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At least 73 records · Page 4

Theoretical studies of the marine sulfur cycle

Several reduced sulfur compounds are produced by marine organisms and then enter the atmosphere, where they are oxidized and ultimately returned to the ocean or the land. The oceanic dimethyl sulfide (DMS) flux, in particular, represents a significant fraction of the annual global sulfur input to the atmosphere. In the atmosphere, this gas is converted to sulfur dioxide (SO2), methane sulfonic acid, and other organic acids which are relatively stable and about which little is known. SO2 is a short lived gas which, in turn, is converted to sulfuric acid and other sulfate compounds which contribute significantly to acid rain. Because of the complexity of the sulfur system, it is not well understood even in the unperturbed atmosphere. However, a number of new observations and experiments have led to a significant increase in the understanding of this system. A number of one dimensional model experiments were conducted on the gas phase part of the marine sulfur cycle. The results indicate the measured concentration of DMS and the amplitude of its diurnal cycle are in agreement with estimates of its global flux. It was also found that DMS can make a large contribution to the background SO2 concentration in the free troposphere. Estimates of CS2 concentrations in the atmosphere are inconsistent with estimated fluxes; however, measured reaction rates are consistent with the observed steep tropospheric gradient in CS2. Observations of CS2 are extremely sparse. Further study is planned.

Toon, Owen B.↗

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

Bluetooth Heart Rate Monitors For Spaceflight

Heart rate monitoring is required for crewmembers during exercise aboard the International Space Station (ISS) and will be for future exploration missions. The cardiovascular system must be sufficiently stressed throughout a mission to maintain the ability to perform nominal and contingency/emergency tasks. High quality heart rate data are required to accurately determine the intensity of exercise performed by the crewmembers and show maintenance of VO2max. The quality of the data collected on ISS is subject to multiple limitations and is insufficient to meet current requirements. PURPOSE: To evaluate the performance of commercially available Bluetooth heart rate monitors (BT_HRM) and their ability to provide high quality heart rate data to monitor crew health aboard the ISS and during future exploration missions. METHODS: Nineteen subjects completed 30 data collection sessions of various intensities on the treadmill and/or cycle. Subjects wore several BT_HRM technologies for each testing session. One electrode-based chest strap (CS) was worn, while one or more optical sensors (OS) were worn. Subjects were instrumented with a 12-lead ECG to compare the heart rate data from the Bluetooth sensors. Each BT_HRM data set was time matched to the ECG data and a +/-5bpm threshold was applied to the difference between the 2 data sets. Percent error was calculated based on the number of data points outside the threshold and the total number of data points. RESULTS: The electrode-based chest straps performed better than the optical sensors. The best performing CS was CS1 (1.6% error), followed by CS4 (3.3% error), CS3 (6.4% error), and CS2 (9.2% error). The OS resulted in 10.4% error for OS1 and 14.9% error for OS2. CONCLUSIONS: The highest quality data came from CS1, but unfortunately it has been discontinued by the manufacturer. The optical sensors have not been ruled out for use, but more investigation is needed to determine how to obtain the best quality data. CS2 will be used in an ISS Bluetooth validation study, because it simultaneously transmits magnetic pulse that is integrated with existing exercise hardware on ISS. The simultaneous data streams allow for beat-to-beat comparison between the current ISS standard and CS2. Upon Bluetooth validation aboard ISS, the research team will down select a new BT_HRM for operational use.

Buxton, R. E.↗

Shake-Down Spectroscopy as State- and Site-Specific Probe of Ultrafast Chemical Dynamics

Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS2 molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the predissociation dynamics is controversial. We present XPS spectra from photoexcited CS2, obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the predissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the predissociation dynamic pathway.

