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At least 19 records

Acetate concentrations and oxidation in salt marsh sediments

Acetate concentrations and rates of acetate oxidation and sulfate reduction were measured in S. alterniflora sediments in New Hampshire and Massachusetts. Pore water extracted from cores by squeezing or centrifugation contained in greater than 0.1 mM acetate and, in some instances, greater than 1.0 mM. Pore water sampled nondestructively contained much less acetate, often less than 0.01 mM. Acetate was associated with roots, and concentrations varied with changes in plant physiology. Acetate turnover was very low whether whole core or slurry incubations were used. Radiotracers injected directly into soils yielded rates of sulfate reduction and acetate oxidation not significantly different from core incubation techniques. Regardless of incubation method, acetate oxidation did not account for a substantial percentage of sulfate reduction. These results differ markedly from data for unvegetated coastal sediments where acetate levels are low, oxidation rate constants are high, and acetate oxication rates greatly exceed rates of sulfate reduction. The discrepancy between rates of acetate oxidation and sulfate reduction in these marsh soils may be due either to the utilization of substrates other than acetate by sulfate reducers or artifacts associated with measurements of organic utilization by rhizosphere bacteria. Care must be taken when interpreting data from salt marsh sediments since the release of material from roots during coring may affect the concentrations of certain compounds as well as influencing results obtained when sediment incubations are employed.

Source record↗

Elevated acetate concentrations in the rhizosphere of Spartina alterniflora and potential influences on sulfate reduction

Acetate is important in anaerobic metabolism of non-vegetated sediments but its role in salt marsh soils was not investigated thoroughly. Acetate concentrations, oxidation (C-14) and SO4(2-) reduction (S-35) were measured in S. alterniflora soils in NH and MA. Pore water from cores contained greater than 0.1 mM acetate and in some instances greater than 1.0 mM. Non-destructive samples contained less than 0.01 mM. Acetate was associated with roots and concentrations were highest during vegetative growth and varied with changes in plant physiology. Acetate turnover was very low whether whole core or slurry incubations were used. Radiotracers injected directly into soils yielded rates of SO4(2-) reduction and acetate oxidation not significantly different from core incubation techniques. Regardless of incubation method, acetate oxidation did not account for a significant percentage of SO4(2-) reduction. These results differ markedly from data for non-vegetated coastal sediments where acetate levels are low, oxidation rate constants are high and acetate oxidation rates greatly exceed rates of SO4(2-) reduction. The discrepancy between rates of acetate oxidation and SO4(2-) reduction in marsh soils may be due either to the utilization of substrates other than acetate by SO4(2-) reducers or artifacts associated with measurements of organic utilization by rhizosphere bacteria.

Hines, Mark E.↗

The Effects of Acetate Buffer Concentration on Lysozyme Solubility

The micro-solubility column technique was employed to systematically investigate the effects of buffer concentration on tetragonal lysozyme solubility. While keeping the NaCl concentrations constant at 2%, 3%, 4%, 5% and 7%, and the pH at 4.0, we have studied the solubility of tetragonal lysozyme over an acetate buffer concentration range of 0.01M to 0.5M as a function of temperature. The lysozyme solubility decreased with increasing acetate concentration from 0.01M to 0.1M. This decrease may simply be due to the net increase in solvent ionic strength. Increasing the acetate concentration beyond 0.1M resulted in an increase in the lysozyme solubility, which reached a peak at - 0.3M acetate concentration. This increase was believed to be due to the increased binding of acetate to the anionic binding sites of lysozyme, preventing their occupation by chloride. In keeping with the previously observed reversal of the Hoffmeister series for effectiveness of anions in crystallizing lysozyme, acetate would be a less effective precipitant than chloride. Further increasing the acetate concentration beyond 0.3M resulted in a subsequent gradual decrease in the lysozyme solubility at all NaCl concentrations.

Forsythe, Elizabeth L.↗

Kinetics of copper ion absorption by cross-linked calcium polyacrylate membranes

The absorption of copper ions from aqueous copper acetate solutions by cross-linked calcium acrylate membranes was found to obey parabolic kinetics similar to that found for oxidation of metals that form protective oxide layers. For pure calcium polyacrylate membranes the rate constant was essentially independent of copper acetate concentration and film thickness. For a cross-linked copolymer film of polyvinyl alcohol and calcium polyacrylate, the rate constant was much greater and dependent on the concentration of copper acetate. The proposed mechanism in each case involves the formation of a copper polyacrylate phase on the surface of the membrane. The diffusion of the copper ion through this phase appears to be the rate controlling step for the copolymer film. The diffusion of the calcium ion is apparently the rate controlling step for the calcium polyacrylate. At low pH, the copper polyacrylate phase consists of the normal copper salt; at higher pH, the phase appears to be the basic copper salt.

