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An investigation of volcanic depressions. Part 1: Airfall and intrusive pyroclastic deposits. Part 2: Subaerial pyroclastic flows and their deposits

Pyroclastic ejecta and the deposits they form were classified in many ways, and many interpretations were given to individual terms. Some classifications are based on the modes of orgin and deposition of the ejecta; others emphasized the chemical and physical composition of the ejecta. Particle-size was used as the prime basis of subdivision, and the same size-limits were used as those employed in the classification of sediments and sedimentary rocks.

Williams, H.

Innovation and application of ANN in Europe demonstrated by Kohonen maps

One of the most important contributions to neural networks comes from Kohonen, Helsinki/Espoo, Finland, who had the idea of self-organizating maps in 1981. He verified his idea by an algorithm of which many applications make use of. The impetus for this idea came from biology, a field where the Europeans have always been very active at several research laboratories. The challenge was to model the self-organization found in the brain. Today one goal is the development of more sophisticated neurons which model the biological neurons more exactly. They should come to a better performance of neural nets with only a few complex neurons instead of many simple ones. A lot of application concepts arise from this idea: Kohonen himself applied it to speech recognition, but the project did not overcome much more than the recognition of the numerals one to ten at that time. A more promising application for self-organizing maps is process control and process monitoring. Several proposals were made which concern parameter classification of semiconductor technologies, design of integrated circuits, and control of chemical processes. Self-organizing maps were applied to robotics. The neural concept was introduced into electric power systems. At Dortmund we are working on a system which has to monitor the quality and the reliability of gears and electrical motors in equipment installed in coal mines. The results are promising and the probability to apply the system in the field is very high. A special feature of the system is that linguistic rules which are embedded in a fuzzy controller analyze the data of the self-organizing map in regard to life expectation of the gears. It seems that the fuzzy technique will introduce the technology of neural networks in a tandem mode. These technologies together with the genetic algorithms start to form the attractive field of computational intelligence.

Goser, Karl

Teaching Soil Science in Primary and Secondary Schools

Earth's thin layer of soil is a fragile resource, made up of minerals, organic materials, air, water, and billions of living organisms. Soils plays a variety of critical roles that sustain life on Earth. If we think about soil, we tend to see it first as the source of most of the food we eat and the fibers we use, such as wood and cotton. Few students realize that soils also provide the key ingredients to many of the medicines (including antibiotics), cosmetics, and dyes that we use. Fewer still understand the importance of soils in integrating, controlling, and regulating the movement of air, water, materials, and energy between the hydrosphere, lithosphere, atmosphere, and biosphere. Because soil sustains life, it offers both a context and a natural laboratory for investigating these interactions. The enclosed poster, which integrates soil profiles with typical landscapes in which soils form, can also help students explore the interrelationships of Earth systems and gain an understanding of our soil resources. The poster, produced jointly by the American Geological Institute and the Soil Science Society of America, aims to increase awareness of the importance of soil, as does the GLOBE (Global Learning and Observations To Benefit the Environment) Program. Vice President Al Gore instituted the GLOBE Program on Earth Day of 1993 to increase environmental awareness of individuals throughout the world, contribute to a better scientific understanding of the Earth, and help all students reach higher levels of achievement in science and mathematics. GLOBE functions as a partnership between scientists, students, and teachers in which scientists design protocols for specific measurements they need for their research that can be performed by K-12 students. Teachers are trained in the GLOBE protocols and teach them to their students. Students make the measurements, enter data via the Internet to a central data archive, and the data becomes available to scientists and the general community. Students benefit by having a "hands-on"experience in science, math, and technology, using their local environment as a learning laboratory, as well as contact with scientists and other students around the world. Soil investigations have become an essential component of GLOBE. The protocols that have been developed so far within the GLOBE program include GPS Location, Atmosphere/Climate, Soil Characterization, Soil Moisture and Temperature, Land Cover/Biometry, Hydrology, and Satellite Image Classification. For the GLOBE Soil Characterization Protocol, students explore the physical. chemical, and morphological properties of the soil at their study site. They are asked to dig a pit or use an auger to about 1 meter at at least 2 sites.

Levine, Elissa R.

