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At least 541 records · Page 30

Oxidation Behavior of Binary Niobium Alloys

This investigation concludes a study to determine the effects of up to 25 atomic percent of 55 alloying additions on the oxidation characteristics of niobium. The alloys were evaluated by oxidizing in an air atmosphere for 4 hours at 1000 C and 2 hours at 1200 C. Titanium and chromium improved oxidation resistance at both evaluation conditions. Vanadium and aluminum improved oxidation resistance at 1000 C, even though the V scale tended to liquefy and the Al specimens became brittle and the scale powdery. Copper, cobalt, iron, and iridium improved oxidation resistance at 1200 C. Other investigations report tungsten and molybdenum are protective up to about 1000 C, and tantalum at 1100 C. The most important factor influencing the rate of oxidation was the ion size of the alloy additions. Ions slightly smaller than the Nb(5+) ion are soluble in the oxide lattice and tend to lower the compressive stresses in the bulk scale that lead to cracking. The solubility of the alloying addition also depends on the valence to some extent. All of the elements mentioned that improve the oxidation resistance of Nb fit this size criterion with the possible exception of Al, whose extremely small size in large concentrations would probably lead to the formation of a powdery scale. Maintenance of a crack-free bulk scale for as long as possible may contribute to the formation of a dark subscale that ultimately is rate- controlling in the oxidation process. The platinum-group metals, especially Ir, appear to protect by entrapment of the finely dispersed alloying element by the incoming Nb2O5 metal-oxide interface. This inert metallic Ir when alloyed in a sufficient amount with Yb appears to give a ductile phase dispersed in the brittle oxide. This scale would then flow more easily to relieve the large compressive stresses to delay cracking. Complex oxide formation (which both Ti and Zr tend to initiate) and valence effects, which probably change the vacancy concentration in the scale, are masked by the overriding tendency for a porous scale.

Barrett, Charles A.↗

Interactions between integrin receptors and fibronectin are required for calvarial osteoblast differentiation in vitro

We previously showed that anti-fibronectin antibodies or soluble fibronectin fragments containing the central cell-binding domain inhibit formation of mineralized nodules by fetal calvarial osteoblasts in vitro. These findings suggest a critical role for fibronectin in osteoblast differentiation and morphogenesis. In this study we tested the hypothesis that fibronectin's effects on osteogenesis are mediated via direct interactions with integrin receptors for fibronectin on osteoblasts. Immunocytochemical analysis identified the integrin fibronectin receptor alpha5ss1 in fetal rat calvarial tissue and in cultured osteoblasts at all stages of differentiation. Three other integrins, alpha3ss1, alpha8ss1 and alphavss3, which can bind fibronectin, as well as other matrix components, were also identified in tissue and at all stages of cell culture. Immunoprecipitation data showed that alpha5ss1 levels are constant throughout osteoblast differentiation whereas levels of alpha3ss1 and alpha8ss1 decline in mature mineralized cultures. To determine whether integrin fibronectin receptors are required for osteoblast formation of mineralized nodules, we examined the extent of nodule formation in the presence and absence of function-perturbing anti-integrin antibodies. The antibodies were present continuously in cultures beginning at confluence (day 3), and nodule formation was measured at days 10 and 20. An anti-alpha5 integrin subunit antibody reduced nodule formation to less than 5% of control values at both time points. Inhibition of nodule formation was reversible and did not affect cell attachment and viability. Function-perturbing antibodies against alpha3ss1 and alpha8ss1 also reduced nodule formation, to less than 20% of control values. In contrast, function-perturbing antibodies to alphavss3 and alphavss5 did not affect nodule formation, indicating that the inhibitions noted were indeed specific. To determine the effect of antibody treatment on gene expression, steady-state mRNA expression was examined and found to be suppressed for osteoblast markers alkaline phosphatase and osteocalcin. Together, these results indicate that direct osteoblast interactions with the extracellular matrix are mediated by a select group of integrin receptors that includes alpha5ss1, alpha3ss1 and alpha8ss1. We further conclude that the specific alpha5ss1 fibronectin receptor mediates critical interactions between osteoblasts and fibronectin required for both bone morphogenesis and osteoblast differentiation.

