Silicon isotopes as a tracer for silicate utilization in the Peruvian upwelling

EGU2011-6081 Natural stable isotopes are a powerful tool in marine sciences to investigate biological processes, such as present and past nutrient utilization. In this study we present the first dissolved silicon isotope data in the upwelling area off Peru, where one of the world’s largest Oxygen Minimum Zones (OMZ) is located. Silicon is the most important component required for phytoplankton (diatom) growth, which dominates primary productivity in this region. Stable Si isotopes are fractionated during diatom growth in that the lighter Si isotopes are preferentially incorporated into diatoms with a fractionation factor of -1.1 promille. The Si isotope composition of dissolved silicic acid of the corresponding surface waters is therefore left isotopically heavier. The Si isotope composition, 30Si/28Si, is expressed as δ30Si values, which stand forh deviations from a given standard (NBS28). Investigation of the dissolved seawater Si isotope composition thus provides a measure for the utilization and, combined with information on the Si isotope composition of the water masses upwelling off Peru, it is a measure for the supply pathways of Si to the coastal upwelling centres. Surface waters on the shelf off Peru are mainly fed by the Equatorial Undercurrent, which mainly consists of waters originating from the western and Central Pacific and which has a characteristic δ30Si of +1.5 promille. In areas and during phases of intense upwelling the fractionation of Si isotopes was observed to be weaker due to upwelling-driven supply of less fractionated Si (δ30Si = 1.7 promille, from water depths of around 100-150 m, whereas under weak upwelling conditions fractionation is higher (δ30Si ~3 promille due to a more complete utilization of the available dissolved silicate. The distribution of dissolved δ30Si correlates strongly with particulate biogenic silicate (opal) concentrations in that highest opal concentrations in the surface waters show the lowest δ30Si values thus strongest upwelling intensity. The most extreme δ30Si values in surface waters (δ30Si = 4.5 promille are observed offshore where silicic acid concentrations are nearly zero. Furthermore we compare the δ30Si data with the dissolved nitrogen isotope distribution, which in addition to nitrate utilization is mainly influenced by denitrification and annamox processes in the OMZ. Combined silicon and nitrogen isotope compositions can thus help to disentangle different fractionation processes within the nitrogen cycle

Controls on the Silicon Isotope Composition of Diatoms in the Peruvian Upwelling

The upwelling area off Peru is characterized by exceptionally high rates of primary productivity, mainly dominated by diatoms, which require dissolved silicic acid (dSi) to construct their frustules. The silicon isotope compositions of dissolved silicic acid (δ 30 Si dSi ) and biogenic silica (δ 30 Si bSi ) in the ocean carry information about dSi utilization, dissolution, and water mass mixing. Diatoms are preserved in the underlying sediments and can serve as archives for past nutrient conditions. However, the factors influencing the Si isotope fractionation between diatoms and seawater are not fully understood. More δ 30 Si bSi data in today’s ocean are required to validate and improve the understanding of paleo records. Here, we present the first δ 30 Si bSi data (together with δ 30 Si dSi ) from the water column in the Peruvian Upwelling region. Samples were taken under strong upwelling conditions and the bSi collected from seawater consisted of more than 98% diatoms. The δ 30 Si dSi signatures in the surface waters were higher (+1.7‰ to +3.0‰) than δ 30 Si bSi (+1.0‰ to +2‰) with offsets between diatoms and seawater (Δ 30 Si) ranging from −0.4‰ to −1.0‰. In contrast, δ 30 Si dSi and δ 30 Si bSi signatures were similar in the subsurface waters of the oxygen minimum zone (OMZ) as a consequence of a decrease in δ 30 Si dSi . A strong relationship between δ 30 Si bSi and [dSi] in surface water samples supports that dSi utilization of the available pool (70 and 98%) is the main driver controlling δ 30 Si bSi . A comparison of δ 30 Si bSi samples from the water column and from underlying core-top sediments (δ 30 Si bSi_ sed. ) in the central upwelling region off Peru (10°S and 15°S) showed good agreement (δ 30 Si bSi_ sed. = +0.9‰ to +1.7‰), although we observed small differences in δ 30 Si bSi depending on the diatom size fraction and diatom assemblage. A detailed analysis of the diatom assemblages highlights apparent variability in fractionation among taxa that has to be taken into account when using δ 30 Si bSi data as a paleo proxy for the reconstruction of dSi utilization in the region

