SEARCH · Search USGS

Results for “Atomic Spectroscopy”

Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 91 records · Page 5Linked to original sources

USGS1997

Nuclear magnetic resonance identification of new sulfonic acid metabolites of chloroacetanilide herbicides

The detection of the sulfonic acid metabolites of the chloroacetanilide herbicides acetochlor, alachlor, butachlor, propachlor, and, more recently, metolachlor in surface and ground water suggests that a common mechanism for dechlorination exists via the glutathione conjugation pathway. The identification of these herbicides and their metabolites is important due to growing public awareness and concern about pesticide levels in drinking water. Although these herbicides are regulated, little is known about the fate of their metabolites in soil. The sulfonic acid metabolites were synthesized by reaction of the parent compounds with an excess of sodium sulfite. Acetochlor, alachlor, butachlor, metolachlor, and propachlor and their sulfonic acid metabolites were studied by nuclear magnetic resonance spectroscopy and fast atom bombardment mass spectrometry. This paper provides a direct method for the preparation and characterization of these compounds that will be useful in the analysis and study of chloracetanilide herbicides and their metabolites.

Journal of Agricultural and Food Chemistry↗

USGS2002

Multielement extraction system for the determination of 18 trace elements in geochemical samples

A M ethyl isobutyl ketone- A mine syner G istic I odide C omplex (MAGIC) extraction system has been developed for use in geochemical exploration which separates a maximum number of trace elements from interfering matrices. Extraction curves for 18 of these trace elements are presented: Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Ga, In, Tl, Sa, Pb, As, Sb, Bi, Se, and Te. The acid normality of the aqueous phase controls the extraction into the organic phase, and each of these 18 elements has a broad range of HCl normality over which H is quantitatively extracted, making H possible to determine all 18 trace elements from a single sample digestion or leach solution. The extract can be analyzed directly by flame atomic absorption or inductively coupled plasma emission spectroscopy. Most of these 18 elements can be determined by Nameless atomic absorption after special treatment of the organic extract.

Analytical Chemistry↗

USGS2020

Nanoscale molecular composition of solid bitumen from the Eagle Ford Group across a natural thermal maturity gradient

Microscopic solid bitumen is a petrographically defined secondary organic matter residue produced during petroleum generation and subsequent oil transformation. The presence of solid bitumen impacts many reservoir properties including porosity, permeability, and hydrocarbon generation and storage, among others. Furthermore, solid bitumen reflectance is an important parameter for assessing the thermal maturity of formations with little to no vitrinite. While the molecular composition of solid bitumen will strongly impact associated parameters such as the development of organic matter porosity, hydrocarbon generation, and optical reflectance, assessing the molecular composition of solid bitumen in situ within shale reservoirs can be challenging due to the small grain sizes (often ≤1 μm in diameter) and the inherent heterogeneity of shale formations. Here we employ the recently developed atomic force microscopy based infrared spectroscopy (AFM-IR) technique to investigate solid bitumen molecular composition in situ within shale samples from the Late Cretaceous Eagle Ford Group. These samples possess sulfur-rich type II kerogens that span a natural thermal maturity gradient from early oil generation to the dry gas window. The application of AFM-IR allows for the rapid collection of thousands of compositional measurements from solid bitumen with ∼50 nm resolution. Our results indicate that (i) solid bitumen from the lower Eagle Ford displays both intra- and intergranular variation in the relative abundance of CH 2 , C═C, and C═O moieties present; (ii) this molecular variation tends to, but does not always, decrease with an increase in thermal maturity; and (iii) the solid bitumen composition between samples, from an atomic ratio perspective, is more similar than analysis of bulk kerogen isolates would indicate. These findings are discussed with perspective toward understanding the impact of thermal stress on the composition of secondary organic matter within the Eagle Ford Shale and highlight the growing awareness that organic matter heterogeneity within petroliferous mudrocks extends down to the nanoscale regime.