NASA Center ARC↗

Determining the Metal/Silicate Partition Coefficient of Germanium: Implications for Core and Mantle Differentiation.

Currently there are several hypotheses for the thermal state of the early Earth. Some hypothesize a shallow magma ocean, or deep magma ocean, or heterogeneous accretion which requires no magma ocean at all. Previous models are unable to account for Ge depletion in Earth's mantle relative to CI chondrites. In this study, the element Ge is used to observe the way siderophile elements partition into the metallic core. The purpose of this research is to provide new data for Ge and to further test these models for Earth's early stages. The partition coefficients (D(sub Ge) = c(sub metal)/c(sub silicate), where D = partition coefficient of Ge and c = concentration of Ge in the metal and silicate, respectively) of siderophile elements were studied by performing series of high pressure, high temperature experiments. They are also dependent on oxygen fugacity, and metal and silicate composition. Ge is a moderately siderophile element found in both the mantle and core, and has yet to be studied systematically at high temperatures. Moreover, previous work has been limited by the low solubility of Ge in silicate melts (less than 100 ppm and close to detection limits for electron microprobe analysis). Reported here are results from 14 experiments studying the partitioning of Ge between silicate and metallic liquids. The Ge concentrations were then analyzed using Laser Ablation Inductively Coupled Mass Spectrometry (LA-ICP-MS) which is sensitive enough to detect ppm levels of Ge in the silicate melt.

King, C.↗

Sol–gel synthesis of iodosodalite precursors and subsequent consolidation with a glass binder made from oxides and sol–gel routes

Radioiodine accumulates in aqueous solutions and off-gas streams during nuclear fuel reprocessing due to its solubility in aqueous solutions and volatility, respectively. Additionally, radioiodine is highly mobile in geological environments and iodine-129 has been found to be one of the largest long-term contributors to chronic dose to humans in scenarios of radionuclide migration from geological repositories. Most of the radioiodine can be captured during fuel reprocessing in off-gas streams using solid sorbents and scrubbing solutions. Once iodine is captured, it must be stored in a durable form for eventual disposal. Iodosodalite has been investigated as a waste form for radioiodine, however these synthesis processes typically result in mixed products and iodine volatilization during consolidation. Therefore, this paper proposes a novel approach to synthesizing iodosodalite utilizing a sol-gel method. This method was chosen to lower processing temperatures and improve product yield. Preliminary experiments conducted to determine the viability of this synthetic method are presented. Additionally, consolidation of sol-gel derived iodosodalite with a glass-binder was explored using three different methods: 1) incorporating the glass-binder during gel preparation using alkoxide precursors; 2) separately preparing the glass binder using a sol-gel method; and 3) separately preparing the glass-binder using a melt-quench technique. Glass-bonded iodosodalite was successfully synthesized using these novel sol-gel approaches.

36 MATERIALS SCIENCE↗

Mineralogical evidence for hydrothermal alteration of Bennu samples

Samples of asteroid (101955) Bennu delivered by the OSIRIS-REx mission offer the opportunity to study pristine planetary materials unchanged by exposure to the terrestrial environment. Here we use a combination of X-ray diffraction and various electron microscopy techniques to explore the detailed mineralogy of Bennu samples and determine the alteration history of the planetesimal protolith from which they originated. The samples consist largely of hydrated sheet-silicate minerals, namely nanoscale serpentine and saponite of varied grain size, which are decorated with micro- to nanoscale Fe-sulfides, magnetite and carbonates. We observe sheet silicates parallel and normal to sulfide surfaces and as inclusions in sulfides; sulfur-rich veins transecting the sheet-silicate matrix; zoned carbonates and phosphates and sulfide and magnetite grains exhibiting embayment. The mineralogical evidence indicates alteration of accreted minerals by a fluid that evolved with time, leading to etching, dissolution and reprecipitation. Sulfide compositions indicate alteration at ~25 °C, similar to conditions inferred for asteroid (162173) Ryugu and Ivuna-type (CI) chondrite meteorites. The fluid probably evolved from neutral to alkaline, culminating with the precipitation of highly soluble salts. We conclude that Bennu’s protolith comprised mainly nanometre to micrometre silicates, with fewer chondrules and calcium–aluminium-rich inclusions than those of most chondrite groups.

