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Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and within its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAH), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C(60,70) carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O(sup +) magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q > 10,000 amu/q anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV, and deeppenetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size > 10 km and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods > several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~ 100 m below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~ 150 m depths) and produce chemically significant dosages over very long timescales ~ 450 Myrs. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~ 2.5 ppb levels near the surface after ~450 Myrs of GCR proton irradiation and potentially to 5 ppb if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗

Examination of the observed synoptic scale cirrus cloud environment: The December 3-6 FIRE cirrus case study

Recently, Sassen provided evidence for supercooled water droplets in cirrus uncinus cell heads at temperatures between 40 and -50 C. Chemistry related to volcanic aerosol of stratospheric origin was evoked as an explanation for this phenomenon. Sassen speculated that injections of sulfuric acid droplets into the upper troposphere were accomplished by tropopause folds associated with subtropical jet streams. He also postulated global climatic perturbations due to the effect of these cirrus microphysical perturbations on radiative fluxes. Using data processing and objective analysis techniques described by Mace and Ackerman, the synoptic scale environment was examined for evidence of tropopause folds that may have served as a source mechanism of stratospheric aerosol in the upper troposphere.

Mace, Gerald G.↗

Exploring dimethyl sulfide (DMS) oxidation and implications for global aerosol radiative forcing

Abstract. Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway and the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and, hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine regions, based on the NASA Atmospheric Tomography (ATom), the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the Variability of the American Monsoon Systems (VAMOS) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden and the burden of sulfate produced from DMS oxidation are relatively insensitive to the assumed isomerization rate, but the burden of HPMTF is very sensitive to a potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg S (+29 %) and 582 Gg S (+8.8 %), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is −0.11 W m−2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (−2.2 W m−2 in standard versus −1.7 W m−2, with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (−2.3 W m−2). This study confirms the sensitivity of aerosol IRF to the PI aerosol loading and the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes.

54 ENVIRONMENTAL SCIENCES↗

Analog Environments for Venus Aerosol Instrument and Mission Concept Testing

The most common hypothesis discussed for life on Venus is a habitat in the dense, persistent clouds, which are primarily sulfuric acid with a secondary water component. Although Earth lacks a complete Venus analog environment, several partial analogs exist which can inform our understanding of the requirements for cloud habitability as well as serving as potential testbeds for future Venus instruments or missions. Earth’s tropospheric clouds have larger particles, more water, and shorter lifetimes than Venus’s; however, they have a partial overlap in pressure and temperature, and are our only example of an airborne habitat.They can inform how particle residence time and microbial generation time constrain habitable atmospheric regions. On the biological side, this includes available nutrients and energy, environmental stressors such as radiation, osmotic potential and acidity, and time spent in protective but inactive forms (endospores, cysts, akinetes); on the physical side, gravity, air density and viscosity, thermal lofting, gravity waves, scavenging due to precipitation, and other airflow dynamics, as well as effective particle radius and electrical charge. They can also enable sampling strategy tests for airborne life detection, ranging from10 2 to10 8 viable cells/mL (10 -3 to 10 -9 cells/particle). Conversely, Earth's stratospheric sulfate layer lacks an active microbial presence, and is at a colder and less dense altitude but has partially analogous values in terms of H2SO4 and water concentration, particle size, and number density. These aerosols are accessible to aircraft and high-altitude balloons. Even more accessible potential analogs include sea spray, which overlaps with the smaller (haze) particle sizes and densities at Venus and contains trace organic constituents; marine fog, which at higher densities can match Venus’s larger (Mode 2) particle properties and contains a range of trace compounds including ammonia, phosphates, sulfates, and nitrates; and spray from acidic hydrothermal systems, which can cover a wide variety of sizes, densities, and chemical compositions. These analogs could improve the development of Venus cloud sampling instruments or sondes, including field tests of material compatibility, particle capture efficiency, and analysis sensitivity.

