Observed coupling between air mass history, secondary growth of nucleation mode particles and aerosol pollution levels in Beijing

Atmospheric aerosols have significant effects on the climate and on human health. New particle formation (NPF) is globally an important source of aerosols but its relevance especially towards aerosol mass loadings in highly polluted regions is still controversial. In addition, uncertainties remain regarding the processes leading to severe pollution episodes, concerning e.g. the role of atmospheric transport. In this study, we utilize air mass history analysis in combination with different fields related to the intensity of anthropogenic emissions in order to calculate air mass exposure to anthropogenic emissions (AME) prior to their arrival at Beijing, China. The AME is used as a semi-quantitative metric for describing the effect of air mass history on the potential for aerosol formation. We show that NPF events occur in clean air masses, described by low AME. However, increasing AME seems to be required for substantial growth of nucleation mode (diameter < 30 nm) particles, originating either from NPF or direct emissions, into larger mass-relevant sizes. This finding assists in establishing and understanding the connection between small nucleation mode particles, secondary aerosol formation and the development of pollution episodes. We further use the AME, in combination with basic meteorological variables, for developing a simple and easy-to-apply regression model to predict aerosol volume and mass concentrations. Since the model directly only accounts for changes in meteorological conditions, it can also be used to estimate the influence of emission changes on pollution levels. We apply the developed model to briefly investigate the effects of the COVID-19 lockdown on PM2.5 concentrations in Beijing. While no clear influence directly attributable to the lockdown measures is found, the results are in line with other studies utilizing more widely applied approaches.Peer reviewe

Estimates of the organic aerosol volatility in a boreal forest using two independent methods

The volatility distribution of secondary organic aerosols that formed and had undergone aging - i. e., the particle mass fractions of semi-volatile, low-volatility and extremely low volatility organic compounds in the particle phase - was characterized in a boreal forest environment of Hyytiala, southern Finland. This was done by interpreting field measurements using a volatility tandem differential mobility analyzer (VTDMA) with a kinetic evaporation model. The field measurements were performed during April and May 2014. On average, 40% of the organics in particles were semi-volatile, 34% were low-volatility organics and 26% were extremely low volatility organics. The model was, however, very sensitive to the vaporization enthalpies assumed for the organics (Delta H-VAP). The best agreement between the observed and modeled temperature dependence of the evaporation was obtained when effective vaporization enthalpy values of 80 kJ mol(-1) were assumed. There are several potential reasons for the low effective enthalpy value, including molecular decomposition or dissociation that might occur in the particle phase upon heating, mixture effects and compound-dependent uncertainties in the mass accommodation coefficient. In addition to the VTDMA-based analysis, semi-volatile and low-volatility organic mass fractions were independently determined by applying positive matrix factorization (PMF) to high-resolution aerosol mass spectrometer (HR-AMS) data. The factor separation was based on the oxygenation levels of organics, specifically the relative abundance of mass ions at m/z 43 (f43) and m/z 44 (f44). The mass fractions of these two organic groups were compared against the VTDMA-based results. In general, the best agreement between the VTDMA results and the PMF-derived mass fractions of organics was obtained when Delta H-VAP D 80 kJ mol(-1) was set for all organic groups in the model, with a linear correlation coefficient of around 0.4. However, this still indicates that only about 16% (R-2)of the variation can be explained by the linear regression between the results from these two methods. The prospect of determining of extremely low volatility organic aerosols (ELVOAs) from AMS data using the PMF analysis should be assessed in future studies.Peer reviewe

Atmospheric data over a solar cycle: no connection between galactic cosmic rays and new particle formation

Aerosol particles affect the Earth's radiative balance by directly scattering and absorbing solar radiation and, indirectly, through their activation into cloud droplets. Both effects are known with considerable uncertainty only, and translate into even bigger uncertainties in future climate predictions. More than a decade ago, variations in galactic cosmic rays were suggested to closely correlate with variations in atmospheric cloud cover and therefore constitute a driving force behind aerosol-cloud-climate interactions. Later, the enhancement of atmospheric aerosol particle formation by ions generated from cosmic rays was proposed as a physical mechanism explaining this correlation. Here, we report unique observations on atmospheric aerosol formation based on measurements at the SMEAR II station, Finland, over a solar cycle (years 1996–2008) that shed new light on these presumed relationships. Our analysis shows that none of the quantities related to aerosol formation correlates with the cosmic ray-induced ionisation intensity (CRII). We also examined the contribution of ions to new particle formation on the basis of novel ground-based and airborne observations. A consistent result is that ion-induced formation contributes typically significantly less than 10% to the number of new particles, which would explain the missing correlation between CRII and aerosol formation. Our main conclusion is that galactic cosmic rays appear to play a minor role for atmospheric aerosol formation events, and so for the connected aerosol-climate effects as well

Sulfuric acid and OH concentrations in a boreal forest site

As demonstrated in a number of investigations, gaseous sulfuric acid plays a central role in atmospheric aerosol formation. Using chemical ionization mass spectrometer the gas-phase sulfuric acid and OH concentration were measured in Hyytiälä, SMEAR II station, Southern Finland during 24 March to 28 June 2007. Clear diurnal cycles were observed as well as differences between new particle formation event days and non-event days. Typically, the daily maximum concentrations of gas phase sulfuric acid varied from 3&times;105 to 2&times;106 molec cm&minus;3 between non-event and event days. Noon-time OH concentrations varied from 3-6&times;105 molec cm&minus;3 and not a clear difference between event and non-events was detected. The measured time series were also used as a foundation to develop reasonable proxies for sulfuric acid concentration. The proxies utilized source and sink terms, and the simplest proxy is radiation times sulfur dioxide divided by condensation sink. Since it is still challenging to measure sulfuric acid in ambient concentrations, and due to its significant role in atmospheric particle formation, reasonable proxies are needed. We use all together three different proxies and one chemical box model and compared their results to the measured data. The proxies for the sulfuric acid concentration worked reasonably well, and will be used to describe sulfuric acid concentrations in SMEAR II station, when no measured sulfuric acid data is available. With caution the proxies could be applied to other environments as well

