Ozone Depletion Events Research Articles

Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic

Abstract. Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack) to correctly simulate the VOC chemistry of the Arctic, and further evidence that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events is presented.

Halogens and their role in polar boundary-layer ozone depletion

Abstract. During springtime in the polar regions, unique photochemistry converts inert halide salt ions (e.g. Br−) into reactive halogen species (e.g. Br atoms and BrO) that deplete ozone in the boundary layer to near zero levels. Since their discovery in the late 1980s, research on ozone depletion events (ODEs) has made great advances; however many key processes remain poorly understood. In this article we review the history, chemistry, dependence on environmental conditions, and impacts of ODEs. This research has shown the central role of bromine photochemistry, but how salts are transported from the ocean and are oxidized to become reactive halogen species in the air is still not fully understood. Halogens other than bromine (chlorine and iodine) are also activated through incompletely understood mechanisms that are probably coupled to bromine chemistry. The main consequence of halogen activation is chemical destruction of ozone, which removes the primary precursor of atmospheric oxidation, and generation of reactive halogen atoms/oxides that become the primary oxidizing species. The different reactivity of halogens as compared to OH and ozone has broad impacts on atmospheric chemistry, including near complete removal and deposition of mercury, alteration of oxidation fates for organic gases, and export of bromine into the free troposphere. Recent changes in the climate of the Arctic and state of the Arctic sea ice cover are likely to have strong effects on halogen activation and ODEs; however, more research is needed to make meaningful predictions of these changes.

An ozone depletion event in the sub-arctic surface layer over Hudson Bay, Canada

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) program, aircraft flights during April 7–11, 2000 revealed a large area air mass capped below ∼500 m altitude over Hudson Bay, Canada in which ozone was reduced from normal levels of 30–40 ppbv to as low as 0.5 ppbv. From some of the in-situ aircraft measurements, back-trajectory calculations, the tropospheric column of BrO derived from GOME satellite measurements, and results from a regional model, we conclude that the event did not originate from triggering of reactive halogen release in the sub-Arctic region of Hudson Bay but resulted from such an event occurring at higher latitudes over the islands of the northern Canada Archipelago and nearby Arctic Ocean with subsequent transport over a distance of 1,000–1,500 km to Hudson Bay. BrOx remained active during this transport despite considerable changes in the conditions of the underlying surface suggesting that chemical recycling during transport dominated any local halogen input from the surface. If all of the tropospheric column density of BrO is distributed uniformly within the surface layer, then the mixing ratio of BrO derived from the satellite measurements is at least a factor of 2–3 larger than derived indirectly from in situ aircraft measurements of the NO/NO2 ratio.

Competition between Hydrogen Abstraction and Halogen Displacement in the Reaction of Br with CH3I, CH3Br, and CH3Cl

Sudden ozone depletion events in the marine boundary layer are associated with jumps in the CH3Br mixing ratio, but current models of atmospheric chemistry explain neither the ozone depletion nor the CH3Br spikes. We have used ab initio theory to predict the forward and reverse rate constants for the competing hydrogen abstraction and homolytic substitution (SH2) channels of the title reactions. Including the spin-orbit stabilization of the transition structures increases the rate constants by factors between 1.3 and 49. For the atmospherically relevant case of CH3I, our findings suggest that the hydrogen abstraction and homolytic substitution reactions are competitive. The predicted branching fraction to CH3Br is about 13%.

Development and Application of a Novel Immunoassay for Measuring Oxidative DNA Damage in the Environment¶

