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Calculation of amorphous silica solubilities at 25° to 300°C and apparent cation hydration numbers in aqueous salt solutions using the concept of effective density of water

The solubility of amorphous silica in aqueous salt solutions at 25° to 300°C can be calculated using information on its solubility in pure water and a model in which the activity of water in the salt solution is defined to equal the effective density. p e , of “free” water in that solution. At temperatures of 100°C and above, p e closely equals the product of the density of the solution times the weight fraction of water in the solution. At 25°C, a correction parameter must be applied to p e that incorporates a term called the apparent cation hydration number, h . Because of the many assumptions and other uncertainties involved in determining values of h , by the model used here, the reported numbers are not necessarily real hydration numbers even though they do agree with some published values determined by activity and diffusion methods. Whether or not h is a real hydration number, it would appear to be useful in its inclusion within a more extensive activity coefficient term that describes the departure of silica solubilities in concentrated salt solutions from expected behavior according to the model presented here. Values of h can be calculated from measured amorphous silica solubilities in salt solutions at 25°C provided there is no complexing of dissolved silica with the dissolved salt, or if the degree of complexing is known. The previously postulated aqueous silica-sulfate complexing in aqueous Na 2 SO 4 solutions is supported by results of the present effective density of water model

Geochimica et Cosmochimica Acta↗

Sr, Nd and Pb isotopes in Proterozoic intrusives astride the Grenville Front in Labrador: Implications for crustal contamination and basement mapping

We report Sr, Nd and Pb isotopic compositions of mid-Proterozoic anorthosites and related rocks (1.45-1.65 Ga) and of younger olivine diabase dikes (1.4 Ga) from two complexes on either side of the Grenville Front in Labrador. Anorthositic or diabasic samples from the Mealy Mountains (Grenville Province) and Harp Lake (Nain-Churchill Provinces) complexes have very similar major, minor and trace element compositions, but distinctly different isotopic signatures. All Mealy Mountains samples have I Sr = 0.7025−0.7033, ε Nd = +0.6 to +5.6 and Pb isotopic compositions consistent with derivation from a mantle source depleted with respect to Nd/Sm and Rb/Sr. Pb isotopic compositions for the Mealy Mountains samples are slightly more radiogenic than model mantle compositions. All Harp Lake samples have I Sr = 0.7032−0.7066, ε Nd = −0.3 to −4.4 and variable, but generally unradiogenic 207 Pb/ 204 Pb and 206 Pb/ 204 Pb compared to model mantle, suggesting mixing between a mantle-derived component and a U-depleted crustal contaminant. Crustal contaminants are probably a variety of Archean high-grade quartzofeldspathic gneisses with low U/Pb ratios and include a component that must be isotopically similar to the early Archean (>3.6 Ga) Uivak gneisses of Labrador or the Amitsoq gneisses of west Greenland. This would imply that the ancient gneiss complex of coastal Labrador and Greenland is larger than indicated by present surface exposure and may extend in the subsurface as far west as the Labrador Trough. If Harp Lake and Mealy Mountains samples were subjected to the same degree of contamination, as suggested by their chemical similarities, then the Mealy contaminants must be much younger, probably early or middle Proterozoic in age. The Labrador segment of the Grenville Front, therefore, appears to coincide with the southern margin of the Archean North Atlantic craton and may represent a pre mid-Proterozoic suture.

Geochimica et Cosmochimica Acta↗

High-resolution 40Ar 39Ar chronology of Oligocene volcanic rocks, San Juan Mountains, Colorado

The central San Juan caldera complex consists of seven calderas from which eight major ash-flow tuffs were erupted during a period of intense volcanic activity that lasted for approximately 2 m.y. about 26–28 Ma. The analytical precision of conventional K-Ar dating in this time interval is not sufficient to unambiguously resolve this complex history. However, 40 Ar 39 Ar "> 40 Ar 39 Ar incremental-heating experiments provide data for a high-resolution chronology that is consistent with stratigraphie relations. Weighted-mean age-spectrum plateau ages of biotite and sanidine are the most precise with standard deviations ranging from 0.08 to 0.21 m.y. The pooled estimate of standard deviation for the plateau ages of 12 minerals is about 0.5 percent or about 125,000 to 135,000 years. Age measurements on coexisting minerals from one tuff and on two samples of each of two other tuffs indicate that a precision in the age of a tuff of better than 100,000 years can be achieved at 27 Ma. New data indicate that the San Luis caldera is the youngest caldera in the central complex, not the Creede caldera as previously thought.

