Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions. II. Rate constants,effective surface area,and the hydrolysis of feldspar

Analysis of experimental data reported by Lagache (1965, 1976), Evans (1965), Busenberg (1975), Busenberg and Clemency (1976), Holdren and Berner (1979), Siegel and Pfannkuch (1984), and Chou and Wollast (1984) with the aid of irreversible thermodynamics and transition state theory (Aagaard and Helgeson, 1977, 1982) suggests that at temperatures at least up to 650°C, the rate of both congruent and incongruent feldspar hydrolysis in aqueous solutions far from equilibrium at pH ? 10.6 ? (2300/T), where T stands for temperature in kelvins, is a function solely of effective surface area and pH at constant pressure and temperature. At higher pH, the rate is apparently pH-independent up to ~pH 8 at 25°C, where it again becomes pH-dependent at higher pH. Observations of scanning electron micrographs indicate that the cross-sectional area of etch pits on hydrolyzed feldspar grains is of the order of 10^?9 to 10^?8 cm² and that the ratio of the effective to total surface area (which may or may not change with reaction progress) ranges from <0.01 to 1, depending on the grain size, dislocation density, and the extent of comminution damage on the surfaces of the grains. Apparent rate constants retrieved from experimental data reported in the literature for feldspar hydrolysis in the lower pH-dependent range extend from ~10^?13 to ~10^?7 moles cm^?2 sec^?1 at temperatures from 25° to 200°C, which is consistent with activation enthalpies for albite and adularia of the order of 20 kcal mole^?1. In contrast, the apparent rate constants for the pH-independent rate law range from ~10^?16 to ~10^?11 moles cm^?2 sec^?1 at temperatures from 25° to 650°C, which requires an activation enthalpy for adularia of ~ 9 kcal mole^?1. These observations are consistent with surface control of reaction rates among minerals and aqueous solutions. The rate-limiting step in the pH-dependent case apparently corresponds at the lower end of the pH scale to breakdown of a protonated configuration of atoms on the surface of the reactant feldspar, but at higher pH the rate is limited by decomposition of an activated surface complex corresponding in stoichiometry to hydrous feldspar. In highly alkaline solutions, an activated complex containing hydroxyl ions apparently controls the rate of feldspar hydrolysis. Nevertheless, near equilibrium, regardless of pH the rate is proportional to the chemical affinity of the overall hydrolysis reaction.     

Filamentary structures in planetary nebulae

We have studied small-scale, filamentary features in 14 planetary nebulae and found that some structures are recurrent and shaped like the letters V and Y, with the apex or stem pointing toward the central parts of the nebula. Two such filaments containing dust, one in NGC 3132 and one in NGC 7293, were investigated in more detail. The mass and density of the filaments were obtained from extinction measurements, and their physical properties were derived. We propose that the structures are confined by magnetic fields, and derive magnetic field strengths of about 10⁻⁸ T, in line with earlier estimates. We also estimate the magnitude of the electric currents that we expect are generated in these dynamic systems. We propose a theory where the magnetic fields control the sculpting and evolution of small-scale filaments. This theory demonstrates how the substructures may form magnetized flux ropes that are twisted around each other, in the shape of double helices. Similar structures, and with similar origin, are found in many other astrophysical environments.     

Distribution of arsenic and its mobility in shallow aquifer sediments from Ambikanagar, West Bengal, India

Sediments from a core retrieved during installation of a shallow drinking water well in Ambikanagar (West Bengal, India) were analyzed for various physical and chemical parameters. The geochemical analyses included: (1) a 4-step sequential extraction scheme to determine the distribution of As between different fractions, (2) As speciation (As³⁺ vs. As⁵⁺), and (3) C, N and S isotopes. The sediments have a low percentage of organic C and N (0.10-0.56% and 0.01-0.05%, respectively). Arsenic concentration is between 2 and 7 mg kg⁻¹, and it is mainly associated with the residual fraction, less susceptible to chemical weathering. The proportion of As³⁺ in these sediments is high and ranges from 24% to 74%. Arsenic in the second fraction (reducible) correlates well with Mn, and in the residual fraction As correlates well with several transition elements. The stable isotope results indicate microbial oxidation of organic matter involving SO₄ reduction. Oxidation of primary sulfide minerals and release of As from reduction of Fe-(oxy)hydroxides do not seem important mechanisms in As mobilization. Instead, the dominance of As³⁺ and presence of As⁵⁺ reducing microorganisms in this shallow aquifer imply As remobilization involving microbial processes that needs further investigations.     