Thompson, Henry J. [Univ. of Southampton (United K↗

Fragmentation dynamics through geometrical distortion in low-energy electron attachment to carbon disulfide

The dissociation dynamics of dissociative electron attachment to carbon disulfide is studied using the velocity map imaging technique. Ion yields of the S− and CS− fragments are measured as a function of incident electron energy between 2 and 12 eV. Energy and angle-differential yields of the S− fragments are analyzed to investigate the dynamics of the CS2− anion around the 3.8-eV peak. The resonances involved in this fragmentation are identified and characterized in calculations using the well-known R-matrix method. Based on our measurements and the geometry dependence of the calculated resonances, we propose that a geometrical distortion of the transient negative-ion state of CS2 is necessary for S-CS bond dissociation to occur.

Paul, Anirban↗

Materials Data on CS30 by Materials Project

S30C crystallizes in the monoclinic C2/m space group. The structure is zero-dimensional and consists of twelve hydrogen disulfide molecules, eight hydrogen sulfide molecules, two CS2 clusters, and eight S clusters. In each CS2 cluster, C4+ is bonded in a linear geometry to two equivalent S+0.13- atoms. Both C–S bond lengths are 1.55 Å. S+0.13- is bonded in a single-bond geometry to one C4+ atom. In each S cluster, there are three inequivalent S+0.13- sites. In the first S+0.13- site, S+0.13- is bonded in a single-bond geometry to two S+0.13- atoms. There are one shorter (1.90 Å) and one longer (3.69 Å) S–S bond lengths. In the second S+0.13- site, S+0.13- is bonded in a single-bond geometry to two S+0.13- atoms. The S–S bond length is 3.85 Å. In the third S+0.13- site, S+0.13- is bonded in a 1-coordinate geometry to two S+0.13- atoms.

36 MATERIALS SCIENCE↗

Study of self-focusing and self-phase-modulation in the picosecond-time regime.

Study of the propagation of a single picosecond pulse of a mode-locked Nd-glass laser in CS2 nitrobenzene and toluene by observations of the birefringence and spectral changes in self-focused laser light. Multiple second-harmonic probing beams are used for birefringence measurements in a single IR pulse in various portions of the active cell. The orientational Kerr effect is found to be the prime factor of induced birefringence in nitrobenzene and toluene. The results for CS2 are also consistent with this mechanism and show that the duration of an IR pulse in the focal volume is less than that of the incident pulse. The properties of beams which are focused within the cell by an external lens are also investigated.

Reintjes, J.↗

Precursor gases of aerosols in the Mount St. Helens eruption plumes at stratospheric altitudes

Nineteen stratospheric samples from the eruption plumes of Mount St. Helens were collected in five flight experiments. The plume samples were collected at various altitudes from 13.1 to 20.7 km by using the Ames cryogenic sampling system on board the NASA U-2 aircraft. The enriched, cryogenically collected samples were analyzed by chromatography. The concentrations of aerosols precursor gases (OCS, SO2, and CS2), CH3Cl, N2O, CF2Cl2, and CFCl3 were measured by gas chromatography. Large enhancement of the mixing ratio of SO2 and moderate enhancement of CS2 and OCS were found in the plume samples compared with similar measurement under pre-volcanic conditions. A fast decay rate of the SO2 mixing ratio in the plume was observed. Measurement of Cl(-), SO2(2-), and NO3(-) by ion chromatography was also carried out on water solutions prepared from the plume samples. The results obtained with this technique imply large mixing ratios of HCl, (NO + NO2 + HNO3), and SO2, in which these constituents are the respective sources of the anions. Measurement of the Rn222 concentration in the plume was made. Other stratospheric constituents in the plume samples, such as H2O, CO2, CH4, and CO, were also observed.

Inn, E. C. Y.↗

The origin of CS in comet IRAS-Araki-Alcock 1983d

It is shown that the IUE observations of CS in the atmosphere of comet IRAS-Araki-Alcock 1983d are consistent with its formation by the photodissociation of CS2 released from the nucleus. The observed scale length can be matched by a calculated scale length, which is based on the photochemical lifetime of CS2 at 1 AU and hydrodynamic models of the velocity field in the coma. A flow velocity of about 0.6 km/s is required to fit the data, which is in excellent agreement with recent calculations of the flow regime in the inner coma.

