The southeastern border of the Upper Rhine Graben: a 3D geological model and its importance for tectonics and groundwater flow

A 3D geological model of the area east of Basel on the southeastern border of the Upper Rhine Graben, consisting of 47 faults and six stratigraphic horizons relevant for groundwater flow, was developed using borehole data, geological maps, geological cross sections, and outcrop data. This model provides new insight into the discussions about the kinematics of the area between the southeastern border of the Upper Rhine Graben and the Tabular Jura east of Basel. A 3D analysis showed that both thin-skinned and thick-skinned tectonic elements occur in the modeled area and that the Anticline and a series of narrow graben structures developed simultaneously during an extensional stress-field varying from E–W to SSE–NNW, which lasted from the Middle Eocene to Late Oligocene. In a new approach the faults and horizons of the 3D geological model were transferred into discrete elements with distributed hydrogeological properties in order to simulate the 3D groundwater flow regime within the modeled aquifers. A three-layer approach with a horizontal regularly spaced grid combined with an irregular property distribution of transmissivity in depth permitted the piezometric head of the steady-state model to be automatically calibrated to corresponding measurements using more than 200 piezometers. Groundwater modeling results demonstrated that large-scale industrial pumping affected the groundwater flow field in the Upper Muschelkalk aquifer at distances of up to 2 km to the south. The results of this research will act as the basis for further model developments, including salt dissolution and solute transport in the area, and may ultimately help to provide predictions for widespread land subsidence risks.     

Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction

Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced ⁵⁶Fe/⁵⁴Fe ratios for Fe(II)_aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)_aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)_aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO₃) and ca. +0.9‰ for Ca-substituted siderite (Ca_0.15Fe_0.85CO₃) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have ⁵⁶Fe/⁵⁴Fe ratios that are up to 1‰ lower than Fe(II)_aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)_aq.The relative order of δ⁵⁶Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)_aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ⁵⁶Fe >0‰, the calculated δ⁵⁶Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ⁵⁶Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ⁵⁶Fe values. Based on this experimental study, formation of low-δ⁵⁶Fe Fe(II)_aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.     

Evidence for sulfurization and the origin of some sudbury-type ores

The suggestion that Sudbury-type ores may be formed by the introduction of country rock sulfur into still hot intrusions (i.e., sulfurization) suffers from a reputed lack of field evidence. Permissive evidence for sulfurization includes the epigenetic nature of many Sudbury-type ores and that many Sudbury-type ores crystallized from sulfide melts. Visual evidence exists for sulfurization of a gabbro in Zambia. The lead isotopic composition of ore minerals at Sudbury implies that at least some of the metals were derived from the erruptive. Published sulfur isotopic data from several Sudbury-type ores differ from and do not exhibit a common pattern of isotopic enrichment with respect to sulfides within associated intrusions. Evidently the sulfur was derived from the country rocks. Sudbury-type ores exhibiting magmatic textures commonly occur within more siliceous dikes than the host intrusions. Inorganic reduction of sulfate occurs only above 600° C. Reduction of sulfate with resultant sulfurization of ferrous iron and traces of other metals originally present in the still hot parental intrusive rock would make the rock more siliceous. Above 1100° C the silicate-residue and newly formed sulfides would form immiscible magmas. Therefore, ore magmas within and near mafic intrusives can be epigenetic. The processes by which sulfur is introduced into intrusions are still speculative.

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Zusammenfassung Für die Annahme, daß Erze vom Sudbury-Typus sich durch Zuführung von Nebengesteinsschwefel in noch heiße Intrusionen bilden können (sulfurization), fehlt es angeblich an Feldunterlagen. Folgende Tatsachen lassen sich mit einer Schwefelung (sulfurization) vereinigen: der epigenetische Charakter vieler Erze vom Sudbury-Typ; auch sind viele Erze von Sudbury-Typus aus sulfidischen Schmelzen kristallisiert. In einem Gabbro in Zambia ist der Beweis für Schwefelung (sulfurization) direkt sichtbar. Die Isotopen-Zusammensetzung von Blei in Erzmineralien in Sudbury zeigt, daß mindestens einige der Metalle aus dem Eruptivgestein stammen. Schwefelisotop-Daten, die für mehrere Lagerstätten von Sudbury-Typen veröffentlicht worden sind, haben hinsichtlich der Isotop-Anreicherung keine gemeinsamen Züge. Offensichtlich stammt der Schwefel aus dem Nebengestein. Erze vom Sudbury-Typ mit magmatischem Gefüge finden sich oft in Gängen, die saurer sind als das Wirtsgestein. Anorganische Reduktion von Sulfat findet nur oberhalb 600°C statt. Reduktion von Sulfat und die entstehende Schwefelung (sulfurization) von zweiwertigem Eisen und Spuren anderer Metalle, die ursprünglich in dem noch heiß eruptiven Gestein anwesend sind, machen das Gestein noch saurer. Oberhalb 1100°C würden der Silicat-Rest und die neugeformten Sulfide nicht mischbare Magmen bilden. Deshalb können sich sulfidische Schmelzen innerhalb und in der Nähe von Mafic-Intrusionen später gebildet haben. Die Prozesse, durch die Schwefel in Intrusionen eingeführt wird, sind noch unbekannt.