Philipp, W. H.↗

Factors that control the stable carbon isotopic composition of methane produced in an anoxic marine sediment

The carbon isotopic composition of methane produced in anoxic marine sediment is controlled by four factors: (1) the pathway of methane formation, (2) the isotopic composition of the methanogenic precursors, (3) the isotope fractionation factors for methane production, and (4) the isotope fractionation associated with methane oxidation. The importance of each factor was evaluated by monitoring stable carbon isotope ratios in methane produced by a sediment microcosm. Methane did not accumulate during the initial 42-day period when sediment contained sulfate, indicating little methane production from 'noncompetitive' substrates. Following sulfate depletion, methane accumulation proceeded in three distinct phases. First, CO2 reduction was the dominant methanogenic pathway and the isotopic composition of the methane produced ranged from -80 to -94 per thousand. The acetate concentration increased during this phase, suggesting that acetoclastic methanogenic bacteria were unable to keep pace with acetate production. Second, acetate fermentation became the dominant methanogenic pathway as bacteria responded to elevated acetate concentrations. The methane produced during this phase was progressively enriched in C-13, reaching a maximum delta(C-13) value of -42 per thousand. Third, the acetate pool experienced a precipitous decline from greater than 5 mM to less than 20 micro-M and methane production was again dominated by CO2 reduction. The delta(C-13) of methane produced during this final phase ranged from -46 to -58 per thousand. Methane oxidation concurrent with methane production was detected throughout the period of methane accumulation, at rates equivalent to 1 to 8 percent of the gross methane production rate. Thus methane oxidation was too slow to have significantly modified the isotopic signature of methane. A comparison of microcosm and field data suggests that similar microbial interactions may control seasonal variability in the isotopic composition of methane emitted from undisturbed Cape Lookout Bight sediment.

Alperin, M. J.↗

A Study of Direct and Cloud-Mediated Radiative Forcing of Climate Due to Aerosols