Jackson, W. M.↗

In situ extraction and analysis of volatiles and simple molecules in interplanetary dust particles, contaminants, and silica aerogel

Results are presented for the analyses of eight interplanetary dust particles (IDPs) for the volatile elements H, C, N, O, and S and their molecular species, as well as of the volatiles associated with contaminants (i.e., the compounds used during the collection and curation of IDPs), which were carried out using a laser microprobe interfaced with a quadrupole mass spectrometer. It was found that the volatile species from contaminants were always present in the spectra of IDPs. Despite the contamination problems, several indigenous molecular species could be identified, including OH, CO2 or C2H4, C and CS2, CO2 along with CO (possibly indicating the presence of carbonate), H2S, SO, COS, SO2, and CS2. In some cases, the sulfur components can be attributed to aerosols; however, in one of the IDPs, the presence of H2S, SO, COS, and SO2 indicates the possible presence of elemental sulfur.

Hartmetz, C. P.↗

A preliminary study of the variability and magnitude of the flux of biogenic sulfur gases from a New Hampshire salt marsh

Salt marshes have highly variable spatial and temporal fluxes of hydrogen sulfide, carbonyl sulfide, methane thiol, dimethyl sulfide, and carbon disulfide (H2S, COS, MeSH, DMS, and CS2, respectively). This variability was tested at nine emission sites in a New Hampshire, USA salt marsh: three replicates in each of three vegetation zones, Spartina alterniflora, S. patens, and a transition zone. Three sites were sampled simultaneously, either within or across vegetation zones, using a dynamic flux chamber technique. Difficulties with calibration and field equipment resulted in fluxes with maximum absolute uncertainties of greater than plus or minus 200 percent. However, the relative uncertainty between subsequent samples was closer to plus or minus 20 percent. Chambers are expected to affect the natural flux of gases by altering the humidity, temperature, and composition of the gas inside the chamber. Summertime fluxes are highest for all gases except COS which demonstrated evidence of a springtime peak. A summertime background flux of 5 to 100 x 10(exp -9) g S/m(sup -2) min was observed for all gases, while S alternifora fluxes of MeSH and DMS were approximately 8 fold and approximately 100 fold higher than S. patens, respectively. DMS and MeSH fluxes were higher during the day than at night. Evidence of COS uptake by plants was observed. CS2 appeared to be the quantitatively least important sulfur gas emitted. Improved laboratory and sample collection techniques and further data collection in the field will yield information on the details of salt marsh variability, will improve estimates of the error associated with single flux measurements, and will allow a more accurate estimation of sulfur fluxes from salt marshes based on vegetation and area coverage data. Inability to control the temperature and humidity inside of the chamber remain significant problems with the chamber design.

Morrison, Michael Cope↗

Sulfur Chemistry in the Wake of Comet Shoemaker-Levy 9

A curious and unexpected result of the impact of P/Shoemaker Levy 9 with Jupiter was the production of enormous amounts of molecular sulfur (S2). Here we show that S2 is the natural product of disequilibrium chemistry at low pressures in shocked Jovian air, its formation a byproduct of hydrogen recombination. The species observed by the Hubble Space Telescope (HST) - S2, CS2, and H2S - imply that the G fragment penetrated the NH4SH cloud but did not reach the water table. A typical impact within or below the NH4SH clouds produces about 0.03 - 0.1 impactor masses of S2. Because comets are relatively hydrogen-poor, SO2, not S2, is the major product of shocking a water-rich comet, while S2, CS2 and OCS are major products of a dessicated comet. In all cases we find that as the gas cools, S2 converts to the stable low temperature allotrope S8, although other chemical fates not modeled here might intervene first.

