scholarly journals Factors controlling Arctic denitrification in cold winters of the 1990s

2003 ◽  
Vol 3 (2) ◽  
pp. 403-416 ◽  
Author(s):  
G.W. Mann ◽  
S. Davies ◽  
K. S. Carslaw ◽  
M. P. Chipperfield
Keyword(s):  
Nitric Acid ◽  
Nucleation Rate ◽  
The Other ◽  
The Arctic ◽  
Optimum Conditions ◽  
Flow Area ◽  
Closed Loops ◽  
Particle Properties ◽  
Sensitivity Studies ◽  
High Degree

Abstract. Denitrification of the Arctic winter stratosphere has been calculated using a 3-D microphysical model for the winters 1994/95, 1995/96, 1996/97 and 1999/2000. Denitrification is assumed to occur through the sedimentation of low number concentrations of large nitric acid trihydrate (NAT) particles (as inferred by e.g. Fahey et al., 2001). We examine whether the meteorological conditions that allowed particles to grow to the very large sizes observed in 1999/2000 also occurred in the other cold winters. The results show that winter 1999/2000 had conditions that were optimum for denitrification by large NAT particles, which are a deep concentric NAT area and vortex. Under these conditions, NAT particles can circulate in the NAT-supersaturated air for several days, reaching several micrometres in radius and leading to a high downward flux of nitric acid. The other winters had shorter periods with optimum conditions for denitrification. However, we find that NAT particles could have grown to large sizes in all of these winters and could have caused significant denitrification. We define the quantity "closed-flow area'' (the fraction of the NAT area in which air parcel trajectories can form closed loops) and show that it is a very useful indicator of possible denitrification. We find that even with a constant NAT nucleation rate throughout the NAT area, the average NAT number concentration and size can vary by up to a factor of 10 in response to this meteorological quantity. These changes in particle properties account for a high degree of variability in denitrification between the different winters. This large meteorologically induced variability in denitrification rate needs to be compared with that which could arise from a variable nucleation rate of NAT particles, which remains an uncertain quantity in models. Sensitivity studies show that although denitrification was likely approaching asymptotic minimum values throughout much of the 1999/2000 vortex, decreases in the volume-averaged nucleation rate would have substantially reduced the denitrification.

scholarly journals Factors controlling Arctic denitrification in cold winters of the 1990s

2002 ◽  
Vol 2 (6) ◽  
pp. 2557-2586
Author(s):  
G. W. Mann ◽  
S. Davies ◽  
K. S. Carslaw ◽  
M. P. Chipperfield
Keyword(s):  
Nitric Acid ◽  
Nucleation Rate ◽  
The Other ◽  
The Arctic ◽  
Cold Pool ◽  
Optimum Conditions ◽  
Flow Area ◽  
Closed Loops ◽  
Particle Properties ◽  
High Degree

Abstract. Denitrification of the Arctic winter stratosphere has been calculated using a 3-D microphysical model for the winters 1994/95, 1995/96, 1996/97 and 1999/2000. Denitrification is assumed to occur through the sedimentation of low number concentrations of large nitric acid trihydrate (NAT) particles, as observed extensively in 1999/2000. We examine whether the meteorological conditions that allowed NAT particles to grow to the very large sizes observed in 1999/2000 also occurred in the other cold winters. The results show that winter 1999/2000 had conditions that were optimum for denitrification by large NAT particles, which are a deep concentric cold pool and vortex. Under these conditions, NAT particles can circulate in the cold pool for several days, reaching several micrometres in radius and leading to a high downward flux of nitric acid. The other winters had shorter periods with optimum conditions for denitrification. However, we find that NAT particles could have grown to large sizes in all of these winters and could have caused significant denitrification. We define the quantity "closed flow area'' (the fraction of the cold pool in which air parcel trajectories can form closed loops) and show that it is a very useful indicator of possible denitrification. We find that even with a constant NAT nucleation rate throughout the cold pool, the average NAT number concentration and size can vary by up to a factor of 10 in response to this meteorological quantity. These changes in particle properties account for a high degree of variability in denitrification between the different winters. This large meteorologically induced variability in denitrification rate needs to be compared with that which could arise from a variable nucleation rate of NAT particles, which remains an uncertain quantity in models.

