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Ultrafast radiographic imaging and tracking: An overview of instruments, methods, data, and applications

Ultrafast radiographic imaging and tracking (U-RadIT) use state-of-the-art ionizing particle and light sources to experimentally study sub-nanosecond transients or dynamic processes in physics, chemistry, biology, geology, materials science and other fields. These processes are fundamental to modern technologies and applications, such as nuclear fusion energy, advanced manufacturing, communication, and green transportation, which often involve one mole or more atoms and elementary particles, and thus are challenging to compute by using the first principles of quantum physics or other forward models. One of the central problems in U-RadIT is to optimize information yield through, e.g. high-luminosity X-ray and particle sources, efficient imaging and tracking detectors, novel methods to collect data, and large-bandwidth online and offline data processing, regulated by the underlying physics, statistics, and computing power. We review and highlight recent progress in: (a.) Detectors such as high-speed complementary metal-oxide semiconductor (CMOS) cameras, hybrid pixelated array detectors integrated with Timepix4 and other application-specific integrated circuits (ASICs), and digital photon detectors; (b.) U-RadIT modalities such as dynamic phase contrast imaging, dynamic diffractive imaging, and four-dimensional (4D) particle tracking; (c.) U-RadIT data and algorithms such as neural networks and machine learning, and (d.) Applications in ultrafast dynamic material science using XFELs, synchrotrons and laser-driven sources. Hardware-centric approaches to U-RadIT optimization are constrained by detector material properties, low signal-to-noise ratio, high cost and long development cycles of critical hardware components such as ASICs. Interpretation of experimental data, including comparisons with forward models, is frequently hindered by sparse measurements, model and measurement uncertainties, and noise. Alternatively, U-RadIT make increasing use of data science and machine learning algorithms, including experimental implementations of compressed sensing. Machine learning and artificial intelligence approaches, refined by physics and materials information, may also contribute significantly to data interpretation, uncertainty quantification and U-RadIT optimization.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Studies of the PfkB Family of Proteins in Arabidopsis thaliana

The phosphofructokinase B (PkfB) family of carbohydrate kinases is a large group that includes members with specificity for a diverse array of carbohydrate substrates, including fructose, ribose, fructose‐6‐phosphate, tagatose‐6‐phosphate, adenosine, myo‐inositol, and others. Although there are 21 genes encoding PfkB family members in the higher plant Arabidopsis thaliana , only a few have been studied in detail. Two Arabidopsis proteins with fructokinase activity were identified and characterized via native PAGE and in‐gel assays, though the genes were not identified. Another class of PfkB proteins identified in Arabidopsis lacks demonstrated enzymatic activity, but is necessary for the accumulation of photosynthetic transcripts in chloroplasts. The fructokinase‐like proteins 1 and 2 (FLN1 and FLN2, respectively) and NARA5 all belong to this class, although the mechanism of how NARA5 exerts it's phenotype remains elusive. FLN1 and 2 have been identified in proteomics studies as members of a large protein complex that interacts with, and likely regulates, the prokaryotic‐type plastid RNA polymerase which specifically transcribes photosynthetic genes in the plastid. We have found that FLN1 and FLN2 interact with each other in an ATP‐dependent manner both in vitro and in vivo . Phenotypic analysis suggests that the presence of both proteins is necessary for proper levels of transcription. Our data on the interaction between FLN1 and FLN2 suggests a mechanism where the FLN proteins act as a biochemical switch to activate transcription under conditions that favor their binding to each other. We have also begun characterization of the remainder of the Arabidopsis PfkB family and have identified a group of seven highly similar Arabidopsis PfkB proteins. These seven proteins were expressed in E. coli and enzymatic assays performed. All are active as fructokinases with high specificity for fructose. T‐DNA mediated inactivation of five of the seven genes resulted in no overt phenotype which hints at possible redundancy between some of these gene products. Using GFP fusions, we have determined that all localize to the cytosol except one, which localizes to plastids. Higher order mutants and biochemical analysis, along with expression analysis will allow us to tease apart the differences and the importance of each of these family members. We have characterized another PfkB protein that appears to be the sole Arabidopsis ribokinase (AtRBSK). Its biochemical properties and cofactor requirements are similar to that of known mammalian and prokaryotic RBSKs. T‐DNA insertion into AtRBSK results in the hyper‐accumulation of ribose in both the roots and leaves of 10 day‐old seedlings compared to wild type. Arabidopsis lacking AtRBSK grow poorly on media supplemented with ribose as the only sugar. We are currently dissecting the pathway that leads to the production of ribose in plants to put AtRBSK into a biological context. Our studies of the PfkB family in Arabidopsis are yielding promising results and will continue to further our understanding of many fundamental processes in plant biology ranging from central metabolism to the regulation of transcription in chloroplasts. Support or Funding Information The authors gratefully acknowledge support from the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, US. Department of Energy (contracts DE‐FG02–09ER16077 and DE‐SC0002175) to JC

