Observation- and model-based estimates of particulate dry nitrogen deposition to the oceans

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° x 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 TM4-ECPL (TM4) model: 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, weighted by grid-cell area and numbers of observations, (RA,n) were used to assess the performance of the models. Comparison in the three study regions suggests that TM4 over-estimates NO3- concentrations (RA,n = 1.4 – 2.9) and under-estimates 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

The transport and fate of microplastic fibres in the Antarctic: The role of multiple global processes

Understanding the transport and accumulation of microplastics is useful to determine the relative risk they pose to global biodiversity. The exact contribution of microplastic sources is hard to elucidate; therefore, investigating the Antarctic Weddell Sea, an area known for its remoteness and little human presence (i.e. limited pollution sources), will help us to better understand microplastic transportation. Here, we investigate the presence of microplastics in a range of Antarctic sample media including air, seawater, and sediment. We hypothesised that multiple transportation processes including atmospheric and oceanic vectors determine the presence of microplastics in the Antarctic. Using techniques including Polarised Light Microscopy and Raman Spectrometry, we identified mostly fibres and categorised them based on their optical and chemical properties. A total of 47 individual microplastic categories (45 of which were fibres) were identified in the air, seawater, and sediment samples. The majority of categories did not overlap multiple media (42/47); however, four fibre categories were present in both air and water samples, and another fibre category was found in all three media (category 27). We suggest that the large variety of fibres identified and the overlap of fibre categories among media indicates that the pollution may result from multiple diffuse sources and transportation pathways. Additionally, our Air Mass Back Trajectory analyses demonstrates that microplastic fibres are being transported by air masses or wind, and strongly suggests that they are transported to the Antarctic from southern South America. We also propose that fibres may be transported into the Antarctic in subsurface waters, and as pollution was identified in our sediment and additional sea ice samples, we suggest that the coastal and Antarctic deep sea may be a sink for microplastic fibres. The results shown here from a remote, near-pristine system, further highlight the need for a global response to the plastic pollution crisis

Vaal Triangle Air Quality Data

This dataset contains data from the Department of Environmental Affairs for the following stations in the Vaal Triangle: Diep KloofKliprivierSebokengSharpevilleThree RiversZamdela </div

A case study in the wintertime Vaal Triangle Air-Shed Priority Area on the utility of the nitrogen stable isotopic composition of aerosol nitrate to identify NOx sources

In South Africa, the Highveld region and the Johannesburg-Pretoria megacity are known as global NOx (NOx = NO + NO2) “hotspots” identified by satellite-based instruments. The ultimate sink for atmospheric NOx is conversion to aerosol nitrate. However, measurements of aerosol nitrate concentrations do not provide information on which NOx sources served as nitrate precursors at that location. This complicates efforts to reduce concentrations of particulate matter (PM) in these air quality priority areas. Here, we measured the nitrogen stable isotopic composition of nitrate from daily wintertime collections of coarse mode PM2.5-10 (PM ≤ 10 and &gt;2.5 µm in diameter) at three air quality monitoring stations located in the Vaal Triangle Air-Shed Priority Area (VTAPA). The overall aim of this case study was to evaluate the use of the distinct stable isotopic signatures of various NOx sources to identify their relative contribution to aerosol nitrate across the Highveld. The nitrogen isotopic ratios of aerosol nitrate were similar across the three sites, with greater day-to-day variability than site to site variability. Air mass history was the main driver of the variability in the nitrogen isotopic ratios of aerosol nitrate, with significantly higher isotopic ratios observed for air masses originating from the southwest. Using an isotope mixing model we determined that NOx from coal-burning is the dominant contributor to aerosol nitrate (66%), followed by biomass burning (16%), vehicles (12%), and soil emissions (6%)

Molecular characterization of water soluble organic nitrogen in marine rainwater by ultra-high resolution electrospray ionization mass spectrometry

Atmospheric water soluble organic nitrogen (WSON) is a subset of the complex organic matter in aerosols and rainwater, which impacts cloud condensation processes and aerosol chemical and optical properties and may play a significant role in the biogeochemical cycle of N. However, its sources, composition, connections to inorganic N, and variability are largely unknown. Rainwater samples were collected on the island of Bermuda (32.27° N, 64.87° W), which experiences both anthropogenic and marine influenced air masses. Samples were analyzed by ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to chemically characterize the WSON. Elemental compositions of 2281 N containing compounds were determined over the mass range m/z+ 50 to 500. The five compound classes with the largest number of elemental formulas identified, in order from the highest number of formulas to the lowest, contained carbon, hydrogen, oxygen, and nitrogen (CHON+), CHON compounds that contained sulfur (CHONS+), CHON compounds that contained phosphorus (CHONP+), CHON compounds that contained both sulfur and phosphorus (CHONSP+), and compounds that contained only carbon, hydrogen, and nitrogen (CHN+). Compared to rainwater collected in the continental USA, average O:C ratios of all N containing compound classes were lower in the marine samples whereas double bond equivalent values were higher, suggesting a reduced role of secondary formation mechanisms. Despite their prevalence in continental rainwater, no organonitrates or nitrooxy-organosulfates were detected, but there was an increased presence of organic S and organic P containing compounds in the marine rainwater. Cluster analysis showed a clear chemical distinction between samples collected during the cold season (October to March) which have anthropogenic air mass origins and samples collected during the warm season (April to September) with remote marine air mass origins. This, in conjunction with patterns identified in van Krevelen diagrams, suggests that the cold season WSON is a mixture of organic matter with both marine and anthropogenic sources while in the warm season the WSON appears to be dominated by marine sources. These findings indicate that, although the concentrations and percent contribution of WSON to total N is fairly consistent across diverse geographic regions, the chemical composition of WSON varies strongly as a function of source region and atmospheric environment

