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1.
Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic reaction cycles involving reactive halogens are now recognized to be of main importance for ozone depletion events in the polar boundary layer. We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br2, BrCl, or Cl2 to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H2O2, DMS, Cl2, C2H6, HONO, NO2, and RONO2 was investigated. Cases with elevated mixing ratios of HCHO, H2O2, DMS, Cl2, and HONO induced a shift in bromine speciation from Br / BrO to HOBr/HBr, while high mixing ratios of C2H6 induced a shift from HOBr/HBr to Br/BrO. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). For all NOy species studied (HONO, NO2, RONO2) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NOx. The production of HNO3 led to the acid displacement of HCl, and the release of chlorine out of salt aerosol (Cl2 or BrCl) increased.  相似文献   

2.
Reactive halogen species (RHS = X, XO, HOX, OXO; X = Cl, Br, I) are known to have an important influence on the chemistry in the polar boundary layer (BL), where they are responsible for ozone depletion events in spring. Recent field campaigns at Mace Head, Ireland, and the Dead Sea, Israel, identified for the first time iodine oxide (IO) at mixing ratios of up to 6.6 ppt and 90 ppt bromine oxide (BrO), respectively, by DOAS also at lower latitudes. These results intensified the discussion about the role of the RHS in the mid-latitude BL.Photochemical box model calculations show that the observed IO mixing ratios can destroy ~0.45 ppb ozone per hour. This is comparable to the rates of the known O3-loss processes in the boundary layer. The model studies also reveal that IO, at these levels, has a strong influence on the BL photochemistry, increasing the OH/HO2- and the NO2/NO - ratios. In combination these changes lead to a reduction of the photochemical ozone formation, which - in addition - reduces ozone mixing ratios by up to 0.15 ppb/h.The studies for the Dead Sea case give no information on the heterogeneous process responsible for the bromine release, but they show that a total of 2 – 4 ppb of total bromine have to be released to explain the observed complete depletion of 60 ppb ozone in 2 – 3 hours.  相似文献   

3.
This study examines the processes controlling the diurnal variability of ozone (O3) in the marine boundary layer of the Kwajalein Atoll, Republic of the Marshall Islands (latitude 8° 43′ N, longitude 167° 44′ E), during July to September 1999. At the study site, situated in the equatorial Pacific Ocean, O3 mixing ratios remained low, with an overall average of 9–10 parts per billion on a volume basis (ppbv) and a standard deviation of 2.5 ppbv. In the absence of convective storms, daily O3 mixing ratios decreased after sunrise and reached minimum during the afternoon in response to photochemical reactions. The peak-to-peak amplitude of O3 diurnal variation was approximately 1–3 ppbv. During the daytime, O3 photolysis, hydroperoxyl radicals, hydroxyl radicals, and bromine atoms contributed to the destruction of O3, which explained the observed minimum O3 levels observed in the afternoon. The entrainment of O3-richer air from the free troposphere to the local marine boundary layer provided a recovery mechanism of surface O3 mixing ratio with a transport rate of 0.04 to 0.2 ppbv per hour during nighttime. In the presence of convection, downward transport of O3-richer tropospheric air increased surface O3 mixing ratios by 3–12 ppbv. The magnitude of O3 increase due to moist convection was lower than that observed over the continent (as high as 20–30 ppbv). Differences were ascribed to the higher O3 levels in the continental troposphere and weaker convection over the ocean. Present results suggest that moist convection plays a role in surface-level O3 dynamics in the tropical marine boundary layer.  相似文献   

4.
Halogens in the atmosphere chemically destroy ozone. In the troposphere, bromine has higher ozone destruction efficiency than chlorine and is the halogen species with the widest geographical spread of natural sources. We investigate the relative strength of various sources of reactive tropospheric bromine and the influence of bromine on tropospheric chemistry using a 6-year simulation with the global chemistry transport model MOZART4. We consider the following sources: short-lived bromocarbons (CHBr3, CH2BrCl, CHBr2Cl, CHBrCl2, and CH2Br2) and CH3Br, bromine from airborne sea salt particles, and frost flowers and sea salt on or in the snowpack in polar regions. The total bromine emissions in our simulations add up to 31.7 Gmol(Br)/yr: 63 % from polar sources, 24.6 % from short-lived bromocarbons and 12.4 % from airborne sea salt particles. We conclude from our analysis that our global bromine emission is likely to be on the lower end of the range, because of too low emissions from airborne sea salt. Bromine chemistry has an effect on the oxidation capacity of the troposphere, not only due to its direct influence on ozone concentrations, but also by reactions with other key chemical species like HO x and NO x . Globally, the impact of bromine chemistry on tropospheric O3 is comparable to the impact of gas-phase sulfur chemistry, since the inclusion of bromine chemistry in MOZART4 leads to a decrease of the O3 burden in the troposphere by 6 Tg, while we get an increase by 5 Tg if gas-phase sulfur chemistry is switched off in the standard model. With decreased ozone burden, the simulated oxidizing capacity of the atmosphere decreases thus affecting species associated with the oxidation capacity of the atmosphere (CH3OOH, H2O2).  相似文献   

