The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 25 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017.This article is part of a special issue entitled: "Cycles of trace elements and isotopes in the ocean – GEOTRACES and beyond" - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González.
We present a comparison of the dissolved stable isotope composition of silicate (Si-30(OH)(4)) and nitrate ((15) NO3-) to investigate the biogeochemical processes controlling nutrient cycling in the upwelling area off Peru, where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Besides strong upwelling of nutrient rich waters mainly favoring diatom growth, an anticyclonic eddy influenced the study area. We observe a tight coupling between the silicon (Si) and nitrogen (N) cycles in the study area. Waters on the shelf showed high Si(OH)(4) concentrations accompanied by diminished NO3- concentration as a consequence of intense remineralization, high Si fluxes from the shelf sediments, and N-loss processes such as anammox/denitrification within the OMZ. Correspondingly, the surface waters show low Si-30(OH)(4) values (+2 parts per thousand) due to low Si utilization but relatively high (15) NO3- (+13 parts per thousand) values due to upwelling of waters influenced by N-loss processes. In contrast, as a consequence of the deepening of the thermocline in the eddy center, a pronounced Si(OH)(4) depletion led to the highest Si-30(OH)(4) values (+3.7 parts per thousand) accompanied by high (15) NO3- values (+16 parts per thousand). In the eddy center, high NO3-: Si(OH)(4) ratios favored the growth of non-siliceous organisms (Synechococcus). Our data show that upwelling processes and the presence of eddies play important roles controlling the nutrient cycles and therefore also exert a major influence on the phytoplankton communities in the Peruvian Upwelling. Our findings also show that the combined approach of Si-30(OH)(4) and (15) NO3- can improve our understanding of paleo records as it can help to disentangle utilization and N-loss processes.
The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEls) as well as classical hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing a strongly inter-linked on-line atlas including more than 300 section plots and 90 animated 3D scenes. The IDP2014 covers the Atlantic, Arctic, and Indian oceans, exhibiting highest data density in the Atlantic. The TEI data in the IDP2014 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at cross-over stations. The digital data are provided in several formats, including ASCII spreadsheet, Excel spreadsheet, netCDF, and Ocean Data View collection. In addition to the actual data values the IDP2014 also contains data quality flags and 1-sigma data error values where available. Quality flags and error values are useful for data filtering. Metadata about data originators, analytical methods and original publications related to the data are linked to the data in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2014 data providing section plots and a new kind of animated 3D scenes. The basin-wide 3D scenes allow for viewing of data from many cruises at the same time, thereby providing quick overviews of large-scale tracer distributions. In addition, the 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of observed tracer plumes, as well as for making inferences about controlling processes. (C) 2015 The Authors. Published by Elsevier B.V.
We present sedimentary geochemical data and in situ benthic flux measurements of dissolved inorganic nitrogen (DIN: NO3−, NO2−, NH4+) and oxygen (O2) from 7 sites with variable sand content along 18°N offshore Mauritania (NW Africa). Bottom water O2 concentrations at the shallowest station were hypoxic (42 μM) and increased to 125 μM at the deepest site (1113 m). Total oxygen uptake rates were highest on the shelf (−10.3 mmol O2 m−2 d−1) and decreased quasi-exponentially with water depth to −3.2 mmol O2 m−2 d−1. Average denitrification rates estimated from a flux balance decreased with water depth from 2.2 to 0.2 mmol N m−2 d−1. Overall, the sediments acted as net sink for DIN. Observed increases in δ15NNO3 and δ18ONO3 in the benthic chamber deployed on the shelf, characterized by muddy sand, were used to calculate apparent benthic nitrate fractionation factors of 8.0‰ (15εapp) and 14.1‰ (18εapp). Measurements of δ15NNO2 further demonstrated that the sediments acted as a source of 15N depleted NO2−. These observations were analyzed using an isotope box model that considered denitrification and nitrification of NH4+ and NO2−. The principal findings were that (i) net benthic 14N/15N fractionation (εDEN) was 12.9 ± 1.7‰, (ii) inverse fractionation during nitrite oxidation leads to an efflux of isotopically light NO2− (−22 ± 1.9‰), and (iii) direct coupling between nitrification and denitrification in the sediment is negligible. Previously reported εDEN for fine-grained sediments are much lower (4–8‰). We speculate that high benthic nitrate fractionation is driven by a combination of enhanced porewater–seawater exchange in permeable sediments and the hypoxic, high productivity environment. Although not without uncertainties, the results presented could have important implications for understanding the current state of the marine N cycle.
