Chemistry and Release of Gases from the Surface Ocean

The sea-surface layer is the very upper part of the sea surface where reduced mixing leads to strong gradients in physical, chemical and biological properties1. This surface layer is naturally reactive, containing a complex chemistry of inorganic components and dissolved organic matter (DOM), the latter including amino acids, proteins, fatty acids, carbohydrates, and humic-type components,2 with a high proportion of functional groups such as carbonyls, carboxylic acids and aromatic moieties.3 The different physical and chemical properties of the surface of the ocean compared with bulk seawater, and its function as a gateway for molecules to enter the atmosphere or ocean phase, make this an interesting and important region for study. A number of chemical reactions are believed to occur on and in the surface ocean; these may be important or even dominant sources or sinks of climatically-active marine trace gases. However the sea surface, especially the top 1um to 1mm known as the sea surface microlayer (ssm), is critically under-sampled, so to date much of the evidence for such chemistry comes from laboratory and/or modeling studies. This review discusses the chemical and physical structure of the sea surface, mechanisms for gas transfer across it, and explains the current understanding of trace gas formation at this critical interface between the ocean and atmosphere.

Global oceanic emission of ammonia: Constraints from seawater and atmospheric observations

Current global inventories of ammonia emissions identify the ocean as the largest natural source. This source depends on seawater pH, temperature, and the concentration of total seawater ammonia (NHx(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare [NHx(sw)] from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated [NHx(sw)] are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NHx within observed ranges. The resulting global ocean emissions is 2.5 TgN a−1, much lower than current literature values (7–23 TgN a−1), including the widely used Global Emissions InitiAtive (GEIA) inventory (8 TgN a−1). Such a weak ocean source implies that continental sources contribute more than half of atmospheric NHx over most of the ocean in the Northern Hemisphere. Ammonia emitted from oceanic sources is insufficient to neutralize sulfate aerosol acidity, consistent with observations. There is evidence over the Equatorial Pacific for a missing source of atmospheric ammonia that could be due to photolysis of marine organic nitrogen at the ocean surface or in the atmosphere. Accommodating this possible missing source yields a global ocean emission of ammonia in the range 2–5 TgN a−1, comparable in magnitude to other natural sources from open fires and soils.

Particulate and dissolved aluminum and titanium in the upper water column of the Atlantic Ocean

This study investigates the oceanic behavior of the lithogenic trace elements Al and Ti in the upper 200 m of the Atlantic Ocean. The distribution of both metals in the dissolved and particulate phases was assessed along an E-W transect in the eastern tropical North Atlantic (December 2009) and along a meridional Atlantic transect (April-May 2010). The surface water concentrations of particulate and dissolved Al and Ti reflected the previously observed pattern of atmospheric inputs into the Atlantic Ocean. Subsurface minima at stations with pronounced fluorescence maxima were observed, suggesting a link between biological productivity and the removal of both dissolved and particulate Al and Ti. This may include uptake mechanisms, adsorption and aggregation processes on biogenic particle surfaces and the formation of large, fast sinking biogenic particles, e.g., fecal pellets. Residence times in the upper water column (100 m) of the tropical and subtropical North Atlantic were estimated to range in the order of days to weeks in the particulate phases (Al: 3-22 days, Ti: 4-37 days) and were 0.9-3.8 years for Al and 10-31 years for Ti in the dissolved phases. Longer residence times in both phases in the South Atlantic are consistent with lower biological productivity and decreased removal rates. In the upper water column, Al was predominantly present in the dissolved form, whereas Ti mostly occurred in the particulate form. Largest deviations in the partition coefficients between the particulate and dissolved phases were found in the surface waters, together with excess dissolved Al over Ti compared to the crustal source. This likely reflects elevated dissolution of Al compared to Ti from atmospheric mineral particles.

