Spectrofluorimetric study of the ageing of mixtions used in the gildings of mediaeval wall paintings

Introduction  

In the Middle Ages, we could find gildings on mural paintings. Gold, silver or tin leaves were applied according to distemper or mixtion technique. For the first one, a binder as glue is necessary, and for the second, a lipidic binder is used to stick the metallic leaf. Studies of gildings materials characterization show that the mixtion technique, with a mordant, is the most common. Linseed oil seems to be the binder used. It is always mixed with a siccative agent as lead. Because of bad conditions of conservation, the gildings do not resist anymore, only remain traces of metal or the adhesive under-layer. Thanks to the binder fluorescence, we can nowadays detect ancient gildings.     

Combining stable isotope (δ13C) of trace gases and aerobiological data to monitor the entry and dispersion of microorganisms in caves

Altamira Cave (north of Spain) contains one of the world's most prominent Paleolithic rock art paintings, which are threatened by a massive microbial colonization of ceiling and walls. Previous studies revealed that exchange rates between the cave and the external atmosphere through the entrance door play a decisive role in the entry and transport of microorganisms (bacteria and fungi) and nutrients to the interior of the cave. A spatial-distributed sampling and measurement of carrier (CO₂) and trace (CH₄) gases and isotopic signal of CO₂ (δ¹³C) inside the cave supports the existence of a second connection (active gas exchange processes) with the external atmosphere at or near the Well Hall, the innermost and deepest area of the cave. A parallel aerobiological study also showed that, in addition to the entrance door, there is another connection with the external atmosphere, which favors the transport and increases microorganism concentrations in the Well Hall. This double approach provides a more complete knowledge on cave ventilation and revealed the existence of unknown passageways in the cave, a fact that should be taken into account in future cave management.     

UV-C-activated persulfate oxidation of a commercially important fungicide: case study with iprodione in pure water and simulated tertiary treated urban wastewater

Recently, the European Food Safety Authority (EFSA) has banned the use of iprodione (IPR), a common hydantoin fungicide and nematicide that was frequently used for the protective treatment of crops and vegetables. In the present study, the treatment of 2 mg/L (6.06 μM) aqueous IPR solution through ultraviolet-C (UV-C)-activated persulfate (PS) advanced oxidation process (UV-C/PS) was investigated. Baseline experiments conducted in distilled water (DW) indicated that complete IPR removal was achieved in 20 min with UV-C/PS treatment at an initial PS concentration of 0.03 mM at pH?=?6.2. IPR degradation was accompanied with rapid dechlorination (followed as Cl^? release) and PS consumption. UV-C/PS treatment was also effective in IPR mineralization; 78% dissolved organic carbon (DOC) was removed after 120-min UV-C/PS treatment (PS?=?0.30 mM) compared with UV-C at 0.5 W/L photolysis where no DOC removal occurred. LC analysis confirmed the formation of dichloroaniline, hydroquinone, and acetic and formic acids as the major aromatic and aliphatic degradation products of IPR during UV-C/PS treatment whereas only dichloroaniline was observed for UV-C photolysis under the same reaction conditions. IPR was also subjected to UV-C/PS treatment in simulated tertiary treated urban wastewater (SWW) to examine its oxidation performance and ecotoxicological behavior in a more complex aquatic environment. In SWW, IPR and DOC removal rates were inhibited and PS consumption rates decreased. The originally low acute toxicity (9% relative inhibition towards the photobacterium Vibrio fischeri) decreased to practically non-detectable levels (4%) during UV-C/PS treatment of IPR in SWW.