Geochimica et Cosmochimica Acta↗

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↗

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.

Geochimica et Cosmochimica Acta↗

Hydrothermal alteration in oceanic ridge volcanics: A detailed study at the Galapagos Fossil Hydrothermal Field

The Galapagos Fossil Hydrothermal Field is composed of altered oceanic crust and extinct hydrothermal vents within the eastern Galapagos Rift between 85°49′W and 85°55′W. The discharge zone of the hydrothermal system is revealed along scarps, thus providing an opportunity to examine the uppermost mineralized, and highly altered interior parts of the crust. Altered rocks collected in situ by the submersible ALVIN show complex concentric alteration zones. Microsamples of individual zones have been analysed for major/minor, trace elements, and strontium isotopes in order to describe the complex compositional details of the hydrothermal alteration. Interlayered chlorite-smectite and chlorite with disequilibrium compositions dominate the secondary mineralogy as replacement phases of primary glass and acicular pyroxene. Phenocrysts and matrix grains of plagioclase are unaffected during alteration. Using a modification of the Gresens' equation we demonstrate that the trivalent rare earth elements (REEs) are relatively immobile, and calculate degrees of enrichment and depletion in other elements. Strontium isotopic ratios increase as Sr concentrations decrease from least-altered cores to most-altered rims and cross-cutting veins in individual samples, and can be modeled by open system behaviour under low fluid-rock ratio (< 10) conditions following a period of lower-temperature weathering of volcanics within the rift zone. The complex patterns of element enrichment and depletion and strontium isotope variations indicate mixing between pristine seawater and ascending hot fluids to produce a compositional spectrum of fluids. The precipitation of base-metal sulfides beneath the seafloor is probably a result of fluid mixing and cooling. If, as suggested here, the discharge zone alteration occurred under relatively low fluid-rock ratios, then this shallow region must play an important role in determining the exit composition of vent fluids in marine hydrothermal systems.

Geochimica et Cosmochimica Acta↗

Preliminary mariner 9 report on the geology of Mars

Mariner 9 pictures indicate that the surface of Mars has been shaped by impact, volcanic, tectonic, erosional and depositional activity. The moonlike cratered terrain, identified as the dominant surface unit from the Mariner 6 and 7 flyby data, has proven to be less typical of Mars than previously believed, although extensive in the mid- and high-latitude regions of the southern hemisphere. Martian craters are highly modified but their size-frequency distribution and morphology suggest that most were formed by impact. Circular basins encompassed by rugged terrain and filled with smooth plains material are recognized. These structures, like the craters, are more modified than corresponding features on the Moon and they exercise a less dominant influence on the regional geology. Smooth plains with few visible craters fill the large basins and the floors of larger craters; they also occupy large parts of the northern hemisphere where the plains lap against higher landforms. The middle northern latitudes of Mars from 90 to 150† longitude contain at least four large shield volcanoes each of which is about twice as massive as the largest on Earth. Steep-sided domes with summit craters and large, fresh-appearing volcanic craters with smooth rims are also present in this region. Multiple flow structures, ridges with lobate flanks, chain craters, and sinuous rilles occur in all regions, suggesting widespread volcanism. Evidence for tectonic activity postdating formation of the cratered terrain and some of the plains units is abundant in the equatorial area from 0 to 120° longitude.Some regions exhibit a complex semiradial array of graben that suggest doming and stretching of the surface. Others contain intensity faulted terrain with broader, deeper graben separated by a complex mosaic of flat-topped blocks. An east-west-trending canyon system about 100–200 km wide and about 2500 km long extends through the Coprates-Eos region. The canyons have gullied walls indicative of extensive headward erosion since their initial formation. Regionally depressed areas called chaotic terrain consist of intricately broken and jumbled blocks and appear to result from breaking up and slumping of older geologic units. Compressional features have not been identified in any of the pictures analyzed to data. Plumose light and dark surface markings can be explained by eolian transport. Mariner 9 has thus revealed that Mars is a complex planet with its own distinctive geologic history and that it is less primitive than the Moon.

