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Research and achievements of the wartime Jet Propulsion Laboratory are outlined. Accomplishments included development of the solid-propellant Private A and private R rockets and the liquid-propellant nitric acid-aniline WAC Corporal rocket.
Vertical profiles of N2O and NO(y) taken by the ER-2 outside the vortex are used to construct average vertical profiles of F(NO(y)) = NO(y)/(A-N2O), where A is the tropospheric content of N2O three years prior to the measurements. The southern hemisphere had less nitrous oxide in the range 400 less than Theta less than 470 K, by up to 25% relative to the northern hemisphere. F(NO(y)) is the ratio of NOy produced to N2O lost in a stratospheric air mass since entry from the troposphere. The profiles of F(NO(y)) have the following characteristics: (1) Relative to 1991-1992, a year without denitrification inside or outside the vortex, the northern hemisphere in 1988-1989 showed denitrification outside the vortex ranging up to 25% and averaging 17% above Theta = 425 K. (2) Relative to the northern hemisphere in 1991-1992, the southern hemisphere in 1987 showed denitrification outside the vortex ranging up to 32% and averaging 20% above Theta = 400 K. (3) Below Theta = 400 K the southern hemisphere showed enhancements of F(NO(y)) relative to the northern hemisphere in 1991-1992 ranging up to 200% at Theta = 375 K, outside the vortex. Corresponding profiles of residual water, R(H2O) = H2O - 2(1.6 - CH4), are considered and shown to be consistent with those of F(NO(y)) in the sense that they show deficits outside the Antarctic vortex, which was both dehydrated and denitrified, but not outside the 1988-1989 Arctic vortex, which was denitrified but not dehydrated. R(H2O) is the water content of stratospheric air with the contribution from methane oxidation subtracted. Comparison of F(NO(y)) and R(H2O) below 400 K outside the Antarctic vortex leads to the suggetion that dehydration in the Antarctic vortex occurs by the sedimentation of ice crystals large enough to fall out of the stratosphere, whereas denitrification occurs mainly on mixed nitric acid-water crystals which evaporate below the base of the vortex at Theta = 400 K but above the tropopause.
We present Microwave Limb Sounder (MLS) measurements fo gas-phase HNO(sub 3) obtained at the beginning of five southern hemisphere winters.
The reaction probabilities of N2O5 and ClONO2 with H2O on.
Polar stratospheric clouds (PSC) play a primary role in the formation of annual ozone holes over Antarctica during the austral sunrise. Meridional temperature gradients in the lower stratosphere and upper troposphere, caused by strong radiative cooling, induce a broad dynamic vortex centered near the South Pole that decouples and insulates the winter polar airmass. PSC nucleate and grow as vortex temperatures gradually fall below equilibrium saturation and frost points for ambient sulfate, nitrate, and water vapor concentrations (generally below 197 K). Cloud surfaces promote heterogeneous reactions that convert stable chlorine and bromine-based molecules into photochemically active ones. As spring nears, and the sun reappears and rises, photolysis decomposes these partitioned compounds into individual halogen atoms that react with and catalytically destroy thousands of ozone molecules before they are stochastically neutralized. Despite a generic understanding of the ozone hole paradigm, many key components of the system, such as cloud occurrence, phase, and composition; particle growth mechanisms; and denitrification of the lower stratosphere have yet to be fully resolved. Satellite-based observations have dramatically improved the ability to detect PSC and quantify seasonal polar chemical partitioning. However, coverage directly over the Antarctic plateau is limited by polar-orbiting tracks that rarely exceed 80 degrees S. In December 1999, a NASA Micropulse Lidar Network instrument (MPLNET) was first deployed to the NOAA Earth Systems Research Laboratory (ESRL) Atmospheric Research Observatory at the Amundsen-Scott South Pole Station for continuous cloud and aerosol profiling. MPLNET instruments are eye-safe, capable of full-time autonomous operation, and suitably rugged and compact to withstand long-term remote deployment. With only brief interruptions during the winters of 2001 and 2002, a nearly continuous data archive exists to the present.
