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At least 397 records · Page 22Linked to original sources
USGS2012

Structural stability of coprecipitated natural organic matter and ferric iron under reducing conditions

The objective was to assess the interaction of Fe coprecipitated with dissolved organic matter (DOM) and its effect on Fe (hydr)oxide crystallinity and DOM retention under abiotic reducing conditions. A Fe-based coagulant was reacted with DOM from an agricultural drain and the resulting precipitate (floc) was exposed to S(-II) and Fe(II). Solution concentrations of Fe(II/III) and DOM were monitored, floc crystallinity was determined using X-ray diffraction, and the composition and distribution of functional groups were assessed using scanning transmission X-ray microscopy (STXM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Results indicate coprecipitation of Fe(III) with DOM forms a non-crystalline floc that withstands crystallization regardless of change in pH, Fe:DOM ratio and type of reductant added. There was no evidence that exposure to reducing conditions led to release of DOM from the floc, indicating that coprecipitation with complex natural DOM in aquatic environments may stabilize Fe (hydr)oxides against crystallization upon reaction with reduced species and lead to long term sequestration of the DOM. STXM analysis identified spatially distinct regions with remarkable functional group purity, contrary to the model of DOM as a relatively uniform complex polymer lacking identifiable organic compounds. Polysaccharide-like OM was strongly and directly correlated with the presence of Fe but showed different Fe binding strength depending on the presence of carboxylic acid functional groups, whereas amide and aromatic functional groups were inversely correlated with Fe content.

Organic Geochemistry↗
USGS2013

Multivariate analysis of ATR-FTIR spectra for assessment of oil shale organic geochemical properties

In this study, attenuated total reflectance (ATR) Fourier transform infrared spectroscopy (FTIR) was coupled with partial least squares regression (PLSR) analysis to relate spectral data to parameters from total organic carbon (TOC) analysis and programmed pyrolysis to assess the feasibility of developing predictive models to estimate important organic geochemical parameters. The advantage of ATR-FTIR over traditional analytical methods is that source rocks can be analyzed in the laboratory or field in seconds, facilitating more rapid and thorough screening than would be possible using other tools. ATR-FTIR spectra, TOC concentrations and Rock–Eval parameters were measured for a set of oil shales from deposits around the world and several pyrolyzed oil shale samples. PLSR models were developed to predict the measured geochemical parameters from infrared spectra. Application of the resulting models to a set of test spectra excluded from the training set generated accurate predictions of TOC and most Rock–Eval parameters. The critical region of the infrared spectrum for assessing S1, S2, Hydrogen Index and TOC consisted of aliphatic organic moieties (2800–3000 cm −1 ) and the models generated a better correlation with measured values of TOC and S2 than did integrated aliphatic peak areas. The results suggest that combining ATR-FTIR with PLSR is a reliable approach for estimating useful geochemical parameters of oil shales that is faster and requires less sample preparation than current screening methods.

Organic Geochemistry↗
USGS2019

Hydrous heating experiments at 130°C yield insights into the occurrence of hydrogen sulfide and light alkanes in natural gas reservoirs

Improved understanding of the origin of produced volatiles from conventional reservoirs and unconventional source rocks is critical for petroleum exploration and production. A series of hydrous heating experiments using two immature Type II siliciclastic source rocks, Pennsylvanian Turner Mine shale (TMS) and Devonian New Albany Shale (NAS), at 130 °C over one to two years were conducted to assess gas generation at low temperature. Elemental sulfur (ES) was added to the NAS samples to evaluate the role of sulfur on thermochemical sulfate reduction (TSR). The produced volatile composition was investigated in situ using Raman spectroscopy at the end of the heating experiments. Results show that the two source rocks yield different types and concentrations of volatiles. Only CH 4 and CO 2 were detected following hydrous heating of the TMS source rock in contrast to CH 4 , C 2 H 6 , C 3 H 8 , and CO 2 which were observed in experiments using NAS. Variations in the produced volatiles are likely the result of compositional differences within the respective source rock organic matter. Experiments involving ES show strong H 2 S signals that are likely due to the formation of H 2 S from the reaction of ES with water at 130 °C. H 2 S signals correlate with a greater relative concentration of CH 4 and CO 2 compared to experiments where ES was not added, on a time-normalized basis. The correlation between the presence of H 2 S and an increase in CH 4 and CO 2 concentration could indicate the occurrence of TSR. Here we propose that H 2 S in siliciclastic shale can be generated in the presence of ES at low temperatures via both disproportionation of ES into H 2 S and SO 4 2– , and TSR. Our findings from this study provide experimental evidence that may aid efforts to interpret the origin of H 2 S in low-temperature sedimentary basins.