5.
The pre-melt energy budget of a snowpack on landfast first-year sea ice at a remote site in the Canadian Arctic Archipelago was analyzed. Over a 19-day period, the total heat conducted into the snowpack at the snow–sea-ice interface was the largest single energy transfer to the snowpack, while each of the turbulent heat fluxes removed comparable amounts of energy. The total energy transferred from the snowpack (∑Q?≈??7027?kJ?m?2) should have reduced its temperature; however, the opposite occurred. The snowpack’s temperature at both the 7 and 13?cm depths increased over the pre-melt period. The total change in internal energy and latent heat of the snowpack (ΔUsnowpack), derived from 15-minute changes in the snowpack’s temperature over the pre-melt period, was approximately 672?kJ?m?2. Closure of the energy budget was not achieved for either the daily or the total pre-melt period. The terms of the energy budget were determined independently; thus, the failure to close the energy budget was the result of the accumulation of errors associated with all the terms. However, for snow on first-year sea ice, the parameterization of the salinity and temperature dependence of the “specific heat” of the basal layer of the snowpack was likely the primary source of error. The snowpack plays a central role in the transfer of energy across the ocean–sea-ice–atmosphere interface, but an adequate method for modelling the evolution of snow on Arctic sea ice including the energy budget, which determines the warming rate and subsequent melt rate of the snow, has yet to be developed.  相似文献   

6.
NOx在雪-气之间的交换能够影响到极地大气边界层的大气成分和大气化学过程,增强极地大气边界层的氧化性,并可能影响对冰雪大气成分记录的解释。近年来,人们认识到冰雪在光照下释放NOx是极地大气边界层NOx的一个重要来源。从以下几方面对大气边界层NOx的冰雪来源进行综述：NOx冰雪来源的观测和实验证据、冰雪释放NOx的机制和影响参数、极地NOx浓度和通量以及极地冰雪NOx化学过程对环境的影响。近年来,笔者已在处于北半球中纬度的青藏高原观测到冰雪表面光照下释放出比极地高1个量级浓度水平的NOx,因此需更深入的科学研究揭示其对青藏高原大气氧化性的影响。  相似文献   

7.
The occurrence of CH2Br2, CH2BrCl, CH2I2, CH2ClI, CHBr3, CHBr2Cl, CHBrCl2 and CH2Br-CH2Br in marine air and seawater from various sampling sites in the region of the Atlantic Ocean have been measured and evaluated. A correlation exists between high concentrations of these compounds in air and in water and the occurrence of algae at the coastlines of various islands (The Azores, Bermuda, Tenerife) and in a region of high bioactivity in the Atlantic Ocean near the West African coast.Real-world air-water concentration ratios derived from measurements in the open ocean identify the water mass near the African coast with its high primary production as a source for the above compounds. This region has to be discussed also as a possible secondary source in which CHBr2Cl, CHBrCl2 and CH2ClI can be formed via halogen-exchange. Whether CHBrCl2 and CH2ClI under-go transformation to CHCl3 and CH2Cl2, respectively, is open to further investigations.Direct photolysis and degradation by OH-radicals lead to a gradient in the marine troposphere with reduced concentrations for the organobromides above the tropospheric boundary layer.Partly presented at: 2nd International Symposium on Biosphere-Atmosphere Exchange, Mainz, F.R.Germany, 16–21 March, 1986. Part VII: Chemosphere 15 (1986) 429–436.  相似文献   

8.
Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 105molecules cm-3 averaged over 24 hours were calculated due to lossof OH and HO2 in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.  相似文献   

