ALBERT

Description: Anthropogenic nitrogen (N) emissions to the atmosphere have increased significantly the deposition of nitrate (NO3−) and ammonium (NH4+) to the surface waters of the open ocean, with potential impacts on marine productivity and the global carbon cycle. Global-scale understanding of the impacts of N deposition to the oceans is reliant on our ability to produce and validate models of nitrogen emission, atmospheric chemistry, transport and deposition. In this work,  ∼  2900 observations of aerosol NO3− and NH4+ concentrations, acquired from sampling aboard ships in the period 1995–2012, are used to assess the performance of modelled N concentration and deposition fields over the remote ocean. Three ocean regions (the eastern tropical North Atlantic, the northern Indian Ocean and northwest Pacific) were selected, in which the density and distribution of observational data were considered sufficient to provide effective comparison to model products. All of these study regions are affected by transport and deposition of mineral dust, which alters the deposition of N, due to uptake of nitrogen oxides (NOx) on mineral surfaces. Assessment of the impacts of atmospheric N deposition on the ocean requires atmospheric chemical transport models to report deposition fluxes; however, these fluxes cannot be measured over the ocean. Modelling studies such as the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), which only report deposition flux, are therefore very difficult to validate for dry deposition. Here, the available observational data were averaged over a 5° × 5° grid and compared to ACCMIP dry deposition fluxes (ModDep) of oxidised N (NOy) and reduced N (NHx) and to the following parameters from the Tracer Model 4 of the Environmental Chemical Processes Laboratory (TM4): ModDep for NOy, NHx and particulate NO3− and NH4+, and surface-level particulate NO3− and NH4+ concentrations. As a model ensemble, ACCMIP can be expected to be more robust than TM4, while TM4 gives access to speciated parameters (NO3− and NH4+) that are more relevant to the observed parameters and which are not available in ACCMIP. Dry deposition fluxes (CalDep) were calculated from the observed concentrations using estimates of dry deposition velocities. Model–observation ratios (RA, n), weighted by grid-cell area and number of observations, were used to assess the performance of the models. Comparison in the three study regions suggests that TM4 overestimates NO3− concentrations (RA, n =  1.4–2.9) and underestimates NH4+ concentrations (RA, n =  0.5–0.7), with spatial distributions in the tropical Atlantic and northern Indian Ocean not being reproduced by the model. In the case of NH4+ in the Indian Ocean, this discrepancy was probably due to seasonal biases in the sampling. Similar patterns were observed in the various comparisons of CalDep to ModDep (RA, n =  0.6–2.6 for NO3−, 0.6–3.1 for NH4+). Values of RA, n for NHx CalDep–ModDep comparisons were approximately double the corresponding values for NH4+ CalDep–ModDep comparisons due to the significant fraction of gas-phase NH3 deposition incorporated in the TM4 and ACCMIP NHx model products. All of the comparisons suffered due to the scarcity of observational data and the large uncertainty in dry deposition velocities used to derive deposition fluxes from concentrations. These uncertainties have been a major limitation on estimates of the flux of material to the oceans for several decades. Recommendations are made for improvements in N deposition estimation through changes in observations, modelling and model–observation comparison procedures. Validation of modelled dry deposition requires effective comparisons to observable aerosol-phase species' concentrations, and this cannot be achieved if model products only report dry deposition flux over the ocean.