Riggs, John W.↗

Fate of Bisphenol A in Terrestrial and Aquatic Environments

We report that bisphenol A (2,2-bis[4-hydroxyphenyl]propane, BPA), the monomer used to produce polycarbonate plastic and epoxy resins, is weakly estrogenic and therefore of environmental and human health interest. Due to the high production volumes and disposal of products made from BPA, polycarbonate plastic and epoxy resins, BPA has entered terrestrial and aquatic environments. In the presence of oxygen, diverse taxa of bacteria, fungi, algae and even higher plants metabolize BPA, but anaerobic microbial degradation has not been documented. Recent reports demonstrated that abiotic processes mediate BPA transformation and mineralization in the absence of oxygen, indicating that BPA is susceptible to degradation under anoxic conditions. Lastly, this review summarizes biological and nonbiological processes that lead to BPA transformation and degradation, and identifies research needs to advance predictive understanding of the longevity of BPA and its transformation products in environmental systems.

54 ENVIRONMENTAL SCIENCES↗

Marine Microeukaryote Metatranscriptomics: Sample Processing and Bioinformatic Workflow Recommendations for Ecological Applications

Microeukaryotes (protists) serve fundamental roles in the marine environment as contributors to biogeochemical nutrient cycling and ecosystem function. Their activities can be inferred through metatranscriptomic investigations, which provide a detailed view into cellular processes, chemical-biological interactions in the environment, and ecological relationships among taxonomic groups. Established workflows have been individually put forth describing biomass collection at sea, laboratory RNA extraction protocols, and bioinformatic processing and computational approaches. Here, we present a compilation of current practices and lessons learned in carrying out metatranscriptomics of marine pelagic protistan communities, highlighting effective strategies and tools used by practitioners over the past decade. We anticipate that these guidelines will serve as a roadmap for new marine scientists beginning in the realms of molecular biology and/or bioinformatics, and will equip readers with foundational principles needed to delve into protistan metatranscriptomics.

Cohen, Natalie R.↗

Earth System science

Recent research has solidified a view of the Earth as a global-scale interactive system with complex chemical, physical, biological and dynamical processes that link the ocean, atmosphere, land (soils, ice, snow) and marine and terrestrial living organisms. These processes both within and between the major parts of the system help determine global and regional climate and control the biogeochemical and hydrologic cycles essential to life. The study of the Earth System requires measurements ranging from the scales of the smallest processes to the global scale. An ambitious satellite observational program, the Earth Observing System (EOS), carried out along with the complementary and ongoing World Climate Research Program (WCRP) and International Geosphere-Biosphere Program (IGBP) represents a major international effort to understand this System and predict its future changes. The complex and intriguing nature of the Earth System is discussed along with a number of closely coupled processes occurring within it. These are: clouds, precipitation and vegetation; ocean circulation, sea-surface temperature and phytoplankton; coupled oceanic and atmospheric circulation (the Southern Oscillation); biological activity, atmospheric chemistry and climate; and biological emissions and the ozone layer.

