Analysis of the surface of different marbles by X-ray photoelectron spectroscopy (XPS) to evaluate decay by SO2 attack

Atmospheric pollution is one of the main agents of decay in monuments and other works of art located in industrialised urban centres. SO₂ is a permanent and abundant component of air pollution and, although it does not have an immediate visual effect, after continuous exposure, it can cause irreversible damage to building materials. Marble is one of the most commonly used ornamental stones in historical monuments and its mineralogical composition makes it very susceptible to damage caused by exposure to SO₂. To measure the chemical reactions caused on marble by the action of atmosphere rich in SO₂, selected calcitic and dolomitic samples were altered by weathering accelerated test. For this, seven marble types (four calcitic and three dolomitic) were exposed to high concentration of sulphur dioxide for 24 h in a climate chamber under controlled temperature and humidity conditions (20 °C and > 90 % HR). Changes on marble surfaces caused by reactions of SO₂ with calcite and dolomite were studied using two non-destructive techniques: chromatic change by means of colorimetry and chemical analysis using X-ray photoelectron spectroscopy (XPS). The development of new mineral phases was also observed by scanning electron microscopy. Colorimetric analysis revealed a decrease in lightness and chromatic parameters suggesting that these changes were due to the development of new mineral phases in all marbles. The XPS technique, which is generally used in the analysis of metals, is relatively new in the field of stone deterioration. It enabled us to recognise the development of sulphites and sulphates on marble surfaces with high precision, after just 24 h of exposure to high SO₂ concentrations and to distinguish different decay paths for calcitic and dolomitic marbles.     

End member and Bayesian mixing models consistently indicate near-surface flowpath dominance in a pristine humid tropical rainforest

The impacts of forest conversion on runoff generation in the tropics have received much interest, but scientific progress is still hampered by challenging fieldwork conditions and limited knowledge about runoff mechanisms. Here, we assessed the runoff generation, flow paths and water source dynamics of a pristine rainforest catchment in Costa Rica using end member mixing analysis (EMMA) and a Bayesian mixing model (MixSIAR). Geochemical tracer data collected over a 4-week field campaign were combined with tritium data used to assess potential deeper groundwater flow pathways to the perennial stream. The streamflow composition was best captured using three end-members, namely throughfall, shallow (5–15 cm) and deeper (15–50 cm) soil water. We estimated the end-member contributions to the main stream and two tributaries using the two mixing approaches and found good agreement between results obtained from EMMA and MixSIAR. The system was overwhelmingly dominated by near-surface sources, with little evidence for deeper and older groundwater as tritium-derived baseflow mean transit time was between 2.0 and 4.4 years. The shallow soil flow pathway dominated streamflow contributions in the main stream (median 39% and 49% based on EMMA and MixSIAR, respectively), followed by the deeper soil (32% and 31%) and throughfall (25% and 19%). The two tributaries had even greater shallow soil water contributions relative to the main stream (83% and 74% for tributary A and 42% and 63% for tributary B). Tributary B had no detectable deep soil water contribution, reflecting the morphology of the hillslope (steeper slopes, shallower soils and lower vegetation density compared to hillslope A). Despite the short sampling campaign and associated uncertainties, this study allowed to thoroughly assess runoff generation mechanisms in a humid tropical catchment. Our results also provide a first comparison of two increasingly used mixing models and suggest that EMMA and MixSIAR yield comparable estimates of water source partitioning in this tropical, volcanic rainforest environment.     

Concentration of Ciprofloxacin in Brazilian Hospital Effluent and Preliminary Risk Assessment: A Case Study

This study was carried out to evaluate the occurrence of the fluoroquinolone antimicrobial agent ciprofloxacin (CIP) in the effluent of the Hospital of the Federal University of Santa Maria (HUSM). Measured environmental concentrations (MECs) of CIP in the hospital wastewater, both before (P1) and after (P2) cesspit/filter system treatment (CFTS), were determined by means of solid phase extraction and reversed‐phase liquid chromatography with fluorescence detection (LC‐FLD) and reversed‐phase liquid chromatography with mass spectrometric detection (LC‐MS/MS). The MECs (n = 7 daily composed samples) were 19 to 155 μg L^–1 (average: 54 ± 21 μg L^–1) and 32 to 99 μg L^–1 (average: 65 ± 45 μg L^–1) in P1 and P2, respectively. No relevant removal was observed from P1 to P2. In a worst case scenario, the final effluent was regarded as MECs of surface water. These MECs were generally 5 to 20,000‐fold higher than what was previously known. If the present data is drawn on to form a model of the situation in developing countries, the picture provides a first rough indication that the environmental risk associated with the use and emission of pharmaceuticals into the environment in developing countries might be higher than in developed countries.     

