Assessment of urban air pollution related to potential nanoparticle emission from photocatalytic pavements.

The main objective was to evaluate whether wearing and weathering of nanofunctionalized photocatalytic pavement in real urban environment can lead to undesirable emission of potentially toxic nanoparticle aerosols in urban air. The photocatalytic material was thoroughly tested before its application for conformity criteria in terms of photocatalytic effectiveness, intrinsic performance and undesired secondary effects, and then applied on a pilot scale in downtown Madrid. The aerosol monitoring on the pilot street before the coating applications as well as on the neighbouring streets during 10 months was used as a benchmark for evaluation of spatial and temporal variations. Analysis of the experimental data did not reveal any statistically significant variations in the aerosol concentrations on the pilot street in comparison with the benchmark. The concentration of Ti-containing particles was assessed by aerosol sampling and yielded values below 10 cm-3 that is more than three orders of magnitude below the toxicological limits. A theoretical model was developed to assess the upper bound of nanoparticle aerosol concentration in air. These findings indicated that photocatalytic pavement materials, which comply with conformity criteria under laboratory tests, can have low impact on the particulate contamination of urban air.

Removal of graffiti paint from construction materials coated with TiO2-based photocatalysts.

Graffiti on construction materials has significant social and economic impacts, especially on artistic and historical artefacts. Anti-graffiti protective coatings are used to generate low surface energies that limit graffiti adhesion to the surface, thereby reducing surface damage and facilitating removal. The anti-graffiti properties of three commercial TiO2-based coatings were tested under outdoor exposure conditions using four colours of graffiti paint (red, blue, black, and white). Chemical removers were used to clean the stained surfaces to understand the impact of the photocatalytic coatings during the conventional cleaning procedure. The effectiveness of cleaning was assessed by visual observations, colour measurements, and the percentage of residual stain. The anti-graffiti efficacy was strongly dependent on the colour of the graffiti and characteristics of the TiO2 coating. The cleaning performance of TiO2-treated samples was likely related to the photocatalytic redox reactions that decompose the graffiti. Additionally, their hydrophilicity may also prevent the adhesion and/or penetration of graffiti paint on the surface and/or pore matrix.

Synergetic adsorption-photocatalysis process for water treatment using TiO2 supported on waste stainless steel slag.

This study presents an economical and efficient method to decolourise dye wastewater using industrial waste stainless steel slag (SSS). Titanium dioxide was immobilised on SSS by a precipitation-calcination method. Samples with different TiO2 loadings (prepared using either titanium isopropoxide precursor or commercial TiO2 nanoparticles) were used to decolourise an organic contaminant (methylene blue) under dark and UV conditions in aqueous solution, and their adsorption and photocatalytic performances were compared. Samples with 15 and 25 TiO2 wt% prepared by the precursor method had normalised photocatalytic efficiencies per gram close to that of bare TiO2; using an adsorption-photocatalysis process led to efficiencies 4.4 and 1.6 times higher than that of pure TiO2. The improvement in catalytic performance (greater for samples with less than 50% TiO2 content) may be due to better UV absorption ability (related to with the improvement of TiO2 particle dispersion) and the close TiO2 support interaction, which can eventually cause a photocatalysis-enhancing shift towards more negative oxidation potentials. The SSS also acted as an efficient adsorption trap for organic compounds. The pollutant was thus transferred to the TiO2 surface and photodegraded more rapidly and efficiently. The outstanding synergetic adsorption-photocatalysis capacities of TiO2 waste stainless steel slag composites for dye water treatment made the proposed conversion approach have great potential in practical applications.

Face Mask Wastes as Cementitious Materials: A Possible Solution to a Big Concern.

After more than two years wearing surgical masks due to the COVID-19 pandemic, used masks have become a significant risk for ecosystems, as they are producing wastes in huge amounts. They are a potential source of disturbance by themselves and as microplastic contamination in the water system. As 5500 tons of face masks are estimated to be used each year, there is an urgent need to manage them according to the circular economy principles and avoid their inadequate disposal. In this paper, surgical wear masks (WM), without any further pretreatment, have been introduced as addition to mortars up to 5% in the weight of cement. Mechanical and microstructural characterization have been carried out. The results indicate that adding MW to the cement supposes a decrease in the properties of the material, concerning both strength and durability behavior. However, even adding a 5% of WM in weight of cement, the aspect of the mortars is quite good, the flexural strength is not significantly affected, and the strength and durability parameters are maintained at levels that-even lower than the reference-are quite reasonable for use. Provided that the worldwide production of cement is around 4.1 Bt/year, the introduction of a 5% of WM in less than 1% of the cement produced, would make it possible to get rid of the mask waste being produced.

Pathophysiology, Diagnosis and Treatment of Spontaneous Coronary Artery Dissection in Peripartum Women.

