In situ detection of tropospheric OH, HO2, NO2, and NO by laser-induced fluorescence in detection chambers at reduced pressures

This report is a brief summary of the status of work on the grant entitled 'In situ detection of tropospheric OH, HO2, NO2, and NO by laser induced fluorescence in detection chambers at low pressures'. The first version of the instrument is essentially complete and operational for about six months, and we continue to make improvements on the instrument sensitivity and reliability. We are focusing our efforts on improving our understanding of the operating characteristics of the instrument - particularly the inlet transmission for OH and HO2, the exact character of the air flow around and within the instrument, and the efficiency of the chemical conversion of HO2 to OH. We are also in the process of converting this laboratory instrument into a field worthy instrument that we can take to remote sites for measurements

In situ observations of BrO over Antarctica: ER-2 aircraft results from 54 S to 72 S latitude

Bromine monoxide was observed in situ at approximately 18 km altitude during nine flights of the NASA ER-2 aircraft from Punta Arenas, Chile (54 altitude) to 72 S latitude over the Palmer Peninsula, Antarctica. The first flight for the BrO detection system was on 28 August. Here, the results from the flights over Antarctica and from the ferry flights from Punta Arenas to Moffett Field, CA (37 N latitude are reported. A key question concerning BrO, then, is how it is distributed with respect to the chemical containment vessel defined by elevated ClO mixing ratios. This question is answered with greatest statistical significance if the data are averaged into five regions: outside the vessel, aircraft heading south; inside the vessel on the same potential temperature surface; in the dive region; inside the vessel on a given potential temperature surface, aircraft heading north; and outside the vessel on the same surface. The result is that the BrO distribution inside the chemical containment vessel was different from that found outside. Inside, the BrO mixing ratio was (5.0 plus or minus 1.1) pptv between the 400 K and 460 K potential temperature surfaces, decreasing only slightly with potential temperature, and was less than 3.6 pptv below the 4 00 K surface. The abundance of BrO inside the chemical containment vessel showed no discernible temporal trend during the course of the nine flights. Outside the vessel, the BrO mixing ratio was (4.7 plus or minus 1.3) pptv near the 450 K surface, but decreased to (2.8 plus or minus 1.0) pptv near the 420 K surface

Aerodynamic design of gas and aerosol samplers for aircraft

The aerodynamic design of airborne probes for the capture of air and aerosols is discussed. Emphasis is placed on the key parameters that affect proper sampling, such as inlet-lip design, internal duct components for low pressure drop, and exhaust geometry. Inlet designs that avoid sonic flow conditions on the lip and flow separation in the duct are shown. Cross-stream velocities of aerosols are expressed in terms of droplet density and diameter. Flow curvature, which can cause aerosols to cross streamlines and impact on probe walls, can be minimized by means of a proper inlet shape and proper probe orientation, and by avoiding bends upstream of the test section. A NASA panel code called PMARC was used successfully to compute streamlines around aircraft and probes, as well as to compute to local velocity and pressure distributions in inlets. A NACA 1-series inlet with modified lip radius was used for the airborne capture of stratospheric chlorine monoxide at high altitude and high flight speed. The device has a two-stage inlet that decelerates the inflow with little disturbance to the flow through the test section. Diffuser design, exhaust hood design, valve loss, and corner vane geometry are discussed

Modeling one-dimensional island growth with mass-dependent detachment rates

We study one-dimensional models of particle diffusion and attachment/detachment from islands where the detachment rates gamma(m) of particles at the cluster edges increase with cluster mass m. They are expected to mimic the effects of lattice mismatch with the substrate and/or long-range repulsive interactions that work against the formation of long islands. Short-range attraction is represented by an overall factor epsilon<<1 in the detachment rates relatively to isolated particle hopping rates [epsilon ~ exp(-E/T), with binding energy E and temperature T]. We consider various gamma(m), from rapidly increasing forms such as gamma(m) ~ m to slowly increasing ones, such as gamma(m) ~ [m/(m+1)]^b. A mapping onto a column problem shows that these systems are zero-range processes, whose steady states properties are exactly calculated under the assumption of independent column heights in the Master equation. Simulation provides island size distributions which confirm analytic reductions and are useful whenever the analytical tools cannot provide results in closed form. The shape of island size distributions can be changed from monomodal to monotonically decreasing by tuning the temperature or changing the particle density rho. Small values of the scaling variable X=epsilon^{-1}rho/(1-rho) favour the monotonically decreasing ones. However, for large X, rapidly increasing gamma(m) lead to distributions with peaks very close to and rapidly decreasing tails, while slowly increasing gamma(m) provide peaks close to /2$ and fat right tails.Comment: 16 pages, 6 figure

Antiferromagnetic MnNi tips for spin-polarized scanning probe microscopy

Spin-polarized scanning tunneling microscopy (SP-STM) measures tunnel magnetoresistance (TMR) with atomic resolution. While various methods for achieving SP probes have been developed, each is limited with respect to fabrication, performance, and allowed operating conditions. In this study, we present the fabrication and use of SP-STM tips made from commercially available antiferromagnetic $\rm{Mn_{88}Ni_{12}}$ foil. The tips are intrinsically SP, which is attractive for exploring magnetic phenomena in the zero field limit. The tip material is relatively ductile and straightforward to etch. We benchmark the conventional STM and spectroscopic performance of our tips and demonstrate their spin sensitivity by measuring the two-state switching of holmium single atom magnets on MgO/Ag(100)