Iron organic speciation determination in rainwater using cathodic stripping voltammetry

A sensitive method using Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) has been developed to determine for the first time iron (Fe) organic speciation in rainwater over the typical natural range of pH. We have adapted techniques previously developed in other natural waters to rainwater samples, using the competing ligand 1-nitroso-2-naphthol (NN). The blank was equal to 0.17 ± 0.05 nM (n = 14) and the detection limit (DL) for labile Fe was 0.15 nM which is 10–70 times lower than that of previously published methods. The conditional stability constant for NN under rainwater conditions was calibrated over the pH range 5.52–6.20 through competition with ethylenediaminetetraacetic acid (EDTA). The calculated value of the logarithm of β′Fe3+3(NN)β′Fe3+(NN)3 increased linearly with increasing pH according to log β′Fe3+3(NN)=2.4±0.6×pH+11.9±3.5log β′Fe3+(NN)3=2.4±0.6×pH+11.9±3.5 (salinity = 2.9, T = 20 °C). The validation of the method was carried out using desferrioxamine mesylate B (DFOB) as a natural model ligand for Fe. Adequate detection windows were defined to detect this class of ligands in rainwater with 40 μM of NN from pH 5.52 to 6.20. The concentration of Fe-complexing natural ligands was determined for the first time in three unfiltered and one filtered rainwater samples. Organic Fe-complexing ligand concentrations varied from 104.2 ± 4.1 nM equivalent of Fe(III) to 336.2 ± 19.0 nM equivalent of Fe(III) and the logarithm of the conditional stability constants, with respect to Fe3+, varied from 21.1 ± 0.2 to 22.8 ± 0.3. This method will provide important data for improving our understanding of the role of wet deposition in the biogeochemical cycling of iron.

Estimation of atmospheric nutrient inputs to the Atlantic Ocean from 50°N to 50°S based on large-scale field sampling: Iron and other dust-associated elements

Atmospheric inputs of mineral dust supply iron and other trace metals to the remote ocean and can influence the marine carbon cycle due to iron's role as a potentially limiting micronutrient. Dust generation, transport, and deposition are highly heterogeneous, and there are very few remote marine locations where dust concentrations and chemistry (e.g., iron solubility) are routinely monitored. Here we use aerosol and rainwater samples collected during 10 large-scale research cruises to estimate the atmospheric input of iron, aluminum, and manganese to four broad regions of the Atlantic Ocean over two 3 month periods for the years 2001–2005. We estimate total inputs of these metals to our study regions to be 4.2, 17, and 0.27 Gmol in April–June and 4.9, 14, and 0.19 Gmol in September–November, respectively. Inputs were highest in regions of high rainfall (the intertropical convergence zone and South Atlantic storm track), and rainfall contributed higher proportions of total input to wetter regions. By combining input estimates for total and soluble metals for these time periods, we calculated overall percentage solubilities for each metal that account for the contributions from both wet and dry depositions and the relative contributions from different aerosol types. Calculated solubilities were in the range 2.4%–9.1% for iron, 6.1%–15% for aluminum, and 54%–73% for manganese. We discuss sources of uncertainty in our estimates and compare our results to some recent estimates of atmospheric iron input to the Atlantic.

The evolving and increasing need for climate change research on the oceans

The 3rd International Symposium on the Effects of Climate Change on the World's Oceans was held in Santos, Brazil, in March 2015, convened by the International Council for the Exploration of the Sea (ICES), the North Pacific Marine Science Organization (PICES), and the Intergovernmental Oceanographic Commission of UNESCO (IOC), and organized locally by the Oceanographic Institute, University of Sao Paulo (IO-USP). The symposium was designed to do two things. First, to get updates on new scientific developments that would address recognized uncertainties that remained from Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report and to contribute to building bridges between research in the natural and social sciences in respect to the human dimensions of climate change, with a focus on coastal communities, management objectives, governance and adaptation measures. The choice of the venue in Santos, Brazil, was aimed to stimulate and widen this thematic discussion in Latin America and southern Atlantic regions, where there still are important knowledge gaps and scientific, politic and societal challenges to be overcome. The meeting was attended by 280 participants from 38 countries, contributing 336 oral and poster presentations. This paper summarizes the main outcomes of the symposium and introduces a number of papers submitted to this special issue.

