Groundwater nitrate vulnerability assessment in alluvial aquifer using process-based models and weights-of-evidence method: Lower Savinja Valley case study (Slovenia)

This paper describes the implementation of process-based models reflecting relative groundwater nitrate vulnerability of the shallow alluvial Lower Savinja Valley (LSV) aquifer in Slovenia. A spatially explicit identification of the potentially vulnerable priority areas within groundwater bodies at risk from a chemical point of view is being required for cost-effective measures and monitoring planning. The shallow LSV unconfined aquifer system consists of high-permeable Holocene and middle- to low-permeable Pleistocene gravel and sand, with a maximum thickness of about 30 m, mainly covered by shallow eutric fluvisoils or variously deep eutric cambisoil. The hydrogeological parameters, e.g. the depth to the groundwater, hydrological role of the topographic slope, etc. usually used in different point count schemes are, in the case of the lowland aquifer and shallow groundwater, spatially very uniform with low variability. Furthermore, the parametric point count methods are generally not able to illustrate and analyze important physical processes, and validation of the results is difficult and expensive. Instead of a parametric point count scheme, we experimentally used the Arc-WofE extension for weights-of-evidence (WofE) modelling. All measurement locations with a concentration higher than the value of 20 mg NO₃ ⁻ per litre of groundwater have been considered as training points (173), and the three process-based models generalized output layers of groundwater recharge (GROWA), nitrate leached from the soil profile (SWAT) and groundwater flow velocity (FEFLOW), served as evidential themes. The technique is based on the Bayesian idea of phenomena occurrences probability before (prior probability) and after consideration of any evidential themes (posterior probability), which were measured by positive and negative weights as an indication of the association between a phenomena and a prediction pattern. The response theme values describe the relative probability that a 100 × 100 m spatial unit will have a groundwater nitrate concentration higher than the training points’ limit values with regard to prior probability value. The lowest probability of groundwater nitrate occurrence is in the parts of the LSV aquifer, which are known as anoxic condition areas with very likely denitrification processes. The cross-validation of the dissolved oxygen and dissolved nitrate response theme confirmed the accuracy of the groundwater nitrate prediction. The WofE model results very clearly indicate regional groundwater nitrate distribution and enable spatial prediction of the probability for increased groundwater nitrate concentration in order to plan the groundwater nitrate reduction measures and optimize the programme for monitoring the effects of these measures.     

The boundary integral calculations of the forward problem for D.C. sounding and MMR methods for a 3-D body near a vertical contact

Summary The paper presents comprehensive theory based on the boundary integral method for calculations of the electric potential, electric field and corresponding magnetic field due to a pair of D.C. source electrodes near a vertical resistivity contact in the halfspace, indlucing a 3-D disturbing body in the vicinity of the contact. Special attention is paid to the case when the disturbing body touches the vertical contact. Results of numerical calculations are presented in the form of sounding curves and a set of isoline graphs for potential, components of the electric and magnetic field (total and anomalous) on the surface of the Earth. It is shown that the presence of the disturbing body at the contact is most pronounced in the electrical characteristics. Anomalies in the magnetic field are small in comparison to the field due to the electric current in the electrode cable and primary currents flowing from the electrodes.     

Plastic litter in sediments from the Croatian marine protected area of the natural park of Telaščica bay (Adriatic Sea)

This paper reports baseline levels of litter (macro, meso and microplastics) in sediments collected from different areas of the Croatian MPA of the Natural Park of Tela??ica bay (Adriatic Sea, GSA n. 17). The distribution of total abundance according to size, for all analysed locations evidences that microplastics are the dominant fraction concerning item's numbers. In all analysed samples no macroplastics were found, while microplastics are 88.71% and mesoplastics are 11.29% of the total.     

Spectral analysis of oscillations with a time-variable frequency

Summary The paper presents a method of evaluating oscillations with a time-variable frequency using a computer. The given function is first interpolated at points which are not distributed equidistantly in time, but the digitizing step varies with time according to a known optional regularity. The spectrum of the obtained function is computed for various of these interpolations and tests are run to determine when the interpolation best compensates the time variation of the frequency. The initial and terminal frequency in the given sample is then determined. The usability of this method with respect to various types of oscillations with a variable frequency and its accuracy in comparison to sonagrams are discussed.     

