Determination of single particle mass spectral signatures from heavy-duty diesel vehicle emissions for PM2.5 source apportionment

The size and chemical composition of individual diesel exhaust particles were measured in order to determine unique mass spectral signatures that can be used to identify particle sources in future ambient studies. The exhaust emissions from seven in-use heavy-duty diesel vehicles (HDDVs) operating on a chassis dynamometer were passed through a dilution tunnel and residence chamber and analyzed in real time by aerosol time-of-flight mass spectrometry (ATOFMS). Seven distinct particle types describe the majority of particles emitted by HDDVs and were emitted by all seven vehicles. The dominant chemical types originated from unburned lubricant oil, and the contributions of the various types varied with particle size and driving conditions. A comparison of light-duty vehicle (LDV) exhaust particles with the HDDV signatures provide insight into the challenges associated with developing an accurate source apportionment technique and possible ways of how they may be overcome.     

Aerosol laser ablation mass spectrometry of suspended powders from PM sources and its implications to receptor modeling

Primary sources of particulate matter (PM) were analyzed by suspending powdered samples into an aerosol laser ablation mass spectrometer (LAMS). PM sources studied included vehicle exhaust particulates, dust from a non-ferrous smelter, cement powder, incinerator fly ash, two coal fly ash samples, and two soils. Marker peaks signified certain PM source sectors: construction particles could be distinguished by abundant Ca and Ca compounds, fuel combustion was marked by elemental carbon clusters, and nonferrous industrial particles showed inorganic As, Cu, Pb, Zn, and SOx. In addition to the distinction between particles from these different source sectors, mass spectral results also showed that for a single source, different particle types existed, and among different sources within a sector, similar spectra were present. The aerosol LAMS results show the difficulty in differentiating among separate fly ash sources as well as among different soil samples. A particle class balance receptor model that measures the amount of specific particle types rather than the amount of a chemical component is suggested as a means of source apportionment when particle spectra with overlapping source possibilities occur. The assumptions and limitations of receptor modeling aerosol LAMS data are also described. In particular, methods need to be developed to account for the contribution of secondary sources.     

Diesel emissions in Vienna

The aerosol in a non-industrial town normally is dominated by emissions from vehicles. Whereas gasoline-powered cars normally only emit a small amount of particulates, the emission by diesel-powered cars is considerable. The aerosol particles produced by diesel engines consist of graphitic carbon (GC) with attached hydrocarbons (HCs) including also polyaromatic HCs. Therefore the diesel particles can be carcinogenic. Besides diesel vehicles, all other combustion processes are also a source for GC; thus source apportionment of diesel emissions to the GC in the town is difficult.A direct apportionment of diesel emissions has been made possible by marking all the diesel fuel used by the vehicles in Vienna by a normally not occurring and easily detectable substance. All emitted diesel particles thus were marked with the tracer and by analyzing the atmospheric samples for the marking substance we found that the mass concentrations of diesel particles in the atmosphere varied between 5 and 23 μg m⁻³. Busy streets and calm residential areas show less difference in mass concentration than expected. The deposition of diesel particles on the ground has been determined by collecting samples from the road surface. The concentration of the marking substance was below the detection limit before the marking period and a year after the period. During the period when marked diesel fuel was used, the concentrations of the diesel particles settling to the ground was 0.012–0.07 g g⁻¹ of collected dust.A positive correlation between the diesel vehicle density and the sampled mass of diesel vehicles exists. In Vienna we have a background diesel particle concentration of 11 μg m⁻³. This value increases by 5.5 μg m⁻³ per 500 diesel vehicles h⁻¹ passing near the sampling location.The mass fraction of diesel particles of the total aerosol mass varied between 12.2 and 33%; the higher values were found in more remote areas, since diesel particles apparently diffuse easily.Estimates of diesel particle concentration by emission inventory or by using lead concentrations as an indicator for vehicle emissions gave similar values to those obtained in this study.Using available cancer risk data and diesel particle concentration found in this study, 1–2.6 additional lung cancers per 100,000 persons yr⁻¹ breathing diesel emissions in the measured concentration the whole lifetime can be expected.     

