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Two articles discuss the recent experimental work of Hong et al. on the production of amino acids and gas-phase organic compounds from the ultraviolet irradiation of simple gases, with hot hydrogen atoms used as the principal energy conversion agent. The reaction possibilities involving frozen ices are mentioned in both articles, as well as the significance of three-body collisions in this situation.
The use of infrared spectra to determine molecular abundances of icy astronomical objects and to study their chemistry requires laboratory measurements of reference spectra and related quantities, such as the index of refraction (n) and density (p) of candidate ices. Here we present new n and p measurements on ices involving over 30 C-, H-, and O-containing compounds, both acyclic and cyclic, representing seven chemical families. We examine the results in a way that is rare in the astrochemical literature, namely one in which data from an ice formed from molecules of a particular chemical family are compared to measurements on another member of the same family, such as of a homologous series or a pair of isomers. Apart from the intrinsic usefulness of the n and data, a structure-based comparison can help establish trends and identify possibly spurious results. As liquid-phase data sometimes are used in low-temperature astrochemical work in the absence of solid-phase measurements, we compare our new ice results to those for the corresponding room-temperature liquids. We emphasize the use of our n and p data to compute the molar refraction (RM) for each of our ices, and how the resulting RM values compare to those expected from molecular structures. The use of calculated RM values and measured n values to calculate ice densities, in the absence of direct measurements, is also addressed.
The return and analysis of pristine material that is relict of a putative period of chemical evolution is a fumdamental goal of the exobiological exploration of Mars. In order to accomplish this objective, it is desirable to find oxidant-free regions where pristine material can be accessed at the shallowest possible depth (ideally directly from the surface). The objective of our ongoing research is to understand the spatial and temporal distribution of oxidants in the martian regolith and the redox chemistry of the soil; in effect to understand the chemical mechanisms and kinetics relating to the in-situ destruction of organics and the formation of the reactive species responsible for the Viking biology results. In this work, we report on experimental studies of oxidizing processes that may contribute to carbonate and organic degradation on Mars. Organic molecules directly exposed to solar UV may decomposed either directly into CO2, or into more volatile organic fragments. Organic macromolecules not directly exposed to high UV flux are most likely to be affected by atmospheric oxidants which can diffuse to their surfaces. The oxidizing processes examined include: gas-phase oxidants, UV photolysis, and UV-assisted heterogeneous catalysis. For example, assuming a meteroritic infall rate of 4 x 10(exp -4) g/m^2yr (Flynn and McKay 1990) and a flux of organic carbon of 2 x 10(exp -5) g/m^2yr, laboratory measurements of the UV-assisted decomposition of benzenehexacarboxylic acid (mellitic acid, a likely intermediate of kerogen oxidation), indicate its decomposition rate on Mars would exceed the total flux of organic carbon to the planet by over four orders of magnitude. Our measurements indicate that although the decomposition temperature of kerogens in some cases exceeds the temperature limit of the Viking GCMS, it is unlikely kerogens or their decomposition intermediates were present at the Viking landings sites at levels above the GCMS detection limits.
Beagle 2 is a 60 kg probe (with a 30 kg lander) developed in the United Kingdom for inclusion on the European Space Agency's 2003 Mars Express. Beagle 2 will deliver to the Martian surface a payload which consists of a high percentage of science instruments to landed spacecraft mass. Beagle 2 will be launched in June, 2003 with Mars Express on a Soyuz-Fregat rocket from the Baikonur Cosmodrome in Kazakhstan. Beagle 2 will land on Mars on December 26, 2003 in the Isidis Planitia basin (approximately 10 degrees N and 275 degrees W), a large sedimentary basin that overlies the boundary between ancient highlands and northern plains. Isidis Planitia, the third largest basin on Mars, which is possibly filled with sediment deposited at the bottom of long-standing lakes or seas, offers an ideal environment for preserving traces of life. Beagle 2 was developed to search for organic material and other volatiles on and below the surface of Mars in addition to the study of the inorganic chemistry and mineralogy. Beagle 2 will utilize a mechanical mole and grinder to obtain samples from below the surface, under rocks and inside rocks. A pair of stereo cameras will image the landing site along with a microscope for examination of surface and rock samples. Analyses will include both rock and soil samples at various wavelengths, X-ray spectrometer and Mossbauer spectrometer as well as a search for organics and other light element species (e.g. carbonates and water) and measurement of their isotopic compositions. Beagle 2 has as its focus the goal of establishing whether evidence for life existed in the past on Mars at the Isidis Planitia site or at least establishing if the conditions were ever suitable. Carbonates and organic components were first recognized as existing on Mars when they were found in the Martian meteorite Nakhla. Romanek et al showed the carbonates in ALH84001 were formed at