Optically continuous silcrete quartz cements of the St. Peter Sandstone: High precision oxygen isotope analysis by ion microprobe

A detailed oxygen isotope study of detrital quartz and authigenic quartz overgrowths from shallowly buried (<1 km) quartz arenites of the St. Peter Sandstone (in SW Wisconsin) constrains temperature and fluid sources during diagenesis. Quartz overgrowths are syntaxial (optically continuous) and show complex luminescent zonation by cathodoluminescence. Detrital quartz grains were separated from 53 rocks and analyzed for oxygen isotope ratio by laser fluorination, resulting in an average δ¹⁸O of 10.0 ± 0.2‰ (1SD, n = 109). Twelve thin sections were analyzed by CAMECA-1280 ion microprobe (6-10 μm spot size, analytical precision better than ±0.2‰, 1SD). Detrital quartz grains have an average δ¹⁸O of 10.0 ± 1.4‰ (1SD, n = 91) identical to the data obtained by laser fluorination. The ion microprobe data reveal true variability that is otherwise lost by homogenization of powdered samples necessary for laser fluorination. Laser fluorination uses samples that are one million times larger than the ion microprobe. Whole rock (WR) samples from the 53 rocks were analyzed by laser fluorination, giving δ¹⁸O between 9.8‰ and 16.7‰ (n = 110). Quartz overgrowths in thin sections from 10 rocks were analyzed by ion microprobe and average δ¹⁸O = 29.3 ± 1.0‰ (1SD, n = 161).Given the similarity, on average, of δ¹⁸O for all detrital quartz grains and for all quartz overgrowths, samples with higher δ¹⁸O(WR) values can be shown to have more cement. The quartz cement in the 53 rocks, calculated by mass balance, varies from <1 to 21 vol.% cement, with one outlier at 33 vol.% cement. Eolian samples have an average of 11% cement compared to marine samples, which average 4% cement.Two models for quartz cementation have been investigated: high temperature (50-110 °C) formation from ore-forming brines related to Mississippi Valley Type (MVT) mineralization and formation as silcretes at low temperature (10-30 °C). The homogeneity of δ¹⁸O for quartz overgrowths determined by ion microprobe rules out a systematic regional variation of temperature as predicted for MVT brines and there are no other known heating events in these sediments that were never buried to depths >1 km. The data in this study suggest that quartz overgrowths formed as silcretes in the St. Peter Sandstone from meteoric water with δ¹⁸O values of −10‰ to −5‰ at 10-30 °C. This interpretation runs counter to conventional wisdom based on fibrous or opaline silica cements suggesting that the formation of syntaxial quartz overgrowths requires higher temperatures. While metastable silica cements commonly form at high degrees of silica oversaturation following rapid break-down reactions of materials such as of feldspars or glass, the weathering of a clean quartz arenite is slower facilitating chemical equilibrium and precipitation of crystallographically oriented overgrowths of α-quartz.     

Arsenic release from chlorine-promoted alteration of a sulfide cement horizon: Evidence from batch studies on the St. Peter Sandstone,Wisconsin, USA

Elevated As concentrations have been measured in wells in the St. Peter Sandstone aquifer of eastern Wisconsin, USA. The primary source is As-bearing sulfide minerals (pyrite and marcasite) within the aquifer. There is concern that well disinfection by chlorination may facilitate As release to groundwater by increasing the rate and extent of sulfide oxidation. The objective of this study was to examine the abiotic processes that mobilize As from the aquifer solids during controlled exposure to chlorinated solutions. Thin sections made from sulfidic aquifer material were characterized by quantitative electron probe micro-analysis before and after 24 h exposure to solutions of different Cl₂ concentrations. Batch experiments using crushed aquifer solids were also conducted to examine changes in solution chemistry over 24 h. Results of the combined experiments indicate that Cl₂ addition affects As release and uptake in two ways. First, Cl₂ increases oxidation of sulfide minerals, releasing more As from the mineral structure. Chlorine addition also increases the rate of Fe(II) oxidation and subsequent hydrous ferric oxide (HFO) precipitation, allowing for increased uptake of As onto the mineral surface. Although HFOs can act as sinks for As, they can release As if biogeochemical conditions (e.g. redox, pH) change. These results have implications not only for disinfection of drinking water wells in the study area, but also suggest that introduction of oxidants may adversely affect water quality during aquifer storage and recovery programs in aquifers containing As-bearing minerals.     

