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At least 19 recordsLinked to original sources
USGS2002

Direct conversion of terpenylalkanolamines to ethylidyne N -nitroso compounds

A series of mono- and diterpenylalkanolamines bearing isopropylidene functionality on the terpene group was reacted with sodium nitrite in aqueous acetic acid to yield ethylidyne N -nitroso analogues. The key feature of this direct conversion involved initial N-nitrosation followed by apparent elimination of a "CH 4 " unit (not necessarily methane) from the isopropylidene double bond. The product distribution data for ethylidyne nitrosamines derived from tertiary terpenyl alkanolamines reflect the conformational outcome of the nitrosative dealkylation process. For β , γ -unsaturated allylic diterpenylethanolamines, electronic effects appeared to be important for controlling the product distribution of ethylidyne nitrosamines in light of the highly selective α -cleavage observed in the nitrosation reactions.

Journal of Organic Chemistry↗
USGS2002

Aromatic fluorine compounds. XI. Replacement of chlorine by fluorine in halopyridines

The α -halogenated pyridines react with potassium fluoride in various solvents to give replacement of the α -halogen by fluorine. A 50% yield of 2-fluoropyridine was obtained from 2-chloropyridine by heating with potassium fluoride in dimethyl sulfone or tetramethylene sulfone for twenty-one days; 2-bromopyridine gave a similar yield with a heating period of only seven days. The α -halogens of the polyhalopyridines undergo the exchange reaction more readily than do the halogens of the α -monohalopyridines. The proposed structures of the fluoropyridines are supported by alternate syntheses and by n.m.r. studies.

Journal of Organic Chemistry↗
USGS2002

Aromatic fluorine compounds. X. The 2,3- and 2,6-difluoropyridines

The preparation of difluoropyridines by the Schiemann reaction was investigated. 2-Amino-6-fluoropyridine (IIIa), necessary for the synthesis of 2,6-difluoropyridine (IVa) by the Schiemann reaction, was conveniently prepared by the Curtius degradation of 6-fluoropicolinic hydrazide (IIa) and by the Hofmann reaction on 6-fluoropicolinamide (IId). Since an α -fluorine on a pyridine nucleus is preferentially replaced by hydrazine when it is either adjacent to or opposite a carbomethoxy group, the hydrazides necessary for the synthesis of 3-amino-2- and 6-fluoropyridine could not be prepared. These amines were prepared from the appropriate 2-fluoropyridinecarboxamide by the Hofmann reaction. The preparation of difluoropyridines was successful with two of the aminofluoropyridines and led to the following new compounds: 2,3-difluoro(IVb) and 2,6-difluoropyridine (IVa).

Journal of Organic Chemistry↗
USGS2002

Oxidation of 2,6-di-tert-butyl-4-methylphenol. The structure of C14H22O3

The acidic compound C14H22O3, previously reported without assignment of structure as an oxidation product of 2,6-di-tert-butyl-4-methylphenol, is now believed to be DL-trans-5,6-di-tert-butyl-2-hydroxy-1,4-diketo-2-cyclohexene (I). Chemical properties are described and infrared spectra are presented in support of this structure. This structure is of interest in relation to the problem of the existence of o-di-tert-alkylbenzene derivatives. The relatively easy racemization of optically active I suggests that its completely enolized form, 5,6-di-tert-butyl-1,2,4-trihydroxybenzene, is capable of transitory existence.

Journal of Organic Chemistry↗
USGS2002

A combined deamination and nitro reduction method for nitroanilines

The hypophosphorous acid-cuprous oxide deamination method on nitroanilines has been modified so that the nitro compounds which are formed are reduced in turn by cuprous oxide to the corresponding amines. Over-all yields of 55-65% are reported for three halogenated nitroanilines.