Energy and Fuels↗

USGS2019

Nanoscale molecular fractionation of organic matter within unconventional petroleum source beds

Fractionation of petroleum during migration through sedimentary rock matrices has been observed across lengths of meters to kilometers. Selective adsorption of specific chemical moieties at mineral surfaces and/or the phase behavior of petroleum during pressure changes typically are invoked to explain this behavior. Such phenomena are of interest as they impact both the quality and recoverability of petroleum resources. Given the current emphasis on unconventional (continuous) resources, there is a need to understand petroleum fractionation occurring during expulsion and migration at the nanometer to micron scale, due to the fine-grained nature of petroliferous mudrocks. Here, organic matter compositional differences observed within kukersites (petroleum source beds containing acritarch Gloeocapsomorpha prisca) and the overlying carbonate reservoir layer from the Ordovician Stonewall Formation are explored using a suite of spectroscopic methods, primarily through atomic force microscopy based infrared spectroscopy (AFM-IR). AFM-IR is capable of providing spatial resolutions approaching 50 nm and allows for assessment of the molecular fingerprint of kukersite organic matter across transition zones from organic-rich ‘source’ layers into neighboring carbonate ‘reservoir’ layers ~150 μm away. Results indicate that organic matter composition begins to vary immediately following expulsion from source layers, with loss of carbonyl groups and a concomitant decrease in alkyl chain-length, as migration distance increases. These chemical transitions correlate with a decrease in fluorescence intensity, increase in solid bitumen reflectance, and increase in Raman aromaticity proxies (D-G band separation) in the organic matter. Our findings are consistent with the retention of polar compounds onto mineral grains during expulsion and migration, following primary cracking and bituminization of the Gloeocapsomorpha prisca kerogen.

Energy and Fuels↗

USGS1982

Methods for collection and analysis of geopressured geothermal and oil field waters

Present methods are described for the collection, preservation, and chemical analysis of waters produced from geopressured geothermal and petroleum wells. Detailed procedures for collection include precautions and equipment necessary to ensure that the sample is representative of the water produced. Procedures for sample preservation include filtration, acidification, dilution for silica, methyl isobutyl ketone (MIBK) extraction of aluminum, addition of potassium permanganate to preserve mercury, and precipitation of carbonate species as strontium carbonate for stable carbon isotopes and total dissolved carbonate analysis. Characteristics determined at the well site are sulfide, pH, ammonia, and conductivity. Laboratory procedures are given for the analysis of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, iron, manganese, zinc, lead, aluminum, .and mercury by atomic absorption and flame emission spectroscopy. Chloride is determined by silver nitrate titration and fluoride by ion-specific electrode. Bromide and iodide concentrations are determined by the hypochlorite oxidation method. Sulfate is analyzed by titration using barium chloride with thorin indicator after pretreatment with alumina. Boron and silica are determined colorimetrically by the carmine and molybdate-blue methods, respectively. Aliphatic acid anions (C2 through C5) are determined by gas chromatography after separation and concentration in a chloroform-butanol mixture.

Water Supply Paper↗

USGS2017

Nanoscale geochemical and geomechanical characterization of dispersed organic matter in shale by infrared nanoscopy

Solid organic matter (OM) plays an essential role in the generation, migration, storage, and production of hydrocarbons from economically important shale rock formations. Electron microscopy images have documented spatial heterogeneity in the porosity of OM at nanoscale, and bulk spectroscopy measurements have documented large variation in the chemical composition of OM during petroleum generation. However, information regarding the heterogeneity of OM chemical composition at the nanoscale has been lacking. Here we demonstrate the first application of atomic force microscopy-based infrared spectroscopy (AFM-IR) to measure the chemical and mechanical heterogeneity of OM in shale at the nanoscale, orders of magnitude finer than achievable by traditional chemical imaging tools such as infrared microscopy. We present a combination of optical microscopy and AFM-IR imaging to characterize OM heterogeneity in an artificially matured series of New Albany Shales. The results document the evolution of individual organic macerals with maturation, providing a microscopic picture of the heterogeneous process of petroleum generation.

