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1.
Chemosphere ; 311(Pt 2): 137197, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36356819

RESUMO

Soil contamination by PCBs is still known as a serious problem across the world, and the development of new technologies or the improvement of existing ones (e.g. higher efficiency, shorter processing time, lower input energy) are more and more important. Moreover, understanding the chemistry of the entire process, from a mechanistic point of view, can accelerate the process of improvement. In these circumstances, we attempted a clarification of the highly efficient degradation of PCBs by nano-sized particle of metallic Ca in CaO ("nCa") at 250 °C in dry solid state conditions. The reaction involved the hydrodechlorination, simple reduction, reductive coupling and hydroxylation processes. The detoxification efficiency reached over 99%. A tentative pathway and mechanism is proposed for explaining the final reactions products. Finally, the process was applied to real PCBs-contaminated soil, containing various amounts of PCBs, with a total success in completely eliminating the toxic polychlorinated compounds.

2.
Materials (Basel) ; 14(22)2021 Nov 10.
Artigo em Inglês | MEDLINE | ID: mdl-34832168

RESUMO

Today's view on gas sensors end-users is more directed toward miniaturization, low power consumption, and intelligent device integration aiming to reply to several hot issues such as high sensitivity, optimum selectivity, fast response/recovery transients, and good long time stability [...].

3.
Materials (Basel) ; 14(2)2021 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-33478089

RESUMO

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)2 have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)2 native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 °C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

4.
Materials (Basel) ; 13(21)2020 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-33143340

RESUMO

Pd deposited on CeOx-MnOx/La-Al2O3 has been prepared as a sensitive material for methane (CH4) detection. The effect of different amounts (1.25%, 2.5% and 5%) of Pd loading has been investigated. The as prepared materials were deposited on Pt microcoils using a drop-coating method, as a way of developing pellistors operated using a Wheatstone bridge configuration. By spanning the operating temperature range between 300 °C and 550 °C, we established the linearity region as well as the maximum sensitivity towards 4900 ppm of CH4. By making use of the sigmoid dependence of the output voltage signal from the Wheatstone bridge, the gas surface reaction and diffusion phenomena have been decoupled. The pellistor with 5% Pd deposited on CeOx-MnOx/La-Al2O3 exhibited the highest selective-sensitivity in the benefit of CH4 detection against threshold limits of carbon monoxide (CO), sulfur dioxide (SO2) and hydrogen sulfide (H2S). Accordingly, adjusting the percent of Pd makes the preparation strategies of pellistors good candidates towards CH4 detection.

5.
Materials (Basel) ; 13(21)2020 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-33121075

RESUMO

In this work, (Ba0.75Sr0.25) (Ti0.95Co0.05) O3 perovskite nanostructured material, denoted subsequently as Co-doped BaSrTiO3, was synthesized in a one-step process in hydrothermal conditions. The obtained powder was heat-treated at 800 °C and 1000 °C, respectively, in order to study nanostructured powder behavior during thermal treatment. The Co-doped BaSrTiO3 powder was pressed into pellets of 5.08 cm (2 inches) then used for thin film deposition onto commercial Al2O3 substrates by RF sputtering method. The microstructural, thermal, and gas sensing properties were investigated. The electrical and thermodynamic characterization allowed the evaluation of thermodynamic stability and the correlation of structural features with the sensing properties revealed under real operating conditions. The sensing behavior with respect to the temperature range between 23 and 400 °C, for a fixed CO2 concentration of 3000 ppm, highlighted specific differences between Co-doped BaSrTiO3 treated at 800 °C compared to that treated at 1000 °C. The influence of the relative humidity level on the CO2 concentrations and the other potential interfering gases was also analyzed. Two possible mechanisms for CO2 interaction were then proposed. The simple and low-cost technology, together with the high sensitivity when operating at room temperature corresponding to low power consumption, suggests that Co-doped BaSrTiO3 has a good potential for use in developing portable CO2 detectors.

