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The transfer of Cadmium from rock to soil and the associated vegetation cover under natural conditions at the Swiss Jura Moutains

2010, Quezada Hinojosa, Raul Percy, Föllmi, Karl, Matera, Virginie, Adatte, Thierry, Verrecchia, Eric, Baize, Denis

As a result of soil-surveying studies conducted in the Swiss and French Jura Mountains during the early 1990's, anomalous cadmium (Cd) concentrations were identified in soils developed mostly on Bajocian and Oxfordian limestone. Measured Cd concentrations exceed in most of the cases the Swiss official tolerance guideline concentration for non-polluted soils established at 0.8 mg⋅kg-1. Several research works have confirmed the geogenic origin of Cd in soils derived mainly from the weathering of a Cd-rich carbonate substrata. Cd is a highly toxic trace element and the pedogenic / physicochemical conditions leading to its transfer from rocks to soils and its potential bioavailability to plants are in need of a detailed geochemical assessment. The aim of the present work is to complete the geochemical database by studying rock-soil-plant interactions with regard to this element under natural conditions in two specific sites. A first study of rock-soil interaction was carried out determining Cd-bearing phases in a soil developed on top of a road-cut section outcropping at the SW-facing slope of the Schleifenberg hill (canton Basel-Land, Switzerland). This section consisting of an oblique succession of Bajocian oolitic carbonate includes several horizons which are anomalously enriched in Cd (0.03–4.90 mg⋅kg-1). Cd contents in this soil are in the 0.3–2.0 mg⋅kg-1 range. Vertical pedogenetic processes (weathering of underlying bedrock) as well as lateral colluvial limestone (weathering of uphill carbonates) are responsible for the origin of Cd in the soil. Half of the Cd still resides in the carbonate fraction, while the Cd released from the weathered carbonates is associated either with organic matter (over 10%) or with Fe and Mn-oxyhydroxides (approximately 30%). Adsorption of a low percentage of Cd on clays is of less importance since Pb, Zn, Cu and Cr ions will compete with Cd to gain adsorbed sites on clays. No exchangeable Cd phase was found and this, together with the buffer capacity of this calcareous soil, suggests that the amount of mobile Cd is quite negligible, which also greatly reduce the amount of bioavailable Cd. Where developed on steep slopes, the soil will hardly accumulate and colluviums will constantly renew it. A second study regarding the transfer and distribution of geogenic Cd in the soil was conducted on six closely spaced soil profiles at the site called Le Gurnigel (canton Neuchâtel, Switzerland). The soils consist mainly of cambisols and cambic-neoluvisols showing an important allochthonous, aeolian fraction. Cd concentrations generally increase down the soil profiles, showing maxima (up to 16.3 mg⋅kg-1) near the soil-bedrock interface. Most Cd resides in the carbonate and organic fractions in topsoils, whereas the amorphous oxyhydroxides fraction becomes the most important Cd-bearing phase in the middle and in subsoils. Cd, Zn and Cr are positively correlated with comparable distributions in the soil profiles suggesting a common bearing phase such as Fe oxyhydroxides for these three elements. A complex transfer pattern of Cd starts with the release of Cd from the underlying bedrock, and then transferred into oxide, hydroxide, carbonate and organic phases. Additionally, the lateral advection of Cd-rich soils formed on steep slopes acts as a local allochthonous input of Cd to these soils, which in turn is transferred from the topsoil towards the deeper horizons by biological and pedogenic processes. The amount of readily exchangeable and therefore potentially bioavailable Cd is low in these soils (on average 0.2 mg⋅kg-1) provided that the pH remains above 5. Under stronger acidic and oxidizing conditions, Cd bound to organic matter may be mobilised and the bioavailability of Cd would range between 3.3–5.4 mg⋅kg-1 in cambisols and reach up to 1.7 mg⋅kg-1 in deeper cambic-neoluvisols. Soil-plant interactions were studied at the Le Gurnigel analyzing six local plants chosen for their ubiquity in the studied soil profiles. Cadmium accumulation was separately determined in roots and shoots. Three herbs, two graminoids and a tree were used for this purpose. They showed that the accumulation of Cd varies from one species to another and even between plants from the same family. Global levels of Cd in the selected vegetation are in the 2–6 mg·kg-1 range, thus exceeding the official limit value of Cd concentration tolerated in vegetal food for animals established at 1 mg·kg-1. The different behaviours were compared as a function of the variability of Cd in soils. A rise in the concentration of Cd in the soil progressively reduces the transport of Cd toward the shoots reducing also the yield production and increasing the accumulation of Cd in roots. Transfer coefficients from soil / rhizosphere to plant are inversely proportional to the total Cd concentration in soils and do not depend on species identity but instead on soil type. Sequential chemical extractions revealed that variations of Cd distribution between distant soil and rhzosperic soil occur mainly in the first three Cdbearing phases due principally to the incorporation of roots exudates that modify pH and redox conditions of the rizhosphere. High levels of Cd (up to 9 mg·kg-1) were found in shoots of three of the studied plants and may represent a mid-term hazard for animals and human health since these plants are used either for grazing of cattle or for medical purposes. The phenomenon of natural enrichment of soils with geogenic Cd and its progressive accumulation in vegetation covers is suspected to have a widespread occurrence elsewhere, as a function of frequent outcrops of Cd-enriched carbonates of Bajocian and Oxfordian age in western and southern Europe principally in France, Spain and Italy.

