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USGS2010

Chemical and textural controls on phosphorus mobility in drylands of southeastern Utah

We investigated several forms of phosphorus (P) in dryland soils to examine the chemical and textural controls on P stabilization on a diverse set of substrates. We examined three P fractions including labile, moderately labile, and occluded as determined by a modified Hedley fractionation technique. The P fractions were compared to texture measurements and total elemental concentrations determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Labile P related to the absence of materials involved in P sorption. Moderately labile P was most strongly associated with high total Al & Fe content that we interpret to represent oxides and 1:1 clay minerals. The occluded P fraction was strongly associated with low total Al & Fe environments and interpreted to represent 2:1 clay minerals where ligand exchange tightly sequesters P. The results indicate that the controls on P fraction distribution are initially closely tied to the chemical and physical properties of the bedrock units that contribute to soil formation. Further, these results suggest that the progression of stabilized P forms in dryland areas differs from the progression observed in mesic environments. Soil development in dryland settings, such as the formation of pedogenic carbonates, may lead to differing controls on P availability and the proportional size of the moderately labile fraction.

Utah↗

USGS2014

Particulate organic matter quality influences nitrate retention and denitrification in stream sediments: evidence from a carbon burial experiment

Organic carbon supply is linked to nitrogen transformation in ecosystems. However, the role of organic carbon quality in nitrogen processing is not as well understood. We determined how the quality of particulate organic carbon (POC) influenced nitrogen transformation in stream sediments by burying identical quantities of varying quality POC (northern red oak ( Quercus rubra ) leaves, red maple ( Acer rubrum ) leaves, red maple wood) in stream mesocosms and measuring the effects on nitrogen retention and denitrification compared to a control of combusted sand. We also determined how POC quality affected the quantity and quality of dissolved organic carbon (DOC) and dissolved oxygen concentration in groundwater. Nitrate and total dissolved nitrogen (TDN) retention were assessed by comparing solute concentrations and fluxes along groundwater flow paths in the mesocosms. Denitrification was measured by in situ changes in N 2 concentrations (using MIMS) and by acetylene block incubations. POC quality was measured by C:N and lignin:N ratios and DOC quality was assessed by fluorescence excitation emission matrix spectroscopy. POC quality had strong effects on nitrogen processing. Leaf treatments had much higher nitrate retention, TDN retention and denitrification rates than the wood and control treatments and red maple leaf burial resulted in higher nitrate and TDN retention rates than burial of red oak leaves. Leaf, but not wood, burial drove pore water to severe hypoxia and leaf treatments had higher DOC production and different DOC chemical composition than the wood and control treatments. We think that POC quality affected nitrogen processing in the sediments by influencing the quantity and quality of DOC and redox conditions. Our results suggest that the type of organic carbon inputs can affect the rates of nitrogen transformation in stream ecosystems.

Wisconsin↗

USGS2022

Optical properties of dissolved organic matter in throughfall and stemflow vary across tree species and season in a temperate headwater forest

Tree-derived dissolved organic matter (DOM) comprises a significant carbon flux within forested watersheds. Few studies have assessed the optical properties of tree-derived DOM. To increase understanding of the factors controlling tree-derived DOM quality, we measured DOM optical properties, dissolved organic carbon (DOC) and calcium concentrations in throughfall and stemflow for 17 individual rain events during summer and fall in a temperate deciduous forest in Vermont, United States. DOC and calcium fluxes in throughfall and stemflow were enriched on average 4 to 70 times incident fluxes in rain. A multiway model was developed using absorbance and fluorescence spectroscopy to further characterize DOM optical properties. Throughfall contained a higher percentage of protein-like DOM fluorescence than stemflow while stemflow was characterized by a higher percentage of humic-like DOM fluorescence. DOM absorbance spectral slopes in yellow birch ( Betula alleghaniensis ) stemflow were significantly higher than in sugar maple ( Acer saccharum ) stemflow. DOM optical metrics were not influenced by rainfall volume, but percent protein-like fluorescence increased in throughfall during autumn when leaves senesced. Given the potential influence of tree-derived DOM fluxes on receiving soils and downstream ecosystems, future modeling of DOM transport and soil biogeochemistry should represent the influence of differing DOM quality in throughfall and stemflow across tree species and seasons.

