Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

The June 4th 1999 severe weather episode in San Quirino, Italy: a tornado event?

On the morning of June 4th 1999, a severe weather event took place in San Quirino, a small village of Friuli-Venezia Giulia in the northeast of Italy. This village is located near the piedmont of the Alps, 40 km west from Udine and 60 km north from Venice.Around 0900 UTC (1100 local time), a thunderstorm with an intense hail fall affected the area of San Quirino. A few minutes later (around 0920 UTC, source: a farmer), a funnel cloud from a cumulonimbus touched the ground, producing damages to houses, trees and sheds. The damaged area was quite narrow (about 300 m) and short (less than 10 km). No injuries to people were reported.In spite of the smallness of the area interested by the phenomenon, this storm is studied here starting from the synoptic scale, moving to the mesoscale and finishing with the storm scale, trying to underline its characteristics. These analyses, especially those coming from the Doppler radar images, bring us to the conclusion that the San Quirino episode was produced by a supercell storm.     

Corrections of Systematic Errors, Data Homogenisation and Climatic Analysis of the Padova Pressure Series (1725-1999)

A short history of the series with daily observations of barometric pressure in Padova (since 1725) is made, with special reference to the types of barometers used, their locations, the types of corrections (which were only partial in the early period), the calibrations and the comparison with primary instruments. The paper also describes the homogenisation of the series and the procedures used to fill the small gaps. The Padova series was compared with previously well investigated series from the ADVICE and IMPROVE projects and especially with the nearby Milan series in order to check its reliability. Trend analysis shows an increase in pressure (some 1 hPa) during the last a hundred year. This trend is a common feature for Northern Italy. An effect of the increased air pressure is a local lowering of the Northern Mediterranean Sea level by 1 cm. The part of the year mostly affected by this increase is from late spring to August and corresponds to an extension of the hot season, characterised by an earlier start, and longer duration of the Azores Anticyclone. This reduces the penetration of the Atlantic disturbances in the Northern Mediterranean and the precipitation associated with the passage of fronts. This change is associated with an increase in thermoconvective activity with thunderstorms and heavy precipitation. This explains why, in the last decades, the annual total amount of precipitation is slightly decreased and at the same time the frequency of intense rainfall is increased. Moreover, a comparison of the day-to-day pressure variability with the Western Mediterranean Oscillation (WeMO) indicates a significant positive correlation during the late autumn-early winter period. An increase of the WeMO index means a strengthening of the baric dipole from Azores to Northern Italy, that could be explained by a deepening of the cyclonic circulation over northern Italy from November to January.     

Towards an operational use of space imagery for oil pollution monitoring in the Mediterranean basin: a demonstration in the Adriatic Sea

Studies of operational pollution carried out by European commission - Joint Research Centre in the Mediterranean Sea for the years 1999-2004 are briefly introduced. The specific analysis of the Adriatic Sea for the same period demonstrates that this area has been characterized by a relevant number of illegal discharges from ships. After setting the historical background of the project AESOP (aerial and satellite surveillance of operational pollution in the Adriatic Sea), the content, partners and aim of the project are presented. Finally, the results of the first phase of the AESOP project are presented. The results seem very encouraging. For the first time in the Adriatic, real time detection of oil spills in satellite images and an immediate verification by the Coast Guard has been undertaken. An exploratory activity has also been carried out in collaboration with the University of Ljubljana to use automatic information system (AIS) to identify the ships detected in the satellite images.     

Geophysical exploration on the subsurface geology of La Garrotxa monogenetic volcanic field (NE Iberian Peninsula)

We applied self-potential (SP) and electrical resistivity tomography (ERT) to the exploration of the uppermost part of the substrate geology and shallow structure of La Garrotxa monogenetic volcanic field, part of the European Neogene–Quaternary volcanic province. The aim of the study was to improve knowledge of the shallowest part of the feeding system of these monogenetic volcanoes and of its relationship with the subsurface geology. This study complements previous geophysical studies carried out at a less detailed scale and aimed at identifying deeper structures, and together will constitute the basis to establish volcanic susceptibility in La Garrotxa. SP study complemented previous smaller-scale studies and targeted key areas where ERT could be conducted. The main new results include the generation of resistivity models identifying dykes and faults associated with several monogenetic cones. The combined results confirm that shallow tectonics controlling the distribution of the foci of eruptive activity in this volcanic zone mainly correspond to NNW–SSE and accessorily by NNE–SSW Neogene extensional fissures and faults and concretely show the associated magmatic intrusions. These structures coincide with the deeper ones identified in previous studies, and show that previous Alpine tectonic structures played no apparent role in controlling the loci of this volcanism. Moreover, the results obtained show that the changes in eruption dynamics occurring at different vents located at relatively short distances in this volcanic area are controlled by shallow stratigraphical, structural and hydrogeological differences underneath these monogenetic volcanoes.     

Application of Bayesian Generative Adversarial Networks to Geological Facies Modeling

Mathematical Geosciences - Geological facies modeling is a key component in exploration and characterization of subsurface reservoirs. While traditional geostatistical approaches are still commonly...