Chronicles of Oklahoma

Article discusses the difficulties faced by Cherokee, Choctaw, Creek, Chickasaw, and Seminole refugees who left Indian Territory during the Civil War and the relief their leaders attempted to secure them as delegates to the Confederate government

An improved criterion for new particle formation in diverse atmospheric environments

A dimensionless theory for new particle formation (NPF) was developed, using an aerosol population balance model incorporating recent developments in nucleation rates and measured particle growth rates. Based on this theoretical analysis, it was shown that a dimensionless parameter <i>L</i><sub>Γ</sub>, characterizing the ratio of the particle scavenging loss rate to the particle growth rate, exclusively determined whether or not NPF would occur on a particular day. This parameter determines the probability that a nucleated particle will grow to a detectable size before being lost by coagulation with the pre-existing aerosol. Cluster-cluster coagulation was shown to contribute negligibly to this survival probability under conditions pertinent to the atmosphere. Data acquired during intensive measurement campaigns in Tecamac (MILAGRO), Atlanta (ANARChE), Boulder, and Hyytiälä (QUEST II, QUEST IV, and EUCAARI) were used to test the validity of <i>L</i><sub>Γ</sub> as an NPF criterion. Measurements included aerosol size distributions down to 3 nm and gas-phase sulfuric acid concentrations. The model was applied to seventy-seven NPF events and nineteen non-events (characterized by growth of pre-existing aerosol without NPF) measured in diverse environments with broad ranges in sulfuric acid concentrations, ultrafine number concentrations, aerosol surface areas, and particle growth rates (nearly two orders of magnitude). Across this diverse data set, a nominal value of <i>L</i><sub>Γ</sub>=0.7 was found to determine the boundary for the occurrence of NPF, with NPF occurring when <i>L</i><sub>Γ</sub><0.7 and being suppressed when <i>L</i><sub>Γ</sub>>0.7. Moreover, nearly 45% of measured <i>L</i><sub>Γ</sub> values associated with NPF fell in the relatively narrow range of 0.1<<i>L</i><sub>Γ</sub><0.3

Observation of neutral sulfuric acid-amine containing clusters in laboratory and ambient measurements

Recent ab initio calculations showed that amines can enhance atmospheric sulfuric acid-water nucleation more effectively than ammonia, and this prediction has been substantiated in laboratory measurements. Laboratory studies have also shown that amines can effectively displace ammonia in several types of ammonium clusters. However, the roles of amines in cluster formation and growth at a microscopic molecular scale (from molecular sizes up to 2 nm) have not yet been well understood. Processes that must be understood include the incorporation of amines into sulfuric acid clusters and the formation of organic salts in freshly nucleated particles, which contributes significantly to particle growth rates. We report the first laboratory and ambient measurements of neutral sulfuric acid-amine clusters using the Cluster CIMS, a recently-developed mass spectrometer designed for measuring neutral clusters formed in the atmosphere during nucleation. An experimental technique, which we refer to as Semi-Ambient Signal Amplification (SASA), was employed. Sulfuric acid was added to ambient air, and the concentrations and composition of clusters in this mixture were analyzed by the Cluster CIMS. This experimental approach led to significantly higher cluster concentrations than are normally found in ambient air, thereby increasing signal-to-noise levels and allowing us to study reactions between gas phase species in ambient air and sulfuric acid containing clusters. Mass peaks corresponding to clusters containing four H<sub>2</sub>SO<sub>4</sub> molecules and one amine molecule were clearly observed, with the most abundant sulfuric acid-amine clusters being those containing a C2- or C4-amine (i.e. amines with masses of 45 and 73 amu). Evidence for C3- and C5-amines (i.e. amines with masses of 59 and 87 amu) was also found, but their correlation with sulfuric acid tetramer was not as strong as was observed for the C2- and C4-amines. The formation mechanisms for those sulfuric acid-amine clusters were investigated by varying the residence time in the inlet. It was concluded that the amines react directly with neutral clusters and that ion-induced clustering of sulfuric acid cluster ions with amines was not a dominant process. Results from ambient measurements using the Cluster CIMS without addition of sulfuric acid have shown that the sulfuric acid-amine clusters were reasonably well correlated with sulfuric acid tetramer and consistent with the SASA experiments at the same Boulder sampling site. Also, clusters that contain C2- or C4-amines were more abundant and better correlated with sulfuric acid tetramer than other types of amine containing clusters. However, ambient measurements of sulfuric acid-amine clusters remain difficult and highly uncertain because their concentrations are only slightly above background levels, even during nucleation events

Particle Dynamics in a Mass-Conserving Coalescence Process

We consider a fully asymmetric one-dimensional model with mass-conserving coalescence. Particles of unit mass enter at one edge of the chain and coalescence while performing a biased random walk towards the other edge where they exit. The conserved particle mass acts as a passive scalar in the reaction process $A+A\to A$, and allows an exact mapping to a restricted ballistic surface deposition model for which exact results exist. In particular, the mass- mass correlation function is exactly known. These results complement earlier exact results for the $A+A\to A$ process without mass. We introduce a comprehensive scaling theory for this process. The exact anaytical and numerical results confirm its validity.Comment: 5 pages, 6 figure