Ion microprobe analysis of oxygen isotope ratios in quartz from Skye granite: healed micro-cracks,fluid flow,and hydrothermal exchange

 Quartz grains in hydrothermally altered granites from the Isle of Skye are highly heterogeneous and not equilibrated in oxygen isotope ratio at the 20 μm scale. Ion microprobe analysis of one grain shows a gradient of 13‰ over 400 μm and a greater range in δ ¹⁸O than all quartz previously analyzed on the Isle of Skye. Other crystals from the same outcrop are homogeneous. Digitized cathodoluminescence images reveal patterns of magmatic zoning and brittle fracturing not otherwise detectable. The ion probe analysis correlates low δ ¹⁸O values on a micro-scale to one set of healed cracks. Thus, quartz exchanges oxygen isotopes primarily by solution and reprecipitation along fractures, in contrast to more reactive feldspar that appears to exchange from the grain boundary inward. Macroscopic models of isotope exchange are not realistic for these rocks; the flow of hydrothermal fluids was heterogeneous, anisotropic and crack controlled. Received: 23 October 1995/Accepted: 9 April 1996     

Ion microprobe measurements of O/O ratios of phosphate minerals in the Martian meteorites ALH84001 and Los Angeles

Oxygen isotope ratios of merrillite and chlorapatite in the Martian meteorites ALH84001 and Los Angeles have been measured by ion microprobe in multicollector mode. δ¹⁸O values of phosphate minerals measured in situ range from ∼3 to 6‰, and are similar to Martian meteorite whole-rock values, as well as the δ¹⁸O of igneous phosphate on Earth. These results suggest that the primary, abiotic, igneous phosphate reservoir on Mars is similar in oxygen isotopic composition to the basaltic phosphate reservoir on Earth. This is an important first step in the characterization of Martian phosphate reservoirs for the use of δ¹⁸O of phosphate minerals as a biomarker for life on Mars. Cumulative textural, major-element, and isotopic evidence presented here suggest a primary, igneous origin for the phosphates in Los Angeles and ALH84001; textural and chemical evidence suggests that phosphates in ALH84001 were subsequently shock-melted in a later event.     

Formation of syngenetic and early diagenetic iron minerals in the late Archean Mt. McRae Shale, Hamersley Basin, Australia: New insights on the patterns, controls and paleoenvironmental implications of authigenic mineral formation

A section through the late Archean Mt. McRae Shale comprising, in ascending order, a lower shale interval (LSI), a banded iron formation (BIF), an upper shale (USI) and a carbonate (C1) has been analyzed for total Fe and Al contents and authigenic Fe present as carbonate, oxide, sulfide and silicate phases. The authigenic mineralogy is controlled by the episodic addition of Fe from hydrothermal activity and removal of Fe by sulfide, relative to rates of clastic sedimentation. The LSI and BIF have mean Fe_T/Al values of 2 and 5, respectively, that record iron enrichment from hydrothermal sources. Iron was precipitated primarily as siderite accompanied by Fe-rich chlorite from anoxic bottom waters rich in dissolved Fe. Pyrite formation was probably limited by the availability of sulfate, which was present at low concentrations and became rapidly depleted. The USI has generally lower Fe_T/Al values (0.6-1.3), similar to those found in Paleozoic shales, with the exception of one interval where enrichment may reflect either a weak hydrothermal source or the operation of an iron shuttle. This interval contains authigenic Fe predominantly as pyrite, where high values for DOP (>0.8) indicate the existence of a water column that became rich in dissolved sulfide (euxinic) when sulfate concentrations increased due to a transient or secular increase in ocean/atmosphere oxygenation. High concentrations of dissolved sulfide maintained low concentrations of dissolved Fe, which allowed only minor amounts of Fe to be precipitated as carbonates and silicates. The USI also has elevated concentrations of organic matter that most probably reflect increased productivity and likely limited euxinia to midportions of the water column on the basin margin. The carbonate C1 represents a basinal chemistry where sulfide has been removed and Fe_T/Al values are ∼1 indicating that hydrothermal activity again produced dissolved Fe-rich bottom waters. Detailed iron speciation of the Mt. McRae Shale can be used to recognize spatial and temporal variations in iron and sulfur inputs to the late Archean Hamersley Basin, just prior to the Paleoproterozoic rise in atmospheric oxygenation, and our refined methods have relevance to all Fe-rich deposits.     

