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At least 181 records · Page 10

Laboratory studies of sticking coefficients and heterogeneous reactions important in the stratosphere

The discovery of ozone depletion during spring in the Antarctic stratosphere has received wide spread attention. Both meteorological and chemical mechanisms have been used in attempts to explain this observation. The chemical theory focused on the chlorofluoromethanes released into the atmosphere. However, gas-phase, homogeneous reactions alone in the model can not adequately explain such a depletion. Heterogeneous reactions on ice surfaces could be important in the Antarctic stratosphere. These reactions are thought to convert ClONO2 and N2O5 into HNO3 in the solid phase while Cl2, HOCl, and ClNO2 are released into the stratosphere as gas-phase products. The photolysis of Cl2, HOCl, and ClNO2, then produces active chlorine which subsequently removes ozone through several catalytic cycles, including the Cl2O2 mechanism. The polar stratospheric clouds are thought to consist of mixtures of water ice, nitric acid, and sulfuric acid. Condensation of HCl onto the PSC's could provide active surfaces for heterogeneous reactions.

Leu, Ming-Taun↗

Croconic acid - An absorber in the Venus clouds?

The absorbing species responsible for the UV cloud features and pale yellow hue of the Venus clouds is presently suggested to be the carbon monoxide-polymer croconic acid, which strongly absorbs in the blue and near-UV. Laboratory absorption-coefficient measurements of a dilute solution of croconic acid in sulfuric acid are used as the bases of cloud-scattering models; the Venus planetary albedo's observed behavior in the blue and near-UV are noted to be qualitatively reproduced. Attention is given to a plausible croconic acid-production mechanism for the Venus cloudtop region.

Hartley, Karen K.↗

Thermal control materials on EOIM-3

Thermal control paints, anodized aluminum, and beta cloth samples were flown on STS-46 as part of the Evaluation of Oxygen Interaction with Materials Experiment (EOIM-3). The thermal control paints flown on EOIM-3 include ceramic and polyurethane-based paints. Passively exposed samples are compared to actively heated samples and controlled exposure samples. Optical property measurements of absorptivity, emissivity, and spectrofluorescence are presented for each paint. Several variations of anodized aluminum, including chromic acid anodize, sulfuric acid anodize, and boric/sulfuric acid anodize were flown on the actively heated trays and the passive exposure trays. The post-flight optical properties are within tolerances for these materials. Also flown were two samples of yellow anodized aluminum. The yellow anodized aluminum samples darkened noticeably. Samples of aluminized and unaluminized beta cloth, a fiberglass woven mat impregnated with TFE Teflon, were flown with passive exposure to the space environment. Data from this part of the experiment is correlated to observations from LDEF and erosion of the Teflon thin film samples also flown on EOIM-3 and LDEF.

Finckenor, Miria M.↗

Emissions from Biomass Burning in the Yucatan

In March 2006 two instrumented aircraft made the first detailed field measurements of biomass burning (BB) emissions in the Northern Hemisphere tropics as part of the MILAGRO project. The aircraft were the National Center for Atmospheric Research C-130 and a University of Montana/US Forest Service Twin Otter. The initial emissions of up to 49 trace gas or particle species were measured from 20 deforestation and crop residue fires on the Yucatan peninsula. This included two trace gases useful as indicaters of BB (HCN and acetonitrile) and several rarely, or never before, measured species: OH, peroxyacetic acid, propanoic acid, hydrogen peroxide, methane sulfonic acid, and sulfuric acid. Crop residue fires emitted more organic acids and ammonia than deforestation fires, but the emissions from the main fire types were otherwise fairly similar. The Yucatan fires emitted unusually amounts of SO2 and particle chloride, likely due to a strong marine influence on the peninsula.

Yokelson, R.↗

Friction Modifier Using Adherent Metallic Multilayered or Mixed Element Layer Conversion Coatings

A process for creating conversion coatings and spin, drawing, and extrusion finishes for surfaces, wherein the conversion coatings and spin, drawing, and extrusion finishes contain potassium, phosphorus, nitrogen, and one or more non-alkaline metals and/or one or more metalloids. The process comprises forming an aqueous solution of water, phosphoric acid or sulfuric acid, ammonium hydroxide, an alkali metal hydroxide, and one or more non-alkaline metals and/or one or more metalloids. The aqueous solution forms an anti-friction multilayer conversion and/or mixed element coating or a spin, drawing, and extrusion finish on a surface when applied to the surface, either directly without the use of applied external electromotive force, or as an additive in lubricating fluids.

