Arthur D Little, Inc. BIOLOGICAL CYCLING of ATMOSPHERIC TRACE GASES
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7 A - BIOLOGICAL CYCLING OF ATMOSPHERIC TRACE GASES final report prepared for NATIONAL AERONAUTICS AND SPACE^ADMINISTRATION WASHINGTON, D. C. 2O546 prepared by ARTHUR D. LITTLE, INC. CAMBRIDGE, MASSACHUSETTS O214O CONTRACT NO. NASW-2128 MARCH 1972 Arthur D Little, Inc. BIOLOGICAL CYCLING OF ATMOSPHERIC TRACE GASES Final Report Prepared For National Aeronautics and Space Administration Washington, D. C. 20546 Dian R. Hitchcock Alfred E. Wechsler Contract No. NASW-2128 March 1972 Arthur D Little, Inc ACKNOWLEDGMENTS The authors are indebted to many individuals who assisted in the conduct of the program. We are especially grateful to Professor Lewis D. Kaplan, University of Chicago, and Dr. Henry H. Blau, Environmental Research and Technology, who made substantial contributions to the studies of the feasibility of satellite monitoring reported in Chapter VIII; to Dr. Richard D. Cadle, National Center for Atmospheric Research, Dr. Edmund S. Deevey, Jr., Florida State Museum, and Professor Frederick E. Smith, Harvard University for information, advice, and helpful criticism they gave freely; and to Dr. George J. Jacobs, and Dr. Richard S. Young, NASA Headquarters, for encouragement and understanding support. D.R. Hitchcock is greatly indebted to The Institute of Ecology for the oppor- tunity to participate in the Workshop on Global Ecology, which it sponsored at Madison, Wisconsin in June, 1971. William Reehl, Jean D'Agostino, Patricia Crawley and Janet Stevens, Arthur D. Little, Inc., deserve special commendation for their contributions to the production of the final report. iii . - : - Arthur D Little, Inc TABLE OF CONTENTS Page I. SUMMARY 1 PART I. BACKGROUND 17 II. INTRODUCTION 21 III. TERRESTRIAL RESERVOIRS 27 PART II. BIOLOGICAL CYCLING OF SELECTED GASES 111 IV. METHANE 117 V. CARBON MONOXIDE 155 VI. NITROGEN COMPOUNDS 205 VII. SULFUR COMPOUNDS 285 PART III. FEASIBILITY OF SATELLITE MONITORING 391 VIII. FEASIBILITY OF SATELLITE MONITORING OF TRACE ATMOSPHERIC CONSTITUENTS 395 Arthur D Little, Inc I. SUMMARY A. PURPOSE AND SCOPE The purpose of this program was to conduct a detailed critical review of present knowledge of the influence of biological processes on the cycling of selected atmospheric gas constituents—methane, carbon monoxide, and gaseous compounds of nitrogen (nitrous oxide, ammonia, nitric oxide, and nitrogen dioxide) and sulfur (hydrogen sulfide and sulfur dioxide). The work included the identification of biological and other sources of each gas, a survey of abundance measurements re- ported in the literature, and a review of the atmospheric fate of each constituent. The study provided information on which to base conclu- sions regarding the importance of biological processes on the atmospheric distribution and surface-atmosphere exchange of each constituent, and a basis for estimating the adequacy of present knowledge of these factors. We also conducted a preliminary analysis of the feasibility of monitor- ing the biologically influenced temporal and spatial variations in abun- dance of these gases in the atmosphere from satellites. At the beginning of this project, we hoped to include carbon dioxide within the scope of the study, but limited resources required us to eliminate it as a major topic. Several publications appearing after we began our project (SCEP, 1970; SMIC, 1971; Manabe, 1971; and Bolin, 1970) appear to provide satisfactory coverage of C0~, and we concluded that we could add little to the published information. The gases we examined are, in our opinion, the most important trace gases in the atmosphere, including the common reduced gases and the gaseous forms of nitrogen and sulfur. Some of them—CO, SO , and NO — £. X are common "pollutant" effluents of industrial processes. Because we are concerned with natural cycles of these compounds, we have given little attention to industrial sources, except to note them and to con- sider the errors that such sources may have introduced into quantitative estimates of global cycles. Arthur D Little, Inc In addition to direct gaseous emissions and consequent increases in the amount annually in circulation, human activity can also affect the natural cycles by altering the biological activities which provide sources or sinks for such constitutents. Where information on these effects was available, we have considered and presented it together with other findings. B. GENERAL CONCLUSIONS (1) There are large biological sources and/or sinks for CO, CH,, N_0, NO, N0~ and S0_, and there may be a significant natural source of H^S. However, available information is in all cases inadequate to estimate accurately the amount of each gas annually cycled through the atmosphere as a consequence of