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At least 289 records · Page 16Linked to original sources
USGS1990

Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density.

Geochimica et Cosmochimica Acta↗
USGS1990

Age determinations and growth rates of Pacific ferromanganese deposits using strontium isotopes

87 Sr 86 Sr ratios, trace element and REE compositions, and textural characteristics were determined for three hydrogenetic Fe-Mn crusts, one hydrothermal deposit, and two mixed hydrothermalhydrogenetic crusts from the Pacific. The Sr isotope data are compared to the Sr seawater curve for the Cenozoic to determine the ages and growth rates of the crusts. The 87 Sr 86 Sr in the crusts does not increase monotonically with depth as expected if the Sr were solely derived from seawater and perfectly preserved since deposition. This indicates post-depositional exchange of Sr or heterogeneous sources for the Sr originally contained in the crusts. Textures of hydrogenetic crusts generally correlate with Sr isotopic variations. The highest porosity intervals commonly exhibit the highest 87 Sr 86 Sr ratios, indicating exchange with younger seawater. Intervals with the lowest porosity commonly have lower 87 Sr 86 Sr and may preserve the original Sr isotopic ratios. Minimum ages of crust growth inception were calculated from dense, low porosity intervals. Growth of the hydrogenetic crusts began at or after 23 Ma, although their substrates are Cretaceous. Estimated average growth rates of the three hydrogenetic crusts vary between 0.9 and 2.7 mm/Ma, consistent with published rates determined by other techniques. Within the Marshall Islands crust, growth rates for individual layers varied greatly between 1.0 and 5.4 mm/Ma. For one crust, very low 87 Sr 86 Sr ratios occurred in detrital-rich intervals. Hydrothermal Fe-Mn oxide from the active Lau Basin back-arc spreading axis (Valu Fa Ridge) has an 87 Sr 86 Sr ratio with a predominantly seawater signature ( 87 Sr 86 Sr 87 Sr 86 Sr 0.709196 "> 0.709196 ), indicating a maximum age of 0.9 Ma. One crust from an off-axis seamount west of Gorda Ridge may have begun precipitating hydrogenetically at 0.5 Ma (0.709211), and had increasing hydrothermal or volcanic input in the top half of the crust, indicated by a significantly lower 87 Sr 86 Sr ratio (0.709052).

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USGS1991

Quartz dissolution in organic-rich aqueous systems

Organic electrolytes are a common component of natural waters and are known to be important in many rock-water interactions. The influence of organic electrolytes on silica mobility, quartz solubility, and quartz dissolution kinetics, however, is less well understood. While there is mounting evidence supporting the presence of an aqueous organic-silica complex in natural waters, the significance of this species is difficult to characterize because of competing interactions in mixed inorganic-organic electrolyte environments. In the experiments reported here, the kinetics of quartz dissolution in dilute aqueous organic-acid solutions between 25 and 70°C were investigated to determine the influence of both organic and inorganic electrolytes. Batch-reactor dissolution experiments in inorganic and organic electrolyte solutions were designed to investigate the hypothesis that organic acids at circum-neutral pH accelerate the dissolution and increase the solubility of quartz in water. Results suggest that multi-functional organic acids such as citrate and oxalate accelerate quartz dissolution by decreasing the activation energy by approximately 20%. The increase in dissolution rate was accompanied by a 100% increase in apparent quartz solubility at 25°C. Experiments using inorganic electrolytes, in contrast, increase the rate of quartz dissolution without decreasing the activation energy, and without increasing solubility. From these data, a model for both a solution complex between dissolved organic acid and monomeric silicic acid, and an activated complex on quartz surfaces is proposed. The model suggests that dissolved organic compounds in natural waters at near-neutral pH and low temperatures are capable of accelerating the dissolution of quartz and increasing its solubility.

