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At least 199 records · Page 11

Evaluation of CMIP6 Model Simulations of PM 2.5 and its Components Over China

Earth system models (ESMs) participating in the latest Coupled Model Intercomparison Project Phase 6 (CMIP6) simulate various components of fine particulate matter (PM 2.5 ) as major climate forcers. Yet the model performance for PM 2.5 components remains little evaluated due in part to a lack of observational data. Here, we evaluate near-surface concentrations of PM 2.5 and its five main components over China as simulated by 14 CMIP6 models, including organic carbon (OC; available in 14 models), black carbon (BC; 14 models), sulfate (14 models), nitrate (4 models), and ammonium (5 models). For this purpose, we collect observational data between 2000 and 2014 from a satellite-based dataset for total PM2.5 and from 2469 measurement records in the literature for PM 2.5 components. Seven models output total PM 2.5 concentrations, and they all underestimate the observed total PM 2.5 over eastern China, with GFDL-ESM4 (−1.5 %) and MPI-ESM-1-2-HAM (−1.1 %) exhibiting the smallest biases averaged over the whole country. The other seven models, for which we recalculate total PM 2.5 from the available component output, underestimate the total PM 2.5 concentrations partly because of the missing model representations of nitrate and ammonium. Concentrations of the five individual components are underestimated in almost all models, except that sulfate is overestimated in MPI-ESM-1-2-HAM by 12.6 % and in MRI-ESM2-0 by 24.5 %. The underestimation is the largest for OC (by −71.2 % to −37.8 % across the 14 models) and the smallest for BC (−47.9 % to −12.1 %). The multi-model mean (MMM) reproduces the observed spatial pattern for OC (R = 0.51), sulfate (R = 0.57), nitrate (R = 0.70) and ammonium (R = 0.74) fairly well, yet the agreement is poorer for BC (R = 0.39). The varying performances of ESMs on total PM 2.5 and its components have important implications for the modeled magnitude and spatial pattern of aerosol radiative forcing.

CMIP6↗

Fixation of nitrogen in the prebiotic atmosphere

Reactions between nitrogen and water in the air surrounding lightning discharges can provide an important source of nitric oxide even under conditions where oxygen is a minor atmospheric constituent. Estimates are given for the associated source of soluble nitrite and nitrate. It is shown that lightning and subsequent atmospheric chemistry can provide a source of nitrate for the primitive ocean as large as one million tons of nitrogen per year, sufficient to fill the ocean to its present level of nitrate in less than one million years.

Yung, Y. L.↗

Aircraft sampling of the sulfate layer near the tropopause following the eruption of Mount St. Helens

Twenty filter sampling flights of the NASA Lewis F-106 aircraft were conducted in the Great Lakes region between June 4 and August 8, 1980, following the major eruption of Mount St. Helens, Washington on May 18. The IPC-1478 filters were exposed over an altitude range spanning the local tropopause. Quarter sections were analyzed for sulfate and nitrate by ion chromatography and selected samples were analyzed for chloride by selective ion electrode. Trace elements were searched by X-ray fluorescence analysis. A filter sample taken above the tropopause on June 5 indicated a sulfate level of 50 times the baseline measurements. Subsequent measurements over a period of 2 months showed an initial dropoff and formation of a persistent layer of sulfate above the tropopause with a concentration of 10 to 18 times previously measured background-levels. Concentrations of nitrate above the tropopause exhibited considerable variability and some enhancement compared with previously measured concentration levels. It is suggested that the source of the nitrate may also be volcanic as evidenced by its temporal relationship to the sulfate concentration changes. Based on the null results of X-ray fluorescence measurements, there is no evidence of ash particle concentrations greater than 3.4 microns g/cubic m persisting in the layer above the tropopause after the second transit of the cloud.

Lezberg, E. A.↗

Recent studies of the ocean nitrogen cycle

The nitrogen cycle in the ocean is dominated by the activities of organisms. External nitrogen inputs from land and from the atmosphere are small compared with rates of consumption and production by organisms and with rates of internal rearrangements of nitrogen pools within the ocean. The chief reservoirs of nitrogen are, in decreasing order of size: nitrogen in sediments, dissolved N2, nitrate, dissolved organic nitrogen (DON), particulate organic nitrogen (PON) (mostly organisms and their by-products). The biogenic fluxes of nitrogen were reviewed. The rate of PON decomposition in the surface layer must be comparable to the rate of ammonium consumption; and at the same time the nitrate consumption rate will be similar to the rates of: (1) sinking of PON out of the surface layer and its decompositon at depth, (2) the rate of nitrification at depth, and (3) the rate of nitrate return to the surface layer by upwelling.

