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Constraints on hydrothermal heat flux through the oceanic lithosphere from global heat flow

A significant discrepancy exists between the heat flow measured at the seafloor and the higher values predicted by thermal models of the cooling lithosphere. This discrepancy is generally interpreted as indicating that the upper oceanic crust is cooled significantly by hydrothermal circulation. The magnitude of this heat flow discrepancy is the primary datum used to estimate the volume of hydrothermal flow, and the variation in the discrepancy with lithospheric age is the primary constraint on how the hydrothermal flux is divided between near-ridge and off-ridge environments. The resulting estimates are important for investigation of both the thermal structure of the lithosphere and the chemistry of the oceans. We reevaluate the magnitude and age variation of the discrepancy using a global heat flow data set substantially larger than in earlier studies, and the GDHI (Global Depth and Heat Flow) model that better predicts the heat flow. We estimate that of the predicted global oceanic heat flux of 32 x 10(exp 12) W, 34% (11 x 10(exp 12) W) occurs by hydrothermal flow. Approximately 30% of the hydrothermal heat flux occurs in crust younger than 1 Ma, so the majority of this flux is off-ridge. These hydrothermal heat flux estimates are upper bounds, because heat flow measurements require sediment at the site and so are made preferentially at topographic lows, where heat flow may be depressed. Because the water temperature for the near-ridge flow exceeds that for the off-ridge flow, the near-ridge water flow will be even a smaller fraction of the total water flow. As a result, in estimating fluxes from geochemical data, use of the high water temperatures appropriate for the ridge axis may significantly overestimate the heat flux for an assumed water flux or underestimate the water flux for an assumed heat flux. Our data also permit improved estimates of the 'sealing' age, defined as the age where the observed heat flow approximately equals that predicted, suggesting that hydrothermal heat transfer has largely ceased. Although earlier studies suggested major differences in sealing ages for different ocean basins, we find that the sealing ages for the Atlantic, Pacific, and Indian oceans are similar and consistent with the sealing age for the entire data set, 65 +/- 10 Ma. The previous inference of a young (approximately 20 Ma) sealing age for the Pacific appears to have biased downward several previous estimates of the global hydrothermal flux. The heat flow data also provide indirect evidence for the mechanism by which the hydrothermal heat flux becomes small, which has often been ascribed to isolation of the igneous crust from seawater due to the hydraulic conductivity of the intervening sediment. We find, however, that even the least sedimented sites show the systematic increase of the ratio of observed to predicted heat flow with age, although the more sedimented sites have a younger sealing age. Moreover, the heat flow discrepancy persists at heavily sedimented sites until approximately 50 Ma. It thus appears that approximately 100-200 m of sediment is neither necessary nor sufficient to stop hydrothermal heat transfer. We therefore conclude that the age of the crust is the primary control on the fraction of heat transported by hydrothermal flow and that sediment thickness has a lesser effect. This inference is consistent with models in which hydrothermal flow decreases with age due to reduced crustal porosity and hence permeability.

Stein, Carol A.↗

Sea-air of CO2 in the North Pacific using shipboard and satellite data

A method has been developed to produce high-resolution maps of pCO2 in surface water for the North Pacific using satellite sea surface temperature (SST) data and statistical relationships between measured pCO2 and temperature. In the subtropical North Pacific the pCO in seawater is controlled primarily by temperature. Accordingly, pCO2 values that are calculated from the satellite SST data have good agreement with the measured values (rms deviation of +/- microatm). In the northwestern subpolar region the pCO2 is controlled not only by temperature, but also by significant seasonal changes in the total CO2 concentration, which are caused by seasonal changes in primary production, mixing with subsurface waters and sea-air exchange. Consequently, the parameterization of oceanic p CO2 based on SST data alone is not totally successful in the northwestern region (rms deviation of +/- 40 microatm). The use of additional satellite products, such as wind and ocean color data, as planned for a future study, is considered necessary to account for the pCO2 variability caused by seasonal changes in the total CO2 concentration. The net CO2 flux for the area of the North Pacific included in this study (north of 10 deg N) has been calculated using the monthly pCO2 distributions computed, and monthly wind speeds from the European Centre for Medium-Range Weather Forecasts. The region is found to be a net source to the atmosphere of 1.9 x 10(exp 12) to 5.8 x 10(exp 12) moles of CO2 per year (or 0.02-0.07 Gt C/yr), most of the outflux occurring in the subtropics.

