We quantified the removal of fixed nitrogen as N 2 production by anammox and N 2 and N 2 O production by denitrification over a distance of 1900 km along the coasts of Chile and Peru, using short-term incubations with 15 N-labeled substrates. The eastern South Pacific contains an oxygen minimum zone (OMZ) characterized by an anoxic, nitrate-and nitrite-rich layer of , 200-m thickness below 30-90 m of oxic water. Anammox and denitrification were almost exclusively recorded when the in situ O 2 concentration was below detection, indicating that the induction of these processes is highly oxygen sensitive. Anammox was detected in 70% of the samples from anoxic depths. Denitrification was detected in fewer samples, but maximum rates were an order of magnitude higher than those of anammox. In our incubations denitrification was responsible for 72% of the total N 2 production and 77% of the total removal of fixed nitrogen including N 2 O production. However, at the individual depths it could be one or the other process that was responsible for all of the nitrogen removal. Anammox activity was highest just below the oxic-anoxic interface and declined exponentially with depth, whereas no depth dependence was discerned for denitrification. Denitrification resulted in net production of N 2 O in some of the samples and consumption of added 15 N 2 O in others. Together with the accumulation of NO

Nitrogen fixation is an essential process that biologically transforms atmospheric dinitrogen gas to ammonia, therefore compensating for nitrogen losses occurring via denitrification and anammox. Currently, inputs and losses of nitrogen to the ocean resulting from these processes are thought to be spatially separated: nitrogen fixation takes place primarily in open ocean environments (mainly through diazotrophic cyanobacteria), whereas nitrogen losses occur in oxygen-depleted intermediate waters and sediments (mostly via denitrifying and anammox bacteria). Here we report on rates of nitrogen fixation obtained during two oceanographic cruises in 2005 and 2007 in the eastern tropical South Pacific (ETSP), a region characterized by the presence of coastal upwelling and a major permanent oxygen minimum zone (OMZ). Our results show significant rates of nitrogen fixation in the water column; however, integrated rates from the surface down to 120 m varied by ∼30 fold between cruises (7.5±4.6 versus 190±82.3 µmol m−2 d−1). Moreover, rates were measured down to 400 m depth in 2007, indicating that the contribution to the integrated rates of the subsurface oxygen-deficient layer was ∼5 times higher (574±294 µmol m−2 d−1) than the oxic euphotic layer (48±68 µmol m−2 d−1). Concurrent molecular measurements detected the dinitrogenase reductase gene nifH in surface and subsurface waters. Phylogenetic analysis of the nifH sequences showed the presence of a diverse diazotrophic community at the time of the highest measured nitrogen fixation rates. Our results thus demonstrate the occurrence of nitrogen fixation in nutrient-rich coastal upwelling systems and, importantly, within the underlying OMZ. They also suggest that nitrogen fixation is a widespread process that can sporadically provide a supplementary source of fixed nitrogen in these regions.

We investigated the pathways of N 2 production in the oxygen-deficient water column of the eastern tropical South Pacific off Iquique, Chile, at 20uS, through short anoxic incubations with 15 N-labelled nitrogen compounds. The location was characterized by steep chemical gradients, with oxygen decreasing to below detection at ,50-m depth, while nitrite reached 6 mmol L 21 and ammonium was less than 50 nmol L 21 . Ammonium was oxidized to N 2 with no lag phase during the incubations, and when only NH þ 4 was 15 N-labeled, 15 N appeared in the form of 14 N 15 N, whereas 15 N 15 N was not detected. Likewise, nitrite was reduced to N 2 at rates similar to the rates of ammonium oxidation, and when only NO 2 2 was 15 N-labeled, 15 N appeared mainly as 14 N 15 N, whereas 15 N 15 N appeared in only one incubation. These observations indicate that ammonium was oxidized and nitrite was reduced through the anammox reaction, whereas denitrification was generally not detected and, therefore, was a minor sink for nitrite. Anammox rates were highest, up to 0.7 nmol N 2 L 21 h 21 , just below the oxycline, whereas rates were undetectable, ,0.2 nmol N 2 L 21 h 21 , deeper in the oxygen-deficient zone. Instead of complete denitrification to N 2 , oxidation of organic matter during the incubations may have been coupled to reduction of nitrate to nitrite. This process was evident from strong increases in nitrite concentrations toward the end of the incubations. The results point to anammox as an active process in the major open-ocean oxygen-deficient zones, which are generally recognized as important sites of denitrification. Still, denitrification remains the simplest explanation for most of the nitrogen deficiency in these zones.