6.
Materials (Basel) ; 13(9)2020 May 11.
Artigo em Inglês | MEDLINE | ID: mdl-32403264

RESUMO

Mesoporous CeO2:Mn3O4 materials (3:7 and 7:3 molar ratio) were prepared by co-precipitation and deposited as porous thick films over alumina (Al2O3) planar substrate provided with Pt meander. The aim was oriented towards detecting low levels methane (CH4) at moderate operating temperatures. Herein we demonstrated that the sensitivity of catalytic micro-converters (CMCs) towards a given peak of CH4 concentration corresponds to specific gas-surface interaction phenomena. More precisely, a transition from thermal conductivity to combustion rate is likely to occur when CMCs are operated under real atmospheric conditions (normal pressure, presence of relative humidity, and constant operating temperature). The response to CH4 was analyzed over different gas flows and different gas concentrations under the same operating regime. The materials were fully characterized by adsorption-desorption isotherms, H2-Temperature Programmed Reduction (H2-TPR), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), and Raman spectroscopies. Thus, the applicative aspect of using CeO2:Mn3O4 as moderate temperature CMC for CH4 detection is brought to the fore.

7.
ACS Sens ; 5(5): 1389-1397, 2020 05 22.
Artigo em Inglês | MEDLINE | ID: mdl-32283927

RESUMO

When the gas sensor active layer film thickness is decreased, increased sensitivity to changes in the adsorbate concentration is expected when measuring the resistance of the layer, in particular when this thickness is on the order of the Debye length of the material (one-tens of nanometers); however, this is demonstrated only for a limited number of materials. Herein, ultrathin NiO films of different thicknesses (8-21 nm) have been deposited via chemical vapor deposition to fabricate gas sensor devices. Sensor performance for a range of NO2 concentrations (800 part-per-billion to 7 part-per-million) was evaluated and an optimum operating temperature of 125 °C determined. The dependence of the potential relative changes with respect to the NO2 concentration and of the sensor signal with respect to the geometrical parameters was qualitatively evaluated to derive a transduction model capable of fitting the experimental results. The selective sensitivity toward NO2 was confirmed by the limited response for different reducing gases, CO, CH4, NH3, and SO2, under optimum operating conditions, and the sensor signal toward NO2 increased with decreasing thickness, demonstrating that the concept of a Debye length dependence of sensitivity is applicable for the p-type semiconductor NiO. In addition, these NiO sensors were exposed to different relative levels of humidity over a wide range of operating temperatures and were found to display humidity tolerance far superior to those in previous reports on SnO2 materials.


Assuntos
Gases , Semicondutores , Umidade , Temperatura
8.
ACS Sens ; 4(9): 2420-2428, 2019 09 27.
Artigo em Inglês | MEDLINE | ID: mdl-31414598

RESUMO

Semiconducting metal oxide (SMOX)-based gas sensors are indispensable for safety and health applications, for example, explosive, toxic gas alarms, controls for intake into car cabins, and monitor for industrial processes. In the past, the sensor community has been studying polycrystalline materials as sensors where the porous and random microstructure of the SMOX does not allow a separation of the phenomena involved in the sensing process. This led to conduction models that can model and predict the behavior of the overall response, but they were not capable of giving fundamental information regarding the basic mechanisms taking place. The study of epitaxial layers is a definite improvement, allowing clarifying the different aspects and contributions of the sensing mechanisms. A detailed analytical model of the transduction function for n- and p-type single-crystalline/compact metal oxide gas sensors was developed that directly relates the conductance of the sample with changes in the surface electrostatic potential. Combined dc resistance and work function measurements were used in a compact SnO2(101) layer in operando conditions that allowed us to check the validity of our model in the region where Boltzmann approximation holds to determine the surface and bulk properties of the material.


