A ship-based methodology for high precision atmospheric oxygen measurements and its application in the Southern Ocean region

A method for achieving continuous high precision measurements of atmospheric O-2 is presented based on a commercially available fuel-cell instrument, (Sable Systems, Oxzilla FC-II) with a precision of 7 per meg (approximately equivalent to 1.2 ppm) for a 6-min measurement. The Oxzilla was deployed on two voyages in the Western Pacific sector of the Southern Ocean, in February 2003 and in April 2004, making these the second set of continuous O-2 measurements ever made from a ship. The results show significant temporal variation in O-2, in the order of +/- 10 per meg over 6-hourly time intervals, and substantial spatial variation. Data from both voyages show an O-2 maximum centred on 50 degrees S, which is most likely to be the result of biologically driven O-2 outgassing in the region of subtropical convergence around New Zealand, and a decreasing O-2 trend towards Antarctica. O-2 from the ship-based measurements is elevated compared with measurements from the Scripps Institution of Oceanography flask-sampling network, and the O-2 maximum is also not captured in the network observations. This preliminary study shows that ship-based continuous measurements are a valuable addition to current fixed site sampling programmes for the understanding of ocean-atmosphere O-2 exchange processes. [References: 39

Trace metal fractional solubility in size-segregated aerosols from the tropical eastern Atlantic Ocean

Soluble and total trace metals were measured in four size fractionated aerosol samples collected over the tropical eastern Atlantic Ocean. In samples that were dominated by Saharan dust, the size distributions of total iron, aluminum, titanium, manganese, cobalt, and thorium were very similar to one another and to the size distributions of soluble manganese, cobalt, and thorium. Finer particle sizes (< ~3 μm) showed enhanced soluble concentrations of iron, aluminum, and titanium, possibly as a result of interactions with acidic sulfate aerosol during atmospheric transport. The difference in fine particle solubility between these two groups of elements might be related to the hyperbolic increase in the fractional solubility of iron, and a number of other elements, during the atmospheric transport of Saharan dust, which is not observed for manganese and its associated elements. In comparison to elements whose solubility varies during atmospheric transport, the stability of thorium fractional solubility should reduce uncertainties in the use of dissolved concentrations of this element in seawater as a proxy for dust deposition, although this topic requires further work

Sea Ice Versus Storms: What Controls Sea Salt in Arctic Ice Cores?

The sea ice surface is thought to be a major source of sea salt aerosol, suggesting that sodium records of polar ice cores may trace past sea ice extent. Here we test this possibility for the Arctic, using a chemical transport model to simulate aerosol emission, transport and deposition in the satellite era. Our simulations suggest that sodium records from inland Greenland ice cores are strongly influenced by the impact of meteorology on aerosol transport and deposition. In contrast, sodium in coastal Arctic cores is predominantly sourced from the sea ice surface and the strength of these aerosol emissions controls the ice core sodium variability. Such ice cores may therefore record decadal to centennial scale Holocene sea ice changes. However, any relationship between ice core sodium and sea ice change may depend on how sea ice seasonality impacts sea salt emissions. Field-based observations are urgently required to constrain this.European Union Horizon 2020 Marie Sklodowska-Curie Individual Fellowship (658120, SEADOG) awarded to RHR. EWW acknowledges support from the Royal Society (RP 120096) XY acknowledges funding from NERC (NE/J023051/1)

Mapping the aerosol over Eurasia from the Zotino Tall Tower

The present study covers more than 5 yr corresponding to more than 40 000 hours of particle and gas data measured at the Siberian tall tower Zotino Tall Tower (ZOTTO) (60.8%26deg%3BN; 89.35%26deg%3BE). Extrapolated along 10-d back trajectories, the ZOTTO measurements cover large parts of the Eurasian land mass. Mapping the extrapolated ZOTTO data points to major anthropogenic source regions and Siberian fire regions, consistent with emission data for CO and vegetation fires. Middle East mid-latitude sources stand out strongly and possibly emissions from Northern China may be seen at times from ZOTTO. The maps of measured light scattering and absorption characteristics support the interpretation of different source types. Three clusters of substantially different submicrometer particle size distributions were found, the maps of which also could be related to major aerosol source regions

Synoptic-scale controls on the δ18O in precipitation across Beringia

Oxygen isotope records of precipitation (δ18Oprecip) from Beringia are thought to reflect synoptic-scale circulation changes associated with the Aleutian Low. To delineate the spatial pattern of δ18Oprecip associated with the two dominant modes of Aleutian Low circulation, we combine modern δ18Oprecip and deuterium excess data with climate reanalysis and back-trajectory modelling. Aleutian Low strength and position are revealed to systematically affect regional moisture source and δ18Oprecip; whereby a strengthened Aleutian Low causes lower (higher) δ18Oprecip in western (eastern) Beringia. We compare a new 100-year-long δ18O record from the Aleutian Islands with the North Pacific Index, the primary indicator of Aleutian Low strength, and find a significant positive relationship (r = 0.43, p < 0.02, n = 28) that tracks late 20th century change. This study demonstrates synoptic-scale circulation controls on our isotope record, and provides a coherent framework for interpreting existing and emerging paleo-isotope data from the region

Trend changes of African airmass intrusions in the marine boundary layer over the subtropical Eastern North Atlantic region in winter