Seasonal and particle size-dependent variations in gas/particle partitioning of PCDD/Fs

This study monitored particle size-dependent variations in atmospheric polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Two gas/particle partitioning models, the subcooled liquid vapor pressure (P(L)(0)) and the octanol-air partition coefficient (K(OA)) model, were applied to each particle sizes. The regression coefficients of each fraction against the gas/particle partition coefficient (K(P)) were similar for separated particles within the same sample set but differed for particles collected during different periods. Gas/particle partitioning calculated from the integral of fractions was similar to that of size-segregated particles and previously measured bulk values. Despite the different behaviors and production mechanisms of atmospheric particles of different sizes, PCDD/F partitioning of each size range was controlled by meteorological conditions such as atmospheric temperature, O(3) and UV, which reflects no source related with certain particle size ranges but mixed urban sources within this city. Our observations emphasize that when assessing environmental and health effects, the movement of PCDD/Fs in air should be considered in conjunction with particle size in addition to the bulk aerosol.     

Experimental analysis of particle concentration heterogeneity in a ventilated scale chamber

The mixing processes of the aerosol particles from an outdoor environment in a ventilated scale chamber were experimentally studied. The particles were classified into five groups by size: 0.3–0.5 μm, 0.5–1.0 μm, 1.0–3.0 μm, 3.0–5.0 μm and 5.0–10.0 μm. The developing process for the concentration of each particle group was measured in different kinds of flow fields.The results show that the flow field configuration can effectively influence the dispersion time rate of the particles at certain positions. The increase in particle diameter can decrease the dispersion time rate. When the gas flow velocity is high, the particle dispersion time rate is independent of particle size; but when the gas flow velocity is low, particle size can significantly affect the particle dispersion time rate because the turbulent diffusion becomes important in the air and particle transport. The uniformity of the particle concentration for certain positions in steady state tends to be controlled by the inflow velocity, flow field configuration and the particle diameters.     

Theoretical versus Observed Gas-Particle Partitioning of Carbonyl Emissions from Motor Vehicles

Abstract

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Impact of particle emissions of new laser printers on modeled office room

In this study, we present how an indoor aerosol model can be used to characterize particle emitter and predict influence of the source on indoor air quality. Particle size-resolved emission rates were quantified and the source’s influence on indoor air quality was estimated by using office model simulations. We measured particle emissions from three modern laser printers in a flow-through chamber. Measured parameters were used as input parameters for an indoor aerosol model, which we then used to quantify the particle emission rates. The same indoor aerosol model was used to simulate the effect of the particle emission source inside an office model. The office model consists of a mechanically ventilated empty room and the particle source. The aerosol from the ventilation air was a filtered urban background aerosol. The effect of the ventilation rate was studied using three different ventilation ratios 1, 2 and 3 h^?1. According to the model, peak emission rates of the printers exceeded 7.0 × 10⁸ s^?1 (2.5 × 10¹² h^?1), and emitted mainly ultrafine particles (diameter less than 100 nm). The office model simulation results indicate that a print job increases ultrafine particle concentration to a maximum of 2.6 × 10⁵ cm^?3. Printer-emitted particles increased 6-h averaged particle concentration over eleven times compared to the background particle concentration.     

Source apportionment of airborne particulate matter using organic compounds as tracers

A chemical mass balance receptor model based on organic compounds has been developed that relates source contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.     

Combustion sources of particles. 1. Health relevance and source signatures

Combustion processes result in generation of a large number of particle and gaseous products that create health and environmental risks. Of particular importance are the very small particles that are emitted in large quantities from all the combustion sources, and that have been shown to be potentially more significant in terms of their impact on health than larger particles. To control and mitigate the particles with a view of health and environmental risk reduction, a good understanding is necessary of the relative and absolute contribution from the emission sources to the airborne concentrations. This understanding could only be achieved by developing source signature libraries through direct emission measurements from the sources on one hand, and by measuring particle concentrations in the air, and apportioning them to the specific local and distant sources using the signatures, on the other hand. This paper is a review of particle characteristics that are used as source signatures as well as their general advantages and limitations. The second part of the paper reviews source signatures of the most common combustion pollution sources.     

