Dissolved organic carbon from the traditional jute processing technique and its potential influence on arsenic enrichment in the Bengal Delta

Dissolved organic C (DOC) plays an important role in the mobilization of As from sediments. In West Bengal, the widely used technique for obtaining jute fiber involves retting of the jute plant in ponds (hereafter such ponds are termed jute decomposing ponds) for several weeks, which produces significant amounts of DOC in the ponds. These ponds thus act as point sources of DOC and supply huge quantities of organic C to the Bengal Delta sediments. This study has been carried out to investigate the role of such DOC in enriching the groundwater with As in the Bengal Delta. Data clearly show that due to the effect of DOC, As is mobilized from the upper 2.6 m of the sediment profile, and is fixed between 2.6 and 6.1 m, while the lower part (6.1–9 m) largely remains unaffected. The reducing conditions mainly developed due to the decay of the percolating DOC seem to help the mobilization and transportation of As and other redox sensitive elements (Fe, Mn), as well as elements (Cu, Zn) attached to oxy-hydroxides of those redox-sensitive elements. Experiments also indicate that if the DOC production at the surface continues for a longer period of time, the zone of As fixation (2.6–6.1 m) may get shifted further downwards and ultimately intercept the water table resulting in As enrichment of groundwater.     

An Adaptive Code for Radial Stellar Model Pulsations

We describe an implicit 1–D adaptive mesh hydrodynamics code that is specially tailored for radial stellar pulsations. In the Lagrangian limit the code reduces to the well tested Fraley scheme. The code has the useful feature that unwanted, long lasting transients can be avoided by smoothly switching on the adaptive mesh features starting from the Lagrangean code. Thus, a limit cycle pulsation that can readily be computed with the relaxation method of Stellingwerf will converge in a few tens of pulsation cycles when put into the adaptive mesh code. The code has been checked with two shock problems, viz. Noh and Sedov, for which analytical solutions are known, and it has been found to be both accurate and stable. Superior results were obtained through the solution of the total energy (gravitational + kinetic + internal) equation rather than that of the internal energy only. This revised version was published online in July 2006 with corrections to the Cover Date.     

Imprints of hydrocarbon-bearing basinal fluids on a karst system: mineralogical and fluid inclusion studies from the Buda Hills,Hungary

Calcite veins and related sulphate–sulphide mineralisation are common in the Buda Hills. Also, abundant hypogenic caves are found along fractures filled with these minerals pointing to the fact that young cave-forming fluids migrated along the same fractures as the older mineralising fluids did. The studied vein-filling paragenesis consists of calcite, barite, fluorite and sulphides. The strike of fractures is consistent—NNW–SSE—concluding a latest Early Miocene maximum age for the formation of fracture-filling minerals. Calcite crystals contain coeval primary, hydrocarbon-bearing- and aqueous inclusions indicating that also hydrocarbons have migrated together with the mineralising fluids. Hydrocarbon inclusions are described here for the first time from the Buda Hills. Mixed inclusions, i.e., petroleum with ‘water-tail’, were also detected, indicating that transcrystalline water migration took place. The coexistence of aqueous and petroleum inclusions permitted to establish the entrapment temperature (80°C) and pressure (85 bar) of the fluid and thus also the thickness of sediments, having been eroded since latest Early Miocene times, was calculated (800 m). Low salinity of the fluids (<1.7 NaCl eq. wt%) implies that hydrocarbon-bearing fluids were diluted by regional karst water. FT-IR investigations revealed that CO₂ and CH₄ are associated with hydrocarbons. Groundwater also contains small amounts of HC and related gases on the basin side even today. Based on the location of the paleo- and recent hydrocarbon indications, identical migration pathways were reconstructed for both systems. Hydrocarbon-bearing fluids are supposed to have migrated north-westward from the basin east to the Buda Hills from the Miocene on.     

Seasonal Variability of Adsorption and Exchange Equilibria in Soil Waters

Chemical analyses for major ions have been conducted on waters,collected on an approximately weekly basis over the period April, 1993 toNovember, 1996, that drain three small experimental ecosystems(sandboxes) at Hubbard Brook, New Hampshire. One sandbox is planted withpine trees, another with grass, and the third is left bare (actually itis covered sporadically by bryophytes and lichens). Results show linearcorrelations, independent of discharge, between the concentrations ofdissolved Na⁺ and K⁺ on the one hand andCa⁺⁺ and Mg⁺⁺ on the other for all threesandboxes. No correlations between singly charged and doubly chargedcations were found. These correlations are interpreted to represent cationexchange equilibria between soil waters and clay minerals plus soil organicmatter. The correlation slope, representing the exchange constant, for Na vsK is different for the pine-covered sandbox than for the other two whereasfor Ca vs Mg the correlation is independent of the presence or absence oftrees. We interpret this as representing a shift of cation exchangeequilibria in the pine sandbox by the activities of growing trees.Concentrations of Na, K, Ca, Mg, and H₄SiO₄from the barren and grass-lined sandboxes were found to vary seasonally witha marked sinusoidal pattern which was independent of the discharge from eachsandbox. (The discernment of a similar pattern in the tree lined sandbox wasdifficult due to a lack of discharge over much of the year.) Concentrationmaxima occurred in August and minima in February, and there is a closeparallelism with soil temperature. We interpret this as representingtemperature induced variations in cation exchange equilibria and silicaadsorption. Independence from highly varying water discharge, e.g.,. thataccompanying severe rainstorms, indicates rapidly re-attained equilibrium.Variations in the concentrations of cations are likely due to exchange withunmeasured cations, probably H⁺ or dissolved Al species, as aresult of possible seasonal changes in internal acid production and externalinput of acid rain to the sandboxes. Internal production may represent aresponse to seasonal changes in respiration rate as it responds toseasonally varying temperature. Added to this is the effect of temperatureon exchange equilibrium. Seasonal variations in dissolved silica are mostlikely due to the dependence of adsorption/desorption equilibria ontemperature. The temperature dependence of a number of silica-consumingreactions are consistent with the measured values.     

Sedimentary pyrite formation: An update

Sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter, dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron minerals are abundant. By contrast, pyrite formation in non-marine, freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh water shales from marine shales. Under marine euxinic conditions sufficient H₂S is produced that the dominant control on pyrite formation is the availability of reactive iron minerals.Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High $\text{C}\text{S}$ ratios during Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time. Low $\text{C}\text{S}$ ratios, compared to today, during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time.     

Phosphate removal from sea water by adsorption on volcanogenic ferric oxides

Chemical data presented in this paper indicate a good correlation between P₂O₅ and Fe₂O₃ in some iron-rich volcanogenic sediments from the East Pacific Rise. In addition, adsorption experiments and chemical analyses of deuterically altered and unaltered samples of submarine basalts strongly suggest that this association is due to the reaction of phosphate in sea water with poorly crystallized hydrous ferric oxides. East Pacific Rise sediments adsorb far greater amounts of phosphate from sea water than either carbonate or non-carbonate sediments from other areas of the ocean. From geochemical flux calculations it is concluded that an appreciable proportion of dissolved phosphate delivered to the oceans by rivers is removed by ridge crest volcanogenic iron oxides either as absorbed surface coatings or as discrete, but highly disordered, ferric phosphate phases. This process should be taken into consideration when considering oceanic phosphate budgets, both in the present and past oceans.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca²⁺, Mg²⁺, and Si(OH)₄ and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M₂ structural sites. Loss mainly from M₂ sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca²⁺ and/or Mg²⁺ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on a_H⁺ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.