Pennsylvania↗
USGS2025

Nanometer-scale relationships between sedimentary organic matter molecular composition, fluorescence, cathodoluminescence, and reflectance: The importance of oxygen content at low thermal maturities

Molecular characterization of sedimentary organic matter (SOM), termed macerals, is a common goal when seeking to understand petroleum generation as well as other geologic processes in deep time. However, unambiguous measurement of discrete macerals is challenging due to the small size of organic particles in sedimentary rocks, the proximity of different organic matter types to one another, mineral-organic matter interactions, and maceral mixing that occurs during SOM isolation prior to ex situ analysis. The recent advent of infrared spectrometers capable of nanometer-scale resolution and the application of these technologies to geologic samples has enabled advances in rapid, in situ molecular characterization of SOM allowing for insights into paleoenvironmental processes, such as organic matter productivity and preservation, among others. Here we employ one such technology, optical photothermal infrared (OPTIR) spectroscopy, to map SOM functional group distributions at 500-nm resolution in a sample from the Lower Cretaceous Sunniland Limestone of the South Florida Basin. Examined fields of view include occurrences of amorphous organic matter (AOM), inertinite, micrinite, solid bitumen, telalginite, and vitrinite. OPTIR data from these macerals are compared against traditional organic petrographic data from the same organic grains including fluorescence intensity and white light reflectance as well as against cathodoluminescence response, an emerging organic petrographic approach. Maceral oxygen content (using carbonyl functional group abundance as a proxy) is observed to vary widely between maceral types but correlates strongly with fluorescence and cathodoluminescence intensity as well as against reflectance. These findings highlight the important role that oxygen content plays in determining the optical properties of SOM and further demonstrate the ability of OPTIR to discriminate subtle molecular differences between SOM types.

Organic Geochemistry↗
USGS2026

Evidence for a biological origin of uranium-rich carbon masses within the Ediacaran Salt Range Formation of Pakistan

Thucholites are unique organic structures found in igneous and sedimentary rocks composed of a U-C-rich interior enclosed by an organic outer shell. Their formation and occurrence have perplexed scientists for over 100 years. Typically, thucholites are sparse in sedimentary rocks but where found in abundance, they may be the result of rapid paleoecological disruptions, e.g., volcanic ashfall. Here, we evaluated thucholites from the Ediacaran Salt Range Formation of the Indus Basin in Pakistan using field emission scanning electron microscopy (FESEM) and nanoscale secondary ion mass spectroscopy (NanoSIMS) to propose a two-stage mechanism for thucholite development. NanoSIMS results suggest organic matter in thucholite cores formed by biological fractionation (represented by the presence of lighter 13 C/ 12 C and 34 S/ 32 S) while the outer organic mantle formed via radiolysis-induced polymerization. FESEM elemental analysis confirms compositional differences between the two thucholite components (core and mantle), further implying their contrasting origins. Dimensional comparison of thucholite cores and their U-bearing mineral morphologies to ancient and modern U-biomineralized microbes suggests that the thucholite cores formed from metal-biological interactions. The presence of volcanogenic biotite, alkali feldspar, and clay spherules (interpreted as devitrified volcanic glass) with thucholite suggests that the thucholite cores in the Salt Range Formation are biological responses to rapid paleoenvironmental change from volcanic eruption which preserved the fossilized morphologies of Proterozoic microorganisms.

