Nitrogen isotopic and opal record of sediments in the Gulf of California

High-resolution records of the nitrogen isotopic composition of organic matter (d15Norg), opal content, and opal accumulation rates from the central Gulf of California reveal large and abrupt variations during deglaciation and gradual Holocene changes coincident with climatic changes recorded in the North Atlantic. Homogenous sediments with relatively low d15Norg values and low opal content were deposited at the end of the last glacial period, during the Younger-Dryas event, and during the middle to late Holocene. In contrast, laminated sediments deposited in the two deglacial stages are characterized by very high d15Norg values (>14 per mil) and opal accumulation rates (29-41 mg/cm**2/yr). Abrupt shifts in d15Norg were driven by widespread changes in the extent of suboxic subsurface waters supporting denitrification and were amplified in the central gulf record due to variations in upwelling, vertical mixing, and/or the latitudinal position of the Intertropical Convergence Zone.

Accumulation rates for western Dronning Maud Land from firn cores and snow pits

As a result of intensive field activities carried out by several nations over the past 15 years, a set of accumulation measurements for western Dronning Maud Land, Antarctica, was collected, based on firn-core drilling and snow-pit sampling. This new information was supplemented by earlier data taken from the literature, resulting in 111 accumulation values. Using Geographical Information Systems software, a first region-wide mean annual snow-accumulation field was derived. In order to define suitable interpolation criteria, the accumulation records were analyzed with respect to their spatial autocorrelation and statistical properties. The resulting accumulation pattern resembles well known characteristics such as a relatively wet coastal area with a sharp transition to the dry interior, but also reveals complex topographic effects. Furthermore, this work identifies new high-return shallow drilling sites by uncovering areas of insufficient sampling density.

Dissolved oxygen, nitrate, nitrite, and ammonum in waters of the Arabian Sea

Distribution of ammonium, nitrite and nitrate nitrogen is examined in a section along 65-67°E between 18°S and 23°N during the transition period from winter to summer monsoons. It is shown that, under conditions of very large oxygen deficit in the 200-400 m layer, denitrification process results in formation of the second deep-sea maximum of nitrites and the intermediate minimum of nitrate nitrogen.

Biogeochemical investigation of the benthic nitrogen cycle in the Arabian Sea off Pakistan

A pronounced deficit of nitrogen (N) in the oxygen minimum zone (OMZ) of the Arabian Sea suggests the occurrence of heavy N-loss that is commonly attributed to pelagic processes. However, the OMZ water is in direct contact with sediments on three sides of the basin. Contribution from benthic N-loss to the total N-loss in the Arabian Sea remains largely unassessed. In October 2007, we sampled the water column and surface sediments along a transect cross-cutting the Arabian Sea OMZ at the Pakistan continental margin, covering a range of station depths from 360 to 1430 m. Benthic denitrification and anammox rates were determined by using 15N-stable isotope pairing experiments. Intact core incubations showed declining rates of total benthic N-loss with water depth from 0.55 to 0.18 mmol N m**-2 day**-1. While denitrification rates measured in slurry incubations decreased from 2.73 to 1.46 mmol N m**-2 day**-1 with water depth, anammox rates increased from 0.21 to 0.89 mmol N m**-2 day**-1. Hence, the contribution from anammox to total benthic N-loss increased from 7% at 360 m to 40% at 1430 m. This trend is further supported by the quantification of cd1-containing nitrite reductase (nirS), the biomarker functional gene encoding for cytochrome cd1-Nir of microorganisms involved in both N-loss processes. Anammox-like nirS genes within the sediments increased in proportion to total nirS gene copies with water depth. Moreover, phylogenetic analyses of NirS revealed different communities of both denitrifying and anammox bacteria between shallow and deep stations. Together, rate measurement and nirS analyses showed that anammox, determined for the first time in the Arabian Sea sediments, is an important benthic N-loss process at the continental margin off Pakistan, especially in the sediments at deeper water depths. Extrapolation from the measured benthic N-loss to all shelf sediments within the basin suggests that benthic N-loss may be responsible for about half of the overall N-loss in the Arabian Sea.

