The modality of particle size distributions of environmental aerosols

Knowledge of the distribution of airborne particulate matter into size fractions has become an increasing area of focus when examining the effects of air pollution. While total number and mass concentrations may play an important role in exposure and risk assessment analyses, often an understanding of the particle size distributions provides more information on the type of atmospheric processes resulting in the distributions. The modality of the particle size distribution is one such aspect that has been associated with the aerosol formation mechanisms. The aim of this work is to provide a detailed analysis of the modal characteristics of a large number of particle size spectra collected over a period of three years for a range of ambient aerosol types. Measurements of over 6000 size distributions in the size range 0.016–30 μm were made using a scanning mobility particle sizer and an aerodynamic particle sizer for various ambient aerosols including: traffic influenced, urban, vegetation burning influenced, marine, modified background and suburban. Advanced data analytical procedures were adopted to combine the distributions from the two instruments for the calculation of the volume size distributions to allow clear interpretation of the modal characteristics. It was determined that, while in most cases there is a distinct nuclei mode in the number size distribution, this does not translate to a nuclei mode in the volume size distribution. Furthermore, while many of the number size distributions were different for each aerosol studied, the volume distributions were similar. This finding has serious implications for the setting of mass-based air quality standards.     

Measurement of ultrafine particle size distributions from coal-, oil-, and gas-fired stationary combustion sources

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h(-1) and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.     

Dissolution and sorption of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4,6-trinitrotoluene (TNT) residues from detonated mineral surfaces

Composition B (Comp B) is a commonly used military formulation composed of the toxic explosive compounds 2,4,6-trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). Numerous studies of the temporal fate of explosive compounds in soils, surface water and laboratory batch reactors have been conducted. However, most of these investigations relied on the application of explosive compounds to the media via aqueous addition and thus these studies do not provide information on the real world loading of explosive residues during detonation events. To address this we investigated the dissolution and sorption of TNT and RDX from Comp B residues loaded to pure mineral phases through controlled detonation. Mineral phases included nontronite, vermiculite, biotite and Ottawa sand (quartz with minor calcite). High Performance Liquid Chromatography and Attenuated Total Reflectance Fourier Transform Infrared spectroscopy were used to investigate the dissolution and sorption of TNT and RDX residues loaded onto the mineral surfaces. Detonation resulted in heterogeneous loading of TNT and RDX onto the mineral surfaces. Explosive compound residues dissolved rapidly (within 9 h) in all samples but maximum concentrations for TNT and RDX were not consistent over time due to precipitation from solution, sorption onto mineral surfaces, and/or chemical reactions between explosive compounds and mineral surfaces. We provide a conceptual model of the physical and chemical processes governing the fate of explosive compound residues in soil minerals controlled by sorption-desorption processes.     

A quantitative description of vehicle exhaust particle size distributions in a highway tunnel

During the period May 18-May 22, 1999, a comprehensive study was conducted in the Tuscarora Mountain Tunnel on the Pennsylvania Turnpike to measure real-world motor-vehicle emissions. As part of this study, size distributions of particle emissions were determined using a scanning mobility particle sizer. Each measured size distribution consisted of two modes: a nucleation mode with midpoint diameter less than 20 nm and an accumulation mode with midpoint diameter less than 100 nm. The nucleation and accumulation components in some distributions also exhibited second maxima, which implies that such particle size distributions are superpositions of two particle size distributions. This hypothesis was utilized in fitting the particle size distributions that exhibited second maxima with four lognormal distributions, two for the nucleation mode and two for the accumulation mode. The fitting assumed that the observed particle size distribution was a combination of two bimodal log-normal distributions, one attributed to the heavy-duty diesel (HDD) vehicles and another attributed either to a different class of HDD vehicles or to the light-duty spark ignition vehicles. Based on this method, estimated particle production rates were 1.8 x 10(13) and 2.8 x 10(14) particles/vehicle-km for light-duty spark ignition and HDD vehicles, respectively, which agreed with independently obtained estimates.     

