Model Studies of Past Changes in the Geochemistry and Physics of the Ocean

As a rule, we work to interpret the data generated in the lab as quantitatively as possible. In our paleoceanographic work, geochemical box models are often used. Through collaboration with researchers GFDL and AOS researchers, we have made some use of more physically realistic ocean/atmosphere models.

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Output from the standard case of an ocean model developed by Agatha de Boer and applied by her to study the interaction of ocean ventilation with climate. See de Boer et al

References

220 Publications
North Atlantic (NA) deep-water formation and the resulting Atlantic meridional overturning cell is generally regarded as the primary feature of the global overturning circulation and is believed to be a result of the geometry of the continents. Here, instead, the overturning is viewed as a global energy-driven system and the robustness of NA…
Seawater samples were collected at discrete depths from five stations across the polar front in the Drake Passage (Antarctic Ocean) by the 20th Korea Antarctic Research Program in December, 2006. Nitrate concentrations of seawater increase with depth within the photic zone above the depth of Upper Circumpolar Deep Water (UCDW). In contrast, δ15N…
We report the first measurements of coupled nitrogen (N) and oxygen (O) isotope fractionation of nitrate by laboratory cultures of denitrifying bacteria. Two seawater strains (Pseudomonas stutzeri, Ochrobactrum sp.) and three freshwater strains (Paracoccus denitrificans, Pseudomonas chlororaphis, Rhodobacter sphaeroides) were examined. Among four…
This chapter reviews the ongoing efforts to use sediment and ice core records to understand the dynamics of oceanic fixed nitrogen (N), focusing on recent glacial-interglacial cycles. Research has, up to this point, followed the reductionist approach of trying to reconstruct either changes in the ocean N budget (largely through low latitude…
N and O isotope analyses of water column nitrate between Bermuda and Puerto Rico document a bolus of low-δ15N nitrate throughout the Sargasso Sea thermocline, which we attribute primarily to the input of recently fixed N. Although previous work suggests southward increases in N2 fixation and ventilation age, no meridional trend in nitrate δ15N is…
The Younger Dryas cooling 12,700 years ago is one of the most abrupt climate changes observed in Northern Hemisphere palaeoclimate records. Annually laminated lake sediments are ideally suited to record the dynamics of such abrupt changes, as the seasonal deposition responds immediately to climate, and the varve counts provide an accurate estimate…
The open subarctic Pacific is, at present, a high nitrate low chlorophyll (HNLC) region, where nitrate is perennially abundant at the surface. Theoretically, the HNLC status of this region is subject to modification by ocean circulation and/or micronutrient supply, with implications for the effectiveness of the biological pump and hence carbon…
Throughout the year 2001, aerosol samples were collected continuously for 10 to 15 days at the French Antarctic Station Dumont d Urville (DDU) (66°40′S, 140°01′E, 40m above mean sea level). The nitrogen and oxygen isotopic ratios of particulate nitrate at DDU exhibit seasonal variations that are among the most extreme observed for nitrate on Earth…
For the last deglaciation and Termination V (the initiation of MIS 11 at around 430 ka) we report high-resolution sedimentary nitrogen isotope (δ15N) records from Cariaco Basin in the Caribbean Sea. During both terminations the previously reported interglacial decrease in δ15N clearly lags local changes such as water column anoxia as well as…
We report 15N/14N ratios of porewater nitrate in sediments from the Bering Sea basin, where microbial nitrate reduction has been identified as a significant sink for fixed nitrogen (N). Strong 15N enrichment in porewater nitrate is observed as one goes deeper in the sediments and nitrate concentration [NO3-] decreases (δ15N generally reaches 25-35…
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…
A growing number of paleoceanographic observations suggest that the ocean s deep ventilation is stronger in warm climates than in cold climates. Here we use a general ocean circulation model to test the hypothesis that this relation is due to the reduced sensitivity of seawater density to temperature at low mean temperature; that is, at lower…
The response of tropical forests to climate change will depend on individual plant species nutritional strategies, which have not been defined in the case of the nitrogen nutrition that is critical to sustaining plant growth and photosynthesis. We used isotope natural abundances to show that a group of tropical plant species with diverse growth…
In a piston core from the central Bering Sea, diatom microfossil-bound N isotopes and the concentrations of Opal, biogenic barium, calcium carbonate, and organic N are measured over the last glacial/interglacial cycle. Compared to the interglacial sections of the core, the sediments of the last ice age are characterized by 3‰ higher diatom-bound…
Interaction with ozone transfers its anomalous (non-mass-dependent) 17O enrichment to atmospheric nitrogen oxides and nitrate. The 17O anomaly (Δ17O) in nitrate can be used to identify atmospheric nitrate inputs into terrestrial and aquatic environments as well as to study the role of ozone in the atmosphere s reactive nitrogen cycle. We report…
Nitrogen fixation is crucial for maintaining biological productivity in the oceans, because it replaces the biologically available nitrogen that is lost through denitrification. But, owing to its temporal and spatial variability, the global distribution of marine nitrogen fixation is difficult to determine from direct shipboard measurements. This…
The Asian-Australian monsoon is an important component of the Earth s climate system that influences the societal and economic activity of roughly half the world s population. The past strength of the rain-bearing East Asian summer monsoon can be reconstructed with archives such as cave deposits, but the winter monsoon has no such signature in the…

