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.     

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.     

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.     

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.     

Trace element partitioning in the Morasko meteorite from Poznan, Poland

The nickel–iron meteorite of Morasko shows isolated inclusions of troilite in the bulk mass of a Fe,Ni-alloy. During a segregation of the FeS phase chalcophile trace elements were collected from the melt. The solidification of the Fe,Ni-phase occurred probably later, incorporating thereby mainly siderophile trace elements. To prove this general assumption selected trace elements were determined and reveal in the two phases of the present meteorite a characteristic distribution pattern. The meteorite of Morasko is in close conformity to the iron meteorite group IAB with rounded dark FeS inclusions.     

Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

Theoretical models predict a marked increase in atmospheric O₂ to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO₂ level. An upper O₂ value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O₂ to 35% increases isotopic fractionation (Δ¹³C) during growth relative to control plants grown at 21% O₂. Despite some effect of the background atmospheric CO₂ level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O₂ could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ¹³C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ¹³C excursion is consistent with the effects of a high O₂ atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ¹³C record against experimental data yields a predicted O₂/CO₂ mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O₂ in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O₂ levels.     

Oceanic events and biotic effects of the Cenomanian-Turonian anoxic event, Tarfaya Basin, Morocco

Profound biotic changes accompanied the late Cenomanian δ¹³C excursion and OAE2 in planktic foraminifera in the Tarfaya Basin of Morocco. Planktic foraminifera experienced a severe turnover, though no mass extinction, beginning with the rapid δ¹³C excursion and accelerating with the influx of oxic bottom waters during the first peak and trough of the excursion. Species extinctions equaled the number of evolving species, though only the disaster opportunists Guembelitria and Hedbergella thrived along with a low oxygen tolerant benthic assemblage. The succeeding δ¹³C plateau and organic-rich black shale deposition marks the anoxic event and maximum biotic stress accompanied by a prolonged drop in diversity to just two species, the dominant (80–90%) low oxygen tolerant Heterohelix moremani and surface dweller Hedbergella planispira. After the anoxic event other species returned, but remained rare and sporadically present well into the lower Turonian, whereas Heterohelix moremani remained the single dominant species. The OAE2 biotic turnover suggests that the stress to calcareous plankton was related to changes in the watermass stratification, intensity of upwelling, nutrient flux and oxic levels in the water column driven by changes in climate and oceanic circulation. Results presented here demonstrate a 4-stage pattern of biotic response to the onset, duration, and recovery of OAE2 that is observed widely across the Tethys and its bordering epicontinental seas.     

Estimation of an upper limit on prehistoric peak ground acceleration using the parameters of intact speleothems in Hungarian caves

The examination of speleothems in the Hajnóczy and Baradla caves (northeastern Hungary) allows estimating an upper limit for horizontal peak ground acceleration generated by paleoearthquakes. The density, the Young’s modulus and the tensile failure stress of the samples originating from a broken speleothem have been measured in a laboratory, whereas the natural frequency of intact speleothems was determined by in situ observations. The value of horizontal ground acceleration resulting in failure, the natural frequency and the inner friction coefficient of speleothems were assessed by theoretical calculations. The ages of the samples taken from a stalagmite 5.1 m in height (Baradla cave) have been determined by inductively coupled plasma mass spectrometry analysis and alpha spectrometry. The measured ages fall between 140,000 and 70,000 years; therefore, we assume the speleothem has not been changed since the end of this time interval. According to our modeling results, this speleothem has not been excited by a horizontal acceleration higher than 0.05 g during the last 70,000 years.     

Magnetic susceptibility as a possible correlation tool in Quaternary alluvial stratigraphy

Correlation of the fluvial magnetic susceptibility (MS) record of borehole Devavanya‐1 in the Körös Basin (eastern Hungary) with Chinese aeolian MS records (Jingbian, Lingtai) and the marine δ¹⁸O record from the Equatorial Pacific (V28‐239) is established here based on cross‐correlations and singular spectral analysis. A basin‐scale well‐to‐well correlation based on magnetic susceptibility records was also performed involving unpublished cores. To refine the age model, a Monte Carlo simulation was conducted using the Chinese Jingbian section as a tuning target. Spectral analysis of the tuned record revealed c. 400, c. 100 and c. 41 ka cycles over the 2.5 million years of the Quaternary fluvial succession. To ensure a complementary palaeoclimate proxy, the full width at half maximum of smectites was measured as a facies‐independent indicator of weathering intensity. This investigation was carried out on a subset of samples involved in MS measurements representing a c. 400 ka time interval across the top of the Olduvai subchron. A phase‐shift between MS and weathering intensity recorded in the clay mineralogy indicates different response times of the considered proxies. The fluvial MS record is determined by the climatic control on delivery and preservation of magnetic minerals, mainly of magnetite. Under cold‐and‐dry climate these minerals were released owing to frost shattering in the adjacent hinterlands and were transported to alluvial plains in the early postglacial periods thanks to the increasing discharge of rivers. With further warming the weathering‐sensitive magnetic minerals soon disappeared from the soils of the catchment area and thus from the fluvial load. As a result, in fluvial successions early postglacial warmings are expressed by the occurrences of MS maxima (magnetic episodes), while the palaeotemperature maximum and the subsequent cooling remain concealed within the tract of low MS values. The early postglacial magnetic episodes may serve as ideal stratigraphical markers in regional and global correlations.     

Inclusion of adsorption in the modelling of early diagenesis

A general one-dimensional diagenetic equation is derived which expresses the effect of the following processes upon the depth and time distribution of a dissolved species in a modern subaqueous sediment: adsorptive or ion exchange equilibrium between pore water and grain surfaces; slower chemical or radiogenic reactions in the pore solution and on the grain surfaces; diffusion in solution and on grain surfaces; advection of grains due to depositional burial; and advection of water due both to burial and to flow past the grains. It is shown that the effects of equilibrium adsorption can be expressed in terms of a lowered diffusion coefficient only in the special case where there is negligible flow of water relative to grains, adsorption is described by a simple linear isotherm, and there is nochemical reaction occurring in the sediment (i.e. only radioactive decay or no reaction at all). Consideration of a commonly used special case of the general equation indicates that if equilibrium adsorption is strong, the depositional term in the resulting diagenetic equation may become quantitatively as important as the terms for diffusion and chemical reaction. Thus, when modelling diagenesis, deposition often cannot be ignored. A coupled pair of differential equations are also derived which express the steady state depth distribution for two ions exhibiting equilibrium ion exchange while undergoing chemical reaction, diffusion, and deposition.