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  • 1
    ISSN: 1476-4687
    Source: Nature Archives 1869 - 2009
    Topics: Biology , Chemistry and Pharmacology , Medicine , Natural Sciences in General , Physics
    Notes: [Auszug] Nitrous oxide (N2O) is an important greenhouse gas that also plays a role in the chemistry of stratospheric ozone depletion, but its atmospheric budget has yet to be well-quantified. However, multi-isotope characterization of N2O emitted from various natural sources is a ...
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  • 2
    Publication Date: 2020-06-18
    Description: Nitrous oxide (N2O) is a climate relevant trace gas, and its production in the ocean generally increases under suboxic conditions. The Atlantic Ocean is well ventilated, and unlike the major oxygen minimum zones (OMZ) of the Pacific and Indian Oceans, dissolved oxygen and N2O concentrations in the Atlantic OMZ are relatively high and low, respectively. This study, however, demonstrates that recently discovered low oxygen eddies in the eastern tropical North Atlantic (ETNA) can produce N2O concentrations much higher (up to 115 nmol L−1) than those previously reported for the Atlantic Ocean, and which are within the range of the highest concentrations found in the open-ocean OMZs of the Pacific and Indian Oceans. N2O isotope and isotopomer signatures, as well as molecular genetic results, also point towards a major shift in the N2O cycling pathway in the core of the low oxygen eddy discussed here, and we report the first evidence for potential N2O cycling via the denitrification pathway in the open Atlantic Ocean. Finally, we consider the implications of low oxygen eddies for bulk, upper water column N2O at the regional scale, and point out the possible need for a reevaluation of how we view N2O cycling in the ETNA.
    Type: Article , PeerReviewed
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  • 3
    Publication Date: 2019-09-23
    Description: Fixed nitrogen (N) loss to biogenic N2 in intense oceanic O2 minimum zones (OMZ) accounts for a large fraction of the global N sink and is an essential control on the ocean's N budget. However, major uncertainties exist regarding microbial pathways as well as net impact on the magnitude of N-loss and the ocean's overall N budget. Here we report the discovery of a N-loss hotspot in the Peru OMZ associated with a coastally trapped mesoscale eddy that is marked by an extreme N deficit matched by biogenic N2 production, high NO2− levels, and the highest isotope enrichments observed so far in OMZ's for the residual NO3−. High sea surface chlorophyll (SSC) in seaward flowing streamers provides evidence for offshore eddy transport of highly productive, inshore water. Resulting pulses in the downward flux of particles likely stimulated heterotrophic dissimilatory NO3− reduction and subsequent production of biogenic N2. The associated temporal/spatial heterogeneity of N-loss, mediated by a local succession of microbial processes, may explain inconsistencies observed among prior studies. Similar transient enhancements of N-loss likely occur within all other major OMZ's exerting a major influence on global ocean N and N isotope budgets.
    Type: Article , PeerReviewed
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  • 4
    Publication Date: 2020-11-04
    Description: O2 minimum zones (OMZ) of the world's oceans are important locations for microbial dissimilatory NO3- reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. This is particularly so when the OMZ is coupled to a region of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N isotope ratios (and O in the case of NO3- and NO2-) can be used as natural tracers of OMZ N-cycling because of distinct kinetic isotope effects associated with microbially-mediated N-cycle transformations. Here we present NO2- and NO3- stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface O2 was generally depleted below about 30 m depth with O2 less than 10 μM, while NO2- concentrations were high, ranging from 6 to 10 μM and NO3- was in places strongly depleted to near 0 μM. We observed for the first time, a positive linear relationship between NO2- δ15N and δ18O at our coastal stations, analogous to that of NO3- N and O isotopes during assimilatory and dissimilatory reduction. This relationship is likely the result of rapid NO2- turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2- facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ε) for N-loss as calculated from the δ15N of [NO3-], DIN, or biogenic N2, values for ε are generally much lower than previously reported, reaching as low as 6.5‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation.
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  • 5
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    AGU (American Geophysical Union)
    In:  Global Biogeochemical Cycles, 8 (1). pp. 103-116.
