Silicon isotopes of sediment core GeoB2107-3

The supply of nutrients to the low-latitude thermocline is largely controlled by intermediate-depth waters formed at the surface in the high southern latitudes. Silicic acid is an essential macronutrient for diatoms, which are responsible for a significant portion of marine carbon export production. Changes in ocean circulation, such as those observed during the last deglaciation, would influence the nutrient composition of the thermocline and, therefore, the relative abundance of diatoms in the low latitudes. Here we present the first record of the silicic acid content of the Atlantic over the last glacial cycle. Our results show that at intermediate depths of the South Atlantic, the silicic acid concentration was the same at the Last Glacial Maximum (LGM) as it is today, overprinted by high silicic acid pulses that coincided with abrupt changes in ocean and atmospheric circulation during Heinrich Stadials and the Younger Dryas. We suggest these pulses were caused by changes in intermediate water formation resulting from shifts in the subpolar hydrological cycle, with fundamental implications for the nutrient supply to the Atlantic.

Figure 2. Downcore variations of total diatom concentration in core MD02-2529

The modern eastern equatorial Pacific (EEP) is a major natural source for atmospheric carbon dioxide and is thought to be connected to high-latitude ocean dynamics by oceanic teleconnections on glacial-interglacial timescales. A wealth of sedimentary records aiming at reconstructing last Quaternary changes in primary productivity and nutrient utilization have been devoted to understanding those linkages between the EEP and other distant oceanic areas. Most of these records are, however, clustered in the pelagic EEP cold tongue, with comparatively little attention devoted to coastal areas. Here we present downcore measurements of the composition and concentration of the diatom assemblage together with opal (biogenic silica) concentration at site MD02-2529 recovered in the coastal Panama Basin. Piston core MD02-2529, collected in an area affected by a multitude of processes, provides evidence for strong variations in diatom production at the millennial timescale during the last glacial cycle. The maxima in total diatom concentration occurred during the early marine isotopic stage (MIS) 4 as well as during the MIS 4/3 transition and MIS 3. Rapid changes in diatom concentrations during the MIS 3 mimics Bond cycles as independently recorded by the SSS estimation derived from planktonic foraminifera from the same core. Such patterns indicate a clear linkage between diatom production in the coastal EEP and rapid climate changes in the high-latitude North Atlantic. In parallel, the long-term succession of the diatom community from coastal diatoms, predominantly thriving during MIS 5 and 4, towards pelagic diatoms, dominant during MIS 3 and 2, points to a long-term change in the surface hydrology. During Heinrich Events, diatoms strongly reduced their production, probably due to enhanced stratification in the upper water column. After the last glacial maximum, diatom production and valve preservation strongly decreased in response to the advection of nutrient (H2SiO4)-depleted, warmer water masses. Our high-resolution record highlights how regional climatic processes can modulate rapid changes in siliceous primary production as triggered by wind-induced local upwelling, indicating that millennial climatic variability can overtake other prominent hydrological processes such as those related to silicic acid leakage.

Net community production, Thorium-234 activity and particle flux during the Southern Ocean iron fertilization experiment LOHAFEX

A closed eddy core in the Subantarctic Atlantic Ocean was fertilized twice with two tons of iron (as FeSO4), and the 300 km**2 fertilized patch was studied for 39 days to test whether fertilization enhances downward particle flux into the deep ocean. Chlorophyll a and primary productivity doubled after fertilization, and photosynthetic quantum yield (FV/FM) increased from 0.33 to >0.40. Silicic acid (<2 µmol/L) limited diatoms, which contributed <10% of phytoplankton biomass. Copepods exerted high grazing pressure. This is the first study of particle flux out of an artificially fertilized bloom with very low diatom biomass. Net community production (NCP) inside the patch, estimated from O2:Ar ratios, averaged 21 mmol POC/m**2/d, probably ±20%. 234Th profiles implied constant export of ~6.3 mmol POC/m**2/d in the patch, similar to unfertilized waters. The difference between NCP and 234Th-derived export partly accumulated in the mixed layer and was partly remineralized between the mixed layer and 100 m. Neutrally buoyant sediment traps at 200 and 450 m inside and outside the patch caught mostly <1.1 mmol POC/m**2/d, predominantly of fecal origin; flux did not increase upon fertilization. Our data thus indicate intense flux attenuation between 100 and 200 m, and probably between the mixed layer and 100 m. We attribute the lack of fertilization-induced export to silicon limitation of diatoms and reprocessing of sinking particles by detritus feeders. Our data are consistent with the view that nitrate-rich but silicate-deficient waters are not poised for enhanced particle export upon iron addition.