Eppley, R. W.↗

Mononitration of durene

Reaction conditions under which the nitration of durene give predominantly, and in high yield, mononitrodurene (I), rather than dinitrodurene were found. The nitrating agent was No2+RF6-. Nitration with nitrosulfuric acid also gave mononitrodurene; however, byproducts such as 2.3.5.6-Me4C6HCH2C6H2Me3-2,4,5, were also formed. The NO2 PF6- gave an intermediate additional compound with durene. The reaction carried out with 3.6-dideuterodurene in D2O shows no isotope effect.

Hanna, S. B.↗

Halobacterium denitrificans sp. nov., an extremely halophilic denitrifying bacterium

Halobacterium denitrificans was one of several carbohydrate-utilizing, denitrifying, extremely halophilic bacteria isolated by anaerobic enrichment in the presence of nitrate. Anaerobic growth took place only when nitrate (or nitrite) was present and was accompanied by the production of dinitrogen. In the presence of high concentrations of nitrate (i.e., 0.5 percent), nitrous oxide and nitrite were also detected. When grown aerobically in a mineral-salts medium containing 0.005 percent yeast extract, H. denitrificans utilized a variety of carbohydrates as sources of carbon and energy. In every case, carbohydrate utilization was accompanied by acid production.

Tomlinson, G. A.↗

Halobacterium denitrificans sp. nov. - An extremely halophilic denitrifying bacterium

Halobacterium denitrificans was one of several carbohydrate-utilizing, denitrifying, extremely halophilic bacteria isolated by anaerobic enrichment in the presence of nitrate. Anaerobic growth took place only when nitrate (or nitrite) was present and was accompanied by the production of dinitrogen. In the presence of high concentrations of nitrate (i.e., 0.5 percent), nitrous oxide and nitrite were also detected. When grown aerobically in a mineral-salts medium containing 0.005 percent yeast extract, H. denitrificans utilized a variety of carbohydrates as sources of carbon and energy. In every case, carbohydrate utilization was accompanied by acid production.

Tomlinson, G. A.↗

Modeling new production in upwelling centers - A case study of modeling new production from remotely sensed temperature and color

A method has been developed for estimating new production in upwelling systems from remotely sensed surface temperatures. A shift-up model predicts the rate of adaptation of nitrate uptake. The time base for the production cycle is obtained from a knowledge of surface heating rates and differences in temperature between the point of upwelling and each pixel. Nitrate concentrations are obtained from temperature-nitrate regression equations. The model was developed for the northwest Africa upwelling region, where shipboard measurements of new production were available. It can be employed in two modes, the first using only surface temperatures, and the second in which CZCS color data are incorporated. The major advance offered by this method is the capability to estimate new production on spatial and time scales inaccessible with shipboard approaches.

Dugdale, Richard C.↗

Exploring the limits of crop productivity: A model to evaluate progress

The goal was to determine the limits of crop productivity when all environmental constraints were removed. Researchers define productivity as food output per unit of input. Researchers evaluated cultivars of wheat with reduced leaf size and number to decrease the leaf area index at high plant densities. These cultivars may also have an improved harvest index. Hydroponic studies indicate that 1 mM nitrate in solution is adequate to support maximum growth in these systems, provided iron nutrition is adequate. Wheat does not accumulate nitrate in leaves even when the solution nitrate concentration is 15 mM. Long-term photosynthetic efficiency (g mol (exp -1) of photons) and harvest index were not altered by photoperiod (16, 20, or 24 hours). Wheat does not need, nor benefit from, a diurnal dark period.

Bugbee, Bruce↗

Annular denuder systems: Precision and applicability to stratospheric sampling

Annular denuder systems (ADS) are designed to sample both gases and particles from ambient air without cross interference. The ADS's were used to detect chemical gradients over rural forest canopies. Accurate and precise methods for the sampling and analysis of low concentrations of gaseous and particulate species over short sampling periods were developed. Typical analytical precision data for nitrate and sulfate are shown. Both sampling and analytical precision data for a 2 hour test using four collocated ADS's are presented. On this particular day, the overall precision for HNO3 was unusually poor. The overall precision for the major constituents of interest is generally about 3 to 5 percent for typical ambient concentrations. The ADS's could potentially be used to determine the concentrations of HNO3 and fine-particle nitrate in the stratosphere, and to simultaneously characterize the chemical composition of stratospheric aerosols. Assuming 50 mb pressure, a 2 hour sampling time, a 50 Lpm sampling rate, and a low blank value, an overal precision of about 15 percent should be possible for 1 ppbv of HNO3 or nitrate, which would include nitric-acid trihydrate (NAT); and pump-driven systems could accommodate more complex systems involving denuders and filter packs in sequence. Alternate coatings could possibly be developed to selectively sample species such as Cl2 and ClNO3. The ADS's might also be useful in laboratory studies of heterogeneous chemical reactions involving NAT aerosols.

