Air pollution records on selenite in the urban environment

Black crusts (BC) on selenite, i.e. gypsum stone used in buildings and monuments in the city of Bologna (northern Italy) have been studied.The crusts have been compared with genetically identical ones encountered on gypsum outcrops in the area surrounding the same city, in a relatively clean rural environment.Because of gypsum's high solubility, also in the past, BC began to form and embed particles of atmospheric aerosol as soon as the stone was used in construction, even though the SO₂ levels in the air were probably much lower than today. Unlike other types of stone (sandstone, limestone, marbles), selenite is currently undergoing a deceleration of dissolution processes, following the acidification of the environment caused by industrialisation. For this reason the BC on selenite are older (up to 580±45 yr), thicker (up to 4 cm) and far more stable than those encountered on other types of building stones used in the same area.The BC are stratified: at the base, in contact with the stone, the crust contains numerous prismatic black particles originating from wood combustion; immediately above the base layer these particles progressively increase; finally, in the outer part of the crust one encounters the characteristic black, spongy spherical fly-ash originating from the combustion of mineral oils.From the chemical point of view, a comparison between urban and rural crusts shows that elements such as C, Si, K, Fe, V, Cr, Ni, Zn, Ga, As and Pb are due to present-day and/or past pollutant sources within the city itself.Moreover, the chemical data from the stratigraphy of the BC show that, while C and K were more abundant in the past than now, elements such as Fe, V, Cr, (Mn, Ni), Cu, (Zn), (Ga), As, Pb characterise recent and current urban atmospheres.     

Origin,characteristics and morphology of weathering crusts on Istria stone in Venice

To evaluate the effects of the environment on weathering of monuments of Istria stone in Venice, systematic mineralogical, petrographical and elemental analyses of depth profiles were performed on samples of surficial crusts (dendritic black, compact black, grey and white). Decay products of deposition and interactions between gases and stone, including wind blown dust, marine salts, anthropic aerosol, gypsum and nitrates, are incorporated into the mineral matrix down to a depth of 10 mm. In areas sheltered from rain, where black and grey crusts are observed, the high general humidity, carbonaceous particles and deposition of aerosols lead to the development of gypsum and other salts. In compact and grey crusts decay products decrease; in grey crusts carbonaceous particles are reduced, but in compact black crust products of previous treatments are found. In white crusts, formed in areas experiencing effective wash-out, chemical and mechanical attack cause surface recession.     

Black layers on historical architecture

Background, aim and scope

The external surface of any building in urban polluted environment is unavoidably destined to be covered with layers that assume a grey to black colour and are generally called ‘black crusts’. These, according to standard protocols and glossary, are deteriorated surface layers of stone material; they can have variable thickness, are hard and fragile and can detach spontaneously from the substrate, which, in general, is quite decayed. Plain visual examination may lead to consider ‘black crusts’ all similar, whilst only a careful diagnostic investigation can distinguish ‘black crusts’ and the consequences of their formation on stone substrates. In this paper, various black layers on marble are studied and compared and the morphological and compositional characteristics discussed according to the related mechanisms of formation. Differences between old (hundred years) and recent crusts (30 years) are investigated and pointed out.

Materials and methods

Samples of black crusts collected from the Milan Cathedral façade (Candoglia Marble) have been studied and compared with the careful and synergic employ of traditional techniques: optical (transmission and reflected VIS light) and electron microscopy, X-ray spectrometry and micro-Fourier transform infrared spectroscopy.

Results

Visual examination of loose fragments does not allow to point out outstanding differences amongst the various samples; black layers have similar main mineral components, gypsum and airborne particles, with different spatial distribution. The microscopic studies allowed to point out the porosity differences, the gypsum crystallisation habit, different amount of embedded particles, level and progress of marble decay.

