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At least 271 records · Page 15Linked to original sources
USGS1989

Coprecipitation and redox reactions of manganese oxides with copper and nickel

Open-system, continuous-titration experiments have been done in which a slow flux of ∼0.02 molar solution of Mn 2+ chloride, nitrate, or perchlorate with Cu 2+ or Ni 2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu 2 Mn 3 O 8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, βMnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO 2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included βMnOOH, Ni(OH) 2 , and the same two forms of MnO 2 . The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu 2+ and Ni 2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems.

Geochimica et Cosmochimica Acta↗
USGS1989

Organic geochemistry and brine composition in Great Salt, Mono, and Walker Lakes

Samples of Recent sediments, representing up to 1000 years of accumulation, were collected from three closed basin lakes (Mono Lake, CA, Walker Lake, NV, and Great Salt Lake, UT) to assess the effects of brine composition on the accumulation of total organic carbon, the concentration of dissolved organic carbon, humic acid structure and diagenesis, and trace metal complexation. The Great Salt Lake water column is a stratified Na-Mg-Cl-SO 4 brine with low alkalinity. Algal debris is entrained in the high density (1.132–1.190 g/cc) bottom brines, and in this region maximum organic matter decomposition occurs by anaerobic processes, with sulfate ion as the terminal electron acceptor. Organic matter, below 5 cm of the sediment-water interface, degrades at a very slow rate in spite of very high pore-fluid sulfate levels. The organic carbon concentration stabilizes at 1.1 wt%. Mono Lake is an alkaline (Na-CO 3 -Cl-SO 4 ) system. The water column is stratified, but the bottom brines are of lower density relative to the Great Salt Lake, and sedimentation of algal debris is rapid. Depletion of pore-fluid sulfate, near l m of core, results in a much higher accumulation of organic carbon, approximately 6 wt%. Walker Lake is also an alkaline system. The water column is not stratified, and decomposition of organic matter occurs by aerobic processes at the sediment-water interface and by anaerobic processes below. Total organic carbon and dissolved organic carbon concentrations in Walker Lake sediments vary with location and depth due to changes in input and pore-fluid sulfate concentrations. Nuclear magnetic resonance studies ( 13 C) of humic substances and dissolved organic carbon provide information on the source of the Recent sedimentary organic carbon (aquatic vs. terrestrial), its relative state of decomposition, and its chemical structure. The spectra suggest an algal origin with little terrestrial signature at all three lakes. This is indicated by the ratio of aliphatic to aromatic carbon and the absence of chemical structures indicative of the lignin of vascular plants. The dissolved organic carbon of the Mono Lake pore fluids is structurally related to humic acid and is also related to carbohydrate metabolism. The alkaline pore fluids, due to high pH, solubilize high molecular weight organic matter from the sediments. This hydrophilic material is a metal complexing agent. Despite very high algal productivities, organic carbon accumulation can be low in stratified lakes if the anoxic bottom waters are hypersaline with high concentrations of sulfate ion. Labile organic matter is recycled to the water column and the sedimentary organic matter is relatively nonsusceptible to bacterial metabolism. As a result, pore-fluid dissolved organic carbon and metal-organic complexation are low.

Geochimica et Cosmochimica Acta↗
USGS1989

Re-Os, Rb-Sr, and O isotopic systematics of the Archean Kolar schist belt, Karnataka, India

The Re-Os, Rb-Sr, and O isotopic compositions of mafic and ultramafic amphibolites, gold ores, and granitic gneisses of the circa 2700 Ma Kolar schist belt reveal at least two episodes of post-magmatic alteration that affected these systems. The Re-Os isotopic systematics of many of the rocks of the belt indicate that Os was introduced to the area via fluids that carried very radiogenic Os ( 187 Os 186 Os 2.4Ga > 39 "> 187 Os 186 Os 2.4Ga > 39 ). The source of the radiogenic Os was likely ancient crust. On an outcrop scale, this alteration is also characterized by relatively minor additions of excess 87 Sr and δ 18 O values higher than magmatic. The Rb-Sr systematics of most of these rocks are consistent with closed-system behavior since a period between 2700 and 2400 Ma ago, indicating that the alteration event likely occurred no later than the early Proterozoic. In contrast to this late Archean or early Proterozoic alteration, samples of several komatiitic amphibolites have very 187 Os-depleted compositions, indicating that open-system behavior also occurred at a much later time. This alteration may have been caused by surficial weathering or the interaction of the rocks with fluids bearing unradiogenic Os. Results suggest that the Re-Os system may have only limited utility for geochronologic applications in regions for which post-crystallization noble metal mineralization is evident (e.g., gold ores). In such regions, however, the system may have an important application in assessing the timing and the ultimate sources of noble metal additions.

