Record low global ozone in 1992

The 1992 global average total ozone, measured by the Total Ozone Mapping Spectrometer (TOMS) on the Nimbus-7 satellite, was 2 to 3 percent lower than any earlier year observed by TOMS (1979 to 1991). Ozone amounts were low in a wide range of latitudes in both the Northern and Southern hemispheres, and the largest decreases were in the regions from 10 degrees S to 20 degrees S and 100N to 60 degrees N. Global ozone in 1992 is at least 1.5 percent lower than would be predicted by a statistical model that includes a linear trend and accounts for solar cycle variation and the quasi-biennial oscillation. These results are confirmed by comparisons with data from other ozone monitoring instruments: the SBUV/2 instrument on the NOAA-11 satellite, the TOMS instrument on the Russian Meteor-3 satellite, the World Standard Dobson Instrument 83, and a collection of 22 ground-based Dobson instruments.     

In Situ Northern Mid-Latitude Observations of ClO, O3, and BrO in the Wintertime Lower Stratosphere

In order to test photochemical theories linking chlorofluorocarbon derivatives to ozone(O(3)) depletion at high latitudes in the springtime, several related atmospheric species, including O(3), chlorine monoxide(ClO), and bromine monoxide (BrO) were measured in the lower stratosphere with instruments mounted on the NASA ER-2 aircraft on 13 February 1988. The flight path from Moffett Field, California (37 degrees N, 121 degrees W), to Great Slave Lake, Canada (61 degrees N, 115 degrees W), extended to the center of the polar jet associated with but outside of the Arctic vortex, in which the abundance of O(3) was twice its mid-latitude value, whereas BrO levels were 5 parts per trillion by volume (pptv) between 18 and 21 kilometers, and 2.4 pptv below that altitude. The ClO mixing ratio was as much as 65 pptv at 60 degrees N latitude at an altitude of 20 kilometers, and was enhanced over mid-latitude values by a factor of 3 to 5 at altitudes above 18 kilometers and by as much as a factor of 40 at altitudes below 17 kilometers. Levels of ClO and O(3) were highly correlated on all measured distance scales, and both showed an abrupt change in character at 54 degrees N latitude. The enhancement of ClO abundance north of 54 degrees N was most likely caused by low nitrogen dioxide levels in the flight path.     

Stratospheric response to trace gas perturbations: changes in ozone and temperature distributions

The stratospheric concentration of trace gases released in the atmosphere as a result of human activities is increasing at a rate of 5 to 8 percent per year in the case of the chlorofluorocarbons (CFCs), 1 percent per year in the case of methane (CH(4)), and 0.25 percent per year in the case of nitrous oxide (N(2)O). The amount of carbon dioxide (CO(2)) is expected to double before the end of the 21st century. Even if the production of the CFCs remains limited according to the protocol for the protection of the ozone layer signed in September 1987 in Montreal, the abundance of active chlorine (2 parts per billion by volume in the early 1980s) is expected to reach 6 to7 parts per billion by volume by 2050. The impact of these increases on stratospheric temperature and ozone was investigated with a two-dimensional numerical model. The model includes interactive radiation, wave and mean flow dynamics, and 40 trace species. An increase in CFCs caused ozone depletion in the model, with the largest losses near the stratopause and, in the vertical mean, at high latitudes. Increased CO(2) caused ozone amounts to increase through cooling, with the largest increases again near 45 kilometers and at high latitudes. This CO(2)-induced poleward increase reduced the CFC-induced poleward decrease. Poleward and downward ozone transport played a major role in determining the latitudinal variation in column ozone changes.     

Nylon production: an unknown source of atmospheric nitrous oxide

Nitrous oxide in the earth's atmosphere contributes to catalytic stratospheric ozone destruction and is also a greenhouse gas component. A precise budgetary accounting of N(2)O sources has remained elusive, and there is an apparent lack of source identification. One source of N(2)O is as a by-product in the manufacture of nylon, specifically in the preparation of adipic acid. Characterization of the reaction N(2)O stoichiometry and its isotopic composition with a simulated industrial adipic acid synthesis indicates that because of high rates of global adipic acid production, this N(2)O may account for approximately 10 percent of the increase observed for atmospheric N(2)O.     