Discussion

The observations lead to define three main types of black crusts: black crust deriving from marble sulphation, compact deposit and encrustation due to exogenic materials deposition. Black crusts show evidence of sulphation in progress, without a clear continuity solution between crust and marble; the lack of separation is particularly evident in ‘recent’ crust, where the sulphation process is more active. Black compact deposits show a higher porosity than black crusts because gypsum is not coming from the chemical corrosion of the substrate but from outside; actually, in the former case, the substrate is sound. Encrustations show a highly regular crystal organisation of gypsum (close packed tabular crystals) that cannot be traced back to casual atmospheric deposit or to corrosion of the substrate but rather to the crystallisation of a solution coming from an external source. Also in this case, the marble is sound; evidence of the effect of some protection treatment is pointed out.

Conclusions

In spite of the apparent similarity of the examined samples, analytical results have evidenced three main types of black crusts: black crust with decayed substrate, compact deposit and black encrustation showing a sound substrate underneath. Experimental evidence of calcite grains sulphation in progress, taking place according to a model recently proposed, has been observed. Sulphation process is prevented where particular conservation treatments had been applied in the past.

Recommendations and perspectives

New experimental studies can be focussed to understand the specific conditions (measurements of micro-climatic and thermodynamic parameters) and mechanisms for black crusts formation in situ. The problem of the kinetic of the sulphation process of marble, the assessment of black layers formation in the case of different carbonate stone materials and the study of acid attack in presence of surface protecting layers deserve further investigation.     

Laser cleaning of historical limestone buildings in Bordeaux appraisal using cathodoluminescence and electron paramagnetic resonance

BACKGROUND: Most historical buildings in Bordeaux city are made of limestone. This yellowish-white rock is rather porous and highly sensitive to pollution. As a consequence of local weathering conditions, these buildings present a dark appearance due to the development of a superficial dark grey to black crust. METHODS: For the last decade, a campaign has been underway to clean these buildings. Eleven techniques of surface treatment have been used, including laser beam technology. As a contribution to the study of laser beam effects on stone buildings, two analytical methods have been used on clean versus unclean surfaces: Cathodoluminescence (CL) and Electron Paramagnetic Resonance (EPR), in addition to SEM-EDX and XRD. RESULTS: The black crust is composed of different types of particles: carbon porous micro-particles of industrial origin, atmospheric dust due to the erosion of soils and rocks, alumino-silicate particles from urban pollution; all these particles being cemented by gypsum. DISCUSSION: As far as heritage conservation is concerned, the laser surface treatment not only preserves the original patina of the stone, but also leaves surface smoothness unaltered. CONCLUSIONS AND PERSPECTIVES: CL and EPR data confirm that lasers--with highly controlled parameters--only get rid of the black crust and, thus, reveal the underneath layer, the so-called patina. This patina shows no luminescence, whereas the limestone on which it has grown shows a bright orange emission of CL. This indicates CL to be a fast and easy way to provide a high quality control for the restoration of polluted ancient stones.     

Application of spectrometric analysis to the identification of pollution sources causing cultural heritage damage

Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO₂-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.     

Composition of weathering crusts on sandstones from natural outcrops and architectonic elements in an urban environment

This work presents mineralogical and chemical characteristics of weathering crusts developed on sandstones exposed to various air pollution conditions. The samples have been collected from sandstone tors in the Carpathian Foothill and from buildings in Kraków. It has been stated that these crusts differ in both fabric and composition. The sandstone black crust from tors is rich in organic matter and composed of amorphous silica. Sulphate incrustations accompanied by dust particles have been only sometimes observed. Beneath the black crust, a zone coloured by iron (oxyhydr)oxides occurs. The enrichment of the surface crust in silica and iron compounds protects the rock interior from atmospheric impact. The sandstones from architectonic details are also covered by a thin carbon-rich black crust, but they are visibly loosened. Numerous salts, mainly gypsum and halite, crystallise here, thus enhancing deterioration of the rock. Moreover, spherical particles originated from industrial emissions are much more common. Gypsum in natural outcrops, forms isolated and well-developed crystals, whilst these found on the architectonic details are finer and densely cover the surface. Such diversity reflects various concentrations of acid air pollutants in solutions.     

