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At least 55 records · Page 3

Kinetics Measurements in Resistive Electrolytes Using Ring-Disk Electrode: Ring as Current “Shield” Enables Uniform Disk Current Distribution

Rotating disk electrodes are commonly used for electrochemical kinetics measurements. A major disadvantage of these types of electrodes is their nonuniform secondary current distribution, especially when performing electroanalytical measurements in resistive electrolytes. Such nonuniform current distribution can render the values of kinetics constants extracted from the disk electrode to be highly inaccurate. Furthermore, one emerging class of electrolytes that suffer from low ionic conductivities is deep eutectic solvents (DES). DES are a promising class of electrolytes for various emerging applications; however, due to their resistive nature, the secondary current distribution when using them is typically highly nonuniform. For example, the Wagner number when measuring Cu²⁺/Cu⁺ kinetics in choline chloride–ethylene glycol DES (1:4 molar ratio of ChCl:EG) is very low (<0.1), indicating highly nonuniform current distribution over the disk electrode. We show here that the Cu²⁺/Cu⁺ exchange current density measured using disk electrodes is very inaccurate due to the aforementioned nonuniform current distribution. To obtain uniform disk current distribution, we employ here a coplanar concentric rotating ring-disk electrode (RRDE), where the ring serves the function of a current “shield.” Specifically, we show using modeling that the ring minimizes the current distribution nonuniformity at the disk by effectively shielding the disk against current spikes near the disk edge. This enables improved precision in electrode kinetics measurements for the Cu²⁺/Cu⁺ couple in resistive DES. To enable broad applicability of this technique, an analytical expression based on the Wagner number is integrated into an iterative algorithm to help users identify ring conditions to achieve uniform current distribution and thus improved electroanalytics at the disk.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A comparison of secondary craters on the moon, Mercury, and Mars

The present investigation is concerned with the distribution of secondary crater sizes and shapes and the relation of these distributions to inferred Martian lithology and ballistic history. Differences in secondary-crater size/range distributions around unmodified craters can be attributed to differences in gravitational potential, lithologic properties, and atmospheric interactions. Wide variations found in secondary crater populations around medium-size (5-50 km) Martian craters can be interpreted as effects of contrasting target lithologies. Extensive secondary cratering and elongate secondaries of Crater I in Chryse Planitia are consistent with a competent lithology of basaltic plains, as inferred from various photogeologic studies. The relatively few large secondaries around Arandas, and their high circularity, are consistent with a lithology exhibiting low yield strength, as inferred for the fractured plains.

Schultz, P. H.↗

Evaluating Secondary Inorganic Aerosols in Three Dimensions

The spatial distribution of aerosols and their chemical composition dictates whether aerosols have a cooling or a warming effect on the climate system. Hence, properly modeling the three-dimensional distribution of aerosols is a crucial step for coherent climate simulations. Since surface measurement networks only give 2-D data, and most satellites supply integrated column information, it is thus important to integrate aircraft measurements in climate model evaluations. In this study, the vertical distribution of secondary inorganic aerosol (i.e., sulfate, ammonium, and nitrate) is evaluated against a collection of 14 AMS flight campaigns and surface measurements from 2000 to 2010 in the USA and Europe. GISS ModelE2 is used with multiple aerosol microphysics (MATRIX, OMA) and thermodynamic (ISORROPIA II, EQSAM) configurations. Our results show that the MATRIX microphysical scheme improves the model performance for sulfate, but that there is a systematic underestimation of ammonium and nitrate over the USA and Europe in all model configurations. In terms of gaseous precursors, nitric acid concentrations are largely underestimated at the surface while overestimated in the higher levels of the model. Heterogeneous reactions on dust surfaces are an important sink for nitric acid, even high in the troposphere. At high altitudes, nitrate formation is calculated to be ammonia limited. The underestimation of ammonium and nitrate in polluted regions is most likely caused by a too simplified treatment of the NH3/NH4(+) partitioning which affects the HNO3/NO3(-) partitioning.

aerosols↗

Metal (Fe, Cu, and As) transformation and association within secondary minerals in neutralized acid mine drainage characterized using X-ray absorption spectroscopy

