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Biological activity, climate and pollution are responsible for the degradation of building stones, especially limestone, which is widely used in the Paris region. In order to determine the respective contribution of physicochemical and biological processes to the degradation of limestone, limestone specimens from the Père-Lachaise cemetery (Paris, France) were exposed for five years under different conditions: sheltered from or exposed to rain and in horizontal or vertical position. After exposure, the collected samples were characterized by light and electron microscopy, X-Ray diffraction and ion chromatography after elution. The results showed an intense biocolonization of the samples exposed to rain, while the sheltered samples were more affected by the pollution (soiling). The characterization of the bacterial and fungal communities using Next Generation Sequencing Illumina 16S for bacteria and ITS for fungi highlighted that five main bacterial phyla were identified: Actinobacteriota, Bacteroidota, Cyanobacteria, Proteobacteria and Deinococcota (major genera Flavobacterium, Methylobacterium-Methylobacter, Sphingomonas, Roseomonas and Nocardiodes). Among the fungi, the phylum Ascomycota was predominant with the genera Cladosporium, Ramularia, Aureobasidium and Lecania. However, the alteration of the limestone is difficult to quantify at this stage. Potassium nitrate of rain origin has been found in the sheltered area, but no gypsum. Therefore, the biocolonization is a fast phenomenon on the stone and the physico-chemical processes derived from it, caused by climate and pollution, are slower. This is in agreement with the long-term observations made on old and unrestored graves of the cemetery described in the literature. [ABSTRACT FROM AUTHOR]

Most stained-glass windows installed during the Middle Ages have deteriorated over time due to climate and pollution. To reconstruct their alteration history over the centuries, evaluate the current environmental risk, and predict their alteration in the future, two modelling methodologies have been used. First, based on the short-term exposure of medieval-type glass in different sites, dose–response functions (DRFs) were established. These DRFs correlate relevant environmental factors (temperature, rain quantity, rain pH, relative humidity, and SO2 concentration) with the response of the material in terms of alteration layer thickness. The second methodology consists of laboratory experiments that aim at parametrising kinetic laws as a function of specific parameters (temperature, rain pH, and relative humidity). These kinetic laws can be extrapolated over long periods, contrary to DRFs. In this study, we compared both methodologies to simulate the alteration of a model stained glass at different European sites or over different time periods. The results highlighted that the kinetic laws were able to closely represent the data, except for the polluted sites where the alteration was underestimated. This indicated that the dependence of the alteration rate on the pollutant concentrations should be included to improve the model. [ABSTRACT FROM AUTHOR]

Abstract Determination of the glass alteration rate requires the knowledge of the reactive surface area that is a key parameter. Many studies have evaluated this parameter for glass monoliths or powders by using either geometrical or BET surface area, but few have focused on the impact of glass roughness on the reactive surface area and on the global alteration. The roughness can be expected to proportionally increase the reactive surface area and to modify local conditions of alteration. Therefore, the aim of this study is to evaluate the impact of surface roughness and asperities on the alteration of a model medieval-type glass. Experiments were performed in aqueous medium on samples with different initial surface roughness level. The results show that, for an initially smooth surface, the altered layer is continuous and tends to scale, whereas for an initially rough surface, the alteration is heterogeneous in morphology and composition and asperities are highly hollowed. Surprisingly, despite these differences, the quantity of altered glass is relatively similar, which shows that the roughness does not significantly increase the reactive surface area. This is explained by a fast solution saturation in asperities that minimizes their contribution to the global alteration. Highlights • Smooth initial surface altered in aqueous medium evolves as a continuous alteration layer. • Rough initial surface evolves as a heterogeneous altered layer in morphology and composition. • The roughness does not significantly affect the quantity of altered glass due to rapid solution saturation inside asperities. [ABSTRACT FROM AUTHOR]

It is important to understand glass alteration mechanisms and to determine their associated kinetics in order to develop models able to predict the alteration of nuclear, basaltic or archaeological glasses. Recent studies revealed that the respective contributions of diffusion, dissolution, condensation and precipitation processes in alteration are still a matter for debate. In this work, the alteration of a medieval-type glass (Si–K–Ca) was investigated as it presents a specific composition (without B and with low Al). Experiments were performed using a dynamic device, at 30 °C, at pH 8 and 9 and during 1 month in order to simulate alteration in contact with water (rainfall or condensation). The solution was doped in 29 Si to discriminate between the silicon from glass (mainly 28 Si) and from solution. The results showed that the external region of the alteration layer is devoid of modifier cations (K, Ca) and presents a 29 Si/ 28 Si ratio close to the solution one. This excludes that the alteration layer is a glass skeleton and highlights a progressive hydrolysis/condensation process, even if non-hydrolyzed silica tetrahedra could remain when the Si isotopic equilibrium is not reached. The internal zone appears to be gradually depleted in modifier cations and partly enriched in 29 Si, but the thickness of this zone is overestimated using SEM-EDS and SIMS techniques. Even if in these experiments the dissolution mechanism is favored, the contribution of interdiffusion cannot be neglected to explain the weathering of ancient stained glassed windows in the atmosphere. The respective contribution of diffusion and dissolution are also discussed as a function of glass composition and surface texture, as well as of experimental conditions (alkaline pH, renewal of the solution). [ABSTRACT FROM AUTHOR]