The Intergovernmental Panel on Climate Change (IPCC) has reported that in the southeastern US and eastern China, the general greenhouse warming due to anthropogenic gaseous emissions is dominated by the cooling effect of anthropogenic aerosols. To verify this model prediction in eastern China and southeastern US, we analyzed regional patterns of climate changes at 72 stations in eastern China during 1951- 94 (44 years), and at 52 stations in the southeastern US during 1949-94 (46 years) to detect the fingerprint of aerosol radiative forcing. It was found that the mean rates of change of annual mean daily, maximum, minimum temperatures and diurnal temperature range (DTR) in eastern China were 0.8, -0.2, 1.8, and -2.0 C/100 years respectively, while the mean rates of change of annual mean daily, maximum, minimum temperatures and DTR in the southeastern US were -0.2, -0.6, 0.2, and -0.8 C/100 years, respectively. This indicates that the high rate of increase in annual mean minimum temperature in eastern China results in a slightly warming trend of daily temperature, while the high rate of decrease in annual mean maximum temperature and low rate of increase in annual mean minimum temperature lead to the cooling trend of daily temperature in the southeastern US. We found that the warming from the longwave forcing due to both greenhouse gases and aerosols was completely counteracted by the shortwave aerosol forcing in the southeastern US in the past 46 years. A slightly overall warming trend in eastern China is evident; winters have become milder. This finding is explained by hypothesizing that increasing energy usage during the past 44 years has resulted in more coal and biomass burning, thus increasing the emission of absorbing soot and organic aerosols in eastern China. Such emissions, in addition to well-known Asia dust and greenhouse gases, may be responsible for the winter warming trend in eastern China that we have reported here. The sensitivity of aerosol radiative properties to aerosol composition, size distribution, relative humidity (RH) is examined for the following aerosol systems: inorganic and organic ions (Cl-, Br-, NO3 -, SO4 2-, Na+, NH4 +, K+, Ca2+, Mg2+, HCOO-, CH3COO-, CH3CH2COO-, CH3COCOO-, OOCCOO2-, MSA-1); water-insoluble inorganic and organic compounds (elemental carbon, n-alkanes, SiO2, Al2O3, Fe2O3 and other organic compounds). The partial molar refraction method was used to calculate the real part of the refractive index. It was found that the asymmetry factor increased by approximately 48% with the real part varying from 1.40 to 1.65, and the single scattering albedo decreased by 24% with the imaginary part varying from -0.005 to -0.1. The asymmetry factor increased by 5.4 times with the geometric standard deviation varying from 1.2 to 3.0. The radiation transmission is very sensitive to the change in size distribution; other factors are not as significant. To determine the aerosol direct radiative forcing (ADRF), the aerosol optical depth (AOD) values at the three operational wavelengths (415, 500 and 673 nm) were determined at a regionally representative site, namely, Mt. Gibbs (35.78 deg N, 82.29 deg W, elevation 2006 m) in Mt. Mitchell State Park, NC, and a site located in an adjacent valley (Black Mountain, 35.66 deg N, 82.38 deg W, elevation 951 m) in the southeastern US. The two sites are separated horizontally by 10 km and vertically by 1 km. It was found that the representative total AOD values at 500 nm at the valley site for highly polluted (HP), marine (M) and continental (C) air masses were 0.68 +/- 0.33, 0.29 +/- 0.19 and 0.10 +/- 0.04, respectively. A search-graph method was used to retrieve the columnar size distribution (number concentration N, effective radius reff and geometric standard deviation=?g) from the optical depth observations at three operational wavelengths. The ground albedo, single scattering albedo and imaginary part of the refractive index were calculated using a mathematically unique procedure involving a Mie code and a radiative transfer code in conjunction with the retrieved aerosol size distribution, AOD, and diffuse-direct irradiance ratio. It was found that N, r(eff) and sigma(g) were in the ranges of 10 to 1.7 x 10(exp 4)/cubic cm, 0.09 to 0.68 micrometers and 1.12 to 2.95, respectively. The asymmetry factor and single scattering albedo were in the ranges of 0.63 to 0.75 and 0.74 to 0.97 respectively. The ground albedo for the forested terrain and imaginary part of refractive index were found to be in the ranges of 0.06 to 0.29 and 0.005 to 0.051 respectively. On the basis of these aerosol radiative properties obtained at the research sites and computations using the Column Radiation Model (CRM) of National Center of Atmospheric Research (NCAR) Community Climate Model (CCM3), it was found that the average cloud-free 24-hour ADRF values were -13 +/- 8, -8 +/- 3, -33 +/- 16 W/square m for marine, continental, and polluted air masses, respectively. On the assumption that the fractional coverage of clouds is 0.61, it was estimated that the annual mean ADRF was 7 +/- 2 W/square m in the southeastern US. The review with respect to the current knowledge of organic acids shows that aerosol formate and acetate concentrations range from 0.02 to 5.3 nmol/cubic m and from 0.03 to 12.4 nmol/cubic m respectively, and that between 34% to 77% of formate and between 21% to 66% of acetate are present in the fine fraction of aerosols. It was found that although most (98-99%) of these volatile organic acids were present in the gas phase, their concentrations in the aerosol particles were sufficient to make them a good candidate for cloud condensation nuclei (CCN). It is hypothesized that organic acids are at least one of the primary sources of CCN in the atmosphere due to their ubiquitous presence in the troposphere, especially over the continental forested areas. The results of our measurements at Palmer Station, Antarctica show that the daily average CCN concentrations at 0.3% and 1% supersaturations ranged from 0.3 to 160/cubic cm and from 4 to 168/cubic cm, respectively, during the period from 17 January to 26 February, 1994. New evidence for substantial and definitive CCN enhancement near and within cloud has been observed at Mt. Mitchell, North Carolina. The results show that the average monthly CCN concentrations were 460 +/- 217, 386 +/- 286, 429 +/- 228 and 238 +/- 134/cubic cm for in-cloud, overcast, clear and rainy conditions, respectively. The typical CCN spectra show that there were a lot of small CCN produced and the ion concentrations (especially H+ and SO4 2-) were very high during the CCN enhancement period. The significantly positive correlation between black carbon (BC) and CCN at 1% supersaturation indicates that a percentage of the BC measured at the site may be in the form of an internal mixture and participated in the formation of CCN.

