Description: Global warming during the Paleocene-Eocene Thermal Maximum (PETM) ĝ1/4 ĝ€55 million years ago (Ma) coincided with a massive release of carbon to the ocean-atmosphere system, as indicated by carbon isotopic data. Previous studies have argued for a role of changing ocean circulation, possibly as a trigger or response to climatic changes. We use neodymium (Nd) isotopic data to reconstruct short high-resolution records of deep-water circulation across the PETM. These records are derived by reductively leaching sediments from seven globally distributed sites to reconstruct past deep-ocean circulation across the PETM. The Nd data for the leachates are interpreted to be consistent with previous studies that have used fish teeth Nd isotopes and benthic foraminiferal δ13C to constrain regions of convection. There is some evidence from combining Nd isotope and δ13C records that the three major ocean basins may not have had substantial exchanges of deep waters. If the isotopic data are interpreted within this framework, then the observed pattern may be explained if the strength of overturning in each basin varied distinctly over the PETM, resulting in differences in deep-water aging gradients between basins. Results are consistent with published interpretations from proxy data and model simulations that suggest modulation of overturning circulation had an important role for initiation and recovery of the ocean-atmosphere system associated with the PETM.

Description: The global Late Pliocene/Early Pleistocene cooling (~3.0–2.0 million years ago – Ma) concurred with extremely high diatom and biogenic opal production in most of the major coastal upwelling regions. This phenomenon was particularly pronounced in the Benguela upwelling system (BUS), off Namibia, where it is known as the Matuyama Diatom Maximum (MDM). Our study focuses on a new diatom silicon isotope (δ30Si) record covering the MDM in the BUS. Unexpectedly, the variations in δ30Si signal follow biogenic opal content, whereby the highest δ30Si values correspond to the highest biogenic opal content. We interpret the higher δ30Si values during the MDM as a result of a stronger degree of silicate utilisation in the surface waters caused by high productivity of mat-forming diatom species. This was most likely promoted by weak upwelling intensity dominating the BUS during the Late Pliocene/Early Pleistocene cooling combined with a large silicate supply derived from a strong Southern Ocean nutrient leakage responding to the expansion of Antarctic ice cover and the resulting stratification of the polar ocean 3.0–2.7 Ma ago. A similar scenario is hypothesized for other major coastal upwelling systems (e.g. off California) during this time interval, suggesting that the efficiency of the biological carbon pump was probably sufficiently enhanced in these regions during the MDM to have significantly increased the transport of atmospheric CO2 to the deep ocean. In addition, the coeval extension of the area of surface water stratification in both the Southern Ocean and the North Pacific, which decreased CO2 release to the atmosphere, led to further enhanced atmospheric CO2 drawn-down and thus contributed significantly to Late Pliocene/Early Pleistocene cooling.

Description: Present day oceans are well ventilated, with the exception of mid-depth oxygen minimum zones (OMZs) under high surface water productivity, regions of sluggish circulation, and restricted marginal basins. In the Mesozoic, however, entire oceanic basins transiently became dysoxic or anoxic. The Cretaceous ocean anoxic events (OAEs) were characterised by laminated organic-carbon rich shales and low-oxygen indicating trace fossils preserved in the sedimentary record. Yet assessments of the intensity and extent of Cretaceous near-bottom water oxygenation have been hampered by deep or long-term diagenesis and the evolution of marine biota serving as oxygen indicators in today's ocean. Sedimentary features similar to those found in Cretaceous strata were observed in deposits underlying Recent OMZs, where bottom-water oxygen levels, the flux of organic matter, and benthic life have been studied thoroughly. Their implications for constraining past bottom-water oxygenation are addressed in this review. We compared OMZ sediments from the Peruvian upwelling with deposits of the late Cenomanian OAE 2 from the north-west African shelf. Holocene laminated sediments are encountered at bottom-water oxygen levels of 〈 7 μmol kg−1 under the Peruvian upwelling and 〈 5 μmol kg−1 in California Borderland basins and the Pakistan Margin. Seasonal to decadal changes of sediment input are necessary to create laminae of different composition. However, bottom currents may shape similar textures that are difficult to discern from primary seasonal laminae. The millimetre-sized trace fossil Chondrites was commonly found in Cretaceous strata and Recent oxygen-depleted environments where its diameter increased with oxygen levels from 5 to 45 μmol kg−1. Chondrites has not been reported in Peruvian sediments but centimetre-sized crab burrows appeared around 10 μmol kg−1, which may indicate a minimum oxygen value for bioturbated Cretaceous strata. Organic carbon accumulation rates ranged from 0.7 and 2.8 g C cm−2 kyr−1 in laminated OAE 2 sections in Tarfaya Basin, Morocco, matching late Holocene accumulation rates of laminated Peruvian sediments under Recent oxygen levels below 5 μmol kg−1. Sediments deposited at 〉 10 μmol kg−1 showed an inverse exponential relationship of bottom-water oxygen levels and organic carbon accumulation depicting enhanced bioirrigation and decomposition of organic matter with increased oxygen supply. In the absence of seasonal laminations and under conditions of low burial diagenesis, this relationship may facilitate quantitative estimates of palaeo-oxygenation. Similarities and differences between Cretaceous OAEs and late Quaternary OMZs have to be further explored to improve our understanding of sedimentary systems under hypoxic conditions.

