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Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HCl HF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C "> HC ratios, X-ray diffraction (XRD), 13 C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C "> HC ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp 2 -hybridized and 20% is sp 3 -hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300°C shows that the materials examined have not previously been subjected to temperatures as high as 300°C.

Witwatersrand goldfields

1H and 13C resonance designation of antimycin A1 by two-dimensional NMR spectroscopy

Complete 1 H and 13 C resonance assignments of antimycin A 1 were accomplished by two-dimensional NMR techniques, viz. 1 H homonuclear COSY correlation, heteronuclear 13 C- 1 H chemical shift correlation and long-range heteronuclear 13 C- 1 H COLOC correlation. Antimycin A 1 was found to consist of two isomeric components in a 2:1 ratio based on NMR spectroscopic evidence. The structure of the major component was newly assigned as the 8-isopentanoic acid ester. The spectra of the minor component were consistent with the known structure of antimycin A 1 .

Magnetic Resonance in Chemistry

Nitrite fixation by humic substances: Nitrogen-15 nuclear magnetic resonance evidence for potential intermediates in chemodenitrification

Studies have suggested that NO − 2 , produced during nitrification and denitrification, can become incorporated into soil organic matter and, in one of the processes associated with chemodenitrification, react with organic matter to form trace N gases, including N 2 O. To gain an understanding of the nitrosation chemistry on a molecular level, soil and aquatic humic substances were reacted with 15 N-labeled NaNO 2 , and analyzed by liquid phase 15 N and 13 C nuclear magnetic resonance (NMR). The International Humic Substances Society (IHSS) Pahokee peat and peat humic acid were also reacted with Na 15 NO 2 and analyzed by solid-state 15 N NMR. In Suwannee River, Armadale, and Laurentian fulvic acids, phenolic rings and activated methylene groups underwent nitrosation to form nitrosophenols (quinone monoximes) and ketoximes, respectively. The oximes underwent Beckmann rearrangements to 2° amides, and Beckmann fragmentations to nitriles. The nitriles in turn underwent hydrolysis to 1° amides. Peaks tentatively identified as imine, indophenol, or azoxybenzene nitrogens were clearly present in spectra of samples nitrosated at pH 6 but diminished at pH 3. The 15 N NMR spectrum of the peat humic acid exhibited peaks corresponding with N-nitroso groups in addition to nitrosophenols, ketoximes, and secondary Beckmann reaction products. Formation of N-nitroso groups was more significant in the whole peat compared with the peat humic acid. Carbon-13 NMR analyses also indicated the occurrence of nitrosative demethoxylation in peat and soil humic acids. Reaction of 15 N-NH 3 fixated fulvic acid with unlabeled NO − 2 resulted in nitrosative deamination of aminohydroquinone N, suggesting a previously unrecognized pathway for production of N 2 gas in soils fertilized with NH 3

Soil Science Society of America Journal

Comprehensive water quality of the Boulder Creek Watershed, Colorado, during high-flow and low-flow conditions, 2000