Analog↗

Molecular understanding of new-particle formation from α-pinene between -50 and +25 °C

Abstract. Highly oxygenated organic molecules (HOMs) contribute substantially to the formation and growth of atmospheric aerosol particles, which affect air quality, human health and Earth's climate. HOMs are formed by rapid, gas-phase autoxidation of volatile organic compounds (VOCs) such as α-pinene, the most abundant monoterpene in the atmosphere. Due to their abundance and low volatility, HOMs can play an important role in new-particle formation (NPF) and the early growth of atmospheric aerosols, even without any further assistance of other low-volatility compounds such as sulfuric acid. Both the autoxidation reaction forming HOMs and their NPF rates are expected to be strongly dependent on temperature. However, experimental data on both effects are limited. Dedicated experiments were performed at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber at CERN to address this question. In this study, we show that a decrease in temperature (from +25 to -50°C) results in a reduced HOM yield and reduced oxidation state of the products, whereas the NPF rates (J1.7 nm) increase substantially. Measurements with two different chemical ionization mass spectrometers (using nitrate and protonated water as reagent ion, respectively) provide the molecular composition of the gaseous oxidation products, and a two-dimensional volatility basis set (2D VBS) model provides their volatility distribution. The HOM yield decreases with temperature from 6.2 % at 25°C to 0.7 % at -50°C. However, there is a strong reduction of the saturation vapor pressure of each oxidation state as the temperature is reduced. Overall, the reduction in volatility with temperature leads to an increase in the nucleation rates by up to 3 orders of magnitude at -50°C compared with 25°C. In addition, the enhancement of the nucleation rates by ions decreases with decreasing temperature, since the neutral molecular clusters have increased stability against evaporation. The resulting data quantify how the interplay between the temperature-dependent oxidation pathways and the associated vapor pressures affect biogenic NPF at the molecular level. Our measurements, therefore, improve our understanding of pure biogenic NPF for a wide range of tropospheric temperatures and precursor concentrations.

54 ENVIRONMENTAL SCIENCES↗

Precipitation chemistry in central Amazonia

Rain samples from three sites in central Amazonia were collected over a period of 6 weeks during the 1987 wet season and analyzed for ionic species and dissolved organic carbon. A continuous record of precipitation chemistry and amount was obtained at two of these sites, which were free from local or regional pollution, for a time period of over 1 month. The volume-weighted mean concentrations of most species were found to be about a factor of 5 lower during the wet season compared with previous results from the dry season. Only sodium, potassium, and chloride showed similar concentrations in both seasons. When the seasonal difference in rainfall amount is taken into consideration, the deposition fluxes are only slightly lower for most species during the wet season than during the dry season, again with the exception of chloride, potassium, and sodium. Sodium and chloride are present in the same ratio as in sea salt; rapid advection of air masses of marine origin to the central Amazon Basin during the wet season may be responsible for the observed higher deposition flux of these species. Statistical analysis suggests that sulfate is, to a large extent, of marine (sea salt and biogenic) origin, but that long-range transport of combustion-derived aerosols also makes a significant contribution to sulfate and nitrate levels in Amazonian rain. Organic acid concentrations in rain were responsible for a large fraction of the observed precipitation acidity; their concentration was strongly influenced by gas/liquid interactions.

Andreae, M. O.↗

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along 5-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode (1) the individual CLAES version 9 ClONO2 and MLS version 5 ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm (exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme. However, the uncertainties in the individual UARS measurements and U.K. Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along five-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode: (1) the individual CLAES ClONO2 and MLS ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm(exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme, However, the uncertainties in the individual UARS measurements and UK Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗

