Oxygen isotope variations in phosphate of biogenic apatites,III. Conodonts

The method for measurement of the isotopic composition of oxygen in phosphates has been improved and adapted for analysis of small quantities of apatite, down to 10 mg. This extension enables one to analyze hand-picked conodont samples with an analytical reproducibility better than ±0.5‰ (1σ).46 samples of conodonts ranging from the Ordovician to the Pennsylvanian of North America were analysed. Some insoluble phosphatic residues, ichthyoliths and inarticulate brachiopods of the same time range were also measured. The range of the δ¹⁸O values of the analysed conodonts is between 15 and 19‰. It shows a general trend of decreasing d¹⁸O with increasing age, from an average value of about 19 in the Pennsylvanian to 17 in the Ordovician. This trend parallels that previously detected in marine phosphorites. For the time range between the Devonian and Pennsylvanian our data are in agreement with independent paleoclimatic information. Specifically, we detect maximum¹⁸O enrichment at the end of the Pennsylvanian, and minimum enrichment at the end of the Devonian. The difference between these two extremes is equivalent to about 10°C (from about 40° to 30°C), assuming constant isotopic composition of ocean water.The success of oxygen isotopic analysis of conodonts raises the possibility of their use in Paleozoic paleo-oceanography in a similar way to foraminifera in the Mesozoic-Cenozoic.     

Interactions of cadmium(II) and protons with dead biomass of marine algae Fucus sp.

Samples of dead biomass from the marine brown algae Fucus ceranoides, Fucus vesiculosus and Fucus serratus were studied for their ability to remove cadmium from aqueous solutions. The metal sorption process is rapid, with 90% of the metal uptake completed within the first 25 min of contact. The kinetic data was described successfully by a pseudo second order chemical sorption process with rate constants of ca. 0.6 g mmol^− 1 min^− 1. At pH 4.5, the raw biomass of the three species exhibited equilibrium uptake capacities for Cd as high as 0.8 mmol g^− 1 (90 mg g^− 1), on a dry weight basis, without chemical pretreatment. These sorption capacities are much higher than those reported for activated carbon and chitin. The sorption of Cd was found to increase as pH increases, reaching a plateau at pH 5.Batch sorption experiments and continuous potentiometric titrations of acid-treated biomass samples in 0.05 M NaNO₃ were used to derive thermodynamic binding parameters according to the NICCA model. The total amount of acid sites was 2.4–2.9 mmol g^− 1, with median values of the affinity distribution for protons and cadmium ions, log K˜_H and log K˜_Cd, of 3.7 and 2.69, respectively (conditional values). The apparent heterogeneity of the sorbent was successfully taken into account by the empirical NICCA isotherm, which described very well the competition between protons and metal ions, in contrast with a simpler discrete competitive Langmuir model.The experimental results demonstrate that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for cadmium removal from wastewaters. This use would represent an example of exploitation of a renewable marine resource in water treatment technologies for the prevention of heavy metal pollution in the environment.     

Clay mineral occurrence and burial transformations: reservoir potential of the Permo‐Triassic sediments of the Iberian Range

The diagenetic evolution of Permian (Autunian and Saxonian) and Triassic (Buntsandstein) sandstones and mudrocks have been studied over 1000 m sequence from the Sigüenza 44‐3 drill core in the Iberian Range, Spain. We compare and contrast the diagenetic processes in these different lithologies and the timing of clay mineral formation. Moreover, we establish the relationship between clay mineral diagenesis and reservoir potential. Both the Permian and Triassic successions are characterised by conglomerates, sandstones and interbedded mudstones of fluvial origin that change upwards into distal deposits of a fluvio‐deltaic system. The clay minerals are illite, illite‐smectite mixed layers, kaolinite and dickite. The illite content in all sequences is not related to diminished feldspars; it is owing to the initial detrital mineralogical composition of the Autunian sandstones. The effect of feldspar alteration to kaolin minerals has a strong influence on the lost of porosity‐permeability in the Saxonian facies. In contrast, illite and mixed layers illite‐smectite are the main clay rims preserving porosity in the Buntsandstein sandstones. However, fibrous illite is the dominant pore‐filling in the Permian Autunian facies, closing porosity and permeability. Kaolinite and dickite show opposite trends: dickite increases yet kaolinite decreases from Triassic to Permian sandstones. Dickite replaced kaolinite during burial‐thermal evolution of the succession. The δD and δ¹⁸O isotopic signatures from silt and clay fractions indicate a mixture of meteoric and marine waters, and suggest a minimum temperature range between 60 and 150 °C for diagenetic pore fluids. The Permian δD values (?24‰ to ?44‰) are relatively similar to Buntsandstein values (?24‰ to ?37‰). However, the Permian δ¹⁸O values (+7.6 and +15.3, average of +13.3‰) are generally higher by ca. 6.2‰ compared to the Buntsandstein data (4.8–10.1‰, average +7.1‰). Such a variation is interpreted as the result of mesodiagenetic pore fluid changes. The extensive dickitisation of kaolinite is attributed to increased hydrogen ions resulting from maturation of organic matter. The vitrinite reflectance of organic matter and the modelled thermal history suggest a maximum burial of 3400 m, accomplished 70 Ma ago. The Permo‐Triassic reached the gas window shortly before major uplift, at 65 Ma, when further maturation and hydrocarbon expulsion ceased.     