We developed a facile, cost-effective competitive binding assay for the analysis of 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodGuo) in DNA, using a polyclonal rabbit antiserum raised against an 8-oxodGuo hapten coupled to bovine serum albumin and radiolabeled synthetic ligand containing multiple 8-oxodGuo residues. This radioimmunoassay (RIA) displays a high affinity for 8-oxodGuo in DNA, with a detection limit of ∼1 adduct in 105 bases of DNA. 8-oxodGuo standards for RIA were quantified by high-performance liquid chromatography and electrochemical detection in DNA diluted in methylene blue and exposed to visible light. As an initial application we quantified 8-oxodGuo in dosimeters deployed at increasing depths in the Southern Ocean during the austral spring of the 1998 field season or at the surface at Palmer Station, Antarctica, throughout the 1999 field season. Cyclobutane pyrimidine dimers (CPD) were quantified using an established RIA. We found that the frequency of both photoproducts decreased with depth. However, CPD induction was attenuated at a faster rate than 8-oxodGuo, correlating with the differential attenuation of solar ultraviolet wavelengths in the water column. CPD induction was closely related with ultraviolet-B radiation (UVB) attenuation, whereas the lower attenuation of 8-oxodGuo suggests that oxidative damage is more closely related to ultraviolet-A radiation (UVA) irradiance. The ratio of 8-oxodGuo : CPD was also found to covary with changes in stratospheric ozone concentrations at Palmer Station. These data demonstrate the usefulness of these assays for environmental photobiology and the potential for their use in studying the relative impacts of UVB versus UVA, including ozone depletion events.

Signature of Arctic surface ozone depletion events in the isotope anomaly (Δ<sup>17</sup>O) of atmospheric nitrate

Abstract. We report the first measurements of the oxygen isotope anomaly of atmospheric inorganic nitrate from the Arctic. Nitrate samples and complementary data were collected at Alert, Nunavut, Canada (82°30 ' N, 62°19 ' W) in spring 2004. Covering the polar sunrise period, characterized by the occurrence of severe boundary layer ozone depletion events (ODEs), our data show a significant correlation between the variations of atmospheric ozone (O3) mixing ratios and Δ17O of nitrate (Δ17O(NO−3)). This relationship can be expressed as: Δ17O(NO−3)/‰, =(0.15±0.03)×O3/(nmol mol–1)+(29.7±0.7), with R2=0.70(n=12), for Δ17O(NO−3) ranging between 29 and 35 ‰. We derive mass-balance equations from chemical reactions operating in the Arctic boundary layer, that describe the evolution of Δ17O(NO−3) as a function of the concentrations of reactive species and their isotopic characteristics. Changes in the relative importance of O3, RO2 and BrO in the oxidation of NO during ODEs, and the large isotope anomalies of O3 and BrO, are the driving force for the variability in the measured Δ17O(NO−3) . BrONO2 hydrolysis is found to be a dominant source of nitrate in the Arctic boundary layer, in agreement with recent modeling studies.

Major influence of BrO on the NOx and nitrate budgets in the Arctic spring, inferred from Δ17O(NO3 - ) measurements during ozone depletion events

Environmental context. Ozone depletion events (ODEs) in the Arctic lower atmosphere drive profound changes in the chemistry of nitrogen oxides (NOx) because of the presence of bromine oxide (BrO). These are investigated using the isotopic composition of atmospheric nitrate (NO3–), which is a ubiquitous species formed through the oxidation of nitrogen oxides. Since BrO is speculated to play a key role in the atmospheric chemistry of marine regions and in the free troposphere, our studies contribute to the improvement of the scientific knowledge on this new topic in atmospheric chemistry. Abstract. The triple oxygen isotopic composition of atmospheric inorganic nitrate was measured in samples collected in the Arctic in springtime at Alert, Nunavut and Barrow, Alaska. The isotope anomaly of nitrate (Δ17O = δ17O–0.52δ18O) was used to probe the influence of ozone (O3), bromine oxide (BrO), and peroxy radicals (RO2) in the oxidation of NO to NO2, and to identify the dominant pathway that leads to the production of atmospheric nitrate. Isotopic measurements confirm that the hydrolysis of bromine nitrate (BrONO2) is a major source of nitrate in the context of ozone depletion events (ODEs), when brominated compounds primarily originating from sea salt catalytically destroy boundary layer ozone. They also show a case when BrO is the main oxidant of NO into NO2.

What is causing high ozone at Summit, Greenland?