Family-level AMBI is valid for use in the north-eastern Atlantic but not for assessing the health of microtidal Australian estuaries

Analysis of benthic macroinvertebrate samples at a higher taxonomic level than species, e.g. family, potentially provides a more cost-effective protocol for environmental impact assessments and monitoring as it requires less time, funds and taxonomic expertise. Using the AMBI database, species ecological group scores are shown to be coherent within families. Faunal data from a wide range of environmental impact scenarios in the north-eastern Atlantic demonstrate that AMBI, calculated from mean values for families, exhibits a strong linear relationship with species-level AMBI, the correlation improving by using square-root transformed rather than untransformed abundances. In many regions of the world, however, the sensitivity of benthic macroinvertebrates to environmental perturbations is unknown, precluding the use of AMBI for environmental assessments. Yet the families are essentially the same as in the AMBI database. The utility of family-level AMBI is tested using data for four south-western Australian estuaries previously subjected to environmental quality assessments, but where only 17 species of the 144 taxa are included in the AMBI database. Although family-level AMBI scores reflect differences in environmental quality spatially and temporally within an estuary, they do not follow variations in environmental quality among estuaries. Indeed, south-western Australia estuaries are numerically dominated by families with high AMBI scores, probably due to the detrimental effects of natural accumulations of organic material in estuaries with long residence times. As taxonomic distinctness follows trends in environmental quality among estuaries, as well as temporally and spatially within a system, it provides an appropriate substitute for assessing the 'heath' of microtidal estuaries.

Attribution of Atmospheric Sulfur Dioxide over the English Channel to Dimethylsulfide and Changing Ship Emissions

Atmospheric sulfur dioxide (SO2) was measured continuously from the Penlee Point Atmospheric Observatory(PPAO) near Plymouth, United Kingdom between May 2014 and November 2015. This coastal site is exposed to marine air across a wide wind sector. The predominant southwesterly winds carry relatively clean background Atlantic air. In contrast, air from the southeast is heavily influenced by exhaust plumes from ships in the English Channel as well as near the Plymouth Sound. New International Maritime Organization (IMO) regulation came into force in January 2015 to reduce sulfur emissions tenfold in Sulfur Emission Control Areas such as the English Channel. Our observations suggest a three-fold reduction from 2014 to 2015 in ship-emitted SO2 from that direction. Apparent fuel sulfur content calculated from coincidental SO2 and carbon dioxide (CO2) peaks from local ship plum es show a high level of compliance to the IMO regulation (> 95 %) in both years. Dimethylsulfide (DMS) is an important source of atmospheric SO2 even in this semi-polluted region. The relative contribution of DMS oxidation to the SO2 burden over the English Channel increased from ~ 1/3 in 2014 to ~ 1/2 in 2015 due to the reduction in ship sulfur emissions. Our diel analysis suggests that SO2 is removed from the marine atmospheric boundary layer in about half a day, with dry deposition to the ocean accounting for a quarter of the total loss.

Assessing the conservation status of marine habitats: thoughts from a sandflat on the Isles of Scilly.

Statutory monitoring of the fauna of the ‘mudflats and sandflats not covered by seawater at low tide’ biotope complex on St Martin’s Flats, a part of the Isles of Scilly Complex Special Area of Conservation, was undertaken in 2000, 2004 and 2009. The targets set by Natural England for “characteristic biotopes” were that “composite species, abundance and diversity should not deviate significantly from an established baseline, subject to natural change”. The three specified biotopes could not be distinguished, and instead three assemblages were subjectively defined based on sediment surface features. There were statistically significant natural changes in diversity and species composition between years, especially in the association initially characterized by the razor-clam Ensis, and possible reasons for this are discussed. It is suggested that setting fixed local limits on natural variability is almost always impractical. Two possible approaches to distinguishing between natural and anthropogenic changes are suggested; a change in ecological condition as indicated by AMBI scores, and a significant change in average taxonomic distinctness (Δ+) compared with expectation. The determination of species biomasses as well as abundances might also open more possibilities for assessment. The practice of setting objectives for a marine SAC feature that include the range and number of biotopes cannot be supported, in view the difficulty in ascribing assemblages to recognised biotopes. A more realistic definition of species assemblages might best be gained from examination of the species that consistently make a substantial contribution to the Bray Curtis similarity among samples collected from specific sites.