Adaptation of an In Situ Ground-Based Tropospheric OH/HO2 Instrument for Aircraft Use

In-situ HO(x) (OH and HO2) measurements are an essential part of understanding the photochemistry of aircraft exhaust in the atmosphere. HO(x) affects the partitioning of nitrogen species in the NO(y) family. Its reactions are important sources and sinks for tropospheric ozone, thus providing a link between the NO(x) in aircraft exhaust and tropospheric ozone. OH mixing ratios are enhanced in aircraft wakes due to the photolysis of the HONO that is made close to the engine. Measurements of HO(x) in aircraft wakes, along with NO(x) measurements, thus provides a constraint on chemical models of the engine combustion and exhaust. The development of the Airborne Tropospheric Hydrogen Oxides Sensor (ATHOS) is reported. We designed, developed, and successfully flew this instrument. It was part of the instrument complement on board the NASA DC-8 during SUCCESS, which took place in Kansas in April and May, 1996. ATHOS has a limit-of-detection for OH (S/N = 2) of 10(exp 5) OH molecules cm(exp -3) in less than 150 seconds. While this sensitivity is about 2-3 times less than the initial projections in the proposal, it is more than adequate for good measurements of OH and HO2 from the planetary boundary layer to the stratosphere. Our participation in SUCCESS was to be engineering test flights for ATHOS; however, the high-quality measurements we obtained are being used to study HO(x) photochemistry in contrails, clouds, and the clear air

In situ detection of tropospheric OH, HO2, NO2, and NO by laser-induced fluorescence in detection chambers at reduced pressures

For detection of OH and HO2, we have met or exceeded most of the goals of the proposal for this grant. We have succeeded in building a prototype instrument for the detection of OH and HO2 that has a detection sensitivity of about 2 x 10 exp 4 (OH molecules/cc)/(ct/s), about five times greater than proposed. The current minimum detectable OH of 1.4 x 10 exp 5 OH molecules/cc (S/N=2; 30 second integration) is less than half that proposed, and will be much lower once scattered light levels are reduced. The instrument displays other important properties. First, interfering signals from other gases and OH losses on the inlet appear to be small under laboratory and field conditions. Second, three different calibration methods, two external to the inlet, give similar results, to within 30 percent. Third, the chemical conversion efficiency of HO2 to OH by addition of reagent NO is better than 90 percent. All of these factors give us great confidence that this technique works. The instrument has gone through several variations that have not affected its potential performance but have affected its use. We were able to undergo the first field trials away from State College in June 1992, when we were able to participate informally in the ROSE experiment in rural Alabama, a year ahead of the proposed schedule for field studies. Because this field experiment was our first and the data analysis was complicated by instrument instabilities, we have not yet released the observations. None-the-less, we have gained insight into instrument design. We have not yet completed all of the proposed work. The calibration systems need to be improved to reduce the 50 percent to 100 percent uncertainties to less than 30 percent. Interference signals from ambient gases and possible losses on the inlet under field conditions need to be quantified. Finally, the detection of NO2 and NO with laser induced fluorescence is only now being seriously pursued

Participation as Mission Scientist for the SPADE 2 Mission

In a 1994 National Research Council report, "Atmospheric Effects of Stratospheric Aircraft: An Evaluation of NASA's Interim Assessment", the assessment panel's key issues for better determining the atmospheric effects of stratospheric aircraft, particularly on ozone, were presented

Measurement of Ozone Production Sensor

A new ambient air monitor, the Measurement of Ozone Production Sensor (MOPS), measures directly the rate of ozone production in the atmosphere. The sensor consists of two 11.3 L environmental chambers made of UV-transmitting Teflon film, a unit to convert NO&lt;sub&gt;2&lt;/sub&gt; to O&lt;sub&gt;3&lt;/sub&gt;, and a modified ozone monitor. In the sample chamber, flowing ambient air is exposed to the sunlight so that ozone is produced just as it is in the atmosphere. In the second chamber, called the reference chamber, a UV-blocking film over the Teflon film prevents ozone formation but allows other processes to occur as they do in the sample chamber. The air flows that exit the two chambers are sampled by an ozone monitor operating in differential mode so that the difference between the two ozone signals, divided by the exposure time in the chambers, gives the ozone production rate. High-efficiency conversion of NO&lt;sub&gt;2&lt;/sub&gt; to O&lt;sub&gt;3&lt;/sub&gt; prior to detection in the ozone monitor accounts for differences in the NO&lt;sub&gt;x&lt;/sub&gt; photostationary state that can occur in the two chambers. The MOPS measures the ozone production rate, but with the addition of NO to the sampled air flow, the MOPS can be used to study the sensitivity of ozone production to NO. Preliminary studies with the MOPS on the campus of the Pennsylvania State University show the potential of this new technique

Island size distributions in submonolayer growth: successful prediction by mean field theory with coverage dependent capture numbers

We show that mean-field rate equations for submonolayer growth can successfully predict island size distributions in the pre-coalescence regime if the full dependence of capture numbers on both the island size and the coverage is taken into account. This is demonstrated by extensive Kinetic Monte Carlo simulations for a growth kinetics with hit and stick aggregation. A detailed analysis of the capture numbers reveals a nonlinear dependence on the island size for small islands. This nonlinearity turns out to be crucial for the successful prediction of the island size distribution and renders an analytical treatment based on a continuum limit of the mean-field rate equations difficult.Comment: 4 pages, 4 figue