Zega, T J↗

Utilization of non-conventional systems for conversion of biomass to food components: Recovery optimization and characterizations of algal proteins and lipids

Protein isolate obtained from green algae (Scenedesmus obliquus) cultivated under controlled conditions was characterized. Molecular weight determination of fractionated algal proteins using SDS-polyacrylamide gel electrophoresis revealed a wide spectrum of molecular weights ranging from 15,000 to 220,000. Isoelectric points of dissociated proteins were in the range of 3.95 to 6.20. Amino acid composition of protein isolate compared favorably with FAO standards. High content of essential amino acids leucine, valine, phenylalanine and lysine makes algal protein isolate a high quality component of closed environment life support system (CELSS) diets. To optimize the removal of algal lipids and pigments supercritical carbon dioxide extraction (with and without ethanol as a co-solvent) was used. Addition of ethanol to supercritical CO2 resulted in more efficient removal of algal lipids and produced protein isolate with a good yield and protein recovery. The protein isolate extracted by the above mixture had an improved water solubility.

Karel, M.↗

Non-conventional approaches to food processing in CELSS, 1. Algal proteins: Characterization and process optimization

Protein isolate obtained from green algae cultivated under controlled conditions was characterized. Molecular weight determination of fractionated algal proteins using SDS-polyacrylamide gel electrophoresis revealed a wide spectrum of molecular weights ranging from 15,000 to 220,000. Isoelectric points of dissociated proteins were in the range of 3.95 to 6.20. Amino acid composition of protein isolate compared favorably with FAO standards. High content of essential amino acids leucine, valine, phenylalanine and lysine make algal protein isolate a high quality component of closed ecological life support system diets. To optimize the removal of algal lipids and pigments supercritical carbon dioxide extraction (with and without ethanol as a co-solvent) was used. Addition of ethanol to supercritical carbon dioxide resulted in more efficient removal of algal lipids and produced protein isolate with a good yield and protein recovery. The protein isolate extracted by the above mixture had an improved water solubility.

Nakhost, Z.↗

Thermochemical Properties of a Water-Soluble Zr(IV)-Flavonolate Complex for Fluoride Sensing

Detection of fluoride in water samples is critical for monitoring many chemical, environmental, and biological processes, however, these measurements often rely on costly instrumentation. Here, this situation has motivated the design of simple to use, fieldable fluoride sensors. Previously, a fluorometric sensor based on (EDTA)­Zr­(H 2 O) 2 (EDTA = ethylenediamine-N,N,N′,N′-tetraacetate) and 3-hydroxyflavone (FlvH) was reported for fluoride detection in ethanol-H 2 O mixtures. Herein, we report the synthesis and characterization of the previously proposed Zr­(IV)-flavonolate complex as the dimethylammonium salt, [(EDTA)­Zr­(Flv)]­[NMe 2 H 2 ] (Flv = 3-hydroxyflavonolate), and detail its utility for aqueous fluoride sensing. This species exhibits an intense blue fluorescence upon excitation with near-UV light (λ ex = 390 nm; λ em = 460 nm) that is quenched in the presence of NaF (100 mM acetate buffer, pH = 5) with good sensitivity (LOD = 20.9 nM; [F – ] from 10 –8 to 10 –4 M) under neat aqueous conditions. The equilibrium constant (K eq = 1.26 ± 0.00184 × 10 8 M –2 ) and free energy (Δ$G^°_{\textrm{rxn}}$ = –11.0 kcal mol –1 ) were determined under the conditions used for fluoride sensing, indicating a highly favorable reaction with F – in water. Finally, we developed paper-based sensing strips for qualitative fluoride sensing by immobilizing the sensor in a deposited gel enabling good selectivity and reduced interference due to slower ion diffusion.

aqueous chemistry↗

Storage and persistence of organic carbon in the upper three meters of soil under arable and native prairie land use

