Patinas developed in environmental burial conditions: the Neolithic steles of Reguers de Seró (Lleida,Spain)

Background, aim and scope  

Weathering patinas in rocks are the result of interaction processes between rock surfaces and atmosphere, biosphere and soil. Therefore, their textural and mineral composition is strongly related to environmental and bioactivity conditions. Whereas the development of weathering patinas in atmospheric conditions is well documented (e.g. typical Mediterranean patina), only very few studies focus on their formation in a burial environment. Our study of patinas developed on the tumular structure of Reguers de Seró deals with the knowledge of burial patinas from a textural and mineralogical point of view. The aims of this study include: (1) the characterisation of the rock used in this megalithic monument as well as inferences regarding the origin of the raw material; (2) the evaluation of the patinas developed on the surface of the carved steles; and (3) the discussion of the environmental conditions (atmospheric or burial) that favoured the development of the patinas.     

The Orange-Brown Patina of Salisbury Cathedral (West Porch) Surfaces: Evidence of its Man-Made Origin (5 pp)

Goal, Scope and Background In this paper, we attempt to elucidate the composition and origin of the orange patina on the surfaces of the West-Porch of Salisbury Cathedral by comparison to other known patinas: (i) the orange-brown patina on the marble surfaces of the Acropolis in Athens and the Arch of Titus in Rome whose analyses have shown very high amounts of phosphates, and generally amino acids from animal-skin glue or other protein binders; (ii) the phosphated patinas which also contain oxalates, found in 1996 on Catalonian calcareous sandstones and in the calcareous dolomites of the Monastery of Silos, Spain, whose origin is either the application of calcium caseinate, or egg yolk and animal glue; and (iii) the patinas with only oxalates found in some of Verona's monuments (St Zeno) and Spanish sites as in the Monastery of Guadalupe and Cuenca cathedral, formed either by the mineralization of algal filaments or by biological reactions yielding oxalate from yolk egg (added to stone as part of preservative empirical treatments). Methods In the winter of 2003, the West-Porch of Salisbury Cathedral received conservation works, but the old patina was not entirely removed. This fact has allowed us to collect the samples for its study. The IR spectra were registered with a Golden Gate ATR Mk II system using attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectrometry. Mineral composition was determined by XRD (Philips PW 1710 spectrometer with Cu tube), whereas major and trace elements analyses were performed by XRF (Philips PW1480 PW). Microscopy examination was performed on a Leica M655 microscope. Phosphate, oxalate, calcium and sulphate contents were analysed by usual chemical methods. Results ATD-FTIR spectra of the Salisbury's patina exhibit peaks at 2361, 2341 and 671 cm–1 (assigned to phosphates); 3410, 1680, 1620, 1122 and 602 cm–1 (assigned to sulphates); and 1447/1437 and 876 cm–1 (attributed to carbonates). The little peaks at 1620 and 798 cm–1 could be assigned to oxalates. XRD and XRF have led to identify the carbonates, phosphates and sulphates as pertaining to the species dolomite, hydroxyapatite and gypsum, respectively. Oxalates are detected only in small amounts by chemical analyses but wewellite and weddellite have not been well identified. The interface between the patina and the calcareous dolomite is very uneven and full of cavities in certain cases, but well-defined and rather smooth in other cases. In accord with the very small amounts of the oxalates found, remnants of micro-organisms are not detected in the patinas. Discussion The Salisbury's patina is a composite material formed by particulates and matrix constituents. Regarding the patina particulate, e.g. animal bones, it is necessary to refer to the apatite phase composition. The bone mineral contains 4–8 wt % of carbonate in animal body and its presence in the apatite phase is advantageous as it increases the mechanical strength. We think that FTIR bands at around 1440 and 876 cm–1 arise from vibration of CO32– ions, but not necessarily from the limestone. They could be attributed to carbonated hydroxyapatite through the substitution of groups PO43– for CO32– in the lattice of hydroxyapatite. Concerning the matrix and also from the FTIR spectra, the absence of specific bands of the following species: proteins (3350–3225, 1660, 1550–1535, 1270–1230 and 620 cm–1), oils (1778, 1738 and 1051 cm–1), bee waxes (3000, 1470, 720–730 and 1700 cm–1) and aged egg-yolk (2954, 2920, 2850, 1650, 1549, 1465 and 1240 cm–1) had led us to exclude these usual binders. On the other hand, the amount of sulphates in the paste that covers the walls of the Salisbury's Cathedral is excessively high (above 20% in weight) to consider it as a biotransformation product of calcium oxalate from fungal biofilms. Consequently, we must think that the gypsum found in the samples has a man-made origin (it was deliberately added as part of a protective paste) and that it is the matrix searched for. Thus, we deduce that the patina of Salisbury's Cathedral is a special stucco made mixing plaster with powdered bone (the colour of the bones is the same that it exhibits in the patina), low quantities of an uncharacterized binder (collagen, possibly) and water. Conclusion We believe that the patina of the Salisbury's Cathedral is a variant of the Greco-Latin empirical protective treatment that included bone as a hardening material. Nevertheless, we also think that the presence of the bones in the paste could be related to an aesthetical intention: gaining a warm tone for the original stone through the ochre colour of the bones. Recommendation and Perspective Our results have been an excuse to contribute to the controversy started at the 80's on the origin of orange-brown patinas observed on stone surfaces of Greco-Latin and medieval monuments. There are two major theories on provenance: biological vs. man-made. In Salisbury Cathedral, neither of them has been proven through scientific evidence as yet. Our opinion is that Salisbury patina can be classified into the man-made group.     

