Mass Accommodation of Water: Bridging the Gap Between Molecular Dynamics Simulations and Kinetic Condensation Models

The condensational growth of submicrometer aerosol particles to climate relevant sizes is sensitive to their ability to accommodate vapor molecules, which is described by the mass accommodation coefficient. However, the underlying processes are not yet fully understood. We have simulated the mass accommodation and evaporation processes of water using molecular dynamics, and the results are compared to the condensation equations derived from the kinetic gas theory to shed light on the compatibility of the two. Molecular dynamics simulations were performed for a planar TIP4P-Ew water surface at four temperatures in the range 268–300 K as well as two droplets, with radii of 1.92 and 4.14 nm at T = 273.15 K. The evaporation flux from molecular dynamics was found to be in good qualitative agreement with that predicted by the simple kinetic condensation equations. Water droplet growth was also modeled with the kinetic multilayer model KM-GAP of Shiraiwa et al. [ Atmos. Chem. Phys. 2012, 12, 2777]. It was found that, due to the fast transport across the interface, the growth of a pure water droplet is controlled by gas phase diffusion. These facts indicate that the simple kinetic treatment is sufficient in describing pure water condensation and evaporation. The droplet size was found to have minimal effect on the value of the mass accommodation coefficient. The mass accommodation coefficient was found to be unity (within 0.004) for all studied surfaces, which is in agreement with previous simulation work. Additionally, the simulated evaporation fluxes imply that the evaporation coefficient is also unity. Comparing the evaporation rates of the mass accommodation and evaporation simulations indicated that the high collision flux, corresponding to high supersaturation, present in typical molecular dynamics mass accommodation simulations can under certain conditions lead to an increase in the evaporation rate. Consequently, in such situations the mass accommodation coefficient can be overestimated, but in the present cases the corrected values were still close to unity with the lowest value at ≈0.99

A taste for aliens: contribution of a novel prey item to native fishes’ diet

Non-indigenous species (NIS) can alter food web structure and function in many ways. While the predatory and competitive roles of NIS in aquatic environments are commonly studied, their role as a prey item for native predators is often overlooked. As the northern Baltic Sea lacks native crabs, the omnivorous estuarine Harris mud crab (Rhithropanopeus harrisii) is a novel invader to the system and provides an opportunity to observe how the species enters the prey field of predatory fish. In fall 2013, 1185 stomachs from 17 fish species were dissected and analyzed for the presence of R. harrisii. Fishermen had previously reported finding crabs mostly in the stomachs of perch (Perca fluviatilis), a frequent catch in recreational and commercial fisheries, but our study also found large numbers of crabs in four-horned sculpins (Myoxocephalus quadricornis) and small numbers in other species’ stomachs (Rutilus rutilus, Leuciscus ide, Gymnocephalus cernuus, and Blicca bjoerkna). In the study area occupied by R. harrisii, four-horned sculpins were the most frequent predator, with 83% having at least one crab in their stomach. In comparison, 7% of perch and roach had consumed R. harrisii. Most crabs eaten were 10–12 mm (carapace width), despite broader size range available (1–26 mm). Predation on R. harrisii in this system may be limited by the predators’ gape size (i.e., physical feeding restriction). These results highlight the need to understand the role of novel invasive species as prey items for native species, ultimately increase understanding of whether native predators can control NIS populations.KeywordsNon-indigenous species Novel invasion Predation control Food web Baltic Sea Rhithropanopeus harrisii </div

A taste for aliens : contribution of a novel prey item to native fishes’ diet

Non-indigenous species (NIS) can alter food web structure and function in many ways. While the predatory and competitive roles of NIS in aquatic environments are commonly studied, their role as a prey item for native predators is often overlooked. As the northern Baltic Sea lacks native crabs, the omnivorous estuarine Harris mud crab (Rhithropanopeus harrisii) is a novel invader to the system and provides an opportunity to observe how the species enters the prey field of predatory fish. In fall 2013, 1185 stomachs from 17 fish species were dissected and analyzed for the presence of R. harrisii. Fishermen had previously reported finding crabs mostly in the stomachs of perch (Perca fluviatilis), a frequent catch in recreational and commercial fisheries, but our study also found large numbers of crabs in four-horned sculpins (Myoxocephalus quadricornis) and small numbers in other species’ stomachs (Rutilus rutilus, Leuciscus ide, Gymnocephalus cernuus, and Blicca bjoerkna). In the study area occupied by R. harrisii, four-horned sculpins were the most frequent predator, with 83% having at least one crab in their stomach. In comparison, 7% of perch and roach had consumed R. harrisii. Most crabs eaten were 10–12 mm (carapace width), despite broader size range available (1–26 mm). Predation on R. harrisii in this system may be limited by the predators’ gape size (i.e., physical feeding restriction). These results highlight the need to understand the role of novel invasive species as prey items for native species, ultimately increase understanding of whether native predators can control NIS populations.peerReviewe

Aerosol dynamics simulations on the connection of sulphuric acid and new particle formation