Schramm, Harry F.↗

Calculation of composition distribution of ultrafine ion-H2O-H2SO4 clusters using a modified binary ion nucleation theory

Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.

Singh, J. J.↗

A determination of the composition of the Venus clouds from aircraft observations in the near infrared

Summary of the evidence showing that the first optical depth of the Venus cloud layer is composed of a water solution of sulfuric acid, including earlier aircraft observations of Venus' reflectivity in the region from 1 to 4 microns obtained at a phase angle of 120 deg. Analyses of these aircraft results indicated that of all the proposed cloud candidates only a sulfuric acid solution with a concentration of 75% or more H2SO4 by weight was consistent with the observed 3-micron cloud feature. Aircraft observations of Venus are presented which were obtained in the same spectral region at a phase angle of 40 deg and in the region from 3 to 6 microns at a phase angle of 136 deg. Comparing the two sets of observations in the region from 1 to 4 microns, a striking phase effect is found: the reflectivity is much lower in the 3-micron region and there is a much more marked decline between 1.3 and 2.5 microns for the data obtained at the smaller phase angle. The observations made at the 40-deg phase angle are consistent with the theoretical behavior of a sulfuric acid cloud and imply that the sulfuric acid is present to at least many tens of optical depth below the cloud tops. Arguments concerning the concentration of the solution are reviewed, and it is concluded that the best current estimate is about 85% H2SO4 by weight.

Pollack, J. B.↗

Latitudinal distribution of black carbon soot in the upper troposphere and lower stratosphere

Black carbon soot from the upper troposphere and lower stratosphere has been systematically collected at latitudes from 90 deg N to 45 deg S. The measured latitudinal distribution of this soot at 10 to 11 km altitude is found to covary with commercial air traffic fuel use, suggesting that aircraft fuel combustion at altitude is the principal source. In addition, at latitudes where the commercial air traffic is high, measured black carbon soot values are high even at 20 km altitude, suggesting that aircraft-generated soot injected just above the tropopause may be transported to higher altitudes. During the volcanically influenced period in which these samples were collected, the number abundances, total mass, and calculated total surface area of black carbon soot are 2-3 orders of magnitude lower than similar measures of sulfuric acid aerosol. During volcanically quiescent periods, the calculated total surface area of black carbon soot aerosol is of the same order of magnitude as that of the background sulfuric acid aerosol. It appears from this comparison that black carbon soot is only capable of influencing lower stratosphere or upper troposphere chemistry during periods when the aerosol budget is not dominated by volcanic activity. It remains to determine the extent to which black carbon soot particles act as nuclei for sulfuric acid aerosol formation. However, mass balance calculations suggest that aircraft soot injected at altitude does not represent a significant source of condensation nuclei for sulfuric acid aerosols.

Blake, David F.↗

Evidence for an elemental sulfur component of the clouds from Venus spectrophotometry

The decrease in the reflectivity of Venus in the near-UV can be explained if the clouds contain particles of elemental sulfur in addition to sulfuric acid. The low-resolution McDonald-Pittsburgh spectrum can be fitted by two sulfur-containing, multiple-scattering cloud models: (1) a mixed cloud consisting of one particle of elemental sulfur of radius 10 microns for every 670 particles of sulfuric acid of radius 1 micron, and (2) a layered cloud of optical thickness tau = 1.0 consisting of one-micron particles of sulfuric acid overlying a thick cloud of elemental sulfur particles of radius 3.6 microns. Some of the sulfur is incompletely polymerized. The source of the sulfur is photo-dissociation of COS, although some may also be recycled from the lower atmosphere. The sulfur plays a crucial role in the planetary meteorology of Venus since it is responsible for the bulk of the absorption of solar energy.

Hapke, B.↗

Microbiological test results using three urine pretreatment regimes with 316L stainless steel

Three urine pretreatments, (1) Oxone (Dupont) and sulfuric acid, (2) sodium hypochlorite and sulfuric acid, (3) and ozone, were studied for their ability to reduce microbial levels in urine and minimize surface attachment to 316L stainless steel coupons. Urine samples inoculated with Bacillus insolitus and a filamentous mold, organisms previously recovered from the vapor compression distillation subsystem of NASA Space Station Freedom water recovery test were tested in glass corrosion cells containing base or weld metal coupons. Microbial levels, changes in pH, color, turbidity, and odor of the fluid were monitored over the course of the 21-day test. Specimen surfaces were examined by scanning electron microscopy at completion of the test for microbial attachment. Ozonated urine samples were less turbid and had lower microbial levels than controls or samples receiving other pretreatments. Base metal coupons receiving pretreatment were relatively free of attached bacteria. However, well-developed biofilms were found in the heat-affected regions of welded coupons receiving Oxone and hypochlorite pretreatments. Few bacteria were observed in the same regions of the ozone pretreatment sample.