Volcanic CO2 Abundance of Kilauea Plume Retrieved by Meand of AVIRIS Data

Absorbing the electromagnetic radiation in several regions of the solar spectrum, CO2 plays an important role in the Earth radiation budget since it produces the greenhouse effect. Many natural processes in the Earth s system add and remove carbon dioxide. Overall, measurements of atmospheric carbon dioxide at different sites around the world show an increased carbon dioxide concentration in the atmosphere. At Mauna Loa Observatory (Hawaii) the measured carbon dioxide increased from 315 to 365 ppm, in the period 1958 2000 [Keeling et al., 2001]. While at the large scale, the relationship between CO2 increase and global warming is established [IPCC, 1996], at the local scale, many studies are still needed to understand regional and local sources of carbon dioxide, such as volcanoes. The volcanic areas are particularly rich in carbon dioxide; this is due to magma degassing in the summit craters region of active volcanoes, and to the presence of fractures and active faults [Giammanco et al., 1998]. Several studies estimate a global flux of volcanic CO2 (34+/-24)10(exp 6) tons/day from effusive volcanic emissions, such as the tropospheric volcanic plume (Table 1) [McClelland et al., 1989]. Plumes are a turbulent mixture of gases, solid particles and liquid droplets, emitted continuously at high temperature from summit craters, fumarolic fields or during eruptive episodes. Inside the plume, water vapour represents 70 90% of the volcanic gases. The main gaseous components are CO2, SO2, HCl, H2, H2S, HF, CO, N2 and CH4. Other plume components are volcanic ash, aqueous and acid droplets and solid sulphur-derived particles [Sparks et al., 1997]. Volcanic gases and aerosols are evidences of volcanic activity [Spinetti et al., 2003] and they have important climatic and environmental effects [Fiocco et al., 1994]. For example, Etna volcano is one of the world s major volcanic gas sources [Allard et al., 1991]. New studies on volcanic gaseous emissions have pointed out that a variation of the gas ratio CO2/SO2 is related to eruptive episodes [Caltabiano et al., 1994]. However, measurements and monitoring of volcanic carbon dioxide are difficult and often hazardous, due to the high background presence of atmospheric CO2 and the inaccessibility of volcanic sites. Hyperspectral remote sensing is a suitable technique to overcome the difficulties of ground measurement. It permits a rapid, comprehensive view of volcanic plumes and their evolution over time, detection of all gases with absorption molecular lines within the sensor s multispectral range and, in general, measurement of all the volatile components evolving from craters. The molecular and particle plume components scatter and absorb incident solar radiation. The integral of the radiation difference composes the signal measured by the remote spectrometer. The inversion technique consists of retrieving the plume component concentrations, hence decomposing the signal into the different contributions. The accuracy of remote sensing techniques depends primarily on the sensor capability and sensitivity.

Spinetti, C.↗

Experimental Evidence for Weathering and Martian Sulfate Formation Under Extremely Cold Weather-Limited Environments

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars [1, 2]. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions [3]. However, there are several problems with the presence of prolonged surface temperatures on Mars above 273 K during the Noachian including the faint young Sun [4] and the presence of suitable greenhouse gases [5]. The geomorphic evidence for early warm conditions may instead be explained by periodic episodes of warming rather than long term prolonged warm temperatures [6]. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history [6]. This view is more consistent with the climate models, but has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars [7, 8]. This study seeks to test whether sulfate formation may be possible at temperatures well below 0 C in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars.

Niles, Paul B.↗

Effects of El Chichon on stratospheric aerosols late 1982 to early 1984

Stratospheric aerosols collected over the western U.S. from late 1982 to early 1984 show the strong effects of El Chichon's eruption. Although mineral particles disappeared during this period, large acid droplets were still common. Because these have never been seen in prevolcanic, background-level collections, they apparently result from increased droplet growth made possible by the unusual abundance of sulfate. Aerosol size distributions show a wide variety of multimodal curves due to mixing of air masses containing aerosols of various ages or histories. Toward the end of the study time there are fewer large aerosols because of gravitational settling and poleward transport. The result is a steady reduction in sulfate, as most aerosol mass is concentrated in a small number of large droplets. Even the later sulfate levels are, however, five times typical prevolcanic background contents. Thus the influence of El Chichon on high-altitude was still considerable 22 months after eruption.

Snetsinger, K. G.↗

Observed Relationships Between Cloud Droplet Effective Radius and Biogenic Gas Concentrations in Summertime Marine Stratocumulus Over the Eastern North Atlantic

