Modelling the non-ideal multiphase chemical processing in aqueous aerosol particles with SPACCIM-SpactMod

Author(s):  
Ralf Wolke ◽  
Andreas Tilgner ◽  
Ahmad Jhony Rusumdar ◽  
Hartmut Herrmann

<p>Tropospheric deliquesced particles including haze particles are a complex multiphase and multi-component environment with simultaneously occurring multiphase chemical transformations. Such chemical processes are able to alter the chemical composition and the deduced physical aerosol properties. Deliquesced particles are characterized by concentrated non-ideal solutions (‘aerosol liquid water’ or ALW) that can affect the occurring multiphase chemical processing. The effects of such non-ideal solutions have generally not been adequately investigated by present complex multiphase chemistry models. Thus, the present study is aimed at investigating the impact of non-ideality on multiphase chemical processing. Therefore, simulations with a multiphase chemistry model (SPACCIM-SpactMod) including the CAPRAM chemical mechanism are performed for polluted and less polluted environmental conditions and different ALW conditions.</p><p>The present study shows that activity coefficients of inorganic ions are often below unity under deliquesced aerosol conditions, and that most uncharged organic compounds exhibit activity coefficient values around or even above unity. The model studies demonstrated that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), key oxidants, and related chemical subsystems, e.g. organic chemistry. In detail, both the chemical formation and oxidation fluxes of Fe(II) are substantially lowered by a factor of 2.8 under polluted haze conditions compared to a case study without non-ideality treatment. The reduced Fe(II) processing in the polluted base case, including lowered chemical fluxes of the Fenton reaction (-70 %), results in a reduced processing of HO<sub>x</sub>/HO<sub>y.</sub> under deliquesced aerosol conditions. Therefore, higher multiphase H<sub>2</sub>O<sub>2</sub> concentrations (by a factor of 3.1 larger) and lower aqueous-phase OH concentrations (by a factor of ≈ 4 lower) were modelled during aerosol conditions. For H<sub>2</sub>O<sub>2</sub>, the consideration of non-ideality increases S(VI) oxidation fluxes under aqueous aerosol conditions by 40 %. Moreover, the chemical fluxes of the OH radical are about 50 % lower in the non-ideal haze case. Accordingly, the consideration of non-ideality affects the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For important organic carboxylic acids, e.g. glyoxylic acid and oxalic acid, the reduced radical oxidation budget under aqueous particle conditions leads to increased concentration levels. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations observed under ambient highly polluted conditions. Furthermore, the simulations show that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes. Overall, the performed studies demonstrate the crucial role of a detailed non-ideality treatment in multiphase models dealing with aqueous aerosol chemistry and the needs to further improve current model implementations.</p>

2019 ◽  
Author(s):  
Ahmad J. Rusumdar ◽  
Andreas Tilgner ◽  
Ralf Wolke ◽  
Hartmut Herrmann

Abstract. Tropospheric deliquesced particles are characterised by concentrated non-ideal solutions (aerosol liquid water or ALW) that can affect the occurring multiphase chemistry. However, such non-ideal solution effects have generally not yet been considered in and investigated by current complex multiphase chemistry models in an adequate way. Therefore, the present study aims at accessing the impact of non-ideality on multiphase chemical processing in concentrated aqueous aerosols. Simulations with the multiphase chemistry model (SPACCIM-SpactMod) are performed in different environmental and microphysical conditions with and without a treatment of non-ideal solutions in order to assess its impact on aqueous-phase chemical processing. The present study shows that activity coefficients of inorganic ions are often below unity under 90 % RH-deliquesced aerosol conditions, and that most uncharged organic compounds exhibit activity coefficient values of around or even above unity. Due to this behaviour, model studies have revealed that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), oxidants, and related chemical subsystems such as organic chemistry. In detail, both the chemical formation and oxidation fluxes of Fe(II) are substantially lowered by a factor of 2.8 in the non-ideal base case compared to the ideal case. The reduced Fe(II) processing in the non-ideal base case, including lowered chemical fluxes of the Fenton reaction (−70 %), leads to a reduced processing of HOx/HOy. under deliquesced aerosol conditions. Consequently, higher multiphase H2O2 concentrations (larger by a factor of 3.1) and lower aqueous-phase OH concentrations (lower by a factor of ≈ 4) are modelled during non-cloud periods. For H2O2, a comparison of the chemical reaction fluxes reveals that the most important sink, the reaction with HSO3−, contributes with a 40 % higher flux in the non-ideal base case than in the ideal case, leading to more efficient sulfate formation. On the other hand, the chemical fluxes of the OH radical are about 50 % lower in the non-ideal base case than in the ideal case, including lower degradation fluxes of organic aerosol components. Thus, considering non-ideality influences the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For example, the reduced oxidation budget under deliquesced particle conditions leads to both increased and decreased concentration levels, e.g. of important C2/C3 carboxylic acids. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations than observed under ambient highly polluted conditions. Furthermore, the simulations implicate that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes.


