Global Troposphere Experiment Project

For the Global Troposphere Experiment project Pacific Exploratory Measurements West B (PEM West B), we made determinations of sulfur dioxide (SO2) and dimethyl sulfide (DMS) using gas chromatography-mass spectrometry with isotopically labelled internal standards. This technique provides measurements with precision of 1 part-per-trillion by volume below 20 pptv and 1% above 20 pptv. Measurement of DMS and SO2 were performed with a time cycle of 5-6 minutes with intermittent zero checks. The detection limits were about 1 pptv for SO2 and 2 pptv for DMS. Over 700 measurements of each compound were made in flight. Volcanic impacts on the upper troposphere were again found as a result of deep convection in the tropics. Extensive emission of SO2 from the Pacific Rim land masses were primarily observed in the lower well-mixed part of the boundary layer but also in the upper part of the boundary layer. Analyses of the SO2 data with aerosol sulfate, beryllium-7, and lead-210 indicated that SO2, contributed to half or more of the observed total oxidized sulfur (SO2 plus aerosol sulfate) in free tropospheric air. Cloud processing and rain appeared to be responsible for lower SO2 levels between 3 and 8.5 km than above or below this region. During both phases of PEM-West, dimethyl sulfide did not appear to be a major source of sulfur dioxide in the upper free troposphere over the western Pacific Ocean. In 1991 the sources Of SO2 at high altitude appeared to be both anthropogenic and volcanic with an estimated 1% being solely from DMS. The primary difference for the increase in the DMS source was the very low concentration of SO2 at high altitude. In the midlatitude region near the Asian land masses, DMS in the mixed layer was lower than in the tropical region of the western Pacific. Convective cloud systems near volcanoes in the tropical convergence in the western Pacific troposphere were a major source of SO2 at high altitudes during PEM-West B. High levels of SO2 were observed in several instances with large number concentrations of ultrafine CN above 9 km in the tropical convergence zone. Conversion of SO2, by OH to SO3 and subsequently to sulfuric acid may have been enhanced by lightning-produced NO levels exceeding 1 part per billion. Coupling of strong convection and volcanic sources of SO2 apparently is an important source of new particle formation at high altitude in the tropical convergence zone

Application of Attenuated Total Reflection Spectroscopy to Fused Inorganic Salts

Physical Chemistr

Transport of sulfur dioxide from the Asian Pacific Rim to the North Pacific troposphere

The NASA Pacific Exploratory Mission over the Western Pacific Ocean (PEM-West B) field experiment provided an opportunity to study sulfur dioxide (SO2) in the troposphere over the western Pacific Ocean from the tropics to 60°N during February–March 1993. The large suite of chemical and physical measurements yielded a complex matrix in which to understand the distribution of sulfur dioxide over the western Pacific region. In contrast to the late summer period of Pacific Exploratory Mission-West A (PEM-West A) (1991) over this same area, SO2showed little increase with altitude, and concentrations were much lower in the free troposphere than during the PEM-West B period. Volcanic impacts on the upper troposphere were again found as a result of deep convection in the tropics. Extensive emission of SO2 from the Pacific Rim land masses were primarily observed in the lower well-mixed part of the boundary layer but also in the upper part of the boundary layer. Analyses of the SO2 data with aerosol sulfate, beryllium-7, and lead-210 indicated that SO2 contributed to half or more of the observed total oxidized sulfur (SO2 plus aerosol sulfate) in free tropospheric air. The combined data set suggests that SO2 above 8.5 km is transported from the surface but with aerosol sulfate being removed more effectively than SO2. Cloud processing and rain appeared to be responsible for lower SO2 levels between 3 and 8.5 km than above or below this region

Research on atmospheric volcanic emissions: An overview

The project Research on Atmospheric Volcanic Emissions is a unique effort by NASA and university scientists to investigate the detailed chemical nature of plumes from volcanic eruptions. The major goals of the project are to: 1) understand the impact major eruptions will have on atmospheric chemistry processes, 2) understand the importance of volcanic emissions in the atmospheric geochemical cycles of selected species, 3) use knowledge of the plume chemical composition to diagnose and predict magmatic processes. Project RAVE\u27S first mission used the NASA Lockheed Orion P-3 outfitted with equipment to measure concentrations of the gases SO2, OCS, H2S, CS2, NO, O3and trace elements in particles in Mt. St. Helens\u27 plume on September 22, 1980. Measurements of SO2 column densities in the plume permitted calculations of SO2 fluxes. This article is an overview of the first experimental design factors and performance of the initial RAVE experiment

Pacific Atmospheric Sulfur Experiment (PASE): dynamics and chemistry of the south Pacific tropical trade wind regime