Zahnle, Kevin↗

Models of Fallback

The impact of a typical Shoemaker-Levy 9 fragment produced three light peaks as seen from Earth. The first peak is related to the entry of the fragment into the jovian atmosphere. The second peak occurs when the exploding fireball rises above Jupiter's limb into direct view from Earth. The third peak, much the brightest, occurs when the ejecta plume falls back on the atmosphere. Here we present a simple, highly idealized model of a ballistic plume, which we then use to fit the observed light curve of the R impact as recorded at Mauna Kea and Mt.Palomar. The nominal R fragment has diameter 500 m and mass 3x10(sup)13 g, with energy release of 5x10(sup)26 ergs. The largest events were about three times more energetic. These sizes agree with those deduced by Ashaug and Benz from the dynamics of tidal disruption. Chemical products of the reentry shock included the sulfur compounds S2, CS, and CS2. These were emplaced very high in the atmosphere (ca. 100 microbars). The yield of the reduced compounds CS and CS2, coupled with the apparent absence of the oxidized compounds SO and SO2, indicate that the explosions occurred above the jovian water clouds.

Zahnle, Kevin↗

Negative Ion Drift Velocity and Longitudinal Diffusion in Mixtures of Carbon Disulfide and Methane

Negative ion drift velocity and longitudinal diffusion has been measured for gas mixtures of carbon disulfide (CS2) and methane (CH4)' Measurements were made as a function of total pressure, CS2 partial pressure and electric field. Constant mobility and thermal-limit longitudinal diffusion is observed for all gas mixtures tested. Gas gain for some of the mixtures is also included.

Dion, Michael P.↗

Sulphur-bearing Compounds Detected by MSL SAM Evolved Gas Analysis of Materials from Yellowknife Bay, Gale Crater, Mars

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of sample fines (<150 μm) from three sites in Yellowknife Bay, an aeolian bedform termed Rocknest (hereafter "RN") and two samples drilled from the Sheepbed mudstone at sites named John Klein ("JK") and Cumberland ("CB"). SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases. The identity of evolved gases and temperature (T) of evolution can support mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or difficult to characterize with XRD (e.g., X-ray amorphous phases). Here, we focus on potential constraints on phases that evolved SO2, H2S, OCS, and CS2 during thermal analysis.

McAdam, A. C.↗

Bluetooth(Registered Trademark) Heart Rate Monitors for Spaceflight

Heart rate monitoring is required during exercise for crewmembers aboard the International Space Station (ISS) and will be for future exploration missions. The cardiovascular system must be sufficiently stressed throughout a mission to maintain the ability to perform nominal and contingency/emergency tasks. High quality heart rate data is required to accurately determine the intensity of exercise performed by the crewmembers and show maintenance of VO2max. The quality of the data collected on ISS is subject to multiple limitations and is insufficient to meet current requirements. PURPOSE: To evaluate the performance of commercially available Bluetooth® heart rate monitors (BT_HRM) and their ability to provide high quality heart rate data to monitor crew health on board ISS and during future exploration missions. METHODS: Nineteen subjects completed 30 data collection sessions of various intensities on the treadmill and/or cycle. Subjects wore several BT_HRM technologies for each testing session. One electrode-based chest strap (CS) was worn, while one or more optical sensors (OS) was worn. Subjects were instrumented with a 12-lead ECG to compare the heart rate data from the Bluetooth sensors. Each BT_RHM data set was time matched to the ECG data and a +/-5bpm threshold was applied to the difference between the two data sets. Percent error was calculated based on the number of data points outside the threshold and the total number of data points. REULTS: The electrode-based chest straps performed better than the optical sensors. The best performing CS was CS1 (1.6%error), followed by CS4 (3.3%error), CS3 (6.4%error), and CS2 (9.2%error). The OS resulted in 10.4% error for OS1 and 14.9% error for OS2. CONCLUSIONS: The highest quality data came from CS1, unfortunately it has been discontinued by the manufacturer. The optical sensors have not been ruled out for use, but more investigation is needed to determine how to get the best quality data. CS2 will be used in an ISS Bluetooth validation study, because it simultaneously transmits Magnetic Pulse which is integrated with existing exercise hardware on ISS. The simultaneous data streams allow for beat to beat comparison between the current ISS standard and CS2.Upon Bluetooth(Registered Trademark) validation aboard ISS, down select of a new BT_HRM for operational use will be made.

Buxton, Roxanne E.↗

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗

Sulfur-bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from ~450 to 800degC during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2 (~3-22 μmol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (~41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (~1-5nmol) and CS2 (~0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

Gale Crater↗