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At least 127 records · Page 7

Recent developments in water quality monitoring for Space Station reclaimed wastewaters

This paper discusses the recent developments in water quality monitoring for Space Station reclaimed wastewaters. A preprototype unit that contains an ultraviolet absorbance organic carbon monitor integrated with pH and conductivity sensors is presented. The preprototype has provisions for automated operation and is a reagentless flow-through system without any gas/liquid interfaces. The organic carbon monitor detects by utraviolet absorbance the organic impurities in reclaimed wastewater which may be correlated to the organic carbon content of the water. A comparison of the preprototype organic carbon detection values with actual total organic carbon measurements is presented. The electrolyte double junction concept for the pH sensor and fixed electrodes for both the pH and conductivity sensors are discussed. In addition, the development of a reagentless organic carbon analyzer that incorporates ultraviolet oxidation and infrared detection is presented. Detection sensitivities, hardware development, and operation are included.

Small, John W.↗

Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

Visscher, P. T.↗

Effect of Anoxic Iron Corrosion on WIPP Brine Geochemistry FY23 Final Report (U)

A 280-day study was completed to evaluate the effect of zero-valent iron (Fe 0 ) on the Waste Isolation Pilot Plant (WIPP) brine geochemistry under anticipated reducing conditions. Hydrogen (H 2 ) gas is expected to be present in the repository after closure due to the anoxic corrosion of a vast quantity of iron contained in the waste forms disposed at WIPP; therefore, a background argon atmosphere containing H 2 was chosen for this study. WIPP groundwater brine pH and E h will impact the mobility and fate of plutonium within the repository. Modeling and laboratory results for Castile WIPP brine indicate that equilibrium E h values relative to the standard hydrogen electrode (SHE) are 40 mV more reducing (i.e., more negative) than those for Salado WIPP brine (-480 mV vs. -440 mV, respectively) because of the higher pH of the Castile brine (pH 9.3 for Castile vs. pH 8.8 for Salado). The E h and pH data were corrected for the effects of high ionic strength. The experimental results for both brines are consistent with thermodynamic predictions using OLI Systems' Mixed Solvent Electrolyte chemical equilibrium model. The measured and corrected pH and E h data from this study are provided in Table ES-1 and Table ES-2, respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mathematical model for steady state, simple ampholyte isoelectric focusing: Development, computer simulation and implementation

The elimination of Ampholine from the system by establishing the pH gradient with simple ampholytes is proposed. A mathematical model was exercised at the level of the two-component system by using values for mobilities, diffusion coefficients, and dissociation constants representative of glutamic acid and histidine. The constants assumed in the calculations are reported. The predictions of the model and computer simulation of isoelectric focusing experiments are in direct importance to obtain Ampholine-free, stable pH gradients.

Palusinski, O. A.↗

Solidification of SRPPF Aqueous Recovery Liquid: Process Disruptions

Savannah River National Laboratory has identified a magnesium oxysulfate grout formulation to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). The formulation uses reactive, light burnt MgO, anhydrous MgSO 4 , and dead burnt MgO and provides good mixability, similar density to the original Portland Cement-based mix, and a leachate pH of 9.39, within the assumed Waste Isolation Pilot Plant (WIPP) brine pH range. The formulation will solidify the effluent using a solid first, lost paddle design, within a 55-gallon drum. A series of seven different process disruptions, or irregular processing during the expected ARS liquid effluent solidification process, were completed to assess the severity of the impact of the process disruption and how the formulation behaves under these conditions. Seven process disruptions were investigated including: No Mixing, Partial Mixing, Compacted/Stratified, Sealed, Overfilled, Underfilled, and Undermixed. The impact on solidification, leachate pH, Er (a Pu/Am surrogate) distribution, and density of the resulting grout were established. Overall, four of the process disruptions, No Mixing, Partial Mixing, Compacted/Stratified, and Overfilled, resulted in basic, unabsorbed liquid that would require additional solidification to be acceptable for WIPP. Most solids generated in this testing met the expected WIPP leachate pH requirements. Solids from the Compacted/Stratified process disruption test, however, produced a leachate pH slightly above the assumed range in the WIPP performance assessment. The distribution of Er for most of the tests was relatively consistent. The No Mixing process disruption test, however, resulted in non-homogeneous Er distribution, indicating that radioactive material would not be evenly distributed throughout this solid’s matrix. The Overfilled test is the only mix with a density slightly below the acceptable value. The Sealed and Overmixed tests produced a solid closest to the standard mix with no unabsorbed liquid, expected leachate pH levels, consistent Er concentrations, and expected density, indicating these process disruptions do not have a negative impact on the final grout form. Based on the other process disruptions, it is critical to have premixed dry materials and a well-defined mixing process to produce a solid, homogeneous magnesium oxysulfate cement, with no unabsorbed liquid. These process disruption tests show that the lack of adequate mixing is fundamental to creating an improperly solidified material that may require remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Design, fabrication and testing of a dual catalyst ammonia removal system for a urine VCD unit