Salt Range↗
USGS2023

Luminescence ages and new interpretations of the timing and deposition of Quaternary sediments at Natural Trap Cave, Wyoming

Natural Trap Cave, located in the Big Horn Mountains of north-central Wyoming, has a history of trapping and preserving a range of North American fauna that plummeted into the deep vertical entrance. These animal remains were buried and preserved within sediments of the main chamber and, in turn, have helped elucidate the procession of faunal dynamics during the latest glacial cycle. The cave location, south of the Laurentide and Cordilleran Ice Sheets, and proximal to Yellowstone, is at an ideal geographical juncture to provide insights to ecological changes in North America. The sediments that the animals are buried in inform us about transport and deposition both inside and outside of the cave that relate to catchment dynamics. We report on a series of optically stimulated luminescence (OSL) ages derived from samples obtained within the cave during excavation work in 2014 and in 2018. We also examine chronology produced by argon, tephrochronology, fission track, and luminescence techniques that have been used for understanding the infilling of the cave. The cave sediment ages and in situ measured gamma spectroscopy as measured in this study helped resolve an improved chronological age model when combined with previous data. The suite of OSL ages is interpreted through the stratigraphic relationships (and vertebrates contained within) which requires the use of an adequate age model; we use either the central age model or minimum age model where appropriate and with justification. Lowest sediments are dated to ∼150 ka with a hiatus at ∼130 to 52 ka. Above this, sediment deposition and entrainment of paleontological materials are representative of Pleistocene and early Holocene times, between 37 ± 6 ka and 7.6 ± 0.5 ka. The stratigraphic architecture suggests that deposition of materials into the cave is episodic and rapid, followed by quiescent periods where hydrologic scour, heavy overland flow , or possibly a cryo-hydrologic process may have altered unit relationships. Thus, the complementary geochronometers and the characteristics of quartz versus feldspar luminescence signals improve temporal interpretations of these complex deposits. This adapted understanding of mixing also sets the stage for future work with the aim to improve our understanding of ages and sources for ash units within these cave deposits. The three ash units recognized in the cave may represent an in-situ reworking of the same ash or may be representative of previously undocumented eruptions from the Yellowstone Caldera.

Wyoming↗
USGS2004

Identification of spectrally similar materials using the USGS Tetracorder algorithm: The calcite-epidote-chlorite problem

A scheme to discriminate and identify materials having overlapping spectral absorption features has been developed and tested based on the U.S. Geological Survey (USGS) Tetracorder system. The scheme has been applied to remotely sensed imaging spectroscopy data acquired by the Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) instrument. This approach was used to identify the minerals calcite, epidote, and chlorite in the upper Animas River watershed, Colorado. The study was motivated by the need to characterize the distribution of calcite in the watershed and assess its acid-neutralizing potential with regard to acidic mine drainage. Identification of these three minerals is difficult because their diagnostic spectral features are all centered at 2.3 ??m, and have similar shapes and widths. Previous studies overestimated calcite abundance as a result of these spectral overlaps. The use of a reference library containing synthetic mixtures of the three minerals in varying proportions was found to simplify the task of identifying these minerals when used in conjunction with a rule-based expert system. Some inaccuracies in the mineral distribution maps remain, however, due to the influence of a fourth spectral component, sericite, which exhibits spectral absorption features at 2.2 and 2.4 ??m that overlap the 2.3-??m absorption features of the other three minerals. Whereas the endmember minerals calcite, epidote, chlorite, and sericite can be identified by the method presented here, discrepancies occur in areas where all four occur together as intimate mixtures. It is expected that future work will be able to reduce these discrepancies by including reference mixtures containing sericite. ?? 2004 Elsevier Inc. All rights reserved.