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USGS1991

U-series ages of solitary corals from the California coast by mass spectrometry

The purpose of this study is to evaluate the feasibility of dating fossil solitary corals from Pleistocene marine strandlines outside tropical latitudes using the recently developed high sensitivity, high-precision U-series technique based on thermal-ionization mass-spectrometry (TIMS). The TIMS technique is much more efficient than conventional a spectrometry and, as a result, multiple samples of an individual coral skeleton, or different specimens from the same bed can be analyzed. Detached and well-rounded fossil specimens of the solitary coral Balanophyllia elegans were collected from relict littoral deposits on emergent marine terraces along the California coast at Cayucos terrace (elevation 8 m, previously dated at 124 and 117 Ky by α counting), Shell Beach terrace (elevation about 25 m, previously undated), Nestor terrace, San Diego (elevation 23 m, previously dated at 131 to 109 Ky ), Bird Rock terrace, San Diego ( elevation 8 m, previously dated at 81 Ky ). Attached living specimens were collected from the intertidal zone on the modern terrace at Moss Beach. Concentrations of 232 Th in both living and fossil specimens are much higher than in reef-building corals (12 to 624 pmol/g vs. 0.1 to 1.6 pmol/g, respectively). However, because 230 Th/ 232 Th in Balanophyllia elegans are very low (2.22 × 10 −3 to 4.33 × 10 −4 ), the high 232 Th concentrations have negligible effect on the 230 Th- 234 U dates. The high 232 Th concentration in the living specimen (33.1 pmol/g) indicates that a significant amount of 232 Th is incorporated in the aragonitic skeleton during growth, or attached to clay-sized silicates trapped in the skeletal material. The calculated initial 234 U activities in the fossil specimens of Balanophyllia elegans are higher than the 234 U activity in modern seawater or in the modern specimen. The higher initial activities could possibly reflect the influx of 234 U-enriched continental water into Pleistocene coastal waters, or it could reflect minor diagenetic alteration, a persistent and fundamental problem in dating all corals. Samples from a compound specimen from the Cayucos terrace were subjected to different preparation procedures. Samples prepared by a standard acid washing procedure yielded 230 Th- 234 U ages of 125, 123, and 122 Ky, whereas samples prepared by an abbreviated procedure without acid washing yield significantly lower ages of 113 and 112 Ky. Two other specimens from the same bed yielded 230 Th- 234 U ages of 118 and 115 Ky. Also, two specimens from a stratigraphically higher bed yielded ages of 120 and 117 Ky, and three specimens from a lower bed yield ages of 115, 113, and 101 Ky. Nine of the twelve ages of the treated samples from the Cayucos terrace range from 125 to 113 Ky. However, the ages do not follow the stratigraphie order. Two possible interpretations are ( 1 ) the age of the terrace deposit is 125 Ky and all younger ages reflect variable diagenetic alteration or (2) the age of the terrace is 125 to 113 Ky and the ages reflect sediment reworking over a period of 12 Ky. Three specimens from a single bed on the Shell Beach terrace yield ages of 126, 122, and 121 Ky, similar to the older ages from Cayucos. The ages of solitary corals from the Cayucos and Shell Beach terraces are similar to ages of reef-building corals from terraces at numerous tropical localities. These are correlated with the last interglacial sea-level highstand, which probably stood 2 to 10 m above present sea level. The youngest ages and present elevations of the Cayucos and Shell Beach terraces yield tectonic uplift rates of 0.01 and 0.15 m/Ky, respectively, assuming the original elevation of each terrace was 7 m. Four specimens from the basal gravel on the Nestor terrace yielded ages of 145, 143, 137, and 133 Ky. The three oldest ages, however, are older than that associated with the last interglacial. The possible explanations for these older ages are ( 1 ) diagenic alteration or ( 2 ) the Nestor terrace deposits reflect in some way a poorly documented early phase of the last interglacial sea level high stand.