A three-man capacity catalytic system for the recovery of water from urine was designed, constructed, and tested, it was designed to operate with feed streams containing high concentrations of urine vapor and only 5 to 7% of oxygen for the oxidation of ammonia and volatile organic vapor.It can operate either in a flow-through or a recycle mode and is capable of accepting the urine vapor produced by a vapor compression distillation evaporator. Testing consisted of short preliminary and optimization test, an endurance test of 74 hours continuous operation, and recycle tests using both air and oxygen. The system was designed for a urine processing rate of 0.86 liters/hr; however, it was tested at rates up to 1.2 liter/hr. Untreated urine evaporated by an electrically heated evaporator was used. The quality of the recovered water meets the U.S. Drinking Water Standards, with the exception of a low pH. Accumulation of solids in the urine sludge is reduced to approximately 65% of the anticipated value.

Budinikas, P.↗

Isoelectric focusing of dansylated amino acids in immobilized pH gradients

The 21 free amino acids commonly encountered in proteins have been transformed into 'carrier ampholyte' species by reacting their primary amino groups with dansyl chloride. These derivatives can thus be focused in an immobilized pH gradient covering the pH interval 3.1 to 4.1, except for arginine, which still retains a pI of 8.8. Due to their inherent fluorescence, the dansyl derivatives are revealed in UV light, with a sensitivity of the order of 2-4 ng/sq mm. All nearest neighbors are separated except for the following couples: Asn-Gln, Gly-Thr, Val-Ile and Cys-Cys2, with a resolving power, in a Delta(pI) scale, of the order of 0.0018 pH units. Except for a few cases (notably the aromatic amino acids), the order of pI values is well correlated with the pK values of carboxyl groups, suggesting that the latter are not altered by dansylation. From the set of pK(COOH)-pI values of the different amino acids, the pK of the tertiary amino group in the dansyl label has been calculated to be 5.11 + or - 0.06. Knowing the pK of the amino-dansyl and the pI of the excess, free dansyl label (pI = 3.34), a pK of 1.57 is derived for its sulfonic acid group.

Bianchi-Bosisio, Adriana↗

Fluorescence Studies of Protein Crystal Nucleation

Fluorescence can be used to study protein crystal nucleation through methods such as anisotropy, quenching, and resonance energy transfer (FRET), to follow pH and ionic strength changes, and follow events occurring at the growth interface. We have postulated, based upon a range of experimental evidence that the growth unit of tetragonal hen egg white lysozyme is an octamer. Several fluorescent derivatives of chicken egg white lysozyme have been prepared. The fluorescent probes lucifer yellow (LY), cascade blue, and 5-((2-aminoethyl)aminonapthalene-1-sulfonic acid (EDANS), have been covalently attached to ASP 101. All crystallize in the characteristic tetragonal form, indicating that the bound probes are likely laying within the active site cleft. Crystals of the LY and EDANS derivatives have been found to diffract to at least 1.7 A. A second group of derivatives is to the N-terminal amine group, and these do not crystallize as this site is part of the contact region between the adjacent 43 helix chains. However derivatives at these sites would not interfere with formation of the 43 helices in solution. Preliminary FRET studies have been carried out using N-terminal bound pyrene acetic acid (Ex 340 nm, Em 376 nm) lysozyme as a donor and LY (Ex -425 nm, Em 525 nm) labeled lysozyme as an acceptor. FRET data have been obtained at pH 4.6, 0.1 M NaAc buffer, at 5 and 7% NaCl, 4 C. The corresponding Csat values are 0.471 and 0.362 mg/ml (approximately 3.3 and approximately 2.5 x 10(exp -5) M respectively). The data at both salt concentrations show a consistent trend of decreasing fluorescence intensity of the donor species (PAA) with increasing total protein concentration. This decrease is more pronounced at 7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations reflected in the lower solubility. The calculated average distance between any two protein molecules at 5 x 10(exp -6) M is approximately 70nm, well beyond the range where any FRET can be expected. Results from these and ongoing studies will be presented.

