The major-ion composition of silurian seawater

One-hundred fluid inclusions in Silurian marine halite were analyzed in order to determine the major-ion composition of Silurian seawater. The samples analyzed were from three formations in the Late Silurian Michigan Basin, the A-1, A-2, and B Evaporites of the Salina Group, and one formation in the Early Silurian Canning Basin (Australia), the Mallowa Salt of the Carribuddy Group. The results indicate that the major-ion composition of Silurian seawater was not the same as present-day seawater. The Silurian ocean had lower concentrations of Mg²⁺, Na⁺, and SO₄²⁻, and much higher concentrations of Ca²⁺ relative to the ocean’s present-day composition. Furthermore, Silurian seawater had Ca²⁺ in excess of SO₄²⁻. Evaporation of Silurian seawater of the composition determined in this study produces KCl-type potash minerals that lack the MgSO₄-type late stage salts formed during the evaporation of present-day seawater. The relatively low Na⁺ concentrations in Silurian seawater support the hypothesis that oscillations in the major-ion composition of the oceans are primarily controlled by changes in the flux of mid-ocean ridge brine and riverine inputs and not global or basin-scale, seawater-driven dolomitization. The Mg²⁺/Ca²⁺ ratio of Silurian seawater was ∼1.4, and the K⁺/Ca²⁺ ratio was ∼0.3, both of which differ from the present-day counterparts of 5 and 1, respectively. Seawaters with Mg²⁺/Ca²⁺ <2 facilitate the precipitation of low-magnesian calcite (mol % Mg < 4) marine ooids and submarine carbonate cements whereas seawaters with Mg²⁺/Ca²⁺ >2 (e.g., modern seawater) facilitate the precipitation of aragonite and high-magnesian calcite. Therefore, the early Paleozoic calcite seas were likely due to the low Mg²⁺/Ca²⁺ ratio of seawater, not the pCO₂ of the Silurian atmosphere.     

Microbial respiration and diffusive transport of O2, O2, and OO in unsaturated soils: a mesocosm experiment

Although the flux of molecular O₂ between the atmosphere and the subsurface is intrinsically linked to the net soil production of greenhouse gasses, few studies have focused on the controls affecting the isotopic composition of O₂ in the subsurface. Here, we developed and tested a stable oxygen isotope tracer technique and gas transport modeling approach to evaluate O₂ cycling and fluxes from the subsurface that used an environmentally controlled soil mescosm. We measured the O₂ and δ¹⁸O₂ profiles in a model unsaturated soil zone and quantified the O₂ consumption rates and the O₂ isotope fractionation factors resulting from the combined processes of subsurface microbial (including bacteria, fungi, and protozoa) consumption of O₂ and diffusive influx of O₂ from the atmosphere. We found that at high respiration rates in the mesocosm, there appeared to be very little isotope fractionation of O₂ by soil microorganisms. Although the mesocosm respiration rates are not typical of natural soils in northern temperate climes, they may be more representative of soils in warm and moist tropical environments. Our findings caution against the indiscriminate application of laboratory-determined oxygen isotope fractionation factors to field settings. The oxygen isotope tracer and modeling approach demonstrated here may be applied to gain a better understanding of biogenic gas production and O₂ cycling in subsurface systems and soils.     

Consequences of diffuse and channelled porous melt migration on uranium series disequilibria

Magmas erupted at mid-ocean ridges (MORB) result from decompression melting of upwelling mantle. However, the mechanism of melt transport from the source region to the surface is poorly understood. It is debated whether melt is transported through melt-filled conduits or cracks on short time scales (<∼ 10³ yrs), or whether there is a significant component of slow, equilibrium porous flow on much longer time scales (>∼ 10³-10⁴ yrs). Radiogenic excess ²²⁶Ra in MORB indicates that melt is transported from the melting region on time scales less than the half life of ²²⁶Ra (∼1600 yrs), and has been used to argue for fast melt transport from the base of the melting column. However, excess ²²⁶Ra can be generated at the bottom of the melt column, during the onset of melting, and at the top of the melt column by reactive porous flow. Determining the depth at which ²²⁶Ra is generated is critical to interpreting the rate and mechanism of magma migration. A recent compilation of high quality U-series isotope data show that in many young basalts, ²²⁶Ra excess in MORB is negatively correlated with ²³⁰Th excess. The data suggest that ²²⁶Ra excess is generated independently of ²³⁰Th excess, and cannot be explained by “dynamic” or fractional melting, where observed radiogenic excesses are all generated at the base of the melt column. One explanation is that the negative correlation of activity ratios is a result of mixing of slow moving melt that has travelled through reactive, low-porosity pathways and relatively fast moving melt that has been transported in unreactive high-porosity channels. We investigate this possibility by calculating U-series disequilibria in a melting column in which high-porosity, unreactive channels form within a low-porosity matrix that is undergoing melting. The results show that the negative correlation of ²²⁶Ra and ²³⁰Th excesses observed in MORB can be produced if ∼60% of the total melt flux travels through the low-porosity matrix. This melt maintains ²²⁶Ra excesses via chromatographic fractionation of Ra and Th during equilibrium transport. Melt that travels through the unreactive, high-porosity channels is not able to maintain significant ²²⁶Ra excesses because Ra and Th are not fractionated from each other during transport and the transport time for melt in the channels to reach the top of the melt column is longer than the time scale for ²²⁶Ra excesses to decay. Mixing of melt from the high porosity channels with melt from the low-porosity matrix at the top of the melting column can produce a negative correlation of ²²⁶Ra and ²³⁰Th excesses with the slope and magnitude observed in MORB. This transport process can also account for other aspects of the geochemistry of MORB, such as correlations between La/Yb, α_Sm/Nd, and Th/U and ²²⁶Ra and ²³⁰Th excess.     