Description: Gasoline- and diesel-fueled engines are ubiquitous sources of air pollution in urban environments. They emit both primary particulate matter and precursor gases that react to form secondary particulate matter in the atmosphere. In this work, we updated the organic aerosol module and organic emissions inventory of a three-dimensional chemical transport model, the Community Multiscale Air Quality Model (CMAQ), using recent, experimentally derived inputs and parameterizations for mobile sources. The updated model included a revised volatile organic compound (VOC) speciation for mobile sources and secondary organic aerosol (SOA) formation from unspeciated intermediate volatility organic compounds (IVOCs). The updated model was used to simulate air quality in southern California during May and June 2010, when the California Research at the Nexus of Air Quality and Climate Change (CalNex) study was conducted. Compared to the Traditional version of CMAQ, which is commonly used for regulatory applications, the updated model did not significantly alter the predicted organic aerosol (OA) mass concentrations but did substantially improve predictions of OA sources and composition (e.g., POA–SOA split), as well as ambient IVOC concentrations. The updated model, despite substantial differences in emissions and chemistry, performed similar to a recently released research version of CMAQ (Woody et al., 2016) that did not include the updated VOC and IVOC emissions and SOA data. Mobile sources were predicted to contribute 30–40 % of the OA in southern California (half of which was SOA), making mobile sources the single largest source contributor to OA in southern California. The remainder of the OA was attributed to non-mobile anthropogenic sources (e.g., cooking, biomass burning) with biogenic sources contributing to less than 5 % to the total OA. Gasoline sources were predicted to contribute about 13 times more OA than diesel sources; this difference was driven by differences in SOA production. Model predictions highlighted the need to better constrain multi-generational oxidation reactions in chemical transport models.

Description: Since September 2014, NASA's Orbiting Carbon Observatory-2 (OCO-2) satellite has been taking measurements of reflected solar spectra and using them to infer atmospheric carbon dioxide levels. This work provides details of the OCO-2 retrieval algorithm, versions 7 and 8, used to derive the column-averaged dry air mole fraction of atmospheric CO2 (XCO2) for the roughly 100 000 cloud-free measurements recorded by OCO-2 each day. The algorithm is based on the Atmospheric Carbon Observations from Space (ACOS) algorithm which has been applied to observations from the Greenhouse Gases Observing SATellite (GOSAT) since 2009, with modifications necessary for OCO-2. Because high accuracy, better than 0.25 %, is required in order to accurately infer carbon sources and sinks from XCO2, significant errors and regional-scale biases in the measurements must be minimized. We discuss efforts to filter out poor-quality measurements, and correct the remaining good-quality measurements to minimize regional-scale biases. Updates to the radiance calibration and retrieval forward model in version 8 have improved many aspects of the retrieved data products. The version 8 data appear to have reduced regional-scale biases overall, and demonstrate a clear improvement over the version 7 data. In particular, error variance with respect to TCCON was reduced by 20 % over land and 40 % over ocean between versions 7 and 8, and nadir and glint observations over land are now more consistent. While this paper documents the significant improvements in the ACOS algorithm, it will continue to evolve and improve as the CO2 data record continues to expand.

Description: The Amazon River transports large amounts of terrestrial organic carbon (OCterr) from the Andean and Amazon neotropical forests to the Atlantic Ocean. In order to compare the biogeochemical characteristics of OCterr in the fluvial sediments from the Amazon drainage basin and in the adjacent marine sediments, we analysed riverbed sediments from the Amazon mainstream and its main tributaries as well as marine surface sediments from the Amazon shelf and fan for total organic carbon (TOC) content, organic carbon isotopic composition (δ13CTOC), and lignin phenol compositions. TOC and lignin content exhibit positive correlations with Al ∕ Si ratios (indicative of the sediment grain size) implying that the grain size of sediment discharged by the Amazon River plays an important role in the preservation of TOC and leads to preferential preservation of lignin phenols in fine particles. Depleted δ13CTOC values (−26.1 to −29.9 ‰) in the main tributaries consistently correspond with the dominance of C3 vegetation. Ratios of syringyl to vanillyl (S ∕ V) and cinnamyl to vanillyl (C ∕ V) lignin phenols suggest that non-woody angiosperm tissues are the dominant source of lignin in the Amazon basin. Although the Amazon basin hosts a rich diversity of vascular plant types, distinct regional lignin compositions are not observed. In the marine sediments, the distribution of δ13CTOC and Λ8 (sum of eight lignin phenols in organic carbon (OC), expressed as mg/100 mg OC) values implies that OCterr discharged by the Amazon River is transported north-westward by the North Brazil Current and mostly deposited on the inner shelf. The lignin compositions in offshore sediments under the influence of the Amazon plume are consistent with the riverbed samples suggesting that processing of OCterr during offshore transport does not change the encoded source information. Therefore, the lignin compositions preserved in these offshore sediments can reliably reflect the vegetation in the Amazon River catchment. In sediments from the Amazon fan, low lignin content, relatively depleted δ13CTOC values and high (Ad ∕ Al)V ratios indicating highly degraded lignin imply that a significant fraction of the deposited OCterr is derived from petrogenic (sourced from ancient rocks) sources.