2020 ◽  
Vol 20 (17) ◽  
pp. 10351-10377
Author(s):  
Ahmad Jhony Rusumdar ◽  
Andreas Tilgner ◽  
Ralf Wolke ◽  
Hartmut Herrmann

Abstract. Tropospheric deliquesced particles are characterised by concentrated non-ideal solutions (“aerosol liquid water” or ALW) that can affect the occurring multiphase chemistry. However, such non-ideal solution effects have generally not yet been considered in and investigated by current complex multiphase chemistry models in an adequate way. Therefore, the present study aims at accessing the impact of non-ideality on multiphase chemical processing in concentrated aqueous aerosols. Simulations with the multiphase chemistry model (SPACCIM-SpactMod) are performed under different environmental and microphysical conditions with and without a treatment of non-ideal solutions in order to assess its impact on aqueous-phase chemical processing. The present study shows that activity coefficients of inorganic ions are often below unity under 90 % RH-deliquesced aerosol conditions and that most uncharged organic compounds exhibit activity coefficient values of around or even above unity. Due to this behaviour, model studies have revealed that the inclusion of non-ideality considerably affects the multiphase chemical processing of transition metal ions (TMIs), oxidants, and related chemical subsystems such as organic chemistry. In detail, both the chemical formation and oxidation rates of Fe(II) are substantially lowered by a factor of 2.8 in the non-ideal base case compared to the ideal case. The reduced Fe(II) processing in the non-ideal base case, including lowered chemical rates of the Fenton reaction (−70 %), leads to a reduced processing of HOx∕HOy under deliquesced aerosol conditions. Consequently, higher multiphase H2O2 concentrations (larger by a factor of 3.1) and lower aqueous-phase OH concentrations (lower by a factor of ≈4) are modelled during non-cloud periods. For H2O2, a comparison of the chemical reaction rates reveals that the most important sink, the reaction with HSO3-, contributes with a 40 % higher rate in the non-ideal base case than in the ideal case, leading to more efficient sulfate formation. On the other hand, the chemical formation rates of the OH radical are about 50 % lower in the non-ideal base case than in the ideal case, leading to lower degradation rates of organic aerosol components. Thus, considering non-ideality influences the chemical processing and the concentrations of organic compounds under deliquesced particle conditions in a compound-specific manner. For example, the reduced oxidation budget under deliquesced particle conditions leads to both increased and decreased concentration levels, e.g. of important C2∕C3 carboxylic acids. For oxalic acid, the present study demonstrates that the non-ideality treatment enables more realistic predictions of high oxalate concentrations than observed under ambient highly polluted conditions. Furthermore, the simulations imply that lower humidity conditions, i.e. more concentrated solutions, might promote higher oxalic acid concentration levels in aqueous aerosols due to differently affected formation and degradation processes.


2020 ◽  
Vol 20 (11) ◽  
pp. 6725-6747 ◽  
Author(s):  
Yanhong Zhu ◽  
Andreas Tilgner ◽  
Erik Hans Hoffmann ◽  
Hartmut Herrmann ◽  
Kimitaka Kawamura ◽  
...  