Remote Sensing of Environment↗
USGS2021

NASA's surface biology and geology designated observable: A perspective on surface imaging algorithms

The 2017–2027 National Academies' Decadal Survey, Thriving on Our Changing Planet , recommended Surface Biology and Geology (SBG) as a “Designated Targeted Observable” (DO). The SBG DO is based on the need for capabilities to acquire global, high spatial resolution, visible to shortwave infrared (VSWIR; 380–2500 nm; ~30 m pixel resolution) hyperspectral (imaging spectroscopy) and multispectral midwave and thermal infrared (MWIR: 3–5 μm; TIR: 8–12 μm; ~60 m pixel resolution) measurements with sub-monthly temporal revisits over terrestrial, freshwater, and coastal marine habitats. To address the various mission design needs, an SBG Algorithms Working Group of multidisciplinary researchers has been formed to review and evaluate the algorithms applicable to the SBG DO across a wide range of Earth science disciplines, including terrestrial and aquatic ecology, atmospheric science, geology, and hydrology. Here, we summarize current state-of-the-practice VSWIR and TIR algorithms that use airborne or orbital spectral imaging observations to address the SBG DO priorities identified by the Decadal Survey: (i) terrestrial vegetation physiology, functional traits, and health; (ii) inland and coastal aquatic ecosystems physiology, functional traits, and health; (iii) snow and ice accumulation, melting, and albedo; (iv) active surface composition (eruptions, landslides, evolving landscapes, hazard risks); (v) effects of changing land use on surface energy, water, momentum, and carbon fluxes; and (vi) managing agriculture, natural habitats, water use/quality, and urban development. We review existing algorithms in the following categories: snow/ice, aquatic environments, geology, and terrestrial vegetation, and summarize the community-state-of-practice in each category. This effort synthesizes the findings of more than 130 scientists.

Remote Sensing of Environment↗
USGS2022

Hyperspectral remote sensing of white mica: A review of imaging and point-based spectrometer studies for mineral resources, with spectrometer design considerations

Over the past ~30 years, hyperspectral remote sensing of chemical variations in white mica have proven to be useful for ore deposit studies in a range of deposit types. To better understand mineral deposits and to guide spectrometer design, this contribution reviews relevant papers from the fields of remote sensing, spectroscopy, and geology that have utilized spectral changes caused by chemical variation in white micas. This contribution reviews spectral studies conducted at the following types of mineral deposits: base metal sulfide, epithermal, porphyry, sedimentary rock hosted gold deposits, orogenic gold, iron oxide copper gold, and unconformity-related uranium. The structure, chemical composition, and spectral features of white micas, in this contribution defined as muscovite, paragonite, celadonite, phengite, illite, and sericite, are given. Reviewed laboratory spectral studies determined that shifts in the position of the white mica 2200 nm combination feature of 1 nm correspond to a change in Al oct content of approximately ±1.05%. Many of the reviewed spectral studies indicated that a shift in the position of the white mica 2200 nm combination feature of 1 nm was geologically significant. A sensitivity analysis of spectrometer characteristics; bandpass, sampling interval, and channel position, is conducted using spectra of 19 white micas with deep absorption features to determine minimum characteristics required to accurately measure a shift in the position of the white mica 2200 nm combination feature. It was determined that a sampling interval < 16.3 nm and bandpass <17.5 nm are needed to achieve a root mean square error (RMSE) of 2 nm, whereas a sampling interval < 8.8 nm and bandpass <9.8 nm are needed to achieve a RMSE of 1 nm. For comparison, commonly used imaging spectrometers HyMap, AVIRIS-Classic, SpecTIR®'s AisaFENIX 1K, and HySpex tm SWIR 384 have 2.1, 1.2, 0.96, and 0.95 nm RMSE in determining the position of the 2200 nm white mica combination feature, respectively. An additional sensitivity analysis is conducted to determine the effect of signal to noise ratio (SNR) on the RMSE of the position of the white mica 2200 nm combination feature, using spectra of 18 white micas with deep absorption features. For a spectrometer with sampling interval and bandpass of 1 nm, we estimate that RMSEs of 1 and 1.5 nm are achievable with spectra having a minimum SNR of approximately 246 and 64, respectively. For a spectrometer with sampling interval and bandpass of 5 nm, we estimate that RMSEs of 1 and 1.5 nm are attainable with spectra having a minimum SNR of approximately 431 and 84, respectively. When using a spectrometer with a sampling interval 8.8 nm and a bandpass of 9.8 nm, a RMSE of 1 is only achievable with convolved, noiseless reference spectra. For the 8.8_9.8 nm spectrometer, spectra with SNR of 250 and 100 result in RMSE of 1.1 and 1.3, respectively. Therefore, fine spectral resolution characteristics achieve RMSEs better than 1 nm for high SNR spectra while spectrometers with coarse spectral resolution have larger RMSE, perform well with noisy data, and are useful for white mica studies if RMSE of 1.1 to 1.5 nm is acceptable.

