Ambient Gas Phase Research Articles

Well-posedness of an evaporation model for a spherical droplet exposed to an air flow

In this paper, we address the well-posedness of an evaporation model for a spherical liquid droplet taking into account the convective impact of an air flow in the ambient gas phase. From a mathematical perspective, we are dealing with a coupled ODE–PDE system for the droplet radius, the temperature distribution, and the vapor concentration. The nonlinear coupling arises from the evaporation rate modeled by the Hertz–Knudsen equation. Under physically meaningful assumptions, we prove existence and uniqueness of a weak solution until the droplet has evaporated completely. Numerical simulations are performed to illustrate how different air flows affect the evaporation process.

An improved multiphase chemistry mechanism for methylamines: significant dimethylamine cloud production

Monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA) are important compounds for atmospheric key processes, e.g., new particle formation (NPF). A description of their multiphase chemical processing within atmospheric models is incomplete, but mandatory to describe their atmospheric budgets. In this study, a detailed multiphase chemistry mechanism was developed and first process model investigations were performed. The simulations focused on pristine marine conditions, where open research questions exist regarding ambient gas-phase concentrations of methylamines, particularly with regards to unexpectedly high DMA levels. The simulations reveal that TMA oxidation in cloud droplets results into DMA formation with a yield of around 87%, a missing DMA production pathway in current models. Also, it is demonstrated that about 21% and 69% of the respective DMA and TMA gas-phase oxidation proceed via autoxidation yielding HOOCH2NHCHO and HOOCH2N(CHO)CH2OOH, respectively. The discussed processes should be included into atmospheric models for advanced predictions of NPF and climate impacts.

<i>In Situ</i> Monitoring of the Ambient Gas Phase during PVT Growth of Nominally Undoped High Resistivity SiC Boules

The aim of this study is to show the applicability of continuous residual gas analysis for growth monitoring of undoped SiC with physical vapor transport (PVT). For this purpose, two crystals were grown, one without doping and one with continuous nitrogen doping. During the processes continuous residual gas analysis were conducted and evaluated with emphasis on the temporal variations of the nitrogen content. The charge carrier concentration of the final crystals was determined by optical methods (spectrally resolved absorption measurement with UV-VIS and Raman spectroscopy) and the results were compared with the residual gas analysis during growth. A correlation was found between the measured nitrogen-related signal and the charge carrier concentration in the samples.

Combining a population balance approach with detailed chemistry to model the condensation of oxide smoke during aluminum combustion in spatially homogeneous reactors

At high temperatures, aluminum particles can be burned exothermally in oxidizing atmospheres in a similar way to carbon-based particulate fuels. The main reaction product, aluminum oxide (Al2O3, alumina), is solid under ambient conditions and may form through two distinct chemical pathways. On the one hand, vapourized aluminum burns in the gas phase, leading to the condensation of aluminum oxide into very fine smoke droplets that are thought to be nano-sized. On the other hand, heterogeneous reactions at the particle surface cause a direct conversion of aluminum into aluminum oxide and result in the transformation into a bi-phasic aluminum/alumina particle. As aluminum powder is being investigated as a potential carbon-free, recyclable energy carrier, we face unanswered questions about the droplet sizes within the oxide smoke and the techniques required for extraction from flue gases. This article constitutes a first step towards a detailed modelling framework for predicting alumina smoke size distributions.Physically, the oxide droplet size distribution is influenced by the ambient gas phase composition and shaped by the mutual competition of nucleation, condensational surface growth, evaporation, dissociation and coagulation. The heat release and dispersion temperature, on the other hand, are affected by chemical reactions, the gas-to-liquid phase change and radiation. In this article, we present a complete set of droplet formation and interaction kinetics for alumina droplets and analyze the interaction, competition and mutual reinforcement of the relevant physical processes in a perfectly stirred reactor and a partially stirred reactor. These simplified model formulations are representative of the dynamics that characterize the changes in gas phase composition and droplet size distribution in a single grid cell during the reaction and droplet formation fractional steps of a spatially inhomogeneous laminar reactive flow solver or a one-point, one-time probability density function (PDF) description. The partially stirred reactor model is extended to account for the presence of a reactive surface with small-scale variability in terms of surface composition. Detailed chemical and heterogeneous surface kinetics, also including NOx formation, are taken into account. Finally, we point out open challenges and incomplete kinetic or constitutive information.