Pseudomorphs of barite and biogenic ZnS after phyto-crystals of calcium oxalate (whewellite) in the peat layer of a poor fen

Pseudomorphs of barite (BaSO₄) and Cd-rich ZnS after whewellite (CaC₂O₄·H₂O) occur within remnants of Scots pine bark tissues in the peat layer of a poor fen located near a zinc smelter in south Poland. A two-step formation of the pseudomorphs is postulated based on SEM observations: (1) complete dissolution of whewellite, possibly caused by oxalotrophic bacteria, and (2) subsequent bacterially induced precipitation of barite and spheroidal aggregates of ZnS together with galena (PbS) in voids left by the dissolved whewellite crystals. Local increase in pH due to microbial degradation of whewellite, elevated concentrations of Zn(II) and Ba(II) in pore water due to the decomposition of atmospheric particles of sphalerite and barite in the acidic (pH 3.5–3.8) environment, oxidation of S species during drying and rewetting of the peat layer, and subsequent partial reduction of sulfate anions by sulfur-reducing bacteria were all factors likely involved in the crystallization of ZnS and barite in the microenvironment of the post-whewellite voids.     

The Beginning of Survival

The majority of coal ash generated by electric utilities and power plants of industrial manufacturers is disposed of in landfills; the remainder is used primarily as admixtures in construction materials. Predictive computer models used to assess the environmental impact of disposal or utilization need quantitative information on ash composition and mineralogy. Typically, compositions are reported as elemental concentrations, but this data does not indicate the mineral or glass (amorphous) phases in which the elements are contained. Such phases affect the leaching mechanisms and rates. X-ray diffraction and scanning electron microscopy combined with energy dispersive X-ray spectrometry, common methods for qualitative mineral identification and particle characterization, were used to quantify coal ash mineral compositions. Samples of industrial coal ash from a stoker boiler and a fluidized bed combustion (FBC) system were analyzed and the results were compared to those for a standard sample of coal ash from the National Institute of Standards and Testing (NIST1633a). The results show that the stoker-boiler ash is similar in composition to the NIST sample. Mullite (AI₆Si₂O₁₃) dominates the composition of the crystalline fraction and silica (SiO₂,) dominates the composition of the amorphous fraction. The FBC ash contains the same minerals, but with large proportions of calcium-based phases: anhydrite (CaSO₄), lime (CaO), calcite (CaCO₃), and portlandite (Ga(OH)₂).     