biological activity. The range between the minimum and the maximum probable quantity cycled per year is very large—an order of magnitude for some gases and a factor of two for others. Information regarding the biological cycling of the industrial pollutants CO, S0 , and NO is insufficient to determine reliably 0Z X whether the anthropogenic emissions represent a large or a small propor- tion of the total in circulation. The uncertainty is such that these pollutant sources could supply as much as one third to one half the total in circulation, or as little as 5% or less. (2) The unreliability of the estimates of the natural cycles is due to inadequacies in many kinds of data, but the most outstanding con- tributors to the present uncertainty are: (a) Information regarding the ionic content of rivers draining the major continents. Present estimates of the total sulfur and nitrogen in circulation are partly based on analyses of river water collected prior to the recent very large increases in fossil fuel consumption in Europe and North America. In the case of Europe, most of the data were collected prior to 1910 and in a manner now regarded as highly unreli- able, due to outmoded technology and statistically inadequate sampling techniques. Data for rivers in the United States are much better than those for Europe, having been collected during the present century, but even these studies are not adequate to the needs of workers wishing Arthur 1) Little K to evaluate the effects of recent industrialization and modification of agricultural techniques on continental runoff. Analyses of rivers in Africa, Asia, and South America are scanty and must be broadened if understanding of the natural background cycles is to be improved. (b) Chemical analyses of precipitation. Many important biologi- cally cycled atmospheric compounds are returned to the surface in pre- cipitation, as gases absorbed from the atmosphere, or as ions derived from particulates washed out of the atmosphere. Most of the analyses now used to estimate global transfer rates were derived from studies of rain collected in regions of Europe and the United States that are almost certainly affected by industry and intensive agriculture. These estimates should be supplemented with analyses of precipitation in remote regions far from pollutant sources. Many of the available analyses of precipitation are of questionable utility insofar as studies of atmospheric nitrogen cycles are concerned; the chemical form of nitrogen compounds may be altered after collection in rain gauges by biological activity, which may oxidize ammonia or organic nitrogen to nitrite or nitrate. (c) Direct measurements of atmospheric trace gas abundances. In general, the biologically cycled atmospheric constituents are present in the non-urban atmosphere in very low concentrations and show considerable variation in abundance due to variations in the kind and amount of local biological activity. The most abundant compounds studied—methane, car- bon monoxide, and nitrous oxide—are present in the range of 0.1 to about 1.5 ppm, while all the remainder—sulfur dioxide, hydrogen sulfide, nitric oxide, ammonia, and nitrogen dioxide—are measured in parts per billion or less. Accurate measurement of such low concentrations in the field presents very difficult problems which have been solved only recently, if at all. Most atmospheric sampling, like most precipitation analysis, has occurred in relatively densely populated regions of industrially ad- vanced nations, usually in attempts to understand the influence of pol- lutant sources. These measurements cannot be reliably extrapolated to the entire globe; baseline studies of atmospheric concentrations should be made in diverse, remote, unpolluted environments. 3 Arthur D Little, Inc. Most existing measurements were made at or very near ground level, so there are few abundance profiles of trace gases, for any locations. This information is essential if we are to improve estimates of the total atmospheric load of any biologically cycled gas and understand its atmospheric fate. (3) Satellite-mounted atmospheric gas sensors appear to have the necessary sensitivity for monitoring biologically influenced variations in atmospheric abundance of trace gases. This potential, combined with the possibility of using such sensors to examine many parts of the globe with the same instrument at nearly the same time, suggests that their use for this purpose may be extremely advantageous. (4) In addition to adding pollutant emissions to the atmospheric load of gases which are biologically cycled, human activities may increase the biological emissions by establishing and maintaining the conditions for anaerobic production of some gases. Thus, there is some evidence that man-made swamps—rice paddies—may be the major source of atmospheric