Spontaneous coronary artery dissection (SCAD) is an infrequent cause of nonobstructive ischemic heart disease in previously healthy young women and therefore is not usually considered in differential diagnoses. The overall incidence of SCAD in angiographic series is between 0.28 and 1.1%, with a clear predominance in young, healthy women (70%) of whom approximately 30% are in the postpartum period. In the United Kingdom, between 2008 and 2012, SCAD was the cause of 27% of acute myocardial infarctions during pregnancy, with a prevalence of 1.81 per 100,000 pregnancies. Regarding the mechanism of arterial obstruction, this may be due to the appearance of an intramural hematoma or to a tear in the intima of the arteries, both spontaneously. Although multiple diagnostic methods are available, it is suggested to include an appropriate anamnesis, an electrocardiogram in the first 10 min after admission to the service or the onset of symptoms, and subsequently, a CT angiography of the coronary arteries or urgent coronary angiography if the hemodynamic status of the patient allows it. Treatment should be individualized for each case; however, the appropriate approach is generally based on two fundamental pillars: conservative medical treatment with antiplatelet agents, beta-blockers, and nitrates, and invasive treatment with percutaneous coronary intervention for stent implantation or balloon angioplasty, if necessary.

Preliminary Study of the Influence of Supplementary Cementitious Materials on the Application of Electro Remediation Processes.

Supplementary cementitious materials (SCMs), based on pozzolanic materials, improve durability against corrosion and mechanical properties of concrete structures by decreasing their permeability. Even though the influence of SCMs on the chloride combination with the cement phases has been widely studied, its effects on electrokinetic remediation processes such as electrochemical chloride extraction (ECE) have not been clarified. For this reason, the influences of two SCMs, fly ash (FA) and blast-furnace slag, on the extraction of chloride through the concrete net pore have been studied in this paper to determine the viability of the application of electrochemical chloride treatments in these structural materials. Alternative electrochemical indicators to the ones included in the standards are also proposed to better determine the final point of the treatment. A cement replacement of 8% on both SCM (FA and slag) has been tested, and in addition to charge density, chloride content, and corrosion measurement at the end of the treatment (included in the standards), different electrical and electrochemical indicators such as electrical resistivity, EIS, or depolarized potentials are used to monitor the ECE. The influence of the treatment on disconnected steel has been also studied. In the case of slag mortar, no steel passivation was reached, while in the case of FA, the passivation of the steels connected to treatment was reached in the same way as in plain CEM I specimens. A degree of protection is also detected in the nonconnected steel, which means that substitution of 8% in FA does not affect treatment efficiency and can also partially protect the metallic elements embedded in the same electrolyte but not connected to the treatment.

Unusual photodegradation reactions of Asteraceae and Poaceae grass pollen enzymatic extracts on P25 photocatalyst.

In previous studies, it was demonstrated that photocatalysis by TiO2 nanoparticles can be effective for decomposition of pollen grains and pollen allergen extracts (PAEs) for Cupressus arizonica and Platanus hybrida species. In this work, the chemical and photochemical processes of five types of PAEs belonging to family Asteraceae, tribe Astereae, and family Poaceae, tribes Poeae and Triticea, were studied. It was confirmed that the PAEs suffered almost complete decomposition, which likely led to gaseous final products. For the species of Poeae tribe, i.e., Poa pratensis, Festuca pratensis, and Avena sativa, an unusual surface chemical modification of the photocatalyst consisting in the appearance of new bands on fine core level spectra of Ti 2p, C 1s, and O 1s was observed. These changes were associated with possible doping of TiO2 with C and N by pollen extracts. This was accompanied by a red shift of absorption spectra. The results suggest that some components of Poeae pollen can be grafted on TiO2 surface and they can activate the photocatalyst in the visible range. These findings can open a new pathway to eco-friendly chemical engineering of photocatalysts using organic biological compounds.

Primary and Secondary Emissions of VOCs and PAHs in Indoor Air from a Waterproof Coal-Tar Membrane: Diagnosis and Remediation.

Primary and secondary emissions of volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) from a waterproof coal tar membrane and their effect on the indoor air quality were investigated through a case study in a residential building situated in Madrid, Spain. The air contaminants were analyzed in situ using photoionization method and several samples of contaminants were taken using three sorbents: activated carbon, XAD2 and Tenax GR. It was found that various VOCs such as toluene, p- and m-Xylene, PAHs such as naphthalene, methyl-naphthalenes, acenaphthene, acenaphthylene, phenanthrene and fluorine, volatile organic halogens including chloroform and trichlorofluoromethane, and alkylbenzene (1,2,4-trimethylbenzene) were found at concentrations, which exceeded the limits established by international and national agencies (WHO, EPA, OSHA). Some of the above organic compounds were found also in the samples of construction and building materials, which were obtained at different heights and places. The analysis of possible sources of the contaminants pointed at the original coal-tar membrane, which was applied on the terrace to be waterproof. During a posterior reparation the membrane was coated with a new one that hindered dissipation of emitted contaminants. The contaminants leached out and were absorbed by construction materials down in the dwelling. These materials then acted as secondary emission sources. To remediate the emission problem as the contaminated materials were removed and then a ventilation system was installed to force the gasses being emitted from the rest of contaminated slab outside. Follow-up has validated the success of the remediation procedure.