Vermont↗

USGS2013

Environmental survey in the Tuul and Orkhon River basins of north-central Mongolia, 2010: Metals and other elements in streambed sediment and floodplain soil

Streambed sediment and subsurface floodplain soil were sampled for elemental analyses from 15 locations in river basins of north-central Mongolia during August 2010. Our primary objective was to conduct a reconnaissance-level assessment of potential inputs of toxicologically important metals and metalloids to Lake Baikal, Russia, that might originate from mining and urban activities within tributaries of the Selenga River in Mongolia. Samples were collected in triplicate from all sites, then dried, and sieved to <2 mm for analysis by portable X-ray florescence spectroscopy and by inductively coupled plasma mass spectrometry after digestion with concentrated nitric and hydrochloric acids. Arsenic, copper, and mercury were greatly elevated in sediment and floodplain soil collected from tributary streams located near two major mining operations. Lead and zinc were moderately elevated in streambed sediment and in floodplain soil obtained from a small tributary in the capital city of Ulaanbaatar, but those concentrations were considerably less than probable effects benchmarks. Historical and possibly present mining activities have led to considerable metal contamination in certain tributaries of the Orkhon River in north-central Mongolia; however, metals originating from those sources did not appear to be accumulating in sediments at our downstream-most sampling sites located near the border between Mongolia and Russia.

Environmental Monitoring and Assessment↗

USGS1984

The group separation of the rare-earth elements and yttrium from geologic materials by cation-exchange chromatography

Demand is increasing for the determination of the rare-earth elements (REE) and yttrium in geologic materials. Due to their low natural abundance in many materials and the interferences that occur in many methods of determination, a separation procedure utilizing gradient strong-acid cation-exchange chromatography is often used to preconcentrate and isolate these elements from the host-rock matrix. Two separate gradient strong-acid cation-exchange procedures were characterized and the major elements as well as those elements thought to provide the greatest interference for the determination of the REE in geologic materials were tested for separation from the REE. Simultaneous inductively coupled argon plasma-atomic emission spectroscopy (ICAP-AES) measurements were used to construct the chromatograms for the elution studies, allowing the elution patterns of all the elements of interest to be determined in a single fraction of eluent. As a rock matrix, U.S. Geological Survey standard reference BCR-1 basalt was digested using both an acid decomposition procedure and a lithium metaborate fusion. Hydrochloric and nitric acids were tested as eluents and chromatograms were plotted using the ICAP-AES data; and we observed substantial differences in the elution patterns of the REE and as well as in the solution patterns of Ba, Ca, Fe and Sr. The nitric acid elution required substantially less eluent to elute the REE and Y as a group when compared to the hydrochloric acid elution, and provided a clearer separation of the REE from interfering and matrix elements. ?? 1984.

Chemical Geology↗

USGS1992

Chemical changes and carbon isotope variations in a cross-section of a large Miocene gymnospermous log

The cross-sectional radius of a 3-m (diam.) brown coal gymnospermous log of Miocene age, previously analyzed for carbohydrate and lignin methoxyl content by solid-state 13 C nuclear magnetic resonance spectroscopy, was examined using stable carbon isotopic ratios in order to determine if the isotopic composition could be related to chemical changes or to radial position. This study found a possible relationship between δ 13 C-values and radial position; however, these changes cannot be linked to carbohydrate content and are probably attributable to changing growth conditions during the lifetime of the tree. An apparent linear relationship between the changes in carbohydrate content after sodium para-periodate treatment and corresponding changes in the δ 13 C-values indicates constant isotopic fractionation between lignin and carbohydrates along the cross-sectional radius. This result indicates that diagenesis has not produced any significant change in the lignin-carbohydrate carbon isotopic fractionation or, alternatively, that diagenesis has erased any fractionation pattern that once existed. A sample of fresh wood from another gymnospermous species was analyzed by the same methods and found to have lignin-carbohydrate carbon isotopic fractionation significantly different from that of the Miocene log section samples, suggesting that differences may be species-related or that the complex mixture of carbohydrates in the fresh wood was isotopically different from that of the degraded wood, and the whole Miocene log was uniformly altered.