Description: Atmospheric processing of iron in dust and combustion aerosols is simulated using an intermediate-complexity soluble iron mechanism designed for Earth system models. The solubilization mechanism includes both a dependence on aerosol water pH and in-cloud oxalic acid. The simulations of size-resolved total, soluble and fractional iron solubility indicate that this mechanism captures many but not all of the features seen from cruise observations of labile iron. The primary objective was to determine the extent to which our solubility scheme could adequately match observations of fractional iron solubility. We define a semi-quantitative metric as the model mean at points with observations divided by the observational mean (MMO). The model is in reasonable agreement with observations of fractional iron solubility with an MMO of 0.86. Several sensitivity studies are performed to ascertain the degree of complexity needed to match observations; including the oxalic acid enhancement is necessary, while different parameterizations for calculating model oxalate concentrations are less important. The percent change in soluble iron deposition between the reference case (REF) and the simulation with acidic processing alone is 63.8 %, which is consistent with previous studies. Upon deposition to global oceans, global mean combustion iron solubility to total fractional iron solubility is 8.2 %; however, the contribution of fractional iron solubility from combustion sources to ocean basins below 15∘ S is approximately 50 %. We conclude that, in many remote ocean regions, sources of iron from combustion and dust aerosols are equally important. Our estimates of changes in deposition of soluble iron to the ocean since preindustrial climate conditions suggest roughly a doubling due to a combination of higher dust and combustion iron emissions along with more efficient atmospheric processing.

Description: The continent-to-ocean supply of phosphorus (P) in the soluble state, recognized as bioavailable P, via the atmosphere is hypothesized to be crucial to the biological cycle in offshore surface seawater. To investigate the solubility of P in aerosol particles moving towards the northwestern Pacific from the Asian continent, we measured the total P (TP), total dissolved P (TDP) and dissolved inorganic P (DIP) in aerosols at Qingdao (36∘06′ N, 120∘33′ E), a coastal city in eastern China. The samples were collected in December 2012 and January 2013 (winter) and in March and April 2013 (spring), when the middle-latitude westerly wind was prevailing. On average, P solubility, i.e., the ratio of TDP to TP, was 32.9±16.7 % in winter and 21.3±9.8 % in spring, and the TP concentrations in the two seasons were similar. This seasonal solubility difference is attributed to the aerosol sources containing the P. Particles in winter were predominantly anthropogenic particles from local and regional areas, and particles in spring were significantly influenced by natural dust from the arid and semiarid areas in the inland part of the continent. Moreover, acidification processes associated with the formation of sulfate and nitrate in the winter samples enhanced P solubility, suggesting that the P in anthropogenic particles was more susceptible to the production of acidic species than that in natural dust particles. There was a strong positive correlation between P solubility and relative humidity (RH). P solubility was usually less than 30 % when RH was below 60 %, even when the content of acidic species and/or anthropogenic particles in the aerosols was high, suggesting humidity had a critical role in the production of TDP. In addition, the proportion of DIP in TDP was high when the particles were predominantly anthropogenic, and the proportion of dissolved organic P (DOP; quantified as TDP minus DIP) in TDP was high when the particles were dominated by natural dust. These results indicate that, as the contents of bioavailable P in Asian continent outflows are closely dependent on the aerosol particle origins, atmospheric acidic processes could convert P into a bioavailable state under certain meteorological conditions. Therefore, the recent severe air pollution over East Asia might have enhanced the input of bioavailable P to downwind marine areas.

