Chemical characterization of fine particulate matter during peak PM10 episodes in Apulia (South Italy)

Some peak PM10 episodes, occurred during PM monitoring campaigns performed on October 2005 and February and June 2006 in Bari town, have been characterized. Moreover back trajectories of air masses and Principal Component Analyses were applied. Three of the peak PM10 episodes investigated were related to local emissions of primary pollutants during poor atmospheric dispersion conditions. The other two peak PM10 episodes considered are related with long range transport air masses toward Apulia region: in one case the chemical characterization and the back trajectories analysis indicate that high PM10 value detected is due to the Saharan dust advection in the Apulia region; in the other case air masses with different origin give rise to high PM10 value.Moreover PM10 daily mean concentrations, presented in this paper collected from January 2005 to August 2007 and obtained by automatic device in six stations of air quality monitoring networks in Bari territory, do not show a seasonal trend for PM10 concentrations, contrary to the PM10 trend shown in the towns of North Italy. This can be explained mostly considering that our region presents generally meteo-climatic conditions that favour pollutants dispersion.     

Copepod grazing during spring blooms: Does Calanus pacificus avoid harmful diatoms?

During late winter and spring of 2002 and 2003, 24, 2–3 day cruises were conducted to Dabob Bay, Washington State, USA, to examine the grazing, egg production, and hatching success rates of adult female Calanus pacificus and Pseudocalanus newmani. The results of the copepod grazing experiments for C. pacificus are discussed here. Each week, copepod grazing incubation experiments from two different depth layers were conducted. Grazing was measured by both changes in chlorophyll concentration and cell counts. In 2002, there was one moderate bloom consisting mainly of Thalassiosira spp. in early February, and a larger bloom in April comprised of two Chaetoceros species and Phaeocystis sp. Similarly, in 2003, there were two blooms, an early one dominated by Thalassiosira spp., and a later one consisting of Chaetoceros spp. and Thalassiosira spp. Clearance rates on individual prey species, as calculated by cell counts, showed that C. pacificus are highly selective in their feeding, and may have much higher clearance rates on individual taxa than rates calculated from bulk chlorophyll disappearance. During weeks of high phytoplankton concentration, the copepods generally ate phytoplankton. However, they often rejected the most abundant phytoplankton species, particularly certain Thalassiosira spp., even though the rejected prey were often of the same genus and similar size to the preferred prey. It is speculated that this avoidance may be related to the possible deleterious effects that certain of these diatom species have on the reproductive success of these copepods. During weeks of medium to low phytoplankton concentration, the copepods selectively ate certain species of phytoplankton, and often had high electivity for microzooplankton. The selection mechanism must consist of active particle rejection most likely based on detection of surface chemical properties, since the diatoms that were selected were of the same genus, nearly the same size, and at lower numerical abundance than those cells that were avoided. The grazing choices made by these copepods may have important consequences for the overall ecosystem function within coastal and estuarine systems through changes in the transfer efficiency of energy to higher trophic levels.     

Snow model sensitivity analysis to understand spatial and temporal snow dynamics in a high‐elevation catchment

In this paper, we addressed a sensitivity analysis of the snow module of the GEOtop2.0 model at point and catchment scale in a small high‐elevation catchment in the Eastern Italian Alps (catchment size: 61 km²). Simulated snow depth and snow water equivalent at the point scale were compared with measured data at four locations from 2009 to 2013. At the catchment scale, simulated snow‐covered area (SCA) was compared with binary snow cover maps derived from moderate‐resolution imaging spectroradiometer (MODIS) and Landsat satellite imagery. Sensitivity analyses were used to assess the effect of different model parameterizations on model performance at both scales and the effect of different thresholds of simulated snow depth on the agreement with MODIS data. Our results at point scale indicated that modifying only the “snow correction factor” resulted in substantial improvements of the snow model and effectively compensated inaccurate winter precipitation by enhancing snow accumulation. SCA inaccuracies at catchment scale during accumulation and melt period were affected little by different snow depth thresholds when using calibrated winter precipitation from point scale. However, inaccuracies were strongly controlled by topographic characteristics and model parameterizations driving snow albedo (“snow ageing coefficient” and “extinction of snow albedo”) during accumulation and melt period. Although highest accuracies (overall accuracy = 1 in 86% of the catchment area) were observed during winter, lower accuracies (overall accuracy < 0.7) occurred during the early accumulation and melt period (in 29% and 23%, respectively), mostly present in areas with grassland and forest, slopes of 20–40°, areas exposed NW or areas with a topographic roughness index of ?0.25 to 0 m. These findings may give recommendations for defining more effective model parameterization strategies and guide future work, in which simulated and MODIS SCA may be combined to generate improved products for SCA monitoring in Alpine catchments.     