Assuntos
Técnicas de Química Analítica/instrumentação , Condutividade Elétrica , Gases/análise , Compostos de Estanho/química
9.
Materials (Basel) ; 12(11)2019 May 31.
Artigo em Inglês | MEDLINE | ID: mdl-31159181

RESUMO

This study presents the synthesis and characterization of lanthanum-modified alumina supported cerium-manganese mixed oxides, which were prepared by three different methods (coprecipitation, impregnation and citrate-based sol-gel method) followed by calcination at 500 °C. The physicochemical properties of the synthesized materials were investigated by various characterization techniques, namely: nitrogen adsorption-desorption isotherms, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and H2-temperature programmed reduction (TPR). This experimental study demonstrated that the role of the catalytic surface is much more important than the bulk one. Indeed, the incipient impregnation of CeO2-MnOx catalyst, supported on an optimized amount of 4 wt.% La2O3-Al2O3, provided the best results of the catalytic combustion of methane on our catalytic micro-convertors. This is mainly due to: (i) the highest pore size dimensions according to the Brunauer-Emmett-Teller (BET) investigations, (ii) the highest amount of Mn4+ or/and Ce4+ on the surface as revealed by XPS, (iii) the presence of a mixed phase (Ce2MnO6) as shown by X-ray diffraction; and (iv) a higher reducibility of Mn4+ or/and Ce4+ species as displayed by H2-TPR and therefore more reactive oxygen species.

10.
Sensors (Basel) ; 18(3)2018 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-29494504

RESUMO

Analyte sensitivity for gas sensors based on semiconducting metal oxides should be highly dependent on the film thickness, particularly when that thickness is on the order of the Debye length. This thickness dependence has previously been demonstrated for SnO2 and inferred for TiO2. In this paper, TiO2 thin films have been prepared by Atomic Layer Deposition (ALD) using titanium isopropoxide and water as precursors. The deposition process was performed on standard alumina gas sensor platforms and microscope slides (for analysis purposes), at a temperature of 200 °C. The TiO2 films were exposed to different concentrations of CO, CH4, NO2, NH3 and SO2 to evaluate their gas sensitivities. These experiments showed that the TiO2 film thickness played a dominant role within the conduction mechanism and the pattern of response for the electrical resistance towards CH4 and NH3 exposure indicated typical n-type semiconducting behavior. The effect of relative humidity on the gas sensitivity has also been demonstrated.

11.
J Hazard Mater ; 331: 150-160, 2017 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-28254662

RESUMO

Development of new sensitive materials by different synthesis routes in order to emphasize the sensing properties for hazardous H2S detection is one of a nowadays challenge in the field of gas sensors. In this study we obtained mesoporous SnO2-CuWO4 with selective sensitivity to H2S by an inexpensive synthesis route with low environmental pollution level, using tripropylamine (TPA) as template and polyvinylpyrrolidone (PVP) as dispersant/stabilizer. In order to bring insights about the intrinsic properties, the powders were characterized by means of a variety of complementary techniques such as: X-Ray Diffraction, XRD; Transmission Electron Microscopy, TEM; High Resolution TEM, HRTEM; Raman Spectroscopy, RS; Porosity Analysis by N2 adsorption/desorption, BET; Scanning Electron Microscopy, SEM and X-ray Photoelectron Spectroscopy, XPS. The sensors were fabricated by powders deposition via screen-printing technique onto planar commercial Al2O3 substrates. The sensor signals towards H2S exposure at low operating temperature (100°C) reaches values from 105 (for SnWCu600) to 106 (for SnWCu800) over the full range of concentrations (5-30ppm). The recovery processes were induced by a short temperature trigger of 500°C. The selective sensitivity was underlined with respect to the H2S, relative to other potential pollutants and relative humidity (10-70% RH).