The formation and transformation of secondary minerals in areas affected by neutralized acid mine drainage (AMD) determine the behavior of toxic elements. To better understand the binding form of toxic elements in the secondary minerals, we focused on the distribution of secondary precipitates and heavy metals in neutralized AMD near a typical Cu-polymetallic deposit located in central Tibet. Compared to background values, the average heavy metal (As, Cu, Co, Cu, Mo, Pb, and Zn) content is higher in sediments close to the neutralized AMD drain. X-ray absorption spectroscopy (XAS) characterization shows the Fe in the suspended particulate matter (SPM) first aggregate as small Fe(III) octahedra clusters and then precipitate as ferrihydrite along the river. The XAS results also show the by-products of neutralization-ferrihydrite and sulfate-are the primary forms of Fe and S in the sediments, respectively. Gypsum retains Cu in the sediments via structural fixation, surface adsorption, and surface coprecipitation. The difference of Cu-O coordination number between the SPM and the sediments reveals the Cu sulfate coprecipitation on the surface of gypsum accompanied by SPM transporting along the river. XAS results confirm that ferrihydrite act as an essential sink for heavy metals, especially As. As (III) mineral in the sediment near the neutralized AMD outfall is dissolved and oxidized to arsenate downstream, which then adsorb to ferrihydrite and/or form As(V)-Fe minerals along the river. Gypsum and ferrihydrite have the potential to release heavy metals with changes in water chemistry, which may pose a threat to the safety of drinking water for downstream residents. These results deepen the understanding of the influence of secondary minerals (especially gypsum and ferrihydrite) on the migration and transformation process of heavy metal pollutants in mine drainage system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the Vulnerabilities of the Direct Transfer Trip Scheme for Network Protector Units in the Secondary Networks of Electric Power Distribution Grids

Network protector units (NPUs) are crucial parts of the protection of secondary networks to effectively isolate faults occurring on the primary feeders. When a fault occurs on the primary feeder, there is a path of the fault current going through the service transformers that causes a negative flow of current on the NPU connected to the faulted feeder. Conventionally, NPUs rely on the direction of current with respect to the voltage to detect faults and make a correct trip decision. However, the conventional NPU logic does not allow the reverse power flow caused by distributed energy resources installed on secondary networks. The communication-assisted direct transfer trip logic for NPUs can be used to address this challenge. However, the communication-assisted scheme is exposed to some vulnerabilities arising from the disruption or corruption of the communicated data that can endanger the reliable operation of NPUs. This paper evaluates the impact of the malfunction of the communication system on the operation of communication-assisted NPU logic. To this end, the impact of packet modification and denial-of-service cyberattacks on the communication-assisted scheme are evaluated. The evaluation was performed using a hardware-in-the-loop (HIL) co-simulation testbed that includes both real-time power system and communication network digital simulators. This paper evaluates the impact of the cyberattacks for different fault scenarios and provides a list of recommendations to improve the reliability of communication-assisted NPU protection.

direct transfer trip↗

Size-frequency distributions of primary and secondary lunar impact craters

The graphs of diameter vs frequency plotted in the present study for primary impact craters produced in four time intervals exhibit an appreciable change in form with age. A deficiency of small craters relative to an extrapolation from the large-diameter parts of the curves is greatest and extends to the largest sizes in the oldest population (pre-Nectarian), whose curve approximates a log-normal form. Successively younger populations (Nectarian, Imbrian, Copernican plus Eratosthenian) have successively more small craters relative to larger ones and more nearly log-log distributions. Many of the craters thought to be small old primaries are here identified as secondary craters of basins, on the basis of previously developed criteria.

Wilhelms, D. E.↗

Persistent Nature of Secondary Diurnal Modes of Precipitation over Oceanic and Continental Regimes

This investigation seeks a better understanding of the assorted mechanisms controlling the global distribution of precipitation diurnal variability based on the use of Tropical Rainfall Measuring Mission (TRMM) microwave radiometer and radar data. The horizontal distributions of precipitation's diurnal cycle are derived from eight years of TRMM Microwave Imager (TMI) and Precipitation Radar (PR) measurements involving three TRMM standard rain rate retrieval algorithms -- the resultant distributions analyzed at various spatiotemporal scales. The results reveal the prominent and expected late-evening to early-morning (LE-EM) precipitation maxima over oceans and the counterpart prominent and expected mid- to late-afternoon (MLA) maxima over continents. Moreover, and not generally recognized, the results reveal a widespread distribution of secondary maxima occurring over both oceans and continents -- maxima which generally mirror their counterpart regime's behavior. That is, many ocean regions exhibit clearcut secondary MLA precipitation maxima while many continental regions exhibit just as evident secondary LE-EM maxima. This investigation is the first comprehensive study of these globally prevalent secondary maxima and their widespread nature, a type of study only made possible when the analysis procedure is applied to a high-quality global-scale precipitation dataset. The characteristics of the secondary maxima are mapped and described on global grids using an innovative clock-face format, while a current study to be published at a later date provides physically-based explanations of the seasonal-regional distributions of the secondary maxima. In addition to an "explicit" maxima identification scheme, a "Fourier decomposition" maxima identification scheme is used to examine the amplitude and phase properties of the primary and secondary maxima -- as well as tertiary and quaternary maxima. Accordingly, the advantages, ambiguities, and pitfalls resulting from use of Fourier harmonic analysis are explained.

