Normal atmosphere: large radical and formaldehyde concentrations predicted

A steady-state model of the normal (unpolluted) surface atmosphere predicts a daytime concentration of hydroxyl, hydroperoxyl, and methylperoxyl radicals approaching 5 x 10(8)molecules per cubic centimeter and a formaldehyde concentration of 5 x 10(10) molecules per cubic centimeter or 2 parts per billion. A radical chain reaction is proposed for the rapid removal of carbon monoxide, leading to a carbon monoxide lifetime as low as 0.2 year in the surface atmosphere.     

Soil as a sink for atmospheric carbon monoxide

The rate of carbon monoxide oxidation by soil increased with increasing carbon monoxide concentration in the gas phase, in line with Michaelis-Menten kinetics. Rates of carbon monoxide oxidation were determined for 20 soils at 0 degrees , 10 degrees , 20 degrees , and 30 degrees C. The observed oxidation rates were used to calculate a global soil uptake rate of atmospheric carbon monoxide of 4.1 x 10(14) grams per year, which is slightly less than the amount of carbon monoxide believed to be produced annually as a result of fossil fuel combustion.     

Carbon Monoxide in the Earth's Atmosphere: Increasing Trend

The results of an analysis of more than 60,000 atmospheric measurements of carbon monoxide taken over 3(1/2) years at Cape Meares, Oregon (45 degrees N, 125 degrees W), indicate that the background concentration of this gas is increasing. The rate of increase, although uncertain, is about 6 percent per year on average. Human activities are the likely cause of a substantial portion of this observed increase; however, because of the short atmospheric lifetime of carbon monoxide and the relatively few years of observations, fluctuations of sources and sinks related to the natural variability of climate may have affected the observed trend. Increased carbon monoxide may deplete tropospheric hydroxyl radicals, slowing down the removal of dozens of man-made and anthropogenic trace gases and thus indirectly affecting the earth's climate and possibly the stratospheric ozone layer.     

Hydroxyl radical photoproduction in the sea and its potential impact on marine processes

Photochemical production rates and steady-state concentrations of hydroxyl radicals (.OH) were measured in sunlight-irradiated seawater. Values ranged from 110 nanomolar per hour and 12 x 10(-18) molar in coastal surface water to 10 nanomolar per hour and 1.1 x 10(-18) molar in open ocean surface water. The wavelengths responsible for this production are in the ultraviolet B region (280 to 320 nanometers) of the solar spectrum. Dissolved organic matter (DOM) appears to be the main source for .OH over most of the oceans, but in upwelling areas nitrite and nitrate photolysis may also be important. DOM in the deep sea is degraded more readily by .OH (and its daughter radicals), by a factor of 6 to 15, than is DOM in open-ocean surface water. This finding may in part bear on major discrepancies among current methods for measuring dissolved organic carbon in seawater.     

Biomass burning in the tropics: impact on atmospheric chemistry and biogeochemical cycles

Biomass burning is widespread, especially in the tropics. It serves to clear land for shifting cultivation, to convert forests to agricultural and pastoral lands, and to remove dry vegetation in order to promote agricultural productivity and the growth of higher yield grasses. Furthermore, much agricultural waste and fuel wood is being combusted, particularly in developing countries. Biomass containing 2 to 5 petagrams of carbon is burned annually (1 petagram = 10(15) grams), producing large amounts of trace gases and aerosol particles that play important roles in atmospheric chemistry and climate. Emissions of carbon monoxide and methane by biomass burning affect the oxidation efficiency of the atmosphere by reacting with hydroxyl radicals, and emissions of nitric oxide and hydrocarbons lead to high ozone concentrations in the tropics during the dry season. Large quantities of smoke particles are produced as well, and these can serve as cloud condensation nuclei. These particles may thus substantially influence cloud microphysical and optical properties, an effect that could have repercussions for the radiation budget and the hydrological cycle in the tropics. Widespread burning may also disturb biogeochemical cycles, especially that of nitrogen. About 50 percent of the nitrogen in the biomass fuel can be released as molecular nitrogen. This pyrdenitrification process causes a sizable loss of fixed nitrogen in tropical ecosystems, in the range of 10 to 20 teragrams per year (1 teragram = 10(12) grams).     

