Reaction of chlorine nitrate with hydrogen chloride and water at antarctic stratospheric temperatures

Laboratory studies of heterogeneous reactions important for ozone depletion over Antarctica are reported. The reaction of chlorine nitrate (ClONO(2)) with H(2)0 and hydrogen chloride (HCl) on surfaces that simulate polar stratospheric clouds [ice and nitric acid (HNO(3))-ice and sulfuric acid] are studied at temperatures relevant to the Antarctic stratosphere. The reaction of ClONO(2) on ice and certain mixtures of HNO(3) and ice proceeded readily. The sticking coefficient of ClONO(2) on ice of 0.009 +/- 0.002 was observed. A reaction produced gas-phase hypochlorous acid (HOCl) and condensed-phase HNO(3); HOC1 underwent a secondary reaction on ice producing dichlorine monoxide (Cl(2)O). In addition to the reaction with H(2)0, ClONO(2) reacted with HCl on ice to form gas-phase chlorine (Cl(2)) and condensed-phase HNO(3.) Essentially all of the HCl in the bulk of the ice can react with ClONO(2) on the ice surface. The gaseous products of the above reactions, HOCl, Cl(2)0, and Cl(2), could readily photolyze in the Antarctic spring to produce active chlorine for ozone depletion. Furthermore, the formation of condensed-phase HNO(3) could serve as a sink for odd nitrogen species that would otherwise scavenge the active chlorine.     

Observations of Stratospheric NO2 and O3 at Thule, Greenland

Scattered sunlight and direct light from the moon was used in two wavelength ranges to measure the total column abundances of stratospheric ozone(O(3)) and nitrogen dioxide (NO(2)) at Thule, Greenland (76.5 degrees N), during the period from 29 January to 16 February 1988. The observed O(3) column varied between about 325 and 400 Dobson units, and the lower values were observed when the center of the Arctic polar vortex was closest to Thule. This gradient probably indicates that O(3) levels decrease due to dynamical processes near the center of the Arctic vortex and should be considered in attempts to derive trends in O(3) levels. The observed NO(2) levels were also lowest in the center of the Arctic vortex and were sometimes as low as 5 x 10(14) molecules per square centimeter, which is even less than comparable values measured during Antarctic spring, suggesting that significant heterogeneous photochemistry takes place during the Arctic winter as it does in the Antarctic.     

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.     

Interhemispheric Differences in Polar Stratospheric HNO3, H2O, CIO, and O3

Simultaneous global measurements of nitric acid (HNO(3)), water (H(2)O), chlorine monoxide (CIO), and ozone (O(3)) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO(3) was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H(2)O after mid-July. By mid-August, near the time of peak CIO, abundances of gas-phase HNO(3) and H(2)O were extremely low. The concentrations of HNO(3) and H(2)O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO(3) or H(2)O were observed in the 1992-1993 Arctic winter vortex. Although CIO was enhanced over the Arctic as it was over the Antarctic, Arctic O(3) depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone "hole" is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.     

Heterogeneous reaction probabilities, solubilities, and the physical state of cold volcanic aerosols

On 19 January 1992, heterogeneous loss of HNO(3), ClNO(3), and HCl was observed in part of the Mount Pinatubo volcanic cloud that had cooled as a result of forced ascent. Portions of the volcanic cloud froze near 191 kelvin. The reaction probability of ClNO(3) and the solubility of HNO(3) were close to laboratory measurements on liquid sulfuric acid. The magnitude of the observed loss of HCl suggests that it underwent a heterogeneous reaction. Such reactions could lead to substantial loss of HCl on background sulfuric acid particles and so be important for polar ozone loss.     

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.     

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.     

Melting of H2SO4·4H2O Particles upon Cooling: Implications for Polar Stratospheric Clouds

Polar stratospheric clouds (PSCs) are important for the chemical activation of chlorine compounds and subsequent ozone depletion. Solid PSCs can form on sulfuric acid tetrahydrate (SAT) (H2SO4·4H2O) nuclei, but recent laboratory experiments have shown that PSC nucleation on SAT is strongly hindered. A PSC formation mechanism is proposed in which SAT particles melt upon cooling in the presence of HNO3 to form liquid HNO3-H2SO4-H2O droplets 2 to 3 kelvin above the ice frost point. This mechanism offers a PSC formation temperature that is defined by the ambient conditions and sets a temperature limit below which PSCs should form.     