scholarly journals Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification

2002 ◽  
Vol 2 (3) ◽  
pp. 669-687 ◽  
Author(s):  
D. A. Knopf ◽  
T. Koop ◽  
B. P. Luo ◽  
U. G. Weers ◽  
T Peter
Keyword(s):  
Experimental Data ◽  
Nitric Acid ◽  
Nucleation Rate ◽  
Homogeneous Nucleation ◽  
Particle Production ◽  
Rate Coefficients ◽  
The Arctic ◽  
Linear Extrapolation ◽  
Acid Hydrate ◽  
Stratospheric Clouds

Abstract. The nucleation of NAD and NAT from HNO3/H2O and HNO3/H2O/H2SO4 solution droplets is investigated both theoretically and experimentally with respect to the formation of polar stratospheric clouds (PSCs). Our analysis shows that homogeneous NAD and NAT nucleation from liquid aerosols is insufficient to explain the number densities of large nitric acid containing particles recently observed in the Arctic stratosphere. This conclusion is based on new droplet freezing experiments employing optical microscopy combined with Raman spectroscopy. The homogeneous nucleation rate coefficients of NAD and NAT in liquid aerosols under polar stratospheric conditions derived from the experiments are < 2 x 10-5 cm-3 s-1 and < 8 x 10-2 cm-3 s-1 , respectively. These nucleation rate coefficients are smaller by orders of magnitude than the value of ~ 103 cm-3 s-1 used in a recent denitrification modelling study that is based on a linear extrapolation of laboratory nucleation data to stratospheric conditions (Tabazadeh et al., Science, 291, 2591--2594, 2001). We show that this linear extrapolation is in disagreement with thermodynamics and experimental data and, therefore, must not be used in microphysical models of PSCs. Our analysis of the experimental data yields maximum hourly production rates of nitric acid hydrate particles per cm3 of air of about 3 x 10-10 cm-3 h-1 under polar stratospheric conditions. Assuming PSC particle production to proceed at this rate for two months we arrive at particle number densities of < 5 x 10-7 cm-3, much smaller than the value of ~ 10-4 cm-3 reported in recent field observations. This clearly shows that homogeneous nucleation of NAD and NAT from liquid supercooled ternary solution aerosols cannot explain the observed polar denitrification.

scholarly journals Homogeneous nucleation of NAD and NAT in liquid stratospheric aerosols: insufficient to explain denitrification

2002 ◽  
Vol 2 (3) ◽  
pp. 207-214 ◽  
Author(s):  
D. A. Knopf ◽  
T. Koop ◽  
B. P. Luo ◽  
U. G. Weers ◽  
T. Peter
Keyword(s):  
Experimental Data ◽  
Nitric Acid ◽  
Nucleation Rate ◽  
Homogeneous Nucleation ◽  
Particle Production ◽  
Rate Coefficients ◽  
The Arctic ◽  
Linear Extrapolation ◽  
Acid Hydrate ◽  
Modelling Study

Abstract. The nucleation of NAD and NAT from HNO3/H2O and HNO3/H2SO4/H2O solution droplets is investigated both theoretically and experimentally with respect to the formation of polar stratospheric clouds (PSCs). Our analysis shows that homogeneous NAD and NAT nucleation from liquid aerosols is insufficient to explain the number densities of large nitric acid containing particles recently observed in the Arctic stratosphere. This conclusion is based on new droplet freezing experiments employing optical microscopy combined with Raman spectroscopy. The homogeneous nucleation rate coefficients of NAD and NAT in liquid aerosols under polar stratospheric conditions derived from the experiments are < 2 x 10-5 cm-3 s-1 and < 8 x 10-2 cm-3 s-1, respectively. These nucleation rate coefficients are smaller by orders of magnitude than the value of ~103 cm-3 s-1 used in a recent denitrification modelling study that is based on a linear extrapolation of laboratory nucleation data to stratospheric conditions (Tabazadeh et al., Science, 291, 2591--2594, 2001). We show that this linear extrapolation is in disagreement with thermodynamics and with experimental data and, therefore, must not be used in microphysical models of PSCs. Our analysis of the experimental data yields maximum hourly production rates of nitric acid hydrate particles per cm3 of air of about 3 x 10-10 cm-3 (air) h-1 under polar stratospheric conditions. Assuming PSC particle production to proceed at this rate for two months we arrive at particle number densities of < 5 x 10-7 cm-3, much smaller than the value of ~10-4 cm-3 reported in recent field observations. In addition, the nitric acid hydrate production rate inferred from our data is much smaller than that required to reproduce the observed denitrification in the modelling study mentioned above. This clearly shows that homogeneous nucleation of NAD and NAT from liquid supercooled ternary solution aerosols cannot explain the observed polar denitrification.

