F. S. Rowland

Potential impact of iodine on tropospheric levels of ozone and other critical oxidants

A new analysis of tropospheric iodine chemistry suggests that under certain conditions this chemistry could have a significant impact on the rate of destruction of tropospheric ozone. In addition, it suggests that modest shifts could result in the critical radical ratio HO2/OH. This analysis is based on the first ever observations of CH3I in the middle and upper free troposphere as recorded during the NASA Pacific Exploratory Mission in the western Pacific. Improved evaluations of several critical gas kinetic and photochemical rate coefficients have also been used. Three iodine source scenarios were explored in arriving at the above conclusions. These include: (1) the assumption that the release of CH3I from the marine environment was the only iodine source with boundary layer levels reflecting a low-productivity source region, (2) same as scenario 1 but with an additional marine iodine source in the form of higher molecular weight iodocarbons, and (3) source scenario 2 but with the release of all iodocarbons occurring in a region of high biological productivity. Based on one-dimensional model simulations, these three source scenarios resulted in estimated Ix (Ix = I + IO + HI + HOI + 2I2O2 + INOx) yields for the upper troposphere of 0.5, 1.5, and 7 parts per trillion by volume (pptv), respectively. Of these, only at the 1.5 and 7 pptv level were meaningful enhancements in O3 destruction estimated. Total column O3 destruction for these cases averaged 6 and 30%, respectively. At present we believe the 1.5 pptv Ix source scenario to be more typical of the tropical marine environment; however, for specific regions of the Pacific (i.e., marine upwelling regions) and for specific seasons of the year, much higher levels might be experienced. Even so, significant uncertainties still remain in the proposed iodine chemistry. In particular, much uncertainty remains in the magnitude of the marine iodine source. In addition, several rate coefficients for gas phase processes need further investigating, as does the efficiency for removal of iodine due to aerosol scavenging processes.

Reactive nitrogen and ozone over the western Pacific: Distribution, partitioning, and sources

Measurements of important reactive nitrogen species (NO, NO2, HNO3, PAN, PPN, NO3−, NOy), C1 to C6 hydrocarbons, O3, chemical tracers (C2Cl4, CO), and meteorological parameters were made in the troposphere (0 to 12 km) over the western Pacific (0°–50°N) during the Pacific Exploratory Mission-West A campaign (September–October 1991). Under clean conditions, mixing ratios of NO, NO2, NOy, and O3 increased with altitude and showed a distinct latitudinal gradient. PAN showed a midtropospheric maximum, while nitric acid mixing ratios were generally highest near the surface. Measured NOy concentrations were significantly greater than the sum of individually measured nitrogen species (mainly NOx, PAN, and HNO3), suggesting that a large fraction of reactive nitrogen present in the atmosphere is made up of hitherto unknown species. This shortfall was larger in the tropics (≈65%) compared to midlatitudes (≈40%) and was minimal in air masses with high HNO3 mixing ratios (>100 ppt). A global three-dimensional photochemical model has been used to compare observations with predictions and to assess the significance of major sources. It is possible that the tropical lightning source is much greater than commonly assumed, and both lightning source and its distribution remain a major area of uncertainty in the budgets of NOy and NOx. A large disagreement between measurement and theory exists in the atmospheric distribution of HNO3. It appears that surface-based anthropogenic emissions provide nearly 65% of the global atmospheric NOy reservoir. Relatively constant NOx/NOy ratios imply that NOy and NOx are in chemical equilibrium and the NOy reservoir may be an important in situ source of atmospheric NOx. Data are interpreted to suggest that only about 20% of the upper tropospheric (7–12 km) NOx is directly attributable to its surface NOx source, and free tropospheric sources are dominant. In situ release of NOx from the NOy reservoir, lightning, direct transport of surface NOx, aircraft emissions, and small stratospheric input collectively maintain the NOx balance in the atmosphere. It is shown that atmospheric ratios of reactive nitrogen and sulfur species, along with trajectory analysis, can be used to pinpoint the source of Asian continental outflow. Compared to rural atmospheres over North America, air masses over the Pacific are highly efficient in net O3 production. Sources of tropospheric NOx cannot yet be accurately defined due to shortcomings in measurements and theory.

Three-dimensional distribution of nonmenthane hydrocarbons and halocarbons over the northwestern Pacific during the 1991 Pacific Exploratory Mission (PEM-West A)

A total of 1667 whole air samples were collected onboard the NASA DC-8 aircraft during the 6-week Pacific Exploratory Mission over the western Pacific (PEM-West A) in September and October 1991. The samples were assayed for 15 C2-C7 hydrocarbons and six halocarbons. Latitudinal (0.5°S to 59.5°N) and longitudinal (114°E to 122°W) profiles were obtained from samples collected between ground level and 12.7 km. Thirteen of the 18 missions exhibited at least one vertical profile where the hydrocarbon mixing ratios increased with altitude. Longitude-latitude color patch plots at three altitude levels and three-dimensional color latitude-altitude and longitude-altitude contour plots exhibit a significant number of middle-upper tropospheric pollution events. These and several lower tropospheric pollution plumes were characterized by comparison with urban data from Tokyo and Hong Kong, as well as with natural gas and the products from incomplete combustion. Elevated levels of nonmethane hydrocarbons (NMHC) and other trace gases in the upper-middle free troposphere were attributed to deep convection over the Asian continent and to typhoon-driven convection near the western Pacific coast of Asia. In addition, NMHCs and CH3CCl3 were found to be useful tracers with which to distinguish hydrocarbon and halocarbon augmented plumes emitted from coastal Asian cities into the northwestern Pacific.

