Effects of Oscillation Amplitude Variations on QCM Response to Microspheres of Different Sizes.

Suspended particulate matter (PMx) is one of the most important environmental pollutants. Miniaturized sensors capable of measuring and analyzing PMx are crucial in environmental research fields. The quartz crystal microbalance (QCM) is one of the most well-known sensors that could be used to monitor PMx. In general, in environmental pollution science, PMx is divided into two main categories correlated to particle diameter (e.g., PM < 2.5 µm and PM < 10 µm). QCM-based systems are capable of measuring this range of particles, but there is an important issue that limits the application. In fact, if particles with different diameters are collected on QCM electrodes, the response will be a result of the total mass of particles; there are no simple methods to discriminate the mass of the two categories without the use of a filter or manipulation during sampling. The QCM response depends on particle dimensions, fundamental resonant frequency, the amplitude of oscillation, and system dissipation properties. In this paper, we study the effects of oscillation amplitude variations and fundamental frequency (10, 5, and 2.5 MHz) values on the response, when particle matter with different sizes (2 µm and 10 µm) is deposited on the electrodes. The results showed that the 10 MHz QCM was not capable of detecting the 10 µm particles, and its response was not influenced by oscillation amplitude. On the other hand, the 2.5 MHz QCM detected the diameters of both particles, but only if a low amplitude value was used.

Pocket Mercury-Vapour Detection System Employing a Preconcentrator Based on Au-TiO2 Nanomaterials.

In environments polluted by mercury vapors that are potentially harmful to human health, there is a need to perform rapid surveys in order to promptly identify the sources of emission. With this aim, in this work, a low cost, pocket-sized portable mercury measurement system, with a fast response signal is presented. It consists of a preconcentrator, able to adsorb and subsequently release the mercury vapour detected by a quartz crystal microbalance (QCM) sensor. The preconcentrator is based on an adsorbing layer of titania/gold nanoparticles (TiO2NP/AuNPs), deposited on a micro-heater that acts as mercury thermal desorption. For the detection of the released mercury vapour, gold electrodes QCM (20 MHz) have been used. The experimental results, performed in simulated polluted mercury-vapour environments, showed a detection capability with a prompt response. In particular, frequency shifts (-118 Hz ± 2 Hz and -30 Hz ± 2 Hz) were detected at concentrations of 65 µg/m3 Hg0 and 30 µg/m3 Hg0, with sampling times of 60 min and 30 min, respectively. A system limit of detection (LOD) of 5 µg/m3 was evaluated for the 30 min sampling time.

Low-Cost Benzene Toluene Xylene Measurement Gas System Based on the Mini Chromatographic Cartridge.

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.

Characteristics and Performances of a Nanostructured Material for Passive Samplers of Gaseous Hg.

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.

Use of Gold Nanoparticles as Substrate for Diffusive Monitoring of Gaseous Mercury.

In the present work, the study and the performances of an adsorbent material for gaseous mercury employed in different diffusive bodies geometries is presented. The material is based on gold nanoparticles (AuNPs) deposited on quartz fibres filters, suitable for bonding the gaseous mercury through an amalgamation process. Following thermal desorption and analysis, the behavior of different diffusive samplers prototypes was compared. Both indoor and outdoor exposures were carried out in order to evaluate the advantages and shortcomings of the geometries in study at different sites. From the outdoor long-term exposures, a constant uptake rate (Ur), with a low influence coming from the environmental conditions, was observed for the axial geometry, reporting a high coefficient of determination (R² 0.97). Indoor exposures showed a higher reproducibility, along with a higher coefficient of determination (R² 0.99). The presented results allowed us to observe different behaviors coming from two kinds of diffusive samplers designs, showing different adsorption rates and data dispersion. This allowed us to focalize our attention on the most suitable design from these two tested prototypes, for this kind of adsorbent material.

Passive Sampling of Gaseous Elemental Mercury Based on a Composite TiO2NP/AuNP Layer.

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.

Thermally Driven Selective Nanocomposite PS-PHB/MGC Nanofibrous Conductive Sensor for Air Pollutant Detection.

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.

VISTA: A µ-Thermogravimeter for Investigation of Volatile Compounds in Planetary Environments.

This paper presents the VISTA (Volatile In Situ Thermogravimetry Analyser) instrument, conceived to perform planetary in-situ measurements. VISTA can detect and quantify the presence of volatile compounds of astrobiological interest, such as water and organics, in planetary samples. These measurements can be particularly relevant when performed on primitive asteroids or comets, or on targets of potential astrobiological interest such as Mars or Jupiter's satellite Europa. VISTA is based on a micro-thermogravimetry technique, widely used in different environments to study absorption and sublimation processes. The instrument core is a piezoelectric crystal microbalance, whose frequency variations are affected by variations of the mass of the deposited sample, due to chemical processes such as sublimation, condensation or absorption/desorption. The low mass (i.e. 40 g), the low volume (less than 10 cm(3)) and the low power (less than 1 W) required makes this kind of instrument very suitable for space missions. This paper discusses the planetary applications of VISTA, and shows the calibration operations performed on the breadboard, as well as the performance tests which demonstrate the capability of the breadboard to characterize volatile compounds of planetary interests.

