Nucleation-accumulation Mode Trade-off in Non-volatile Particle Emissions From a Small Non-road Small Diesel Engine

Small (\u3c 8 kW) non-road engines are a significant source of pollutants such as particle number (PN) emissions. Many small non-road engines do not have diesel particulate filters (DPFs). They are so designed that air–fuel ratio (AFR) can be adjusted to control visible diesel smoke and particulate matter (PM) resulting from larger accumulation mode particles. However, the effect of AFR variation on smaller nucleation mode nanoparticle emissions is not well understood. Several studies on larger engines have reported a trade-off between smaller and larger particles. In this study, AFR was independently varied over the entire engine map of a naturally aspirated (NA) non-road small diesel engine using forced induction (FI) of externally compressed air. AFR’s ranged from 57 to 239 compared to the design range of 23–92 for the engine, including unusually high AFR’s at full-load operation, not previously reported for conventional combustion. As expected, larger accumulation mode particles were lowered (up to 15 times) for FI operation. However, the smaller nucleation mode nanoparticles increased up to 15 times. Accumulation mode particles stopped decreasing above an AFR threshold while nucleation particles continuously increased. In-cylinder combustion analysis showed a slightly smaller ignition delay and higher burn rate for FI cases relative to NA operation. Much higher peak cylinder pressures were accompanied by much lower combustion and exhaust gas temperatures (EGT), due to higher in-cylinder mass during FI operation. Peak nucleation mode emissions were shown to be negatively correlated to EGT for all the data, collapsing on a single curve. This is consistent with some other studies reporting increased nucleation mode emissions (and higher accumulation mode particles) with decreased load, lower speed, lower EGR, advanced combustion phasing, and higher injection pressure, all of which reduce EGT. The nucleation-accumulation trade-off has been explained by the ‘adsorption hypothesis’ by some investigators. In the current work, an alternative/supplemental argument has been made for the possibility that lower cylinder temperatures during the late-burning phase (correlated to lower EGT) phase hampers oxidation of nucleation mode particles and increases nucleation mode emissions

Effect of organic compounds on nanoparticle formation in diluted diesel exhaust

International audienceThe nucleation of nanoparticles in the exhaust of a modern light-duty diesel vehicle was investigated on a chassis dynamometer. This laboratory study is focused on the influence of volatile organic compounds (VOCs) on nucleation of volatile nanoparticles. Different organic compounds were added to the dilution air of the particle sampling under different sampling conditions. Sample temperature and relative sample humidity were varied in a wide range. The number size distribution of the particles was measured with a scanning mobility particle sizer (SMPS) and showed significant differences in response to the added organic compounds. While the nucleation mode particles showed a large variation in concentration, the accumulation mode particles remained unchanged for all compounds. Depending on the functional group, organic compounds were capable of initiating and increasing (alcohols and toluene) or decreasing (acetone, aniline, and methyl tert-butyl ether (MTBE)) nucleation mode particles. Short volatile aliphatic hydrocarbons (hexane and cyclohexane) turned out to be without effect on nucleation of nanoparticles. Possible reasons for the differences are discussed

Ion — particle interactions during particle formation and growth at a coniferous forest site in central Europe

In this work, we examined the interaction of ions and neutral particles during atmospheric new particle formation (NPF) events. The analysis is based on simultaneous field measurements of atmospheric ions and total particles using a neutral cluster and air ion spectrometer (NAIS) across the diameter range 2–25 nm. The Waldstein research site is located in a spruce forest in NE Bavaria, Southern Germany, known for enhanced radon concentrations, presumably leading to elevated ionization rates. Our observations show that the occurrence of the ion nucleation mode preceded that of the total particle nucleation mode during all analyzed NPF events. The time difference between the appearance of 2 nm ions and 2 nm total particles was typically about 20 to 30 min. A cross correlation analysis showed a rapid decrease of the time difference between the ion and total modes during the growth process. Eventually, this time delay vanished when both ions and total particles did grow to larger diameters. Considering the growth rates of ions and total particles separately, total particles exhibited enhanced growth rates at diameters below 15 nm. This observation cannot be explained by condensation or coagulation, because these processes would act more efficiently on charged particles compared to neutral particles. To explain our observations, we propose a mechanism including recombination and attachment of continuously present cluster ions with the ion nucleation mode and the neutral nucleation mode, respectively