     

Evolution of volcanic islands

It is shown that there is no significant correlation between the chemistry of volcanic islands and their distance from the axes of oceanic rises. The composition and the distribution of those oceanic volcanic islands that are not associated with subduction zones is considered to be related to the distribution of a series of thermal plumes that originated either within the upper mantle or at the coremantle interface.     

Evolution of La Palma,Canary archipelago

La Palma is the northwestern island in the Canary archipelago. The island is volcanically active and in recent years there have been two eruptions (1949 and 1971). The oldest rocks that crop out on the island are altered spilitic lavas and they are intruded by numerous dykes and a number of mafic and ultramafic plutonic rocks. These rocks form part of the floor of the huge Caldera de Taburiente. In the walls of the Caldera one finds a 1000 metres thick unit that is composed of lavas and tephra. The rocks are called the El Time formation; and they together with the rocks of the Cumbre Vieja ridge are mainly composed of accumulative mafic rocks, basanites, hawaiites, benmoreites and phonolitic trachytes. These sodarich alkalic rocks are considered to have evolved by fractional crystallization of a basanitic magma in a near surface environment.It is proposed that La Palma developed on a relatively cold section of a plate of oceanic lithosphere that was over 100 m.y. old. During the Alpine-Atlas orogeny this section of the African plate was disrupted and a basanitic magma was extruded onto the sea floor. The volcanic focus of this eruption became established as a local centre for the degassing of the mantle and as a result this area has experienced a long series of eruptions.During the first phase in the evolution of La Palma the submarine edifice of the island was constructed and the rocks of the Caldera Floor formation were emplaced. After a period of marine erosion the huge old volcano Taburiente developed in the northern half of the island. During the final phase in the evolution of the island the southern section of the volcanic edifice subsided and formed the El Paso tectonic basin and the volcanic rift zone along which the many smaller volcanoes of the Cumbre Vieja ridge have developed.     

Isotopic studies of leaf water. Part 2: Between-age isotopic variations in pine needles

We studied between-age oxygen and hydrogen isotopic variations of two pine species, red pine (Pinus resinosa Ait) and white pine (Pinus strobus L.), with particular attention paid to variations associated with needle maturity. The 2D model by Shu et al. (this volume) was applied to simulate oxygen isotopic ratios of the pine needles; calculated results were compared with data collected from trees in the Hanover, NH area. The calculations indicate that the mechanism most responsible for age-dependent isotopic variations is the variation in transpiration rate along the needle. Because stomata mature progressively from needle tip to needle base, young needles transpire most of their water near the tip. Mature needles, on the other hand, transpire water more evenly along their lengths. We cannot successfully simulate hydrogen isotopic variations, and it remains to be investigated what mechanism or physical process is not included in the model that affects hydrogen isotopic compositions in leaf water.     

Geochemical characteristics of basalts related to incipient oceanization: The example from the Alpine‐Tethys OCTs

Basalts exposed in the Platta and Tasna nappes (SE Switzerland) derive from the Alpine‐Tethys ocean–continent transitions (OCT) and overlie subcontinental lithospheric mantle (SCLM). We show that the trace element signatures of these basalts differ from mid‐ocean ridge basalts (MORB). Two types of basalts occur in the OCT: a type‐1 showing a ‘garnet signature’ that can be modelled by the partial melting of the SCLM in the spinel stability field and a type‐2 characterized by an enrichment in incompatible elements that can be explained by the mixing between garnet‐pyroxenite‐derived melts and the melting of either a depleted MORB mantle or a refertilized SCLM. Based on the geological and geochemical observations, we propose that the basalts from the Alpine‐Tethys OCTs result from a poly‐phase magmatic system that carries an inherited SCLM signature. These basalts should therefore be referred to as OCT‐basalts rather than as MOR‐basalts.     

What Is Going on with <Emphasis Type="Italic">Perkinsus marinus</Emphasis> in the Gulf of Mexico?

The National Oceanic and Atmospheric Administration (NOAA) Status and Trends Mussel Watch Program sampled the largest oysters in nearly every major US coastal lagoon and estuary in the Gulf of Mexico once during the winter from 1986 to 2010. This contribution examines trends in the principal oyster disease in the Gulf of Mexico, Dermo, caused by Perkinsus marinus, and some related population dynamic characteristics for its host, Crassostrea virginica. During the 1986–2000 period, P. marinus prevalence and infection intensity and oyster population dynamics followed the El Niño-Southern Oscillation (ENSO) cycle, responding to variations in salinity caused by variations in rainfall and freshwater inflow. The ENSO signal in the oyster population effectively ceased circa 2002. Beginning around this time, wintertime P. marinus prevalence and weighted prevalence began a decadal decline, as did the length of the largest oysters and the fraction of these largest animals that were female. The trends in Dermo disease, oyster length, and oyster sex ratio are all consistent with the following hypothesis: increasing temperature during the 2000s resulted in an increase in P. marinus infection intensity sufficient to increase the mortality rate in late summer and fall in the larger animals. This simultaneously reduced Dermo prevalence and infection intensity in the winter at the time of sampling and also resulted in the decline in the length of the largest animals targeted by Mussel Watch. Coincident with the decline in length is the expected decline in the fraction female, such that the percent female in the largest animals dropped to ≤50 % throughout much of the Gulf of Mexico. The decline in length leading to fewer large animals reproducing and the loss of females are predicted to have reduced oyster population reproductive capacity substantially during the 2000s. The early 60 % of the Mussel Watch time series took place during a period of negative Atlantic Multidecadal Oscillation (AMO) indices. The AMO moved into positive territory circa 2000. A positive AMO index is consistent with observed warmer water temperatures, and increased water temperature is consistent with an increase in Dermo-induced mortality.     