Stephens, Mark P.↗

Accumulation of Dissolved DMSP by Marine Bacteria and its Degradation Via Bacterivory

Several bacterial isolates enriched from seawater using complex media were able to accumulate dimethylsulfoniopropionate (DMSP) from media into cells over several hours without degrading it. Uptake only occurred in metabolically active cells, and was repressed in some strains by the presence of additional carbon sources. Accumulation was also more rapid in osmotically-stressed cells, suggesting DMSP is used as an osmotic solute. Uptake could be blocked by inhibitors of active transport systems (2,4-dinitrophenol, azide, arsenate) and of protein synthesis (chloramphenicol). Some structural analogs such as glycine betaine and S-methyl methionine also blocked DMSP uptake, suggesting that the availability of alternate organic osmolytes may influence DMSP uptake. Stresses such as freezing, heating, or osmotic down shock resulted in partial release of DMSP back to the medium. One strain which contained a DMSP-lyase was also able to accumulate DMSP, and DMS was only produced in the absence of alternate carbon sources. Bacteria containing DMSP were prepared as prey for bacterivorous ciliates and flagellates, to examine the fate of the DMSP during grazing. In all cases, predators metabolized the DMSP in bacteria. In some cases, DMS was produced, but it is not clear if this was due to the predators or to associated bacteria in the non-axenic grazer cultures. Bacterivores may influence DMSP cycling by either modulating populations of DMSP-metabolizing bacteria, or by metabolizing DMSP accumulated by bacterial prey.

Wolfe, Gordon V.↗

Forward Modeling of Carbonate Proxy Data from Planktonic Foraminifera using Oxygen Isotope Tracers in a Global Ocean Model

The distribution and variation of oxygen isotopes in seawater are calculated using the Goddard Institute for Space Studies global ocean model. Simple ecological models are used to estimate the planktonic foraminiferal abundance as a function of depth, column temperature, season, light intensity, and density stratification. These models are combined to forward model isotopic signals recorded in calcareous ocean sediment. The sensitivity of the results to the changes in foraminiferal ecology, secondary calcification, and dissolution are also examined. Simulated present-day isotopic values for ecology relevant for multiple species compare well with core-top data. Hindcasts of sea surface temperature and salinity are made from time series of the modeled carbonate isotope values as the model climate changes. Paleoclimatic inferences from these carbonate isotope records are strongly affected by erroneous assumptions concerning the covariations of temperature, salinity, and delta (sup 18)O(sub w). Habitat-imposed biases are less important, although errors due to temperature-dependent abundances can be significant.

Schmidt, Gavin A.↗

Global Mapping of Underwater UV Irradiances and DNA-Weighted Exposures using TOMS and SeaWiFS Data Products

The global stratospheric ozone-layer depletion results In an increase in biologically harmful ultraviolet (UV) radiation reaching the surface and penetrating to ecologically significant depths in natural waters. Such an increase can be estimated on a global scale by combining satellite estimates of UV irradiance at the ocean surface from the Total Ozone Mapping Spectrometer (TOMS) satellite instrument with the SeaWIFS satellite ocean-color measurements in the visible spectral region. In this paper we propose a model of seawater optical properties in the UV spectral region based on the Case I water model in the visible range. The inputs to the model are standard monthly SeaWiFS products: chlorophyll concentration and the diffuse attenuation coefficient at 490nm. Penetration of solar UV radiation to different depths in open ocean waters is calculated using the RT (radiative transfer) quasi-single scattering approximation (QSSA). The accuracy of the QSSA approximation in the water is tested using more accurate codes. The sensitivity study of the underwater UV irradiance to atmospheric and oceanic optical properties have shown that the main environmental parameters controlling the absolute levels of the UVB (280-320nm) and DNA-weighted irradiance underwater are: solar-zenith angle, cloud transmittance, water optical properties, and total ozone. Weekly maps of underwater UV irradiance and DNA-weighted exposure are calculated using monthly-mean SeaWiFS chlorophyll and diffuse attenuation coefficient products, daily SeaWiFS cloud fraction data, and the TOMS-derived surface UV irradiance daily maps. The final products include global maps of weekly-average UVB irradiance and DNA-weighted daily exposures at 3m and 10m, and depths where the UVB irradiance and DNA-weighted dose rate at local noon are equal to 10% of their surface values.

