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).     

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...     

Topographical controls on small‐volume pyroclastic flows

Emplacement of small‐volume (<0·1 km³) pyroclastic flows is significantly influenced by topography. The Arico ignimbrite on Tenerife (Canary Islands) is a characteristic small‐volume pyroclastic flow deposit emplaced on high relief topography. The pyroclastic flow flowed down pre‐existing valleys on the southern slopes of the island. In proximal areas deep (up to 100 m) valleys acted as efficient conduits for the pyroclastic flow, which was mostly channelled; in this particular area the ignimbrite corresponds to a homogeneous, moderately welded deposit, consisting of flattened pumices in an abundant ashy matrix with a relatively low lithic fragment content. In intermediate zones significant changes occur in the steepness of the slope and, although still channelled, here the pyroclastic flow was influenced by hydraulic jumps. In this area, two different units can be clearly distinguished in the ignimbrite: the lower unit is composed of a lithic‐rich ground‐layer deposit that formed at the turbulent, highly concentrated head of the flow; the upper unit consists of a well welded pumice‐rich deposit that occasionally reveals a basal layer formed by shearing with the lower part. This division into two units is maintained as far as distal areas near the present‐day coastline, where the slope is very gentle or null and the ignimbrite is not channelled. The ground layer is not found in distal areas. The ignimbrite here only consists of the upper unit, which is occasionally repeated due to a surging process provoked by the lower flow speed, as the pyroclastic flow spread out of the channelled zone. A theoretical model on how topography controlled the deposition of the Arico ignimbrite is derived by interpreting the observed lithological and sedimentological variations in terms of changes in topography and bedrock morphology. This new model is of general applicability and will help to explain other deposits of similar characteristics.     

Calibration and Instrumental Errors in Early Measurements of Air Temperature

Calibration and instrumental errors of early thermometers are analysed. The first concepts, the development of scientific ideas, the main problems linked to the construction of early thermometers and the calibration are considered in order to evaluate errors. The operating principle of the `constant-volume' air thermometer is presented andits limits are discussed. The theory shows that for an ideal Amontons' thermometer, only one calibration point is sufficient from which the other can be calculated; it is therefore possible to determine the difference from an ideal instrument. A comparison is made between calibrations and instruments made by G. Amontons (1699), G. Poleni (Venice, 1709; Padova 1725), and J.H. Lambert (1779). Amontons' thermometer needs to be integrated with a barometric reading; an important error arises from the different density of mercury during calibration and usage. The calibration was made in winter and at the upper point the thermometer was at 100 ° C, while the barometer remained near 0 ° C. However, field observations were made with both instruments at the same temperature and this caused an error that in the cold season is negligible, but in the hot season reaches 1 ° C. Problems connected with the calibration and scale linearity are discussed in view of the beliefs of the time and the operative methodologies used in early meteorology. Emphasis is given to comparability of different instruments, thermometric scales and calibration methodologies used in Padova in the 18th century for Amontons' Poleni's, Fahrenheit's, Réaumur's and Delisle's thermometers. The instrument supports and the incision of the scale were subject to expand or contract depending on temperature or humidity changes, and this was a source of error that can be corrected with the help of observed or estimated data. Problems linked to the construction of thermometers have been evaluated, as well as the linearity of displacements of the thermometric liquid, or the drift due to ageing and transformation of the thermometric liquid, the glass or the support. All these errors have been evaluated and some of them have been found negligible, but some are of the order of 0.5 ° C. The quantitative resultsobtained here can also be usefully applied to correct and validate other long series.     

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.     

Seismic hazard assessment for Iceland in terms of macroseismic intensity using a site approach

We present the results of probabilistic seismic hazard assessment for Iceland in the framework of the EU project UPStrat-MAFA using the so-called site approach implemented in the SASHA computational code. This approach estimates seismic hazard in terms of macroseismic intensity by basically relying on local information about documented effects of past seismic events in the framework of a formally coherent and complete treatment of intensity data. In the case of Iceland, due to the lack of observed intensities for past earthquakes, local seismic histories were built using indirect macroseismic estimates deduced from epicentral information through an empirical attenuation relationship in probabilistic form. Seismic hazard was computed for four exceedance probabilities for an exposure time of 50 years, equivalent to average return periods of 50, 200, 475 and 975 years. For some localities, further return periods were examined and deaggregation analysis was performed. Results appear significantly different from previous seismic hazard maps, though just a semi-qualitative comparison is possible because of the different shaking measure considered (peak ground acceleration versus intensity), and the different computational methodology and input data used in these studies.