This work presents data regarding the occurrence and treatment of Contaminants of Emerging Concern (CECs) in Brazil in the past decade. The literature review (2011−2021) revealed the detection of 87 ...pharmaceutical drugs and personal care products, 58 pesticides, 8 hormones, 2 illicit drugs, caffeine and bisphenol A in distinct matrices (i.e.: wastewater, groundwater, sea water, rainwater, surface water, drinking water and hospital effluent). Concentrations of CECs varied from ng-μg L−1 depending on the location, compound and matrix. The inefficiency of conventional wastewater treatment methods on the removal of CECs and lack of basic sanitation in some regions in the country aggravates contamination of Brazilian aquatic environments and poses potential environmental and health risks. Advanced oxidation processes (AOPs) are pointed out as viable and efficient alternatives to degrade CECs and prevent environmental contamination. A total of 375 studies involving the use of AOPs in Brazilian aqueous matrices were published in the last decade. Fenton and photo-Fenton processes, photo-peroxidation, ozonation, electrochemical advanced oxidation and heterogeneous photocatalysis are some of the AOPs applied by Brazilian research groups. Although many works discuss the importance of applying these technologies for CECs removal in real treatment plants, most of these studies assess the treatment of distilled water or simulated effluent. Therefore, the conduction of studies applying AOPs in real matrices are critical to drive the implementation of these processes coupled to conventional water and wastewater treatment in real plants in order to prevent the contamination of environmental matrices by CECs in Brazil.
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•Occurrence and impact of CECs in Brazilian waters were carefully revised.•PPCPs and pesticides were among the most dominant classes of CECs.•Economic and social activities directly impact types of CECs detected per region.•Studies evaluating CECs removal via AOPs were summarized.•There is critical need for evaluation of AOPs in real matrices and in pilot-scale.
SiO2@TiO2 core-shell nanoparticles were successfully synthesized via a simple, reproducible, and low-cost method and tested for methylene blue adsorption and UV photodegradation, with a view to their ...application in wastewater treatment. The monodisperse SiO2 core was obtained by the classical Stöber method and then coated with a thin layer of TiO2, followed by calcination or hydrothermal treatments. The properties of SiO2@TiO2 core-shell NPs resulted from the synergy between the photocatalytic properties of TiO2 and the adsorptive properties of SiO2. The synthesized NPs were characterized using FT-IR spectroscopy, HR-TEM, FE–SEM, and EDS. Zeta potential, specific surface area, and porosity were also determined. The results show that the synthesized SiO2@TiO2 NPs that are hydrothermally treated have similar behaviors and properties regardless of the hydrothermal treatment type and synthesis scale and better performance compared to the SiO2@TiO2 calcined and TiO2 reference samples. The generation of reactive species was determined by EPR, and the photocatalytic activity was evaluated by the methylene blue (MB) removal in aqueous solution under UV light. Hydrothermally treated SiO2@TiO2 showed the highest adsorption capacity and photocatalytic removal of almost 100% of MB after 15 min in UV light, 55 and 89% higher compared to SiO2 and TiO2 reference samples, respectively, while the SiO2@TiO2 calcined sample showed 80%. It was also observed that the SiO2-containing samples showed a considerable adsorption capacity compared to the TiO2 reference sample, which improved the MB removal. These results demonstrate the efficient synergy effect between SiO2 and TiO2, which enhances both the adsorption and photocatalytic properties of the nanomaterial. A possible photocatalytic mechanism was also proposed. Also noteworthy is that the performance of the upscaled HT1 sample was similar to one of the lab-scale synthesized samples, demonstrating the potentiality of this synthesis methodology in producing candidate nanomaterials for the removal of contaminants from wastewater.