Platinum nanoparticles on electrospun titania nanofibers as hydrogen sensing materials working at room temperature.

Platinum nanoparticles (PtNPs), with diameters of 3-10 nm, were synthesized by water phase reduction, using 3-mercapto-1-propanesulfonate (3MPS) as a hydrophilic capping agent. PtNPs were deposited by a dipcoating technique on titania nanofibers (TiO2NFs), obtained by electrospinning. The investigated properties of the Pt-TiO2 hybrid at room temperature show that this material combines the properties of photoconduction of titania and the photocatalytic activity of the hybrid. To assess the best performance of Pt-TiO2, different measurements were performed at room temperature, comparing hydrogen response under UV of the uncoated TiO2NFs, compared with the Pt-TiO2 system prepared with two different amounts of PtNPs. During the sensing tests toward hydrogen an enhancement of photoconductivity (150%), an increase in response (400%) and an overall improvement of their dynamic behaviour were observed.

A nanostructured composite based on polyaniline and gold nanoparticles: synthesis and gas sensing properties.

Nanostructured composite materials based on polyaniline (PANI) and gold nanoparticles have been prepared by means of an osmosis based method. Several morphologies have been obtained for the pristine nanoPANI and for nanoPANI-Au composite, ranging from amorphous to sponge-like and spherical shapes. On the basis of this morphological investigation, different materials with high surface area have been selected and tested as chemical interactive materials for room temperature gas and vapor sensing. The resistive sensor devices have been exposed to different vapor organic compounds (VOCs) of interest in the fields of environmental monitoring and biomedical applications, such as toluene, acetic acid, ethanol, methanol, acetonitrile, water, ammonia and nitrogen dioxide. The effect of doping with H2SO4 has been studied for both nanoPANI and nanoPANI-Au samples. In particular, nanoPANI-Au showed sensitivity to ammonia (up to 10 ppm) higher than that to other VOCs or interfering analytes. The facile preparation method and the improved properties achieved for the polyaniline-gold composite materials are significant in the nanomaterials field and have promise for applications in ammonia vapor monitoring.

Self-assembled copolymeric nanoparticles as chemically interactive materials for humidity sensors.

Chemical interactive materials (CIM), based on poly(methylmethacrylate-co-bis(benzocyclobutene)) P(MMA-co-BCB) and poly(styrene-co-bis(benzocyclobutene)) P(S-co-BCB) nanoparticles, have been prepared through modified emulsion technique. Experimental conditions, in particular the co-monomer ratio and reaction time, have been tuned to modulate nanoparticles' dimension and optimize their monodispersity. Resistive relative humidity (RH) sensors based on self-assembled copolymeric nanoparticles, cast deposited onto metal interdigitated electrodes (Al, Au, Cr), have been fabricated. The electrical response and the devices' stability have been studied in the range 10-90% RH. Applying 1 V to interdigitated electrodes, a variation of four orders of magnitude, from 10(-12) to 10(-8) A, has been observed and a response time of 130 s has been calculated. Response reproducibility and stability have been tested in subsequent cycles of measurements (working times as long as two days and after six months), confirming the stable performance of the CIMs. Copolymeric nanoparticle assembly has also been studied by quartz microbalance (QMB) devices, where phase shift occurred, by varying RH in the range 10-90%. The CIM coated device shows a sensitivity of about 30 Hz/% (at 10-70% RH), that rapidly increases up to about 2000 Hz/% at 90% RH. The results give evidence for versatile applications of P(MMA-co-BCB) and P(S-co-BCB) nanoparticles for sensing applications.

Enhanced Sensory Properties of a Multichannel Quartz Crystal Microbalance Coated with Polymeric Nanobeads.

In this study the sensorial performances of a four-channel quartz crystalmicrobalance implemented on a single quartz plate are reported and compared with those offour independent quartz crystal microbalances. Particular attention has been devoted to bothcross talk in responses and sensor sensitivity. A recently synthesized nanostructuredpolymer, poly[phenylacetylene-(co-2-hydroxyethyl methacrylate)], has been used aschemical interactive material. The interactions of our sensor system with relative humidityare also reported. The multichannel device shows a better homogeneity of the masssensitivity with a spread of the values less then 4% compared to a 50% spread observed inthe set of four microbalances.