Randtke, Stephen J.↗

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Niki, Hiromi↗

Airplane dopes and doping

Cellulose acetate and cellulose nitrate are the important constituents of airplane dopes in use at the present time, but planes were treated with other materials in the experimental stages of flying. The above compounds belong to the class of colloids and are of value because they produce a shrinking action on the fabric when drying out of solution, rendering it drum tight. Other colloids possessing the same property have been proposed and tried. In the first stages of the development of dope, however, shrinkage was not considered. The fabric was treated merely to render it waterproof. The first airplanes constructed were covered with cotton fabric stretched as tightly as possible over the winds, fuselage, etc., and flying was possible only in fine weather. The necessity of an airplane which would fly under all weather conditions at once became apparent. Then followed experiments with rubberized fabrics, fabrics treated with glue rendered insoluble by formaldehyde or bichromate, fabrics treated with drying and nondrying oils, shellac, casein, etc. It was found that fabrics treated as above lost their tension in damp weather, and the oil from the motor penetrated the proofing material and weakened the fabric. For the most part the film of material lacked durability. Cellulose nitrate lacquers, however were found to be more satisfactory under varying weather conditions, added less weight to the planes, and were easily applied. On the other hand, they were highly inflammable, and oil from the motor penetrated the film of cellulose nitrate, causing the tension of the fabric to be relaxed.

PROTECTIVE COATINGS AND COVERINGS↗

Investigation of new hypergol scrubber technology

The ultimate goal of this work is to minimize the liquid waste generated from the scrubbing of hypergolic vent gases. In particular, nitrogen tetroxide, a strong oxidizer used in hypergolic propellant systems, is currently scrubbed with a sodium hydroxide solution resulting in a hazardous liquid waste. This study investigated the use of a solution of potassium hydroxide and hydrogen peroxide for the nitrogen textroxide vent scrubber system. The potassium nitrate formed would be potentially usable as a fertilizer. The hydrogen peroxide is added to convert the potassium nitrite that is formed into more potassium nitrate. Smallscale laboratory tests were conducted to establish the stability of hydrogen peroxide in the proposed scrubbing solution and to evaluate the effectiveness of hydrogen peroxide in converting nitrite to nitrate.

Glasscock, Barbara H.↗

Process and Equipment for Nitrogen Oxide Waste Conversion to Fertilizer

The present invention describes a process for converting vapor streams from sources containing at least one nitrogen-containing oxidizing agent therein to a liquid fertilizer composition comprising the steps of: (1) directing a vapor stream containing at least nitrogen-containing oxidizing agent to a first contact zone; (2) contacting said vapor stream with water to form nitrogen oxide(s) from said at least one nitrogen- containing oxidizing agent; (3) directing said acid(s) as a second stream to a second contact zone; (4) exposing said second stream to hydrogen peroxide which is present within said second contact zone in a relative amount of at least 0.1% by weight of said second stream within said second contact zone to convert at least some of any nitrogen oxide species or ions other than in the nitrite form present within said second stream to nitrate ion; (5) sampling said stream within said second contact zone to determine the relative amount of hydrogen peroxide within said second contact zone; (6) adding hydrogen peroxide to said second contact zone when a level on hydrogen peroxide less than 0.1% by weight in said second stream is determined by said sampling; (7) adding a solution comprising potassium hydroxide to said second stream to maintain a pH between 6.0 and 11.0 within said second stream within said second contact zone to form a solution of potassium nitrate; and (8) removing sais solution of potassium nitrate from said second contact zone.

Lueck, Dale E.↗

Update on N2O4 Molecular Sieving with 3A Material at NASA/KSC

During its operational life, the Shuttle Program has experienced numerous failures in the Nitrogen Tetroxide (N2O4) portion of Reaction Control System (RCS), many of which were attributed to iron-nitrate contamination. Since the mid-1980's, N2O4 has been processed through a molecular sieve at the N2O4 manufacturer's facility which results in an iron content typically less than 0.5 parts-per-million-by-weight (ppmw). In February 1995, a Tiger Team was formed to attempt to resolve the iron nitrate problem. Eighteen specific actions were recommended as possibly reducing system failures. Those recommended actions include additional N2O4 molecular sieving at the Shuttle launch site. Testing at NASA White Sands Test Facility (WSTF) determined an alternative molecular sieve material could also reduce the water-equivalent content (free water and HNO3) and thereby further reduce the natural production of iron nitrate in N2O4 while stored in iron-alloy storage tanks. Since April '96, NASA Kennedy Space Center (KSC) has been processing N2O4 through the alternative molecular sieve material prior to delivery to Shuttle launch pad N2O4 storage tanks. A new, much larger capacity molecular sieve unit has also been used. This paper will evaluate the effectiveness of N2O4 molecular sieving on a large-scale basis and attempt to determine if the resultant lower-iron and lower-water content N2O4 maintains this new purity level in pad storage tanks and shuttle flight systems.