建筑物对高架点源大气污染物扩散影响的模拟研究

运用数值方法对城市中高架点源排放大气污染物的扩散规律进行了模拟研究,在计算区域内建立了三维数学模型,并将拉格朗日法描述的颗粒轨道模型耦合到风场。本研究计算了地面风速为3 m/s时的大气流场,并模拟研究了该风场条件下气体污染物的扩散和固体颗粒污染物的运动轨迹。通过分析模拟结果,给出了高架点源中排放的气体污染物的扩散区域和固体颗粒污染物运动轨迹的变化规律。     

大气超细颗粒物观测和扩散模拟研究进展

总结了近年来不同地区对不同环境下大气超细颗粒物的观测和扩散模拟研究进展。大量的观测研究结果表明,大气超细颗粒物的时空分布、组成特征、形成和成长的特性因观测地区的不同而存在很大差异,受气象因素和局部污染源的影响很大;其来源主要包括固定、移动燃烧源的直接排放和大气中颗粒成核现象,前一种来源一般是局部的,而后一种来源则是区域性的。目前,大多数关于大气超细颗粒物扩散的模拟研究都是针对其质量浓度的,对其数浓度扩散的模拟研究主要集中在小范围(机动车排放烟云的研究方面),在城市区域范围上的研究和应用还很少。最后,探讨和展望了大气超细颗粒物今后的主要研究方向和研究中面临的挑战。     

Volatile nanoparticle formation and growth within a diluting diesel car exhaust

A major source of particle number emissions is road traffic. However, scientific knowledge concerning secondary particle formation and growth of ultrafine particles within vehicle exhaust plumes is still very limited. Volatile nanoparticle formation and subsequent growth conditions were analyzed here to gain a better understanding of "real-world" dilution conditions. Coupled computational fluid dynamics and aerosol microphysics models together with measured size distributions within the exhaust plume of a diesel car were used. The impact of soot particles on nucleation, acting as a condensational sink, and the possible role of low-volatile organic components in growth were assessed. A prescribed reduction of soot particle emissions by 2 orders of magnitude (to capture the effect of a diesel particle filter) resulted in concentrations of nucleation-mode particles within the exhaust plume that were approximately 1 order of magnitude larger. Simulations for simplified sulfuric acid-water vapor gas-oil containing nucleation-mode particles show that the largest particle growth is located in a recirculation zone in the wake of the car. Growth of particles within the vehicle exhaust plume up to detectable size depends crucially on the relationship between the mass rate of gaseous precursor emissions and rapid dilution. Chassis dynamometer measurements indicate that emissions of possible hydrocarbon precursors are significantly enhanced under high engine load conditions and high engine speed. On the basis of results obtained for a diesel passenger car, the contributions from light diesel vehicles to the observed abundance of measured nucleation-mode particles near busy roads might be attributable to the impact of two different time scales: (1) a short one within the plume, marked by sufficient precursor emissions and rapid dilution; and (2) a second and comparatively long time scale resulting from the mix of different precursor sources and the impact of atmospheric chemistry.     

Modelling aerosol number distributions from a vehicle exhaust with an aerosol CFD model

