Roger Francois

The δ15N of nitrate in the southern ocean: Consumption of nitrate in surface waters

We report nitrogen isotope data for nitrate from transects of hydrocast and surface samples collected in the eastern Indian and Pacific sectors of the Southern Ocean, focusing here on the data from the upper water column to study the effect of nitrate consumption by phytoplankton. The δ15N of nitrate increases by 1–2‰ from deep water into the Antarctic summertime surface layer, due to kinetic isotopic fractionation during nitrate uptake. Estimation of the nitrate uptake isotope effect from Antarctic depth profiles yields values in the range of 5–6‰ in east Indian sector and 4–5‰ in the east Pacific sector. Surface transect data from the Pacific sector also yield values of 4–5‰. The major uncertainty in the profile-based estimation of the isotope effect involves the δ15N of nitrate from the temperature minimum layer below the summertime Antarctic surface layer, which deviates significantly from the predictions of simple models of isotope fractionation. For the Subantarctic surface, it is possible to distinguish between nitrate supplied laterally from the surface Antarctic and nitrate supplied vertically from the Subantarctic thermocline because of the distinctive relationships between the δ15N and concentration of nitrate in these two potential sources. Our Subantarctic samples, collected during the summer and fall, indicate that nitrate is supplied to the Subantarctic surface largely by northward transport of Antarctic surface water. Isotopic data from the Pacific sector of the Subantarctic suggest an isotope effect of 4.5‰, indistinguishable from the Antarctic estimates in this sector.

The δ15N of nitrate in the Southern Ocean: Nitrogen cycling and circulation in the ocean interior

We report analyses of the nitrogen isotopic composition of nitrate in the eastern Indian and Pacific sectors of the Southern Ocean. In this paper, we focus on the subsurface data as well as data from the deep waters of other ocean basins. Nitrate δ15N is relatively invariant in much of the abyssal ocean (i.e., below 2.5 km), with a value of 4.8±0.2‰ observed in Lower Circumpolar Deep Water, North Atlantic Deep Water, and central Pacific deep water. The isotopic invariance of deep ocean nitrate stems fundamentally from the completeness of nitrate utilization in most of the global surface ocean, the Southern Ocean surface being an important exception. In the Subantarctic Zone (north of the Polar Frontal Zone) the nitrate δ15N of Upper Circumpolar Deep Water is ∼0.7‰ greater than that of Lower Circumpolar Deep Water. This isotopic enrichment appears to result from denitrification in the low-latitude water masses with which Upper Circumpolar Deep Water communicates. The isotopic enrichment of Upper Circumpolar Deep Water is diminished in the Antarctic, probably because of the remineralization of sinking organic N, which has a low δ15N in the Antarctic. Relative to the other water masses of the Southern Ocean, the Subantarctic thermocline has a very low nitrate δ15N for its nitrate concentration because of exchange with the low-latitude thermocline, where this isotopic signature appears to originate. This signature of the low-latitude thermocline has two probable causes: (1) mixing with low-nitrate surface water and (2) the oxidation of newly fixed N.

A study of sulphur enrichment in the humic fraction of marine sediments during early diagenesis

Abstract The evolution of the sulphur content of humic acids extracted from a near-shore sediment core was investigated. Special attention was taken to avoid S contamination of the humic materials during extraction. The S C ratios increased continuously with depth to values which strongly suggest S addition to the humic matrix during early diagenesis by reactions between organic matter and H2S or its oxidation products. Their light isotopic composition supports this view, however, subsequent isotopic exchange has obscured the mechanism initially involved. Since a large fraction of the enrichment occurred above the sulphidic zone, redox boundaries, such as the interface of anoxic microniches within more oxidized zones, or the sulphidic/suboxic boundary of the sediment column, must have been important sites for S addition. Bioturbation, by increasing the contact between sedimentary zones of a different redox regime, will likely enhance such processes.

Carbon dioxide release from the North Pacific abyss during the last deglaciation.

Atmospheric carbon dioxide concentrations were significantly lower during glacial periods than during intervening interglacial periods, but the mechanisms responsible for this difference remain uncertain. Many recent explanations call on greater carbon storage in a poorly ventilated deep ocean during glacial periods, but direct evidence regarding the ventilation and respired carbon content of the glacial deep ocean is sparse and often equivocal. Here we present sedimentary geochemical records from sites spanning the deep subarctic Pacific that—together with previously published results—show that a poorly ventilated water mass containing a high concentration of respired carbon dioxide occupied the North Pacific abyss during the Last Glacial Maximum. Despite an inferred increase in deep Southern Ocean ventilation during the first step of the deglaciation (18,000–15,000 years ago), we find no evidence for improved ventilation in the abyssal subarctic Pacific until a rapid transition ∼14,600 years ago: this change was accompanied by an acceleration of export production from the surface waters above but only a small increase in atmospheric carbon dioxide concentration. We speculate that these changes were mechanistically linked to a roughly coeval increase in deep water formation in the North Atlantic, which flushed respired carbon dioxide from northern abyssal waters, but also increased the supply of nutrients to the upper ocean, leading to greater carbon dioxide sequestration at mid-depths and stalling the rise of atmospheric carbon dioxide concentrations. Our findings are qualitatively consistent with hypotheses invoking a deglacial flushing of respired carbon dioxide from an isolated, deep ocean reservoir, but suggest that the reservoir may have been released in stages, as vigorous deep water ventilation switched between North Atlantic and Southern Ocean source regions.