The potential for ozone depletion in the arctic polar stratosphere

The nature of the Arctic polar stratosphere is observed to be similar in many respects to that of the Antarctic polar stratosphere, where an ozone hole has been identified. Most of the available chlorine (HCl and ClONO(2)) was converted by reactions on polar stratospheric clouds to reactive ClO and Cl(2)O(2) throughout the Arctic polar vortex before midwinter. Reactive nitrogen was converted to HNO(3), and some, with spatial inhomogeneity, fell out of the stratosphere. These chemical changes ensured characteristic ozone losses of 10 to 15% at altitudes inside the polar vortex where polar stratospheric clouds had occurred. These local losses can translate into 5 to 8% losses in the vertical column abundance of ozone. As the amount of stratospheric chlorine inevitably increases by 50% over the next two decades, ozone losses recognizable as an ozone hole may well appear.     

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.     

Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.     

Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice: release of active chlorine

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO(2)) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO(2) on the surface of ice with HCl in the mole fraction range from approximately 0.003 to 0.010 is in the range from approximately 0.05 to 0.1 for temperatures near 200 K. Chlorine (Cl(2)) is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO(3)), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO(3) and thus removes nitrogen dioxide (NO(2)) from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals. In the absence of HCl, ClONO(2) also reacts irreversibly with ice with a collision efficiency of approximately 0.02 at 200 K; the product hypochlorous acid (HOCI) is released to the gas phase on a time scale of minutes.     

The role of Br2 and BrCl in surface ozone destruction at polar sunrise

Bromine atoms are believed to play a central role in the depletion of surface-level ozone in the Arctic at polar sunrise. Br2, BrCl, and HOBr have been hypothesized as bromine atom precursors, and there is evidence for chlorine atom precursors as well, but these species have not been measured directly. We report here measurements of Br2, BrCl, and Cl2 made using atmospheric pressure chemical ionization-mass spectrometry at Alert, Nunavut, Canada. In addition to Br2 at mixing ratios up to approximately 25 parts per trillion, BrCl was found at levels as high as approximately 35 parts per trillion. Molecular chlorine was not observed, implying that BrCl is the dominant source of chlorine atoms during polar sunrise, consistent with recent modeling studies. Similar formation of bromine compounds and tropospheric ozone destruction may also occur at mid-latitudes but may not be as apparent owing to more efficient mixing in the boundary layer.     

Antarctic Ozone Depletion Chemistry: Reactions of N2O5 with H2O and HCl on Ice Surfaces

The reactions of dinitrogen pentoxide (N(2)O(5)) with H(2)O and hydrochloric acid (HCl) were studied on ice surfaces in a Knudsen cell flow reactor. The N(2)O(5) reacted on ice at 185 K to form condensed-phase nitric acid (HNO(3)). This reaction may provide a sink for odd nitrogen (NO(x)) during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. A lower limit to the sticking coefficient, gamma, for N(2)O(5) on ice is 1 x 10(-3). Moreover, N(2)O(5) reacted on HCl-ice surfaces at 185 K, with gamma greater than 3 x 10(-3). This reaction, which produced gaseous nitryl chloride (ClNO(2)) and condensed-phase HNO(3), proceeded until all of the HCl within the ice was depleted. The ClNO(2), which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide (NO(2)), may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.     

Stratospheric ozone effects on temperature

Calculated surface temperature changes, DeltaT(8), due to stratospheric ozone depletion (at 35 degrees N latitude in April) are less than previously estimated and range between -0.6 and +0.9 degrees K. The sign of DeltaT(8), is determined by the surface albedo and the presence or absence of a low-lying particulate layer (heating with particles, cooling without particles). The calculations indicate that a 90 percent stratospheric ozone depletion does not cause the temperature inversion at the tropopause to vanish, although it is weakened substantially.     