A proposition for the classification of carbonaceous chondritic micrometeorites

Classification of interplanetary dust particles (IDP's) should be unambiguous and, if possible, provide an opportunity to interrelate these ultrafine IDP's with the matrices of undifferentiated meteorites. I prefer a scheme of chemical groupings and petrologic classes that is based on primary IDP properties that can be determined without prejudice by individual investigators. For IDP's of 2-50 microns these properties are bulk elemental chemistry, morphology, shape, and optical properties. The two major chemical groups are readily determined by energy dispersive spectroscopic analysis using the scanning or analytical electron microscope. Refinement of chondritic IDP classification is possible using the dominant mineral species, e.g. olivine, pyroxene, and layer silicates, and is readily inferred from FTIR, and automated chemical analysis. Petrographic analysis of phyllosilicate-rich IDP's will identify smectite-rich and serpentine-rich particles. Chondritic IDP's are also classified according to morphology, viz., CP and CF IDP's are aggregate particles that differ significantly in porosity, while the dense CS IDP's have a smooth surface. The CP IDP's are characterized by an anhydrous silicate mineralogy, but small amounts of layer silicates may be present. Distinction between the CP and CF IDP's is somewhat ambiguous, but the unique CP IDP's are fluffy, or porous, ultrafine-grained aggregates. The CP IDP's, which may contain silicate whiskers, are the most carbon-rich extraterrestrial material presently known. The CF IDP's are much less porous that CP IDP's. Using particle type definitions, CP IDP's in the NASA JSC Cosmic Dust Catalogs are approx. 15 percent of all IDP's that include nonchondritic spheres. Most aggregate particles are of the CF type.

Rietmeijer, Frans J. M.

Shock metamorphism of granulated lunar basalt

The paper deals with an extensive series of shock-recovery experiments performed on both nonporous crystalline basalt and its granulated and sieved counterpart to study the role of porosity and grain size in shock motomorphic effects under otherwise identical conditions. Shocked samples are compared with unshocked starting material in terms of textural and mineralogical modifications attributable to shock. A comparative petrographic and chemical characterization is presented of pulverized and sieved lunar basalt 75035 shocked between 6 and 75 GPa in comparison with holocrystalline disks of the same basalts shocked in 10 earlier experiments. Specifically, a petrographic classification of shock features is given, along with an estimation of relative amounts of shock glasses and a chemical characterization of shock glasses in each shocked granular basalt.

Schaal, R. B.

Enhanced Detection of Primary Biological Aerosol Particles Using Machine Learning and Single-Particle Measurement

Accurately identifying primary biological aerosol particles (PBAPs) using analytical techniques poses inherent challenges due to their resemblance to other atmospheric carbonaceous particles. Here, we present a study of an enhanced method for detecting PBAPs by combining single-particle measurement with advanced supervised machine learning (SML) techniques. We analyzed ambient particles from a variety of environments and lab-generated standards, focusing on chemical composition for traditional rule-based and clustering approaches and incorporating morphological features into the SML approaches, neural networks and XGBoost, for improved accuracy. This study demonstrates that SML methods outperform traditional methods in quantifying PBAPs, achieving significant improvements in precision, recall, F1-score, and accuracy, leading to an increased number of detected PBAPs by at least 19%. The adaptability of the proposed XGBoost-based SML model is showcased in comparison to traditional methods in categorizing PBAPs for blind data sets from different geographical locations. Two field case studies were investigated, over agricultural land and Amazonia rain forest, representing relatively low and high concentrations of PBAPs, respectively, where XGBoost consistently detected up to 3.5 times more PBAPs than traditional methods. Precise detection of PBAPs in the atmosphere could significantly improve the prediction of climatic impacts by them.

42 ENGINEERING

Fossil Signatures Using Elemental Abundance Distributions and Bayesian Probabilistic Classification

