RESUMEN
Benzene, toluene and xylene (BTX) are an important part of the volatile organic compounds (VOCs) to be detected and monitored in the air, due to their toxicity towards human health. One of the most reliable technique used in BTX detection is gas chromatography (GC), which presents a high sensitivity. On the other hand, it has important drawbacks, such as high costs, the need for qualified personnel and frequent maintenance. To overcome these drawbacks, this work reports the development of a low cost and portable BTX gas detection system based on a mini chromatographic cartridge, a photo ionization detector (PID), a simple control unit (based on Arduino architecture) and a mini pump. In order to separate the BTX components, we propose the use of a cartridge 80 mm in length, composed of several commercial chromatographic column sections. To test the system performances, we have injected different amounts (from about 0.3 to 5.3 µg) of benzene, toluene and xylene and two of the most frequent possible interferents (ethanol, acetone). Experimental results have shown different retention time values (i.e., 25 ± 0.5 s, 51 ± 1.2 s and 117 ± 4 s, respectively) for benzene, toluene and xylene.
RESUMEN
Passive air samplers (PASs) have been used for mapping gaseous mercury concentration in extensive areas. In this work, an easy-to-use and -prepare gold nanoparticle (NP)-based PAS has been investigated. The PAS is constituted of a microfibrous quartz disk filter impregnated of gold NP photo-growth on TiO2 NPs (Au@TiO2) and used as gaseous mercury adsorbing material. The disk was housed in a cylinder glass container and subjected to an axial diffusive sampling. The adsorbed mercury was measured by thermal desorption using a Tekran® instrument. Different amounts of Au@TiO2 (ranging between 4.0 and 4.0 × 10-3 mg) were deposited by drop-casting onto the fibrous substrate and assessed for about 1 year of deployment in outdoor environment with a mercury concentration mean of about 1.24 ± 0.32 ng/m3 in order to optimize the adsorbing layer. PASs showed a linear relation of the adsorbed mercury as a function of time with a rate of 18.5 ± 0.4 pg/day (≈1.5% of the gaseous concentration per day). However, only the PAS with 4 mg of Au@TiO2, provided with a surface density of about 3.26 × 10-2 mg/mm2 and 50 µm thick inside the fibrous quartz, kept stability in working, with a constant sampling rate (SR) (0.0138 ± 0.0005 m3/day) over an outdoor monitoring experimental campaign of about 1 year. On the other hand, higher sampling rates have been found when PASs were deployed for a few days, making these tools also effective for one-day monitoring. Furthermore, these PASs were used and re-used after each thermal desorption to confirm the chance to reuse such structured layers within their samplers, thus supporting the purpose to design inexpensive, compact and portable air pollutant sampling devices, ideal for assessing both personal and environmental exposures. During the whole deployment, PASs were aided by simultaneous Tekran® measurements.
RESUMEN
Humic acids (HA) exhibit fascinating multifunctional features, yet degradation phenomena as well as poor stability in aqueous environments strongly limit their use. Inorganic nanoparticles are emerging as a powerful interface for the development of robust HA bio-hybrid materials with enhanced chemical stability and tunable properties. Hybrid organic-inorganic SiO2/HA nanostructures were synthesized via an in-situ sol-gel route, exploiting both physical entrapment and chemical coupling. The latter was achieved through amide bond formation between carboxyl groups of HA and the amino group of 3-aminopropyltriethoxysilane (APTS), as confirmed by Fourier-Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopy. Monodisperse hybrid nanoparticles about 90 nm in diameter were obtained in both cases, yet Electron Paramagnetic Resonance (EPR) spectroscopy highlighted the different supramolecular organization of HA. The altered HA conformation was reflected in different antioxidant properties of the conjugated nanoparticles that, however, resulted in being higher than for pure HA. Our findings proved the key role of both components in defining the morphology of the final system, as well as the efficacy of the ceramic component in templating the HA supramolecular organization and consequently tuning their functional features, thus defining a green strategy for bio-waste valorization.
RESUMEN
One of the main issues in preparing polymer-based nanocomposites with effective properties is to achieve a good dispersion of the nanoparticles into the matrix. Chemical interfacial modifications by specific coupling agents represents a good way to reach this objective. Actually, time consuming compatibilization procedures strongly compromise the sustainability of these strategies. In this study, the role of particles' architectures in their dispersion into a poly-lactic acid matrix and their subsequent influences on physical-chemical properties of the obtained nanocomposites were investigated. Two kinds of silica nanoparticles, "smooth" and "wrinkled," with different surface areas (≈30 and ≈600 m2/g respectively) were synthesized through a modified Stöber method and used, without any chemical surface pre-treatments, as fillers to produce poly-lactic acid based nanocomposites. The key role played by wrinkled texture in modifying the physical interaction at the polymer-filler interface and in driving composite properties, was investigated and reflected in the final bulk properties. Detailed investigations revealed the presence of wrinkled nanoparticles, leading to (i) an enormous increase of the chain relaxation time, by almost 30 times compared to the neat PLA matrix; (ii) intensification of the shear-thinning behavior at low shear-rates; and (iii) slightly slower thermal degradation of polylactic acid.