Nature Communications↗

USGS2000

Formation evaluation of gas hydrate-bearing marine sediments on the Blake Ridge with downhole geochemical log measurements

The analyses of downhole log data from Ocean Drilling Program (ODP) boreholes on the Blake Ridge at Sites 994, 995, and 997 indicate that the Schlumberger geochemical logging tool (GLT) may yield useful gas hydrate reservoir data. In neutron spectroscopy downhole logging, each element has a characteristic gamma ray that is emitted from a given neutron-element interaction. Specific elements can be identified by their characteristic gamma-ray signature, with the intensity of emission related to the atomic elemental concentration. By combining elemental yields from neutron spectroscopy logs, reservoir parameters including porosities, lithologies, formation fluid salinities, and hydrocarbon saturations (including gas hydrate) can be calculated. Carbon and oxygen elemental data from the GLT was used to determine gas hydrate saturations at all three sites (Sites 994, 995, and 997) drilled on the Blake Ridge during Leg 164. Detailed analyses of the carbon and oxygen content of various sediments and formation fluids were used to construct specialized carbon/oxygen ratio (COR) fan charts for a series of hypothetical gas hydrate accumulations. For more complex geologic systems, a modified version of the standard three-component COR hydrocarbon saturation equation was developed and used to calculate gas hydrate saturations on the Blake Ridge. The COR-calculated gas hydrate saturations (ranging from about 2% to 14% bulk volume gas hydrate) from the Blake Ridge compare favorably to the gas hydrate saturations derived from electrical resistivity log measurements.

Conference Paper↗

USGS1999

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↗

USGS2021

The Confocal Laser Scanning Microscopy Working Group of the ICCP: Final report 2021

This report summarizes the activities and results of the Confocal Laser Scanning Microscopy (CLSM) working group (WG) of the International Committee for Coal and Organic Petrology (ICCP), from its inception in September, 2015, to the present day (September, 2021). The purpose of this report is to document the history of the working group and to compile and evaluate its results. The CLSM WG examined an immature, organic-rich sample of Kimmeridge Clay, which was characterized via CLSM imaging and spectroscopy. In addition, mechanically polished and broad ion beam (BIB) milled sample preparations were characterized via atomic force microscopy. Highlights of findings from the CLSM WG include: the interpreted presence of Botryococcus; incomplete blocking of laser light from highly reflective materials; surface roughening and surface flattening induced by differential BIB milling dependent on location and scale of measurement; substitution of uranium for iron in sulfides; red-shift of reflectance and auto-fluorescence from below the sample surface; positive alteration from laser-induced photo-oxidation of the sample surface including fluorescence blue-shift; blueshift associated to higher fluorescence intensity regions in amorphous organic matter; need for fluorescence spectroscopy standardization as applied via CLSM; and the suitability of CLSM to predict solid bitumen reflectance via calibration to an extant data set. Due to the inability of WG members to continue participating in a WG format, the CLSM WG is hereby finalized. This report represents the final product of WG activity, with the aim to summarize the information included herein for a future peer-reviewed manuscript.

Final Report↗

USGS2020

Investigating the effects of broad ion beam milling to sedimentary organic matter: Surface flattening or heat-induced aromatization and condensation?

