Temperature and nitrogen-induced modification of activated carbons for efficient catalytic ozonation of salicylic acid as a model emerging pollutant.

The occurrence of emerging pollutants on effluents of wastewater treatment plants makes unfeasible their reutilization and consequently to comply with the sixth goal of 2030 Agenda for sustainable development. Thus, it is extremely important to find ways to remove these pollutants without compromising the quality of reclaimed water. Ozonation has been successfully explored for this purpose, but it still presents limitations towards some oxidant-resistant pollutants. To surpass this, the conversion of ozone (O3) into more reactive species is required, which can be accomplished by using catalysts. Carbon catalysts, such as activated carbons (ACs), represent a more environmentally attractive option than traditional metal-based catalysts, with the advantage of being easily modified to tune their textural and surface properties to the reaction chemistry. In this study, two different sources of ACs were tested in the catalytic ozonation of a frequently detected emerging pollutant: salicylic acid (SalAc). These ACs were submitted to thermal treatment under H2 and functionalization with N precursors, such as melamine and poly(ethyleneimine), to induce changes in the surface properties, especially in the nitrogen content. Although no correlation was found between the N-content and catalytic activity, the thermal treatment under H2 increased the mesopores surface area (Smeso), which reflected in greater catalytic activity. As that, the best-performing AC was the one with the highest Smeso, which revealed also to be resistant to O3 and able to convert O3 into more reactive species, evidenced by the capacity of oxalic acid, a well-known ozone-resistant by-product. The same AC was then submitted to three consecutive reutilization cycles and a more significant activity loss was observed in terms of SalAc degradation rate (⁓ 40%) then total organic carbon removal (⁓ 25%), from the first to the third cycle. This decline in efficiency was ascribed to the presence of by-products adhered to the catalyst surface, which impede its ability to react effectively with O3.

Degradation of p-Nitrophenol by activated persulfate with carbon-based materials.

The removal of p-nitrophenol (PNP) from wastewater was evaluated by the activated persulfate process using different materials - carbon xerogels (XG), carbon nanotubes (CNT), and activated carbon (AC) -, and also using such materials doped with nitrogen (XGM, CNTM and ACM). These carbon materials were impregnated with 2 wt.% of iron and tested in the oxidative process to assess the influence of their textural and surface chemical properties. The carbon-based materials' properties influence the efficiencies of the adsorption and oxidative processes; in adsorption, the materials with higher specific surface areas (SBET), i.e. AC (824 m2/g) and Fe/AC (807 m2/g), have shown to be the most promising (having achieved a PNP removal of about 20%); on the other hand, in the activated persulfate process the carbon or iron-containing carbon materials with the highest mesoporous areas (Smeso) were the preferential ones - XG and Fe/XG, respectively - reaching removals of 47.3% and 75.7% for PNP and 44.9 and 63.3% for TOC, respectively. Moreover, the presence of nitrogen groups on the samples' surface benefits both processes, being found that PNP degradation and mineralization increase with the nitrogen content. The stability of the best materials (XGM and Fe/XGM) was evaluated during four cycles, being noticed that while XGM lost catalytic activity, the Fe/XGM sample remained stable without leaching of iron. The quantification of intermediate compounds formed during persulfate oxidation was performed, and only oxalic acid was detected, in addition to PNP, being that their contribution to the TOC measured was higher than 99%. Experiments carried out in the presence of radical scavengers proved that only the sulfate radical is present under the acidic conditions used. Complete PNP oxidation and TOC removal of ∼96% were reached for the activated persulfate process, proving to be more attractive than the Fenton one.

Dose to the interventional radiologist in CTF-guided procedures.