Geochimica et Cosmochimica Acta↗
USGS1989

Crystallization of accessory phases in magmas by local saturation adjacent to phenocrysts

Accessory minerals commonly occur attached to or included in the major crystalline phases of felsic and some intermediate igneous rocks. Apatite is particularly common as inclusions, but Fe-Ti oxides, pyrrhotite, zircon, monazite, chevkinite and xenotime are also known from silicic rocks. Accessories may nucleate near the host crystal/ liquid interface as a result of local saturation owing to formation of a differentiated chemical boundary layer in which accessory mineral solubility would be lower than in the surrounding liquid. Differentiation of this boundary layer would be greatest adjacent to ferromagnesian phenocrysts, especially Fe-Ti oxides; it is with oxides that accessories are most commonly associated in rocks. A boundary layer may develop if the crystal grows more rapidly than diffusion can transport incorporated and rejected elements to and from the phenocryst. Diffusion must dominate over convection as a mode of mass transfer near the advancing crystal/liquid interface in order for a boundary layer to exist. Accumulation of essential structural constituent elements of accessory minerals owing to their slow diffusion in evolved silicate melt also may force local saturation, but this is not a process that applies to all cases. Local saturation is an attractive mechanism for enhancing fractionation during crystallization differentiation. If accessory minerals attached to or included in phenocrysts formed because of local saturation, their host phenocrysts must have grown rapidly when accessories nucleated in comparison to lifetimes of magma reservoirs. Some inconsistencies remain in a local saturation origin for accessory phases that cannot be evaluated without additional information.

Geochimica et Cosmochimica Acta↗
USGS1989

Influence of Shimada Seamount on sediment composition in the eastern tropical North Pacific

Shimada Seamount is a large, young volcanic edifice in the east-central Pacific that is not associated with any active spreading center or known hot spot. The sediments on the abyssal plain surrounding Shimada Seamount consist of pelagic clay with ferromanganese micronodules and zeolites. The pelagic clay is mostly barren of microfossils except for a few occurrences of highly corroded specimens of Radiolaria and diatoms. Eolian terrigenous material is the dominant component of the pelagic clay to a depth of at least 8 m below sea floor, with minor contributions from volcanic debris and hydrothermal and hydrogenous sources. The average amount of basaltic debris is only 0.25%, but concentrations are as high as 10% in some samples. The average hydrothermal component (metalliferous sediment) is 8.8% with a maximum of about 13% at 7.5 m below sea floor in one core. The hydrogenous component, mostly as ferromanganese micronodules, averages 4.1% with a maximum of 5.6%. There is no calcareous biogenic debris and essentially no siliceous biogenic debris. In the past, a decrease in hydrothermal components through time may have been the result of a decrease in relative importance of hydrothermal influences, or an increase in the flux of terrigenous debris transported by the northeast trade winds. Because volcanic activity is still active on Shimada Seamount, or has been in the recent past, the observed increase in relative abundance of terrigenous components probably was the result of increased wind transport and not decreased hydrothermal activity. Shimada Seamount may be an important local source of metalliferous sediment in the eastern equatorial North Pacific, and may have been an even more important source in the past.