Remote Sensing of Environment↗
USGS2024

An accuracy assessment of the surface reflectance product from the EMIT imaging spectrometer

The Earth surface Mineral dust source InvesTigation (EMIT) is an imaging spectrometer launched to the International Space Station in July 2022 to measure the mineral composition of Earth’s dust-producing regions. We present a systematic accuracy assessment of the EMIT surface reflectance product in two parts. First, we characterize the surface reflectance product’s overall performance using multiple independent vicarious calibration field experiments with hand-held and automated field spectrometers. We find that the EMIT surface reflectance product has a standard error of ±1.0 % in absolute reflectance units for temporally coincident observations. Discrepancies rise to ±2.7 % for spectra acquired at different dates and times of day, which we attribute mainly to changes in solar geometry. Second, we develop an error budget that explains the differences between EMIT and in-situ field spectrometer data. We find that uncertainties in spatial footprints, field spectroscopy, and the EMIT-reported measurement were sufficient to explain discrepancies in most cases. Our approach did not detect any systematic calibration or reflectance errors in the timespan considered. Together, these findings demonstrate that a space-based imaging spectrometer can acquire high-quality spectra across a wide range of observational and atmospheric conditions.

Nevada↗
USGS2021

Quantification of manganese for ChemCam Mars and laboratory spectra using a multivariate model

We report a new calibration model for manganese using the laser-induced breakdown spectroscopy instrument that is part of the ChemCam instrument suite onboard the NASA Curiosity rover. The model has been trained using an expanded set of 523 manganese-bearing rock, mineral, metal ore, and synthetic standards. The optimal calibration model uses the Partial Least Squares (PLS) and Least Absolute Shrinkage and Selection Operator (LASSO) multivariate techniques, with a novel “double blending” technique. We determined the detection limit for manganese is 82 ppm using a method blank procedure and is possibly as low as 27 ppm based on visual inspection of the spectra. Based on a representative test set consisting of measurements on 93 standards, the double blended multivariate model shows a Root Mean Squared Error of Prediction (RMSEP) accuracy of 1.39 wt% MnO for the full blended model. Employing a local RMSEP estimate where the model performance is evaluated based on nearby test samples, the accuracy is 0.03 wt% at the quantification limit (0.05 wt% MnO), 0.4 wt% accuracy at 1.0 wt% MnO, and 4.4 wt% accuracy at 100 wt% MnO. Precision is estimated using the standard deviation of the test set measurements, and is ±0.01 wt% MnO at the quantification limit, ±0.09 wt% MnO at 1.0 wt% MnO, and ± 2.1 wt% MnO at 100 wt% MnO (all 1 standard deviation). This new calibration is important for understanding the variation of manganese in the bedrock with the Curiosity rover on Mars, which provides insight into past redox conditions on Mars.

Spectrochimica Acta B↗
USGS2022

Dissolved organic matter within oil and gas associated wastewaters from U.S. unconventional petroleum plays: Comparisons and consequences for disposal and reuse