12.
Waste Manag ; 60: 428-438, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-28089400

RESUMO

The separation of plastics containing brominated flame retardants (BFR) like (acrylonitrile-butadiene-styrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) from automobile and electronic waste shredder residue (ASR/ESR) are a major concern for thermal recycling. In laboratory scale tests using a hybrid nano-Fe/Ca/CaO assisted ozonation treatment has been found to selectively hydrophilize the surface of ABS/HIPS and PVC plastics, enhancing ABS wettability and thereby promoting its separation from ASR/ESR by means of froth flotation. The water contact angles, of ABS/HIPS and PVC decreased, about 18.7°, 18.3°, and 17.9° in ASR and about 21.2°, 20.7°, and 20.0° in ESR respectively. SEM-EDS, FT-IR, and XPS analyses demonstrated a marked decrease in [Cl] and a significant increase in the number of hydrophilic groups, such as CO, CO, and (CO)O, on the PVC or ABS surface. Under froth flotation conditions at 50rpm, about 99.1% of combined fraction of ABS/HIPS in ASR samples and 99.6% of ABS/HIPS in ESR samples were separated as settled fraction. After separation, the purity of the recovered combined ABS/HIPS fraction was 96.5% and 97.6% in ASR and ESR samples respectively. Furthermore, at 150rpm a 100% PVC separation in the settled fraction, with 98% and 99% purity in ASR and ESR plastics, respectively. Total recovery of non-ABS/HIPS and PVC plastics reached nearly 100% in the floating fraction. Further, this process improved the quality of recycled ASR/ESR plastics by removing surface contaminants or impurities.


Assuntos
Automóveis , Resíduo Eletrônico , Ozônio/química , Reciclagem/métodos , Acrilonitrila , Butadienos , Cálcio/química , Compostos de Cálcio/química , Interações Hidrofóbicas e Hidrofílicas , Ferro/química , Nanotecnologia/métodos , Óxidos/química , Poliestirenos , Cloreto de Polivinila , Eliminação de Resíduos/métodos , Espectroscopia de Infravermelho com Transformada de Fourier , Resíduos/análise
13.
Environ Sci Pollut Res Int ; 24(1): 591-597, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27743324

RESUMO

Both hexachlorobenzene and hexabromobenzene were successfully hydrodehalogenated to the monohalogenated derivative and ultimately to benzene (which was subsequently reduced to cyclohexane) using a mixture of metallic Ca, ethanol, and Rh/C, by simple stirring in diethyl ether, at room or mild temperature (60 °C). Various experiments were performed in order to assess the role of the solvent and Rh/C catalyst, as well as for elucidating the reaction pathway.


Assuntos
Bromobenzenos/química , Cálcio/química , Etanol/química , Hexaclorobenzeno/química , Ródio/química , Solventes/química , Carbono/química , Catálise , Temperatura
14.
Environ Sci Pollut Res Int ; 24(5): 4469-4479, 2017 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-27943143

RESUMO

One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.


Assuntos
Compostos de Cálcio/química , Cálcio/química , Retardadores de Chama/análise , Ferro/química , Nanoestruturas/química , Óxidos/química , Ozônio/química , Plásticos/química , Automóveis , Catálise , Halogenação , Interações Hidrofóbicas e Hidrofílicas , Propriedades de Superfície
15.
Chemosphere ; 164: 92-97, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-27580262

RESUMO

In order to elucidate the metal-alcohol hydrodechlorination reaction mechanism, several experiments using chloroanisoles as substrates were performed. Thus, chloroanisoles were stirred at 60 °C for 2 h with a mixture of Ca, methanol and various reduction catalysts. The use of deuterated methanol and zeta potential experiments offered supplementary informations, pointing toward a probable radicalic mechanism that occurs on Ca and Pd/C surfaces.