Vehicular traffic contributes significantly to the aerosol number concentrations at the local scale by emitting primary soot particles and forming secondary nucleated nanoparticles. Because of their potential health effects, more attention is paid to the traffic induced aerosol number distributions.The aim of this work is to explain the phenomenology leading to the formation and the evolution of the aerosol number distributions in the vicinity of a vehicle exhaust using numerical modelling. The emissions are representative of those of a light-duty diesel truck without a diesel particle filter. The atmospheric flow is modelled with a computational fluid dynamics (CFD) code to describe the dispersion of pollutants at the local scale. The CFD code, coupled to a modal aerosol model (MAM) describing the aerosol dynamics, is used to model the tailpipe plume of a vehicle with emissions corresponding to urban driving conditions. On the basis of available measurements in Schauer et al. (1999), three surrogate species are chosen to treat the semi-volatile organic compounds in the emissions.The model simulates the formation of the aerosol distribution in the exhaust plume of a vehicle as follows. After emission to the atmosphere, particles are formed by nucleation of sulphuric acid and water vapour depending strongly on the thermodynamic state of the atmosphere and on the dilution conditions. The semi-volatile organic compounds are critical for the rapid growth of nanoparticles through condensation. The semi-volatile organic compounds are also important for the evolution of primary soot particles and can contribute substantially to their chemical composition.The most influential parameters for particle formation are the sulphur fuel content, the semi-volatile organic emissions and also the mass and initial diameter of the soot particles emitted. The model is able to take into account the complex competition between nucleation, condensation and dilution, as well as the interactions among the different aerosol modes. This type of model is a useful tool to better understand the dynamics leading to the formation of traffic induced aerosol distributions. However, some key issues such as the turbulence in the exhaust plume and in the wake of the car, the magnitude and chemical composition of semi-volatile organic emissions and the possible nucleation of organic species need to be investigated further to improve our understanding of ultrafine particle formation.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Chemical composition and source apportionment of PM2.5 particles in the Sihwa area, Korea

To investigate the chemical characteristics of fine particles in the Sihwa area, Korea, atmospheric aerosol samples were collected using a dichotomous PM10 sampler and two URG PM2.5 cyclone samplers during five intensive sampling periods between February 1998 and February 1999. The Inductively Coupled Plasma (ICP)-Atomic Emission Spectrometry (AES)/ICP-Mass Spectrometry (MS), ion chromatograph (IC), and thermal manganese dioxide oxidation (TMO) methods were used to analyze the trace elements, ionic species, and carbonaceous species, respectively. Backward trajectory analysis, factor analysis, and a chemical mass balance (CMB) model were used to estimate quantitatively source contributions to PM2.5 particles collected in the Sihwa area. The results of PM2.5 source apportionment using the CMB7 receptor model showed that (NH4)2SO4 was, on average, the major contributor to PM2.5 particles, followed by nontraffic organic carbon (OC) emission, NH4NO3, agricultural waste burning, motor vehicle emission, road dust, waste incineration, marine aerosol, and others. Here, the nontraffic OC sources include primary anthropogenic OC emitted from the industrial complex zone, secondary OC, and organic species from distant sources. The source impact of waste incineration emission became significant when the dominant wind directions were from southwest and west sectors during the sampling periods. It was found that PM2.5 particles in the Sihwa area were influenced mainly by both anthropogenic local sources and long-range transport and transformation of air pollutants.     

The influence of tropical cyclone Melor on PM10 concentrations during an aerosol episode over the Pearl River Delta region of China: Numerical modeling versus observational analysis

In this article, numerical simulations and observational analyses have been made for the aerosol episode that occurred over the Pearl River Delta (PRD) region in China during 1–3 November 2003. An air quality modeling system that consisted of the mesoscale model MM5, chemical transport model MODELS-3/CMAQ, and air pollutant emission model SMOKE, was employed. Studies have shown that this particulate matter (PM) pollution episode was apparently associated with the activity of tropical cyclone (TC) Melor. Model simulations revealed that Melor spawned this PM episode through dynamic and thermodynamic processes. The strong compensating subsidence induced by Melor's peripheral circulations created favorable meteorological conditions that enhanced local aerosol pollution. This strong downward motion produced significant adiabatic warming (2–4 °C daily) and dramatic drying in the low-level troposphere over the PRD. As a result, the PRD region was blanketed with a dry and warm air layer that strengthened the static stability of the lower troposphere. The descending motion also tended to dramatically lower the heights of the planetary boundary layer (PBL) through its dynamic effect. The fair weather created by this synoptic pattern further intensified the nocturnal temperature inversions through enhanced radiative cooling. All of these factors promoted a stagnant local atmosphere with very light winds near the surface. The horizontal and vertical dispersions of locally emitted aerosol particles were largely suppressed, leading to the accumulation of large amounts of PMs near local emission sources in the PRD region. As Melor drew near, changes in surface winds strengthened the horizontal transport of aerosol particles from inland sources to the area of Hong Kong downstream. This horizontal advection greatly contributed to the high PM₁₀ (particulate matters less than 10 μm in diameters) concentrations in Hong Kong.     

