ALBERT

Description: The SAFIRED (Savannah Fires in the Early Dry Season) campaign took place from 29 May until 30 June 2014 at the Australian Tropical Atmospheric Research Station (ATARS) in the Northern Territory, Australia. The purpose of this campaign was to investigate emissions from fires in the early dry season in northern Australia. Measurements were made of biomass burning aerosols, volatile organic compounds, polycyclic aromatic carbons, greenhouse gases, radon, speciated atmospheric mercury and trace metals. Aspects of the biomass burning aerosol emissions investigated included; emission factors of various species, physical and chemical aerosol properties, aerosol aging, micronutrient supply to the ocean, nucleation, and aerosol water uptake. Over the course of the month-long campaign, biomass burning signals were prevalent and emissions from several large single burning events were observed at ATARS.Biomass burning emissions dominated the gas and aerosol concentrations in this region. Dry season fires are extremely frequent and widespread across the northern region of Australia, which suggests that the measured aerosol and gaseous emissions at ATARS are likely representative of signals across the entire region of north Australia. Air mass forward trajectories show that these biomass burning emissions are carried north-west over the Timor Sea and could influence the atmosphere over Indonesia and the tropical atmosphere over the Indian Ocean. Here we present characteristics of the biomass burning observed at the sampling site and provide an overview of the more specific outcomes of the SAFIRED campaign.

Description: A 120 m ice core was drilled on Mill Island, East Antarctica (65°30′ S, 100°40′ E) during the 2009/2010 Australian Antarctic field season. Contiguous discrete 5 cm samples were measured for hydrogen peroxide, water stable isotopes, and trace ion chemistry. The ice core was annually dated using a combination of chemical species and water stable isotopes. The Mill Island ice core preserves a climate record covering 97 years from 1913 to 2009 CE, with a mean snow accumulation of 1.35 m (ice-equivalent) per year (mIE yr−1). This northernmost East Antarctic coastal ice core site displays trace ion concentrations that are generally higher than other Antarctic ice core sites (e.g. mean sodium levels were 254 µEq L−1). The trace ion record at Mill Island is characterised by a unique and complex chemistry record with three distinct regimes identified. The trace ion record in regime A displays clear seasonality from 2000 to 2009 CE; regime B displays elevated concentrations with no seasonality from 1934 to 2000 CE; and regime C displays relatively low concentrations with seasonality from 1913 to 1934 CE. Sea salts were compared with instrumental data, including atmospheric models and satellite-derived sea-ice concentration, to investigate influences on the Mill Island ice core record. The mean annual sea salt record does not correlate with wind speed. Instead, sea-ice concentration to the east of Mill Island likely influences the annual mean sea salt record. A mechanism involving formation of frost flowers on sea ice is proposed to explain the extremely high sea salt concentration. The Mill Island ice core records are unexpectedly complex, with strong modulation of the trace chemistry on long timescales.

Description: There is a lack of knowledge of how biomass burning aerosols in the tropics age, including those in the fire-prone Northern Territory in Australia. This paper reports chemical characterization of fresh and aged aerosols monitored during the 1-month-long SAFIRED (Savannah Fires in the Early Dry Season) field study, with an emphasis on the chemical signature and aging of organic aerosols. The campaign took place in June 2014 during the early dry season when the surface measurement site, the Australian Tropical Atmospheric Research Station (ATARS), located in the Northern Territory, was heavily influenced by thousands of wild and prescribed bushfires. ATARS was equipped with a wide suite of instrumentation for gaseous and aerosol characterization. A compact time-of-flight aerosol mass spectrometer was deployed to monitor aerosol chemical composition. Approximately 90 % of submicron non-refractory mass was composed of organic material. Ozone enhancement in biomass burning plumes indicated increased air mass photochemistry. The diversity in biomass burning emissions was illustrated through variability in chemical signature (e.g. wide range in f44, from 0.06 to 0.18) for five intense fire events. The background particulate loading was characterized using positive matrix factorization (PMF). A PMF-resolved BBOA (biomass burning organic aerosol) factor comprised 24 % of the submicron non-refractory organic aerosol mass, confirming the significance of fire sources. A dominant PMF factor, OOA (oxygenated organic aerosol), made up 47 % of the sampled aerosol, illustrating the importance of aerosol aging in the Northern Territory. Biogenic isoprene-derived organic aerosol factor was the third significant fraction of the background aerosol (28 %).

