Description: Highlights • High lithogenic input in surface waters in the Panama Basin results in radiogenic εNd of up to +4.3. • Radiogenic Nd derived from particles can reset the Nd IC of water masses within time scales years. • Lithogenic input of REEs and corresponding Nd IC in surface waters are seasonally influenced. The distribution of dissolved rare earth elements (REEs) and neodymium isotopes (εNd) in the open ocean traces water mass mixing and provides information on lithogenic inputs to the source regions of the water masses. However, the processes influencing the REE budget at the ocean margins, in particular source and sink mechanisms, are not yet well quantified. In this study the first dissolved REE concentrations and Nd isotope compositions of seawater from the Panama Basin (RV Meteor cruise M90) in the Eastern Equatorial Pacific (EEP) are presented. The EEP is characterized by one of the world's largest oxygen minimum zones (OMZs). It is dominated by high particle fluxes that are expected to enhance the removal of REEs from the water column by scavenging. The measured REE concentrations peak at the surface indicating high lithogenic input, which is supported by shale-normalized REE patterns in surface waters and highly radiogenic εNd signatures ranging between +1.4 and +4.3, the latter value constituting the most radiogenic value measured for seawater to date. In contrast, intermediate and deep water REE concentrations are low compared to other Pacific Basins and suggest enhanced removal via scavenging associated with high particle fluxes. The εNd signatures of intermediate and deep waters are less radiogenic than surface waters ranging between −1.4 and +1.3 but significantly more radiogenic than source water masses in the EEP. The εNd signatures consequently do not reflect mixing of intermediate and deep water masses entering the Panama Basin but can only be explained by lithogenic inputs originating from source rocks with highly radiogenic Nd isotope signatures such as the Central American Volcanic Arc (εNd=+3 to +10). Our data demonstrate significant surface input via continental particles, which are partially dissolved in the water column and thereby release REEs and particularly radiogenic Nd isotope signatures to the subsurface ocean. Data obtained from a re-occupied station in the southern Panama Basin for the first time shows that these processes can partially reset water mass Nd isotope and REE signatures of the entire water column proximal to continental sources on time scales of a few years.

Description: Dissolved silicon isotope compositions have been analysed for the first time in pore waters (δ30SiPW) of three short sediment cores from the Peruvian margin upwelling region with distinctly different biogenic opal content in order to investigate silicon isotope fractionation behaviour during early diagenetic turnover of biogenic opal in marine sediments. The δ30SiPW varies between +1.1‰ and +1.9‰ with the highest values occurring in the uppermost part close to the sediment–water interface. These values are of the same order or higher than the δ30Si of the biogenic opal extracted from the same sediments (+0.3‰ to +1.2‰) and of the overlying bottom waters (+1.1‰ to +1.5‰). Together with dissolved silicic acid concentrations well below biogenic opal saturation, our collective observations are consistent with the formation of authigenic alumino-silicates from the dissolving biogenic opal. Using a numerical transport-reaction model we find that approximately 24% of the dissolving biogenic opal is re-precipitated in the sediments in the form of these authigenic phases at a relatively low precipitation rate of 56 μmol Si cm−2 yr−1. The fractionation factor between the precipitates and the pore waters is estimated at −2.0‰. Dissolved and solid cation concentrations further indicate that off Peru, where biogenic opal concentrations in the sediments are high, the availability of reactive terrigenous material is the limiting factor for the formation of authigenic alumino-silicate phases.

Description: The stable silicon isotopic composition (δ30Si) of waters and diatoms has increasingly been used to investigate the biogeochemical cycling of Si in the major ocean basins. Here we present the first Si isotope data set from the northern South China Sea (NSCS), a large marginal sea system in the western North Pacific to examine sources and utilization of silicic acid (Si(OH)4). During two cruises in July–August 2009 (summer) and January 2010 (winter), samples for isotope measurements of dissolved Si(OH)4 (δ30SiSi(OH)4) and of biogenic silica (δ30SiBSi) in suspended particles were collected along a transect perpendicular to the coast from the inner shelf to the deep-water slope, as well as at the South East Asian Time-series Study (SEATS) station located in the NSCS basin. Surface δ30SiSi(OH)4 generally increased from values ∼+2.3‰ on the inner shelf to ∼+2.8‰ above the deep basin, suggesting an increasing utilization of dissolved Si(OH)4 reflecting the transition from eutrophic to oligotrophic conditions. The δ30SiBSi values were systematically lower than the corresponding δ30SiSi(OH)4 in the euphotic zone (above 100 m) on the shelf and slope. In contrast at station SEATS in the NSCS basin, δ30SiBSi signatures in both seasons were within error equal to δ30SiSi(OH)4 in the surface mixed layer (above 50 m) and δ30SiBSi in waters below were significantly higher than the corresponding δ30SiSi(OH)4. By comparing the field data with the Si isotope fractionation revealed by the Rayleigh or the steady state models, we demonstrate the existence of variable Si(OH)4 origins in different areas of the NSCS. Surface waters on the inner shelf were largely fed by nutrients from the Pearl River input. While the primary source of Si(OH)4 for the euphotic zone on the outer shelf and slope was upwelling or vertical mixing from underlying waters, the Si(OH)4 in the surface mixed layer of the NSCS basin might have originated from horizontal mixing with other highly fractionated surface waters. As a consequence, the Si isotope dynamics in the NSCS are largely controlled by variable biological fractionation of Si in waters from different sources with different initial Si isotopic compositions rather than any single source water.