Description: Large and effective reductions in emissions of long-lived ozone-depleting substance (ODS) are being achieved through the Montreal Protocol, the effectiveness of which can be seen in the declining atmospheric abundances of many ODSs. An important remaining uncertainty concerns the role of very short-lived substances (VSLSs) which, owing to their relatively short atmospheric lifetimes (less than 6 months), are not regulated under the Montreal Protocol. Recent studies have found an unexplained increase in the global tropospheric abundance of one VSLS, dichloromethane (CH2Cl2), which has increased by around 60 % over the past decade. Here we report dramatic enhancements of several chlorine-containing VSLSs (Cl-VSLSs), including CH2Cl2 and CH2ClCH2Cl (1,2-dichloroethane), observed in surface and upper-tropospheric air in East and South East Asia. Surface observations were, on occasion, an order of magnitude higher than previously reported in the marine boundary layer, whilst upper-tropospheric data were up to 3 times higher than expected. In addition, we provide further evidence of an atmospheric transport mechanism whereby substantial amounts of industrial pollution from East Asia, including these chlorinated VSLSs, can rapidly, and regularly, be transported to tropical regions of the western Pacific and subsequently uplifted to the tropical upper troposphere. This latter region is a major provider of air entering the stratosphere, and so this mechanism, in conjunction with increasing emissions of Cl-VSLSs from East Asia, could potentially slow the expected recovery of stratospheric ozone.

Description: Australian seasonal rainfall is strongly affected by large-scale ocean–atmosphere climate influences. In this study, we exploit the links between these precipitation influences, regional rainfall variations, and palaeoclimate proxies in the region to reconstruct Australian regional rainfall between four and eight centuries into the past. We use an extensive network of palaeoclimate records from the Southern Hemisphere to reconstruct cool (April–September) and warm (October–March) season rainfall in eight natural resource management (NRM) regions spanning the Australian continent. Our bi-seasonal rainfall reconstruction aligns well with independent early documentary sources and existing reconstructions. Critically, this reconstruction allows us, for the first time, to place recent observations at a bi-seasonal temporal resolution into a pre-instrumental context, across the entire continent of Australia. We find that recent 30- and 50-year trends towards wetter conditions in tropical northern Australia are highly unusual in the multi-century context of our reconstruction. Recent cool-season drying trends in parts of southern Australia are very unusual, although not unprecedented, across the multi-century context. We also use our reconstruction to investigate the spatial and temporal extent of historical drought events. Our reconstruction reveals that the spatial extent and duration of the Millennium Drought (1997–2009) appears either very much below average or unprecedented in southern Australia over at least the last 400 years. Our reconstruction identifies a number of severe droughts over the past several centuries that vary widely in their spatial footprint, highlighting the high degree of diversity in historical droughts across the Australian continent. We document distinct characteristics of major droughts in terms of their spatial extent, duration, intensity, and seasonality. Compared to the three largest droughts in the instrumental period (Federation Drought, 1895–1903; World War II Drought, 1939–1945; and the Millennium Drought, 1997–2005), we find that the historically documented Settlement Drought (1790–1793), Sturt's Drought (1809–1830) and the Goyder Line Drought (1861–1866) actually had more regionalised patterns and reduced spatial extents. This seasonal rainfall reconstruction provides a new opportunity to understand Australian rainfall variability by contextualising severe droughts and recent trends in Australia.