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

2008, Keller, Gerta, Adatte, Thierry, Berner, Zsolt, Chellai, E.H., Stueben, Doris

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.

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Platform-induced clay-mineral fractionation along a northern Tethyan basin-platform transect: implications for the interpretation of Early Cretaceous climate change (Late Hauterivian-Early Aptian)

2008, Godet, Alexis, Bodin, Stéphane, Adatte, Thierry, Föllmi, Karl B.

High-resolution clay-mineral analyses were performed on upper Hauterivian to lower Aptian sediments along a platform-to-basin transect through the northern Tethyan margin from the Neuchâtel area (Switzerland), to the Vocontian Trough (France) in order to investigate links between climate change, carbonate platform evolution, and fractionation patterns in clay minerals during their transport.
During the Hauterivian, the northern Tethyan carbonate platform developed in a heterozoan mode, and the associated ramp-like topography facilitated the export of detrital material into the adjacent basin, where clay-mineral assemblages are dominated by smectite and kaolinite is almost absent, thereby suggesting dry-seasonal conditions. During the Late Hauterivian Balearites balearis ammonite zone, a change to a more humid climate is documented by the appearance of kaolinite, which reaches up to 30% of the clay fraction in sediments in the Vocontian Trough. This prominent change just preceded the Faraoni Oceanic Anoxic Event and the onset of the demise of the Helvetic Carbonate Platform, which lasted to the late early Barremian.
From the Late Barremian onwards, the renewed growth of the northern Tethyan carbonate platform in a photozoan mode and the associated development of a marginally confined platform topography fractionated the clay-mineral assemblages exported into hemipelagic settings: kaolinite particles were preferentially retained in proximal, platform settings, due to their size and their relatively high specific weight. In the inner platform environment preserved in the Swiss Jura, an average of 32% of kaolinite in the clay fraction is observed during the latest Barremian–earliest Aptian, whereas clay-mineral assemblages of coeval sediments from deeper depositional settings are dominated by smectite and show only minor amounts of kaolinite.
This signifies that besides palaeoclimate conditions, the morphology and ecology of the carbonate platform had a significant effect on the distribution and composition of clay assemblages during the Late Hauterivian–Early Aptian along the northern Tethyan margin.

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Characterization of metalliferous sediment from a low-temperature hydrothermal environment on the Eastern Flank of the East Pacific Rise

2008, Bodeï, S., Buatier, M., Steinmann, M., Adatte, Thierry, Wheat, C. G.

Metalliferous deposits are described from the eastern flank of the East Pacific Rise (EPR) offshore Costa Rica, close to a basaltic seamount called “Dorado high”. Based on heat-flow data and porewater profiles, the site is an area of active low-temperature hydrothermal discharge. We focus on the mineralogical and chemical analysis from a 124 cm long gravity core (GC50), located on the northwestern slope of the 100 m high Dorado. In this core, the sediments consist of detrital clay minerals as well as authigenic minerals such as zeolites, apatites, and Fe/Mn-rich oxyhydroxides. In contrast, the reference sediments from adjacent areas without hydrothermal activity are olive gray hemipelagic muds composed of volcanic glass particles, clay minerals, siliceous microfossils, and some detrital quartz and feldspar.