Yang, S.↗

A design for an intelligent monitor and controller for space station electrical power using parallel distributed problem solving

The emphasis is on defining a set of communicating processes for intelligent spacecraft secondary power distribution and control. The computer hardware and software implementation platform for this work is that of the ADEPTS project at the Johnson Space Center (JSC). The electrical power system design which was used as the basis for this research is that of Space Station Freedom, although the functionality of the processes defined here generalize to any permanent manned space power control application. First, the Space Station Electrical Power Subsystem (EPS) hardware to be monitored is described, followed by a set of scenarios describing typical monitor and control activity. Then, the parallel distributed problem solving approach to knowledge engineering is introduced. There follows a two-step presentation of the intelligent software design for secondary power control. The first step decomposes the problem of monitoring and control into three primary functions. Each of the primary functions is described in detail. Suggestions for refinements and embelishments in design specifications are given.

Morris, Robert A.↗

HRI observations of the A2384 cluster of galaxies

The cores of subclusters at redshifts approximately 0.1 were observed by the Rosat high resolution imager (HRI). The analysis of a 26 ksec observation of A 2384, a BM II-III with a cD galaxy are reported on. The cluster appears to be composed of a primary subcluster with a secondary peak. The galaxy distribution suggests a secondary peak at the approximate location of the secondary X-ray peak. The primary and the secondary peak are connected, with the X-ray emission elongated in the direction of the merger axis. The central particle density is 0.01/cu cm, but falls rapidly as a function of the radius. The accretion rate is estimated to be 4 solar mass/yr. Cooling flows must grow appreciably after a merger in order to equal the large accretion rates typical of rich clusters.

Henriksen, Mark J.↗

High-speed impact of micron-sized diesel drop trains—Splashing dynamics, secondary droplet formation, and effects of pre-existing film thickness

This work investigates surface impingement of monodispersed diesel drop trains using computational simulations. The three-dimensional simulations include high-speed impact of micrometer-sized fuel drops onto initially dry and wetted stainless steel substrates. The drop size and impact velocity are representative of fuel injection conditions in internal combustion engines (ICEs). The drop trains serve as a simplified representation of fuel spray. To accurately capture the film that naturally develops on initially dry substrates, a dynamic diesel-stainless steel contact angle model was developed using experiments of single drop impact under ICE representative temperature. Simulations are presented for a highly splashing case and the effects of a pre-existing film on splashing dynamics were investigated, including the temporal evolution of splashed mass and film thickness. It was concluded that for thin films, the effect of pre-existing film thickness is less significant than in single drop impingement. Secondary droplet characterization was performed on simulation results, leading to instantaneous and time-averaged distributions of secondary droplet size, velocity magnitude, and trajectory angle. It was found that for each drop impingement, approximately 58% of the splashed mass is from the impinging drop itself, while the remainder of the splashed mass is composed of film liquid. From a high resolution case, details of secondary droplet formation are observed and three distinct phases of secondary droplet formation are identified. The detailed analysis of drop train impingement under engine-relevant conditions serves as a first step toward a robust understanding of fuel impingement and the development of cleaner and more efficient ICEs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Saprotrophic Fungus Induces Microscale Mineral Weathering to Source Potassium in a Carbon-Limited Environment

Plants rely on potassium for many critical biological processes, but most soils are potassium limited. Moving potassium from the inaccessible, mineral-bound pool to a more bioavailable form is crucial for sustainably increasing local potassium concentrations for plant growth and health. Here, we use a synthetic soil habitat (mineral doped micromodels) to study and directly visualize how the saprotrophic fungus, Fusarium sp. DS 682, weathers K-rich soil minerals. After 30 days of fungal growth, both montmorillonite and illite (secondary clays) had formed as surface coatings on primary K-feldspar, biotite, and kaolinite grains. The distribution of montmorillonite differed depending on the proximity to a carbon source, where montmorillonite was found to be associated with K-feldspar closer to the carbon (C) source, which the fungus was inoculated on, but associated with biotite at greater distances from the C source. The distribution of secondary clays is likely due to a change in the type of fungal exuded organic acids; from citric to tartaric acid dominated production with increasing distance from the C source. Thus, the main control on the ability of Fusarium sp. DS 682 to weather K-feldspar is proximity to a C source to produce citric acid via the TCA cycle.