low temperatures. McKay et al noted possible evidence of early life on Mars within the ALH84001 meteorite. Thomas-Keprta et al showed the magnetite biomarkers in ALH84001's carbonates are indistinguishable from those formed by magnetotactic bacteria found on Earth. Gibson et al showed there was significant evidence for liquid water and biogenic products present on Mars across a 3.9 billion year period. A mechanical arm (PAW) operates from the lander and is used for science operations along with sample acquisition. Instruments attached to the PAW include: stereo cameras, Mossbauer instrument, X-ray fluorescence instrument, microscope, environmental sensors, rock corer/grinder, a spoon, mirror, brushes, a mole attachment for acquisition of subsurface to depths of 1 to 2 meters and an illumination device. Each camera has 14 filters which have been optimized for mineralogy composition, dust and water vapor detection. The microscope's camera is designed for viewing the size and shape of dust particles, rock surfaces, microfossils, and characteristics of the samples prior to introduction into the gas analysis package (GAP). The camera has a resolution of 4 microns/pixel, features four color capability (red, green, blue and UV (ultraviolet) fluoresence), a depth of focus of 40 micrometers and translation stage of +3 millimeters. The heart of the Beagle 2's life detection package is the gas analysis package (GAP), which consists of a mass spectrometer with collectors at fixed masses for precise isotopic ratio measurements and voltage scanning for spectral analysis. Primary aim of the GAP is to search for the presence of bulk constituents, individual species, and isotopic fractionations for both extinct and extent life along with studying the low-temperature geochemistry of the hydrogen, carbon, nitrogen and oxygen components on Mars from both the surface and atmosphere. GAP is a magnetic sector mass spectrometer with the range of 1 to 140 amu which can be operated in both the static and dynamic modes. A triple Faraday collector array will be used for C, N and O ratios along with a double Faraday array for H/D. Pulse counting electron multiplier will be utilized for noble gases and selected organics. Anticipated detection limits are at the picomole level for operation in the static mode of operation and high precision isotopic measurements will be made in the dynamic mode. Sample processing and preparation system consists of reaction vessels along with references. Sample ovens capable of being heated are attached to the manifold for sample combustion. Surface, subsurface materials and interior rock specimens will be combusted in pure oxygen gas at various temperature intervals to release organic matter and volatiles. Combustion process will permit detection of all forms and all atoms of carbon present in the samples. A chemical processing system is capable of a variety of conversion reactions. Gases are manipulated either by cryogenic or chemical reactions and passed through the gas handling portion of the vacuum system. There are two modes of operation: quantitative analysis and precise isotopic measurements. Additional information is contained in the original extended abstract.
The Nakhla meteorite possesses discrete, well defined, structurally coherent morphologies of carbonaceous phases present within iddingsite alteration zones. Based upon both isotopic measurements and analysis of organic phases the presence of pre-terrestrial organics is now recognized. Within the microcrystalline layers of Nakhla s iddingsite, discrete clusters of salt crystals are present. These salts are predominantly halite (NaCl) with minor MgCl2 crystals. Some CaSO4, likely gypsum, appears to be partially intergrown with some of the halite. EDX mapping shows discrete C-rich features are interspersed among these crystals. A hollow semi-spherical bowl structure (~ 3 m ) has been identified and analyzed after using a focused ion beam (FIB) to cut a transverse TEM thin section of the feature and the underlying iddingsite. TEM/EDX analysis reveals that the feature is primarily carbonaceous containing C with lesser amounts of Si, S, Ca, Cl, F, Na, and minor Mn and Fe; additionally a small peak consistent with N, which has been previously seen in Nakhla carbonaceous matter, is also present. Selected area electron diffraction (SAED) shows that this C-rich material is amorphous (lacking any long-range crystallographic order) and is not graphite or carbonate. Micro-Raman spectra acquired from the same surface from which the FIB section was extracted demonstrate a typical kerogen-like D and G band structure with a weak absorption peak at 1350 and a stronger peak at 1600/cm. The C-rich feature is intimately associated with both the surrounding halite and underlying iddingsite matrix. Both iddingsite and salts are interpreted as having formed as evaporate assemblages from progressive evaporation of water bodies on Mars. This assemblage, sans the carbonaceous moieties, closely resembles iddingsite alteration features previously described which were interpreted as indigenous Martian assemblages. These distinctive macromolecular carbonaceous structures in Nakhla may represent one of the sources of the high molecular weight organic material previously identified in Nakhla. While we do not speculate on the origin of these unique carbonaceous structures, we note that the significance of such observations is that it may allow us to construct a C-cycle for Mars based on the C chemistry of the Martian meteorites with obvious implications for astrobiology and the prebiotic evolution of Mars. In any case, our observations strongly suggest that organic C exists as micrometersize, discrete structures on Mars.
