Seasonal transport pattern of chromium(III and VI) in a stream receiving wastewater from tanneries

Water, suspended matter and sediment samples from a system heavily impacted by wastewater from numerous small tanneries (the upper Dunajec River, southern Poland) were collected to establish the annual cycle of Cr. To study possible oxidation processes the speciation of Cr and Mn concentrations were also investigated. This study showed that Cr(III and VI) temporal and spatial distributions are regulated by coupled anthropogenic (source location and emissions) and hydrologic factors (water flow and particle transport). Chromium(III) concentrations in all compartments varied seasonally as a function of the hydrological regime, production cycle in tanneries and distance from the discharge location. Cr(III) was largely associated with the particulate phase and rapidly deposited in river bed sediments. Contaminated river sediments were however flushed during flood periods to the reservoir located downstream from tanneries. During the tanning season (November to March), Chromium(III) concentrations in the water column and total Cr concentration in sediments exceeded relevant ecotoxicological guidelines only upstream from the reservoir, which trapped about 70% of the annual Cr(III) load transported by the Dunajec river. A correlation between Cr(VI)/Cr(III) ratios and Mn concentration in sediments downstream from the reservoir suggests the possibility of Cr(III) oxidation in natural conditions.     

Estimation of rainfall thresholds triggering shallow landslides for an operational warning system implementation

The Piemonte regional warning system service, managed by the Environmental Protection Agency of Piemonte (“ARPA Piemonte” as official Italian acronym), is based on an advanced meteo-hydrological automatic monitoring system, and it is integrated with forecasting activities of severe weather-related natural hazards. At present, a meteo-hydrological chain is operated to provide flood forecasting on the main river pattern. The development of a forecasting tool for shallow landslides triggered by heavy rainfall is presented. Due to the difficulties in modelling shallow landslides triggering in a large and complex area like the Piemonte region, an empirical model is developed on the basis of the correlation between rainfall and previous landslides in historical documents. The research focuses on establishing rainfall thresholds for landslides triggering, differentiating the critical rainfall values through a geological characterisation of the different territories. The period from 1990 to 2002 is considered. A total number of 160 landslides with hourly information and time of triggering are used to calibrate the system. As a first outcome, two different zones have been identified: (1) zones in alpine environments, principally characterised by a bedrock composed of metamorphic rocks, igneous rocks, dolostones or limestones that require high values of critical rainfall and (2) zones in hilly environments, principally characterised by sedimentary bedrock that require low values of critical rainfall. Verification has been performed on a total number of 429 landslides with known date of occurrence. The results show a good agreement with the model with no missed alarms and a very low number of false alarms, thus suggesting an effective operational implementation.     

Synthetic and natural chromium-bearing spinels: an optical spectroscopy study

Four samples of synthetic chromium-bearing spinels of (Mg, Fe²⁺)(Cr, Fe³⁺)₂O₄ composition and four samples of natural spinels of predominantly (Mg, Fe²⁺)(Al, Cr)₂O₄ composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr₂O₄ spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr³⁺ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed ⁴ A _2g  → ⁴ T _2g and ⁴ A _2g  → ⁴ T _1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spinels is related to trigonal distortion of the octahedral site in the spinel structure. A small, if any, splitting of the U-band can only be resolved at curve-fitting analysis. In all synthetic high-chromium spinels, a couple of relatively narrow and weak bands of the spin-allowed transitions ⁴ A _2g  → ² E _g and ⁴ A _2g  → ² T _1g of Cr³⁺, intensified by exchange-coupled interaction between Cr³⁺ and Fe³⁺ at neighboring octahedral sites of the structure, appear at ~14,400 and ~15,100 cm^?1. A vague broad band in the range from ca. 15,000 to 12,000 cm^?1 in synthetic spinels is tentatively attributed to ^IVCr²⁺ + ^VICr³⁺ → ^IVCr³⁺ + ^VICr²⁺ intervalence charge-transfer transition. Iron, mainly as octahedral Fe³⁺, causes intense high-energy absorption edge in near UV-range (ligand–metal charge-transfer O^2? → Fe³⁺, Fe²⁺ transitions). As tetrahedral Fe²⁺, it appears as a strong infrared absorption band at around 4,850 cm^?1 caused by electronic spin-allowed ⁵ E → ⁵ T ₂ transitions of ^IVFe²⁺. From the composition shift of the U-band in natural and synthetic MgCr₂O₄ spinels, the coefficient of local structural relaxation around Cr³⁺ in spinel MgAl₂O₄–MgCr₂O₄ system was evaluated as ~0.56(4), one of the lowest among (Al, Cr)O₆ polyhedra known so far. The octahedral modulus of Cr³⁺ in MgCr₂O₄, derived from pressure-induced shift of the U-band of Cr³⁺, is ~313 (50) GPa, which is nearly the same as in natural low-chromium Mg, Al-spinel reported by Langer et al. (1997). Calculated from the results of the curve-fitting analysis, the Racah parameter B of Cr³⁺ in natural and synthetic MgCr₂O₄ spinels indicates that Cr–O-bonding in octahedral sites of MgCr₂O₄ has more covalent character than in the diluted natural samples. Within the uncertainty of determination in synthetic MgAl₂O₄ spinel, B does not much depend on pressure.     