Activity-induced migration of viscous droplets on a solid substrate

Active matter exploits motion to induce changes in shape and conformation via external input. In this paper, we establish theoretically that viscous liquid droplets containing magnetic nanoparticles with frozen-in magnetic moments, sitting on a solid substrate and surrounded by an ambient gas phase, can deform and migrate under the influence of a magnetic torque. The effect arises because the collective rotation of the magnetic nanoparticles at the liquid–gas interface tilts the droplet away from a symmetric configuration, breaks the reflection symmetry with respect to the centre axis, and leads to a left–right asymmetry of the contact angles. A sufficiently strong magnetic torque leads the contact angles to overcome hysteresis effects leading the droplet to migrate. We develop a general framework to explain how symmetry-breaking affects droplet migration. Thus previous results of droplet spreading and migration can be recovered as special cases. Such droplets can be employed as agents in active surfaces and can move against gravity, chemical and thermal gradients, providing a mechanism that could be utilized by both industry and medicine.

Analysis of gaseous polycyclic aromatic hydrocarbon emissions from cooking devices in selected rural and urban kitchens in Bomet and Narok counties of Kenya.

Traditional combustion devices and fuels such as charcoal, wood and biomass, are widely utilised in rural and urban households in Africa. Incomplete combustion can generate air pollutants which are of human toxicological importance, including polycyclic aromatic hydrocarbons (PAHs). In this study, portable multi-channel polydimethylsiloxane rubber traps were used to sample gas phase emissions from cooking devices used in urban and rural households in Bomet and Narok counties of Kenya. A wide range of total PAH concentrations was found in samples collected (0.82 - 173.69 µg/m3), which could be attributed to the differences in fuel type, combustion device, climate, and nature of households. Wood combustion using the 3-stone device had the highest average total PAH concentration of ~71 µg/m3. Narok had higher indoor total gas phase PAH concentrations averaging 35.88 µg/m3 in urban and 70.84 µg/m3 in rural households, compared to Bomet county (2.91 µg/m3 in urban and 9.09 µg/m3 in rural households). Ambient total gas phase PAH concentrations were more similar (Narok: 1.26 - 6.28 µg/m3 and Bomet: 2.44 - 6.30 µg/m3). Although the 3-stone device and burning of wood accounted for higher PAH emissions, the charcoal burning jiko stove produced the highest toxic equivalence quotient. Monitoring of PAHs emitted by these cooking devices and fuels is critical to public health and sustainable pollution mitigation.

Experimental and Numerical Analysis on Two-Phase Induced Low-Speed Pre-Ignition

The root cause of the initial low-speed pre-ignition (LSPI) is not yet clarified. The literature data suggest that a two-phase phenomenon is most likely triggering the unpredictable premature ignitions in highly boosted spark-ignition engines. However, there are different hypotheses regarding the actual initiator, whether it is a detached liquid oil-fuel droplet or a solid-like particle from deposits. Therefore, the present work investigates the possibility of oil droplet-induced pre-ignitions using a modern downsized engine with minimally invasive endoscopic optical accessibility incorporating in-cylinder lubrication oil detection via light-induced fluorescence. This setup enables the differentiation between liquid and solid particles. Furthermore, the potential of hot solid particles to initiate an ignition under engine-relevant conditions is analyzed numerically. To do so, the particle is generalized as a hot surface transferring heat to the reactive ambient gas phase. The gas-phase reactivity is represented as a TRF/air mixture based on RON/MON specifications of the investigated fuel. The chemical processes are predicted using a semi-detailed reaction mechanism, including 137 species and 633 reactions in a 2D CFD simulation framework. In the optical experiments, no evidence of a liquid oil droplet-induced pre-ignition could be found. Nevertheless, all observed pre-ignitions had a history of flying light-emitting objects. There are strong hints towards solid-like deposit LSPI initiation. The application of the numerical methodology to mean in-cylinder conditions of an LSPI prone engine operation point reveals that particles below 1000 K are not able to initiate a pre-ignition. A sensitivity analysis of the thermodynamic boundary conditions showed that the particle temperature is the most decisive parameter on the calculated ignition delay time.