Geochimica et Cosmochimica Acta↗
USGS1989

Organic markers as source discriminants and sediment transport indicators in south San Francisco Bay, California

Sediment samples from nearshore sites in south San Francisco Bay and from streams flowing into that section of the Bay have been characterized in terms of their content of biogenic and anthropogenic molecular marker compounds. The distributions, input sources, and applicability of these compounds in determining sediment movement are discussed. By means of inspection and multivariate analysis, the compounds were grouped according to probable input sources and the sampling stations according to the relative importance of source contributions. A suite of polycyclic aromatic hydrocarbons (PAHs) dominated by pyrene, fluoranthene and phenanthrene, typical of estuarine environments worldwide, and suites of mature sterane and hopane biomarkers were found to be most suitable as background markers for the Bay. A homologous series of long-chain n-aldehydes (C12-C32) with a strong even-over-odd carbon number dominance in the higher molecular weight range and the ubiquitous n-alkanes (n-C24-C34) with a strong odd-over-even carbon number dominance were utilized as terrigenous markers. Several ratios of these terrigenous and Bay markers were calculated for each station. These ratios and the statistical indicators from the multivariate analysis point toward a strong terrigenous signal in the terminus of South Bay and indicate net directional movement of recently introduced sediment where nontidal currents had been considered to be minimal or nonexistent and tidal currents had been assumed to be dominant.

California↗
USGS1989

Groundwater chemistry and water-rock interactions at Stripa

Groundwaters from near surface to a depth of 1232 m in the Stripa granite have been sampled and analyzed for major and trace constituents. The groundwater composition consists of two general types: a typical recharge water of Ca-HCO 3 type (<300 m depth) and a deeper Na-Ca-Cl type (>700 m depth) of high pH (8–10) that reaches a maximum of 1250 mg/L in total dissolved solids (TDS). Intermediate depths show mixtures of the two types that are highly fracture-dependent rather than depth-dependent. Any borehole can vary significantly and erratically in TDS for either a horizontal or vertical direction. The general transition from Ca-HCO 3 type to Na-Ca-Cl type correlates with the depth profile for hydraulic conductivity that drops from 10 −8 m/s to 10 −11 m/s or lower. Thermomechanical stress (from heater experiments) clearly shows an effect on the groundwater composition that could be caused by changing flow paths, leakage of fluid inclusions or both. Dissolution and precipitation of calcite, fluorite and barite, aluminosilicate hydrolysis, and addition of a saline source (possibly fluid inclusion leakage) play the major roles in defining the groundwater composition. The low permeability of the Stripa granite has produced a groundwater composition that appears intermediate between the dilute, shallow groundwaters typical of recharge in a crystalline rock terrain and the saline waters and brines typical of cratonic shield areas at depth.

Geochimica et Cosmochimica Acta↗
USGS1989

Assessment of the U-Th-Pb system in two Archean metabasalts: Deciphering the complex histories of sulphides and silicates using acid leaching methods

A U-Th-Pb study of Archean metabasalts from two greenstone belts in the eastern Wawa Subprovince of the Canadian shield indicated variable disturbances had occurred in both whole rock systems. Changes in the Pb content appear to predominate over loss of parent elements, and meaningful Pb isochron ages could not be obtained from either of the metabasalts. Detailed leaching experiments on the rocks and analysis of associated disseminated sulphides indicate that the Pb isotopic compositions of the whole rocks are dominated by updated, but for the most part cogenetic, sulphides. Model ages for Pb released by sulphides and metabasalt acid leaches suggest that the sulphide Pb has been updated or remobilized during discrete (thermal ?) episodes. The validity of the inferred events is supported by ages indicated by other isotopic systems for nearby rocks. The silicate residues of the acid leached volcanics give well-defined Pb isochron ages. The Gamitagama belt metabasalt has a Pb isochron age of 2694 ± 54 Ma . Zircons from this rock unit have been dated by U-Pb at 2691 Ma, demonstrating that the acid leaching technique on whole rocks can isolate residues which give meaningful ages. Sulphides in this metabasalt appear to be affected by an event at 2.55 Ga. A similar rock from the Michipicoten belt has undergone a multistage history and yields a Pb isochron age of 2761 ± 36 Ma , consistent with a zircon U-Pb date for overlying felsic metavolcanic rocks. Later events affecting this basalt occurred at approximately 2.4, 2.2 and 1.6 Ga. The results show that through acid leaching, the primary ages of metabasalts and their later overprinting histories can be approximated. Initial Pb ratios for these metabasalts have been estimated. It appears that both depleted and enriched mantle reservoirs contributed to volcanism in this area. Acid leaching, combined with measurement of U and Th contents, appears to be a useful tool for better understanding the Pb isotope systematics of Archean metabasalts.