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USGS1991

Iodine-xenon, chemical, and petrographie studies of Semarkona chondrules: Evidence for the timing of aqueous alteration

We have performed INAA, petrographie, and noble gas analyses on seventeen chondrules from the Semarkona meteorite (LL3.0) primarily to study the relationship of the I-Xe system to other measured properties. We observe a range of ≥10 Ma in apparent I-Xe ages. The three latest apparent ages fall in a cluster, suggesting the possibility of a common event. The initial 129 I/ 127 I ratio ( R 0 ) is apparently related to chondrule type and/or mineralogy, with nonporphyritic and pyroxene-rich chondrules showing evidence for lower R 0 'S (later apparent I-Xe ages) than porphyritic and olivine-rich chondrules. In addition, chondrules with sulfides on or near the surface have lower R 0 S than other chondrules. The 129 Xe/ 132 Xe ratio in the trapped Xe component anticorrelates with R 0 , consistent with evolution of a chronometer in a closed system or in multiple similar systems. On the basis of these correlations, we conclude that the variations in R 0 represent variations in ages, and that later event(s), possibly aqueous alteration, preferentially affected chondrules with nonporphyritic textures and/or sulfide-rich exteriors about 10 Ma after the formation of the chondrules.

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USGS1991

Gaylussite formation at Mono Lake, California

The salinity of Mono Lake has steadily increased since 1941 from 50%. to about 90%. due to diversion of tributary streams. This increase has resulted in the newly discovered precipitation of gaylussite (Na 2 Ca(CO 3 ) 2 · 5H 2 O). Chemical modeling of the lake water using Pitzer equations suggests that gaylussite has been forming year round since about 1970 when the salinity first exceeded 80%., and that it was earlier forming intermittently at lower salinities in the winter shortly after diversion began, breaking down incongruently to aragonite during summers. Lake water appears to remain at a constant 9-fold supersaturation with aragonite at all salinities, perhaps buffered by monohydrocalcite which appears to be just at saturation for all salinities. Other saline lakes also appear to be buffered by monohydrocalcite.

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USGS1991

Melting and thermodynamic properties of pyrope (Mg3Al2Si3O12)

The heat capacity of Mg 3 Al 2 Si 3 O 12 glass has been measured from 10 to 1000 K by adiabatic and differential scanning calorimetry. The heat capacity of crystalline pyrope has been determined from drop-calorimetry measurements between 820 and 1300 K. From these and previously published results a consistent set of thermodynamic data is presented for pyrope and Mg 3 Al 2 Si 3 O 12 glass and liquid for the interval 0–2000 K. The enthalpy of fusion at 1570 ± 30 "> 1570 ± 30 K, the metastable congruent 1-bar melting point, is 241 ± 12 kJ/mol "> 241 ± 12kJ/mol .

Geochimica et Cosmochimica Acta↗
USGS1991

Strontium isotopic constraints on the origin of ore-forming fluids of the Viburnum Trend, southeast Missouri

We have measured 87 Sr 86 Sr "> 87Sr86Sr and Rb and Sr concentrations in several minerals, primarily sulfides, spanning the paragenesis of hydrothermal mineralization in the Viburnum Trend in southeast Missouri. Separate measurements were made for fluid inclusions opened by crushing or thermal decrepitation and for the solids. For comparison, measurements were also made on samples of probable local aquifers, the Bonneterre Formation and the Lamotte Sandstone. For some of the samples, concentrations of K, Ca, Cl, Na, and Mg are also reported. In several cases 87 Sr 86 Sr ratios "> 87Sr86Srratios are different (higher) in the solids than in the fluid inclusions. We have investigated the possibility that either type of sample gives spurious results, e.g., that the fluid inclusions are secondary or contaminated by host dolomite, or that Sr in the solids reflects a detrital rather than an authigenic source. Consideration of mass balance, overall solute chemistry, and examination of non-sulfide dissolution residue, however, suggests that both types of sample reflect primary fluid Sr composition. We thus adopt the working hypothesis that Sr isotopic composition in fluids at the time of hydrothermal mineralization was highly variable. The observed results for the Viburnum Trend do not conform well to expected trends for Mississippi Valley-type (MVT) mineralization based primarily on analyses of gangue carbonates, barite, and fluorite. Fluid inclusion Sr in some of the Viburnum Trend samples is more radiogenic than in the host dolomite but only moderately so; in other samples, notably main-stage octahedral galena, fluid inclusion Sr composition is within the range observed for the host dolomite. In contrast, Sr in some of the sulfides is very radiogenic, much more so than previously reported for MVT minerals, and is very radiogenic early in the paragenesis (pyrite, chalcopyrite, sphalerite), less radiogenic during main-stage ore deposition, and again more radiogenic in later paragenetic stages.