This manuscript describes the synthesis and characterization of five new organic–inorganic hybrid (OIH) sol-gel materials that were obtained from a functionalized siloxane ...3-glycidoxypropyltrimethoxysilane (GPTMS) by the reaction with the new Jeffamine®, namely three different diamines, i.e., EDR-148, RFD-270, and THF-170, a secondary diamine, i.e., SD-2001, and a triamine, i.e., T-403. The OIH sol-gel materials were characterized by UV-visible absorption spectrophotometry, steady-state photoluminescence spectroscopy, and electrochemical impedance spectroscopy. The reported OIH sol-gel materials showed that, with the exception of the samples prepared with Jeffamine® SD-2001, the transmittance values ranged between 61% and 79%. Regarding the capacitance data, the values reported changed between 0.008 and 0.013 nF cm−2. Due to their optical and electrical properties these new OIH materials show promising properties for applications as support films in an optical sensor area such as fiber sensor devices. Studies to assess the chemical stability of the OIH materials in contact with cement pastes after 7, 14, and 28 days were also performed. The samples prepared with THF–170 and GPTMS, when compared to the samples prepared with RFD-270 and T-403, exhibited improved behavior in the cement paste (alkaline environment), showing promising properties for application as support film in optical fiber sensors in the civil engineering field.
The development of sensors for pH monitoring is of extreme importance in the monitoring of concrete and reinforced concrete structures. Imidazole derivatives are promising probes for pH sensing due ...to the amphoteric nature of their heterocyclic ring, which can be protonated/deprotonated upon pH changes. In this work, a triarylimidazole was synthesised and used as a dopant in an organic-inorganic hybrid (OIH) sol-gel matrix to obtain a pH-sensitive membrane for further application in optical fibre sensors (OFS). The triarylimidazole probe shows fluorimetric response in pH between 9 and 13, which is the desired range for monitoring carbonation of concrete. This degradation process lowers the highly alkaline pH of concrete (12.5-13) to values below 9, which creates favourable conditions for corrosion of concrete reinforcement. The OIH membranes used were based on Jeffamine THF170 and 3-glycidoxypropytrimethoxysilane precursors, which had already been shown to be suitable and resistant in contact with cement-based materials. The OIHs were doped with three different contents of the triarylimidazole and the structural, dielectric, thermal and optical properties of the pure and doped OIH materials were evaluated. The structural analysis showed that the presence of the triarylimidazole did not change the structural properties of the OIH material. Electrochemical impedance spectroscopy showed that in the doped samples the conductivity increased with the imidazole concentration. The
r
obtained for the doped samples ranged approximately from 11 to 19 and for the pure matrices was 8. Thermal analysis showed that these materials are stable up to 350 °C and that the presence of the probe did not change that feature. The optical properties showed that the prepared OIH materials have promising properties to be used as pH sensitive fluorimetric probes.
OIH sol-gel materials based on Jeffamine THF-170 and GPTMS, doped with triarylimidazole, were synthesized. The
r
obtained for the OIH doped samples ranged between 11 and 19. The OIHs are thermally stable for fresh concrete purposes.
The role of different operational parameters related to Fenton reactions (pH, concentration of Fe
2+
and H
2
O
2
, and reaction time) and of Cl
−
and SO
4
−
was investigated in the degradation of ...the azo dye Direct Red 81, expressed in terms of its decolorization. The factorial design and Pareto’s charts showed that only Fe
2+
concentration and pH influence the decolorization under the conditions evaluated. So, only these parameters were optimized using the response surface model. Under the best experimental conditions (initial pH 2.5, 11 mg L
−1
Fe
2+
, 78 mg L
−1
H
2
O
2
, and 20 min of reaction), 94 % of decolorization was achieved. However, even under the these conditions, but in the presence of Cl
−
and SO
4
−
, a striking loss of efficiency was observed as the concentration of these ions was increased, due the formation of chloride- and sulfate-iron complexes and less reactive inorganic radicals (Cl
2
•–
and SO
4
•–
). The results show that the presence of Cl
−
is more deleterious, since sulfate-iron complexes are more reactive towards H
2
O
2
, and the SO
4
•–
turns out to favor the degradation. On the other hand, the negative effect of Cl
−
can be compensated by increasing the chloride concentration up to 300 mmol L
−1
. In addition, although a high degradation level has been obtained by monitoring the dye absorbance and by HPLC-UV, a low mineralization occurred, being generated degradation products of higher ecotoxicity to
Vibrio fischeri
, showing the need of subsequent studies to identify these compounds as well as the application of additional treatments aiming the complete mineralization of the dye.