Causes for the unusually high and seasonally anomalous ozone concentrations at Summit, Greenland were investigated. Surface data from continuous monitoring, ozone sonde data, tethered balloon vertical profiling data, correlation of ozone with the radionuclide tracers 7Be and 210Pb, and synoptic transport analysis were used to identify processes that contribute to sources and sinks of ozone at Summit. Northern Hemisphere (NH) lower free troposphere ozone mixing ratios in the polar regions are ∼20 ppbv higher than in Antarctica. Ozone at Summit, which is at 3212 m above sea level, reflects its altitude location in the lower free troposphere. Transport events that bring high ozone and dry air, likely from lower stratospheric/higher tropospheric origin, were observed ∼40% of time during June 2000. Comparison of ozone enhancements with radionuclide tracer records shows a year-round correlation of ozone with the stratospheric tracer 7Be. Summit lacks the episodic, sunrise ozone depletion events, which were found to reduce the annual, median ozone at NH coastal sites by up to ∼3 ppbv. Synoptic trajectory analyses indicated that, under selected conditions, Summit encounters polluted continental air with increased ozone from central and western Europe. Low ozone surface deposition fluxes over long distances upwind of Summit reduce ozone deposition losses in comparison to other NH sites, particularly during the summer months. Surface-layer photochemical ozone production does not appear to have a noticeable influence on Summit's ozone levels.

Carbonate precipitation in brine – a potential trigger for tropospheric ozone depletion events

Abstract. Tropospheric ozone depletion events (ODEs) at high latitudes were discovered 20 years ago and are attributed to bromine explosions. However, an unresolved issue is the explanation of how the acid-catalyzed reaction cycle is triggered in atmospheric particles derived from alkaline sea water. By simulating the chemistry occuring in polar regions over recently formed sea ice, we can model successfully the transformation of inert sea-salt bromide to reactive bromine monoxide (BrO) and the subsequent ODE when precipitation of calcium carbonate from freezing sea water is taken into account. In addition, we found the temperature dependence of the equilibrium BrCl+Br−↔Br2Cl− to be important.

Chlorine and bromine atom ratios in the springtime Arctic troposphere as determined from measurements of halogenated volatile organic compounds

The concentrations of a suite of halogenated volatile organic compounds (HVOCs) were measured near Barrow, Alaska, from January to April 2005. The HVOCs are produced from the reaction of bromine and chlorine atoms with ethene and propene. During periods of decreasing ozone concentration, increases in the HVOC concentrations allowed for the calculation of the ratio of bromine to chlorine radical concentrations, based on available kinetic data. We use these concentration data to interrogate the chemistry that results in tropospheric ozone depletion in the Arctic, the possible sources of ozone depleting halogen molecules, and the spatial scale in which ozone depletion occurs. We report calculated halogen atom concentration ratios ([Br]/[Cl]) during partial ozone depletion events. The concentration ratio was observed to range from 80 ± 30 to 990 ± 300 when ozone concentrations were above 15 ppb. These data make it clear that chlorine and bromine atom chemistry is active in the Arctic troposphere beginning at twilight, even absent large‐scale ozone depletion, and that the sources of the chlorine atoms are poorly understood.

Observation of a fast ozone loss in the marginal ice zone of the Arctic Ocean

In both polar regions tropospheric ozone regularly decreases during springtime to negligible concentrations in the atmospheric boundary layer. Here we report the observation of a dramatic ozone depletion event in the atmospheric boundary layer in the vicinity of new ice fields in the marginal ice zone (MIZ) of the Arctic Ocean monitored by instrumentation on board the icebreaker RV Polarstern. The ozone mixing ratio decreased from approximately 40 to below 1 ppbV in less than 7 hours. The analyses of backward trajectories and the synoptic conditions indicate that the observed decrease was not caused by the transport of ozone‐free air, but that the ozone depletion occurred locally. Accordingly, bromine oxide, which is formed during the photochemical destruction of ozone in the presence of reactive bromine compounds, was significantly enhanced: Bromine oxide concentrations of approximately 1.8 · 109 molecules cm−3 are retrieved around the same location from SCIAMACHY satellite observations assuming a uniform vertical distribution within the boundary layer. The release of bromine in the MIZ where the new ice formation took place appears to be the most likely explanation for the activation of reactive bromine compounds and subsequent depletion of ozone. Since the conditions were favorable for the formation of frost flowers, we suggest that these are the most likely sources of the reactive bromine. However, contributions of heterogeneous reactions on other surfaces like the highly saline brine on the new ice, aerosols generated from frost flowers, and sea salt aerosols deposited on the snowpack on top of the sea ice cannot be ruled out.