Chemical Geology↗

USGS1996

Constraints on the thermal history of Taylorsville Basin, Virginia, U.S.A., from fluid-inclusion and fission-track analyses: Implications for subsurface geomicrobiology experiments

Microbial populations have been found at the depth of 2621-2804 m in a borehole near the center of Triassic Taylorsville Basin, Virginia. To constrain possible scenarios for long-term survival in or introduction of these microbial populations to the deep subsurface, we attempted to refine models of thermal and burial history of the basin by analyzing aqueous and gaseous fluid inclusions in calcite/quartz veins or cements in cuttings from the same borehole. These results are complemented by fission-track data from the adjacent boreholes. Homogenization temperatures of secondary aqueous fluid inclusions range from 120?? to 210??C between 2027- and 3069-m depth, with highest temperatures in the deepest samples. The salinities of these aqueous inclusions range from 0 to ??? 4.3 eq wt% NaCl. Four samples from the depth between 2413 and 2931 m contain both two-phase aqueous and one-phase methane-rich inclusions in healed microcracks. The relative CH4 and CO2 contents of these gaseous inclusions was estimated by microthermometry and laser Raman spectroscopy. If both types of inclusions in sample 2931 m were trapped simultaneously, the density of the methane-rich inclusions calculated from the Peng - Robinson equation of state implies an entrapment pressure of 360 ?? 20 bar at the homogenization temperature (162.5 ?? 12.5??C) of the aqueous inclusions. This pressure falls between the hydrostatic and lithostatic pressures at the present depth 2931 m of burial. If we assume that the pressure regime was hydrostatic at the time of trapping, then the inclusions were trapped at 3.6 km in a thermal gradient of ??? 40??C/km. The high temperatures recorded by the secondary aqueous inclusions are consistent with the pervasive resetting of zircon and apatite fission-track dates. In order to fit the fission-track length distributions of the apatite data, however, a cooling rate of 1-2??C/Ma following the thermal maximum is required. To match the integrated dates, the thermal maximum would have occurred at ??? 200 Ma. The timing of the maximum temperature is consistent with rapid burial of the Taylorsville Basin to twice its present-day depth and thermal re-equilibration with a 40??C/km geothermal gradient, followed by slow exhumation. The results may imply that the microorganisms did not survive in situ, but were transported from the cooler portions of the basin sometime after maximum burial and heating.

Chemical Geology↗

USGS1968

The geochronology of foraminiferal ooze deposits in the "Southern Ocean"

Many cores raised from the Drake Passage are characterized by alternating zones of foraminiferal ooze and sandysilt. Cores raised from the East Pacific Rise are foraminiferal ooze or alternating siliceous and carbonate ooze. The uranium and thorium concentrations and isotopic ratios in foraminifers separated from these cores were measured by alpha-spectroscopy. 230 Th in foraminiferal tests is found to be out of equilibrium with its parent ( 234 U), enabling the “excess 230 Th” method to be used in estimating sedimentation rates. The uranium concentration of the tests is constant, suggesting constant uranium concentrations in the sea and thus constant production of 230 Th during periods of foraminiferal production. 232 Th concentration is 2.1 ± 0.7 ppm in the Drake Passage and below the level of detection in tests from the East Pacific Rise. Within each core the 232 Th is constant, varying closely with distance from the source. Based on the degree of disequilibrium of 230 Th, correlations between cores can be made. Age estimates of the foraminiferal zones indicate deposition occurred between 8 000 and 120 000 and between 190 000 and 280 000 years before present. Reported dates of high stands of the sea fall between the ages estimated for the foraminiferal zones, suggesting these zones were deposited during northern hemisphere glacial maxima.

