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At least 451 records · Page 25

Modeling of the partitioning of reactive odd nitrogen in the lower stratosphere using aircraft measurements of NOy, NO, and other trace species

The objective of this research was to gain a more thorough understanding of the atmospheric processes which control the partitioning of species within the reactive nitrogen (NO(y)) reservoir in the lower stratosphere. This understanding is crucial to predicting ozone loss in the stratosphere. NO(y) is defined as NO + NO2 + HNO3 + N2O5 + ClONO2 + HO2NO2 + NO3 + particulate nitrate. The research focuses on deriving the partitioning among these species using the combined set of measurements from the NASA ER-2 aircraft during recent missions designed to study stratospheric ozone depletion.

Kawa, Stephan Randolph↗

Measurements of stratospheric composition using a star pointing spectrometer

Measurements of stratospheric composition have been made with a novel star-pointing spectrometer. The instrument consists of a telescope that focuses light from stars, planets, or the moon onto a spectrometer and two dimensional CCD array detector. Atmospheric absorptions can be measured, from which atmospheric columns of several gases can be determined. The instrument was deployed in Abisko, 69 deg N, during the European Arctic Stratospheric Ozone Experiment (EASOE). The instrument has the potential for measuring O3, OClO, NO2, and NO3. In this paper, a method for the retrieval of vertical columns is described, and some examples of ozone measurements given.

Fish, Deb J.↗

Derivation of water vapour absorption cross-sections in the red region

Absorption spectrum in 436 to 448 nm wavelength region gives NO2 and O3 column densities. This spectrum can also give H2O column density. The spectrum in the range of 655 to 667 nm contains absorption due to NO3 and H2O. Combining the absorption spectra in the wavelength ranges of 436 to 448 and 655 to 667 nm, water vapor absorption cross-sections in this range comes out to be of the order of 2.0 x 10(exp -24) cm(exp -2).

Lal, M.↗

Summertime distribution of PAN and other reactive nitrogen species in the northern high-latitude atmosphere of eastern Canada

Aircraft measurements of key reactive nitrogen species (NO, NO2, HNO3, PAN, PPN, NO3(-), NO(y)), C1 to C6 hydrocarbons, acetone, O3, chemical tracers (C2Cl4, CO), and important meteorological parameters were performed over eastern Canada during July to August 1990 at altitudes between 0 and 6 km as part of an Arctic Boundary Layer Expedition (ABLE3B). In the free troposphere, PAN was found to be the single most abundant reactive nitrogen species constituting a major fraction of NO(y) and was significantly more abundant than NO(x) and HNO3. PAN and O3 were well correlated both in their fine and gross structures. Compared to data previously collected in the Arctic/subarctic atmosphere over Alaska (ABLE3A), the lower troposphere (0-4 km) over eastern Canada was found to contain larger reactive nitrogen and anthropogenic tracer concentrations. At higher altitudes (4-6 km) the atmospheric composition was in many ways similar to what was seen over Alaska and supports the view that a large-scale reservoir of PAN (and NO(y)) is present in the upper troposphere over the entire Arctic/subarctic region. The reactive nitrogen budget based on missions conducted from the North Bay site (missions 2-10) showed a small shortfall, whereas the budget for data collected from the Goose Bay operation (missions 11-19) showed essential balance. It is calculated that 15-20 ppt of the observed NO(x) may find its source from the available PAN reservoir. Meteorological considerations as well as relationships between reactive nitrogen and tracer species suggest that the atmosphere over eastern Canada during summer is greatly influenced by forest fires and transported industrial pollution.

Singh, H. B.↗

Summertime distribution and relations of reactive odd nitrogen species and NO(y) in the troposphere over Canada

We report here large-scale features of the distribution of NO(x), HNO3, PAN, particle NO3, and NO(y) in the troposphere from 0.15 to 6 km altitude over central Canada. These measurements were conducted in July - August 1990 from the NASA Wallops Electra aircraft as part of the joint United States-Canadian Arctic Boundary Layer Expedition (ABLE) 3B-Northern Wetlands Study. Our findings show that this region is generally NO(x) limited, with NO(x) mixing ratios typically 20-30 parts per trillion by volume (pptv). We found little direct evidence for anthropogenic enhancement of mixing ratios of reactive odd nitrogen species and NO(y) above those in 'background' air. Instead, it appears that enhancements in the mixing ratios of these species were primarily due to emissions from several day old or CO-rich-NO(x)-poor smoldering local biomass-burning fires. NO(x) mixing ratios in biomass-burning impacted air masses were usually less than 50 pptv, but those of HNO3 and PAN were typically 100-300 pptv representing a twofold-threefold enhancement over 'background' air. During our study period, inputs of what appeared to be aged tropical air were a major factor influencing the distribution of reactive odd nitrogen in the midtroposphere over northeastern North America. These air masses were quite depleted in NO(y) (generally less than 150 pptv), and a frequent summertime occurrence of such air masses over this region would imply a significant influence on the reactive odd nitrogen budget. Our findings show that the chemical composition of aged air masses over subarctic Canada and those documented in the Arctic during ABLE 3A have strikingly similar chemistries, suggesting large-scale connection between the air masses influencing these regions.