Single frequency processing of Ørsted GPS radio occultation measurements

The Global Positioning System (GPS) radio occultation measurements obtained using the TurboRogue GPS receiver on the Danish satellite Ørsted have been processed using the single frequency method. Atmospheric profiles of refractivity and temperature are derived and validated against numerical weather prediction data from the European Centre for Medium-Range Weather Forecast (ECMWF). Results from the Ørsted GPS measurement campaign in February 2000 indicate that the single frequency method can provide retrievals with accuracy comparable to that of using two frequencies. From comparisons between measured dry temperature profiles and corresponding dry temperature profiles derived from ECMWF analysis fields, we find a mean difference of less than 0.5 K and a standard deviation of 2–4 K between 500 and 30 hPa in height. Above 30 hPa the impact of the ionosphere becomes more dominant and more difficult to eliminate using the single frequency method, and the results show degraded accuracy when compared to previous analysis results of occultation data from other missions using the dual frequency method. At latitudes less than 40° (denoted low latitudes), the standard deviation is generally smaller than at latitudes higher than 40° (denoted high latitudes). A small temperature bias is observed centered at 200 hPa for low latitudes and at 300 hPa for high latitudes. This indicates that the ECMWF analyses do not adequately resolve the tropopause temperature minimum. In the lowest part of the troposphere an observed warm bias is thought to be due to erroneous tracking of the GPS signal in cases of atmospheric multipath propagation.     

Petroleum geoscience in Norden - exploration, production and organization

Offshore exploration in Norway and Denmark-in the North Sea, the Norwegian Sea and the Barents Sea-has involved drilling about 850 wildcat wells, resulting in about 300 oil and gas finds, of which 84 are fields with production. The recoverable resources of all these finds total about 65 billion barrels of oil equivalent. Almost all these hydrocarbons come from a Jurassic source and the main reservoirs and traps are Jurassic sandstones in fault blocks and Paleocene sandstones or Cretaceous chalks in gentle domes. The article describes four major fields-Ekofisk, Gullfaks, Ormen Lange and SnФhvitto illustrate some of the many challenges in developing and producing the hydrocarbons.
Elsewhere in Norden, there has been much less exploration. Drilling results have mostly been negative in mainland Sweden, onshore Denmark, onshore Svalbard and on- and offshore West Greenland. Minor oil finds have been made in Palaeozoic rocks in the Baltic Sea. The first wells have recently been drilled off the Faroe Islands, resulting in one discovery. No drilling has taken place on- or offshore East Greenland.
As a result of the hydrocarbon activities in Norway and Denmark, petroleum geoscience there has flourished, with 2000 geoscientists currently employed in the industry, many technical innovations made, a wealth of publically available information and a great increase in the understanding of the geology.     

Marginal formation of De Geer moraines and their implications to the dynamics of grounding‐line recession

De Geer moraine ridges occur in abundance in the coastal zone of northern Sweden, preferentially in areas with proglacial water depths in excess of 150 m at deglaciation. From detailed sedimentological and structural investigations in machine‐dug trenches across De Geer ridges it is concluded that the moraines formed due to subglacial sediment advection to the ice margin during temporary halts in grounding‐line retreat, forming gradually thickening sediment wedges. The proximal part of the moraines were built up in submarginal position as stacked sequences of deforming bed diamictons, intercalated with glaciofluvial canal‐infill sediments, whereas the distal parts were built up from the grounding line by prograding sediment gravity‐flow deposits, distally interfingering with glaciolacustrine sediments. The rapid grounding‐line retreat (ca. 400 m yr^?1) was driven by rapid calving, in turn enhanced by fast iceflow and marginal thinning of ice due to deforming bed conditions. The spatial distribution of the moraine ridges indicates stepwise retreat of the grounding line. It is suggested that this is due to slab and flake calving of the ice cliff above the waterline, forming a gradually widening subaqueous ice ledge which eventually breaks off to a new grounding line, followed by regained sediment delivery and ridge build‐up. Copyright © 2005 John Wiley & Sons, Ltd.     