Ion-particle interactions during particle formation and growth at a coniferous forest site in central Europe

In this work, we examined the interaction of ions and neutral particles during atmospheric new particle formation (NPF) events. The analysis is based on simultaneous field measurements of atmospheric ions and total particles using a neutral cluster and air ion spectrometer (NAIS) across the diameter range 2–25 nm. The Waldstein research site is located in a spruce forest in NE Bavaria, Southern Germany, known for enhanced radon concentrations, presumably leading to elevated ionization rates. Our observations show that the occurrence of the ion nucleation mode preceded that of the total particle nucleation mode during all analyzed NPF events. The time difference between the appearance of 2 nm ions and 2 nm total particles was typically about 20 to 30 min. A cross correlation analysis showed a rapid decrease of the time difference between the ion and total modes during the growth process. Eventually, this time delay vanished when both ions and total particles did grow to larger diameters. Considering the growth rates of ions and total particles separately, total particles exhibited enhanced growth rates at diameters below 15 nm. This observation cannot be explained by condensation or coagulation, because these processes would act more efficiently on charged particles compared to neutral particles. To explain our observations, we propose a mechanism including recombination and attachment of continuously present cluster ions with the ion nucleation mode and the neutral nucleation mode, respectively

Bimodal Distribution of Sulfuric Acid Aerosols in the Upper Haze of Venus

The upper haze (UH) of Venus is variable on the order of days and it is populated by two particle modes. We use a 1D microphysics and vertical transport model based on the Community Aerosol and Radiation Model for Atmospheres to evaluate whether interaction of upwelled cloud particles and sulfuric acid particles nucleated in situ on meteoric dust are able to generate the two size modes and whether their observed variability are due to cloud top vertical transient winds. Nucleation of photochemically produced sulfuric acid onto polysulfur condensation nuclei generates mode 1 cloud droplets that then diffuse upwards into the UH. Droplets generated in the UH from nucleation of sulfuric acid onto meteoric dust coagulate with the upwelled cloud particles and cannot reproduce the observed bimodal size distribution. The mass transport enabled by cloud top transient winds are able to generate a bimodal size distribution in a time scale consistent with observations. Sedimentation and convection in the middle and lower clouds causes the formation of large mode 2 and mode 3 particles. Evaporation of these particles below the clouds creates a local sulfuric acid vapor maximum that causes upwelling of sulfuric acid back into the clouds. If the polysulfur condensation nuclei are small and their production rate is high, coagulation of small droplets onto larger droplets in the middle cloud may result in sulfuric acid "rain" below the clouds once every few Earth months. Reduction of the polysulfur condensation nuclei production rate destroys this oscillation and reduces the mode 1 particle abundance in the middle cloud by two orders of magnitude, though it better reproduces the sulfur-to-sulfuric-acid mass ratio in the cloud and haze droplets. In general we find satisfactory agreement between our results and observations, though improvements could be made by incorporating sulfur microphysics.Comment: 62 pages, 18 figures, 1 table. Accepted for publication in Icaru