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.

Description: Mesoscale eddies seem to play an important role for both the hydrography and biogeochemistry of the eastern tropical Pacific Ocean (ETSP) off Peru. However, detailed surveys of these eddies are not available, which has so far hampered an in depth understanding of their implications for nutrient distribution and biological productivity. In this study, three eddies along a section at 16°45´ S have been surveyed intensively during R/V Meteor cruise M90 in November 2012. A coastal mode water eddy, an open ocean mode water eddy and an open ocean cyclonic eddy have been identified and sampled in order to determine both their hydrographic properties and their influence on the biogeochemical setting of the ETSP. In the thermocline the temperature of the coastal anticyclonic eddy was up to 2 °C warmer, 0.2 more saline and the swirl velocity was up to 35 cm s−1. The observed temperature and salinity anomalies, as well as swirl velocities of both types of eddies were about twice as large as had been described for the mean eddies in the ETSP. The observed heat and salt anomalies (AHA, ASA) of the anticyclonic eddy near the shelf-break of 17.7 × 1018 J and 36.6 × 1010 kg are more than twice as large as the mean AHA and ASA for the ETSP. We found that the eddies contributed to the productivity by maintaining pronounced subsurface maxima of chlorophyll of up to 6 μg L−1. Based on a comparison of the coastal (young) mode water eddy and the open ocean (old) mode water eddy we suggest that the ageing of eddies when they detach from the shelf-break and move westward to the open ocean influences the eddies' properties: chlorophyll maxima are reduced to about half (2.5–3 μg L−1) and nutrients are subducted. However, different settings at the time of formation may also contribute to the observed differences between the young and old mode water eddies. The coastal mode water eddy was found to be a site of nitrogen (N) loss in the OMZ with a maximum ΔNO3− anomaly (i.e. N loss) of about −25 μmol L−1 in 250 m water depth, whereas, the open ocean mode water and cyclonic eddies were of minor and negligible importance for the N loss, respectively. Our results show that the important role of eddies for the distribution of nutrients, as well as biogeochemical processes in the ETSP (and other OMZ/upwelling regions) can only be fully deciphered and understood through dedicated high spatial and temporal resolution oceanographic/biogeochemical surveys.

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: The global ocean–climate system has been highly sensitive to the formation and advection of deep overflow water from the Nordic Seas as integral part of the Atlantic Meridional Overturning Circulation (AMOC) but its evolution over the Pliocene–Pleistocene global cooling is not fully understood. In particular, changes in the sources and mixing of prevailing deep waters that were involved in driving overturning throughout the Pliocene–Pleistocene climate transitions are not well constrained. Here we investigate the evolution of a substantial deep southward return overflow of the AMOC over the last 4 million years. We present new records of the bottom-water radiogenic neodymium isotope (ϵNd) variability obtained from three sediment cores (DSDP site 610 and ODP sites 980/981 and 900) at water depths between 2170 and 5050 m in the northeast Atlantic. We find that prior to the onset of major Northern Hemisphere glaciation (NHG) ∼3 million years ago (Ma), ϵNd values primarily oscillated between −9 and −11 at all sites, consistent with enhanced vertical mixing and weak stratification of the water masses during the warmer-than-today Pliocene period. From 2.7 Ma to ∼2.0 Ma, the ϵNd signatures of the water masses gradually became more distinct, which documents a significant advection of Nordic Seas overflow deep water coincident with the intensification of NHG. Most markedly, however, at ∼1.6 Ma the interglacial ϵNd signatures at sites 610 (2420 m water depth (w.d.)) and 980/981 (2170 m w.d.) synchronously and permanently shifted by 2 to 3 ϵNd units to less radiogenic values, respectively. Since then the difference between glacial and interglacial ϵNd values has been similar to the Late Quaternary at each site. A decrease of ∼2ϵNd units at 1.6 Ma was also recorded for the deepest water masses by site 900 (∼5050 m w.d.), which thereafter, however, evolved to more radiogenic values again until the present. This major ϵNd change across the 1.6 Ma transition reflects a significant reorganization of the overturning circulation in the northeast Atlantic paving the way for the more stratified water column with distinct water masses prevailing thereafter.