Geochimica et Cosmochimica Acta↗
USGS1989

Reactive iron transport in an acidic mountain stream in Summit County, Colorado: A hydrologic perspective

A pH perturbation experiment was conducted in an acidic, metal-enriched, mountain stream to identify relative rates of chemical and hydrologic processes as they influence iron transport. During the experiment the pH was lowered from 4.2 to 3.2 for three hours by injection of sulfuric acid. Amorphous iron oxides are abundant on the streambed, and dissolution and photoreduction reactions resulted in a rapid increase in the dissolved iron concentration. The increase occurred simultaneously with the decrease in pH. Ferrous iron was the major aqueous iron species. The changes in the iron concentration during the experiment indicate that variation exists in the solubility properties of the hydrous iron oxides on the streambed with dissolution of at least two compartments of hydrous iron oxides contributing to the iron pulse. Spatial variations of the hydrologic properties along the stream were quantified by simulating the transport of a coinjected tracer, lithium. A simulation of iron transport, as a conservative solute, indicated that hydrologie transport had a significant role in determining downstream changes in the iron pulse. The rapidity of the changes in iron concentration indicates that a model based on dynamic equilibrium may be adequate for simulating iron transport in acid streams. A major challenge for predictive solute transport models of geochemical processes may be due to substantial spatial and seasonal variations in chemical properties of the reactive hydrous oxides in such streams, and in the physical and hydrologic properties of the stream.

Geochimica et Cosmochimica Acta↗
USGS1990

Actinide abundances in ordinary chondrites

Measurements of 244 Pu fission Xe, U, Th, and light REE (LREE) abundances, along with modal petrographic determinations of phosphate abundances, were carried out on equilibrated ordinary chondrites in order to define better the solar system Pu abundance and to determine the degree of variation of actinide and LREE abundances. Our data permit comparison of the directly measured Pu/ U ratio with that determined indirectly as ( Pu / Nd ) × ( Nd / U ) assuming that Pu behaves chemically as a LREE. Except for Guareña, and perhaps H chondrites in general, Pu concentrations are similar to that determined previously for St. Séverin, although less precise because of higher trapped Xe contents. Trapped 130 Xe 136 Xe "> 130 Xe 136 Xe ratios appear to vary from meteorite to meteorite, but, relative to AVCC, all are similar in the sense of having less of the interstellar heavy Xe found in carbonaceous chondrite acid residues. The Pu/U and Pu/Nd ratios are consistent with previous data for St. Séverin, but both tend to be slightly higher than those inferred from previous data on Angra dos Reis. Although significant variations exist, the distribution of our Th/U ratios, along with other precise isotope dilution data for ordinary chondrites, is rather symmetric about the CI chondrite value; however, actinide/(LREE) ratios are systematically lower than the CI value. Variations in actinide or LREE absolute and relative abundances are interpreted as reflecting differences in the proportions and/or compositions of more primitive components (chondrules and CAI materials?) incorporated into different regions of the ordinary chondrite parent bodies. The observed variations of Th/U, Nd/U, or Ce/U suggest that measurements of Pu/U on any single equilibrated ordinary chondrite specimen, such as St. Séverin, should statistically be within ±20–30% of the average solar system value, although it is also clear that anomalous samples exist.

Geochimica et Cosmochimica Acta↗
USGS1990

Carbon dioxide retention and carbon exchange on unsaturated Quaternary sediments

Retention of CO 2 on three air-dried and partly water-saturated glacial and eolian sediments was measured at 20°C for a range in, P CO 2 that commonly occurs in unsaturated zones. Ratios of the relative losses of CO 2 and 14 CO 2 from a surrogate atmosphere overlying the sediments were 1:1 for the dry condition. For the wet condition, those relative losses were generally ⪯ 1:2, indicating bicarbonateion formation and C-isotope exchange. Mass losses of CO 2 per surface area of sediment were similar for dry and wet conditions; however, CO 2 losses for the wet condition were 8 to 17 times greater than losses predicted by calcite equilibria. Occurrence of this comparatively large reservoir of immobile, exchangeable C in unsaturated zones can cause alteration of the C-isotope composition of soil CO 2 and of dissolved inorganic C in interstitial water, and needs to be considered when modeling 14 CO 2 movement in the unsaturated zone or when interpreting radiocarbon ages of infiltrating water.