Eastern Pacific cooling and Atlantic overturning circulation during the last deglaciation

Surface ocean conditions in the equatorial Pacific Ocean could hold the clue to whether millennial-scale global climate change during glacial times was initiated through tropical ocean–atmosphere feedbacks or by changes in the Atlantic thermohaline circulation. North Atlantic cold periods during Heinrich events and millennial-scale cold events (stadials) have been linked with climatic changes in the tropical Atlantic Ocean and South America, as well as the Indian and East Asian monsoon systems, but not with tropical Pacific sea surface temperatures. Here we present a high-resolution record of sea surface temperatures in the eastern tropical Pacific derived from alkenone unsaturation measurements. Our data show a temperature drop of ∼1 °C, synchronous (within dating uncertainties) with the shutdown of the Atlantic meridional overturning circulation during Heinrich event 1, and a smaller temperature drop of ∼0.5 °C synchronous with the smaller reduction in the overturning circulation during the Younger Dryas event. Both cold events coincide with maxima in surface ocean productivity as inferred from 230Th-normalized carbon burial fluxes, suggesting increased upwelling at the time. From the concurrence of equatorial Pacific cooling with the two North Atlantic cold periods during deglaciation, we conclude that these millennial-scale climate changes were probably driven by a reorganization of the oceans’ thermohaline circulation, although possibly amplified by tropical ocean–atmosphere interaction as suggested before.

Moored sediment trap measurements of carbon export in the Subantarctic and Polar Frontal Zones of the Southern Ocean, south of Australia

Sediment trap moorings were deployed from September 21, 1997 through February 21, 1998 at three locations south of Australia along 140°E: at ∼47°S in the central Subantarctic Zone (SAZ) with traps at 1060, 2050, and 3850 m depth, at ∼51°S in the Subantarctic Front with one trap at 3080 m, and at ∼54°S in the Polar Frontal Zone (PFZ) with traps at 830 and 1580 m. Particle fluxes were high at all the sites (18–32 g m−2 yr−1 total mass and 0.5–1.4 g organic carbon m−2 yr−1 at −1000 m, assuming minimal flux outside the sampled summer period). These values are similar to other Southern Ocean results and to the median estimated for the global ocean by Lampitt and Antia [1997], and emphasize that the Southern Ocean exports considerable carbon to the deep sea despite its “high-nutrient, low chlorophyll” characteristics. The SAZ site was dominated by carbonate (>50% of total mass) and the PFZ site by biogenic silica (>50% of total mass). Both sites exhibited high export in spring and late summer, with an intervening low flux period in December. For the 153 day collection period, particulate organic carbon export was somewhat higher in all the traps in the SAZ (range 0.57–0.84 gC m−2) than in the PFZ (range 0.31–0.53), with an intermediate value observed at the SAF (0.60). The fraction of surface organic carbon export (estimated from seasonal nutrient depletion, Lourey and Trull [2001]) reaching 1000 m was indistinguishable in the SAZ and PFZ, despite different algal communities.

A review of nitrogen isotopic alteration in marine sediments

Key Points: Use of sedimentary nitrogen isotopes is examined; On average, sediment 15N/14N increases approx. 2 per mil during early burial; Isotopic alteration scales with water depth Abstract: Nitrogen isotopes are an important tool for evaluating past biogeochemical cycling from the paleoceanographic record. However, bulk sedimentary nitrogen isotope ratios, which can be determined routinely and at minimal cost, may be altered during burial and early sedimentary diagenesis, particularly outside of continental margin settings. The causes and detailed mechanisms of isotopic alteration are still under investigation. Case studies of the Mediterranean and South China Seas underscore the complexities of investigating isotopic alteration. In an effort to evaluate the evidence for alteration of the sedimentary N isotopic signal and try to quantify the net effect, we have compiled and compared data demonstrating alteration from the published literature. A >100 point comparison of sediment trap and surface sedimentary nitrogen isotope values demonstrates that, at sites located off of the continental margins, an increase in sediment 15N/14N occurs during early burial, likely at the seafloor. The extent of isotopic alteration appears to be a function of water depth. Depth-related differences in oxygen exposure time at the seafloor are likely the dominant control on the extent of N isotopic alteration. Moreover, the compiled data suggest that the degree of alteration is likely to be uniform through time at most sites so that bulk sedimentary isotope records likely provide a good means for evaluating relative changes in the global N cycle.