Nutrient utilisation and weathering inputs in the Peruvian upwelling region since the Little Ice Age

For this study two sediment cores from the Peruvian shelf covering the time period between the Little Ice Age (LIA) and present were examined for changes in productivity (biogenic opal concentrations (bSi)), nutrient utilisation (stable isotope compositions of silicon (δ30Siopal) and nitrogen (δ15Nsed)), as well as in ocean circulation and material transport (authigenic and detrital radiogenic neodymium (εNd) and strontium (87Sr/86Sr) isotopes). For the LIA the proxies recorded weak primary productivity and nutrient utilisation reflected by low average bSi concentrations of ~10%, δ15Nsed values of ~ +5‰ and intermediate δ30Siopal values of ~+0.97‰. At the same time the radiogenic isotope composition of the detrital sediment fraction indicates dominant local riverine input of lithogenic material due to higher rainfall in the Andean hinterland. These patterns were caused by permanent El Niño-like conditions characterized by a deeper nutricline, weak upwelling and low nutrient supply. At the end of the LIA, δ30Siopal dropped to low values of +0.6‰ and opal productivity reached its minimum of the past 650 years. During the following transitional period of time the intensity of upwelling, nutrient supply and productivity increased abruptly as marked by the highest bSi contents of up to 38%, by δ15Nsed of up to ~ +7‰, and by the highest degree of silicate utilisation with δ30Siopal reaching values of +1.1‰. At the same time detrital εNd and 87Sr/86Sr signatures documented increased wind strength and supply of dust to the shelf due to drier conditions. Since about 1870, productivity has been high but nutrient utilisation has remained at levels similar to the LIA indicating significantly increased nutrient availability. Comparison between the δ30Siopal and δ15Nsed signatures suggests that during the past 650 years the δ15Nsed signature in the Peruvian Upwelling area has most likely primarily been controlled by surface water utilisation and not, as previously assumed, by subsurface nitrogen loss processes in the water column

Controls on Dissolved Silicon Isotopes along the US GEOTRACES Eastern Pacific Zonal Transect (GP16)

The distribution of dissolved silicon isotopes (δ30Si) was examined along the US GEOTRACES East Pacific Zonal Transect (GP16) extending from Peru to Tahiti (10°S and 15°S latitude). Surface waters in the subtropical gyre displayed high δ30Si due to strong utilization of silicic acid (DSi). In contrast, surface waters close to the Peruvian coast where upwelling prevailed were less depleted and only moderately fractionated. δ30Si of water masses along the transect were compared with the results of an Optimum Multiparameter Analysis that quantified the fractional contributions of endmember water masses in each sample. Strong admixture of intermediate waters obscured the expected heavy isotopic signatures of Subantarctic Mode Water and Antarctic Intermediate Water. Isotope values were nearly homogenous below 2000 m (Average: +1.3 ± 0.1 ‰, 1 s.d.) despite the 25 μmol kg‐1 range in the DSi content among water masses. This homogeneity confirms prior observations and model results that predict nearly constant δ30Si values of +1.0 to +1.2 ‰ for Pacific deep waters with [DSi] > 100 μmol kg‐1. Waters above the East Pacific Rise (EPR) influenced by hydrothermal activity showed a small increase in [DSi] together with dissolved iron, but overall stations close to the EPR were slightly depleted in [DSi] (3 to 6 μmol kg‐1) with no significant shift in δ30Si compared to adjacent waters. Hydrothermal [DSi] appears to precipitate within the conduit of the EPR or upon contact with cold seawater resulting in a negligible influence of hydrothermal fluids on δ30Si in deep water. Key Points Surface waters have a large range in dissolved silicon isotopes covering nutrient‐rich coastal upwelling to oligotrophic waters Deep water masses with DSi concentrations > 100 μmol kg‐1 show homogenous silicon isotope signatures despite up to 25 μmol kg‐1 differences in [DSi] Hydrothermal fluids have a negligible effect on Si isotope distributions in the deep Pacifi