Vasilkov, Alexander↗

Chemical Sensing of Unexploded Ordnance with the Mobile Underwater Survey System (MUDSS)

The ability to sense explosives residues in the marine environment is a critical tool for identification and classification of underwater unexploded ordnance (UXO). Trace explosives signatures of TNT and DNT have been extracted from multiple sediment samples adjacent to unexploded undersea ordnance at Halifax Harbor, Canada. The ordnance was hurled into the harbor during a massive explosion fifty years earlier, in 1945 after World War II had ended. Laboratory sediment extractions were made using the solid-phase microextraction (SPME) method in seawater, and detection using the Reversal Electron Attachment Detection (READ) technique and, in the case of DNT, a commercial gas-chromatography/mass spectrometer (GC/MS). Results show that, after more than 50 years in the environment, ordnance which appeared to be physically intact gave good explosives signatures at the parts-per-billion level, whereas ordnance which had been cracked open during the explosion gave no signatures at the 10 parts-per-trillion sensitivity level. These measurements appear to provide the first reported data of explosives signatures from undersea UXOs.

Darrach, M. R.↗

UV-Visible Spectroscopic Method and Models for Assessment and Monitoring of Harmful Algal Blooms

The development of an enhanced predictive and early warning capability for the occurrence and impact of harmful algal blooms (HABs) would be of great benefit to coastal communities. A critical issue for early detection and monitoring of HABs is the need to detect harmful algal species within a mixed-species phytoplankton assemblage. Possession of UV-absorbing compounds called mycosporine-like amino acids (MAAs) may be one factor that allows HAB species to out-compete their phytoplankton neighbors. Possession of MAAs, which we believe can be inferred from strong UV-absorption signals in phytoplankton absorption coefficients, can be used as a flag for potential HAB outbreak. The goal of this project was to develop a solar simulating UV-visible incubator to grow HAB dinoflagellates, to begin MAA analysis of samples collected on global cruises, and to carry out initial experiments on HAB dinoflagellate species in pure culture. Our scientific objectives are to quantify MAA production and spectral induction mechanisms in HAB species, to characterize spectral absorption of MAAs, and to define the ecological benefit of MAAs (i.e. photoprotection). Data collected on cruises to the global oceans will be used to parameterize phytoplankton absorption in the UV region, and this parameterization could be incorporated into existing models of seawater optical properties in the UV spectral region. Data collected in this project were used for graduate fellowship applications by Elizabeth Frame. She has been awarded an EPA STAR fellowship to continue the work initiated by this project.

Mitchell, B. Greg↗

Trace Explosives Signatures from World War II Unexploded Undersea Ordnance

Trace explosives signatures of TNT and DNT have been extracted from multiple sediment samples adjacent to unexploded undersea ordnance at Halifax Harbor, Canada. The ordnance was hurled into the harbor during a massive explosion some 50 years earlier, in 1945 after World War II had ended. Laboratory sediment extractions were made using the solid-phase microextraction (SPME) method in seawater and detection using the Reversal Electron Attachment Detection (READ) technique and, in the case of DNT, a commercial gas chromatograph/mass spectrometer (GC/MS). Results show that, after more than 50 years in the environment, ordnance that appeared to be physically intact gave good explosives signatures at the parts per billion level, whereas ordnance that had been cracked open during the explosion gave no signatures at the 10 parts per trillion sensitivity level. These measurements appear to provide the first reported data of explosives signatures from undersea unexploded ordnance.

Darrach, M. R.↗

EOS Aqua AMSR-E Sea Ice Validation Program: Meltpond2000 Flight Report

This flight report describes the field component of Meltpond2000, the first in a series of Arctic and Antarctic aircraft campaigns planned as part of NASA's Earth Observing System Aqua sea ice validation program for the Advanced Microwave Scanning Radiometer (AMSR-E). This prelaunch Arctic field campaign was carried out between June 25 and July 6, 2000 from Thule, Greenland, with the objective of quantifying the errors incurred by the AMSR-E sea ice algorithms resulting from the presence of melt ponds. A secondary objective of the mission was to develop a microwave capability to discriminate between melt ponds and seawater using low-frequency microwave radiometers. Meltpond2000 was a multiagency effort involving personnel from the Navy, NOAA, and NASA. The field component of the mission consisted of making five 8-hour flights from Thule Air Base with a Naval Air Warfare Center P-3 aircraft over portions of Baffin Bay and the Canadian Arctic. The aircraft sensors were provided and operated by the Microwave Radiometry Group of NOAA's Environmental TechnologyLaboratory. A Navy ice observer from the National Ice Center provided visual documentation of surface ice conditions during each of the flights. Two of the five flights were coordinated with Canadian scientists making surface measurements of melt ponds at an ice camp located near Resolute Bay, Canada. Coordination with the Canadians will provide additional information on surface characteristics and will be of great value in the interpretation of the aircraft and high-resolution satellite data sets.