Prinn, R. G.↗

Measurements of Aerosols, Radiation, and Clouds over the Southern Ocean (MARCUS) Ice Nucleating Particle Measurements Field Campaign Report

Evidence exists that sea-spray-sourced ice nucleating particles (INPs) are organic in origin, resulting from biological and biochemical processes in seawater and the sea surface microlayer, and represent a distinctly different and variable, but oftentimes much less effective, INP population in comparison to long-range transported desert dust (DeMott et al. 2016; McCluskey et al. 2018a). Over the Southern Ocean (SO), far from land sources, these INPs may dominate in the marine boundary layer (McCluskey et al. 2018b). Thereby, marine INPs may affect cloud phase and lifetime in this region where pervasive supercooled and mixed-phase boundary-layer clouds appear underrepresented in climate models. This motivated collection of ice nucleating particle concentration measurements during the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility Measurements of Aerosols, Radiation and Clouds over the Southern Ocean (MARCUS) deployment of the second ARM Mobile Facility (AMF2) on the Aurora Australis vessel from early November, 2017 (Austral spring) to late March, 2018 (Austral fall). During this period, four voyages were made from Hobart, Tasmania to the Australian Antarctic Division bases at Casey, Davis, and Mawson, as well as a final resupply cruise to Macquarie Island, the sight of the related Macquarie Island Cloud and Radiation Experiment (MICRE) campaign. Aerosol filter collections of alternating 24- and 48-hour duration were made during all voyages. These filters were returned frozen for subsequent processing to determine variability in the temperature spectrum of the concentrations of INPs active via the immersion freezing mechanism and to conduct additional analyses to indicate the chemical and biological nature of INPs over the SO. The MARCUS data set provides the first spatial and seasonal picture of INP concentrations over the SO in more than four decades, complementing the full annual cycle of INP data we collected for a point location in MICRE.

Ice nucleation, aerosols, arctic processes, marine↗

Preliminary evaluation of waste processing in a CELSS

Physical/chemical, biological, and hybrid methods can be used in a space environment for processing wastes generated by a Closed Ecological Life Support System (CELSS). Two recycling scenarios are presented. They reflect differing emphases on and responses to the waste system formation rates and their composition, as well as indicate the required products from waste treatment that are needed in a life support system.

Jacquez, Ricardo B.↗

Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2

Our central premise is that catalytic scientists can learn by studying how these important metabolic processes occur in nature. Complementarily, biochemists can learn by studying how catalytic scientists view these same chemical transformations promoted by synthetic catalysts. From these studies, hypotheses can be developed and tested through manipulation of enzyme structure and by synthesizing simple molecular catalysts to incorporate different structural features of the enzymes. It is hoped that these studies will lead to new and useful concepts in catalyst design for fuel production and utilization. This paper describes the results of a workshop held to explore these concepts in regard to the development of new and more efficient catalytic processes for the conversion of CO2 to a variety of carbon-based fuels. The organization of this overview/review is as follows: 1) The first section briefly explores how interactions between the catalysis and biological communities have been fruitful in developing new catalysts for the reduction of protons to hydrogen, the simplest fuel generation reaction. 2) The second section assesses the state of the art in both biological and chemical reduction of CO2 by two electrons to form either carbon monoxide (CO) or formate (HCOO-). It also attempts to identify common principles between biological and synthetic catalysts and productive areas for future research. 3) The third section explores both biological and chemical processes that result in the reduction of CO2 beyond the level of CO and formate, again seeking to identify common principles and productive areas of future research. 4) The fourth section explores the formation of carbon-carbon bonds in biological and chemical systems in the same vein as the other sections. 5) A fifth section addresses the role of non-redox reactions of CO2 in biological systems and their role in carbon metabolism, with a parallel discussion of chemical systems. 6) In section 6, the topics of electrode modification, photochemical systems, and tandem catalysis are briefly discussed. These areas may be important for developing practical systems for CO2 reduction, and they share the common theme of coupling chemical reactions. 7) Section 7 describes some of the crosscutting activities that are critical for advancing the science underpinning catalyst development. 8) The last section attempts to summarize common issues in biological and chemical catalysis and to identify challenges that must be addressed to achieve practical catalysts that are suitable for the reduction of CO2 to fuels.