Talbot, R. W.↗

Origin of tropospheric NO(x) over subarctic eastern Canada in summer

The original of NO(X) in the summertime troposphere over subarctic eastern Canada is investigated by photochemical modeling of aircraft and ground-based measurements from the Arctic Boundary Layer Expedition (ABLE 3B). It is found that decomposition of peroxyacetyl nitrate (PAN) can account for most of the NO(X) observed between the surface and 6.2 km altitude (aircraft ceiling). Forest fires represent the principal source of PAN in the region, implying the same origin for NO(X). There is, however, evidence for an unidentified source of NO(X) in occasional air masses subsiding from the upper troposphere. Isoprene emissions from boreal forests maintain high NO(X) concentrations in the continental boundary layer over eastern Canada by scavenging OH and NO3, thus slowing down conversion of NO(X) to HNO3, both in the daytime and at night. This effect is partly compensated by the production of CH3CO3 radicals during isoprene oxidation, which slows down the decomposition of PAN subsiding from the free troposphere. The peroxy radical concentrations estimated from concurrent measurements of NO and NO2 concentrations during ABLE 3B are consistent with values computed from our photochemical model below 4 km, but model values are low at higher altitudes. The discrepancy may reflect either a missing radical source in the model or interferences in the NO2 measurement.

Fan, S.-M↗

A discharge flow-photoionization mass spectrometric study of the FO(X 2 Pi i) radical. Photoionization efficiency spectrum and ionization energy

Photoionization efficiency spectra of FO were measured over the wavelength range 80.0-100.0 nm and in the ionization threshold region, 94.0-100.0 nm, using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. FO was generated by the reaction of F2P atoms with NO3 and via a F2O2 discharge. A value of 12.78 +/- 0.03 eV was obtained for the adiabatic ionization energy of FO from photoion thresholds which corresponds to FO(+)(X 3 Sigma -) from FO(X 2 Pi i). These results, which are the first to be obtained by direct Photo-ionization mass spectrometry (PIMS) measurements, corroborate those of a photoelectron spectroscopy (PES) study; however, the ionization energy determined here is free from interferences due to other species which complicated the PES measurement. A value of 109.5 +/- 8.0 kJ/mol for Delta f H 0 298(FO) is computed from the present value of IE(FO) and a previous appearance energy measurement, and a value for the proton affinity of FO is calculated to be 511.5 +/- 10.0 kJ/mol.

Zhang, Zhengyu↗

Development of airborne eddy-correlation flux measurement capabilities for reactive oxides of nitrogen

This research is aimed at producing a fundamental new research tool for characterizing the source strength of the most important compound controlling the hemispheric and global scale distribution of tropospheric ozone. Specifically, this effort seeks to demonstrate the proof-of-concept of a new general purpose laser-induced fluorescence based spectrometer for making airborne eddy-correlation flux measurements of nitric oxide (NO) and other reactive nitrogen compounds. The new all solid-state laser technology being used in this advanced sensor will produce a forerunner of the type of sensor technology that should eventually result in highly compact operational systems. The proof-of-concept sensor being developed will have over two orders-of-magnitude greater sensitivity than present-day instruments. In addition, this sensor will offer the possibility of eventual extension to airborne eddy-correlation flux measurements of nitrogen dioxide (NO2) and possibly other compounds, such as ammonia (NH3), peroxyradicals (HO2), nitrateradicals (NO3) and several iodine compounds (e.g., I and IO). Demonstration of the new sensor's ability to measure NO fluxes will occur through a series of laboratory and field tests. This proof-of-concept demonstration will show that not only can airborne fluxes of important ultra-trace compounds be made at the few parts-per-trillion level, but that the high accuracy/precision measurements currently needed for predictive models can also. These measurement capabilities will greatly enhance our current ability to quantify the fluxes of reactive nitrogen into the troposphere and significantly impact upon the accuracy of predictive capabilities to model O3's distribution within the remote troposphere. This development effort also offers a timely approach for producing the reactive nitrogen flux measurement capabilities that will be needed by future research programs such as NASA's planned 1999 Amazon Biogeochemistry and Atmospheric Chemistry Experimental portion of LBA.