Abstract Biogenic gases are a prominent component of the summertime marine boundary layer (MBL) over the Eastern North Atlantic. One of these gases, dimethyl sulfide (DMS), can produce sulfate cloud condensation nuclei (CCN) that, in theory, can brighten clouds through photolysis, and produces a reaction product, methane sulfonic acid (MSA). It is also possible that DMS can interact with sea‐salt or other marine aerosols changing their CCN activation spectrum, which could also modify cloud microphysical structure. Data collected aboard the G1 aircraft during the Aerosol Cloud Experiment Eastern North Atlantic (ACE‐ENA) in well‐mixed and decoupled marine boundary layers (MBLs) were used to examine relationships between the cloud droplet effective radii, , and the concentrations of DMS and MSA in constant cloud liquid water content (LWC) bins. A weak but statistically significant negative correlation was observed between CCN concentration and in most LWC bins, regardless of the source of the CCN, while a weak but statistically significant positive correlation between and DMS was observed. No correlation between the cloud droplet number concentration and DMS was found. The presence of MSA indicated that DMS‐to‐sulfate photolysis was likely occurring, but data sparsity prevented a statistically significant conclusion regarding the relationship between MSA and . Data sparsity in decoupled conditions also prevented statistically significant conclusions. To properly address biogenic gas impacts on cloud microphysics, it is recommended that aircraft data be supplemented by long‐term biogenic gas measurements at the surface in marine locations with appropriate remote and in‐situ cloud sensing capabilities, and the analysis limited to well‐mixed MBL's.

54 ENVIRONMENTAL SCIENCES↗

Composition and Plume Gas Interaction Control Iron Fractional Solubility More Than Particle Size in Volcanic Ash: Implications for Fertilization of the North Atlantic

Deposition of volcanic ash is thought to impact marine biogeochemical cycling by adding soluble iron (Fe) to the surface ocean. The magnitude of this input is a function of the amount of ash deposited, the total Fe content in the ash, and ash‐derived Fe's fractional solubility. However, the relative importance of chemical composition, acidic processing by the volcanic plume, and ash particle size in determining solubility is unclear. We paired an aerosol leach meant to provide an upper limit for fractional Fe solubility with chemical analyses of ash from the Cumbre Vieja (CV) and La Soufrière eruptions, which both impacted the North Atlantic in 2021. Fe in the ash samples is <6% soluble, but Fe fractional solubility in CV ash is approximately triple that of La Soufrière ash. Compared to La Soufrière, a larger proportion of the Fe in CV ash is in silicate rather than oxide minerals, which release more soluble Fe. Elevated levels of surficial fluorine (F) also suggest that CV ash was subjected to a more fluorine‐rich eruption plume and underwent more acidic processing. Particle size does not appear to be a primary control on Fe release. We estimate that the CV eruption had a much larger impact on dissolved Fe (DFe) concentration in the surface ocean than the La Soufrière eruption because of differences in soluble Fe content and particle deposition velocity. These differences may help explain why some eruptions elicit a biological response in the ocean while others do not.

Elliott, Hope E. [Univ. of Miami, FL (United State↗

Lidar determination of the composition of atmosphere aerosols

Theoretical and experimental studies of the feasibility of using DIfferential SCatter (DISC) lidar to measure the composition of atmospheric aerosols are described. This technique involves multiwavelength measurements of the backscatter cross section of aerosols in the middle infrared, where a number of materials display strong restrahlen features that significantly modulate the backscatter spectrum. The theoretical work indicates that a number of materials of interest, including sulfuric acid, ammonium sulfate, and silicates, can be discriminated among with a CO2 lidar. An initial evaluation of this procedure was performed in which cirrus clouds and lower altitude tropospheric aerosols were developed. The observed ratio spectrum of the two types of aerosol displays structure that is in crude accord with theoretical expectations.

Wright, M. L.↗

The Photochemistry of Amino Acids Produced on the Polar Cryovolcanic Regions of Titan

The cryovolcanic regions of Titan offer transient opportunities for prebiotic molecules to exist in water–ammonia solutions on the surface of the Saturnian moon. The upcoming NASA’s Dragonfly mission will search for high nitrogen concentrations and amino acids on Titan’s equatorial terrains. Cryovolcanic features, however, are most common on the polar regions. To mitigate the distance, bubble bursting may encapsulate the prebiotic molecules into aerosols, which Titan’s Hadley circulation would subsequently transport to the equator. Here we investigate whether alanine and glycine survive this meridional journey. Despite the unconstrained meridional wind velocities, our results suggest that the amino acids can survive the transport through the mesosphere. Dragonfly may find cryo-volcanogenic amino acids on Titan’s equator. Further, the interaction between the two amino acids increased 10-fold the photodegradation rate of glycine. We justify it based on changes in the environment polarity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneous reactions with NaCl in the El Chichon volcanic aerosols