Previous work has proposed transfer of kinetic heat energy from low-energy broad ion beam (BIB) milling causes thermal alteration of sedimentary organic matter, resulting in increases of organic matter reflectance. Whereas, other studies have suggested the organic matter reflectance increase from BIB milling is due to decreased surface roughness. To test if reflectance increases to sedimentary organic matter (vitrinite) caused by BIB milling were related to molecular aromatization and condensation, Raman and Fourier transform infrared (FTIR) spectroscopies were used to evaluate potential compositional changes in the same vitrinite locations pre- and post-BIB milling. The same locations also were examined by atomic force microscopy (AFM) to determine topographic changes caused by BIB milling (as quantified by the areal root-mean-square roughness parameter S q ). Samples consisted of four medium volatile bituminous coals. A non-aggressive BIB milling approach was used with conditions of 5 min, 4 keV, 15°incline, 360° rotation at 25 rpm and 100% focus (1.5 kV discharge; ∼100 μA). This gentle BIB milling caused vitrinite reflectance (VR o ) increases of 12 to 36% of the original values determined optically before milling (average 26% increase). When molecular proxies from FTIR (A- and C-factor, branching ratio) were plotted against each other for the same vitrinite locations pre- and post-milling, mean data points for each sample generally lie within error of a 1:1 line. Likewise, mean Raman thermal proxy [full-width half maximum of G-band (G-FWHM), Raman band separation (RBS) and D1/G band intensity ratio] values were similar for pre- and post-milled locations, also plotting within error of a 1:1 line. AFM confirms the majority (24 of 36) of pre- and post-ion milled surface pairs were smoother (lower S q values) after BIB milling. These results are interpreted to indicate VR o increase induced by the gentle BIB milling conditions used in this study is an effect of decreased diffuse reflectance due to flatter surfaces, causing more photons to reflect directly back to the detector. Little evidence was observed for molecular aromatization and condensation of vitrinite molecules following BIB milling (with the conditions used). The presence of milling-induced artifacts, including differential milling effects dependent on location and the development of self-organized patterned structures, indicate much work remains in standardization of BIB milling before its promulgation as a routine sample preparation technique for organic petrography. These results provide better understanding of anthropogenic-induced changes to geological samples caused by the now widespread adoption of BIB milling as a disruptive innovation in sample preparation.

Fuel↗

USGS1986

Organic geochemical analysis of sedimentary organic matter associated with uranium

Samples of sedimentary organic matter from several geologic environments and ages which are enriched in uranium (56 ppm to 12%) have been characterized. The three analytical techniqyes used to study the samples were Rock-Eval pyrolysis, pyrolysis-gas chromatography-mass spectrometry, and solid-state C-13 nuclear magnetic resonance (NMR) spectroscopy. In samples with low uranium content, the pyrolysis-gas chromatography products contain oxygenated functional groups (as hydroxyl) and molecules with both aliphatic and aromatic carbon atoms. These samples with low uranium content give measurable Rock-Eval hydrocarbon and organic-CO 2 yields, and C-13 NMR values of > 30% aliphatic carbon. In contrast, uranium-rich samples have few hydrocarbon pyrolysis products, increased Rock-Eval organic-CO 2 contents and > 70% aromatic carbon contents from C-13 NMR. The increase in aromaticity and decrease in hydrocarbon pyrolysis yield are related to the amount of uranium and the age of the uranium minerals, which correspond to the degree of radiation damage. The three analytical techniques give complementary results. Increase in Rock-Eval organic-CO 2 yield correlates with uranium content for samples from the Grants uranium region. Calculations show that the amount of organic-CO 2 corresponds to the quantity of uranium chemically reduced by the organic matter for the Grants uranium region samples.

Applied Geochemistry↗

USGS2025

USGS addresses needs for lithium calibration and quality control materials for pLIBS analysis

Lithium (Li) is a globally important commodity used for energy storage, national defense, human health, and advanced technologies. Lithium resource development requires identifying deposits with elevated concentrations and optimal mineralogy, typically associated with select clays and pegmatites. Lithium is a light, highly reactive alkali metal with low atomic mass that is difficult to detect and quantify using conventional portable geochemical techniques such as X-ray fluorescence (XRF). However, portable laser-induced breakdown spectroscopy (pLIBS) is a powerful analytical technique for lithium exploration due to its ability to analyze solids quickly with minimal preparation. The expanded utility of pLIBS is hampered by the lack of matrix-matched calibration and quality control (QC) materials. The United States Geological Survey (USGS) has developed in-house lithium calibration and QC materials for lithium in clay and pegmatite matrices to address this limitation. We present the workflow and implementation of a custom-built matrix specific calibration on a SciAps Z-300 pLIBS, using proprietary Profile Builder software. The implementation of the custom calibration and quality control standards enables us to collect semiquantitative results directly from the pLIBS while in the field. Ultimately, this calibration has improved confidence in sample selection and collection in the field, providing more efficient site characterization.