The Li isotope signatures of hydrothermal fluids are remarkably constant ( δ Li 7 = 8.0 ± 1.9 ‰ ) irrespective of the water/rock ratio ( W / R ), permeability, temperature or fluid involved (seawater or meteoric). High temperature hydrothermal fluids represent the second most significant source of Li to the ocean, yet the homogeneity of the Li isotopic signatures of this source remains to be explained and in this context, the lack of data for the corresponding altered phases is problematic. We measured Li contents and Li isotope signatures (as well as mineralogy, composition and local fluid temperature) in hyaloclastites collected from a borehole in the Hellisheidi geothermal system (Iceland) which have been altered by high temperature aqueous fluids (from 170 to 300 °C). Li is more enriched in the solid phases than the other alkali metals, highlighting its greater ability to be incorporated into secondary phases, especially at high temperatures (>250 °C). Mass balance calculations show that the low Li concentrations in hydrothermal fluids are best explained by a high water/rock ratio and a high permeability of this system. The Li isotopic signature of the altered hyaloclastites ( δ Li 7 between +1.9 and + 4.0 ‰ ) remains close to the fresh basalt at deep levels and high temperatures (290–300 °C) (as measured δ Li 7 range between +3.7 and + 4.0 ‰ ), and decreases at shallower depths and lower temperatures (150–270 °C) ( δ Li 7 between +1.9 and + 3.1 ‰ ). A mass balance model involving basalt dissolution, secondary phase formation, and successive isotope equilibrium during the migration and the cooling of the percolating fluid was developed. The corresponding apparent mineral-fluid Li isotope fractionation factors resulting from precipitation of secondary phases ( Δ Li minerals - fluid 7 ) range between 0‰ at 300 °C and − 8.5 ‰ at 170 °C and highlight a key role of chlorite. Applying the same approach to mid-ridge oceanic hydrothermal systems allows the relatively homogeneous isotope signatures of high temperature fluids of various locations to be explained. [ABSTRACT FROM AUTHOR]

Abstract: Soiling results from the deposition of pollutants on materials. On glass, it leads to an alteration of its intrinsic optical properties. The nature and intensity of this phenomenon mirrors the pollution of an environment. This paper proposes a new statistical model in order to predict the evolution of haze (H) (i.e. diffuse/direct transmitted light ratio) as a function of time and major pollutant concentrations in the atmosphere (SO2, NO2, and PM10 (Particulate Matter<10μm)). The model was parameterized by using a large set of data collected in European cities (especially, Paris and its suburbs, Athens, Krakow, Prague, and Rome) during field exposure campaigns (French, European, and international programs). This statistical model, called NEUROPT-Glass, comes from an artificial neural network with two hidden layers and uses a non-linear parametric regression named Multilayer Perceptron (MLP). The results display a high determination coefficient (R 2 =0.88) between the measured and the predicted hazes and minimizes the dispersion of data compared to existing multilinear dose–response functions. Therefore, this model can be used with a great confidence in order to predict the soiling of glass as a function of time in world cities with different levels of pollution or to assess the effect of pollution reduction policies on glass soiling problems in urban environments. [Copyright &y& Elsevier]

Abstract: In order to use lithium isotopes as tracers of silicate weathering, it is of primary importance to determine the processes responsible for Li isotope fractionation and to constrain the isotope fractionation factors caused by each process as a function of environmental parameters (e.g. temperature, pH). The aim of this study is to assess Li isotope fractionation during the dissolution of basalt and particularly during leaching of Li into solution by diffusion or ion exchange. To this end, we performed dissolution experiments on a Li-enriched synthetic basaltic glass at low ratios of mineral surface area/volume of solution (S/V), over short timescales, at various temperatures (50 and 90°C) and pH (3, 7, and 10). Analyses of the Li isotope composition of the resulting solutions show that the leachates are enriched in 6Li (δ7Li=+4.9 to +10.5‰) compared to the fresh basaltic glass (δ7Li=+10.3±0.4‰). The δ7Li value of the leachate is lower during the early stages of the leaching process, increasing to values close to the fresh basaltic glass as leaching progresses. These low δ7Li values can be explained in terms of diffusion-driven isotope fractionation. In order to quantify the fractionation caused by diffusion, we have developed a model that couples Li diffusion with dissolution of the glassy silicate network. This model calculates the ratio of the diffusion coefficients of both isotopes (a = D 7/D 6), as well as its dependence on temperature, pH, and S/V. a is mainly dependent on temperature, which can be explained by a small difference in activation energy (0.10±0.02kJ/mol) between 6Li+ and 7Li+. This temperature dependence reveals that Li isotope fractionation during diffusion is low at low temperatures (T <20°C), but can be significant at high temperatures. However, concerning hydrothermal fluids (T >120°C), the dissolution rate of basaltic glass is also high and masks the effects of diffusion. These results indicate that the high δ7Li values of river waters, in particular in basaltic catchments, and the fractionated values of hydrothermal fluids are mainly controlled by precipitation of secondary phases. [Copyright &y& Elsevier]