Icarus↗

Alkaline igneous rocks of Magnet Cove, Arkansas: Mineralogy and geochemistry of syenites

Syenites from the Magnet Cove alkaline igneous complex form a diverse mineralogical and geochemical suite. Compositional zoning in primary and late-stage minerals indicates complex, multi-stage crystallization and replacement histories. Residual magmatic fluids, rich in F, Cl, CO2 and H2O, reacted with primary minerals to form complex intergrowths of minerals such as rinkite, fluorite, V-bearing magnetite, F-bearing garnet and aegirine. Abundant sodalite and natrolite formed in pegmatitic segregations within nepheline syenite where Cl- and Na-rich fluids were trapped. During autometasomatism compatible elements such as Mn, Ti, V and Zr were redistributed on a local scale and concentrated in late-stage minerals. Early crystallization of apatite and perovskite controlled the compatible behavior of P and Ti, respectively. The formation of melanite garnet also affected the behaviour of Ti, as well as Zr, Hf and the heavy rare-earth elements. Pseudoleucite syenite and garnet-nepheline syenite differentiated along separate trends, but the two groups are related to the same parental magma by early fractionation of leucite, the presumed precursor of intergrowths of K-feldspar and nepheline. The Diamond Jo nepheline syenite group defines a different differentiation trend. Sphene-nepheline syenite, alkali syenite and several miscellaneous nepheline syenites do not consistently plot with the other syenite groups or each other on element and oxide variation diagrams, indicating that they were derived from still other parental syenite magmas. Mineral assemblages indicate that relatively high f{hook};O2, at or above the fayalite-magnetite-quartz buffer, prevailed throughout the crystallization history of the syenites. ?? 1990.

LITHOS↗

Coastal currents and mass transport of surface sediments over the shelf regions of Monterey Bay, California

In Monterey Bay, the highest concentrations of medium and fine sands occur nearshore between ten and thirty fathoms. Silt and clay accumulate in greater depths. Contours of median diameter roughly parallel the isobaths. Fine-grained materials are supplied to the bay region from erosion of cliffs which partly surround Monterey Bay, from sediment laden river discharge, and from continual reworking of widespread Pleistocene and Recent sea floor sediments. These sediments in turn are picked up by coastal currents and distributed over the shelf regions by present day current regimes. Studies of bottom currents over the shelf regions and in Monterey Canyon have revealed patterns which vary with seasonal changes. Current patterns during August and September exhibit remarkable symmetry about the axis of Monterey Submarine Canyon. Central Shelf currents north and south of Monterey Canyon flowed northwest at an average rate of 0.2 knots and south at 0.3 knots respectively. On the North Shelf between January and March currents flowed east to southeast at 0.3–0.5 knots with mirror image patterns above the South Shelf during the same period. Irregular current flow in the canyon indicates a complex current structure with frequent shifts in counterclockwise and clockwise direction over very short periods of time. Bottom topography of the canyon complex often causes localization of canyon currents. One particular observation at a depth of 51 fathoms indicated up-canyon flow at a rate of 0.2 knots. Most of the observed currents are related to seasonal variations, upwelling, ocean swell patterns, and to changes in the California and Davidson currents. Changes in current regimes are reflected in the patterns of sediment distribution and transport. Sediment transport is chiefly parallel to the isobaths, particularly on the North and South Shelf regions. Complex dispersal patterns are observed near Monterey Canyon and Moss Landing Harbor jetties. Longshore currents move sediments southward except near Monterey Canyon which acts as a physiographic barrier and the extreme southern end of the bay where currents are non persistent. Some sediments are also transported offshore by rip currents and other agencies and deposited in deeper, quieter waters. Supply of sediments to the canyon head results in over-filling and steepening with subsequent mass movement of sediments seaward followed by deposition in channels and on the broad deep sea fan.