     

Mechanisms of photosynthetic inactivation on growth suppression of Microcystis aeruginosa under UV-C stress

This study aims to investigate the effects of UV-C irradiation on photosynthetic processes of Microcystis aeruginosa to unravel the mechanism(s) involved in how and in what ways UV-C mediates growth suppression and cellular recovery. Changes in the concentration of photosynthetic pigments, photochemical efficiency, PS II core protein (D1) content, and the coding genes expressions were measured. The results indicate that UV-C doses at 20–200 mJ cm⁻² lead to rapid reduction in gene expression of both psbA (for D1) and cpc (for phycocyanin), but the suppression was short term and recoverable within 3 d of post-UV incubation. Conversely, UV-C doses at ?50 mJ cm⁻² could induce marked decline in photochemical efficiency (represented by the optimal PS II quantum yield, F_V/F_M, and the effective PS II quantum yield, Y) as well as decreases in D1 content and water soluble pigments (phycoerythrins, phycocyanins, allophycocyanins) in M. aeruginosa during the post UV-C incubation period. The results suggest that interruption of both the light energy harvesting apparatus (especially the water soluble pigments) and the photochemical process mainly accounted for the growth suppression effect in UV-C irradiated M. aeruginosa.     

Measurements of aerosol particles in the Škocjan Caves,Slovenia

For the first time, continuous aerosol measurements were performed in the ?kocjan Caves, one of the most important cave systems in the world, and listed by UNESCO as a natural and cultural world heritage site since 1986. Measurements of PM₁₀ were performed during three different periods: (1) in December 2011, the average background concentration was found to be about 4 μg m^?3; (2) in June 2012, a higher concentration was measured (8 μg m^?3); and (3) from 8 to 20 August 2012, the highest concentration of 15.3 μg m^?3 was measured. Based on the PM₁₀ measurement results, and as compared to similar measurements outside the cave, it can be hypothesized that the increase in the cave's aerosol concentration during the summer was connected to both the higher number of visitors and the polluted atmospheric air entering the cave upon entering of the cave system. Additional measurement of nanoparticles with scanning mobility particle sizer spectrometer (size between 14.1 and 710.5 nm) confirmed these findings; during the summer period, a severe raise in the total aerosol concentration of 30–50 times was found when groups of visitors entered the cave. Our results on nanoparticles demonstrated that we were able to detect very small changes and variations in aerosol concentration inside the cave. To our knowledge, these are the first results on nanoaerosol measurements in a cave, and we believe that such measurements may lead to the implementation of better protection of delicate cave systems.     

Solar photocatalytic decolorization of methylene blue in water

In this study, a photocatalytic decolorization system equipped with immobilized TiO2 and illuminated by solar light was used to remove the color of wastewater. To examine the decoloring efficiency of this system, photocatalytic decolorization of an organic dye such as methylene blue was studied as an example. The effects of light source, pH, as well as the initial concentration of dye were also investigated. It was observed that the solution of methylene blue could be almost completely decolorized by the solar light/TiO2 film process while there was about 50% color remaining with solar irradiation only. In addition, it was found that the decoloring efficiency of solution was higher with solar light irradiation than with artificial UV light irradiation, even though the artificial UV light source supplied higher UV intensity at 254 nm. The color removal rate of methylene blue with solar light irradiation was almost twice that of artificial UV light irradiation. This phenomena was mainly attributed to that some visible light range of solar light was useful for exciting the methylene blue molecules adsorbed on TiO2 film, leading to a photosensitization process undergoing and decoloring efficiency promoted. This solar-assisted photocatalytic device showed potential application for decoloring organic dyes in wastewater.     

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets

Purpose

The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants.

Methods

In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol?Cgel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV?Cvis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation.

Results

Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO₂ powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity.

Conclusion

We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.     

Cleaning painted surfaces: evaluation of leaching phenomenon induced by solvents applied for the removal of gel residues

