A high-resolution analyser for the measurement of ammonium in oligotrophic seawater

In this work, we describe a high-resolution fluorometric shipboard analyser and an improved method to determine NH₄⁺ in oligotrophic seawater. The limit of detection is <5 nM, calculated with 95% confidence level using the weighted regression line applied to the standard addition method using real samples prepared with low nutrient seawater from the Atlantic. The results are summarised and cross-compared with spiked artificial seawater (ASW) and spiked Milli-Q water samples. The analyser has a precision of ±1–4% with a high performance over a wide range from 5 nM to 25 μM. The methodology of NH₄⁺ analysis is based on the fluorescent product formed between o-pthaldialdehyde and NH₄⁺ in the presence of sulfite. Due to the high resolution of the developed system, we were able to study in depth the sensitivity of the method to salinity, amines, amino acids and potential interferences from particles/algae. The method was found to be sensitive to salinity variations, reducing the signal by up to 85% at 5 nM; this effect decreased at higher concentrations of ammonium. It was noted that the interference from amines at low concentrations was negligible; however, at either high amino acid or high amine concentrations, the signal was depressed. To test for the effect of particles on the system, the system was tested with samples containing phytoplankton (Dunaliella primolecta) cells at different concentrations prepared with ASW to simulate the effect of a phytoplankton bloom. This experiment assessed the potential impact of both particles and other potential fluorescence interferences from cells and/or ammonium leaching from cells. This experiment showed that a phytoplankton bloom could potentially have an impact of up to 12% on the signal of interest. Thus, we propose that this method is suitable for oligotrophic environments rather than coastal and eutrophic environments. The reagent was found to be stable for 17 days and standards of 1 μM were stable for 6 days under laboratory conditions. The developed analyser was successfully demonstrated in the North Atlantic Ocean, in an area of oligotrophic, low NH₄⁺ oceanic waters.     

Cosmogenic isotope burial dating of fluvial sediments from the Lower Rhine Embayment,Germany

Cosmogenic isotope burial dating, using ¹⁰Be and ²⁶Al, was applied to Plio–Pleistocene fluvial successions from the Lower Rhine Embayment, Germany. The approach consists of three principal steps: (1) measurement of cosmogenic nuclides in depth profiles, (2) modelling of hypothetical nuclide concentrations based on a first-order conceptualisation of the geological context and the principal succession of depositions and subsequent erosional and burial phases, and (3) using parameter estimation to identify values for the a priori unknown model parameters (burial age, initial nuclide concentrations, terrace erosion rates) that result in minimal disagreement between hypothetical and measured nuclide concentrations.The Late Pliocene Kieseloolite Formation was dated to 3650 ± 1490 ka and the Early Pleistocene Waalre Formation to 900 ± 280 ka. The unconformably overlying Upper Terrace Formation revealed ages of 740 ± 210 ka and 750 ± 250 ka for the two different sites. These findings are in good agreement with independent age control derived by bio-, magneto-, and litho-stratigraphy. Furthermore, identifiability and uncertainty analysis reveal a relationship between burial depth and sensitivity of isotope concentrations to burial age and erosion rate. Our results indicate that using shallower buried samples would enable a considerably more robust estimation of the burial age and the terrace erosion rate. Uncertainties arose mainly from nuclide measurements, and not from the uncertainties derived from modelling or insufficient knowledge of nuclide production and decay properties.     

