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At least 19 records

Shallow Remineralization in the Sargasso Sea Estimated from Seasonal Variations in Oxygen and Dissolved Inorganic Carbon

A diagnostic model of the mean annual cycles of dissolved inorganic carbon (DIC) and oxygen below the mixed layer at the Bermuda Atlantic Time-series Study (BATS) site is presented and used to estimate organic carbon remineralization in the seasonal thermocline. The model includes lateral and vertical advection as well as vertical, diffusion. Very good agreement is found for the remineralization estimates based on oxygen and DIC. Net remineralization averaged from mid-spring to early fall is found to be a maximum between 120 and 140 in. Remineralization integrated between 100 (the compensation depth) and 250 m during this period is estimated to be about 1 mol C/sq m. This flux is consistent with independent estimates of the loss of particulate and dissolved organic carbon.

Ono, S.↗

The Sensitivity of Simulated Ocean Biogeochemistry to Forcing Fields Derived from NCEP and MERRA Reanalysis Products

Ocean biogeochemistry models are typically forced by atmospheric and oceanic data derived from reanalysis products. For the NASA Ocean Biogeochemistry Model (NOBM) such reanalysis forcing fields include: surface wind stress, sea surface temperature, ice distributions, shortwave radiation, surface wind speeds and surface atmospheric pressure. Additionally, proper computation of ocean irradiance requires reanalysis products of relative humidity and precipitable water (in addition to aerosol and cloud information which is derived from satellite data). The question posed here is, does the choice of reanalysis products make a difference in the representation of ocean biology and biogeochemistry? NOBM was forced by NCEP and MERRA reanalysis products for the period 2002-2009. We find that in 2009 global distributions and abundances of biological variables (total chlorophyll and nutrients) and carbon (dissolved inorganic and organic carbon and surface pCO2) were similar between the two different forcing fields. Global statistical comparisons with satellite and in situ data also showed negligible differences.

Gregg, Watson↗

Biogeochemical Protocols and Diagnostics for the CMIP6 Ocean Model Intercomparison Project (OMIP)

The Ocean Model Intercomparison Project (OMIP) focuses on the physics and biogeochemistry of the ocean component of Earth system models participating in the sixth phase of the Coupled Model Intercomparison Project (CMIP6). OMIP aims to provide standard protocols and diagnostics for ocean models, while offering a forum to promote their common assessment and improvement. It also offers to compare solutions of the same ocean models when forced with reanalysis data (OMIP simulations) vs. when integrated within fully coupled Earth system models (CMIP6). Here we detail simulation protocols and diagnostics for OMIP's biogeochemical and inert chemical tracers. These passive-tracer simulations will be coupled to ocean circulation models, initialized with observational data or output from a model spin-up, and forced by repeating the 1948-2009 surface fluxes of heat, fresh water, and momentum. These so-called OMIP-BGC simulations include three inert chemical tracers (CFC-11, CFC-12, SF [subscript] 6) and biogeochemical tracers (e.g., dissolved inorganic carbon, carbon isotopes, alkalinity, nutrients, and oxygen). Modelers will use their preferred prognostic BGC model but should follow common guidelines for gas exchange and carbonate chemistry. Simulations include both natural and total carbon tracers. The required forced simulation (omip1) will be initialized with gridded observational climatologies. An optional forced simulation (omip1-spunup) will be initialized instead with BGC fields from a long model spin-up, preferably for 2000 years or more, and forced by repeating the same 62-year meteorological forcing. That optional run will also include abiotic tracers of total dissolved inorganic carbon and radiocarbon, CTabio and 14CTabio, to assess deep-ocean ventilation and distinguish the role of physics vs. biology. These simulations will be forced by observed atmospheric histories of the three inert gases and CO2 as well as carbon isotope ratios of CO2. OMIP-BGC simulation protocols are founded on those from previous phases of the Ocean Carbon-Cycle Model Intercomparison Project. They have been merged and updated to reflect improvements concerning gas exchange, carbonate chemistry, and new data for initial conditions and atmospheric gas histories. Code is provided to facilitate their implementation.

Carbon↗

Will Global Change Effect Primary Productivity in Coastal Ecosystems?

