Seasonally resolved stable isotope chronologies from northern Thailand deciduous trees

Author Posting. © The Authors, 2005. This is the author's version of the work. It is posted here by permission of Elsevier B. V. for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 235 (2005): 752-765, doi:10.1016/j.epsl.2005.05.012.Despite the existence of a number of climate proxies, the terrestrial expression of tropical climate variability over the past few centuries remains poorly resolved. We explore the applicability of stable isotope dendroclimatology as a tool for chronology and paleo-hydrology reconstruction on deciduous trees from monsoonal northern Thailand. Analysis of 11 trees coming from 4 different regions of northern Thailand yielded 7 records with varying degrees of δ18O and δ13C seasonality. We develop age models for trees lacking visible rings based on the seasonality of the δ18O and find agreement to within ≤ 3 years with radiocarbon age estimates. We use the isotopic age models to reconstruct estimates of growth rates and find a significant positive correlation between growth and amplitude of the oxygen and carbon seasonal isotopic signals. A comparison of a reconstructed dendro-isotopic index from Pangmapa with regional rainfall records indicates significant correlations consistent with the locally derived patterns but with decreased representation of the variance. Individual isotopic chronologies stemming from different tree species share common trends, which are also consistent with patterns of rainfall variability. We see an increase in the amplitude of the seasonal δ18O cycle along with an increase in δ18Omax over the past few decades suggesting a tracking of the recent drying trend of Thailand's monsoon.This research was supported by NSERC and the Teresa Heinz Scholarship for Environmental Research to PFP and Award #0402425 from the Paleoclimate Program of the Atmospheric Sciences Division of NSF to DPS

Neutralizing Carbonic Acid in Deep Carbonate Strata below the North Atlantic

Our research is aimed at investigating several technical issues associated with carbon dioxide sequestration in calcium carbonate sediments below the sea floor through laboratory experiments and chemical transport modeling. Our goal is to evaluate the basic feasibility of this approach, including an assessment of optimal depths, sediment types, and other issues related to site selection. The results of our modeling efforts were published this past summer in the Proceedings of the National Academy of Sciences. We are expanding on that work through a variety of laboratory and modeling efforts. In the laboratories at Columbia and at Harvard, we are studying the flow of liquid carbon dioxide and carbon dioxide-water mixtures through calcium carbonate sediments to better understand the geomechanical and structural stability of the sediments during and after injection. We are currently preparing the results of these findings for publication. In addition, we are investigating the kinetics of calcium carbonate dissolution in the presence of CO{sub 2}-water fluids, which is a critical feature of the system as it allows for increased permeability during injection. We are also investigating the possibility of carbon dioxide hydrate formation in the pore fluid, which might complicate the injection procedure by reducing sediment permeability but might also provide an upper seal in the sediment-pore fluid system, preventing release of CO{sub 2} into the deep ocean, particularly if depth and temperature at the injection point rule out immediate hydrate formation. This is done by injecting liquid CO{sub 2} into various types of porous media, and then monitoring the changes in permeability. Finally, we are performing an economic analysis to estimate costs of drilling and gas injection, site monitoring as well as the availability of potential disposal sites with particular emphasis on those sites that are within the 200-mile economic zone of the United States. We present some preliminary results from these analyses. A paper discussing the site selection based on data from the Ocean Drilling Program and Deep Sea Drilling Program is currently in preparation

Clumped Isotope Measurements of Small Carbonate Samples Using a High-Efficiency Dual-Reservoir Technique

Rationale: The measurement of multiply substituted isotopologues of CO2 derived from carbonate has allowed the reconstruction of paleotemperatures from a single phase (CaCO3), circumventing uncertainty inherent in other isotopic paleothermometers. Traditional analytical techniques require relatively large amounts of carbonate (3–8 mg per replicate), which limits the applicability of the clumped isotope proxy to certain geological materials such as marine microfossils, commonly used for paleoclimate reconstructions. Methods: Clumped isotope ratio measurements of small samples were made on a new, high-efficiency, dual-reservoir sample-preparation inlet system attached to a Thermo-Finnigan MAT 253 mass spectrometer. Sample gas produced on the inlet is introduced from a 10 mL reservoir directly into the source via a capillary. Reference gas fills an identical 10 mL reservoir installed between the reference bellows and the capillary. The gas pressures in the two reservoirs are initially balanced, and are allowed to decrease together over the run. Results: Carbonate samples from 1 mg to 2.6 mg produced Δ47 values equivalent to those from the traditional two-bellows method with identical single-sample precision (1 SE = 0.005–0.015‰) and external standard error (SE = 0.006–0.015‰, n = 4–6). The size of sample needed to achieve good precision is controlled by the sensitivity of the mass spectrometer and the size of the fixed reservoirs and adjacent U-trap installed on our inlet. Conclusions: The high-precision clumped isotope measurements of small aliquots of carbonate obtained in this method allows for the application of this proxy to a wider range of geological sample materials, such as marine microfossils, that until now have been nearly impossible to analyze given sample size limitation.Engineering and Applied Science