Abstract. We review here the available information on methane (CH 4 ) and nitrous oxide (N 2 O) from major marine, mostly coastal, oxygen (O 2 )-deficient zones formed both naturally and as a result of human activities (mainly eutrophication). Concentrations of both gases in subsurface waters are affected by ambient O 2 levels to varying degrees. Organic matter supply to seafloor appears to be the primary factor controlling CH 4 production in sediments and its supply to (and concentration in) overlying waters, with bottom-water O 2 -deficiency exerting only a modulating effect. High (micromolar level) CH 4 accumulation occurs in anoxic (sulphidic) waters of silled basins, such as the Black Sea and Cariaco Basin, and over the highly productive Namibian shelf. In other regions experiencing various degrees of O 2 -deficiency (hypoxia to anoxia), CH 4 concentrations vary from a few to hundreds of nanomolar levels. Since coastal O 2 -deficient zones are generally very productive and are sometimes located close to river mouths and submarine hydrocarbon seeps, it is difficult to differentiate any O 2 -deficiency-induced enhancement from in situ production of CH 4 in the water column and its inputs through freshwater runoff or seepage from sediments. While the role of bottom-water O 2 -deficiency in CH 4 formation appears to be secondary, even when CH 4 accumulates in O 2 -deficient subsurface waters, methanotrophic activity severely restricts its diffusive efflux to the atmosphere. As a result, an intensification or expansion of coastal O 2 -deficient zones will probably Correspondence to: S. W. A. Naqvi (naqvi@nio.org) not drastically change the present status where emission from the ocean as a whole forms an insignificant term in the atmospheric CH 4 budget. The situation is different for N 2 O, the production of which is greatly enhanced in low-O 2 waters, and although it is lost through denitrification in most suboxic and anoxic environments, the peripheries of such environments offer most suitable conditions for its production, with the exception of enclosed anoxic basins. Most O 2 -deficient systems serve as strong net sources of N 2 O to the atmosphere. This is especially true for coastal upwelling regions with shallow O 2 -deficient zones where a dramatic increase in N 2 O production often occurs in rapidly denitrifying waters. Nitrous oxide emissions from these zones are globally significant, and so their ongoing intensification and expansion is likely to lead to a significant increase in N 2 O emission from the ocean. However, a meaningful quantitative prediction of this increase is not possible at present because of continuing uncertainties concerning the formative pathways to N 2 O as well as insufficient data from key coastal regions.

Mineral dust aerosols play a major role in present and past climates. To date, we rely on climate models for estimates of dust fluxes to calculate the impact of airborne micronutrients on biogeochemical cycles. Here we provide a new global dust flux data set for Holocene and Last Glacial Maximum (LGM) conditions based on observational data. A comparison with dust flux simulations highlights regional differences between observations and models. By forcing a biogeochemical model with our new data set and using this model's results to guide a millennial‐scale Earth System Model simulation, we calculate the impact of enhanced glacial oceanic iron deposition on the LGM‐Holocene carbon cycle. On centennial timescales, the higher LGM dust deposition results in a weak reduction of <10 ppm in atmospheric CO2 due to enhanced efficiency of the biological pump. This is followed by a further ~10 ppm reduction over millennial timescales due to greater carbon burial and carbonate compensation.