Algae are the base of coastal food webs because they provide the source of organic carbon for the remaining members of the community. Thus, the rate that they produce organic carbon to a large extent controls the productivity of the entire ecosystem. Factors that control algal productivity range from the physical (e.g., temperature, light), chemical (e.g., nutrient levels) to the biological (e.g., grazing). Currently, levels of atmospheric carbon dioxide surficial fluxes of ultraviolet radiation are rising. Both of these environmental variables can have a profound effect on algal productivity. Atmospheric carbon dioxide may increase surficial levels of dissolved inorganic carbon. Our laboratory and field studies of algal mats and phytoplankton cultures under ambient and elevated levels of pCO2 show that elevated levels of inorganic carbon can cause an increase in photosynthetic rates. In some cases, this increase will cause an increase in phytoplankton numbers. There may be an increase in the excretion of fixed carbon, which in turn may enhance bacterial productivity. Alternatively, in analogy with studies on the effect of elevated pCO2 on plants, the phytoplankton could change their carbon to nitrogen ratios, which will effect the feeding of the planktonic grazers. The seasonal depletion of stratospheric ozone has resulted in elevated fluxes of UVB radiation superimposed on the normal seasonal variation. Present surface UV fluxes have a significant impact on phytoplankton physiology, including the inhibition of the light and dark reactions of photosynthesis, inhibition of nitrogenase activity, inhibition of heterocyst formation, reduction in motility, increased synthesis of the UV-screening pigment scytonemin, and mutation. After reviewing these issues, recent work in our lab on measuring the effect of UV radiation on phytoplankton in the San Francisco Bay Estuary will be presented.

Rothschild, Lynn J.↗

The carbon isotope biogeochemistry of methane production in anoxic sediments. 1: Field observations

The natural abundance C-13/C-12 ratio of methane from anoxic marine and freshwater sediments in temperate climates varies seasonally. Carbon isotopic measurements of the methanogenic precursors, acetate and dissolved inorganic carbon, from the marine sediments of Cape Lookout Bight, North Carolina were used to determine the sources of the seasonal variations at that site. Movement of the methanogenic zone over an isotopic gradient within the dissolved CO2 pool appears to be the dominant control of the methane C-13/C-12 ratio from February to June. The onset of acetoclastic methane-production is a second important controlling process during mid-summer. An apparent temperature dependence on the fractionation factor for CO2-reduction may have a significant influence on the isotopic composition of methane throughout the year.

Blair, Neal E.↗

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41º32'N, 120º5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4 2-, respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 oC, and higher than the values measured at orifices (77.3 to 90.0 oC). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The 13C fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 oC) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41 deg 32'N, 120 deg 5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4(2-), respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated by both dissolved SiO2 and Na-K-Ca geothermometers are in the range of 125.0 to 135.4 C, and higher than the values measured at orifices (77.3 to 90.0 C). CO2 and homologs of straight chain alkanes (C1-C5) were identified in gas samples. Carbon isotope values of alkanes increase with carbon numbers. The C-13 fractionation between CO2 and dissolved inorganic carbon suggests they are out of carbon isotope equilibrium. The hypothesis regarding the formation of carbon-bearing compounds in SVHS may involve two processes: 1) Under high heat flow conditions which are caused by regional faulting and crustal extension, original high molecular weight organic compounds (kerogens) in clay-rich rocks decomposed to generate methane and other alkane homologs. 2) The SVHS area is associated with outflow structures, and distant from the heat source. Anaerobic oxidation of methane (AOM) with sulfate at shallow depth (< 90 C) is suggested as being responsible for the generation of CO2 in SVHS.

Fu, Qi↗

Technical Report Series on Global Modeling and Data Assimilation: Global Surface Ocean Carbon Estimates in a Model Forced by MERRA - Volume 31

MERRA products were used to force an established ocean biogeochemical model to estimate surface carbon inventories and fluxes in the global oceans. The results were compared to public archives of in situ carbon data and estimates. The model exhibited skill for ocean dissolved inorganic carbon (DIC), partial pressure of ocean CO2 (pCO2) and air-sea fluxes (FCO2). The MERRA-forced model produced global mean differences of 0.02% (approximately 0.3 microns) for DIC, -0.3% (about -1.2 (micro) atm; model lower) for pCO2, and -2.3% (-0.003 mol C/sq m/y) for FCO2 compared to in situ estimates. Basin-scale distributions were significantly correlated with observations for all three variables (r=0.97, 0.76, and 0.73, P<0.05, respectively for DIC, pCO2, and FCO2). All major oceanographic basins were represented as sources to the atmosphere or sinks in agreement with in situ estimates. However, there were substantial basin-scale and local departures.

