Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain)

Background, aim, and scope  The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed. Materials and methods  Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Results  XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite. Discussion  Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.). Conclusions  In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas. Recommendations and perspectives  The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.     

Photocatalysis of fluorene adsorbed onto TiO2

The adsorption of fluorene onto TiO2 has been investigated by conducting equilibrium and kinetic experiments. Adsorption isotherms have been evaluated at two different pHs in the range of temperatures 296-325 K. The type III isotherm shapes obtained were modelled by considering several expressions taken from the literature. Temperature exerted a positive influence in fluorene uptake. Addition of phosphates involved a negative effect when computing the final equilibrium fluorene removal. The kinetic experiments carried out at 296 K corroborated the competitiveness of phosphates to occupy the active sites on the titania surface. Nevertheless, equilibrium conditions are faster achieved at pH 2 than at pH 5. The photocatalysis of fluorene at different initial concentrations of the parent compound revealed a slight improvement of the process at pH 5 if compared to the results obtained at pH 2. A Langmuir-Hinselwood representation of the data confirms the previous statement. Catalyst load shows an optimum, concentration values of the photocatalyst above the optimum provoke a decrease in the fluorene abatement rate. Reutilisation of the catalyst indicates that fluorene is completely eliminated from the solid, i.e. it is suggested that fluorene and intermediates are surface oxidised.     

Time Trends and Seasonal Variation of the Rainwater Chemical Composition in Spain

Abstract

A multiple regression model was used to describe temporal variations of the concentrations of H⁺, SO₄ ^{2 -}, NO₃ ^- and NH₄ ⁺ in Spanish rainwater. The model included the effects of linear trend, annual cycle, and precipitation quantity simultaneously.

The model fit very well for SO₄ ^{2 -} and NO₃ ^-, with statistical evidence of annual cycle and effect of precipitation quantity for these two ions and for NH₄ ⁺, but not for H⁺. There is no trend for any ion, with the single exception of a decreasing trend for H⁺ in one of the stations used.     

Modelling of the migration of trace elements along groundwater flowpaths by using a steady state approach application to the site at El Berrocal (Spain)

The applications of geochemical modelling to natural water systems mostly rely upon the equilibrium assumption. This is in principle justified for deep groundwater systems with long water residence times.In addition, trace element behaviour in these natural systems has been normally modelled by taking into account the precipitation and dissolution of individual trace element phases.Recent geochemical modelling work related to natural analogue systems would indicate that: (1) the equilibrium condition is restricted to a limited number of components in long water residence times and (2) the behaviour of trace metals is very much connected to the major component cycling in the system.There is a need to develop our geochemical modelling capabilities to take these two facts into account in order to be able to predict the behaviour of trace components (radionuclides) in a geological repository.In this work we report on the successful application of steady-state kinetics in conjunction with co-dissolution/co-precipitation approaches to model trace element geochemistry in the natural analogue system at El Berrocal. The evolution of major components of the system (Ca (II), Al (III), CO₃²⁻ and Si) as well the trace elements investigated (U, Ba and Mn) is well reproduced by using the coupling between steady-state kinetics and co-dissolution/co-precipitation approaches.     

Relationship between air pollutants emission patterns and concentrations

Emission patterns of NO_x and S‐compounds are analyzed to study their influence on the concentrations of SO₂, NO_x, sulphate and nitrate in the air. Air mass trajectories, emission inventories and cluster analysis are used to define the emission patterns.

The scheme that characterized most of the days is defined by low emissions from 48 hours until 18 hours before the measurements and it produces average concentrations. High concentrations are due to emission peaks. The time between these emission peaks and the measurement determines the importance of the emission peak on the concentration.     