(Table 2) Age determination of Southern Ocean sediments

The silicic acid leakage hypothesis (SALH) predicts that during glacial periods excess silicic acid was transported from the Southern Ocean to lower latitudes, which favored diatom production over coccolithophorid production and caused a drawdown of atmospheric CO2. Downcore records of 230Th-normalized opal (biogenic silica) fluxes from 31 cores in the Pacific sector of the Southern Ocean were used to compare diatom productivity during the last glacial period to that of the Holocene and to examine the evidence for increased glacial Si export to the tropics. Average glacial opal fluxes south of the modern Antarctic Polar Front (APF) were less than during the Holocene, while average glacial opal fluxes north of the APF were greater than during the Holocene. However, the magnitude of the increase north of the APF was not enough to offset decreased fluxes to the south, resulting in a decrease in opal burial in the Pacific sector of the Southern Ocean during the last glacial period, equivalent to approximately 15 Gt opal/ka1. This is consistent with the work of Chase et al. (2003, doi:10.1016/S0967-0645(02)00595-7), and satisfies the primary requirement of the SALH, assuming that the upwelled supply of Si was approximately equivalent during the Holocene and the glacial period. However, previous results from the equatorial oceans are inconsistent with the other predictions of the SALH, namely that either the Corg:CaCO3 ratio or the rate of opal burial should have increased during glacial periods. We compare the magnitudes of changes in the Southern Ocean and the tropics and suggest that Si escaping the glacial Southern Ocean must have had an alternate destination, possibly the continental margins. There is currently insufficient data to test this hypothesis, but the existence of this sink and its potential impact on glacial pCO2 remain interesting topics for future study.

Silicon isotope ratios of ODP Site 177-1089 and sediment core E33-22

Reconstruction of nutrient concentrations in the deep Southern Ocean has produced conflicting results. The cadmium/calcium (Cd/Ca) data set suggests little change in nutrient concentrations during the last glacial period, whereas the carbon isotope data set suggests that nutrient concentrations were higher. We determined the silicon isotope composition of sponge spicules from the Atlantic and Pacific sectors of the Southern Ocean and found higher silicic acid concentrations in the Pacific sector during the last glacial period. We propose that this increase results from changes in the stoichiometric uptake of silicic acid relative to nitrate and phosphate by diatoms, thus facilitating a redistribution of nutrients across the Pacific and Southern Oceans. Our results are consistent with the global Cd/Ca data set and support the silicic acid leakage hypothesis.

Age, 232Th, 230Th, 238U, CaCO3, organic carbon, lithogenic fraction and opal concentrations of 4 sediment cores from the southwest Pacific, with calculated 230Th-normalized mass flux

No clear scenario has yet been able to explain the full carbon drawdown that occurred during the Last Glacial Maximum (LGM); however, increased export production (EP) in the Subantarctic Zone (SAZ) of the Southern Ocean due to iron (Fe) fertilisation has been proposed to have provided a key mechanism affecting the air-sea partitioning of carbon. We chronicle changes in marine EP based on four sediment cores in Subtropical Waters (STW) and SAZ around New Zealand since the LGM. For the first time in this region, we present 230-Thorium normalised fluxes of biogenic opal, carbonate (CaCO3), excess Barium (xsBa), and organic Carbon (Corg). In STW and SAZ, these flux variations show that EP did not change markedly since the LGM. The only exception was a site in the SAZ close to the STF, where we suggest the STF shifted over the core site, driving increased EP. To understand why EP was mostly low and constant we investigated dust deposition changes by measuring lithogenic fluxes at the four sites. These data are coherent with an increased dust deposition in the southwest Pacific during the LGM. Additionally, we infer an increased lithogenic material discharge from erosion and glacier melts during the deglaciation, limited to the Campbell Plateau. Therefore, we propose that even though increased glacial dust deposition may have relieved Fe limitation within the SAZ, the availability of silicic acid (Si(OH)4) limited any resultant increase in carbon export during the LGM. Consequently, we infer low Si(OH)4 concentrations in the SAZ that have not significantly changed since the LGM. This result suggests that both Si(OH)4 and Fe co-limit EP in the SAZ around New Zealand, which would be consistent with modern process studies.