Abstract: The knowledge of the long-term behavior of nuclear waste in anticipation of ultimate disposal in a deep geological formation is of prime importance in a waste management strategy. If phenomenological models have been developed to predict the long-term behavior of these materials, validating these models remains a challenge, when considering the time scale of radioactive decay of radionuclides of environmental concern, typically 104–105 yrs. Here we show how natural or archaeological analogues provide critical constraints not only on the phenomenology of glass alteration and the mechanisms involved, but also on the ability of experimental short-term data to predict long-term alteration in complex environments. [Copyright &y& Elsevier]

Abstract: Nuclear energy produces long-lived radioactive waste. Glass containment matrices are used to stabilize such waste and to prevent radionuclide dispersion. Over the past few decades, phenomenological models have been developed to predict the long-term behavior of these materials in anticipation of disposal in a deep geological formation. But considering the geological time scales necessary for radioactive decay validating these models is a challenge. Here we show how the validation of the predictive capacity of a mechanistic model applied to archaeological glass alteration bridges the gap between the short-term laboratory data and the long-term evolution of natural system in complex environment. This model applied to nuclear glass provides reliable uncertainties on long-term alteration rates and demonstrates that present models used in the safety calculations are conservative. [ABSTRACT FROM AUTHOR]

Abstract: To better understand glass alteration mechanisms, especially alteration layers formation, leaching experiments of a borosilicate glass (SON68) doped with a different rare earth element (La, Ce, or Nd) with solutions rich in 29Si and 18O were carried out. The coupled analyses of glass, alteration products, and solution led to a complete elemental and isotopic (29Si and 18O) budget. They revealed different behaviours of elements that depend not only on their structural role in the glass, but also on their affinity for alteration products (gel, phyllosilicates, phosphates). However, analyses of both glass and solution are not sufficient to describe the real exchanges occurring between glass and solution. The use of 29Si and 18O tracers gives new insights on the formation of alteration layers. During alteration the phyllosilicates records the isotopic variations of the leaching solution. Their isotopic signatures highlight a mechanism of dissolution/precipitation, which implies equilibrium between the secondary phases and the solution. On the other hand the gel isotopic signature, that is intermediate between the glass and the solution, substantiates the hypothesis that the gel is formed by hydrolysis/condensation reactions. This mechanism can thus explain the influence of the gel formation conditions (alteration conditions, solution saturation) on the structure (reorganisation) and texture (porosity) of this layer and on its protective effect. These hydrolysis/condensation reactions are also certainly involved in the aluminosilicate glass alteration and in the formation of palagonite. [Copyright &y& Elsevier]

Abstract: To improve confidence in glass alteration models, as used in nuclear and natural applications, their long-term predictive capacity has to be validated. For this purpose, we develop a new model that couples geochemical reactions with transport and use a fractured archaeological glass block that has been altered for 1800years under well-constrained conditions in order to test the capacity of the model. The chemical model considers three steps in the alteration process: (1) formation of a hydrated glass by interdiffusion, whose kinetics are controlled by a pH and temperature dependent diffusion coefficient; (2) the dissolution of the hydrated glass, whose kinetics are based on an affinity law; (3) the precipitation of secondary phases if thermodynamic saturation is reached. All kinetic parameters were determined from experiments. The model was initially tested on alteration experiments in different solutions (pure water, Tris, seawater). It was then coupled with diffusive transport in solution to simulate alteration in cracks within the glass. Results of the simulations run over 1800years are in good agreement with archaeological glass block observations concerning the nature of alteration products (hydrated glass, smectites, and carbonates) and crack alteration thicknesses. External cracks in direct contact with renewed seawater were altered at the forward dissolution rate and are filled with smectites (400−500μm). Internal cracks are less altered (by 1 or 2 orders of magnitude) because of the strong coupling between alteration chemistry and transport. The initial crack aperture, the distance to the surface, and sealing by secondary phases account for these low alteration thicknesses. The agreement between simulations and observations thus validates the predictive capacity of this coupled geochemical model and increases more generally the robustness and confidence in glass alteration models to predict long-term behavior of nuclear waste in geological disposal or natural glass in the environment. [Copyright &y& Elsevier]

Abstract: Fractured archaeological glass blocks altered 1800 years in seawater are investigated because of their morphological analogy with vitrified nuclear waste. They provide an opportunity for understanding glass alteration in variable confined media (cracks), by studying an actual ancient system in a known stable natural environment. Characterization of the crack network from two-dimensional trace maps (length, alteration thickness, orientation) allows us to determine the three-dimensional geometric parameters (crack density, fracture ratio) and the percentage of alteration, using stereological relations. This methodology could be applied to nuclear glass. From a representative archaeological glass block, we showed that the surface developed by the cracks is 86±27 times greater than the geometric surface but the volumetric alteration is 12.2±4.1%, which is only 12 times greater than the volumetric alteration of the block periphery (about 1 vol%). This unexpected low value is explained by the large variation of the alteration thicknesses in the different types of cracks in relation with their location in the block. The alteration thickness is usually smaller in the internal zone than in the border zone. The alteration layers resulted from three main mechanisms (interdiffusion, glass dissolution, and secondary phase precipitation) leading to two different alteration products (a sodium-depleted layer and mainly a Mg-smectite). Geometric parameters such as the glass surface area/solution volume ratio and transport parameters (renewal of the alteration solution) strongly affected the glass dissolution kinetics. The confined conditions and the diffusive transport of reactive species favor low alteration kinetics. The precipitation of secondary phases also results in sealing of the cracks. Consequently, although it is not known if subcritical crack growth occurred, internal cracks account for only a minor contribution to the overall alteration. These results improve our understanding of alteration in cracks for assessing the predominant physical and chemical parameters that must be considered in long-term nuclear glass modeling. [Copyright &y& Elsevier]