Abstract. Despite the high abundance of secondary aerosols in the atmosphere, their formation mechanisms remain poorly understood. In this study, the Master Chemical Mechanism (MCM) and the Chemical Aqueous-Phase Radical Mechanism (CAPRAM) are used to investigate the multiphase formation and processing of secondary aerosol constituents during the advection of air masses towards the measurement site of Mt. Tai in northern China. Trajectories with and without chemical–cloud interaction are modeled. Modeled radical and non-radical concentrations demonstrate that the summit of Mt. Tai, with an altitude of ∼1.5 km a.m.s.l., is characterized by a suburban oxidants budget. The modeled maximum gas-phase concentrations of the OH radical are 3.2×106 and 3.5×106 molec. cm−3 in simulations with and without cloud passages in the air parcel, respectively. In contrast with previous studies at Mt. Tai, this study has modeled chemical formation processes of secondary aerosol constituents under day vs. night and cloud vs. non-cloud cases along the trajectories towards Mt. Tai in detail. The model studies show that sulfate is mainly produced in simulations where the air parcel is influenced by cloud chemistry. Under the simulated conditions, the aqueous reaction of HSO3- with H2O2 is the major contributor to sulfate formation, contributing 67 % and 60 % in the simulations with cloud and non-cloud passages, respectively. The modeled nitrate formation is higher at nighttime than during daytime. The major pathway is aqueous-phase N2O5 hydrolysis, with a contribution of 72 % when cloud passages are considered and 70 % when they are not. Secondary organic aerosol (SOA) compounds, e.g., glyoxylic, oxalic, pyruvic and malonic acid, are found to be mostly produced from the aqueous oxidations of hydrated glyoxal, hydrated glyoxylic acid, nitro-2-oxopropanoate and hydrated 3-oxopropanoic acid, respectively. Sensitivity studies reveal that gaseous volatile organic compound (VOC) emissions have a huge impact on the concentrations of modeled secondary aerosol compounds. Increasing the VOC emissions by a factor of 2 leads to linearly increased concentrations of the corresponding SOA compounds. Studies using the relative incremental reactivity (RIR) method have identified isoprene, 1,3-butadiene and toluene as the key precursors for glyoxylic and oxalic acid, but only isoprene is found to be a key precursor for pyruvic acid. Additionally, the model investigations demonstrate that an increased aerosol partitioning of glyoxal can play an important role in the aqueous-phase formation of glyoxylic and oxalic acid. Overall, the present study is the first that provides more detailed insights in the formation pathways of secondary aerosol constituents at Mt. Tai and clearly emphasizes the importance of aqueous-phase chemical processes on the production of multifunctional carboxylic acids.


2017 ◽  
pp. 454-461
Author(s):  
Sérgio Machado Corrêa ◽  
Jorgina Rosete Teixeira ◽  
Eduardo Delfino Sodré ◽  
Carolina Vieira De Souza

This paper attempts to demonstrate the impact on tropospheric ozone according to VOC emissions from a landfill, located in the Rio de Janeiro Metropolitan Area (RJMA) at Niteroi city. It is well known that ozone is formed by the reactions of VOC, NOx and sunlight. The actual situation of this area is a low-medium ozone concentration due to high levels of NOx. The contribution of high VOC values from the landfill emissions will lead to a new situation with higher ozone values. The emissions of Morro do Céu Controlled Landfill (ACMC) (Niterói) were compiled together with meteorological data using OZIPR trajectory model coupled with SAPRC chemical mechanism. The input data for SAPRC were obtained using a VOC speciation by a representative sample collected at December, 2009 above the landfill soil. The samplings were done using evacuated electropolished canisters, and the chemical analyses were done by GC-MS following U.S.EPA TO-15 methodology. The base case used was adjusted for the RJMA using the annual emissions inventory done by INEA (Environmental Agency of Rio de Janeiro State) and the VOC speciation was performed at Rio de Janeiro downtown area. The ozone modeled for RJMA was compared with the ozone modeled for the landfill area, where the differences between the modeling procedures were the VOC speciation and hourly emissions. The results indicated an increase of 27% for ozone in the region of the landfill, indicating that the VOC emissions have to be considered.


2016 ◽  
Author(s):  
Camille Mouchel-Vallon ◽  
Laurent Deguillaume ◽  
Anne Monod ◽  
Hélène Perroux ◽  
Clémence Rose ◽  
...  

