One of the shallowest, most intense oxygen minimum zones (OMZs) is found in the eastern tropical South Pacific, off northern Chile and southern Peru. It has a strong oxygen gradient (upper oxycline) and high N 2 O accumulation. N 2 O cycling by heterotrophic denitrification along the upper oxycline was studied by measuring N 2 O production and consumption rates using an improved acetylene blockage method.

Coastal upwelling areas are highly productive marine systems in which the development of oxygen-depleted conditions and the availability of diverse electron donors (e.g., organic matter, NH z 4 , H 2 S) favor the processes involved in nitrogen (N) loss. We characterize the temporal and vertical variability of anammox and denitrification over the continental shelf off central Chile (36.5uS), through 15 N and 13 C tracer experiments, including amendments with H 2 S and S 2 O 2{ 3 along with measurements of 15 N 2 and 15 N 2 O production and oceanographic variables during a year (2009 to 2010). Restricted to the bottom waters, both anammox and denitrification contributed similarly (, 500 nmol N 2 L 21 d 21 ) to N loss during spring, while a marked decrease in the activity of these processes occurred in summer (103 and 14 nmol N 2 L 21 d 21 for anammox and denitrification, respectively). During fall, denitrification was the only contributor to the observed nitrogen deficit (894 nmol N 2 L 21 d 21 ). Interestingly, a substantial increase in the rates of denitrification (, 1200 nmol N 2 L 21 d 21 ) and dark 13 C assimilation were observed after the addition of H 2 S, indicating an autotrophic contribution to denitrification, which could be fueled in situ by H 2 S emitted from sediments or produced in the water column. The observed patterns seem to be controlled (stimulated or inhibited) by the availability of oxygen, organic matter, and H 2 S. This study establishes the magnitude and co-occurrence of the different processes responsible for N removal in the coastal upwelling system of central Chile. This linkage of the nitrogen, carbon, and sulfur cycles is relevant to a global climate change scenario.

Abstract. The high availability of electron donors occurring in coastal upwelling ecosystems with marked oxyclines favours chemoautotrophy, in turn leading to high N 2 O and CH 4 cycling associated with aerobic NH + 4 (AAO) and CH 4 oxidation (AMO). This is the case of the highly productive coastal upwelling area off central Chile (36 • S), where we evaluated the importance of total chemolithoautotrophic vs. photoautotrophic production, the specific contributions of AAO and AMO to chemosynthesis and their role in gas cycling. Chemolithoautotrophy was studied at a time-series station during monthly (2007)(2008)(2009)) and seasonal cruises (January 2008, September 2008, January 2009) and was assessed in terms of the natural C isotopic ratio of particulate organic carbon (δ 13 POC), total and specific (associated with AAO and AMO) dark carbon assimilation (CA), and N 2 O and CH 4 cycling experiments. At the oxycline, δ 13 POC averaged −22.2‰; this was significantly lighter compared to the surface (−19.7‰) and bottom layers (−20.7‰). Total integrated dark CA in the whole water column fluctuated between 19.4 and 2.924 mg C m −2 d −1 , was higher during active upwelling, and contributed 0.7 to 49.7% of the total integrated autotrophic CA (photo plus chemoautotrophy), which ranged from 135 to 7.626 mg C m −2 d −1 , and averaged 20.3% for the whole sampling period. Dark CA was reduced by 27 to 48% after adding a specific AAO inhibitor (ATU) and by 24 to 76% with GC7, a specific archaea inhibitor. This indicates that AAO and AMO microbes (most of them archaea) were performing dark CA through the oxidation of NH

Despite the importance of nitrous oxide (N2O) in the global radiative balance and atmospheric ozone chemistry, its sources and sinks within the Earth’s system are still poorly understood. In the ocean, N2O is produced by microbiological processes such as nitrification and partial denitrification, which account for about a third of global emissions. Conversely, complete denitrification (the dissimilative reduction of N2O to N2) under suboxic/anoxic conditions is the only known pathway accountable for N2O consumption in the ocean. In this work, it is demonstrated that the biological assimilation of N2O could be a significant pathway capable of directly transforming this gas into particulate organic nitrogen (PON). N2O is shown to be biologically fixed within the subtropical and tropical waters of the eastern South Pacific Ocean, under a wide range of oceanographic conditions and at rates ranging from 2 pmol N L−1 d− to 14.8 nmol N L−1 d−1 (mean ± SE of 0.522±1.06 nmol N L−1 d−1, n = 93). Additional assays revealed that cultured cyanobacterial strains of Trichodesmium (H-9 and IMS 101), and Crocosphaera (W-8501) have the capacity to directly fix N2O under laboratory conditions; suggesting that marine photoautotrophic diazotrophs could be using N2O as a substrate. This metabolic capacity however was absent in Synechococcus (RCC 1029). The findings presented here indicate that assimilative N2O fixation takes place under extreme environmental conditions (i.e., light, nutrient, oxygen) where both autotrophic (including cyanobacteria) and heterotrophic microbes appear to be involved. This process could provide a globally significant sink for atmospheric N2O which in turn affects the oceanic N2O inventory and may also represent a yet unexplored global oceanic source of fixed N.

Abstract. Coastal upwelling ecosystems with marked oxyclines (redoxclines) present high availability of electron donors that favour chemoautotrophy, leading in turn to high N2O and CH4 cycling associated with aerobic NH4+ (AAO) and CH4 oxidation (AMO). This is the case of the highly productive coastal upwelling area off Central Chile (36° S), where we evaluated the importance of total chemolithoautotrophic vs. photoautotrophic production, the specific contributions of AAO and AMO to chemosynthesis and their role in gas cycling. Chemoautotrophy (involving bacteria and archaea) was studied at a time-series station during monthly (2002–2009) and seasonal cruises (January 2008, September 2008, January 2009) and was assessed in terms of dark carbon assimilation (CA), N2O and CH4 cycling, and the natural C isotopic ratio of particulate organic carbon (δ13POC). Total Integrated dark CA fluctuated between 19.4 and 2.924 mg C m−2 d−1. It was higher during active upwelling and represented on average 27% of the integrated photoautotrophic production (from 135 to 7.626 mg C m−2d−1). At the oxycline, δ13POC averaged -22.209‰ this was significantly lighter compared to the surface (-19.674‰) and bottom layers (-20.716‰). This pattern, along with low NH4+ content and high accumulations of N2O, NO2- and NO3- within the oxycline indicates that chemolithoautotrophs and specifically AA oxydisers were active. Dark CA was reduced from 27 to 48% after addition of a specific AAO inhibitor (ATU) and from 24 to 76% with GC7, a specific archaea inhibitor, indicating that AAO and maybe AMO microbes (most of them archaea) were performing dark CA through oxidation of NH4+ and CH4. AAO produced N2O at rates from 8.88 to 43 nM d−1 and a fraction of it was effluxed into the atmosphere (up to 42.85 μmol m−2 d−1). AMO on the other hand consumed CH4 at rates between 0.41 and 26.8 nM d−1 therefore preventing its efflux to the atmosphere (up to 18.69 μmol m−2 d−1). These findings show that chemically driven chemoautotrophy (with NH4+ and CH4 acting as electron donors) could be more important than previously thought in upwelling ecosystems and open new questions concerning its future relevance.