Huff, Timothy L.↗

Reduction and analysis of seasons 15 and 16 (1991 - 1992) Pioneer Venus radio occultation data and correlative studies with observations of the near-infrared emission of Venus

Radio occultation experiments, and radio astronomical observations have suggested that significant variations (both spatial and temporal) in the abundances of sulfur-bearing gases are occurring below the Venus cloud layers. In addition, recent Near Infra-Red images of the nightside of Venus revealed large-scale features which sustain their shape over multiple rotations (the rotation periods of the features are 6.0 +/- 0.5 days). Presumably, the contrast variations in the NIR images are caused by variations in the abundance of large particles in the cloud deck. If these particles are composed of liquid sulfuric acid, one would expect a strong anticorrelation between regions with a high abundance of sulfuric acid vapor, and regions where there are large particles. One technique for monitoring the abundance and distribution of sulfuric acid vapor (H2SO4) at and below the main Venus cloud layer (altitudes below 50 km) is to measure the 13-cm wavelength opacity using Pioneer Venus Orbiter Radio Occultation Studies (PV-ORO). We are working to characterize variations in the abundance and distribution of subcloud H2SO4(g) in the Venus atmosphere by using a number of 13-cm radio occultation measurements conducted with the Pioneer Venus Orbiter near the inferior conjunction of 1991. When retrieved, the vertical profiles of the abundance of H2SO4(g) will be compared and correlated with NIR images of the night side of Venus made during the same period of time. Hopefully, the combination of these two different types of data will make it possible to constrain or identify the composition of the large particles causing the features observed in the NIR images. Considered on their own, however, the parameters retrieved from the radio occultation experiments are valuable science products.

Jenkins, Jon M.↗

Assessing and Improving Biooxidation for Acid Generation and Rare Earth Element Extraction

Microorganisms (Acidithiobacillus ferrooxidanns) are effective in oxidizing ferrous ions that can be used to oxidize pyrite and produce sulfuric acid. Many coal waste resources contain significant concentrations of rare earth elements (REE) and critical materials (CM) that can be extracted using sulfuric acid. These coal waste resources often contain significant concentrations of pyrite, which if not utilized or removed present a future environmental liability for potential acid mine drainage. Thus, the combination of pyrite and REE/CM in coal waste provides a significant resource opportunity for sulfuric acid generation that can be utilized using biooxidation. In addition, the pyrite concentrate used for acid generation also contains REE/CM content that is released during biooxidation of the pyrite concentrate that augments the REE/CM release from the main ore being leached with the acid generated from the pyrite. Thus, this approach provides a very significant environmental advantage as well as augmented REE/CM recovery. Although there are many studies associated with biooxidation in relation to mineral oxidation, there is a lack of information regarding the effects of operating parameters on biooxidation performance and optimization for practical applications. In this study, findings from research in assessing and improving biooxidation for acid generation for REE/CM extraction are presented. Results show that bacteria can very effectively and efficiently oxidize ferrous ions to ferric ions, which oxidize pyrite to produce acid for REE/CM extraction. The factors that showed significant impact on biooxidation performance include air flow rate, stirring speed, residence time, solids concentration, and temperature. The dominance of Leptospirillum ferriphilum species was noted in the bioreactor after a prolonged period of operation, although Acidithiobacillus ferrooxidanns was used in the beginning.

Free, Michael L.↗

Uptake of Organic Vapors by Sulfate Aerosols: Physical and Chemical Processes

While it is known that upper tropospheric sulfate particles contain a significant amount of organic matter, both the source of the organic fraction and its form in solution are unknown. These studies explore how the chemical characteristics of the molecules and surfaces in question affect heterogeneous interactions. The solubilities of acetaldehyde [CH3CHO] and ethanol [CH3CH20H] in cold, aqueous sulfuric acid solutions have been measured by Knudsen cell studies. Henry's law solubility coefficients range from 10(exp 2) to 10(exp 5) M/atm for acetaldehyde, and from 10(exp 4) to 10(exp 9) M/atm for ethanol under upper tropospheric conditions (210-240 K, 40-80 wt. % H2S04). The multiple solvation pathways (protonation, enolization, etc.) available to these compounds in acidic aqueous environments will be discussed. Preliminary results from the interaction of acetaldehyde with solutions of formaldehyde in sulfuric acid will be presented as well. The physical and chemical processes that affect organic uptake by aqueous aerosols will be explored, with the aim of evaluating organic species not yet studied in low temperature aqueous sulfuric acid.