Determining the sources of total nitrate (TNIT NO-3 + HNO3) reaching Antarctica is a long-standing challenge. Here we analyze the monthly sensitivity of surface-level TNIT in Antarctica to primary sources using a global 3-D chemical transport model, GEOS-Chem, and its adjoint. Modeled seasonal variation of TNIT concentrations shows good agreement with several measurement studies, given that the lack of post-depositional processing in the model leads to an expected underestimate of maximum values in November through January. Remote NOx sources have the greatest impact May-July, during when the model background concentrations are sensitive to NOx emissions from fossil fuel combustion, soil, and lightning originating from 25S to 65S. In this season, NOx is transported to Antarctica as TNIT, which is formed above continental source regions at an altitude of 5-11 km. In other seasons, more NOx is transported as a reservoir species (e.g., peroxyacetyl nitrate, PAN) through the free troposphere, transforming into TNIT within a cone of influence that extends to 35S and above 4 km altitude. Photolysis of PAN over Antarctica is the main driver of modeled NOx seasonality. Stratospheric production and loss of tracers are relatively unimportant in monthly sensitivities in GEOS-Chem, driving only a few percent of surface level variability of TNIT. A small peak concentration in August is captured by the model, although some measured values in August fall outside the range of simulated concentrations. Modifications to the model to represent sedimentation of polar stratospheric clouds (PSCs) lead to increased surface level August TNIT concentrations. However, this simple representation does not explicitly account for PSC particle deposition or disappearance of the tropopause in the middle of winter, and thus the influence of stratospheric nitrate sources estimated in this study is likely a lower bound.
In the framework of the INDAAF (International Network to study Deposition and Atmospheric chemistry in AFrica) programme, part of the ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure), European Research Infrastructure for the long-term observation of Aerosol, Cloud, and Trace gases, this paper aims to study trends and seasonal variability of surface atmospheric NO2 and HNO3 concentrations, and OMI (Ozone Monitoring Instrument) NO2 over 6 sites in tropical Africa. Sites are located in west and central Africa to represent the major African biomes: dry savanna (Banizoumbou, Niger and Katibougou, Mali), wet savanna (Djougou, Benin and Lamto, Côte d’Ivoire) and forest (Bomassa, Republic of Congo and Zoétélé, Cameroon). Ground-based NO2 and HNO3 concentrations were obtained over the period 1998–2015 using INDAAF passive samplers at a monthly basis, and NO2 Vertical Column Densities (VCDs) from OMI for a 1-degree grid cell around each sites were obtained from 2005 to 2015. Mean annual NO2 concentrations ranged from 2.3 plus or minus 1.2 to 0.9 plus or minus 0.4 parts per billion (ppb) from dry savannas to forests, representing a north-south gradient. In dry savannas, we observe two concentration peaks of NO2 appearing at the beginning and the end of the wet season both for ground-based and satellite measurements, whereas at wet savannas and forest sites, NO2 concentrations are highest in the dry season. The seasonality of surface NO2 observations provide further evidence for a large role of microbial soil NOx emissions in dry savannas and of biomass burning NOx emissions in wet savanna and forest sites. Mean annual HNO3 concentrations ranged from 0.4 to 0.5 ppb in dry and wet savannas to 0.2 to 0.3 ppb in forest. In dry ecosystems, higher HNO3 concentrations are measured in the early wet season, consistent with NO2 results. The analysis of a long-term dataset of surface O3 concentrations indicates that HNO3 production can mainly be explained by the photo-oxidation of NOx. Mann-Kendall and Seasonal Kendall statistical tests showed that NO2 surface concentrations have a significant decreasing seasonal and annual trends at multiple sites (p-value less than 0.05) ranging from -2.96 percent per year (at Zoétélé) to -0.64 percent per year (at Banizoumbou). HNO3 results indicate no trends except at Bomassa (1.07 percent per year). The decreasing NO2 ground-based concentration trends observed in wet savannas sites are correlated with OMI NO2 decreasing trends at these sites. Trends obtained for NO2 concentrations in wet savanna and forest ecosystems are consistent with trends of NOₓ biomass burning emissions.
Highlight slides for DOE EM TDO mid-year program review.