Limestone Dissolution in Flue Gas Scrubbing: Effect of Sulfite

Batch limestone dissolution experiments were carried out in a pH stat apparatus at 55°C with CO2 sparging and dissolved sulfite. Particle size distribution, utilization, sulfite in solution, limestone type, and the approach to calcite equilibrium were all found to contribute to the limestone reactivity. In the absence of sulfite, limestone dissolution was controlled solely by mass transfer. For a given stone under mass transfer control, film thickness was found to be independent of pH. The dissolution rate in the presence of sulfite was controlled by a combined surface kinetics/mass transfer regime. SEM micrographs supported this conclusion. A surface rate correlation was developed which accounted for observed inhibition by an inverse dependence on calcium sulfite concentration at the limestone surface. While the form of the rate expression was applicable to all stones, the surface rate constant was stone dependent. A computer code which accounted for mass transfer with surface kinetics was tested against experimental observations of four limestone types. Changes in pH and the concentrations of calcium, carbonate, sulfite, sulfate, and adipic acid were accurately modeled.     

Different decay patterns observed in a nineteenth-century building (Palma,Spain)

The effects of atmospheric pollutants and climatic conditions were studied in a decayed column in the Seminary of Sant Pere. This nineteenth-century building is situated in the historic centre of Palma (Mallorca, Spain), less than 0.5 km from the sea. Samples were collected from the internal and external part of the crusts formed in the four sides of the column. The samples were analysed by means of thermal analysis, X-ray diffractometry, scanning electron microscopy, Fourier transform infrared spectroscopy and ion chromatography. Results show significant differences in the four sides of the column. A high degree of carbonate stone sulfation is observed in all of the samples analysed. A synergistic effect between atmospheric factors and micropollutants on the deterioration of stone is observed. A high uptake of atmospheric particulate matter is found in the external part of the black crusts.     

The characterisation of carbonaceous fly-ash particles from major European fossil-fuel types and applications to environmental samples

This paper describes the development of a technique to characterise carbonaceous fly-ash particles produced from five major European fuel-types (coal, oil, brown coal, peat and oil shale) using individual particle chemistries derived from energy dispersive spectroscopy as part of the EU COPERNICUS funded FLAME project. The final classification employed an hierarchy of quadratic discriminant functions such that 80% of the particles could be allocated to the correct fuel-type. The technique was then applied to particles extracted from the surface sediments of 196 lakes across four countries (UK, Estonia, Czech Republic and Ireland) so that the spatial distribution of impacts from these fuel sources could be determined. Spatial trends in fuel-type showed good agreement with known emission sources but absolute percentages were low in all countries due to high allocations to the “coal” fuel-type. It is thought that these high coal values are due to mineral particles surviving the acid pre-treatment. However, the results can still be used to determine sources of pollutant deposition. The technique is applicable to particles extracted from any depositional sink including, atmospheric collectors, building stone crusts, leaves and soils.     

Carbon isotope exchange during calcite sulphation

Sulphation of limestone and carbonaceous sandstone is a well-known process in the deterioration of natural stone, playing havoc with our cultural heritage over bygone decades. The overall mechanism in this process is not completely understood. Current studies using a laser-ablation technique followed by mass spectrometry indicated a surprising shift in carbon isotopes after sulphation. Naturally weathered century-old carbonaceous sandstone as well as laboratory exposed fresh stone of the same rocktype showed a consistent change in carbon isotopes (δ¹³C) during sulphation, indicating that atmospheric CO₂ plays a part in the process.     

Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: a new methodological approach

Introduction  

In this work, we propose an innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a methodological approach for the chemical characterisation of black crusts on stone monuments, associated with traditional micro-morphological (optical and scanning electron microscopy) and infrared spectroscopic techniques (FTIR).     