Isostasy of the Eastern Anatolia (Turkey) and Discontinuities of its Crust

This paper presents a probable isostatic model of the East Anatolian Region, which lies in a belt of significant plate movements. Probable locations of the horizontal and vertical discontinuities in the crust structure were determined using the normalized full gradient (NFG) method. For the purpose of explaining the mechanism that supports topography corresponding to the crust thickness in the region, calculations of effective elastic thickness (T _e) were carried out initially by utilizing admittance and misfit functions. According to these results, the effective elastic thickness value obtained was less than the crust thickness, even though the isostatic model does not conform with the Airy model. Consequently, it was assumed that there could be problems beneath the crust. Hence, the NFG method was applied on the Bouguer gravity data of the region in order to investigate probable discontinuities in the crust structure. According to the NFG results, vertical structural transitions were observed at a depth ranging between 10 and 30 km, which begin immediately north of the Bitlis Zagros Suture Zone (BZSZ) and continue in a northerly direction. The relationship between the effective elastic thickness (T _e; 13 km in average as determined in the last stage), and the seismogenic zone in the region was investigated. If the T _e value happens to be less then the crustal thickness, then one can say that there are problems in the crustal structure of the region similar to Eastern Anatolia. Indeed, when NFG results of the study area are examined, numerous vertical and horizontal discontinuities in the crust can be observed. These discontinuities, which correspond to low Bouguer gravity anomalies and shallow focal depth-earthquakes, are probably the source of the factors which rule the tectonic mechanism of the region.     

Regional gravimetric quasi-geoid model and transformation surface to national height system for Turkey (THG-09)

Turkish regional geoid models have been developed by employing a reference earth gravitational model, surface gravity observations and digital terrain models. The gravimetric geoid models provide a ready transformation from ellipsoidal heights to the orthometric heights through the use of GPS/leveling geoid heights determined through the national geodetic networks. The recent gravimetric models for Turkish territory were computed depending on OSU91 (TG-91) and EGM96 (TG-03) earth gravitational models. The release of the Earth Gravitational Model 2008 (EGM08), the collection of new surface gravity observations, the advanced satellite altimetry-derived gravity over the sea, and the availability of the high resolution digital terrain model have encouraged us to compute a new geoid model for Turkey. We used the Remove-Restore procedure based on EGM08 and applied Residual Terrain Model (RTM) reduction of the surface gravity data. Fast Fourier Transformation (FFT) was then used to obtain the residual quasigeoid from the reduced gravity. We restored the individual contributions of EGM08 and RTM to the whole quasi-geoid height (TQG-09). Since the Helmert orthometric height system is adopted in Turkey, the quasi-geoid model (TQG-09) was then converted to the geoid model (TG-09) by making use of Bouguer gravity anomalies and digital terrain model. After all we combined a gravimetric geoid model with GPS/leveling geoid heights in order to obtain a hybrid geoid model (THG-09) (or a transformation surface) to be used in GPS applications. The RMS of the post-fit residuals after the combination was found to be ± 0.95 cm, which represents the internal precision of the final combination. And finally, we tested the hybrid geoid model with GPS/leveling data, which were not used in the combination, to assess the external accuracy. Results show that the external accuracy of the THG-09 model is ± 8.4 cm, a precision previously not achieved in Turkey until this study.     

Evaluation of meteorological controls of reconstructed rockfall activity in the Czech Flysch Carpathians

Rockfall is an important process in the final sculpturing of escarpments and scree slopes that originate in bedrock landslides in the Flysch Carpathians. The spatio‐temporal characteristics of rockfall activity were studied at four localities representative of old landslides in the highest part of the Czech Flysch Carpathians (Moravskoslezské Beskydy Mountains). Historical activity, chronology, and spatial context of rockfall activity were reconstructed using dendrogeomorphic techniques and rockfall rate index (RR). A total of 1132 increment cores from 283 trees growing in the rockfall transport and accumulation zones enabled the dating of 989 rockfall events. Reconstruction of a 78‐year‐long RR chronology suggests similar rockfall histories and trends at all study sites, indicating the existence of major common factors driving rockfall dynamics in the region. Temporal analysis and correlation of the RR series obtained with monthly mean temperatures, numbers of days with temperature transitions through 0 °C and monthly precipitation totals show that meteorological characteristics have evident but variable influence on rockfall activity. The most important factor is the effect of freeze–thaw cycles throughout the year, supplemented by low temperatures, especially during autumn. The influence of precipitation totals is of lesser importance. Copyright © 2011 John Wiley & Sons, Ltd.     