    Publication Date: 2016-10-27
    Description: In two contrasting regions of the ocean, the equatorial Pacific and the southern ocean, the δ15N of core top sediments were strongly related to [NO3−] in surface waters. With distance from the equator in the equatorial Pacific, δ15N increased from 7‰ to 16‰ as [NO3−] decreased from 8μM to 〈 0.1 μM. Going from 60° to 30° S in the SE Indian Ocean, core top δ15N increased from 5‰ to 11‰ as surface [NO3−] decreased from 25μM to 〈 0.1 μM. These results are strong evidence that sedimentary δ15N in these regions is recording the increasing isotopic enrichment of near-surface NO3− with its depletion by phytoplankton. In the case of the equatorial Pacific, δ15N values for sinking particles collected at 150 m matched well the core top sediment values, demonstrating little diagenetic alteration of the near-surface generated isotopic signal. These equatorial Pacific data sets have variations with near-surface [NO3−] consistent with Rayleigh fractionation kinetics for a fractionation factor (ϵu) of 2.5‰. This value is substantially lower than previously found for temperate or polar regions, perhaps as a result of differences in phytoplankton species assemblage or growth condition. In the southern ocean south of the polar front, comparison of δ15N values for opal-rich sediments south and sinking particles indicates an apparent +5‰ diagenetic enrichment relative to the surface-generated signal that requires further investigation. This exception aside, our observations show that the surface-water relationship of increasing δ15N with increasing NO3− depletion is generally transmitted to and preserved in the sediments, an important requirement for further development and application of this important paleoceanographic tool.
    Type: Article , PeerReviewed
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  • 6
    Publication Date: 2019-09-23
    Description: Mesoscale eddies play a major role in controlling ocean biogeochemistry. By impacting nutrient availability and water column ventilation, they are of critical importance for oceanic primary production. In the eastern tropical South Pacific Ocean off Peru, where a large and persistent oxygen deficient zone is present, mesoscale processes have been reported to occur frequently. However, investigations on their biological activity are mostly based on model simulations, and direct measurements of carbon and dinitrogen (N2) fixation are scarce. We examined an open ocean cyclonic eddy and two anticyclonic mode water eddies: a coastal one and an open ocean one in the waters off Peru along a section at 16° S in austral summer 2012. Molecular data and bioassay incubations point towards a difference between the active diazotrophic communities present in the cyclonic eddy and the anticyclonic mode water eddies. In the cyclonic eddy, highest rates of N2 fixation were measured in surface waters but no N2 fixation signal was detected at intermediate water depths. In contrast, both anticyclonic mode water eddies showed pronounced maxima in N2 fixation below the euphotic zone as evidenced by rate measurements and geochemical data. N2 fixation and carbon (C) fixation were higher in the young coastal mode water eddy compared to the older offshore mode water eddy. A co-occurrence between N2 fixation and biogenic N2, an indicator for N loss, indicated a link between N loss and N2 fixation in the mode water eddies, which was not observed for the cyclonic eddy. The comparison of two consecutive surveys of the coastal mode water eddy in November and December 2012 revealed also a reduction of N2 and C fixation at intermediate depths along with a reduction in chlorophyll by half, mirroring an aging effect in this eddy. Our data indicate an important role for anticyclonic mode water eddies in stimulating N2 fixation and thus supplying N offshore.
    Type: Article , PeerReviewed
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  • 7
    Publication Date: 2019-09-23
    Type: Conference or Workshop Item , NonPeerReviewed
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  • 8
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    In:  [Poster] In: AGU Fall Meeting 2011, 05.-09.12.2011, San Francisco, USA .
    Publication Date: 2012-02-23
    Type: Conference or Workshop Item , NonPeerReviewed
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  • 9
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    In:  [Talk] In: AGU Fall Meeting 2010, 13.-17.12.2010, San Francisco, USA .