Eight landed missions demonstrated that martian soils (defined as loose, unconsolidated surface material) consist of basaltic mineralogy, iron (hydr)oxides, amorphous material, sulfate, chloride, (per)chlorate, nitrate, carbonate, and possible organic C. The Viking Lander 1 and 2 (1976), Mars Pathfinder (1997), and Mars Exploration Rover (MER-A,B) (2004) missions determined that martian soil was similar at all landing sites by having mafic chemistry, high S (~ 7 wt.% SO3) and Cl (0.7 wt.%), and spectral detections of poorly crystalline and crystalline Fe-(hydr)oxide phases. The MER Mössbauer spectrometers detected Fe-bearing olivine and pyroxene along with magnetite, nano-phase Fe-oxides (npOx), hematite, and ferric sulfate. The 2008 Phoenix Lander instrumentation measured a soil pH of 7.7 and detected ~0.6 wt.% perchlorate, 3-5 wt.% Ca-rich carbonate and carbon (500 gC/g) consistent with oxidized organics and Fe-rich carbonate. The 2012 Mars Science Laboratory (MSL) rover (Gale Crater) through X-ray diffraction detected plagioclase feldspar, pyroxene, magnetite, hematite, anhydrite, and quartz, with the balance being composed of Si/Fe-containing amorphous (30 to 40 wt.%) material. MSL evolved gas analysis detected (per)chlorate (0.4 wt.% ClO4), nitrate (0.23 wt.%), along with minor Fe/Mg sulfate and oxidized organic C (~2000 gC/g). Limited pedogenesis may have occurred at the 2018 InSight landing site and in one Gusev Crater soil (MER-B) which have 3 to 10 cm-thick duricrust horizons consistent with atmospheric water vapor interactions with soil salts. Martian soil primary mineralogy was derived mostly from local rock (volcanic, sedimentary) that is largely basaltic planet wide. Secondary minerals [e.g., sulfate, chloride, perchlorate, nitrate, carbonate, Fe-(hydr)oxides] in martian soils formed from oxidative aqueous alteration processes and were likely derived from a combination of local sedimentary rock sources and the global bright dust. The Mars 2020 mission will collect soil for Earth return to enable a thorough assessment of the nature and origin of martian soil.
A mechanism is proposed for the formation of complex organic nitrogen compounds in the dense lower atmosphere of Titan. The mechanism is based on three-body association reactions with HCNH(+) ions formed by the reaction of N(+) with CH4, which lead to the production of ethyl cyanide, vinyl cyanide and cyanoacetylene. Calculations for a model atmosphere consistent with the preliminary interpretation of Voyager 1 data for the region of maximum cosmic ray activated chemistry, corresponding to a temperature between 150 and 160 K and a pressure of 20 mbar, are presented which show substantial organic nitrile and hydrogen cyanide production rates. Based on these production rates, it is expected that significant equilibrium concentrations of these compounds will be found on Titan.
Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.
Anharmonic vibrational frequencies and intensities are calculated for OH(H2O)n and H(H2O)n radicals (that form on icy particles of the interstellar medium), HCO radical (the main intermediate in the synthesis of organic molecules in space), NH2(-) and C2H(-) anions, H5(+) cation, and other systems relevant to interstellar chemistry. In addition to pure ions and radicals, their complexes with water are studied to assess the effects of water environment on infrared spectra. The calculations are performed using the correlation-corrected vibrational self-consistent field (CC-VSCF) method with ab initio potential surfaces at the MP2 and CCSD(T) levels. Fundamental, overtone, and combination excitations are computed. The results are in good agreement with available experimental data and provide reliable predictions for vibrational excitations not yet measured in laboratory experiments. The data should be useful for interpretation of astronomically observed spectra and identification of ions and radicals present in the interstellar medium and in planetary atmospheres.