Yu, Shao-Cai↗

Spaceflight Maximum Allowable Concentrations for Ethyl Acetate

Ethyl acetate is a simple organic compound that occurs naturally and is used industrially as a solvent. It has been detected in the ISS atmosphere and is known to off-gas from building materials. As NASA astronauts have been and will be exposed to ethyl acetate during space missions, Spaceflight Maximum Allowable Concentrations (SMACs) were developed following an extensive review of the available literature.

E Spencer Williams↗

An intercomparison of measurement systems for vapor and particulate phase concentrations of formic and acetic acids

During June 1986, eight systems for measuring vapor phase and four for measuring particulate phase concentrations of formic acid (HCOOH) and acetic acid (CH3COOH) were intercompared in central Virginia. HCOOH and CH3COOH vapors were sampled by condensate, mist, Chromosorb 103 GC resin, NaOH-coated annular denuders, NaOH-impregnated quartz filters, K2CO3 and NaCO3-impregnated cellulose filters, and Nylasorb membranes. Atmospheric aerosol was collected on Teflon and Nuclepore filters using both hi-vol and lo-vol systems to measure particulate phase concentrations. Performances of the mist chamber and K2CO3-impregnated filter techniques were evaluated using zero air and ambient air spiked with HCOOH(g) and CH3COOH(g), and formaldehyde from permeation sources. The advantages and drawbacks of these methods are reported and discussed.

Keene, William C.↗

Supporting technology for the development of Controlled Ecological Life Support Systems (CELSS)

To support the development of Controlled Ecological Life Support Systems (CELSS) in the space program, a metabolic simulator has been selected for use in a closed chamber to test functions of the CELSS. This metabolic simulator is a catalytic reactor which oxidizes the methyl acetate to produce carbon dioxide and water vapor. In this project, kinetic studies of catalytic oxidation of methyl acetate were conducted using monolithic and pellet catalysts with 0.5% (by weight) platinum (Pt) on aluminum oxide (Al2O3). The reaction was studied at a pressure of one atmosphere and at temperatures varying from 160 C to 420 C. By-products were identified at the exit of the preheater and reactor. For the kinetic study with the monolithic catalyst, a linear regression method was used to correlate the kinetic data with zero-order, first-order and Langmuir-Hinshelwood models. Results indicate that the first-order model represents the data adequately at low concentrations of methyl acetate. For higher concentrations of methyl acetate, the Langmuir-Hinshelwood model best represents the kinetic data. Both rate constant and adsorption equilibrium constants were estimated from the regression. A Taguchi orthogonal array (L(sub 9)) was used to investigate the effects of temperature, flow rate, and concentration on the catalytic oxidation of methyl acetate. For the monolithic catalyst, temperature exerts the most significant effect, followed by concentration of methyl acetate. For the pellet catalyst, reaction temperature is the most significant factor, followed by gas flow rate and methyl acetate concentration. Concentrations of either carbon dioxide or oxygen were seen to have insignificant effect on the methyl acetate conversion process. Experimental results indicate that the preheater with glass beads can accomplish thermal cracking and catalytic reaction of methyl acetate to produce acetic acid, methanol, methyl formate, and 1-propanol. The concentration of all by-products was measured in ppmv (parts per million by volume). At higher temperatures, greater amounts of these products are produced, as expected. In all cases, methanol was the predominant concentration detected, followed by methyl formate. At temperatures lower than 320 C for the P-type monolithic catalyst, methanol, acetic acid, and acetone were detected, whereas, for the E-type monolithic catalyst, only methanol was detected at 160 C. Both P and E types of the monolithic catalyst were specified with the same substrates (ceramic), washcoat (Al2O3), and promoter (Pt). However, the manufacturing and treatment procedures were quite different. It was therefore concluded that the performance of the E-type monolithic catalyst is superior to that of the P-type for oxidation of methyl acetate. At higher reaction temperatures, e.g., above 420 C, all reactants and byproducts were completely oxidized using these two types of monolithic catalyst to produce carbon dioxide and water vapor. A complex heterogenous catalytic reaction mechanism was proposed to explain the formation of the byproducts (methanol, acetic acid, and methyl formate) as the methyl acetate traveled through the preheater packed with glass beads. The by-product, 1-propanol, may be formed only through a homogeneous reaction, since it is difficult to develop a reasonable sequence of heterogeneous reaction steps to explain its formation. The homogeneous thermal decomposition of methyl acetate to form free radicals was proposed to explain the formation of 1-propanol, and also methanol, in the preheater. A dual-site catalytic reaction mechanism was proposed for the oxidation of methyl acetate over Pt/Al2O3 monolithic catalyst. The dual-site mechanism describes the chemisorption of oxygen molecules as well as a physical adsorption of methyl acetate on the active sites. On the active sites, methyl acetate is oxidized rapidly to form carbon dioxide and water vapor. A rate equation derived from this mechanism gives the Langmuir-Hinshelwood rate formula which has been observed from the experimental data obtained in this project for high methyl acetate concentration (greater than 1000 ppmv) over a monolithic catalyst. If the oxygen concentration is very high and methyl acetate concentration is very low, the reaction rate equation is then reduced to a first-order with respect to methyl acetate concentration. The first-order model has also been observed from the experimental data obtained in this project for low methyl acetate concentration (less than 1000 ppmv).