The aim of this work was to assess the occupational dose received by an interventional radiologist (IR) during computed tomography fluoroscopy (CTF)-guided procedures; to identify the most exposed areas of the body including the hands and fingers; to suggest recommendations for individual monitoring; and to improve radiation safety of the practice. A total of 53 CTF-guided procedures were studied. Twelve whole-body dosimeters were worn by the IR in each procedure for the assessment of the personal dose equivalent, Hp(10), on the chest, waist, and back, both over and under the lead apron, as well as the personal dose equivalent, Hp(0.07), on both arms, knees, and feet. Special gloves with casings to fit extremity dosimeters were prepared to assess Hp(0.07) to the fingers. The measured chest dose values were higher than those on the waist and back; the dominant hand or the left side was the most exposed. In general, the ring, middle, and index fingers of the dominant hand were the most exposed (maximum in the 36-39 mSv range), while wrist dose was negligible compared to finger doses. Based on the results obtained the following recommendations are suggested: protective devices (lead aprons, thyroid shield, and goggles) should be worn; Hp(10) should be assessed at the chest level both above and below the lead apron; finger doses can be measured on the basis of each middle finger; the arm closer to the beam should be monitored; and finally, a wrist dosimeter will not provide useful information.

Photocatalytic ozonation of aniline with TiO2-carbon composite materials.

The photocatalytic ozonation of aniline (ANL) aqueous solutions was carried out in the presence of neat titanium dioxide (TiO2), multi-walled carbon nanotubes (MWCNT) and a composite of TiO2 and MWCNT. Independent tests for catalytic ozonation and photocatalysis were also carried out in order to explore the potential occurrence of a synergetic effect. Photocatalytic and catalytic ozonation carried out with an ozone dose of 50 g m-3 converted ANL in 15 min. Photocatalysis using P25, commercial TiO2, and an 80:20 (w/w) composite of P25 and MWCNT also led to total ANL conversion, but at longer reaction times. Removal of TOC was higher than 70% for all photocatalytic ozonation systems at 1 h of reaction. With the exception of neat MWCNT, photocatalytic ozonation in the presence of the selected samples led to nearly complete mineralization after 3 h of reaction. Photocatalytic ozonation completely removed oxalic acid (OXA) formed during ANL degradation. The concentration of oxamic acid (OMA, other ANL degradation by-product more refractory than OXA) generally increased with time, and in the photocatalytic ozonation with P25 based materials its concentration decreased earlier. The presence of nitrates and ammonium was confirmed during ANL degradation by all tested treatments, with the exception of the cation in TiO2 catalysed reactions.

Removal of oxalic acid, oxamic acid and aniline by a combined photolysis and ozonation process.

Aniline (ANL), an aromatic amine, oxalic acid (OXA) and oxamic acid (OMA), short-chain carboxylic acids, were chosen as model organic pollutants for testing the combined effect of neat photolysis and ozonation in the treatment of aqueous effluents. In order to better understand the results, single ozonation and neat photolysis were also carried out. OXA has a high refractory character relatively to single ozonation and neat photolysis only accounted for 26% conversion of OXA after 2 h of reaction. On the other hand, OXA complete degradation was observed in less than an hour when ozone and light were used simultaneously. Despite OMA, a compound never studied before by a combined ozonation and photolysis treatment, being highly refractory to oxidation, more than 50% was removed by photo-ozonation after 3 h of reaction. In the case of ANL, both single ozonation and photo-ozonation resulted in 100% removal in a short reaction period due to the high reactivity of ozone to attack this type of molecules; however, only the combined method leads to efficient mineralization (89%) after 3 h of reaction. A significant synergetic effect was observed in the degradation of the selected contaminants by the simultaneous use of ozone and light, since the mineralization rate of combined method is higher than the sum of the mineralization rates of the individual treatments. The promising results observed in the degradation of the selected contaminants are paving the way to the application of photo-ozonation in the treatment of wastewater containing this type of pollutants.

Coupling of THz radiation with intervalence band transitions in microcavities.

