Current model capabilities for simulating black carbon and sulfate concentrations in the Arctic atmosphere: a multi-model evaluation using a comprehensive measurement data set

The concentrations of sulfate, black carbon (BC) and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality and especially the high concentrations associated with Arctic Haze. In this study, we evaluate sulfate and BC concentrations from eleven different models driven with the same emission inventory against a comprehensive pan-Arctic measurement data set over a time period of 2 years (2008–2009). The set of models consisted of one Lagrangian particle dispersion model, four chemistry transport models (CTMs), one atmospheric chemistry-weather forecast model and five chemistry climate models (CCMs), of which two were nudged to meteorological analyses and three were running freely. The measurement data set consisted of surface measurements of equivalent BC (eBC) from five stations (Alert, Barrow, Pallas, Tiksi and Zeppelin), elemental carbon (EC) from Station Nord and Alert and aircraft measurements of refractory BC (rBC) from six different campaigns. We find that the models generally captured the measured eBC or rBC and sulfate concentrations quite well, compared to previous comparisons. However, the aerosol seasonality at the surface is still too weak in most models. Concentrations of eBC and sulfate averaged over three surface sites are underestimated in winter/spring in all but one model (model means for January–March underestimated by 59 and 37 % for BC and sulfate, respectively), whereas concentrations in summer are overestimated in the model mean (by 88 and 44 % for July–September), but with overestimates as well as underestimates present in individual models. The most pronounced eBC underestimates, not included in the above multi-site average, are found for the station Tiksi in Siberia where the measured annual mean eBC concentration is 3 times higher than the average annual mean for all other stations. This suggests an underestimate of BC sources in Russia in the emission inventory used. Based on the campaign data, biomass burning was identified as another cause of the modeling problems. For sulfate, very large differences were found in the model ensemble, with an apparent anti-correlation between modeled surface concentrations and total atmospheric columns. There is a strong correlation between observed sulfate and eBC concentrations with consistent sulfate/eBC slopes found for all Arctic stations, indicating that the sources contributing to sulfate and BC are similar throughout the Arctic and that the aerosols are internally mixed and undergo similar removal. However, only three models reproduced this finding, whereas sulfate and BC are weakly correlated in the other models. Overall, no class of models (e.g., CTMs, CCMs) performed better than the others and differences are independent of model resolution.

Two case studies of sulfate scavenging processes in the Amazon region (Rondonia)

The scavenging processes of chemical species have been previously studied with numerical modeling, in order to understand the gas and particulate matter intra-reservoir transferences. In this study, the atmospheric (RAMS) and scavenging (B.V.2) models were used, in order to simulate sulfate concentrations in rainwater using scavenging processes as well as the local atmospheric conditions obtained within the LBA Project in the State of Rondonia, during a dry-to-wet transition season. Two case studies were conducted. The RAMS atmospheric simulation of these events presented satisfactory results, showing the detailed microphysical processes of clouds in the Amazonian region. On the other hand, with cloud entrainments, observed values have been overestimated. Modeled sulfate rainwater concentration, using exponential decay and cloud heights of 16 km and no entrainments, presented the best results, reaching 97% of the observed value. The results, using shape parameter 5, are the best, improving the overall result. (C) 2008 Elsevier Ltd. All rights reserved.

The Mobility of Chondroitin Sulfate in Articular and Artificial Cartilage Characterized by (13)C Magic-Angle Spinning NMR Spectroscopy

We have studied the molecular dynamics of one of the major macromolecules in articular cartilage, chondroitin sulfate. Applying (13)C high-resolution magic-angle spinning NMR techniques, the NMR signals of all rigid macromolecules in cartilage can be suppressed, allowing the exclusive detection of the highly mobile chondroitin sulfate. The technique is also used to detect the chondroitin sulfate in artificial tissue-engineered cartilage. The tissue-engineered material that is based on matrix producing chondrocytes cultured in a collagen gel should provide properties as close as possible to those of the natural cartilage. Nuclear relaxation times of the chondroitin sulfate were determined for both tissues. Although T(1) relaxation times are rather similar, the T(2) relaxation in tissue-engineered cartilage is significantly shorter. This suggests that the motions of chondroitin sulfate in data:rat and artificial cartilage different. The nuclear relaxation times of chondroitin sulfate in natural and tissue-engineered cartilage were modeled using a broad distribution function for the motional correlation times. Although the description of the microscopic molecular dynamics of the chondroitin sulfate in natural and artificial cartilage required the identical broad distribution functions for the correlation times of motion, significant differences in the correlation times of motion that are extracted from the model indicate that the artificial tissue does not fully meet the standards of the natural ideal. This could also be confirmed by macroscopic biomechanical elasticity measurements. Nevertheless, these results suggest that NMR is a useful tool for the investigation of the quality of artificially engineered tissue. (C) 2010 Wiley Periodicals, Inc. Biopolymers 93: 520-532, 2010.