40Ar/39Ar ages of detrital muscovite and whole-rock slate/phyllite,Narragansett Basin,RI-MA,USA: implications for rejuvenation during very low-grade metamorphism

Late Pennsylvanian sedimentary rocks in the Narragansett basin were metamorphosed (lower anchizone to sillimanite grade) during late Paleozoic regional metamorphism at ca. 275–280 Ma. Twenty-five variably sized concentrates of detrital muscovite were prepared from samples collected within contrasting low-grade areas (diagenesis — lower greenschist facies). Microprobe analyses suggest that the constituent detrital grains are not chemically internally zoned; however, some grains within several concentrates display very narrow (<25 m), compositionally distinct, low-grade, epitaxial peripheral overgrowths. Detrital muscovite concentrates from the lower anchizone are characterized by internally concordant ⁴⁰Ar/³⁹Ar age spectra which define plateau ages of ca. 350–360 Ma. These are interpreted to date post-Devonian (Acadian) cooling within proximal source areas. Concentrates from lower grade sectors of the middle anchizone display slightly discordant spectra in which apparent ages systematically increase from ca. 250–275 Ma to define intermediate- and high-temperature plateaus of ca. 360–400 Ma. Detrital muscovite within samples from higher grade sectors of the middle anchizone and the upper anchizone are characterized by systematic low age discordance throughout both low-and intermediate-temperature increments. High-temperature ages only range up to ca. 330 Ma. Six size fractions of detrital muscovite from a sample collected within the lower greenschist facies have similarly discordant spectra, in which, apparent ages increase slightly throughout the analyses from ca. 250 Ma to 275 Ma. The detrital muscovite results are interpreted to reflect variable affects of late Paleozoic regional metamorphism. However, it is uncertain to what extent the systematic low age spectra discordance reflects intracrystalline gradients in the concentration of ⁴⁰Ar and/or experimental evolution of gas from relatively non-retentive epitaxial overgrowths. However, low age discordance occurs regardless of the extent of epitaxial overgrowth. Intermediate-temperature increments evolved during ⁴⁰Ar/³⁹Ar whole-rock analyses of five slate/phyllite samples are characterized by internally consistent apparent K/Ca ratios. These are attributed to gas evolved from constituent, very fine-grained white mica. Samples from lower grade portions of the middle anchizone are characterized by intermediate-temperature apparent ages which systematically increase from ca. 275–300 Ma to ca. 360–375 Ma before evolution of a high-temperature contribution from detrital plagioclase feldspar. This age variation may reflect partial late Paleozoic rejuvenation of very fine-grained detrital material with a source age similar to that for the detrital muscovites. Slate/phyllite samples from upper sectors of the middle anchizone and from the upper anchizone were completely rejuvenated during late Paleozoic metamorphism and record intermediate-and high-temperature plateau ages of ca. 270–290 Ma. These data document that metamorphic conditions of the lower to middle biotite zone (ca. 325–350 °C) are required to completely rejuvenate intracrystalline argon systems of detrital muscovite. Therefore, the ⁴⁰Ar/³⁹Ar dating method may be useful in determination of detrital muscovite provenance and in resolution of the metamorphic evolution of low-grade terranes.     

Ion microprobe (SHRIMP) dating of detrital zircon grains from quartzites of the Eckergneiss Complex, Harz Mountains (Germany): implications for the provenance and the geological history

The Eckergneiss Complex (EGC) is a geologically unique medium- to high-grade metamorphic unit within the Rhenohercynian domain of the Mid-European Variscides. A previously, poorly defined conventional lower U–Pb intercept age of about 560 Ma from detrital zircons of metasedimentary rocks has led to speculations about an East Avalonian affinity of the EGC. In order to unravel the provenance and to constrain the age of the sediment protolith, we carried out sensitive high-resolution ion microprobe U–Pb analyses on detrital zircons from five different EGC quartzite occurrences. The obtained age spectrum indicates a SW Baltica provenance of the detritus. Sveconorwegian ages between 0.9–1.2 Ga are particularly well represented by analyses from metamorphic recrystallization/alteration zones penetrating into igneous zircon. Cadomian (Pan-African) ages, which might reflect a metamorphic event, could not be substantiated. Instead, zircons of igneous origin yielded concordant Lower Devonian and Silurian ages of 410±10, 419±10, and 436±6 Ma (1), implying that sedimentation of the EG protolith must have taken place after 410±10 Ma. The lower age limit of the EGC metamorphism is constrained by 295 Ma intrusion ages of the adjacent, nonmetamorphosed Harzburg Gabbronorite and Brocken Granite. Sedimentation and metamorphism must thus have taken place between about 410 Ma and 295 Ma. Given that this time span coincides with most of the sedimentation within the virtually nonmetamorphosed (lowest grade) Rhenohercynian in the Harz Mountains, including the direct vicinity of the EGC, along with the high-grade metamorphism, the EGC can hardly be seen as uplifted local basement. A possible candidate for the root region is an easterly, concealed marginal segment of the Rhenohercynian domain of the Variscides, which is tectonically overridden and suppressed by the Mid-German Crystalline Rise during continent collision. However, based on the concept of strike-slip movement of Variscan terranes with different P–T–t histories as a result of postaccretion intraplate deformation, the EGC could also represent a fault-bounded complex with an origin located far east or south east of the present location.

