Improving Aerosol Characterization Using an Optical Particle Counter Coupled with a Quartz Crystal Microbalance with an Integrated Microheater.

Aerosols, as well as suspended particulate matter, impact atmospheric pollution, the climate, and human health, directly or indirectly. Particle size, chemical composition, and other aerosol characteristics are determinant factors for atmospheric pollution dynamics and more. In the last decade, low-cost devices have been widely used in instrumentation to measure aerosols. However, they present some issues, such as the problem of discriminating whether the aerosol is composed of liquid particles or solid. This issue could lead to errors in the estimation of mass concentration in monitoring environments where there is fog. In this study, we investigate the use of an optical particle counter (OPC) coupled to a quartz crystal microbalance with an integrated microheater (H-QCM) to enhance measurement performances. The H-QCM was used not only to measure the collected mass on its surface but also, by using the integrated microheater, it was able to heat the collected mass by performing heating cycles. In particular, we tested the developed system with aerosolized saline solutions of sodium chloride (NaCl), with three decreasing concentrations of salt and three electronic cigarette solutions (e-liquid), with different concentrations of propylene glycol and glycerin mixtures. The results showed that the OPC coherently counted the salt dilution effects, and the H-QCM output confirmed the presence of liquid and solid particles in the aerosols. In the case of e-liquid aerosols, the OPC counted the particles, and the HQCM output highlighted that in the aerosol, there were no solid particles but a liquid phase only. These findings contribute to the refinement of aerosol measurement methodologies by low-cost sensors, fostering a more comprehensive understanding.

A Polyvinylpyrrolidone Nanofibrous Sensor Doubly Decorated with Mesoporous Graphene to Selectively Detect Acetic Acid Vapors.

An original approach has been proposed for designing a nanofibrous (NF) layer using UV-cured polyvinylpyrrolidone (PVP) as a matrix, incorporating mesoporous graphene carbon (MGC) nanopowder both inside and outside the fibers, creating a sandwich-like structure. This architecture is intended to selectively adsorb and detect acetic acid vapors, which are known to cause health issues in exposed workers. The nanocomposite MGC-PVP-NFs layer was fabricated through electrospinning deposition onto interdigitated microelectrodes (IDEs) and stabilized under UV-light irradiation. To enhance the adhesion of MGC onto the surface of the nanocomposite polymeric fibers, the layer was dipped in a suspension of polyethyleneimine (PEI) and MGC. The resulting structure demonstrated promising electrical and sensing properties, including rapid responses, high sensitivity, good linearity, reversibility, repeatability, and selectivity towards acetic acid vapors. Initial testing was conducted in a laboratory using a bench electrometer, followed by validation in a portable sensing device based on consumer electronic components (by ARDUINO®). This portable system was designed to provide a compact, cost-effective solution with high sensing capabilities. Under room temperature and ambient air conditions, both laboratory and portable tests exhibited favorable linear responses, with detection limits of 0.16 and 1 ppm, respectively.

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.

Characterization of Thermal Gradient Effects on a Quartz Crystal Microbalance.

Quartz crystal microbalances are widely used sensors with applications for the detection of very-low-mass deposition in many different fields, from contamination monitoring in the high vacuum of deep space missions to the monitoring of biological activity or pollution using specifically designed active substrates. These sensors are very stable over time; nevertheless, their sensitivity to the temperature is well known, and different implementations have been devised to correct it, e.g., through compensation with a dual crystal. This paper deals with the effects of temperature on QCM but separates the case of uniform crystal temperature from the case of in-plane temperature gradients considering a QCM based on quartz crystals with deposited film resistors used as both RTDs and heaters. This configuration allows both an accurate temperature measurement and efficient thermal control, allowing the achievement of crystals temperatures in the order of 400 °C higher than the environment with a low power dissipation of the order of 1 W. The film resistors deposited around the electrodes allow directly measuring the average crystal temperature and directly delivering power to the crystal for thermal control. The localized delivery of the heat nevertheless also determines uncommon temperature fields on the crystal, and thus, an analysis of both the effects of temperature on the new microbalance was performed. The temperature gradient has strong effects on the frequency; therefore, along with the temperature, the thermal gradients have tobe compensated. The calibration of the QCM thermometers and the assessment of the achievable measurement accuracy were performed, as well as the determination of the frequency-temperature relationship. The comparison between frequency changes in the case of uniform temperature and those observed while using crystal heaters proved that temperature gradients have a strong effect on the crystal frequency. To identify the temperature field on the crystal surface of a QCM crystal, the gold coating of the deposited films was removed to achieve an emissivity acceptable for thermal imaging with an IR camera. Moreover, image processing for emissivity correction was developed. In order to correlate the temperature gradient with the frequency variation, a test campaign was performed to measure the frequency changes derived from different power levels delivered to the crystal heaters. From this test campaign and thermal analysis, the effect of the thermal gradient was assessed.

ROADS-Rover for Bituminous Pavement Distress Survey: An Unmanned Ground Vehicle (UGV) Prototype for Pavement Distress Evaluation.