Selective N2/H2O adsorption onto 2D amphiphilic amorphous photocatalysts for ambient gas-phase nitrogen fixation

The gas-phase Haber–Bosch process has been the main industrial source of ammonia over the last century. However, its reliance on high temperature and high pressure for enormous energy input emits greenhouse gas to air and is associated with the depletion of fossil fuels. The need of the hour is to replace this method with environmentally sustainable processes, among which, photocatalytic nitrogen reduction has attracted much attention. In this work, we report a low cost, scalable manufacturing of gas-phase photoreactors for nitrogen reduction under ambient conditions based on 2D amorphous molybdenum oxysulfides, i.e. MoS2+x-MoO3-y composites. They show excellent nitrogen reduction efficiencies of ∼141 μmol/g/h with remarkably stable performance. The amphiphilic MoS2+x and MoO3-y composites selectively chemisorb and activate N2 and H2O molecules, respectively, and enable multiple photodriven redox reactions towards NH3 evolution. Such photoreactors for ambient ammonia synthesis provides a potentially feasible route towards next-generation gas-phase industrial ammonia production.

Thermocapillary instabilities in a liquid layer subjected to an oblique temperature gradient: Effect of a prescribed normal temperature gradient at the substrate

We consider thermocapillary instability in a three-dimensional liquid layer with a deformable interface with an ambient gas phase and subjected to an oblique temperature gradient when the temperature gradient at the substrate is prescribed. We demonstrate that this configuration leads to a drastic change in the instability features with respect to those emerging when either a purely vertical temperature gradient (VTG) or a purely horizontal temperature gradient (HTG) is present. In the case of the return flow as the base state, the spanwise long-wave instability mode dominates except for the range of small Bond numbers Bo. Slippage at the substrate has a stabilizing (destabilizing) effect on streamwise (spanwise) long-wave modes in the presence of a HTG. In the case of linear flow as the base state, both streamwise and spanwise long-wave modes play a major role in the instability onset depending on the ratio between the HTG and the VTG η for higher values of the capillary number Ca, e.g., Ca > 0.001. However, for lower values of Ca, e.g., Ca < 0.001, streamwise and spanwise instability modes become finite-waves at large η. In contrast to the return flow, for the linear flow, slippage at the substrate destabilizes both long-wave modes.

Influence of vessel characteristics and atmospheric processes on the gas and particle phase of ship emission plumes: in situ measurements in the Mediterranean Sea and around the Arabian Peninsula