Isotopic evidence for a marine ammonium source in rainwater at Bermuda

Emissions of anthropogenic nitrogen (N) to the atmosphere have increased tenfold since preindustrial times, resulting in increased N deposition to terrestrial and coastal ecosystems. The sources of N deposition to the ocean, however, are poorly understood. Two years of event‐based rainwater samples were collected on the island of Bermuda in the western North Atlantic, which experiences both continent‐ and ocean‐influenced air masses. The rainwater ammonium concentration ranged from 0.36 to 24.6 μM, and the ammonium δ15N from −12.5 to 0.7‰; and neither has a strong relationship with air mass history (6.0 ± 4.2 μM, −4.1 ± 2.6‰ in marine air masses and 5.9 ± 3.2 μM, −5.8 ± 2.5‰ in continental air masses; numerical average ± standard deviation). A simple box model suggests that the ocean can account for the concentration and isotopic composition of ammonium in marine rainwater, consistent with the lack of correlation between ammonium δ15N and air mass history. If so, ammonium deposition reflects the cycling of N between the ocean and the atmosphere, rather than representing a net input to the ocean. The δ15N data appear to require that most of the ammonium/a flux to the ocean is by dissolution in surface waters rather than atmospheric deposition. This suggests that the atmosphere and surface ocean are near equilibrium with respect to air/sea gas exchange, implying that anthropogenic ammonia will equilibrate near the coast and not reach the open marine atmosphere. Whereas ~90% of the ammonium deposition to the global ocean has previously been attributed to anthropogenic sources, the evidence at Bermuda suggests that the anthropogenic contribution could be much smaller

Insights into anthropogenic nitrogen deposition to the North Atlantic investigated using the isotopic composition of aerosol and rainwater nitrate

Identifying the dominant sources of atmospheric reactive nitrogen (Nr) is critical for determining the influence of anthropogenic emissions on Nr deposition, especially in marine ecosystems. To test the influence of anthropogenic versus marine air masses, samples were collected in Bermuda, where seasonal atmospheric circulation patterns lead to greater continental transport during the cool season. The 15N/14N of aerosol nitrate (NO3–) indicates changes in Nr sources and its 18O/16O indicates a seasonal shift in the relative strength of pathways of NO3– formation. The aerosol δ15N‐NO3– was consistently lower than or equal to the rainwater from the same sampling period, the opposite trend of that observed in polluted systems. We propose that this is due to HNO3(g) uptake onto aerosol particles with a kinetic isotope effect, lowering the aerosol δ15N‐NO3– relative to residual HNO3(g). The aerosol δ18O‐NO3– was higher than that in rainwater during the cool season, but was not different during the warm season, which we tentatively attribute to the increased importance of heterogeneous halogen chemistry on the formation of NO3– during the cool season

Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments, Atmos

Abstract Aqueous-phase photooxidation of glyoxal, a ubiquitous water-soluble gas-phase oxidation product of many compounds, is a potentially important global and regional source of oxalic acid and secondary organic aerosol (SOA). Reaction kinetics and product analysis are needed to validate and refine current aqueous-phase mechanisms to facilitate prediction of in-cloud oxalic acid and SOA formation from glyoxal. In this work, aqueous-phase photochemical reactions of glyoxal and hydrogen peroxide were conducted at pH values typical of clouds and fogs (i.e., pH ¼ 4-5). Experimental time series concentrations were compared to values obtained using a published kinetic model and reaction rate constants from the literature. Experimental results demonstrate the formation of oxalic acid, as predicted by the published aqueous phase mechanism. However, the published mechanism did not reproduce the glyoxylic and oxalic acid concentration dynamics. Formic acid and larger multifunctional compounds, which were not previously predicted, were also formed. An expanded aqueous-phase oxidation mechanism for glyoxal is proposed that reasonably explains the concentration dynamics of formic and oxalic acids and includes larger multifunctional compounds. The coefficient of determination for oxalic acid prediction was improved from 0.001 to 40.8 using the expanded mechanism. The model predicts that less than 1% of oxalic acid is formed through the glyoxylic acid pathway. This work supports the hypothesis that SOA forms through cloud processing of glyoxal and other water-soluble products of alkenes and aromatics of anthropogenic, biogenic and marine origin and provides reaction kinetics needed for oxalic acid prediction.