Direct Measurement of the OH + HO 2 Cross Reaction Using Infrared Kinetic Spectroscopy
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The HO (sub 2) + CIO reaction is the key rate-limiting step in the chlorine-catalyzed destruction of ozone in the lower and middle stratosphere. Product channels leading to HOC1 and HC1 are both exothermic and a small HC1 channel will significantly alter the partitioning of inorganic chlorine in the lower stratosphere.
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Rate coefficients for the reaction HO(sub 2)+ NO(sub 2) + N(sub 2) --> HO(sub 2)NO(sub 2) + N(sub 2) (reaction 1) were measured using simultaneous near-IR and UV spectroscopy from 220 to 298 K and from 45 to 200 Torr.
An efficient 19 W, TEM(sub 00) mode, Ho:YLF laser pumped by continuous wave Tm:fiber laser has been demonstrated at the room temperature. The slope efficiency and optical-to-optical efficiency are 65% and 55%, respectively.
The development of eye-safe, solid-state Lidar systems is discussed, with an emphasis on Coherent Doppler Lidar for Atmospheric Wind Measurements. The following subject areas are covered: tunable Ho DIAL (Differential Absorption Lidar)/lidar atmospheric measurements; atmospheric turbulence measurements and detector arrays; diurnal measurements of C(sub n)(sup 2) for KSC lidar measurements; and development of single-frequency Ho laser/lidar.
Discussion of laboratory measurements which indicate that the reaction of the thermalized HO(2) radical with CO is exceedingly slow and that this reaction should not, therefore, be of any significance in atmospheric chemistry. The large discrepancy between the new results and data obtained earlier by Westenberg and de Haas (1972) is explained in terms of the reacting hydroperoxyl radical being in a non-Boltzmann distribution in the former study. It appears that the most important reactions of thermalized HO(2) in the atmosphere are those involving the trace gases of NO and sulfur dioxide.
Perhydroxyl radical electron spin resonance spectrum in solution of hydrogen peroxide and water at 77 K, noting g factor, hyperfine splitting and molecular structure
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Data analysis has been improved by recalibration of the instrument for atmospheric studies, incorporation of updated laboratory spectroscopic work, and use of an improved photchemical model.
The kinetics of the H02+CIO reaction was studied using the flash photolysis/ultraviolet absorption technique over the temperature range 203-364 K and pressure range 50-700 Torr of N2.
A large solar flare with an associated coronal mass ejection occurred in mid-July and caused a very large solar proton event at the earth in the time period July 14-16, 2000. So far this is the largest solar storm of solar cycle 23. The solar proton fluxes were measured by instruments aboard the GOES-10 satellite and used in our proton energy deposition model to help quantify the energy input to the middle atmosphere during this large solar event. Using this computed energy deposition in the GSFC 2D atmospheric model resulted in a prediction of $>$ 20\% increases in HO$-(x)$ (H, OH, HO$-(2)$) and $>$ 100\% increases in NO$-(x)$ (N, NO, NO$-(2)$) constituents in the mesosphere and upper stratosphere at polar latitudes ($>$ 60 degrees geomagnetic). Both the HO$-(x)$ and NO$_fx)$ increases impacted ozone. Large atmospheric impacts have been measured with the NOAA 14 SBUV/2 instrument (0$_(3)$), the UARS HALOE instrument (NO, NO$-(2)$, 0$-(3)$), and the POAM III instrument (0$_{3}$, NO$-(2)$). Preliminary analysis indicates that measured (SBUV/2) and modelled 0$_{3}$ decreases from this solar event are generally in agreement in the Northern Hemisphere. Short-term ozone changes (during the event) indicate $\sim$ 15% reduction at 2 hPa ($\sim$ 45 km) up to $\sim$ 40% reduction at 0.5 hPa ($\sim$ 55 km). A longer-term ozone depletion of $\sim$ 5% is indicated between 4 and 2 hPa ($\sim$ 40-45 km). The middle atmospheric changes caused by this solar event were very large and occurred fairly quickly ($\sim$ 1-2 days). Such a significant natural perturbation provides a good test of our understanding of the middle atmosphere. The measured and modelled impacts of this solar event will be compared and discussed in this paper.