The strong coupling of THz radiation and material excitations can improve the quantum efficiency of THz emitters. In this paper, we investigate THz polaritons and antipolaritons based on valence band transitions, which allow TE coupling in a simple configuration. The approach can improve the quantum efficiency of THz based devices based on TE mode in the strong coupling regime of THz radiations and intervalence bands transitions in a GaAs/AlGaAs quantum wells. A Nonequilibrium Many Body Approach for the optical response beyond the Hartree-Fock approximation is used as input to the effective dielectric function formalism for the polariton/antipolariton problem. The energy dispersion relations in the THz range are obtained by adjusting the full numerical solutions to simple analytical expressions, which can be used for non specialists in a wide number of new structures and material systems. The combination of manybody and nonparabolicity at high densities leads to dramatic changes in the polariton spectra in a nonequilibrium configuration, which is only possible for intervalence band transitions.

Process design for wastewater treatment: catalytic ozonation of organic pollutants.

Emerging micropollutants have been recently the target of interest for their potential harmful effects in the environment and their resistance to conventional water treatments. Catalytic ozonation is an advanced oxidation process consisting of the formation of highly reactive radicals from the decomposition of ozone promoted by a catalyst. Nanocarbon materials have been shown to be effective catalysts for this process, either in powder form or grown on the surface of a monolithic structure. In this work, carbon nanofibers grown on the surface of a cordierite honeycomb monolith are tested as catalyst for the ozonation of five selected micropollutants: atrazine (ATZ), bezafibrate, erythromycin, metolachlor, and nonylphenol. The process is tested both in laboratorial and real conditions. Later on, ATZ was selected as a target pollutant to further investigate the role of the catalytic material. It is shown that the inclusion of a catalyst improves the mineralization degree compared to single ozonation.

A conserved tooth resorption mechanism in modern and fossil snakes.

Whether snakes evolved their elongated, limbless bodies or their specialized skulls and teeth first is a central question in squamate evolution. Identifying features shared between extant and fossil snakes is therefore key to unraveling the early evolution of this iconic reptile group. One promising candidate is their unusual mode of tooth replacement, whereby teeth are replaced without signs of external tooth resorption. We reveal through histological analysis that the lack of resorption pits in snakes is due to the unusual action of odontoclasts, which resorb dentine from within the pulp of the tooth. Internal tooth resorption is widespread in extant snakes, differs from replacement in other reptiles, and is even detectable via non-destructive µCT scanning, providing a method for identifying fossil snakes. We then detected internal tooth resorption in the fossil snake Yurlunggur, and one of the oldest snake fossils, Portugalophis, suggesting that it is one of the earliest innovations in Pan-Serpentes, likely preceding limb loss.

Microstructural analysis of Iberian expanded clay aggregates.

This article presents a detailed study of the microstructure of Iberian expanded clay lightweight aggregates (LWA). Other than more commonly used mercury porosimetry (MP) and water absorption methods, the experimental study involves optical microscopy, scanning electron microscopy (SEM), and microtomography (µ-CT). Pore connectivity and how it is deployed are shown to some degree, and the pore size spectrum is estimated. LWA are in general characterized by a dense outer shell up to 200 µm thick, encasing an inner cellular structure of 10-100 times bigger pore size. Aggregate pore sizes may span from some hundreds of nanometers up to over 1 mm, though the range of 1-25 µm is more typical. A noteworthy fraction of these pores is closed, and they are mainly up to 1 µm. It is also shown that macropore spatial arrangement is affected by the manufacturing process. A step forward is given to understanding how the outer shell and the inner pore network influence the mechanical and physical LWA properties, particularly the density and water absorption. The joint consideration of µ-CT and SEM seems to be the most appropriate methodology to study LWA microstructure. MP analysis is likely to distort LWA pore spectrum assessment.

Catalytic ozonation of oxalic acid using carbon nanofibres on macrostructured supports.

Carbon nanofibres (CNFs) were grown on different macrostructured supports such as cordierite monoliths, carbon felts and sintered metal fibres. The resulting composites exhibited excellent resistance to attrition/corrosion and its porosity is mainly due to mesoporous structures. The CNF/structured materials were tested in the ozonation of oxalic acid in a conventional semi-batch reactor after being crushed to powder form, and in a newly designed reactor that may operate in semi-batch or continuous operation. The CNFs supported on the different structured materials exhibited high catalytic activity in the mineralization of oxalic acid.