scholarly journals Nitric acid trihydrate nucleation and denitrification in the Arctic stratosphere

2014 ◽  
Vol 14 (2) ◽  
pp. 1055-1073 ◽  
Author(s):  
J.-U. Grooß ◽  
I. Engel ◽  
S. Borrmann ◽  
W. Frey ◽  
G. Günther ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Nucleation Rate ◽  
Regional Scale ◽  
Lagrangian Model ◽  
The Arctic ◽  
Orthogonal Polarization ◽  
Rate Model ◽  
Formation Pathway ◽  
Improved Model

Abstract. Nitric acid trihydrate (NAT) particles in the polar stratosphere have been shown to be responsible for vertical redistribution of reactive nitrogen (NOy). Recent observations by Cloud–Aerosol Lidar with Orthogonal Polarization (CALIOP) aboard the CALIPSO satellite have been explained in terms of heterogeneous nucleation of NAT on foreign nuclei, revealing this to be an important formation pathway for the NAT particles. In state of the art global- or regional-scale models, heterogeneous NAT nucleation is currently simulated in a very coarse manner using a constant, saturation-independent nucleation rate. Here we present first simulations for the Arctic winter 2009/2010 applying a new saturation-dependent parametrisation of heterogeneous NAT nucleation rates within the Chemical Lagrangian Model of the Stratosphere (CLaMS). The simulation shows good agreement of chemical trace species with in situ and remote sensing observations. The simulated polar stratospheric cloud (PSC) optical properties agree much better with CALIOP observations than those simulated with a constant nucleation rate model. A comparison of the simulated particle size distributions with observations made using the Forward Scattering Spectrometer Probe (FSSP) aboard the high altitude research aircraft Geophysica, shows that the model reproduces the observed size distribution, except for the very largest particles above 15 μm diameter. The vertical NOy redistribution caused by the sedimentation of the NAT particles, in particular the denitrification and nitrification signals observed by the ACE-FTS satellite instrument and the in situ SIOUX instrument aboard the Geophysica, are reproduced by the improved model, and a small improvement with respect to the constant nucleation rate model is found.

Extraction of iron, cobalt, nickel and copper with dibenzyl sulfoxide solution in toluene

1979 ◽  
Vol 44 (7) ◽  
pp. 2024-2031 ◽  
Author(s):  
František Vláčil ◽  
Huynh Dang Khanh
Keyword(s):  
Nitric Acid ◽  
Hydrochloric Acid ◽  
Distribution Ratio ◽  
Separation Factor ◽  
Chromatographic Separation ◽  
The Other ◽  
Iron Cobalt ◽  
Cobalt Nickel ◽  
Factor Α

The dependence of the distribution ratio of the metal on the concentration of hydrochloric of nitric acid was examined for Fe, Co, Ni and Cu extraction with 0.05M solution of dibenzylsulfoxide in toluene. Iron is extracted considerably more than the other metals, and is better extracted from hydrochloric acid than from nitric acid. The separation factor αFe/M (for 8M-HCl) is of the order of 104; this is not sufficient for a separation of trace quantities of iron from Co, Ni and Cu, but even at lower concentrations of HCl (e.g., 5M) the values is high enough for extraction chromatographic separation. The composition of the iron solvate extracted from HCl or LiCl medium was determined to be HFeCl4.2 B (B = dibenzyl sulfoxide).