Executive Summary The Boulder Creek Watershed, Colorado, is 1160 square kilometers in area and ranges in elevation from 1480 to 4120 meters above sea level. Streamflow originates primarily as snowmelt near the Continental Divide, and thus discharge varies seasonally and annually (Chapter 1). Most of the water in Boulder Creek is diverted for domestic, agricultural, and industrial use. Some diverted water is returned to the creek as wastewater effluent and by ditch returns, and additional water enters as groundwater and by transbasin diversions. These diversions and returns lead to complex temporal and spatial variations in discharge. The variations in discharge, along with natural factors such as geology and climate, and anthropogenic factors such as wastewater treatment, agriculture, mining, and urbanization, can affect water chemistry. As with many watersheds in the American West, dependable water quality and sufficient water supply are issues facing local water managers and users. Detailed water-quality and sediment sampling allows the identification of sources and sinks of chemical constituents and an understanding of the processes at work in a river system. This study, the most comprehensive water-quality analysis performed for Boulder Creek to date, was a cooperative effort of the U.S. Geological Survey (USGS) and the city of Boulder. Geographic information systems and modeling programs were used to delineate watershed boundaries, land cover, and geology (Chapter 2). During high-flow (June 2000) and low-flow (October 2000) conditions, researchers evaluated 226 water-quality variables, including basic water-quality indicators (Chapter 3), major ions and trace elements (Chapter 4), wastewater-derived organic compounds (Chapter 5), and pesticides (Chapter 6). Discharge (Chapter 1) and bed-sediment particle size and mineralogy (Chapter 7) were also evaluated. This cooperative study was facilitated by the Boulder Area Sustainability Information Network (BASIN), which provides public access to environmental information about the Boulder Creek Watershed on a website, www.basin.org. In addition to the USGS and city of Boulder data, researchers at the Institute of Arctic and Alpine Research at the University of Colorado provided water chemistry data for the headwaters of North Boulder Creek, upstream of the reach of the USGS/city of Boulder sampling sites (Chapter 8). Snowmelt produces high flows in Boulder Creek in late spring to early summer (Chapter 1). Because precipitation falling in the headwaters is very dilute (specific conductance about 5 microsiemens per centimeter), most chemical constituents are present in lower concentrations during high flows (Chapters 3, 4, 5, 6, and 8). However, concentrations of some constituents, such as total suspended solids (Chapter 3) and organic carbon (Chapter 5), increase during the spring snowmelt flush. The upper basin, which consists of alpine, subalpine, montane, and foothills regions west of the mouth of Boulder Canyon, is underlain by Precambrian igneous and metamorphic rocks (Chapter 1). Major dissolved inorganic constituents in headwater sites were found to be enriched by factors of 10 to 20 relative to precipitation; this is consistent with minor weathering of the local crystalline bedrock (Chapter 4). Some anthropogenic input is observed in the headwaters; precipitation introduces nitrogen derived from fossil fuel combustion and agricultural activities (Chapter 8). The lower basin, which consists of the plains region east of the mouth of Boulder Canyon, is underlain by Mesozoic sedimentary rock and Quaternary alluvium, and has substantially more anthropogenic sources. Concentrations of most dissolved inorganic constituents increased in the lower basin. Differentiation between natural and anthropogenic sources of some dissolved constituents is difficult because both sources contribute to the water composition in this region. The increase of most major constituents (bicarbonate, calcium, chloride, magnesium, sodium, and sulfate) is consistent with weathering of the underlying sedimentary bedrock (Chapter 4). It is likely that anthropogenic loading of constituents in this reach occurs during storm events. Fecal coliform concentrations were variable and in some cases exceeded state standards, primarily during low-flow conditions (Chapter 3). Effluent from Boulder’s 75th Street Wastewater Treatment Plant (WWTP) has a substantial impact on the water chemistry of lower Boulder Creek. The WWTP increases the concentrations of nutrients such as nitrogen and phosphorus (Chapter 3), major ions and trace metals (Chapter 4), and organic carbon (Chapter 5) in Boulder Creek. The effluent contained a spike in gadolinium, a rare earth element that is ingested for magnetic resonance imaging as a contrasting agent and then excreted to the urban wastewater system. The effluent also contained trace organic compounds such as surfactants, pharmaceuticals, hormones (Chapter 5), and pesticides (Chapter 6), which also were detected at downstream Boulder Creek sites. Water chemistry of Boulder Creek downstream of the WWTP is largely controlled by the degree of dilution of the wastewater effluent, which varies depending on the baseflow of Boulder Creek, the volume of wastewater effluent, and depletion by agricultural diversions. Coal Creek, a tributary of Boulder Creek, contains wastewater effluent from four additional WWTPs, and increases the load of many constituents in Boulder Creek. In addition to the impact from wastewater effluent, lower Boulder Creek is affected by agricultural land use. Eleven of 84 analyzed pesticides were detected in Boulder Creek or its inflows, primarily in the eastern section of the watershed (Chapter 6). This collaborative study provides an in-depth evaluation of the hydrology, water chemistry, and sediment mineralogy of North Boulder Creek, Middle Boulder Creek, Boulder Creek, and major inflows. The detailed sampling and analysis in this report provide a baseline for future reference, as well as information on the effect of land use and geology on water chemistry.

Colorado

Analysis of antimycin A by reversed-phase liquid chromatography/nuclear magnetic-resonance spectrometry

A mixture of closely related streptomyces fermentation products, antimycin A, Is separated, and the components are identified by using reversed-phase high-performance liquid chromatography with directly linked 400-MHz proton nuclear magnetic resonance detection. Analyses of mixtures of three amino acids, alanine, glycine, and valine, are used to determine optimal measurement conditions. Sensitivity increases of as much as a factor of 3 are achieved, at the expense of some loss in chromatographic resolution, by use of an 80-μL NMR cell, Instead of a smaller 14-μL cell. Analysis of the antimycin A mixture, using the optimal analytical high performance liquid chromatography/nuclear magnetic resonance conditions, reveals it to consist of at least 10 closely related components.