Geochimica et Cosmochimica Acta↗
USGS1990

Mechanisms controlling Cu, Fe, Mn, and Co profiles in peat of the Filson Creek Fen, northeastern Minnesota

Filson Creek Fen, located in northeastern Minnesota, overlies a Cu-Ni sulfide deposit. A site in the fen was studied to evaluate the hydrogeochemical mechanisms governing the development of Fe, Mn, Co, and Cu profiles in the peat. At the study site, surface peat approximately 1 m thick is separated from the underlying mineralized bedrock by a 6–12 m thickness of lake and glaciofluvial sediments and till. Concentrations of Fe, Mn, Co, and Cu in peat and major elements in pore water delineate a shallow, relatively oxidized, Cu-rich zone overlying a deeper, reduced, Fe-, Mn-, and Co-rich zone within the peat. Sequential metal extractions from peat samples reveal that 40–55% of the Cu in the shallow zone is associated with organic material, whereas the remaining Cu is distributed between iron-oxide, sulfide, and residual fractions. Sixty to seventy percent of the Fe, Mn, and Co concentrated in the deeper zone occur in the residual phase. The metal profiles and associations probably result from non-steady-state input of metals and detritus into the fen during formation of the peat column. The enrichment of organic-associated Cu in the upper, oxidized zone represents a combination of Cu transported into the fen with detrital plant fragments and soluble Cu, derived from weathering of outcrop and subcrop of the mineral deposit, transported into the fen, and fixed onto organic matter in the peat. The variable stratigraphy of the peat indicates that weathering processes and surface vegetation have changed through time in the fen. The Fe, Mn, and Co maxima at the base of the peat are associated with a maximum in detrital matter content of the peat resulting from a transition between the underlying inorganic sedimentary environment to an organic sedimentary environment. The chemistry of sediments and ground water collected beneath the peat indicate that mobilization of metals from sulfide minerals in the buried mineral deposit or glacial deposits is minimal. Therefore, the primary source of Cu to the peat at the study site is outcrops and shallow subcrops of the mineral deposit adjacent to the fen.

Geochimica et Cosmochimica Acta↗
USGS1990

Coupled variations in helium isotopes and fluid chemistry: Shoshone Geyser Basin, Yellowstone National Park

Early studies of 3 He/ 4 He variations in geothermal systems have generally attributed these fluctuations to either differences in the source of the magmatic 3 He-rich helium or to local differences in the deep flux of magmatic 3 He-rich helium. Kennedy et al. (1987), however, show that near-surface processes such as boiling and dilution may also drastically affect 3 He 4 "> 3 He 4 He ratios of geothermal vapors. Helium isotope ratios were determined for several hot springs at Shoshone Geyser Basin of Yellowstone National Park for this study, along with other noble gas data. Stable isotope data and water and gas chemistry data for each spring were also compiled. The water chemistry indicates that there is one deep, hot thermal water in the area which is mixing with dilute meteoric water that has entered the system at depth. Spring HCO 3 − concentrations correlate with 3 He 4 He "> 3 He 4 He values, as in nearby Lower Geyser Basin. This correlation is attributed to variable amounts of deep dilution of thermal waters with a relatively cool water that inhibits boiling at depth, thus preventing the loss of CO 2 (and therefore HCO 3 − ) and magmatic He in the most diluted samples. Oxygen and hydrogen isotope data also support a boiling and dilution model, but to produce the observed fractionations, the boiling event would have to be extensive, with steam loss at the surface, whereas the boiling that affected the helium isotope ratios was probably a small scale event with steam loss at depth. It is possible that deep boiling occurred in the basin and that small amounts of steam escaped along fractures at about 500 m below the surface while all subsequently produced steam was lost near or at the surface.

Geochimica et Cosmochimica Acta↗
USGS1990

Comparison of methods to determine degree of pyritization

Degree of pyritization (DOP) is a measure of the ratio pyrite iron/(pyrite iron + reactive iron) that can be related to the depositional environment of a sediment. Several methods of DOP determination have been used but not systematically evaluated. The determination/extraction of reactive (usually acid soluble) iron is critical to the DOP determination, and the method generally used is reaction of the sample for 1 to 2 min with hot 12 N HCl. We present results for timed experiments with 1 N, 6 N, and 12 N HCl on three different samples. We also show that a 24 h room temperature treatment with 1 N HCl is equivalent to the 24 h treatment with Na-dithionite. Experiments with several suites of samples show that all three of these methods leach comparable amounts of iron; therefore, the DOP values are similar. However, the 1 N HCl, 24 h procedure is preferable because laboratory handling is less and easier.