Risk assessments for forest trees: the performance of the ozone flux versus the AOT concepts

Published ozone exposure-response relationships from experimental studies with young trees performed at different sites across Europe were re-analysed in order to test the performance of ozone exposure indices based on AOTX (Accumulated exposure Over a Threshold of X nmol mol(-1)) and AF(st)Y (Accumulated Stomatal Flux above a threshold of Y nmol m(-2) s(-1)). AF(st)1.6 was superior, as compared to AOT40, for explaining biomass reductions, when ozone sensitive species with differing leaf morphology were included in the analysis, while this was not the case for less sensitive species. A re-analysis of data with young black cherry trees, subject to different irrigation regimes, indicated that leaf visible injuries were more strongly related to the estimated stomatal ozone uptake, as compared to the ozone concentration in the air. Experimental data with different clones of silver birch indicated that leaf thickness was also an important factor influencing the development of ozone induced leaf visible injury.     

Ozone exposure induces the activation of leaf senescence-related processes and morphological and growth changes in seedlings of Mediterranean tree species

Four Mediterranean tree taxa, Quercus ilex subsp. ilex, Quercus ilex subsp. ballota, Olea europaea cv. vulgaris and Ceratonia siliqua, were exposed to different ozone (O(3)) concentrations in open top chambers (OTCs) during 2 years. Three treatments were applied: charcoal-filtered air (CF), non-filtered air (NF) and non-filtered air plus 40 ppb(v) of O(3) (NF +). The photochemical maximal efficiency, Fv/Fm, decreased in NF + plants during the second year of exposure, especially during the most stressful Mediterranean seasons (winter and summer). An increase of delta(13)C was found in three of the four studied species during the first year of exposure. This finding was only maintained in C. siliqua during the second year. Decreases in the chlorophyll content were detected during the first year of fumigations in all the species studied, but not during the second year. The NF + treatment induced changes in foliar anatomical characteristics, especially in leaf mass per area (LMA) and spongy parenchyma thickness, which increased in some species. A reduction in N content and an increase in delta(15)N were found in all species during the second year when exposed in the NF + OTCs, suggesting a change in their retranslocation pattern linked to an acceleration of leaf senescence, as also indicated by the above mentioned biochemical and anatomical foliar changes. The two Q. ilex subspecies were the most sensitive species since the changes in N concentration, delta(15)N, chlorophyll, leaf area, LMA and biomass occurred at ambient O(3) concentrations. However, C. siliqua was the most responsive species (29% biomass reduction) when exposed to the NF + treatment, followed by the two Q. ilex subspecies (14-20%) and O. europaea (no significant reduction). Ozone resistance of the latter species was linked to some plant traits such as chlorophyll concentrations, or spongy parenchyma thickness.     

Changes in tropopause height for the Eurasian region determined from CARDS radiosonde data

Previous studies have identified the tropopause height (TH) as a promising fingerprint of climatic change. In the present paper, we report variations in TH for the Eurasian region over the period 1973–1998 and analyse the influence of the Northern Annular Mode (NAM) on these variations. As previous studies indicate that the greatest increases in TH occur in the extratropics, we focused our attention on this area. We applied a set of homogenization procedures to radiosonde data and considered three different scenarios that take into account change points and the main volcanic eruptions over the study period. Our results demonstrate that the number of stations with positive TH trends is very sensitive to the quality of data and the methods used to remove inhomogeneities. Consequently, when change points were included in the analysis, the number of stations with positive trends decreased markedly. Furthermore, stratospheric NAM appears to control TH in stations located at latitudes higher than 55°N.Electronic supplementary materials  Supplementary material is available for this article at and is accessible to authorized users.     

Simulation of stomatal conductance for Aleppo pine to estimate its ozone uptake

The data from a previous experiment carried out in open-top chambers to assess the effects of ozone (O3) exposure on growth and physiology of Aleppo pine (Pinus halepensis Mill.) were re-assessed to test the performance of the EMEP O3 stomatal conductance model used to estimate tree O3 uptake at a European scale. Aleppo pine seedlings were exposed during three consecutive years to three different O3 treatments: charcoal filtered air, non-filtered air and non-filtered air supplemented with 40 nl l(-1). The results of the model using the default parameterisation already published for Mediterranean conifers showed a poor performance when compared to measured data. Therefore, modifications of g(max), f(min), and new f(VPD), f(temp) and f(phen) functions were developed according to the observed data. This re-parameterisation resulted in a significant improvement of the performance of the model when compared to its original version.