Consolidation of degraded ornamental porous limestone stone by calcium carbonate precipitation induced by the microbiota inhabiting the stone

Although it has already been shown that calcareous stone can be consolidated by using a bacterially inoculated culture medium, a more user-friendly method is the in situ application of a sterile culture medium that is able to activate, among the microbial community of the stone, those bacteria with a potential for calcium carbonate precipitation. In order to test this new method for stone consolidation, non-sterilized decayed porous limestone was immersed in sterile nutritional media. Results were compared to those of the runs in which stone sterilized prior to the treatment was used. The effects of the microbial community on stone consolidation were determined by recording the evolution of the culture media chemistry. The treated stone was tested for mechanical resistance and porosity. Results demonstrate that the tested media were able to activate bacteria from the microbial community of the stone. As a consequence of the growth of these bacteria, an alkalinization occurred that resulted in calcium carbonate precipitation. The new precipitate was compatible with the substrate and consolidated the stone without pore plugging. Therefore, a good candidate to in situ consolidate decayed porous limestone is the application of a sterile culture medium with the characteristics specified in the present study.     

Interaction of limestone grains and acidic solutions from the oxidation of pyrite tailings

To characterise the coatings formed and to analyse element partitioning between the aqueous and solid phase, suspensions were prepared with four grain sizes of limestone and three different amounts of acidic solution from oxidized pyrite tailings. In all cases, red coatings with three different layers covered the grain surface, sealing off the acidic solution. The inner layer was composed mainly of basaluminite, the middle layer of schwertmannite, and the outer layer of gypsum and jarosite. Zn, Cd and Tl were co-precipitated by Fe and Al; As and Pb were co-precipitated almost completely by Fe; and Cu formed mainly Cu sulphates. All trace elements reached almost total precipitation at pH 6.3, but the precipitation of As and Pb tended to decrease as the pH rose. Consequently, liming should be calculated so that the soil pH does not exceed 6.3. This calculation should take into account that the armouring of the limestone grains can cause underestimations in the amount of liming material needed.     

Seasonal changes in an intertidal community affected by sewage pollution

Seasonal changes in structure of a rocky intertidal community affected by sewage pollution at Quequén (Argentina) were studied over a period of 2 years. Most species showed a decrease in cover values in the polluted area. On the other hand, a small proportion of organisms favoured by organic enrichment predominated around the outfall during the period of study. Community structure was not significantly altered by frosts or windstorms. Desiccation is identified as the main physical stress. A combination of late spring high temperatures with extreme midday low-tides caused by northerly winds was responsible for heavy losses in dominant algae. Major seasonal changes in community structure were primarily due to variations in area covered by the chlorophyte Ulva lactuca, and crusts of blue-green algae and diatoms in the vicinity of the outfall. Highest diversity values were attained during either late winter or spring, due to increased abundances of several seasonal algae. Abundance of the dominant organism, the bivalve Brachidontes rodriguezi, remained stable, showing only slight, non-seasonal, changes. Since the absence of B. rodriguezi is an indication of heavy pollution, temporal stability of this species suggests that the intensity of sewage discharges did not vary over the period of study.     

Soiling of Building Materials

Six building materials were exposed at five sites in Birmingham, Alabama, to determine the rates of soiling by different levels of suspended particulate. The exposed materials were (1) painted cedar siding, (2) concrete block, (3) brick, (4) limestone, (5) asphalt shingles, and (6) window glass. Suspended particulate levels ranged from an annual geometric mean of 60 μg/m³ at the clean site to 250 μg/m³ at the most polluted site.

Degrees of soiling were determined by measuring reflectance from the opaque surfaces and haze through the glass. Excellent dose-response relationships were obtained for the white surfaces— painted cedar siding and asphalt shingles. The degree of soiling of the paints was directly proportional to the square root of the suspended particulate dose. The shingle soiling was directly proportional to the dose. These regression equations can account for from 74 to 92% of the variability in reflectance measurements.

Similar regressions for brick can account for from 34 to 50 % of the variability. Poor correlations were obtained for concrete, limestone, and window glass.     