Effects of biomass burning on summertime nonmethane hydrocarbon concentrations in the Canadian wetlands

Approximately 900 whole air samples were collected and assayed for selected C2-C10 hydrocarbons and seven halocarbons during the 5-week Arctic Boundary Layer Expedition (ABLE) 3B conducted in eastern Canadian wetland areas. In more than half of the 46 vertical profiles flown, enhanced nonmethane hydrocarbon (NMHC) concentrations attributable to plumes from Canadian forest fires were observed. Urban plumes, also enhanced in many NMHCs, were separately identified by their high correlation with elevated levels of perchloroethene. Emission factors relative to ethane were determined for 21 hydrocarbons released from Canadian biomass burning. Using these data for ethane, ethyne, propane, n-butane, and carbon monoxide enhancements from the literature, global emissions of these four NMHCs were estimated. Because of its very short atmospheric lifetime and its below detection limit background mixing ratio, 1,3-butadiene is an excellent indicator of recent combustion. No statistically significant emissions of nitrous oxide, isoprene, or CFC 12 were observed in the biomass-burning plumes encountered during ABLE 3B. The presence of the short-lived biogenically emitted isoprene at altitudes as high as 3000 m implies that mixing within the planetary boundary layer (PBL) was rapid. Although background levels of the longer-lived NMHCs in this Canadian region increase during the fire season, isoprene still dominated local hydroxyl radical photochemistry within the PBL except in the immediate vicinity of active fires. The average biomass-burning emission ratios for hydrocarbons from an active fire sampled within minutes of combustion were, relative to ethane, ethene, 2.45; ethyne 0.57; propane, 0.25; propene, 0.73; propyne, 0.06; n-butane, 0.09; i;-butane, 0.01; 1-butene, 0.14; cis-2-butene, 0.02; trans-2-butene, 0.03; i-butylene, 0.07; 1,3-butadiene, 0.12; n-pentane, 0.05; i-pentane, 0.03; 1-pentene, 0.06; n-hexane, 0.05; 1-hexene, 0.07; benzene, 0.37; toluene, 0.16.

Exhaled methyl nitrate as a noninvasive marker of hyperglycemia in type 1 diabetes

Recent technical advances allow detection of several hundred volatile organic compounds (VOCs) in human exhaled air, many of which reflect unidentified endogenous pathways. Our group has previously estimated plasma glucose levels in healthy adults during a standard oral glucose tolerance test via exhaled VOC analysis. As a result of the metabolic characteristics of hyperglycemia in the diabetic (low insulin and increased free fatty acids and ketones), we hypothesized that different exhaled VOC profiles may be present in children with type 1 diabetes mellitus (T1DM) during spontaneous hyperglycemia. Exhaled methyl nitrate strongly correlated specifically with the acute, spontaneous hyperglycemia of T1DM children. Eighteen experiments were conducted among 10 T1DM children. Plasma glucose and exhaled gases were monitored during either constant euglycemia (n = 5) or initial hyperglycemia with gradual correction (n = 13); all subjects received i.v. insulin and glucose as needed. Gas analysis was performed on 1.9-liter breath samples via gas chromatography using electron capture, flame ionization, and mass selective detection. Among the ≈100 measured exhaled gases, the kinetic profile of exhaled methyl nitrate, commonly present in room air in the range of 5–10 parts per trillion, was most strongly statistically correlated with that of plasma glucose (P = 0.003–0.001). Indeed, the kinetic profiles of the two variables paralleled each other in 16 of 18 experiments, including repeat subjects who at different times displayed either euglycemia or hyperglycemia.

Large‐scale air mass characteristics observed over western Pacific during summertime

Remote and in situ measurements of gases and aerosols were made with airborne instrumentation to investigate the sources and sinks of tropospheric gases and aerosols over the western Pacific during the NASA Global Tropospheric Experiment (GTE)/Pacific Exploratory Mission-West A (PEM-West A) conducted in September–October 1991. This paper discusses the 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 and airborne in situ instrumentation for comprehensive measurements of air mass composition. In low latitudes of the western Pacific the airflow was generally from the east, and under these conditions the air was observed to have low aerosol loading and low ozone levels throughout the troposphere. Ozone was found to be below 10 parts per billion volume (ppbv) near the surface to 40–50 ppbv in the middle to upper troposphere. In the middle and high latitudes the airflow was mostly westerly, and the background O3 was generally less than 55 ppbv. On 60% of the PEM-West A flights, O3 was observed to exceed these levels in regions that were determined to be associated with stratospheric intrusions. In convective outflows from typhoons, near-surface air with low ozone ( 10 km). Several cases of continental plumes from Asia were observed over the Pacific during westerly flow conditions. These plumes were found in the lower troposphere with ozone levels in the 60–80 ppbv range and enhanced aerosol scattering. At low latitudes over the central Pacific the troposphere primarily contained air with background or low ozone levels; however, stratospherically influenced air with enhanced ozone (40–60 ppbv) was observed several times in the lower troposphere. The frequency of observation of the air masses and their average chemical composition are also discussed in this paper.