Wastewater generated during petroleum extraction (produced water) may contain high concentrations of dissolved organics due to their intimate association with organic-rich source rocks, expelled petroleum, and organic additives to fluids used for hydraulic fracturing of unconventional (e.g., shale) reservoirs. Dissolved organic matter (DOM) within produced water represents a challenge for treatment prior to beneficial reuse. High salinities characteristic of produced water, often 10× greater than seawater, coupled to the complex DOM ensemble create analytical obstacles with typical methods. Excitation-emission matrix spectroscopy (EEMS) can rapidly characterize the fluorescent component of DOM with little impact from matrix effects. We applied EEMS to evaluate DOM composition in 18 produced water samples from six North American unconventional petroleum plays. Represented reservoirs include the Eagle Ford Shale (Gulf Coast Basin), Wolfcamp/Cline Shales (Permian Basin), Marcellus Shale and Utica/Point Pleasant (Appalachian Basin), Niobrara Chalk (Denver-Julesburg Basin), and the Bakken Formation (Williston Basin). Results indicate that the relative chromophoric DOM composition in unconventional produced water may distinguish different lithologies, thermal maturity of resource types (e.g., heavy oil vs. dry gas), and fracturing fluid compositions, but is generally insensitive to salinity and DOM concentration. These results are discussed with perspective toward DOM influence on geochemical processes and the potential for targeted organic compound treatment for the reuse of produced water.

Colorado, Montana, Nebraska, New York, North Dakot↗
USGS2024

Assessing microplastics contamination in unviable loggerhead sea turtle eggs

Sea turtles, in comparison with marine mammals, sea birds, and fishes, are the most affected by microplastics in terms of number of individuals impacted and concentration within each organism. The ubiquitous nature and persistence of microplastics in the environment further compromises sea turtles as many species are currently vulnerable, endangered, or critically endangered. The objective of this study was to quantify microplastic contamination in unviable loggerhead sea turtle eggs (Caretta caretta). Eggs were collected from seven locations along the northwest coast of Florida. A total of 70 nests and 350 eggs were examined. Microplastics (n = 510) were found in undeveloped loggerhead sea turtle eggs across all seven sites, suggesting that maternal transference and/or exchange between the internal and external environment were possible. The frequency found was 7.29 ± 1.83 microplastic pieces per nest and 1.46 ± 0.01 per egg. Microplastics were categorized based on color, shape, size, and type of polymer. The predominant color of microplastics were blue/green (n = 236), shape was fibers (n = 369), and length was 10–300 μm (n = 191). Identified fragments, films, beads and one foam (n = 187) had the most common area of 1–10 μm2 (n = 45). Micro-Fourier Transform Infrared (μ-FTIR) spectroscopy analysis demonstrated that polyethylene (11 %) and polystyrene (7 %) were the main polymer types. For the first time microplastics were found in unviable, undeveloped loggerhead sea turtle eggs collected in northwest Florida. This work provides insight into the distribution patterns of microplastic pollutants in loggerhead sea turtle eggs and may extend to other species worldwide.

Florida↗
USGS2025

Geographic determination of Pinus ponderosa using DART TOFMS, ICP-MS, and LIBS handheld analyzer

Due to legal requirements on international imports, it is important for law enforcement and regulatory agencies to identify the geographical provenance of timber. Current methods for geographic identification utilize data generated by direct analysis in real time time-of-flight mass spectrometry (DART TOFMS), genetics, and isotope-ratio mass spectrometry (IRMS), but identification methods based on genetics and IRMS data require months to years to create usable databases. This study used machine learning algorithms to compare the results of DART TOFMS, inductively coupled plasma mass spectrometry (ICP-MS), and a handheld laser-induced breakdown spectroscopy (LIBS) analyzer for use in geographic identification of five populations of Pinus ponderosa spaced between 14 to 72 km apart. The results of the study showed comparable performances from machine learning algorithms applied to the ICP-MS and LIBS data with accuracy and kappa values over 90% while the DART TOFMS had an accuracy of 76% and a kappa value of 70%. This study demonstrated that data from the LIBS handheld analyzer is a viable and intriguing alternative to ICP-MS and DART TOFMS analyses in generating training databases and further indicates that trace elemental analysis via ICP-MS is a promising method for generating databases used to identify the origin of timber.