Only a few studies deals with the alteration of glass by water vapor. This study aims to investigate the mechanisms and to determine the kinetics of alteration of potash-lime silicate glass typical of the Middle Ages. For that, model glass samples were exposed to different conditions (relative humidity -RH-, temperatures) for several durations. The water vapor used in experiments was enriched in deuterium (D) and oxygen-18 (18O). Results show that mechanisms are highly temperature-dependent. At 50 °C, the alteration is driven by interdiffusion, whereas at 20 °C, the alteration is mainly governed by hydration without significant ion exchange. Then, the isotopic profiles of H, D, 18O and 16O show that after sorption of water molecules at the glass surface, the diffusing species in the glass matrix are mainly H+ or D+. Concerning the hydration kinetics, they evolve exponentially with time in the first stages of the alteration. Moreover, at 50 °C, the hydration follows a linear trend below 83% RH and strongly increases for higher RH values. [ABSTRACT FROM AUTHOR]

Potash lime silicate glasses were extensively used during the Middle Ages as components of stained glass windows. Their external faces have been subjected to alteration in the atmospheric medium for centuries, leading to the development of thick alteration layers on the surfaces. This alteration is mainly caused by water in liquid (rainfall) or gaseous (vapor) form. In order to implement geochemical models simulating the long-term behavior of these glasses by coupling the different atmospheric factors, it is necessary to study mechanisms and kinetics of alteration induced by these different hygroscopic situations (rainfall and relative humidity). The aim of this study is here to evaluate the impact of liquid water on stained glass windows and especially to determine alteration rate laws of dissolution and interdiffusion as a function of pH and temperature. For that, a medieval model glass was altered in aqueous solution in batch experiments at different pH values (from 2 to 11), temperatures (from 5 to 70 °C) and saturation states of the solution. From the elemental concentrations in solution, the release rate of elements was calculated and the pH- and T-dependencies were determined. The dissolution and interdiffusion rate laws can now be used to simulate the alteration of a medieval glass submitted to a rainfall event. Moreover, this study highlights that the Si-K-Ca medieval glass presents a very low pH-dependency at alkaline pH, which can be explained by its composition. [ABSTRACT FROM AUTHOR]

This paper reports estimated maintenance-cleaning costs, cost savings and cleaning interval increases for structural surfaces and windows in Europe obtainable by reducing the air pollution. Methodology and data from the ICP-materials project were used. The average present (2018) cleaning costs for sheltered white painted steel surfaces and modern glass due to air pollution over background, was estimated to be ~2.5 Euro/m2∙year. Hypothetical 50% reduction in the air pollution was found to give savings in these cleaning costs of ~1.5 Euro/m2∙year. Observed reduction in the air pollution, from 2002–2005 until 2011–2014, have probably increased the cleaning interval for white painted steel with ~100% (from 12 to 24 years), representing reductions in the single intervention cleaning costs from 7 to 4%/year (= % of one cleaning investment, per year during the cleaning interval) and for the modern glass with ~65% (from 0.85 to 1.3 years), representing reductions in the cleaning cost from 124 to 95%/year. The cleaning cost reductions, obtainable by 50% reduction in air pollution, would have been ~3 %/year for white painted steel and ~60%/year for the modern glass, representing ~100 and 50% additional cleaning interval increases. These potential cleaning cost savings are significantly higher than previously reported for the weathering of Portland limestone ornament and zinc monuments. [ABSTRACT FROM AUTHOR]

The Mn-bearing medieval stained-glass windows are affected by a browning phenomenon that could have a microbiological origin. This study investigates the direct and indirect impact of a model Mn-oxidizing and siderophore productive bacterial strain (Pseudomonas putida) on the alteration of medieval glass. For that, five model glasses with variable contents of Mn and Fe were altered during 1 week at 25 °C and pH 6.5 either in the presence of the siderophore desferrioxamine B (DFOB) at 50 mM or with the bacterial strain P. putida with or without external sources of iron. DFOB was shown to accelerate the dissolution of the Mn- and Fe-bearing glasses. By contrast, the presence of bacteria, had no apparent effect on glass dissolution, but led to the formation of a biofilm that was enriched in some elements of the glass, especially Si. The results also underlined the key-role of P of the glass as a nutrient for bacterial growth. Brown Mn oxides phases were only formed either when bacteria were incubated with Mn- and P-bearing glasses and after the production of the siderophore pyoverdine. Conversely, no browning was observed for the glass containing MnO and FeO with bacteria, which highlights that the absence of Fe plays a triggering role in the formation of manganese oxides. • The presence of the siderophore DFOB accelerates the dissolution of glasses. • The phosphorus in the glasses is sufficient to trigger bacterial growth. • The formation of MnO 2 , linked to the production of pyoverdine, has a positive impact on reactive oxygen species. • The iron in the glass triggers the formation of MnO 2 through a bacterial process. [ABSTRACT FROM AUTHOR]