Predictive Power Evaluation of a Physically Based Model for Shallow Landslides in the Area of Oltrepò Pavese,Northern Italy

The use of real-time landslide early warning systems is attracting the attention of the scientific community, since it allows to assess “where” and “when” a shallow rainfall-induced landslide might occur by coupling rainfall amounts, hydrological models and slope-stability analysis. The paper deals with the main results of a back analysis, which refers to the application of a physically based stability model [Shallow Landslides Instability Prediction (SLIP)] on regional scale. The analysis concerns the occurrence of some recent rainfall-induced shallow landslides in the municipal territory of Broni, in the area of Oltrepò Pavese (Northern Italy). The study area is a hilly region 2.4 km² wide, where more than 40 % of the territory has slopes steeper than 15° and altitudes are between 90 and 250 m a.s.l. As regards the geologic setting, clayey-silty shallow colluvial deposits, with a maximum thickness of about 3 m, overlap a bedrock made of clayey shales, calcareous flysch and marls. The SLIP model is based on the limit equilibrium method applied to an infinite slope and on the Mohr–Coulomb strength criterion for the soil. By assuming that the main hydro-geotechnical process that leads to failure is the saturation of parts of the soil, the model allows to take into account the condition of partial saturation of the soil. The safety factor (F _S ) of a slope is also function of previous rainfalls. After the implementation of the model at territory scale, the input data have been introduced through a geographic information systems platform. In the current paper we mainly intend to evaluate the performance of SLIP at catchment scale, by comparison to (1) observed landslide events and (2) another well-established physically based model (TRIGRS). Further, we want to assess the suitability of the model as early warning tool. The results produced by the model are analyzed both in terms of safety factor maps, corresponding to some particular rainfall events, and in terms of the time-varying percentage of unstable areas over a 2-year span period. The paper shows the comparison between observed landslide localizations and model predictions. A quantitative comparison between the SLIP model and TRIGRS is presented, only for the most important event that occurred during the analyzed period. Overall, the results of the stability analyses based on observed rainfalls show the capability of the SLIP model to predict, in real-time and on a wide area, the occurrence of the analyzed phenomena.     

Methods for the analysis of data from the Planetary Fourier Spectrometer on the Mars Express Mission

This work presents an algorithm for the scientific analysis of individual calibrated measurements from the Planetary Fourier spectrometer (PFS).The instrument, included in the scientific payload of the ESA Mars Express mission to Mars, acquires spectra in the range between 250 and 8200 cm⁻¹, with a sampling step of ∼1 cm⁻¹ and an effective resolution of ∼2 cm⁻¹. The observed radiance depends on several parameters of the atmosphere and surface of Mars as described by the radiative transfer equation. Adopting the very general formalism of Bayesian analysis, we determined which quantities are actually retrievable from individual measurements. Namely, they are: the surface temperature, the column density of dust and water ice aerosols in the atmosphere, the air temperature as a function of altitude (in the indicative range 5-45 km above the surface), the surface pressure, and the column density of water vapor and carbon monoxide. These evaluations are carried out taking into account the noise equivalent radiance (NER) of the instrument and the natural variabilities of the investigated parameters in the Martian environment, as estimated from the expectations of the European Martian Climate Dataset v3.1 (EMCD). Other parameters included in the radiative transfer equation shall be assumed as known, because they are not retrievable from individual measurements due to the instrumental NER or an underconstrained inverse problem: the surface emissivity in the thermal infrared, the optical properties of suspended dust and the analytical shape of dust concentration vs. altitude.During the development of the algorithm devoted to these studies, different approaches were evaluated on the basis of formal, computational and scientific considerations, with the aim to develop the general design of an integrated software package.The resulting code was extensively tested on a wide set of simulated PFS spectra. These spectra were computed from the atmospheric and surface conditions extracted from the EMCD, assumed to be representative of the Martian environment for different values of latitude, local time and season. Their comparison with the retrievals from simulated observations allowed us to evaluate the systematic and random errors affecting the procedures with respect to the different quantities involved. The code evaluates the surface temperature with an error in the order of 1 K, while the vertical air temperature profile is computed with an uncertainty less than 2 K from in the region between 5 and 20 km above the surface, increasing up to 7 K at 50 km. The column opacity of dust, measured in terms of integrated optical thickness at 1100 cm⁻¹, is computed with an error of around 0.13. The surface pressure determination is carried out with a typical uncertainty of 0.2-0.3 millibar. Several auxiliary tests allowed us to study the correlations between the different retrieval errors and the possible causes of incorrect PFS data interpretation. The choice of a suitable model for the dust optical properties is demonstrated to be particularly critical.This paper also presents the first discussion about application of the procedure to actual PFS Martian data. Despite the calibration issues still affecting the determination of absolute radiance in the near-infrared, the algorithm is able to achieve a satisfactory modeling of observations in a wide range of situations.     