Atmospheric trends in methylchloroform and the global average for the hydroxyl radical

Frequent atmospheric measurements of the anthropogenic compound methylchloroform that were made between 1978 and 1985 indicate that this species is continuing to increase significantly around the world. Reaction with the major atmospheric oxidant, the hydroxyl radical (OH), is the principal sink for this species. The observed mean trends for methylchloroform are 4.8, 5.4, 6.4, and 6.9 percent per year at Aldrigole (Ireland) and Cape Meares (Oregon), Ragged Point (Barbados), Point Matatula (American Samoa), and Cape Grim (Tasmania), respectively, from July 1978 to June 1985. These measured trends, combined with knowledge of industrial emissions, were used in an optimal estimation inversion scheme to deduce a globally averaged methylchloroform atmospheric lifetime of 6.3 (+ 1.2, -0.9) years (1sigma uncertainty) and a globally averaged tropospheric hydroxyl radical concentration of (7.7 +/- 1.4) x 10(5) radicals per cubic centimeter (1sigma uncertainty). These 7 years of gas chromatographic measurements, which comprise about 60,000 individual calibrated real-time air analyses, provide the most accurate estimates yet of the trends and lifetime of methylchloroform and of the global average for tropospheric hydroxyl radical levels. Accurate determination of hydroxyl radical levels is crucial to understanding global atmospheric chemical cycles and trends in the levels of trace gases such as methane.     

Rate constants for the reactions of hydroxyl and hydroperoxyl radicals with ozone

Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 3000 degrees K for OH + O(3)-->HO(2) + O(2) is 8 x 10(-14) cubic centimeters per second. The rate constant for HO(2) + O(3)--> OH + 2O(2), is 3 x 10(-15) cubic centimeters per second. These results have implications concerning stratospheric ozone.     

Postglacial change in sea level in the Western north atlantic ocean

Radioactive carbon determinations of the age of peat indicate that at Bermuda, southern Florida, North Carolina, and Louisiana the relative sea level has risen at approximately the same rate, 2.5 x 10(-3) foot per year (0.76 x 10(-3) meter per year), during the past 4000 years. It is proposed tentatively that this is the rate of eustatic change in sea level. The rise in sea level along the northeastern coast of the United States has been at a rate much greater than this, indicating local subsidence of the land. Between Cape Cod and northern Virginia, coastal subsidence of 13 feet appears to have occurred between 4000 and 2000 years ago and has continued at a rate of about 1 x 10(-3) foot per year since then. On the northeastern coast of Massachusetts, subsidence of 6 feet occurred between 4000 and 3000 years ago; since then sea level has risen at about the eustatic rate. Between 12,000 and 4000 years ago, sea level rose at an average of about 11 x 10(-3) foot per year. The part played by local subsidence or temporary departures from the average rate during this period is uncertain.     

Hydrogen radicals, nitrogen radicals, and the production of O3 in the upper troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.     

Airborne lead and carbon monoxide at 45th Street, New York City

Daily business-day traffic determines the diurnal lead concentration as well as diurnal carbon monoxide concentration. Daily averages of 7.5 micrograms per cubic meter for lead and 13 parts per million of carbon monoxide were found for the 10-week period of the study. Correlations were demonstrated for lead and traffic and lead and carbon monoxide.     

Atmospheric halocarbons, hydrocarbons, and sulfur hexafluoride: global distributions, sources, and sinks

The global distribution of fluorocarbon-12 and fluorocarbon-11 is used to establish a relatively fast interhemispheric exchange rate of 1 to 1.2 years. Atmospheric residence times of 65 to 70 years for fluorocarbon-12 and 40 to 45 years for fluorocarbon-l1 best fit the observational data. These residence times rule out the possibility of any significant missing sinks that may prevent these fluorocarbons from entering the stratosphere. Atmospheric measurements of methyl chloroform support an 8-to 10-year residence time and suggest global average hydroxyl radical (HO) concentrations of 3 x 10(5) to 4 x 10(5) molecules per cubic centimeter. These are a factor of 5 lower than predicted by models. Additionally, methyl chloroform global distribution supports Southern Hemispheric HO levels that are a factor of 1.5 or more larger than the Northern Hemispheric values. The long residence time and the rapid growth of methyl chloroform cause it to be a potentially significant depleter of stratospheric ozone. The oceanic sink for atmospheric carbon tetrachloride is about half as important as the stratospheric sink. A major source of methyl chloride (3 x 10(12)grams per year), sufficient to account for nearly all the atmospheric methyl chloride, has been identified in the ocean.     

Large yearly production of phytoplankton in the Western bering strait

Production in the western Bering Strait is estimated at 324 grams of carbon per square meter per year over 2.12x 10(4) square kilometers. An ice-reduced growing season makes this large amount of primary production unexpected, but it is consistent with the area's large upper trophic level stocks. The productivity is fueled by a cross-shelf flow of nutrient-rich water from the Bering Sea continental slope. This phytoplankton production system from June through September is analogous to a laboratory continuous culture.     