Description: We combine the stable silicon isotope composition (δ30Si) of diatoms and the radiogenic neodymium isotope compositions (εNd) of past seawater extracted from the authigenic fraction of the sediments (Mn–Fe coatings of particles and benthic foraminifers), as well as the radiogenic isotope compositions (Nd, Sr) of the detrital material itself to reconstruct silicic acid utilisation, water mass mixing, and upwelling intensity from the same marine sediments in the Peruvian upwelling region during the past 20,000 years. Additionally, the sedimentary signals were compared to the water column isotope compositions. Along the Peruvian shelf, the dissolved εNd in the water column ranges from −5.7 to +0.6. The corresponding εNd signatures of the coatings and the benthic foraminifers of the surface sediments range from −4.5 to +1.8 and from −2.5 to +2.2, respectively. The detrital εNd (87Sr/86Sr) signatures range from −6.3 to 0 (0.70508–0.71049). All phases show a trend from more radiogenic εNd values in the north towards less radiogenic values in the south broadly reflecting local weathering inputs and hinterland geology. The εNd signatures of the coatings extracted from sediment core SO147-106KL located in the present day centre of coastal upwelling near 12°S have been essentially constant (−1.5) throughout the past 20,000 years, while the detrital εNd (87Sr/86Sr) varied between values of −0.7 (0.70620) during the Last Glacial and −4.5 (0.70849) during the late Holocene reflecting changes in the origin of the sediment and current transport from a more northerly towards a more southerly source and from overall stronger to weaker upwelling. The δ30Si signature of both total biogenic opal (δ30Siopal) and of hand-picked diatoms (δ30Sidiatom) ranged from +0.3‰ (Last Glacial) to +1.4‰ (late Holocene) confirming large variations in upwelling intensity driving silicic acid utilisation by diatoms. Our combined bSiO2 MAR, δ30Siopal and detrital radiogenic isotope results demonstrate that the strongest El Niño-Southern Oscillation conditions off Peru of the past 20 ka have prevailed during the past 5 ka.

Description: Silicon isotopes are a powerful tool to investigate the cycling of dissolved silicon (Si). In this study the distribution of the Si isotope composition of dissolved silicic acid (δ30Si(OH)4) was analyzed in the water column of the Eastern Equatorial Pacific (EEP) where one of the globally largest Oxygen Minimum Zones (OMZs) is located. Samples were collected at 7 stations along two meridional transects from the equator to 14°S at 85°50′W and 82°00′W off the Ecuadorian and Peruvian coast. Surface waters show a large range in isotope compositions δ30Si(OH)4 (+2.2‰ to +4.4‰) with the highest values found at the southernmost station at 14°S. This station also revealed the most depleted silicic acid concentrations (0.2 μmol/kg), which is a function of the high degree of Si utilization by diatoms and admixture with waters from highly productive areas. Samples within the upper water column and the OMZ at oxygen concentrations below 10 μmol/kg are characterized by a large range in δ30Si(OH)4, which mainly reflects advection and mixing of different water masses, even though the highly dynamic hydrographic system of the upwelling area off Peru does not allow the identification of clear Si isotope signals for distinct water masses. Therefore we cannot rule out that also dissolution processes have an influence on the δ30Si(OH)4 signature in the subsurface water column. Deep water masses (〉2000 m) in the study area show a mean δ30Si(OH)4 of +1.2±0.2‰, which is in agreement with previous studies from the eastern and central Pacific. Comparison of the new deep water data of this study and previously published data from the central Pacific and Southern Ocean reveal substantially higher δ30Si(OH)4 values than deep water signatures from the North Pacific. As there is no clear correlation between δ30Si(OH)4 and silicic acid concentrations in the entire data set the distribution of δ30Si(OH)4 signatures in deep waters of the Pacific is considered to be mainly a consequence of the mixing of several end member water masses with distinct Si isotope signatures including Lower Circumpolar Deep Water (LCDW) and North Pacific Deep Water (NPDW).