9.
Chemical amplification, CA, a method commonly used for the detection of peroxy radicals, HO2 and RO2, was found to be sensitive towards ClOx (Cl+ClO+OClO) as well. ClOx is reduced by NO to Cl atoms which react with carbon monoxide in the presence of O2. The reaction sequence thus initiated oxidizes CO to CO2 and NO to NO2, with a chain length of 300 ± 60. This allows the atmospheric ClOx content to be measured under ambient conditions with a detection limit of better than 1 ppt. In parallel peroxy radicals are indicated with a chain length of 160 ± 15. Chemical amplification is not specific and does not indicate which radical chain it is seeing. Identification relies solely on plausibility. During the ARCtic Tropospheric Ozone Chemistry (ARCTOC) campaign in spring 1995 and 1996 the CA technique was used at Ny-Ålesund. ClOx at mixing ratios of up to 2 ppt were found in the boundary layer under certain conditions. The low concentrations of ClOx indicate that the arctic boundary ozone depletion is mainly driven by bromine.  相似文献   

10.
Abstract

Arctic haze has been attributed to industrial pollution released at mid‐latitudes. Our current understanding has been pieced together from routine meteorological data, ground‐based air chemistry observations and limited aircraft measurements. This study investigates the relationship between synoptic boundary‐layer meteorology and the composition of the near‐surface atmosphere during the polar sunrise at Alert, N.W.T. A secondary objective is to characterize the influence of local activity on the atmospheric composition at a site for a new baseline monitoring station and at a location where aerosol chemistry and grab‐flask samples for CO2 have been made for many years. Detailed measurements of the vertical distribution of aerosols were obtained from an upward‐looking lidar to complement the ground‐based measurements. Meteorological profiles of the near‐surface boundary layer were obtained from both free‐flying and tethered balloons. Near‐surface measurements were made of aerosol physical and chemical properties, O3, NO2, NO/NOx, Peroxyacetylnitrate (PAN) and hydrocarbons.

The study period was characterized by prolonged periods with strong surface inversions, which were broken up occasionally by intrusions of cold air into the warmer air aloft. Lidar observations showed that ice crystals often accompanied aerosols and were responsible for reducing visibility below 30–40 km. There was a strong correlation between aerosol mass in the diameter size range 0.15 to 1.5 μm and total SO4 = . PAN found at concentrations of about 200 ppt(v) was the main carrier of atmospheric nitrogen. Aerosol trace elements were divisible into anthropogenic soil, mixed soil/anthropogenic sea salt and halogens. Vertical transport in the surface boundary layer, as regulated by the strength of the surface radiation inversion, may play an important role in influencing the chemical composition of the air at the ground. The location of the new baseline monitoring laboratory was found to be generally windier and warmer than the lower altitude weather station, and the influence of local activity was found to be minimal.  相似文献   

11.
The heat budget of the upper Arctic Ocean is examined in an ensemble of coupled climate models under idealised increasing CO2 scenarios. All of the experiments show a strong amplification of surface air temperatures but a smaller increase in sea surface temperature than the rest of the world as heat is lost to the atmosphere as the sea-ice cover is reduced. We carry out a heat budget analysis of the Arctic Ocean in an ensemble of model runs to understand the changes that occur as the Arctic becomes ice free in summer. We find that as sea-ice retreats heat is lost from the ocean surface to the atmosphere contributing to the amplification of Arctic surface temperatures. Furthermore, heat is mixed upwards into the mixed layer as a result of increased upper ocean mixing and there is increased advection of heat into the Arctic as the ice edge retreats. Heat lost from the upper Arctic Ocean to the atmosphere is therefore replenished by mixing of warmer water from below and by increased advection of warm water from lower latitudes. The ocean is therefore able to contribute more to Arctic amplification.  相似文献   

12.
At Amphitrite Point, ozone (O3) mixing ratios are observed to drop steadily to 5–15?ppb over a period of 12 hours or less with a frequency approaching one event per week (with highest frequencies occurring in summer and fall). Analysis of 47 such O3 depletion events reveals that low O3 episodes are a predominantly nocturnal phenomenon associated with anticyclonic conditions characterized by light onshore or alongshore winds and an absence of fog and mist. Back-trajectories show air carried to the Amphitrite Point Observatory (APO) during depletion events remains in the marine boundary layer and is not brought to the surface from aloft. There is no strong correlation with other “criteria” pollutants (CO, NOx, SO2, PM2.5) that might be indicative of a mechanism for O3 destruction linked to human, terrestrial, or marine pollutant sources. However, CO2 mixing ratios are observed to increase, coincident with O3 depletion. Together, these results point to a natural marine boundary layer phenomenon in which O3 destruction dominates O3 production and/or replenishment by vertical mixing. While there are several candidate mechanisms, the conditions for O3 depletion (and CO2 buildup) to occur are set by meteorology and, in particular, development of a stable marine boundary layer in which vertical mixing is suppressed. Support for this interpretation is provided by simultaneous increases in CO2 in the stable marine boundary that are indicative of an important role played by marine biogenic processes (respiration). Future research should be directed at elucidating the chemical mechanisms responsible for O3 destruction in the coastal zone, which means that there would be a need for a much broader range of measurements at APO (including halogenated species) as well as offshore measurements of both chemical and marine boundary layer meteorological variables.  相似文献   