Physical and chemical properties of the waters of saline lakes and their importance for deep-water renewal: Lake Issyk-Kul, Kyrgyzstan

The relationships between electrical conductivity, temperature, salinity, and density are studied for brackish Lake Issyk-Kul. These studies are based on a newly determined major ion composition, which for the open lake shows a mean absolute salinity of 6.06 g kg⁻¹. The conductivity-temperature relationship of the lake water was determined experimentally showing that the lake water is about 1.25 times less conductive than seawater diluted to the same absolute salinity as that of the lake water. Based on these results, an algorithm is presented to calculate salinity from in-situ conductivity measurements. Applied to the field data, this shows small but important vertical salinity variations in the lake with a salinity maximum at 200 m and a freshening of the surface water with increasing proximity to the shores. The algorithm we adopt to calculate density agrees well with earlier measurements and shows that at 20°C and 1 atm Lake Issyk-Kul water is about 530 g m⁻³ denser than seawater at the same salinity. The temperature of maximum density at 1 atm is about 0.15°C lower than that for seawater diluted to the same salinity. Despite its small variations, salinity plays an important role, together with temperature changes, in the static stability and in the production of deep-water in this lake. Changes in salinity may have had important consequences on the mixing regime and the fate of inflowing river water over geological time. Uncharged silicic acid is negligible for the stability of the water column except near an ∼15 m thick nepheloid layer observed at the bottom of the deep basin.     

A Comparison of Two-Phase Dynamic Upscaling Methods Based on Fluid Potentials

Although a number of methods for calculating dynamic pseudo-functions have been developed over the years, there is still a lack of understanding as to why a certain method will succeed in some cases but fail in others. In this paper, we describe the results of an assessment of several upscaling methods, namely the Kyte and Berry (KB) method, the Stone method, the Hewett and Archer (HA) method and the Transmissibility-Weighted (TW) method. We have analyzed the equations for deriving the methods and investigated the results of numerical simulations of gas displacing oil, in a variety of models to enable us to gain new insights into these, and related, upscaling methods. In particular, some novel observations on methods based on fluid potential are presented and the issue of using predicted fluid mobilities as a criterion of accuracy of an upscaling method is clarified.     

Paleomagnetic dating of Alleghanian orogenesis and mineralisation in the Mascot–Jefferson City zinc district of East Tennessee, USA

The Mascot–Jefferson City (M-JC) Mississippi Valley-type (MVT) deposits are in the Valley and Ridge province of the Appalachian orogen in East Tennessee. They have been a major source of zinc for the USA but their age is uncertain and thus their genesis controversial. About 10 specimens from each of 37 sites have been analysed paleomagnetically using alternating field and thermal step demagnetisation methods and saturation isothermal remanence methods. The sites sample limestones, dolostones, breccia clasts and sphalerite–dolomite MVT mineralisation from mines in the Lower Ordovician Kingsport and Mascot formations of the Knox Group. The characteristic remanent magnetisation (ChRM) is carried by magnetite in the limestones, by both magnetite and pyrrhotite in the dolostones and by pyrrhotite preferentially to magnetite in the mineralisation. Mineralized sites have a more intense ChRM than non-mineralised, indicating that the mineralising and magnetisation event are coeval. Paleomagnetic breccia tests on clasts at the three sites are negative, indicating that their ChRM is post-depositional remagnetisation, and a paleomagnetic fold test is negative, indicating that the ChRM is a remagnetisation, and a post-dates peak Alleghanian deformation. The unit mean ChRM direction for the: (a) limestones gives a paleopole at 129°E, 12°N (d_p=18°, d_m=26°, N=3), indicating diagenesis formed a secondary chemical remanent magnetisation during the Late Ordovician–Early Silurian; (b) dolomitic limestones and dolostone host rocks gives a paleopole at 125.3°E, 31.9°N (d_p=5.3°, d_m=9.4°, N=7), recording regional dolomitisation at 334±14 Ma (1σ); and (c) MVT mineralisation gives a paleopole at 128.7°E, 34.0°N (d_p=2.4°, d_m=4.4°, N=25), showing that it acquired its primary chemical remanence at 316±8 Ma (1σ). The mineralisation is interpreted to have formed from hydrothermal fluid flow, either gravity or tectonically driven, after peak Alleghanian deformation in eastern Tennessee with regional dolomitisation of the host rocks occurring as part of a continuum during the 20 Ma prior to and during peak deformation.     