Cavalieri, Donald J.↗

Carbon Dioxide Cycling And The Climate of Ancient Earth

The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

Zahnle, Kevin↗

Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard properties of organic sulfur gases. However, a number of the properties for aqueous organic sulfur compounds have not been experimentally determined. Furthermore, most of thermodynamic data that are available are for 25 C and 1 bar. In order to determine reaction properties to temperatures and pressures appropriate to the hydrothermal conditions in which thermophilic organisms actually live, we use equations of state developed by Helgeson and co-workers (Helgeson et al., 1981, AJS 281, 1249). A key piece of information needed to go up in temperature is the partial molal heat capacity, which is one of the properties for which experimental data are unavailable for nearly all organic sulfur compounds. We have used correlation methods to determine the partial molal heat capacities and volumes of many organic solutes. These estimates allow us to asses the role of organic sulfur compounds during the reduction of carbon in hydrothermal settings. We will present these data, along with examples of the thermodynamic properties of reactions involving aqueous organic sulfur compounds.

Schulte, Mitchell↗

Optical Measurements and Modeling to Estimate Concentrations and Fluxes of Organic Matter in the Southern Ocean

This project was a collaboration between two Principal Investigators, Dr. Dariusz Stramski and Dr. Greg Mitchell of Scripps Institution of Oceanography, University of California San Diego. Our overall goal was to conduct optical measurements and modeling to estimate concentrations of organic matter in the Southern Ocean in support of the U.S. JGOFS Process Study in this region. Key variables and processes of high relevance to accomplish the JGOFS goals include time and space resolution of phytoplankton pigments, particulate organic carbon, and the formation and export of organic carbon. Our project focused on establishing the fundamental relationships for parameterization of these variables and processes in terms of the optical properties of seawater, and developing understanding of why the Southern Ocean differs from other low-latitude systems, or has differentiation within. Our approach builds upon historical observations that optical properties provide a useful proxy for key reservoirs of organic matter such as chlorophyll alpha (Chl) and particulate organic carbon (POC) concentrations, which are of relevance to the JGOFS objectives. We carried out detailed studies of in situ and water sample optical properties including spectral reflectance, absorption, beam attenuation, scattering, and backscattering coefficients. We evaluated the ability to estimate Chl from the spectral reflectance (ocean color) in the Southern Ocean. We examined relationships between the ocean optical properties and particulate organic carbon. We developed, for the first time, an algorithm for estimating particulate organic carbon concentration in the surface ocean from satellite imagery of ocean color. With this algorithm, we obtained maps of POC distribution in the Southern Ocean showing the seasonal progression of POC in the austral spring-summer season. We also developed a semianalytical reflectance model for the investigated polar waters based on our field measurements of absorption and backscattering coefficients and Chl-dependent parameterizations of these coefficients. With this model, libraries of expected reflectance spectra for various chlorophyll concentrations can be generated with high spectral resolution for specific oceanic regions. In addition, our semianalytical reflectance model provided insight into the mechanisms which drive the empirical relationships between the ocean color and chlorophyll concentration. Our optical approach to the study of pigment and carbon concentrations will be directly relevant to development of system models and long-term monitoring of the Southern Ocean.

Stramski, Dariusz↗

Tidal Implications for the GRACE Satellite Mission

A fundamental part of the processing of the GRACE satellite data will be correction for the gravitational effect of tides. This includes solid earth, ocean, and atmospheric tides. The most problematic are ocean tides in shallow seas and in high latitudes (above the 66$^{\circ}$ inclination of Topex). Somewhat smaller, but still important, errors are associated with the S$_1$ air tide and the ocean's dynamic response to it. In this paper we explore several facets of the tidal error budget. The ocean tide error spectrum is estimated (a) by inverse methods and (b) by simple differencing of several of the best tidal models. The tidal error spectrum is flatter than the tidal signal spectrum, and it exceeds 10\% of the signal at degrees 15 and above. The tide errors also exceed the anticipated sensitivity of GRACE for all degrees below 40, and possibly below 50. The assumption of constant seawater density (of about 1035 kg\,M$^{-3}$) is a minor error source. Owing to GRACE's high inclination, solar tides are aliased to long periods, which is potentially problematic for geophysical interpretation of the gravity signal. Simulations of the effect of high-latitude solar-tide errors on gravity estimates around Antarctica will be discussed.