The availability of formaldehyde (HCHO) (a proxy for volatile organic compound reactivity) and nitrogen dioxide (NO 2 ) (a proxy for nitrogen oxides) tropospheric columns from ultraviolet–visible (UV–Vis) satellites has motivated many to use their ratios to gain some insights into the near-surface ozone sensitivity. Strong emphasis has been placed on the challenges that come with transforming what is being observed in the tropospheric column to what is actually in the planetary boundary layer (PBL) and near the surface; however, little attention has been paid to other sources of error such as chemistry, spatial representation, and retrieval uncertainties. Here we leverage a wide spectrum of tools and data to quantify those errors carefully. Concerning the chemistry error, a well-characterized box model constrained by more than 500 h of aircraft data from NASA's air quality campaigns is used to simulate the ratio of the chemical loss of HO 2 + RO 2 (LRO x ) to the chemical loss of NO x (LNO x ). Subsequently, we challenge the predictive power of HCHO/NO 2 ratios (FNRs), which are commonly applied in current research, in detecting the underlying ozone regimes by comparing them to LRO x /LNO x . FNRs show a strongly linear (R 2 =0.94) relationship with LRO x /LNO x , but only on the logarithmic scale. Following the baseline (i.e., ln(LRO x /LNO x ) = −1.0 ± 0.2) with the model and mechanism (CB06, r2) used for segregating NO x -sensitive from VOC-sensitive regimes, we observe a broad range of FNR thresholds ranging from 1 to 4. The transitioning ratios strictly follow a Gaussian distribution with a mean and standard deviation of 1.8 and 0.4, respectively. This implies that the FNR has an inherent 20 % standard error (1σ) resulting from not accurately describing the RO x –HO x cycle. We calculate high ozone production rates (PO 3 ) dominated by large HCHO × NO 2 concentration levels, a new proxy for the abundance of ozone precursors. The relationship between PO 3 and HCHO × NO 2 becomes more pronounced when moving towards NO x -sensitive regions due to nonlinear chemistry; our results indicate that there is fruitful information in the HCHO × NO 2 metric that has not been utilized in ozone studies. The vast amount of vertical information on HCHO and NO 2 concentrations from the air quality campaigns enables us to parameterize the vertical shapes of FNRs using a second-order rational function permitting an analytical solution for an altitude adjustment factor to partition the tropospheric columns into the PBL region. We propose a mathematical solution to the spatial representation error based on modeling isotropic semivariograms. Based on summertime-averaged data, the Ozone Monitoring Instrument (OMI) loses 12 % of its spatial information at its native resolution with respect to a high-resolution sensor like the TROPOspheric Monitoring Instrument (TROPOMI) (> 5.5 × 3.5 km 2 ). A pixel with a grid size of 216 km 2 fails at capturing ∼ 65 % of the spatial information in FNRs at a 50 km length scale comparable to the size of a large urban center (e.g., Los Angeles). We ultimately leverage a large suite of in situ and ground-based remote sensing measurements to draw the error distributions of daily TROPOMI and OMI tropospheric NO 2 and HCHO columns. At a 68 % confidence interval (1σ), errors pertaining to daily TROPOMI observations, either HCHO or tropospheric NO 2 columns, should be above 1.2–1.5 × 10 16 molec. cm −2 to attain a 20 %–30 % standard error in the ratio. This level of error is almost non-achievable with the OMI given its large error in HCHO. The satellite column retrieval error is the largest contributor to the total error (40 %–90 %) in the FNRs. Due to a stronger signal in cities, the total relative error (< 50 %) tends to be mild, whereas areas with low vegetation and anthropogenic sources (e.g., the Rocky Mountains) are markedly uncertain (> 100 %). Our study suggests that continuing development in the retrieval algorithm and sensor design and calibration is essential to be able to advance the application of FNRs beyond a qualitative metric.