Ion microprobe analysis of graphite from ca. 3.8 Ga metasediments, Isua supracrustal belt, West Greenland: Relationship between metamorphism and carbon isotopic composition

In-situ ion microprobe measurements of carbon isotopic compositions of graphite were made in seven metasediments and two carbonate rocks from the ca. 3.8 Ga Isua supracrustal belt, West Greenland. The δ¹³C values of micron-scale graphite globules in the metasediments and the carbonate rocks vary from -18 to +2‰ and from -7 to -3‰, respectively. The maximum δ¹³C value of graphite globules in the metasediment rises from -14 to -5‰, as the metamorphic grade increases from epidote-amphibolite to upper amphibolite facies. In a single hand specimen, the δ¹³C values of graphite inclusions in garnet are ∼7‰ lower on average than those outside garnet. Similarly, graphite armored by quartz apparently shows a few permil lower δ¹³C values than those on grain boundaries between noncarbonate minerals. The fact that early crystallized minerals include relatively ¹³C-depleted graphite indicates that the regional metamorphism increased the δ¹³C values of the Isua graphite. This is consistent with the regional trend of ¹³C-enrichment accompanied by the increase of metamorphic grade. The minimum fractionation between graphite and carbonate is consistent with the equilibrium fractionation at about 400 to 550 °C. These observations indicate that isotopic exchange with isotopically heavy carbonate caused ¹³C-enrichment of Isua graphite. The δ¹³C values of graphite reported here (δ¹³C > -18‰) were produced either as a metamorphic modification of organic carbon with initially much lower δ¹³C values, or as an abiological reaction such as decomposition of carbonate. If the isotopic exchange between carbonate and graphite during regional metamorphism controlled the ¹³C-enrichment of Isua graphite, previously reported large ¹³C-depletion of graphite, especially armored by apatite (Mojzsis et al., 1996) was probably premetamorphic in origin. This supports the existence of life at Isua time (ca. 3.8 Ga).     

Therm odynamics of Diagenetic Fluid and Fluid／Mineral Reactions in the Eogene Xingouzui Formation,Oil Field T,Jianghan Basin

This study focuses on the thermodynamics of diagenetic fluid from the Eogene Xingouzui Formation which represents the most important reservoir in Field Oil T in the Jianghan Basin. The measured homogenization temperatures (110–139 °C) of fluid inclusions in diagenetic minerals fell within the range of 67 –155 °C at the middle diagenetic stage. The pressure of diagenetic fluid is estimated at 10.2 –56 MPa. The activity of ions in the fluid shows a tendency of Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ > Fe³⁺ > Fe²⁺ for cations, and HCO ₃ ⁻ > SO ₄ ²⁻ > F⁻ > Cl⁻ > CO ₃ ²⁻ for anions. For the gaseous facies, there is a tendency of CO₂> CO> H₂S> CH₄> H₂. According to the thermodynamic calculations, the pH and Eh of the fluid are 5.86–6.47 and −0.73–−0.64V, respectively. As a result of the interaction between such a diagenetic fluid and minerals in the sediments, feldspars were dissolved or alterated by other minerals. The clay mineral kaolinite was instable and hence was replaced by illite and chloritoid. This project was jointly funded by the National Natural Science Foundation of China (49133080) and the Open Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences.     

Authigenic iron and titanium oxides in triassic red beds: (St. Bees Sandstone), Cumbria,Northern England

Authigenic iron and titanium oxides occur in three main textural varieties in the St. Bees Sandstone, a Triassic red bed succession in Cumbria. These are: (a) overgrowths of haematite, titaniferous haematite, anatase, and rutile which generally occur on detrital host grains of similar compositions. The overgrowths may occur as syntaxial rim cements or rhombohedral and prismatic projections and are always in optical continuity, (b) discrete crystals of anatase (including octahedrite) and haematite 10-40 μm in size occur in pore spaces, and (c) fine grained ( < 1 μm) pigmentary haematite occurs as grain coatings around detrital grains and in the interstitial matrix. The euhedral nature and pore-filling habit clearly indicate the authigenic origin of these iron- and titanium oxides. All three textural varieties are believed to have been precipitated from ground waters containing dissolved ferrous and titanium ions. These ions were derived from the intrastratal solution of detrital iron and titanium bearing grains including ferromagnesian silicates and iron-titanium oxides. The precipitation of iron oxides from migrating ground waters in the manner described here goes some way to explaining how thick, uniformly red successions can be formed.     