Abstract. A total of 252 emission plumes of ships operating in the Mediterranean Sea and around the Arabian Peninsula were investigated using a comprehensive dataset of gas- and submicron-particle-phase properties measured during the 2-month shipborne AQABA (Air Quality and Climate Change in the Arabian Basin) field campaign in summer 2017. The post-measurement identification of the corresponding ship emission events in the measured data included the determination of the plume sources (up to 38 km away) as well as the plume ages (up to 115 min) and was based on commercially available historical records of the Automatic Identification System. The dispersion lifetime of chemically inert CO2 in the ship emission plumes was determined as 70±15 min, resulting in levels indistinguishable from the marine background after 260±60 min. Emission factors (EFs) as quantities that are independent of plume dilution were calculated and used for the investigation of influences on ship emission plumes caused by ship characteristics and the combustion process as well as by atmospheric processes during the early stage of exhaust release and during plume ageing. Combustion efficiency and therefore emission factors of black carbon and NOx were identified to depend mostly on the vessel speed and gross tonnage. Moreover, larger ships, associated with higher engine power, were found to use fuel with higher sulfur content and have higher gas-phase SO2, particulate sulfate, particulate organics, and particulate matter EFs. Despite the independence of EFs of dilution, a significant influence of the ambient wind speed on the particle number and mass EFs was observed that can be traced back to enhanced particle coagulation in the case of slower dilution and suppressed vapour condensation on particles in the case of faster dilution of the emission plume. Atmospheric reactions and processes in ship emission plumes were investigated that include NOx and O3 chemistry, gas-to-particle conversion of NOx and SO2, and the neutralisation of acids in the particle phase through the uptake of ambient gas-phase ammonia, the latter two of which cause the inorganic particulate content to increase and the organic fraction to decrease with increasing plume age. The results allow for us to describe the influences on (or processes in) ship emission plumes quantitatively by parameterisations, which could be used for further refinement of atmospheric models, and to identify which of these processes are the most important ones.

Real-time quantification of the total HO2 reactivity of ambient air and HO2 uptake kinetics onto ambient aerosols in Kyoto (Japan)

HO2 radicals play important roles in tropospheric chemistry. The large discrepancies among field measurements and sophisticated model predictions for the overall HO2 concentrations can be attributed to the HO2 uptake coefficients onto ambient aerosols (γ) have not yet been properly quantified. This study presents the first online measurement of the total HO2 reactivity caused by the ambient gas phase (kg') and aerosol phase (ka') in the summer of 2018 in Kyoto, Japan, using a combined laser-flash photolysis and laser-induced fluorescence (LFP–LIF) technique coupled with a versatile aerosol concentration enrichment system (VACES) that enriches ambient aerosols. The results denote that kg' ranged from 0.1 s−1 (25th percentile) to 0.32 s−1 (75th percentile) with an average value of 0.22 ± 0.16 s−1 (1σ), which can be primarily explained by the reaction of HO2 with NO2. With the application of VACES and the auto-switching aerosol filter, ka' ranged from 0.004 s−1 (25th percentile) to 0.028 s−1 (75th percentile) with an average value of 0.017 ± 0.015 s−1. When converted ka' to ambient conditions (by dividing with the enrichment factor), this result was ~10 times higher than the HO2 reactivity caused by its self-reaction under ambient concentration levels (~5 ppt) at 298 K. The related γ ranged from 0.08 (25th percentile) to 0.36 (75th percentile), with an average value of 0.24, which is comparable with the values used in previous modeling studies (~0.2); however, it presents a large variation of ±0.20 (1σ) within the measurement time. This indicates that a large bias may exist with respect to the estimation of HO2 concentrations when using a constant γ value. Further, we suggest that different γ values should be applied in modeling studies depending on the environment conditions; the γ value obtained here can be used as an upper limit value for urban areas in the summer due to possible aerosol phase changes. The analysis of ambient air backward trajectories indicates that the predominant NO2 emission sources originated from the mainland of Japan. However, no significant differences regarding HO2 uptake coefficients were observed when air masses came through the mainland or from the coastal direction. This study provides considerably reliable γ, which could increase the modeling accuracy of heterogeneous processes in tropospheric chemistry. However, combining online and offline methods appears to be more suitable for addressing the variation in γ and model discrepancies in further studies.