Early stage of weathering of medieval-like potash–lime model glass: evaluation of key factors

Purpose  

Throughout history, a consequent part of the medieval stained glass windows have been lost, mostly because of deliberate or accidental mechanic destruction during war or revolution, but, in some cases, did not withstand the test of time simply because of their low durability. Indeed, the glasses that remain nowadays are for many in a poor state of conservation and are heavily deteriorated. Under general exposure conditions, stained glass windows undergo different kinds of weathering processes that modify their optical properties, chemistry, and structure: congruent dissolution, leaching, and particle deposition (the combination of those two leading together to the formation of neocrystallisations and eventually crusts). Previous research has studied the weathering forms and the mechanisms from which they are originated, some others identified the main environmental parameters responsible for the deterioration and highlighted that both intrinsic (glass composition) and extrinsic (environmental parameters) factors influence glass degradation. Nevertheless, a clear quantification of the impact of the different deterioration extrinsic factors has not been performed.     

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes.     

Heavy metal-rich wastes sequester in mineral phases through a glass-ceramic process

Certain sludges generated by industry are rich in contaminating elements and are a major environmental problem. In this study, we determine the ability of these contaminating elements to be incorporated into a glass-matrix and in various mineral phases after a crystallization process. The contaminating elements studied were obtained from sewage sludges (SS) and galvanic sludges (GS), our raw materials. The sludge samples were taken from urban wastewater treatment plant in Catalonia (NE Spain) with high levels of phosphorus oxide (P(2)O(5)). In silica glasses, P(2)O(5) acts as a network former. We determined the chemical composition of both the SS and GS, as well as their thermal behaviour by differential thermal analysis and thermal gravimetric analysis (DTA-TG) to obtain their melting curves. The vitreous transition temperature of the obtained glass was established by dilatometer technique at 725 degrees C. The DTA-TG curve of the glass obtained has an exothermal wide peak at 860 degrees C corresponding to crystallization of the two phases: a spinel phase and a phosphate phase. A second exothermal wide peak at 960 degrees C was attributed to the crystallization of aluminium pyroxene, anorthite and fluor-apatite, with two exothermal phenomena attributed to the evolution of these phases. An exothermal peak at 1100 degrees C was attributed to gehlenite crystallization. Scanning electron microscope observations and energy-dispersed X-ray spectroscopy microanalyses of glass-ceramic showed that the contaminating elements were concentrated in the spinel phases, which are the first phases to crystallize during the cooling of glass. Finally, the spinel structure permits the incorporation of all the contaminating elements into it.     

