Description: Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.

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: 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.

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: We present a comparison of the dissolved stable isotope composition of silicate (δ30Si(OH)4) and nitrate (δ15 inline image) 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 inline image 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 δ30Si(OH)4 values (+2‰) due to low Si utilization but relatively high δ15 inline image (+13‰) 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 δ30Si(OH)4 values (+3.7‰) accompanied by high δ15 inline image values (+16‰). In the eddy center, high inline image: 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 δ30Si(OH)4 and δ15 inline image can improve our understanding of paleo records as it can help to disentangle utilization and N-loss processes.