Healing of thermocapillary film rupture by viscous heating

Thin liquid films sitting on a heated solid substrate and surrounded by a colder ambient gas phase are strongly affected by surface-shear stresses induced by surface tension and temperature gradients, as well as by viscous and capillary forces. The temperature dependence of surface tension may lead to thinning of liquid-film depressions promoting instability which takes place when a critical temperature difference $\unicode[STIX]{x0394}\unicode[STIX]{x1D717}_{cr}$ between the substrate and the ambient gas phase is exceeded. In this article we show theoretically that viscous heating, previously neglected in related literature, may delay or suppress the thermocapillary instability and leads to film healing. The viscous heating effect, by inhibiting heat transfer, prevents the system from reaching the critical value $\unicode[STIX]{x0394}\unicode[STIX]{x1D717}_{cr}$ required to bring about instability. As a consequence, the system remains within the stability region, suppressing film rupture. The presence of the viscous heating effect leads to a persistent circulating motion of two counter-rotating vortices lying diametrically opposite to a depression of the liquid–gas interface reducing the wavelength of disturbances to one half of its initial value. This effect has yet to be observed in experiment.

Chemical Composition of Gas-Phase Positive Ions during Laboratory Simulations of Titan’s Haze Formation

The organic haze in the atmosphere of Saturn’s moon Titan affects the moon’s atmospheric and surface properties. Ions are known to play an important role in haze formation chemistry; however, the role of ions in laboratory simulations of haze formation is poorly characterized. Here, we use a high-resolution time-of-flight mass spectrometer with an atmospheric pressure interface to chemically characterize the ambient gas-phase cations formed as haze is produced by the far ultraviolet photolysis of CH4 in N2. These experiments show that the chemical composition of the cations is complex. High molecular weight ions up to m/z 400 are observed, with organic nitrogen ions, including ions with multiple nitrogen atoms, accounting for the majority of the identified ion peaks. Many of the ions identified in this work have been observed in Titan’s upper atmosphere by the Cassini Ion and Neutral Mass Spectrometer. While the chemistry in this study is likely more representative of Titan’s lower atmosphere than of its ...

Evidence for the Importance of Semivolatile Organic Ammonium Salts in Ambient Particulate Matter.

The gas/particle phase partitioning behavior of NH3/NH4+ and other semivolatile constituents was measured by a custom-designed Denuder-MOUDI-Denuder integrated sampling system in Toronto, Canada. In this setup, upstream denuders were used to capture alkaline and acidic gaseous components, and particle phase components were captured by the filters on MOUDI stages. Downstream denuders captured any alkaline and acidic gases that exited the MOUDI apparatus, likely representing semivolatile constituents. In the ambient gas phase HCOOH was the most abundant acidic gas, with an average mixing ratio ∼2-3 times higher than that of SO2 and HNO3. It was found that the majority (49-96%) of filter-collected NH4+ volatilized during collection. NO3- volatilization could only explain 0.9-15% of NH4+ loss from the filters. Instead, a strong correlation and nearly 1:1 molar ratio between downstream HCOO- and NH4+ indicated that most of the semivolatile NH4+ was originally balanced by organic acids in the ambient particle phase. The thermodynamic properties of HCOOH/HCOO- suggest that it should not have been present at high levels in the ambient particle phase, and we interpret its detection in the downstream denuder as evidence for larger organic acids that reacted to generate HCOOH prior to our offline measurement.

Seasonal soil/snow-air exchange of semivolatile organic pollutants at a coastal arctic site (Tromsø, 69°N)

Soils are a major reservoir of semivolatile organic pollutants such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), and exert a control on their atmospheric occurrence. We present here an assessment of the atmospheric occurrence and seasonality of soil/snow-air partitioning and exchange of PCBs, PAHs, hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCHs) in the arctic city Tromsø, northern Norway. The fugacities of the organic pollutants in soils and snow were determined using a soil fugacity sampler by equilibrating the air concentrations with those in the surface soil/snow. The concentrations in soils did not show a significant seasonality. Conversely, the ambient air concentrations and the soil (or snow) fugacity showed a clear seasonality for PCBs, HCH, HCB and some PAHs, related to temperature. Fugacities in soil/snow were correlated with those in the ambient gas phase, suggesting a close seasonal air-soil/snow coupling. Generally, there was a net deposition or close to equilibrium conditions during the winter, which contrasts with the net volatilization observed during the warmer periods. The chemicals with lower octanol-air partition coefficients showed a larger tendency for being volatilized and thus remobilized from this coastal arctic environment. Conversely, the more hydrophobic compounds were close to air-soil/snow equilibrium or showed a net deposition.