Authigenic iron and titanium oxides in Triassic red beds: (St. Bees Sandstone), Cumbria,Northern England

Authigenic iron and titanium oxides occur in three main textural varieties in the St. Bees Sandstone, a Triassic red bed succession in Cumbria. These are: (a) overgrowths of haematite, titaniferous haematite, anatase, and rutile which generally occur on detrital host grains of similar compositions. The overgrowths may occur as syntaxial rim cements or rhombohedral and prismatic projections and are always in optical continuity, (b) discrete crystals of anatase (including octahedrite) and haematite 10-40 μm in size occur in pore spaces, and (c) fine grained ( < 1 μm) pigmentary haematite occurs as grain coatings around detrital grains and in the interstitial matrix. The euhedral nature and pore-filling habit clearly indicate the authigenic origin of these iron- and titanium oxides. All three textural varieties are believed to have been precipitated from ground waters containing dissolved ferrous and titanium ions. These ions were derived from the intrastratal solution of detrital iron and titanium bearing grains including ferromagnesian silicates and iron-titanium oxides. The precipitation of iron oxides from migrating ground waters in the manner described here goes some way to explaining how thick, uniformly red successions can be formed.     

合肥盆地圆筒山组物源分析及其地质意义：来自碎屑锆石的证据

合肥盆地位于华北板块东南缘,形成于华南、华北板块碰撞过程中。合肥盆地形成时表现为大别造山带向北逆冲形成的前陆挠曲盆地,早白垩世在区域伸展背景下转变为断陷盆地。中侏罗统圆筒山组是合肥盆地前陆挠曲阶段的沉积地层之一,主要表现为湖泊相沉积,与下伏的防虎山组典型的河流相沉积明显不同。为了获得圆筒山组更详细的物源信息,对肥西地区出露的圆筒山组紫红色粉砂岩开展了碎屑锆石LA-ICP MS U-Pb定年。定年结果显示,两个粉砂岩样品均获得了约2.0 Ga和约770 Ma两个主要峰值以及约2.4 Ga次要峰值。该特征与扬子板块锆石年龄分布特征几乎完全一致,指示圆筒山组物源应来自扬子板块。考虑到盆地地层的物源不应来自其周边隆起区分水岭的另一侧,因而推测圆筒山组物源应来自张八岭隆起中侏罗世时地表出露岩石。在燕山运动A幕影响下,下扬子地区发生逆冲褶皱活动,张八岭隆起发生明显隆升,上部岩石被剥蚀殆尽,仅保留现今出露的新元古代张八岭群及肥东杂岩,被剥蚀的岩石搬运沉积于合肥盆地内,形成圆筒山组。     

Textural and chemical variation in plagioclase phenocrysts from the 1980 eruptions of Mount St. Helens,USA

This study presents major- and trace-element chemistry of plagioclase phenocrysts from the 1980 eruptions of Mount St. Helens volcano. Despite the considerable variation in textures and composition of plagioclase phenocrysts, distinct segments have been cross-correlated between crystals. The variation of Sr and Ba concentration in the melt, as calculated from the concentration in the phenocrysts using partition coefficients, suggests the cores and rims crystallised from compositionally different melts offset by the plagioclase crystallisation vector. In both of these melts Sr and Ba are correlated despite the abundance of plagioclase in the 1980 dacites. We propose that rapid crystallisation of plagioclase upon magma ascent caused a shift in melt composition towards lower Sr and higher Ba, as documented in the rims of the phenocrysts. Although the cores of the phenocrysts crystallised at relatively shallow depths, they preserve the Sr and Ba of the deep-seated melts as they ascended from a deeper region. Further magma ascent resulted in microlite nucleation, which is responsible for a similar shift to even lower Sr concentration as observed in the groundmass of post-18 May 1980 samples. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Provenance, age, and environment of mid-Wisconsinan slackwater lake sediment in the St. Louis Metro East area, USA

