Surface Consolidation of Pentelic Marble: Criteria for the selection of methods and materials - The Acropolis case (6 pp)

Goal and Scope In order to realize surface consolidation of Pentelic marble on the Acropolis monuments, we have collected the criteria that have to be fulfilled by the methods and materials without side effects on the marbles (and other stones). When the existing methods and materials did not satisfy the requirements (criteria), we invented new ones.Methods The criteria were collected from the literature, by thermodynamic and kinetic viewpoints, by laboratory experiments and in situ observations on monuments, both in Greece and in several countries in which the various methods and materials were applied. Concerning our method of ‘Inversion of sulfation’, performed by spraying a K2CO3 solution, its concentration and its temperature were controlled in order to have a total inversion (certified by liquid crystals) of gypsum back to CaCO3. For the new material of ours, ‘Reinforced Lime’, in order to eliminate the disadvantages of plain lime (low carbonation rate, low mechanical properties of CaCO3 formed, lack of carbonation in the bulk of lime), measurements of the rate of carbonation were performed in plain lime and in lime with a different CaCO3 concentration beforehand as well as in a different CO2 environments, using DTG and XRD to measure the rate of carbonation. The detachment (kg/cm2) of marble specimens stuck by lime in each case was also measured. A microscope was also used to measure the dimensions of the grain in each case as well as ammonium citrate and thymolphthalein to certify the depth of carbonation in each case. Part of the work was communicated in an international congress.Results A table with the criteria of the selection of the methods and materials for the consolidation of Pentelic marble surfaces (and other stones) was established. None of the employed methods and materials fulfilled the criteria. Only the ‘Inversion of gypsum ‘ and the ‘Reinforced Lime’ were adopted and applied to the Acropolis monuments and to other monuments in Greece and in several other countries.Recommendation and Outlook All criteria must be used for the selection of methods and materials for the consolidation of the monument surfaces. This is why we have already studied with the same procedures, methods and materials for restoration, surface cleaning and protection.     

Results and evaluation of the first study of organochlorine contaminants (PCDDs, PCDFs, PCBs and DDTs), heavy metals and metalloids in birds from Baja California, México

Organochlorine compounds (OCs) including polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p-p'-DDE), heavy metals (Pb, Cd, Zn, Cu), and arsenic were measured in house sparrows (Passer domesticus) and common ground doves (Columbina passerina) from Baja California Sur, México. Concentrations of PCDD/Fs were low, with 21 pg/g for house sparrows, and 7.7 pg/g for common ground doves. Non-ortho-PCB concentrations in house sparrow and common ground doves were 58 and 254 pg/g, respectively, and are within the highest concentrations reported in species that are in the low levels of food webs. The major differences in organochlorine levels between species were found for ortho-PCBs and DDTs. ortho-PCB levels were higher in the seedeater species, whereas DDT levels were higher in the omnivorous species. Heavy metal levels were far below those associated with negative effects.     

Modelling of the life cycle of Chironomus species using an energy-based model

Little is known about the differences between the species of the genus Chironomus relatively to their life cycle strategies. This knowledge is however crucial to fully understand the response of the Chironomus community to field perturbations. Here, we proposed to study four Chironomus species by using an energy-based model to describe growth, emergence and reproduction. We used data from the literature for two species (Chironomus plumosus and Chironomus tentans) and data from our experiments for two other species (Chironomus prasinus and Chironomus riparius). We showed that our model is able to accurately describe the life-history attributes for all the species tested, which suggests that Chironomus species have the same fundamental characteristics (low maintenance energetic costs, isomorphism), which makes possible the building of a common modelling framework to assess effects of toxicants at individual and population level. The species showed a few differences relatively to the parameters of the models with possible consequences when assessing effects of chemicals on Chironomus community. For instance, due to differences in growth parameters, C. riparius population dynamics should be more sensitive to effects on individual growth than C. prasinus or C. plumosus ones.     