Empirical models of the electron temperature and density in the nightside venus ionosphere

Empirical models of the electron temperature and electron density of the late afternoon and nightside Venus ionosphere have been derived from Pioneer Venus measurements acquired between 10 December 1978 and 23 March 1979. The models describe the average ionosphere conditions near 18 degrees N latitude between 150 and 700 kilometers altitude for solar zenith angles of 80 degrees to 180 degrees . The average index of solar flux was 200. A major feature of the density model is the factor of 10 decrease beyond 90 degrees followed by a very gradual decrease between 120 degrees and 180 degrees . The density at 150 degrees is about five times greater than observed by Venera 9 and 10 at solar minimum (solar flux approximately 80), a difference that is probably related to the effects of increased solar activity on the processes that maintain the nightside ionosphere. The nightside electron density profile from the model (above 150 kilometers) can be reproduced theoretically either by transport of 0(+) ions from the dayside or by precipitation of low-energy electrons. The ion transport process would require a horizontal flow velocity of about 300 meters per second, a value that is consistent with other Pioneer Venus observations. Although currently available energetic electron data do not yet permit the role of precipitation to be evaluated quantitatively, this process is clearly involved to some extent in the formation of the nightside ionosphere. Perhaps the most surprising feature of the temperature model is that the electron temperature remains high throughout the nightside ionosphere. These high nocturnal temperatures and the existence of a well-defined nightside ionopause suggest that energetic processes occur across the top of the entire nightside ionosphere, maintaining elevated temperatures. A heat flux of 2 x 10(10) electron volts per square centimeter per second, introduced at the ionopause, is consistent with the average electron temperature profile on the nightside at a solar zenith angle of 140 degrees .     

泥蚶与牡蛎净化工艺优化初探

应用臭氧与二氧化氯对活体泥蚶和牡蛎进行微生物净化处理。首先对泥蚶和牡蛎进行暂养吐泥,每5 h换水一次,收集排泄物经离心计算相对吐泥量;臭氧净化处理浓度分别为0.4、0.8、1.6 mg/L,二氧化氯浓度分别为5、10、20 mg/L。结果表明：经5 h暂养吐泥即基本完成;用臭氧浓度0.4～1.6 mg/L或二氧化氯浓度5～20 mg/L净化处理24 h,细菌总数减少90%左右,大肠菌群与致病菌则由净化前的超标变成净化后的全面达标;净化处理后的泥蚶与牡蛎在5 ℃的条件下保存,10 d以内存活率为100%,净化处理后的泥蚶保存10 d再进行微生物检测依然达标。得出简便可行的净化工艺流程为：暂养吐泥5 h,再用0.4 mg/L臭氧净化24 h,然后用尼龙袋密封在5 ℃条件下保存。     

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric chlorine monoxide was carried out during May and October 1981 with an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric nitric acid and tropospheric carbonyl sulfide were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of chlorine monoxide in this same region were not seen. Stratospheric chlorine monoxide is less abundant by at least a factor of 7 than is indicated by in situ measurements, and the upper limit for the integrated vertical column density of chlorine monoxide is 2.3 x 10(13) molecules per square centimeter at the 95 percent confidence level. These results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone than is currently thought.     

Stable isotope enrichment in stratospheric nitrous oxide

Nitrous oxide is a greenhouse gas that also plays a role in the cycling of stratospheric ozone. Air samples from the lower stratosphere exhibit 15N/14N and 18O/16O enrichment in nitrous oxide, which can be accounted for with a simple model describing an irreversible destruction process. The observed enrichments are quite large and incompatible with those determined for the main stratospheric nitrous oxide loss processes of photolysis and reaction with excited atomic oxygen. Thus, although no stratospheric source needs to be invoked, the data indicate that present understanding of stratospheric nitrous oxide chemistry is incomplete.     

