Soluble organic compounds in fog and cloud droplets: what have we learned over the past few years?

We have recently set up a new procedure for characterising the water soluble organic compounds (WSOC) in fog water, for which information is still rather limited. Fog samples collected during the 1998–1999 fall–winter season in the Po Valley (Italy) were analysed following this procedure, which allows a quantitative determination of three main classes of organic compounds (neutral species, mono- and di-carboxylic acids, polycarboxylic acids), together accounting for ca. 85% of the total WSOC. This procedure also provides information on the main chemical characteristics of these three classes of compounds (functional groups, aliphatic vs. aromatic character, etc.). The enhanced chemical knowledge on fog/cloud chemical composition opens new scenarios as far as chemical and microphysical processes in clouds and fogs are concerned.     

Simultaneous use of geochemical and geophysical methods to characterise abandoned landfills

. Groundwater sampling and geophysical methods determined a serious contamination problem associated with refilled exploitation sites at the Cal Dimoni area, Llobregat delta, Barcelona, Spain. To characterise this process, hydrogeochemical analyses were performed and showed the following modifications to groundwater chemical composition: increasing pH values, changing redox conditions, significant increases in total organic carbon (TOC) and certain trace elements, and high groundwater conductivity values. Major ion content accumulations were found under the refilled area. In contrast, elements involved in the oxidation–reduction processes, such as iron, manganese and nitrates, clearly diminished. Electromagnetic prospecting methods were also performed and delineated the contamination plume extent. These methods also showed separate sources of contamination, one clearly related to the groundwater–refilled zone leachate interaction, another as a consequence of the manure–accumulation surface site. Geochemical and geophysical methods have shown similar results for locating groundwater contamination sources, and for determining leachate generation mechanisms and flow paths.     

A powder diffraction quantification method (ALJOR) for atmospheric particulate matter

The percentage calculation of crystalline phases in atmospheric particulate matter samples by means of an adiabatic approach of the matrix-flushing method with preferred preparations that avoids preferential orientations, should never be interpreted as absolute values. On the contrary, it should be seen as an indicator of the significant differences between each and every analyzed sample. Factors such as the application of constants, which are only useful for preparations of polycrystalline samples free of preferential orientation, and/or like the deficient resolution shown by the diffraction diagrams for certain phyllosilicate phases, bring a high degree of uncertainty to these percentage calculations. An alternative method of crystalline and amorphous phase quantification is presented below. Once the majority phases in the samples were identified, appropriate pure phases corresponding to each of them were selected. Then, the corresponding calibration curves were built using corundum (number 676 NIST) as a reference pattern phase. After validating the obtained calibration curves, the constants corresponding to each phase and selected spacing were calculated. The ALJOR method has been used for the quantification of five samples.     

U–Pb evidence for a polyorogenic evolution of the HP–HT units of the NW Iberian Massif

. A isotope dilution thermal ionisation mass spectrometry U-Pb geochronological study was carried out on the high-pressure and high-temperature units (HP-HT units) overlying the oceanic suture in the Allochthonous Complexes of the NW Iberian Variscan Belt. The rocks investigated are seven granulite- to eclogite-facies paragneisses and one leucosome within mafic high-pressure granulites in the Ordenes and Cabo Ortegal Complexes of NW Spain. U-Pb dating of zircon, monazite, titanite and rutile reveal the presence of a pervasive Early Ordovician metamorphic event at ca. 500-480 Ma and a later Early Devonian event at ca. 400-380 Ma. The U-Pb ages, in conjunction with petrological and structural data, indicate that the high-pressure event recorded by these rocks is Early Ordovician in age. Monazite ages in the paragneisses suggest that peak metamorphic conditions were reached at ca. 500-485 Ma. Subsequently, the rock ensemble underwent exhumation accompanied by partial melting and zircon growth at ca. 485-470 Ma. Melting of mafic granulites was coeval with this latter episode as indicated by zircon crystallisation age in the leucosomes dated at ca. 486 Ma. Based on these data and on the general features of magmatism and metamorphic evolution, it is proposed that this process took place at a convergent plate boundary within a peri-Gondwanan oceanic domain. Monazite, titanite and rutile data in some of the samples studied show evidence of a second metamorphic episode that took place between ca. 400 and 380 Ma (with a peak at ca. 390-385 Ma). This Early Devonian event, at variance with the previous one, was not pervasive, but, rather, was localised in areas of intense Variscan tectonothermal reworking. It is claimed that this later metamorphic event was recorded by the U-Pb system in areas where monazite and titanite growth was enhanced by fluid circulation in highly strained rocks (Variscan shear zones). According to previous structural studies and Ar-Ar dating of fabrics, this Early Devonian episode took place as the HP-HT units were deformed and thrusted upon the ophiolitic units in the early stages of the Variscan collision.     

Al hematites prepared by homogeneous precipitation of oxinates: material characterization and determination of the Morin transition

A novel method for synthesis of aluminium hematites, based upon the homogeneous precipitation of Fe and Al oxinates in various proportions, is presented. The precursor precipitates are heated in air at 700?°C. X-ray diffraction, thermal analyses, BET, FTIR, optical reflection analysis, TEM and Mössbauer spectroscopy at room temperature and 80?K of the resulting products indicate that single-phase hematites are formed with structural Al substitution of up to 10 at%. Interestingly, the particle size (>100?nm) is not substantially reduced by the Al content. Although it remains difficult to obtain a homogeneously distributed Al substitution in the final hematite, this processing line offers a unique opportunity to separate the effects of grain size and Al substitution on the Morin transition temperature (T _M) of Al hematite. From the comparison between the present hematites and a series of Al-substituted hematites with lepidocrocite as precursor, it could be shown that the effect on T _M, associated with a change of a factor 10 in grain size, is about 1/3 of the effect caused by a change of 10 in the degree of substitution. Finally, it is suggested that proper thermal treatments under different conditions of the same precursors are likely to produce spinel phases.     