California↗

Structure, age and origin of the bay-mouth shoal deposits, Chesapeake Bay, Virginia

The mouth of Chesapeake Bay contains a distinctive shoal complex and related deposits that result from the complex interaction of three different processes: (1) progradation of a barrier spit at the southern end of the Delmarva Peninsula, (2) strong, reversing tidal currents that transport and rework sediment brought to the bay mouth from the north, and (3) landward (bayward) net non-tidal circulation and sediment transport. Together, these processes play a major role in changing the configuration of the estuary and filling it with sediment. The deposits at the mouth of the bay hold keys both to the evolution of the bay during the Holocene transgression and to the history of previous generations of the bay. The deposit associated with the shoals at the mouth of the bay, the bay-mouth sand, is a distinct stratigraphic unit composed mostly of uniform, gray, fine sand. The position and internal structure of the unit shows that it is related to near-present sea level, and thus is less than a few thousand years old. The processes affecting the upper surface of the deposit and the patterns of erosion and deposition at this surface are complex, but the geometry and structure of the deposit indicate that it is a coherent unit that is prograding bayward and tending to fill the estuary. The source of the bay-mouth sand is primarily outside the bay in the nearshore zone of the Delmarva Peninsula and on the inner continental shelf. The internal structure of the deposit, its surface morphology, its heavy-mineral composition, bottom-current studies, comparative bathymetry, and sediment budgets all suggest that sand is brought to the bay mouth by southerly longshore drift along the Delmarva Peninsula and then swept into the bay. In addition to building the southward- and bayward-prograding bay-mouth sand, these processes result in sand deposition tens of kilometers into the bay.

Marine Geology↗

Synthesis of late Paleozoic and Mesozoic eolian deposits of the Western Interior of the United States

Late Paleozoic and Mesozoic eolian deposits include rock units that were deposited in ergs (eolian sand seas), erg margins and dune fields. They form an important part of Middle Pennsylvanian through Upper Jurassic sedimentary rocks across the Western Interior of the United States. These sedimentary rock units comprise approximately three dozen major eolian-bearing sequences and several smaller ones. Isopach and facies maps and accompanying cross sections indicate that most eolian units display varied geometry and complex facies relations to adjacent non-eolian rocks. Paleozoic erg deposits are widespread from Montana to Arizona and include Pennsylvanian formations (Weber, Tensleep, Casper and Quadrant Sandstones) chiefly in the Northern and Central Rocky Mountains with some deposits (Hermosa and Supai Groups) on the Colorado Plateau. Lower Permian (Wolfcampian) erg deposits (Weber, Tensleep, Casper, Minnelusa, Ingleside, Cedar Mesa, Elephant Canyon, Queantoweap and Esplanade Formations) are more widespread and thicken into the central Colorado Plateau. Middle Permian (Leonardian I) erg deposits (De Chelly and Schnebly Hill Formations) are distributed across the southern Colorado Plateau on the north edge of the Holbrook basin. Leonardian II erg deposits (Coconino and Glorieta Sandstones) are slightly more widespread on the southern Colorado Plateau. Leonardian III erg deposits formed adjacent to the Toroweap-Kaibab sea in Utah and Arizona (Coconino and White Rim Sandstones) and in north-central Colorado (Lyons Sandstone). Recognized Triassic eolian deposits include major erg deposits in the Jelm Formation of central Colorado-Wyoming and smaller eolian deposits in the Rock Point Member of the Wingate Sandstone and upper Dolores Formation, both of the Four Corners region. None of these have as yet received a modern or thorough study. Jurassic deposits of eolian origin extend from the Black Hills to the southern Cordilleran arc terrain. Lower Jurassic intervals include the Jurassic part of the Wingate Sandstone and the Navajo-Aztec-Nugget complex and coeval deposits in the arc terrain to the south and west of the Colorado Plateau. Major Middle Jurassic deposits include the Page Sandstone on the Colorado Plateau and the widespread Entrada Sandstone, Sundance Formation, and coeval deposits. Less extensive eolian deposits occur in the Carmel Formation, Temple Cap Sandstone, Romana Sandstone and Moab Tongue of the Entrada Sandstone, mostly on the central and western Colorado Plateau. Upper Jurassic eolian deposits include the Bluff Sandstone Member and Recapture Member of the Morrison Formation and Junction Creek Sandstone, all of the Four Corners region, and smaller eolian deposits in the Morrison Formation of central Wyoming and apparently coeval Unkpapa Sandstone of the Black Hills. Late Paleozoic and Mesozoic eolian deposits responded to changing climatic, tectonic and eustatic controls that are documented elsewhere in this volume. All of the eolian deposits are intricately interbedded with non-eolian deposits, including units of fluvial, lacustrine and shallow-marine origin, clearly dispelling the myth that eolian sandstones are simple sheet-like bodies. Rather, these units form some of the most complex bodies in the stratigraphic record.

