A generalized garnet-forming reaction for metaigneous rocks in the Adirondacks

A generalized reaction is presented to account for garnet formation in a variety of Adirondack metaigneous rocks. This reaction, which is the sum of five partial reactions written in aluminum-fixed frames of reference, is given by: 4(y+1+w)Anorthite+4k(y+1+2w)Olivine +4(1–k)(y+1+2w)Fe-oxide+(8(y+1) –4k(y+1+2w))Orthopyroxene = 2(y+1)Garnet +2(y+1+2w)Clinopyroxene+4wSpinel where y is a function of plagioclase composition, k refers to the relative amounts of olivine and Fe-oxide participating in the reaction, and w is a measure of silicon mobility. When mass balanced for Mg and Fe, this reaction is found to be consistent with analyzed mineral compositions in a wide range of Adirondack metaigneous rocks. The reaction applies equally well whether the garnets were formed directly from the rectants given above or went through an intermadiate stage involving the formation of spinel, orthopyroxene, and clinopyroxene.The actual reactions which have produced garnet in both undersaturated and quartz-bearing rocks are special cases of the above general reaction. The most important special cases appear to be those in which the reactants include either olivine alone (k=1) or Fe-oxide alone (k=0). Silicon is relatively immobile (w =2) in olivine bearing, magnesium-rich rocks (k1), and this correlates with the increased intensity in spinel clouding of plagioclase in these rocks. Silicon mobility apparently increases in the more iron-rich rocks, which also tend to contain clear or lightly clouded plagioclase. In all the rocks studied the most common composition of metamorphic plagioclase is close to An₃₃ (i.e., y=1). Plagioclase of lower anorthite content may be too sodic to participate in garnet formation at the P-T conditions involved.Published by permission of the Director, New York State Museum and Science Service; Journal Series No. 282     

Karst system developed in salt layers of the Lisan Peninsula,Dead Sea,Jordan

The Lisan Peninsula, Jordan, is a massive salt layer accumulated in the inner part of the Dead Sea’s precursory lakes. This tongue-shaped, emergent land results in a salt diapir uplifted in the Dead Sea strike-slip regional stress field and modified by the water level fluctuations of the last lake during the Holocene. These two elements, associated with dissolution caused by rainfall and groundwater circulation, resulted in an authentic karst system. Since the 1960s, the Dead Sea lowering of 80 cm to 1 m per year caused costly damages to the industrial plant set up on the peninsula. The Lisan karst system is described in this article and the components of the present dynamic setting clarified.     

Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids

Fe(III) solid phases are the products of Fe(II) oxidation by Fe(II)-oxidizing bacteria, but the Fe(III) phases reported to form within growth experiments are, at times, poorly crystalline and therefore difficult to identify, possibly due to the presence of ligands (e.g., phosphate, carbonate) that complex iron and disrupt iron (hydr)oxide precipitation. The scope of this study was to investigate the influences of geochemical solution conditions (pH, carbonate, phosphate, humic acids) on the Fe(II) oxidation rate and Fe(III) mineralogy. Fe(III) mineral characterization was performed using ⁵⁷Fe-Mössbauer spectroscopy and μ-X-ray diffraction after oxidation of dissolved Fe(II) within Mops-buffered cell suspensions of Acidovorax sp. BoFeN1, a nitrate-reducing, Fe(II)-oxidizing bacterium. Lepidocrocite (γ-FeOOH) (90%), which also forms after chemical oxidation of Fe(II) by dissolved O₂, and goethite (α-FeOOH) (10%) were produced at pH 7.0 in the absence of any strongly complexing ligands. Higher solution pH, increasing concentrations of carbonate species, and increasing concentrations of humic acids promoted goethite formation and caused little or no changes in Fe(II) oxidation rates. Phosphate species resulted in Fe(III) solids unidentifiable to our methods and significantly slowed Fe(II) oxidation rates. Our results suggest that Fe(III) mineralogy formed by bacterial Fe(II) oxidation is strongly influenced by solution chemistry, and the geochemical conditions studied here suggest lepidocrocite and goethite may coexist in aquatic environments where nitrate-reducing, Fe(II)-oxidizing bacteria are active.     