Abstract. Organic compounds of both anthropogenic and natural origin are ubiquitous in the multiphasic atmospheric medium. Their transformation in the atmosphere affects air quality and the global climate. Modelling provides a useful tool to investigate the chemistry of organic compounds in the tropospheric multiphase system. While several comprehensive explicit mechanisms exist in the gas phase, explicit mechanisms are much more limited in the aqueous phase. Recently, new empirical methods have been developed to estimate HO• reaction rates in the aqueous phase: structure-activity relationships (SARs) provide global rate constants and branching ratios for HO• abstraction from and addition to atmospheric organic compounds. Based on these SARs, a new detailed aqueous-phase mechanism, named the cloud explicit physico-chemical scheme (CLEPS), to describe the oxidation of hydrosoluble organic compounds resulting from isoprene oxidation is proposed. In this paper, a protocol based on reviewed experimental data and evaluated prediction methods is described in detail. The current version of the mechanism includes approximately 850 aqueous reactions and 465 equilibria. Inorganic reactivity is described for 67 chemical species (e.g., transition metal ions, HxOy, sulphur species, nitrogen species, and chlorine). For organic compounds, 87 chemical species are considered in the mechanism, corresponding to 657 chemical forms that are individually followed (e.g., hydrated forms, anionic forms). This new aqueous-phase mechanism is coupled with the detailed gas phase mechanism MCM v3.3.1 through mass transfer parameterization for the exchange between the gas phase and aqueous phase. The GROMHE SAR enables the evaluation of the Henry's law constants for undocumented organic compounds. The resulting multiphase mechanism is implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP). This model allows simulation of the time evolution of the concentrations of each individual chemical species in addition to detailed time-resolved flux analyses. The variable photolysis in both phases is calculated using the TUV 4.5 radiative transfer model. To evaluate our chemical mechanism, an idealized cloud event with fixed microphysical cloud parameters is simulated. The simulation is performed for a low-NOx situation. The results indicate the formation of oxidized mono- and diacids in the aqueous phase, as well as a significant influence on the gas phase chemistry and composition. For this particular simulation, the aqueous phase mechanism is responsible for the efficient fragmentation and functionalization of organic compounds. This new cloud chemistry model allows for the analysis of individual aqueous sub systems and can be used to analyze the results from cloud chamber experiments and field campaigns.


2010 ◽  
Vol 10 (3) ◽  
pp. 5863-5910 ◽  
Author(s):  
A. T. Archibald ◽  
M. C. Cooke ◽  
S. R. Utembe ◽  
D. E. Shallcross ◽  
R. G. Derwent ◽  
...  

Abstract. Recently reported model-measurement discrepancies for the concentrations of the HOx radical species (OH and HO2) in locations characterized by high emission rates of isoprene have indicated possible deficiencies in the representation of OH recycling and formation in isoprene mechanisms currently employed in numerical models; particularly at low levels of NOx. Using version 3.1 of the Master Chemical Mechanism (MCM v3.1) as a base mechanism, the sensitivity of the system to a number of detailed mechanistic changes is examined for a wide range of NOx levels, using a simple box model. These studies place emphasis on processes for which experimental or theoretical evidence has been reported in the peer-reviewed literature, in addition to examining the impact of an intrinsic simplification in the MCM v3.1 chemistry. Although all the considered mechanistic changes lead to simulated increases in the concentrations of OH at low NOx levels, the greatest impact is achieved by implementation of a recently postulated mechanism involving isomerisation of the δ-hydroxyalkenyl peroxy radical isomers, formed from the sequential addition of OH and O2 to isoprene. In conjunction with necessary rapid photolysis of the resultant hydroperoxyaldehyde products, this mechanism yields approximately a factor of three increase in the simulated OH concentration at low NOx, and is the only considered mechanism which achieves enhancements which approach those necessary to explain the reported model-measurement discrepancies. Combination of all the considered mechanistic changes has an effect which is approximately additive, yielding an overall enhancement of about a factor of 3.2 in the simulated OH concentration at the lowest NOx input rate considered, with the simulated mean NOx mixing ratios at this input rate being 42 ppt and 29 ppt with the base case and modified mechanisms respectively. A parameterized representation of the mechanistic changes is optimized and implemented into a reduced variant of the Common Representative Intermediates mechanism (CRI v2-R5), for use in the STOCHEM global chemistry-transport model. The impacts of the modified chemistry in the global model are shown to be consistent with those observed in the box model sensitivity studies, and the results are illustrated and discussed with a particular focus on the tropical forested regions of the Amazon and Borneo where unexpectedly elevated concentrations of OH have recently been reported.