Study on the dose profile in CT-fluoroscopy.

This work aims to contribute to the description of the dose profile in Computed Tomography Fluoroscopy (CTF). Our approach uses a function model to fit the single slice dose profiles (SSDP) for any point inside the gantry of the CT unit, with special attention to points off the rotation axis. The function model was successfully tested with measurements performed using GafChromic film. The parameters of the SSDP at the rotation axis (isocenter) and at 8 cm and 16 cm off the isocenter were determined. The model allows an estimation of the slice thickness at the isocenter and for points at 8 cm and 16 cm off the isocenter. The differences between the slice thicknesses results in overestimation of the Computed Tomography Dose Index, CTDI, by values as high as 20% if the nominal slice thickness instead of the model estimated value is used. The results obtained in this work provided a good description of the dose profiles, which can be used in further studies such as comparisons with measurements performed with phantoms and patients.

Detection of enteroparasites in foliar vegetables commercialized in street- and supermarkets in Aparecida de Goiânia, Goiás, Brazil.

Foliar vegetables contaminated with fecal residues are an important route of transmission of intestinal parasites to humans. The aim of this study was to evaluate the presence of parasitic forms of protozoa and helminths on lettuces (Lactuca sativa) and collard greens (Brassica oleracea) sold in street- and supermarkets in the city of Aparecida de Goiânia, Goiás, Brazil. A total of 30 samples of each vegetable (15 samples from each supermarkets and street markets) was analyzed. All samples were processed by spontaneous sedimentation method and centrifugal flotation. In 45% of the samples, immature forms of intestinal parasites were identified with 66.7% helminths eggs and 33.3% protozoan cysts or oocysts. Significantly more lettuce samples were contaminated with eggs, cysts or oocyst of at least one parasite than collard green samples (U=216; Z=-3.45; P <0.001). The parasitic forms were identified morphologically up to the family level with eggs of Ancylostomatidae, Strongyloididae, Ascarididae and Taeniidae, or oocysts of Eimeriidae, to the genus with Cystoisospora sp. and Toxocara sp., and to the species level with Cystoisospora canis, Dipylidium caninum and Hymenolepis nana. The presence of these infective agents in lettuce and collard green from both street- and supermarkets highlights the high risk of spreading parasites by eating raw vegetables sold in Aparecida de Goiânia.

The potential of FT-IR spectroscopy for improving healthcare in sepsis - An animal model study.

Fourier Transform-Infrared (FT-IR) absorption spectroscopy has been used to investigate pathophysiological changes caused by sepsis. Sepsis has been defined as a potentially fatal organic dysfunction caused by a dysregulated host response to infection and can lead a patient to risk of death. This study used samples consisting of the blood plasma of mice which were induced to sepsis state, compared to a healthy group using FT-IR associated with attenuated total reflectance (ATR) spectroscopy. For statistical analysis, principal components analysis (PCA) and linear discriminant analysis (LDA) were applied, independently, to the second derivative spectra of both the fingerprint (900-1800 cm-1) and the high wavenumber (2800-3100 cm-1) regions. The technique efficiently differentiated the blood plasma of the two groups, sepsis and healthy mice, the analysis indicating that fatty acids and lipids in the blood samples could be an important biomarker of sepsis.

Giant controllable gigahertz to terahertz nonlinearities in superlattices.

Optical nonlinearities are of perpetual importance, notably connected with emerging new materials. However, they are difficult to exploit in the gigahertz-terahertz (GHz-THz) range at room temperature and using low excitation power. Here, we present a clear-cut theoretical and experimental demonstration of real time, low power, room temperature control of GHz-THz nonlinearities. The nonlinear susceptibility concept, successful in most materials, cannot be used here and we show in contrast, a complex interplay between applied powers, voltages and asymmetric current flow, delivering giant control and enhancement of the nonlinearities. Semiconductor superlattices are used as nonlinear sources and as mixers for heterodyne detection, unlocking their dual potential as compact, room temperature, controllable sources and detectors. The low input powers and voltages applied are within the range of compact devices, enabling the practical extension of nonlinear optics concepts to the GHz-THz range, under controlled conditions and following a predictive design tool.