This paper reports XPS analysis of jet exhaust particulate from a B737, Lear, ERJ, and A300 aircraft during the APEX III NASA led field campaign. Carbon hybridization and bonding chemistry are identified by high-resolution scans about the C1s core-shell region. Significant organic content as gauged by the sp3/sp2 ratio is found across engines and platforms. Polar oxygen functional groups include carboxylic, carbonyl and phenol with combined content of 20 percent or more. By lower resolution survey scans various elements including transition metals are identified along with lighter elements such as S, N, and O in the form of oxides. Burning additives within lubricants are probable sources of Na, Ba, Ca, Zn, P and possibly Sn. Elements present and their percentages varied significantly across all engines, not revealing any trend or identifiable cause for the differences, though the origin is likely the same for the same element when observed. This finding suggests that their presence can be used as a tracer for identifying soots from aircraft engines as well as diagnostic for monitoring engine performance and wear.
An electride may provide surface enhanced Raman scattering (SERS). The electride, a compound where the electrons serve as anions, may be a ceramic electride, such as a conductive ceramic derived from mayenite, or an organic electride, for example. The textured electride surface or electride particles may strongly enhance the Raman scattering of organic or other Raman active analytes. This may also provide a sensitive method for monitoring the chemistry and electronic environment at the electride surface. The results are evidence of a new class of polariton (i.e., a surface electride-polariton resonance mechanism) that is analogous to the surface plasmon-polariton resonance that mediates conventional SERS.
The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.
Ellipsometric measurement of ion adsorption on mercury, and reversibility of organic reactions /chemistry of fuel cell reactions/
The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer of interstellar components has been deuterium (D) excesses. In some cases these enrichments are seen in bulk meteoritic materials, but D enrichments have also been observed in meteoritic subfractions and even within specific classes of molecular species, such as amino and carboxylic acids. These anomalies are not thought to be the result of nucleosynthetic processes, but are instead ascribed to chemical and physical processes occurring in the interstellar medium (ISM). The traditional explanation of these D excesses has been to invoke the presence of materials made in the ISM by low temperature gas phase ion-molecule reactions. Indeed, the DM ratios seen in the simple interstellar gas phase molecules in cold dense clouds amenable to measurement using radio spectral techniques are generally considerably higher than the values seen in enriched Solar System materials. However, the true linkage between the DM ratios in interstellar and meteoritic materials is obscured by several effects. First, current observations of D enrichment in the ISM have been made of only a few simple molecules, molecules that are not the main carriers of D in Solar System materials. Second, some of the interstellar D enrichment is likely to reside on labile moieties that will have exchanged to some degree with more isotopically normal material during incorporation into the warm protosolar nebula, parent body processing, delivery, recovery, and analysis. Third, ion-molecule reactions represent only one of at least four processes that can produce strong D-H fractionation in the ISM.
Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.
Carbonaceous chondrites exhibit a wide range of aqueous and thermal alteration characteristics, while some are known to demonstrate mineralogical and petrologic evidence of having been thermally metamorphosed after aqueous alteration. This group of meteorites are commonly referred as thermally met-amorphosed carbonaceous chondrites (TMCCs), and their reflectance spectra show resemblances to that of C-type asteroids which typically have low albedos. This suggests that the surfaces of the C-type asteroids are also composed of both hydrous and dehydrated minerals, and thus TMCCs are among the best samples that can be studied in laboratory to reveal the true nature of the C-type asteroids. Although TMCCs are usually meteorites that were previously categorized as CI and CM chondrites, they are not strictly CI/CM because they exhibit isotopic and petrographic characteristics that significantly deviate from typical CI/CM. More appropriately, they are called CI-like and/or CM-like chondrites. Typical examples of TMCCs include the C2-ung/CM2TIV Belgica (B)-7904 and Yamato (Y) 86720. Thermal alteration is virtually complete in these meteorites and thus they are considered typical end-members of TMCCs exhibiting complete dehydration of matrix phyllosilicates. The estimated heating conditions are 10 to 103 days at 700 C to 1 to 100 hours at 890 C, i.e. short-term heating induced by impact and/or solar radiation. While the petrology and chemistry of TMCCs have only recently been extensively characterized, we have just begun to study in detail their organic contents. In order to understand how short-term heating affects the maturity of insoluble organic matter (IOM) in hydrous chondrites, we investigated experimentally-heated Tagish Lake meteorite using Raman spectroscopy, as the chemical and bulk oxygen isotopic compositions of the matrix of the carbonate (CO3)-poor lithology of the Tagish Lake (hereafter Tag) meteorite bears similarities to the TMCCs.