International audienceWe have performed a series of simulations with an aerosol dynamics box model to study the connection between new particle formation and sulphuric acid concentration. For nucleation either activation mechanism with a linear dependence on the sulphuric acid concentration or ternary H2O-H2SO4-NH3 nucleation was assumed. We investigated the factors that affect the sulphuric acid dependence during the early stages of particle growth, and tried to find conditions which would yield the linear dependence between the particle number concentration at 3?6 nm and sulphuric acid, as observed in field experiments. The simulations showed that the correlation with sulphuric acid may change during the growth from nucleation size to 3?6 nm size range, the main reason being the size dependent growth rate between 1 and 3 nm. In addition, the assumed size for the nucleated clusters had a crucial impact on the sulphuric acid dependence at 3 nm. The simulations yielded a linear dependence between the particle number concentration at 3 nm and sulphuric acid, when a low saturation vapour pressure for the condensable organic vapour was assumed, or when nucleation took place at ~2 nm instead of ~1 nm. Comparison of results with activation and ternary nucleation showed that ternary nucleation cannot explain the experimentally observed linear or square dependence on sulphuric acid

Global emissions of terpenoid VOCs from terrestrial vegetation in the last millennium

Peer reviewe

Growth rates of nucleation mode particles in Hyytiälä during 2003&minus;2009: variation with particle size, season, data analysis method and ambient conditions

The condensational growth rate of aerosol particles formed in atmospheric new particle formation events is one of the most important factors influencing the lifetime of these particles and their ability to become climatically relevant. Diameter growth rates (GR) of nucleation mode particles were studied based on almost 7 yr of data measured during the years 2003–2009 at a boreal forest measurement station SMEAR II in Hyytiälä, Finland. The particle growth rates were estimated using particle size distributions measured with a Differential Mobility Particle Sizer (DMPS), a Balanced Scanning Mobility Analyzer (BSMA) and an Air Ion Spectrometer (AIS). Two GR analysis methods were tested. The particle growth rates were also compared to an extensive set of ambient meteorological parameters and trace gas concentrations to investigate the processes/constituents limiting the aerosol growth. The median growth rates of particles in the nucleation mode size ranges with diameters of 1.5–3 nm, 3–7 nm and 7–20 nm were 1.9 nm h⁻¹, 3.8 nm h⁻¹, and 4.3 nm h⁻¹, respectively. The median relative uncertainties in the growth rates due to the size distribution instrumentation in these size ranges were 25%, 19%, and 8%, respectively. For the smallest particles (1.5–3 nm) the AIS data yielded on average higher growth rate values than the BSMA data, and higher growth rates were obtained from positively charged size distributions as compared with negatively charged particles. For particles larger than 3 nm in diameter no such systematic differences were found. For these particles the uncertainty in the growth rate related to the analysis method, with relative uncertainty of 16%, was similar to that related to the instruments. The growth rates of 7–20 nm particles showed positive correlation with monoterpene concentrations and their oxidation rate by ozone. The oxidation rate by OH did not show a connection with GR. Our results indicate that the growth of nucleation mode particles in Hyytiälä is mainly limited by the concentrations of organic precursors

Measurement of the ambient organic aerosol volatility distribution: application during the Finokalia Aerosol Measurement Experiment (FAME-2008)

A variable residence time thermodenuder (TD) was combined with an Aerodyne Aerosol Mass Spectrometer (AMS) and a Scanning Mobility Particle Sizer (SMPS) to measure the volatility distribution of aged organic aerosol in the Eastern Mediterranean during the Finokalia Aerosol Measurement Experiment in May of 2008 (FAME-2008). A new method for the quantification of the organic aerosol volatility distribution was developed combining measurements of all three instruments together with an aerosol dynamics model. &lt;br&gt;&lt;br&gt; Challenges in the interpretation of ambient thermodenuder-AMS measurements include the potential resistances to mass transfer during particle evaporation, the effects of particle size on the evaporated mass fraction, the changes in the AMS collection efficiency and particle density as the particles evaporate partially in the TD, and finally potential losses inside the TD. Our proposed measurement and data analysis method accounts for all of these problems combining the AMS and SMPS measurements. &lt;br&gt;&lt;br&gt; The AMS collection efficiency of the aerosol that passed through the TD was found to be approximately 10% lower than the collection efficiency of the aerosol that passed through the bypass. The organic aerosol measured at Finokalia is approximately 2 or more orders of magnitude less volatile than fresh laboratory-generated monoterpene (α-pinene, β-pinene and limonene under low NO&lt;sub&gt;x&lt;/sub&gt; conditions) secondary organic aerosol. This low volatility is consistent with its highly oxygenated AMS mass spectrum. The results are found to be highly sensitive to the mass accommodation coefficient of the evaporating species. This analysis is based on the assumption that there were no significant reactions taking place inside the thermodenuder

Volatility and hygroscopicity of aging secondary organic aerosol in a smog chamber

Peer reviewe