, favor the precipitation process over As(V) adsorption to Fe oxides, despite a 2% average Fe content in the soils studied. Under these conditions bicarbonate was found to be a highly unsuitable extractant due to its indirect As release from the solid arsenates, via heavy metal carbonate precipitation processes.     

Uniform half-plane elastodynamic problems by an approximate boundary element method

In this paper the applicability of an approximate Boundary Element Method to uniform half-plane elastodynamic problems is investigated. This method employs the concept of images to construct approximate fundamental solutions for the half-plane and does not require any half-plane surface discretization. The method is formulated in the frequency domain for the case of harmonic disturbances or the Laplace transform domain for the case of transient disturbances. In the latter case a numerical inversion of the transformed solution is necessary to obtain the time domain response. The proposed method can be used as an alternative to boundary element methods that either utilize the infinite plane fundamental solution and thus require a half-plane surface discretization, or employ the exact half-plane fundamental solution, which even though leads to no surface discretization, is of a very lengthy and complicated form. Two characteristics numerical examples are used to illustrate the proposed method and study its advantages and disadvantages.     

On a modal damping identification model for non-classically damped linear building structures subjected to earthquakes

A simple modal damping identification model developed by the present authors for classically damped linear building frames is extended here to the non-classically damped case. The modal damping values are obtained with the aid of the frequency domain modulus of the roof-to-basement transfer function and the resonant frequencies of the structure (peaks of the transfer function) as well as the modal participation factors and mode shapes of the undamped structure. The assumption is made that the modulus of the transfer function of the non-classically damped structure matches the one of the classically damped structure in a discrete manner, i.e., at the resonant frequencies of that function modulus. This proposed approximate identification method is applied to a number of plane building frames with and without pronounced non-classical damping under different with respect to their frequency content earthquakes and its limitations and range of applicability are assessed with respect to the accuracy of both the identified damping ratios and that of the seismic structural response obtained by classical mode superposition and use of those identified modal damping ratios.     

Future regional projections of extreme temperatures in Europe: a nonstationary seasonal approach

This paper analyzes changes of maximum temperatures in Europe, which are evaluated using two state-of-the-art regional climate models from the EU ENSEMBLES project. Extremes are expressed in terms of return values using a time-dependent generalized extreme value (GEV) model fitted to monthly maxima. Unlike the standard GEV method, this approach allows analyzing return periods at different time scales (monthly, seasonal, annual, etc). The study focuses on the end of the 20th century (1961?C2000), used as a calibration/validation period, and assesses the changes projected for the period 2061?C2100 considering the A1B emission scenario. The performance of the regional models is evaluated for each season of the calibration period against the high-resolution gridded E-OBS dataset, showing a similar South-North gradient with larger values over the Mediterranean basin. The inter-RCM changes in the bias pattern with respect to the E-OBS are larger than the bias resulting from a change in the boundary conditions from ERA-40 to ECHAM5 20c3m. The maximum temperature response to increased green house gases, as projected by the A1B scenario, is consistent for both RCMs. Under that scenario, results indicate that the increments for extremes (e.g. 40-year return values) will be two or three times higher than those for the mean seasonal temperatures, particularly during Spring and Summer in Southern Europe.     

Late Miocene to Quaternary slip history across the Qiulitag anticline in the southern Tianshan piedmont

In this study, we reconstruct the Miocene to Quaternary shortening history across the Qiulitag anticline, a complex fault‐bend fold located in southern Tianshan. We studied the Yaha and Kuche sections, where we combined surface structural measurements and seismic imaging to model the stratigraphic horizons. The history of folding was reconstructed based on magnetostratigraphic analyses and eight cosmogenic burial ages in Kuche. Pleistocene deformation rates were also quantified in Yaha based on a deformed fluvial terrace that we dated to ~67 ka using a cosmogenic depth profile. Our results suggest that the fold grew at a mean slip rate of 0.9–1.3 mm/a in both sections but accelerated to ~2.5 mm/a during the Pleistocene in Kuche. These results support a migration of the deformation towards the basin during the Pleistocene and suggest that most of the present deformation in the Tianshan is accommodated across the external structures of the range.     

Storylines: an alternative approach to representing uncertainty in physical aspects of climate change

Investigating the relationships between climate extremes and crop yield can help us understand how unfavourable climatic conditions affect crop production. In this study, two statistical models, multiple linear regression and random forest, were used to identify rainfall extremes indices affecting wheat yield in three different regions of the New South Wales wheat belt. The results show that the random forest model explained 41–67% of the year-to-year yield variation, whereas the multiple linear regression model explained 34–58%. In the two models, 3-month timescale standardized precipitation index of Jun.–Aug. (SPI_JJA), Sep.–Nov. (SPI_SON), and consecutive dry days (CDDs) were identified as the three most important indices which can explain yield variability for most of the wheat belt. Our results indicated that the inter-annual variability of rainfall in winter and spring was largely responsible for wheat yield variation, and pre-growing season rainfall played a secondary role. Frequent shortages of rainfall posed a greater threat to crop growth than excessive rainfall in eastern Australia. We concluded that the comparison between multiple linear regression and machine learning algorithm proposed in the present study would be useful to provide robust prediction of yields and new insights of the effects of various rainfall extremes, when suitable climate and yield datasets are available.     