Simulating coseismic deformation of quartz in the middle crust and fabric evolution during postseismic stress relaxation — An experimental study

Non-steady state deformation and annealing experiments on vein quartz are designed to simulate earthquake-driven episodic deformation in the middle crust. Three types of experiments were carried out using a modified Griggs-type solid medium deformation apparatus. All three start with high stress deformation at a temperature of 400 °C and a constant strain rate of 10^− 4 s^− 1 (type A), some are followed by annealing in the stability field of α-quartz for 14–15 h at zero nominal differential stress and temperatures of 800–1000 °C (type A + B), or by annealing for 15 h at 900 °C and at a residual stress (type A + C).The quartz samples reveal a very high strength > 2 GPa at a few percent of permanent strain. The microstructures after short-term high stress deformation (type A) record localized brittle and plastic deformation. Statisc annealing (type A + B) results in recrystallisation restricted to the highly damaged zones. The new grains aligned in strings and without crystallographic preferred orientation, indicate nucleation and growth. Annealing at non-hydrostatic conditions (type A + C) results in shear zones that also develop from deformation bands or cracks that formed during the preceding high stress deformation. In this case, however, the recrystallised zone is several grain diameters wide, the grains are elongate, and a marked crystallographic preferred orientation indicates flow by dislocation creep with dynamic recrystallisation. Quartz microstructures identical to those produced in type A + B experiments are observed in cores recovered from Long Valley Exploratory Well in the Quaternary Long Valley Caldera, California, with considerable seismic activity.The experiments demonstrate the behaviour of quartz at coseismic loading (type A) and subsequent static annealing (type A + B) or creep at decaying stress (type A + C) in the middle crust. The experimentally produced microfabrics allow to identify similar processes and conditions in exhumed rocks.     

Spectroscopic Characterization of Organic Structures and Organic‐Inorganic Interactions in Paper Mill Sludge

The organic composition and organic‐inorganic interaction in paper mill sludge (PS) solvent extracts (hexane, ethyl acetate, acetone and ethanol) and humic fractions, humic acid (HA) and humin (HU) were studied by electron paramagnetic resonance spectroscopy (EPR), proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H NMR; ¹³C NMR), Fourier‐transformed infrared spectroscopy (FTIR), and ultraviolet‐visible spectroscopy (UV‐vis). The strategy of fractionating the PS, sequentially, with organic solvents of increasing polarity is a reliable analytical procedure for humic substance sample separation because it results in more purified fractions. FTIR, ¹H NMR and ¹³C NMR results showed that hexane extract consisted mainly of aliphatic hydrocarbon structures. Their contents in the extracts decreased as the polarity of the extracting solvent increased and the content of oxygen functional groups increased. Carboxylic and carboxylate functional groups were found in the acetone extract, and ester and ether functions were predominantly found in the ethanol extract. EPR spectra revealed some Fe³⁺ complexes with rhombic structure (g₁ = 4.3; g₂ = 9.0) in the humic fractions and in all solvent extracts, except hexane. Quasi‐octahedral Fe³⁺ complexes (g = 2.3; ΔH_pp ≤ 400 G) were found in the HU fraction and in the acetone extract. The organic free radical content in the HA fraction was higher than the non‐fractionated PS sample and HU fraction.     

