Spark ablation is a highly effective and versatile method for producing nanoparticles from bulk conductive electrode materials. For a number of applications, however, the production throughput of the process needs to be increased with respect to the current state of the art. Here we show that this can be achieved by decreasing the diameter of the employed bulk-material electrodes from ca. 12 to 0.15 mm, corroborating previous observations, and demonstrate that the throughput is associated with the ablation efficiency (i.e., the energy spent to produce nanoparticles per total input energy) that respectively increases by a factor of 10. It is also shown that the commonly used theory for predicting the mass of nanoparticles produced by spark ablation cannot capture this effect, and thus we extend it to account for heat losses that affect the process when electrode diameter reduces below ca. 2 mm. Through this exercise we also show that reduced heat losses associated with thinner electrodes provide an effective recipe to increase the ablation efficiency, also referred as the nanoparticle production yield. The new extended theory for estimating spark ablation nanoparticle mass production throughput is also accompanied by an empirical equation predicting its dependence on electrode diameter.

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Portable instruments that can measure the number concentration and size of airborne nanoparticles are very useful for assessing their impacts on human health and climate, mainly because they can enable personal monitoring when carried by individuals, and/or 2- or 3-dimensional mappings when employed onboard mobile platforms. Partector 2 (P2), which is a lightweight and portable instrument manufactured by Naneos Particle Solutions GmbH (Windisch, Switzerland), can determine the concentration (up to 10⁶ #/cm³) and average diameter of aerosol particles having sizes from 10 to 300 nm, making it an excellent candidate for such measurements. Although its performance has been investigated at standard conditions (i.e., ground level pressure and room temperatures), it has not been assessed under reduced pressure and temperature conditions that are typically encountered at higher altitudes; e.g., when employed outdoors in mountainous environments and/or onboard Unmanned Aerial Systems; UASs. Here we assess the counting and sizing capabilities of P2 at temperatures from ca. 22 down to 4 °C, and pressures from 1013 down to 710 hPa that correspond to altitudes from sea level to ca. 3 km. Our results show that the performance of the instrument is not substantially affected when operated at these conditions, remaining within the accuracy thresholds of ±30% reported by the manufacturer. P2, therefore, qualifies for outdoor use at higher altitudes, and can be employed in such environments to determine the number concentration and mean size of sub-300 nm aerosol particles, complementing existing portable optical particle counters that are already employed onboard aerial systems.

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Positive and negative ions produced by radioactive sources and corona discharges in gases find a number of applications, including charging aerosol particles prior to their measurement by electrical and/or electrical mobility techniques. The degree to which these ions can charge aerosol particles depends on their mobility and mass; properties that are strongly affected by the composition of the carrier gas and the impurities that it contains. We show that when the purity of the carrier gas is increased, the mobility of both positive and negative ions increases by more than 50%, whereas the respective masses reduce by more than 50%. In most cases, the dominant positive species is N ₄ ⁺, whereas NO ₂ ^- and NO ₃ ^- prevail for the negative polarity. Differences in ion mobility and mass resulting from the two ionization methods (i.e., radioactive source and corona discharges) remain limited. When volatile methyl siloxanes (VMS) are introduced deliberately to the gas, the mobility of the cations decreases by 39% and their mass increases by 385%, while the dominant mobility and mass peaks of the negative ions remains almost unaffected. Interestingly, introduction of VMS also leads to consistent and reproducible positive ion properties across all variations of the experiments, which can be especially relevant for charging aerosol particles in a reproducible manner. Taken together, the new measurements we report in this paper corroborate prior knowledge that the composition and purity of the carrier gas strongly influence the properties of positive and negative ions generated in aerosol neutralizers, and provide new evidence regarding their evolution in the presence of impurities.

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Sub-10 nm metal-based nanoparticles have garnered immense interest due to their unique properties and versatile applications. In this study, we created sub-10 nm Ag-based particles with a spark discharge generator and explored the parameters impacting their size distribution and charging properties, including carrier gas flow rates, spark discharge voltage, electrode gap distances, and capacitance. Our findings illuminate that there is a comparable influence of different factors on both self-charged and neutral particles. Among the different factors, carrier gas flow rates emerging as a paramount determinant in particle size. While increasing spark discharge voltage and capacitance within the spark circuit increases particle concentrations, the associated changes in particle size prove to be less straightforward. Significant differences between the concentration of positive and negative self-charged particles manifest when the carrier gas flow rate surpasses 5.0 L min⁻¹, with positive particles ranging from 0.8 to 1.2 nm and negative particles spanning 0.8 to 3.0 nm. Self-charged particles close to 1 nm tend to exhibit positive charges, whereas those larger than 2 nm tend to acquire negative charges, which suggests the growth of negative particles is faster than positive ones in the spark chamber. Nevertheless, these disparities between bipolar particles diminish with the increase of residence time, leading to the observation of similar particle size distributions. Positive particles consistently bear a single charge, while some negative particles exceeding 3 nm exhibit multiple charges, primarily under carrier gas flow rates exceeding 7.5 L min⁻¹. This study provides insights into the control of properties of nano-sized metal particles, which are crucial for their practical utilization.