13.
Measurements of NOx (NO +NO2) and the sum of reactive nitrogenconstituents, NOy, were made near the surface atAlert (82.5°N), Canada during March and April1998. In early March when solar insolation was absentor very low, NOx mixing ratios were frequentlynear zero. After polar sunrise when the sun was abovethe horizon for much or all of the day a diurnalvariation in NOx and NOy was observed withamplitudes as large as 30–40 pptv. The source ofactive nitrogen is attributed to release from the snowsurface by a process that is apparently sensitized bysunlight. If the source from the snowpack is a largescale feature of the Arctic then the diurnal trendsalso require a competing process for removal to thesurface. From the diurnal change in the NO/NO2ratio, mid-April mixing ratios for the sum of peroxyand halogen oxide radicals of 10 pptv werederived for periods when ozone mixing ratios were inthe normal range of 30–50 ppbv. Mid-day ozoneproduction and loss rates with the active nitrogensource were estimated to be 1–2 ppbv/day and in nearbalance. NOy mixing ratios which averaged only295±66 pptv do not support a large accumulation inthe high Arctic surface layer in the winter and springof 1998. The small abundance of NOy relative tothe elevated mixing ratios of other long-livedanthropogenic constituents requires that reactivenitrogen be removed to the surface during transport toor during residence within the high Arctic.  相似文献   

14.
Thirty-six aerosol filter samples collected in tropospheric Arctic haze layers, in the stratosphere, and in the marine boundary layer during the 1983 Arctic Gas and Aerosol Sampling Program were analyzed for trace elements using instrumental neutron activation analysis. Average crustal dust concentrations were 540 ng/m3 and 330 ng/m3 for samples collected in Arctic haze over the North American and Norwegian Arctic, respectively. An average marine salt concentration of 120 ng/m3 was obtained for haze samples collected above the marine boundary layer on both sides of the Arctic.Meteorological and wind trajectory information were used to identify specific haze transport pathways, which brought relatively unmixed aerosol from the central Soviet Union into the AGASP sampling areas. Results from individual filters collected within these transport zones are discussed, with emphasis on certain trace metal ratos which have been proposed by other researchers as discriminators of aerosols from different source regions. Our aircraft-collected data are compared with previously-collected ground-based measurements, and show reasonably good agreement for most tracer elements and ratios. Specifically, we have determined the As/Sb ratio tracer, named by other researchers as the most effective elemental discriminator of aerosol from the central Soviet Union, to be approximately 5–6. This relatively high tracer value is consistent with previous ground-based findings. A significantly lower V/Sb ratio was observed throughout this study, possibly indicating a change in the source signature.  相似文献   

15.
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, NO x , 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 NO x 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.  相似文献   

16.
High-frequency measurements of dibromomethane (CH2Br2) and bromoform (CHBr3) at Hateruma Island, in the subtropical East China Sea, were performed using automated preconcentration gas chromatography/mass spectrometry. Their baseline concentrations, found in air masses from the Pacific Ocean, were 0.65 and 0.26 ppt, respectively, in summer and 1.08 and 0.87 ppt, respectively, in winter. Air masses transported from Southeast Asia were rich in bromocarbons, suggesting strong emissions in this area. The passage of cold fronts from the Asian continent was associated with sharp increases in observed concentrations of bromocarbons derived from coastal regions of the continent. Comparison of the relationships between [CH2Br2]/[CHBr3] and [CHBr3] in the Hateruma Island data with those in monthly mean data from 14 globally distributed U.S. National Oceanic and Atmospheric Administration ground stations suggested that these gases are produced primarily from a common process on a global scale.  相似文献   