Quantifying Transport Between the Tropical and Mid-Latitude Lower Stratosphere

Airborne in situ observations of molecules with a wide range of lifetimes (methane, nitrous oxide, reactive nitrogen, ozone, chlorinated halocarbons, and halon-1211), used in a tropical tracer model, show that mid-latitude air is entrained into the tropical lower stratosphere within about 13.5 months; transport is faster in the reverse direction. Because exchange with the tropics is slower than global photochemical models generally assume, ozone at mid-latitudes appears to be more sensitive to elevated levels of industrial chlorine than is currently predicted. Nevertheless, about 45 percent of air in the tropical ascent region at 21 kilometers is of mid-latitude origin, implying that emissions from supersonic aircraft could reach the middle stratosphere.     

Chlorine monoxide radical, ozone, and hydrogen peroxide: stratospheric measurements by microwave limb sounding

Profiles of stratospheric ozone and chlorine monoxide radical (C1O) have been obtained from balloon measurements of atmospheric limb thermal emission at millimeter wavelengths. The C1O measurements, important for assessing the predicted depletion of stratospheric ozone by chlorine from industrial sources, are in close agreement with present theory, The predicted decrease of C1O at sunset was measured. A tentative value for the stratospheric abundance of hydrogen peroxide was also determined.     

Chemical loss of ozone in the arctic polar vortex in the winter of 1991-1992

In situ measurements of chlorine monoxide, bromine monoxide, and ozone are extrapolated globally, with the use of meteorological tracers, to infer the loss rates for ozone in the Arctic lower stratosphere during the Airborne Arctic Stratospheric Expedition II (AASE II) in the winter of 1991-1992. The analysis indicates removal of 15 to 20 percent of ambient ozone because of elevated concentrations of chlorine monoxide and bromine monoxide. Observations during AASE II define rates of removal of chlorine monoxide attributable to reaction with nitrogen dioxide (produced by photolysis of nitric acid) and to production of hydrochloric acid. Ozone loss ceased in March as concentrations of chlorine monoxide declined. Ozone losses could approach 50 percent if regeneration of nitrogen dioxide were inhibited by irreversible removal of nitrogen oxides (denitrification), as presently observed in the Antarctic, or without denitrification if inorganic chlorine concentrations were to double.     

Diurnal variation of stratospheric chlorine monoxide: a critical test of chlorine chemistry in the ozone layer

This article reports measurements of the column density of stratospheric chlorine monoxide and presents a complete diurnal record of its variation (with 2-hour resolution) obtained from ground-based observations of a millimeter-wave spectral line at 278 gigahertz. Observations were carried out during October and December 1982 from Mauna Kea, Hawaii. The results reported here indicate that the mixing ratio and column density of chlorine monoxide above 30 kilometers during the daytime are approximately 20 percent lower than model predictions based on 2.1 parts per billion of total stratospheric chlorine. The observed day-to-night variation of chlorine monoxide is, however, in good agreement with recent model predictions, confirms the existence of a nighttime reservoir for chlorine, and verifies the predicted general rate of its storage and retrieval. From this evidence, it appears that the chlorine chemistry above 30 kilometers is close to being understood in current stratospheric models. Models based on this chemistry and measured reaction rates predict a reduction in the total stratospheric ozone content in the range of 3 to 5 percent in the final steady state for an otherwise unperturbed atmosphere, although the percentage decrease in the upper stratosphere is much higher.     

Atomic Chlorine and the Chlorine Monoxide Radical in the Stratosphere: Three in situ Observations

Three simultaneous observations of atomic chlorine (Cl) and the chlorine monoxide radical (ClO) are reported which encompass the altitude interval between 25 and 45 kilometers. Together, Cl and ClO form a gas-phase catalytic cycle potentially capable of depleting stratospheric ozone. Observed Cl and C1O densities, although variable, imply that chlorine compounds constitute an important part of the stratospheric ozone budget. The results are compared with recent models of stratospheric photochemistry which have been used as a basis for predicting ozone depletion resulting from fluorocarbon release.