Limestone buildings in urban areas are weathered due to climatic factors, to pollution but also to biological activity. Many studies have focused on microbially-mediated precipitation of calcite but few on their influence on limestone dissolution rates. In this study, a cultivable approach for studying bacterial dissolution of limestone is proposed. The results show, for the first time, that limestone has selected a specific structure in the bacterial communities and that each bacterial class has its own metabolism inducing a different efficiency on the alteration of limestone grains. Cultivable bacterial and fungal strains in our study permit to considerably increase (by 100 to 1,000,000 times) the chemical weathering rates compared to laboratory or field experiments. Individually, the results bring information on the ability to alter limestone by dissolution. Moreover, taken together, a functional ecological adaptation of bacterial and fungal classes to the alteration of the limestone monument has been highlighted. In order to release calcium into solution, these strains slightly acidify the medium and produce low molecular mass organic acids during experiments, especially lactic and oxalic acids. [ABSTRACT FROM AUTHOR]

Buildings and monuments are often colonized by microorganisms that can result in colour change and aesthetical and physico-chemical damages. This bio-colonization is dependent of the material and on the environment. In order to better understand and correlate the microbial development at the surface of buildings with meteorological parameters, concentration of green algae and cyanobacteria have been measured using an in situ instrument on the wall of a private habitation in the Parisian region during two periods: spring and fall-winter. Different locations were also chosen to assess the influence of the position (horizontal or vertical) and of the situation (shaded vs. sunny microclimate). The results show that the microorganism development rapidly responds to rainfall events but the response is more intense in winter as temperature is lower and relative humidity (RH) higher. Cyanobacteria are less sensitive to this seasonal effect as they are more resistant to desiccation than green algae. Based on all the data, different dose-response functions have been established to correlate RH, rain and temperature to the green algae concentration. The influence of the microclimate is considered via specific fitting parameters. This approach has to be extended to new campaign measurements but could be very useful to anticipate the effect of climate change. [ABSTRACT FROM AUTHOR]

The browning phenomenon is a pathology affecting Mn-bearing medieval stained-glass-windows in potash-lime-silicate glass system. In order to unravel the potential implication of microorganisms in the appearance of this pathology, three model glasses respectively containing no MnO, 1 wt% and 2 wt% MnO were altered at circumneutral pH, with and without organic exudates (oxalic acid (OA) 1000 μM and siderophore desferrioxamine B (DFOB) 50–1000 μM) likely to be produced by bacteria and fungi. In the absence of exudates, the dissolution rates are inversely dependent on the Mn content of the glasses (0.8, 0.5 and 0.4 g m−2d−1 respectively for no MnO, 1 wt% and 2 wt% MnO glasses). In contact with exudates, an opposite trend is observed. The prevalent mechanisms are interpreted as a strong ligand-promoted dissolution for DFOB (dissolution rate increase up to 270%) and a dominant proton-promoted dissolution for OA (dissolution rate increase up to 60%). When DFOB and OA are added together, the effect of DFOB on the dissolution rate is prevailing, while OA effect is tangible on the stoichiometry of the dissolution of the alteration. These results suggest that an indirect biological activity could be involved in the mobilization of Mn from a Mn-bearing glass, thus playing a role in the appearance of the browning phenomenon. • In water, a Mn-bearing glass has a lower dissolution rate than a Mn-free glass. • The Mn-bearing glass dissolution is more affected by the addition of microbial exudates. • The DFOB siderophore has a stronger effect than the oxalic acid on the dissolution. • The dissolution rates increase when the concentration of DFOB increases. • No synergistic effect was observed on dissolution rates when both exudates were added. [ABSTRACT FROM AUTHOR]

In order to better constrain the geochemical budget of Si in the ocean, and potentially other elements released by the dissolution of silicates, the alteration of riverine particulate material in estuaries and seawater needs to be estimated. For this, a series of alteration experiments of basaltic glass were performed at various degrees of salinity (from 0 to 3.5 g L −1 ) in far-from-equilibrium conditions. The solution used is a filtered natural seawater standard from the Atlantic Ocean. The forward dissolution rates increase from 2.1 ⋅ 10 − 7 mol Si m − 2 s − 1 ( S = 0 g L − 1 ) to 7.7 ⋅ 10 − 7 mol Si m − 2 s − 1 ( S = 3.5 g L − 1 ) at 90 °C and were extrapolated at 16 °C (from 2.9 ⋅ 10 − 10 mol Si m − 2 s − 1 at S = 0 g L − 1 to 1.1 ⋅ 10 − 9 mol Si m − 2 s − 1 at S = 3.5 g L − 1 ). This positive relationship between glass dissolution rate and salinity degree is consistent with published investigations concerning the role of specific cations and ligands present in seawater, which can promote dissolution at the glass surface. These results illustrate the potential of river basaltic glass particles to dissolve quickly in the water column after entering into the brackish waters of estuaries, and before sinking on continental margins. Based on these dissolution rates and on assumptions on the particulate solid flux of fresh basaltic glass exported by rivers towards the ocean, the corresponding flux of dissolved Si is estimated to range between 2 and 8 ⋅ 10 12 mol Si yr − 1 . This is of the same order of magnitude as the estimated river dissolved Si flux, which represents therefore a significant input of Si into the ocean. Additionally, if the glass dissolution process remains congruent during the residence time of suspended particles into the water column, the K flux to the ocean could also be significantly affected. [ABSTRACT FROM AUTHOR]