Analytical Chemistry

Determination of alkylbenzenesulfonate surfactants in groundwater using macroreticular resins and carbon-13 nuclear magnetic resonance spectrometry

Alkylbenzenesulfonate surfactants were determined in groundwater at concentrations as low as 0.3 mg/L. The method uses XAD-8 resin for concentration, followed by elution with methanol, separation of anionic and nonionic surfactants by anion exchange, quantitation by titration, and identification by 13C nuclear magnetic resonance spectrometry. Laboratory standards and field samples containing straight-chain and branched-chain alkylbenzenesulfonates, sodium dodecyl sulfate, and alkylbenzene ethoxylates were studied. The XAD-8 extraction of surfactants from groundwater was completed in the field, which simplified sample preservation and reduced the cost of transporting samples.

Analytical Chemistry

Groundwater chemistry, hydrogeologic properties, bioremediation potential, and three-dimensional numerical simulation of the sand and gravel aquifer at Naval Air Station Whiting Field, near Milton, Florida, 2015–20

The U.S. Geological Survey completed a study between 2015 and 2020 of groundwater contamination in the sand and gravel aquifer at a Superfund site in northwestern Florida. Groundwater-quality samples were collected from representative monitoring wells located along a groundwater-flow pathway and analyzed in the field and laboratory. In general, ambient groundwater in the sand and gravel aquifer is acidic, dilute, and oxic. Groundwater age-dating results indicate recharge to the contaminated parts of the aquifer occurred between the 1970s and 1980s. Natural gamma, electromagnetic induction, and borehole nuclear magnetic resonance logs indicated that aquifer hydraulic conductivities generally increased with depth as the aquifer formation material became coarser, characteristic of a prograding marginal-marine delta depositional environment. Aquifer formation material incubated with radiocarbon (carbon-14) cis -1,2-Dichloroethylene demonstrated biodegradation directly to carbon dioxide in contaminated and uncontaminated parts of the aquifer. A three-dimensional, numerical groundwater-flow MODFLOW model of the sand and gravel aquifer in the study area was constructed. The calibrated model reasonably reproduced measured groundwater heads and streamflows. Moreover, the model can be used to run simulations of outcomes of potential remedial strategies, such as monitored natural attenuation, as part of future feasibility studies in the area.

Florida

13C NMR spectral characterization of epimeric rotenone and some related tetrahydrobenzopyranofurobenzopyranones

The 13 C nuclear magnetic resonance (nmr) spectra of epimers of rotenone and four 12a-hydroxy-analogues were examined to determine the stereochemical effect of the B/C ring fusion involving the 6a- and 12a-carbon centers. Chemical shift differences between the epimeric carbon resonances of cis- and trans-6a,12a-compounds were notably larger than those of diastereoisomers derived from the same B/C ring junction stereochemistry. Results of the spectral analysis have been useful for the quantification of mixtures of epimers and for the measurement of rates of epimerization and oxygenation.

Journal of Heterocyclic Chemistry

Iron- and 4-hydroxy-2-alkylquinoline-containing periplasmic inclusion bodies of Pseudomonas aeruginosa: A chemical analysis

Dark aggregated particles were seen on pellets of iron-rich, mid-logarithmic phase Pseudomonas aeruginosa. Transmission electron microscopy of these cells showed inclusion bodies in periplasmic vacuoles. Aggregated particles isolated from the spent medium of these cells contained iron as indicated by atomic absorption spectroscopy and by electron paramagnetic resonance spectroscopy that revealed Fe3+. Scanning electron microscopy/energy dispersive X-ray analysis of whole cells revealed the presence of iron-containing particles beneath the surface of the cell, indicating that the isolated aggregates were the intracellular inclusion bodies. Collectively, mass spectroscopy and nuclear magnetic resonance spectroscopy of the isolated inclusion bodies revealed the presence of 3,4-dihydroxy-2-heptylquinoline which is the Pseudomonas quinolone signaling compound (PQS) and an iron chelator; 4-hydroxy-2-heptylquinoline (pseudan VII), which is an iron chelator, antibacterial compound and precursor of PQS; 4-hydroxy-2-nonylquinoline (pseudan IX) which is an iron chelator and antibacterial compound; 4-hydroxy-2-methylquinoline (pseudan I), and 4-hydroxy-2-nonylquinoline N-oxide. ?? 2006 Elsevier Inc. All rights reserved.

Bioorganic Chemistry

Structural analysis of geochemical samples by solid-state nuclear magnetic resonance spectrometry. Role of paramagnetic material

An examination of coals, coal tars, a fulvic acid, and soil fractions by solid-state 13C NMR spectrometry has demonstrated widely differing behavior regarding quantitative representation in the spectrum. Spin counting experiments on coal tars and the fulvic acid show that almost all the sample carbon is observed in both solution and solid-state NMR spectra. Similar experiments on two coals (a lignite and a bituminous coal) show that most (70-97%) of the carbon is observed; however, when the lignite is ion exchanged with 3% (w/w) Fe3+, the fraction of carbon observed drops to below 10%. In additional experiments signal intensity from soil samples is enhanced by a simple dithionite treatment. This is illustrated by 13C, 27Al, and 29Si solid-state NMR experiments on soil fractions.