Elemental abundances (C6, N7, O8, Na11, Mg12, Al3, P15, S16, Cl17, K19, Ca20, Ti22, Mn25, Fe26, and Ni28) were obtained for a set of terrestrial fossils and the rock matrix surrounding them. Principal Component Analysis extracted five factors accounting for the 92.5% of the data variance, i.e. information content, of the elemental abundance data. Hierarchical Cluster Analysis provided unsupervised sample classification distinguishing fossil from matrix samples on the basis of either raw abundances or PCA input that agreed strongly with visual classification. A stochastic, non-linear Artificial Neural Network produced a Bayesian probability of correct sample classification. The results provide a quantitative probabilistic methodology for discriminating terrestrial fossils from the surrounding rock matrix using chemical information. To demonstrate the applicability of these techniques to the assessment of meteoritic samples or in situ extraterrestrial exploration, we present preliminary data on samples of the Orgueil meteorite. In both systems an elemental signature produces target classification decisions remarkably consistent with morphological classification by a human expert using only structural (visual) information. We discuss the possibility of implementing a complexity analysis metric capable of automating certain image analysis and pattern recognition abilities of the human eye using low magnification optical microscopy images and discuss the extension of this technique across multiple scales.

Hoover, Richard B.

Systematics of the CHON and other light-element particle populations in Comet Halley

Based on chemical signatures measured by the PIA experiment during the Giotto flyby of comet Halley, particle classifications were designated. In addition to silicate-like grains and particles of mixed (cosmic) composition, there appear to be several light-element rich populations, including the CHON, (H,C), (H,C,O), and (H,C,N) particle types. These compositional classes are further distinguished by differences in mass distributions, a density indicator, and variations in relative abundance within the coma. These particle populations are evidence for chemical heterogeneity in the surface of the cometary nucleus. Particles found mainly in the inner coma may be volatile icy grains. Most of the N of the comet may be found in up to three different populations of grains; one or more of these may be responsible for the observation of cyanojets.

Clark, Benton

The Effect of Air Separations on Fast Pyrolysis Products for Forest Residue Feedstocks

This study investigates the intricate relationship between biomass preprocessing and pyrolysis product yields, employing the air classification technique for the treatment of loblolly pine residues with varying moisture content. A comprehensive exploration of the physicochemical properties of air-classified loblolly pine informs a sophisticated pyrolysis simulation model. Given the complex and multifaceted nature of biomass pyrolysis, operating across diverse temporal and spatial scales, a pyrolysis kinetics-based CFD–DEM simulation method is employed to predict product yields. Results showed that the elevated moisture content amplifies particle adhesiveness, necessitating augmented air velocities for effective separation, thereby influencing the efficiency of the separation process. While carbon and hydrogen contents exhibit relative stability across diverse moisture contents and blower frequencies, the oxygen content undergoes noticeable changes. For example, the oxygen contents were measured as 29.2 and 38.6 wt% in the light fraction of 30% moisture content sample at blower frequencies of 10 and 20 Hz, respectively. An intriguing finding emerges from pyrolysis simulation, indicating that a lower blower frequency in air classification moderately enhances bio-oil yield and significantly improves its quality, particularly in terms of water content. For instance, the water content in the bio-oil was about 1.5% and 10% in the heavy and light fractions, respectively from 10% moisture sample under 15 Hz blower frequency. In summary, a detailed understanding and strategic manipulation of critical material attributes in biomass through efficient fractionation techniques are imperative for advancing fast pyrolysis as a sustainable avenue for renewable energy and chemical production.

09 BIOMASS FUELS

Super Capacitor Development At NASA MSFC

A viewgraph presentation outlines super capacitor development at NASA Marshall Space Flight Center. The concept, proof of concept testing and the test set-ups are described. An overview of super capacitor classification is shown and several types of capacitors are detailed: Ni-C chemical double layer (CDL), Ru-Oxide pseudo-cap, and a Ru-Oxide 2 F 30 V capacitor.

Hall, David K.

An energetic link between order and strength in metals: A nanocrystalline strength limit in high-entropy alloys and intermetallic compounds