Cleaning is one of the most important, delicate, and at the same time controversial processes in the conservation treatment of paintings. Although a strict definition of cleaning would be the removal of dirt, grime, or other accretions (surface cleaning), in the conservation field, cleaning is used in the broader meaning to include thinning/removing altered or “unwanted layers” of materials without damaging or altering the physicochemical properties of the surfaces to be preserved. The cleaning of unvarnished paintings is one of the most critical issues that are currently discussed. Several studies exist regarding different cleaning tools, such as gels, soaps, enzymes, ionic liquids, and foams, as well as various dry methods and lasers, but only a few have been performed on the risk associated with the use of water and organic solvents for the cleaning treatments in relation to the original paint binder. The aim of the study is to verify analytically the behavior of water gelling agents during cleaning treatments and the interaction of the following elements: water or organic solvents applied for the removal of gel residues with the original lipid paint binder. For this purpose, the study was conducted on a fragment of canvas painting (sixteenth to seventeenth century) of Soprintendenza per i Beni Storici, Artistici ed Etnoantropologici del Friuli Venezia Giulia (Superintendence for the Historical, Artistic and Ethno-anthropological Heritage of Friuli Venezia Giulia), Udine by means of Fourier transform infrared spectroscopy, gas chromatography/mass spectrometry, and scanning electron microscopy.     

Synthesis of Fe-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocatalyst and its sonophotocatalytic activity on synthetic dye and real textile wastewater

The catalysts such as Fe, Bi₂O₃, and Fe-doped Bi₂O₃ were synthesized for the sonophotocatalytic treatment of synthetic dye and real textile wastewater. The resultant catalysts were characterized for its size and uniform shape using x-ray diffractogram (XRD) and scanning electron microscopy (SEM) which signified the nanorod shape formed Bi₂O₃. The higher ultraviolet light absorbance capacity of the catalysts was also evident using diffuse reflectance spectroscopy (DRS). Initially, the effect of conventional parameters such as initial pH, gas bubbling (argon, oxygen, air and nitrogen) and oxidant addition (H₂O₂ and peroxymonosulfate) in the presence of sonolysis (22 and 37 kHz frequency) and photolysis (UV-C light) on 10 ppm Basic Brown 1 dye was studied. The results showed that highest decolorization of 62 % was attained for 3 g/L peroxymonosulfate under 37 kHz frequency sonolysis treatment. Secondly, with the catalyst study, highest of 46 % dye color removal was obtained with 4 g/L Fe under 37 kHz frequency sonolysis treatment. The sonophotocatalytic treatment of dye with Fe-doped Bi₂O₃ catalyst in combination with peroxymonosulfate showed highest color removal of 99 %. Finally, the sonophotocatalytic treatment of real textile wastewater in the presence of 3 g/L Fe-doped Bi₂O₃ and 6 g/L peroxymonosulfate reduced the total organic carbon (TOC) and chemical oxygen demand (COD) level to 77 and 91 %, respectively, in 180 min. The reported treatment process was found to treat the synthetic dye and real textile wastewater effectively.     

各种影响因子对电解法预处理医药废水的影响研究

探讨了电解法预处理医药废水时停留时间、电解电压、废水初始浓度、温度和废水pH值等影响因子对去除色度、COD和提高废水可生化性等处理效果的影响,并考察了其应用于工业实际废水处理的可行性.实验结果表明:电解法更适合高浓度医药废水的处理,色度的去除率可达到90%以上;电解时间宜控制在40～60 min;电解电压越高,废水COD和色度去除效果越好;在实验温度范围内,温度对色度和COD去除率的影响不大;废水pH值为7.5时电解效果最佳,工程运用宜控制在6～9之间.     

High incidence of deformity in aquatic turtles in the John Heinz National Wildlife Refuge

The John Heinz National Wildlife Refuge is subject to pollution from multiple sources. We studied development of snapping turtle (Chelydra serpentina) and painted turtle (Chrysemys picta) embryos from the refuge from 2000 through 2003. Mean annual deformity rate of pooled painted turtle clutches over four years ranged from 45 to 71%, while that of snapping turtle clutches ranged from 13 to 19%. Lethal deformities were more common than minor or moderate deformities in embryos of both species. Adult painted turtles had a higher deformity rate than adult snapping turtles. Snapping turtles at JHNWR had high levels of PAH contamination in their fat. This suggests that PAHs are involved in the high level of deformities. Other contaminants may also play a role. Although the refuge offers many advantages to resident turtle populations, pollution appears to place a developmental burden on the life history of these turtles.     