Description: We present the first systematic study of the silicon isotope composition in the water column (δ30SiSi(OH)4) and in diatoms (δ30Sidiatom) from the underlying surface sediments in a coastal upwelling region. The surface waters upwelling on the shelf off Peru are mainly fed by southward flowing subsurface waters along the coast, which show a mean δ30SiSi(OH)4 of +1.5‰. The concentration of dissolved silicic acid (Si(OH)4) increases towards the south in these waters and with increasing water depth, suggesting lateral mixing with water masses from the south and intense remineralisation of particulate biogenic silica (bSiO2) in the water column and in the surface sediments. Surface waters in the realm of the most intense upwelling between 5°S and 15°S have only marginally elevated δ30SiSi(OH)4 values (δ30SiSi(OH)4 = +1.7‰) with respect to the source Si isotope composition, whereas further north and south, where upwelling is less pronounced, surface waters are more strongly fractionated (δ30SiSi(OH)4 up to +2.8‰) due to the stronger utilisation of the smaller amounts of available Si(OH)4. The degree of Si(OH)4 utilisation in the surface waters along the shelf estimated from the Si(OH)4 concentration data ranges from 51% to 93%. The δ30Sidiatom values of hand-picked diatoms in the underlying surface sediments vary from +0.6‰ to +2.0‰, which is within the range of the expected fractionation between surface waters and diatoms. The fractionation signal in the surface waters produced during formation of the diatoms is reflected by the δ30Sidiatom values in the underlying sediments, with the lowest δ30Sidiatom values in the main upwelling region. The silicon isotope compositions of bSiO2 (δ30SibSiO2) from the same surface sediment samples are generally much lower than the δ30Sidiatom signatures indicating a significant contamination of the bSiO2 with biogenic siliceous material other than diatoms, such as sponge spicules. This shift towards lighter δ30SibSiO2 values by up to −1.3‰ compared to δ30Sidiatom signatures for the same surface sediment samples potentially biases the interpretation of δ30Si paleorecords from sediments with low bSiO2 concentrations, and thus the reconstruction of past Si(OH)4 utilisation in surface waters.

Description: In this study we combine for the first time silicon (Si) isotope compositions of small mixed diatom species (δ30SibSiO2) and of large handpicked mono-generic (i.e. genus = Coscinodiscus) diatom samples (δ30SiCoscino) with diatom assemblages extracted from marine sediments in the Peruvian upwelling region in order to constrain present and past silicate utilisation. The extension of a previous core-top data set from the Peruvian shelf demonstrates that δ30SiCoscino values record near-complete Si utilisation, as these are similar to the isotopic composition of the subsurface source waters feeding the upwelling. In contrast, the δ30SibSiO2 of small mixed diatom species increase southward along the shelf as well as towards the shore. We attribute highest δ30SibSiO2 values partly to transient iron limitation but primarily to the gradual increase of Si isotope fractionation within the seasonal diatom succession, which are mainly recorded by small diatom species during intense bloom events. In contrast, lower δ30SibSiO2 values are related to initial Si isotope utilisation during periods of weak upwelling, when low Si(OH)4 concentrations do not permit intense blooms and small diatom species record substantially lower δ30Si signatures. As such, we propose that the intensity of the upwelling can be deduced from the offset between δ30SibSiO2 and δ30SiCoscino (Δ30Sicoscino–bSiO2), which is low for strong upwelling conditions and high for prevailing weak upwelling. We apply the information extracted from surface sediments to generate a record of the present-day main upwelling region covering the past 17,700 years and find that this location has also been characterized by a persistent offset (Δ30Sicoscino–bSiO2). By comparison with the diatom assemblages we show that the coastal upwelling system changed markedly between weak and strong upwelling conditions. In addition, our model calculations to quantify species-specific Si isotope fractionation effects based on the diatom assemblages indicate an overall minor influence that cannot explain the high amplitude in the measured δ30SibSiO2 record.