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USGS1991

Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn 2+ and Cd 2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd 2 Mn 3 4+ O 8 , Mn 2+ 2 Mn 4+ 3 O 8 , MnO 2 (ramsdellite), and CdCO 3 . Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn 2+ Mn 2 3+ O 4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35°C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn 4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn 4+ oxide formation in the presence of Cd 2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn 2 O 4 Int , an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd 2+ during the titration, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn 3+ ions. The Mn 2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn 2+ to Mn 4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd 2 Mn 3 O 8 and MnO 2 increased at the expense of other precipitate components.

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USGS1991

Rare earth elements in Japan Sea sediments and diagenetic behavior of Ce/Ce∗: results from ODP Leg 127

The relative effects of paleoceanographic and paleogeographic variations, sediment lithology, and diagenetic processes on the recorded rare earth element (REE) chemistry of Japan Sea sediments are evaluated by investigating REE total abundances and relative fractionations in 59 samples from Ocean Drilling Program Leg 127. REE total abundances (ΣREE) in the Japan Sea are strongly dependent upon the paleoceanographic position of a given site with respect to terrigenous and biogenic sources. REE concentrations at Site 794 (Yamato Basin) overall correspond well to aluminosilicate chemical indices and are strongly diluted by SiO 2 within the late Miocene-Pliocene diatomaceous sequence. Eu/Eu* values at Site 794 reach a maximum through the diatomaceous interval as well, most likely suggesting an association of Eu/Eu* with the siliceous component, or reflecting slight incorporation of a detrital feldspar phase. ΣREE at Site 795 (Japan Basin) also is affiliated strongly with aluminosilicate phases, yet is diluted only slightly by siliceous input. At Site 797 (Yamato Basin), REE is not as clearly associated with the aluminosilicate fraction, is correlated moderately to siliceous input, and may be sporadically influenced by detrital heavy minerals originating from the nearby rifted continental fragment composing the Yamato Rise. The biogenic influence is largest at Site 794, moderately developed at Site 797, and of only minor importance at Site 795, reflecting basinal contrasts in productivity such that the Yamato Basin records greater biogenic input than the Japan Basin, while the most productive waters overlie the easternmost sequence of Site 794. Ce/Ce* profiles at all three sites increase monotonically with depth, and record progressive diagenetic LREE fractionation. The observed Ce/Ce* record does not respond to changes in oxygenation state of the overlying water, and Ce/Ce* correlated slightly better with depth than with age. The downhole increase in Ce/Ce* at Site 794 and Site 797 is a passive response to diagenetic transfer of LREE (except Ce) from sediment to interstitial water. At Site 795, the overall lack of correlation between Ce/Ce* and L (l n /Yb n suggests that other processes are occurring which mask the diagenetic behavior of all LREEs. First-order calculations of the Ce budget in Japan Sea waters and sediment indicate that ~20% of the excess Ce adsorbed by settling particles is recycled within the water column, and that an additional ~38% is recycled at or near the seafloor (data from Masuzawa and Koyama, 1989). Thus, because the remaining excess Ce is only ~10% of the total Ce, there is not a large source of Ce to the deeply buried sediment, further suggesting that the downhole increase in Ce/Ce* is a passive response to diagenetic behavior of the other LREEs. The REE chemistry of Japan Sea sediment therefore predicts successive downhole addition of LREEs to deeply-buried interstitial waters.