Maintenance has a major impact on the financial plan of road managers. To ameliorate road conditions and reduce safety constraints, distress evaluation methods should be efficient and should avoid being time consuming. That is why road cadastral catalogs should be updated periodically, and interventions should be provided for specific management plans. This paper focuses on the setting of an Unmanned Ground Vehicle (UGV) for road pavement distress monitoring, and the Rover for bituminOus pAvement Distress Survey (ROADS) prototype is presented in this paper. ROADS has a multisensory platform fixed on it that is able to collect different parameters. Navigation and environment sensors support a two-image acquisition system which is composed of a high-resolution digital camera and a multispectral imaging sensor. The Pavement Condition Index (PCI) and the Image Distress Quantity (IDQ) are, respectively, calculated by field activities and image computation. The model used to calculate the IROADS index from PCI had an accuracy of 74.2%. Such results show that the retrieval of PCI from image-based approach is achievable and values can be categorized as "Good"/"Preventive Maintenance", "Fair"/"Rehabilitation", "Poor"/"Reconstruction", which are ranges of the custom PCI ranting scale and represents a typical repair strategy.

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.

Aspergillus Species Discrimination Using a Gas Sensor Array.

The efficiency of electronic noses in detecting and identifying microorganisms has been proven by several studies. Since volatile compounds change with the growth of colonies, the identification of strains is highly dependent on the growing conditions. In this paper, the effects of growth were investigated with different species of Aspergillus, which is one of the most studied microorganisms because of its implications in environmental and food safety. For this purpose, we used an electronic nose previously utilized for volatilome detection applications and based on eight porphyrins-functionalized quartz microbalances. The volatile organic compounds (VOCs) released by cultured fungi were measured at 3, 5, and 10 days after the incubation. The signals from the sensors showed that the pattern of VOCs evolve with time. In particular, the separation between the three studied strains progressively decreases with time. The three strains could still be identified despite the influence of culture time. Linear Discriminant Analysis (LDA) showed an overall accuracy of 88% and 71% in the training and test sets, respectively. These results indicate that the presence of microorganisms is detectable with respect to background, however, the difference between the strains changes with the incubation time.

Measuring Enthalpy of Sublimation of Volatiles by Means of Piezoelectric Crystal Microbalances.

Piezoelectric Crystal Microbalances (PCM's) are widely used to study the chemical processes involving volatile compounds in any environment, such as condensation process. Since PCM's are miniaturized sensor, they are very suitable for planetary in situ missions, where can be used to detect and to measure the mass amount of astrobiologically significant compounds, such as water and organics. This work focuses on the realization and testing of a new experimental setup, able to characterize volatiles which can be found in a planetary environment. In particular the enthalpy of sublimation of some dicarboxylic acids has been measured. The importance of dicarboxylic acids in planetology and astrobiology is due to the fact that they have been detected in carbonaceous chondritic material (e.g. Murchinson), among the most pristine material present in our Solar System. In this work, a sample of acid was heated in an effusion cell up to its sublimation. For a set of temperatures (from 30 °C to 75 °C), the deposition rate on the PCM surface has been measured. From these measurements, it has been possible to infer the enthalpy of sublimation of Adipic acid, i.e. ΔH = 141.6 ± 0.8 kJ/mol and Succinic acid, i.e. ΔH = 113.3 ± 1.3 kJ/mol. This technique has so demonstrated to be a good choice to recognise a single compound or a mixture (with an analysis upstream) even if some improvements concerning the thermal stabilization of the system will be implemented in order to enhance the results' accuracy. The experiment has been performed in support of the VISTA (Volatile In Situ Thermogravimetry Analyzer) project, which is included in the scientific payload of the ESA MarcoPolo-R mission study.

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.

Induced movements of giant vesicles by millimeter wave radiation.

Our previous study of interaction between low intensity radiation at 53.37GHz and cell-size system - such as giant vesicles - indicated that a vectorial movement of vesicles was induced. This effect among others, i.e. elongation, induced diffusion of fluorescent dye di-8-ANEPPS, and increased attractions between vesicles was attributed to the action of the field on charged and dipolar residues located at the membrane-water interface. In an attempt to improve the understanding on how millimeter wave radiation (MMW) can induce this movement we report here a real time evaluation of changes induced on the movement of giant vesicles. Direct optical observations of vesicles subjected to irradiation enabled the monitoring in real time of the response of vesicles. Changes of the direction of vesicle movement are demonstrated, which occur only during irradiation with a "switch on" of the effect. This MMW-induced effect was observed at a larger extent on giant vesicles prepared with negatively charged phospholipids. The monitoring of induced-by-irradiation temperature variation and numerical dosimetry indicate that the observed effects in vesicle movement cannot be attributed to local heating.

Electrospinning of Polystyrene/Polyhydroxybutyrate Nanofibers Doped with Porphyrin and Graphene for Chemiresistor Gas Sensors.

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 graphene⁻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 60⁻70 °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.

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.

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.

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.

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.