Comparison of particle size distributions and elemental partitioning from the combustion of pulverized coal and residual fuel oil

U.S. Environmental Protection Agency (EPA) research examining the characteristics of primary PM generated by the combustion of fossil fuels is being conducted in efforts to help determine mechanisms controlling associated adverse health effects. Transition metals are of particular interest, due to the results of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal and residual fuel oils. Further, elemental speciation may influence this toxicity, as some species are significantly more water-soluble, and potentially more bio-available, than others. This paper presents results of experimental efforts in which three coals and a residual fuel oil were combusted in three different systems simulating process and utility boilers. Particle size distributions (PSDs) were determined using atmospheric and low-pressure impaction as well as electrical mobility, time-of-flight, and light-scattering techniques. Size-classified PM samples from this study are also being utilized by colleagues for animal instillation experiments. Experimental results on the mass and compositions of particles between 0.03 and > 20 microns in aerodynamic diameter show that PM from the combustion of these fuels produces distinctive bimodal and trimodal PSDs, with a fine mode dominated by vaporization, nucleation, and growth processes. Depending on the fuel and combustion equipment, the coarse mode is composed primarily of unburned carbon char and associated inherent trace elements (fuel oil) and fragments of inorganic (largely calcium-alumino-silicate) fly ash including trace elements (coal). The three coals also produced a central mode between 0.8- and 2.0-micron aerodynamic diameter. However, the origins of these particles are less clear because vapor-to-particle growth processes are unlikely to produce particles this large. Possible mechanisms include the liberation of micron-scale mineral inclusions during char fragmentation and burnout and indicates that refractory transition metals can contribute to PM < 2.5 microns without passing through a vapor phase. When burned most efficiently, the residual fuel oil produces a PSD composed almost exclusively of an ultrafine mode (approximately 0.1 micron). The transition metals associated with these emissions are composed of water-soluble metal sulfates. In contrast, the transition metals associated with coal combustion are not significantly enriched in PM < 2.5 microns and are significantly less soluble, likely because of their association with the mineral constituents. These results may have implications regarding health effects associated with exposure to these particles.     

Impact of roadside noise barriers on particle size distributions and pollutants concentrations near freeways

Increasing epidemiological evidence has established an association between a host of adverse health effects and exposure to ambient particulate matter (PM) and co-pollutants, especially those emitted from motor vehicles. Although PM and their co-pollutants dispersion profiles near the open freeway have been extensively characterized by means of both experimental measurements and numerical simulations in recent years, such investigations near freeways with roadside barriers have not been well documented in the literature. A few previous studies suggested that the presence of roadside structures, such as noise barriers and vegetation, may impact the decay of pollutant concentrations downwind of the freeway by limiting the initial dispersion of traffic emissions and increasing their vertical mixing due to the upward deflection of airflow. Since the noise barriers are now common roadside features of the freeways, particularly those running through populated urban areas, it is pertinent to investigate the impact of their presence on the particles and co-pollutants concentrations in areas adjacent to busy roadways. This study investigated two highly trafficked freeways (I-710 and I-5) in Southern California, with two sampling sites for each freeway, one with and the other without the roadside noise barriers. Particle size distributions and co-pollutants concentrations were measured in the immediate proximity of freeways and at different distances downwind of the freeways. The results showed the formation of a “concentration deficit” zone in the immediate vicinity of the freeway with the presence of roadside noise barrier, followed by a surge of pollutant concentrations further downwind at 80–100 m away from freeway. The particle and co-pollutants concentrations reach background levels at farther distances of 250–400 m compared to 150–200 m at the sites without roadside noise barriers.     