Effect of oral vanadyl sulfate treatment on serum enzymes and lipids of streptozotocin-diabetic young rats

In this work we investigate the possible toxicity of vanadyl sulfate (VOSO4), a compound capable of reducing hyperglycemia, on the following serum enzymes of diabetic young rats: alanine aminotransferase (ALT), aspartate aminotransferase (AST), lactate dehydrogenase (LD) and creatine kinase (CK), as well as its effects on serum lipids. We find that at a concentration of 1 mg/mL VOSO4 has no toxic effect on the liver and muscles of diabetics young rats. These findings suggest that VOSO4 may be an alternative to insulin in the near future, due to its low cost, low toxicity and ready availability.

Zuspan's Scheme Versus an Alternative Magnesium Sulfate Scheme: Randomized Clinical Trial of Magnesium Serum Concentrations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Bone healing in critical-size defects treated with new bioactive glass/calcium sulfate: A histologic and histometric study in rat calvaria

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Crystal structure of human PNP complexed with hypoxanthine and sulfate ion

Purine nucleoside phosphorylase (PNP) is a ubiquitous enzyme, which plays a key role in the purine salvage pathway, and PNP deficiency in humans leads to an impairment of T-cell function, usually with no apparent effects on B-cell function. Human PNP has been submitted to intensive structure-based design of inhibitors, most of them using low-resolution structures of human PNP. Here we report the crystal structure of human PNP in complex with hypoxanthine, refined to 2.6 Angstrom resolution. The intermolecular interaction between ligand and PNP is discussed. (C) 2004 Elsevier B.V. All rights reserved.

Calcium sulfate and PTFE nonporous barrier for regeneration of experimental bone defects

The aim of the study was to evaluate the possibility to obtain guided bone regeneration with two types of physical barriers (calcium sulfate and PTFE nonporous barrier) in surgical defects created in rat parietal bones. In the right parietal bone the calcium sulfate barrier filled out the whole defect and in the left parietal bone the barrier of PTFE was positioned in the floor and externally to the surgical defect. After 7, 14, 30 and 45 days four animals were sacrificed in each period and the bone containing the defects were submitted to the microscopic analysis. The results of the study revealed that the PTFE barrier was more effective for bone regeneration in shallow transcortical defects compared to the calcium sulfate. However, additional experiments are necessary to determine if calcium sulfate would be successful in other bone defects types or the use of the material under another consistence could complement the results obtained in this work.

Methanogenic potential and microbial community of anaerobic batch reactors at different ethylamine/sulfate ratios

Methylamine and sulfate are compounds commonly found in wastewaters. This study aimed to determine the methanogenic potential of anaerobic reactors containing these compounds and to correlate it with their microbial communities. Batch experiments were performed at different methylamine/sulfate ratios of 0.71, 1.26 and 2.18 (with respect to mass concentration). Control and experimental runs were inoculated with fragmented granular sludge. The maximum specific methane formation rates were approximately 2.3 mmol CH4 L-1 g TVS-1 day-1 for all conditions containing methylamine, regardless of sulfate addition. At the end of the experiment, total ammonium-N and methane formation were proportional to the initial concentrations of methylamine. In the presence of methylamine and sulfate, Firmicutes (46%), Deferribacteres (13%) and Proteobacteria (12%) were the predominant phyla of the Bacteria domain, while Spirochaetes (40%), Deferribacteres (17%) and Bacteroidetes (16%) predominated in the presence of methylamine only. There was no competition for methylamine between sulfate-reducing bacteria and methanogenic archaea.