Description: High-resolution, well-dated climate archives provide an opportunity to investigate the dynamic interactions of climate patterns relevant for future projections. Here, we present data from a new, annually-dated ice core record from the eastern Ross Sea. Comparison of the Roosevelt Island Climate Evolution (RICE) ice core records with climate reanalysis data for the 1979–2012 calibration period shows that RICE records reliably capture temperature and snow precipitation variability of the region. RICE is compared with data from West Antarctica (West Antarctic Ice Sheet Divide Ice Core) and the western (Talos Dome) and eastern (Siple Dome) Ross Sea. For most of the past 2,700 years, the eastern Ross Sea was warming with perhaps increased snow accumulation and decreased sea ice extent. However, West Antarctica cooled whereas the western Ross Sea showed no significant temperature trend. From the 17th Century onwards, this relationship changes. All three regions now show signs of warming, with snow accumulation declining in West Antarctica and the eastern Ross Sea, but increasing in the western Ross Sea. Analysis of decadal to centennial-scale climate variability superimposed on the longer term trend reveal that periods characterised by opposing temperature trends between the Eastern and Western Ross Sea have occurred since the 3rd Century but are masked by longer-term trends. This pattern here is referred to as the Ross Sea Dipole, caused by a sensitive response of the region to dynamic interactions of the Southern Annual Mode and tropical forcings.

Description: Model intercomparison studies in the climate and earth sciences communities have been crucial to build credibility and coherence for future projections. They have quantified variability among models, spurred model development, contrasted within- and among-model uncertainty, assessed model fits to historical data, and provided ensemble projections of future change under specified scenarios. Given the speed and magnitude of anthropogenic change in the marine environment, and consequent effects on food security, biodiversity, marine industries and society, the time is ripe for similar comparisons among models of fisheries and marine ecosystems. Here, we describe the Fisheries and Marine Ecosystem Model Intercomparison Project protocol version 1.0 (Fish-MIP v1.0), part of the Inter-Sectoral Impact Model Intercomparison Project (ISIMIP), a cross-sectoral network of climate impact modellers. Given the complexity of the marine ecosystem, this class of models has substantial heterogeneity of purpose, scope, theoretical underpinning, processes considered, parameterizations, resolution (grain size) and spatial extent. This heterogeneity reflects the lack of a unified understanding of the marine ecosystem, and implies that the assemblage of all models is more likely to include a greater number of relevant processes than is any single model. The current Fish-MIP protocol is designed to allow these heterogeneous models to be forced with common Earth System Model (ESM) CMIP5 outputs under prescribed scenarios for historic (from 1950s) and future (to 2100) time periods; it will be adapted to CMIP6 in future iterations. It also describes a standardized set of outputs for each participating Fish-MIP model to produce. This enables the broad characterization of differences between, and uncertainties within, models and projections when assessing climate and fisheries impacts on marine ecosystems and the services they provide. The systematic generation, collation and comparison of results from Fish-MIP will inform understanding of the range of plausible changes in marine ecosystems, and improve our capacity to define and convey strengths and weaknesses of model-based advice on future states of marine ecosystems and fisheries. Ultimately, Fish-MIP represents a step towards bringing together the marine ecosystem modelling community to produce consistent ensemble medium- and long-term projections of marine ecosystems.

Description: The shells of two marine bivalve species (Fulvia tenuicostata and Soletellina biradiata), endemic to south Western Australia, have been characterised using a combined crystallographic, spectroscopic and geochemical approach. Both species have been described previously as purely aragonitic, however, this study identified the presence of three phases, namely aragonite, calcite and Mg-calcite using XRD analysis. Data obtained via confocal Raman spectroscopy, electron probe microanalysis, and laser ablation inductively coupled plasma-mass spectrometry (LA ICP-MS) show correlations between Mg/S and Mg/P in F. tenuicostata, and Sr/S and S/Ba in S. biradiata. The composition of organic macromolecules that constitute the shell organic matrix (i.e. soluble phosphorus-dominated and/or insoluble sulphur-dominated fraction) influences the incorporation of Mg, Sr and Ba into the crystal lattice. Ionic substitution, particularly Ca2+ by Mg2+ in calcite in F. tenuicostata, appears to have been promoted by the combination of both S- and P-dominated organic macromolecules. The elemental composition of these two marine bivalve shells is species-specific and is influenced by many factors such as crystallographic structure, organic macromolecule composition and environmental setting. In order to reliably use bivalve shells as proxies for paleoenvironmental reconstructions, both the organic and inorganic crystalline material need to be characterised to account for all influencing factors and accurately describe the "vital effect".