Risk assessment of boron in glass wool insulation

Background, aim and scope  Glass wools are man-made vitreous fibres, which consist principally of sodium, calcium and magnesium silicates, but may contain smaller amounts of other elements, including boron. The boron contents originate from the use of borates in the glass melting process as a glass former and a flux agent. During the production and application of glass wool insulation products, workers may legally be exposed to glass fibre up to the occupational limit value, commonly of 1 fibre/cm³. However, in practice, the fibre exposure will be at least ten times lower. Boron is a non-metallic element widely distributed in nature, where it occurs as boric acid, borates and borosilicates. Humans are mainly exposed to boron via vegetarian food and drinking water, mineral supplements and various consumer products. Boron is an essential element for plant growth, but the essentiality for humans is not proven, although intakes of trace amounts of the element seem to be useful for bone health and proper brain function; higher concentrations of boron, however, may be toxic. In relation to the European Union legislation on dangerous substances, an EU Expert Group has recommended classifying boric acid and borates with risk phrases for reproductive toxicity. The aim of this paper is to assess whether the new EU hazard classification of boron compounds should imply that glass wool products used for building insulation in the future should be labelled, “may impair fertility and cause harm to the unborn child”, because of the low boron content. Materials and methods  Boron intakes are estimated in a worst-case occupational situation with human exposure to glass wool fibres at the occupational limit of 1 fibre/cm³ by calculation of the mass of the amount of fibres inhaled during an 8-h work day. Fibres are supposed to be cylinders of glass with a length of 30 μm, an average diameter of 1.5–2 μm and containing either 1.5% or 3.5% boron. As a worst-case scenario, the density of the fibres is set to 2,700 kg/m³. The inhalation rate of the individuals at moderate work load was set to 2 m³/h. A worst-case scenario also corresponds to 100% retention and to 100% solubility of the retained fibres in the lungs. Results  With the normal boron content of 1.5% in glass wool fibres for building insulation, the extra daily occupational boron intake/uptake will be 0.03–0.06 mg B for 5 days a week. For more uncommon glass wool with maximum boron content of 3.5%, the worst-case daily boron intake/uptake will be 0.08–0.16 mg B. The main boron exposure in the general population is from vegetarian food, and the average daily dietary intake with food is estimated to 1.2–1.5 mg B/day. In addition, significant intakes may come with drinking water, especially from mineral water. In some instances, exposure from mineral supplements, cosmetics and other consumer products may be significant. For example, individuals taking mineral supplements, e.g. for bodybuilding, may have an additional intake to that of 1–10 mg/day. During the years, various organisations have recommended safe intake values for boron. Recently, the Scientific Panel on Dietetic Products, Nutrition and Allergies of the European Food Safety Authority (EFSA) has established the ‘Tolerable Upper Intake Level’ (UL) for the intake of boron (boric acid and borates) at 0.16 mg B/kg body weight per day or about 10 mg B/day for an adult. Discussion  The calculated, worst-case exposure scenario during an 8-h work day will result in an extra daily boron intake that only corresponds to about 10% of the average daily adult boron intakes through food and drinks of about 1.5 mg. The inter-individual variations in boron intakes from foods, water and supplements will be much greater than an eventual, very worst-case, additional intake of boron from inhalation of glass wool fibres. In addition, the combined intakes are far lower than the ‘Tolerable Upper Intake Level’ of 10 mg B/day for a person weighing 60 kg, as recommended by the European Food Safety Agency. The potential boron intake from inhalation of glass wool fibres is also much lower than boron intakes by workers in the boron industry, who at the present occupational limit value will be exposed to 50 mg of boron 5 days a week, or 100 times more than the worst case for glass wool fibres. Furthermore, in practice, exposure levels will mostly be ten to 100 times lower than the occupational limit used here as a worst case. Conclusions  The estimated boron intake from inhalation of glass wool fibres in occupational settings will be insignificant and without any health risks, even in the case of non-compliance with the occupational limit value. Any proposal requiring hazard labels on commercial glass wool products for building insulation, because of the boron content, is not supported by the present scientific knowledge. Recommendations and perspectives  The European Commission should ensure that the new EU hazard classification of boron compounds is not applied to commercial glass wool products for building insulation having a low content of boron.     

Heterogeneous uptake of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) onto mineral dust aerosol under variable RH conditions

We have carried out kinetic studies to characterize the heterogeneous decay of octamethylcyclotetrasiloxane (D₄) and decamethylcyclopentasiloxane (D₅) in the presence of representative mineral dust aerosol in order to obtain a better understanding of the atmospheric fate of these siloxanes. The heterogeneous chemistry of D₄ and D₅ with various mineral dusts was studied in an environmental aerosol reaction chamber using FTIR absorption spectroscopy to monitor the reaction. The apparent heterogeneous uptake coefficient, γ_app, for D₄ and D₅ with various mineral dusts was measured under dry conditions and as a function of relative humidity (RH). In addition, the effect of initial D₄ and D₅ concentration on the rate and yield of the reaction was examined. The uptake coefficient, γ_app, for D₄ and D₅ was similar for the most reactive aerosols tested, with kaolinite ≈hematite > silica. Limited uptake onto carbon black and calcite surfaces was observed for either siloxane. Reaction with hematite and kaolinite resulted in multilayer coverages, suggesting extensive polymerization of D₄ and D₅ on the aerosol surface.     

Source apportionment of ambient PM2.5 at five spanish centres of the european community respiratory health survey (ECRHS II)