Nitrogen, a limiting element for biological productivity, plays a key role in regulating the biogeochemical processes in the ocean. In today’s ocean, all of the major reactions in the N cycle are mediated by assimilatory or dissimilatory functions of marine organisms. Because marine organisms preferentially incorporate lighter stable isotope of nitrogen 14N instead of 15N, each major metabolic reaction in the N cycle involves irreversible kinetic fractionation of nitrogen.
We present new data for the stable isotope ratio of inorganic nitrogen species from the contrasting oxygen minimum zones (OMZs) of the Eastern Tropical North Atlantic, south of Cape Verde, and the Eastern Tropical South Pacific off Peru. Differences in minimum oxygen concentration and corresponding N-cycle processes for the two OMZs are reflected in strongly contrasting δ15N distributions. Pacific surface waters are marked by strongly positive values for δ15N-NO3–) reflecting fractionation associated with subsurface N-loss and partial NO3– utilization. This contrasts with negative values in NO3– depleted surface waters of the Atlantic which are lower than can be explained by N supply via N2 fixation. We suggest the negative values reflect inputs of nitrate, possibly transient, associated with deposition of Saharan dust. Strong signals of N-loss processes in the subsurface Pacific OMZ are evident in the isotope and N2O data, both of which are compatible with a contribution of canonical denitrification to overall N-loss. However the apparent N isotope fractionation factor observed is relatively low (ϵd=11.4 ‰) suggesting an effect of influence from denitrification in sediments. Identical positive correlation of N2O vs. AOU for waters with oxygen concentrations ([O2] < 5 μmol l−1) in both regions reflect a nitrification source. Sharp decrease in N2O concentrations is observed in the Pacific OMZ due to denitrification under oxygen concentrations O2 < 5 μmol l−1.
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.
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 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 within the OMZ. A shallower biogenic N2 maximum within the oxycline is likely a feature advected by the eddy streamer from the shelf. Eddy-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.
We investigate the influence of chloride concentration on the performance of the chemical reduction method for measurement of the nitrogen isotopic ratio (δ15N) in NO3− in natural waters (McIlvin and Altabet, 2005). In this method, NO3− is first reduced to NO2− using activated cadmium metal, with further reduction to N2O using sodium azide in an acetic acid buffer. N2O is introduced into an isotope ratio mass spectrometer (IRMS) for isotopic measurement. Previously, it was recognized that the presence of halides was necessary for the speed and efficiency of the second step but not thought to be important for the first step. Whereas quantitative Cd reduction of NO3− to NO2− had been noted for seawater samples, here we report, for freshwater and low‐salinity (S < 30) samples, a variable conversion efficiency (both under‐ and overreduction were observed) and significant variation in δ15N determination. Addition of 5 M NaCl to all samples resulted in rapid (<4 h) and quantitative (>99%) reduction of NO3− to NO2− as well as stable δ15N values that closely matched expected values for standards (within 0.3‰ of standard value). The positive effect of NaCl is likely due to a decrease in free Cd2+ produced over the course of the reaction due to formation of CdCl2.
Fixed nitrogen (N) loss to biogenic N 2 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 N 2 production, high NO−2 levels, and the highest isotope enrichments observed so far in OMZ’s for the residual NO −3 . High sea surface chlorophyll 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 NO −3 reduction and subsequent production of biogenic N 2 within the OMZ. A shallower biogenic N2 maximum within the oxycline is likely a feature advected by the eddy streamer from the shelf. Eddy-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.