Carbon and nitrogen isotopic composition of Early Toarcian sediments

Bulk sedimentary nitrogen isotope (d15Ntot) data have been generated from Lower Jurassic black, carbon-rich shales in the British Isles and northern Italy deposited during the early Toarcian oceanic anoxic event. A pronounced positive d15Ntot excursion through the exaratum Subzone of the falciferum Zone (defined by characteristic ammonites in the British Isles) broadly correlates with a relative maximum in weight percent total organic carbon and, in some sections, with a negative d13Corg excursion. Upwelling of a deoxygenated water mass that had undergone partial denitrification is the likely explanation for relative enrichment of d15Ntot, and parallels may be drawn with Quaternary sediments of the Arabian Sea, Gulf of California, and northwest Mexican margin. The development of Early Toarcian suboxic water masses and consequent partial denitrification is attributed to increases in organic productivity. Approximately coincident phenomena include the following: a relative climatic optimum, realignment of major oceanic current systems, and a possible release of methane gas hydrates from continental margin sediments early in the history of the oceanic anoxic event.

Geochemistry of continental slope and deep sea basin sediments off Uruguay

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement (<6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1 N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24 h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe2+. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.

TOC, TN, d15N isotopes and alkenone concentration in equatorial Pacific sediments

The largest increase in export production in the eastern Pacific of the last 5.3 Myr (million years) occurred between 2.2 and 1.6 Myr, a time of major climatic and oceanographic reorganization in the region. Here, we investigate the causes of this event using reconstructions of export production, nutrient supply and oceanic conditions across the Pliocene-Pleistocene in the eastern equatorial Pacific (EEP) for the last 3.2 Myr. Our results indicate that the export production peak corresponds to a cold interval marked by high nutrient supply relative to consumption, as revealed by the low bulk sedimentary 15N/14N (d15N) and alkenone-derived sea surface temperature (SST) values. This ?0.6 million year long episode of enhanced delivery of nutrients to the surface of the EEP was predominantly initiated through the upwelling of nutrient-enriched water sourced in high latitudes. In addition, this phenomenon was likely promoted by the regional intensification of upwelling in response to the development of intense Walker and Hadley atmospheric circulations. Increased nutrient consumption in the polar oceans and enhanced denitrification in the equatorial regions restrained nutrient supply and availability and terminated the high export production event.

Age models for sediment cores in the eastern tropical Pacific

We present new high-resolution N isotope records from the Gulf of Tehuantepec and the Nicaragua Basin spanning the last 50-70 ka. The Tehuantepec site is situated within the core of the north subtropical denitrification zone while the Nicaragua site is at the southern boundary. The d15N record from Nicaragua shows an 'Antarctic' timing similar to denitrification changes observed off Peru-Chile but is radically different from the northern records. We attribute this to the leakage of isotopically heavy nitrate from the South Pacific oxygen minimum zone (OMZ) into the Nicaragua Basin. The Nicaragua record leads the other eastern tropical North Pacific (ETNP) records by about 1000 years because denitrification peaks in the eastern tropical South Pacific (ETSP) before denitrification starts to increase in the Northern Hemisphere OMZ, i.e., during warming episodes in Antarctica. We find that the influence of the heavy nitrate leakage from the ETSP is still noticeable, although attenuated, in the Gulf of Tehuantepec record, particularly at the end of the Heinrich events, and tends to alter the recording of millennial timescale denitrification changes in the ETNP. This implies (1) that sedimentary d15N records from the southern parts of the ETNP cannot be used straightforwardly as a proxy for local denitrification and (2) that denitrification history in the ETNP, like in the Arabian Sea, is synchronous with Greenland temperature changes. These observations reinforce the conclusion that on millennial timescales during the last ice age, denitrification in the ETNP is strongly influenced by climatic variations that originated in the high-latitude North Atlantic region, while commensurate changes in Southern Ocean hydrography more directly, and slightly earlier, affected oxygen concentrations in the ETSP. Furthermore, the d15N records imply ongoing physical communication across the equator in the shallow subsurface continuously over the last 50-70 ka.