Extraction of Am(III) by benzyldibutylamine from nitrate solutions of lanthanides

1981 ◽  
Vol 46 (1) ◽  
pp. 194-200 ◽  
Author(s):  
Marta Vojtíšková ◽  
Věra Jedináková ◽  
Libor Kuča
Keyword(s):  
Nitric Acid ◽  
Nuclear Fuel ◽  
Organic Phase ◽  
Spent Nuclear Fuel ◽  
Optimum Conditions ◽  
Separation Factors ◽  
Nitrate Solutions

Benzyldibutylamine is a suitable extractant for the separation of Am(III) and Ln(III) from the acidic nitrate solutions. The effect of lanthanides and yttrium on the extraction of Am(III) has been followed under the conditions modelling the content of these components in the spent nuclear fuel. The separation factors αAm/Ln were evaluated for the optimum conditions found for the separation of Am(III) from the lanthanides. The coextraction of nitric acid and water into the organic phase is discussed.

C-Terminal amino acid sequence of chicken pepsinogen and its homology with sequences of other acid proteases

1980 ◽  
Vol 45 (4) ◽  
pp. 1144-1154 ◽  
Author(s):  
Miroslav Baudyš ◽  
Helena Keilová ◽  
Vladimír Kostka
Keyword(s):  
Amino Acid ◽  
Amino Acid Sequence ◽  
The Other ◽  
Terminal Sequence ◽  
Terminal Part ◽  
Terminal Amino Acid ◽  
Tryptic Peptides ◽  
Terminal Amino ◽  
High Degree ◽  
Terminal Amino Acid Sequence

To determine the primary structure of the C-terminal part of the molecule of chicken pepsinogen the tryptic, chymotryptic and thermolytic digest of the protein were investigated and peptides derived from this region were sought. These peptides permitted the following 21-residue C-terminal sequence to be determined: ...Ile-Arg-Glu-Tyr-Tyr-Val-Ile-Phe-Asp-Arg-Ala-Asn-Asn-Lys-Val-Gly-Leu-Ser-Pro-Leu-Ser.COOH. A comparison of this structure with the C-terminal sequential regions of the other acid proteases shows a high degree of homology between chicken pepsinogen and these proteases (e.g., the degree of homology with respect to hog pepsinogen and calf prochymosin is about 66%). Additional tryptic peptides, derived from the N-terminal part of the zymogen molecule whose amino acid sequence has been reported before, were also obtained in this study. This sequence was extended by two residues using an overlapping peptide. An ancillary result of this study was the isolation of tryptic peptides derived from other regions of the zymogen molecule.

scholarly journals IX. The electric conductivity of nitric acid

1898 ◽  
Vol 191 ◽  
pp. 365-398 ◽  
Keyword(s):  
Nitric Acid ◽  
Physical Properties ◽  
Nitrous Acid ◽  
Internal Resistance ◽  
The Other ◽  
Reasonable Degree ◽  
Mineral Acids ◽  
Artificial Illumination ◽  
The Subject ◽  
Deep Green

Of the commoner mineral acids the chemical changes of Nitric Acid, from their evident complexity, have formed the subject of numerous memoirs, while those of sulphuric acid, from their assumed simplicity, have been to some degree neglected; on the other hand, the physical properties of the latter have been studied with considerable elaboration, while those of the former have been passed over, doubtless on account of the corrosive nature of the acid and the difficulty of preparing and preserving it in a reasonable degree of purity. Further, with certain exceptions, the alterations in physical properties induced by the products of reduction, be they nitrogen peroxide or nitrous acid, either singly or conjointly, have attracted but little attention, though it is a common matter of observation that the current intensity of a Grove’s or other cell containing nitric acid remains constant, even though the fuming acid, originally colourless or red, has become of a deep green tint. It is more than probable that of the factors of Ohm’s law, both the E. M. F. and internal resistance are continually varying. At the earliest stages of the enquiry it was found that the passage of a few bubbles of nitric oxide gas into a considerable volume of nitric acid produced an alteration of one percent, in the resistance, and the same result could be effected to a less degree by exposure to sunlight, and to a still less degree by exposure to artificial illumination. Therefore, we determined to investigate the alterations of conductivity produced by changes of concentration and temperature in samples of acid purified with necessary precautions, more especially as former workers upon the subject have either used samples of acid confessedly impure, or have been silent as to any method of purification, or have adopted no special care in dealing with a substance so susceptible of polarisation.