Li, Ku-Yen↗

Formic and acetic acid over the central Amazon region, Brazil. I - Dry season

The concentrations of formic and acetic acids in the gas phase, atmospheric aerosol, and rainwater samples collected in Amazonia at ground level and in the atmosphere during the Amazon Boundary Layer Experiment in July/August 1985 were analyzed by ion exchange chromatography. The diurnal behavior of both acids at ground level and their vertical distribution in the forest canopy point to the existence of vegetative sources as well as to production by chemical reactions in the atmosphere. The concentrations of formic and acetic acids in the gas phase were about 2 orders of magnitude higher than the corresponding concentrations in the atmospheric aerosol. In rainwater, the total formate and acetate represented about one half of the anion equivalents, in contrast to less than 10 percent of the soluble anionic equivalents contributed by these acids in the atmospheric aerosol. The observed levels of these ions in rainwater are considered to be the result of a combination of chemical reactions in hydrometeors and the scavenging of the gaseous acids by cloud droplets.

Andreae, M. O.↗

Rainfall and surface kinematic conditions over central amazonia during ABLE 2B

Rainfall, rainfall systems, and surface kinematics of the central Amazon basin wet season are investigated using meteorological and chemical data collected during the wet season Amazon Boundary Layer Experiment (ABLE) near Manaus, Brazil. Through analysis of (GOES-West) imagery, it is determined that, based on location of the initial development, there are three main types of convective systems which influence a mesoscale network near Manaus, namely the Coastal Occurring Systems (COS), the Basin Occurring Systems (BOS), and the Locally Occurring Systems (LOS). Chemical analysis of rainwater delivered by these systems shows significant differences in concentrations of formate, acetate, pyruvate, sulfate, and hydrogen ion, and measurements of aerosol concentrations near Manaus show large influxes of aerosols into central Amazonia after passage of BOS and COS. Results of satellite based classification of the rain-producing systems are discussed.

Greco, Steven↗

Atmospheric geochemistry of formic and acetic acids at a mid-latitude temperate site

Tropospheric concentrations of formic and acetic acids in the gas, the aerosol, and the rainwater phases were determined in samples collected 1-2 m above ground level at an open field site in eastern Virginia. These acids were found to occur principally (98 percent or above) in the gas phase, with a marked annual seasonality, averaging 1890 ppt for formate and 1310 ppt for acetate during the growing season, as compared to 695 ppt and 700 ppt, respectively, over the nongrowing season. The data support the hypothesis that biogenic emissions from vegatation are important sources of atmospheric formic and acetic acid during the local growing season. The same time trends were observed for precipitation, although with less defined seasonality. The relative increase of the acetic acid/formic acid ratio during the nongrowing season points to the dominance of anthropogenic inputs of acetic acid from motor vehicles and biomass combustion in the wintertime.

Talbot, R. W.↗

Molecular Distribution, 13C-Isotope, and Enantiomeric Compositions of Carbonaceous Chondrite Monocarboxylic Acids