(Table 1) Interstitial water geochemistry at DSDP Leg 84 Holes

On DSDP Leg 84, drilling was conducted at three gas-hydrate-bearing sites on the Middle America Trench slope off Costa Rica (Site 565) and off Guatemala (Sites 568 and 570). At Site 569, on the mid-slope off Guatemala, hydrates may be present, according to the seismic profile (GUA-13), although the pore-water composition does not provide clear evidence. Sites 566 and 567, on the lower Guatemala Trench slope, appear to be free of hydrates, except in fractures of serpentinite at the bottom of Hole 566. Hydrate-bearing Sites 565, 568, and 570 show the effects of hydrate decomposition on pore-water chemistry that have been established during previous drilling at Sites 496 and 497 on the Guatemala Trench slope. These include a chlorinity decrease and d18O increase downsection. The new results, however, reveal more complex relationships between the chlorinity decrease and d18O increase than previously recognized. At Site 565, d18O values decrease in the middle section of the hole, whereas chlorinity continues to decrease from the top to near the bottom of the hole. Early diagenetic alteration of volcanic glass is suggested as a mechanism for the unexpected minimum in the O-isotope curve. Multiple fractionation by the pore-water/hydrate system is required to explain d18O-values greater than 2.7 per mil at the bottom of Hole 568, because with a fractionation factor of alpha = 1.0027, this is the maximum figure a single-stage fractionation could produce. In situ water samples from hydrate zones in most cases failed to display the elevated salinities expected for the residual pore waters not involved in hydrate formation. This is probably because the in situ sampling device still allows a systematic pressure drop sufficient to trigger hydrate decomposition in the immediate vicinity of the sample port.

Chlorophyll-a, primary production rates, carbon concentrations and cell counts of coccolithophores, diatoms and microzooplankton measured in water samples from the North Atlantic during the M87/1 cruise in April 2012

The Deep Convection cruise repeatedly sampled two locations in the North Atlantic, sited in the Iceland and Norwegian Basins, onboard the RV Meteor (19 March - 2 May 2012). Samples were collected from multiple casts of a conductivity-temperature-depth (CTD) - Niskin rosette at each station. Water samples for primary production rates, community structure, chlorophyll a [Chl a], calcite [PIC], particulate organic carbon [POC] and biogenic silicic acid [BSi] were collected from predawn casts from six light depths (55%, 20%, 14%, 7%, 5% and 1% of incident PAR). Additional samples for community structure and ancillary parameters were collected from a second cast. Carbon fixation rates were determined using the 13C stable isotope method. Water samples for diatom and micro zooplankton counts, collected from the predawn casts, were preserved with acidic Lugol's solution (2% final solution) and counted using an inverted light microscope. Water samples for coccolithophore counts were collected onto cellulose nitrate filters and counted using polarising light microscopy. Water samples for Chl a analysis were filtered onto MF300 and polycarbonate filters and extracted in 90% acetone. PIC and BSi samples were filtered onto polycarbonate filters and analysed using an inductively coupled plasma emission optical spectrometer and a SEAL QuAAtro autoanalyser respectively.

(Table 3) Geochemistry of borehole fluids of ODP Hole 137-504B

Circulation of seawater through basaltic basement for several million years after crustal emplacement has been inferred from studies of surface heat flow, and may play a significant role in the exchange of elements between the oceanic crust and seawater. Without direct observation of the fluid chemistry, interpretations regarding the extent and timing of this exchange must be based on the integrated signal of alteration found in sampled basalts. Much interest has thus been expressed in obtaining and analyzing fluids directly from basaltic formations. It has been proposed that open oceanic boreholes can be used as oceanic groundwater wells to obtain fluids that are circulating within the formation. Water samples were collected from the open borehole in Hole 504B prior to drilling operations on Leg 137, with the original intention of collecting formation fluids from the surrounding basaltic rocks. Past results have yielded ambiguous conclusions as to the origin of the fluids recovered-specifically, whether or not the fluids were true formation fluids or merely the result of reaction of seawater in the borehole environment. The chemistry of eight borehole fluid samples collected during Leg 137 is discussed in this paper. Large changes in major, minor, and isotopic compositions relative to unaltered seawater were observed in the borehole fluids. Compositional changes increased with depth in the borehole. The samples exhibit the effect of simple mixing of seawater, throughout the borehole, with a single reacted fluid component. Analysis and interpretation of the results from Leg 137 in light of past results suggest that the chemical signals observed may originate predominantly from reaction with basaltic rubble residing at the bottom of the hole during the interim between drilling legs. Although this endeavor apparently did not recover formation waters, information on the nature of reaction between seawater and basalt at the prevalent temperatures in Hole 504B (>160°C) has been gained that can be related to reconstruction of the alteration history of the oceanic crust. Isotopic analyses allow calculation of element-specific water/rock mass ratios (Li and Sr) and are related to the extent of chemical exchange between the borehole fluids and basalt.