Bulk sediment chemistry and chemical enrichment factors calculated with respect to the reference sediment indicate that the most important chemical changes occurred at the base of the core from 100 to 124 cm bsf, with strong enrichments in MnO, CaO, P2O5, and Fe2O3. These enrichments are correlated with the occurrence of authigenic Fe-oxyhydroxide (goethite) and Mn oxide (todorokite and vernadite, at 100 cm bsf), and hydrothermal apatite (110–124 cm bsf). In the upper section of the core from 12 to 70 cm, the sediment is composed of abundant smectite and authigenic phillipsite, and only minor chemical changes can be observed with respect to the reference sediments.

The ubiquitous presence of phillipsite suggests that the entire sedimentary column of core GC50 was first affected by diagenesis. However, below 70 cm bsf, these phillipsites are partially dissolved and Fe oxides occur from 110 to 124 cm, followed upward by Mn oxides at 100 cm. This transition from Fe to Mn-rich sediments can be interpreted in terms of an upward increasing redox potential. PAAS-normalized REY patterns of GC50 sediments present clearly negative Ce and positive Y anomalies inherited from seawater at the base of core GC50. These anomalies decrease upward, which we interpret together with the transition from Fe to Mn-rich sediments by an upward migrating low-temperature hydrothermal fluid. Thus, after a first stage of diagenesis, the discharge of a low-temperature hydrothermal fluid occurred through the sedimentary column, leading to the precipitation of hydrothermal compounds that are lacking towards the surface.

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Biotic effects of the Chicxulub impact, K–T catastrophe and sea level change in Texas

2009, Keller, Gerta, Abramovich, S., Berner, Zsolt, Adatte, Thierry

Biotic effects of the Chicxulub impact, the K–T event and sea level change upon planktic foraminifera were evaluated in a new core and outcrops along the Brazos River, Texas, about 1000 km from the Chicxulub impact crater on Yucatan, Mexico. Sediment deposition occurred in a middle neritic environment that shallowed to inner neritic depths near the end of the Maastrichtian. The sea level fall scoured submarine channels, which were infilled by a sandstone complex with reworked Chicxulub impact spherules and clasts with spherules near the base. The original Chicxulub impact ejecta layer was discovered 45–60 cm below the sandstone complex, and predates the K–T mass extinction by about 300,000 years.
Results show that the Chicxulub impact caused no species extinctions or any other significant biotic effects. The subsequent sea level fall to inner neritic depth resulted in the disappearance of all larger (> 150 μm) deeper dwelling species creating a pseudo-mass extinction and a survivor assemblage of small surface dwellers and low oxygen tolerant taxa. The K–T boundary and mass extinction was identified 40–80 cm above the sandstone complex where all but some heterohelicids, hedbergellids and the disaster opportunistic guembelitrids went extinct, coincident with the evolution of first Danian species and the global δ13C shift. These data reveal that sea level changes profoundly influenced marine assemblages in near shore environments, that the Chicxulub impact and K–T mass extinction are two separate and unrelated events, and that the biotic effects of this impact have been vastly overestimated.

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Organic carbon deposition and phosphorus accumulation during Oceanic Anoxic Event 2 in Tarfaya, Morocco

2008, Mort, Haydon P., Adatte, Thierry, Keller, Gerta, Bartels, David, Föllmi, Karl B., Steinmann, Philipp, Berner, Zsolt, Chellai, E.H.