The water-soluble organic compounds in carbonaceous chondrite meteorites constitute a record of the synthetic reactions occurring at the birth of the solar system and those taking place during parent body alteration and may have been important for the later origins and development of life on Earth. In this present work, we have developed a novel methodology for the simultaneous analysis of the molecular distribution, compound-specific (delta)(exp 13)C, and enantiomeric compositions of aliphatic monocarboxylic acids (MCA) extracted from the hot-water extracts of 16 carbonaceous chondrites from CM, CR, CO, CV, and CK groups. We observed high concentrations of meteoritic MCAs, with total carbon weight percentages which in some cases approached those of carbonates and insoluble organic matter. Moreover, we found that the concentration of MCAs in CR chondrites is higher than in the other meteorite groups, with acetic acid exhibiting the highest concentration in all samples. The abundance of MCAs decreased with increasing molecular weight and with increasing aqueous and/or thermal alteration experienced by the meteorite sample. The (delta)(exp 13)C isotopic values of MCAs ranged from 52 to +27(0/00), and aside from an inverse relationship between (delta)(exp 13)C value and carbon straight-chain length for C3–C6 MCAs in Murchison, the 13C-isotopic values did not correlate with the number of carbon atoms per molecule. We also observed racemic compositions of 2-methylbutanoic acid in CM and CR chondrites. We used this novel analytical protocol and collective data to shed new light on the prebiotic origins of chondritic MCAs.

Aponte, Jose C.↗

Microgravity Compatible Reagentless Instrumentation for Detection of Dissolved Organic Acids and Alcohols in Potable Water

The Organic Acid and Alcohol Monitor (OAAM) program has resulted in the successful development of a computer controlled prototype analyzer capable of accurately determining aqueous organic acids and primary alcohol concentrations over a large dynamic range with high sensitivity. Formic, acetic, and propionic acid were accurately determined at concentrations as low as 5 to 10 micrograms/L in under 20 minutes, or as high as 10 to 20 mg/L in under 30 minutes. Methanol, ethanol, and propanol were determined at concentrations as low as 20 to 100 micrograms/L, or as high as 10 mg/L in under 30 minutes. Importantly for space based application, the OAAM requires no reagents or hazardous chemicals to perform these analyses needing only power, water, and CO2 free purge gas. The OAAM utilized two membrane processes to segregate organic acids from interfering ions. The organic acid concentration was then determined based upon the conductiometric signal. Separation of individual organic acids was accomplished using a chromatographic column. Alcohols are determined in a similar manner after conversion to organic acids by sequential biocatalytic and catalytic oxidation steps. The OAAM was designed to allow the early diagnosis of under performing or failing sub-systems within the Water Recovery System (WRS) baselined for the International Space Station (ISS). To achieve this goal, several new technologies were developed over the course of the OAAM program.

Akse, James R.↗

Manufacturing Ethyl Acetate From Fermentation Ethanol

Conceptual process uses dilute product of fermentation instead of concentrated ethanol. Low-concentration ethanol, extracted by vacuum from fermentation tank, and acetic acid constitutes feedstock for catalytic reaction. Product of reaction goes through steps that increases ethyl acetate content to 93 percent by weight. To conserve energy, heat exchangers recycle waste heat to preheat process streams at various points.

Rohatgi, Naresh K.↗

A Modified LC/MS/MS Method with Enhanced Sensitivity for the Determination of Scopolamine in Human Plasma

Intranasal scopolamine is a choice drug for the treatment of motion sickness during space flight because of its quick onset of action, short half-life and favorable sideeffects profile. The dose administered usually ranges between 0.1 and 0.4 mg. Such small doses make it difficult to detect concentrations of scopolamine in biological fluids using existing sensitive LC/MS/MS method, especially when the biological sample volumes are limited. To measure scopolamine in human plasma to facilitate pharmacokinetic evaluation of the drug, we developed a sensitive LC/MS/MS method using 96 well micro elution plates for solid phase extraction (SPE) of scopolamine in human plasma. Human plasma (100-250 micro L) were loaded onto Waters Oasis HLB 96 well micro elution plate and eluted with 50 L of organic solvent without evaporation and reconstitution. HPLC separation of the eluted sample was performed using an Agilent Zorbax SB-CN column (50 x 2.1 mm) at a flow rate of 0.2 mL/min for 3 minutes. The mobile phase for separation was 80:20 (v/v) methanol: ammonium acetate (30 mM) in water. Concentrations of scopolamine were determined using a Micromass Quattro Micro(TM) mass spectrometer with electrospray ionization (ESI). ESI mass spectra were acquired in positive ion mode with multiple reaction monitoring for the determination of scopolamine m/z = 304.2 right arrow 138.1 and internal standard hyoscyamine m/z = 290.2 right arrow 124.1. The method is rapid, reproducible, specific and has the following parameters: scopolamine and the IS are eluted at about 1.1 and 1.7 min respectively. The linear range is 25-10000 pg/mL for scopolamine in human plasma with correlation coefficients greater than 0.99 and CV less than 0.5%. The intra-day and inter-day CVs are less than 15% for quality control samples with concentrations of 75,300, and 750 pg/mL of scopolamine in human plasma. SPE using 96 well micro elution plates allows rapid sample preparation and enhanced sensitivity for the LC/MS/MS determination of scopolamine in a small volume of biological samples. The new method is also cost effective since it uses a small volume of organic solvents compared to the methods using SPE cartridges or regular 96 well SPE plates. This method can be successfully used for bioavailability and pharmacokinetic evaluations of scopolamine, especially when volumes of biological samples are limited. Further investigation to use automated SPE system with 96 well micro elution plates is planned.