Environmental Molecular Sciences Laboratory↗

Evaluating the Impact of Ocean Eddies in the Global Marine Carbon Cycle

The ocean plays a crucial role in the Earth’s carbon cycle due to its ability to exchange carbon dioxide (CO2) with the atmosphere, and subsequently store it for long periods of time. Part of this sequestration is due to a mechanism known as the Biological Pump, a process where phytoplankton and autotrophic bacteria convert dissolved CO2 to organic matter via photosynthesis, much of which ends up sinking and can remain in the deep ocean for hundreds or thousands of years. If the strength of the Biological Pump changes due the human-induced increase in atmospheric CO2, it will affect the rate of global warming. Earth System Models (ESMs) are now including ocean biogeochemical processes in order to quantify changes in the global carbon cycle under climate change scenarios by embedding a model that represents ocean chemistry and the dynamics of marine ecosystems within an ocean circulation framework. Due to the increased computational cost of including marine biogeochemistry (BGC), they are typically run with relatively low complexity and coarse horizontal grid resolution. Our project utilizes Institutional Computing power to undertake an ESM simulation using a moderate complexity BGC model (35 constituents) and an increased grid resolution that allows the formation of turbulent mesoscale eddies (30 to 200 km in size) in the ocean. Comparing with low resolution runs will allow us to assess whether standard ESMs are biased in their representation of the carbon cycle due to parameterized effects of sub-grid scale physics.

54 ENVIRONMENTAL SCIENCES↗

SU-E-T-54: Benefits of Biological Cost Functions

Purpose: To verify the benefits of the biological cost functions. Methods: TG166 patients were used for the test case scenarios. Patients were planned using Monaco V5.0 (CMS/Elekta, St.Louis, MO) Monaco has 3 biological and 8 physical CFs. In this study the plans were optimized using 3 different scenarios. 1- Biological CFs only 2-Physical CFs only 3- Combination of Physical and Biological CFsMonaco has 3 biological CFs. Target EUD used for the targets, derived from the poisson cell kill model, has an α value that controls the cold spots inside the target. α values used in the optimization were 0.5 and 0.8. if cold spots needs to be penalized α value increased. Serial CF: it's called serial to mimic the behaviour of the serial organs, if a high k value like 12 or 14 is used it controls the maximum dose. Serial CF has a k parameter that is used to shape the whole dvh curve. K value ranges between 1–20. k:1 is used to control the mean dose, lower k value controls the mean dose, higher k value controls the higher dose, using 2 serial CFs with different k values controls the whole DVH. Paralel CF controls the percentage of the volume that tolerates higher doses than the reference dose to mimic the behaviour of the paralel organs. Results: It was possible to achive clinically accepted plans in all 3 scenarios. The benefit of the biological cost functions were to control the mean dose for target and OAR, to shape the DVH curve using one EUD value and one k value simplifies the optimization process. Using the biological CFs alone, it was hard to control the dose at a point. Conclusion: Biological CFs in Monaco doesn't require the ntcp/tcp values from the labs and useful to shape the whole dvh curve. I work as an applications support specialist for Elekta and I am a Ph.D. Student in Istanbul University for radiation therapy physics.

60 APPLIED LIFE SCIENCES↗

SeaWiFS Postlaunch Technical Report Series: AMT-5 Cruise Report - Volume 2

This report documents the scientific activities on board the Royal Research Ship (RRS) James Clark Ross (JCR) during the fifth Atlantic Meridional Transect (AMT-5), 14 September to 17 October 1997. There are three objectives of the AMT Program. The first is to derive an improved understanding of the links between biogeochemical processes, biogenic gas exchange, air-sea interactions, and the effects on, and responses of, oceanic ecosystems to climate change. The second is to investigate the functional roles of biological particles and processes that influence ocean color in ecosystem dynamics. The Program relates directly to algorithm development and the validation of remotely-sensed observations of ocean color. Because the Sea-viewing Wide Field-of-view Sensor (SeaWiFS) instrument achieved operational status during the cruise (on 18 September), AMT-5 was designated the SeaWiFS Atlantic Characterization Experiment (SeaACE) and was the only major research cruise involved in the validation of SeaWiFS data during the first 100 days of operations. The third objective involved the near-real time reporting of in situ light and pigment observations to the SeaWiFS Project, so the performance of the satellite sensor could be determined.