The metallurgy and materials communities have long understood and exploited fundamental links between chemical and structural ordering in metallic solids to tailor their mechanical properties. We extend these ideas to include prediction of the nanocrystalline strength limit in high-entropy alloys and intermetallic compounds, where a breakdown occurs in the classical Hall-Petch strengthening behavior. The highest reported strength achievable through alloying has rapidly climbed and given rise to new classifications of materials with extraordinary properties, with a notable case being nanocrystalline metals. High-entropy alloys (chemically disordered, concentrated solid solutions) and intermetallic compounds are two boundary cases of how tailored order can be used to manipulate mechanical behavior. Here, we show that the complex electronic-structure mechanisms governing the peak strength of alloys and pure metals can be reduced to a few physically meaningful parameters based on their atomic arrangements and used – with no fitting parameters – to predict the maximum strength of these materials. This includes a generalized energy-based accounting for the degree of structural and chemical ordering that allows for rapid and reasonably accurate prediction of peak strength (validated in the nanocrystalline limit) as a function of temperature. Predictions of maximum strength based on the activation energy (with all materials properties derived from DFT calculations or experiments) for a stress-driven transition to an amorphous state is shown to accurately describe the breakdown in Hall-Petch behavior at the smallest crystallite sizes for pure metals, intermetallic compounds, high-entropy alloys, and metallic glasses. Further, this activation energy is also shown to be directly proportional to interstitial electronic charge density, which is a good predictor of ductility, stiffness (moduli), and phase stability in high-entropy alloys and solid metals generally. The proposed framework suggests the possibility of coupling ordering and intrinsic strength to mechanisms like dislocation nucleation, hydrogen embrittlement, and transport properties, such as through correlations between the activation energies for amorphization with stacking-fault and grain boundary energies. It additionally opens the prospect for greatly accelerated structural materials design and development to address materials challenges limiting more sustainable and efficient use of energy.

36 MATERIALS SCIENCE

In Situ Measurements of Angular-Dependent Light Scattering by Aerosols over the Contiguous United States

This work provides a synopsis of aerosol phase function (F (sub 11)) and polarized phase function (F (sub 12)) measurements made by the Polarized Imaging Nephelometer (PINeph) during the Studies of Emissions, Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Deep Convection Clouds and Chemistry (DC3) field campaigns. In order to more easily explore this extensive dataset, an aerosol classification scheme is developed that identifies the different aerosol types measured during the deployments. This scheme makes use of ancillary data that include trace gases, chemical composition, aerodynamic particle size and geographic location, all independent of PI-Neph measurements. The PI-Neph measurements are then grouped according to their ancillary data classifications and the resulting scattering patterns are examined in detail. These results represent the first published airborne measurements of F (sub 11) and minus F (sub 12) divided by F (sub 11) for many common aerosol types. We then explore whether PI-Neph light-scattering measurements alone are sufficient to reconstruct the results of this ancillary data classification algorithm. Principal component analysis (PCA) is used to reduce the dimensionality of the multi-angle PI-Neph scattering data and the individual measurements are examined as a function of ancillary data classification. Clear clustering is observed in the PCA score space, corresponding to the ancillary classification results, suggesting that, indeed, a strong link exists between the angular scattering measurements and the aerosol type or composition. Two techniques are used to quantify the degree of clustering and it is found that in most cases the results of the ancillary data classification can be predicted from PI-Neph measurements alone with better than 85 percent recall. This result both emphasizes the validity of the ancillary data classification as well as the PI-Neph's ability to distinguish common aerosol types without additional information.

Aerosol phase function

Probabilistic Classification Using Elemental Abundance Distributions and Lossless Image Compression in Apollo 17 Lunar Dust Samples from Mare Serenitatis

We have previously outlined a strategy for the detection of fossils [Storrie-Lombardi and Hoover, 2004] and extant microbial life [Storrie-Lombaudi and Hoover, 20051 during robotic missions to Mars using co-registered structural and chemical signatures. Data inputs included image lossless compression indices to estimate relative textural complexity and elemental abundance distributions. Two exploratory classification algorithms (principal component analysis and hierarchical cluster analysis) provide an initial tentative classification of all targets. Nonlinear stochastic neural networks are then trained to produce a Bayesian estimate of algorithm classification accuracy. The strategy previously has been successful in distinguishing regions of biotic and abiotic alteration of basalt glass from unaltered samples. [Storrie-Lombardi and Fisk, 2004; Storrie-Lombardi and Fisk, 2004] Such investigations of abiotic versus biotic alteration of terrestrial mineralogy on Earth are compromised by .the difficulty finding mineralogy completely unaffected by the ubiquitous presence of microbial life on the planet. The renewed interest in lunar exploration offers an opportunity to investigate geological materials that may exhibit signs of aqueous alteration, but are highly unlikely to contain contaminating biological weathering signatures. We here present an extension of our earlier data set to include lunar dust samples obtained during the Apollo 17 mission. Apollo 17 landed in the Taurus-Littrow Valley in Mare Serenitatis. Most of the rock samples from this region of the lunar highlands are basalts comprised primarily of plagioclase and pyroxene and selected examples of orange and black volcanic glass. SEM images and elemental abundances (C6, N7, O8, Na11, Mg12, Al13, Si14, P15, S16, Cll7, K19, Ca20, Fe26) for a series of targets in the lunar dust samples are compared to the extant cyanobacteria, fossil trilobites, Orgueil meteorite, and terrestrial basalt targets previously discussed. The data set provides a first step in producing a quantitative probabilistic methodology for geobiological analysis of returned lunar samples or in situ exploration.