scholarly journals Involvement of loop 5 lysine residues and the N-terminal β-hairpin of the ribotoxin hirsutellin A on its insecticidal activity

2016 ◽  
Vol 397 (2) ◽  
pp. 135-145 ◽  
Author(s):  
Miriam Olombrada ◽  
Lucía García-Ortega ◽  
Javier Lacadena ◽  
Mercedes Oñaderra ◽  
José G. Gavilanes ◽  
...  
Keyword(s):  
Active Sites ◽  
Structural Changes ◽  
The Other ◽  
Spatial Proximity ◽  
Ribonucleolytic Activity ◽  
The Family ◽  
Lysine Residues ◽  
Hirsutella Thompsonii ◽  
Close Spatial Proximity ◽  
High Degree

Abstract Ribotoxins are cytotoxic members of the family of fungal extracellular ribonucleases best represented by RNase T1. They share a high degree of sequence identity and a common structural fold, including the geometric arrangement of their active sites. However, ribotoxins are larger, with a well-defined N-terminal β-hairpin, and display longer and positively charged unstructured loops. These structural differences account for their cytotoxic properties. Unexpectedly, the discovery of hirsutellin A (HtA), a ribotoxin produced by the invertebrate pathogen Hirsutella thompsonii, showed how it was possible to accommodate these features into a shorter amino acid sequence. Examination of HtA N-terminal β-hairpin reveals differences in terms of length, charge, and spatial distribution. Consequently, four different HtA mutants were prepared and characterized. One of them was the result of deleting this hairpin [Δ(8-15)] while the other three affected single Lys residues in its close spatial proximity (K115E, K118E, and K123E). The results obtained support the general conclusion that HtA active site would show a high degree of plasticity, being able to accommodate electrostatic and structural changes not suitable for the other previously known larger ribotoxins, as the variants described here only presented small differences in terms of ribonucleolytic activity and cytotoxicity against cultured insect cells.

Degradation of chlorpyriphos in water by advanced oxidation processes

2010 ◽  
Vol 10 (1) ◽  
pp. 1-6 ◽  
Author(s):  
R. Murillo ◽  
J. Sarasa ◽  
M. Lanao ◽  
J. L. Ovelleiro
Keyword(s):  
Reaction Time ◽  
Light Source ◽  
Advanced Oxidation Processes ◽  
Advanced Oxidation ◽  
The Other ◽  
Molar Ratio ◽  
Optimum Conditions ◽  
Oxidation Processes ◽  
Other Hand ◽  
Initial Ph

The degradation of chlorpyriphos by different advanced oxidation processes such as photo-Fenton, TiO2, TiO2/H2O2, O3 and O3/H2O2 was investigated. The photo-Fenton and TiO2 processes were optimized using a solar chamber as light source. The optimum dosages of the photo-Fenton treatment were: [H2O2]=0.01 M; [Fe3 + ]=10 mg l−1; initial pH = 3.5. With these optimum conditions total degradation was observed after 15 minutes of reaction time. The application of sunlight was also efficient as total degradation was achieved after 60 minutes. The optimum dosage using only TiO2 as catalyst was 1,000 mg l−1, obtaining the maximum degradation at 20 minutes of reaction time. On the other hand, the addition of 0.02 M of H2O2 to a lower dosage of TiO2 (10 mg l−1) provides the same degradation. The ozonation treatment achieved complete degradation at 30 minutes of reaction time. On the other hand, it was observed that the degradation was faster by adding H2O2 (H2O2/O3 molar ratio = 0.5). In this case, total degradation was observed after 20 minutes.

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