The influence of model structure on groundwater recharge rates in climate-change impact studies

Numerous modeling approaches are available to provide insight into the relationship between climate change and groundwater recharge. However, several aspects of how hydrological model choice and structure affect recharge predictions have not been fully explored, unlike the well-established variability of climate model chains—combination of global climate models (GCM) and regional climate models (RCM). Furthermore, the influence on predictions related to subsoil parameterization and the variability of observation data employed during calibration remain unclear. This paper compares and quantifies these different sources of uncertainty in a systematic way. The described numerical experiment is based on a heterogeneous two-dimensional reference model. Four simpler models were calibrated against the output of the reference model, and recharge predictions of both reference and simpler models were compared to evaluate the effect of model structure on climate-change impact studies. The results highlight that model simplification leads to different recharge rates under climate change, especially under extreme conditions, although the different models performed similarly under historical climate conditions. Extreme weather conditions lead to model bias in the predictions and therefore must be considered. Consequently, the chosen calibration strategy is important and, if possible, the calibration data set should include climatic extremes in order to minimise model bias introduced by the calibration. The results strongly suggest that ensembles of climate projections should be coupled with ensembles of hydrogeological models to produce credible predictions of future recharge and with the associated uncertainties.     

The partitioning of copper and molybdenum between silicate melts and aqueous fluids

The partitioning of copper and molybdenum between silicate melts and aqueous fluids has been determined at 750°C, and 1.4 Kb. The experiments were conducted in a $\text{1}\text{2}$ inch ID, rapid quench, cold seal pressure vessel. The aqueous and glass phase run products were analyzed by atomic absorption spectrophotometry and ion microprobe, respectively. The vapor/melt partition coefficient for copper, $\text{D}{}^{\mathrm{<mtext>v</mtext><mtext>l</mtext>}}{}_{\mathrm{Cu}}$, defined as the ratio of the concentrations of copper in the vapor to copper in the melt was found to be $\text{D}{}^{\mathrm{<mtext>v</mtext><mtext>l</mtext>}}{}_{\mathrm{Cu}}\text{= (9.1 ± 2.5)m}{}^{\mathrm{v}}{}_{\mathrm{Cl}}$ at NNO up to at least 4.5 moles of chlorine per kg of solution. The partition coefficient for molybdenum is equal to 2.5 ± 1.6 at NNO and QFM; its value is independent of the fluorine concentration of the melt up to at least 1.7 wt. percent fluorine, and of the chlorine concentration up to at least 4.5 moles of chlorine per kg of solution. Copper is probably present in the univalent state in both the silicate melt and in the associated aqueous phase at NNO; the most important aqueous complex of copper is probably CuCl⁰. Molybdenum is probably present in the aqueous phase as one or more molybdate species.     

Experimental determination of partition coefficients for Rb,Sr and Ba between alkali feldspar and silicate liquid

Partitioning of Rb, Sr and Ba between alkali feldspar and a synthetic granitic melt has been determined at 8 kb and 720 to 780°C for a single quaternary granite composition. The results suggest that Henry's law is obeyed by Rb up to ~0.8 wt.% Rb₂O in both the liquid and in the alkali feldspar. The measured D values for Rb range from 0.77 to 1.1. For Ba, Henry's Law is obeyed up to ~0.6 wt.% BaO in the liquid and ~5 wt.% BaO in the alkali feldspar. D values for Ba range from 6.4 to 14. For Sr there is only a crude relationship between concentration in the liquid and concentration in the alkali feldspar at concentrations greater than ~0.6 wt.% SrO in the liquid and ~0.4 wt.% SrO in the alkali feldspar. D values for Sr range from 1.2 to 5.0. Partitioning of Sr is apparently sensitive to the concentration of Ba in the system and this partly explains the failure of Sr to obey Henry's Law.Linear least-squares fits to the partitioning data as a function of temperature suggest inverse correlation between temperature and D values. Rb shows only a slight temperature effect whereas Ba and Sr appear to be rather strongly affected by temperature, but the temperature range examined here is small compared to the scatter in the data making these trends relatively uncertain. Other factors that appear to affect partitioning, especially of Sr, are growth rate, development of sector zoning and Or content of the alkali feldspar. These factors severely limit the use of partitioning of these elements in alkali feldspar as geothermometers.The technique for measuring growth rates utilized here combined with measurement of trace element depletion in diffusion boundary layers adjacent to the alkali feldspar crystals makes it possible to estimate diffusivities for Ba and Sr. These estimates suggest a difference of 2 orders of magnitude between diffusivities for Ba and Sr in a vapor-saturated melt and those measured by HOFMANN and MAGARITZ (1976) for a dry obsidian glass.     