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The Condensation Particle Counter (CPC) is an effective instrument for measuring the number concentration of aerosol particles in different environments. With only a few exceptions, CPCs are bench instruments with limited portability for use in the field, and have a cost that prevents their use in large numbers for distributed air quality measurements. This has motivated the development of compact and cost-effective CPCs that are already available in the market. Here we test the performance of such a CPC, designed and built by National Air Quality Testing Services Ltd (NAQTS), Lancaster, UK, which is a part of the V2000 compact air quality monitor that also includes gas sensors. The tests were carried out using monodisperse particles produced by atomization and electrical mobility classification. We found that the NAQTS V2000 CPC has a 50% detection efficiency for particles having diameter of ca. 14 nm. Our results also show that the coincidence error of the core CPC occurs at concentrations higher than 1 × 104 #/cm−3. Considering that the standalone CPC employs an ejector pump that provides a nominal dilution factor between 20 and 50 at its inlet, the coincidence error threshold of the system when sampling particles from ambient air is 2–5 × 105 #/cm−3. To extend its range for aerosols with particle concentrations by one order of magnitude higher, and thus expand its capabilities for a wide range of applications, we provide a simple correction equation. Overall, our results demonstrate that the NAQTS V2000 CPC is a highly effective instrument, and considering that it is currently the most cost-effective CPC in the market, to the best of our knowledge, makes it a highly attractive solution for air quality monitoring.@en

Inhalation of nanosized metal oxides may occur at the workplace. Thus, information on potential hazardous effects is needed for risk assessment. We report an investigation of the genotoxic potential of different metal oxide nanomaterials. Acellular and intracellular reactive oxygen species (ROS) production were determined for all the studied nanomaterials. Moreover, mice were exposed by intratracheal instillation to copper oxide (CuO) at 2, 6, and 12 μg/mouse, tin oxide (SnO₂) at 54 and 162 μg/mouse, aluminum oxide (Al₂O₃) at 18 and 54 μg/mouse, zinc oxide (ZnO) at 0.7 and 2 μg/mouse, titanium dioxide (TiO₂) and the benchmark carbon black at 162 μg/mouse. The doses were selected based on pilot studies. Post-exposure time points were 1 or 28 days. Genotoxicity, assessed as DNA strand breaks by the comet assay, was measured in lung and liver tissue. The acellular and intracellular ROS measurements were fairly consistent. The CuO and the carbon black bench mark particle were potent ROS generators in both assays, followed by TiO₂. Al₂O₃, ZnO, and SnO₂ generated low levels of ROS. We detected no increased genotoxicity in this study using occupationally relevant dose levels of metal oxide nanomaterials after pulmonary exposure in mice, except for a slight increase in DNA damage in liver tissue at the highest dose of CuO. The present data add to the body of evidence for risk assessment of these metal oxides.

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Experimental evidence shows that hydroxylated metal ions are often produced during cluster synthesis by atmospheric pressure spark ablation. In this work, we predict the ground state equilibrium structures of AgOkHm± clusters (k and m = 1–4), which are readily produced when spark ablating Ag, using the coupled cluster with singles and doubles (CCSD) method. The stabilization energy of these clusters is calculated with respect to the dissociation channel having the lowest energy, by accounting perturbative triples corrections to the CCSD method. The interatomic interactions in each of the systems have been investigated using the frontier molecular orbital (FMO), natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) methods. Many of the ground states of these ionic clusters are found to be stable, corroborating experimental observations. We find that clusters having singlet spin states are more stable in terms of dissociation than the clusters that have doublet or triplet spin states. Our calculations also indicate a strong affinity of the ionic and neutral Ag atom towards water and hydroxyl radicals or ions. Many 3-center, 4-electron (3c/4e) hyperbonds giving rise to more than one resonance structure are identified primarily for the anionic clusters. The QTAIM analysis shows that the O–H and O–Ag bonds in the clusters of both polarities are respectively covalent and ionic. The FMO analysis indicates that the anionic clusters are more reactive than the cationic ones. Using the cluster structures predicted by the CCSD method, we calculate the collision cross sections of the AgOkHm± family, with k and m ranging from 1 to 4, by the trajectory method. In turn, we predict the electrical mobilities of these clusters when suspended in helium at atmospheric pressure and compare them with experimental measurements.@en