Left-lateral active deformation along the Mosha–North Tehran fault system (Iran): Morphotectonics and paleoseismological investigations

The Mosha and North Tehran faults correspond to the nearest seismic sources for the northern part of the Tehran megacity. The present-day structural relationships and the kinematics of these two faults, especially at their junction in Lavasanat region, is still a matter of debate. In this paper, we present the results of a morphotectonic analysis (aerial photos and field investigations) within the central part of the Mosha and eastern part of the North Tehran faults between the Mosha valley and Tehran City. Our investigations show that, generally, the traces of activity do not follow the older traces corresponding to previous long-term dip–slip thrusting movements. The recent faulting mainly occurs on new traces trending E–W to ENE–WSW affecting Quaternary features (streams, ridges, risers, and young glacial markers) and cutting straight through the topography. Often defining en-echelon patterns (right- and left-stepping), these new traces correspond to steep faults with either north- or south-dipping directions, along which clear evidences for left-lateral strike–slip motion are found. At their junction zone, the two sinistral faults display a left-stepping en-echelon pattern defining a positive flower structure system clearly visible near Ira village. Further west, the left-lateral strike–slip motion is transferred along the ENE–WSW trending Niavaran fault and other faults. The cumulative offsets associated with this left-lateral deformation is small compared with the topography associated with the previous Late Tertiary thrusting motion, showing that it corresponds to a recent change of kinematics.     

Report on the 4th International Meeting of the IUGS Lower Cretaceous Ammonite Working Group, the “Kilian Group” (Dijon, France, 30th August 2010)

The 4th Kilian Group meeting (Dijon, France, 30th August 2010) focused on the Aptian and Albian Stages. For the Aptian, a two-fold division of the stage was adopted for the Mediterranean area with a boundary between the Dufrenoyia furcata and Epicheloniceras martini Zones. The main changes to the zonal scheme concern the Lower Aptian with: the introduction of a Deshayesites luppovi Subzone in the upper part of the Deshayesites oglanlensis Zone; the replacement of Deshayesites weissi by Deshayesites forbesi as new index-species of the second interval zone; the introduction of a Roloboceras hambrovi Subzone in the upper part of the D. forbesi Zone; and the subdivision of the D. furcata Zone into the D. furcata and Dufrenoyia dufrenoyi Subzones. For the Albian, the upper part of the Douvilleiceras mammillatum Zone (Lower Albian) is now characterized by a Lyelliceras pseudolyelli Subzone. The main amendments concern the Upper Albian. The base of this substage is defined by the base of the Dipoloceras cristatum Zone. Above it, the Upper Albian zonal scheme comprises in stratigraphic order the Mortoniceras pricei, Mortoniceras inflatum, Mortoniceras fallax, Mortoniceras rostratum, Mortoniceras perinflatum and Arrhaphoceras briacensis Zones.     

Insights into cation exchange selectivity of a natural clinoptilolite by means of dielectric relaxation spectroscopy

Purified natural clinoptilolite from the Tasajeras deposit, Cuba, and some of its metal exchanged forms are studied, at the dehydrated state, by means of dielectric relaxation spectroscopy (DRS) using two different modus operandi: complex impedance spectroscopy and dielectric dynamic thermal analysis. Data analysis yields the determination of the extra-framework cation (EFC) population into the various possible crystallographic sites of the zeolitic framework as well as of the activation energy characterizing the localized hopping mechanism of EFC. First, it is shown that the DRS responses obtained here match well with the previous reported data, which were previously localized EFCs in positions close to M1 and M2 sites when the clinoptilolite is modified to almost homoionic form. From this outcome, it can be concluded that all EFCs are in the same crystallographic situation regarding solvation or, in other terms, that no steric effect can be taken into account to explain cationic selectivity. Second, based on the assumption that the activation energy for EFC hopping is directly connected to the EFC/framework interaction and on simple thermodynamics consideration, we show this interaction does not govern the EFC exchange reaction. So, it is emphasized that EFC/H₂O interaction is the key factor for cation exchange selectivity.     