The Pacific Atmospheric Sulfur Experiment (PASE) was a comprehensive airborne study of the chemistry and dynamics of the tropical trade wind regime (TWR) east of the island of Kiritibati (Christmas Island, 157º, 20′ W, 2º 52′ N). Christmas Island is located due south of Hawaii. Geographically it is in the northern hemisphere yet it is 6–12º south of the intertropical convergence zone (ITCZ) which places it in the southern hemisphere meteorologically. Christmas Island trade winds in August and September are from east south east at 3–15 ms−1. Clouds, if present, are fair weather cumulus located in the middle layer of the TWR which is frequently labeled the buffer layer (BuL). PASE provided clear support for the idea that small particles (80 nm) were subsiding into the tropical trade wind regime (TWR) where sulfur chemistry transformed them to larger particles. Sulfur chemistry promoted the growth of some of these particles until they were large enough to activate to cloud drops. This process, promoted by sulfur chemistry, can produce a cooling effect due to the increase in cloud droplet density and changes in cloud droplet size. These increases in particle size observed in PASE promote additional cooling due to direct scattering from the aerosol. These potential impacts on the radiation balance in the TWR are enhanced by the high solar irradiance and ocean albedo of the TWR. Finally because of the large area involved there is a large factional impact on earth’s radiation budget. The TWR region near Christmas Island appears to be similar to the TWR that persists in August and September, from southwest of the Galapagos to at least Christmas Island. Transport in the TWR between the Galapagos and Christmas involves very little precipitation which could have removed the aerosol thus explaining at least in part the high concentrations of CCN (≈300 at 0.5% supersaturation) observed in PASE. As expected the chemistry of sulfur in the trade winds was found to be initiated by the emission of DMS into the convective boundary layer (BL, the lowest of three layers). However, the efficiency with which this DMS is converted to SO2 has been brought into further question by this study. This unusual result has come about as result of our using two totally different approaches for addressing this long standing question. In the first approach, based on accepted kinetic rate constants and detailed steps for the oxidation of DMS reflecting detailed laboratory studies, a DMS to SO2 conversion efficiency of 60–73% was determined. This range of values lies well within the uncertainties of previous studies. However, using a completely different approach, involving a budget analysis, a conversion value of 100% was estimated. The latter value, to be consistent with all other sulfur studies, requires the existence of a completely independent sulfur source which would emit into the atmosphere at a source strength approximately half that measured for DMS under tropical Pacific conditions. At this time, however, there is no credible scientific observation that identifies what this source might be. Thus, the current study has opened for future scientific investigation the major question: is there yet another major tropical marine source of sulfur? Of equal importance, then, is the related question, is our global sulfur budget significantly in error due to the existence of an unknown marine source of sulfur? Pivotal to both questions may be gaining greater insight about the intermediate DMS oxidation species, DMSO, for which rather unusual measurements have been reported in previous marine sulfur studies. The 3 pptv bromine deficit observed in PASE must be lost over the lifetime of the aerosol which is a few days. This observation suggests that the primary BrO production rate is very small. However, considering the uncertainties in these observations and the possible importance of secondary production of bromine radicals through aerosol surface reactions, to completely rule out the importance of bromine chemistry under tropical conditions at this time cannot be justified. This point has been brought into focus from prior work that even at levels of 1 pptv, the effect of BrO oxidation on DMS can still be quite significant. Thus, as in the case of DMS conversion to SO2, future studies will be needed. In the latter case there will need to be a specific focus on halogen chemistry. Such studies clearly must involve specific measurements of radical species such as BrO

Ozone and aerosol distributions and air mass characteristics over the South Pacific during the burning season

In situ and laser remote measurements of gases and aerosols were made with airborne instrumentation to establish a baseline chemical signature of the atmosphere above the South Pacific Ocean during the NASA Global Tropospheric Experiment (GTE)/Pacific Exploratory Mission‐Tropics A (PEM‐Tropics A) conducted in August‐October 1996. This paper discusses general characteristics of the air masses encountered during this experiment using an airborne lidar system for measurements of the large‐scale variations in ozone (O3) and aerosol distributions across the troposphere, calculated potential vorticity (PV) from the European Centre for Medium‐Range Weather Forecasting (ECMWF), and in situ measurements for comprehensive air mass composition. Between 8°S and 52°S, biomass burning plumes containing elevated levels of O3, over 100 ppbv, were frequently encountered by the aircraft at altitudes ranging from 2 to 9 km. Air with elevated O3 was also observed remotely up to the tropopause, and these air masses were observed to have no enhanced aerosol loading. Frequently, these air masses had some enhanced PV associated with them, but not enough to explain the observed O3 levels. A relationship between PV and O3 was developed from cases of clearly defined O3 from stratospheric origin, and this relationship was used to estimate the stratospheric contribution to the air masses containing elevated O3 in the troposphere. The frequency of observation of the different air mass types and their average chemical composition is discussed in this paper

THE VIBRATIONAL SPECTRA OF MOLTEN SALTS BY ATR INFRARED SPECTROSCOPY∗SPECTROSCOPY^{\ast}

$^{\ast}$ Aided by National Science Foundation. $^{1}$ J. K. Wilmshurst and S. Senderoff, J. Chem. Phys., 35, 1078 (1961).Author Institution: Department of Chemistry, Oklahoma State UniversityThe infrared spectra of lithium and silver nitrate in the $7 \mu$ region has been re-examined by using Fahrenfort's ATR technique with a silicon reflecting prism. An angle of incidence considerably greater than the critical, so that the absorption coefficient largely determines the spectrum, has been used. The resulting effective pathlength is in the range required for successful study of the structure of the very intense band produced by the asymmetric stretching modes of the nitrate group. The structure of this band is indicative of the nature of the environment of the nitrate ion. The observed band structure and its interpretation will be compared with that reported by $Wilmshurst.^{1}