Storrie-Lombardi, Michael C.

Evaluating Material Design Principles for Calcium-Ion Mobility in Intercalation Cathodes

Multivalent-ion batteries offer an alternative to Li-based technologies, with the potential for greater sustainability, improved safety, and higher energy density, primarily due to their rechargeable system featuring a passivating metal anode. Although a system based on the Ca 2+ /Ca couple is particularly attractive given the low electrochemical plating potential of Ca 2+ , the remaining challenge for a viable rechargeable Ca battery is to identify Ca cathodes with fast ion transport. In this work, a high-throughput computational pipeline is adapted to (1) discover novel Ca cathodes in a largely unexplored space of empty intercalation hosts and (2) develop material design rules for Ca-ion mobility. One candidate from the screening, W 2 O 3 (PO 4 ) 2 , is confirmed to have a low Nudged Elastic Band (NEB) barrier of 168 meV within a one-dimensional (1D) ion percolation topology. This candidate is subsequently synthesized and electrochemically tested, achieving reversible Ca cycling with a capacity of 25 mA h/g. To further accelerate the screening for promising Ca intercalation electrodes, machine learning (ML) Random Forest (RF) and Extreme Gradient Boosting (XGB) classification models are created with local environment descriptors based on a large, structurally and chemically diverse dataset of minimum energy pathways, spanning over 5,000 density functional theory (DFT) site energy calculations. Accuracies of 92% are achieved, material design metrics are quantified, ML force-fields are leveraged in an accelerated iteration of the screening, and a total of 27 novel Ca cathode materials are highlighted for further investigation.

25 ENERGY STORAGE

Design and Impacts of Land-Biogenic-Atmosphere Coupling in the NASA-Unified WRF (NU-WRF) Modeling System

Land-Atmosphere coupling is typically designed and implemented independently for physical (e.g. water and energy) and chemical (e.g. biogenic emissions and surface depositions)-based models and applications. Differences in scale, data requirements, and physics thus limit the ability of Earth System models to be fully coupled in a consistent manner. In order for the physical-chemical-biological coupling to be complete, treatment of the land in terms of surface classification, condition, fluxes, and emissions must be considered simultaneously and coherently across all components. In this study, we investigate a coupling strategy for the NASA-Unified Weather Research and Forecasting (NU-WRF) model that incorporates the traditionally disparate fluxes of water and energy through NASA's LIS (Land Information System) and biogenic emissions through BEIS (Biogenic Emissions Inventory System) and MEGAN (Model of Emissions of Gases and Aerosols from Nature) into the atmosphere. In doing so, inconsistencies across model inputs and parameter data are resolved such that the emissions from a particular plant species are consistent with the heat and moisture fluxes calculated for that land cover type. In turn, the response of the atmospheric turbulence and mixing in the planetary boundary layer (PBL) acts on the identical surface type, fluxes, and emissions for each. In addition, the coupling of dust emission within the NU-WRF system is performed in order to ensure consistency and to maximize the benefit of high-resolution land representation in LIS. The impacts of those self-consistent components on' the simulation of atmospheric aerosols are then evaluated through the WRF-Chem-GOCART (Goddard Chemistry Aerosol Radiation and Transport) model. Overall, this ambitious project highlights the current difficulties and future potential of fully coupled. components. in Earth System models, and underscores the importance of the iLEAPS community in supporting improved knowledge of processes and innovative approaches for models and observations.

