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At least 19 records

The detection of the FlPi(u)-XlSigma(+)g system of diatomic carbon toward X Persei

The 0-0 vibrational band of the F1Pi(u)-X1Sigma(+)g electronic system of C2 has been detected with the IUE in the interstellar medium along the line of sight toward X Per. A column density of 3 (+ or - 1) x 10 to the 12th/f(00) per sq cm was derived by a profile fitting method. The lower limit for 0-0 band oscillator strength was determined from a comparison of the upper limits of observations of the A-X and D-X systems, and an excitation temperature of 40 K was also obtained from the profile fitting. A statistical calculation of the level population with radiative pumping shows that the 0-0 band profile corresponds to a range of values for kinetic temperature, density, and near-IR radiation. An upper limit of 50 K for kinetic temperature was determined from the statistical equilibrium analysis.

Lien, D. J.↗

Diffuse interstellar clouds as a chemical laboratory - The chemistry of diatomic carbon species

The chemistry of C2, CH, and CO in diffuse interstellar clouds is analyzed and compared to absorption line measurements toward background stars. Analytical expressions in terms of column densities are derived for the rate equations. The results indicate that in clouds with 4 mag of visual extinction, the abundance of C+ has to decrease by a factor of about 15 from the value traditionally used for clouds with 1 mag of extinction. The rate coefficients for the reactions C+ + CH - C2+ + H and C+ + H2 - CH2+ + h-nu need to be reduced from previous estimates. Chemical arguments are presented for the revised rate coefficients.

Federman, S. R.↗

Continuum laser absorption spectroscopy of C 2 (a 3 Π u ) in a sublimating cloud of carbon black

A direct optical absorption diagnostic has been developed for rotationally resolved measurements of diatomic carbon (a 3 Π u →d 3 Π g (0,0) and (1,1)) at a repetition rate of 525 kHz and resolution of 7.3 pm over the range of 511.1–514.1 nm. The diagnostic utilizes a high-power pulsed continuum laser light source dispersed in a spectrograph and imaged by a high-speed camera. Measurements have been performed that capture the temporal evolution of C 2 number density and temperature of a cloud of carbon black sublimating in shock heated gas at high temperature and pressure (T = 5500 K, P = 3.7 atm). A simultaneous light absorption measurement of the condensed phase enables comparisons of the gaseous C 2 number density to the condensed phase mass. The continuum laser absorption diagnostic is applied to C 2 in this work but shows promise in being a simple “drop-in” system for absorption spectroscopy in the visible range at rapid repetition rates and high dispersion, filling an important gap for laser diagnostic systems.

Willhardt, Colton Dean [Univ. of Illinois at Urban↗

Phytoplankton exudates and lysates support distinct microbial consortia with specialized metabolic and ecophysiological traits

Marine dissolved organic matter, which originates from phytoplankton, holds as much carbon as Earth’s atmosphere; yet, the biological processes governing its fate are primarily studied under idealized laboratory conditions or through indirect measures such as genome sequencing. In this work, we used isotope labeling to directly quantify uptake of complex carbon pools from the two primary sources of marine organic carbon (diatoms and cyanobacteria) by a natural microbial community. Furthermore, our data show that carbon pools are partitioned into distinct microbial lineages whose physiological properties and resource acquisition strategies match the chemical nature of their preferred substrates. Our results provide ecological and functional insights into the patterns of microbial community structure changes that occur during marine phytoplankton blooms.

59 BASIC BIOLOGICAL SCIENCES↗

Spectroscopic investigation of early light emission from anode-initiated surface flashover in vacuum

Time-resolved optical emission spectroscopy is used to explore the early development of anode-initiated flashover in vacuum. An experimental apparatus for collecting flashover self-luminosity is introduced, which enables spatially resolved light collection from regions adjacent to the anode and cathode triple junctions. The emitted light is spectrally and temporally resolved utilizing an imaging spectrograph and a fast electronic shutter camera. The first light detectable from flashovers across both Rexolite and polytetrafluoroethylene (PTFE) insulators begins less than 10 ns prior to the flashover gap's impedance collapse and consists of faint broadband feature in primarily visible wavelengths. This suggests luminosity due to excitation in the solid, possibly occurring as a result of field emitted electrons. In the few nanoseconds leading up to and including the impedance collapse, the broadband spectrum grows in intensity and extends into the UV, eventually accompanied by a few emission lines of the insulator material. This is strong evidence that the early stages of anode-initiated flashover include surface layer breakdown of the insulator, as a contrast from cathode-initiated flashover, which is predominately an above-surface process. Spectra accumulated over longer exposures of PTFE flashovers indicate that, in the first few hundred nanoseconds after the impedance collapse, ions from the insulator material constitute the majority of the emission lines. Later, neutral and ionic metal species from the electrode contribute with similar prominence as well as molecular bands from diatomic carbon. Finally, a comparison is provided of the results of these studies to other spectroscopic investigations of vacuum flashover from the literature.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Geological Factors Impacted Cadmium Availability and use as an Alternative Cofactor for Zinc in the Carbon Fixation Pathways of Marine Diatoms