Diatom isotope data (d18Odiatom and d30Sidiatom) from IODP Site 303-U1304 (North Atlantic)

The Last Interglacial (LIG), corresponding to Marine Isotope Stage (MIS) 5e, provides a reference of interglacial climate variability in the absence of anthropogenic forcing. Using an expanded section of the LIG gained at Integrated Ocean Drilling Program Site U1304 in the Subarctic Atlantic, we demonstrate that the early MIS 5e was marked by oceanographic conditions conducive for high diatom production and accumulation. The appearance of diatom-dominated laminated oozes ~3 k.y. after the beginning of MIS 5e at ca. 125 ka coincides with a shift to higher d30Sidiat values together with the dominance of Thalassiothrix longissima, indicative of increased nutrient availability and silicic acid utilization in surface waters. Though the Subarctic Front provided the physical conditions for high diatom production and deposition, these processes alone are insufficient to explain the high rates of siliceous productivity and the formation of diatomaceous sediments. Instead, the additional presence of an increased nutrient pool provided by Subantarctic Mode Water played the decisive role in initiating and sustaining diatom production. The high diatom productivity and the occurrence of diatomaceous sediments in the late Quaternary challenge the current hypothesis of a silica-depleted North Atlantic during the LIG.

The seasonal sea-ice zone in the glacial Southern Ocean as a carbon sink, supplementary datasets

Reduced surface-deep ocean exchange and enhanced nutrient consumption by phytoplankton in the Southern Ocean have been linked to lower glacial atmospheric CO2. However, identification of the biological and physical conditions involved and the related processes remains incomplete. Here we specify Southern Ocean surface-subsurface contrasts using a new tool, the combined oxygen and silicon isotope measurement of diatom and radiolarian opal, in combination with numerical simulations. Our data do not indicate a permanent glacial halocline related to melt water from icebergs. Corroborated by numerical simulations, we find that glacial surface stratification was variable and linked to seasonal sea-ice changes. During glacial spring-summer, the mixed layer was relatively shallow, while deeper mixing occurred during fall-winter, allowing for surface-ocean refueling with nutrients from the deep reservoir, which was potentially richer in nutrients than today. This generated specific carbon and opal export regimes turning the glacial seasonal sea-ice zone into a carbon sink.

Diatom oxygen and silicon isotopes data from IODP Hole 323-U1341B in the Bering Sea through the late Pliocene and over the onset of major Northern Hemisphere Glaciation

The Bering Sea is one of the most biologically productive regions in the marine system and plays a key role in regulating the flow of waters to the Arctic Ocean and into the subarctic North Pacific Ocean. Cores from Integrated Ocean Drilling Program (IODP) Expedition 323 to the Bering Sea provide the first opportunity to obtain reconstructions from the region that extend back to the Pliocene. Previous research at Bowers Ridge, south Bering Sea, has revealed stable levels of siliceous productivity over the onset of major Northern Hemisphere Glaciation (NHG) (circa 2.85-2.73 Ma). However, diatom silica isotope records of oxygen (d18Odiatom) and silicon (d30Sidiatom) presented here demonstrate that this interval was associated with a progressive increase in the supply of silicic acid to the region, superimposed on shift to a more dynamic environment characterized by colder temperatures and increased sea ice. This concluded at 2.58 Ma with a sharp increase in diatom productivity, further increases in photic zone nutrient availability and a permanent shift to colder sea surface conditions. These transitions are suggested to reflect a gradually more intense nutrient leakage from the subarctic northwest Pacific Ocean, with increases in productivity further aided by increased sea ice- and wind-driven mixing in the Bering Sea. In suggesting a linkage in biogeochemical cycling between the south Bering Sea and subarctic Northwest Pacific Ocean, mainly via the Kamchatka Strait, this work highlights the need to consider the interconnectivity of these two systems when future reconstructions are carried out in the region.