Ray, Richard D.↗

Carbon Dioxide Cycling and the Climate of Ancient Earth

The continental cycle of silicate weathering and metamorphism dynamically buffers atmospheric CO2 and climate. Feedback is provided by the strong temperature dependence of silicate weathering. Here we argue that hydrothermal alteration of oceanic basalts also dynamically buffers CO2. The oceanic cycle links with the mantle via subduction and the midocean ridges. Feedback is provided by the dependence of carbonatization on dissolved carbonates in seawater. Unlike the continental cycle, the oceanic cycle has no thermostat. Currently the continental cycle is more important, but earlier in Earth's history, especially if heat flow were higher than it is now, more vigorous plate tectonics would have made the oceanic cycle dominant. We find that CO2 greenhouses thick enough to defeat the faint early Sun are implausible and that, if no other greenhouse gases are invoked, very cold climates are expected for much of the Proterozoic and the Archean. We echo current fashion and favor biogenic methane as the chief supplement to CO2. Fast weathering and probable subduction of abundant impact ejecta would have reduced CO2 levels still further in the Hadean. Despite its name, the Hadean would have been the coldest era in the history of the Earth.

Zahnle, Kevin↗

Modeling South Pacific Ice-Ocean Interactions in the Global Climate System

The objective of this project has been to improve the modeling of interactions between large Antarctic ice shelves and adjacent regions of the Southern Ocean. Our larger goal is to gain a better understanding of the extent to which the ocean controls ice shelf attrition, thereby influencing the size and dynamics of the Antarctic Ice Sheet. Melting and freezing under ice shelves also impacts seawater properties, regional upwelling and sinking and the larger-scale ocean circulation. Modifying an isopycnal coordinate general circulation model for use in sub-ice shelf cavities, we found that the abrupt change in water column thickness at an ice shelf front does not form a strong barrier to buoyancy-driven circulation across the front. Outflow along the ice shelf base, driven by melting of the thickest ice, is balanced by deep inflow. Substantial effort was focused on the Filchner-Ronne cavity, where other models have been applied and time-series records are available from instruments suspended beneath the ice. A model comparison indicated that observed changes in the production of High Salinity Shelf Water could have a major impact on circulation within the cavity. This water propagates into the cavity with an asymmetric seasonal signal that has similar phasing and shape in the model and observations, and can be related to winter production at the sea surface. Even remote parts of the sub-ice shelf cavity are impacted by external forcing on sub-annual time scales. This shows that cavity circulations and products, and therefore cavity shape, will respond to interannual variability in sea ice production and longer-term climate change. The isopycnal model gives generally lower net melt rates than have been obtained from other models and oceanographic data, perhaps due to its boundary layer formulation, or the lack of tidal forcing. Work continues on a manuscript describing the Ross cavity results.

Holland, David M.↗

EOS Aqua AMSR-E Sea Ice Validation Program: Meltpond 2000 Flight Report

This flight report describes the field component of Meltpond2000, the first in a series of Arctic and Antarctic aircraft campaigns planned as part of NASA's Earth Observing System Aqua sea ice validation program for the Advanced Microwave Scanning Radiometer (AMSR-E). This prelaunch Arctic field campaign was carried out between June 25 and July 6, 2000 from Thule, Greenland, with the objective of quantifying the errors incurred by the AMSR-E sea ice algorithms resulting from the presence of melt ponds. A secondary objective of the mission was to develop a microwave capability to discriminate between melt ponds and seawater using low-frequency microwave radiometers. Meltpond2000 was a multiagency effort involving personnel from the Navy, National Oceanic and Atmospheric Administration (NOAA), and NASA. The field component of the mission consisted of making five eight-hour flights from Thule Air Base with a Naval Air Warfare Center P-3 aircraft over portions of Baffin Bay and the Canadian Arctic. The aircraft sensors were provided and operated by the Microwave Radiometry Group of NOAA's Environmental Technology Laboratory. A Navy ice observer from the National Ice Center provided visual documentation of surface ice conditions during each of the flights. Two of the five flights were coordinated with Canadian scientists making surface measurements of melt ponds at an ice camp located near Resolute Bay, Canada. Coordination with the Canadians will provide additional information on surface characteristics and will be of great value in the interpretation of the aircraft and high-resolution satellite data sets.

Cavalieri, Donald J.↗

The Effects of Chemical Wash Additives on the Corrosion of Aerospace Alloys in Marine Environments

This paper presents the methodology for comparing the relative effectiveness of four chemical products used for rinsing airplanes and helicopters. The products were applied on a weekly basis to a series of flat alloy panels exposed to an oceanfront marine environment for one year. The results are presented along with comparisons of exposures of the same alloys that were not washed, were washed with seawater, or washed with de-ionized water.

MacDowell, Louis↗