Water uptake characteristics of individual atmospheric particles having coatings

We used an environmental transmission electron microscope to observe deliquescence and hygroscopic growth of atmospheric particles with hygroscopic coatings over the range 0–100% relative humidity (RH). The particles were collected from polluted and clean environments. Types included a sulfate-coated NaCl/silicate aggregate particle, a sulfate-coated sea-salt particle, and a Mg-rich, chloride-coated sea-salt particle. They all exhibited initial water uptake between 50% and 60% RH, although the first major morphological changes occurred at 70% RH. A deliquescence sphere, adjacent to the core particle, formed between 70% and 76% RH when deliquescence occurred or when the liquid phase was able to break out of the solid exterior coating. The deliquescence sphere grew to engulf the particle with increasing RH. Some particles developed a splatter zone associated with a particle coating. Efflorescence occurred over the range 49–44% RH. Our results indicate that some coated particles undergo a multi-step deliquescence process and that composition of the different phases within the coating affects deliquescence and hygroscopic growth below 76% RH. Above 76% RH, the dominant hygroscopic growth was due to water uptake by NaCl. Efflorescence of these particles also was strongly linked to NaCl, although the presence of other phases inhibited formation of a single NaCl crystal. Our results show that the observed coatings can both enhance particle solubility and lower the effective deliquescence RH of the particle. Thus, these coatings cause important phase and size changes for aerosol particles that could feed back into many other chemical and physical processes that contribute to radiative forcing within the atmosphere.     

Dynamic of submicrometer particles in urban environment

Many studies show that particle toxicity increases with decreasing their size, emphasizing the role of submicrometric particles, in particular of ultrafine particles (<100 nm). In fact, particles greater than 2.5 μm are quickly removed through dry and wet deposition on the timescale of hours whereas submicrometer particles may reside in atmosphere for weeks, penetrate in indoor environment, and be long-range transported. High aerosol size resolution measurements are important for a correct assessment of the deposition efficiency in the human respiratory system, and time resolution is another important requisite. Starting from such considerations, time-resolved aerosol particle number size distributions have been measured in downtown Rome. Fast Mobility Particle Sizer (FMPS) and Scanning Mobility Particle Sizer (SMPS) measurements have been carried out at the INAIL’s Pilot Station, located in downtown Rome, in an area characterized by high density of autovehicular traffic. The two instruments have allowed to investigate deeply the urban aerosol in the range of 5.6–560 and 3.5–117 nm, respectively. In particular, the FMPS measurements have confirmed the interpretation about the transition phenomena in the time interval of few seconds, timescale typically associated with the emission of gasoline and diesel engines. In downtown Rome, the hourly average size distribution is bimodal or trimodal with maxima at about 5–15, 20–30, and 70–100 nm. Particle formation in the nucleation mode was associated to freshly emitted autovehicular exhaust.     

Mesoscale Air Pollution Transport in the Chicago Lake Breeze

A two-day field program in Chicago studied mesoscale pollution transport during typical lake breezes. Streamlines calculated from serial pibal data suggest that a nearly closed circulation cell traps pollutants emitted near a shore line. Optically tracked tetroons confirm the helical trajectory of air within the lake breeze regime. Pollutants released within the inflow layer move inland, rise in a narrow zone of updrafts (100 cm/sec) at the lake breeze front, advect lakeward in the return flow layer aloft, and then subside back down into the inflow layer. Pollution then fumigates back to the surface as the air returns inland a second time causing concentrations higher than would otherwise be expected. Spectral aerosol measurements (0.5-3.0 and 7.0-9.0 micrometer size ranges) made by an instrumented aircraft reveal a marked particle size sorting.     

Halogen production from aqueous tropospheric particles

Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values.For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986.It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations.The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea-salt aerosols shows that the particle phase can act as a main source of halogen containing molecules (Cl(2), BrCl, Br(2)) which are photolysed in the gas phase to yield halogen atoms (about 70% of all Cl sources and more than 99% for Br).