Organic-inorganic hybrids (OIH) are materials that can be easily synthesized by the sol-gel method and combine the advantages of organic and inorganic moieties within a single polymeric matrix. ...Imidazole derivatives are versatile organic compounds that can change their optical properties with the variation of pH due to the protonation or deprotonation of the nitrogen atoms. This work reports the preparation of different OIHs doped with different contents of two imidazole compounds (
,
). The obtained materials were characterized structurally by FTIR, and the dielectric properties were studied by electrochemical impedance spectroscopy. The optical properties were studied by UV-Vis absorption and fluorescence spectroscopies. The FTIR analysis showed that the presence of the imidazole does not change the structural properties of the matrices. The normalized resistance values obtained for the doped matrices ranged between 8.57 and 9.32 Ω cm
, all being higher than the undoped matrix. The σ ranged between 9.49 and 10.28 S cm
, being all higher than the pure OIH samples. Compound
showed a maximum absorption peak at 390 nm, which is present in the OIH spectra, proving the presence of the compound. In the case of compound
, a maximum absorption wavelength at 412 nm was found, and the compound peak was not clear, which may indicate that an interaction between the compound and the matrix occurred. A synergetic effect between the intrinsic emission of the matrix and the fluorescence of
is found on the OIH-doped matrices.
The use of advanced sensing devices for concrete and reinforced concrete structures (RCS) is considered a rational approach for the assessment of repair options and scheduling of inspection and ...maintenance strategies. The immediate benefits are cost reduction and a reliable prevention of unpredictable events. The use of optical fiber sensors (OFS) for such purposes has increased considerably in the last few years due to their intrinsic advantages. In most of the OFS, the chemical transducer consists of immobilized chemical reagents placed in the sensing region of the optical sensor by direct deposition or by encapsulation in a polymeric matrix. The choice of the support matrix impacts directly on the performance of the OFS. In the last two decades, the development of OFS functionalized with organic–inorganic hybrid (OIH) sol–gel membranes have been reported. Sol–gel route is considered a simple method that offers several advantages when compared to traditional synthesis processes, allowing to obtain versatile materials with unique chemical and physical properties, and is particularly valuable in the design of OIH materials. This review will provide an update of the current state-of-the-art of the OFS based on OIH sol-gel materials for concrete and RCS since 2016 until mid-2021. The main achievements in the synthesis of OIH membranes for deposition on OFS will be discussed. The challenges and future directions in this field will also be considered, as well as the main limitations of OFS for RCS monitoring.
SiOsub.2 @TiOsub.2 core-shell nanoparticles were successfully synthesized via a simple, reproducible, and low-cost method and tested for methylene blue adsorption and UV photodegradation, with a view ...to their application in wastewater treatment. The monodisperse SiOsub.2 core was obtained by the classical Stöber method and then coated with a thin layer of TiOsub.2 , followed by calcination or hydrothermal treatments. The properties of SiOsub.2 @TiOsub.2 core-shell NPs resulted from the synergy between the photocatalytic properties of TiOsub.2 and the adsorptive properties of SiOsub.2 . The synthesized NPs were characterized using FT-IR spectroscopy, HR-TEM, FE–SEM, and EDS. Zeta potential, specific surface area, and porosity were also determined. The results show that the synthesized SiOsub.2 @TiOsub.2 NPs that are hydrothermally treated have similar behaviors and properties regardless of the hydrothermal treatment type and synthesis scale and better performance compared to the SiOsub.2 @TiOsub.2 calcined and TiOsub.2 reference samples. The generation of reactive species was determined by EPR, and the photocatalytic activity was evaluated by the methylene blue (MB) removal in aqueous solution under UV light. Hydrothermally treated SiOsub.2 @TiOsub.2 showed the highest adsorption capacity and photocatalytic removal of almost 100% of MB after 15 min in UV light, 55 and 89% higher compared to SiOsub.2 and TiOsub.2 reference samples, respectively, while the SiOsub.2 @TiOsub.2 calcined sample showed 80%. It was also observed that the SiOsub.2 -containing samples showed a considerable adsorption capacity compared to the TiOsub.2 reference sample, which improved the MB removal. These results demonstrate the efficient synergy effect between SiOsub.2 and TiOsub.2 , which enhances both the adsorption and photocatalytic properties of the nanomaterial. A possible photocatalytic mechanism was also proposed. Also noteworthy is that the performance of the upscaled HT1 sample was similar to one of the lab-scale synthesized samples, demonstrating the potentiality of this synthesis methodology in producing candidate nanomaterials for the removal of contaminants from wastewater.