Previous investigations of the effects of the 1982 eruption of the El Chichon volcano could not explain all the observations of changes in O3, HCl, NO and NO2 simultaneously without proposing unproven chemical reactions. Since reactions between solid NaCl and gaseous ClNO3 and N2O5 rapidly produce photochemically active chlorine species and solid NaNO3 in laboratory experiments, it is suggested that these reactions could have occurred with the NaCl observed to be present in the El Chichon sulfuric acid areosols. As a consequence, it is predicted that HCl should increase substantially, while NO(x) should decrease, in agreement with the measurements after the eruption. Ozone should be only slightly affected by these reactions. Reactions between solid NaCl and the acids H2SO4 and HNO3 might prove to be important, but sufficient evidence regarding their efficiency and the pressure of HNO3 in the aerosols is lacking.

Michelangeli, Diane V.↗

CANOZE measurements of the Arctic ozone hole

In CANOZE 1 (Canadian Ozone Experiment), a series of 20 ozone profile measurements were made in April, 1986 from Alert at 82.5 N. CANOZE is the Canadian program for study of the Arctic winter ozone layer. In CANOZE 2, ozone profile measurements were made at Saskatoon, Edmonton, Churchill and Resolute during February and March, 1987 with ECC ozonesondes. Ground based measurements of column ozone, nitrogen dioxide and hydrochloric acid were conducted at Saskatoon. Two STRATOPROBE balloon flights were conducted on February 26 and March 19, 1987. Two aerosol flights were conducted by the University of Wyoming. The overall results of this study will be reported and compared with the NOZE findings. The results from CANOZE 3 in 1988, are also discussed. In 1988, as part of CANOZE 3, STRATOPROBE balloon flights were conducted from Saskatchewan on January 27 and February 13. A new lightweight infrared instrument was developed and test flown. A science flight was successfully conducted from Alert (82.5 N) on March 9, 1988 when the vortex was close to Alert; a good measurement of the profile of nitric acid was obtained. Overall, the Arctic spring ozone layer exhibits many of the features of the Antarctic ozone phenomenon, although there is obviously not a hole present every year. The Arctic ozone field in March, 1986 demonstrated many similarities to the Antarctic ozone hole. The TOMS imagery showed a crater structure in the ozone field similar to the Antarctic crater in October. Depleted layers of ozone were found in the profiles around 15 km, very similar to those reported from McMurdo. Enhanced levels of nitric acid were measured in air which had earlier been in the vortex. The TOMS imagery for March 1987 did not show an ozone crater, but will be examined for an ozone crater in February and March, 1988, the target date for the CANOZE 3 project.

Evans, W. F. J.↗

Linking Internal Dosimetries of the Propyl Metabolic Series in Rats and Humans Using Physiologically Based Pharmacokinetic (PBPK) Modeling

The metabolic series approach has successfully linked internal dosimetries of metabolically related compounds reducing cost and time for chemical risk assessments. Here, we developed a physiologically based pharmacokinetic (PBPK) model in rats and humans for the propyl metabolic series including propyl acetate, 1-propanol, propionaldehyde, and propionic acid. Manufacturers use these compounds as organic solvents and intermediates during chemical synthesis. Public exposures can occur through using consumer products containing propyl compounds like cosmetics, aerosol sprays, or foods. To develop the PBPK model, we measured in vitro metabolism of propyl acetate in blood and liver S9 fractions. We measured concentrations of propyl compounds in blood following intravenous (iv) infusion of 13C-propanol or 13C-propionic acid and closed chamber inhalation exposures to propyl acetate or propanol in rats. Using these studies and other published data, we modified an existing PBPK model for the butyl metabolic series to simulate time course concentrations of propyl compounds in rats and humans. Consistent with measured in vitro and in vivo data, the optimized propyl series model predicts rapid clearance of propyl acetate, higher concentrations of propanol in blood from propyl acetate inhalation compared to propanol inhalation, and low concentrations of propionic acid in blood from exposures to propyl acetate or propanol. Regulators can use this model as a tool for propyl compound risk assessment by linking internal dosimetries under various exposure scenarios.

Smith, Jordan N.↗