石煤渣制橡胶填料的研究

以钛酸酯偶联剂为表面处理剂,对石煤渣进行表面改性处理,制得橡胶填料,测试了该填料对橡胶的补强作用,并与陶土、碳酸钙、炭黑等填料的补强性能进行了比较。实验表明,表面改性后的石煤渣填料对橡胶具有较好的补强作用,可完全替代碳酸钙、碳酸镁或陶土,产生较好的补强效果,用替代部分炭黑,可以减少炭黑用量,降低橡胶成本。     

白泥脱硫性能和副产品石膏脱水特性分析

造纸白泥作为造纸业的副产品已在部分电厂脱硫中得到应用,但仍然存在一些技术问题。采用XRD、EDS、SEM等表征手段研究造纸白泥的理化特性,分析了白泥脱硫副产品石膏难以脱水的原因。由于白泥中残留氢氧化钠产生的高pH值以及其中MgO等所起到的脱硫助催化作用,使得白泥的脱硫活性高于常规脱硫吸收剂石灰石;白泥浆液pH值较高,有利于提高脱硫效率,但不利于脱硫浆液中亚硫酸盐的氧化,石膏产物中CaSO3·1/2H2O含量偏高,导致石膏品质下降。研究结果对分析白泥脱硫石膏脱水困难原因,以及找出有效的解决措施有较大的参考价值。     

Effect of acid rain on building material of the El Tajín archaeological zone in Veracruz, Mexico

Three limestone slabs (approx. 20 cm2 each) were extracted from the El Tajin archaeological zone in Veracruz, Mexico. X-ray diffraction analysis revealed three components: calcite (81.2%), quartz (17.9%) and feldspar (0.9%). Calcite content by x-ray diffraction analysis was slightly higher than that determined by chemical reaction between the limestone sample and nitric acid. The latter analysis, carried out in triplicate, yielded a calcite content of 77.1%. Mean water absorption, density and porosity of the limestone samples were also determined. Dissolution of limestone samples was investigated using an experimental rainfall simulation chamber, in which the stone samples were irrigated with artificial rain matching the pH and the ionic composition with 40 rainfall samples collected at El Tajin from August 18, 2002, to April 9, 2003. According to calcium and bicarbonate net concentrations found in the effluent of the chamber, a chemical mechanism by which limestone at El Tajin is dissolved by acid rain is proposed. A model used to investigate the air transport pathways corresponding to precipitation events at El Tajin shows that air parcels come mainly from the Gulf of Mexico, although no directional preference is evident for acidic vs. non-acidic events.     

改性粉煤灰在酸雾治理方面的研究

为去除化工生产等过程中产生的酸雾废气,首先用水作用法、微波法和传统湿法对粉煤灰进行改性试验,结果显示:传统湿法中的碱法效果最佳,改性后粉煤灰的BET比表面积是改性前的8.23倍.再用改性后的粉煤灰与廉价易得的天然矿物沸石和熟石灰作为活性组分,制得一种新型的复合吸附剂.常温常压下,动态吸附盐酸雾,实验结果表明:由改性粉煤灰制作的吸附剂G对盐酸雾的吸附性能比未经改性的吸附剂W有所提高,在文中所述条件下,饱和吸附量由改性前的331.4 mg/g提高到改性后的445.2 mg/g.     

Growth reduction of the Japanese black pine corresponding to an air pollution episode

Changes of tree-ring widths of Japanese black pine (Pinus thunbergii Parl.) trees growing in air-polluted and unpolluted areas were analyzed. In the stand close to an industrial complex, a large reduction in the series of tree-ring index (TRI), which were computed by removing endogenous effects from the measured series, appeared from the 1960s to 1970s. This reduction in radial tree growth was not explained by the climatic response model calibrated for a pre-pollution period. TRI changes corresponding with changes in concentrations of sulfur dioxide (SO(2)), and a significant negative correlation between the TRI and SO(2) concentration were found in the polluted area. Reduction in tree-ring growth was not seen in the unpolluted area. These results indicate that the past reduction in the growth of Japanese black pine trees growing in an industrial area was mainly caused by SO(2).