Michelsen, R. R.↗

High Time Resolution Modelled and Measured New Particle Formation Rates During the 2023 Pittsburgh, PA Campaign

Particle size distributions are used to calculate nucleation rates during new particle formation (NPF). However, the low time resolution and poor sensitivity of instruments deployed to observe particle size distributions can lead to inaccurate estimates of nucleation rates. We calculated nucleation rates in Pittsburgh, PA from particle size distributions measured with the new high time resolution Condensation Particle Counters For Atmospheric Rapid Measurements (CPC FARM) and from gas precursor concentrations measured with a chemical ionization mass spectrometer. The CPC FARM nucleation rates were calculated by examining the appearance rate of particles in the smallest size bin at 1.6 nm. The nucleation rate of 1.6 nm determined every second resulted in positive and negative rates, indicating the influence of inhomogeneous mixing and advection of precursor gases and clusters. These effects are not currently considered when estimating nucleation rates from measurements. The nucleation rates from the CPC FARM were compared to the nucleation rates determined from a transient acid‐base reaction model using measured sulfuric acid concentration, strong base concentrations, and CPC detection efficiencies. The transient form of the model allowed the advection of heterogeneously mixed precursors to influence the nucleation rate. Good agreement between particle and gas‐based nucleation rates is observed during sulfuric acid‐driven NPF events. This study demonstrates that high time resolution measurements of short‐lived and rapidly formed particles are needed to accurately capture nucleation rates, which are likely influenced by advection of nucleation precursors and clusters in heterogeneous environments such as urban areas.

Cheng, D. [Carnegie Mellon Univ., Pittsburgh, PA (↗

Chemical analysis of aerosol in the Venusian cloud layer by reaction gas chromatography on board the Vega landers

The experiment on sulfuric acid aerosol determination in the Venusian cloud layer on board the Vega landers is described. An average content of sulfuric acid of approximately 1 mg/cu m was found for the samples taken from the atmosphere at heights from 63 to 48 km and analyzed with the SIGMA-3 chromatograph. Sulfur dioxide (SO2) was revealed in the gaseous sample at the height of 48 km. From the experimental results and blank run measurements, a suggestion is made that the Venusian cloud layer aerosol consists of more complicated particles than the sulfuric acid water solution does.

Gelman, B. G.↗

Understanding and Mitigating Stickiness in Biochar Produced through Acid Hydrolysis and Dehydration

Levulinic acid is a platform chemical with significant potential for conversion into a wide range of biobased chemicals and fuels. A common process for producing levulinic acid from lignocellulosic feedstocks involves acid hydrolysis and dehydration (AHDH), where hexose polymers are hydrolyzed into monomeric sugars and subsequently dehydrated to levulinic acid and formic acid in the presence of dilute sulfuric acid. However, scaling the AHDH process is challenging because of the formation of byproducts such as sticky biochar, which accumulates in continuous-flow reactors, reducing effective reaction volume and increasing process downtime. This study investigates the effect of a chemical preconditioning step on mitigating sticky biochar formation. Woody biomass was preconditioned at 170 °C with 0.26 wt % sulfuric acid for 30 min, resulting in substantial removal of hemicellulose and acid-soluble lignin. AHDH of these preconditioned solids produced biochar that did not adhere to reactor surfaces. TGA analysis confirmed that the chemical preconditioning step minimized interactions between hemicellulose-derived degradation products and lignin side chains, reducing sticky char formation. Additionally, the study observed a 6% higher yield of organic acids from softwood species compared to hardwoods, with bark content shown to negatively impact yield. These findings suggest that targeted preconditioning of lignocellulosic biomass can enhance reactor operability and improve organic acid production efficiency in AHDH processes.

biopolymers↗

Stratospheric aerosol properties and their effects on infrared radiation.

This paper presents a stratospheric aerosol model and infers its effects on terrestrial radiation. Composition of the aerosol is assumed to be concentrated sulfuric acid. An appropriate size distribution has been determined from available size distribution measurements of other investigators. Aerosols composed of concentrated sulfuric acid emit energy in the atmospheric window region of the infrared spectrum, 8-13 microns. Laboratory measurements of optical constant data obtained at room temperature are presented for 75 and 90% aqueous sulfuric acid. Calculations of an aerosol extinction coefficient are then performed by using the above data. Effects of changes in aerosol phase and temperature are discussed but not resolved.

Remsberg, E. E.↗