RESUMEN
Structural and functional properties of polymer composites based on carbon nanomaterials are so attractive that they have become a big challenge in chemical sensors investigation. In the present study, a thin nanofibrous layer, comprising two insulating polymers (polystyrene (PS) and polyhydroxibutyrate (PHB)), a known percentage of nanofillers of mesoporous graphitized carbon (MGC) and a free-base tetraphenylporphyrin, was deposited onto an Interdigitated Electrode (IDE) by electrospinning technology. The potentials of the working temperature to drive both the sensitivity and the selectivity of the chemical sensor were studied and described. The effects of the porphyrin combination with the composite grapheneâ»polymer system appeared evident when nanofibrous layers, with and without porphyrin, were compared for their morphology and electrical and sensing parameters. Porphyrin fibers appeared smoother and thinner and were more resistive at lower temperature, but became much more conductive when temperature increased to 60â»70 °C. Both adsorption and diffusion of chemicals seemed ruled by porphyrin according its combination inside the composite fiber, since the response rates dramatically increased (toluene and acetic acid). Finally, the opposite effect of the working temperature on the sensitivity of the porphyrin-doped fibers (i.e., increasing) and the porphyrin-free fibers (i.e., decreasing) seemed further confirmation of the key role of such a macromolecule in the VOC (volatile organic compound) adsorption.
RESUMEN
Passive sampling systems (PASs) are a low cost strategy to quantify Hg levels in air over both different environmental locations and time periods of few hours to weeks/months. For this reason, novel nanostructured materials have been designed and developed. They consist of an adsorbent layer made of titania nanoparticles (TiO2NPs, ≤25 nm diameter) finely decorated with gold nanoparticles. The TiO2NPs functionalization occurred for the photocatalytic properties of titania-anatase when UV-irradiated in an aqueous solution containing HAuCl4. The resulting nanostructured suspension was deposited by drop-casting on a thin quartz slices, dried and then incorporated into a common axial sampler to be investigated as a potential PAS device. The morphological characteristics of the sample were studied by High-Resolution Transmission Electron Microscopy, Atomic Force Microscopy, and Optical Microscopy. UV-Vis spectra showed a blue shift of the membrane when exposed to Hg° vapors. The adsorbed mercury was thermally desorbed for a few minutes, and then quantified by a mercury vapor analyzer. Such a sampling system reported an efficiency of adsorption that was equal to ≈95%. Temperature and relative humidity only mildly affected the membrane performances. These structures seem to be promising candidates for mercury samplers, due to both the strong affinity of gold with Hg, and the wide adsorbing surface.
RESUMEN
The potentials to use the working temperature to tune both the sensitivity and the selectivity of a chemical sensor based on a nanostructured and nanocomposite polymer layer have been investigated and described. Thus, in a single step, a peculiar chemical layer was grown up onto IDE (Interdigitated Electrode) microtransducers by electrospinning deposition and using a single-needle strategy. The 3-component nanofibers, obtained from a mixture of polystyrene and polyhydroxibutyrate (insulating thermoplastics) and a known concentration of mesoporous graphitized carbon nanopowder, appeared highly rough on the surface and decorated with jagged islands but homogeneous in shape and diameter, with the nanofillers aggregated into clusters more or less densely packed through the fibers. The resulting sensor was conductive at room temperature and could work between 40 and 80°C without any apparent degradation. As the fibrous sensing layer was heated, the current increased and the sensitivity to some classes of VOCs such as an oxidizing gas drastically changed depending on the working temperature. More in detail, the sensor resulted highly sensitive and selective to acetic acid at 40°C but the sensitivity fell down, decreasing by 96%, when the sensor operated at 80°C. On the other hand, although an increase in temperature caused a general decrease in sensitivity to the tested VOCs (with a maximum of 14, 81, and 78% for amine, acetone and toluene, respectively) and water vapors (with a maximum of 55%), higher temperature affected only slightly the amine permeation, thus modifying the partial selectivity of the sensor to these chemicals. Conversely, when the operating temperature increased, the sensitivity to the detected gas, NO2, increased too, reporting a ~2 ppb limit of detection (LOD), thus confirming that the temperature was able to drive the selectivity of nanocomposite polymeric sensors.