We have previously argued that the Antarctic and subarctic North Pacific are stratified during ice ages, causing to a large degree the observed low CO2 levels of ice age atmospheres by sequestering respired CO2 in the ocean abyss. Here, we suggest a mechanism for the major deglaciations of the late Pleistocene. The mechanism begins with…

We report nitrate (NO3-) nitrogen isotope ratios for seawater samples collected in the Subantarctic Zone of the Southern Ocean during both winter and summer as part of the Australian Antarctic CRC Subantarctic Zone (SAZ) Project. The concentration and 15N/14N of the wintertime surface nitrate are very close to those of the subantarctic thermocline…
We describe a method to remove nitrite from seawater and freshwater samples to determine the nitrogen (N) and oxygen (O) isotopic composition of nitrate in aqueous samples (15N/14N and 18O/16O, respectively). This method is simple, inexpensive, and effective in the removal of nitrite without compromising the natural N and O isotopic composition of…
The nitrogen isotopic composition (15N/14N) of forested ecosystems varies systematically worldwide. In tropical forests, which are elevated in 15N relative to temperate biomes, a decrease in ecosystem 15N/14N with increasing rainfall has been reported. This trend is seen in a set of well characterized Hawaiian rainforests, across which we have…
The 15N/14N and 18O/16O ratios of nitrate in the Greenland Ice Sheet Project 2 (GISP2) (Summit, Greenland) ice core are much higher in ice from the last glacial period than in the pre-industrial Holocene, despite the lack of a significant glacial/interglacial change in nitrate concentration. While both the 15N/14N and 18O/16O records are…
On the basis of the normalization to phosphate, a significant amount of nitrate is missing from the deep Bering Sea (BS). Benthic denitrification has been suggested previously to be the dominant cause for the BS nitrate deficit. We measured water column nitrate 15N/14N and 18O/16O as integrative tracers of microbial denitrification, together with…
Diatom-bound 15N/14N was used to reconstruct the glacial nutrient status of the Subantarctic Zone in the Southern Ocean. Down-core records from both the Pacific and Indian sectors show δ 15N of 5 to 6%‰ during the Last Glacial Maximum and a decrease, coincident with the glacial termination, to values as low as 2‰. The effect of either diatom…
Since the first evidence of low algal productivity during ice ages in the Antarctic Zone of the Southern Ocean was discovered, there has been debate as to whether it was associated with increased polar ocean stratification or with sea-ice cover, shortening the productive season. The sediment concentration of biogenic barium at Ocean Drilling…
To better constrain the dynamics of the dissolved organic nitrogen (DON) pool and the role of N2 fixation in the nitrogen cycle at the Bermuda Atlantic Time-series Study (BATS) site, we measured the 15N/14N ratio of total nongaseous nitrogen (TN) in the upper 250 m and of nitrate in the upper 1000 m of monthly water column profiles from June 2000…
In the context of gradual Cenozoic cooling, the timing of the onset of significant Northern Hemisphere glaciation 2.7 million years ago is consistent with Milankovitch s orbital theory, which posited that ice sheets grow when polar summertime insolation and temperature are low. However, the role of moisture supply in the initiation of large…
Water column depth profiles along the North Pacific margin from Point Conception to the tip of Baja California indicate elevation of nitrate (NO3-) 15N/14N and 18O/16O associated with denitrification in the oxygen-deficient thermocline waters of the eastern tropical North Pacific. The increase in δ18O is up to 3%o greater than in δ15N, whereas our…
We report 15N/14N and 18O/16O ratios of nitrate in benthic chamber incubations in the continental shelf sediments of the Santa Monica Bay (SMB) to deconvolve the effects of nitrification and denitrification. Estimates of denitrification rate from benthic flux stoichiometry range from 0.9 to 2.5 mmol N m-2 d -1. Between 46% and 100% of the total…
The low-latitude ocean is strongly stratified by the warmth of its surface water. As a result, the great volume of the deep ocean has easiest access to the atmosphere through the polar surface ocean. In the modern polar ocean during the winter, the vertical distribution of temperature promotes overturning, with colder water over warmer, while the…
We report the first measurements of coupled nitrogen (N) and oxygen (O) isotopic variations of nitrate (NO3-) during its assimilation by laboratory cultures of marine phytoplankton and derive the N and O kinetic isotope effects for nitrate assimilation by three species of diatoms (Thalassiosira weissflogii, Thalassiosira oceanica, and…
The 15N/14N of nitrate in the external medium and intracellular pool of the cultured marine diatom Thalassiosira weissflogii (Grun.) Fryxell et Hasle was measured during nitrate assimilation under low light, a 12:12-h light:dark cycle, low temperature, or low iron conditions. The 15N/14N of the nitrate in the medium and the particulate matter both…