Decolourisation of dye solutions by oxidation with H(2)O(2) in the presence of modified activated carbons.

The decolourisation of dye solutions by oxidation with H(2)O(2), using activated carbon as catalyst, is studied. For this purpose, three different samples, mainly differing in the respective surface chemistries, were prepared and characterized. Moreover, this work involved three pH levels, corresponding to acid, neutral and alkaline solutions, and six dyes belonging to several classes. The catalytic decolourisation tests were performed in a laboratorial batch reactor. Adsorption on activated carbon and non-catalytic peroxidation kinetic experiments were also carried out in the same reactor, in order to compare the efficiencies of the three processes. The non-catalytic reaction is usually inefficient and, typically, adsorption presents a low level of decolourisation. In these cases, the combination of activated carbon with hydrogen peroxide may significantly enhance the process, since the activated carbon catalyses the decomposition of H(2)O(2) into hydroxyl radicals, which are very reactive. Based on the experiments with the different activated carbon samples, which have similar physical properties, it is proved that the surface chemistry of the catalyst plays a key role, being the basic sample the most active. This is discussed considering the involvement of the free electrons on the graphene basal planes of activated carbon as active centres for the catalytic reaction. Additionally, it is shown that the decolourisation is enhanced at high pH values, and a possible explanation for this observation, based on the proposed mechanism, is given.

TYPE TESTING OF LiF:Mg,Cu,P (TLD-100H) WHOLE-BODY DOSEMETERS FOR THE ASSESSMENT OF Hp(10) AND Hp(0.07).

In this work, the initial results of the type testing of the LiF:Mg,Cu,P (TLD-100H) whole-body personal dosemeters are presented. An assessment of reproducibility, linearity of the response, the residual signal as a function of the dose, energy and angular dependence of the response was performed. In general, the dosemeters show good reproducibility for different dose values and a linear behaviour for a range between 0.1 and 300 mSv. The detection limits obtained are lower than 50 µSv. The system presents a good energy and angular response for different radiation qualities.

Continuous ozonation of urban wastewater: Removal of antibiotics, antibiotic-resistant Escherichia coli and antibiotic resistance genes and phytotoxicity.

This work evaluated the removal of a mixture of eight antibiotics (i.e. ampicillin (AMP), azithromycin (AZM), erythromycin (ERY), clarithromycin (CLA), ofloxacin (OFL), sulfamethoxazole (SMX), trimethoprim (TMP) and tetracycline (TC)) from urban wastewater, by ozonation operated in continuous mode at different hydraulic retention times (HRTs) (i.e. 10, 20, 40 and 60 min) and specific ozone doses (i.e. 0.125, 0.25, 0.50 and 0.75 gO3 gDOC- 1). As expected, the efficiency of ozonation was highly ozone dose- and contact time-dependent. The removal of the parent compounds of the selected antibiotics to levels below their detection limits was achieved with HRT of 40 min and specific ozone dose of 0.125 gO3 gDOC- 1. The effect of ozonation was also investigated at a microbiological and genomic level, by studying the efficiency of the process with respect to the inactivation of Escherichia coli and antibiotic-resistant E. coli, as well as to the reduction of the abundance of selected antibiotic resistance genes (ARGs). The inactivation of total cultivable E. coli was achieved under the experimental conditions of HRT 40 min and 0.25 gO3 gDOC-1, at which all antibiotic compounds were already degraded. The regrowth examinations revealed that higher ozone concentrations were required for the permanent inactivation of E. coli below the Limit of Quantification (

Anandamide and NADA bi-directionally modulate presynaptic Ca2+ levels and transmitter release in the hippocampus.