Mode resolved density of atmospheric aerosol particles

In this study, we investigate the mode resolved density of ultrafine atmospheric particles measured in boreal forest environment. The method used here enables us to find the distinct density information for each mode in atmospheric fine particle population: the density values for nucleation, Aitken, and accumulation mode particles are presented. The experimental data was gained during 2 May 2005–19 May 2005 at the boreal forest measurement station "SMEAR II" in Hyytiälä, Southern Finland. The density values for accumulation mode varied from 1.1 to 2 g/cm<sup>3</sup> (average 1.5 g/cm<sup>3</sup>) and for Aitken mode from 0.4 to 2 g/cm<sup>3</sup> (average 0.97 g/cm<sup>3</sup>). As an overall trend during the two weeks campaign, the density value of Aitken mode was seen to gradually increase. With the present method, the time dependent behaviour of the particle density can be investigated in the time scale of 10 min. This allows us to follow the density evolution of the nucleation mode particles during the particle growth process following the nucleation burst. The density of nucleation mode particles decreased during the growth process. The density values for 15 nm particles were 1.2–1.5 g/cm<sup>3</sup> and for grown 30 nm particles 0.5–1 g/cm<sup>3</sup>. These values are consistent with the present knowledge that the condensing species are semi-volatile organics, emitted from the boreal forest

Dust ice nuclei effects on cirrus clouds

In order to study aerosol–cloud interactions in cirrus clouds, we apply a new multiple-mode ice microphysical scheme to the general circulation model ECHAM5-HAM. The multiple-mode ice microphysical scheme allows for analysis of the competition between homogeneous freezing of solution droplets, deposition nucleation of pure dust particles, and immersion freezing of coated dust particles and pre-existing ice. We base the freezing efficiencies of coated and pure dust particles on the most recent laboratory data. The effect of pre-existing ice, which has been neglected in previous ice nucleation parameterizations, is to deplete water vapour by depositional growth and thus prevent homogeneous and heterogeneous freezing from occurring

Effect of photochemical ageing on the ice nucleation properties of diesel and wood burning particles

A measurement campaign (IMBALANCE) conducted in 2009 was aimed at characterizing the physical and chemical properties of freshly emitted and photochemically aged combustion particles emitted from a log wood burner and diesel vehicles: a EURO3 Opel Astra with a diesel oxidation catalyst (DOC) but no particle filter and a EURO2 Volkswagen Transporter TDI Syncro without emission aftertreatment. Ice nucleation experiments in the deposition and condensation freezing modes were conducted with the Portable Ice Nucleation Chamber (PINC) at three nominal temperatures, −30 °C, −35 °C and −40 °C. Freshly emitted diesel particles showed ice formation only at −40 °C in the deposition mode at 137% relative humidity with respect to ice (RH<sub>i</sub>) and 92% relative humidity with respect to water (RH<sub>w</sub>), and photochemical ageing did not play a role in modifying their ice nucleation behaviour. Only one diesel experiment where α-pinene was added for the ageing process, showed an ice nucleation enhancement at −35 °C. Wood burning particles also act as ice nuclei (IN) at −40 °C in the deposition mode at the same conditions as for diesel particles and photochemical ageing also did not alter the ice formation properties of the wood burning particles. Unlike diesel particles, wood burning particles form ice via condensation freezing at −35 °C whereas no ice nucleation was observed at −30 °C. Photochemical ageing did not affect the ice nucleation ability of the diesel and wood burning particles at the three different temperatures investigated but a broader range of temperatures below −40 °C need to be investigated in order to draw an overall conclusion on the effect of photochemical ageing on deposition/condensation ice nucleation across the entire temperature range relevant to cold clouds

On the mode-segregated aerosol particle number concentration load : contributions of primary and secondary particles in Hyytiälä and Nanjing

Aerosol particle concentrations in the atmosphere are governed by their sources and sinks. Sources include directly-emitted (primary) and secondary aerosol particles formed from gas-phase precursor compounds. The relative importance of primary and secondary aerosol particles varies regionally and with time. In this work, we investigated primary and secondary contributions to mode-segregated particle number concentrations by using black carbon as a tracer for the primary aerosol number concentration. We studied separately nucleation, Aitken and accumulation mode concentrations at a rural boreal forest site (Hyytiala, Finland) and in a rather polluted megacity environment (Nanjing, China) using observational data from 2011 to 2014. In both places and in all the modes, the majority of particles were estimated to be of secondary origin. Even in Nanjing, only about half of the accumulation mode particles were estimated to be of primary origin. Secondary particles dominated particularly in the nucleation and Aitken modes.Peer reviewe