Meridional distributions of NOx, NOy, and other species in the lower stratosphere and upper troposphere during AASE II

The meridional distribution of NOx in the lower stratosphere and upper troposphere is inferred from 10 flights of the NASA DC-8 in the northern winter of 1992, along with like distributions of NOy, NOx/NOy, CO, and C2Cl4. In the lowest few km of the stratosphere there is little vertical gradient in NOx over the range of latitudes measured (40°–90°N). There is a substantial latitudinal gradient, with 50 pptv above the pole and 120 pptv near 40°N. In the uppermost few km of the troposphere, background values range from 30 pptv over the pole to 90 pptv near 40°N. On two occasions higher values, up to 140 pptv in the mean, were seen 2–3 km below the tropopause in association with frontal systems. The meridional distributions of CO and C2Cl4 show the same feature, suggesting that the source of the elevated NOx is near the earths surface.

Mercury Concentrations in Museum Specimens of Tuna and Swordfish

The mercury levels of museum specimens of seven tuna caught 62 to 93 years ago and a swordfish caught 25 years ago have been determined by instrumental neutron activation analysis. These levels are in the same range as those found in specimens caught recently.

Model study of tropospheric trace species distributions during PEM-West A

A three-dimensional mesoscale transport/photochemical model is used to study the transport and photochemical transformation of trace species over eastern Asia and western Pacific for the period from September 20 to October 6, 1991, of the Pacific Exploratory Mission-West A experiment. The influence of emissions from the continental boundary layer that was evident in the observed trace species distributions in the lower troposphere over the ocean is well simulated by the model. In the upper troposphere, species such as O3, NOy (total reactive nitrogen species), and SO2 which have a significant source in the stratosphere are also simulated well in the model, suggesting that the upper tropospheric abundances of these species are strongly influenced by stratospheric fluxes and upper tropospheric sources. In the case of SO2 the stratospheric flux is identified to be mostly from the Mount Pinatubo eruption. Concentrations in the upper troposphere for species such as CO and hydrocarbons, which are emitted in the continental boundary layer and have a sink in the troposphere, are significantly underestimated by the model. Two factors have been identified to contribute significantly to the underestimate: one is emissions upwind of the model domain (eastern Asia and western Pacific); the other is that vertical transport is underestimated in the model. Model results are also grouped by back trajectories to study the contrast between compositions of marine and continental air masses. The model-calculated altitude profiles of trace species in continental and marine air masses are found to be qualitatively consistent with observations. However, the difference in the median values of trace species between continental air and marine air is about twice as large for the observed values as for model results. This suggests that the model underestimates the outflow fluxes of trace species from the Asian continent and the Pacific rim countries to the ocean. Observed altitude profiles for species like CO and hydrocarbons show a negative gradient in continental air and a positive gradient in marine air. A mechanism which may be responsible for the altitude gradients is proposed.

Factors influencing the upper free tropospheric distribution of reactive nitrogen over the South Atlantic during the TRACE A experiment

This paper evaluates the potential sources of the enhanced levels of NO that were observed throughout the upper troposphere over the equatorial and tropical South Atlantic. During September/October 1992 NOx (NO + NO2) mixing ratios in the 8- to 13-km region averaged 150 parts per trillion by volume (pptv) and were greatly affected by what appeared as spatially large “plumes” (100 to 1000 km) with NO enhancements of over 800 parts per trillion by volume. Other trace gases were also enhanced within these plumes (e.g., CO, CO2, CH4, CH3Cl, C2H2, C2H6, C3H8, and PAN). However, for these tracers of surface emissions, inconsistent patterns of enhancement were found with respect to one another and to NO. We analyzed these plumes for indications of coherent relationships between the enhanced levels of NO and the enhanced levels of biogenic and combustion-related tracers. This analysis indicated that the tracer relationships were primarily produced by their common injection via deep convection into the upper troposphere. A corollary analysis using a combustion tracer reference frame in combination with meteorological analysis indicates a longer than expected lifetime of NOx in the upper troposphere. This analysis also suggests that an efficient mechanism may exist in the upper troposphere for recycling HNO3 back into NOx with a rate comparable to that predicted for the HNO3 formation. During the Transport and Atmospheric Chemistry Near the Equator Atlantic study period this in-situ formation of NOx is estimated to provide the equivalent of approximately 0.7 TgN/yr of NOx within the South Atlantic basins upper troposphere. This magnitude of local in situ source is estimated to be comparable to the combined inputs from lightning and biomass burning, which are both injected via deep convection. Our analysis also suggests that lightning can contribute as much as half of the external input of NOx into this region of the upper troposphere with biomass burning possibly representing the remainder.