The stability of nanoparticle (NP) production by atmospheric-pressure spark ablation was studied and found to depend on the composition of the electrodes and the carrier gas (here N₂ or Ar). For materials that do not react with N₂, such as Pd and Ni, NP production was rather stable regardless of the carrier gas employed. In contrast, for materials that can easily produce nitride species (e.g., Al and Mg), both the concentration and size of the resulting NPs exhibited noticeable fluctuations, when ablating them in N₂, which are more pronounced when the electrical energy input to the system is low. The variation in concentration and particle size is attributed to the formation of a metal-nitride region on the face of the electrodes where the sparks hit, as a result of its reaction with the carrier gas, altering the electrical and thermal conductivity, and consequently the ablatability of the electrode at that region. This explanation was corroborated by offline analysis of the face surface of the electrodes, showing two chemically distinct regions: one with high content of N and one without. In addition, the concentration of the Al and Mg NPs produced in N₂ decreased gradually over time until it reached a plateau after several hours. When using Ar, the fluctuation and decreasing trend in NP production, and consequently the formation of nitride compounds on the face surface of the electrodes, were negligible, providing an effective solution for stable ablation of materials that can easily react with N₂.

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Poor air quality in workplaces constitutes a great concern on human health as a good fraction of our time is spent at work. In Greece, very unique workplaces are the street corner kiosks, which are freestanding boxes placed on sidewalks next to city streets and vehicular traffic, where one can find many consumer goods. As such, its employees are exposed to both outdoor and indoor air pollutants. Very few studies have examined the occupational exposure of kiosk workers to air pollutants, and thus the magnitude of this unique indoor and outdoor exposure remains unknown. The objective of this study is to investigate and compare the levels of indoor and outdoor particulate matter (PM₁₀ and PM_2.5), ultrafine particles (UFPs) and black carbon (BC) in different kiosks located in Athens, Greece, in urban-traffic and urban-background environments. Continuous measurements of the above-mentioned pollutants were carried out on a 24-h basis over 7 consecutive days at three kiosks from September to October 2019. Indoor PM₁₀ concentrations in the urban kiosk ranged from 19.0 to 44.0 μg/m³, PM_2.5 values ranged from 14.0 to 33.0 μg/m³, whereas BC concentrations ranged from 1.2 to 7.0 μg/m³ and UFPs from almost 9.5 to 47.0 × 10³ pt/cm³. Outdoor PM₁₀ and PM_2.5 measurements ranged from 29.0 to 59.0 μg/m³ and from 22.0 to 39.0 μg/m³, respectively. BC outdoor concentrations ranged from 1.1 to 2.2 μg/m³. The mean hazard quotient (HQ) for PM₁₀ (4.9) and PM_2.5 (4.7) among all participants was >1. The health risk of exposure to PM₁₀ and PM_2.5 was found to be at moderate hazard levels, although in some cases we observed HQ values higher than 10 due to high PM₁₀ and PM_2.5 concentrations in the kiosks. Overall our study indicates that people working at kiosks can be exposed to very high concentrations on particulate pollution depending on a number of factors including the traffic that strongly depends on location and the time of the day.

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Stone-built cultural heritage faces threats from natural forces and anthropogenic pollutants, including local climate, acid rain, and outdoor conditions like temperature fluctuations and wind exposure, all of which impact their structural integrity and lead to their degradation. The development of a water-based, environmentally-friendly protective coatings that meet a combination of requirements posed by the diversity of the substrates, different environmental conditions, and structures with complex geometries remains a formidable challenge, given the numerous obstacles faced by current conservation strategies. Here we report the structural, electrical, and mechanical characterization, along with performance testing, of a nanostructured hydrophilic and self-healing hybrid coating based on hydroxyapatite (HAp) nanocrystals and polyelectrolyte multilayers (PEM), formed in-situ on Greek marble through a simple spray layer-by-layer surface functionalization technique. The polyelectrolyte-hydroxyapatite multilayer (PHM) structure resembled the design of naturally forming trabecular bone, attained at a short procedural time. It exhibited chemical affinity, aesthetical compatibility and resistance to weathering while offering reversibility. The proposed method is able to generate micron-sized coatings with controlled properties, such as adhesion and self-healing, leading to less weathered surfaces. Our results show that the PHM is a highly effective protective material that can be applied for stone protection and other similar applications.@en