Factor analysis of submicron particle size distributions near a major United States-Canada trade bridge

A factor analytic model has been applied to resolve and apportion particles based on submicron particle size distributions downwind of a United States-Canada bridge in Buffalo, NY. The sites chosen for this study were located at gradually increasing distances downwind of the bridge complex. Seven independent factors were resolved, including four factors that were common to all of the five sites considered. The common factors were generally characterized by the existence of two or more number and surface area modes. The seven factors resolved were identified as follows: fresh tail-pipe diesel exhaust, local/street diesel traffic, aged/evolved diesel particles, spark-ignition gasoline emissions, background urban emissions, heavy-duty diesel agglomerates, and secondary/transported material. Submicron (<0.5 microm) and ultrafine (<0.1 microm) particle emissions downwind of the bridge were dominated by commercial diesel truck emissions. Thus, this study obtained size distinction between fresh versus aged vehicle exhaust and spark-ignition versus diesel emissions based on the measured high time-resolution particle number concentrations. Because this study mainly used particles <300 nm in diameter, some sources that would usually exhibit number modes >100 nm were not resolved. Also, the resolved profiles suggested that the major number mode for fresh tailpipe diesel exhaust might exist below the detection limit of the spectrometer used. The average particle number contributions from the resolved factors were highest closest to the bridge.     

Indoor particle size distributions in homes with open fires and improved Patsari cook stoves

Particulate pollution has been clearly linked with adverse health impacts from open fire cookstoves, and indoor air concentrations are frequently used as a proxy for exposures in health studies. Implicit are the assumptions that the size distributions for the open fire and improved stove are not significantly different, and that the relationship between indoor concentrations and personal exposures is the same between stoves. To evaluate the impact of these assumptions size distributions of particulate matter in indoor air were measured with the Sioutas cascade impactor in homes using open fires and improved Patsari stoves in a rural Purepecha community in Michoacan, Mexico. On average indoor concentrations of particles less than 0.25 μm were 72% reduced in homes with improved Patsari stoves, reflecting a reduced contribution of this size fraction to PM_2.5 mass concentrations from 68% to 48%. As a result the mass median diameter of indoor PM_2.5 particulate matter was increased by 29% with the Patsari improved stove compared to the open fire (from 0.42 μm to 0.59 μm, respectively). Personal PM_2.5 exposure concentrations for women in homes using open fires were approximately 61% of indoor concentration levels (156 μg m^?3 and 257 μg m^?3 respectively). In contrast personal exposure concentrations were 77% times indoor air concentration levels for women in homes using improved Patsari stoves (78 μg m^?3and 101 μg m^?3 respectively). Thus, if indoor air concentrations are used in health and epidemiologic studies significant bias may result if the shift in size distribution and the change in relationship between indoor air concentrations and personal exposure concentrations are not accounted for between different stove types.     

Characterization of emissions from portable household combustion devices: particle size distributions,emission rates and factors,and potential exposures

A series of source tests were conducted to characterize emissions of particulate matter (PM), carbon monoxide (CO), carbon dioxide (CO₂), methane (CH₄), and total hydrocarbon (THC ) from five types of portable combustion devices. Tested combustion devices included a kerosene lamp, an oil lamp, a kerosene space heater, a portable gas range, and four unscented candles. All tests were conducted either in a well-mixed chamber or a well-mixed room, which enables us to determine emission rates and emission factors using a single-compartment mass balance model. Particle mass concentrations and number concentrations were measured using a nephelometric particle monitor and an eight-channel optical particle counter, respectively. Real-time CO concentrations were measured with an electrochemical sensor CO monitor. CO₂, CH₄, and THC were measured using a GC-FID technique. The results indicate that all particles emitted during steady burning in each of the tested devices were smaller than 1.0 μm in diameter with the vast majority in the range between 0.1 and 0.3 μm. The PM mass emission rates and emission factors for the tested devices ranged from 5.6±0.1 to 142.3±40.8 mg h⁻¹ and from 0.35±0.06 to 9.04±4.0 mg g⁻¹, respectively. The CO emission rates and emission factors ranged from 4.7±3.0 to 226.7±100 mg h⁻¹ and from 0.25±0.12 to 1.56±0.7 mg g⁻¹, respectively. The CO₂ emission rates and emission factors ranged from 5500±700 to 210,000±90,000 mg h⁻¹ and from 387±45 to 1689±640 mg g⁻¹, respectively. The contributions of CH₄ and THC to emission inventories are expected to be insignificant due both to the small emission factors and to the relatively small quantity of fuel consumed by these portable devices. An exposure scenario analysis indicates that every-day use of the kerosene lamp in a village house can generate fine PM exposures easily exceeding the US promulgated NAAQS for PM_2.5.     