A major observational challenge in cometary science is to quantify the extent to which chemical compounds can be linked to either interstellar or nebular chemistry. Recently, there have been complimentary observations from multiple facilities to try to unravel the chemical complexity of comets and their origins. Incorporating results from various techniques can gain further insight into the abundances, production rates, distributions, and formation mechanisms of molecules in these objects [I]. Such studies have provided great detail towards molecules with a-typical chemistries, such as H2CO [2]. We report multiwavelength spectral observations of comets from two dynamical families including the JFC 103P/Hartley 2 and a long period comet C/2009 PI (Garradd) with the Arizona Radio Observatory's SMT and 12-m telescopes, as well as the NRAO Greenbank telescope, and the James Clerk Maxwell Telescope. Multiple parent volatiles (e.g. HCN, CH30H, CO) as well as daughter products (e.g, CS and 01-1) have been detected in these objects. We will present a comparison of molecular abundances in these comets to those observed in others, supporting a long-term effort of building a comet taxonomy based on composition. Previous work has revealed a range of abundances of parent species (from "organics-poor" to "organics-rich") with respect to water among comets [3,4,5], however the statistics are not well constrained.
We present here a first global modeling study on the influence of gas-phase chemistry/aerosol interactions on estimates of anthropogenic forcing by tropospheric O3 and aerosols. Concentrations of gas-phase species and sulfate, nitrate, ammonium, black carbon, primary organic carbon, secondary organic carbon, sea salt, and mineral dust aerosols in the preindustrial, present-day, and year 2100 (IPCC SRES A2) atmospheres are simulated online in the Goddard Institute for Space Studies general circulation model II' (GISS GCM II'). With fully coupled chemistry and aerosols, the preindustrial, presentday, and year 2100 global burdens of tropospheric ozone are predicted to be 190, 319, and 519 Tg, respectively. The burdens of sulfate, nitrate, black carbon, and organic carbon are predicted respectively to be 0.32. 0.18, 0.01, 0.33 Tg in preindustrial time, 1.40, 0.48, 0.23, 1.60 Tg in presentday, and 1.37, 1.97, 0.54, 3.31 Tg in year 2100. Anthropogenic O3 is predicted to have a globally and annually averaged present-day forcing of +0.22 W m(sup -2) and year 2100 forcing of +0.57 W m(sup -2) at the top of the atmosphere (TOA). Net anthropogenic TOA forcing by internally mixed sulfate, nitrate, organic carbon, and black carbon aerosols is estimated to be virtually zero in the present-day and +0.34 W m(sup -2) in year 2100, whereas it is predicted to be -0.39 W m(sup -2) in present-day and -0.61 W m(sup -2) in year 2100 if the aerosols are externally mixed. Heterogeneous reactions are shown to be important in affecting anthropogenic forcing. When reactions of N2O5, NO3, NO2, and HO2 on aerosols are accounted for, TOA anthropogenic O3 forcing is less by 20-45% in present-day and by 20-32% in year 2100 at mid to high latitudes in the Northern Hemisphere, as compared with values predicted in the absence of heterogeneous gas aerosol reactions. Mineral dust uptake of HNO3 and O3 is shown to have practically no influence on anthropogenic O3 forcing. Heterogeneous reactions of N2Os, NO3, NO2, and HO2 are predicted to have noticeable impacts on anthropogenic aerosol forcing over industrialized areas, leading to 0-2 W m(sup -2) more anthropogenic aerosol cooling in present-day and 2-8 W m(sup -2) more cooling in year 2100 in these areas as compared with forcings calculated in the absence of heterogeneous reactions. Sea salt uptake of SO2 reduces the magnitude of TOA aerosol cooling by 0.5-1 W m(sup -2) over the oceans around 60 N in the present-day and year 2100 scenarios. Near dust sources, mineral dust uptake of SO2 and HNO3 leads to less anthropogenic aerosol cooling by 0.5-1 W m(sup -2) in the present day and 1-2 W m(sup -2) in year 2100.