The density functional theory (DFT) framework was used to investigate the intermolecular interactions between cyanogen chloride (CNCl) pollutant gas molecule with pristine boron nitride nanotubes (BNNT), Al-doped boron nitride nanotubes (BNAlNT), and carbon boron nitride nanotubes (BC₂NNT). The geometric structures of the resulting systems have been optimized using different methods, including B3LYP-D3(GD3BJ)/6-311G(d), ωB97XD/6-311G(d), and M06-2X/6-311G(d). The computed adsorption energies suggest that the studied nanotubes can enhance adsorption of CNCl, and thus promote its detection when employed as sensing materials. Wave function analysis has been implemented to study the type of intermolecular interactions at ωB97XD/6-311G(d,p) level of theory. Natural bond orbital (NBO) analysis has been used to study the charge transfer and bond order. Quantum theory of atoms in molecules (QTAIM) analysis has also been used to determine the type of interactions between the target gas and the nanotubes. To investigate the weak intermolecular interactions we also carried out non-covalent interaction analysis (NCI). The results also indicate that the CNCl-nanotube systems are created through physisorption as they are dominated by non-covalent interactions. The predicted adsorption energies increase as follows: BNAlNT: −1.175 eV > BC₂NNT: −0.281 eV > BNNT: −0.256 eV; this shows that the aluminum-doped boron nitride nanotube is the best option from promoting adsorption of the target gas among them. The HOMO–LUMO energy gaps were as follows: BNNT: 7.090, BNAlNT: 9.193, and BC₂NNT: 7.027 eV at B3LYP-D3/6-311G(d) level of theory.

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Background: Acute phase response (APR) is characterized by a change in concentration of different proteins, including C-reactive protein and serum amyloid A (SAA) that can be linked to both exposure to metal oxide nanomaterials and risk of cardiovascular diseases. In this study, we intratracheally exposed mice to ZnO, CuO, Al₂O₃, SnO₂ and TiO₂ and carbon black (Printex 90) nanomaterials with a wide range in phagolysosomal solubility. We subsequently assessed neutrophil numbers, protein and lactate dehydrogenase activity in bronchoalveolar lavage fluid, Saa3 and Saa1 mRNA levels in lung and liver tissue, respectively, and SAA3 and SAA1/2 in plasma. Endpoints were analyzed 1 and 28 days after exposure, including histopathology of lung and liver tissues. Results: All nanomaterials induced pulmonary inflammation after 1 day, and exposure to ZnO, CuO, SnO₂, TiO₂ and Printex 90 increased Saa3 mRNA levels in lungs and Saa1 mRNA levels in liver. Additionally, CuO, SnO₂, TiO₂ and Printex 90 increased plasma levels of SAA3 and SAA1/2. Acute phase response was predicted by deposited surface area for insoluble metal oxides, 1 and 28 days post-exposure. Conclusion: Soluble and insoluble metal oxides induced dose-dependent APR with different time dependency. Neutrophil influx, Saa3 mRNA levels in lung tissue and plasma SAA3 levels correlated across all studied nanomaterials, suggesting that these endpoints can be used as biomarkers of acute phase response and cardiovascular disease risk following exposure to soluble and insoluble particles.

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Nanoparticles (NPs) mixed at the atomic scale have been synthesized by atmospheric-pressure spark ablation using pairs of Pd and Hf electrodes. Gravimetric analysis of the electrodes showed that the fraction of each material in the resulting mixed NPs can be varied from ca. 15-85 at% to 85-15 at% by employing different combinations of electrode polarities and thicknesses. These results were also qualitatively corroborated by microscopy and elemental analysis of the produced NPs. When using pairs of electrodes having the same diameter, the material from the one at negative polarity was represented at a substantially higher fraction in the mixed NPs regardless of whether a pair of thin or thick electrodes were employed. This can be attributed to the higher ablation rate of the electrodes at the negative polarity, as already known from earlier experiments. When using electrodes of different diameters, the fraction of the element from the thinner electrode was always higher. This is because thinner electrodes are ablated more effectively due to, at least in part, the increased importance of the associated heat losses compared to its thicker counterpart. In those cases, the polarity of the electrodes had a significantly smaller effect. Overall, our results demonstrate, for the first time, that spark ablation can be used to control atomic scale mixing and thus produce alloyed NPs with compositions that can be tuned to a good extent by simply using different combinations of electrode diameters and polarities. This expands the capabilities of the technique for producing mixed nanoparticle building blocks of well-defined composition that are highly desired for a wide range of applications.