Semi‐Micro Reflux Procedure for Minimization of Chloride Interference by COD Determination

In this study, a semi‐micro procedure for the COD (Chemical Oxygen Demand) was undertaken to allow the measurement of effluent samples with a high chloride content. It was found that the COD values for standard and effluent samples, corresponded closely to those obtained using the standard method of Burns and Marshall. When the method was applied to samples of industrial wastewater, with a very high chloride content, the recommended procedure proved to be accurate and precise, with RSDs of 6% and 4.3% for the standard and effluent solutions, respectively. The required amount of hazardous reagents was similar to that found in the standard closed reflux method. It was also possible to determine the total amount of oxidized halides. The use of this low‐cost, laboratory‐made system made it unnecessary to acquire an expensive, imported analytical system, while maintaining a high level of accuracy in the determinations.     

Regional provenance from southwestern Colombia fore‐arc and intra‐arc basins: implications for Middle to Late Miocene orogeny in the Northern Andes

Andean orogenic processes controlled the spatial and temporal distribution of the magmatic and sedimentary record. This contribution integrates new U/Pb zircon ages, heavy mineral analyses and biostratigraphic constraints from the Neogene sedimentary record of the fore‐arc and intra‐arc basins and volcano‐plutonic rocks of southwestern Colombia, to reconstruct these orogenic processes. The results reveal continuous arc magmatism since the Late Oligocene, with a major post‐Middle Miocene magmatic peak and exhumation. When integrated with other geological constraints, the tectonic evolution of the margin includes Eocene‐Oligocene oblique convergence with limited magmatic activity, followed by the initiation of a Late Oligocene‐Early Miocene arc that migrated to the east in the Middle Miocene, when it experienced a major increase in magmatic activity, crustal deformation, exhumation and thickening. This orogenic evolution is related to the shallowing of the slab dip due to the subduction of the Neogene Nazca Plate.     

Crack patterns in clayey soils: Experiments and modeling

The paper presents an experimental and numerical study to investigate the behavior of desiccated clayey soils. The performed tests permit to evaluate the crack pattern as well as the tensile strength as a function of suction. A new model that relates the porosity evolution to the suction and to the tensile strength was developed and implemented in the finite element program CODE_BRIGHT. The proposed model captured the initiation and propagation of cracks in a thin layer of desiccated clay and predicted crack patterns in terms of the Minkowski densities (i.e. average crack length and crack intensity factor). The effect of the heterogeneity of the tested specimens, modeled by random clusters, was also quantified. Copyright © 2011 John Wiley & Sons, Ltd.     

Cyclical salt efflorescence weathering: an invisible threat to the recovery of underground mine environment for tourist exploitation

Enhancing the value of an underground mine environment for tourist exploitation involves altering the physico-chemical balance of stone materials whose original mechanical properties guaranteed the structural stability of the site’s galleries and chambers. Humidity and temperature changes caused by the public exhibition of this kind of assets are the main causes of such disorders. After the intervention in the Agrupa-Vicenta mine in La Union (Spain) there were still runoff-water leaks into the mine. These water runoffs through the fault and schistosity planes of the enclosing rock mass give rise to salt precipitation over time. Adapting this mine and turning it into a museum have meant a decrease in relative indoors humidity and an increase in temperature. These variations have caused rocks, which were stable in the original conditions, to increase their rate of physico-chemical weathering due to the polycyclic supergene alteration of the metal sulfides they contain. The resulting release of sulfates into the solution and their subsequent precipitation as single and double salt efflorescence causes haloclasty, deteriorating the rock’s mechanical properties and diminishing the structural stability of the operation. This paper presents the results of characterizing the supergene mineral phases of salt efflorescence in the rock bed enclosing an underground sulfide mine value enhanced for tourist exploitation. Dangers for the structural stability of this type of architectural intervention, associated to the formation of efflorescences, are also identified; these efflorescences are caused by the weathering of rocks that make up its supporting structure.     