Geochemical behavior of inorganic germanium in an unperturbed estuary

Eleven monthly estuarine profiles of dissolved inorganic germanium (Ge_i) and silica (Si) in a natural, pristine river/bay system demonstrate that Ge-removal and -input parallel the seasonal silica cycle, reflecting Ge-uptake by and -dissolution from diatoms. The Ge/Si atom ratio of the river is 0.6 ± 0.15 × 10^?6, which is near the average value for continental granites and for uncontaminated, remote, natural rivers (0.7 ± 0.3 × 10^?6). The $\text{Ge}\text{Si}$ ratio escaping this estuary to the ocean is 0.8 × 10^?6, reflecting some estuarine enhancement of the fluvial Ge-flux, probably due to release of Ge_i from fluvial particulates. Nevertheless, the post-estuarine $\text{Ge}\text{Si}$ ratio is not significantly different from the continental crustal ratio but is very different from the ratio in sea-floor hot springs and mid-ocean ridge hydrothermal plumes (4 ± 2 × 10^?6) and in oceanic basalts (2.6 × 10^?6). Thus natural estuarine processes do not obscure the contrasting $\text{Ge}\text{Si}$ signatures entering the ocean from dissolution of continental and sea-floor silicates.     

Origins and accumulation of organic matter in expanded Albian to Santonian black shale sequences on the Demerara Rise, South American margin

Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ¹³C_org values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C₃ land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ¹³C_org values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.     

Terrestrial weathering rates defined by extraterrestrial materials

In studies attempting to quantify the effects of climate on weathering rate, meteorites offer a number of advantages over terrestrial rocks—material from one outcrop (in this case, an asteroid parent body) delivers samples of similar composition and texture over the whole of the Earth's surface, in all climatic regimes; the starting composition prior to weathering is known in detail; the terrestrial residence time may be accurately determined from cosmogenic radionuclides; and the degree of weathering can be tracked by measuring the abundance of ferric iron. When analysing meteorites found in different deserts, we can discriminate a range of weathering rates. We observe a rapid initial weathering phase with the majority of weathering occurring in the first few hundred years after fall. Although the overall degree of weathering and the suite of weathering products observed will be specific to meteorites, the relative differences in weathering rate between different sites should be similar for terrestrial rocks.     

Quantifying stream-loss recovery in a spring using dual-tracer injections in the Snake Creek drainage,Great Basin National Park,Nevada, USA

Simultaneous short-pulse injections of two tracers (sodium bromide [Br^–] and fluorescein dye) were made in a losing reach of Snake Creek in Great Basin National Park, Nevada, USA, to evaluate the quantity of stream loss through permeable carbonates that resurfaces at a spring approximately 10 km down drainage. A revised hydrogeologic cross section for a possible flow path of the infiltrated Snake Creek water is presented, and the results may inform water management in the region. First arrival and peak concentration of the two tracers occurred at 9.5 and 12.7 days after injection, respectively. Fracture transport simulations indicate that Br^– preferentially diffuses into immobile regions of the aquifer, and this diffusive flux is likely responsible for the major differences in the breakthrough curves. When considering the diffusive tracer flux, total apparent Br^– and fluorescein dye recoveries were 16.9–22.1% and 21.7–24.3%, respectively. These findings imply that consideration of diffusive flux and long-term monitoring in fracture-dominated flow may support accurate quantification of tracer recovery. In addition, the apparent power law slopes of the breakthrough tails for both tracers were steeper at early times than have been attributed to heterogeneous advection or channeling in meter-scale tests, but the late-time Br^– power law slope becomes less steep than has been attributed to diffusive exchange. These deviations may reflect fracture transport patterns that occur at larger scales.