Implications for behavior of volatile elements during impacts—Zinc and copper systematics in sediments from the Ries impact structure and central European tektites

Moldavites are tektites genetically related to the Ries impact structure, located in Central Europe, but the source materials and the processes related to the chemical fractionation of moldavites are not fully constrained. To further understand moldavite genesis, the Cu and Zn abundances and isotope compositions were measured in a suite of tektites from four different substrewn fields (South Bohemia, Moravia, Cheb Basin, Lusatia) and chemically diverse sediments from the surroundings of the Ries impact structure. Moldavites are slightly depleted in Zn (~10–20%) and distinctly depleted in Cu (>90%) relative to supposed sedimentary precursors. Moreover, the moldavites show a wide range in δ⁶⁶Zn values between 1.7 and 3.7‰ (relative to JMC 3‐0749 Lyon) and δ⁶⁵Cu values between 1.6 and 12.5‰ (relative to NIST SRM 976) and are thus enriched in heavy isotopes relative to their possible parent sedimentary sources (δ⁶⁶Zn = ?0.07 to +0.64‰; δ⁶⁵Cu = ?0.4 to +0.7‰). In particular, the Cheb Basin moldavites show some of the highest δ⁶⁵Cu values (up to 12.5‰) ever observed in natural samples. The relative magnitude of isotope fractionation for Cu and Zn seen here is opposite to oxygen‐poor environments such as the Moon where Zn is significantly more isotopically fractionated than Cu. One possibility is that monovalent Cu diffuses faster than divalent Zn in the reduced melt and diffusion will not affect the extent of Zn isotope fractionation. These observations imply that the capability of forming a redox environment may aid in volatilizing some elements, accompanied by isotope fractionation, during the impact process. The greater extent of elemental depletion, coupled with isotope fractionation of more refractory Cu relative to Zn, may also hinge on the presence of carbonyl species of transition metals and electromagnetic charge, which could exist in the impact‐induced high‐velocity jet of vapor and melts.     

Characterization of atmospheric surfactants in the bulk precipitation by electrochemical tools

Characterization of atmospheric surfactants in bulk precipitations was carried out by adsorption study at the mercury electrode/solution interface using phase sensitive AC voltammetry. The structure and permeability of the adsorbed organic films at the mercury electrode was tested using the redox processes of lead and cadmium ions as electrochemical tools. The effects of organic matter from the bulk precipitations (rainwater and melted snow) were compared to those obtained for aqueous solutions of model substances: aromatic hydrocarbon (naphtalene), anionic surfactant (sodium dodecylbenzene sulfonate, NDBS), protein (albumine) and selected model substances suggested to be representative of water soluble organic compounds (WSOC) in atmospheric water (monocarboxylic, dicarboxylic, and polyacidic compounds and levoglucosan). It was found that substances like humic acid and 3-hydroxybutanoic acid may play an important role in atmospheric heterogeneous chemistry because of their surface active potential.     

Attenuation Correction Procedures for Water Vapour Fluxes from Closed-Path Eddy-Covariance Systems

Evapotranspiration is a source of water vapour to the atmosphere, and as a crucial indicator of landscape behaviour its accurate measurement has widespread implications. Here we investigate errors that are prevalent and systematic in the closed-path eddy-covariance measurement of latent heat flux: the attenuation of fluxes through dampened cospectral power at high frequencies. This process is especially pronounced during periods of high relative humidity through the adsorption and desorption of water vapour along the tube walls. These effects are additionally amplified during lower air temperature conditions. Here, we quantify the underestimation of evapotranspiration by a closed-path system by comparing its flux estimate to simultaneous and adjacent measurements from an open-path sensor. We apply models relating flux loss to relative humidity itself, to the lag time of the cross-correlation peak between the water vapour and vertical wind velocity signals, and to models of cospectral attenuation relative to the cospectral power of simultaneous sensible heat-flux measurements. We find that including the role of temperature in modifying the attenuation–humidity relationship is essential for unbiased flux correction, and that physically based cospectral attenuation methods are effective characterizers of closed-path instrument signal loss relative to the unattenuated flux value.