17.
Observations from the summer Arctic Ocean Experiment 2001 (AOE-2001) are analysed with a focus on the interactions between mesoscale and boundary-layer dynamics. Wavelet analyses of surface-pressure variations show daylong periods with different characteristics, some featuring episodes of pronounced high-frequency surface-pressure variability, here hypothesized to be caused by trapped gravity waves. These episodes are accompanied by enhanced boundary-layer turbulence and an enhanced spectral gap, but with only minor influence on the surface stress. During these episodes, mesoscale phenomena were often encountered and usually identified as front-like features in the boundary layer, with a peak in drizzle followed by changing temperature. These phenomena resemble synoptic fronts, though they are generally shallow, shorter-lasting, have no signs of frontal clouds, and do not imply a change in air mass. Based on this analysis, we hypothesize that the root cause of the episodes with high-frequency surface-pressure variance are shallow, mesoscale fronts moving across the pack ice. They may be formed due to local-to-regional horizontal contrasts, for example, between air with different lifetimes over the Arctic or with perturbations in the cloud field causing differential cooling of the boundary layer. Thermal contrasts sharpen as the air is transported with the mean flow. The propagating mesoscale fronts excite gravity waves, which affect the boundary-layer turbulence and also seem to favour entrainment of free tropospheric air into the boundary layer.  相似文献   

18.
Simultaneous observations of several chlorine source gases, as well asHCl and ClO, have been performed in the Arctic stratosphere on 1 and 9February 1994, using balloon-borne instrumentation as a contribution toSESAME (Second European Stratospheric Arctic and Mid latitude Experiment).The observed mixing ratios of HCl and N2O show a clearanticorrelation. No severe loss of HCl was observed inside the vortex duringour measurement. These measurements showed that during this period at 20 kmand above, HCl was either in excess, or at least as abundant, asClONO2 and comprised between 50 and 70% of theavailable chlorine, Cly. On 1 February, measurements were madeinside the polar vortex. The air mass sampled on this day showed a clearsignature of diabatic descent, and also enhanced levels of ClO with amaximum of 230 pptv at 22.5 km. A 10 day backward trajectory analysis showedthat these air masses had passed a large region of low temperatures a fewhours prior to the measurement. Temperatures along the back trajectory atthe 475 K and 550 K levels (20.1 and 23.7 km respectively) were cold enoughfor heterogeneous chlorine activation to occur, in agreement with theobserved elevated ClO mixing ratios.  相似文献   

19.
Using the chemical composition of snow and ice of a central Greenland ice core, we have investigated changes in atmospheric HNO3 chemistry following the large volcanic eruptions of Laki (1783), Tambora (1815) and Katmai (1912). The concentration of several cations and anions, including SO 4 2– and NO 3 – , were measured using ion chromatography. We found that following those eruptions, the ratio of the concentration of NO 3 – deposited during winter to that deposited during summer was significantly higher than during nonvolcanic periods. Although we cannot rule out that this pattern originates from snow pack effects, we propose that increased concentrations of volcanic H2SO4 particles in the stratosphere may have favored condensation and removal of HNO3 from the stratosphere during Arctic winter. In addition, this pattern might have been enhanced by slower formation of HNO3 during summer, caused by direct consumption of OH through oxidation of volcanic SO2.  相似文献   

20.
Gas phase elemental mercury (Hg°) was measured aboard the NASA DC-8 research aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign conducted in spring 2008 primarily over the North American Arctic. We examined the vertical distributions of Hg° and ozone (O3) together with tetrachloroethylene (C2Cl4), ethyne (C2H2), and alkanes when Hg°- and O3-depleted air masses were sampled near the surface (<1 km). This study suggests that Hg° and O3 depletions commonly occur over linear distances of ~20–200 km. Horizontally there was a sharp decreasing gradient of ~100 ppqv in Hg° over <10 km in going from the bay near Ellesmere Island to the frozen open ocean. There was a distinct land-ocean difference in the vertical thickness of the Hg°-depleted layer – being variable but around a few 100 meters over the ocean whereas occurring only very near the surface over land. Data support that atmospheric mercury depletion events are driven by Hg° reactions with halogen atoms. Derived from data collected aboard the DC-8, we present mathematical expressions giving the rates of Hg° and O3 depletions as a function of the radical concentrations. These relationships can be a useful metric to evaluate models that attempt to reproduce springtime Arctic Hg° and/or O3 depletion events, and they can also be employed to obtain order-of-magnitude estimates of radical concentrations and the ratio [Br]/[Cl].  相似文献   

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