The energy penalty of post-combustion CO2 capture & storage and its implications for retrofitting the U.S. installed base

A review of the literature has found a factor of 4 spread in the estimated values of the energy penalty for post-combustion capture and storage of CO2 from pulverized-coal (PC) fired power plants. We elucidate the cause of that spread by deriving an analytic relationship for the energy penalty from thermodynamic principles and by identifying which variables are most difficult to constrain. We define the energy penalty for CCS to be the fraction of fuel that must be dedicated to CCS for a fixed quantity of work output. That penalty can manifest itself as either the additional fuel required to maintain a power plant's output or the loss of output for a constant fuel input. Of the 17 parameters that constitute the energy penalty, only the fraction of available waste heat that is recovered for use and the 2nd-law separation efficiency are poorly constrained. We provide an absolute lower bound for the energy penalty of ~11%, and we demonstrate to what degree increasing the fraction of available-waste-heat recovery can reduce the energy penalty from the higher values reported. It is further argued that an energy penalty of ~40% will be easily achieved while one of ~29% represents a decent target value. Furthermore, we analyze the distribution of PC plants in the U.S. and calculate a distribution for the additional fuel required to operate all these plants with CO2 capture and storage (CCS).Earth and Planetary SciencesEngineering and Applied Science

Biologically Induced Initiation of Neoproterozoic Snowball-Earth Events

The glaciations of the Neoproterozoic Era (1,000 to 542 MyBP) were preceded by dramatically light C isotopic excursions preserved in preglacial deposits. Standard explanations of these excursions involve remineralization of isotopically light organic matter and imply strong enhancement of atmospheric $CO_2$ greenhouse gas concentration, apparently inconsistent with the glaciations that followed. We examine a scenario in which the isotopic signal, as well as the global glaciation, result from enhanced export of organic matter from the upper ocean into anoxic subsurface waters and sediments. The organic matter undergoes anoxic remineralization at depth via either sulfate- or iron-reducing bacteria. In both cases, this can lead to changes in carbonate alkalinity and dissolved inorganic pool that efficiently lower the atmospheric $CO_2$ concentration, possibly plunging Earth into an ice age. This scenario predicts enhanced deposition of calcium carbonate, the formation of siderite, and an increase in ocean pH, all of which are consistent with recent observations. Late Neoproterozoic diversification of marine eukaryotes may have facilitated the episodic enhancement of export of organic matter from the upper ocean, by causing a greater proportion of organic matter to be partitioned as particulate aggregates that can sink more efficiently, via increased cell size, biomineralization or increased C∶N of eukaryotic phytoplankton. The scenario explains isotopic excursions that are correlated or uncorrelated with snowball initiation, and suggests that increasing atmospheric oxygen concentrations and a progressive oxygenation of the subsurface ocean helped to prevent snowball glaciation on the Phanerozoic Earth.Earth and Planetary Science

Uncovering the Neoproterozoic Carbon Cycle

Interpretations of major climatic and biological events in Earth history are, in large part, derived from the stable carbon isotope records of carbonate rocks and sedimentary organic matter1,2. Neoproterozoic carbonate records contain unusualand large negative isotopic anomalies within long periods (10–100 million years) characterized by d13C in carbonate (d13Ccarb) enriched to more than +5 per mil. Classically, d13Ccarb is interpreted as a metric of the relative fraction of carbon buried as organic matter in marine sediments2–4, which can be linked to oxygen accumulation through the stoichiometry of primary production3,5. If a change in the isotopic composition of marine dissolved inorganic carbon is responsible for these excursions, it is expected that records of d13Ccarb and d13C in organic carbon (d13Corg) will covary, offset by the fractionation imparted by primary production5. The documentation of several Neoproterozoic d13Ccarb excursions that are decoupled from d13Corg, however, indicates that other mechanisms6–8 may account for these excursions. Here we present d13C data from Mongolia, northwest Canada and Namibia that capture multiple large-amplitude (over 10 per mil) negative carbon isotope anomalies, and use these data in a new quantitative mixing model to examine the behaviour of the Neoproterozoic carbon cycle. We find that carbonate and organic carbon isotope data from Mongolia and Canada are tightly coupled through multiple d13Ccarb excursions, quantitatively ruling out previously suggested alternative explanations, such as diagenesis7,8 or the presence and terminal oxidation of a large marine dissolved organic carbon reservoir6. Our data from Namibia, which do not record isotopic covariance, can be explained by simple mixing with a detrital flux of organic matter. We thus interpret d13Ccarb anomalies as recording a primary perturbation to the surface carbon cycle. This interpretation requires the revisiting of models linking drastic isotope excursions to deep ocean oxygenation and the opening of environments capable of supporting animals9–11.Earth and Planetary Science