Davis, Chuck↗

Ammonia Formation by the Reduction of Nitrite/Nitrate by FeS: Ammonia Formation Under Acidic Conditions

FeS reduces nitrite to, ammonia at pHs lower than the corresponding reduction by aqueous Fe+2. The reduction follows a reasonable first order decay, in nitrite concentration, with a half life of about 150 min (room temperature, CO2, pH 6.25). The highest ammonia product yield measured was 53%. Under CO2, the product yield decreases from pH 5.0 to pH 6.9. The increasing concentration of bicarbonate at higher pH interferes with the reaction. Bicarbonate interference is shown by comparing runs under N2 and CO2. The reaction proceeds well in the presence of such species as chloride, sulfate, and phosphate though the yield drops significantly with phosphate. FeS also reduces nitrate and, unlike with Fe+2, the reduction shows more reproducibility. Again, the product yield decreases with increasing pH, from 7% at pH 4.7 to 0% at pH 6.9. It appears as if nitrate is much more sensitive to the presence of added species, perhaps not competing as well for binding sites on the FeS surface. This may be the cause of the lack of reproducibility of nitrate reduction by Fe+2 (which also can be sensitive to binding by certain species).

Summers, David P.↗

New Chemical, Bio-Optical and Physical Observations of Upper Ocean Response to the Passage of a Mesoscale Eddy Off Bermuda

A mesoscale eddy advected across the Bermuda Testbed Mooring site over a 30-day period centered on July 14, 1995. Temperature and current measurements along with biogeochemical measurements were used to characterize the biological response of the upper ocean associated with the introduction of nitrate into the euphotic layer due to the doming of isotherms associated with the eddy. Complementary shipboard data showed an anomalous water mass, which extended from a depth of approximately 50 to 1000 m, manifesting as a cold surface expression and warm anomaly at depth. Although mesoscale eddies are frequently observed in the Sargasso Sea, the present observations are particularly unique because of the high-temporal-resolution measurements of the new instrumentation deployed on the mooring. Analyzers that measure nitrate plus nitrite were placed at depths of 80 and 200 m and bio-optical sensors were located at depths of 20, 35, 45, 71, and 86 m. Peak nitrate values of nearly 3.0 micro-M at 80 m and chlorophyll a values of 1.4 mg/cubic m at 71 m were observed, a well as a 25- to 30-meter shoaling of the 1% light level depth. A Doppler shift from the inertial period (22.8 hours) to 25.2 hours was observed in several time series records due to the movement of the eddy across the mooring. Inertial pumping brought cold, nutrient-rich waters farther into the euphotic zone than would occur solely by isothermal lifting. Silicic acid was depleted to undetectable levels owing to the growth of diatoms within the eddy. The chlorophyll a values associated with the eddy appear to be the largest recorded during the eight years of the ongoing US JGOFS Bermuda Atlantic Time Series Study program.

McNeil, J. D.↗

New Chemical, Bio-Optical and Physical Observations of Upper Ocean Response to the Passage of a Mesoscale Eddy off Bermuda

A mesoscale eddy advected across the Bermuda Testbed Mooring site over a 30-day period centered on July 14, 1995. Temperature and current measurements along with biogeochemical measurements were used to characterize the biological response of the upper ocean associated with the introduction of nitrate into the euphoric layer due to the doming of isotherms associated with the eddy. Complementary shipboard data showed an anomalous water mass, which extended from a depth of approximately 50 to 1000 m, manifesting as a cold surface expression and warm anomaly at depth. Although mesoscale eddies are frequently observed in the Sargasso Sea, the present observations are particularly unique because of the high-temporal-resolution measurements of the new instrumentation deployed on the mooring. Analyzers that measure nitrate plus nitrite were placed at depths of 80 and 200 m and bio-optical sensors were located at depths of 20, 35, 45, 71, and 86 m. Peak nitrate values of nearly 3.0 microns at 80 m and chlorophyll alpha values of 1.4 mg/cu m at 71 m were observed, as well as a 25- to 30-meter shoaling of the 1% light level depth. A Doppler shift from the inertial period (22.8 hours) to 25.2 hours was observed in several time series records due to the movement of the eddy across the mooring. Inertial pumping brought cold, nutrient-rich waters farther into the euphotic zone than would occur solely by isothermal lifting. Silicic acid was depleted to undetectable levels owing to the growth of diatoms within the eddy. The chlorophyll alpha values associated with the eddy appear to be the largest recorded during the 8 years of the ongoing U.S. JGOFS Bermuda Atlantic Time Series Study (BATS) program.

McNeil, J. D.↗