[1] Among the biosphere-atmosphere interactions that influence climate, the emission of dimethylsulfide (DMS) from the ocean plays a prominent role for its high potential in cloud albedo regulation. In order to advance in our understanding and quantification of this coupled ocean-atmosphere system, both synoptic and predictive capabilities must be largely improved. Hitherto, large-scale oceanic DMS has eluded being captured from remote sensing, correlated with synoptic variables, or simulated by mechanistic modeling. We have found a simple empirical relationship that permits global-ocean monthly distributions of DMS concentration to be computed from a combination of remotely sensed biospheric data (chlorophyll a) and climatological geophysical data (mixed layer depth). This relationship allows for the desired synopticity and predictability in the ocean-toatmosphere sulfur flux, which we have globally quantified as 23-35 Tg S yr À1 . Also, our algorithm stands in support of a biogenic-DMS/solar-radiation negative feedback and opens the door toward quantifying its strength and its response to global warming.

Abstract. The oxygen isotopic composition (Δ17O) of atmospheric nitrate is a function of the relative abundance of atmospheric oxidants (O3, ROx=OH+HO2+RO2) and the formation pathway of nitrate from its precursor NOx (=NO+NO2). Coupled observations and modeling of nitrate Δ17O can be used to quantify the relative importance of chemical formation pathways leading to nitrate formation and reduce uncertainties in the budget of reactive nitrogen chemistry in the atmosphere. We present the first global model of atmospheric nitrate Δ17O and compare with available observations. The largest uncertainty for calculations of nitrate Δ17O is the unconstrained variability in the Δ17O value of tropospheric ozone. The model shows the best agreement with a global compilation of observations when assuming a Δ17O value of tropospheric ozone equal to 35‰ and preferential oxidation of NOx by the terminal oxygen atoms of ozone. Calculated values of annual-mean nitrate Δ17O in the lowest model layer (0–200 m above the surface) vary from 7‰ in the tropics to 41‰ in the polar-regions. The global, annual-mean tropospheric inorganic nitrate burden is dominated by nitrate formation via NO2+OH (76%), followed by N2O5 hydrolysis (18%) and NO3+DMS/HC (4%). Calculated nitrate Δ17O is sensitive to the relative importance of each nitrate formation pathway, suggesting that observations of nitrate Δ17O can be used to quantify the importance of individual reactions (e.g. N2O5 hydrolysis) leading to nitrate formation if the Δ17O value of ozone is known.

Abstract. The oxygen isotopic composition (Δ17O) of atmospheric nitrate is a function of the relative abundance of atmospheric oxidants (O3, HOx=OH +HO2+RO2) and the formation pathway of nitrate from its precursor NOx (=NO+NO2). Coupled observations and modeling of nitrate Δ17O can be used to quantify the relative importance of chemical formation pathways leading to nitrate formation and reduce uncertainties in the budget of reactive nitrogen chemistry in the atmosphere. We present the first global model of atmospheric nitrate Δ17O and compare with available observations. The model shows the best agreement with a global compilation of observations when assuming a Δ17O value of tropospheric ozone equal to 35‰ and preferential oxidation of NOx by the terminal oxygen atoms of ozone. Calculated values of annual-mean nitrate Δ17O in the lowest model layer (0–200 m above the surface) vary from 6‰ in the tropics to 41‰ in the polar-regions. On the global scale, O3 is the dominant oxidant (81% annual-mean) during NOx cycling reactions. The global, annual-mean tropospheric inorganic nitrate burden is dominated by nitrate formation via NO2+OH (76%), followed by N2O5 hydrolysis (18%) and NO3+DMS/HC (4%). Model discrepancies are largest in the polar spring and summer, most likely due to the lack of reactive halogen chemistry in the model. The influence of organic nitrates on observations of nitrate Δ17O needs to be determined, especially for observations in summertime and tropical forested regions where organic nitrates can contribute up to 80% of the total NOy (organic plus inorganic nitrate) budget.

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