Transition metal cofactors are crucial for many biological processes. Despite being primarily considered to be toxic, the transition metal cadmium (Cd) was discovered to be a substitute cofactor for zinc (Zn) in photosynthetic carbon fixation pathways of marine diatoms. However, it is not known how conditions in the geosphere impacted Cd availability and its incorporation as an alternative metal cofactor for phytoplankton. We employed mineral chemistry network analysis to investigate which geochemical factors may have influenced the availability of Cd and Zn during the putative time period that the alternative Cd-based pathway evolved. Our results show that Zn minerals are more chemically diverse than are Cd minerals, but Zn- and Cd-containing minerals have similar network centrality values when specifically considering sulfur (S)-containing species. Cadmium and Zn sulfides are the most common Cd- and Zn-containing mineral species over the past 500 million years. In particular, the Cd and Zn sulfides, respectively greenockite and sphalerite, were highly abundant during this time period. Furthermore, S-containing Cd and Zn minerals are commonly co-located in geologic time, allowing them to be weathered and transported to the ocean in tandem, rather than from separate sources. We suggest that the simultaneous weathering of Cd and Zn sulfides allowed for Cd to be a bioavailable direct substitute for Zn in protein complexes during periods of Zn depletion. The biogeochemical cycles of Zn and Cd exemplify the importance of the coevolution of the geosphere and biosphere in shaping primary production in the modern ocean.

Naman Srivastava↗

Observation of site-selective chemical bond changes via ultrafast chemical shifts

The concomitant motion of electrons and nuclei on the femtosecond time scale marks the fate of chemical and biological processes. Here we demonstrate the ability to initiate and track the ultrafast electron rearrangement and chemical bond breaking site-specifically in real time for the carbon monoxide diatomic molecule. We employ a local resonant x-ray pump at the oxygen atom and probe the chemical shifts of the carbon core-electron binding energy. We observe charge redistribution accompanying core-excitation followed by Auger decay, eventually leading to dissociation and hole trapping at one site of the molecule. The presented technique is general in nature with sensitivity to chemical environment changes including transient electronic excited state dynamics. This work provides a route to investigate energy and charge transport processes in more complex systems by tracking selective chemical bond changes on their natural timescale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Wave function analysis with a maximum flow algorithm

An efficient algorithm for computing the maximum-flow path in a network is applied to the identification of the dominant configuration state functions (CSFs) in a graphically contracted function (GCF), configuration interaction, wave function. The flow network is a space of spin-adapted CSFs represented by a Shavitt graph, wherein the nodes correspond to orbital occupations and spin quantum numbers. The graph nodes are connected by arcs, and an arc density is defined as sums of the associated squared CSF coefficients. A max-min approach determines an upper bound to the maximum possible incoming flow for each graph node. A backtracking step generates a candidate walk and is followed by a limited search of alternative branching paths for the dominant CSF. The arc density contributions are removed from the graph, and the algorithm is reapplied to the updated graph. This list of generated walks can be partitioned in order to guarantee that the dominant CSFs have been identified. All of the steps in this algorithm are computationally efficient and do not depend on the potentially large dimension of the underlying linear CSF expansion space. An analysis of low-lying valence states of C-2 illustrates the method.

74 ATOMIC AND MOLECULAR PHYSICS↗

Revealing the Bacterial Quorum-Sensing Effect on the Biofilm Formation of Diatom Cylindrotheca sp. Using Multimodal Imaging

Diatoms contribute to carbon fixation in the oceans by photosynthesis and always form biofouling organized by extracellular polymeric substances (EPS) in the marine environment. Bacteria-produced quorum-sensing signal molecules N-acyl homoserine lactones (AHLs) were found to play an important role in the development of Cylindrotheca sp. in previous studies, but the EPS composition change was unclear. This study used the technology of alcian blue staining and scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to directly observe the biofilm formation process. The results showed that AHLs promote the growth rates of diatoms and the EPS secretion of biofilm components. AHLs facilitated the diatom-biofilm formation by a forming process dependent on the length of carbon chains. AHLs increased the biofilm thickness and the fluorescence intensity and then altered the three-dimensional (3D) structures of the diatom-biofilm. In addition, the enhanced EPS content in the diatom-biofilm testified that AHLs aided biofilm formation. This study provides a collection of new experimental evidence of the interaction between bacteria and microalgae in fouling biofilms.

59 BASIC BIOLOGICAL SCIENCES↗

Manganese Limitation of Phytoplankton Physiology and Productivity in the Southern Ocean

Although iron and light are understood to regulate the Southern Ocean biological carbon pump, observations have also indicated a possible role for manganese. Low concentrations in Southern Ocean surface waters suggest manganese limitation is possible, but its spatial extent remains poorly constrained and direct manganese limitation of the marine carbon cycle has been neglected by ocean models. Here, using available observations, we develop a new global biogeochemical model and find that phytoplankton in over half of the Southern Ocean cannot attain maximal growth rates because of manganese deficiency. Manganese limitation is most extensive in austral spring and depends on phytoplankton traits related to the size of photosynthetic antennae and the inhibition of manganese uptake by high zinc concentrations in Antarctic waters. Importantly, manganese limitation expands under the increased iron supply of past glacial periods, reducing the response of the biological carbon pump. Overall, these model experiments describe a mosaic of controls on Southern Ocean productivity that emerge from the interplay of light, iron, manganese and zinc, shaping the evolution of Antarctic phytoplankton since the opening of the Drake Passage.

54 ENVIRONMENTAL SCIENCES↗