Various space shuttle ascent configurations were tested in a trisonic wind tunnel to determine the aerodynamic characteristics. The ascent configuration consisted of a NASA/MSC 040 orbiter in combination with various HO centerline tank and booster geometries. The aerodynamic interference between components of the space shuttle and the effect on the orbiter aerodynamics was determined. The various aerodynamic configurations tested were: (1) centerline HO tanks T1 and T2, (2) centerline HO tank T3, and (3) centerline HO tank H4.
A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.
A highly efficient, versatile, single frequency 2-micron pulsed laser can be used in a pulsed Differential Absorption Lidar (DIAL) / Integrated Path Differential Absorption (IPDA) instrument to make precise, high-resolution measurements to investigate sources and sinks of CO2. For a direct detection IPDA lidar, the desired 2 m Ho:YLF laser should generate 30-40 mJ pulses at the repetition rate of 100 to 200 Hz, with short pulse length (<100 ns) and better than 2% wall plug efficiency. A Tm fiber laser in-band pumped Ho:YLF laser has been developed to meet this technical challenge. This Ho:YLF laser is designed in a four mirror ring resonator with bow tie configuration, which helps to obtain high beam quality. It is end-pumped by a 40 W linearly polarized Tm fiber laser at 1.94μm. The resonator length is 1.10 meters with output coupler reflectivity at 45%. The laser crystal size is 3 x 3 x 60 mm (w, h, l) with a doping concentration of 0.5% Holmium. The laser beam and pump beam are mode-matched in the active medium. Thus, the pump and laser beams have the same confocal parameters. Mode-matching is also helpful for operating the laser in a single transverse mode. The laser beam waist is slightly less than 0.5 mm at the center of the laser crystal. Based on quasi-four level modeling, pump absorption and saturation depend on laser intensity. Laser amplification and saturation also depend on the pump intensity in the crystal. The laser is injection seeded to obtain the single frequency required by an IPDA lidar measurement. The seed beam is entered into the resonator through an output coupler. The laser is mounted on a water cooled optical bench for stable and reliable operation. The size of the optical bench is 22.16 x 9.20 x 1.25 inches. It is stiffened so that the laser can be operated in any orientation of the optical bench. This packaged Ho:YLF laser is designed for either mobile trailer or airborne platform operation. The engineering prototype Ho:YLF laser has been fully characterized to demonstrate laser performance. Figure 1 shows the laser output power as a function of pump power at different pulse repetition rates from 100 Hz to 333 Hz. The threshold of the laser is less than 14 W. The slope efficiencies are 28%, 40%, 41% and 43% for pulse repetition rates of 100, 200, 250 and 333 Hz, respectively. Maximum power increases with the pulse repetition rate. Output power of 4.2 W, 6 W, 6.7 W, and 7.7 W is achieved for pulse repetition rates of 100, 200, 250 and 333Hz, respectively. This represents the optical conversion efficiency of 16.7%, 22.4%, 23.7%, and 26.5% at these various pulse repletion rates. It is the most efficient and compact Ho:YLF laser demonstrated in the high pulse energy (>20mJ) and moderate pulse repetition rate (100's Hz) operation range. As shown in Figure 1, the maximum pulse energy at 100 Hz is 42 mJ. This is limited due to optical damage. The laser stability is characterized and found to be very stable. A relative pulse energy standard deviation of 2% was measured. The beam quality of the Ho:YLF was measured by a Spiricon infrared laser beam camera. Figure 2 shows the beam profile image of the laser. Both the X-profile of the beam (horizontal direction) and the Y-profile of the beam (vertical direction) are well fitted by a Gaussian profile. The qualitative beam quality measurement shows excellent beam quality in both axis. The M-square value for the laser beam is measured at 1.06 and 1.09 for the x and y axis respectively.-
Results of a performance analysis of an airborne Doppler radar wind shear detection system are given in vugraph form. It was concluded that both CO sub 2 and Ho:YAG lasers are feasible for dry microburst applications, but with limited performance in wet microbursts. The Ho:YAG performs better than the CO sub 2 for a set of identical lidar parameters.