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USGS1991

Age and geomorphic history of Meteor Crater, Arizona, from cosmogenic 36Cl and 14C in rock varnish

Using cosmogenic 36 Cl buildup and rock varnish radiocarbon, we have measured the exposure age of rock surfaces at Meteor Crater, Arizona. Our 36 Cl measurements on four dolomite boulders ejected from the crater by the impact yield a mean age of 49.7 ± 0.85 ka, which is in excellent agreement with an average age of 49 ± 3 ka obtained from thermoluminescence studies on shock-metamorphosed dolomite and quartz. These ages are supported by undetectably low 14 C in the oldest rock varnish sample.

Geochimica et Cosmochimica Acta↗
USGS1991

An aem-tem study of weathering and diagenesis, Abert Lake, Oregon: I. Weathering reactions in the volcanics

Abert Lake in south-central Oregon provides a site suitable for the study of sequential weathering and diagenetic events. In this first of two papers, transmission electron microscopy was used to characterize the igneous mineralogy, subsolidus alteration assemblage, and the structural and chemical aspects of silicate weathering reactions that occur in the volcanic rocks (basalts, basaltic andesites, and dacitic/ rhyolitic extrusive and pyroclastics) that outcrop around the lake. Olivine and pyroxene replacement occurred topotactically, whereas feldspar and glass alteration produced randomly oriented smectite in channels and cavities. The tetrahedral, octahedral, and interlayer compositions of the weathering products, largely dioctahedral smectites, varied with primary mineral composition, rock type, and as the result of addition of elements released from adjacent reaction sites. Weathering of the highly evolved, Fe-rich Jug Mountain complex at the north end of the lake produced a homogeneous smectite assemblage that contrasts with the heterogeneous smectite assemblage replacing the volcanics along the eastern margin of the lake. The variability within and between the smectite assemblages highlights the microenvironmental diversity, fluctuating redox conditions, and variable solution chemistry associated with mineral weathering reactions in the surficial environment. Late-stage exhalative and aqueous alteration of the volcanics redistributed many components and formed a variety of alkali and alkali-earth carbonate, chloride, sulfate, and fluoride minerals in vugs and cracks. Overall, substantial Mg, Si, Na, Ca, and K are released by weathering reactions that include the almost complete destruction of the Mg-smectite that initially replaced olivine. The leaching of these elements from the volcanics provides an important source of these constituents in the lake water. The nature of subsequent diagenetic reactions resulting from the interaction between the materials transported to the lake and the solution will be described in part II ( Banfield et al., 1991).

Geochimica et Cosmochimica Acta↗
USGS1992

Extraction of whole versus ground source rocks: Fundamental petroleum geochemical implications including oil-source rock correlation

In petroleum geochemistry, extractable hydrocarbons (HCs) in source rocks have typically been studied by grinding the rock to a fine powder (≤100 mesh) and then extracting the HCs from the rock with a solvent. This procedure carries the implicit assumption that the HCs are homogeneously distributed throughout the rock. However, sequential Soxhlet extractions of whole (unpowdered) source rocks have shown that progressive extracts from the same rock can be quite different and may not even correlate with each other. A crude oil-like material clearly has been fractionated from indigenous bitumen in these rocks, has moved to cracks and parting laminae in the rocks, is ready for expulsion from the rocks, and is thus most accessible to the first extracting solvents. This process, which we believe is largely due to HC gases and carbon dioxide generated over all maturation ranks in source rocks, carries petroleum geochemical implications of a fundamental nature for oil-source rock correlations and gives insight into primary migration mechanisms, origin of oil deposits, and use of maturity and organic-facies indices.