Deep structure of the northeastern margin of the Parnaiba Basin, Brazil, from magnetotelluric imaging

The magnetotelluric (MT) method has been applied to the determination of the deep resistivity structure of the northeastern margin of the Parnaiba Basin. Transient electromagnetic (TEM) and MT data were collected in early 1999 along a 95 km long N–S line, extending from the coast across the projected subcrop position of a discontinuous fault found to the west of the study area that is believed to be a possible basin‐bounding fault. The MT data were processed to yield the TE‐ and TM‐mode responses and then corrected for static shift using central‐loop and single‐loop TEM data, respectively. Regularized 2D MT inversion was subsequently undertaken using a structured initial model with the near‐surface constrained by TEM inversion results. As a consistency check, we performed another set of 2D inversions using different smooth initial models. The various optimal 2D inversion models show clearly the presence of a major basement trough, over 2 km deep, located about 70 km from the coast. We interpret it as possibly marking the main basin margin and suggest that it may have implications for groundwater resource development in the area.     

Relationships between tissue concentrations of chlorinated hydrocarbons (polychlorinated biphenyls and chlorinated pesticides) and antioxidative responses of marine mussels, Perna viridis

Marine mussels, Perna viridis, were transplanted from a reference site to various polluted sites around Hong Kong. After 30 d of exposure, antioxidative responses in the gills and hepatopancreas and tissue concentrations of chlorinated hydrocarbons [polychlorinated biphenyls (PCBs) and chlorinated pesticides (CPs)] were determined for individual mussels. Glutathione S transferase (GST) and glutathione (GSH) were positively correlated with tissue PCB concentrations. Only one of the enzymatic antioxidants, glutathione peroxidase (GPx), showed significant response to tissue PCB. No significant correlation was found between tissue concentrations of chlorinated hydrocarbons and other enzymatic antioxidants (superoxide dismutase (SOD), catalase (CAT), glutathione reductase (GR) and NADPH DT-diaphorase (DT-d). Oxidative stress, measured as thiobarbituric acid reactive substances, was correlated with chlorinated pesticide concentrations in tissues. This study demonstrated a correlation between GST/GSH and chlorinated hydrocarbons. The apparent lack of correlation between trace organic pollutants and some of the enzymatic antioxidants may be due to the inhibitory effects caused by these chemicals. The above results suggest that more investigations are needed before these enzymes can be used as biomarkers.     

Mathematical modeling of PCB bioaccumulation in Perna viridis

In the present work, we built a mathematical model of polychlorinated biphenyl (PCB) bioaccumulation in Perna viridis, namely, a one-compartment model with a time dependent incorporation rate R (μg g⁻¹ lipid per ppb water per day), with positive substrate cooperativity as the underlying physical mechanism. The temporal change of the PCB concentration Q (μg g⁻¹ lipid) in the soft tissues of the mussel depends on the competition of the input rate RW and the output rate kQ, where W is the concentration of PCB in water (ppb water) and k is the elimination rate (per day). From our experimental data, k=0.181±0.017 d⁻¹. The critical concentration in water W_c for positive substrate cooperativity was found to be 2.4 ppb. Below W_c, R is a constant. For a water concentration of 0.5 ppb Aroclor 1254, R=24.0±2.4 μg g⁻¹ lipid ppb⁻¹ d⁻¹. Above W_c, positive substrate cooperativity comes into effect and R becomes a function of time and dependent on the concentration Q in a form R=γQ/(Q+δ). This is the case for a water concentration of 5 ppb Aroclor 1254, where γ=15.1 μg g⁻¹ lipid ppb⁻¹ d¹ and δ≈200 μg g⁻¹ lipid. From this model, the uptake is exponentially increasing when the PCB concentration in the mussel is small compared to 200 μg g⁻¹ lipid, and hyperbolically increasing when the concentration is large compared to 200 μg g⁻¹ lipid, which are consistent with the experimental data. The model is useful for understanding the true processes taking place during the bioaccumulation and for risk assessment with higher confidence. Future experimental data which challenge the present model are anticipated and in fact desirable for improvement and perfection of the model.     

Solar–terrestrial effects possibly stronger in biblical times

Paleomagnetic studies have shown that, moving backwards in time, the geomagnetic dipole moment increased to a peak nearly 50% greater than at present ca. 2500 years ago. Attempts to model how changes in dipole moment affect solar–terrestrial relations have hitherto invoked a scaling relation for the size of the magnetosphere based on finding where the magnetic pressure of the dipole field balances the ram pressure of the solar wind. This approach predicts that, following a solar storm, the strength of the terrestrial response represented by the electrical potential across the auroral zones in the ionosphere should vary as the 1/3 power of dipole moment. Such a weak dependence suggests that a 50% increase in dipole moment would minimally effect (14%) terrestrial manifestations of solar storms. Recent work, however, based on a feedback mechanism involving electrical currents coupling the magnetosphere and ionosphere has identified a stronger 4/3, power scaling relation applicable to storm conditions. Here we use a global MHD simulation to calculate for a 50% increased dipole moment the correspondingly increased auroral-zone potential and its extension to low latitudes.