L. E. Heidt

Biomass Burning as a Source of Atmospheric Gases CO, H2, N2O, NO, CH3Cl and COS

The potential importance of deforestation and biomass burning for the atmospheric CO2 cycle has received much attention and caused some controversy. Biomass burning can contribute extensively to the budgets of several gases which are important in atmospheric chemistry. In several cases the emission is comparable to the technological source. Most burning takes place in the tropics in the dry season and is caused by man’s activities. The potential importance of deforestation and biomass burning for the atmospheric CO2 cycle has received much attention and caused some controversy. In this article we will show the probable importance of biomass burning as a trace gas source, which is caused by man’s activities in the tropics. We used the results of our global biomass burning analysis to derive some rough estimates of the sources of the important atmospheric trace gases CO, H2, CH4, N2O, NOx (NO and NO2), COS and CH3Cl from the worldwide burning of biomass.

Tropospheric chemical composition measurements in Brazil during the dry season

Field measurement programs in Brazil during the dry seasons in August and September 1979 and 1980 have demonstrated the large importance of the continental tropics in global air chemistry. Many important trace gases are produced in large amounts over the continents. During the dry season, much biomass burning takes place, especially in the cerrado regions, leading to a substantial emission of air pollutants, such as CO, NOx, N2O, CH4 and other hydrocarbons. Ozone concentrations are enhanced due to photochemical reactions. The large biogenic organic emissions from tropical forests play an important role in the photochemistry of the atmosphere and explain why CO is present in such high concentrations in the boundary layer of the tropical forest. Carbon monoxide production may represent more than 3% of the net primary productivity of the tropical forests. Ozone concentrations in the boundary layer of the tropical forests indicate strong removal processes. Due to atmospheric supply of NOx by lightning, there is probably a large production of O3 in the free troposphere over the Amazon tropical forests. This is transported to the marine-free troposphere and to the forest boundary layer.

On the evaluation of ozone depletion potentials

Observations of methane, CFC-11, and ozone losses are used along with insights from models and observations regarding interrelationships between tracers to develop a semi-empirical framework for evaluating global ozone depletion potentials. Direct measurements of some hydrochlorofluorocarbons including HCFC-22 in the Arctic lower stratosphere are also used to evaluate the local ozone depletion potentials there. This approach assumes that all of the observed ozone destruction in the contemporary atmosphere is due to chlorine and that the depletion is proportional to the local relative chlorine release. It is shown that the global ozone depletion potentials for compounds with relatively long stratospheric lifetimes such as HCFC-22 and HCFC-142b are likely to be larger than those generally predicted by gas phase chemical models, due largely to the importance of lower stratospheric ozone losses that are not simulated in gas phase studies. The analysis presented suggests that the globally averaged efficiency for ozone depletion by HCFC-22 is as much as a factor of 2 larger than some gas phase model estimates. For compounds with short stratospheric lifetimes such as (CCl4). and (CH3CCl3), on the other hand, gas phase models likely overestimate the ozone depletion potentials for the present-day stratosphere. Observations of polar ozone loss and reactive halogen radical abundances also imply that the globally averaged ozone depletion potentials for brominated species for the contemporary stratosphere could be as much as 1.5–3 times greater than some gas phase model predictions, depending upon lower stratospheric loss processes.

Measurements of Halogenated Organic Compounds near the Tropical Tropopause

The amount of organic chlorine and bromine entering the stratosphere have a direct influence on the magnitude of chlorine and bromine catalyzed ozone losses. Twelve organic chlorine species and five organic bromine species were measured from 12 samples collected near the tropopause between 23.8°N and 25.3°N during AASE II. The average mixing ratios of total organic chlorine and total organic bromine were 3.50 ± 0.06 ppbv and 21.1 ± 0.8 pptv, respectively. CH3Cl represented 15.1% of the total organic chlorine, with CFC 11 (CCl3F) and CFC 12 (CCl2F2) accounting for 22.6% and 28.2%, respectively, with the remaining 34.1% primarily from CCl4, CH3CCl3, and CFC 113 (CCl2FCClF2). CH3Br represented 54% of the total organic bromine. The 95% confidence intervals of the mixing ratios of all but four of the individual compounds were within the range observed in low and mid-latitude mid-troposphere samples. The four compounds with significantly lower mixing ratios at the tropopause were CHCl3, CH2Cl2, CH2Br2, and CH3CCl3. The lower mixing ratios may be due to entrainment of southern hemisphere air during vertical transport in the tropical region and/or to exchange of air across the tropopause between the lower stratosphere and upper troposphere.

Photochemical partitioning of the reactive nitrogen and chlorine reservoirs in the high‐latitude stratosphere