Pusey, Marc L.↗

Energetics of muscle contraction: the whole is less than the sum of its parts

Understanding muscle energetics is a problem in optimizing supply of ATP to the demands of ATPases. The complexity of reactions and their fluxes to achieve this balance is greatly reduced by recognizing constraints imposed by the integration of common metabolites at fixed stoichiometry among modular units. ATPase is driven externally. Oxidative phosphorylation and glycogenolysis are the suppliers. We focus on their regulation which involves different controls, but reduces to two principles that enable facile experimental analysis of the supply and demand fluxes. The ratio of concentration of phosphocreatine (PCr) to ATP, not their individual values, sets the range of achievable concentrations of ADP in resting and active muscle (at fixed pH) in different cell types. This principle defines the fraction of available flux of oxidative phosphorylation utilized (at fixed enzyme activities). Then the kinetics of PCr recovery defines the kinetics of oxygen supply and substrate utilization. The second principle is the constancy of PCr and H(+) (lactate) production by glycogenolysis due to the coupling of ATPase and glycolysis. This principle enables glycogenolytic flux to be measured from intracellular proton loads. Further simplification occurs because the magnitude of the interacting fluxes and metabolite concentrations are specified within narrow limits when both the resting and active fluxes are quantified. Thus there is a small set of rules for assessing and understanding the thermodynamics and kinetics of muscle energetics.

NASA Program Biomedical Research and Countermeasur↗

Environmental Monitoring of Microbe Metabolic Transformation

Mobile system and method for monitoring environmental parameters involved in growth or metabolic transformation of algae in a liquid. Each of one or more mobile apparati, suspended or partly or wholly submerged in the liquid, includes at least first and second environmental sensors that sense and transmit distinct first and second environmental, growth or transformation parameter values, such as liquid temperature, temperature of gas adjacent to and above the exposed surface, liquid pH, liquid salinity, liquid turbidity, O.sub.2 dissolved in the liquid, CO.sub.2 contained in the liquid, oxidization and reduction potential of the liquid, nutrient concentrations in the liquid, nitrate concentration in the liquid, ammonium concentration in the liquid, bicarbonate concentration in the liquid, phosphate concentration in the liquid, light intensity at the liquid surface, electrical conductivity of the liquid, and a parameter.alpha.(alga) associated with growth stage of the alga, using PAM fluorometry or other suitable parameter measurements.

Bebout, Brad↗

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Lowery, Thomas J., Jr.↗

Ecosystem and physiological controls over methane production in northern wetlands