    Publication Date: 2012-02-23
    Description: residual nitrate. Through upwelling, phytoplankton assimilation, and downward particle flux, this signal is transferred to the underlying sediments and has been used to reconstruct past changes in denitrification and OMZ intensity in relation to climate change. However, there remain a number of impediments to quantitative interpretation of downcore δ15N records from OMZ’s with respect to past magnitude of N loss. One of these is knowledge of initial δ15N for nitrate prior to denitrification which cannot be assumed to be the modern oceanic average. In the case of the Peru-Chile OMZ, δ15N for nitrate in source waters from the Equatorial Undercurrent average 7‰ as compared to the oceanic average of ~5‰. This suggests processes external to the OMZ leading to isotopic enrichment such as partial phytoplankton nitrate utilization in the Subantarctic water mass formation region. In contrast, it has been surmised that initial δ15N for OMZ denitrification could be relatively low as a result of N2 fixation in geographically adjacent oligotrophic regions. High N2 fixation rates in the SE Pacifc Gyre are thought to be stimulated by low N/P waters upwelled from the Peru-Chile OMZ. As seen in the Sargasso Sea, subsurface remineralization of export production influenced by near-surface N2 fixation produces 15N-depleted nitrate in the subtropical mode water and the upper thermocline. Potentially, these SE Pacific gyre waters could mix back into the Peru-Chile OMZ at its southern boundary. We have investigated the relevance of such a phenomenon in the SE Pacific by examining samples collected during two CLIVAR repeat section (P6 and P18) which transected these highly oligotrophic water adjacent to the Peru-Chile OMZ in both the N-S and Ε-W directions. Surprisingly, nutrient data shows no positive subsurface nitrate anomaly as would be expected from significant rates of N2 fixation. Nitrate isotope data also shows no evidence of depleted values. In fact nitrate δ15N and δ18O in the upper 500 m are elevated (up to 10‰) and appear to be the result of subduction and advection of nitrate partially consumed at the surface in the vicinity of the subtropical front. At present, N2 fixation in the SE Pacific does not appear to be an important biogeochemical process and cannot be contributing a 15N-depleted signal to the Peru-Chile OMZ
    Type: Conference or Workshop Item , NonPeerReviewed
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  • 10
    Publication Date: 2019-09-23
    Description: We present new nitrogen isotope data from the water column and surface sediments for paleo–proxy validation collected along the Peruvian and Ecuadorian margins between 1°N and 18°S. Productivity proxies in the bulk sediment (organic carbon, total nitrogen, biogenic opal, C37 alkenone concentrations) and 15N/14N ratios were measured at more than 80 locations within and outside the present-day Peruvian oxygen minimum zone (OMZ). Microbial N-loss to N2 in subsurface waters under O2 deficient conditions leaves a characteristic 15N-enriched signal in underlying sediments. We find that phytoplankton nutrient uptake in surface waters within the high nutrient, low chlorophyll (HNLC) regions of the Peruvian upwelling system influences the sedimentary signal as well. How the δ15Nsed signal is linked to these processes is studied by comparing core-top values to the 15N/14N of nitrate and nitrite (δ15NNOx) in the upper 200 m of the water column. Between 1°N and 10°S, subsurface O2 is still high enough to suppress N-loss keeping δ15NNOx values relatively low in the subsurface waters. However δ15NNOx values increase toward the surface due to partial nitrate utilization in the photic zone in this HNLC portion of the system. δ15Nsed is consistently lower than the isotopic signature of upwelled NO3−, likely due to the corresponding production of 15N depleted organic matter. Between 10°S and 15°S, the current position of perennial upwelling cells, HNLC conditions are relaxed and biological production and near-surface phytoplankton uptake of upwelled NO3− are most intense. In addition, subsurface O2 concentration decreases to levels sufficient for N-loss by denitrification and/or anammox, resulting in elevated subsurface δ15NNOx values in the source waters for coastal upwelling. Increasingly higher production southward is reflected by various productivity proxies in the sediments, while the north–south gradient towards stronger surface NO3− utilization and subsurface N-loss is reflected in the surface sediment 15N/14N ratios. South of 10°S, δ15Nsed is lower than maximum water column δ15NNOx values most likely because only a portion of the upwelled water originates from the depths where highest δ15NNOx values prevail. Though the enrichment of δ15NNOx in the subsurface waters is unambiguously reflected in δ15Nsed values, the magnitude of δ15Nsed enrichment depends on both the depth of upwelled waters and high subsurface δ15NNOx values produce by N-loss. Overall, the degree of N-loss influencing subsurface δ15NNOx values, the depth origin of upwelled waters, and the degree of near-surface nitrate utilization under HNLC conditions should be considered for the interpretation of paleo δ15Nsed records from the Peruvian oxygen minimum zone.
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