Journal of Organic Chemistry↗
USGS2002

The oxidation of 2,6-di-tert-butyl-4-methylphenol

The products formed in the oxidation of 2,6-di- tert -butyl-4-methylphenol with oxygen and sodium hydroxide at about 100° are 3,5-di- tert -butyl-4-hydroxybenzaldehyde, trimethylacetic acid, an acidic compound C 14 H 22 O 3 , and probably 2,6-di- tert -butylbenzoquinone (which was actually isolated in the similar oxidation of the above-named benzaldehyde), in addition to compounds previously reported. Some of the properties of C 14 H 22 O 3 are given, and the oxidation of it to 2,3-di- tert -butylsuccinic anhydride is described, but assignment of structure is reserved pending the completion of more experimental work.

Journal of Organic Chemistry↗
USGS1999

The types of data needed for assessing the environmental and human health impacts of coal

Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.Coal is one of the most important sources of energy. Its worldwide use will continue to expand during the next several decades, particularly in rapidly developing countries such as China and India. Unfortunately, coal use may bring with it environmental and human health costs. Many of the environmental and health problems attributed to coal combustion are due to mobilization of potentially toxic elements. Some of these problems could be minimized or even avoided if comprehensive databases containing appropriate coal quality information were available to decision makers so that informed decisions could be made regarding coal use. Among the coal quality parameters that should be included in these databases are: C, H, N, O, pyritic sulfur, organic sulfur, major, minor, and trace element concentrations, modes of occurrence of environmentally sensitive elements, cleanability, mineralogy, organic chemistry, petrography, and leachability.

International Journal of Coal Geology↗
USGS1977

Occurrence of bloedite and related minerals in marine shale of Diablo and Temblor Ranges, California

Bloedite, epsomite, and related minerals occur in small amounts throughout the arid eastern foothills of the Diablo and Temblor Ranges, as efflorescences on siliceous shale and as deposits around small springs and a brine pond. These minerals ultimately are products of weathering of underlying organic shale, and they are reminders that the chemistry of weathering of reduced organic shale is largely a reversal of the chemistry of its early diagenesis.

California↗
USGS1982

Chemical characterization of gas- and oil-bearing shales by instrumental neutron activation analysis

The concentration of As, Ba, Ca, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, K, La, Lu, Mn, Mo, Na, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, U, Yb, and Zn were determined by instrumental neutron activation analysis in block shale samples of the New Albany Group (Devonian-Mississippian) in the in the Illinois Basin. Uranium content of the samples was as high as 75 ppm and interfered in the determination of samarium, molybdenum, barium and cerium. In the determination of selenium a correction was made for interference from tantalum. U, As, Co, Mo, Ni and Sb as well as Cu, V and pyritic sulphur which were determined by other methods, were found to correlate positively with the organic carbon content of the samples. ?? 1982 Akade??miai Kiado??.

Journal of Radioanalytical Chemistry↗
USGS2006

Description, Properties, and Degradation of Selected Volatile Organic Compounds Detected in Ground Water--A Review of Selected Literature

This report provides abridged information describing the most salient properties and biodegradation of 27 chlorinated volatile organic compounds detected during ground-water studies in the United States. This information is condensed from an extensive list of reports, papers, and literature published by the U.S. Government, various State governments, and peer-reviewed journals. The list includes literature reviews, compilations, and summaries describing volatile organic compounds in ground water. This report cross-references common names and synonyms associated with volatile organic compounds with the naming conventions supported by the International Union of Pure and Applied Chemistry. In addition, the report describes basic physical characteristics of those compounds such as Henry's Law constant, water solubility, density, octanol-water partition (log Kow), and organic carbon partition (log Koc) coefficients. Descriptions and illustrations are provided for natural and laboratory biodegradation rates, chemical by-products, and degradation pathways.

