Becky Alexander

A large atomic chlorine source inferred from mid-continental reactive nitrogen chemistry.

Halogen atoms and oxides are highly reactive and can profoundly affect atmospheric composition. Chlorine atoms can decrease the lifetimes of gaseous elemental mercury and hydrocarbons such as the greenhouse gas methane. Chlorine atoms also influence cycles that catalytically destroy or produce tropospheric ozone, a greenhouse gas potentially toxic to plant and animal life. Conversion of inorganic chloride into gaseous chlorine atom precursors within the troposphere is generally considered a coastal or marine air phenomenon. Here we report mid-continental observations of the chlorine atom precursor nitryl chloride at a distance of 1,400 km from the nearest coastline. We observe persistent and significant nitryl chloride production relative to the consumption of its nitrogen oxide precursors. Comparison of these findings to model predictions based on aerosol and precipitation composition data from long-term monitoring networks suggests nitryl chloride production in the contiguous USA alone is at a level similar to previous global estimates for coastal and marine regions. We also suggest that a significant fraction of tropospheric chlorine atoms may arise directly from anthropogenic pollutants.

Sulfate Formation in Sea-Salt Aerosols: Constraints from Oxygen Isotopes

imparts a large D 17 O signature to the resulting sulfate (8.8%) relative to oxidation by H2O2 (0.9% )o r by OH or O 2 (0%). Ship data from two Indian Ocean Experiment (INDOEX) cruises in the Indian Ocean indicate D 17 O values usually 70%) and increases MBL sulfate concentrations by typically >10% (up to 30%). Globally, this mechanism contributes 9% of atmospheric sulfate production and 1% of the sulfate burden. The impact on H2SO4 (g) formation and implications for the potential formation of new particles in the MBL warrants inclusion in models examining the radiative effects of sulfate aerosols.

Transition metal-catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

[1] We use observations of the oxygen-17 excess (Δ 17 O) of sulfate in the Arctic to quantify the sulfate source from aqueous SO 2 (S(IV)) oxidation by O 2 catalyzed by transition metals. Due to the lack of photochemically produced OH and H 2 O 2 in high latitudes during winter, combined with high anthropogenic SO 2 emissions in the Northern Hemisphere, oxidation by O 3 is predicted to dominate sulfate formation during winter in this region. However, Δ 17 O measurements of sulfate aerosol collected in Alert, Canada, are not consistent with O 3 as the dominant oxidant and indicate that a S(IV) oxidant with near-zero Δ 17 O values (O 2 ) is important during winter. We use a global chemical transport model to interpret quantitatively the Alert observations and assess the global importance of sulfate production by Fe(III)- and Mn(II)-catalyzed oxidation of S(IV) by O 2 . We scale anthropogenic and natural atmospheric metal concentrations to primary anthropogenic sulfate and dust concentrations, respectively. The solubility and oxidation state of these metals is determined by cloud liquid water content, source, and sunlight. By including metal-catalyzed S(IV) oxidation, the model is consistent with the Δ 17 O magnitudes in the Alert data during winter. Globally, we find that this mechanism contributes 9-17% to sulfate production. The inclusion of metal-catalyzed oxidation does not resolve model discrepancies with surface SO 2 and sulfate observations in Europe. Oxygen isotope measurements of sulfate aerosols collected near anthropogenic and dust sources of metals would help to verify the importance of this sulfur oxidation pathway.

Nitrogen isotopes in ice core nitrate linked to anthropogenic atmospheric acidity change.

Significance The specific cause of the long-term decrease in stable nitrogen isotope ratio (15N/14N) of ice core nitrate beginning ∼1850 is a subject of debate, hindering the efforts to understand changes in the global nitrogen cycle. Our high-resolution record of ice core 15N/14N combined with model calculations suggests that the decrease is mainly caused by equilibrium shift in gas−particle partitioning of atmospheric nitrate due to increasing atmospheric acidity resulting from anthropogenic emissions of nitrogen and sulfur oxides. Our high-resolution record also reveals a leveling off of 15N/14N ∼1970, synchronous with changes in acidity and sulfate and nitrate concentrations. This leveling off suggests a measurable reduction in air pollution following the implementation of the US Clean Air Act of 1970. Nitrogen stable isotope ratio (δ15N) in Greenland snow nitrate and in North American remote lake sediments has decreased gradually beginning as early as ∼1850 Christian Era. This decrease was attributed to increasing atmospheric deposition of anthropogenic nitrate, reflecting an anthropogenic impact on the global nitrogen cycle, and the impact was thought to be amplified ∼1970. However, our subannually resolved ice core records of δ15N and major ions (e.g., , ) over the last ∼200 y show that the decrease in δ15N is not always associated with increasing concentrations, and the decreasing trend actually leveled off ∼1970. Correlation of δ15N with H+, , and HNO3 concentrations, combined with nitrogen isotope fractionation models, suggests that the δ15N decrease from ∼1850–1970 was mainly caused by an anthropogenic-driven increase in atmospheric acidity through alteration of the gas−particle partitioning of atmospheric nitrate. The concentrations of and also leveled off ∼1970, reflecting the effect of air pollution mitigation strategies in North America on anthropogenic NOx and SO2 emissions. The consequent atmospheric acidity change, as reflected in the ice core record of H+ concentrations, is likely responsible for the leveling off of δ15N ∼1970, which, together with the leveling off of concentrations, suggests a regional mitigation of anthropogenic impact on the nitrogen cycle. Our results highlight the importance of atmospheric processes in controlling δ15N of nitrate and should be considered when using δ15N as a source indicator to study atmospheric flux of nitrate to land surface/ecosystems.