Plutonium plays a critical role in nuclear fuel cycle technologies, but our understanding of its fundamental radiation-induced redox chemistry is limited. Changes in oxidation states affect the speciation and transport of plutonium ions in solution. For example, solvent extraction techniques used to separate and recover plutonium from used nuclear fuel rely on the selective formation, maintenance, and complexation of specific plutonium oxidation states. However, radiolytically generated radicals, ions, and molecules can drive the oxidation state distribution of plutonium ions far from equilibrium, ultimately changing the physical and chemical properties of the bulk system. These radiation-induced processes are inevitable due to the ionizing radiation fields generated by the radioactive decay of plutonium and its daughter nuclides. Therefore, mechanistically understanding how plutonium's various oxidation states respond to ionizing radiation is essential for predicting its behavior in solution. Here, we present significant advances in our understanding of radiation-induced plutonium redox chemistry by using time-resolved (electron pulse) and dose accumulation (alpha and gamma) irradiation techniques, along with quantitative multiscale modeling methods.
Reduction of nitrite anions (NO 2 - ) to nitric oxide (NO), nitrous oxide (N 2 O) and ultimately dinitrogen (N 2 ) takes place in a variety of environments, including in the soil as part of the biogeochemical nitrogen cycle and in acidified nuclear waste. Nitrite reduction typically takes place within the coordination sphere of a redox-active transition metal. In this report we show that Lewis acid coordination can substantially modify the reduction potential of this polyoxoanion to allow for its reduction under non-aqueous conditions (-0.74 V versus NHE). Detailed characterization confirms the formation of the borane-capped radical nitrite dianion (NO 2 2- ), which features a N(II) oxidation state. Protonation of the nitrite dianion results in the facile loss of nitric oxide (NO), whereas its reaction with NO results in disproportionation to nitrous oxide (N 2 O) and nitrite (NO 2 - ). This system connects three redox levels in the global nitrogen cycle and provides fundamental insights into the conversion of NO 2 - to NO.
Following a mandate by the International Aerosol Climatology Program under the auspices of International Association of Meteorology and Atmospheric Physics International Radiation Commission, 45 scientists from five nations convened to discuss relevant issues associated with the measurement, properties, and effects of stratospheric aerosols. A summary is presented of the discussions on formation and evolution, transport and fate, effects on climate, role in heterogeneous chemistry, and validation of lidar and satellite remote sensing of stratospheric aerosols. Measurements are recommended of the natural (background) and the volcanically enhanced aerosol (sulfuric acid and silica particles), the exhaust of shuttle, civil aviation and supersonic aircraft operations (alumina, soot, and ice particles), and polar stratospheric clouds (ice, condensed nitric and hydrochloric acids).
Metal sulfide ion exchange materials (MSIEs) are of interest for nuclear waste remediation applications. Here, we report the high stability of two structurally related metal sulfide ion exchange materials, Na 2x Mg 2y–x Sn 4–y S 8 (Mg-NMS) and Na 2 SnS 3 (Na-NMS), in strongly acid media, in addition to the preparation of Na 2x Ni 2y–x Sn 4–y S 8 (Ni-NMS). Their formation progress during synthesis is studied with in-situ methods, with the target phases appearing in <15 min, reaction completion in <12 h, and high yields (75–80%). Upon contact with nitric or hydrochloric acid, these materials topotactically exchange Na + for H + , proceeding in a stepwise protonation pathway for Na 5.33 Sn 2.67 S 8 . Na-NMS is stable in 2 M HNO 3 and Mg-NMS is stable in 4 M HNO 3 for up to 4 h, while both NMS materials are stable in 6 M HCl for up to 4 days. However, the treatment of Mg-NMS and Na-NMS with 2–6 M H 2 SO 4 reveals a much slower protonation process since after 4 h of contact both NMS and HMS are present in the solution. The resultant protonated materials, H 2x Mg 2y–x Sn 4–y S 8 and H 4x [(H y Na y–1 ) 1.33x Sn 4––1.33x ]S 8 , are themselves solid acids and readily react with and intercalate a variety of organic amines, where the band gap of the resultant adduct is influenced by amine choice and can be tuned within the range of 1.88(5)–2.27(5) eV. The work function energy values for all materials were extracted from photoemission yield spectroscopy in air (PYSA) measurements and range from 5.47 (2) to 5.76 (2) eV, and the relative band alignments of the materials are discussed. DFT calculations suggest that the electronic structure of Na 2 MgSn 3 S 8 and H 2 MgSn 3 S 8 makes them indirect gap semiconductors with multi-valley band edges, with carriers confined to the [MgSn 3 S 8 ] 2– layers. Light electron effective masses indicate high electron mobilities.