Open-File Report↗
USGS2006

Organic geochemistry - A retrospective of its first 70 years

Organic geochemistry had its origin in the early part of the 20th century when organic chemists and geologists realized that detailed information on the organic materials in sediments and rocks was scientifically interesting and of practical importance. The generally acknowledged "father" of organic geochemistry is Alfred E. Treibs (1899-1983), who discovered and described, in 1936, porphyrin pigments in shale, coal, and crude oil, and traced the source of these molecules to their biological precursors. Thus, the year 1936 marks the beginning of organic geochemistry. However, formal organization of organic geochemistry dates from 1959 when the Organic Geochemistry Division (OGD) of The Geochemical Society was founded in the United States, followed 22 years later (1981) by the establishment of the European Association of Organic Geochemists (EAOG). Organic geochemistry (1) has its own journal, Organic Geochemistry (beginning in 1979) which, since 1988, is the official journal of the EAOG, (2) convenes two major conferences [International Meeting on Organic Geochemistry (IMOG), since 1962, and Gordon Research Conferences on Organic Geochemistry (GRC), since 1968] in alternate years, and (3) is the subject matter of several textbooks. Organic geochemistry is now a widely recognized geoscience in which organic chemistry has contributed significantly not only to geology (i.e., petroleum geochemistry, molecular stratigraphy) and biology (i.e., biogeochemistry), but also to other disciplines, such as chemical oceanography, environmental science, hydrology, biochemical ecology, archaeology, and cosmochemistry.

Conference Paper↗
USGS1993

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Journal of Photochemistry and Photobiology A: Chem↗
USGS2018

Fire, flood, and drought: Extreme climate events alter flow paths and stream chemistry

Extreme climate events—such as hurricanes, droughts, extreme precipitation, and wildfires—have the potential to alter watershed processes and stream response. Yet due to the destructive and hazardous nature and unpredictability of such events, capturing their hydrochemical signal is challenging. A 5‐year postwildfire study of stream chemistry in the Fourmile Creek watershed, Colorado Front Range, USA, focused on high‐frequency storm sampling. During the study, the watershed was impacted by three additional extreme climate events—drought and two periods of extreme rainfall totals. These events altered concentration‐discharge relationships in ways that elucidate how hydrologic flow paths and source material availability affect stream water chemistry. Reduced infiltration after wildfire led to overland flow during thunderstorms, which conveyed ash and soil into streams. This resulted in elevated stream concentrations of constituents elevated in ash—Ca, K, Mg, alkalinity, and dissolved organic carbon—along with sediment and nitrate. Subsurface flow paths were bypassed, leading to low concentrations of Na and SiO 2 , which are bedrock derived and not elevated in ash. During drought conditions, when stream discharge was <20% of average, concentrations of sediment, dissolved organic carbon, and Ca fell below average concentrations, but SiO 2 did not. Extreme rainfall totals saturated the subsurface and led to prolonged elevated stream discharge. Concentration‐discharge relationships for bedrock‐derived constituents, such as Ca and SiO 2 , were altered in that time period, while those for dissolved organic carbon were not. Previous disturbances, including historical mining, also affect stream chemistry, and water‐quality impairment can be exacerbated by extreme climate events.

Colorado↗
USGS2004

Potential sources of hydrogel stabilization of Florida Bay lime mud sediments and implications for organic matter preservation