Hooker, Stanford B.↗

A Review of Global Satellite-Derived Snow Products

Snow cover over the Northern Hemisphere plays a crucial role in the Earth's hydrology and surface energy balance, and modulates feedbacks that control variations of global climate. While many of these variations are associated with exchanges of energy and mass between the land surface and the atmosphere, other expected changes are likely to propagate downstream and affect oceanic processes in coastal zones. For example, a large component of the freshwater flux into the Arctic Ocean comes from snow melt. The timing and magnitude of this flux affects biological and thermodynamic processes in the Arctic Ocean, and potentially across the globe through their impact on North Atlantic Deep Water formation. Several recent global remotely sensed products provide information at unprecedented temporal, spatial, and spectral resolutions. In this article we review the theoretical underpinnings and characteristics of three key products. We also demonstrate the seasonal and spatial patterns of agreement and disagreement amongst them, and discuss current and future directions in their application and development. Though there is general agreement amongst these products, there can be disagreement over certain geographic regions and under conditions of ephemeral, patchy and melting snow.

Frei, Allan↗

A Review of Global Satellite-Derived Snow Products

Snow cover over the Northern Hemisphere plays a crucial role in the Earth s hydrology and surface energy balance, and modulates feedbacks that control variations of global climate. While many of these variations are associated with exchanges of energy and mass between the land surface and the atmosphere, other expected changes are likely to propagate downstream and affect oceanic processes in coastal zones. For example, a large component of the freshwater flux into the Arctic Ocean comes from snow melt. The timing and magnitude of this flux affects biological and thermodynamic processes in the Arctic Ocean, and potentially across the globe through their impact on North Atlantic Deep Water formation. Several recent global remotely sensed products provide information at unprecedented temporal, spatial, and spectral resolutions. In this article we review the theoretical underpinnings and characteristics of three key products. We also demonstrate the seasonal and spatial patterns of agreement and disagreement amongst them, and discuss current and future directions in their application and development. Though there is general agreement amongst these products, there can be disagreement over certain geographic regions and under conditions of ephemeral, patchy and melting snow

Frei, Allan↗

A Review of Global Satellite-derived Snow Products

Snow cover over the Northern Hemisphere plays a crucial role in the Earth's hydrology and surface energy balance, and modulates feedbacks that control variations of global climate. While many of these variations are associated with exchanges of energy and mass between the land surface and the atmosphere, other expected changes are likely to propagate downstream and affect oceanic processes in coastal zones. For example, a large component of the freshwater flux into the Arctic Ocean comes from snow melt. The timing and magnitude of this flux affects biological and thermodynamic processes in the Arctic Ocean, and potentially across the globe through their impact on North Atlantic Deep Water formation. Several recent global remotely sensed products provide information at unprecedented temporal, spatial, and spectral resolutions. In this article we review the theoretical underpinnings and characteristics of three key products. We also demonstrate the seasonal and spatial patterns of agreement and disagreement amongst them, and discuss current and future directions in their application and development. Though there is general agreement amongst these products, there can be disagreement over certain geographic regions and under conditions of ephemeral, patchy and melting snow.

