Lana, Arantxa ... et. al.-- 17 pages, 6 figures, 2 tables, supporting information http://dx.doi.org/10.1029/2010GB003850The potentially significant role of the biogenic trace gas dimethylsulfide (DMS) in determining the Earth's radiation budget makes it necessary to accurately reproduce seawater DMS distribution and quantify its global flux across the sea/air interface. Following a threefold increase of data (from 15,000 to over 47,000) in the global surface ocean DMS database over the last decade, new global monthly climatologies of surface ocean DMS concentration and sea-to-air emission flux are presented as updates of those constructed 10 years ago. Interpolation/extrapolation techniques were applied to project the discrete concentration data onto a first guess field based on Longhurst's biogeographic provinces. Further objective analysis allowed us to obtain the final monthly maps. The new climatology projects DMS concentrations typically in the range of 1–7 nM, with higher levels occurring in the high latitudes, and with a general trend toward increasing concentration in summer. The increased size and distribution of the observations in the DMS database have produced in the new climatology substantially lower DMS concentrations in the polar latitudes and generally higher DMS concentrations in regions that were severely undersampled 10 years ago, such as the southern Indian Ocean. Using the new DMS concentration climatology in conjunction with state-of-the-art parameterizations for the sea/air gas transfer velocity and climatological wind fields, we estimate that 28.1 (17.6–34.4) Tg of sulfur are transferred from the oceans into the atmosphere annually in the form of DMS. This represents a global emission increase of 17% with respect to the equivalent calculation using the previous climatology. This new DMS climatology represents a valuable tool for atmospheric chemistry, climate, and Earth System models.This work was the core of DiMethylSulfide concentrations and emission fluxes in the Global Ocean (DMS‐GO), a joint initiative of the SOLAS Integration Project and the EU projects COST Action 735 and EUR‐OCEANS. Tom Bell, Peter Liss, and SOLAS Project Integration are supported by a U.K. SOLAS Knowledge Transfer grant (NE/E001696/1). Further support was provided by the Spanish Ministry of Science and Innovation through the projects MIMOSA, Malaspina 2010, and a Ph.D. studentship to A.L.Peer reviewe

Volatile halogenated organic compounds containing bromine and iodine, which are naturally produced in the ocean, are involved in ozone depletion in both the troposphere and stratosphere. Three prominent compounds transporting large amounts of marine halogens into the atmosphere are bromoform (CHBr₃), dibromomethane (CH₂Br₂) and methyl iodide (CH₃I). The input of marine halogens to the stratosphere has been estimated from observations and modelling studies using low-resolution oceanic emission scenarios derived from top-down approaches. In order to improve emission inventory estimates, we calculate data-based high resolution global sea-to-air flux estimates of these compounds from surface observations within the HalOcAt (Halocarbons in the Ocean and Atmosphere) database (https://halocat.geomar.de/). Global maps of marine and atmospheric surface concentrations are derived from the data which are divided into coastal, shelf and open ocean regions. Considering physical and biogeochemical characteristics of ocean and atmosphere, the open ocean water and atmosphere data are classified into 21 regions. The available data are interpolated onto a 1°×1° grid while missing grid values are interpolated with latitudinal and longitudinal dependent regression techniques reflecting the compounds' distributions. With the generated surface concentration climatologies for the ocean and atmosphere, global sea-to-air concentration gradients and sea-to-air fluxes are calculated. Based on these calculations we estimate a total global flux of 1.5/2.5 Gmol Br yr⁻¹ for CHBr₃, 0.78/0.98 Gmol Br yr⁻¹ for CH₂Br₂ and 1.24/1.45 Gmol Br yr⁻¹ for CH₃I (robust fit/ordinary least squares regression techniques). Contrary to recent studies, negative fluxes occur in each sea-to-air flux climatology, mainly in the Arctic and Antarctic regions. "Hot spots" for global polybromomethane emissions are located in the equatorial region, whereas methyl iodide emissions are enhanced in the subtropical gyre regions. Inter-annual and seasonal variation is contained within our flux calculations for all three compounds. Compared to earlier studies, our global fluxes are at the lower end of estimates, especially for bromoform. An under-representation of coastal emissions and of extreme events in our estimate might explain the mismatch between our bottom-up emission estimate and top-down approaches.