With a multi-proxy approach, an attempt was made to constrain productivity and bottom-water redox conditions and their effects on the phosphorus accumulation rate at the Mohammed Plage section on the Tarfaya coast, Morocco, during the Cenomanian-Turonian Anoxic Event (OAE 2). A distinct δ13Corg isotope excursion of +2.5‰ occurs close to the top of the section. The unusually abrupt shift of the isotope excursion and disappearance of several planktonic foraminiferal species (e.g. Rotalipora cushmani and Rotalipora greenhornensis) in this level suggests a hiatus of between 40–60 kyrs at the excursion onset. Nevertheless, it was possible to determine both the long-term environmental history as well as the processes that took place immediately prior to and during OAE 2. TOC% values increase gradually from the base of the section to the top (from ~ 2.5% to ~ 10%). This is interpreted as the consequence of a long-term eustatic sea-level rise and subsidence causing the encroachment of less oxic waters into the Tarfaya Basin. Similarly a reduction in the mineralogically constructed ‘detrital index’ can be explained by the decrease in the continental flux of terrigenous material due to a relative sea-level rise. A speciation of phosphorus in the upper part of the section, which spans the start and mid-stages of OAE 2, shows overall higher abundances of Preactive mass accumulation rates before the isotope excursion onset and lower values during the plateau. Due to the probable short hiatus, the onset of the decrease in phosphorus content relative to the isotope excursion is uncertain, although the excursion plateau already contains lower concentrations. The Corg/Ptotal and V/Al ratios suggest that this reduction was mostly likely caused by a decrease in the available bottom oxygen content (probably as a result of higher productivity) and a corresponding fall in the phosphorus retention ability of the sediment. Productivity appears to have remained high during the isotope plateau possibly due to a combination of ocean-surface fertilisation via increased aridity (increased K/Al and Ti/Al ratios) and/or higher dissolved inorganic phosphorus content in the water column as a result of the decrease in sediment P retention. The evidence for decreased P-burial has been observed in many other palaeoenvironments during OAE 2. Tarfaya's unique upwelling paleosituation provides strong evidence that the nutrient recycling was a global phenomenon and therefore a critical factor in starting and sustaining OAE 2.

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Main Deccan volcanism phase ends near the K–T boundary: Evidence from the Krishna–Godavari Basin, SE India

2008, Keller, Gerta, Adatte, Thierry, Gardinc, S., Bartolinic, A., Bajpai, S.

Recent studies indicate that the bulk (80%) of the Deccan trap eruptions occurred over less than 0.8 m.y. in magnetic polarity C29r spanning the Cretaceous–Tertiary (K–T) boundary. Determining where within this major eruptive phase the K–T mass extinction occurred has remained problematic. For this reason, models estimating the biotic and environmental consequences have generally underestimated the rate and quantity of Deccan gas emissions by orders of magnitude leading to conclusions that volcanism could not have been one of the major causes for the K–T mass extinction. In this study we report that the most massive Deccan trap eruption occurred near the K–T mass extinction.

These results are based on sedimentologic, microfacies and biostratigraphic data of 4–9 m thick intertrappean sediments in four quarry outcrops in the Rajahmundry area of the Krishna–Godavari Basin of southeastern India. In this area two Deccan basalt flows, known as the Rajahmundry traps, mark the longest lava flows extending 1500 km across the Indian continent and into the Bay of Bengal. The sediments directly overlying the lower Rajahmundry trap contain early Danian planktic foraminiferal assemblages of zone P1a, which mark the evolution in the aftermath of the K–T mass extinction. The upper Rajahmundry trap was deposited in magnetic polarity C29n, preceding full biotic recovery. These results suggest that volcanism may have played critical roles in both the K–T mass extinction and the delayed biotic recovery.

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Illite crystallinity patterns in the Anti-Atlas of Morocco

2008, Ruiz, Geoffrey M. H., Helg, Urs, Negro, François, Adatte, Thierry, Burkhard, Martin

The low-grade metamorphism of the sedimentary cover of the Moroccan Anti-Atlas is investigated using Illite crystallinity (IC) method. More than 200 samples from three key areas (southwestern, central and eastern Anti-Atlas) have been taken from a maximum of different stratigraphic levels and have been analysed. The metamorphism is of low to very low degree throughout the southern flank of the Anti-Atlas. It increases from northeast to southwest. Whereas in the eastern Anti-Atlas diagenetic and anchizonal IC-values are predominant, in the western and central Anti-Atlas also epizonal IC-values are found. In every respective area the IC improves with stratigraphic age. At the scale of the entire Palaeozoic Anti-Atlas basin the IC correlates best with estimated paleo-overburden. However, burial metamorphism cannot be the cause even though considering missing sedimentary pile of Late Carboniferous age. The ‘abnormal’ paleo-geothermal gradient of 43–35 °C/km we evidenced for the Carboniferous is a true one, and has to be related to a basement sequence enriched in heat producing elements such as series of the West African Craton.

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Life and the environment during the Cretaceous: Editorial

2008, Föllmi, Karl B., Adatte, Thierry

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Reply to ‘Chicxulub impact predates K–T boundary: New evidence from Brazos, Texas’ Comment by Schulte et al.

2008, Keller, Gerta, Adatte, Thierry, Baum, Gerald, Zsolt Berner