The influence of a mature cyclonic eddy on particle export in the lee of Hawaii

Mesoscale eddies may enhance primary production (PP) in the open ocean by bringing nutrient-rich deep waters into the euphotic zone, potentially leading to increased transport of particles to depth. This hypothesis remains controversial, however, due to a paucity of direct particle export measurements. In this study, we investigated particle dynamics using ²³⁴Th–²³⁸U disequilibria within a mesoscale cold-core eddy, Cyclone Opal, which formed in the lee of the Hawaiian Islands. ²³⁴Th samples were collected along two transects across Cyclone Opal as well as during a time-series within the eddy core during a decaying diatom bloom. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO₂) fluxes at 150 m varied spatially and temporally within the eddy and strongly depended on the ²³⁴Th model formulation used (e.g., steady state versus non-steady state, inclusion of upwelling, etc.). Particle fluxes estimated from a steady state model assuming an upwelling rate of 2 m day⁻¹ yielded the best fit to sediment-trap data. These ²³⁴Th-derived particle fluxes ranged from 332±14 to 1719±53 μmol C m⁻² day⁻¹, 27±3 to 114±12 μmol N m⁻² day⁻¹, and 33±20 to 309±73 μmol Si m⁻² day⁻¹. Although PP rates within Cyclone Opal were elevated by a factor of 2–3, PC and PN fluxes were the same, within error, inside and outside of Cyclone Opal. The ratio of PC export to PP remained surprisingly low at <0.03 and similar to those measured in surrounding waters. In contrast, bSiO₂ fluxes within the eddy core were three times higher. Detailed analyses of ²³⁴Th depth profiles consistently showed excess ²³⁴Th at 100–175 m, associated with the remineralization and possible accumulation of suspended and dissolved organic matter from the surface. We suggest that strong microzooplankton grazing facilitated particulate organic matter recycling and resulted in the export of empty diatom frustules. Thus, while eddies may increase PP, they do not necessarily increase PC and PN export to deep waters. This may be a general characteristic of wind-driven cyclonic eddies of the North Pacific Subtropical Gyre and suggests that eddies may preferentially act as a silica pump, thereby playing an important role in promoting silicic-acid limitation in the region.     

Experimental solidification of anhydrous latitic and trachytic melts at different cooling rates: The role of nucleation kinetics

Two sets of cooling experiments were run at atmospheric conditions for two anhydrous starting latitic and trachytic melts: 1) five cooling rates (25, 12.5, 3, 0.5, and 0.125 °C/min) between 1300° and 800 °C, and 2) a 0.5 °C/min cooling rate from 1300 °C with quench temperatures at 1200°, 1100°, 1000° and 900 °C. Trachytic run-products are invariably glassy. Nucleation is also suppressed in the latitic run-products at the three highest cooling rates. Conversely, in the 0.5 and 0.125 °C/min runs, latites have a crystal content of  90 vol.%. The phases are: plagioclase, clinopyroxene, glass and iron-bearing oxide (in order of abundance). The variable quench temperatures, investigated by coupling experiments with Pt wire and Pt capsule sample containers in set 2, again did not produce crystallization of trachyte, whereas latitic samples are characterized by  10 vol.% of oxides, pyroxenes and plagioclase (in order of appearance), at temperature < 1000 °C. Effects of (preferential) heterogeneous nucleation on sample holders, of superheating degree, and chemical species loss during cooling are absent for both melt compositions. The difference of solidification paths between these two silicate melts can be ascribed only to their small chemical differences. In comparison with calculated equilibrium conditions all the experimental latitic and trachytic run-products revealed strong kinetic effects, interpretable in the light of the nucleation theory. The glass-forming ability (GFA) of trachyte is higher, whereas their critical cooling rate (Rc) is lower (< 0.125 °C/min), in comparison to latitic melts (Rc > 0.5 °C/min). The experimental results carried out in this study can be applied to lava flows and domes; trachytic lavas are able to flow for longer period with respect to latitic ones in a metastable condition. Glass-rich terrestrial lavas, i.e. obsidians, can be the result of sluggish nucleation kinetics due to the relative high polymerisation of evolved silicate melts.     

Quality control algorithms for rainfall measurements

One of the basic requirements for a scientific use of rain data from raingauges, ground and space radars is data quality control. Rain data could be used more intensively in many fields of activity (meteorology, hydrology, etc.), if the achievable data quality could be improved. This depends on the available data quality delivered by the measuring devices and the data quality enhancement procedures. To get an overview of the existing algorithms a literature review and literature pool have been produced. The diverse algorithms have been evaluated to meet VOLTAIRE objectives and sorted in different groups. To test the chosen algorithms an algorithm pool has been established, where the software is collected. A large part of this work presented here is implemented in the scope of the EU-project VOLTAIRE (Validation of multisensors precipitation fields and numerical modeling in Mediterranean test sites).