Structural organization of cetyltrimethylammonium sulfate in aqueous solution: the effect of Na2SO4

We used dynamic light scattering (DLS), a steady-state fluorescence, time resolved fluorescence quenching (TRFQ), tensiometry, conductimetry, and isothermal titration calorimetry (ITC) to investigate the self-assembly of the cationic surfactant cetyltrimethylammonium sulfate (CTAS) in aqueous solution, which has SO42- as divalent counterion. We obtained the critical micelled concentration (cmc), aggregation number (N-agg), area per monomer (a(0)), hydrodynamic radius (R-H), and degree of counterion dissociation (alpha) of CTAS micelles in the absence and presence of up to 1 M Na2SO4 and at temperatures of 25 and 40 degrees C. Between 0.01 and 0.3 M salt the hydrodynamic radius of CTAS micelle R-H approximate to 16 angstrom is roughly independent on Na2SO4 concentration; below and above this concentration range R-H increases steeply with the salt concentration, indicating micelle structure transition, from spherical to rod-like structures. R-H increases only slightly as temperature increases from 25 to 40 degrees C, and the cmc decreases initially very steeply with Na2SO4 concentration up to about 10 mM, and thereafter it is constant. The area per surfactant at the water/air interface, a(0), initially increases steeply with Na2SO4 concentration, and then decrases above ca. 10 mM. Conductimetry gives alpha = 0.18 for the degree of counterion dissociation, and N-agg obtained by fluorescence methods increases with surfactant concentration but it is roughly independent of up to 80 mM salt. The ITC data yield cmc of 0.22 mM in water, and the calculated enthalpy change of micelle formation, Delta H-mic = 3.8 kJ mol(-1), Gibbs free energy of micellization of surfactant molecules, Delta G(mic) = -38.0 kJ mol(-1) and entropy T Delta S-mic = 41.7 kJ mol(-1) indicate that the formation of CTAS micelles is entropy-driven. (c) 2006 Elsevier B.V. All rights reserved.

Determination of interfacial co-ion concentration in ionic micelles by chemical trapping: Halide concentration at the interface of sodium dodecyl sulfate micelles

Products from the spontaneous reaction of a long-chain arenediazonium salt, 2,6-dimethyl-4-hexadecylbenzenediazonium tetrafluoroborate(16-ArN2BF4), in aqueous micellar solutions of sodium dodecyl sulfate (SDS)? are used to estimate the local concentration of chloride and bromide ions at the micellar surface. The arenediazonium ion, 16-ArN2+, which is totally bound to the SDS micelle, reacts by rate-determining loss of N-2 to give an aryl cation that traps available nucleophiles, i,e., H2O, Cl-, and Br-, to give stable phenol, 16-ArOH, and halobenzene products, 16-ArCl and 16-ArBr, respectively. Product yields, determined by HPLC, are related to local concentrations using calibration curves obtained from independent standards. The local concentrations determined by this method are consistent with co-ion concentrations calculated, using a cell model, by numerical integration of the Poisson-Boltzmann equation (PBE) taking into account salt-induced micellar growth. The salt dependence of the intel facial concentrations of Cl- and Br- are identical. indicating no specific interactions in the interfacial co-ion compartment. PBE calculations predict that, in micellar SDS, increasing the concentration of a particular halide salt (NaX) at constant concentration of another halide (NaY) should result in an increase in the local concentrations of both co-ions. Using this chemical-trapping method, this prediction was demonstrated experimentally.

Mixed micelles of the anionic surfactant sodium dodecyl sulfate and the nonionic pentaethylene glycol mono-n-dodecyl ether in solution

Dynamic light scattering, surface tension, and clouding temperature have been monitored to elucidate the solution properties of mixed micelles formed between the anionic surfactant sodium dodecyl sulfate (SDS) and the nonionic surfactant pentaethylene glycol mono-n-dodecyl ether (C12E5) over a wide range of surfactant concentration and temperature. Addition of 0.1 M NaCl shifts the relaxational modes to higher frequency and lowers the clouding temperature (T-c) of the nonionic surfactant solution by about 1 degrees C compared to the salt-free system. T-c for the mixed surfactant solutions is higher than that of the binary C12E5 solutions and depends sensitively on the concentration of the two surfactants but increases only slightly when the total surfactant concentration is increased at a given molar C12E5/SDS concentration ratio. With C12E5/SDS = 5.7, for example, T-c is 46.0 and 47.5 degrees C, respectively, at 5 and 70 mM of C12E5 the mixed solutions are homogeneous and stable and contain nonspherical micelles, which are close to monodisperse over a range of surfactant concentrations and temperature. The mixed system has a lower Krafft point than binary SDS solutions and shows an approximately ideal behavior in contrast to the binary C12E5 solution. The hydrodynamic radius (RH) of the mixed micelle increases with temperature as do C12E5 micelles in the binary solutions and also with increasing C12E5/SDS ratio. At 25 degrees C, the critical micelle concentration of the mixed solution lies between those of the individual surfactants and decreases as the C12E5/SDS ratio is increased.