An integrated assessment of estrogenic contamination and biological effects in the aquatic environment of The Netherlands

An extensive study was carried out in the Netherlands on the occurrence of a number of estrogenic compounds in surface water, sediment, biota, wastewater, rainwater and on the associated effects in fish. Compounds investigated included natural and synthetic hormones, phthalates, alkylphenol(ethoxylate)s and bisphenol-A. The results showed that almost all selected (xeno-)estrogens were present at low concentrations in the aquatic environment. Locally, they were found at higher levels. Hormones and nonylphenol(ethoxylate)s were present in concentrations that are reportedly high enough to cause estrogenic effects in fish. Field surveys did not disclose significant estrogenic effects in male flounder (Platichthys flesus) in the open sea and in Dutch estuaries. Minor to moderate estrogenic effects were observed in bream (Abramis brama) in major inland surface waters such as lowland rivers and a harbor area. The prevalence of feminizing effects in male fish is largest in small regional surface waters that are strongly influenced by sources of potential hormone-disrupting compounds. High concentrations of plasma vitellogenin and an increased prevalence of ovotestes occurred in wild male bream in a small river receiving a considerable load of effluent from a large sewage treatment plant. After employing in vitro and in vivo bioassays, both in situ and in the laboratory, we conclude that in this case hormones (especially 17 alpha-ethynylestradiol) and possibly also nonylphenol(ethoxylate)s are primarily responsible for these effects.     

A case study of molinate application in a Portuguese rice field: herbicide dissipation and proposal of a clean-up methodology

This study was designed to monitor molinate losses in surface and underground waters during Ordram application in a rice field situated in central Portugal. Water samples were collected from different sites, before, during and about one month and a half after Ordram application. Molinate quantification was based on a solid-phase microextraction (SPME) method followed by gas chromatography with flame photometric detector (GC-FPD) analysis, and led to the conclusion that the herbicide was dissipated in the environment, reaching levels as high as 3.9 microgl(-1) in underground water and 15.8 microgl(-1) in the river receiving tail waters. The feasibility of the application of treatment methodologies based on adsorption or biodegradation as processes to remove molinate from real-world waters was assessed. These methods seem suitable to reduce molinate concentrations to values in the range of the legally recommended limits (<0.5 microgl(-1)).     

Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.     

Efficient use of Fe metal as an electron transfer agent in a heterogeneous Fenton system based on Fe0/Fe3O4 composites

In this work a novel heterogeneous Fenton system based on Fe(0)/Fe3O4 composites is described. The composites with several Fe(0)/Fe3O4 ratios were prepared by two different methods, i.e. mechanical alloying of Fe(0) and Fe3O4 powders and controlled reduction of Fe3O4 with H2. Reaction studies and detailed Conversion Electron M?ssbauer surface characterization of the composites Fe(0)/Fe3O4, Fe(0), Fe3O4, alpha-Fe2O3 and gamma-Fe2O3 suggested that Fe2+surf species are essential to produce an active Fenton system. Kinetic studies for the oxidation of the dye methylene blue, used as an organic model molecule, and for the peroxide decomposition suggest that the reactions proceed via HO* radicals generated from Fe2+surf species and H2O2 in a Fenton like mechanism. The increase in activity caused by the addition of Fe(0) is discussed in terms of a creation of Fe2+surf species during the preparation of the composite and by an electron transfer mechanism from Fe(0) to Fe3+surf during the Fenton reaction to regenerate the Fe2+surf active species.     

Use of the aquatic lichen Dermatocarpon luridum as bioindicator of copper pollution: accumulation and cellular distribution tests

Laboratory experiments were conducted to investigate the potential use of the aquatic lichen Dermatocarpon luridum as bioindicator of copper pollution. Lichen thalli were exposed to 0.00, 0.25, 0.50, 0.75 and 1.00 mM copper in synthetic freshwater to solve the problems of metal bioavailability. The mineral composition of this media was prepared so that it corresponded to the ion composition of natural waters in D. luridum ecosystems. Sequential elution procedures using NiCl2 or Na2-EDTA (20 mM) were used to determine the distribution of metals at different cellular sites. The copper concentration extracted from thalli was correlated with pollution intensity, the greater correlation being with the Na2-EDTA extractant. The malondialdehyde concentration in thalli can be used as indicator of copper pollution; however, similar membrane degradation was observed for 0.25 and 0.50 mM copper and for 0.75 and 1.00 mM copper.     

Modeling the Entrepe?as Reservoir.

The Entrepe?as Reservoir is a monomictic reservoir located in River Tagus (Spain). The aim of this work is to establish a feasible model to predict the depth of the thermocline that is developed in the reservoir during the period of natural thermal stratification. Entrainment, eddy diffusion, inflow of external energy, and other factors are considered to calibrate the parameters of the model. The methodology involves the measure of actual temperature and electrical conductivity profiles, use of meteorological data and reservoir parameters, and selection and application of several models from the literature. The calculations and predictions are integrated to a software packet that is able to predict thermocline depth and water temperature profile during a 1-year period on a day-by-day basis. In the thermocline depth, the prediction error, on the basis of real data, is less than 6% and, in the water temperature, it is 2 degrees C.