Recent changes in atmospheric carbon monoxide

Measurements of carbon monoxide (CO) in air samples collected from 27 locations between 71 degrees N and 41 degrees S show that atmospheric levels of this gas have decreased worldwide over the past 2 to 5 years. During this period, CO decreased at nearly a constant rate in the high northern latitudes. In contrast, in the tropics an abrupt decrease occurred beginning at the end of 1991. In the Northern Hemisphere, CO decreased at a spatially and temporally averaged rate of 7.3 (+/-0.9) parts per billion per year (6.1 percent per year) from June 1990 to June 1993, whereas in the Southern Hemisphere, CO decreased 4.2 (+/-0.5) parts per billion per year (7.0 percent per year). This recent change is opposite a long-term trend of a 1 to 2 percent per year increase inferred from measurements made in the Northern Hemisphere during the past 30 years.     

Free-radical oxidants in natural waters

Photooxidation of cumene (isopropylbenzene) and pyridine in dilute solution in natural waters gives products characteristic of reactions with alkylperoxy (RO(2).) and hydroxyl (HO.) radicals. On the basis of the rates of formation of the products, the average concentrations of RO(2). and HO. are estimated to be about 10(-9) and 10(-17) mole per liter, respectively. The concentration of RO(2). is large enough that, for some classes of reactive chemicals, oxidation can be an important process in natural waters.     

薄荷提取物的抗氧化性研究

[目的]探究薄荷不同溶剂提取物对羟基自由基的抗氧化活性(即自由基的清除作用)。[方法]采用超声波提取法,分别以蒸馏水、50%乙醇和95%乙醇为溶剂,在40℃条件下提取30 min,获得了薄荷的不同溶剂提取物,并以邻二氮菲氧化法比较了不同溶剂提取物对体系产生的羟基自由基的清除作用,并研究随时间延长羟基自由基清除速率的变化情况。[结果]结果表明,随着提取液浓度的增大,羟基自由基清除率升高,并且随时间延长,3种提取液对羟基自由基清除率均呈下降趋势。[结论]该研究为探索或寻找安全性更高的天然抗氧化物质提供了依据。     

Photochemical Production of Formaldehyde in Earth's Primitive Atmosphere

Formaldehyde could have been produced by photochemical reactions in Earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 10(11) moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.     

Carbon monoxide: residence time in the atmosphere

A lower limit of 0.1 year for the residence time of carbon monIoxide in the atmosphere is derived from radiocarbon measurements. The action of certain microorganisms and atmospheric photochemical reactions are possible mechanisms for the removal of carbon monoxide. This value can be compared with 2.7 years, a value deduced from estimated rates of carbon monoxide production and global measurements of atmospheric concentrations of carbon monoxide.     

Carbon monoxide on jupiter and implications for atmospheric convection

A study of the equilibrium and disequilibrium thermochemistry of the recently discovered carbon monoxide on Jupiter suggests that the presence of this gas in the visible atmosphere is a direct result of very rapid upward mixing from levels in the deep atmosphere where the temperature is about 1100 degrees K and where carbon monoxide is thermodynamically much more stable. As a consequence the observed carbon monoxide mixing ratio is a sensitive function of the vertical eddy mixing coefficient. We infer a value for this latter coefficient which is about three to four orders of magnitude greater than that in the earth's troposphere. This result directly supports existing structural and dynamical theories implying very rapid convection in the deep Jovian atmosphere, driven by an internal heat source.     

Marine macrophytes as a global carbon sink

Marine macrophyte biomass production, burial, oxidation, calcium carbonate dissolution, and metabolically accelerated diffusion of carbon dioxide across the air-sea interface may combine to sequester at least 10(9) tons of carbon per year in the ocean. This carbon sink may partially account for discrepancies in extant global carbon budgets.     

Soil: a natural sink for carbon monoxide

A potting soil mixture depleted carbon monoxide in a test atmosphere from a concentration of 120 parts per million to near zero within 3 hours. Maximum activity occurred at 30 degrees C. Steam sterilization of the soil, the addition of antibiotics or 10 percent (by weight) saline solution, and anaerobic conditions all prevented carbon monoxide uptake. Sterilized soil inoculated with nonsterile soil acquired activity with time. Samples of various natural soils differed in their ability to remove carbon monoxide from the air. Acidic soils with a high content of organic matter were generally the most active. The soil's ability to remove carbon monoxide from the atmosphere is ascribed to the activity of soil micro-organisms.