First measurements of the number size distribution of 1-2nm aerosol particles released from manufacturing processes in a cleanroom environment

This study was conducted to observe a potential formation and/or release of aerosol particles related to manufacturing processes inside a cleanroom. We introduce a novel technique to monitor airborne sub 2nm particles in the cleanroom and present results from a measurement campaign during which the total particle number concentration (>1nm and >7 nm) and the size resolved concentration in the 1 to 2nm size range were measured. Measurements were carried out in locations where atomic layer deposition (ALD), sputtering, and lithography processes were conducted, with a wide variety of starting materials. During our campaign in the clean room, we observed several time periods when the particle number concentration was 10(5) cm(-3) in the sub 2nm size range and 10(4) cm(-3) in the size class larger than 7nm in one of the sampling locations. The highest concentrations were related to the maintenance processes of the manufacturing machines, which were conducted regularly in that specific location. Our measurements show that around 500cm(-3) sub 2nm particles or clusters were in practice always present in this specific cleanroom, while the concentration of particles larger than 2nm was less than 2cm(-3). During active processes, the concentrations of sub 2nm particles could rise to over 10(5) cm(-3) due to an active new particle formation. The new particle formation was most likely induced by a combination of the supersaturated vapors, released from the machines, and the very low existing condensation sink, leading to pretty high formation rates J(1.4 nm) = (9 4) cm(-3) s(-1) and growth rates of particles (GR(1.1-1.3 nm) = (6 +/- 3) nm/h and GR(1.3-1.8 nm) = (14 +/- 3) nm/h).Copyright (c) 2017 American Association for Aerosol ResearchPeer reviewe

High concentrations of sub-3nm clusters and frequent new particle formation observed in the Po Valley, Italy, during the PEGASOS 2012 campaign

The concentrations of neutral and charged sub3nm clusters and their connection to new particle formation (NPF) were investigated during the PEGASOS campaign (7 June-9 July 2012) at the San Pietro Capofiume measurement station in the Po Valley, Italy. Continuous high concentrations of sub-3nm clusters were detected during the measurement period, although the condensation sink was relatively high (median value 1.1 x 10(-2) s(-1)). The median cluster concentrations were 2140 and 7980 cm 3 in the size bins of 1.5-1.8 and 1.8-3 nm, and the majority of them were electrically neutral. NPF events were observed during the measurement period frequently, on 86% of the days. The median growth rates of clusters during the events were 4.3, 6.0 and 7.2 nm h(-1) in the size ranges of 1.5-3, 3-7 and 720 nm. The median formation rate of 1.6 nm clusters was high, 45 cm 3 s(-1), and it exceeded the median formation rate of 2 nm clusters by 1 order of magnitude. The ion-induced nucleation fraction was low; the median values were 0.7% at 1.6 nm and 3.0% at 2 nm. On NPF event days the neutral cluster concentration had a maximum around 09: 00 (local winter time), which was absent on a non-event day. The increase in the cluster concentrations in the morning coincided with the increase in the boundary layer height. At the same time radiation, temperature and SO2 concentration increased, and RH and condensation sink decreased. The concentrations of neutral and charged clusters were observed to have a positive correlation with sulfuric acid proxy, indicating the significance of sulfuric acid for the cluster formation in San Pietro Capofiume. The condensation sink had a negative correlation with the concentration of charged clusters but no clear relation to the neutral cluster concentration. This finding, together with back-trajectory analysis, suggests that the precursor vapors of the clusters and background aerosol particles, acting as their sink, have possibly originated from the same sources, including e.g., power plants and industrial areas in the Po Valley.Peer reviewe

