The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Na depletion in modern adakites via melt / rock reaction within the sub-arc mantle

Interaction between slab-derived melt and mantle peridotite and the role of slab melt as a metasomatizing agent in the sub-arc mantle is being increasingly recognized. Adakite, the slab melt erupted on the surface, usually exhibits anomalously high MgO, CaO, Cr and Ni contents that indicate interaction with mantle peridotitite. Here we note that Cenozoic adakites have Na₂O contents below 5.8 wt.% with ∼95% samples lower than 5.0 wt.%, and are generally depleted in this component relative to experimental basalt partial melts (mostly beyond 5.0 wt.% and up to 9.0 wt.% Na₂O) produced under 1.5-3.0 GPa conditions that are most relevant to adakite production. We interpret the adakite Na depletion to be also a consequence of the melt / rock reaction that takes place within the hot mantle wedge. During ascent and reaction with mantle peridotite, primary adakite melts gain mantle components MgO, CaO, Cr and Ni but lose Na₂O, SiO₂ and perhaps K₂O to the mantle, leading to Na-rich mantle metasomatism. Selective assimilation of predominately mantle clinopyroxene, some spinel and minor olivine at high T/P has been considered to be an important process in producing high-Mg adakites from primary low-Mg slab melts [Killian, R., Stern, C. R., 2002. Constraints on the interaction between slab melts and the mantle wedge from adakitic glass in peridotite xenoliths. Eur. J. Mineral. 14, 25-36]. In such a process, Na depletion in the assimilated melt is the result of dilution due to the increase in melt mass. Phase relationships in the reaction system siliceous melt + peridotite and quantitative calculation suggest that assimilation of mantle clinopyroxene, olivine and spinel and fractional crystallization of sodic amphibole and orthopyroxene, under conditions of moderate T/P and increasing melt mass, is also an important process that modifies the composition of adakites and causes the Na depletion.     

Early diagenesis of trace metals (Cd, Cu, Co, Ni, U, Mo, and V) in the freshwater reaches of a macrotidal estuary

Vertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O₂ dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities.     

Laboratory condensation of refractory dust in protosolar and circumstellar conditions

In order to better understand condensation processes that took place in the solar nebula and to evaluate the effect of kinetics on the condensed matter, we have built an experimental apparatus for studying condensation of multi-elemental refractory gases at high-temperature and low-pressure. The condensation of a Mg-Si-rich gas, with solar interelement ratios of Ca, Al, Mg and Si, and of a Ca-Al-rich gas under a total pressure of ∼4 × 10⁻³ bar at temperatures from 1045 to 1285 °C and for run times of 4-60 min results in direct formation of crystalline oxides or silicates such as corundum, spinel, anorthite, melilite, Al-diopside, forsterite and enstatite. The mineralogy of the condensates, close to that predicted at equilibrium, varies with the duration of an experiment and the temperature of condensation. The chemical reactions between gas and condensates are rapid enough to attain a steady state in less than one hour. The condensation results in chemical fractionation of the gas, i.e. a depletion of the gas in refractory elements at high temperature. Finally, besides revealing the textures of refractory crystals, which condense from a gas of complex chemical composition, this study shows that certain phases, such as spinel, have favored kinetics of condensation. Our experimental results confirm that refractory inclusions in primitive meteorites could have formed by condensation from a hot nebular gas. Similarly, we confirm that crystalline grains can condense at high temperature in the outflows of evolved stars. In both cases, our results indicate that kinetic processes certainly influence grain mineralogy. Kinetic processes must thus be taken into account in modeling the pressure-temperature conditions of circumstellar environments.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

A critical look at iron paleoredox proxies: New insights from modern euxinic marine basins