The influence of humic substances on the geochemistry of iodine in nearshore and hemipelagic marine sediments

Iodine is characteristically enriched at the surface of hemipelagic and nearshore sediments deposited under oxygenated conditions. In such sediments, bulk I/Corg ratios usually decrease with depth to values which are characteristic of anoxic sediments, reflecting a preferential release of I during early diagenesis. There is some debate as to whether sedimentary I is associated with the iron oxyhydroxide phase or with the organic fraction, and whether the decrease in I/Corg with depth is due to the dissolution of the iron oxyhydroxides or the decomposition of labile organic matter. It is shown that in a surficial hemipelagic sediment sample and in a nearshore sediment core I is mainly associated with the organic fraction and, moreover, that humic substances are involved in the surficial iodine enrichment. Laboratory experiments on the uptake and release of I by and from sedimentary humic substances also suggest a mechanism whereby humic materials reduce iodate at the sediment/water interface to an electrophilic I species which further reacts with the organic matter to produce iodinated organic molecules. During burial, this excess I could be displaced from the organic matrix by nucleophiles such as sulphide ions or thiosulphate, thus providing a possible explanation for the decrease in I/Corg ratio with depth observed in many nearshore and hemipelagic sediments.

Thorium-230 normalized particle flux and sediment focusing in the Panama Basin region during the last 30,000 years

[1] Application of the 230 Th normalization method to estimate sediment burial fluxes in six cores from the eastern equatorial Pacific (EEP) reveals that bulk sediment and organic carbon fluxes display a coherent regional pattern during the Holocene that is consistent with modern oceanographic conditions, in contrast with estimates of bulk mass accumulation rates (MARs) derived from core chronologies. Two nearby sites (less than 10 km apart), which have different MARs, show nearly identical 230 Th-normalized bulk fluxes. Focusing factors derived from the 230 Th data at the foot of the Carnegie Ridge in the Panama Basin are >2 in the Holocene, implying that lateral sediment addition is significant in this part of the basin. New geochemical data and existing literature provide evidence for a hydrothermal source of sediment in the southern part of the Panama Basin and for downslope transport from the top of the Carnegie Ridge. The compilation of core records suggests that sediment focusing is spatially and temporally variable in the EEP. During oxygen isotope stage 2 (OIS 2, from 13–27 ka BP), focusing appears even higher compared to the Holocene at most sites, similar to earlier findings in the eastern and central equatorial Pacific. The magnitude of the glacial increase in focusing factors, however, is strongly dependent on the accuracy of age models. We offer two possible explanations for the increase in glacial focusing compared to the Holocene. The first one is that the apparent increase in lateral sediment redistribution is partly or even largely an artifact of insufficient age control in the EEP, while the second explanation, which assumes that the observed increase is real, involves enhanced deep sea tidal current flow during periods of low sea level stand.

Deglacial pulses of deep-ocean silicate into the subtropical North Atlantic Ocean.

Growing evidence suggests that the low atmospheric CO2 concentration of the ice ages resulted from enhanced storage of CO2 in the ocean interior, largely as a result of changes in the Southern Ocean. Early in the most recent deglaciation, a reduction in North Atlantic overturning circulation seems to have driven CO2 release from the Southern Ocean, but the mechanism connecting the North Atlantic and the Southern Ocean remains unclear. Biogenic opal export in the low-latitude ocean relies on silicate from the underlying thermocline, the concentration of which is affected by the circulation of the ocean interior. Here we report a record of biogenic opal export from a coastal upwelling system off the coast of northwest Africa that shows pronounced opal maxima during each glacial termination over the past 550,000 years. These opal peaks are consistent with a strong deglacial reduction in the formation of silicate-poor glacial North Atlantic intermediate water (GNAIW). The loss of GNAIW allowed mixing with underlying silicate-rich deep water to increase the silicate supply to the surface ocean. An increase in westerly-wind-driven upwelling in the Southern Ocean in response to the North Atlantic change has been proposed to drive the deglacial rise in atmospheric CO2 (refs 3, 4). However, such a circulation change would have accelerated the formation of Antarctic intermediate water and sub-Antarctic mode water, which today have as little silicate as North Atlantic Deep Water and would have thus maintained low silicate concentrations in the Atlantic thermocline. The deglacial opal maxima reported here suggest an alternative mechanism for the deglacial CO2 release. Just as the reduction in GNAIW led to upward silicate transport, it should also have allowed the downward mixing of warm, low-density surface water to reach into the deep ocean. The resulting decrease in the density of the deep Atlantic relative to the Southern Ocean surface promoted Antarctic overturning, which released CO2 to the atmosphere.