Assuntos
Anisóis/química , Descontaminação/métodos , Poluentes Ambientais/química , Recuperação e Remediação Ambiental/métodos , Halogenação , Cálcio/química , Carbono/química , Etanol/química , Paládio/química
16.
Environ Sci Pollut Res Int ; 23(22): 22783-22792, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27562813

RESUMO

Simultaneous immobilization of heavy metals and decomposition of halogenated organic compounds in different fractions of automobile shredder residue (ASR) were achieved with a nano-sized metallic calcium through a 60-min ball milling treatment. Heavy metal (HM) immobilization and chlorinated/brominated compound (CBC) decomposition efficiencies both reached 90-100 %, after ball milling with nanometallic calcium/calcium oxide (Ca/CaO) dispersion, regardless of ASR particle size (1.0, 0.45-1.0, and 0.250 mm). Concentrations of leachable HMs substantially decreased to a level lower than the regulatory standard limits (Co and Cd 0.3 mg L-1; Cr 1.5 mg L-1; Fe, Pb, and Zn 3.0 mg L-1; Mn and Ni 1 mg L-1) proposed by the Korean hazardous waste elution standard regulatory threshold. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) element maps/spectra showed that while the amounts of HMs and CBCs detectable in ASR significantly decreased, the calcium mass percentage increased. X-ray powder diffraction (XRD) patterns indicate that the main fraction of enclosed/bound materials on ASR includes Ca-associated crystalline complexes that remarkably inhibit HM desorption and simultaneously transform dangerous CBCs into harmless compounds. The use of a nanometallic Ca/CaO mixture in a mechanochemical process to treat hazardous ASR (dry conditions) is an innovative approach to remediate cross-contaminated residues with heavy metals and halogenated compounds.


Assuntos
Cálcio/química , Resíduos Perigosos/análise , Hidrocarbonetos Halogenados/química , Metais Pesados/química , Gerenciamento de Resíduos/métodos , Automóveis , Compostos de Cálcio/química , Indicadores e Reagentes , Óxidos/química , Espectrometria por Raios X
17.
J Air Waste Manag Assoc ; 65(10): 1247-55, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26230452

RESUMO

UNLABELLED: This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO4], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO4-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO4] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO4mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals. IMPLICATIONS: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO4], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO4mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.


Assuntos
Cinza de Carvão/análise , Incineração , Nanopartículas Metálicas/química , Metais Pesados/análise , Cálcio/química , Indicadores e Reagentes/química , Ferro/química , Microscopia Eletrônica de Varredura , Resíduos Sólidos/análise , Espectrometria por Raios X
18.
J Hazard Mater ; 297: 74-82, 2015 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-25942697

RESUMO

This study assessed the synthesis and application of nano-Fe/Ca/CaO-based composite material for use as a separation and immobilizing treatment of dry soil contaminated by stable ((133)Cs) and radioactive cesium species ((134)Cs and (137)Cs). After grinding with nano-Fe/CaO, nano-Fe/Ca/CaO, and nano-Fe/Ca/CaO/[PO4], approximately 31, 25, and 22 wt% of magnetic fraction soil was separated. Their resultant (133)Cs immobilization values were about 78, 81, and 100%, respectively. When real radioactive cesium contaminated soil obtained from Fukushima was treated with nano-Fe/Ca/CaO/[PO4], approximately 27.3 wt% of magnetic and 72.75% of non-magnetic soil fractions were separated. The highest amount of entrapped (134)Cs and (137)Cs was found in the lowest weight of the magnetically separated soil fraction (i.e., 80% in 27.3% of treated soil). Results show that (134)Cs and (137)Cs either in the magnetic or non-magnetic soil fractions was 100% immobilized. The morphology and mineral phases of the nano-Fe/Ca/CaO/[PO4] treated soil were characterized using SEM-EDS, EPMA, and XRD analysis. The EPMA and XRD patterns indicate that the main fraction of enclosed/bound materials on treated soil included Ca/PO4 associated crystalline complexes. These results suggest that simple grinding treatment with nano-Fe/Ca/CaO/[PO4] under dry conditions might be an extremely efficient separation and immobilization method for radioactive cesium contaminated soil.