Distribution and speciation of mercury in soil in the area of an ancient mercury ore roasting site,Frbejžene trate (Idrija area,Slovenia)

In the initial period of mining activities in the Idrija basin (the16^th and the first half of the17^th centuries), Hg ore processing was performed at various small-scale roasting sites in the woods surrounding Idrija, by roasting ore in earthen vessels. The recovery rate of this method was very low; about half of Hg was lost, causing soil contamination and considerable amounts of waste material that could potentially leach Hg into the surrounding environment. The main aims of present geochemical study were to determine the contents, vertical distribution and speciation of Hg in soils at the roasting site at Frbej?ene trate in order to verify the extreme pollution of ancient Hg ore roasting sites in the Idrija area and to establish their significance in the wider spatial contamination of soils and aquatic systems. Soil sampling was performed at the area of the former roasting site. The organic matter-rich surface soil layer (SOM) and underlying mineral soil were sampled at 63 sampling locations. Mercury speciation was performed using Hg thermo-desorption-AAS to distinguish cinnabar from potentially bioavailable forms. The results indicate extremely high Hg concentrations with a maximum of 37,000 mg/kg in SOM and 19,900 mg/kg in mineral soil. The established Hg median in soil was 370 mg/kg and in SOM 96.3 mg/kg. Spatial distributions of Hg in SOM and soil showed very high Hg contents in the central area and decreased rapidly with distance. The results of Hg thermo-desorption measurements indicated the presence of cinnabar (HgS) and Hg bound to organic or mineral soil matter. A significant portion (35–40%) of Hg in the investigated soil and SOM samples was comprised of non-cinnabar compounds, which are potentially bioavailable. It has been shown that soils contain high amounts of potentially transformable non-cinnabar Hg, which is available for surface leaching and runoff into the surrounding environment. Therefore, contaminated soils and roasted residues at the studied area are important for persistent Hg release into the aquatic ecosystem.     

An Integrated Study of the Dynamics of Electromagnetic and Acoustic Regimes During Failure of Complex Macrosystems Using Rock Blocks

The development of the failure process in complex macrosystems using large rock samples subjected to biaxial compression has been studied by means of electromagnetic radiation (EMR) and acoustic emission (AE). In order to increase the stage of macrofailure development, a special procedure of rock loading was used to reveal regularities of nucleation and evolution of electromagnetic and acoustic structures. The synchronised measurements of EMR and AE allowed the control of the stress–strain state in the rocks and the structural developments of fracturing. Non-homogeneous distribution of the rock spatial crystalline structure subject to load leads to a mosaic distribution of EMR and AE characteristics. As a result, the crack scale effect may be observed in the EMR and AE structure behaviours. The EMR and AE following the failure at different levels behave differently according to the difference in the scale and type of cracks. Intense high-frequency EMR pulses were recorded during the initial stage of microcrack generation occurring prior to major failure of material. This was not the case for AE. The nucleation and development of the macroscopic progressive failure evolution caused an alternation in energetic and frequencial properties of electromagnetic and acoustic events. It has been detected that the tensile cracks were more efficient than shear cracks in capacity of EMR generation. The analysis of self potentials allowed reaching the maximum of registered anomalous variations in the stage of microcracking interaction. This stage showed an increase in the EMR activity, which implies the nucleation of microcracks in various regions of rock interfaces. The gradual accumulation of these defects led to weakening some parts of the rock along with a disintegration of electric anomalies, increase of AE and a significant fluctuation in the rate of EMR. When crack concentration attains its critical value, which results in the formation of dangerous macroscopic failure of higher level, AE shows an intense activity as well as an EMR lower frequency. The hierarchical development of rock failure using the ratio of the average crack size and the mean distance between cracks as a statistical concentration criterion is used to control the boundary of the transition from small dispersed cracks accumulation to gradual crack merger and the formation of the main macrofailure. These results could be transferred into larger scale levels to forecast dynamic events in the earth crust.