Wang, Zuwei↗

Development of a Photoacoustic Formaldehyde Monitor

Key indoor air quality pollutant formaldehyde (H2CO) is tracked on International Space Station (ISS) using passive badges returned to the ground periodically for analysis. The process is time-consuming both in preparation and for analysis upon return 6-12 months later. Badges also require precious crew time for deploy, retrieval and stow. As NASA’s focus in space exploration shifts to the Moon and Mars, archival sample return becomes increasingly impractical, so the aim of this project is to develop a highly reliable real-time analyzer for H2CO at low concentrations with data downlinked. Potential sources of H2CO include materials off gassing, use of formalin as a tissue fixative in biological payloads and overheating of acetal polymers. The Spacecraft Maximum Allowable Concentration (SMAC) for H2CO is 100 ppb for exposures of 7 days or longer. ISS concentrations recently run only 10 - 30 ppb but have spiked as high as 60 ppb in the past. Gateway real time monitoring requirements call for a range of 8 - 140 ppb. For this project, a concentration range of 5 - 500 ppb H2CO is targeted. The core tunable diode laser spectroscopy (TDLS) technology was developed by Vista Photonics through the NASA and US Navy Small Business Innovation Research (SBIR) programs. Monitors based on this technology have been demonstrated on ISS, trialed on a nuclear submarine and are in production as Anomaly Gas Analyzers for both ISS and Orion. Initially, direct absorption TDLS was used exclusively in these monitors, however, the H2CO target concentration is much lower, and a longer wavelength required, so a photoacoustic spectroscopy (PAS) technique was adapted, where the laser excitation is detected by a sensitive microphone vs. a conventional photodetector. This paper will discuss the results of NASA-JSC laboratory testing of a prototype PAS based formaldehyde monitor and explore potential adaptations for Gateway missions and beyond.

Paul D Mudgett↗

Development of a Photoacoustic Formaldehyde Monitor

Key indoor air quality pollutant formaldehyde (H 2 CO) is tracked on International Space Station (ISS) using passive badges returned to the ground periodically for analysis. The process is time-consuming both in preparation and for analysis upon return 6-12 months later. Badges also require precious crew time for deploy, retrieval and stow. As NASA’s focus in space exploration shifts to the Moon and Mars, archival sample return becomes increasingly impractical, so the aim of this project is to develop a highly reliable real-time analyzer for H 2 CO at low concentrations with data downlinked. Potential sources of H 2 CO include materials off gassing, use of formalin as a tissue fixative in biological payloads and overheating of acetal polymers. The Spacecraft Maximum Allowable Concentration (SMAC) for H 2 CO in air is 100 ppb for exposures of 7 days or longer. ISS concentrations of H 2 CO are running only 10 - 30 ppb in the recent several years but have spiked as high as 60 ppb. Gateway real time monitoring requirements for H 2 CO call for a range of 8 - 138 ppb. For this project, a concentration range of 5 - 500 ppb H 2 CO is targeted. The core tunable diode laser spectroscopy (TDLS) technology used for this project was developed by Vista Photonics through the NASA and US Navy Small Business Innovation Research (SBIR) programs. Monitors based on TDLS have been demonstrated on ISS, trialed on a nuclear submarine and are being certified as portable Anomaly Gas Analyzers (AGA) for both ISS and Orion. Initially, direct absorption TDLS was used exclusively in these devices. The H 2 CO target concentration, however, is low ppb, and a longer wavelength is required, so a photoacoustic spectroscopy (PAS) technique was adapted, where the laser excitation is detected by a sensitive microphone vs. a conventional photodetector. This paper will discuss the results of NASA-JSC laboratory testing of a prototype PAS based formaldehyde in air monitor and briefly discuss next steps.

Photoacoustic Formaldehyde Monitor↗