Description: The tropical South East Pacific is characterized by strong coastal upwelling on the narrow continental shelf and an intense oxygen minimum zone (OMZ) in the intermediate water layer. These hydrographic properties are responsible for a permanent supply of intermediate water masses to the surface rich in nutrients and with a remarkably low inorganic N:P stoichiometry. To investigate the impact of OMZ-influenced upwelling waters on phytoplankton growth, elemental and taxonomical composition we measured hydrographic and biogeochemical parameters along an east–west transect at 10°S in the tropical South East Pacific, stretching from the upwelling region above the narrow continental shelf to the well-stratified oceanic section of the eastern boundary regime. New production in the area of coastal upwelling was driven by large-sized phytoplankton (e.g. diatoms) with generally low N:P ratios (〈16:1). While nitrate and phosphate concentrations were at levels not limiting phytoplankton growth along the entire transect, silicate depletion prohibited diatom growth further off-shore. A deep chlorophyll a maximum consisting of pico-/nano- (Synechococcus, flagellates) and microphytoplankton occurred within a pronounced thermocline in subsurface waters above the shelf break and showed intermediate N:P ratios close to Redfield proportions. High PON:POP (〉20:1) ratios were observed in the stratified open ocean section of the transect, coinciding with the abundance of two strains of the pico-cyanobacterium Prochlorococcus; a high-light adapted strain in the surface layer and a low-light adapted strain occurring along the oxic-anoxic transition zone below the thermocline. Excess phosphate present along the entire transect did not appear to stimulate growth of nitrogen-fixing phytoplankton, as pigment fingerprinting did not indicate the presence of diazotrophic cyanobacteria at any of our sampling stations. Instead, a large fraction of the excess phosphate generated within the oxygen minimum zone was consumed by non-Redfield production of large phytoplankton in shelf surface waters.

Description: The radiogenic isotope composition of the Rare Earth Element (REE) neodymium (Nd) is a powerful water mass proxy for present and past ocean circulation. The processes controlling the Nd budget of the global ocean are not quantitatively understood and in particular source and sink mechanisms are still under debate. In this study we present the first full water column data set of dissolved Nd isotope compositions and Nd concentrations for the Eastern Equatorial Pacific (EEP), where one of the globally largest Oxygen Minimum Zones (OMZ) is located. This region is of particular interest for understanding the biogeochemical cycling of REEs because anoxic conditions may lead to release of REEs from the shelf, whereas high particle densities and fluxes potentially remove the REEs from the water column. Data were obtained between 1°40′N and 16°S along a nearshore and an offshore transect. Near surface zonal current bands, such as the Equatorial Undercurrent (EUC) and the Subsurface Countercurrent (SSCC), which are supplying oxygen-rich water to the OMZ are characterized by radiogenic Nd isotope signatures (εNd=−2). Surface waters in the northernmost part of the study area are even more radiogenic (εNd=+3), most likely due to release of Nd from volcanogenic material. Deep and bottom waters at the southernmost offshore station (14°S) are clearly controlled by advection of water masses with less radiogenic signatures (εNd=−7) originating from the Southern Ocean. Towards the equator, however, the deep waters show a clear trend towards more radiogenic values of up to εNd=−2. The northernmost station located in the Panama basin shows highly radiogenic Nd isotope signatures in the entire water column, which indicates that particle scavenging, downward transport and release processes play an important role. This is supported by relatively low Nd concentrations in deep waters (3000–6000 m) in the EEP (20 pmol/kg) compared to locations in the Northern and Central Pacific (40–60 pmol/kg), which suggests enhanced removal of Nd in the EEP.

Description: The marine chromium (Cr) cycle is still insufficiently understood, in particular the mechanisms modulating the spatial distribution of dissolved stable Cr isotopes in seawater. Redox transformations between its main oxidation states, Cr(VI) and Cr(III), have been held accountable for the observed tight inverse logarithmic relationship between the dissolved Cr concentration [Cr] and its isotopic composition (δ53Cr), whereby isotopically light Cr(III) is removed in surface waters and oxygen minimum zones (OMZs), and subsequently released to deeper waters from remineralized particles or sediments. Seawater [Cr] and δ53Cr were investigated in a series of depth profiles across the Peruvian margin OMZ, covering a wide spectrum of dissolved oxygen concentrations ranging from 2 to 242 µmol/kg. We found [Cr] ranging from 1.5 to 5.5 nmol/kg, associated with δ53Cr variations between +1.59 and +0.72 ‰, but no systematic relationship to dissolved oxygen concentrations. However, distinctly different seawater profiles were observed above the suboxic/anoxic shelf compared to those located further offshore, with substantial Cr removal restricted to suboxic or anoxic environments on the shelf. This suggests that suboxic conditions ([O2] 〈 5 µmol/kg) alone are not sufficient to account for substantial Cr removal. Given that environmental conditions under which Cr can be reduced remain restricted spatially, the role of this sink in the marine Cr cycle may therefore be small. Additionally, some observations corroborate the assumption that Cr reduction is not necessarily accompanied by immediate adsorption of the formed Cr(III) onto particles, leading to its removal from the dissolved phase. Instead, partial removal of Cr(III) via particles, leaving a residual dissolved Cr(III) pool, may be more widespread in suboxic waters.