Annual distributions and sources of Arctic aerosol components, aerosol optical depth, and aerosol absorption

Radiative forcing by aerosols and tropospheric ozone could play a significant role in recent Arctic warming. These species are in general poorly accounted for in climate models. We use the GEOS-Chem global chemical transport model to construct a 3-D representation of Arctic aerosols and ozone that is consistent with observations and can be used in climate simulations. We focus on 2008, when extensive observations were made from different platforms as part of the International Polar Year. Comparison to aircraft, surface, and ship cruise observations suggests that GEOS-Chem provides in general a successful year-round simulation of Arctic black carbon (BC), organic carbon (OC), sulfate, and dust aerosol. BC has major fuel combustion and boreal fire sources, OC is mainly from fires, sulfate has a mix of anthropogenic and natural sources, and dust is mostly from the Sahara. The model is successful in simulating aerosol optical depth (AOD) observations from Aerosol Robotics Network stations in the Arctic; the sharp drop from spring to summer appears driven in part by the smaller size of sulfate aerosol in summer. The anthropogenic contribution to Arctic AOD is a factor of 4 larger in spring than in summer and is mainly sulfate. Simulation of absorbing aerosol optical depth (AAOD) indicates that non-BC aerosol (OC and dust) contributed 24% of Arctic AAOD at 550 nm and 37% of absorbing mass deposited to the snow pack in 2008. Open fires contributed half of AAOD at 550 nm and half of deposition to the snowpack.

Analysis of atmospheric inputs of nitrate to a temperate forest ecosystem from Δ17O isotope ratio measurements

(dry deposited HNO3 and wet deposited NO3 )i n northern Michigan is derived from atmospheric deposition. To test this idea, soil, rainfall, and cloud water were sampled in a temperate forest in northern Lower Michigan. The fraction of the soil solution NO3 pool directly from atmospheric deposition was quantified using the natural isotopic tracer, D 17 O. Our results show that on average 9% of the soil solution NO3 is unprocessed (no microbial turnover) N derived directly from the atmosphere. This points to the potential importance of anthropogenic N deposition and contributes to the long‐standing need to improve our understanding of the impacts of atmospheric nitrogen processing and deposition on forest ecosystems and forest productivity. Citation: Costa, A. W., G. Michalski, A. J. Schauer, B. Alexander, E. J. Steig, and P. B. Shepson (2011), Analysis of atmospheric inputs of nitrate to a temperate forest ecosystem from D 17 O isotope ratio measurements, Geophys. Res. Lett., 38,

Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL.

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate

RATIONALE Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. METHODS Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. RESULTS The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). CONCLUSIONS Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data.

Paleo-Perspectives on Potential Future Changes in the Oxidative Capacity of the Atmosphere Due to Climate Change and Anthropogenic Emissions

The oxidizing capacity of the atmosphere, defined as the global mean tropospheric abundance of the hydroxyl radical (OH·), strongly influences air pollution by controlling the lifetimes of gaseous pollutants and the production of particulate matter. Predicting future changes in OH· due to anthropogenic emissions and climate change is of interest to air quality managers, but it is difficult because of multiple competing effects. Models of atmospheric chemistry suggest that these competing effects buffer significant change in OH· in the past and in the near future. However, proxy-based observations for past changes in OH· and other oxidants over the preindustrial-industrial and glacial-interglacial time scales suggest much larger changes than models estimate. Model sensitivity studies show that variability in past and future OH· is highly sensitive to relative emissions of reactive nitrogen and carbon, water vapor, lightning, and stratospheric ozone, implying that one or more of these variables is highly sensitive to climate.

Analysis of oxygen‐17 excess of nitrate and sulfate at sub‐micromole levels using the pyrolysis method

RATIONALE The oxygen-17 excess (Δ(17)O) of nitrate and sulfate contains valuable information regarding their atmospheric formation pathways. However, the current pyrolysis method to measure Δ(17)O requires large sample amounts (>4 µmol for nitrate and >1 µmol for sulfate). We present a new approach employing a Gas Bench interface which cryofocuses O2 produced from sample pyrolysis, enabling the analysis of sub-micromole size samples. METHODS Silver nitrate or sulfate at sub-micromole levels in a sample container was thermally decomposed to O2 and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Byproducts (mainly NO2 for silver nitrate and SO2 for silver sulfate) were removed in a liquid nitrogen trap and the sample O2 was carried by ultra-pure helium (He) gas to a Gas Bench II interface where it was cryofocused prior to entering an isotope ratio mass spectrometer. RESULTS Analysis of the international nitrate reference material USGS35 (Δ(17)O = 21.6‰) within the size range of 300-1000 nmol O2 gave a mean Δ(17)O value of (21.6 ± 0.69) ‰ (mean ±1σ). Three inter-laboratory calibrated sulfate reference materials, Sulf-α, Sulf-β and Sulf-ε, each within the size range of 180-1000 nmol O2, were analyzed and shown to possess mean Δ(17)O values of (0.9 ± 0.10)‰, (2.1 ± 0.25)‰ and (7.0 ± 0.63)‰, respectively. CONCLUSIONS The analyses of nitrate and sulfate reference materials at sub-micromole levels gave Δ(17)O values consistent with their accepted values. This new approach of employing the Gas Bench to cryofocus O2 after the pyrolysis of AgNO3 and Ag2SO4 particularly benefits the effort of measuring Δ(17)O in sample types with a low abundance of nitrate and sulfate such as ice cores.