Theories for the origin of life require the availability of reduced nitrogen for the formation of such species as amino acid and nucleic acids. In a strongly reducing atmosphere, compounds essential to the chemical evolution of life, such as amino acids, can form by reactions between HCN, NH3, and carbonyl compounds produced in spark discharges. However, under non-reducing atmospheres, electric discharges produced NO rather than HCN or NH3. This raises the questions of; how ammonia can be formed under a neutral atmosphere, and what conditions are needed such formation to occur? On possibility is the conversion of NO into nitric and nitrous acids (through HNO) and rained into the oceans. The reduction of nitrite by aqueous Fe(II) (6 Fe(+2) + 7 H(+) + NO2(-) yields 6 Fe(III) + 2 H2O + NH3) such as was present on the early Earth could then have produced ammonia. However, this reaction does not proceed at pHs less than 7.3. An alternative is reduction by other forms of Fe(II), such as FeS. We will present results that show that FeS can reduce nitrite to ammonia at pHs as low as pH 5 under a variety of conditions.
Mercury extraction has been studied in nitric and hydrochloric acids with hexathia-18-crown-6 dissolved in carbon tetrachloride. Batch study experiments have been performed to determine the best conditions for maximum extraction. In both acids, Hg(II) was best extracted at low molarity while almost no extraction was observed above 2 M. Furthermore, speciation studies were carried out in an attempt to describe the extraction mechanism, but the exact composition of the extracted species was not determined. The extraction kinetics were studied to assess the feasibility of this crown ether for extracting Cn and/or Fl in a future online experiment.
Here, in preparation for implementing the Nitric-Glycolic (NG) acid flowsheet for the Savannah River Site (SRS) Liquid Waste System (LWS), analytical methods for determining glycolate at low concentration, below 20 mg/L in radioactive samples, were developed to support system management and safety. To accommodate the wide range of LWS matrix conditions, two alternative methods were developed, refined, and demonstrated for glycolate analysis in radioactive waste samples: ion chromatography (IC) and a proton nuclear magnetic resonance (H NMR). Investigators validated IC and H NMR methods for glycolate analysis, defined the range of applicability, and demonstrated key supporting analytical protocols. The deployed IC method is applicable in low to moderate ionic strength samples and requires sample pretreatment using a Dionex OnGuard II H + cartridge. The deployed H NMR method is more labor intensive but provides options for a broader range of matrices. Based on the results, high quality glycolate analysis of the Defense Waste Processing Facility (DWPF) condensate in Tank 22 is feasible by IC down to approximately 12 mg/L. Using H NMR, glycolate may be determined to 8 mg/L or lower depending on the run time with the potential for broader applicability of the method to higher ionic strength conditions in other tanks of the SRS LWS.
Liners for nitric and hydrofluoric acid tanks show no sign of deterioration after 18 months of continuous use. Each side of each edge of the polypropylene sheets is chamfered, and sheets are welded from both sides with polypropylene filler rod and a special hot-air welding torch.
Preferential etching by mixture of nitric and hydrochloric acids reveals crystal dislocation defects (type D) and impurity-dislocation defects (type S) in these crystals, which have optical and electrical applications.
A mixture of nitric and hydrochloric acids was found to yield etch pits on mercury cadmium telluride crystals grown by chemical vapor transport using iodine or mercuric iodide as the transport agent. Two types of pits were observed by optical microscopy: triangular pyramidal and round saucer shaped pits. Transmission electron microscopy confirmed that two types of defects were present: dislocations and second phase occlusions. The present study suggests that the defects are near the crystal surface and therefore will probably not significantly affect the electrical characteristics.