Gregg, Watson W.↗

Modeling Biogeochemical-Physical Interactions and Carbon Flux in the Sargasso Sea (Bermuda Atlantic Time-series Study site)

An ecosystem-carbon cycle model is used to analyze the biogeochemical-physical interactions and carbon fluxes in the Bermuda Atlantic Time-series Study (BATS) site for the period of 1992-1998. The model results compare well with observations (most variables are within 8% of observed values). The sea-air flux ranges from -0.32 to -0.50 mol C/sq m/yr, depending upon the gas transfer algorithm used. This estimate is within the range (-0.22 to -0.83 mol C/sq m/yr) of previously reported values which indicates that the BATS region is a weak sink of atmospheric CO2. The overall carbon balance consists of atmospheric CO2 uptake of 0.3 Mol C/sq m/yr, upward dissolved inorganic carbon (DIC) bottom flux of 1.1 Mol C/sq m/yr, and carbon export of 1.4 mol C/sq m/yr via sedimentation. Upper ocean DIC levels increased between 1992 and 1996 at a rate of approximately 1.2 (micro)mol/kg/yr, consistent with observations. However, this trend was reversed during 1997-1998 to -2.7 (micro)mol/kg/yr in response to hydrographic changes imposed by the El Nino-La Nina transition, which were manifested in the Sargasso Sea by the warmest SST and lowest surface salinity of the period (1992-1998).

Signorini, Sergio R.↗

The Change in Oceanic O2 Inventory Associated with Recent Global Warming

Oceans general circulation models predict that global warming may cause a decrease in the oceanic O2 inventory and an associated O2 outgassing. An independent argument is presented here in support of this prediction based on observational evidence of the ocean's biogeochemical response to natural warming. On time scales from seasonal to centennial, natural O2 flux/heat flux ratios are shown to occur in a range of 2 to 10 nmol O2 per Joule of warming, with larger ratios typically occurring at higher latitudes and over longer time scales. The ratios are several times larger than would be expected solely from the effect of heating on the O2 solubility, indicating that most of the O2 exchange is biologically mediated through links between heating and stratification. The change in oceanic O2 inventory through the 1990's is estimated to be 0.3 - 0.4 x 10(exp 14) mol O2 per year based on scaling the observed anomalous long-term ocean warming by natural O2 flux/heating ratios and allowing for uncertainty due to decadal variability. Implications are discussed for carbon budgets based on observed changes in atmospheric O2/N2 ratio and based on observed changes in ocean dissolved inorganic carbon.

Keeling, Ralph↗

Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was likely less saline. The division of marine cyanobacterium P. subcapitatum is associated with periodic deposition and dissolution of CaCO3, the rhythms and intensity of which are dependent on concentrations of both OH(-) and Na(+). Thus, the role of present-day marine cyanobacteria in the global carbonate cycle might be reduced to aggregation and recrystallization of available CaCO3 particles in marine water rather than long-term precipitation and accumulation of CaCO3 deposits. For lower Na(+) concentrations, precipitation of carbonates by cyanobacteria would be even less significant. These results suggest that the lack of calcified cyanobacteria in stromatalite-bearing Precambrian sequences can be explained not only by high dissolved inorganic carbon concentrations but also by lower salinity, as well as possible lower pH compared to present-day oceans.