Hydrochemical and isotopic characterization of the hydrological budget of a MAB Reserve: Mar Chiquita lagoon,province of Buenos Aires,Argentina

Mar Chiquita is a coastal lagoon located in the Argentine Buenos Aires province in South America. The aim of this study was to perform a hydrochemical and stable isotopes characterization in order to better the understanding of the hydrology of the Mar Chiquita lagoon’s catchment and its water budget. Groundwater samples were taken from 144 wells and 21 samples from main streams, and seven lagoon water samples were also collected. Chemical analyses were carried out using standard laboratory methods, and isotopic determinations were made through laser spectroscopy using a DLT-100 liquid–water isotope analyzer. Hydrochemical analysis permits a general classification of groundwater and streamwater as sodium bicarbonate waters, while the lagoon chemical composition shows an evolution toward seawater composition, from the north to its mouth, which is located southerly. Isotopic data show a source of aquifer recharge from rainfall and a groundwater domain into the streams’ flow. Three main components can be recognized as end members in a plot of electrical conductivity (EC) versus δ¹⁸O: seawater, streamwater and groundwater. Obtained EC values for groundwater in the discharge zone (EC average value = 3,516 μS/cm) allow minimizing its direct contribution and to take into consideration two dominating end members: streamwater and seawater. Mar Chiquita lagoon’s water falls close to the line between streamwater and seawater end members according to its EC and δ¹⁸O. The obtained seawater proportion for these samples ranges from 84 % in the lagoon’s mouth to around 0 % in the more distal area.     

Frequency of hyperbolic and interstellar meteoroids

Hyperbolic meteor orbits from the catalog of 64,650 meteors observed by the multistation video meteor network located in Japan (SonotaCo 2009) have been investigated with the aim of determining the relation between the frequency of hyperbolic and interstellar meteors. The proportion of hyperbolic meteors in the data decreased significantly (from 11.58% to 3.28%) after a selection of quality orbits, which shows its dependence on the quality of observations. Initially, the hyperbolic orbits were searched for meteors unbound due to planetary perturbation. It was determined that 22 meteors from the 7489 hyperbolic orbits in the catalog (and 2 from the selection of the orbits with the highest quality) had had a close encounter with a planet, none of which, however, produced essential changes in their orbits. Similarly, the fraction of hyperbolic orbits in the data, which could be hyperbolic by reason of a meteor's interstellar origin, was determined to be at most 3.9 × 10^?2. From the statistical point of view, the vast majority of hyperbolic meteors in the database have definitely been caused by inaccuracy in the velocity determination. This fact does not necessarily assume great measurement errors, since, especially near the parabolic limit, a small error in the value of the heliocentric velocity of a meteor can create an artificial hyperbolic orbit that does not really exist. The results show that the remaining 96% of meteoroids with apparent hyperbolic orbits belong to the solar system meteoroid population. This is also supported by their high abundance (about 50%) among the meteor showers.     

Geostatistical improvements of evapotranspiration spatial information using satellite land surface and weather stations data

The objective of the present study was to use the simple cokriging methodology to characterize the spatial variability of Penman–Monteith reference evapotranspiration and Thornthwaite potential evapotranspiration methods based on Moderate Resolution Imaging Spetroradiometer (MODIS) global evapotranspiration products and high-resolution surfaces of WordClim temperature and precipitation data. The climatic element data referred to 39 National Institute of Meteorology climatic stations located in Minas Gerais state, Brazil and surrounding states. The use of geostatistics and simple cokriging technique enabled the characterization of the spatial variability of the evapotranspiration providing uncertainty information on the spatial prediction pattern. Evapotranspiration and precipitation surfaces were implemented for the climatic classification in Minas Gerais. Multivariate geostatistical determined improvements of evapotranspiration spatial information. The regions in the south of Minas Gerais derived from the moisture index estimated with the MODIS evapotranspiration (2000–2010), presented divergence of humid conditions when compared to the moisture index derived from the simple kriged and cokriged evapotranspiration (1961–1990), indicating climate change in this region. There was stronger pattern of crossed covariance between evapotranspiration and precipitation rather than temperature, indicating that trends in precipitation could be one of the main external drivers of the evapotranspiration in Minas Gerais state, Brazil.