Aims: Land use change from native grasslands to arable lands globally impacts soil ecosystem functions, including the storage of soil organic carbon (SOC). Understanding the factors affecting SOC changes in topsoil and subsoil due to land use is crucial for effective mitigation strategies. We determined SOC storage and persistence as affected by land use change from native prairies to arable lands. Methods: Here we examined SOC stocks, soil δ 13 C and Δ 14 C signatures, microbial communities (bacteria and fungi), and soil mineral characteristics under native prairies and long-term arable lands (i.e., > 40 years) down to 3 m in the U.S. Midwest. Results: Native prairie soils had higher SOC stocks in the A horizon and 0–50 cm depth increment than arable soils. For both land use types, the δ 13 C and Δ 14 C values significantly decreased with depth, with the latter pointing towards highly stabilized SOC, especially in the B- and C-horizons. Analysis of the microbial communities indicated that the diversity of bacteria and fungi decreased with increasing soil depth. The content of oxalate soluble Al appeared to be the single most important predictor of SOC across horizons and land use types. Conclusion: Our data suggest that most SOC gains and losses and transformation and translocation processes seem to be restricted to the uppermost 50 cm. Increasing SOC retention in the A and B horizons within the 0–50 cm depth would enhance organic material serving as substrate and nutrients for microbes and plants (A horizon) and facilitate long-term SOC storage in the subsoil (B horizon).

54 ENVIRONMENTAL SCIENCES↗

Evaluation of Technologies for Destruction of LDR Organics in Hanford Tank Waste

Aqueous Hanford tank wastes contain soluble organics and some tanks contain small amounts (<100 mg/L) of organics that are regulated under the Land Disposal Restrictions (LDR) portions of the Resource Conservation and Recovery Act (RCRA). Most of these organics can be removed by evaporation, but some are not. Methods to destroy/remove organics that are regulated by the LDR section of the RCRA and that are not removed by evaporation may be needed if ambient temperature waste treatment processes are used to immobilize aqueous Hanford tank wastes. To identify viable and compatible organic removal or destruction pretreatment methods an evaluation was performed by a team of researchers. The team utilized a Systems Engineering Approach that examines all aspects of the technology, based on information available in the literature and the experience of the team members. That evaluation led to recommendations by the team to perform testing on technologies to determine efficacy in destroying organics in Hanford tank waste liquids. The primary technologies recommended are chemical oxidants, including permanganate, peroxymonosulfate or peroxydisulfate (PMS/PDS), hydrogen peroxide, and ozone. Ultraviolet light irradiation of the stream with a solid catalyst sorbent is also recommended for testing. A generalized description of the test program is also included.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Volatile Concentrations and H-Isotope Composition of Unequilibrated Eucrites

Eucrites are among the oldest and best studied asteroidal basalts (1). They represent magmatism that occurred on their parent asteroid, likely 4-Vesta, starting at ~ 4563 Ma and continuing for approx. 30 Myr. Two hypotheses are debated for the genesis of eucrites, a magma ocean model (2), and a mantle partial melting model. In general, volatiles (H, C, F, Cl) have been ignored for eucrites and 4-Vesta, but solubility of wt% levels of H2O are possible at Vestan interior PT conditions. Targeted measurements on samples could aid our understanding considerably. Recent studies have found evidence of volatile elements in eucrites, but quantifying the abundance of volatiles remains problematic (6). Volatile elements have a disproportionately large effect on melt properties and phase stability, relative to their low abundance. The source of volatile elements can be elucidated by examining the hydrogen isotope ratio (D/H), as different H reservoirs have drastically different H isotope compositions. Recent studies of apatite in eucrites have shown that the D/H of 4-Vesta matches that of Earth and carbonaceous chondrites, however, the D/H of apatites may not represent the D/H of a primitive 4-Vesta melt due to the possibility of degassing prior to the crystallization of apatite. Therefore, the D/H of early crystallizing phases must be measured to determine if the D/H of 4-Vesta is equal to that of the Earth and carbonaceous chondrites.