A New Mechanism for Dansgaard-Oeschger Cycles

[1] We present a new hypothesis to explain the millennial-scale temperature variability recorded in ice cores known as Dansgaard-Oeschger (DO) cycles. We propose that an ice shelf acted in concert with sea ice to set the slow and fast timescales of the DO cycle, respectively. The abrupt warming at the onset of a cycle is caused by the rapid retreat of sea ice after the collapse of an ice shelf. The gradual cooling during the subsequent interstadial phase is determined by the timescale of ice-shelf regrowth. Once the ice shelf reaches a critical size, sea ice expands, driving the climate rapidly back into stadial conditions. The stadial phase ends when warm subsurface waters penetrate beneath the ice shelf and cause it to collapse. This hypothesis explains the full shape of the DO cycle, the duration of the different phases, and the transitions between them and is supported by proxy records in the North Atlantic and Nordic Seas.Engineering and Applied Science

Stratigraphic evolution of the Neoproterozoic Callison Lake Formation: Linking the break-up of Rodinia to the Islay carbon isotope excursion

The ∼780 to 540 Ma Windermere Supergroup of western North America records the protracted development of the western Laurentian passive margin and provides insights into the nature, timing, and kinematics of Rodinia's fragmentation. Here we present a refined tectono- and chemo-stratigraphic model for circa 780 to 720 Ma sedimentation in NW Canada through a study of the Callison Lake Formation (formalized herein) of the Mount Harper Group, spectacularly exposed in the Coal Creek and Hart River inliers of the Ogilvie Mountains of Yukon, Canada. Twenty-one stratigraphic sections are integrated with geological mapping, facies analysis, carbon and oxygen isotope chemostratigraphy, and Re-Os geochronology to provide a depositional reconstruction for the Callison Lake Formation. Mixed siliciclastic, carbonate, and evaporite sediments accumulated in marginal marine embayments formed in discrete hangingwall depocenters of a prominent Windermere extensional fault zone. Deposition of the Windermere Supergroup in NW Canada post dates the eruption of the circa 780 Ma Gunbarrel Large Igneous Province by ∼30 million years, is locally associated with compressional or transpressional tectonism, and predates the successful rift-drift transition by ∼200 million years. In order to accommodate evidence for coeval extensional and compressional tectonism, abrupt facies change, and Neoproterozoic fault geometries, we propose that NW Laurentia experienced strike-slip deformation during the ∼740 to 660 Ma early fragmentation of the supercontinent Rodinia. Sequence stratigraphic data from the Callison Lake Formation and other basal Windermere successions in the northern Canadian Cordillera delineate three distinct depositional sequences, or transgressive-regressive (T-R) cycles, that are coeval with similar stratigraphic packages in the ∼780 to 720 Ma Chuar-Uinta Mountain-Pahrump basins of the western United States. The global circa 735 Ma Islay carbon isotope excursion is consistently present in carbonate strata of the third T-R cycle and is interpreted to represent a primary perturbation to the global carbon cycle, possibly driven by the uplift and weathering of extensive shallow epicontinental seaways and evaporite basins.Earth and Planetary Science

Phosphorus sources for phosphatic Cambrian carbonates

The fossilization of organic remains and shell material by calcium phosphate minerals provides an illuminating, but time-bounded, window into Ediacaran–Cambrian animal evolution. For reasons that remain unknown, phosphatic fossil preservation declined significantly through Cambrian Series 2. Here, we investigate the phosphorus (P) sources for phosphatic Cambrian carbonates, presenting sedimentological, petrographic, and geochemical data from the Cambrian Series 2–3 Thorntonia Limestone, Australia, some of the youngest Cambrian strata to display exceptional phosphatic preservation of small shelly fossils. We find that within Thorntonia sediments, phosphate was remobilized by organic decay and bacterial iron reduction, with subsequent reprecipitation largely as apatite within the interiors of small shelly fossils. We discuss the merits of bioclastic-derived, organic matter–bound, or iron-bound P as potential sources to these strata. Petrographic observations suggest that the dissolution of phosphatic skeletal material did not provide the P for fossil preservation. In contrast, high organic carbon contents imply significant organic fluxes of P to Thorntonia sediments. Sedimentology and iron-speciation data indicate that phosphorus enrichment occurred during times of expanded anoxic, ferruginous conditions in subsurface water masses, suggesting that phosphorus adsorption to iron minerals precipitating from the water column provided a second significant P source to Thorntonia sediments. Simple stoichiometric models suggest that, by themselves, neither organic carbon burial nor an iron shuttle can account for the observed phosphorus enrichment. Thus, we infer that both processes were necessary for the observed phosphorus enrichment and subsequent fossil preservation in the Thorntonia Limestone.Earth and Planetary Science

Effect of First-Line Chemotherapy Combined With Cetuximab or Bevacizumab on Overall Survival in Patients With KRAS Wild-Type Advanced or Metastatic Colorectal Cancer: A Randomized Clinical Trial

Combining biologic monoclonal antibodies with chemotherapeutic cytotoxic drugs provides clinical benefit to patients with advanced or metastatic colorectal cancer, but the optimal choice of the initial biologic therapy in previously untreated patients is unknown