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Sand and dust storms (SDS) are a major disruptor in both the source areas where they occur and at distant locations. This critical review aims to address the question of whether mitigation and adaptation measures have been or can be implemented and what is the optimal scale of their implementation to negate the impacts of SDS in Eastern Mediterranean Region (EMR)? Measures which differ in approach are also assessed by recording their successes, failures, and future challenges. We conclude that developing and implementing appropriate mitigation or adaptation measures for SDS at the local level is feasible but, at a wider scale, is a new challenge. This challenge is even more complex in areas like the EMR and the SDS sources affecting it, as it is a crossroad of air masses originating from three major SDS areas, which exhibit economic, political, and social diversity. This review also aims to identify successful mitigation strategies that have been used for similar environmental issues and to draw attention to the lack of adaptation measures in the region. This critical synthesis will serve as a guide for public stakeholders considering measures to mitigate or adapt to SDS based on their effectiveness and the area of implementation.

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Inhalation studies are the gold standard for assessing the toxicity of airborne materials. They require considerable time, special equipment, and large amounts of test material. Intratracheal instillation is considered a screening and hazard assessment tool as it is simple, quick, allows control of the applied dose, and requires less test material. The particle-induced pulmonary inflammation and acute phase response in mice caused by intratracheal instillation or inhalation of molybdenum disulphide or tungsten particles were compared. End points included neutrophil numbers in bronchoalveolar lavage fluid, Saa3 mRNA levels in lung tissue and Saa1 mRNA levels in liver tissue, and SAA3 plasma protein. Acute phase response was used as a biomarker for the risk of cardiovascular disease. Intratracheal instillation of molybdenum disulphide or tungsten particles did not produce pulmonary inflammation, while molybdenum disulphide particles induced pulmonary acute phase response with both exposure methods and systemic acute phase response after intratracheal instillation. Inhalation and intratracheal instillation showed similar dose–response relationships for pulmonary and systemic acute phase response when molybdenum disulphide was expressed as dosed surface area. Both exposure methods showed similar responses for molybdenum disulphide and tungsten, suggesting that intratracheal instillation can be used for screening particle-induced acute phase response and thereby particle-induced cardiovascular disease.

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Molybdenum disulphide (MoS₂) is a constituent of many products. To protect humans, it is important to know at what air concentrations it becomes toxic. For this, we tested MoS₂ particles by nose-only inhalation in mice. Exposures were set to 13, 50 and 150 mg MoS₂/m³ (=8, 30 and 90 mg Mo/m³), corresponding to Low, Mid and High exposure. The duration was 30 min/day, 5 days/week for 3 weeks. Molybdenum lung-deposition levels were estimated based on aerosol particle size distribution measurements, and empirically determined with inductively coupled plasma-mass spectrometry (ICP-MS). Toxicological endpoints were body weight gain, respiratory function, pulmonary inflammation, histopathology, and genotoxicity (comet assay). Acellular reactive oxygen species (ROS) production was also determined. The aerosolised MoS₂ powder had a mean aerodynamic diameter of 800 nm, and a specific surface area of 8.96 m²/g. Alveolar deposition of MoS₂ in lung was estimated at 7, 27 and 79 µg/mouse and measured as 35, 101 and 171 µg/mouse for Low, Mid and High exposure, respectively. Body weight gain was lower than in controls at Mid and High exposure. The tidal volume was decreased with Low and Mid exposure on day 15. Increased genotoxicity was seen in bronchoalveolar lavage (BAL) fluid cells at Mid and High exposures. ROS production was substantially lower than for carbon black nanoparticles used as bench-mark, when normalised by mass. Yet if ROS of MoS₂ was normalised by surface area, it was similar to that of carbon black, suggesting that a ROS contribution to the observed genotoxicity cannot be ruled out. In conclusion, effects on body weight gain and genotoxicity indicated that Low exposure (13 mg MoS₂/m³, corresponding to 0.8 mg/m³ for an 8-hour working day) was a No Observed Adverse Effect Concentration (NOAEC,) while effects on respiratory function suggested this level as a Lowest Observed Adverse Effect Concentration (LOAEC).

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