Fine particulate matter (PM_2.5) was sampled at 5 Spanish locations during the European Community Respiratory Health Survey II (ECRHS II). In an attempt to identify and quantify PM_2.5 sources, source contribution analysis by principal component analysis (PCA) was performed on five datasets containing elemental composition of PM_2.5 analysed by ED-XRF. A total of 4–5 factors were identified at each site, three of them being common to all sites (interpreted as traffic, mineral and secondary aerosols) whereas industrial sources were site-specific. Sea-salt was identified as independent source at all coastal locations except for Barcelona (where it was clustered with secondary aerosols). Despite their typically dominant coarse grain-size distribution, mineral and marine aerosols were clearly observed in PM_2.5. Multi-linear regression analysis (MLRA) was applied to the data, showing that traffic was the main source of PM_2.5 at the five sites (39–53% of PM_2.5, 5.1–12.0 μg m⁻³), while regional-scale secondary aerosols accounted for 14–34% of PM_2.5 (2.6–4.5 μg m⁻³), mineral matter for 13–31% (2.4–4.6 μg m⁻³) and sea-salt made up 3–7% of the PM_2.5 mass (0.4–1.3 μg m⁻³). Consequently, despite regional and climatic variability throughout Spain, the same four main PM_2.5 emission sources were identified at all the study sites and the differences between the relative contributions of each of these sources varied at most 20%. This would corroborate PM_2.5 as a useful parameter for health studies and environmental policy-making, owing to the fact that it is not as subject to the influence of micro-sitting as other parameters such as PM₁₀. African dust inputs were observed in the mineral source, adding on average 4–11 μg m⁻³ to the PM_2.5 daily mean during dust outbreaks. On average, levels of Al, Si, Ti and Fe during African episodes were higher by a factor of 2–8 with respect to non-African days, whereas levels of local pollutants (absorption coefficient, S, Pb, Cl) showed smaller variations (factor of 0.5–2).     

Enrichment of trace elements in the clay size fraction of mining soils

Reactive waste dumps with sulfide minerals promote acid mine drainage (AMD), which results in water and soil contamination by metals and metalloids. In these systems, contamination is regulated by many factors, such as mineralogical composition of soil and the presence of sorption sites on specific mineral phases. So, the present study dedicates itself to understanding the distribution of trace elements in different size fractions (<2-mm and <2-μm fractions) of mining soils and to evaluate the relationship between chemical and mineralogical composition. Cerdeirinha and Penedono, located in Portugal, were the waste dumps under study. The results revealed that the two waste dumps have high degree of contamination by metals and arsenic and that these elements are concentrated in the clay size fraction. Hence, the higher degree of contamination by toxic elements, especially arsenic in Penedono as well as the role of clay minerals, jarosite, and goethite in retaining trace elements has management implications. Such information must be carefully thought in the rehabilitation projects to be planned for both waste dumps.     

Adsorption of arsenic(V) by iron-oxide-coated diatomite (IOCD)

Purposes and aims  

Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water.     

Sorption of thallium(I) onto geological materials: influence of pH and humic matter

The sorption behaviour of the severely toxic heavy metal thallium (Tl) as a monovalent cation onto three representative materials (goethite, pyrolusite and a natural sediment sampled from a field site) was examined as a function of pH in the absence and presence of two natural humic acids (HAs), using ²⁰⁴Tl(I) as a radiotracer. In order to obtain a basic understanding of trends in the pH dependence of Tl(I) sorption with and without HA, sorption of HAs and humate complexation of Tl(I) as a function of pH were investigated as well. In spite of the low complexation between Tl(I) and HAs, the presence of HAs results in obvious alterations of Tl(I) sorption onto pyrolusite and sediment. An influence on Tl(I) sorption onto goethite was not observed. Predictions of K_d (distribution coefficient) for Tl(I) on goethite in the presence of HAs, based on a linear additive model, agree well with the experimental data, while a notable disagreement occurs for the pyrolusite and sediment systems. Accordingly, it is suggested that HAs and goethite may act as a non-interacting sorbent mixture under the given conditions, but more complex interactions may take place between the HAs and the mineral phases of pyrolusite or sediment.     

Endocrine disruptors in bottled mineral water: total estrogenic burden and migration from plastic bottles

Background, aim, and scope  Food consumption is an important route of human exposure to endocrine-disrupting chemicals. So far, this has been demonstrated by exposure modeling or analytical identification of single substances in foodstuff (e.g., phthalates) and human body fluids (e.g., urine and blood). Since the research in this field is focused on few chemicals (and thus missing mixture effects), the overall contamination of edibles with xenohormones is largely unknown. The aim of this study was to assess the integrated estrogenic burden of bottled mineral water as model foodstuff and to characterize the potential sources of the estrogenic contamination. Materials, methods, and results  In the present study, we analyzed commercially available mineral water in an in vitro system with the human estrogen receptor alpha and detected estrogenic contamination in 60% of all samples with a maximum activity equivalent to 75.2 ng/l of the natural sex hormone 17β-estradiol. Furthermore, breeding of the molluskan model Potamopyrgus antipodarum in water bottles made of glass and plastic [polyethylene terephthalate (PET)] resulted in an increased reproductive output of snails cultured in PET bottles. This provides first evidence that substances leaching from plastic food packaging materials act as functional estrogens in vivo. Discussion and conclusions  Our results demonstrate a widespread contamination of mineral water with xenoestrogens that partly originates from compounds leaching from the plastic packaging material. These substances possess potent estrogenic activity in vivo in a molluskan sentinel. Overall, the results indicate that a broader range of foodstuff may be contaminated with endocrine disruptors when packed in plastics.     