Polar tropospheric ozone depletion events observed in the International Geophysical Year of 1958

Abstract. The Royal Society expedition to Antarctica established a base at Halley Bay, in support of the International Geophysical Year of 1957–1958. Surface ozone was measured during 1958 only, using a prototype Brewer-Mast sonde. The envelope of maximum ozone was an annual cycle from 10 ppbv in January to 22 ppbv in August. These values are 35% less at the start of the year and 15% less at the end than modern values from Neumayer, also a coastal site. This may reflect a general increase in surface ozone since 1958 and differences in summer at the less windy site of Halley, or it may reflect ozone loss on the inlet together with long-term conditioning. There were short periods in September when ozone values decreased rapidly to near-zero, and some in August when ozone values were rapidly halved. Such ozone-loss episodes, catalysed by bromine compounds, became well-known in the Artic in the 1980s, and were observed more recently in the Antarctic. In 1958, very small ozone values were recorded for a week in midwinter during clear weather with light winds. The absence of similar midwinter reductions at Neumayer, or at Halley in the few measurements during 1987, means we must remain suspicious of these small values, but we can find no obvious reason to discount them. The dark reaction of ozone and seawater ice observed in the laboratory may be fast enough to explain them if the salinity and surface area of the ice is sufficiently amplified by frost flowers.

Frost flower influence on springtime boundary‐layer ozone depletion events and atmospheric bromine levels

Springtime boundary layer ozone depletion events have been observed in both the Arctic and Antarctic. It has been suggested that these bromine‐catalyzed depletion events may be caused by bromine released from frost flowers. We have measured the pH and ion concentrations of snow and frost flowers in the Ross Island, Antarctica area and find that if these are representative, frost flowers are unlikely to be a direct source of atmospheric bromine. The pH of the sampled frost flowers is too alkaline to support the release of molecular bromine resulting from the heterogeneous reaction of HOBr with Br ions. It is more likely that frost flowers are a source of aerosol bromine from which gas‐phase bromine can be released through subsequent reactions in aerosol form or on the snow pack.

A role for newly forming sea ice in springtime polar tropospheric ozone loss? Observational evidence from Halley station, Antarctica

Since March 2003, measurements of surface ozone have been made at the British Antarctic Survey Clean Air Sector Laboratory (CASLab) at Halley station in coastal Antarctica. Detailed measurements of boundary layer meteorology, as well as standard meteorological parameters, are also measured at the CASLab. Combining these data allows us to probe the transport pathway of air masses during ozone depletion events (ODEs). ODEs were observed at Halley on several occasions during Antarctic spring 2003. On some occasions, extremely rapid loss of ozone was observed (loss of 16 ppbv in 1 min on one occasion), which was associated with regional‐scale transport. For each such event during 2003, the air mass originated in the southern Weddell Sea, an area of vigorous sea‐ice production. On other occasions the development of the event and its recovery were strongly associated with the build‐up and decline of a stable boundary layer. In these cases, air masses had had recent contact with a nearby open water lead where sea‐ice production is known to occur. The data presented here are entirely consistent with the idea that halogens responsible for ozone loss are derived during new sea‐ice formation from an associated surface such as brine slush or frost flowers.