Partitioning of the major components of the reactive nitrogen and inorganic chlorine reservoirs is derived from aircraft measurements in the lower stratosphere during the winter season in both hemispheres at latitudes of about 60° to 80°. The goal of this work is to exercise the power of the correlated set of measurements from polar missions of the NASA ER-2 to extend what can be learned from looking at the measurements individually. The results provide a consistent method for comparing distributions, and hence the controlling processes, between different areas of the near-polar regions. The analysis provides clear evidence of the effects of heterogeneous processes in the atmosphere. Values for NO2, ClONO2, N2O5, and Cl2O2 are derived in a simplified steady state model based on in situ NO, ClO, O3, temperature, and pressure measurements; laboratory-measured reaction rates; and modeled photodissociation rates. Values for the reservoir totals are independently derived from measurements of N2O, organic chlorine, and total reactive nitrogen. The relative abundances of the measured and derived species within the reservoirs are calculated, and the longer-lived species HCl and HNO3 are estimated as the residuals of their respective reservoirs. The resulting latitude distributions in the Arctic outside the vortex agree reasonably well with predictions of a two-dimensional photochemical model, indicating that partitioning in this region is largely controlled by standard homogeneous gas phase chemistry. Inside the Arctic vortex a large fraction of the HCl has been converted to reactive chlorine species ClO and Cl2O2, consistent with the extensive action of known heterogeneous reactions, presumably occurring on the surfaces of polar stratospheric clouds formed in the cold temperatures of the vortex. The partitioning in the Antarctic suggests that nearly the entire range of latitudes sampled by the ER-2 is affected by heterogeneous processes in situ, including that portion of the “collar” region equatorward of the nominal chemically perturbed region (CPR). Consideration of heterogeneous processing in the region outside the CPR is important in predicting the possible expansion of Antarctic ozone depletion and the transport of chemically perturbed air to lower latitudes.

On the age of stratospheric air and ozone depletion potentials in polar regions

Observations of the nearly inert, man-made chlorofluorocarbon CFC-115 obtained during January 1989 are used to infer the age of air in the lower stratosphere. These observations together with estimated release rates suggest an average age of high-latitude air at pressure altitudes near 17-21 km of about 3 to 5 years. This information is used together with direct measurements of HCFC-22, HCFC-142b, CH{sub 3}Br, H-1301, H-1211, and H-2402 to examine the fractional dissociation of these species within the Arctic polar lower stratosphere compared to that of CFC-11 and hence to estimate their local ozone depletion potentials in this region. It is shown that these HCFCs are much less efficiently dissociated within the stratosphere than CFC-11, lowering their ozone depletion potentials to only about 30-40% of their chlorine loading potentials. In contrast, the observations of CH{sub 3}Br and the Halons considered here confirm that they are rapidly dissociated within the stratosphere, with important implications for their ozone depletion potentials. 20 refs., 4 figs., 3 tabs.

In situ measurements of BrO During AASE II

BrO measured from the NASA ER-2 during AASE II exhibited a mean value (for 20-minute averages) of 5.4±0.3 pptv, with a standard deviation of 3.1 pptv. Ratios of BrO to available inorganic bromine (Bry) show only slight increases in polar regions relative to midlatitudes. A comparison between observed latitudinal and diurnal variations of this same ratio and that calculated by photochemical models shows reasonable agreement in behavior, but significant discrepancies in magnitude. It is unclear whether this difference is due to errors in measurements, models or both.

On the age of stratospheric air and inorganic chlorine and bromine release

We estimate the average transport time from the tropical tropopause to various regions of the northern hemisphere lower stratosphere (stratospheric age) using simultaneous mixing ratio measurements of CFC-115 and CO2 measured by the Whole Air Sampler (WAS) during Airborne Arctic Stratospheric Expedition II (AASE II). Our inferred ages are consistent with those presented in previous studies. We discuss sources of uncertainties that affect age estimates in general, as well as specific uncertainties arising from inferring ages using CO2 and CFC-115 abundances. We infer inorganic chlorine (Cly) and bromine (Bry) at various lower stratospheric locations using the WAS organic chlorine and bromine measurements in combination with modeled tropospheric halocarbon trends and with our estimated ages. Inferred Cly and Bry abundances generally increase with increasing latitude and altitude. For our analyzed locations inside the polar vortex, we estimate a maximum Cly abundance of about 2.7 parts per billion by volume (ppbv) and a maximum Bry abundance of about 13.7 parts per trillion by volume (pptv). The locations of these maxima correspond to an average N2O mixing ratio of about 100 ppbv, and to a fractional dissociation of organic chlorine and bromine of 0.85 and 0.90, respectively. Finally, we discuss the expected future limitations of using CFC-115 to estimate stratospheric age due to the production limitations prescribed by the amendments and adjustments to the Montreal Protocol.

OCS, H2S, and CS2 fluxes from a salt water marsh

The diurnal-to-monthly behavior of the fluxes of OCS, H2S, and CS2 from a mixed-Spartina grass-covered site in a Wallops Island salt water marsh was determined through a series of experiments in August and September, 1982. Absolute flux values were determined for OCS and H2S, while only relative values were determined for CS2. The rates of emission of OCS and H2S were observed to vary diurnally and to be strongly influenced by tides. The time-averaged flux values show that such mixed-Spartina stands are insignificant (≪ 1%) global sources of H2S or CS2 and insignificant contributors to the global OCS cycle (< 1%). These results demonstrate that some marsh regions play a minor role in the global sulfur budget and, consequently, that the inclusion of such areas in extrapolations of measurements of more productive regions could lead to an overestimate of the role of salt water marshes in the global sulfur budget.

Balloon‐borne low temperature air sampler

Design, construction, and performance of a balloon borne low temperature air sampler are described. The sampler can collect 16 samples of 10 liter STP at different stratospheric altitudes. The collected samples allow measurement of the trace gases H2, H2O, CH4, CO, CO2, and N2O. In the future, measurements will include the Freons, CCl4, SF6, CH3OH, and ΣNOx; also, the altitudes will be extended from the present 35 km to above 45 km.