Western Interior↗

Geology of the Zambales ophiolite, Luzon, Philippines

The Zambales ophiolite of western Luzon, Philippines, exposes a typical succession of basalt flows, diabasic dikes, gabbro and tectonized harzburgite. The age established by limiting strata is late Eocene. Lack of evidence of thrust faulting and the general domal disposition of the lithologie units indicate that the ophiolitic rocks are exposed by uplift. Highly complex internal layered structures within the complex are related to processes developed during formation of the ophiolite and the Zambales ophiolite may be one of the least disturbed (by emplacement) ophiolitic masses known. The exposed mass trends north and the upper surface plunges at low angles (a few degrees) to the north and south. The chemistry and composition of the rocks in the northwest part of the Zambales area (Acoje block) is distinct from that in the southeastern segment (Coto block). The Acoje block, according to Evans (1983) and Hawkins and Evans (1983), resembles (on a chemical basis) arc-tholeiite series rocks from intra-island arcs and the rocks in the Coto block are typical back-arc basin rock series. The present writer believes that the ophiolite composes a single genetic unit and that the changes in composition are the result of changes that took place during the initial formation. The gabbro probably formed below a spreading center in an elongate, in cross section, V-shaped, magma chamber. The gabbro is estimated by the writer to be less than 2 km thick and may be less than 1 km in places. Numerous erosional windows through the gabbro in the northern and eastern side of the Zambales area show that the gabbro remaining in those areas is likely to be only a few hundred meters thick. Harzburgite is exposed to a depth of about 800 m in the Bagsit River area and this may be the deepest part of the ophiolite accessible for study on which there is any control on depth. A transitional zone, about 200 m thick lying between the gabbro and harzburgite, is composed of serpentinized dunite. Commonly the dunite contains disseminated sulfide minerals and at the Acoje Mines, platinum-group elements. A compositional layering within the gabbro is in places cumulate in the lower part of the unit but may have formed by nucleation higher up on the relatively steep sides of the magma chamber. A widespread gneissic banding in the gabbro forms large mappable structures which are many times more complex than is the disposition of the major rock units. These structures are believed to be the result of extensive slumping in the magma chamber. The structure produced by the cumulate layering merges with the gneissic banding, commonly without discernible change in attitude. This tectonic layered structure crosses the gabbro-peridotite boundary at any angle without seeming to disturb the original rock distribution. At greater depths below the boundary (ca. 800 m), the harzburgite contains low dipping banding, which probably reflects the result of differential movement within the mantle. Chromite occurs almost exclusively in a zone that generally lies no more than 200–300 m below the gabbro-peridotite boundary. Refractory-grade chromite is found in this zone below the olivine gabbro in the Goto block and as low-grade metallurgical grade chromite below norite in the Acoje block. At Acoje Mines the chromite is present in layers in dunite, which the writer interprets as being distributed in a zone along the gently dipping (ca. 25°) gabbro-peridotite boundary. The steeply dipping (ca. 60–80 ° ) individual layers lie en echelon along the boundary at an angle (ca. 50 ° ) to the contact. At Coto the chromite forms large discontinuous masses in the lowest dunite and in the uppermost harzburgite. Except for the chromite present as layers at Acoje, the regional tectonic layering crosses the chromite deposits without structural deviation. The chromite deposits and associated peridotite may be cumulate in origin, but have been modified to such an extent that cumulate textures are generally obliterated. The angle of repose of cumulate layers in the Acoje area and in the Coto block dip towards each other raising the possibility that the Zambales area may contain the relics of a spreading center. Initial emplacement of the Zambales ophiolite took place by uplift and the ultramafic portion was exposed to erosion in the earliest Miocene or late Oligocene. Submergence of some of the ophiolite followed the previous uplift and on the west side of the Zambales Range submergence of several kilometers is indicated. Final emergence appears to have taken place in Pliocene or Pleistocene time by block uplift and areas of greatest uplift closely conform to the present topographic surface.