Tan, Qian

Probabilisitc Geobiological Classification Using Elemental Abundance Distributions and Lossless Image Compression in Recent and Modern Organisms

Last year we presented techniques for the detection of fossils during robotic missions to Mars using both structural and chemical signatures[Storrie-Lombardi and Hoover, 2004]. Analyses included lossless compression of photographic images to estimate the relative complexity of a putative fossil compared to the rock matrix [Corsetti and Storrie-Lombardi, 2003] and elemental abundance distributions to provide mineralogical classification of the rock matrix [Storrie-Lombardi and Fisk, 2004]. We presented a classification strategy employing two exploratory classification algorithms (Principal Component Analysis and Hierarchical Cluster Analysis) and non-linear stochastic neural network to produce a Bayesian estimate of classification accuracy. We now present an extension of our previous experiments exploring putative fossil forms morphologically resembling cyanobacteria discovered in the Orgueil meteorite. Elemental abundances (C6, N7, O8, Na11, Mg12, Ai13, Si14, P15, S16, Cl17, K19, Ca20, Fe26) obtained for both extant cyanobacteria and fossil trilobites produce signatures readily distinguishing them from meteorite targets. When compared to elemental abundance signatures for extant cyanobacteria Orgueil structures exhibit decreased abundances for C6, N7, Na11, All3, P15, Cl17, K19, Ca20 and increases in Mg12, S16, Fe26. Diatoms and silicified portions of cyanobacterial sheaths exhibiting high levels of silicon and correspondingly low levels of carbon cluster more closely with terrestrial fossils than with extant cyanobacteria. Compression indices verify that variations in random and redundant textural patterns between perceived forms and the background matrix contribute significantly to morphological visual identification. The results provide a quantitative probabilistic methodology for discriminating putatitive fossils from the surrounding rock matrix and &om extant organisms using both structural and chemical information. The techniques described appear applicable to the geobiological analysis of meteoritic samples or in situ exploration of the Mars regolith. Keywords: cyanobacteria, microfossils, Mars, elemental abundances, complexity analysis, multifactor analysis, principal component analysis, hierarchical cluster analysis, artificial neural networks, paleo-biosignatures

Storrie-Lombardi, Michael C.

SHERLOC: Results of the first 350 sols of operations

On February 18th 2021, the Perseverance rover landed in Jezero crater, Mars. This site was chosen because orbiter data analysis provides evidence that the crater hosted a stream-fed lake during the Martian Noachian period. The Octavia Butler landing site is located ~1.9 km east of the remnants of a river delta. Deltaic and lacustrine sediments can preserve biosignatures, making Jezero crater a prime target for Mars sample return science. One of the seven instruments on Perseverance’s science payload is SHERLOC –Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals. SHERLOC combines fluorescence and Raman spectroscopy with microscopic imaging to analyze surface material to better understand the history of the aqueous environments recorded in the rocks of Jezero crater and to search for potential biosignatures. SHERLOC imaging obtains high spatial resolution images of geological targets to identify grain-scale structure and texture. SHERLOC spectroscopy enables high-sensitivity detection, characterization, and spatially resolved correlation of trace organic materials. Native fluorescence emissions from aromatic organic species allow for detection and classification of aromatic organic molecules, whereas Raman scattered photons from molecules allow identification of functional groups of organics, chemicals, and minerals. In the first 300 sols, SHERLOC has analyzed 3 natural surfaces, and 5 abraded rock patches created during the Crater Floor Campaign within Jezero crater. SHERLOC has been able to identify phosphates, amorphous/microcrystalline silicate (AMS), olivine, sulfates, and carbonates in abraded patches in the green zone campaign within Jezero Crater Máaz and Séítah formations. Within these detections we have begun to tell the story of what this crater was like when it was full of liquid water over 3 billion years ago. In each of these samples we have identified fluorescence features that are likely aromatic organics native to the rock interiors. We have identified multiple unique fluorescence signatures, within each of the abraded patches. The organic signatures have either been widely distributed over an extended area, which is probably due to planetary wide dust, or have spatially resolved locations that are collocated with different mineral signatures. Note: Additional information available on attachment.

L. W. Beegle

Classification and properties of iron meteorites

The paper describes the general requirements for a genetically significant scheme for classifying iron meteorites. Some of the properties which may be used to classify iron meteorites are reviewed, and a classification scheme based on Ga-Ni and Ge-Ni plots, taxonomic properties, and chemical properties is proposed. It is found that 95% of the irons can be assigned to a genetic group or an anomalous class.

Scott, E. R. D.