Ambient temperature gas phase sulfonation: A mild route towards acid functionalized ordered mesoporous organosilica

Sulfonation is a versatile method for the production of acidic materials, e. g. for applications in catalysis. In this study different sulfonation techniques for the production of acidic ordered mesoporous materials are investigated. SBA-15-like mesoporous organosilanes bearing aromatic moieties are sulfonated in the liquid phase with oleum as well as in the gas phase under significantly milder conditions with sulfur trioxide. Functionalization via liquid phase sulfonation at elevated temperatures proceeds at the expense of partial or complete collapse of the pore system. In contrast, gas phase sulfonation with sulfur trioxide at ambient temperature allows for similar sulfonation yields, while maintaining the textural properties due to the milder reaction conditions. Overall, acid functionalization of mesoporous organosilica using a gas phase sulfonation route is reported for the first time, enabling both high acid capacities and preservation of the pore structure.

Catalytic conversion of Kraft lignin to bio-multilayer graphene materials under different atmospheres

Kraft lignin was catalytic graphitized by iron at 1000 °C in argon, hydrogen, CO2, methane, and natural gas atmospheres, respectively. The effect of atmospheric agent types on product distribution (gas, liquid, and solid carbon yields) was analyzed. The solid products were characterized by scanning electron microscopy, Raman, high-resolution transmission electron microscopy, and X-ray diffraction. Experimental results have shown that the degree of graphitization of Kraft lignin depends not only on the highest temperature, but also the type of ambient gas phase during heat treatment. Methane and natural gas in the ambient gas phase seem to accelerate the formation of multilayer graphene materials with a range of 2–30 layers, and hydrogen and carbon dioxide have an etching effect on solid carbon species during the catalytic graphitization process, while multilayer graphene-encapsulated iron nanoparticles were the main products in the case of argon.

Characterization of Gas-Phase Organics Using Proton Transfer Reaction Time-of-Flight Mass Spectrometry: Residential Coal Combustion.

Residential coal combustion is a significant contributor to particulate urban air pollution in Chinese mega cities and some regions in Europe. While the particulate emission factors and the chemical characteristics of the organic and inorganic aerosol from coal combustion have been extensively studied, the chemical composition and nonmethane organic gas (NMOG) emission factors from residential coal combustion are mostly unknown. We conducted 23 individual burns in a traditional Chinese stove used for heating and cooking using five different coals with Chinese origins, characterizing the NMOG emissions using a proton transfer reaction time-of-flight mass spectrometer. The measured emission factors range from 1.5 to 14.1 g/kgcoal for bituminous coals and are below 0.1 g/kgcoal for anthracite coals. The emission factors from the bituminous coals are mostly influenced by the time until the coal is fully ignited. The emissions from the bituminous coals are dominated by aromatic and oxygenated aromatic compounds with a significant contribution of hydrocarbons. The results of this study can help to improve urban air pollution modeling in China and Eastern Europe and can be used to constrain a coal burning factor in ambient gas phase positive matrix factorization studies.