Sarafian, Adam R.↗

The Earliest Ion Channels in Protocellular Membranes

Cellular membranes with their hydrophobic interior are virtually impermeable to ions. Bulk of ion transport through them is enabled through ion channels. Ion channels of contemporary cells are complex protein molecules which span the membrane creating a cylindrical pore filled with water. Protocells, which are widely regarded as precursors to modern cells, had similarly impermeable membranes, but the set of proteins in their disposal was much simpler and more limited. We have been, therefore, exploring an idea that the first ion channels in protocellular membranes were formed by much smaller peptide molecules that could spontaneously selfassemble into short-lived cylindrical bundles in a membrane. Earlier studies have shown that a group of peptides known as peptaibols is capable of forming ion channels in lipid bilayers when they are exposed to an electric field. Peptaibols are small, non-genetically encoded peptides produced by some fungi as a part of their system of defense against bacteria. They are usually only 14-20 residues long, which is just enough to span the membrane. Their sequence is characterized by the presence of non-standard amino acids which, interestingly, are also expected to have existed on the early earth. In particular, the presence of 2-aminoisobutyric acid (AIB) gives peptaibols strong helix forming propensities. Association of the helices inside membranes leads to the formation of cylindrical bundles, typically containing 4 to 10 monomers. Although peptaibols are excellent candidates for models of the earliest ion channels their structures, which are stabilized only by van der Waals forces and occasional hydrogen bonds between neighboring helices, are not very stable. Although it might properly reflect protobiological reality, it is also a major obstacle in studying channel behavior. For this reason we focused on two members of the peptaibol family, trichotoxin and antiamoebin, which are characterized by a single conductance level. This indicates that their structures are unique and stable. In addition, it is also believed that the trichotoxin channel displays some selectivity between potassium and chloride ions. This makes trichotoxin and antiamoebin ideal models of the earliest ion channels that could provide insight into the origins of ion conductance and selectivity. In the absence of crystal structure of the trichotoxin and antiamoebin channels, we propose their molecular models based on experimentally determined number of monomers forming the bundles. We use molecular dynamics simulations to validate the models in terms of their conductance and selectivity. On the basis of our simulations we show that the emergence of channels built of small, alpha-helical peptides was protobiologically plausible and did not require highly specific amino acid sequences, which is a convenient evolutionary trait. Despite their simple structure, such channels could possess properties that, at the first sight, appear to require markedly larger complexity. To this end, we will discuss how the amino acid sequence and structure of primitive channels give rise to the phenomena of ionic conductance and selectivity across the earliest cell walls, which were essential functions for the emergence and early evolution of protocells. Furthermore, we will argue that even though architectures of membrane proteins are not nearly as diverse as those of water-soluble proteins, they are sufficiently flexible to adapt readily to the functional demands arising during evolution.

Mijajlovic, Milan↗

Data for "Relative Reactivity and Bioavailability of Mercury Sorbed to or Coprecipitated with Aged Iron Sulfides"

The potential for inorganic mercury (Hg) to be converted to methylmercury depends, in part, on the chemical form of Hg and its bioavailability to anaerobic microorganisms that can methylate Hg. In anaerobic settings, Hg can be associated with sulfide phases, including ferrous iron sulfide (FeS), which can sorb or coprecipitated with Hg. The objective of this study was to determine if the aging state of FeS alters the Hg coordination environment as well as the reactivity and bioavailability of sorbed and coprecipitated Hg species. FeS particles were synthesized with and without Hg2+ and aged in anaerobic conditions for multiple time frames spanning from 1 hour to 1 month. For FeS particles synthesized without Hg, Hg2+ was subsequently sorbed to the FeS for 1 day. Analysis of Hg speciation of these materials by X-ray absorption near edge spectroscopy revealed a predominance of 4-coodinate Hg-S species in the sorbed Hg-FeS solids and a mixture of 2- and 4-coordinate Hg-S in the coprecipitated Hg-FeS. The leaching potential of the Hg was assessed by exposing the particles to a solution of dissolved glutathione (a thiolate-based Hg chelator). As expected, the sorbed Hg-FeS released more soluble Hg compared to the co-precipitated Hg-FeS. However, when these particles were exposed to Desulfovibrio desulfuricans ND132 (a known Hg methylator), more Hg was methylated from the co-precipitated Hg-FeS than the sorbed Hg-FeS, consistent with expectations from the Hg-S coordination state and inconsistent with the selective leaching results. Overall, these results suggest that the bioavailability of particulate Hg cannot be easily discerned by leaching potential into bulk solution. Rather, bioavailability entails more subtle interactions at particle-cell interfaces and perhaps correlates with the local Hg-S coordination state in the particles. This data package contains data shown in the referenced publication, including all figures. Each figure is available in the respective *.csv file and a summary of all files are also included in the the xlsx file. Additional formatted data include X-ray diffraction data of the FeS solids are also available in a HPF format (Panalytical software), X-ray absorption spectroscopy data as *.prj files (Athena), and X-ray fluorescence data in its raw data form.