Biogeochemical investigations on sediment core MD04-2876

Modern seawater profiles of oxygen, nitrate deficit, and nitrogen isotopes reveal the spatial decoupling of summer monsoon-related productivity and denitrification maxima in the Arabian Sea (AS) and raise the possibility that winter monsoon and/or ventilation play a crucial role in modulating denitrification in the northeastern AS, both today and through the past. A new high-resolution 50-ka record of d15N from the Pakistan margin is compared to five other denitrification records distributed across the AS. This regional comparison unveils the persistence of east-west heterogeneities in denitrification intensity across millennial-scale climate shifts and throughout the Holocene. The oxygen minimum zone (OMZ) experienced east-west swings across Termination I and throughout the Holocene. Probable causes are (1) changes in ventilation due to millennial-scale variations in Antarctic Intermediate Water formation and (2) postglacial reorganization of intermediate circulation in the northeastern AS following sea level rise. Whereas denitrification in the world's OMZs, including the western AS, gradually declined following the deglacial maximum (10-9 ka BP), the northeastern AS record clearly witnesses increasing denitrification from about 8 ka BP. This would have impacted the global Holocene climate through sustained N2O production and marine nitrogen loss.

Organic carbon content, stable isotopes and planktonic foraminifera in sediments of tghe norther Arabian Sea oxygen minimum zone

The northern Arabian Sea is one of the few regions in the open ocean where thermocline water is severely depleted in oxygen. The intensity of this oxygen minimum zone (OMZ) has been reconstructed over the past 225,000 years using proxies for surface water productivity, water column denitrification, winter mixing, and the aragonite compensation depth (ACD). Changes in OMZ intensity occurred on orbital and suborbital timescales. Lowest O2 levels correlate with productivity maxima and shallow winter mixing. Precession-related productivity maxima lag early summer insolation maxima by ~6 kyr, which we attribute to a prolonged summer monsoon season related to higher insolation at the end of the summer. Periods with a weakened or even non-existent OMZ are characterized by low productivity conditions and deep winter mixing attributed to strong and cold winter monsoonal winds. The timing of deep winter mixing events corresponds with that of periods of climatic cooling in the North Atlantic region.

Modeled uncertainties in marine N2O emissions with links to source files (52 MB, zipped)

The ocean is responsible for up to a third of total global nitrous oxide (N2O) emissions, but uncertainties in emission rates of this potent greenhouse gas are high (>100%). Here we use a marine biogeochemical model to assess six major uncertainties in estimates of N2O production, thereby providing guidance in how future studies may most effectively reduce uncertainties in current and future marine N2O emissions. Potential surface N2O production from nitrification causes the largest uncertainty in N2O emissions (estimated up to ~1.6 Tg N/yr, or 48% of modeled values), followed by the unknown oxygen concentration at which N2O production switches to N2O consumption (0.8 Tg N/yr, or 24% of modeled values). Other uncertainties are minor, cumulatively changing regional emissions by <15%. If production of N2O by surface nitrification could be ruled out in future studies, uncertainties in marine N2O emissions would be halved.

Model results of sensitivity experiments for marine nitrogen cycle in four NetCDF files

The marine nitrogen (N) inventory is thought to be stabilized by negative feedback mechanisms that reduce N inventory excursions relative to the more slowly overturning phosphorus inventory. Using a global biogeochemical ocean circulation model we show that negative feedbacks stabilizing the N inventory cannot persist if a close spatial association of N2 fixation and denitrification occurs. In our idealized model experiments, nitrogen deficient waters, generated by denitrification, stimulate local N2 fixation activity. But, because of stoichiometric constraints, the denitrification of newly fixed nitrogen leads to a net loss of N. This can enhance the N deficit, thereby triggering additional fixation in a vicious cycle, ultimately leading to a runaway N loss. To break this vicious cycle, and allow for stabilizing negative feedbacks to occur, inputs of new N need to be spatially decoupled from denitrification. Our idealized model experiments suggest that factors such as iron limitation or dissolved organic matter cycling can promote such decoupling and allow for negative feedbacks that stabilize the N inventory. Conversely, close spatial co-location of N2 fixation and denitrification could lead to net N loss.