54 ENVIRONMENTAL SCIENCES↗

Secondary emission effects on spacecraft charging: Energy distribution considerations

The conditions under which multiple valued solutions occur by computing the floating potential of an isolated eclipses surface on a geosynchronous orbit spacecraft were examined. Different approximations for the electron spectra during a geomagnetic substorm were used. The result indicates that if the incident electron flux has a Maxwellian energy distribution, the ratio of the secondary emitted current to the incident electron current is independent of the spacecraft potential. In this case a single value solution to the current equation occurs.

Sanders, N. L.↗

Vibrations of three-dimensional pipe systems with acoustic coupling

A general algorithm is developed to calculate the beam-type dynamic response of three dimensional multiplane finite length pipe systems, consisting of elbow and straight ducts with continuous interfaces. Emphasis is on secondary acoustic wave effects giving rise to coupling mechanisms; and the simulation accounts for one-dimensional elastoacoustic coupling from a plane acoustic wave and secondary loads resulting from wave asymmetries. The transfer matrix approach is adopted in modeling the elastodynamics of each duct, with allowance for distribution loads. Secondary loads from plane wave distortion are considered with a solution of the Helmholtz equation in an equivalent rigid waveguide, and effects of path imperfection are introduced as a perturbation from the hypothetical perfectly straight pipe. Computations indicate that the one-dimensional acoustic assumption is valid for frequencies below one-half the first cut-off frequency, and the three-dimensional acoustic effects produce an increase in response levels near and above cut-off.

El-Raheb, M.↗

Modeling the Size Distribution and Chemical Composition of Secondary Organic Aerosols during the Reactive Uptake of Isoprene-Derived Epoxydiols under Low-Humidity Condition

Reactive uptake of isoprene epoxydiols (IEPOX), which are isoprene oxidation products, onto acidic sulfate aerosols is recognized to be an important mechanism for the formation of isoprene-derived secondary organic aerosol (SOA). While a mechanistic understanding of IEPOX-SOA formation exists, several processes affecting their formation remain uncertain. Evaluating mechanistic IEPOX-SOA models with controlled laboratory experiments under longer atmospherically relevant timescales is critical. Here, we implement our latest understanding of IEPOX-SOA formation within a box model to simulate the measured reactive uptake of IEPOX on polydisperse ammonium bisulfate seed aerosols within an environmental Teflon chamber. The model is evaluated with single-particle measurements of size distribution, volume, density, and composition of aerosols due to IEPOX-SOA formation at timescales of hours. Additionally, we find that the model can simulate the growth of particles due to IEPOX multiphase chemistry, as reflected in increases of the mean particle size and volume concentrations, and a shift of number size distribution to larger sizes. The model also predicts the observed evolution of particle number mean diameter and total volume concentrations at the end of the experiment. We show that in addition to self-limiting effects of IEPOX-SOA coatings, accounting for the molar balance between inorganic and organic sulfate and mass accommodation coefficient of IEPOX are important parameters governing modeling of IEPOX-SOA formation. Thus, models which do not account for the molar sulfate balance and/or diffusion limitations within IEPOX-SOA coatings are likely to predict too high IEPOX-SOA formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical analysis of the density within an orbiting molecular shield

An analytical model based on the kinetic theory of a drifting Maxwellian gas is used to determine the nonequilibrium molecular density distribution within a hemispherical shell open aft with its axis parallel to its velocity. Separate numerical results are presented for the primary and secondary density distribution components due to the drifting Maxwellian gas for speed ratios between 2.5 and 10. An analysis is also made of the density component due to gas desorbed from the wall of the hemisphere, and numerical results are presented for the density distribution. It is shown that the adsorption process may be completely ignored. The results are applicable to orbital trajectories in any planet-atmosphere system and interplanetary transfer trajectories. Application to the earth's atmosphere is mentioned briefly.

Hueser, J. E.↗