54 ENVIRONMENTAL SCIENCES↗

Genotype-Environment-Management Interactions in Biomass Yield and Feedstock Composition of Photoperiod-Sensitive Energy Sorghum

Recently introduced photoperiod-sensitive (PS) biomass sorghum (Sorghum bicolor L. Moench) needs to be investigated for their yield potential under different cultivation environments with reasonable nitrogen (N) inputs. The objectives of this study were to (1) evaluate the biomass yield and feedstock quality of four sorghum hybrids with different levels of PS ranging from very PS (VPS) hybrids and to moderate PS (MPS) hybrids, and (2) determine the optimal N inputs (0~168 kg N ha -1 ) under four environments: combinations of both temperate (Urbana, IL) and subtropical (College Station, TX) regions during 2018 and 2019. Compared to TX, the PS sorghums in central IL showed higher yield potential and steady feedstock production with an extended day length and with less precipitation variability, especially for the VPS hybrids. The mean dry matter (DM) yields of VPS hybrids were 20.5 Mg DM ha -1 and 17.7 Mg DM ha -1 in IL and TX, respectively. The highest N use efficiency occurred at a low N rate of 56 kg N ha -1 by improving approximately 33 kg DM ha -1 per 1.0 kg N ha -1 input. Approximately 70% of the PS sorghum biomass can be utilized for biofuel production, consisting of 58-65% of the cell-wall components and 4-11% of the soluble sugar. Finally, this study demonstrated that the rainfed temperate area (e.g., IL) has a great potential for the sustainable cultivation of PS energy sorghum due to their observed high yield potential, stable production, and low N requirements.

09 BIOMASS FUELS↗

Data from Genotype-Environment-Management Interactions in Biomass Yield and Feedstock Composition of Photoperiod-Sensitive Energy Sorghum

Recently introduced photoperiod-sensitive (PS) biomass sorghum ( Sorghum bicolor L. Moench) needs to be investigated for yield potential under different cultivation environments with reasonable nitrogen (N) inputs. The objectives of this study were to (1) evaluate the biomass yield and feedstock quality of four sorghum hybrids with different levels of PS ranging from very PS (VPS) hybrids and to moderate PS (MPS) hybrids, and (2) determine the optimal N inputs (0~168 kg N ha−1) under four environments: combinations of both temperate (Urbana, IL) and subtropical (College Station, TX) regions during 2018 and 2019. Compared to TX, the PS sorghums in central IL showed higher yield potential and steady feedstock production with an extended day length and with less precipitation variability, especially for the VPS hybrids. The mean dry matter (DM) yields of VPS hybrids were 20.5 Mg DM ha−1 and 17.7 Mg DM ha−1 in IL and TX, respectively. The highest N use efficiency occurred at a low N rate of 56 kg N ha−1 by improving approximately 33 kg DM ha−1 per 1.0 kg N ha−1 input. Approximately 70% of the PS sorghum biomass can be utilized for biofuel production, consisting of 58-65% of the cell-wall components and 4-11% of the soluble sugar. This study demonstrated that the rainfed temperate area (e.g., IL) has a great potential for the sustainable cultivation of PS energy sorghum due to their observed high yield potential, stable production, and low N requirements.