Description: We present an electrospray ion source coupled to an orthogonal continuous-flow atmospheric pressure chemical ionization region. The source can generate intense and stable currents of several specific reagent ions using a range of salt solutions prepared in methanol, thereby providing both an alternative to more common radioactive ion sources and allowing for the generation of reagent ions that are not available in current chemical ionization mass spectrometry (CIMS) techniques, such as alkaline cations. We couple the orthogonal electrospray chemical ionization (ESCI) source to a high-resolution time-of-flight mass spectrometer (HR-ToF-MS), and assess instrument performance through calibrations using nitric acid (HNO3), formic acid (HCOOH), and isoprene epoxydiol (trans-β-IEPOX) gas standards, and through measurements of oxidized organic compounds formed from ozonolysis of α-pinene in a continuous-flow reaction chamber. When using iodide as the reagent ion, the HR-ToF-ESCIMS prototype has a sensitivity of 11, 2.4, and 10 cps pptv−1 per million counts per second (cps) of reagent ions and a detection limit (3σ, 5 s averaging) of 4.9, 12.5, and 1.4 pptv to HNO3, HCOOH, and IEPOX, respectively. These values are comparable to those obtained using an iodide-adduct HR-ToF-CIMS with a radioactive ion source and low-pressure ion–molecule reaction region. Applications to the α-pinene ozonolysis system demonstrates that HR-ToF-ESCIMS can generate multiple reagent ions (e.g., I−, NO3−, acetate, Li+, Na+, K+, and NH4+) having different selectivity to provide a comprehensive molecular description of a complex organic system.

Description: The vast majority of Australia's fires occur in the tropical north of the continent during the dry season. These fires are a significant source of aerosol and cloud condensation nuclei (CCN) in the region, providing a unique opportunity to investigate the biomass burning aerosol (BBA) in the absence of other sources. CCN concentrations at 0.5 % supersaturation and aerosol size and chemical properties were measured at the Australian Tropical Atmospheric Research Station (ATARS) during June 2014. CCN concentrations reached over 104 cm−3 when frequent and close fires were burning – up to 45 times higher than periods with no fires. Both the size distribution and composition of BBA appeared to significantly influence CCN concentrations. A distinct diurnal trend in the proportion of BBA activating to cloud droplets was observed, with an activation ratio of 40 ± 20 % during the night and 60 ± 20 % during the day. BBA was, on average, less hygroscopic during the night (κ = 0. 04 ± 0.03) than during the day (κ =  0.07 ± 0.05), with a maximum typically observed just before midday. Size-resolved composition of BBA showed that organics comprised a constant 90 % of the aerosol volume for aerodynamic diameters between 100 and 200 nm. While this suggests that the photochemical oxidation of organics led to an increase in the hygroscopic growth and an increase in daytime activation ratios, it does not explain the decrease in hygroscopicity after midday. Modelled CCN concentrations assuming typical continental hygroscopicities produced very large overestimations of up to 200 %. Smaller, but still significant, overpredictions up to  ∼  100 % were observed using aerosol mass spectrometer (AMS)- and hygroscopicity tandem differential mobility analyser (H-TDMA)-derived hygroscopicities as well as campaign night and day averages. The largest estimations in every case occurred during the night, when the small variations in very weakly hygroscopic species corresponded to large variations in the activation diameters. Trade winds carry the smoke generated from these fires over the Timor Sea, where aerosol–cloud interactions are likely to be sensitive to changes in CCN concentrations, perturbing cloud albedo and lifetime. Dry season fires in northern Australia are therefore potentially very important in cloud processes in this region.