Geochimica et Cosmochimica Acta↗
USGS1990

Carbon isotope constraints on degassing of carbon dioxide from Kilauea Volcano

We examine models for batch-equilibrium and fractional-equilibrium degassing of CO 2 from magma at Kilauea Volcano. The models are based on 1. (1) the concept of two-stage degassing of CO 2 from magma supplied to the summit chamber, 2. (2) C isotope data for CO 2 in eruptive and noneruptive (quiescent) gases from Kilauea and 3. (3) data for the isotopic fractionation of C between CO 2 and C dissolved in tholeiitic basalt melt. The results of our study indicate that 1. (1) both eruptive and noneruptive degassing of CO 2 most closely approach a batch equilibrium process, 2. (2) the δ 13 C of parental magma supplied to the summit chamber is in the range −4.1 to−3.4‰ and 3. (3) the δ 13 C of melt after summit chamber degassing is in the range −7 to −8‰, depending upon the depth of equilibration. We also present δ 13 C data for CO 2 in eruptive gases from the current East Rift Zone eruption. These are the first C isotope data for CO 2 in high-temperature (>900°C) eruptive gases from Kilauea; they have a mean δ 13 C value of &#x2212;7.82 &#xB1; 0.24&#x2030; "> −7.82 ± 0.24‰ and are similar to those predicted for the melt after summit chamber degassing. The minor role played by fractional degassing of ascending magma at Kilauea means that exsolved CO 2 tends to remain entrained in and coherent with its host melt during ascent from both mantle source regions and crustal magma reservoirs. This has important implications for magma dynamics at Kilauea.

Geochimica et Cosmochimica Acta↗
USGS1990

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO 4 and (Sr, Ca)C̈O 3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO 3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H 2 O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation G E = χ KBr χ KCl RT [ a 0 + a 1 (2 χ KBr −1)], where a 0 is 1.40 ± 0.02, a 1 , is −0.08 ± 0.03 at 25°C, and χ KBr and χ KCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at χ KBr = 0.676 and at a total solubility product, ΣΠ = [ K + ]([ Cl − ] + [ Br − ]) = 15.35.

Geochimica et Cosmochimica Acta↗
USGS1990

Diagenesis associated with subaerial exposure of Miocene strata, southeastern Spain: Implications for sea-level change and preservation of low-temperature fluid inclusions in calcite cement

Many ancient carbonate rocks contain calcite cements that precipitated from shallow, fresh groundwater that entered strata during events of subaerial exposure. Such low-temperature cementation may be difficult to interpret from fluid inclusion studies because some of the inclusions may reequilibrate during later thermal events. Miocene rocks of southeast Spain provide an example of the utility of fluid inclusion studies in rocks that have not been subjected to significant heating. In the Mesa Roldan area, one type of calcite cement occurs exclusively below a regional stratigraphic surface of enigmatic origin. The cement has petrographic characteristics indicative of cementation in the vadose zone (generally thought to be a zone of oxidation) but has cathodoluminescent bands containing reduced manganese and iron. Primary fluid inclusions contain mostly fresh water, have variable ratios of vapor to liquid, and are at one atmosphere of pressure. Our observations indicate that calcite precipitated from a freshwater vadose zone, which was subjected to local or repetitive saturation, and minor brackish water. The fluid inclusion data indicate that low-temperature fluid inclusions can be preserved in ancient sequences despite a later history of different pore fluids. This indication of subaerial diagenesis of distal slope deposits suggests a relative sea-level drop of at least 50–55 m during the Late Miocene. Similar petrographic and fluid inclusion observations can be used to interpret sea-level changes in other areas.

Geochimica et Cosmochimica Acta↗
USGS1990

Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n - C 17 /pristane and n - C 18 /phytane ratios and loss of n-C 7 , 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C 6 and C 7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as −16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as −39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65°–96°C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95°–130°C) which are much higher than the temperatures of known occurrences of biodegraded oil.

Geochimica et Cosmochimica Acta↗