Highlights: [•] New findings on long term atmospheric corrosion of medieval stained glasses. [•] Use of model and ancient stained glass altered in real atmospheric conditions. [•] Multiscale study (SEM+TEM) of short and long terms alteration layers. [•] Refining of atmospheric corrosion mechanisms of stained glass. [Copyright &y& Elsevier]

While the IUFM (University Institutes for Teachers' Training) are going to become part of universities, this article questions one of the bases validating the teachers' training: the professional report. This assessment concerns exercising teachers in having a critical mind towards their practical experience, because its purpose is to prepare teachers to adapt to the different types of pupils they are going to teach. This is the reason why the Government can only define this assessment briefly, even if they want to have better control over the teachers' training. To be precise concerning this assessment, the Government has to trust the teachers' trainers' control and the latter are only lightly encouraged. Despite the positive opinion expressed by specialists, this assessment could disappear because the Government favours a training efficient in a short-term period and ignores the analyses which would take long-term needs into account... [ABSTRACT FROM AUTHOR]

This study investigates the direct and indirect bacterial contributions that influence the dissolution of basaltic glass. In this regard, three different types of glasses – with or without Fe, in the reduced Fe(II) or oxidized Fe(III) states – were prepared on the basis of a simplified basaltic glass composition. In order to prevent the direct contact between the glasses and the model siderophore-producing strain Pseudomonas aeruginosa , the glass samples were isolated in dialysis bags and immersed at 25 °C and pH 6.5 in bacterial cultures. Throughout the dissolution experiments, the following parameters were monitored: determination of bacterial growth, quantification of siderophore (i.e. pyoverdine) production, microscopic observation of the glass surface and determination of dissolution kinetics. Isolating the glass from the bacterial suspension only triggered the biosynthesis of siderophores in the Fe(III)-bearing glass dissolution experiments. Siderophores were produced in the presence of Fe(II)-bearing and Fe-free glass, independently on the experimental setup. The siderophore production appeared to be either continuous in the absence of Fe (glass-free control, Fe-free glass dissolution experiments) or stopped as soon as the bacteria entered their stationary phase when an Fe source was present (Fe(II) and Fe(III)-bearing glass dissolution experiments). The increase in the dissolution rates of each glass was correlated to the complex stability constants of the siderophore with the metallic cations in presence (KFe2+ < KAl3+ ≪ KFe3+). Among the three glasses, only the Fe(III)-bearing one seemed to be significantly impacted by the dialysis process: its dissolution rate was doubled by isolating the glass grains from the cells. These results particularly allow to separate the impact of such bacterial exudates from physical contact effects: they showed the efficiency of pyoverdine in increasing the dissolution of an Fe(III)-bearing glass and evidenced that a direct bacterial cell attachment to the surface of such a glass results in a more moderate enhancement of its dissolution process. This work is a new contribution regarding the high affinity of microorganisms for basaltic glasses as an Fe-source. It highlights the role of Fe(III) accessibility upon the bacterial cells as a key parameter regulating their activity and their efficiency in accelerating the dissolution. [ABSTRACT FROM AUTHOR]

This work is focused on the effect of marine aerosols on soda-lime, potash-lime and lead silicate glass samples. Two kinds of tests were carried out, the first one under laboratory controlled condition during 36 days to evaluate the alteration of glass surface by NaCl aerosols, and the second one in a marine atmosphere in Cabo Vilano (Galicia, Spain) for up to three months. Both tests showed similar results. NaCl aerosols acted as condensation nuclei in high humidity environments favoring the lixiviation of the alkaline and alkaline-earth ions from the glass surface and the solubilization of atmospheric gases (CO 2 , SO 2 ). Marine aerosols could also accelerate the corrosion attack inducing the loss of the surface hydrogen bonds and the opening of the network accelerating the corrosion mechanism. Results also confirmed that high humidity favored the alteration of the glass surface and the formation of new crystalline phases. Soda-lime silicate and lead silicate glasses were the most durable ones, whereas potash-lime silicate glass presented a fissured alteration layer due to the hydrolytic attack of the surface. New crystalline phases including chlorides, carbonates and sulfates were detected on the glass surfaces which can be related to marine aerosols, environmental particles and the reaction of the cations lixiviated from the glass with the atmospheric gases. [ABSTRACT FROM AUTHOR]

Results from the international cooperative programme on effects on materials including historic and cultural monuments are presented from the period 1987-2014 and include pollution data (SO2, NO2, O3, HNO3 and PM10), corrosion data (carbon steel, weathering steel, zinc, copper, aluminium and limestone) and data on the soiling of modern glass for nineteen industrial, urban and rural test sites in Europe. Both one-year and four-year corrosion data are presented. Corrosion and pollution have decreased significantly and a shift in the magnitude is generally observed around 1997: from a sharp decrease to a more modest decrease or to a constant level without any decrease. SO2 levels, carbon steel and copper corrosion have decreased even after 1997, which is more pronounced in urban areas, while corrosion of the other materials shows no decrease after 1997, when looking at one-year values. When looking at four-year values, however, there is a significant decrease after 1997 for zinc, which is not evident when looking at the one-year values. This paper also presents results on corrosion kinetics by comparison of one- and four-year values. For carbon steel and copper, kinetics is relatively independent of sites while other materials, especially zinc, show substantial variation in kinetics for the first four years, which needs to be considered when producing new and possibly improved models for corrosion. [ABSTRACT FROM AUTHOR]