Assuntos
Compostos de Cálcio/química , Cálcio/química , Césio/isolamento & purificação , Ferro/química , Nanocompostos/química , Óxidos/química , Fosfatos/química , Poluentes Radioativos do Solo/isolamento & purificação , Adsorção , Radioisótopos de Césio/isolamento & purificação , Microscopia Eletrônica de Varredura , Modelos Teóricos , Solubilidade , Propriedades de Superfície
19.
J Environ Radioact ; 139: 118-124, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25464047

RESUMO

Although direct radiation induced health impacts were considered benign, soil contamination with (137)Cs, due to its long-term radiological impact (30 years half-life) and its high biological availability is of a major concern in Japan in the aftermath of the Fukushima nuclear power plant disaster. Therefore (137)Cs reduction and immobilization in contaminated soil are recognized as important problems to be solved using suitable and effective technologies. One such thermal treatment/vitrification with nanometallic Ca/CaO amendments is a promising treatment for the ultimate immobilization of simulated radionuclide (133)Cs in soil, showing low leachability and zero evaporation. Immobilization efficiencies were 88%, 95% and 96% when the (133)Cs soil was treated at 1200 °C with activated carbon, fly ash and nanometallic Ca/CaO additives. In addition, the combination of nanometallic Ca/CaO and fly ash (1:1) enhanced the immobilization efficiency to 99%, while no evaporation of (133)Cs was observed. At lower temperatures (800 °C) the leachable fraction of Cs was only 6% (94% immobilization). Through the SEM-EDS analysis, decrease in the amount of Cs mass percent detectable on soil particle surface was observed after soil vitrified with nCa/CaO + FA. The (133)Cs soil was subjected to vitrified with nCa/CaO + FA peaks related to Ca, crystalline phases (CaCO3/Ca(OH)2), wollastonite, pollucite and hematite appeared in addition to quartz, kaolinite and bentonite, which probably indicates that the main fraction of enclosed/bound materials includes Ca-associated complexes. Thus, the thermal treatment with the addition of nanometallic Ca/CaO and fly ash may be considered potentially applicable for the remediation of radioactive Cs contaminated soil at zero evaporation, relatively at low temperature.


Assuntos
Compostos de Cálcio/química , Radioisótopos de Césio/química , Acidente Nuclear de Fukushima , Óxidos/química
20.
J Hazard Mater ; 279: 52-9, 2014 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-25038573

RESUMO

In this work, the capability of nanometallic Ca/CaO methanol suspension in removing and/or immobilizing stable ((133)Cs) and radioactive cesium species ((134)Cs and (137)Cs) in contaminated fly ash was investigated. After a first methanol and second water washing yielded only 45% of (133)Cs removal. While, after a first methanol washing, the second solvent with nanometallic Ca/CaO methanol suspension yielded simultaneous enhanced removal and immobilization about 99% of (133)Cs. SEM-EDS analysis revealed that the mass percent of detectable (133)Cs on the fly ash surface recorded a 100% decrease. When real radioactive cesium contaminated fly ash (containing an initial 14,040Bqkg(-1)(134)Cs and (137)Cs cumulated concentration) obtained from burning wastes from Fukushima were reduced to 3583Bqkg(-1) after treatment with nanometallic Ca/CaO methanol suspension. Elution test conducted on the treated fly ash gave 100BqL(-1) total (134)Cs and (137)Cs concentrations in eluted solution. Furthermore, both ash content and eluted solution concentrations of (134)Cs and (137)Cs were much lower than the Japanese Ministry of the Environment regulatory limit of 8000Bqkg(-1) and 150BqL(-1) respectively. The results of this study suggest that the nanometallic Ca/CaO methanol suspension is a highly potential amendment for the remediation of radioactive cesium-contaminated fly ash.


Assuntos
Compostos de Cálcio/química , Cálcio/química , Radioisótopos de Césio/química , Césio/química , Cinza de Carvão/análise , Metanol/química , Óxidos/química , Césio/isolamento & purificação , Isótopos de Césio/química , Isótopos de Césio/isolamento & purificação , Radioisótopos de Césio/isolamento & purificação , Incineração , Microscopia Eletrônica de Varredura , Eliminação de Resíduos , Suspensões
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