Bradshaw, John↗

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS Ozone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the North Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(sub y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(sub y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(sub y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(sub y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope > 0.9 and r(exp 2) > 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(sub x). (NO + NO2), HNO3, and PAN. Median values of NO(sub x)/NO(sub y) were approximately equal to 0.25, HNO3/NO(sub y) were approximately equal to 0.35 and Peroxyacetyl Nitrate (PAN)/NO(sub y) were approximately equal to 0. 17. Particulate NO3 and alkyl nitrates together composed <10 % of NO(sub y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗

Measurements of Nitric Acid and Aerosol Species Aboard the NASA DC-8 Aircraft During the SASS OZone and Nitrogen Oxide Experiment (SONEX)

The SASS Ozone and Nitrogen Oxides Experiment (SONEX) over the north Atlantic during October/November 1997 offered an excellent opportunity to examine the budget of total reactive nitrogen (NO(y)) in the upper troposphere (8 - 12 km altitude). The median measured NO(y) mixing ratio was 425 parts per trillion by volume (pptv). Two different methods were used to measure HNO3: (1) the mist chamber technique and, (2) chemical ionization mass spectrometry. Two merged data sets using these HNO3 measurements were used to calculate NO(y) by summing the reactive nitrogen species (a combination of measured plus modeled results) and comparing the resultant values to measured NO(y) (gold catalytic reduction method). Both comparisons showed good agreement in the two quantities (slope greater than 0.9 and r(sup 2) greater than 0.9). Thus, the total reactive nitrogen budget in the upper troposphere over the North Atlantic can be explained in a general manner as a simple mixture of NO(x). (NO + NO2), HNO3, and PAN. Median values of NO(x)/NO(y) were approx. = 0.25, HNO3/NO(y) approx. = 0.35 and PAN/NO(y) approx. = 0.17. Particulate NO3 and alkyl nitrates together composed less than 10% of NO(y), while model estimated HNO4 averaged 12%.

Talbot, Robert W.↗

Effects of Solar Proton Events on the Middle Atmosphere

Solar proton events (SPEs) can result in increases in both HOx (H, OH, HO2) and NOx (N, NO, NO2) constituents in the polar middle atmosphere. Decreases in mesospheric and upper stratospheric ozone caused by HOx constituents produced by SPEs have been observed during several events, however, ozone levels generally recover within a few hours after the end of these events because of the short lifetime of the HOx species. The NOx species feed into the more inclusive odd nitrogen family, NOy (N, NO, NO2, NO3, N2O5, HNO3, HNO4, ClONO2), over a period of hours to weeks. In low sun and lower altitude conditions, the NOy family lasts several months or more in the stratosphere causing prolonged ozone changes over these longer periods. Observations of mesospheric winds during and after SPEs have also indicated some variations as a result of these atmospheric perturbations. An overview of the influence of SPEs on the polar neutral middle atmosphere will be presented in this paper.

Jackman, Charles H.↗

Stimulated Raman amplification, oscillation, and linewidth in barium nitrate

Measurements of Raman gain in a Ba(NO3)2 crystal are reported at 532 nm using a Raman oscillator/amplifier arrangement for differential absorption lidar measurements of ozone. The experimentally determined gain coefficient will be compared with theoretical results. The effect of single and multi-longitudinal mode pumping upon the amplification process will be discussed. Measurement of the Raman linewidth for 1st 2nd and 3d stokes shifts arc presented.

McCray, Christopher J.↗

Wheat Response to Differences In Water and Nutritional Status Between Zeoponic and Hydroponic Growth Systems

Hydroponic culture has traditionally been used for controlled environment life support systems (CELSS) because the optimal environment for roots supports high growth rates. Recent developments in zeoponic substrate and microporous tube irrigation (ZPT) also offer high control of the root environment. This study compared the effect of differences in water and nutrient status of ZPT or hydroponic culture on growth and yield of wheat (Triticum aestivum L., CV 'USU-Apogee'). In a side-by-side test in a controlled environment, wheat was grown in ZPT and recirculating hydroponics to maturity. Water use by plants grown in both culture systems peaked at 15-20 L per square meters per d up to day 40, after which it declined more rapidly for plants grown in ZPT culture due to earlier senescence of leaves. No consistent differences were noted in water status between plants grown in the two culture systems. Although yield was similar, harvest index was 28% lower for plants grown in ZPT versus hydroponic culture. Sterile green tillers made up 12% and 0% of the biomass of plants grown in ZPT and hydroponic culture, respectively. Differences in biomass partitioning were attributed primarily to NH4 -N nutrition of plants grown in ZPT as compared with NO3-N in hydroponic nutrient solution. It was likely that NH4-N induced Ca deficiency produced excess tillering and lower harvest index for plants grown in ZPT culture. These results suggest that further refinements in zeoponic substrate would make ZPT culture a viable alternative for achieving high productivity in a CELSS.