Valleys tributary to the Mississippi River contain fossiliferous slackwater lake sediment (Equality Formation) deposited in response to aggradation of the Mississippi River valley during the last glaciation. In the St. Louis Metro East area, the lower part of the Equality Formation is primarily laminated, fossiliferous silt and clay deposited from about 44,150 to 24,310 ¹⁴C yr B.P. The upper Equality Formation is primarily very fine sand to silt deposited from about 21,200 to 17,000 ¹⁴C yr B.P. Among the four cores that sample this succession in the St. Louis Metro East area, core MNK-3 (38.64EN, 90.01EW) was selected for detailed study. Three sources are distinguished by the following characteristics: (1) gray smectite-quartz-Se-rich, feldspar-poor material of the Des Moines, Wadena, and James lobes; (2) reddish brown kaolinite-Cu-Fe-rich sediment of the Superior and Rainy lobes; and (3) brown illite-dolomite-Sr-rich sediment of the Lake Michigan and Green Bay lobes. The earliest sediments (44,150 to 41,700 ¹⁴C yr B.P.) were derived from the central and western provenances and are chronocorrelative with the lower Roxana Silt. A hiatus occurred from about 41,700 to 29,030 ¹⁴C yr B.P. when much of the middle Roxana Silt (Meadow Member) was deposited on adjacent uplands. The youngest sediment includes evidence of heightened activity of the Superior Lobe at about 29,000 ¹⁴C yr B.P., the Lake Michigan and Green Bay lobes from about 25,000 to 24,000 ¹⁴C yr B.P., and the Wadena-Des Moines-James lobes at about 21,000 ¹⁴C yr B.P.     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

Hydrochemical tracers in the middle Rio Grande Basin,USA: 1. Conceptualization of groundwater flow

Chemical and isotopic data for groundwater from throughout the Middle Rio Grande Basin, central New Mexico, USA, were used to identify and map groundwater flow from 12 sources of water to the basin, evaluate radiocarbon ages, and refine the conceptual model of the Santa Fe Group aquifer system.Hydrochemical zones, representing groundwater flow over thousands to tens of thousands of years, can be traced over large distances through the primarily siliciclastic aquifer system. The locations of the hydrochemical zones mostly reflect the modern predevelopment hydraulic-head distribution, but are inconsistent with a trough in predevelopment water levels in the west-central part of the basin, indicating that this trough is a transient rather than a long-term feature of the aquifer system. Radiocarbon ages adjusted for geochemical reactions, mixing, and evapotranspiration/dilution processes in the aquifer system were nearly identical to the unadjusted radiocarbon ages, and ranged from modern to more than 30 ka. Age gradients from piezometer nests ranged from 0.1 to 2 year cm^–1 and indicate a recharge rate of about 3 cm year^–1 for recharge along the eastern mountain front and infiltration from the Rio Grande near Albuquerque. There has been appreciably less recharge along the eastern mountain front north and south of Albuquerque.

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Resumen Se utilizaron datos químicos e isotópicos de agua subterránea a lo largo de la cuenca central del río Grande, Nuevo México, EEUU, para identificar y mapear el flujo de agua subterránea de 12 fuentes de agua a la cuenca para evaluar edades por medio de radio carbon y para refinar el modelo conceptual del sistema acuífero del Grupo Santa Fé. Se puede establecer zonas hidrotérmicas que representan el flujo de agua subterránea a lo largo de miles a miles de decenas de años en grandes distancias a través del sistema acuífero principalmente siliclástico. Las ubicaciones de las zonas hidroquímicas mayormente reflejan la distribucion de la cabeza hidráulica pre-desarollo moderna pero son inconsistentes con una depresión en los niveles de agua pre-desarollo en la zona central oeste de la cuenca. Esto indica que esta depresión es un rasgo transitorio y no un rasgo de largo plazo del sistema acuífero. Las edades de radio carbon ajustadas para los procesos de reaciones geoquímicas, de mezclado y de evapotranspiración-dilución son casi idénticas a los edades de radio carbon no ajustadas oscilan en un rango desde la modernidad a 30 mil años. Las gradientes de edad de nidos de piezometros van de 0.1 a 2 años cm^–1 e indican un sitio de recarga de aproximadamente 3 cm/yr para la recarga a lo largo del frente montañoso oriental e infiltración del río Grande cerca de Albuquerque. Se aprecia una recarga menor a lo largo del frente oriental de montañas al norte y al sur de Albuquerque.