We investigate the response of the 15N/14N of oceanic nitrate to glacial/interglacial changes in the N budget, using a geochemical box model of the oceanic N cycle that includes N2 fixation and denitrification in the sediments and suboxic water column. This model allows us to quantify the isotopic response of different oceanic nitrate pools to…
Nitrogen and oxygen isotopes of NO3- have been measured in snow and firn from Summit, Greenland. The 15N/ 14N and 18O/16O ratios of NO 3- in recently fallen snow are similar to those of surface snow. Diurnal variation is observed in 15N/ 14N of NO3-, and possibly 18O/16O, suggesting fractionating loss of NO3- from snow during the day, which is…
Isotopic measurements of diatom-bound nitrogen, using a wet chemical oxidation combined with the "denitrifier" method for nitrate analysis, show significant offsets from previously published combustion-based measurements. This offset is attributed to a gaseous nitrogen blank associated with the diatom s opal frustule. Moreover, experimentation…
We report 15N/14N measurements of water column nitrate and ammonium, sinking particles, and sediments from the Cariaco Basin, an anoxic marine basin off the coast of Venezuela. Water column denitrification occurring in the basin has only a very small isotopic imprint on nitrate in the basin because nitrate consumption is nearly complete in the…
Rainwater collected on the island of Bermuda between January 2000 and January 2001 shows pronounced seasonal variation in the nitrogen and oxygen isotopic composition of nitrate. Higher 15N/14N and lower 18O/16O ratios are observed in the warm season (April-September) in comparison to the cool season (October-March): The mean δ15N of nitrate for…
Recent evidence from the sulfur isotopic record indicates a transition ∼2.5 billion years ago from an ocean chemistry first dominated by iron and then by sulfide. It has been hypothesized that the selection of metal centers in metalloenzymes has been influenced by the availability of metals through geological time, in particular as a result of…
The link between similarity in amino acid sequence,for ammonia monooxygenase (AMO) and isotopic discrimination for ammonia oxidation (εAMO) was investigated in β-subdivision ammonia-oxidizing bacteria. The isotope effects for ammonia oxidation in pure cultures of the nitrifying strains. Nitrosomonas marina, Nitrosomonas C-113a, Nitrosospira tenuis…
[1] Below its sill depth, the Santa Barbara Basin (SBB) is commonly suboxic ([O2] ̃ 3 μM), with only brief periods of ventilation. Associated with development of suboxia, the concentration of nitrate decreases with depth into the basin without an associated decrease in phosphate, indicating that a substantial fraction of the nitrate supplied to…
In the anoxic Cariaco Basin of the southern Caribbean, the bulk titanium content of undisturbed sediment reflects variations in riverine input and the hydrological cycle over northern tropical South America. A seasonally resolved record of titanium shows that the collapse of Maya civilization in the Terminal Classic Period occurred during an…
Using an ocean box model, we have studied the effect of altered circulation on the oceanic distributions of phosphate (PO4-3) and the 13C/12C and 14C/12C of dissolved inorganic carbon to evaluate competing hypotheses for the cause of observed nutrient depletion and 13C enrichment at intermediate depths of the Atlantic during the last ice age…
We report measurements of the δ15N of nitrate, suspended particulate nitrogen (PN), and sinking PN from cruises and moored sediment traps in the Subantarctic Zone (SAZ) and Polar Frontal Zone (PFZ) south of Australia. As expected, surface water nitrate δ15N increased as nitrate was consumed during the spring/summer bloom. In contrast, the seasonal…
The 15N composition of sediments has been used as a proxy for nitrate utilization in surface waters to assess the role of Southern Ocean export production in glacial/interglacial changes in atmospheric CO2 concentration. Interpretation has relied on a temporally constant isotope effect (ε) associated with uptake and assimilation of nitrate by…
Phytoplankton in the Antarctic deplete silicic acid (Si(OH)4) to a far greater extent than they do nitrate (NO3-). This pattern can be reversed by the addition of iron which dramatically lowers diatom Si(OH)4:NO3- uptake ratios. Higher iron supply during glacial times would thus drive the Antarctic towards NO3- depletion with excess Si(OH)4…
Atmospheric deposition of nitrogen (N) and base cations was measured for 5-7 years on the island of Hawaii and for 1.5 years on Kauai. On Hawaii, mean annual fluxes of K+, Mg2+, and Ca2+ were 15, 17, and 13 kg ha-1 yr-1, respectively. Fog interception was the largest deposition pathway. Sea salt contributed the majority of cations, although…