High-capacity adsorbents from stainless steel slag for the control of dye pollutants in water.

Adsorbent materials for the control of dye pollutants in water were synthetized from stainless steel slag (SSS) using different acid-base treatments. Using HCl (SS-Cl) and HNO3 (SS-NO3) produced high-capacity adsorbents, with BET areas of 232 m2/g and 110 m2/g respectively. Specifically, the SS-Cl had a structure of amorphous silica sponge. Treatment with H2SO4 (SS-SO4) did not enhance the adsorption capabilities with respect to the raw sample (SSS). Activated carbon (AC) was also tested as reference. The materials were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), N2 adsorption-desorption isotherms, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) zeta potential, and infrared spectroscopy (FTIR). Batch adsorption experiments with methylene blue (MB) showed that the maximum sorption capacities were 9.35 mg/g and 8.97 mg/g for SS-Cl and SS-NO3 at 240 h, respectively. These values, even at slower rate, were close to the adsorption capacity of the AC (9.72 mg/g). This behavior has been attributed to the high porosity in the range of nanopores (0.6-300 nm) and the high-surface area for both samples. Preferential involvement of certain functional groups in the adsorption of dye ions on their surface indicative of chemisorption has been found. Although optimization, repeatability, and reproducibility of the process and environmental assessment have to be done before practical applications, these preliminary results indicate that application of these cost-effective adsorbents from raw SSS may be used in water pollution treatment and contribute to the sustainable development of the steel manufacturing industry.

Environmental impact of nano-functionalized construction materials: leaching of titanium and nitrates from photocatalytic pavements under outdoor conditions.

There is a growing use of nano-functionalized construction materials, which contain nanoparticles embedded in their bulk or deposited on their surfaces. In the case of photocatalytic materials, nano-TiO2 is usually added to provide it's functionality. One concern about these materials, in addition to release of nanoparticles as airborne, is that they can be leached into the aquatic environment. Moreover, water eutrophication could be caused due to the increase in NO3- as a product of the photocatalytic oxidation of NOx in runoff. In this paper, a systematic long term campaign assessing these potential side effects in the real outdoor environment has been carried out. Rainwater leachates from 4 m2 slabs of 7 different photocatalytic materials exposed outdoors in two different locations (platforms) were collected and analysed over more than 800 days. Ti, NO3-, pH and conductivity were analysed. Ti was found in the leachates of almost every material, without a clear relation with the type of application (percolated cementitious slurry, suspension/emulsion or TiO2 built-in). The highest concentration found was of 60 µg/L, which seems to be rather small when comparing with some threshold values for drinking water. In all the cases, the detected TiO2 nanoparticles from water leachates were embedded in large microparticle agglomerates coming from the construction material matrix, which are less dangerous than nanoparticles. Nitrates were leached in clear relation with the NOx oxidation photocatalytic performance, and the observed concentrations were not higher than those in the recycled water used by the Madrid City Council to clean the streets.

New Holistic Conceptual Framework for the Assessment of the Performance of Photocatalytic Pavement.

Despite serious health and environmental burdens associated with air pollution by NOx, the emission ceilings have been systematically exceeded in big European cities for several years. Photocatalytic technology can be an efficient solution for the removal of chemical air pollutants. Because diesel engine exhaust is the main source of NOx emissions, the application of a photocatalyst onto road pavement appears to be an effective NOx abatement method due to the large surface area, proximity to the emission source, and relatively good solar irradiance. Several laboratory-scale studies provided evidence demonstrating that most harmful contaminants can be readily mineralized. Furthermore, several projects were aiming to scale up this technology to pilot and real scales. Although the photocatalytic performances of selected materials in real urban environments were determined in some of these studies, the data are not conclusive for evaluating the overall performance because other material characteristics relevant to their functionality were not assessed. The lack of conformity criteria suitable for the evaluation of the overall performance of photocatalytic pavement under real operational conditions has generated skepticism and mistrust among public authorities and relevant stakeholders, which constrains the widespread implementation of this promising technology. In this context, the project LIFE-Photoscaling was focused on developing a new holistic conceptual framework to assess the photocatalytic pavement performance using the decision tool "Photoscaling Decision Maker" based on a set of quantitative indicators. For this purpose, a large volume of data obtained for 10 types of photocatalytic pavement materials was systemized on both the laboratory and pilot plant scales and three main indicators were defined: (1) photocatalytic performance effectiveness, (2) intrinsic performance, and (3) undesired secondary effects. Each top-level indicator includes several low-level subindicators associated with specific material characteristics. Finally, the ranges of the main indicators and subindicators and methods for their assessment were determined. These methods include standard, adopted, and original characterization techniques, which were selected based on the criteria such as simplicity, cost- and time-effectiveness, and relevance regarding the operational conditions.