2020 ◽  
pp. 50-64
Author(s):  
Kuladeep Kumar Sadevi ◽  
Avlokita Agrawal

With the rise in awareness of energy efficient buildings and adoption of mandatory energy conservation codes across the globe, significant change is being observed in the way the buildings are designed. With the launch of Energy Conservation Building Code (ECBC) in India, climate responsive designs and passive cooling techniques are being explored increasingly in building designs. Of all the building envelope components, roof surface has been identified as the most significant with respect to the heat gain due to the incident solar radiation on buildings, especially in tropical climatic conditions. Since ECBC specifies stringent U-Values for roof assembly, use of insulating materials is becoming popular. Along with insulation, the shading of the roof is also observed to be an important strategy for improving thermal performance of the building, especially in Warm and humid climatic conditions. This study intends to assess the impact of roof shading on building’s energy performance in comparison to that of exposed roof with insulation. A typical office building with specific geometry and schedules has been identified as base case model for this study. This building is simulated using energy modelling software ‘Design Builder’ with base case parameters as prescribed in ECBC. Further, the same building has been simulated parametrically adjusting the amount of roof insulation and roof shading simultaneously. The overall energy consumption and the envelope performance of the top floor are extracted for analysis. The results indicate that the roof shading is an effective passive cooling strategy for both naturally ventilated and air conditioned buildings in Warm and humid climates of India. It is also observed that a fully shaded roof outperforms the insulated roof as per ECBC prescription. Provision of shading over roof reduces the annual energy consumption of building in case of both insulated and uninsulated roofs. However, the impact is higher for uninsulated roofs (U-Value of 3.933 W/m2K), being 4.18% as compared to 0.59% for insulated roofs (U-Value of 0.33 W/m2K).While the general assumption is that roof insulation helps in reducing the energy consumption in tropical buildings, it is observed to be the other way when insulation is provided with roof shading. It is due to restricted heat loss during night.


Author(s):  
Mark Blaxill ◽  
Toby Rogers ◽  
Cynthia Nevison

AbstractThe cost of ASD in the U.S. is estimated using a forecast model that for the first time accounts for the true historical increase in ASD. Model inputs include ASD prevalence, census population projections, six cost categories, ten age brackets, inflation projections, and three future prevalence scenarios. Future ASD costs increase dramatically: total base-case costs of $223 (175–271) billion/year are estimated in 2020; $589 billion/year in 2030, $1.36 trillion/year in 2040, and $5.54 (4.29–6.78) trillion/year by 2060, with substantial potential savings through ASD prevention. Rising prevalence, the shift from child to adult-dominated costs, the transfer of costs from parents onto government, and the soaring total costs raise pressing policy questions and demand an urgent focus on prevention strategies.


2021 ◽  
Vol 13 (13) ◽  
pp. 7251
Author(s):  
Mushk Bughio ◽  
Muhammad Shoaib Khan ◽  
Waqas Ahmed Mahar ◽  
Thorsten Schuetze

Electric appliances for cooling and lighting are responsible for most of the increase in electricity consumption in Karachi, Pakistan. This study aims to investigate the impact of passive energy efficiency measures (PEEMs) on the potential reduction of indoor temperature and cooling energy demand of an architectural campus building (ACB) in Karachi, Pakistan. PEEMs focus on the building envelope’s design and construction, which is a key factor of influence on a building’s cooling energy demand. The existing architectural campus building was modeled using the building information modeling (BIM) software Autodesk Revit. Data related to the electricity consumption for cooling, building masses, occupancy conditions, utility bills, energy use intensity, as well as space types, were collected and analyzed to develop a virtual ACB model. The utility bill data were used to calibrate the DesignBuilder and EnergyPlus base case models of the existing ACB. The cooling energy demand was compared with different alternative building envelope compositions applied as PEEMs in the renovation of the existing exemplary ACB. Finally, cooling energy demand reduction potentials and the related potential electricity demand savings were determined. The quantification of the cooling energy demand facilitates the definition of the building’s electricity consumption benchmarks for cooling with specific technologies.


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