Metastable phases in polar stratospheric aerosols

Phase changes in stratospheric aerosols were studied by cooling a droplet of sulfuric acid (H(2)SO(4)) in the presence of nitric acid (HNO(3)) and water vapor. A sequence of solid phases was observed to form that followed Ostwald's rule for phase nucleation. For stratospheric partial pressures at temperatures between 193 and 195 kelvin, a metastable ternary H(2)SO(4)-HNO(3) hydrate, H(2)SO(4) . HNO(3) . 5H(2)O, formed in coexistence with binary H(2)SO(4) . kH(2)O hydrates (k = 2, 3, and 4) and then transformed to nitric acid dihydrate, HNO(3) . 2H(2)O, within a few hours. Metastable HNO(3) . 2H(2)O always formed before stable nitric acid trihydrate, HNO(3).3H(2)O, under stratospheric conditions and persisted for long periods. The formation of metastable phases provides a mechanism for differential particle growth and sedimentation of HNO(3) from the polar winter stratosphere.     

Terrestrial ages of four allan hills meteorites: consequences for antarctic ice

The terrestrial ages of three Allan Hills meteorites are between 3 x 10(4) and 3 x 10(5) years and one is (1.54(-0.28)(+0.14)) x 10(6) years old. The Antarctic ice sheet is therefore older than (1.54(-0.28)(+0.14)) x 10(6) years and the meteorite accumulation process at Allan Hills probably began between 3 x 10(4) and 3 x 10(5)years ago.     

Clathrate hydrates of air in antarctic ice

Measurements of the dissociation pressure of nitrogen hydrate and oxygen hydrate show that the clathrate hydrate of air with the formula (N(2), O(2)) 6H(2)O should exist below about 800 meters in the Antarctic ice sheet. This accounts for the disappearance of gas bubbles at depths greater than 1200 meters. The hydrate should exist from this depth to prise 0.06 percent of the ice.     

A Reevaluation of the Ozone Budget with HALOE UARS Data: No Evidence for the Ozone Deficit

Recently, additional ozone production mechanisms have been proposed to resolve the ozone deficit problem, which arises from greater ozone destruction than production in several photochemical models of the upper stratosphere and lower mesosphere. A detailed ozone model budget analysis was performed with simultaneous observations of O(3), HCl, H(2)O, CH(4), NO, and NO(2) from the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) under conditions with the strongest photochemical control of ozone. The results indicate that an ozone deficit may not exist. On the contrary, the use of currently recommended photochemical parameters leads to insufficient ozone destruction in the model.     

Nightglow in the upper atmosphere of Mars and implications for atmospheric transport

We detected light emissions in the nightside martian atmosphere with the SPICAM (spectroscopy for the investigation of the characteristics of the atmosphere of Mars) ultraviolet (UV) spectrometer on board the Mars Express. The UV spectrum of this nightglow is composed of hydrogen Lyman alpha emission (121.6 nanometers) and the gamma and delta bands of nitric oxide (NO) (190 to 270 nanometers) produced when N and O atoms combine to produce the NO molecule. N and O atoms are produced by extreme UV photodissociation of O2, CO2, and N2 in the dayside upper atmosphere and transported to the night side. The NO emission is brightest in the winter south polar night because of continuous downward transport of air in this region at night during winter and because of freezing at ground level.     

Vapor pressures of solid hydrates of nitric Acid: implications for polar stratospheric clouds

Thermodynamic data are presented for hydrates of nitric acid: HNO(3).H(2)O, HNO(3).2H(2)O, HNO(3).3H(2)O, and a higher hydrate. Laboratory data indicate that nucleation and persistence of metastable HNO(3).2H(2)O may be favored in polar stratospheric clouds over the slightly more stable HNO(3).3H(2)O. Atmospheric observations indicate that some polar stratospheric clouds may be composed of HNO(3).2H(2)O and HNO(3).3H(2)O. Vapor transfer from HNO(3).2H(2)O to HNO(3).3H(2)O could be a key step in the sedimentation of HNO(3), which plays an important role in the depletion of polar ozone.     

Observations of ozone formation in power plant plumes and implications for ozone control strategies

Data taken in aircraft transects of emissions plumes from rural U.S. coal-fired power plants were used to confirm and quantify the nonlinear dependence of tropospheric ozone formation on plume NO(x) (NO plus NO(2)) concentration, which is determined by plant NO(x) emission rate and atmospheric dispersion. The ambient availability of reactive volatile organic compounds, principally biogenic isoprene, was also found to modulate ozone production rate and yield in these rural plumes. Differences of a factor of 2 or greater in plume ozone formation rates and yields as a function of NO(x) and volatile organic compound concentrations were consistently observed. These large differences suggest that consideration of power plant NO(x) emission rates and geographic locations in current and future U.S. ozone control strategies could substantially enhance the efficacy of NO(x) reductions from these sources.     