Photocatalytic Activity of Zn x Mn3-x O4 Oxides and ZnO Prepared From Spent Alkaline Batteries.

Oxides with Zn x Mn3-xO4 stoichiometries and ZnO were synthesized from the "black mass" material recovered from spent alkaline batteries. The oxides were characterized by XRF, XRD with Rietveld refinement, SEM, and TEM methods. Optical characterization included diffuse reflectance (DRS) and photoluminescence (PL) measurements. ZnO presented a clear band edge in the UV region, and PL signals were detected. The Zn/Mn oxides showed strong absorption in the UV region and a continuous absorption band in the Vis-IR regions. There is a non-detected PL signal due to excited charges being trapped on sub-band energy states and/or transfer by non-radiative paths. Photocatalytic activity under both irradiation conditions was evaluated using the resazurin dye test, terephthalic acid fluorescence probe method, and NOx air purification evaluation. In the three photoactivity tests, ZnO performed well under both UV and Vis irradiation, whereas no evidence of any appreciable photocatalytic activity was observed for the Zn/Mn oxides. The results are discussed in terms of the findings of previously reported optical measurements.

In situ evaluation of the NOx removal efficiency of photocatalytic pavements: statistical analysis of the relevance of exposure time and environmental variables.

In the recent past, the NOx removal efficiency of photocatalytic materials has been subject of many studies with promising results. However, many of these studies involve laboratory tests carried out under standardized climatic exposure conditions, often not representative of the real-world environment. With the aim to bridge this gap, selected photocatalytic materials have been applied to different substrates in outdoor demonstrator platforms at pilot scale as part of the project LIFE-PHOTOSCALING. The paper presents the results of in situ measurements of NOx removal efficiency of the materials, performed during 17 months. Statistical models accounting for the influence of exposure time and relevant environmental variables are derived. They suggest that photocatalytic emulsions on the tested asphalt experience a significant loss of activity over time irrespective of climatic conditions. The efficiency of photocatalytic slurries on asphalt and of concrete tiles, with the photocatalyst applied on surface or in bulk, mainly depends on substrate humidity.

Nondestructive decontamination of mortar and concrete by electro-kinetic methods: application to the extraction of radioactive heavy metals.

Because the service lives of nuclear power plants are limited to a certain number of years, the need for the management of quite a large volume of radioactive contaminated concrete arises, which, in most cases, was not taken into account when the capacities of the low and medium activity repositories were designed. Therefore, the decontamination of these structures would be of great interest in order to declassify the wastes as radioactive and manage them as conventional ones. This research studies the reliability of the application of electrical fields to decontaminate radioactive contaminated concrete. Three series of decontamination experiments have been carried out, using Cs+, Sr2-, Co2+, and Fe3+ ions added during casting and that have penetrated from the outside, testing carbonated and uncarbonated matrixes, and using laboratory devices as well as the homemade device for in situ application named "honeycomb device". As a result, the application of electrical fields to concrete-contaminated structures has been developed as a new technique to extract radioactive ionic species from concrete. This method of decontamination has been patented by ENRESA (Spanish Company for the Management of Radioactive Wastes) in association with the IETcc.

Radioactively contaminated electric arc furnace dust as an addition to the immobilization mortar in low- and medium-activity repositories.

Electric arc furnace dust (EAFD), generated by the steel-making industry, is in itself an intrinsic hazardous waste; however, the case may also be that scrap used in the process is accidentally contaminated by radioactive elements such as cesium. In this case the resulting EAFD is to be handled as radioactive waste, being duly confined in low- and medium-activity repositories (LMAR). What this paper studies is the reliability of using this radioactive EAFD as an addition in the immobilization mortar of the containers of the LMAR, that is, from the point of view of the durability. Different mixes of mortar containing different percentages of EAFD have been subjected to flexural and compressive strength, initial and final setting time, XRD study, total porosity and pore size distribution, determination of the chloride diffusion coefficient, dimensional stability tests, hydration heat, workability of the fresh mix, and leaching behavior. What is deduced from the results is that for the conditions used in this research, (cement + sand) can be replaced by EAFD upto a ratio [EAFD/(cement + EAFD)] of 46% in the immobilization mortar of LMAR, apparently without any loss in the long-term durability properties of the mortar.