A magnetostratigraphic comparison between 14C years and varve years during the Late Weichselian,indicating significant differences between the time-scales

A ¹⁴C-dated magnetostratigraphy of absolute declination and inclination between 12500 and 10000 ¹⁴C yr BP was recently developed for southern Sweden. Recently also the Swedish geochronological time-scale, based on c. 11 500 annually deposited clay-varves, was connected with the present. It should therefore be possible to compare the two chronologies with a reliable magnetostratigraphic record in an appropriate clay-varve section. We have found such a site within the Middle Swedish end-moraine zone. Statistical correlations between the two independently dated time-scales suggest that at 10500–10200 ¹⁴Cy r BP the varve chronology exceeds the ¹⁴C chronology by the order of 500-600 varve yr. Other correlations indicate that the difference between the two chronologies was less at 11000 ¹⁴C yr BP, and further correlations between the time-scales at 12000 ¹⁴C yr BP suggest that the difference between the chronologies increased steadily from 12000 to 10000 ¹⁴C yr BP. If these correlations are correct they imply that the ¹⁴C production rate increased steadily during the Late Weichselian.     

Partitioning of semi-soluble organic compounds between the water phase and oil droplets in produced water

When selecting produced water treatment technologies, one should focus on reducing the major contributors to the total environmental impact. These are dispersed oil and semi-soluble hydrocarbons, alkylated phenols, and added chemicals. Experiments with produced water have been performed offshore on the Statoil operated platforms Gullfaks C and Statfjord B. These experiments were designed to find how much of the environmentally relevant compounds were dissolved in the water phase and not associated to the dispersed oil in the produced water. Results show that the distribution between the dispersed oil and the water phase varies highly for the different components groups. For example the concentration of PAHs and the C6-C9 alkylated phenols is strongly correlated to the content of dispersed oil. Therefore, the technologies enhancing the removal of dispersed oil have a higher potential for reducing the environmental impact of the produced water than previously considered.     

APEX and ATCA observations of the southern hot core G327.3-0.6 and its environs

There is no generally accepted evolutionary scheme for high mass star formation yet. A simple approach to address this problem is to cover several of the known stages during the formation of massive stars in the same cloud and then investigate their properties trying to construct an evolutionary sequence. Here we present such a project conducted with complementary APEX and ATCA observations. These observations show a compact and bright single hot core in the G327.3-0.6 region on a 0.03 pc scale with a mass of 500 M_⊙ and 0.5–1.5 10⁵ L_⊙. Additionally a clumpy filament is seen in N₂H⁺. Together with cm continuum observations, the data reveal like pearls on a string several stages of massive star formation, with likely the youngest stages hiding in the cold N₂H⁺ cores analysed with a multilevel study of the APEX and ATCA observations.     

The POC / Th ratio of settling particles isolated using split flow-thin cell fractionation (SPLITT)

The common assumption that the ratio between particulate organic carbon (POC) and particulate ²³⁴Th obtained from shallow sediment traps and filterable particles are representative of the ratio in the total particle settling flux should be treated with caution in view of well-known biases associated with tethered shallow sediment traps and the decoupling between size and settling velocity of many natural particle regimes. To make progress toward reliably constraining the POC / ²³⁴Th ratio on truly settling particles, we have tested here a settling collection technique designed to remove any hydrodynamic bias; split flow-thin cell fractionation (SPLITT). These first results from a North Sea fjord and an open Baltic Sea time-series station indicates that the POC / ²³⁴Th ratio on the more complete particle-settling spectrum, isolated with SPLITT, was higher than the POC / ²³⁴Th ratio obtained simultaneously from tethered shallow sediment traps in seven out of seven parallel deployments with an average factor of 210%. The POC / ²³⁴Th ratio from the SPLITT was either in the same range or higher than that obtained on filtered “bulk” particles. To explain this novel data we hypothesize that the slowest settling fraction is organic-matter rich and does not strongly complex ²³⁴Th (i.e., high POC / ²³⁴Th). We suggest that this ultra-slow sinking fraction is better collected by SPLITT than with tethered sediment traps because of minimized hydrodynamic bias.This was tested using the ratio of POC / Al as a tracer of detrital mineral-ballast influenced settling velocity. The higher POC / Al ratios in SPLITT samples relative to in traps is consistent with the hypothesis that SPLITT is better suited for collecting also the slow-settling component of sinking particles. This important slow-settling component appears to here consist primarily of non-APS/TEP components of plankton exudates or other less-strongly ²³⁴Th-complexing organic matter. Further applications of the SPLITT technique are likely to return increasingly new insights on the composition (including “truly settling” POC / ²³⁴Th) of the total spectrum of particles settling out of the upper ocean.