Vertical profiles of sub-3nm particles over the boreal forest

This work presents airborne observations of sub-3 nm particles in the lower troposphere and investigates new particle formation (NPF) within an evolving boundary layer (BL). We studied particle concentrations together with supporting gas and meteorological data inside the planetary BL over a boreal forest site in Hyytiala, southern Finland. The analysed data were collected during three flight measurement campaigns: May-June 2015, August 2015 and April-May 2017, including 27 morning and 26 afternoon vertical profiles. As a platform for the instrumentation, we used a Cessna 172 aircraft. The analysed flight data were collected horizontally within a 30 km distance from SMEAR II in Hyytiala and vertically from 100 m above ground level up to 2700 m. The number concentration of 1.5-3 nm particles was observed to be, on average, the highest near the forest canopy top and to decrease with increasing altitude during the mornings of NPF event days. This indicates that the precursor vapours emitted by the forest play a key role in NPF in Hyytiala. During daytime, newly formed particles were observed to grow in size and the particle population became more homogenous within the well-mixed BL in the afternoon. During undefined days with respect to NPF, we also detected an increase in concentration of 1.5-3 nm particles in the morning but not their growth in size, which indicates an interrupted NPF process during these undefined days. Vertical mixing was typically stronger during the NPF event days than during the undefined or non-event days. The results shed light on the connection between boundary layer dynamics and NPF.Peer reviewe

Activation of sub-3 nm organic particles in the particle size magnifier using humid and dry conditions

The accurate measurement of aerosol particles and clusters smaller than 3 nm in diameter is crucial for the understanding of new particle formation processes. The particle counters used for measuring these particles are typically calibrated with metal or salt particles under dry conditions, which does not always represent the field conditions where these instruments are later used. In this study, we calibrated the All nano Condensation Nucleus Counter (nCNC), consisting of the PSM (Particle Size Magnifier) and a laminar flow butanol based CPC (Condensational Particle Counter), with well-defined biogenic oxidation products from beta-caryophyllene oxidation and compared it to a calibration with tungsten oxide under the same conditions. The organic particles were detected less efficiently than the inorganic ones. This resulted in a higher cut-off size for beta-caryophyllene oxidation products than for tungsten oxide. At the same PSM settings, the cut-off size for tungsten oxide was 1.2 nm and for beta-caryophyllene oxidation products 1.9 nm. However, repeating the calibration of the biogenic particles at 13% relative humidity at 31 degrees C, increased their detection efficiency in the PSM, increasing the cut-off diameter to 1.6 nm. Additionally, we present a comparison of the ion concentrations measured with the PSM and the NAIS (Neutral Cluster and Air Ion Spectrometer) during new particle formation experiments in the CLOUD (Cosmics Leaving Outdoors Droplets) chamber. In these experiments, we produced particles from different organic precursors, such as alpha-pinene, beta-caryophyllene and isoprene, as well as iodine. This way, we could determine the shift in cut-off diameter of the PSM for several different atmospherically relevant chemical compounds and compare it to the laboratory calibrations. We saw a diameter shift for the organic precursors of +0.3 nm in the PSM compared to the NAIS. These two approaches agreed well with each other and show that it is important to know the chemical composition of the measured particles to determine the exact size distribution using a supersaturation scanning method.Peer reviewe

New particle formation in the sulfuric acid-dimethylamine-water system: reevaluation of CLOUD chamber measurements and comparison to an aerosol nucleation and growth model

A recent CLOUD (Cosmics Leaving OUtdoor Droplets) chamber study showed that sulfuric acid and dimethylamine produce new aerosols very efficiently and yield particle formation rates that are compatible with boundary layer observations. These previously published new particle formation (NPF) rates are reanalyzed in the present study with an advanced method. The results show that the NPF rates at 1.7 nm are more than a factor of 10 faster than previously published due to earlier approximations in correcting particle measurements made at a larger detection threshold. The revised NPF rates agree almost perfectly with calculated rates from a kinetic aerosol model at different sizes (1.7 and 4.3 nm mobility diameter). In addition, modeled and measured size distributions show good agreement over a wide range of sizes (up to ca. 30 nm). Furthermore, the aerosol model is modified such that evaporation rates for some clusters can be taken into account; these evaporation rates were previously published from a flow tube study. Using this model, the findings from the present study and the flow tube experiment can be brought into good agreement for the high base-to-acid ratios (similar to 100) relevant for this study. This confirms that nucleation proceeds at rates that are compatible with collision-controlled (a.k.a. kinetically controlled) NPF for the conditions during the CLOUD7 experiment (278 K, 38% relative humidity, sulfuric acid concentration between 1 x 10(6) and 3 x 10(7) cm(-3), and dimethylamine mixing ratio of similar to 40 pptv, i.e., 1 x 10(9) cm(-3)).Peer reviewe