Investigation of the connections between atmospheric new particle formation and organics at an urban site of Beijing

Non peer reviewe

Size-segregated particle number and mass concentrations from different emission sources in urban Beijing

Although secondary particulate matter is reported to be the main contributor of PM2.5 during haze in Chinese megacities, primary particle emissions also affect particle concentrations. In order to improve estimates of the contribution of primary sources to the particle number and mass concentrations, we performed source apportionment analyses using both chemical fingerprints and particle size distributions measured at the same site in urban Beijing from April to July 2018. Both methods resolved factors related to primary emissions, including vehicular emissions and cooking emissions, which together make up 76% and 24% of total particle number and organic aerosol (OA) mass, respectively. Similar source types, including particles related to vehicular emissions (1.6 +/- 1.1 mu gm(-3); 2.4 +/- 1.8 x 10(3) cm(-3) and 5.5 +/- 2.8 x 10(3) cm(-3) for two traffic-related components), cooking emissions (2.6 +/- 1.9 mu gm(-3) and 5.5 +/- 3.3 x 10(3) cm(-3)) and secondary aerosols (51 +/- 41 mu gm(-3) and 4.2 +/- 3.0 x 10(3) cm(-3)), were resolved by both methods. Converted mass concentrations from particle size distributions components were comparable with those from chemical fingerprints. Size distribution source apportionment separated vehicular emissions into a component with a mode diameter of 20 nm ("traffic-ultrafine") and a component with a mode diameter of 100 nm ("traffic-fine"). Consistent with similar day- and nighttime diesel vehicle PM2.5 emissions estimated for the Beijing area, traffic-fine particles, hydrocarbon-like OA (HOA, traffic-related factor resulting from source apportionment using chemical fingerprints) and black carbon (BC) showed similar diurnal patterns, with higher concentrations during the night and morning than during the afternoon when the boundary layer is higher. Traffic-ultrafine particles showed the highest concentrations during the rush-hour period, suggesting a prominent role of local gasoline vehicle emissions. In the absence of new particle formation, our re-sults show that vehicular-related emissions (14% and 30% for ultrafine and fine particles, respectively) and cooking-activity-related emissions (32 %) dominate the particle number concentration, while secondary particulate matter (over 80 %) governs PM2.5 mass during the non-heating season in Beijing.Peer reviewe

Vertical and horizontal distribution of regional new particle formation events in Madrid

The vertical profile of new particle formation (NPF) events was studied by comparing the aerosol size number distributions measured aloft and at surface level in a suburban environment in Madrid, Spain, using airborne instruments. The horizontal distribution and regional impact of the NPF events was investigated with data from three urban, urban background, and suburban stations in the Madrid metropolitan area. Intensive regional NPF episodes followed by particle growth were simultaneously recorded at three stations in and around Madrid during a field campaign in July 2016. The urban stations presented larger formation rates compared to the suburban station. Condensation and coagulation sinks followed a similar evolution at all stations, with higher values at urban stations. However, the total number concentration of particles larger than 2.5 nm was lower at the urban station and peaked around noon, when black carbon (BC) levels are at a minimum. The vertical soundings demonstrated that ultrafine particles (UFPs) are formed exclusively inside the mixed layer. As convection becomes more effective and the mixed layer grows, UFPs are detected at higher levels. The morning soundings revealed the presence of a residual layer in the upper levels in which aged particles (nucleated and grown on previous days) prevail. The particles in this layer also grow in size, with growth rates significantly smaller than those inside the mixed layer. Under conditions with strong enough convection, the soundings revealed homogeneous number size distributions and growth rates at all altitudes, which follow the same evolution at the other stations considered in this study. This indicates that UFPs are detected quasi-homogenously in an area spanning at least 17 km horizontally. The NPF events extend over the full vertical extension of the mixed layer, which can reach as high as 3000 m in the area, according to previous studies. On some days a marked decline in particle size (shrinkage) was observed in the afternoon, associated with a change in air masses. Additionally, a few nocturnal nucleation-mode bursts were observed at the urban stations, for which further research is needed to elucidate their origin.Peer reviewe

Improved Cellular Specificity of Plasmonic Nanobubbles versus Nanoparticles in Heterogeneous Cell Systems

The limited specificity of nanoparticle (NP) uptake by target cells associated with a disease is one of the principal challenges of nanomedicine. Using the threshold mechanism of plasmonic nanobubble (PNB) generation and enhanced accumulation and clustering of gold nanoparticles in target cells, we increased the specificity of PNB generation and detection in target versus non-target cells by more than one order of magnitude compared to the specificity of NP uptake by the same cells. This improved cellular specificity of PNBs was demonstrated in six different cell models representing diverse molecular targets such as epidermal growth factor receptor, CD3 receptor, prostate specific membrane antigen and mucin molecule MUC1. Thus PNBs may be a universal method and nano-agent that overcome the problem of non-specific uptake of NPs by non-target cells and improve the specificity of NP-based diagnostics, therapeutics and theranostics at the cell level