Description: The sedimentary stable nitrogen isotope compositions of bulk organic matter (δ15Nbulk) and silicon isotope composition of diatoms (δ30SiBSi) both mainly reflect the degree of past nutrient utilization by primary producers. However, in ocean areas where anoxic and suboxic conditions prevail, the δ15Nbulk signal ultimately recorded within the sediments is also influenced by water column denitrification causing an increase in the subsurface δ15N signature of dissolved nitrate (δ15NO3−) upwelled to the surface. Such conditions are found in the oxygen minimum zone off Peru, where at present an increase in subsurface δ15NO3− from North to South along the shelf is observed due to ongoing denitrification within the pole-ward flowing subsurface waters, while the δ30Si signature of silicic acid (δ30Si(OH)4) at the same time remains unchanged. Here, we present three new δ30SiBSi records between 11° S and 15° S and compare these to previously published δ30SiBSi and δ15Nbulk records from Peru covering the past 600 years. We present a new approach to calculate past subsurface δ15NO3− signatures based on the correlation of δ30SiBSi and δ15Nbulk signatures at a latitudinal resolution for different time periods. Our results show source water δ15NO3− compositions during the last 200 years, the Current Warm Period (CWP) and during short-term arid events prior to that, which are close to modern values increasing southward from 7 to 10 ‰ (between 11° S and 15° S). In contrast, humid conditions during the Little Ice Age (LIA) reflect consistently low δ15NO3− values between 6 and 7.5‰. Furthermore, we are able to relate the short-term variability in both isotope compositions to changes in the ratio of nutrients (NO3− : Si(OH)4) taken up by different dominating phytoplankton groups (diatoms and non-siliceous phytoplankton) under the variable climatic conditions of the past 600 years.

Description: 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.

Description: Ocean deoxygenation is a rising threat to marine ecosystems and food resources under present climate warming conditions. Organic-rich sapropel layers deposited in the Mediterranean Sea provide a natural laboratory to study the processes that have controlled changes in seawater oxygen levels in the recent geological past. Our study is based on three sediment cores spanning the last 10 000 years and located on a bathymetric transect offshore from the western distributaries of the Nile delta. These cores are partly to continuously laminated in the sections recording sapropel S1, which is indicative of bottom-water anoxia above the western Nile deep-sea fan. We used a combination of microfacies analyses and inorganic and organic geochemical measurements to reconstruct changes in oxygenation conditions at seasonal to millennial timescales. Millimetre-thick laminations are composed of detrital, biogenic and chemogenic sublayers reflecting seasonal successions of sedimentation. Dark layers reflect the deposition of summer floods and two types of light layers correspond to autumn plankton blooms and authigenic carbonates formed in the water column during spring–early summer, respectively. The isotopic signature of the authigenic carbonates suggests permanent anoxic to euxinic bottom waters resulting in high levels of anaerobic remineralization of organic matter and highlights their potential to reconstruct seawater chemistry at times when benthic fauna was absent. Ratios of major elements combined with biomarkers of terrestrial and marine organic matter and redox-sensitive compounds allow changes in terrigenous input, primary productivity and past deoxygenation dynamics on millennial timescales to be tracked. Rapid fluctuations of oxygenation conditions in the upper 700 m water depth occurred above the Nile deep-sea fan between 10 and 6.5 ka BP, while deeper cores recorded more stable anoxic conditions. Synchronous changes in terrigenous input, primary productivity and past oxygenation dynamics after 6.5 ka BP show that runoff-driven eutrophication played a central role in rapid oxygenation changes in the south-eastern Levantine Basin. These findings are further supported by other regional records and reveal time-transgressive changes in oxygenation state driven by rapid changes in primary productivity during a period of long-term deep-water stagnation.