Seismic Hazard and Ground Motion Characterization at the Itoiz Dam (Northern Spain)

This paper presents a new hazard-consistent ground motion characterization of the Itoiz dam site, located in Northern Spain. Firstly, we propose a methodology with different approximation levels to the expected ground motion at the dam site. Secondly, we apply this methodology taking into account the particular characteristics of the site and of the dam. Hazard calculations were performed following the Probabilistic Seismic Hazard Assessment method using a logic tree, which accounts for different seismic source zonings and different ground-motion attenuation relationships. The study was done in terms of peak ground acceleration and several spectral accelerations of periods coinciding with the fundamental vibration periods of the dam. In order to estimate these ground motions we consider two different dam conditions: when the dam is empty (T?=?0.1?s) and when it is filled with water to its maximum capacity (T?=?0.22?s). Additionally, seismic hazard analysis is done for two return periods: 975?years, related to the project earthquake, and 4,975?years, identified with an extreme event. Soil conditions were also taken into account at the site of the dam. Through the proposed methodology we deal with different forms of characterizing ground motion at the study site. In a first step, we obtain the uniform hazard response spectra for the two return periods. In a second step, a disaggregation analysis is done in order to obtain the controlling earthquakes that can affect the dam. Subsequently, we characterize the ground motion at the dam site in terms of specific response spectra for target motions defined by the expected values SA (T) of T?=?0.1 and 0.22?s for the return periods of 975 and 4,975?years, respectively. Finally, synthetic acceleration time histories for earthquake events matching the controlling parameters are generated using the discrete wave-number method and subsequently analyzed. Because of the short relative distances between the controlling earthquakes and the dam site we considered finite sources in these computations. We conclude that directivity effects should be taken into account as an important variable in this kind of studies for ground motion characteristics.     

Assessing drought in the drylands of northeast Brazil under regional warming exceeding 4 °C

Natural Hazards - Historically, during periods of extreme drought, food security in the drylands of the semiarid region of Northeast Brazil (NEB) is under severe risk due to agricultural collapse....     

Season‐based rainfall–runoff modelling using the probability‐distributed model (PDM) for large basins in southeastern Brazil

Southeastern Brazil is characterized by seasonal rainfall variability. This can have a great social, economic, and environmental impact due to both excessive and deficient water availability. During 2014 and 2015, the region experienced one of the most severe droughts since 1960. The resulting water crisis has seriously affected water supply to the metropolitan region of São Paulo and hydroelectric power generation throughout the entire country. This research considered the upstream basins of the southeastern Brazilian reservoirs Cantareira (2,279 km²; water supply) and Emborcação (29,076 km²), Três Marias (51,576 km²), Furnas (52,197 km²), and Mascarenhas (71,649 km²; hydropower) for hydrological modelling. It made the first attempt at configuring a season‐based probability‐distributed model (PDM‐CEMADEN) for simulating different hydrological processes during wet and dry seasons. The model successfully reproduced the intra‐annual and interannual variability of the upstream inflows during 1985–2015. The performance of the model was very satisfactory not only during the wet, dry, and transitional seasons separately but also during the whole period. The best performance was obtained for the upstream basin of Furnas, as it had the highest quality daily precipitation and potential evapotranspiration data. The Nash–Sutcliffe efficiency and logarithmic Nash–Sutcliffe efficiency were 0.92 and 0.93 for the calibration period 1984–2001, 0.87 and 0.88 for the validation period 2001–2010, and 0.93 and 0.90 for the validation period 2010–2015, respectively. Results indicated that during the wet season, the upstream basins have a larger capacity and variation of soil water storage, a larger soil water conductivity, and quicker surface water flow than during the dry season. The added complexity of configuring a season‐based PDM‐CEMADEN relative to the traditional model is well justified by its capacity to better reproduce initial conditions for hydrological forecasting and prediction. The PDM‐CEMADEN is a simple, efficient, and easy‐to‐use model, and it will facilitate early decision making and implement adaptation measures relating to disaster prevention for reservoirs with large‐sized upstream basins.