Magnetic torque-induced suppression of van-der-Waals-driven thin liquid film rupture

An ultra-thin film of a carrier liquid containing nanosize ferromagnetic particles sitting on a solid substrate and surrounded by an ambient gas phase can be acted upon, apart from viscous and capillary forces, by attractive van der Waals forces which may promote instability leading to film rupture and substrate dewetting. In this article we show that the collective rotation of the particles on the liquid–gas interface, due to a magnetic torque, competes against the instability induced by the van der Waals forces that tend to deepen depressions of the liquid. The competition between the two effects (forcing and instability) leads to the generation of a permanent nonlinear interfacial viscous–capillary wave. Thus, film rupture and substrate dewetting are both averted. This is a general effect that may also be employed to suppress other types of instabilities such as the Rayleigh–Taylor and thermocapillary instabilities. This effect has yet to be observed in experiment.

Designing global climate and atmospheric chemistry simulations for 1 and 10 km diameter asteroid impacts using the properties of ejecta from the K-Pg impact

Abstract. About 66 million years ago, an asteroid about 10 km in diameter struck the Yucatan Peninsula creating the Chicxulub crater. The crater has been dated and found to be coincident with the Cretaceous–Paleogene (K-Pg) mass extinction event, one of six great mass extinctions in the last 600 million years. This event precipitated one of the largest episodes of rapid climate change in Earth's history, yet no modern three-dimensional climate calculations have simulated the event. Similarly, while there is an ongoing effort to detect asteroids that might hit Earth and to develop methods to stop them, there have been no modern calculations of the sizes of asteroids whose impacts on land would cause devastating effects on Earth. Here, we provide the information needed to initialize such calculations for the K-Pg impactor and for a 1 km diameter impactor. There is considerable controversy about the details of the events that followed the Chicxulub impact. We proceed through the data record in the order of confidence that a climatically important material was present in the atmosphere. The climatic importance is roughly proportional to the optical depth of the material. Spherules with diameters of several hundred microns are found globally in an abundance that would have produced an atmospheric layer with an optical depth around 20, yet their large sizes would only allow them to stay airborne for a few days. They were likely important for triggering global wildfires. Soot, probably from global or near-global wildfires, is found globally in an abundance that would have produced an optical depth near 100, which would effectively prevent sunlight from reaching the surface. Nanometer-sized iron particles are also present globally. Theory suggests these particles might be remnants of the vaporized asteroid and target that initially remained as vapor rather than condensing on the hundred-micron spherules when they entered the atmosphere. If present in the greatest abundance allowed by theory, their optical depth would have exceeded 1000. Clastics may be present globally, but only the quartz fraction can be quantified since shock features can identify it. However, it is very difficult to determine the total abundance of clastics. We reconcile previous widely disparate estimates and suggest the clastics may have had an optical depth near 100. Sulfur is predicted to originate about equally from the impactor and from the Yucatan surface materials. By mass, sulfur is less than 10 % of the observed mass of the spheres and estimated mass of nanoparticles. Since the sulfur probably reacted on the surfaces of the soot, nanoparticles, clastics, and spheres, it is likely a minor component of the climate forcing; however, detailed studies of the conversion of sulfur gases to particles are needed to determine if sulfuric acid aerosols dominated in late stages of the evolution of the atmospheric debris. Numerous gases, including CO2, SO2 (or SO3), H2O, CO2, Cl, Br, and I, were likely injected into the upper atmosphere by the impact or the immediate effects of the impact such as fires across the planet. Their abundance might have increased relative to current ambient values by a significant fraction for CO2, and by factors of 100 to 1000 for the other gases. For the 1 km impactor, nanoparticles might have had an optical depth of 1.5 if the impact occurred on land. If the impactor struck a densely forested region, soot from the forest fires might have had an optical depth of 0.1. Only S and I would be expected to be perturbed significantly relative to ambient gas-phase values. One kilometer asteroids impacting the ocean may inject seawater into the stratosphere as well as halogens that are dissolved in the seawater. For each of the materials mentioned, we provide initial abundances and injection altitudes. For particles, we suggest initial size distributions and optical constants. We also suggest new observations that could be made to narrow the uncertainties about the particles and gases generated by large impacts.