Karakis, S. G.↗

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

McLaughlin Natural Reserve↗

Carbon and Oxygen Budgets of Subtidal and Intertidal Cyanobacterial Mats

Intertidal cyanobacterial mats (Lyngbya-dominated) are contrasted with mats (Microcoleus-dominated) that grow in subtidal (0.7m water depth) hypersaline (90-110 permil) environments. In benthic chamber experiments conducted in Oct., 1999, mats exhibited greater net uptake of dissolved inorganic carbon (DIC) from overlying water during the daylight period than Microcoleus mats (e.g., 200 vs 120 mmol C/m. at 26 deg C, respectively). Net DIC release at night was similar for both mats (approx. 80 mmol C/m). Daytime net O2 release by Lyngby mats exceeded that by Microcoleus mats (150 vs 100 mmol O2/m), and O2 uptake at night was comparable for both mats (60-80 mmol O2/m). Nonphotosynthetic populations are more prominent within the subtidal versus intertidal mats, and accordingly exhibited greater internal 02 uptake and DIC production during the day. Over 24 hours, Lyngby-dominated mats exhibited greater net uptake of DIC than subtidal Microcoleus mats, consistent with these intertidal mats being "pioneer" communities that constantly recover from periodic physical disruption in energetic environments. The Microcoleus-dominated mats achieve steady-state mat thicknesses by balancing primary production against diagenetic decomposition of cellular and extracellular organic constituents.

DesMarais, David J.↗

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.

NASA Discipline Number 52-30↗

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.

Non-NASA Center↗

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.

NASA Discipline Exobiology↗

Constraining Oceanic Sources and Sinks of CO2 by Inverse Modeling: A First Step Toward Assimilation of In Situ and Remote Data

The primary goal of this collaborative project, lead by Nicholas Gruber at UCLA, is to better quantify the air-sea fluxes of pre-industrial and anthropogenic carbon dioxide CO2 for the global ocean with a newly developed inverse method. The method involves using ocean general circulation models (OGCMs) to characterize the subsurface distribution of tracers injected for different regions of the ocean surface. By linearly combining a series of these basis (or Greens) functions, one should be able to recreate any arbitrary ocean tracer field. In our case, we are using the global database of ocean dissolved inorganic carbon (DIC) from the WOCE/JGOFS global CO2 survey from the 1990s. The observed DIC field has been partitioned into pre-industrial and anthropogenic components using the empirical C* technique. We then solve for an optimal combination of the regional basis functions that best match the two sets observations in a least-squares sense with singular value decomposition. This in turn provides solutions for the regional air-sea CO2 fluxes (pre-industrial and anthropogenic) that are independent of more traditional estimates derived from surface water disequilibria in the partial pressure of CO2 and wind speed gas exchange parameterizations. We are apply the method to a suite of nine different OGCMs to test the robustness of the derived surface fluxes fields to differences in ocean circulation. Together with a collegue Keith Lindsay at NCAR, S. Doney's role in this project was to create the appropriate steady-state and temporally evolving basis functions from the NCAR CSM-1 ocean circulation model. Because of a slow start across the project in defining a common set of experimental protocols, we requested and were given a one year, no cost extension. Both the steady-state and temporally evolving basis functions were delivered to the UCLA group for further analysis. Additional information is included in the original extended abstract.

Doney, Scott↗

Climatic forcing of carbon-oxygen isotopic covariance in temperate-region marl lakes

Carbon and oxygen stable isotopic compositions of lacustrine carbonate from a southeastern Michigan marl lake display linear covariance over a range of 4.0% Peedee belemnite (PDB) in oxygen and 3.9% (PDB) in carbon. Mechanisms of delta 13 C-delta 18 O coupling conventionally attributed to lake closure in arid-region basins are inapplicable to hydrologically open lake systems. Thus, an alternative explanation of isotopic covariance in temperate region dimictic marl lakes is required. We propose that isotopic covariance is a direct record of change in regional climate. In short-residence-time temperate-region lake basins, summer meteoric precipitation is enriched in 18O relative to winter values, and summer organic productivity enriches epilimnic dissolved inorganic carbon in 13C. Thus, climate change toward longer summers and/or shorter winters could result in greater proportions of warm-month meteoric precipitation, longer durations of warm-month productivity, and net long-term enrichment in carbonate 18O and 13C. Isotopic covariance observed in the Michigan marl lake cores is interpreted to reflect postglacial warming from 10 to 3 ka followed by cooler mean annual temperature, a shift toward greater proportions of seasonal summer precipitation, a shortening of the winter season, or some combination of these three factors.

NASA Discipline Number 52-30↗