In order to explore the role of bacteria in the alteration of stained glass windows, and especially on the browning phenomenon, it is necessary to have an overview of the microbial inhabitants likely to be found on this kind of material. In this study, biological samples were collected on stained glass of different colours, both on site and stored in a conservation workshop. Cultivable bacterial communities were identified by 16S rDNA sequencing. Similarity values ranged from 99 to 100% to known bacteria. Sequence analysis showed different bacterial communities depending on the sampling site. The more represented genera were Arthrobacter, Micrococcus, Paenibacillus and Bacillus. Some of the identified bacteria are known for their weathering potential. • Microbiological samples were collected on stained glass from 4 French sites. • Bacterial diversity was observed depending on the sampling site. • Geographical, internal/external exposure, and glass composition might have an impact on bacterial diversity. • Some of the identified bacteria have weathering potential. • Arthrobacter crystallopoietes was associated to murrey glass. [ABSTRACT FROM AUTHOR]

The alteration of “Saint-Maximin Roche fine” limestones exposed to the Parisian urban environment during more than 60 years has been studied. It leads to changes of the texture and morphology, to the neo-formation of gypsum on the subsurface and to the deposition of carbon containing phases on the surface. Depending on the location of the blocks on the monuments, the alteration states are different related to different water activities that could influence the further alteration processes. The multiscale characterization has enabled to correlate the macrometric properties to the mesoscopic behavior, what is essential to understand the alteration mechanisms. [ABSTRACT FROM AUTHOR]

This study aims to evaluate the role of micro-organisms and their siderophores in the first steps of the alteration processes of basaltic glasses in aqueous media. In this regard, three different types of glasses – with or without iron, in the reduced Fe(II) or oxidized Fe(III) states – were prepared on the basis of a simplified basaltic glass composition. Control and Pseudomonas aeruginosa inoculated experiments were performed in a buffered (pH 6.5) nutrient depleted medium to stimulate the production of the pyoverdine siderophore. Results show that the presence of P. aeruginosa has an effect on the dissolution kinetics of all glasses as most of the calculated elemental release rates are increased compared to sterile conditions. Reciprocally, the composition of the glass in contact with P. aeruginosa has an impact on the bacterial growth and siderophore production. As an essential nutrient for this microbial strain, Fe notably appears to play a central role during biotic experiments. Its presence in the glass stimulates the bacterial growth and minimizes the synthesis of pyoverdine. Moreover the initial Fe 2+ /Fe 3+ ratio in the glasses modulates this synthesis, as pyoverdine is not detected at all in the system in contact with Fe(III)-bearing glass. Finally, the dissolution rates appear to be correlated to siderophore concentrations as they increase with respect to sterile experiments in the order Fe(III)-bearing glass < Fe(II)-bearing glass < Fe-free glass. This increase is attributed to complexation reactions between siderophores and Fe or Al for Fe(II)-bearing glass or Fe-free glass, respectively. The dissolution of an Fe-free glass is significantly improved in the presence of bacteria, as initial dissolution rates are increased by a factor of 3. This study attests to the essential role of siderophores in the P. aeruginosa -promoted dissolution processes of basaltic glasses as well as to the complex relationships between the nutritional potential of the glass and its dissolution rates. [ABSTRACT FROM AUTHOR]

The cyclic nature of atmospheric conditions triggers different weathering responses. Although studied in the past in solution, the complex alteration mechanisms were not adequately described. In the present work, atmospheric weathering of medieval SiO 2 -K 2 O-CaO glass was studied via field exposure of model-glasses and ancient stained glasses. Local dissolution and precipitation of secondary minerals, mainly calcite, create a fracture network, allowing water to move into the glass enhancing alteration processes and scaling of the surface. In fine, the renewal of glass surface by removal of altered scales helps accelerate the alteration rate and prevents the formation of a protective layer. [ABSTRACT FROM AUTHOR]

Although microorganisms seem to play an important role in the alteration processes of basaltic glasses in solution, the elementary mechanisms involved remain unclear in particular with regard to the role of organic ligands excreted by the cells. Two glasses, one with Fe and one without Fe were synthesized to model basaltic glass compositions. Fe in the glass was mostly Fe(III) for enhancing interaction with siderophores, yet with small but significant amounts of Fe(II) (between 10% and 30% of iron). The prepared samples were submitted to abiotic alteration experiments in buffered (pH 6.4) diluted solutions of metal-specific ligands, namely oxalic acid (OA, 10 mM), desferrioxamine (DFA, 1 mM) or 2,2′-bipyridyl (BPI, 1 mM). Element release from the glass into the solution after short term alteration (maximum 1 week) was measured by ICP-OES, and normalized mass losses and relative release ratios (with respect to Si) were evaluated for each element in each experimental condition. The presence of organic ligands had a significant effect on the dissolution of both glasses. Trivalent metals chelators (OA, DFA) impacted on the release of Fe 3+ and Al 3+ , and thus on the global dissolution of both glasses, enhancing all release rates and dissolution stoichiometry (release rates were increased up to 7 times for Al or Fe). As expected, the mostly divalent metal chelator BPI interacted preferentially with Ca 2+ , Mg 2+ and Fe 2+ . This study thus allows to highlight the central roles of iron and aluminium in interaction with some organic ligands in the alteration processes of basaltic glasses. It thus provides a step toward understanding the biological contribution of this fundamental geological process. [ABSTRACT FROM AUTHOR]