Isotopic constraints on non‐photochemical sulfate production in the Arctic winter

The oxygen isotopic composition (Δ17O) of non‐seasalt sulfate (NSS) aerosol was measured in samples from Alert, Canada over one year (July 1999–June 2000) and used to quantify the S(IV) oxidants. Measurements of Δ17O in NSS are used to evaluate the relative contributions of O3, H2O2, and OH oxidation leading to the formation of SO42− compared to a model of Feichter et al. (1996). The isotopic values suggest that there is a twofold overestimate of ozone oxidation in the model during winter. The isotopic composition is consistent with 10 to 18% contribution from a non‐photochemical oxidation pathway, likely Fe3+/Mn2+‐catalyzed O2 oxidation, during the dark Arctic winter. Isotopic evidence also invokes a 3 to 10% contribution of a mass dependent oxidant during springtime Arctic ozone depletion events.

Retrieval and characterization of ozone vertical profiles from a thermal infrared nadir sounder

This paper presents the first retrievals and validations of ozone vertical distributions from a set of high‐resolution nadir thermal infrared measurements. These were obtained by the Interferometric Monitor for Greenhouse gases (IMG) instrument, which has operated on board the Japanese ADEOS platform between 1996 and 1997. The Optimal Estimation Method is used for the retrievals, along with a priori profile and covariance matrix built from model climatologies. We compare the retrieved IMG profiles with high‐vertical‐resolution ozone sonde measurements. Therefore we selected a set of IMG spectra collocated to within 3° of longitude and latitude with a representative distribution of ground‐based stations. We demonstrate that thanks to the two to four independent pieces of vertical information contained in the spectroscopic measurements with a maximum sensitivity in the upper troposphere–middle stratosphere, the thermal infrared nadir sounders are able to capture most of the ozone spatial and temporal variations. In particular, the latitudinal variations of the stratospheric ozone maximum are well represented in the retrievals, as are the high ozone concentrations observed in the upper troposphere–lower stratosphere at northern midlatitudes during springtime. Ozone depletion events in the Arctic vortex are also well reproduced. The measurements provide an accurate view of the tropospheric ozone content, except when the latter is very low. A detailed error budget reveals that the major part of the error in the IMG retrieved ozone profile is due to the smoothing of the true profile by the averaging kernel matrix, with additional contributions associated with the measurement noise and the inaccurate knowledge of the temperature profile and of the Instrument Line Shape (ILS).

Photochemical production and loss of organic acids in high Arctic aerosols during long-range transport and polar sunrise ozone depletion events

Abstract Unique daily measurements of water-soluble organics in fine ( 2 μm) aerosols were conducted at Alert in the Canadian Arctic in winter to spring of 1992. They yield insight into photochemical production and loss of organics during long-range transport and ozone depletion events following polar sunrise. Comprehensive analyses of α, ω-dicarboxylic acids (C2–C12), ω-oxocarboxylic acids (C2–C9) and α-dicarbonyls (C2, C3) as well as pyruvic acid and aromatic (phthalic) diacid were conducted using GC and GC/MS techniques. Oxalic (C2) acid was generally the dominant diacid species in both fine and coarse fractions, followed by malonic (C3) and succinic (C4) acids. Concentrations of total diacids in the fine aerosol fraction (0.2–64 ng m−3) were 5–60 times higher than those in the coarse fraction (0.01–3 ng m−3). After polar sunrise in early-March, the total concentration of fine aerosol diacids increased by a factor of 3–5 while the coarse mode did not change significantly. From dark winter to sunlit spring, temporal changes in correlations and ratios of these water-soluble organics to vanadium and sulfate measured simultaneously suggest that atmospheric diacids and related organic compounds are largely controlled by long-range atmospheric transport of polluted air during winter, but they are significantly affected by photochemical production. The latter can occur in sunlight either during transport to the Arctic or during photochemical events associated with surface ozone depletion and bromine chemistry near Alert in spring. Conversion of gaseous precursors to particulate matter via photochemical oxidation was intensified at polar sunrise, resulting in a peak in the ratio of total diacids to V. During ozone depletion events, complex patterns are indicated in photochemical production and loss depending on the diacid compound. Unsaturated (maleic and phthalic) diacids were inversely correlated with particulate Br whereas saturated diacids (C2–C4) positively correlated with particulate Br. These results suggest that Br chemistry associated with ozone depletion leads to degradation of unsaturated diacids and to the production of smaller saturated diacids.