Critical effect of hydrogen peroxide concentration in photochemical oxidative degradation of C.I. Acid Red 27 (AR27)

The photochemical decolorization of C.I. Acid Red 27 (AR27), an anionic monoazo dye, was studied in the UV/H2O2 process by using a batch reactor with a UV-C lamp emitting at 254 nm (30 W). The decolorization rate follows pseudo-first order kinetic with respect to the AR27 concentration. The results indicate that the apparent reaction rate constant in the UV/H2O2 process is a function of H2O2 concentration. In this work, a mathematical relation between the apparent reaction rate constant of the AR27 removal and used H2O2 was established. The applied amount of H2O2 was performed in two forms: (i) the light fraction absorbed by H2O2 in 254 nm, (ii) the initial concentration ratio of H2O2 to AR27. The results obtained from this mathematical model are in good agreement with experimental results.     

Assessment of the mechanical stability and chemical leachability of immobilized electroplating waste

The effectiveness of cement based treatment technology, in immobilizing chromium laden electroplating sludge was assessed by conducting toxicity characteristic leaching procedure (TCLP). The mechanical stability of the blocks was tested by measuring the compressive strength. Other leaching tests such as NEN 7341 test, ANS 16.1 and multiple TCLP (MTCLP) test conducted on select solidified blocks showed that chromium was immobilized by the binder studied. A linear relationship was obtained between the cumulative fraction of chromium leached (CFL) and square root of time in the solidified samples proving that diffusion is the controlling mechanism for leaching of chromium. The leachability indices (LI) obtained for the solidified materials using cement and cement-fly ash system (EPC6, EPFC6A and EPFC6B) satisfy the guidance value as per US NRC, which clearly indicates that chromium is well retained within the solid matrix. Chromium concentrations in the TCLP leachates of the above mix ratios were well within the regulatory level of United States Environmental Protection Agency (USEPA). Molecular characterization of the solidified material was carried out using Fourier transformation infra red (FTIR) technique.     

Effect of sediment turbidity and color on light output measurement for Microtox Basic Solid-Phase Test

In this work, sediment samples collected from several Spanish harbours were tested with two toxicity procedures, designed for solid samples: the Microtox Basic Solid-Phase Test (BSPT) and a modified procedure of the previous test protocol (mBSPT). According to the BSPT procedure, after initial light readings, pure bacteria were exposed to sediment suspension dilutions and light production was directly measured on suspended sediments without any further manipulation. As measurements are likely to be affected by sediment turbidity and color, a variation in initial light measurement has been here suggested, in order to consider the sample effect at all time readings during the test. Firstly, when sediment suspensions at different concentrations were added to bacteria suspension, immediately the initial light output drastically decayed by more than 50% in signal difference, resulting in a false inhibition, as effect of sample turbidity/color. This effect was more evident at high EC50 values, when slightly or not toxic samples were assessed. Secondly, the comparison of the EC50 obtained with both procedures, demonstrated that the mBSPT produced higher EC50 values (less toxic) than those obtained with the standard procedure. The mBSPT procedure resulted rapid and effective and it could be applied simultaneously with BSPT, in order to better evaluate the toxicity.     

Combined UV-C/H2O2-VUV processes for the treatment of an actual slaughterhouse wastewater