Earth and Planetary Science Letters↗

USGS1990

Structure and morphology of magnetite anaerobically-produced by a marine magnetotactic bacterium and a dissimilatory iron-reducing bacterium

Intracellular crystals of magnetite synthesized by cells of the magnetotactic vibroid organism, MV-1, and extracellular crystals of magnetite produced by the non-magnetotactic dissimilatory iron-reducing bacterium strain GS-15, were examined using high-resolution transmission electron microscopy, electron diffraction and 57 Fe Mo¨ssbauer spectroscopy. The magnetotactic bacterium contained a single chain of approximately 10 crystals aligned along the long axis of the cell. The crystals were essentially pure stoichiometric magnetite. When viewed along the crystal long axis the particles had a hexagonal cross-section whereas side-on they appeared as rectangules or truncated rectangles of average dimension, 53 × 35 nm. These findings are explained in terms of a three-dimensional morphology comprising a hexagonal prism of 110 faces which are capped and truncated by 111 end faces. Electron diffraction and lattice imaging studies indicated that the particles were structurally well-defined single crystals. In contrast, magnetite particles produced by the strain, GS-15 were irregular in shape and had smaller mean dimensions (14 nm). Single crystals were imaged but these were not of high structural perfection. These results highlight the influence of intracellular control on the crystallochemical specificity of bacterial magnetites. The characterization of these crystals is important in aiding the identification of biogenic magnetic materials in paleomagnetism and in studies of sediment magnetization.

Earth and Planetary Science Letters↗

USGS1988

The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

Geochimica et Cosmochimica Acta↗

USGS1992

Surface chemistry associated with the cooling and subaerial weathering of recent basalt flows

The surface chemistry of fresh and weathered historical basalt flows was characterized using surface-sensitive X-ray photoelectron spectroscopy (XPS). Surfaces of unweathered 1987–1990 flows from the Kilauea Volcano, Hawaii, exhibited variable enrichment in Al, Mg, Ca, and F due to the formation of refractory fluoride compounds and pronounced depletion in Si and Fe from the volatilization of SiF 4 and FeF 3 during cooling. These reactions, as predicted from shifts in thermodynamic equilibrium with temperature, are induced by diffusion of HF from the flow interiors to the cooling surface. The lack of Si loss and solid fluoride formation for recent basalts from the Krafla Volcano, Iceland, suggest HF degassing at higher temperatures. Subsequent short-term subaerial weathering reactions are strongly influenced by the initial surface composition of the flow and therefore its cooling history. Successive samples collected from the 1987 Kilauea flow demonstrated that the fluoridated flow surfaces leached to a predominantly SiO 2 composition by natural weathering within one year. These chemically depleted surfaces were also observed on Hawaiian basalt flows dating back to 1801 AD. Solubility and kinetic models, based on thermodynamic and kinetic data for crystalline AlF 3 , MgF 2 , and CaF 2 , support observed elemental depletion rates due to chemical weathering. Additional loss of alkalis from the Hawaiian basalt occurs from incongruent dissolution of the basalt glass substrate during weathering.

Geochimica et Cosmochimica Acta↗

USGS1992

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO 2 -saturated non-stoichiometric solutions of Sr(HCO 3 ) 2 and Ca(HCO 3 ) 2 at 25°C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO 3 ) 2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO 3 ) 2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0–10 atomic layers thick in Sr(HCO 3 ) 2 solutions and 0–4 layers thick in Ca(HCO 3 ) 2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO 3 ) 2 and Ca(HCO 3 ) 2 solutions, respectively. In Sr(HCO 3 ) 2 solutions, the XPS signal from the outer ~ 60 Å on aragonite indicates a composition of 16 mol% SrCO 3 after only 2 min of contact, and 14–18 mol% SrCO 3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO 3 after 2 min of contact with Ca(HCO 3 ) 2 solution, and is 34–39 mol% CaCO 3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 Å (as much as 26 mol% SrCO 3 on aragonite and 44 mol% CaCO 3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO 3 ) 2 )) than in solutions spiked with the more soluble component (Ca(HCO 3 ) 2 ), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates.