Influence of thermally activated paper sludge on the behaviour of blended cements subjected to saline and non-saline environments

Background, aim and scope  One of the problems to affect Portland cement matrices is low resistance to aggressive agents, due principally to the presence of a high content of portlandite in the hydrated cements. Pozzolanic materials have played an important role in the improving the durability of cement-based materials for decades. This work studies the behaviour of cement mortar matrices blended with 10% calcined paper sludge (source for metakaolinite) and exposed to different environmental conditions (saline and non-saline environments) after 6 and 12 months of exposure. Materials and methods  Two cements were studied: an ordinary Portland cement (CEM 1, 42.5R), acting as reference cement, and a blended cement formulated by mixing 90% (by mass) of CEM 1, 42.5R with 10% (by mass) of paper sludge calcined at 700°C for 2 h. The specimens were exposed 1 year to saline and non-saline environments. All the mineralogy samples were studied through X-ray diffraction and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray analyser. The in-depth study on ionic mobility was performed on samples subjected to natural exposure (coast and tableland) for 6 and 12 months. Results  Portland cement was composed of quartz, calcite, calcium hydroxide and tobermorite gels. The pozzolanic cement (10% calcined paper sludge) is of the same composition but a high calcite concentration and barium carbonate. SEM analysis from coastline show deposits of variable composition. The deposits are identified on the surface of different mineral components. The minerals from tableland are much fractured, i.e. calcite and feldspars. Inside the fractures, the deposits and the ions are located and trapped superficially. Discussion  SEM analysis of control cement Portland and 10% calcined paper sludge shows deposits on quartz and calcite with a very high concentration of Pb, Zn, Cl and barium sulphate. A very porous aspect is due to the presence of the different aggregate types. This porous configuration permits retention of the ion environment. The pozzolanic cement in environments subject to the saline mist favours the retention and transport of ions observed. Something similar also happens with the increase in exposure to outdoor weather. Non-saline samples show temperature changes (ice or thaw cycles). Barium retention is kept on the surface in fracture lines by the gelification processes. In general, it may be inferred that an increase in exposure time increases the diffusion of ions towards test piece interiors. The chemical composition profiles show that the ions present different penetration speeds. Conclusions  The results indicate the better vulnerability of pozzolanic cements from calcined paper sludge in saline and non-saline environments. The cements with a 10% addition of calcined paper sludge favour retention and transport of ion has been observed. Recommendations and perspectives  Today, projects are centred on a new recycling line for industrial waste of this kind, with special attention on its incorporation in cement manufacture as a pozzolanic material, setting the most appropriate activation conditions of the mineralogical compound in this waste (kaolinite and metakaolinite) and taking them as a starting point for this project. The use of pozzolanic cement with 10% addition of calcined paper sludge is a system which favours ionic retention.     

Semivolatile behavior of dicarboxylic acids and other polar organic species at a rural background site (Nylsvley,RSA)

In this study aerosol samples from the South African savanna were analyzed for their polar organic constituents. Samples were collected with a front/back-up filter tandem system of quartz fiber filters (dual filter strategy). In all samples (n=15) dicarboxylic acids and a variety of phthalates, aldehydes and monocarboxylic acids were observed. Oxalic acid was the dominating compound with an average amount of 79.2 ng m⁻³ on the front filter and 11.3 ng m⁻³ on the back-up filter. The presence of significant concentrations of dicarboxylic acids on the back-up filter was rather unexpected. There are two possible sources to explain the presence of individual compounds on the back-up filter – particle penetration through the front filter or adsorption of compound parts from the gas phase. Interpretation of the data indicates that the dicarboxylic acid concentrations on the back-up filters appear to be caused by the adsorption of gaseous organic species. Dicarboxylic acids semivolatilic behavior is evident with this results. This conclusion refutes the commonly held view that dicarboxylic acids in the atmosphere were associated with the aerosol phase only. Additionally, it was found that the distribution of dicarboxylic acids between the gas and particle phase in the atmosphere is not only dependent on their vapor pressures. The actual gas phase concentration appears to be more determined by the chemical properties of the particles than by pure physical influences. Surprisingly, malonic acid exhibits an anomaly, as it does not show a semivolatile tendency.     

Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces

Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (K_d) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log K_d and the corresponding water solubility of the subcooled liquid (log S_w) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on K_d. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal’s forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log K_d and log S_w may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.     

Atmospheric fall-out of metals around the Murano glass-making district (Venice,Italy)

Background, aim and scope  

Murano’s glass-makers have held a monopoly on quality glass-making for centuries known all over the world. Artistic glass manufacture entails exposure to complex mixtures of pollutants, including metals. A few studies have reported high levels of trace elements in marine waters, sediments and mussels around Murano and shown that emissions from Murano glass-making workshops significantly influence air quality in the Venice area. Nevertheless, to date, there is very little information on atmospheric concentrations and virtually none on atmospheric deposition fluxes of trace elements around the island. This study presents data on the distribution of trace elements in the air and atmospheric depositions around Murano, based on a 2-year sampling period.     

Modeling interactions of Hg(II) and bauxitic soils

The adsorptive interactions of Hg(II) with gibbsite-rich soils (hereafter SOIL-g) were modeled by 1-pK surface complexation theory using charge distribution multi-site ion competition model (CD MUSIC) incorporating basic Stern layer model (BSM) to account for electrostatic effects. The model calibrations were performed for the experimental data of synthetic gibbsite-Hg(II) adsorption. When [NaNO(3)] > or = 0.01M, the Hg(II) adsorption density values, of gibbsite, Gamma(Hg(II)), showed a negligible variation with ionic strength. However, Gamma(Hg(II)) values show a marked variation with the [Cl(-)]. When [Cl(-)] > or = 0.01M, the Gamma(Hg(II)) values showed a significant reduction with the pH. The Hg(II) adsorption behavior in NaNO(3) was modeled assuming homogeneous solid surface. The introduction of high affinity sites, i.e., >Al(s)OH at a low concentration (typically about 0.045 sites nm(-2)) is required to model Hg(II) adsorption in NaCl. According to IR spectroscopic data, the bauxitic soil (SOIL-g) is characterized by gibbsite and bayerite. These mineral phases were not treated discretely in modeling of Hg(II) and soil interactions. The CD MUSIC/BSM model combination can be used to model Hg(II) adsorption on bauxitic soil. The role of organic matter seems to play a role on Hg(II) binding when pH>8. The Hg(II) adsorption in the presence of excess Cl(-) ions required the selection of high affinity sites in modeling.     

Effects of copper(II) and copper oxides on THMs formation in copper pipe

Little is known about how the growth of trihalomethanes (THMs) in drinking water is affected in copper pipe. The formation of THMs and chlorine consumption in copper pipe under stagnant flow conditions were investigated. Experiments for the same water held in glass bottles were performed for comparison. Results showed that although THMs levels firstly increased in the presence of chlorine in copper pipe, faster decay of chlorine as compared to the glass bottle affected the rate of THMs formation. The analysis of water phase was supplemented by surface analysis of corrosion scales using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDX). The results showed the scales on the pipe surface mainly consisted of Cu₂O, CuO and Cu(OH)₂ or CuCO₃. Designed experiments confirmed that the fast depletion of chlorine in copper pipe was mainly due to effect of Cu₂O, CuO in corrosion scales on copper pipe. Although copper(II) and copper oxides showed effect on THMs formation, the rapid consumption of chlorine due to copper oxide made THM levels lower than that in glass bottles after 4 h. The transformations of CF, DCBM and CDBM to BF were accelerated in the presence of copper(II), cupric oxide and cuprous oxide. The effect of pH on THMs formation was influenced by effect of pH on corrosion of copper pipe. When pH was below 7, THMs levels in copper pipe was higher as compared to glass bottle, but lower when pH was above 7.