Stream chloride concentrations as a function of land use: a comparison of an agricultural watershed to an urban agricultural watershed

The concentration of chloride (Cl^?) in streams in northern regions has increased as a result of applications of deicers. This study focused on quantifying the relationship between land use and stream Cl^? concentrations. The study area comprises two adjacent watersheds in central Illinois, with similar geology and climate but different land uses (agricultural and urban). GIS analysis delineated watershed land use and calculated road surface areas. Stream water samples were collected and analyzed for anionic composition. During the winter months, streams dominated with urban land use experienced a 20-fold increase in Cl^? concentrations (range between 36 and 1350 mg L^?1); Cl^? concentrations in agricultural dominated streams also increased, but the increase was smaller (3X) and concentrations remained low (between 11 and 58 mg L^?1). As road salts are not the sole source of Cl^? in a stream, Cl^? and bromide (Br^?) mass ratios (Cl/Br) and Cl^? and sodium (Na) molar ratios ([Cl]/[Na]) were used to identify potential sources of Cl^?. The ratios indicate urbanized watersheds were impacted by road salts; agricultural watersheds ratios indicate other anthropogenic sources. A nonlinear relationship between urban land use and stream Cl^? concentrations indicates urban land use as low as 23% results in elevated Cl^? concentrations (greater than 150 mg L^?1) in stream waters.     

Is soil natural organic matter a sink or source for mobile radioiodine (I) at the Savannah River Site?

¹²⁹I is one of the three major radiation risk contributors to the public as a consequence of past nuclear processing activities at Department of Energy (DOE) facilities. Elevated levels of ¹²⁹I are present in the surface soils of F-Area of Savannah River Site, which used to be an isotope separation facility for the production of nuclear weapons components. The ¹²⁹I in soils is thought to be bound predominantly to soil organic matter (SOM). Measurements of stable ¹²⁷I and radioactive ¹²⁹I in humic acids (HAs) and fulvic acids (FAs) obtained by five successive alkaline, two glycerol and one citric acid-alkaline extraction, demonstrated that these extractable humic substances (HS) together account for 54-56% and 46% of the total ¹²⁷I and ¹²⁹I in the soil, respectively. The remainder was likely bound to residual SOM. The iodine content (μg-I/g-C) generally decreased with each subsequent extract, while ¹²⁹I/¹²⁷I increased concurrently. The coincident variations in chemical compositions, aromaticity (estimated by UV spectroscopy), functional groups (e.g., aliphatic), degree of humification, relative migration in the hydrophobic interaction column, and molecular weight indicated that: (1) iodine in different HAs was bound to a small-size aromatic subunit (∼10 kDa); (2) the large-size subunit (∼90 kDa), which likely linked the small-size unit through some weak chemical forces (hydrogen bonds, hydrophobic or electrostatic interactions), determined the relative mobility of iodine bound to organic matter; (3) from the strong correlation between iodine content and aromaticity in the HAs, we suggested that iodine incorporation into the SOM via covalent aromatic C-I bond is the key mechanism controlling iodine behavior in this system. However, this relationship is not universal for all fractions of organic matter as evidenced from the different slopes of this relationship at the two sampling sites, as well as from the different relationships for HAs and FAs, respectively. These differences in iodination are due to different SOM molecular sizes, compositions, and availability of preferred iodination sites. ¹²⁹I in the soil downstream from the contaminated site and near a wetland abruptly dropped below our detection limit (0.5 pCi-¹²⁹I/g-soil), which suggests that the high SOM in the plume soil around the ¹²⁹I-contaminated F-Area might be a natural barrier to scavenge radioiodine released from the nuclear waste repository by forming organo-iodine compounds. Soil resuspension experiments showed that mobile ¹²⁹I was mostly associated with a low average molecular weight amphiphilic organic carrier (13.5-15 kDa). SOM clearly behaves as a sink for iodine at the Savannah River Site F-Area. However, this work demonstrates that a small fraction of the SOM can also behave as a source, namely that a small fraction that may be readily dispersible under some environmental conditions and presumably release iodine in the organic-colloidal form. This radioiodinated organo-colloid likely can get into the groundwater through infiltration or surface runoff where it might migrate further into the wetlands. Results from this study provide the geochemical basis for future ¹²⁹I migration controls, remediation, and/or land-groundwater management strategies.