Abstract: This study revisits the measurements of the MULTI-ASSESS and Long Term Soiling programs for understanding physically, and modeling, the processes controlling the soiling of modern glass in polluted conditions. The results show a strong correlation between the size distribution of particles and the evolution of the mass deposited at the surface of the glass. Over observation periods covering more than 2 years, the mass deposition on glass panels sheltered from the rain is observed to accelerate regularly with time at the sites closest to the sources of particulate matter (Roadside sites). At these sites the deposit is also richer in coarse (supermicron) mineral particles than at more distant (Urban Background and Suburban) sites, where the contribution of submicron particles (among which a significant fraction of particulate organic matter) is larger. This size and compositional segregation probably explains that the mass accumulation tends to slow down with time and finally saturate after an estimated duration of more than 10 years at the Suburban sites. The analysis of the correlation between the measured accumulated mass and haze shows that the haze-creating mass efficiency of the deposit decreases progressively as the density of particles increases on the glass panels. This is interpreted as being a consequence of the increasing influence of multiple scattering. A steady-state is eventually obtained when layers of closely packed particles are formed, which occurs for surface masses of the order of a few tens of μg cm−2. After this stage is reached, the haze increases linearly with further mass deposition at a pace conditioned by the size-distribution of the deposit. The parameterization of the evolution of the deposited mass with time, and of the correlation linking this mass to the haze allows proposing a new physically-based model able to predict the development of the haze on sheltered glass. Finally, a comparison of the model predictions with the independent measurements performed at the experimental sites of the AERO program shows that the model is able to simulate correctly the development of the haze at a variety of urban sites ranging from the Suburban to Roadside categories. This predictive tool should help developing conservation strategies adapted to the real environmental conditions of the historical and modern buildings. [Copyright &y& Elsevier]

Abstract: The medieval SiO2–CaO–K2O stained glasses are particularly vulnerable to the impact of their environment. In the urban atmosphere, they will tend to rapidly deteriorate either by loss of matter or by addition of atmospheric material, that tend to form a crust on the surface of the glass. If the glass surface is protected from the rain run-off, this second phenomenon will be favoured. In the early stage of crust formation, it was shown that primary constituents were salts, called neocrystallisations. However, it is still not clear, if their presence induce further deterioration of the glass matrix. In order to answer this question both field exposure and laboratory experiments were carried out. Model glasses, chosen with compositions similar to those of ancient stained glasses, were exposed to the urban atmosphere in sheltered conditions. Samples exposed were analysed in order to identify the neocrystallisations and further tests were undertaken in order to observe their impact on the glass itself. The analyses of the weathering products on the glasses showed the presence of three principal minerals: syngenite, gypsum, and potassium carbonate. The observed mineral phases were then artificially deposited on model glass surfaces submitted to cycles of relative humidity. It was found that the presence of salts increased the glass degradation by extending the time of wetness of the glass surface and forming saline solutions in the case of deliquescent salts. Evidence of strong leaching could be observed on the glass surface and even more so when considering glass samples in contact with multiple salts. Finally, the impact of potassium carbonate (K2CO3) on the glass was dramatic, since it induced a loss of matter caused by the dissolution of the lattice in contact with the alkaline solution. [Copyright &y& Elsevier]

The deterioration of monument or building stone materials is mostly due to the growth of black crusts that cause blackening and disaggregation of the exposed surface. This study reports on new oxygen (δ17O, δ18O and Δ17O) and sulphur (δ33S, δ34S, δ36S, Δ33S and Δ36S) isotopic analyses of black crust sulphates formed on building stones in Sicily (Southern Italy). The measurements are used to identify the possible influence of volcanic emissions on black crust formation. Black crusts were mostly sampled on carbonate stone substrate in different locations subject to various sulphur emission sources (marine, anthropogenic and volcanic). Unlike atmospheric sulphate aerosols that mostly exhibit Δ33S > 0‰, here most of the analysed black crust sulphates show negative Δ33S. This confirms that black crust sulphates do not result from deposition of sulphate aerosols or of rainwater but mostly from the oxidation of dry deposited SO 2 onto the stone substrate. The δ34S and δ18O values indicate that most of black crust sulphate originates from anthropogenic activities. Δ17O values are found to be related to the sampling location. The largest 17O-anomalies (up to ~4‰) are measured in black crust from areas highly influenced by volcanic emissions, which demonstrates the strong involvement of ozone in the formation of black crusts in volcanically influenced environments. Unlabelled Image • Black crusts are mostly collected on carbonate building stones from different environments (coastal, rural, urban and volcanic environments). • δ34S and δ18O indicate that black crust sulphur is mostly derived from anthropogenic sources. • Δ33S and Δ36S of black crust sulphate are distinct from those of atmospheric sulphate aerosols. • The largest Δ17O anomalies are measured in black crust sampled in locations downwind of an active volcano (Mt Etna). [ABSTRACT FROM AUTHOR]