Determination of airborne particle size distributions: Calculation of cross-sensitivity and discreteness effects in cascade impaction

A theory is developed which permits numerical evaluation of errors associated with the determination of aerosol size distributions using cascade impactors. Account is taken of errors due to the overlap of a given particle size between adjacent impaction stages and to the discrete nature of cascade impaction. The theory is applied to both log-normal and polynomial functional approximations to an aerosol size distribution.Numerical determination of errors considered shows that the mass of large and small particles present in the wings of a log-normal aerosol distribution is over-estimated manyfold by most cascade impactors but that the mass of particles having aerodynamic diameters close to the aerosol mass median diameter is generally subject to quite small (<20%) negative errors. Even under extremely unfavorable conditions the mass median diameter of an aerosol can be determined to well within 25% of the true value.     

A detailed numerical study of the evolution of soot particle size distributions in laminar premixed flames

In this work, two numerical techniques, viz. the method of moments and a discrete h-p-Galerkin method, have been applied for numerical simulation of soot formation in a laminar premixed acetylene/oxygen/argon flame. From the evolution of the PAH and the soot particle size distributions, new insight into the different processes of soot formation is provided. For this, the single submodels have been examined with respect to their influence on the PAH and the soot particle size distributions. The particle inception step was studied in detail by comparing the simulated PAH size distributions with experimental results. Additionally, an estimation of the interaction energy of layered PAH dimers was performed by quantum chemical calculations. From these results, some evidence for the particle inception model employing coalescence of PAH molecules has been found. The numerical results for the gas phase chemical species, the particle number densities and volume fractions of soot as well as for the soot particle size distributions are compared with experimental data. Thereby, the consistency of the entire model is demonstrated.     

Development of a measuring technique for simultaneous in situ detection of nanoscaled particle size distributions and gas temperatures

Point measurements of time-resolved LII signals have been performed in sooting premixed low pressure flames. Soot particle size distribution and gas temperature in these flames are known from independent measurements. This data is used to validate parameters of an improved LII model, where special emphasis is taken on the accurate modelling of mass and heat transfer rates. Using this model particle size distributions and gas temperatures can be estimated from time-resolved LII signals using non-linear regression. Standard numerical methods are applied. An experimental setup is presented, which allows measuring one-dimensional maps of particle size distribution and gas temperature. The technique is based on the one-dimensional and time-resolved detection of LII signals using a Streak camera.     

On-road measurements of ultrafine particle concentration profiles and their size distributions inside the longest highway tunnel in Southeast Asia

This study measured ultrafine particle (UFP) levels and their size distributions in the Hsuehshan tunnel from August 12 to 19, 2009, using a Fast Mobility Particle Sizer. Measurement results demonstrate that traffic volume, the slope of the tunnel (downhill or uphill) and the ventilation system affected UFP levels inside the tunnel. Average UFP levels were about 1.0 × 10⁵–3.0 × 10⁵ particles cm^?3 at normal traffic volume. A traffic jam in the tunnel could raise UFP levels to over 1.0 × 10⁶ particles cm^?3. UFP levels at the uphill bore were significantly higher than those at the downhill bore due to high UFP levels exhausted from vehicles going uphill at high engine load conditions. UFP levels eventually diluted 10–50% with fresh air from tunnel air shafts. Gas-to-particle condensation conversion markedly produced nucleation mode particles at the tunnel entrance section. Observations also showed Aitken mode particles markedly formed by coagulation growth of nucleation mode particles in the tunnel middle section and exit section. That is, the particle size distributions changed significantly inside the tunnel. Measurement results suggest that particles in the Aitken mode in the long tunnel governed UFP levels.     