Peat chemistry appears to exert primary control over methane production rates in the Canadian Northern Wetlands Study (NOWES) area. We determined laboratory methane production rate potentials in anaerobic slurries of samples collected from a transect of sites through the NOWES study area. We related methane production rates to indicators of resistance to microbial decay (peat C: N and lignin: N ratios) and experimentally manipulated substrate availability for methanogenesis using ethanol (EtOH) and plant litter. We also determined responses of methane production to pH and temperature. Methane production potentials declined along the gradient of sites from high rates in the coastal fens to low rates in the interior bogs and were generally highest in surface layers. Strong relationships between CH4 production potentials and peat chemistry suggested that methanogenesis was limited by fermentation rates. Methane production at ambient pH responded strongly to substrate additions in the circumneutral fens with narrow lignin: N and C: N ratios (delta CH4/delta EtOH = 0.9-2.3 mg/g) and weakly in the acidic bogs with wide C: N and lignin: N ratios (delta CH4/delta EtOH = -0.04-0.02 mg/g). Observed Q(sub 10) values ranged from 1.7 to 4.7 and generally increased with increasing substrate availability, suggesting that fermentation rates were limiting. Titration experiments generally demonstrated inhibition of methanogenesis by low pH. Our results suggest that the low rates of methane emission observed in interior bogs during NOWES likely resulted from pH and substrate quality limitation of the fermentation step in methane production and thus reflect intrinsically low methane production potentials. Low methane emission rates observed during NOWES will likely be observed in other northern wetland regions with similar vegetation chemistry.

Valentine, David W.↗

Cytoplasmic pH influences cytoplasmic calcium in MC3T3-E1 osteoblast cells

We found that the cytoplasmic concentration of calcium (Cai) of MC3T3-E1 osteoblasts was influenced by the type of pH buffer we used in the perfusing medium, suggesting that intracellular pH (pHi) might influence Cai. To study this effect, the Cai and pHi were monitored as we applied various experimental conditions known to change pHi. Exposure to NH4Cl caused a transient increase in both pHi and Cai without a change in extracellular pH (pHo). Decreasing pHo and pHi by lowering the bicarbonate concentration of the medium decreased Cai, and increasing pHi by the removal of 5% CO2 increased Cai. Clamping pHi to known values with 10 microM nigericin, a potassium proton ionophore, also influenced Cai: acid pHi lowered Cai, whereas alkaline pHi increased it. The rise in Cai appears to be very sensitive to the extracellular concentration of calcium, suggesting the existence of a pH-sensitive calcium influx mechanism. We conclude that physiologic changes in pH could modulate Cai by controlling the influx of calcium ions and could change the time course of the Cai transient associated with hormonal activation.

NASA Program Space Biology↗

The corrosion protection of 6061-T6 aluminum by a polyurethane-sealed anodized coat

The corrosion protection of 6061-T6 anodized aluminum afforded by a newly patented polyurethane seal was studied using the ac impedance technique. Values of the average corrosion rates over a 27-day exposure period in 3.5 percent NaCl solutions at pH 5.2 and pH 9.5 compared very favorably for Lockheed-prepared polyurethane-sealed and dichromate-sealed coats of the same thickness. Average corrosion rates for both specimens over the first 7 days of exposure compared well with those for a hard anodized, dichromate-sealed coat, but rose well above those for the hard anodized coat over the entire 27-day period. This is attributed both to the greater thickness of the hard anodized coat, and possibly to its inherently better corrosion protective capability.