Geochimica et Cosmochimica Acta↗

USGS1994

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, Fe s OH and Fe w OH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO 2 )UO 2 . The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO 2 CO 3 0 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Geochimica et Cosmochimica Acta↗

USGS1996

Reduction of aqueous transition metal species on the surfaces of Fe(II)-containing oxides

Experimental studies demonstrate that structural Fe(II) in magnetite and ilmenite heterogeneously reduce aqueous ferric, cupric, vanadate, and chromate ions at the oxide surfaces over a pH range of 1–7 at 25°C. For an aqueous transition metal m , such reactions are 3 [ Fe 2 + Fe 2 3 + ] O 4 (magnetite) + 2 / n m z → 4 [ Fe 2 3 + ] O 3 (magnetite) + Fe 2 + + 2 / n m z − n "> 3[Fe2+Fe23+]O4(magnetite)+2/nmz→4[Fe23+]O3(magnetite)+Fe2++2/nmz−n and 3 [ Fe 2 + Ti ] O 3 (ilmenite) + 2 / n m z → Fe 2 3 + Ti 3 O 9 (pseudorutile) + Fe 2 + + 2 / n m z − n , "> 3[Fe2+Ti]O3(ilmenite)+2/nmz→Fe23+Ti3O9(pseudorutile)+Fe2++2/nmz−n, where z is the valance state and n is the charge transfer number. The half cell potential range for solid state oxidation [Fe(II)] → [Fe(III)] is −0.34 to −0.65 V, making structural Fe(II) a stronger reducing agent than aqueous Fe 2+ (−0.77 V). Reduction rates for aqueous metal species are linear with time (up to 36 h), decrease with pH, and have rate constants between 0.1 and 3.3 × 10 −10 mol m −2 s −1 . Iron is released to solution both from the above reactions and from dissolution of the oxide surface. In the presence of chromate, Fe 2+ is oxidized homogeneously in solution to Fe 3+ . X-ray photoelectron spectroscopy (XPS) denotes a Fe(III) oxide surface containing reduced Cr(III) and V(IV) species. Magnetite and ilmenite electrode potentials are insensitive to increases in divalent transition metals including Zn(II), Co(II), Mn(II), and Ni(II) and reduced V(IV) and Cr(III) but exhibit a log-linear concentration-potential response to Fe(III) and Cu(II). Complex positive electrode responses occur with increasing Cr(VI) and V(V) concentrations. Potential dynamic scans indicate that the high oxidation potential of dichromate is capable of suppressing the cathodic reductive dissolution of magnetite. Oxide electrode potentials are determined by the Fe(II)/Fe(III) composition of the oxide surface and respond to aqueous ion potentials which accelerate this oxidation process. Natural magnetite sands weathered under anoxic conditions are electrochemically reactive as demonstrated by rapid chromate reduction and the release of aqueous Fe(III) to experimental solution. In contrast, magnetite weathered under oxidizing vadose conditions show minimum reactivity toward chromate ions. The ability of Fe(II) oxides to reduce transition metals in soils and groundwaters will be strongly dependent on the redox environment.

Geochimica et Cosmochimica Acta↗

USGS1991

Infrared spectroscopic examination of the interaction of urea with the naturally occurring zeolite clinoptilolite

Infrared spectroscopy has shown for the first time that the naturally occurring zeolite clinoptilolite can absorb urea, (NH 2 ) 2 CO, under ambient conditions from either aqueous or ethanolic solutions. The two strongest NH stretching bands at 3441 and 3344 cm −1 in pure, solid urea shift to higher frequency (about 3504 and 3401 cm −1 ) after absorption. Two of the four urea bands in the 1800-1300 cm −1 range (at 1683 and 1467 cm −1 ) undergo marked downward shifts to about 1670 and 1445 cm −1 . The other two bands show little change in frequency. The strong band at 1602 cm −1 , however, diminishes in intensity to little more than an ill-defined shoulder on the 1626-cm −1 peak. When clinoptilolite is heated to 450 °C and then treated with molten urea (ca. 140 °C) for several minutes, and finally washed twice with ethanol to remove excess unreacted urea, further changes become apparent in the spectrum of the urea-treated clinoptilolite. The two NH stretching bands broaden without significant change in frequency. Two new bands appear in the midfrequency range at 1777 (weak) and 1719 (medium strong) cm −1 . Of the four original midfrequency peaks, the one at 1602 cm −1 is now absent. Two others (1627 and 1440 cm −1 ) exhibit little change, while the fourth has broadened and shifted down to 1663 cm −1 , where it appears as a shoulder on the band at 1627 cm −1 . Both treatments clearly induce interaction between urea and the zeolite which seems to result in significant modifications in the nature of the hydrogen bonding of the substrate.