The origin of sea salt in snow on Arctic sea ice and in coastal regions

Abstract. Snow, through its trace constituents, can have a major impact on lower tropospheric chemistry, as evidenced by ozone depletion events (ODEs) in oceanic polar areas. These ODEs are caused by the chemistry of bromine compounds that originate from sea salt bromide. Bromide may be supplied to the snow surface by upward migration from sea ice, by frost flowers being wind-blown to the snow surface, or by wind-transported aerosol generated by sea spray. We investigate here the relative importance of these processes by analyzing ions in snow near Alert and Ny-Ålesund (Canadian and European high Arctic) in winter and spring. Vertical ionic profiles in the snowpack on sea ice are measured to test upward migration of sea salt ions and to seek evidence for ion fractionation processes. Time series of the ionic composition of surface snow layers are investigated to quantify wind-transported ions. Upward migration of unfractionated sea salt to heights of at least 17cm was observed in winter snow, leading to Cl- concentration of several hundred µM. Upward migration thus has the potential to supply ions to surface snow layers. Time series show that wind can deposit aerosols to the top few cm of the snow, leading also to Cl- concentrations of several hundred µM, so that both diffusion from sea ice and wind transport can significantly contribute ions to snow. At Ny-Ålesund, sea salt transported by wind was unfractionated, implying that it comes from sea spray rather than frost flowers. Estimations based on our results suggest that the marine snowpack contains about 10 times more Na+ than the frost flowers, so that both the marine snowpack and frost flowers need to be considered as sea salt sources. Our data suggest that ozone depletion chemistry can significantly enhance the Br- content of snow. We speculate that this can also take place in coastal regions and contribute to propagate ODEs inland. Finally, we stress the need to measure snow physical parameters such as permeability and specific surface area to understand quantitatively changes in snow chemistry.

Peroxyacetyl nitrate photochemistry and interactions with the Arctic surface

Peroxyacetyl nitrate (PAN) is a NOx reservoir compound that has the ability to transport NOx to remote environments, allowing for NOx photochemistry and/or deposition of nitrogen to these clean locations. Measurements of PAN have been made at Alert, Nunavut, and Summit, Greenland, aimed at understanding the impact of PAN chemistry on atmospheric nitrogen in the Arctic. These measurements show concentrations of PAN that are only slowly varying, even during ozone depletion events at polar sunrise, when free radical photochemistry is relatively active. We used a zero‐dimensional photochemical model incorporating known gas‐phase chemistry to simulate the observed behavior of PAN at Alert, Nunavut, and Summit, Greenland. The model simulations suggest a substantial net production rate for PAN over sunlit surfaces, which is inconsistent with the measured gas‐phase concentrations. These observations thus indicate a fundamental problem with our understanding of PAN chemistry in low‐temperature, snow‐covered environments. We explore the possibility that we are missing an important sink for atmospheric PAN above snow‐covered surfaces. If the loss is caused by snowpack deposition, the data result in calculated deposition velocities ranging from 0.05 to 1 cm s−1, which would represent a significant fraction of the unidentified total nitrate input to the snowpack and glacial ice at Summit, Greenland.

Frost flowers on sea ice as a source of sea salt and their influence on tropospheric halogen chemistry

Frost flowers grow on newly‐formed sea ice from a saturated water vapour layer. They provide a large effective surface area and a reservoir of sea salt ions in the liquid phase with triple the ion concentration of sea water. Recently, frost flowers have been recognised as the dominant source of sea salt aerosol in the Antarctic, and it has been speculated that they could be involved in processes causing severe tropospheric ozone depletion events during the polar sunrise. These events can be explained by heterogeneous autocatalytic reactions taking place on salt‐laden ice surfaces which exponentially increase the reactive gas phase bromine (“bromine explosion”). We analyzed tropospheric bromine monoxide (BrO) and the sea ice coverage both measured from satellite sensors. Our model based interpretation shows that young ice regions potentially covered with frost flowers seem to be the source of bromine found in bromine explosion events.