Chondroitin sulfate proteoglycans are structural renewable constituents of the rabbit vitreous body

Purpose: To characterize the vitreous intrinsic proteoglycans, investigate their dynamics, and examine their role in the supramolecular organization of the vitreous. Methods: Vitreous from normal rabbits was collected and processed for observation with the transmission electron microscope after treatment with glycosidases. Also, rabbits were injected intravitreally with [S-35]-sodium sulfate and sacrificed at several time intervals after the injection. Proteoglycans (PGs) were assayed in the vitreous supernatant or in whole samples extracted with guanidine hydrochloride by polyacrylamide or agarose gel electrophoresis, followed respectively by fluorography or autoradiography, and ion-exchange chromatography and gel-filtration chromatography, combined with glycolytic treatment of the samples. The sulfated glycosaminoglycans (GAGs) were characterized by agarose gel electrophoresis after treating vitreous samples with protease and specific glycosidases. Results: the electron microscopic study revealed a network with hyaluronic acid ( HA) as thin threads coating and connecting collagen fibrils. The elimination of the HA coat showed chondroitin sulfate granules (8-25 nm) arranged at regular intervals on the fibril surface. The chondroitinase ABC digestion, besides removing the granules, also caused the formation of thicker bundles of the collagen fibrils. The PG and GAG analysis indicated that there are three renewable PGs in the vitreous ( e. g., one heparan-and two chondroitin-sulfate ones). Conclusions: At least one of the chondroitin sulfate PGs is involved in the interactions that occur in the vitreous structure, mainly by providing adequate spacing between the collagen fibrils, a condition that is probably required for the transparency of the vitreous.

pH at the micellar interface: Synthesis of pH probes derived from salicylic acid, acid-base dissociation in sodium dodecyl sulfate micelles, and Poisson-Boltzmann simulation

The study of the H+ concentration at the micellar interface is a convenient system for modeling the distribution of H+ at interfaces. We have synthesized salicylic acid derivatives to analyze the proton dissociation of both the carboxylic and phenol groups of' the probes, determining spectrophotometrically the apparent pK(a)'s (pK(ap)) in sodium dodecyl Sulfate, SDS, micelles with and without added salt. The synthesized probes were 2-hydroxy-5-(2-trimethylammoniumacetyl)benzoate; 2-hydroxy-5-(2-dimethylhexadecylammoniumacetyl)benzoate- 2-hydroxy-5-(2-dimethylhexadecylammoniumhexanoyl)benzoate-, 2-hydroxy-5-(2-diniethylhexadecylammoniumundecanoyl)betizoate; 2-hydroxy-5-acetylbenzoic acids and 2-hydroxy-5-dodecanoylbenzoic acid. Upon incorporation into SDS micelles the pK(ap)'s of both carboxylic and phenol groups increased by ca. 3 pH units and NaCl addition caused a decrease in the probe-incorporated pKap. The experimental results were fitted with a cell model Poisson-Boltzmann (P-B) equation taking in consideration the effect of salt on the aggregation number of SDS and using the distance of' the dissociating group as a parameter. The conformations of the probes were analyzed theoretically using two dielectric constants, e.g., 2 and 78. Both the P-B analysis and conformation calculations can be interpreted by assuming that the acid groups dissociate very close to, or at, the interface. Our results are consistent with the assumption that the intrinsic pK(a)'s of both carboxylic and phenol groups of the salicylic acid probes used here can be taken as those in water. Using this assumption the micellar and salt effects on the pKap's of the (trialkylammonium)benzoate probes were described accurately using a cell model P-B analysis. (c) 2005 Elsevier B.V. All rights reserved.