In this study, a three-factor, three-level Box-Behnken design with response surface methodology were used to maximize the TOC removal and minimize the H₂O₂ residual in the effluent of the combined UV-C/H₂O₂-VUV system for the treatment of an actual slaughterhouse wastewater (SWW) collected from one of the meat processing plants in Ontario, Canada. The irradiation time and the initial concentrations of total organic carbon (TOC_o) and hydrogen peroxide (H₂O_2o) were the three predictors, as independent variables, studied in the design of experiments. The multiple response approach was used to obtain desirability response surfaces at the optimum factor settings. Subsequently, the optimum conditions to achieve the maximum percentage TOC removal of 46.19% and minimum H₂O₂ residual of 1.05% were TOC_o of 213 mg L^?1, H₂O_2o of 450 mg L^?1, and irradiation time of 9 min. The attained optimal operating conditions were validated with a complementary test. Consequently, the TOC removal of 45.68% and H₂O₂ residual of 1.03% were achieved experimentally, confirming the statistical model reliability. Three individual processes, VUV alone, VUV/H₂O₂, and UV-C/H₂O₂, were also evaluated to compare their performance for the treatment of the actual SWW using the optimum parameters obtained in combined UV-C/H₂O₂-VUV processes. Results confirmed that an adequate combination of the UV-C/H₂O₂-VUV processes is essential for an optimized TOC removal and H₂O₂ residual. Finally, respirometry analyses were also performed to evaluate the biodegradability of the SWW and the BOD removal efficiency of the combined UV-C/H₂O₂-VUV processes.     

Parameters that control the cleanup of fractured permeable aquifers

This study develops a modeling approach for simulating and evaluating entrapped light nonaqueous-phase liquid (light NAPL-LNAPL) dissolution and transport of the solute in a fractured permeable aquifer (FPA). The term FPA refers to an aquifer made of porous blocks of high permeability that embed fractures. The fracture network is part of the domain characterized by high permeability and negligible storage. Previous studies show that sandstone aquifers often represent FPAs. The basic model developed in this study is a two-dimensional (2-D) model of permeable blocks that embed oblique equidistant fractures with constant aperture and orientation. According to this model, two major parameters govern NAPL dissolution and transport of the solute. These parameters are: 1) the dimensionless interphase mass transfer coefficient, K(f0), and 2) the mobility number, N(M0). These parameters represent measures of heterogeneity affecting flow, NAPL dissolution, and transport of the solute in the domain. The parameter K(f0) refers to the rate at which organic mass is transferred from the NAPL into the water phase. The parameter N(M0) represents the ratio of flow through the porous blocks to flow through the fracture network in regions free of entrapped NAPL. It also provides a measure of groundwater flow bypassing regions contaminated by entrapped NAPL. In regions contaminated by entrapped NAPL our simulations have often indicated very low permeability of the porous blocks, enabling a significant increase of the fracture flow at the expense of the permeable block flow. Two types of constitutive relationships also affect the rate of FPA cleanup: 1) the relationship between the saturation of the entrapped NAPL and the permeability of the porous blocks, and 2) the relationships representing effects of the entrapped NAPL saturation and the permeable block flow velocity on rates of interphase mass transfer. This study provides basic tools for evaluating the characteristics of pump-and-treat cleanup of FPAs by referring to sets of parameters and constitutive relationships typical of FPAs. The numerical simulations carried out in this study show that at high initial saturation of the entrapped NAPL, during initial stages of the FPA cleanup the contaminant concentration increases, but later it decreases. This phenomenon originates from significant groundwater bypassing the NAPL entrapped in the permeable blocks via the fracture network.     

Denitrification with acrylamide by pure culture of bacteria isolated from acrylonitrile-butadiene-styrene resin manufactured wastewater treatment system

Acrylamide is widely used in industrial applications as cement binder and solidification agent. Due to its carcinogenicity and toxicity, discharge of acrylamide to the natural water and soil systems may lead to an adverse environmental impact on water quality and thus endanger public health and welfare. This study attempts to isolate and identify the denitrifying bacteria, which utilize acrylamide as the substrate from the acrylonitrile-butadiene-styrene resin manufactured wastewater treatment system. The performance of the denitrifying bacteria for treating different initial acrylamide concentrations was also investigated under aerobic and anaerobic conditions. The test results indicated that the Pseudomonas stutzeri could remove acrylamide at concentrations below 440 mg/l under aerobic conditions. The acrylic acid and ammonia intermediates were used as carbon and nitrogen sources, respectively. However, P. stutzeri did not show the capability of metabolizing acrylonitrile under aerobic conditions. Furthermore, the P. stutzeri could utilize both acrylamide and acrylic acid in the presence of nitrate (denitrification) and acrylamide could be removed completely from the wastewater.     