Conference Paper↗

USGS2013

Gallium--A smart metal

Gallium is a soft, silvery metallic element with an atomic number of 31 and the chemical symbol Ga. The French chemist Paul-Emile Lecoq de Boisbaudran discovered gallium in sphalerite (a zinc-sulfide mineral) in 1875 using spectroscopy. He named the element "gallia" after his native land of France (formerly Gaul; in Latin, Gallia). The existence of gallium had been predicted in 1871 by Dmitri Mendeleev, the Russian chemist who published the first periodic table of the elements. Mendeleev noted a gap in his table and named the missing element "eka-aluminum" because he determined that its location was one place away from aluminum in the table. Mendeleev thought that the missing element (gallium) would be very much like aluminum in its chemical properties, and he was right. Solid gallium has a low melting temperature (~29 degrees Celsius, or °C) and an unusually high boiling point (~2,204 °C). Because of these properties, the earliest uses of gallium were in high-temperature thermometers and in designing metal alloys that melt easily. The development of a gallium-based direct band-gap semiconductor in the 1960s led to what is now one of the most well-known applications for gallium-based products--the manufacture of smartphones and data-centric networks.

Fact Sheet↗

USGS2013

Hydration free energies of cyanide and hydroxide ions from molecular dynamics simulations with accurate force fields

The evaluation of hydration free energies is a sensitive test to assess force fields used in atomistic simulations. We showed recently that the vibrational relaxation times, 1D- and 2D-infrared spectroscopies for CN(-) in water can be quantitatively described from molecular dynamics (MD) simulations with multipolar force fields and slightly enlarged van der Waals radii for the C- and N-atoms. To validate such an approach, the present work investigates the solvation free energy of cyanide in water using MD simulations with accurate multipolar electrostatics. It is found that larger van der Waals radii are indeed necessary to obtain results close to the experimental values when a multipolar force field is used. For CN(-), the van der Waals ranges refined in our previous work yield hydration free energy between -72.0 and -77.2 kcal mol(-1), which is in excellent agreement with the experimental data. In addition to the cyanide ion, we also study the hydroxide ion to show that the method used here is readily applicable to similar systems. Hydration free energies are found to sensitively depend on the intermolecular interactions, while bonded interactions are less important, as expected. We also investigate in the present work the possibility of applying the multipolar force field in scoring trajectories generated using computationally inexpensive methods, which should be useful in broader parametrization studies with reduced computational resources, as scoring is much faster than the generation of the trajectories.

Physical Chemistry Chemical Physics↗

USGS2014

Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe 2 O 3 /FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 ·5H 2 O, kornelite, coquimbite, Fe(SO 4 )(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm −1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe 3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe 2+ /[Fe 2+ + Fe 3+ ] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

California↗

USGS2021

Chemical analysis of archived stream-sediment samples, Alaska

Geochemical data are presented for more than 1,500 archived stream-sediment samples and accompanying quality control samples. The archived sediments were reanalyzed to improve the stream geochemical dataset for Alaska and to support ongoing U.S. Geological Survey (USGS) studies. Sediment samples were primarily from the USGS Mineral Resources Program’s sample archive in Denver, Colorado, but a few were from the Alaska Geological & Geophysical Surveys’ Geologic Materials Center in Anchorage, Alaska. All samples were submitted to the USGS contract laboratory, AGAT Laboratories, for analysis. All samples were analyzed using a 60-element analytical method involving fusion of the sample by sodium peroxide, dissolution of the fusion cake by nitric acid, and elemental analysis by inductively coupled plasma-optical emission spectroscopy and inductively coupled plasma-mass spectroscopy. Additionally, 106 samples from the Nixon Fork area were analyzed by a second multi-element method involving decomposition by a mixture of hydrochloric, nitric, perchloric, and hydrofluoric acids and the elemental analysis of the resulting solution by inductively coupled plasma-optical emission spectroscopy and inductively coupled plasma-mass spectroscopy. The latter method was used because the detection limit is lower for several elements including As, Cd, Pb, and Sb. Mercury concentrations in 296 samples from southeast Alaska were determined using a cold-vapor atomic absorption spectrometry method. The concentration data from the archived samples are presented along with concentration data from the standard reference material that was submitted with the samples.