Isotopic evidence for complex biogeochemical cycling of Cd in the eastern tropical South Pacific

Over the past decades, observations have confirmed decreasing oxygen levels and shoaling of oxygen minimum zones (OMZs) in the tropical oceans. Such changes impact the biogeochemical cycling of micronutrients such as Cd, but the potential consequences are only poorly constrained. Here, we present seawater Cd concentrations and isotope compositions for 12 depth profiles at coastal, nearshore and offshore stations from 4◦S to 14◦S in the eastern tropical South Pacific, where one of the world’s strongest OMZs prevails. The depth profiles of Cd isotopes display high δ114/110Cd at the surface and decreasing δ114/110Cd with increasing water depth, consistent with preferential utilization of lighter Cd isotopes during biological uptake in the euphotic zone and subsequent remineralization of the sinking biomass. In the surface and subsurface ocean, seawater displays similar δ114/110Cd signatures of 0.47 ± 0.23‰ to 0.82 ± 0.05‰ across the entire eastern tropical South Pacific despite highly variable Cd concentrations between 0.01 and 0.84 nmol/kg. This observation, best explained by an open system steady-state fractionation model, contrasts with previous studies of the South Atlantic and South Pacific Oceans, where only Cd-deficient waters have a relatively constant Cd isotope signature. For the subsurface to about 500 m depth, the variability of seawater Cd isotope compositions can be modeled by mixing of remineralized Cd with subsurface water from the base of the mixed layer. In the intermediate and deep eastern tropical South Pacific (>500 m), seawater [Cd] and δ114/110Cd appear to follow the distribution and mixing of major water masses. We identified modified AAIW of the ETSP to be more enriched in [Cd] than AAIW from the source region, whilst both water masses have similar δ114/110Cd. A mass balance estimate thus constrains a δ114/110Cd of between 0.38‰ and 0.56‰ for the accumulated remineralized Cd in the ETSP. Nearly all samples show a tight coupling of Cd and PO4 concentrations, whereby surface and deeper waters define two distinct linear trends. However, seawater at a coastal station located within a pronounced plume of H2S, is depleted in [Cd] and features significantly higher δ114/110Cd. This signature is attributed to the formation of authigenic CdS with preferential incorporation of lighter Cd isotopes. The process follows a Rayleigh fractionation model with a fractionation factor of α114/110Cdseawater-CdS = 1.00029. Further deviations from the deep Cd–PO4 trend were observed for samples with O2 < 10 μmol/kg and are best explained by in situ CdS precipitation within the decaying organic matter even though dissolved H2S was not detectable in ambient seawater

An eddy-stimulated hotspot for fixed nitrogen-loss from the Peru 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 (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

Does the European Union achieve comprehensive blue growth? Progress of EU coastal states in the Baltic and North Sea, and the Atlantic Ocean against sustainable development goal 14

Highlights • European Union Blue Growth is assessed by set of 18 indicators for 15 EU coastal states. • The results put into question that the EU has achieved comprehensive blue growth. • Unsustainable development is in particular driven by increasing fishing mortality. Abstract The Sustainable Development Goal for the oceans and coasts (SDG 14) as part of the 2030 Agenda can be considered as an important step towards achieving comprehensive blue growth. Here, we selected a set of 18 indicators to measure progress against SDG 14 for 15 EU coastal countries in the Baltic and the North Sea and the Atlantic Ocean since 2012. In our assessment we distinguish between a concept of weak and strong sustainability, assuming high and low substitution possibilities, respectively. Our results indicate that there are countries which managed to achieve sustainable development under both concepts of sustainability (most notably Estonia, achieving the strongest improvement), but that there are also countries which failed to achieve sustainable development under both concepts (most notably Ireland and Belgium, experiencing the strongest decline). Unsustainable development is in particular driven by increasing fishing mortality and reduced willingness to set total allowable catch in accordance with scientific advice