Tectonophysics↗

A-type granite and the Red Sea opening

Miocene-Oligocene A-type granite intrudes the eastern side of the Red Sea margin within the zone of extension from Jiddah, Saudi Arabia south to Yemen. The intrusions developed in the early stages of continental extension as Arabia began to move slowly away from Africa (around 30–20 Ma). Within the narrow zone of extension silicic magmas formed dikes, sills, small plutons and extrusive equivalents. In the Jabal Tirf area of Saudi Arabia these rocks occur in an elongate zone consisting of late Precambrian basement to the east, which is gradually invaded by mafic dikes. The number of dikes increases westward until an igneous complex is produced parallel to the present Red Sea axis. The Jabal Tirf igneous complex consists of diabase and rhyolite-granophyre sills (20–24 Ma). Although these are intrusine intrusive rocks their textures indicate shallow depths of intrusion (< 1 km). To the south, in the Yemen, contemporaneous with alkali basaltic eruptions (26–30 Ma) and later silicic eruptions, small plutons, dikes, and stocks of alkali granite invaded thick (1500 m) volcanic series, at various levels and times. Erosion within the uplifted margin of Yemen suggests that the maximum depth of intrusion was less than 1–2 km. Granophyric intrusions (20–30 Ma) within mafic dike swarms similar to the Jabal Tirf complex are present along the western edge of the Yemen volcanic plateau, marking a north-south zone of continental extension. The alkali granites of Yemen consist primarily of perthitic feldspar and quartz with some minor alkali amphiboles and acmite. These granites represent water-poor, hypersolvus magmas generated from parent alkali basalt magmas. The granophyric, two-feldspar granites associated with the mafic dike swarms and layered gabbros formed by fractional crystallization from tholeiitic basalt parent developed in the early stages of extension. Initial 87 Sr/ 86 Sr ratios of these rocks and their bulk chemistry indicate that production of peralkaline and metaluminous granitic magmas involved both fractiónation and partial melting as they ascended through the late Precambrian crust of the Arabian plate.

Red Sea↗

Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.

Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70–120°C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are Na Ca Cl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H 2 S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H 2 S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl 4 2− and ZnCl 4 2− , respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters.

Applied Geochemistry↗

Hydrological connectivity in intermittent rivers and ephemeral streams

In intermittent rivers and ephemeral streams (hereafter, IRES), hydrological connectivity mediated by either flowing or nonflowing water extends along three spatial dimensions—longitudinal, lateral, and vertical—and varies over time. Flow intermittence disrupts this connectivity, operating through complex hydrological transitions (e.g., between flowing and nonflowing phases). These transitions occur concurrently and interact along all three spatial dimensions, primarily driven by flow regime and catchment geomorphology, modified by human activities. Longitudinally, streamflow cessation and drying interrupt hydrological connectivity, contributing to physicochemical patchiness, habitat isolation, and fragmentation of metapopulations and metacommunities. Laterally, hydrological connectivity established during overbank flows is lost when water levels fall, reducing water-mediated transfers of energy, materials, and organisms from the floodplain and riparian zone. Vertically, flow cessation impairs exchange of surface and shallow groundwater, severely altering hydrological, chemical, and microbial gradients within the sediments. Concurrent interactions and physical discontinuities in hydrological connectivity along these three dimensions produce complex mosaics of physicochemical patches at different scales whose boundaries fluctuate over time in response to the flow regime. This complex patchiness underpins the characteristic physical, chemical, and biological diversity at multiple scales along longitudinal, lateral, and vertical hydrological dimensions in IRES.