An experimental and numerical study of particle nucleation and growth during low-pressure thermal decomposition of silane

Abstract This paper discusses an experimental and numerical study of the nucleation and growth of particles during low-pressure (∼1:0 Torr) thermal decomposition of silane (SiH 4 ). A Particle Beam Mass Spectrometer was used to measure particle size distributions in a parallel-plate showerhead-type semiconductor reactor. An aerosol dynamics moment-type formulation coupled with a chemically reacting uid ow model was used to predict particle concentration, size, and transport in the reactor. Particle nucleation kinetics via a sequence of chemical clustering reactions among silicon hydride molecular clusters, growth by heterogeneous chemical reactions on particle surfaces and coagulation, and transport by convection, di usion, and thermophoresis were included in the model. The e ect of pressure, temperature, ow residence time, carrier gas, and silane concentration were examined under conditions typically used for low-pressure (∼1 Torr) thermal chemical vapor deposition of polysilicon. The numerical simulations predict that several pathways involving linear and polycyclic silicon hydride molecules result in formation of particle "nuclei," which subsequently grow by heterogeneous reactions on the particle surfaces. The model is in good agreement with observations for the pressure and temperature at which particle formation begins, particle sizes and growth rates, and relative particle concentrations at various process conditions. A simpliÿed, computationally inexpensive, quasi-coupled modeling approach is suggested as an engineering tool for process equipment design and contamination control during low-pressure thermal silicon deposition.

Emissions from Ethanol-Gasoline Blends: A Single Particle Perspective

Due to its agricultural origin and function as a fuel oxygenate, ethanol is being promoted as an alternative biomass-based fuel for use in spark ignition engines, with mandates for its use at state and regional levels. While it has been established that the addition of ethanol to a fuel reduces the particulate mass concentration in the exhaust, little attention has been paid to changes in the physicochemical properties of the emitted particles. In this work, a dynamometer-mounted GM Quad-4 spark ignition engine run without aftertreatment at 1,500 RPM and 100% load was used with four different fuel blends, containing 0, 20, 40 and 85 percent ethanol in gasoline. This allowed the effects of the fuel composition to be isolated from other effects. Instrumentation employed included two Aerosol Time-of-Flight Mass Spectrometers covering different size ranges for analysis of single particle composition, an Aethalometer for black carbon, a Scanning Mobility Particle Sizer for particle size distributions, a Photoelectric Aerosol Sensor for particle-bound polycyclic aromatic hydrocarbon (PAH) species and gravimetric filter measurements for particulate mass concentrations. It was found that, under the conditions investigated here, additional ethanol content in the fuel changes the particle size distribution, especially in the accumulation mode, and decreases the black carbon and total particulate mass concentrations. The molecular weight distribution of the PAHs was found to decrease with added ethanol. However, PAHs produced from higher ethanol-content fuels are associated with NO2 − (m/z—46) in the single-particle mass spectra, indicating the presence of nitro-PAHs. Compounds associated with the gasoline (e.g., sulfur-containing species) are diminished due to dilution as ethanol is added to the fuel relative to those associated with the lubricating oil (e.g., calcium, zinc, phosphate) in the single particle spectra. These changes have potential implications for the health effect impacts of particulate emissions from biofuel blends

An overview of ISCAT 2000

The Investigation of Sulfur Chemistry in the Antarctic Troposphere (ISCAT) took place over the timer period of 15 November to 31 December in the year 2000. The study location was the Amundsen Scott Station in Antarctica. ISCAT 2000 defines the second phase of a program designed to explore tropospheric chemistry in Antarctica. As in 1998, the 2000 ISCAT study revealed a strong oxidizing environment at South Pole (SP). During the 2000 investigation, however, the suite of measurements was greatly expanded. These new measurements established the recycling of reactive nitrogen as a critical component of this unique environment. This paper first presents the historical background leading up to the ISCAT 2000 observations; then it focuses on providing a summary of the year 2000 results and contrasts these with those recorded during 1998. Important developments made during the 2000 study included the recording of SP data for several species being emitted from the snowpack. These included NO, H 2O2 and CH2O. In this context, eddy-diffusion flux measurements provided the first quantitative estimates of the SP NO and NOx snow-to-atmosphere fluxes. This study also revealed that HNO 3 and HO2NO2 were major sink species for HOx and NOx radicals. And, it identified the critical factors responsible for SP NO levels exceeding those at other polar sites by nearly an order of magnitude. Finally, it reports on the levels of gas phase sulfur species and provides evidence indicating that the absence of DMS at SP is most likely due to its greatly shorten chemical lifetime in the near vicinity of the plateau. It is proposed that this is due to the influence of NO on the distribution of OH in the lower free troposphere over a region that extends well beyond the plateau itself. Details related to each of the above findings plus others can be found in the 11 accompanying Special Issue papers. © 2004 Elsevier Ltd. All rights reserved