BACKGROUND AND PURPOSE: Inhibitory CB(1) cannabinoid receptors and excitatory TRPV(1) vanilloid receptors are abundant in the hippocampus. We tested if two known hybrid endocannabinoid/endovanilloid substances, N-arachidonoyl-dopamine (NADA) and anandamide (AEA), presynapticaly increased or decreased intracellular calcium level ([Ca(2+)](i)) and GABA and glutamate release in the hippocampus. EXPERIMENTAL APPROACH: Resting and K(+)-evoked levels of [Ca(2+)](i) and the release of [(3)H]GABA and [(3)H]glutamate were measured in rat hippocampal nerve terminals. KEY RESULTS: NADA and AEA per se triggered a rise of [Ca(2+)](i) and the release of both transmitters in a concentration- and external Ca(2+)-dependent fashion, but independently of TRPV(1), CB(1), CB(2), or dopamine receptors, arachidonate-regulated Ca(2+)-currents, intracellular Ca(2+) stores, and fatty acid metabolism. AEA was recently reported to block TASK-3 potassium channels thereby depolarizing membranes. Common inhibitors of TASK-3, Zn(2+), Ruthenium Red, and low pH mimicked the excitatory effects of AEA and NADA, suggesting that their effects on [Ca(2+)](i) and transmitter levels may be attributable to membrane depolarization upon TASK-3 blockade. The K(+)-evoked Ca(2+) entry and Ca(2+)-dependent transmitter release were inhibited by nanomolar concentrations of the CB(1) receptor agonist WIN55212-2; this action was sensitive to the selective CB(1) receptor antagonist AM251. However, in the low micromolar range, WIN55212-2, NADA and AEA inhibited the K(+)-evoked Ca(2+) entry and transmitter release independently of CB(1) receptors, possibly through direct Ca(2+) channel blockade. CONCLUSIONS AND IMPLICATIONS: We report here for hybrid endocannabinoid/endovanilloid ligands novel dual functions which were qualitatively similar to activation of CB(1) or TRPV(1) receptors, but were mediated through interactions with different targets.

Anchoring of a [Mn(salen)Cl] complex onto mesoporous carbon xerogels.

Carbon xerogels were synthesized by the conventional sol-gel approach using formaldehyde and resorcinol. The wet gel was dried by two different procedures followed by carbonization, leading to mesoporous carbon xerogels with considerably different pore size distributions. The materials were subsequently oxidized with air, in order to introduce functional groups on the surface, in particular phenols, anhydrides and carbonyls. The capacity of the carbon xerogels for direct immobilization of metal complexes was tested with a manganese(III) salen complex which possesses an extended ligand pi system and two reactive hydroxyl groups on the aldehyde fragment. The manganese loadings of the various samples indicate that larger amounts of Mn(III) complex were immobilized in the oxidized carbon xerogels when compared with the parent unactivated materials, suggesting that complex immobilization took place preferably by covalent bond between the surface oxygen functional groups and the ligand reactive groups, rather than by pi-pi interactions. The size and shape of the carbon xerogel pores were also shown to play an important role in the final loading of the manganese(III) salen complex.

Ozonation of aniline promoted by activated carbon.

The removal of aniline from aqueous solutions by simultaneous use of ozone and activated carbon was investigated at different solution pH. For comparative purposes, single ozonation and adsorption on activated carbon were carried out in the same experimental set-up. In order to evaluate the role of the activated carbon surface chemistry during ozonation, a commercial activated carbon, Norit GAC 1240 PLUS, was submitted to oxidation in the liquid phase with HNO(3). The texture and surface chemistry of the activated carbon samples were characterized. During ozonation, complete conversion of aniline was achieved after approximately 20 min, regardless of the presence of activated carbon. In all cases, several by-products were formed during ozonation. Nitrobenzene, o- and p-aminophenol were the primary aromatic oxidation by-products identified. In terms of TOC removal, best results were achieved by the simultaneous use of ozone and activated carbon. Though there is a strong contribution of adsorption, a considerable synergetic effect between ozone and activated carbon is observed. In general, activated carbon promotes the reaction of ozonation enhancing the efficiency of this treatment process. The basic activated carbon presented greater activity in this process leading to higher mineralization rates.