African dust intrusions in the marine mixing layer of the Eastern North Atlantic subtropical region (23.5°N to 35°N) are favoured in winter when the eastern edge of the Azores High covers Southwestern Europe and North Africa. In situ ground pressure observations and reanalysis from National Centers for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) and European Centre for Medium-Range Weather Forecasts (ECMWF) indicate that the Azores High has strengthened and shifted eastward in winter over the last three decades. This is evidenced by the increase over time of the Madrid–Tenerife Index which is defined as the geopotential height anomaly difference at 1000 mb between Tenerife (28.5°N; 16.3°W) and Madrid (40.5°N; 3.5°W) in winter and of the African Index which is defined as the residence time over Africa of air mass trajectories entering the subtropical Eastern North Atlantic Ocean. Barcelona Supercomputing Center/Dust Regional Atmospheric Model (BSC-DREAM) dust regional model simulations from 1958 to 2006 were performed, assuming that the soil characteristics of dust sources remained unchanged over time. Simulated winter dust concentration levels are well correlated (0.67) with the available background observations for the 1998–2004 period. The model results show a two-fold increase in winter dust concentrations over the 1980–2006 period with respect to the 1958–1979 period, corresponding to the strengthening and eastward shift of the Azores High

Initial growth of platinum on oxygen-covered Ni(1 1 0) surfaces

Abstract The initial growth of Pt on the Ni(1 1 0)-(3 · 1)-O and NiO(1 1 0) surfaces has been studied by coaxial impact collision ion scattering spectroscopy (CAICISS), low energy electron diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). Prior to Pt deposition, the atomic structure of the near-surface regions of the Ni(1 1 0)-(3 · 1)-O and NiO(1 1 0) structures were studied using CAICISS, finding changes to the interlayer spacings due to the adsorption of oxygen. Deposition of Pt on the Ni(1 1 0)-(3 · 1)-O surface led to a random substitutional alloy in the near-surface region at Pt coverages both below and in excess of 1 ML. In contrast, when the surface was treated with 1800 L of atomic oxygen in order to form a NiO(1 1 0) surface, a thin Pt layer was formed upon room temperature Pt deposition. XPS and LEED data are presented throughout to support the CAICISS observations

Large emissions from floodplain trees close the Amazon methane budget

Wetlands are the largest global source of atmospheric methane (CH4), a potent greenhouse gas. However, methane emission inventories from the Amazon floodplain, the largest natural geographic source of CH4 in the tropics, consistently underestimate the atmospheric burden of CH4 determined via remote sensing and inversion modelling, pointing to a major gap in our understanding of the contribution of these ecosystems to CH4 emissions. Here we report CH4 fluxes from the stems of 2,357 individual Amazonian floodplain trees from 13 locations across the central Amazon basin. We find that escape of soil gas through wetland trees is the dominant source of regional CH4 emissions. Methane fluxes from Amazon tree stems were up to 200 times larger than emissions reported for temperate wet forests6 and tropical peat swamp forests, representing the largest non-ebullitive wetland fluxes observed. Emissions from trees had an average stable carbon isotope value (δ13C) of −66.2 ± 6.4 per mil, consistent with a soil biogenic origin. We estimate that floodplain trees emit 15.1 ± 1.8 to 21.2 ± 2.5 teragrams of CH4 a year, in addition to the 20.5 ± 5.3 teragrams a year emitted regionally from other sources. Furthermore, we provide a ‘top-down’ regional estimate of CH4 emissions of 42.7 ± 5.6 teragrams of CH4 a year for the Amazon basin, based on regular vertical lower-troposphere CH4 profiles covering the period 2010–2013. We find close agreement between our ‘top-down’ and combined ‘bottom-up’ estimates, indicating that large CH4 emissions from trees adapted to permanent or seasonal inundation can account for the emission source that is required to close the Amazon CH4 budget. Our findings demonstrate the importance of tree stem surfaces in mediating approximately half of all wetland CH4 emissions in the Amazon floodplain, a region that represents up to one-third of the global wetland CH4 source when trees are combined with other emission sources

Nitrate stable isotopes and major ions in snow and ice samples from four Svalbard sites

Increasing reactive nitrogen (N-r) deposition in the Arctic may adversely impact N-limited ecosystems. To investigate atmospheric transport of N-r to Svalbard, Norwegian Arctic, snow and firn samples were collected from glaciers and analysed to define spatial and temporal variations (1 10 years) in major ion concentrations and the stable isotope composition (delta N-15 and delta O-18) of nitrate (NO3-) across the archipelago. The delta N-15(NO3-) and delta O-18(NO3-) averaged -4 parts per thousand and 67 parts per thousand in seasonal snow (2010-11) and -9 parts per thousand and 74 parts per thousand in firn accumulated over the decade 2001-2011. East-west zonal gradients were observed across the archipelago for some major ions (non-sea salt sulphate and magnesium) and also for delta N-15(NO3-) and delta O-18(NO3-) in snow, which suggests a different origin for air masses arriving in different sectors of Svalbard. We propose that snowfall associated with long-distance air mass transport over the Arctic Ocean inherits relatively low delta N-15(NO3-) due to in-transport N isotope fractionation. In contrast, faster air mass transport from the north-west Atlantic or northern Europe results in snowfall with higher delta N-15(NO3-) because in-transport fractionation of N is then time-limited