Geological and environmental implications of the evaporite karst in Spain

In Spain, evaporite outcrops cover approximately 7% of the total area of the country. Most of the evaporitic formations are made up of Ca-sulfates (gypsum/anhydrite) or Ca-sulfates and halite. Certain Paleogene marine evaporites also contain K-Mg-chlorides, and some Tertiary continental formations bear substantial amounts of Na-sulfates in the subsurface (glauberite and thenardite). Mesozoic evaporitic formations commonly wedge out towards the ground surface, passing into condensed sequences and dissolution-collapse breccias. Some of these highly porous breccias constitute major regional aquifers. In several areas, interstratal karstification of the evaporites has given rise to gravitational deformations such as basin structures, monoclines, and collapse structures covering several square kilometers that record a cumulative subsidence in excess of 200 m (Teruel and Calatayud Grabens). A widespread consequence of evaporite dissolution processes in Spain is the hydrochemical degradation of surface waters. Some of the largest and most outstanding lake systems, from an environmental perspective, occur in karstic depressions developed in evaporitic formations (Fuente de Piedra, Gallocanta, Bujaraloz, and Bañolas lakes). Sinkhole activity is a major geohazard in several evaporite karst areas. The sinkhole risk has a particularly high impact in sectors where Tertiary evaporites are overlain by Quaternary alluvial aquifers (Calatayud, Zaragoza, and Madrid areas). Some of the detrimental effects of subsidence include severe damage to historical monuments (Calatayud), the demolition of a whole village (Puilatos), or the derailment of a freight train (Zaragoza area). The deepest gypsum caves are found in Triassic diapiric structures (El Sumidor Cave, 210 m deep), and the longest ones are developed in horizontally lying Neogene sequences (Sorbas caves, and Estremera maze cave). The Cardona diapir hosts salt caves up to 4,300 m long whose genesis is related to flooding of mine galleries caused by the interception of a phreatic conduit. The main anthropogenic impacts on the endokarstic systems are related to the disposal of wastewaters and the destruction of caves by quarrying. The fluvial valleys that cross Tertiary evaporitic outcrops commonly show peculiar geological characteristics related to dissolution-induced synsedimentary subsidence phenomena: (1) Thickened alluvium filling dissolution basins up to several tens of kilometers long and more than 100 m deep. The largest thickenings are found in areas where the bedrock contains halite and glauberite. (2) Superimposed alluvial units locally bounded by angular unconformities. (3) Abundant deformational structures and paleosinkholes related to the rockhead and/or interstratal karstification of the substratum. These fluvial valleys typically are flanked by a prominent gypsum escarpment. Rock-falls favored by the dissolutional enlargement of joints derived from these scarps are the type of mass movement which has caused the highest number of casualties in Spain.     

Environmental problems and geological implications derived from evaporite dissolution in the Barbastro salt anticline (NE Spain)

The halite-bearing Barbastro Formation crops out in the core of the Barbastro Anticline (Ebro Tertiary Basin). This anticline is traversed perpendicularly by some of the most important Pyrenean drainages such as the Cinca and Noguera-Ribagorzana Rivers. The terrace sequences of these fluvial systems have been used as markers to identify and assess dissolution-induced subsidence and salt tectonics. In the limbs of the anticline, terrace deposits underlain by detrital bedrock do not show any evidence of deformation and have a consistent thickness of less than 10 m. The deposits of certain terrace levels of the Noguera-Ribagorzana River and its tributary, the Lo Reguer Creek, are locally thickened filling basins generated by dissolution-induced synsedimentary subsidence up to several kilometers long and more than 100 m deep. Conversely, terraces of the Cinca River do not show anomalously high thicknesses, but local uplifts related to differential upward flow of the halite-bearing bedrock. Locally, a minimum uplift rate of 0.3 mm/year has been estimated from a 64-ka terrace tilted away from the valley. The subsidence hazards occur chiefly in areas where the ground receives artificial water recharge. Serviceability of some canals has been notoriously affected by evaporite karstification. The problem has been mitigated to acceptable levels by grouting. Numerous buildings of Ivars de Noguera are severely damaged by dissolution subsidence, and possibly, by hydrocompaction of gypsiferous silts. The pipe network has been replaced to ameliorate the subsidence risk. In the Cinca River valley, cavities with a total volume of about 180,500 m³ have been created by solution mining at depths greater than 500 m. No investigation methods are applied in the brine field to monitor the distribution and evolution of artificial voids. Substantial increase in salinity of the Cinca River is another evidence of subjacent evaporite dissolution.     

A genetic classification of sinkholes illustrated from evaporite paleokarst exposures in Spain

This contribution analyses the processes involved in the generation of sinkholes from the study of paleokarst features exposed in four Spanish Tertiary basins. Bedrock strata are subhorizontal evaporites, and in three of the basins they include halite and glauberite in the subsurface. Our studies suggest that formation of dolines in these areas results from a wider range of subsidence processes than those included in the most recently published sinkhole classifications; a new genetic classification of sinkholes applicable to both carbonate and evaporite karst areas is thus proposed. With the exception of solution dolines, it defines the main sinkhole types by use of two terms that refer to the material affected by downward gravitational movements (cover, bedrock or caprock) and the main type of process involved (collapse, suffosion or sagging). Sinkholes that result from the combination of several subsidence processes and affect more than one type of material are described by combinations of the different terms with the dominant material or process followed by the secondary one (e.g. bedrock sagging and collapse sinkhole). The mechanism of collapse includes any brittle gravitational deformation of cover and bedrock material, such as upward stoping of cavities by roof failure, development of well-defined failure planes and rock brecciation. Suffosion is the downward migration of cover deposits through dissolutional conduits accompanied with ductile settling. Sagging is the ductile flexure of sediments caused by differential corrosional lowering of the rockhead or interstratal karstification of the soluble bedrock. The paleokarsts we analysed suggest that the sagging mechanism (not included in previous genetic classifications) plays an important role in the generation of sinkholes in evaporites. Moreover, collapse processes are more significant in extent and rate in areas underlain by evaporites than in carbonate karst, primarily due to the greater solubility of the evaporites and the lower mechanical strength and ductile rheology of gypsum and salt rocks.