California, Oregon↗
USGS2023

Prevailing impacts of river management on microplastic transport in contrasting US streams: Rethinking global microplastic flux estimations

While microplastic inputs into rivers are assumed to be correlated with anthropogenic activities and to accumulate towards the sea, the impacts of water management on downstream microplastic transport are largely unexplored. A comparative study of microplastic abundance in Boulder Creek (BC), and its less urbanized tributary South Boulder Creek (SBC), (Colorado USA), characterized the downstream evolution of microplastics in surface water and sediments, evaluating the effects of urbanization and flow diversions on the up-to-downstream profiles of microplastic concentrations and loads. Water and sediment samples were collected from 21 locations along both rivers and microplastic properties determined by fluorescence microscopy and Raman spectroscopy. The degree of catchment urbanization affected microplastic patterns, as evidenced by greater water and sediment concentrations and loads in BC than the less densely populated SBC, which is consistent with the differences in the degree of urbanization between both catchments. Microplastic removal through flow diversions was quantified, showing that water diversions removed over 500 microplastic particles per second from the river, and caused stepwise reductions of downstream loads at diversion points. This redistribution of microplastics back into the catchment should be considered in large scale models quantifying plastic fate and transport to the oceans.

Colorado↗
USGS1990

The uniqueness of humic substances in each of soil, stream and marine environments

Definitive compositional differences are shown to exist for both fulvic acids and humic acids from soil, stream and marine environments by five different methods (1H and 13C NMR spectroscopy, 14C age and ?? 13C isotopic analyses, amino acid analyses and pyrolysis-mass spectrometry). Definitive differences are also found between fulvic acids and humic acids within each environment. These differences among humic substances from various sources are more readily discerned because the method employed for the isolation of humic substances from all environments excludes most of the non-humic components and results in more purified humic isolates from water and soils. The major compositional aspects of fulvic acids and humic acids which determine the observed characteristic differences in each environment are the amounts and compositions of saccharide, phenolic, methoxyl, aromatic, hydrocarbon, amino acid and nitrogen moieties.

Analytica Chimica Acta↗
USGS1999

Simultaneous determination of Ca, Cu, Ni, Zn and Cd binding strengths with fulvic acid fractions by Schubert's method

The equilibrium binding of Ca 2+ , Ni 2+ , Cd 2+ , Cu 2+ and Zn 2+ with unfractionated Suwannee river fulvic acid (SRFA) and an enhanced metal binding subfraction of SRFA was measured using Schubert’s ion-exchange method at pH 6.0 and at an ionic strength ( μ ) of 0.1 (NaNO 3 ). The fractionation and subfractionation were directed towards obtaining an isolate with an elevated metal binding capacity or binding strength as estimated by Cu 2+ potentiometry (ISE). Fractions were obtained by stepwise eluting an XAD-8 column loaded with SRFA with water eluents of pH 1.0 to pH 12.0. Subfractions were obtained by loading the fraction eluted from XAD-8 at pH 5.0 onto a silica gel column and eluting with solvents of increasing polarity. Schuberts ion exchange method was rigorously tested by measuring simultaneously the conditional stability constants ( K ) of citric acid complexed with the five metals at pH 3.5 and 6.0. The log K of SRFA with Ca 2+ , Ni 2+ , Cd 2+ , Cu 2+ and Zn 2+ determined simultaneously at pH 6.0 follow the sequence of Cu 2+ > Cd 2+ > Ni 2+ > Zn 2+ > Ca 2+ while all log K values increased for the enhanced metal binding subfraction and followed a different sequence of Cu 2+ > Cd 2+ > Ca 2+ > Ni 2+ > Zn 2+ . Both fulvic acid samples and citric acid exhibited a 1 : 1 metal to ligand stochiometry under the relatively low metal loading conditions used here. Quantitative 13 C "> 13C nuclear magnetic resonance spectroscopy showed increases in aromaticity and ketone content and decreases in aliphatic carbon for the elevated metal binding fraction while the carboxyl carbon, and elemental nitrogen, phosphorus, and sulfur content did not change. The more polar, elevated metal binding fraction did show a significant increase in molecular weight over the unfractionated SRFA.

Analytica Chimica Acta↗
USGS2000

Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO 6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO 2 (OH) 2 . Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

Geochimica et Cosmochimica Acta↗