Alaska↗

USGS2011

Metallothionein-like multinuclear clusters of mercury(II) and sulfur in peat

Strong mercury(II)–sulfur (Hg-SR) bonds in natural organic matter, which influence mercury bioavailability, are difficult to characterize. We report evidence for two new Hg-SR structures using X-ray absorption spectroscopy in peats from the Florida Everglades with added Hg. The first, observed at a mole ratio of organic reduced S to Hg (S red /Hg) between 220 and 1140, is a Hg 4 S x type of cluster with each Hg atom bonded to two S atoms at 2.34 Å and one S at 2.53 Å, and all Hg atoms 4.12 Å apart. This model structure matches those of metal–thiolate clusters in metallothioneins, but not those of HgS minerals. The second, with one S atom at 2.34 Å and about six C atoms at 2.97 to 3.28 Å, occurred at S red /Hg between 0.80 and 4.3 and suggests Hg binding to a thiolated aromatic unit. The multinuclear Hg cluster indicates a strong binding environment to cysteinyl sulfur that might impede methylation. Along with a linear Hg(SR) 2 unit with Hg—S bond lengths of 2.34 Å at S red /Hg of about 10 to 20, the new structures support a continuum in Hg-SR binding strength in natural organic matter.

Environmental Science & Technology↗

USGS2016

Novel insights from NMR spectroscopy into seasonal changes in the composition of dissolved organic matter exported to the Bering Sea by the Yukon River

Seasonal (spring freshet, summer–autumn, and winter) variability in the chemical composition of dissolved organic matter (DOM) from the Yukon River was determined using advanced one- and two-dimensional (2D) solid-state NMR spectroscopy, coupled with isotopic measurements and UV–visible spectroscopy. Analyses were performed on two major DOM fractions, the hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions obtained using XAD resins. Together these two fractions comprised 64–74% of the total DOM. Carboxyl-rich alicyclic molecules (CRAM) accounted for the majority of carbon atoms in the HPOA (63–77%) and TPIA (54–78%) samples, and more so in winter and summer than in spring samples. 2D and selective NMR data revealed association of abundant nonprotonated O-alkyl and quaternary alkyl C (OC np , OC np O and C q , 13–17% of HPOA and 15–20% of TPIA) and isolated O–CH structures with CRAM, which were not recognized in previous studies. Spectral editing and 2D NMR allowed for the discrimination of carbohydrate-like O-alkyl C from non-carbohydrate O-alkyl C. Whereas two spring freshet TPIA samples contained carbohydrate clusters such as carboxylated carbohydrates (16% and 26%), TPIA samples from other seasons or HPOA samples mostly had small amounts (<8%) of sugar rings dispersed in a nonpolar alkyl environment. Though nonprotonated aromatic C represented the largest fraction of aromatic C in all HPOA/TPIA isolates, only a small fraction (&sim;5% in HPOA and 3% in TPIA) was possibly associated with dissolved black carbon. Our results imply a relatively stable portion of DOM exported by the Yukon River across different seasons, due to the predominance of CRAM and their associated nonprotonated C–O and O–C–O structures, and elevated reactivity (bio- and photo-lability) of spring DOM due to the presence of terrestrial inputs enriched in carbohydrates and aromatic structures.

Alaska, Yukon↗