Milan: The city of constant renewal

Traditional models of urban development are no longer adequate to describe current metropolitan transformations. These are now at the centre of a debate concerning management and administration. In Italy, delays in resolving problems of urban and metropolitan government, despite the legal framework provided by Law 142/90, have weighed heavily on the larger urban areas of the country: Rome, Naples, Milan, which have not been able to tackle the issue of metropolitan government. Recent legislation, while not providing a pre-defined institutional solution, allows separate administrative districts to collectively establish metropolitan institutions of `variable geometry'. The Milan urban area is not one city, but a system of mutually-dependent cities, linked to each other and the rest of the world by a transport network still requiring much investment. The vitality of its economic structure (especially its small firms) is held back by seriously inadequate infrastructure and low external economic efficiency. The provincial capital may boast `historic centrality' but the most interesting potential for development is to be found on the periphery and in the administrative districts immediately surrounding it, in the recovery of derelict industrial areas and dormitory towns established in the 1950s and 1960s, especially to the north. Recovery of derelict areas, green areas, and better transport links within the urban area and with the outside world are the key elements in the reorganization of `Greater Milan'. In this situation of rapid transformation the most appropriate political strategies involve negotiated planning. This revised version was published online in August 2006 with corrections to the Cover Date.     

Anhydrite-bearing rocks from the Rožná district (Moldanubian zone,Czech Republic): high-grade metamorphosed exhalites?

Several types of anhydrite-bearing rocks have been found in the amphibolite-facies metamorphosed rocks at the north-eastern margin of the Moldanubian Zone. Anhydrite either forms monomineralic bands up to 40 cm thick, or occurs in the form of disseminated grains in surrounding calc-silicate gneiss together with feldspar, scapolite, amphibole, pyroxene, epidote and pyrite. The isotopic composition of sulphur ('³⁴S=30.6 to 32.3‰) and strontium (⁸⁷Sr/⁸⁶Sr=0.70797 to 0.70781) in anhydrite may indicate a marine source of sulphate. The isotopic ratio of strontium is in the same range as that of metamorphosed strata-bound barite-sulphide ores, which have been previously described in the same area. The '³⁴S values of coexisting pyrite range from 21.4 to 22.5‰, the (³⁴S_{anhydrite-pyrite} corresponding to the metamorphic temperature of 600 to 660 °C. In contrast to many submarine-exhalative deposits, the oxygen isotopic compositions of anhydrite ('¹⁸O=9.3 to 10.2‰) are lighter than that of barite ('¹⁸O=10.4 to 13.8‰). This indicates that the both minerals are not in isotopic equilibrium. Therefore, it is probable that anhydrite and barite from the Ro—ná district were deposited from fluids that contained different proportions of seawater and hydrothermal fluids or from hydrothermal fluids that underwent variable extent of oxygen isotope exchange with seafloor rocks. The '¹³C values in calcite ('¹³C=-17.2 to -18.7‰) from anhydrite-bearing rock are lower than those in distant marbles. As graphite is absent in anhydrite- and calcite-bearing rocks, impoverishment in the ¹³C isotope cannot be attributed to the graphite-carbonate isotopic exchange during metamorphism. It is proposed that low '¹³C values in carbonates are caused by pre-metamorphic oxidation of organic matter in course of hydrothermal processes. Anhydrite and anhydrite-bearing calc-silicate gneiss from the north-eastern part of the Moldanubian Zone are interpreted to be the high-grade metamorphosed analogue of anhydrite-rich exhalites commonly found in submarine-exhalative hydrothermal deposits.     

Spatial and temporal variation of the nekton and hyperbenthos from a temperate European estuary with regulated freshwater inflow

The aquatic macrofauna of the Guadalquivir estuary were sampled (1 mm mesh persiana net) at 5 sampling sites located along the entire (except the tidal freshwater region) estuarine gradient of salinity (outer 50 km). A total of 134 fish and macroinvertebrate species was collected but only 62 were considered common or regularly present in the estuary. Univariate measures of the community structure showed statistically significant differences among sampling sites: species richness, abundance, and biomass decreased in the upstream direction, being positively correlated with the salinity. Temporal differences of these three variables were also statistically significant. While a clear seasonal pattern (minimum densities in winter and maximum in spring-summer) was observed for abundance and biomass, no such pattern existed for the number of species. Mysids was the most dominant group throughout the estuary (96% to 99% of abundance; 49% to 85% of biomass), although fish biomass was also important at the outer estuary (36% to 38%). Multivariate analyses indicated highly significant spatial variation in the macrofaunal communities observed along the salinity gradient. These analyses suggest that the underlying structure was a continuum with more or less overlapping distributions of the species dependent on their ability to tolerate different physicochemical conditions. There were also significant temporal (intermonthly + interannual) variation of the estuarine community; the relative multivariate dispersion indicated that monthly variation was more considerable (relative multivariate dispersion >1) at the outer part of the estuary during the wet year (last 20 km) and was higher in the inner stations during the dry year (32 to 50 km from the river mouth). Since a clear negative exponential relationship was observed between the freshwater input (from a dam located 110 km upstream) and water salinity at all sampling stations, it is concluded that the human freshwater management is probably affecting the studied estuarine communities. While the higher seasonal (long-term) stability of the salinity gradient, due to the human control of the freshwater input, may facilitate the recruitment of marine species juveniles during the meteorologically unstable early-spring, the additional (short-term) salinity fluctuations during the warm period may negatively affect species that complete their lifecycle within the estuary.