Comparative investigation of toxicity induced by UV-A and UV-C radiation using Allium test

Organisms are increasingly exposed to ultraviolet (UV) rays of sunlight, due to the thinning of the ozone layer and its widespread use in sterilization processes, especially against the SARS-CoV-2 virus. The present study was conducted with the purpose of evaluating the damages of UV-A and UV-C radiations in Allium cepa L. roots. The effects of two different types of UV on some physiological, biochemical, cytogenotoxic, and anatomical parameters were investigated in a multifaceted study. Three groups were formed from Allium bulbs, one of which was the control group. One of the other groups was exposed to 254 nm (UV-C) and the other to 365 nm (UV-A) UV. Growth retardation effect of UV was investigated with respect to germination percentage, total weight gain, and root elongation, while cytogenotoxicity arisen from UV exposure was analyzed using mitotic index (MI) and chromosomal aberration (CA) and micronucleus (MN) frequency. Oxidative stress due to UV application was investigated based on the accumulation of malondialdehyde (MDA) and the total activities of superoxide dismutase (SOD) and catalase (CAT) enzymes. Also, anatomical changes induced by UV-A and UV-C were analyzed in root meristematic cells. UV treatments caused significant reductions in growth-related parameters. Both UV treatments caused a significant increase in MDA levels and induction of SOD and CAT enzymes in root meristematic cells. A decrease in MI and an increase in the frequency of MN and CAs were observed in root tip cells, indicating the cytogenotoxic effect of UV application. Anatomical damages such as epidermis cell damage, cortex cell damage, necrotic zones, giant cell nucleus, and indistinct transmission tissue occurred in cells exposed to UV. All of the physiological, biochemical, cytogenetic, and anatomical damages observed in this study were more severe in cells treated with UV-C compared to UV-A. This study suggested that UV exposure triggered growth inhibition, cytogenotoxicity, oxidative stress, and meristematic cell damages in A. cepa roots depending on the wavelength.

     

Development of a Smoke Guide for the Evaluation of White Plumes

A smoke guide for use with white plumes has been developed by suspending size-graded industrial diamond dust in transparent plastic blocks. The guide consists of a series of four blocks containing dusts with white light transmittances of 20, 40, 60, and 80 per cent and scattering characteristics similar to those of white (oil) plumes commonly used for training smoke inspectors. The luminances of experimental plumes and guides with like transmittances are compared when viewed under different illuminating and viewing conditions. Similar tests with a U. S. Public Health Service Black Smoke Guide are also described.     

Competitive removal of pharmaceuticals from environmental waters by adsorption and photocatalytic degradation

This work explores the competitive removal of pharmaceuticals from synthetic and environmental waters by combined adsorption-photolysis treatment. Five drugs usually present in waterways have been used as target compounds, some are pseudo-persistent pollutants (carbamazepine, clofibric acid, and sulfamethoxazole) and others are largely consumed (diclofenac and ibuprofen). The effect of the light source on adsorption of drugs onto activated carbons followed by photolysis with TiO₂ was assessed, being UV-C light the most effective for drug removal in both deionized water and river water. Different composites prepared from titania nanoparticles and powdered activated carbons were tested in several combined adsorption-photocatalysis assays. The composites prepared by calcination at 400 °C exhibited much better performance than those synthesized at 500 °C, being the C400 composite the most effective one. Furthermore, some synthetic waters containing dissolved species and environmental waters were used to investigate the effect of the aqueous matrix on each drug removal. In general, photocatalyst deactivation was found in synthetic and environmental waters. This was particularly evident in the experiments performed with bicarbonate ions as well as with wastewater effluent. In contrast, tests conducted in seawater showed adsorption and photocatalytic degradation yields comparable to those obtained in deionized water. Considering the peculiarities of substrate competition in each aqueous matrix, the combined adsorption-photolysis treatment generally increased the overall elimination of drugs in water.