Steinberg, Susan L.↗

Optical and Atomic Force Microscopy Characterization of PbI2 Quantum Dots

Lead iodide (PbI2) clusters were synthesized from the chemical reaction of NaI (or KI) with Pb(NO3)2 in H2O, D2O, CH3OH, and C3H7OH media. The observation of the absorption features above 350 nm with the help of integrating sphere accessory strongly suggests the quantum dot formation of PbI2 in solution. Spectral comparison between the synthesized PbI2 clusters in solution and PbI2 nanophase by impregnation of PbI2 in four different pore-sized porous silica indicates that the PbI2 cluster size in solution is less than 2.5 nm in lateral dimension. Atomic force microscopy (AFM) measurements show that the PbL clusters deposited onto three different molecularly flat surfaces are single-layered. The measured height is 1.0 - 0.1 nm. The swollen layer thickness can be attributed to the intralayer contraction from the strong lateral interaction among PbI2 molecules, which is supported by ab initio calculation. Raman scattering measurement of LO and TO modes of PbI2 in bulk and in the confined state were also conducted in 50-150 cu cm region. The observed three bands at 74, %, 106 1/cm are assigned to TO2, LO2, and LO, mode, respectively. The relatively small red-shift in LO modes may be caused by the surface phonon polaritons of PbI2 nanophase in the porous silica.

Mu, R.↗

Measures of Water Quality in Merrit Island National Wildlife Refuge Impoundments and Adjacent Indian River Lagoon

The goal of this project was to conduct preliminary investigations to determine appropriate sampling strategies to measure the flux of dissolved nutrients (specifically, NH4+, NO3-, NO2-, and PO4(3-)) and suspended particulate matter (TSS) between impoundments and the IRL in preparation for an intensive three-year monitoring program. In addition to nutrients and TSS, a variety of common water quality indicators were also measured during these preliminary studies. Six impoundments and a single restored marsh were selected for study. Over a month long period, water samples were collected weekly at selected impoundment culverts. Water was collected in duplicate as independent grab samples from both the lagoon side and within the perimeter ditch directly adjacent to the culverts. Water quality indicators inside and outside the marsh impoundments were different. Ammonium, salinity, bacteria, and chlorophyll-a were higher inside the impoundments as expected possibly as a result of the great affect of evaporation on impoundment water. Water quality indicators responded rapidly both inside and outside the impoundments as exemplified by the increase in NH4(+)-N concentrations during a horseshoe crab die-off. Water quality indicators were high variable during the month in which water samples were collected. Because the impoundments are widely spaced it is logistically unrealistic to sample each of the impoundments and associated seagrass beds on a single day, sampling must be stratified to allow patterns of material movement and the annual flux of materials to and from the impoundments to be determined.

Blum, Linda K.↗

The Effect of Solar Proton Events on Ozone and Other Constituents in the Middle Atmosphere

Solar proton events (SPEs) can result in increases in both HO(x) (H, OH, HO2) and NO(x) (N, NO, NO2) constituents in the middle atmosphere polar region (>60 degrees geomagnetic). FlO(x) constituents produced by SPEs caused decreases in mesospheric and upper stratospheric ozone observed during several events. Recent SPEs in July and November of 2000 caused ozone decreases of over 30 percent during the event as measured by UARS HALOE and NOAA 14 SBUV/2. These HO(x)-driven ozone depletions last only during the SPEs (several hours to a few days) because of the short lifetimes of HO(x) constituents in the atmosphere. The NO(x) species feed into the entire odd nitrogen family NO(y) (N, NO, NO2, NO3, N2O5, HNO,14NO4, CIONO2, BrONO2) over a period of hours to weeks. The NO(y) family lasts several months or more in the stratosphere with low sun conditions. The two largest SPEs in the past 30 years, October 1989 and August 1972, caused polar stratospheric ozone depletions >10 percent for weeks past the events. The SPE in July 2000, third largest in 30 years, was measured by NOAA 14 SBUV/2 to decrease ozone by several percent for days past the event. Enhancements in mesospheric NO(x) of over 50 ppbv were also measured by UARS HALOE during this event. A review of the influence of SPEs on ozone and other constituents in the middle atmosphere will be given in this talk.

Jackman, Charles H.↗