Geochimica et Cosmochimica Acta↗
USGS1992

Laser microprobe analyses of noble gas isotopes and halogens in fluid inclusions: Analyses of microstandards and synthetic inclusions in quartz

Ar, Kr, Xe, Cl, Br, I, and K abundances and isotopic compositions have been measured in microscopic fluid inclusions in minerals by noble gas mass spectrometry following neutron irradiation and laser extraction. The laser microprobe noble gas mass spectrometric (LMNGMS) technique was quantified by use of microstandards, including air-filled capillary tubes, synthetic basalt glass grains, standard hornblende grains, and synthetic fluid inclusions in quartz. Common natural concentrations of halogens (Cl, Br, and I) and noble gases (Ar and Kr) in trapped groundwaters and hydrothermal fluids can be analyzed simultaneously by LMNGMS in as little as 10 −11 L of inclusion fluid, with accuracy and precision to within 5–10% for element and isotope ratios. Multicomponent element and isotope correlations indicate contaminants or persistent reservoirs of excess Xe and/or unfractionated air in some synthetic and natural fluid inclusion samples. LMNGMS analyses of natural fluid inclusions using the methods and calibrations reported here may be used to obtain unique information on sources of fluids, sources of fluid salinity, mixing, boiling (or unmixing), and water-rock interactions in ancient fluid flow systems.

Geochimica et Cosmochimica Acta↗
USGS1992

Laser microprobe analyses of Cl, Br, I, and K in fluid inclusions: Implications for sources of salinity in some ancient hydrothermal fluids

The relative concentrations of Cl, Br, I, and K in fluid inclusions in hydrothermal minerals were measured by laser microprobe noble gas mass spectrometry on irradiated samples containing 10 −10 to 10 −8 L of fluid. Distinctive halogen signatures indicate contrasting sources of fluid salinity in fluid inclusions from representative “magmatic” (St. Austell), “metamorphic” (Alleghany), and “geothermal” (Creede, Salton Sea) aqueous systems. Br/Cl mol ratios are lowest at Salton Sea (0.27–0.33 × 10 −3 ), where high salinities are largely due to halite dissolution; intermediate at St. Austell (0.85 × 10 −3 ), possibly representative of magmatic volatiles; and highest (near that of seawater) at Creede (1.5–2.1 × 10 −3 ) and Alleghany (1.2–2.4 × 10 −3 ), where dissolved halogens probably were leached from volcanic and (or) nonevaporitic sedimentary rocks. I C1 "> IC1 mol ratios are lowest (near that of seawater) at Creede (1–14 × 10 −6 ), possibly because organisms scavenged I during low temperature recharge; intermediate at Salton Sea (24–26 × 10 −6 ) and St. Austell (81× 10 −6 ); and highest at Alleghany (320–940 × 10 −6 ), probably because the fluids interacted with organic-rich sediments at high temperatures before being trapped. K Cl "> KCl mol ratios indicate disequilibrium with respect to hypothetical feldspathic alkali-Al-silicate mineral buffers at fluid inclusion trapping temperatures at Creede, and large contributions of (Na, K)-bicarbonate to total fluid ionic strength at Alleghany. Significant variations in Cl/Br/I/K ratios among different fluid inclusion types are correlated with previously documented mineralization stages at Creede, and with the apparent oxidation state of dissolved carbon at Alleghany. The new data indicate that Cl/ Br/I ratios in hydrothermal fluid inclusions vary by several orders of magnitude, as they do in modern surface and ground waters. This study demonstrates that halogen signatures of fluid inclusions determined by microanalysis yield important information about sources of fluid salinity and provide excellent definition of fluid reservoirs and tracers of flow and interaction in ancient hydrothermal systems.

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USGS1992

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H 2 C 2 O 4 · 2H 2 O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230–750°C, with bulk fluid densities in the range 0.01–0.53 g/cm 3 . Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230–350°C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO 2 + CO + 3 H 2 O . A process of the form CO + H 2 O = CO 2 + H 2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H 2 O-CO 2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH 4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600–650°C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H 2 O-CO 2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions.

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.

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