Enrichments in reactive iron occur under euxinic marine conditions, that is, where dissolved sulfide is present in the water column. These enrichments result primarily from the export of remobilized iron from the oxic shelf, which is scavenged from the euxinic water column during syngenetic pyrite formation and deposited in the underlying sediments. Strongly elevated ratios of highly reactive iron to total iron (Fe_HR/Fe_T) and total iron to aluminum (Fe_T/Al) and high degrees of pyritization (DOP) are each products of this enrichment process. These paleoredox proxies are among the most faithful recorders of ancient euxinia.Contrary to previous arguments, iron enrichment is decoupled from biogenic sediment inputs, but it does appear to be a uniquely euxinic phenomenon. In other words, we can rule out a major contribution from preferential physical transport of Fe_HR-rich detrital sediment to the deep basin, which could also operate under oxic conditions. Furthermore, enrichment via the shuttling of iron remobilized from oxic shelves appears to be limited by inefficient transport and trapping processes in deep oxic basins. Elevated Fe_T/Al ratios in the euxinic sediments also cannot be a product of internal enhancement of the reactivity of the detrital iron pool without net Fe_HR addition. These conclusions are supported by observations in the modern Black Sea, Orca Basin, and Effingham Inlet.Fe_T/Al ratios are unambiguous recorders of paleoredox even in sediments that have experienced high degrees of metamorphic alteration. However, this study suggests that high siliciclastic accumulation rates can swamp the enrichment mechanism, resulting in only intermediate DOP values for euxinic sediments and Fe_T/Al ratios that mimic the oxic shelf. Such dilution effects are well expressed in Black Sea basinal turbidites and rapidly accumulating muds on euxinic basin margins. Under conditions of persistent euxinia, varying extents of Fe_HR enrichment can illuminate spatial and temporal gradients in siliciclastic sedimentation. The magnitude of enrichment is a function of the source (shelf) to sink (ocean basin) areal ratio, suggesting that iron proxies can also record ocean-scale paleoenvironmental properties through muted enrichments at times of very widespread euxinia. For the first time, manganese data are interpreted in light of the redox shuttle model. As for the iron data, the Black Sea, Orca Basin, and Effingham Inlet show enrichments in total manganese in the deep euxinic basin, suggesting export from the suboxic porewaters of the oxic shelf and scavenging and burial in the basin. The Black Sea data reveal iron and manganese enrichment across the broad, deep euxinic basin, suggesting efficient lateral transport and deep-water mixing tied to the physical properties of the water column.     

Memories of Fire: Eduardo Galeano and the Geography of Guatemala

In Memory of Fire, a poetic narration of the history of the Americas from pre-Columbian times to the late 20th century, Eduardo Galeano furnishes readers with over 1200 of his trademark vignettes, some 35 of which pertain to Guatemala. Galeano evokes disparate aspects of the geography of Guatemala, past and present, in grounded miniatures of time, place, and episode. His sketches of the experiences of Maya peoples allow us to see them as survivors of three cycles of conquest: (1) conquest by imperial Spain; (2) conquest by local and international capitalism; and (3) conquest by state terror. Composed in the literary mode of creative non-fiction, Memory of Fire serves as an inspirational classroom text, exposing students not only to factual detail but also a powerful artistic imagination.     

Magnetostratigraphic evidence from the Cold Creek bar for onset of ice-age cataclysmic floods in eastern Washington during the Early Pleistocene

This study provides a detailed magnetostratigraphy of sediments composing the Cold Creek cataclysmic flood bar in the Pasco Basin, Washington. Our interpretation suggests onset of Missoula floods or similar events prior to 1.1 myr, later than previously suggested by Bjornstad et al. [Bjornstad, B.N., Fecht, K.R., Pluhar, C.J., 2001. Long history of pre-Wisconsin, Ice Age cataclysmic floods: evidence from southeastern Washington State. Journal of Geology 109 (6), 695-713]. Nonetheless these data suggest that Channeled Scabland features formed over a much longer timespan than commonly cited, that continental ice sheets of the early Pleistocene reached as far south as those of the late Pleistocene, and that similar physiography existed in eastern Washington and perhaps Montana to both generate and route Missoula-flood-like events. This study adds paleomagnetic polarity results from 213 new samples of silts and sands derived from nine new drill cores penetrating the Cold Creek cataclysmic flood bar to our previous database of 53 samples from four boreholes, resulting in a much more robust and detailed magnetostratigraphy. Rock magnetic studies on these sediments show pure magnetite to be the predominant remanence-carrying magnetic mineral, ruling out widespread remagnetization by secondary mineralization. The magnetostratigraphy at eastern Cold Creek bar is characterized by a normal polarity interval bracketed by reversed polarities. Equating the normal zone with the Jaramillo subchron (0.99-1.07 myr) affords the simplest correlation to the magnetic polarity timescale. Western Cold Creek bar was likely deposited during the Brunhes chron (0-0.78 myr) since it exhibits mainly normal polarities with only two thin reversed-polarity horizons that we interpret as magnetic excursions during the Brunhes.     

Carbon, sulfur and O2 across the Permian–Triassic boundary

A model for the carbon and sulfur cycles across the Permian–Triassic boundary has been constructed from carbon and sulfur isotopic data. Results indicate a drop in global organic matter burial, the formation of an anoxic deep ocean, and a large drop in atmospheric oxygen over the time span 270 to 240 Ma. Much of these changes were probably due to a drop in terrestrial productivity and preservation and an increase in global aridity.