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 (NH_x(sw)), which reflects a balance between remineralization of organic matter, uptake by plankton, and nitrification. Here we compare [NH_x(sw)] from two global ocean biogeochemical models (BEC and COBALT) against extensive ocean observations. Simulated [NH_x(sw)] are generally biased high. Improved simulation can be achieved in COBALT by increasing the plankton affinity for NH_x 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 NH_x 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.

This paper presents an updated estimation of the bottom-up global surface seawater dimethyl sulfide (DMS) climatology. This update, called DMS-Rev3, is the third of its kind and includes five significant changes from the last climatology, L11 (Lana et al., 2011), that was released about a decade ago. The first change is the inclusion of new observations that have become available over the last decade, creating a database of 873 539 observations leading to an ∼ 18-fold increase in raw data as compared to the last estimation. The second is significant improvements in data handling, processing, and filtering, to avoid biases due to different observation frequencies which result from different measurement techniques. Thirdly, we incorporate the dynamic seasonal changes observed in the geographic boundaries of the ocean biogeochemical provinces. The fourth change involves the refinement of the interpolation algorithm used to fill in the missing data. Lastly, an upgraded smoothing algorithm based on observed DMS variability length scales (VLS) helps to reproduce a more realistic distribution of the DMS concentration data. The results show that DMS-Rev3 estimates the global annual mean DMS concentration to be ∼ 2.26 nM (2.39 nM without a sea-ice mask), i.e., about 4 % lower than the previous bottom-up L11 climatology. However, significant regional differences of more than 100 % as compared to L11 are observed. The global sea-to-air flux of DMS is estimated at ∼ 27.1 TgS yr⁻¹, which is about 4 % lower than L11, although, like the DMS distribution, large regional differences were observed. The largest changes are observed in high concentration regions such as the polar oceans, although oceanic regions that were under-sampled in the past also show large differences between revisions of the climatology. Finally, DMS-Rev3 reduces the previously observed patchiness in high productivity regions. The new climatology, along with the algorithm, can be found in the online repository: https://doi.org/10.17632/hyn62spny2.1 (Mahajan, 2021).

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.

Marine dimethyl sulfide (DMS) is important to climate due to the ability of DMS to alter Earth's radiation budget. Knowledge of the global-scale distribution, seasonal variability, and sea-to-air flux of DMS is needed in order to improve understanding of atmospheric sulfur, aerosol/cloud dynamics, and albedo. Here we examine the use of an artificial neural network (ANN) to extrapolate available DMS measurements to the global ocean and produce a global climatology with monthly temporal resolution. A global database of 82 996 ship-based DMS measurements in surface waters was used along with a suite of environmental parameters consisting of latitude–longitude coordinates, time of day, time of year, solar radiation, mixed layer depth, sea surface temperature, salinity, nitrate, phosphate, and silicate. Linear regressions of DMS against the environmental parameters show that on a global-scale mixed layer depth and solar radiation are the strongest predictors of DMS. These parameters capture ∼9 % and ∼7 % of the raw DMS data variance, respectively. Multilinear regression can capture more of the raw data variance (∼39 %) but strongly underestimates DMS in high-concentration regions. In contrast, the artificial neural network captures ∼66 % of the raw data variance in our database. Like prior climatologies our results show a strong seasonal cycle in surface ocean DMS with the highest concentrations and sea-to-air fluxes in the high-latitude summertime oceans. We estimate a lower global sea-to-air DMS flux (20.12±0.43 Tg S yr⁻¹) than the prior estimate based on a map interpolation method when the same gas transfer velocity parameterization is used. Our sensitivity test results show that DMS concentration does not change unidirectionally with each of the environmental parameters, which emphasizes the interactions among these parameters. The ANN model suggests that the flux of DMS from the ocean to the atmosphere will increase with global warming. Given that larger DMS fluxes induce greater cloud albedo, this corresponds to a negative climate feedback.