Biomass Analytics↗

Optimizing a chemical cleaning protocol to determine the nickel isotopic composition of ancient seawater from carbonates

Reconstructing the ancient marine cycle of Ni, a trace metal in the oceans essential to enzymes regulating the C, N, and O cycles, would inform how Ni bioavailability shaped early life. The Ni isotopic composition of seawater (δ 60 Ni SW ) through time could provide insight, but this approach requires sedimentary archives that faithfully record δ 60 Ni SW . Carbonates are an often-used record of seawater chemistry, but contaminants could bias the measured δ 60 Ni of bulk sediment. To isolate the true carbonate-bound δ 60 Ni signal, we optimized a chemical cleaning protocol designed to minimize non‑carbonate Ni contributions and maximize carbonate recovery. We analyzed ODP Site 1007 sediments and evaluated oxidative and reductive pre-cleaning steps and carbonate dissolution protocols. Our results show that only reductive cleaning significantly altered the subsequent carbonate leachate composition, lowering Ni/Ca ratios by up to 60% and δ 60 Ni values by as much as 0.4 ‰. In contrast, δ 60 Ni values were largely insensitive to premature carbonate dissolution during pre-cleaning or to partial leaching of silicates during carbonate dissolution, even at higher acid molarities or longer reaction times. We recommend an evidence-based protocol that removes hydro-soluble salts and clays, applies reductive cleaning and oxidative cleaning for certain sample compositions, and dissolves carbonate using 0.5 M acetic acid, adjusted to pH 5. Using these results, we infer a ∼ 0.9 ‰ Ni isotopic fractionation between chemically cleaned deep-water carbonates (+0.4 ± 0.1 ‰) and deep seawater. This method development is a key step toward accurately reconstructing ancient marine Ni cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural and energetic consequences of mutations in a solvated hydrophobic cavity

The structural and energetic consequences of modifications to the hydrophobic cavity of interleukin 1-beta (IL-1beta) are described. Previous reports demonstrated that the entirely hydrophobic cavity of IL-1beta contains positionally disordered water. To gain a better understanding of the nature of this cavity and the water therein, a number of mutant proteins were constructed by site-directed mutagenesis, designed to result in altered hydrophobicity of the cavity. These mutations involve the replacement of specific phenylalanine residues, which circumscribe the cavity, with tyrosine, tryptophan, leucine and isoleucine. Using differential scanning calorimetry to determine the relative stabilities of the wild-type and mutant proteins, we found all of the mutants to be destabilizing. X-ray crystallography was used to identify the structural consequences of the mutations. No clear correlation between the hydrophobicities of the specific side-chains introduced and the resulting stabilities was found.

Solvents/chemistry↗

Physiological responses in potato plants under continuous irradiation

The physiological responses of four potato (Solanum tuberosum L.) cultivars to continuous irradiation were determined in a controlled environment. Under a constant 18C and a constant photoperiod of 470 micromoles s-1 m-2 of photosynthetic photon flux, 'Denali' and 'Haig' grew well and produced large plant and tuber dry weights when harvested 56 days after transplanting. 'Kennebec' and 'Superior' were severely stunted, producing only 10% of the plant dry matter produced by 'Denali' and 'Haig'. The differences in leaf chlorophyll concentration and stomatal conductance were not consistent between these two groups of cultivars. The leaf net CO2 assimilation rates in 'Kennebec' and 'Superior' were lower, and intercellular CO2 partial pressures were higher than in 'Denali' and 'Haig'. These results indicate that inhibition of net CO2 assimilation in 'Kennebec' and 'Superior' was not due to a limiting amount of chlorophyll or to CO2 in the leaf tissues. Concentrations of starch in leaflets of 'Kennebec' and 'Superior' plants were only 10% of those in 'Denali' and 'Haig' plants, although soluble sugar concentrations were similar in the four cultivars. Therefore, the lower net CO2 assimilation rates in stunted 'Kennebec' and 'Superior' plants were not associated with an excess carbohydrate accumulation in the leaves.

NASA Program CELSS↗