Atmospheric CO2: principal control knob governing Earth's temperature

Ample physical evidence shows that carbon dioxide (CO(2)) is the single most important climate-relevant greenhouse gas in Earth's atmosphere. This is because CO(2), like ozone, N(2)O, CH(4), and chlorofluorocarbons, does not condense and precipitate from the atmosphere at current climate temperatures, whereas water vapor can and does. Noncondensing greenhouse gases, which account for 25% of the total terrestrial greenhouse effect, thus serve to provide the stable temperature structure that sustains the current levels of atmospheric water vapor and clouds via feedback processes that account for the remaining 75% of the greenhouse effect. Without the radiative forcing supplied by CO(2) and the other noncondensing greenhouse gases, the terrestrial greenhouse would collapse, plunging the global climate into an icebound Earth state.     

黔苦2号苦荞高产栽培数学模型研究

[目的]为黔苦2号高产栽培提供理论依据。[方法]以黔苦2号为试材,根据播种量(x1)、氮肥施用量(x2)、磷肥施用量(x3)、钾肥施用量(x4)对黔苦2号产量的影响,建立了相应的数学模型,并进行模拟寻优。[结果]荞麦产量与各因子间的回归方程为:y=2 155.60-94.03x1-76.73x12-53.25x22-65.18x32-68.29x42。通过模拟研究,黔苦2号在试验条件下的最高产量为2 172.90 kg/hm2。其相应的播种量、纯N、P2O5、K2O分别为41.25、60.00、195.00和52.50 kg/hm2。产量≥2 025.00 kg/hm2的相应的播种量、N、P2O5、K2O为:45.36~52.14、52.50~67.50、173.16~216.84和46.62~58.38 kg/hm2。各因素对黔苦2号产量的影响为播种量>磷肥>钾肥>氮肥;不同因素的互作表现为播种量氮肥互作>播种量钾肥互作>磷钾肥互作>氮磷肥互作>氮钾肥互作>播种量磷肥互作。[结论]建立了黔苦2号高产栽培的数学模型,并可用于指导生产。     

容城县冬小麦施肥模型及其效应分析

采用"3414"回归设计模型进行田间试验,初步建立了容城县高、中、低3种产田冬小麦产量与氮、磷、钾肥的效应方程,求得不同产田各养分的最佳施用量。结果表明:不同产田的施肥效应方程不同,其中,高产田为Y=4 392.388 0+8.037 3N+6.739 9P+6.463 2K-0.025 3N2-0.035 79P2-0.025 7K2+0.027 5NP+0.010 2NK-0.006 1PK,中产田为Y=4 137.239 7+7.310 7N+4.935 5P+7.333 8K-0.028 0N2-0.020 5P2-0.030 7K2+0.023 3NP+0.014 3NK-0.011 7PK,低产田为Y=3 438.261 0+7.198 1N+6.052 5P+9.925 5K-0.030 5N2-0.023 5P2-0.037 4K2+0.029 0NP+0.017 2NK-0.027 7PK;经济最佳施肥量为纯N 145~185 kg/hm2、P2O5109~119 kg/hm2、K2O 82~86 kg/hm2。目前磷钾素已不是限制容城县小麦产量的主要因子,该区施肥措施应为保障氮肥供应、控制磷钾肥投入。     

Variability in nocturnal nitrogen oxide processing and its role in regional air quality

Nitrogen oxides in the lower troposphere catalyze the photochemical production of ozone (O3) pollution during the day but react to form nitric acid, oxidize hydrocarbons, and remove O3 at night. A key nocturnal reaction is the heterogeneous hydrolysis of dinitrogen pentoxide, N2O5. We report aircraft measurements of NO3 and N2O5, which show that the N2O5 uptake coefficient, g(N2O5), on aerosol particles is highly variable and depends strongly on aerosol composition, particularly sulfate content. The results have implications for the quantification of regional-scale O3 production and suggest a stronger interaction between anthropogenic sulfur and nitrogen oxide emissions than previously recognized.     

Removal of Stratospheric O3 by Radicals: In Situ Measurements of OH, HO2, NO, NO2, ClO, and BrO

Simultaneous in situ measurements of the concentrations of OH, HO(2), ClO, BrO, NO, and NO(2) demonstrate the predominance of odd-hydrogen and halogen free-radical catalysis in determining the rate of removal of ozone in the lower stratosphere during May 1993. A single catalytic cycle, in which the rate-limiting step is the reaction of HO(2) with ozone, accounted for nearly one-half of the total O(3) removal in this region of the atmosphere. Halogen-radical chemistry was responsible for approximately one-third of the photochemical removal of O(3); reactions involving BrO account for one-half of this loss. Catalytic destruction by NO(2), which for two decades was considered to be the predominant loss process, accounted for less than 20 percent of the O(3) removal. The measurements demonstrate quantitatively the coupling that exists between the radical families. The concentrations of HO(2) and ClO are inversely correlated with those of NO and NO(2). The direct determination of the relative importance of the catalytic loss processes, combined with a demonstration of the reactions linking the hydrogen, halogen, and nitrogen radical concentrations, shows that in the air sampled the rate of O(3) removal was inversely correlated with total NOx, loading.