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Résumé Des données sur les éléments chimiques et les isotopes présents dans leau souterraine prélevée à divers endroits dans le bassin moyen du Rio Grande, au centre du Nouveau-Mexique (É-U), ont permis de déterminer lexistence et létendue de douze sources deau régionales dans le bassin, dévaluer les âges radiocarbones et de raffiner le modèle conceptuel du système aquifère du groupe de Santa Fe. Des zones hydro-chimiques qui représentent lécoulement de leau souterraine depuis des dizaines de milliers dannées peuvent être suivies sur de longues distances à travers laquifère principalement siliclastique. La position des zones hydro-chimiques reflète principalement la distribution moderne des charges hydrauliques mais est incohérente avec une dépression dans le niveau deau dans la partie centre-ouest du bassin, ce qui indique que cette dépression est un élément transitoire du système aquifère plutôt quun élément à long terme. Les âges radiocarbones ajustés aux réactions géochimiques et aux processus de mélange et dévapotranspiration/dilution qui ont lieu dans laquifère sont presque identiques aux âges non ajustés et varient de la période moderne jusquà 30 ka. Les gradients dâge établis à partir des nids de piézomètres sétendent de 0.1 à 2 a cm^–1 et suggèrent un taux de recharge denviron 3 cm a^–1 le long du front des montagnes à lest et pour linfiltration provenant du Rio Grande près dAlbuquerque. Il y a eu substantiellement moins de recharge le long du front des montagnes à lest, au nord et au sud dAlbuquerque.

     

Hydrochemical tracers in the middle Rio Grande Basin,USA: 2. Calibration of a groundwater-flow model

The calibration of a groundwater model with the aid of hydrochemical data has demonstrated that low recharge rates in the Middle Rio Grande Basin may be responsible for a groundwater trough in the center of the basin and for a substantial amount of Rio Grande water in the regional flow system. Earlier models of the basin had difficulty reproducing these features without any hydrochemical data to constrain the rates and distribution of recharge. The objective of this study was to use the large quantity of available hydrochemical data to help calibrate the model parameters, including the recharge rates. The model was constructed using the US Geological Surveys software MODFLOW, MODPATH, and UCODE, and calibrated using ¹⁴C activities and the positions of certain flow zones defined by the hydrochemical data. Parameter estimation was performed using a combination of nonlinear regression techniques and a manual search for the minimum difference between field and simulated observations. The calibrated recharge values were substantially smaller than those used in previous models. Results from a 30,000-year transient simulation suggest that recharge was at a maximum about 20,000 years ago and at a minimum about 10,000 years ago.

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Resumen La calibración de un modelo de aguas subterráneas con el apoyo de datos hidroquímicos ha demostrado que la recarga relativamente baja en la cuenca media del Río Grande es probablemente responsable de una depresión de aguas subterráneas en el centro de la cuenca y de la presencia de una cantidad considerable de agua del Río Grande en el acuífero del Grupo Santa Fe. Los modelos propuestos con anterioridad para la cuenca tenían dificultades para reproducir estas características ya que no tenían datos hidroquímicos que permitieran delimitar los ritmos y distribución de recarga. El objetivo del presente estudio consistió en utilizar una gran cantidad de datos hidroquímicos disponibles para ayudar a calibrar los parámetros del modelo, incluyendo los ritmos de recarga. El modelo se construyó utilizando los modelos MODFLOW, MODPATH, y UCODE del USGS, mientras que la calibración se realizó en base a concentraciones de ¹⁴C y a la posición de ciertas zonas definidas con los datos hidroquímicos. La estimación de parámetros se realizó en base a una combinación de técnicas de regresiones no lineares y a una búsqueda a viva fuerza del error mínimo entre los datos observados y los simulados. Los valores de recarga calibrados fueron significativamente más bajos que los estimados en los modelos anteriores. Los resultados de una simulación transitoria de 30,000 años sugieren que la recarga durante la última glacial máxima (LGM) fue diez veces el ritmo moderno, pero que la recarga que ocurrió inmediatamente después de la LGM fue más baja que el ritmo moderno.

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Résumé Le calibrage dun modèle hydrogéologique avec laide de données hydrochimiques a démontré que la recharge relativement faible dans le Grand Bassin du Middle Rio est vraisemblablement responsable dune dépression des eaux souterraines dans le centre du bassin et de la présence dune quantité substantielle deau du Rio Grande dans laquifère du Groupe de Santa Fe. Les modèles antérieurs avaient des difficultés à reproduire ses conclusions sans laide de données hydrochimiques pour contraindre les taux et la distribution de la recharge. Lobjectif de cette étude était dutiliser une grande quantité de données hydrochimiques permettant de calibrer les paramètres du modèle, et notamment les taux de recharge. Le modèle a été construit avec les logiciels MODFLOW, MODPATH et UCODE, et calibré en utilisant les concentrations en ¹⁴C et la position de certaines zones définies par les données hydrochimiques. Lestimation de certains paramètres a été réalisée en utilisant une combinaison de techniques de régression non linéaire et une méthode de recherche exhaustive (Brute Force Search) de lerreur minimum entre les résultats des observations et les simulations. Les valeurs de la recharge calibrée sont substantiellement plus basses que celles estimées dans les modèles antérieurs. Les résultats dune simulation en régime transitoire sur 30.000 ans suggèrent que la recharge au maximum de la dernière glaciation (last glacial maximum, LGM) était 10 fois supérieure au taux actuel, mais que la recharge qui a suivit la LGM était plus bas que la recharge actuelle.