Description: This study investigates the impact of reactive halogen species (RHS, containing chlorine (Cl), bromine (Br) or iodine (I)) on atmospheric chemistry in the tropical troposphere and explores the sensitivity to uncertainties in the fluxes of RHS to the atmosphere and their chemical processing. To do this, the regional chemistry transport model WRF-Chem has been extended to include Br and I, as well as Cl chemistry for the first time, including heterogeneous recycling reactions involving sea-salt aerosol and other particles, reactions of Br and Cl with volatile organic compounds (VOCs), along with oceanic emissions of halocarbons, VOCs and inorganic iodine. The study focuses on the tropical east Pacific using field observations from the Tropical Ocean tRoposphere Exchange of Reactive halogen species and Oxygenated VOC (TORERO) campaign (January–February 2012) to evaluate the model performance. Including all the new processes, the model does a reasonable job reproducing the observed mixing ratios of bromine oxide (BrO) and iodine oxide (IO), albeit with some discrepancies, some of which can be attributed to difficulties in the model's ability to reproduce the observed halocarbons. This is somewhat expected given the large uncertainties in the air–sea fluxes of the halocarbons in a region where there are few observations of their seawater concentrations. We see a considerable impact on the inorganic bromine (Bry) partitioning when heterogeneous chemistry is included, with a greater proportion of the Bry in active forms such as BrO, HOBr and dihalogens. Including debromination of sea salt increases BrO slightly throughout the free troposphere, but in the tropical marine boundary layer, where the sea-salt particles are plentiful and relatively acidic, debromination leads to overestimation of the observed BrO. However, it should be noted that the modelled BrO was extremely sensitive to the inclusion of reactions between Br and the oxygenated VOCs (OVOCs), which convert Br to HBr, a far less reactive form of Bry. Excluding these reactions leads to modelled BrO mixing ratios greater than observed. The reactions between Br and aldehydes were found to be particularly important, despite the model underestimating the amount of aldehydes observed in the atmosphere. There are only small changes to the inorganic iodine (Iy) partitioning and IO when the heterogeneous reactions, primarily on sea salt, are included. Our model results show that tropospheric Ox loss due to halogens ranges between 25 % and 60 %. Uncertainties in the heterogeneous chemistry accounted for a small proportion of this range (25 % to 31 %). This range is in good agreement with other estimates from state-of-the-art atmospheric chemistry models. The upper bound is found when reactions between Br and Cl with VOCs are not included and, consequently, Ox loss by BrOx, ClOx and IOx cycles is high (60 %). With the inclusion of halogens in the troposphere, O3 is reduced by 7 ppbv on average. However, when reactions between Br and Cl with VOCs are not included, O3 is much lower than observed. Therefore, the tropospheric Ox budget is highly sensitive to the inclusion of halogen reactions with VOCs and to the uncertainties in current understanding of these reactions and the abundance of VOCs in the remote marine atmosphere.

Description: The Arctic terrestrial and sub-sea permafrost region contains approximately 30 % of the global carbon stock, and therefore understanding Arctic methane emissions and how they might change with a changing climate is important for quantifying the global methane budget and understanding its growth in the atmosphere. Here we present measurements from a new in situ flux observation system designed for use on a small, low-flying aircraft that was deployed over the North Slope of Alaska during August 2013. The system combines a small methane instrument based on integrated cavity output spectroscopy (ICOS) with an air turbulence probe to calculate methane fluxes based on eddy covariance. We group surface fluxes by land class using a map based on LandSat Thematic Mapper (TM) data with 30 m resolution. We find that wet sedge areas dominate the methane fluxes with a mean flux of 2.1 µg m−2 s−1 during the first part of August. Methane emissions from the Sagavanirktok River have the second highest at almost 1 µg m−2 s−1. During the second half of August, after soil temperatures had cooled by 7 °C, methane emissions fell to between 0 and 0.5 µg m−2 s−1 for all areas measured. We compare the aircraft measurements with an eddy covariance flux tower located in a wet sedge area and show that the two measurements agree quantitatively when the footprints of both overlap. However, fluxes from sedge vary at times by a factor of 2 or more even within a few kilometers of the tower demonstrating the importance of making regional measurements to map out methane emissions spatial heterogeneity. Aircraft measurements of surface flux can play an important role in bridging the gap between ground-based measurements and regional measurements from remote sensing instruments and models.