Analytical Chemistry

Effects of humic substances on the bioconcentration of polycyclic aromatic hydrocarbons: Correlations with spectroscopic and chemical properties of humic substances

The presence of dissolved humic substances (HS, fulvic and humic acids) generally reduces the up take of hydrophobic organic compounds into aquatic organisms. The extent of this effect depends both on the concentration and on the origin of the HS. The aim of this study was to investigate the role of qualitative differences between HS from different origins. The effects of seven different HS on the bioconcentration of pyrene and benzo[ a ]pyrene (B a P) in the nematode Caenorhabditis elegans were related to the spectroscopic and chemical properties of the HS. The effect of each humic material on the bioconcentration of pyrene or B a P was quantified as a “biologically determined” partition coefficient K DOC . We observed significant linear relationships between K DOC and the atomic H/C ratio, the specific absorptivity at 254 nm, the content of aromatic carbons (as determined by 13 C nuclear magnetic resonance spectroscopy, the copper-complexing capacity, the content of phenolic OH groups, and the molecular weight of the HS. There was no discernible relationship of K DOC with the atomic (N + O)/C ratio, an indicator of the polarity of HS. Taken together, our results show that the variability in the effects of HS from different origins could be related to variations in bulk properties of the HS. Parameters describing the aromaticity of the humic materials seemed to be most useful for estimating effects of HS on the bioconcentration of pyrene and B a P.

Environmental Toxicology and Chemistry

A new comprehensive approach to characterizing carbonaceous aerosol with an application to wintertime Fresno, California PM2.5

Fine particulate matter (PM2.5) samples were collected during a three week winter period in Fresno (CA). A composite sample was characterized by isolating several distinct fractions and characterizing them by infrared and nuclear magnetic resonance (NMR) spectroscopy. More than 80% of the organic matter in the aerosol samples was recovered and characterized. Only 35% of the organic matter was water soluble with another third soluble in dichloromethane and the remainder insoluble. Within the isolated water soluble material, hydrophobic acid and hydrophilic acids plus neutrals fractions contained the largest amounts of carbon. The hydrophobic acids fraction appears to contain significant amounts of lignin type structures, spectra of the hydrophilic acids plus neutrals fraction are indicative of carbohydrates and secondary organic material. The dichloromethane soluble fraction contains a variety of organic compound families typical of many previous studies of organic aerosol speciation, including alkanes, alkanols, alkanals and alkanoic acids. Finally the water and solvent insoluble fraction exhibits a strong aromaticity as one would expect from black or elemental carbon like material; however, these spectra also show a substantial amount of aliphaticity consistent with linear side chains on the aromatic structures.

Atmospheric Chemistry and Physics Discussions

Linking field-based metabolomics and chemical analyses to prioritize contaminants of emerging concern in the Great Lakes basin

The ability to focus on the most biologically relevant contaminants affecting aquatic ecosystems can be challenging because toxicity-assessment programs have not kept pace with the growing number of contaminants requiring testing. Because it has proven effective at assessing the biological impacts of potentially toxic contaminants, profiling of endogenous metabolites (metabolomics) may help screen out contaminants with a lower likelihood of eliciting biological impacts, thereby prioritizing the most biologically important contaminants. The authors present results from a study that utilized cage-deployed fathead minnows ( Pimephales promelas ) at 18 sites across the Great Lakes basin. They measured water temperature and contaminant concentrations in water samples (132 contaminants targeted, 86 detected) and used 1 H-nuclear magnetic resonance spectroscopy to measure endogenous metabolites in polar extracts of livers. They used partial least-squares regression to compare relative abundances of endogenous metabolites with contaminant concentrations and temperature. The results indicated that profiles of endogenous polar metabolites covaried with at most 49 contaminants. The authors identified up to 52% of detected contaminants as not significantly covarying with changes in endogenous metabolites, suggesting they likely were not eliciting measurable impacts at these sites. This represents a first step in screening for the biological relevance of detected contaminants by shortening lists of contaminants potentially affecting these sites. Such information may allow risk assessors to prioritize contaminants and focus toxicity testing on the most biologically relevant contaminants. Environ Toxicol Chem 2016;35:2493–2502.

Environmental Toxicology and Chemistry