     

Dating cleavage formation in slates and phyllites with the 40Ar/39Ar laser microprobe: an example from the western New England Appalachians, USA

Determinations of the absolute age of cleavage formation can provide fundamental information about the evolution of orogenic belts. However, when applied to cleavages in slates and phyllites, conventional dating methods are complicated by problems related to mineral separation and the presence of multiple cleavage generations. In situ high-spatial-resolution ⁴⁰Ar/³⁹Ar laser microprobe geochronology and microstructural observations indicate that the age of cleavage formation in slates and phyllites can be constrained by analysing zones of tightly packed cleavage domains. Three regionally developed cleavages (S₂, S₃, and S₄) are present in the northern Taconic Allochthon of Vermont and New York. Representative samples were studied from a variety of localities where these cleavages, which are defined by white micas, are well developed. In the suite of samples, only S₃ and S₄ are expressed as domains that are sufficiently wide and spatially isolated in thin section to permit quantitative ⁴⁰Ar/³⁹Ar geochronology. Mean ⁴⁰Ar/³⁹Ar laser microprobe ages for these domains are 370.7 ± 1.0 Myr for S₃ and 345.5 ± 1.7 Myr for S₄. Because estimates of the Ar closure temperature for white micas are substantially higher than the inferred growth temperatures of the micas defining S₃ and S₄, these values are interpreted as periods since cleavage formation. This interpretation is consistent with independent geochronological constraints on the age of the Acadian orogeny in the region.     

Petrographic and geochemical characteristics of dolomite types and the origin of ferroan dolomite in the Trenton Formation, Ordovician, Michigan Basin, U.S.A.

Three major types of dolomite occur in the Trenton Formation (Mid-Ordovician) of the Michigan Basin. These are: (1) ‘regional dolomite’ which is confined to the extreme western edge of the basin; (2) ‘cap dolomite’ which occurs in the upper portion of the Trenton and is confined to the basin's southern margin; and (3) ‘fracture-related’ dolomite which occurs in association with both large- and small-scale faults and fractures. These three dolomite types can be distinguished from one another by their major element chemistry, oxygen isotope ratios and rock texture. The regional dolomite is fine-grained, has <0.34 mol% FeCO₃, and mean δ¹⁸O of ?6·8‰_OPBD. The cap dolomite is texturally similar to regional dolomite but contains 3–13·0 mol% FeCO₃ and has a mean δ¹⁸O of ?7·7‰. Fracture-related dolomites are coarse-grained, low in iron, and have the most depleted δ¹⁸O ratios (x?=–9·0%_PDB). Petrographic relationships imply that the regional dolomite, formed prior to the cap dolomite probably during early diagenesis. The cap dolomite formed at relatively shallow depths as a result of the interaction of the overlying Utica Shale and the Trenton Limestone. Fracture-related dolomites post-date the cap dolomite and formed during deeper burial. A temperature of precipitation of approximately 80°C was calculated for fracture-related dolomites using oxygen isotope data. The distribution of the cap dolomite was controlled by the availability of Fe^2? which was in turn controlled by the availability of S^2?. In the centre of the basin Trenton-Utica deposition was continuous. The upper Trenton contained relatively high concentrations of organic matter which was used by sulphate reducing bacteria to produce H_2S from seawater sulphate. The precipitation of iron sulphides (pyrite + iron monosulphide) followed and used up most of the available Fe^2?. As a result only small amounts of ferroan dolomite formed. On the periphery of the basin, subaerial exposure resulted in the oxidation of most of the available organic matter. Sulphate reducing bacteria were therefore limited and produced limited amounts of H₂S. As a result only a minor amount of iron sulphide (iron monosulphide) formed. The remaining Fe^2- was then available for the formation of the ferroan cap dolomite. This model is supported by the following: (1) In the southern margin of the basin, the contact between Trenton cap dolomite and the overlying Utica Shale is sharp and probably unconformable. In the centre of the basin the contact is gradational. (2) In the centre of the basin, the total organic carbon content in the upper Trenton is an order of magnitude higher than in the cap dolomite. (3) The whole-rock concentration of iron is high in both the cap dolomite and in slightly dolomitized equivalent beds in the basin centre. (4) Iron sulphides are abundant in the centre of the basin and mostly in the form of pyrite. In the cap dolomite, iron sulphide is minor and primarily in the form of iron monosulphide.