Georeferencing Animal Specimen Datasets

For biodiversity research, the field of study that is concerned with the richness of species of our planet, it is of the utmost importance that the location of an animal specimen find is known with high precision. Due to specimens often having been collected over the course of many years, their accompanying geographical data is often ambiguous or may be very imprecise. In this article, we detail an approach that utilizes reasoning and external sources to improve the geographical information of animal finds. Our main contribution is to show that adding external domain knowledge improves the ability to georeference locations over traditional methods that focus solely on analyzing geographical information. Additionally, our system is able to output the confidence it has in its decisions through a confidence measure based on the difficulty of the instance and the steps undertaken to disambiguate it. Our results show that adding domain knowledge to the georeferencing process increases the accuracy @5km from 38.9% to 61.7% and from 47.0% to 74.5% @25km. Furthermore, we reduce the mean distance by more than half, from 251.1km to 114.5km, and decrease the number of records for which no reference can be found from 26.2% to 7.4%.     

Effects of continuous flow centrifugation on measurements of trace elements in river water: intrinsic contamination and particle fragmentation

Continuous flow centrifugation (CFC) is a well‐established technique used in natural surface water studies to collect large amounts of suspended solids, thus allowing a broad spectrum of measurements. However, a potential contamination or changes in the particle size distribution during the centrifugation may restrain the use of CFC effluents for element analysis in the colloidal and dissolved fractions. In this paper we evaluate the possibility of using the effluent of a Westfalia centrifuge (type KA2‐06‐075, 9700 rpm) for such analysis. This evaluation is based on two laboratory experiments with deionized and tap water and two field experiments in rivers. Elemental concentration changes across the CFC were assessed from the CFC influent and effluent after a filtration at 0·45 µm. Significant increases were found, mainly in the field experiments at a high suspended solids level and a slightly acid pH. A hypothesis was made on the origin of these increases as a superposition of a centrifuge intrinsic contamination and a particle fragmentation effect. A numerical model based on elemental concentration measurements (inductively coupled plasma mass spectrometry) gave a particle fragmentation level of 0·55% (mass percentage of particles broken up into smaller fragments during centrifugation). In another experiment, a direct particle counting (single particle counter) shows an excess of particles smaller than 500 nm in the CFC effluent, corresponding to a fragmentation level of 0·11%. In consequence, the use of CFC effluent for element analysis is possible in low‐turbidity river or lake waters, but should be carefully considered in waters with high suspended matter contents. Copyright © 2006 John Wiley & Sons, Ltd.     

Thrust front segmentation induced by differential slab retreat in the Apennines (Italy)

New seismic reflection data reveal that the south‐eastward prolongation of the Apennine thrust front in the central Adriatic Sea is most likely located in a more external position with respect to the traditional interpretation. In this new interpretation, the Apennine thrust front shows a segmented geometry in correspondence to the Tremiti lithospheric transfer zone. The available data suggest that the north‐eastward flexural retreat of the subducting Adriatic lithosphere and the related frontal accretion of the Apennine accretionary prism have acted during the last 5 Ma and may be considered still lively in both the Po plain and in the Central Adriatic domain, north of the Tremiti lineament. By analysing the tectonic evolution of the Apulo‐Adriatic areas, it may be argued that the differential slab retreat between the central and southern sectors of the subducting Adriatic plate has been able to induce the segmentation of the Apennine thrust front.