Frei, Allan↗

Evaluating the Impact of Ocean Eddies in the Global Marine Carbon Cycle

The ocean plays a crucial role in the Earth’s carbon cycle due to its ability to exchange carbon dioxide (CO 2 ) with the atmosphere, and subsequently store it for long periods of time. Part of this sequestration is due to a mechanism known as the Biological Pump, a process where phytoplankton and autotrophic bacteria convert dissolved CO 2 to organic matter via photosynthesis, much of which ends up sinking and can remain in the deep ocean for hundreds or thousands of years. If the strength of the Biological Pump changes due the human-induced increase in atmospheric CO 2 , it will affect the rate of global warming. Earth System Models (ESMs) are now including ocean biogeochemical processes in order to quantify changes in the global carbon cycle under climate change scenarios by embedding a model that represents ocean chemistry and the dynamics of marine ecosystems within an ocean circulation framework. Due to the increased computational cost of including marine biogeochemistry (BGC), they are typically run with relatively low complexity and coarse horizontal grid resolution. Our project utilizes Institutional Computing power to undertake an ESM simulation using a moderate complexity BGC model (35 constituents) and an increased grid resolution that allows the formation of turbulent mesoscale eddies (30 to 200 km in size) in the ocean. Comparing with low resolution runs will allow us to assess whether standard ESMs are biased in their representation of the carbon cycle due to parameterized effects of sub-grid scale physics.

54 ENVIRONMENTAL SCIENCES↗

ORNL Second Target Station Project: Biological & Environmental Science Workshop

Recent advances in neutron sources and instrumentation have opened up many new opportunities for the application of neutron scattering techniques in the biological and environmental sciences. Neutrons enable studies of the structure and dynamics of biological and environmental samples with a particular sensitivity to light elements, such as hydrogen, which is a key component of biological and environmental samples. Studies using neutrons are complementary to X-rays and have the unique advantage of being non-destructive and highly-penetrating. Oak Ridge National Laboratory’s upcoming Spallation Neutron Source (SNS) Second Target Station (STS) will provide high brightness cold neutron sources that significantly advance the scientific capabilities of neutron scattering instruments. The STS will advance our understanding of biological and environmental processes across spatial and temporal scales. The capabilities will enhance our ability to discover, design, and develop new materials essential for advanced sustainable technologies to address society’s most pressing needs. This report summarizes the discussions and recommendations from a joint workshop held by the STS Project and the Biological and Environmental Systems Science Directorate (BESSD) in June 2022. The purpose of the workshop was to explore science opportunities and capabilities related to biological and environmental systems that could be incorporated into both current and future STS instrument designs, as well as additional instruments at the SNS First Target Station (FTS) and High Flux Isotope Reactor (HFIR). With six breakout sessions, each with two invited plenary speakers from other institutions, the participants discussed a wide range of topics relevant to biological and environmental research. Based on the input from participants, a number of recommendations on instrumentation, sample environments, complementary multi-modal methods, data processing and analysis and sample deuteration are provided in the report. The participants also identified science opportunities that are emerging from the planned instrument capabilities at STS. Selected recommendations and science opportunities are listed in the Executive Summary.

54 ENVIRONMENTAL SCIENCES↗

Molecular Processes Underlying the Structure and Assembly of Thin Films and Nanoparticles at Complex interfaces