Danford, M. D.↗

Fluorescence Studies of Protein Crystal Nucleation

We have postulated that, in the case of tetragonal chicken egg white lysozyme, crystal growth occurs by the addition of pre-critical nuclei sized n-mers that form in the bulk solution, and that the n-mer growth units were multiples of the tetrameric 4(sub 3) helical structure. These have the strongest intermolecular bonds in the crystal and are therefore likely to be the first species formed. High resolution AFM studies provide strong supporting evidence for this model, but the data also suggest that the actual species in solution may not be identical in structure to that found in the crystal. We are using fluorescence resonance energy transfer (FRET) to study the initial solution phase self-assembly process, using covalent fluorescent derivatives which crystallize in the characteristic P4(sub 3)2(sub 1)2(sub 1) space group. FRET studies are being carried out between the cascade blue (CB-lys, donor, Ex(sub max) 366 nm, Em 420 nm) and lucifer yellow (LY-lys, acceptor, Ex(sub max) 430 nm, Em 528 nm) asp101 derivatives. The estimated R(sub 0) for this probe pair, the distance where 50% of the donor energy is transferred to the acceptor, is approx. 1.2 nm, compared to 2.2 nm between the side chain carboxyls of adjacent asp101's in the crystalline 4(sub 3) helix. The short donor lifetime of 2.80 ns (chi(sup 2) = 0.644), coupled with the large average distances between the molecules (greater than or equal to 50 nm) in solution, ensure that any energy transfer observed is not due to random diffusive interactions. Lifetime data show that CB-lys has a single lifetime when it is the only species in solution. Similarly, LY-lys also exhibits a single lifetime of 4.63 ns (chi(sup 2) = 0.42) when alone in solution. Addition of LY-lys to CB-lys results in the appearance of a third lifetime component of 0.348ns for the CB-lys. The fractional intensities of the different species present can be used to estimate the distribution of monomer and n-mers in solution. The self-association process is a function of the protein concentration relative to the saturation concentration, and observing it in dilute solution (conc. less than or equal to 10(exp -5)M) requires that the experiments be performed under low solubility conditions, i.e., low temperatures and high salt concentrations. Data from preliminary steady state FRET studies with N-terminal bound pyrene acetic acid (PAA-lys, donor, Ex 340 nm, Em 376 nm) and asp101 LY-lys as an acceptor showed a consistent trend of decreasing donor fluorescence intensity with increasing total protein concentration. The FRET data have been obtained at pH 4.6, 0.1M NaAc buffer, at 5 and 7% NaCl, 4 C. The corresponding C(sub sat) values are 0.471 and 0.362 mg/ml (approx. 3.3 and approx. 2.5 x 10(exp -5)M respectively). The donor fluorescence decrease is more pronounced at7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations as reflected in the lower solubility. Results from these and other ongoing studies will be discussed in conjunction with an emerging model for how tetragonal lysozyme crystals nucleate and the relevance of that model to other proteins.

Pusey, Marc↗

Tissue oxygen measurement system

A device and method in accordance with the invention for determining the oxygen partial pressure (PO.sub.2) of a tissue by irradiating the tissue with optical radiation such that the light is emitted from the tissue, and by collecting the reflected or transmitted light from the tissue to form an optical spectrum. A spectral processor determines the PO.sub.2 level in tissue by processing this spectrum with a previously-constructed spectral calibration model. The tissue may, for example, be disposed underneath a covering tissue, such as skin, of a patient, and the tissue illuminated and light collected through the skin. Alternatively, direct tissue illumination and collection may be effected with a hand-held or endoscopic probe. A preferred system also determines pH from the same spectrum, and the processor may determine critical conditions and issue warnings based on parameter values.

Soller, Babs R.↗

A Gamma-Ray Burst Trigger Toolkit

The detection rate of a gamma-ray burst detector can be increased by using a count rate trigger with many accumulation times DELTAt and energy bands DELTAE Because a burst's peak flux varies when averaged over different DELTAt and DELTAE the nominal sensitivity (the numerical value of the peak flux) of a trigger system is less important than how much fainter a burst could be at the detection threshold as DELTAt and DELTAE are changed. The relative sensitivity of different triggers can be quantified by referencing the detection threshold back to the peak flux for a fiducial value of DELTAt and DELTA E. This mapping between peak flux values for different sets of DELTAt and DELTAE varies from burst to burst. Quantitative estimates of the burst detection rate for a given detector and trigger system can be based on the observed rate at a measured peak flux value in this fiducial trigger. Predictions of a proposed trigger's burst detection rate depend on the assumed burst population, and these predictions can be wildly in error for triggers that differ significantly from previous missions. I base the fiducial rate on the BATSE observations: 550 bursts per sky above a peak flux of 0.3 ph per square centimeter per second averaged over DELTAt=1.024 sec and DELTAE=50-300 keV. Using a sample of 100 burst lightcurves I find that triggering on any value of DELTAt that is a multiple of 0.064 sec decreases the average threshold peak flux on the 1.024 sec timescale by a factor of 0.6. Extending DELTAE to lower energies includes the large flux of the X-ray background, increasing the background count rate. Consequently a low energy DELTAE is advantageous only for very soft bursts. Whether a large fraction of the population of bright bursts is soft is disputed; the new population of X-ray Flashes is soft but relatively faint.

Band, David L.↗