Simulation of the evolution of particle size distributions in a vehicle exhaust plume with unconfined dilution by ambient air

Over the past several years, numerous studies have linked ambient concentrations of particulate matter (PM) to adverse health effects, and more recent studies have identified PM size and surface area as important factors in determining the health effects of PM. This study contributes to a better understanding of the evolution of particle size distributions in exhaust plumes with unconfined dilution by ambient air. It combines computational fluid dynamics (CFD) with an aerosol dynamics model to examine the effects of different streamlines in an exhaust plume, ambient particle size distributions, and vehicle and wind speed on the particle size distribution in an exhaust plume. CFD was used to calculate the flow field and gas mixing for unconfined dilution of a vehicle exhaust plume, and the calculated dilution ratios were then used as input to the aerosol dynamics simulation. The results of the study show that vehicle speed affected the particle size distribution of an exhaust plume because increasing vehicle speed caused more rapid dilution and inhibited coagulation. Ambient particle size distributions had an effect on the smaller sized particles (approximately 10 nm range under some conditions) and larger sized particles (>2 microm) of the particle size distribution. The ambient air particle size distribution affects the larger sizes of the exhaust plume because vehicle exhaust typically contains few particles larger than 2 microm. Finally, the location of a streamline in the exhaust plume had little effect on the particle size distribution; the particle size distribution along any streamline at a distance x differed by less than 5% from the particle size distributions along any other streamline at distance x.     

Relationship between pressure fluctuations and generation of organic pollutants with different particle size distributions in a fluidized bed incinerator

The hydrodynamic behaviors of fluidization perhaps significantly influence the uniformity of fluidization in fluidized bed incinerator. Good uniformity of fluidization expressed the air across uniformly through the bed and the particles being distributed well in the fluid stream. The aggregates, flocs and channels of particles do not happen during fluidization. The Good uniformity will maintain high heat and mass distribution to improve reaction efficiency. These parameters include the height of static bed, gas velocity, mixing and distribution of bed particle, which have rarely been studied in previous investigations. Consequently, this study examines how the hydrodynamic parameters affect the generation of organic pollutants (BTEXs and PAHs) during incineration. The statistical and power spectral analysis of the measured pressure fluctuation during incineration are used to elucidate the relationship between behaviors of fluidization and generation of pollutants during incineration. Experimental results show the organic concentration does not increase with uniformity of fluidization decreasing. The reason may be the explosion of the gas and the consequent thermal shock destroy the coalescent bubbles to form small bubbles again and enhance the efficiency of transfer of oxygen to increase combustion efficiency. Additionally, the mean amplitude and fluidized index of pressure fluctuation similarly vary with the concentration of organic pollutants. These two indices can be used to assess the efficiency of combustion. The four particle size distributions could be divided into two groups by statistical analysis. The Gaussian and narrow distributions belong to one group and the binary and flat the other. The organic concentration of the Gaussian and narrow distributions are lower than that of the other distributions. Consequently, the bed materials should maintain narrow or Gaussian distributions to maintain a good combustion efficiency during incineration.     

Simulation of the evolution of particle size distributions containing coarse particulate in the atmospheric surface layer with a simple convection-diffusion-sedimentation model