Since 1995 we have pursued a number of different studies that are quite diverse in nature but with the common theme of using novel laser based methods to study important processes at buried interfaces. Studies of Corrosion, Passivation on n-GaAs(100)Methanol Photoelectrochemical Cell In these studies we have used picosecond photoluminescence and electrochemical studies to understand the GaAs/methanol interface. In our most extensive set of studies we conducted photo-illumination and XPS experiments to understand the chemistry occurring in the GaAs/methanol photoelectrochemical during photoexcitation. An important distinction between photocorrosion and photoetching of GaAs is elucidated by these studies. The dependence of GaAs photocorrosion on light intensity has been explored to better understand intrinsic differences between the lamplight studies and the picosecond photoluminescence studies. The effect of coating the GaAs with a sulfide layer prior to immersion in the cell has also been explored. This last result has led us to examine n-GaAs as a function of crystallographic orientation after exposure to aqueous Na 2 S containing solutions has been studied as a function of crystallographic orientation of the GaAs surface. The (100) and (110) surfaces are relatively similar, with significant amounts of As-S species present at the interface. The (111)B surface lacks this constituent, but shows significant amounts of metallic As. The XPS results have been correlated with the results of previous photocorrosion and passivation studies conducted in a photoelectrochemical cell. The studies indicate that the metallic As present at (111)B surface contributes strongly to the large surface recombination velocity found there, and to the inability of Na 2 S to passivate the (111)B surface. SAMS Under Water: Water Molecular Structure and Bonding at Hydrophobic Surfaces In these DOE sponsored studies we have been interested in learning the similarities and differences in how water behaves at hydrophobic self-assembled monolayer (SAMS)/water interfaces relative to the organic liquid/water interfaces. Several monolayer films have been examined in these studies using a combination of vibrational sum frequency spectroscopy (VSFS), contact angle measurements and AFM. At the hydrocarbon monolayer/water interface we find that water has a weak bonding interaction with the monolayer film that results in an orientation of water at the terminus of these hydrocarbon chains. The water-film interaction is still present for fluorinated films but it is found to be considerably weaker. Hydration and Surfactant Adsorption at Salt/Water Interfaces This set of studies has examined the molecular characteristics of the CaF 2 /water interface using VSFS. Our first studies detailed the structure and orientation of water molecules adsorbed at this mineral surfaces including studies of the surface in the presence of aqueous solutions of salts. These studies have been followed by a series of static and time-resolved studies of the adsorption of carboxylic acid containing organics at this surface, specifically carboxylic acid surfactants and acetic acid. In the latter we have developed a new method for time resolved studies that involve sequential wavelength tuning and automated control of spatial beam overlap at the target can probe amplitude changes of sum-frequency resonances in widely spaced infrared regions. This offers great advantages for the study of the synchronism of molecular processes at interfaces. This approach is particularly suitable to investigate the synchronization of interfacial processes such as surfactant adsorption at charged mineral surfaces. Macromolecular Assembly at Liquid/Liquid Interfaces Macromolecular assembly at the interface between water and a hydrophobic surface underlies some of the most important biological and environmental processes on the planet. Our work has examined polymer adsorption and assembly of carboxylic acid-containing polyelectrolytes at the carbon tetrachloride–water interface, a model system for an oil–water interface. Using VSFS and interfacial tension techniques, these unique set of studies identify the factors that dictate whether or not polyelectrolytes will adsorb to the oil–water interface and also describe the specifics of the adsorption process that depend upon factors such as polymer size, charge density, hydrophobicity, conformation, and the effect of metal ion electrostatics and bonding. The systems studied include polyelectrolytes polyacrylic acid (PAA) and polymethylacrylic acid (PMA) of different polymer sizes and under different aqueous solution conditions. The studies are the first to show the highly ordered nature of the adsorption of the first monolayer with subsequent monolayers disordered. The second set of studies have examined how peptoid nanosheets assemble at the oil/water interface. Peptoid nanosheets are a recently discovered class of two-dimensional (2D) nanomaterial, which form from the self-assembly of a sequence-specific peptoid polymer at an air-water interface. Nanosheet formation occurs first through the assembly of a peptoid monolayer and subsequent compression into a bilayer structure. In these highly successful studies we have shown that the oil-water interface provides another opportunity for growth of these unique and highly ordered peptoid sheets. The monolayer formed at this interface are found through surface spectroscopic measurements to be highly ordered and electrostatic interactions between the charged moieties, namely carboxylate and ammonium residues, of the peptoid are essential in the ability of these peptoids to form ordered nanosheets at the oil-water interface.

36 MATERIALS SCIENCE↗

The biota as ancient and modern modulator of the earth's atmosphere

The composition of the terrestrial atmosphere is thought to have been markedly modified by surface microbiota and modulated around quantities of gases optimized for growth of these microbiota. Three diagrams illustrating these suppositions are presented. The first shows a probable order of appearance of major metabolic pathways in microbes that interact with sediment and atmosphere. It is based on evolutionary considerations and is devised independently of the fossil record. The second diagram shows the qualitative emissions and removals of atmospheric gases by anaerobic organisms; it approximates those processes thought to have dominated the terrestrial atmosphere in Archean times. The third diagrams gaseous emissions and removals by the major groups of organisms, including oxygen-releasing and -utilizing forms. Biological gas exchange processes thought to have dominated the atmosphere since the Proterozoic are thus represented.

Margulis, L.↗