Groundwater resource degradation in coastal plains: The example of the Cecina area (Tuscany – Central Italy)

The paper describes the degradation of the groundwater resources in the Cecina area, where seawater intrusion, B contamination and NO₃ pollution are all affecting the heavily exploited Pleistocene aquifer. Over-pumping has brought water levels to about 0 m.a.s.l. as far as about 7 km from the shore line, thereby promoting the seawater intrusion. The intrusion, which is characterized by cation exchange phenomena and Ca–Cl type waters, enters the plain mostly through the shallower horizons. The saline front, which advanced from 0.5 to 1 km in 4 a, has by now reached the foot of the hills to the east of the town, where it is also affecting wells of the local aqueduct. Boron contamination, linked to past discharge of industrial waste transported downstream by the river, reached concentrations as high as 3.5 mg/L in the mid-1980s. Although a decreasing trend is now under way, B content is still close to 1 mg/L. The presence of high NO₃, which, together with the seawater intrusion, represents a major issue for groundwater management in the area, is linked to the widespread utilization of fertilizers. Nitrate concentration, which reaches a maximum of about 300 mg/L in the shallow aquifer horizons and then decreases rather regularly with depth, is strongly influenced by precipitation. However, irrigation also contributes significantly to transporting the NO₃ contamination to depth, as clearly shown by δ¹⁸O data. The severe decline in the quality of the groundwater resource in the Cecina area is further compounded by an overall decrease in water availability in the region of Tuscany, as evidenced by long-term monitoring of precipitation and fluvial discharge.     

Sensitivity analysis of seismic hazard for Western Liguria (North Western Italy): A first attempt towards the understanding and quantification of hazard uncertainty

The use of logic trees in probabilistic seismic hazard analyses often involves a large number of branches that reflect the uncertainty in the selection of different models and in the selection of the parameter values of each model. The sensitivity analysis, as proposed by Rabinowitz and Steinberg [Rabinowitz, N., Steinberg, D.M., 1991. Seismic hazard sensitivity analysis: a multi-parameter approach. Bull. Seismol. Soc. Am. 81, 796–817], is an efficient tool that allows the construction of logic trees focusing attention on the parameters that have greater impact on the hazard.In this paper the sensitivity analysis is performed in order to identify the parameters that have the largest influence on the Western Liguria (North Western Italy) seismic hazard. The analysis is conducted for six strategic sites following the multi-parameter approach developed by Rabinowitz and Steinberg [Rabinowitz, N., Steinberg, D.M., 1991. Seismic hazard sensitivity analysis: a multi-parameter approach. Bull. Seismol. Soc. Am. 81, 796–817] and accounts for both mean hazard values and hazard values corresponding to different percentiles (e.g., 16%-ile and 84%-ile). The results are assessed in terms of the expected PGA with a 10% probability of exceedance in 50 years for rock conditions and account for both the contribution from specific source zones using the Cornell approach [Cornell, C.A., 1968. Engineering seismic risk analysis. Bull. Seismol. Soc. Am. 58, 1583–1606] and the spatially smoothed seismicity [Frankel, A., 1995. Mapping seismic hazard in the Central and Eastern United States. Seismol. Res. Lett. 66, 8–21]. The influence of different procedures for calculating seismic hazard, seismic catalogues (epicentral parameters), source zone models, frequency–magnitude parameters, maximum earthquake magnitude values and attenuation relationships is considered. As a result, the sensitivity analysis allows us to identify the parameters with higher influence on the hazard. Only these parameters should be subjected to careful discussion or further research in order to reduce the uncertainty in the hazard while those with little or no effect can be excluded from subsequent logic-tree-based seismic hazard analyses.     

Using a regional numerical weather prediction model for GNSS positioning over Brazil

The global navigation satellite system (GNSS) can provide centimeter positioning accuracy at low costs. However, in order to obtain the desired high accuracy, it is necessary to use high-quality atmospheric models. We focus on the troposphere, which is an important topic of research in Brazil where the tropospheric characteristics are unique, both spatially and temporally. There are dry regions, which lie mainly in the central part of the country. However, the most interesting area for the investigation of tropospheric models is the wet region which is located in the Amazon forest. This region substantially affects the variability of humidity over other regions of Brazil. It provides a large quantity of water vapor through the humidity convergence zone, especially for the southeast region. The interconnection and large fluxes of water vapor can generate serious deficiencies in tropospheric modeling. The CPTEC/INPE (Center for Weather Forecasting and Climate Studies/Brazilian Institute for Space Research) has been providing since July 2012 a numerical weather prediction (NWP) model for South America, known as Eta. It has yield excellent results in weather prediction but has not been used in GNSS positioning. This NWP model was evaluated in precise point positioning (PPP) and network-based positioning. Concerning PPP, the best positioning results were obtained for the station SAGA, located in Amazon region. Using the NWP model, the 3D RMS are less than 10 cm for all 24 h of data, whereas the values reach approximately 60 cm for the Hopfield model. For network-based positioning, the best results were obtained mainly when the tropospheric characteristics are critical, in which case an improvement of up to 7.2 % was obtained in 3D RMS using NWP models.     

Analysis of stratigraphical sequences at Cocina Cave (Spain) using rare earth elements geochemistry

This study investigates the stratigraphical sequence of Cocina Cave (Spain) employing and testing for the first time the capability of rare earth elements as markers of human activities in caves. Located in Dos Aguas (Valencian Community, Spain), Cocina Cave is characterized by the presence of several Holocene archaeological deposits from the final Mesolithic to the present day and is a pivotal site for understanding the socio-ecological dynamics of the last hunter-gatherer inhabitants of the Iberian Peninsula and the transition to pastoral and agricultural economies in the Western Mediterranean. However, the identification of strata from particular time-periods in the cave is often difficult due to the homogeneity of layers, the poor archaeological record in some strata and the presence of severe disturbance phenomena. The methodological approach of this study consisted of cross-referencing rare earth elements and other chemical markers with the archaeological stratigraphical interpretation, in an attempt to not only support the identification of the anthropic contribution to the formation of Cocina Cave strata, but also to characterize and confirm different natural and occupational episodes, particularly those associated with hunter-gatherer, early agriculturalist, and shepherd activities. Sediments were collected from different excavation areas and analysed for major elements, trace elements, rare earth elements (REE), soil organic matter (SOM) amounts and pH. Multivariate statistics were employed to group samples according to their elemental profile, and these were then compared to the archaeological temporal interpretation. The obtained results showed that REE amount and fractionation geochemical processes were regulated by carbonates, phosphates and pH. The use of REE as markers was particularly useful as their concentrations and their calculated ratios and anomaly distributions were demonstrated to be highly consistent with the archaeological stratigraphical interpretation.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²