The main volatile organic compounds found at gasoline stations are benzene, toluene, ethylbenzene, and xylene isomers (BTEX). They cause several harmful effects on human health. Regulatory Norm 7 ...(1978) provides that, in Brazil, biological monitoring of toluene and xylene is carried out by measuring the urinary metabolites hippuric acid (HA) and methylhippuric acid (MHA), respectively. The objective of this study was to assess the exposure to toluene and xylene and to identify related signs and symptoms in gasoline station workers. A cross-sectional epidemiological study was conducted with workers occupationally exposed to fuels. These gasoline station workers were divided into two groups: 94 workers exposed mainly by inhalation (convenience store workers (CSWs)) and 181 workers exposed by inhalation and dermal route (filling station attendants (FSAs)). A comparison group was formed by 119 workers not occupationally exposed to fuels (office workers (OWs)). Workers exposed to fuels had higher average levels of these exposure biomarkers (HA and MHA), which were also higher in convenience store workers than in filling station attendants. In addition, individuals exposed to the solvents present in gasoline had altered mood/depression, cramps, dizziness, drowsiness, headaches, irritability/nervousness, weakness, weight loss, and other symptoms more frequently and had higher urinary levels of HA and MHA compared to the comparison group. Gasoline station workers showed high levels of HA and MHA, reflecting high occupational exposure to the solvents toluene and xylene present in gasoline, demonstrating that changes in the current legislation and in the work environment are necessary to ensure better health protection for these workers.
Alpha-synuclein (aSyn) is a central player in the pathogenesis of synucleinopathies due to its accumulation in typical protein aggregates in the brain. However, it is still unclear how it contributes ...to neurodegeneration. Type-2 diabetes mellitus is a risk factor for Parkinson's disease (PD). Interestingly, a common molecular alteration among these disorders is the age-associated increase in protein glycation. We hypothesized that glycation-induced neuronal dysfunction is a contributing factor in synucleinopathies. Here, we dissected the impact of methylglyoxal (MGO, a glycating agent) in mice overexpressing aSyn in the brain. We found that MGO-glycation potentiates motor, cognitive, olfactory, and colonic dysfunction in aSyn transgenic (Thy1-aSyn) mice that received a single dose of MGO via intracerebroventricular injection. aSyn accumulates in the midbrain, striatum, and prefrontal cortex, and protein glycation is increased in the cerebellum and midbrain. SWATH mass spectrometry analysis, used to quantify changes in the brain proteome, revealed that MGO mainly increase glutamatergic-associated proteins in the midbrain (NMDA, AMPA, glutaminase, VGLUT and EAAT1), but not in the prefrontal cortex, where it mainly affects the electron transport chain. The glycated proteins in the midbrain of MGO-injected Thy1-aSyn mice strongly correlate with PD and dopaminergic pathways. Overall, we demonstrated that MGO-induced glycation accelerates PD-like sensorimotor and cognitive alterations and suggest that the increase of glutamatergic signaling may underly these events. Our study sheds new light into the enhanced vulnerability of the midbrain in PD-related synaptic dysfunction and suggests that glycation suppressors and anti-glutamatergic drugs may hold promise as disease-modifying therapies for synucleinopathies.
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