The fine grained carbonate mud sediments of central Florida Bay are resuspended quite easily. However, this disturbance is usually limited to the surficial ('floc') layer, as the underlying sediments appear to be stabilized by an hydrogelation involving the bulk organic matter. That gelation has occurred within these sediments is suggested from their physical behavior and an observed mathematical relationship between the percentages of organic carbon (C org) and water. Specifically, when extruded from a core barrel, the sediment maintains its integrity and has the consistency of a fine spackling compound. However, upon homogenization, as with a stirring rod prior to sieving, these sediments break into two distinct phases, 1/2-2/3 milky water and 1/3-1/2 sediment grains, by volume. The relationship observed between Corg and water was modeled as both linear (% water = (0.0777) Corg + 0.2984, R2 = 0.8664) and logarithmic (% water = 0.2489 Ln Corg + 0.2842, R2 = 0.9455) functions. As this relationship tends to be asymptotic at higher Corg (>3.5% dry)/water values (>60%) and given an higher correlation, the relationship appears better modeled as a logarithmic function. Values of C org from 1.2 to over 6.5%dry wt. and water contents from 30 to over 70%wt. were observed. The calculated intercept revealed that, without organic carbon (viz. hydrogel formation), these carbonates would likely contain only ???30% water by weight ('m' from linear model). This gelation is proposed to involve exopolymeric substances (EPS), likely polysaccharides, derived from diatoms and cyanobacteria of the microphytobenthos. A cyanobacterial-diatomaceous biofilm/mat underlain by purple sulfur bacteria was shown, by pigment based chemotaxonomy, to form the main components of the microphytobenthos. Additional water column detrital biomass, also mainly cyanobacteria and diatoms, is admixed with the living microphytobenthos in a flocculent/nephloid layer above the sediments prior to final incorporation into the gel-stabilized sediment column. Loss of seagrass cover appears to have allowed higher energy wave induced effects to reach the water-(nephloid)-sediment interface and increase overall turbidity in the bay. The effects of these gelatinized organics upon sediment stability, pore water chemistry and dissolved species flux in/out of the sediments are discussed as areas for future research which takes this (hydro-) gelation phenomenon into account.

Journal of Coastal Research↗
USGS2013

Accumulation of atmospheric sulfur in some Costa Rican soils

Sulfur is one of the macronutrient elements whose sources to terrestrial ecosystems should shift from dominance by rock-weathering to atmospheric deposition as soils and underlying substrate undergo progressive weathering and leaching. However, the nature and timing of this transition is not well known. We investigated sources of sulfur to tropical rain forests growing on basalt-derived soils in the Osa Peninsula region of Costa Rica. Sulfur sources were examined using stable isotope ratios (δ 34 S) and compared to chemical indices of soil development. The most weathered soils, and the forests they supported, are dominated by atmospheric sulfur, while a less weathered soil type contains both rock-derived and atmospheric sulfur. Patterns of increasing δ 34 S with increasing soil sulfur concentration across the landscape suggest atmospheric sulfur is accumulating, and little rock-derived sulfur has been retained. Soil sulfur, minus adsorbed sulfate, is correlated with carbon and nitrogen, implying that sulfur accumulation occurs as plants and microbes incorporate sulfur into organic matter. Only the lower depth increments of the more weathered soils contained significant adsorbed sulfate. The evidence suggests a pattern of soil development in which sulfur-bearing minerals in rock, such as sulfides, weather early relative to other minerals, and the released sulfate is leached away. Sulfur added via atmospheric deposition is retained as organic matter accumulates in the soil profile. Adsorbed sulfate accumulates later, driven by changes in soil chemistry and mineralogy. These aspects of sulfur behavior during pedogenesis in this environment may hasten the transition to dominance by atmospheric sources.

Journal of Geophysical Research: Biogeosciences↗
USGS1995

Bibliography, indices, and data sources of water-related studies, upper Colorado River basin, Colorado and Utah, 1872-1995

As part of the U.S. Geological Survey's National Water-Quality Assessment Program, current water-quality conditions in the Upper Colorado River Basin in Colorado and Utah are being assessed. This report is an initial effort to identify and compile information on water-related studies previously conducted in the basin and consists of a bibliography, coauthor and subject indices, and sources of available water-related data. Computerized literature searches of scientific data bases were carried out to identify past water-related studies in the basin, and government agencies and private organizations were contacted regarding their knowledge or possession of water-related publications and data. Categories of information in the bibliography include: aquatic biology, climate, energy development, geology, land use, limnology, runoff, salinity, surface- and ground-water hydrology, water chemistry, water quality and quantity, and water use and management. The approximately 1,400 indexed references date from 1872 through February 1995 and include books, journal articles, maps, and reports. In many instances, an abstract has been provided for a given reference. Sources of water-related data in the basin are included in a table.

Colorado, Utah↗