Intercomparison of air ion spectrometers: An evaluation of results in varying conditions

We evaluated 11 air ion spectrometers from Airel Ltd. after they had spent one year in field measurements as a part of the EUCAARI project: 5 Air Ion Spectrometers (AIS), 5 Neutral cluster and Air Ion Spectrometers (NAIS) and one Airborne NAIS (ANAIS). This is the first time that an ANAIS is evaluated and compared so extensively. The ion spectrometers' mobility and concentration accuracy was evaluated. Their measurements of ambient air were compared between themselves and to reference instruments: a Differential Mobility Particle Sizer (DMPS), a Balanced Scanning Mobility Analyzer (BSMA), and an Ion-DMPS. We report on the simultaneous measurement of a new particle formation (NPF) event by all 11 instruments and the 3 reference instruments. To our knowledge, it is the first time that the size distribution of ions and particles is measured by so many ion spectrometers during a NPF event. The new particle formation rates (~0.2 cm−3 s−1 for ions and ~2 cm−3 s−1 for particles) and growth rates (~25 nm h−1 in the 3–7 nm size range) were calculated for all the instruments. The NAISs and the ANAIS gave higher concentrations and formation rates than the AISs. For example, the AISs agreed with the BSMA within 11 % and 28 % for negative and positive ion concentration respectively, whereas the NAISs agreed within 23 % and 29 %. Finally, based on the results presented here, we give guidelines for data evaluation, when data from different individual ion spectrometers are compared

Measuring Composition & Growth of Ion Clusters of Sulfuric Acid, Ammonia, Amines & Oxidized Organics as First Steps of Nucleation in the CLOUD Experiment

The mechanisms behind the nucleation of vapors forming new particles in the atmosphere had been proven difficult to establish. One main aim of the CLOUD experiment was to explore in detail these first steps of atmospheric new particle formation by performing extremely well controlled laboratory experiments. We examined nucleation and growth in the presence of different mixtures of vapors, including sulfuric acid, ammonia, dimethylamine, and oxidation products of pinanediol or α-pinene. Among the employed state-of-the-art instrumentation, a high-resolution mass spectrometer that directly sampled negatively charged ions and clusters proved particularly useful. We were able to resolve most of the chemical compositions found for charged sub-2nm clusters and to observe their growth in time. These compositions reflected the mixture of condensable vapors in the chamber and the role of each individual vapor in forming sub-2nm clusters could be explored. By inter-comparing between individual experiments and ambient observations, we try to establish which vapors participate in nucleation in the actual atmosphere, and how

Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

The formation of new aerosol particles in the atmosphere is a key process influencing the aerosol number concentration as well as the climate, in particular at high altitude, where the newly formed particles directly influence cloud formation. However, free tropospheric new particle formation (NPF) is poorly documented due to logistic limitations and complex atmospheric dynamics around high-altitude stations that make the observation of this day-time process challenging. Recent improvements in measurement techniques make now possible the detection of neutral clusters down to similar to 1 nm sizes, which opens new horizons in our understanding of the nucleation process. Indeed, only the charged fraction of clusters has been reported in the upper troposphere up to now. Here we report day-time concentrations of charged and neutral clusters (1 to 2.5 nm mobility diameter) recorded at the interface between the boundary layer (BL) and the FT as well as in the FT at the altitude site of Puy de Dome (1465 m a.s.l.), central France, between 10 and 29 February 2012. Our findings demonstrate that in the FT, and especially at the interface between the BL and the FT, the formation of 1.5 nm neutral clusters significantly exceeds the one of ionic clusters during NPF events, clearly indicating that they dominate in the nucleation process. We also observe that the total cluster concentration significantly increases during NPF events compared to the other days, which was not clearly observed for the charged cluster population in the past. During the studied period, the nucleation process does not seem to be sulfuric acid-limited and could be promoted by the transport of pollutants to the upper troposphere, coupled with low temperatures.Peer reviewe

CO2-induced terrestrial climate feedback mechanism : From carbon sink to aerosol source and back

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