Microchemical Journal↗

USGS1986

Separation and preconcentration of the rare-earth elements and yttrium from geological materials by ion-exchange and sequential acid elution

The abundance of rare-earth elements (REE) and yttrium in geological materials is generally low, and most samples contain elements that interfere in the determination of the REE and Y, so a separation and/or preconcentration step is often necessary. This is often achieved by ion-exchange chromatography with either nitric or hydrochloric acid. It is advantageous, however, to use both acids sequentially. The final solution thus obtained contains only the REE and Y, with minor amounts of Al, Ba, Ca, Sc, Sr and Ti. Elements that potentially interfere, such as Be, Co, Cr, Fe, Mn, Th, U, V and Zr, are virtually eliminated. Inductively-coupled argon plasma atomic-emission spectroscopy can then be used for a final precise and accurate measurement. The method can also be used with other instrumental methods of analysis.

Talanta↗

USGS1996

Chemistry and potential mutagenicity of humic substances in waters from different watersheds in Britain and Ireland

Humic substances are amorphous organic macromolecules responsible for the hue of natural waters. They are also known to be precursors of mutagens formed on chlorination prior to distribution of drinking water. In this study humic substances from the waters of primary streams, from major rivers, and from reservoirs were isolated and fractionated into humic acids (HA), fulvic acids (FA) and XAD-4 acids using columns of XAD-8 and of XAD-4 resins in tandem, and the fractions from the different sources were chlorinated and assayed for mutagenicity. CPMAS 13C NMR spectroscopy showed marked differences in compositions not only between HA, FA, and XAD-4 acids from the same water samples, but also between the same fractions from water samples from different watersheds. There were found to be strong similarities between the fractions from watersheds which had closely related soil types. Aromaticity was greatest in HAs, and lowest in XAD-4 acids, and carboxyl contents and aliphatic character were greatest in the XAD-4 acids. Carbon content decreased in the order HA > FA > XAD-4 acids, and amino acids and neutral sugars contents decreased in the order HA > XAD-4 > FA. Titration data complemented aspects of the NMR data, demonstrating that carboxyl content decreased in the order XAD-4 acids > FA > HA, and indicated that phenolic character was highest in HAs and lowest in the XAD-4 acids. All samples tested gave rise to bacterial mutagens on chlorination. Although the mutagenicities were of the same order of magnitude for the chlorinated humic samples from the different sources, the samples which showed the greatest number of revertant bacterial colonies were from the Thames and Trent, large rivers with humic materials from diverse environments, and relatively high in amino acid contents.

Water Research↗

USGS1977

The organic geochemistry of black sedimentary barite: Significance and implications of trapped fatty acids

Fatty acids isolated in sedimentary black barite (BaSO 4 ) from Arkansas and Nevada were identified by gas chromatography-mass spectroscopy. The dominant or major fatty acids found in these beds of barite are C 16:0 , C 18:0 , and C 18:1 . The occurrence and distribution of these acids in this type of rock may serve as “molecular fingerprints” of microbial biogeochemical processes. The organic matter and associated microorganisms are shown to be trapped within the finely crystalline barite, thus forming a closed system for microbial diagenesis. Important differences that occur in the distribution of the lesser or minor fatty acids probably result from: (1) the nature of the progenitor organic detritus in the environment of barite deposition: and (2) the subsequent degree of microbiological alteration of the parent organic debris swept into and trapped in the depositional environment. Three general models of sedimentary environments are proposed in which anoxic conditions may prevail and where barium sulfate (BaSO 4 ) may precipitate: (1) in a silled basin with semi-restricted circulation; (2) on an outer continental shelf where the slope is encroached upon by water of the oxygen minimum layer; (3) on a low-energy, inner shelf or semi-restricted embayment impinged by a wedge of anoxic water. The major geochemical and geological parameters which are believed to be the significant factors controlling the formation and high grade of these organic-rich, black bedded barites are: (1) a unique source of barium-rich fluid that only contains trace amounts of other elements; (2) the presence of an anoxic bottom environment within the depositional basin; (3) a reflux source of sulfate ion; (4) an adequate source of organic matter. The results of this study may serve as guidelines for future exploration in similar, untested sedimentary basins, especially those with rocks of middle Paleozoic age.

Arkansas, Nevada↗