The Fugitive Dust Model (FDM) and Industrial Source Complex (ISC), widely used coarse particulate dispersion models, have been shown inaccurate due to the neglect of vertical variations in atmospheric wind speed and turbulent diffusivity (Vesovic et al., 2001), omission of the gravitational advection velocity, and an underestimation of the ground deposition velocity (Kim and Larson, 2001). A simple, transient two-dimensional convection-diffusion-sedimentation model is proposed to simulate the evolution in particle size distribution of an aerosol ‘puff’ containing coarse particulate in the atmospheric surface layer. Monin-Okhubov similarity theory, accompanied by empirical observations made by Businger et al. (1971), is adopted to characterize the surface layer wind speed and turbulent diffusivity profiles over a wide range of atmospheric conditions. A first order analysis of the crossing trajectories effect suggests simulation data presented here are not significantly affected by particle inertia. The model is validated against Suffield experimental data in which coarse particulate deposition was measured out to a distance of 800 m from the source (Walker, 1965). Good agreement is found for the decay in ground deposits with distance from the source for stable atmospheres. Deposition data was also simulated for unstable atmospheric stratification and the current model was determined to modestly underestimate the peak concentration with increasing accuracy further downwind of the release. The current model's effective deposition velocity was compared to that suggested by Kim et al. (2000) and shows improvement with respect to FDM. Lastly, the model was used to simulate the dispersion of nine lognormal aerosol puffs in the lowest 50 m of the atmospheric surface layer for four classes of atmospheric stability. The simulated mass median aerodynamic diameters (MMAD) at multiple downwind sampling locations were calculated and plotted with distance from the source. The first 50 m from the source was found to have a substantial impact on the evolution of MMAD for stable atmospheric conditions. Away from the source, it was observed that particle size distributions were truncated by removal of all particles larger than about 60 μm. A particle Peclet number was also defined to quantify the relative importance of turbulent dispersion and sedimentation on particle motion in the vertical direction.     

Spatial-temporal variability of aerosol sources based on chemical composition and particle number size distributions in an urban settlement influenced by metallurgical industry

Environmental Science and Pollution Research - The Moravian-Silesian region of the Czech Republic with its capital city Ostrava is a European air pollution hot spot for airborne particulate matter...     

元素硫颗粒粒径对污泥重金属生物沥滤的影响

以城市污水处理厂剩余污泥作为处理介质,土著嗜酸氧化硫硫杆菌(Acidithiobacillus thiooxidans,A.thiooxi-dans)为主要沥滤微生物,采用序批式生物沥滤装置,就投加150~725μm的不同粒径元素硫对沥滤的酸化效果、硫酸根产率和重金属去除效果的影响进行了研究。结果表明,在元素硫投配量为3 g/L,曝气强度为1.0 L/(min.L)的条件下,元素硫粒径在165~215μm范围减小时能显著改善污泥酸化速度、提高酸化程度和硫酸根产率。底物元素硫的最佳粒径为165μm,此时沥滤体系pH下降速率为0.85个pH单位/d,硫酸根的产率为454.9 mg/(L.d),沥滤6 d后污泥中高浓度重金属Cu、Zn、Cd的去除率达到70.3%、81.2%、87.8%.     

Effect of temperature and particle size on the thermal desorption of PCBs from contaminated soil

Thermal desorption is widely used for remediation of soil contaminated with volatiles, such as solvents and distillates. In this study, a soil contaminated with semivolatile polychlorinated biphenyls (PCBs) was sampled at an interim storage point for waste PCB transformers and heated to temperatures from 300 to 600 °C in a flow of nitrogen to investigate the effect of temperature and particle size on thermal desorption. Two size fractions were tested: coarse soil of 420–841 μm and fine soil with particles <250 μm. A PCB removal efficiency of 98.0 % was attained after 1 h of thermal treatment at 600 °C. The residual amount of PCBs in this soil decreased with rising thermal treatment temperature while the amount transferred to the gas phase increased up to 550 °C; at 600 °C, destruction of PCBs became more obvious. At low temperature, the thermally treated soil still had a similar PCB homologue distribution as raw soil, indicating thermal desorption as a main mechanism in removal. Dechlorination and decomposition increasingly occurred at high temperature, since shifts in average chlorination level were observed, from 3.34 in the raw soil to 2.75 in soil treated at 600 °C. Fine soil particles showed higher removal efficiency and destruction efficiency than coarse particles, suggesting that desorption from coarse particles is influenced by mass transfer.