Impact of ambient conditions on the Si isotope fractionation in marine pore fluids during early diagenesis

Benthic fluxes of dissolved silica (Si) from sediments into the water column are driven by the dissolution of biogenic silica (bSiO2) and terrigenous Si minerals and modulated by the precipitation of authigenic Si phases. Each of these processes has a specific effect on the isotopic composition of silica dissolved in sediment pore waters such that the determination of pore water δ30Si values can help to decipher the complex Si cycle in surface sediments. In this study, the δ30Si signatures of pore fluids and bSiO2 in the Guaymas Basin (Gulf of California) were analyzed, which is characterized by high bSiO2 accumulation and hydrothermal activity. The δ30Si signatures were investigated in the deep basin, in the vicinity of a hydrothermal vent field, and at an anoxic site located within the pronounced oxygen minimum zone (OMZ). The pore fluid δ30Sipf signatures differ significantly depending on the ambient conditions. Within the basin, δ30Sipf is essentially uniform averaging +1.2 ± 0.1 ‰ (1SD). Pore fluid δ30Sipf values from within the OMZ are significantly lower (0.0 ± 0.5 ‰, 1SD), while pore fluids close to the hydrothermal vent field are higher (+2.0 ± 0.2 ‰, 1SD). Reactive transport modelling results show that the δ30Sipf is mainly controlled by silica dissolution (bSiO2 and terrigenous phases) and Si precipitation (authigenic aluminosilicates). Precipitation processes cause a shift to high pore fluid δ30Sipf signatures, most pronounced at the hydrothermal site. Within the OMZ however, additional dissolution of isotopically depleted Si minerals (e.g. clays) facilitated by high mass accumulation rates of terrigenous material (MARterr) is required to promote the low δ30Sipf signatures while precipitation of authigenic aluminosilicates seems to be hampered by high water / rock ratios. Guaymas OMZ δ30Sipf values are markedly different from those of the Peruvian OMZ, the only other marine setting where Si isotopes have been investigated to constrain early diagenetic processes. These differences highlight the fact that δ30Sipf signals in OMZs worldwide are not alike and each setting can result in a range of δ30Sipf values as a function of the environmental conditions. We conclude that the benthic silica cycle is more complex than previously thought and that additional Si isotope studies are needed to decipher the controls on Si turnover in marine sediment and the role of sediments in the marine silica cycle

Isotopic Characterization of Water Masses in the Southeast Pacific Region: Paleoceanographic Implications

In this study, we used stable isotopes of oxygen (δ18O), deuterium (δD), and dissolved inorganic carbon (δ13CDIC) in combination with temperature, salinity, oxygen, and nutrient concentrations to characterize the coastal (71°–78°W) and an oceanic (82°–98°W) water masses (SAAW—Subantarctic Surface Water; STW—Subtropical Water; ESSW—Equatorial Subsurface water; AAIW—Antarctic Intermediate Water; PDW—Pacific Deep Water) of the Southeast Pacific (SEP). The results show that δ18O and δD can be used to differentiate between SAAW-STW, SAAW-ESSW, and ESSW-AAIW. δ13CDIC signatures can be used to differentiate between STW-ESSW (oceanic section), SAAW-ESSW, ESSW-AAIW, and AAIW-PDW. Compared with the oceanic section, our new coastal section highlights differences in both the chemistry and geometry of water masses above 1,000 m. Previous paleoceanographic studies using marine sediments from the SEP continental margin used the present-day hydrological oceanic transect to compare against, as the coastal section was not sufficiently characterized. We suggest that our new results of the coastal section should be used for past characterizations of the SEP water masses that are usually based on continental margin sediment samples

Online preconcentration ICP-MS analysis of rare earth elements in seawater

The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (similar to pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available "seaFAST" system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2 sigma) of the technique to be estimated at <23% for all REEs and <15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired.Keywords: ICP-MS, Rare earth element