Description: Size-resolved and vertical profile measurements of single particle chemical composition (sampling altitude range 50–3000 m) were conducted in July 2014 in the Canadian high Arctic during an aircraft-based measurement campaign (NETCARE 2014). We deployed the single particle laser ablation aerosol mass spectrometer ALABAMA (vacuum aerodynamic diameter range approximately 200–1000 nm) to identify different particle types and their mixing states. On the basis of the single particle analysis, we found that a significant fraction (23 %) of all analyzed particles (in total: 7412) contained trimethylamine (TMA). Two main pieces of evidence suggest that these TMA-containing particles originated from emissions within the Arctic boundary layer. First, the maximum fraction of particulate TMA occurred in the Arctic boundary layer. Second, compared to particles observed aloft, TMA particles were smaller and less oxidized. Further, air mass history analysis, associated wind data and comparison with measurements of methanesulfonic acid give evidence of a marine-biogenic influence on particulate TMA. Moreover, the external mixture of TMA-containing particles and sodium and chloride (Na ∕ Cl-) containing particles, together with low wind speeds, suggests particulate TMA results from secondary conversion of precursor gases released by the ocean. In contrast to TMA-containing particles originating from inner-Arctic sources, particles with biomass burning markers (such as levoglucosan and potassium) showed a higher fraction at higher altitudes, indicating long-range transport as their source. Our measurements highlight the importance of natural, marine inner-Arctic sources for composition and growth of summertime Arctic aerosol.

Description: This study discusses an analysis of combined airborne and ground observations of particulate nitrate (NO3−(p)) concentrations made during the wintertime DISCOVER-AQ (Deriving Information on Surface Conditions from COlumn and VERtically resolved observations relevant to Air Quality) study at one of the most polluted cities in the United States – Fresno, CA – in the San Joaquin Valley (SJV) and focuses on developing an understanding of the various processes that impact surface nitrate concentrations during pollution events. The results provide an explicit case-study illustration of how nighttime chemistry can influence daytime surface-level NO3−(p) concentrations, complementing previous studies in the SJV. The observations exemplify the critical role that nocturnal chemical production of NO3−(p) aloft in the residual layer (RL) can play in determining daytime surface-level NO3−(p) concentrations. Further, they indicate that nocturnal production of NO3−(p) in the RL, along with daytime photochemical production, can contribute substantially to the buildup and sustaining of severe pollution episodes. The exceptionally shallow nocturnal boundary layer (NBL) heights characteristic of wintertime pollution events in the SJV intensify the importance of nocturnal production aloft in the residual layer to daytime surface concentrations. The observations also demonstrate that dynamics within the RL can influence the early-morning vertical distribution of NO3−(p), despite low wintertime wind speeds. This overnight reshaping of the vertical distribution above the city plays an important role in determining the net impact of nocturnal chemical production on local and regional surface-level NO3−(p) concentrations. Entrainment of clean free-tropospheric (FT) air into the boundary layer in the afternoon is identified as an important process that reduces surface-level NO3−(p) and limits buildup during pollution episodes. The influence of dry deposition of HNO3 gas to the surface on daytime particulate nitrate concentrations is important but limited by an excess of ammonia in the region, which leads to only a small fraction of nitrate existing in the gas phase even during the warmer daytime. However, in the late afternoon, when diminishing solar heating leads to a rapid fall in the mixed boundary layer height (BLH), the impact of surface deposition is temporarily enhanced and can lead to a substantial decline in surface-level particulate nitrate concentrations; this enhanced deposition is quickly arrested by a decrease in surface temperature, which drops the gas-phase fraction to near zero. The overall importance of enhanced late-afternoon gas-phase loss to the multiday buildup of pollution events is limited by the very shallow nocturnal boundary layer. The case study here demonstrates that mixing down of NO3−(p) from the RL can contribute a majority of the surface-level NO3−(p) in the morning (here,  ∼  80 %), and a strong influence can persist into the afternoon even when photochemical production is maximum. The particular day-to-day contribution of aloft nocturnal NO3−(p) production to surface concentrations will depend on prevailing chemical and meteorological conditions. Although specific to the SJV, the observations and conceptual framework further developed here provide general insights into the evolution of pollution episodes in wintertime environments.