Book chapter↗

lasertram: A Python library for time resolved analysis of laser ablation inductively coupled plasma mass spectrometry data

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) data has a wide variety of uses in the geosciences for in-situ chemical analysis of complex natural materials. Improvements to instrument capabilities and operating software have drastically reduced the time required to generate large volumes of data relative to previous methodologies. Raw data from LA-ICP-MS, however, is in counts per unit time (typically counts per second), not elemental concentrations and converting these count ratesto concentrations requires additional processing. For complex materials where the ablated volume may contain a range of material compositions, a moderate amount of user input is also required if appropriate concentrations are to be accurately calculated. In geologic materials such as glasses and minerals that potentially have numerous heterogeneities (e.g., microlites or other inclusions) within them, this is typically determiningwhether the total ablation signal should be filtered to remove these heterogeneities. This necessitates that the LA-ICP-MS data processing pipeline is one that is not automated, but is also designed to enable rapid and efficient processing of large volumes of data. Here we introduce , a Python library for the time resolved analysis of LA-ICP-MS data. We outline its mathematical theory, code structure, and provide an example of how it can be used to provide the time resolved analysis necessitated by LA-ICP-MS data of complex geologic materials. Throughout the pipeline we show how metadata and data are incrementally added to the objects created such that virtually any aspect of an experiment may be interrogated and its quality assessed. We also show, that when combined with other Python libraries for building graphical user interfaces, it can be utilized outside of a pure scripting environment. can be found at https://doi.org/10.5066/P1DZUR3Z

Applied Computing and Geosciences↗

Modeling the surface water and groundwater budgets of the US using MODFLOW-OWHM

Assessments of groundwater and surface water budgets at a large scale, such as the contiguous United States, often separately analyze the complex dynamics linking the surface and subsurface categories of water resources. These dynamics include recharge and groundwater contributions to streamflow. The time-varying simulation of these complex hydrologic dynamics, across large spatial and temporal scales, remains a scientific challenge due to the complexity of the processes and data availability. In this study, groundwater fluxes and surface hydrologic processes are simulated across the contiguous US for 1950-2010. The simulation estimates the monthly water budget components, such as groundwater recharge, surface runoff, and evapotranspiration; streamflow in major rivers is routed while accounting for groundwater exchange. Human impacts are included through groundwater pumping, and climate variability is included, including variability in precipitation, temperature and potential evapotranspiration. The simulated groundwater level and river discharge have strong correlation with USGS observation wells and streamflow gages, with R 2 values of 0.992 and 0.946, respectively. The simulated evapotranspiration is compared with three other published estimation methods, showing that it is able to capture the magnitude and seasonality of evapotranspiration over the Mississippi River basin. As such, the model is able to reasonably simulate the surface and groundwater budgets over the US, allowing for questions of the relative importance of climate and human impacts to be explored in the future.

Advances in Water Resources↗

Evaluation of sulfate reduction at experimentally induced mixing interfaces using small-scale push-pull tests in an aquifer-wetland system

This paper presents small-scale push–pull tests designed to evaluate the kinetic controls on SO 4 2 - "> SO42- reduction in situ at mixing interfaces between a wetland and aquifer impacted by landfill leachate at the Norman Landfill research site, Norman, OK. Quantifying the rates of redox reactions initiated at interfaces is of great interest because interfaces have been shown to be zones of increased biogeochemical transformations and thus may play an important role in natural attenuation. To mimic the aquifer–wetland interface and evaluate reaction rates, SO 4 2 - "> SO42- -rich anaerobic aquifer water ( &#x223C; 100 mg / L SO 4 2 - ) "> (∼100mg/LSO42-) was introduced into SO 4 2 - "> SO42- -depleted wetland porewater via push–pull tests. Results showed SO 4 2 - "> SO42- reduction was stimulated by the mixing of these waters and first-order rate coefficients were comparable to those measured in other push–pull studies. However, rate data were complex involving either multiple first-order rate coefficients or a more complex rate order. In addition, a lag phase was observed prior to SO 4 2 - "> SO42- reduction that persisted until the mixing interface between test solution and native water was recovered, irrespective of temporal and spatial constraints. The lag phase was not eliminated by the addition of electron donor (acetate) to the injected test solution. Subsequent push–pull tests designed to elucidate the nature of the lag phase support the importance of the mixing interface in controlling terminal electron accepting processes. These data suggest redox reactions may occur rapidly at the mixing interface between injected and native waters but not in the injected bulk water mass. Under these circumstances, push–pull test data should be evaluated to ensure the apparent rate is actually a function of time and that complexities in rate data be considered.

Oklahoma↗