Characterization of dissolved organic matter in anoxic rock extracts and in situ pore water of the Opalinus Clay

Dissolved organic matter (DOM) from the Opalinus Clay, a potential host rock for the disposal of radioactive waste, was isolated under strictly anoxic conditions from ground rock material and compared with DOM of in situ pore water samples. For the extractions, deionized water, synthetic pore water (SPW, water containing all major ions at pore water concentrations but no organic matter) and 0.1 M NaOH were used. The influence of the solid-to-liquid ratio, extraction time, acid-pretreatment and O₂ exposure of the rock material on the isolated DOM were investigated. Liquid chromatography coupled with a total organic C detector (LC-OCD) and reverse-phase ion chromatography were used to characterize the DOM size distributions and to determine the low molecular weight organic acid (LMWOA) contents in the pore water samples and the rock extracts.The results revealed that only a small portion of the total organic C of the rock material (<0.38%) was extractable, even after removal of carbonates by acid-pretreatment. The concentrations of dissolved organic C (DOC) were found to range from 3.9 ± 0.4 to 8.0 ± 0.8 mg/L in the anoxic extracts. The pore waters exhibited similar DOC concentrations ranging from 1.2 to 15.8 ± 0.5 mg/L. The analysis by LC-OCD showed that the DOM extracted under anoxic conditions and the pore water DOM mainly consisted of hydrophilic compounds of less than 500 Da. The DOM extracted with SPW was most similar in size to the pore water DOM. Grinding the rock under oxic conditions increased the DOC yields and shifted the size distribution toward higher molecular weight compounds compared to the strictly anoxic treatment. Acetate, lactate and formate were identified in all extracts and in the pore water. In total, LMWOA accounted for 36% of the total DOC in both pore water and SPW extracts. The results imply that controlled anoxic conditions and the use of SPW as an extractant are required to isolate DOM from Opalinus Clay rocks which most resembles the in situ pore water DOM with respect to its size distribution and the LMWOA contents.     

Assessment of toxicological status of a SW Mediterranean segment population of striped dolphin (Stenella coeruleoalba) using skin biopsy

Various studies have revealed high concentrations of contaminants such as organochlorines (OCs) and heavy metals in Mediterranean cetaceans. A geographical trend of contamination (PCBs and DDTs) has been found for striped dolphin (Stenella coeruleoalba). In this study we used a non-lethal approach (skin biopsy) to investigate bioaccumulation of OCs, including polychlorobiphenyls (PCBs), DDTs, polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), trace elements (Hg, Cd, Pb) and CYP1A activity (BPMO) in nine striped dolphins sampled in the Aeolian area (Sicily - Italy) in summer 2002. The arithmetic mean value of BPMO activity in this group was 43.46 AUF/g tissue/h. This value is approximately 3 times and 5 times lower, respectively, than the value found in the Ionian and in the Ligurian groups. Skin biopsies of striped dolphins emerged as a suitable material for assessing the toxicological status of the various Mediterranean groups.     

Tectonic evolution of an intraplate basin: the Lower Tagus Cenozoic Basin,Portugal

This article focuses on the reinterpretation of well, seismic reflection, magnetic, gravimetric, surface wave and geological surface data, together with the acquisition of seismic noise data to study the Lower Tagus Cenozoic Basin tectono‐sedimentary evolution. For the first time, the structure of the base of the basin in its distal and intermediate sectors is unravelled, which was previously only known in the areas covered by seismic reflection data (distal and small part of intermediate sectors). A complex geometry was found, with three subbasins delimited by NNE‐SSW faults and separated by WNW‐ESE to NW‐SE oriented horsts. In the area covered by seismic reflection data, four horizons were studied: top of the Upper Miocene, Lower to Middle Miocene top, the top of the Palaeogene and the base of Cenozoic. Seismic data show that the major filling of the basin occurred during Upper Miocene. The fault pattern affecting Neogene and Palaeogene units derived here points to that of a polyphasic basin. In the Palaeogene, the Vila Franca de Xira (VFX) and a NNE‐SSW trending previously unknown structure (ABC fault zone) probably acted as the major strike‐slip fault zones of the releasing bend of a pull‐apart basin, which produced a WNW‐ESE to NW‐SE fault system with transtensional kinematic. During the Neogene, as the stress regime rotated anticlockwise to the present NW‐SE to WNW‐ESE orientation, the VFX and Azambuja fault zones acted as the major transpressive fault zones and Mesozoic rocks overthrusted Miocene sediments. The reactivation of WNW‐ESE to NW‐SE fault systems with a dextral strike‐slip component generated a series of horsts and grabens and the partitioning of the basin into several subbasins. Therefore, we propose a polyphasic model for the area, with the formation of an early pull‐apart basin during the Palaeogene caused by an Iberia–Eurasia plates collision that later evolved into an incipient foreland basin along the Neogene due to a NW‐SE to WNE‐ESE oriented Iberia–Nubia convergence. This convergence is producing uplift in the area since the Quaternary except for the Tagus estuary subbasin around the VFX fault, where subsidence is observed. This may be due to the locking or the development of a larger component of strike‐slip movement of the NNE‐SSW to N‐S thrust fault system with the exception of the VFX fault, which is more favourably oriented to the maximum compressive stress.     

Local coordination of Zn in hydroxy-interlayered minerals and implications for Zn retention in soils

The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615-8600 mg/kg Zn) were evaluated by shell fitting. In Zn-HIS, Zn was octahedrally coordinated to oxygen at 2.06-2.08 Å and surrounded by Al atoms at 3.03-3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251-1039 mg/kg Zn) with acidic to neutral pH (pH 4.1-6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29-84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn-HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn-HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.     

Collapse and explosion in a rotating star

The collapse, bounce, shock wave and expansion of the envelope of a rotating star have been analysed in the adiabatic approximation using the particle-in-cell method. The bounce takes place first in the equatorial plane and a shock wave arises there which shortly afterwards crosses the surface of the star. In the envelope, and to a less extent in the remainder of the star, there is a fast and lasting meridional motion the direction of which changes. As a consequence of the fast meridional motion in the envelope, mass and angular momentum are transported towards the axis of rotation. If the initial star rotates fast enough this will cause a secondary radial expansion in the polar region and a mass ejection. These motions reduce the strong anisotropy caused originally by the equatorial expansion. Strong whirls may arise along the axis of rotation. In the remainder of the star the meridional motion becomes supersonic. The temperature in the envelope depends to a high degree on the choice of the equation of state. Massloss is proportional to the energy initially added. The final loss of angular momentum and of energy is quite large, both losses being about 25%.     

Paleomagnetism of early cretaceous arapey formation (Northern Uruguay)

We report detailed rock-magnetic and paleomagnetic directional data from 35 lava flows (302 standard paleomagnetic cores) sampled in the Central-Northern region of Uruguay in order to contribute to the study of the paleosecular variation of the Earth’s magnetic field during early Cretaceous and to obtain precise Cretaceous paleomagnetic pole positions for stable South America. The average unit direction is rather precisely determined from 29 out of 35 sites. All A₉₅ confidence angles are less than 8°, which points to small within-site dispersion and high directional stability. Normal polarity magnetizations are revealed for 19 sites and 10 are reversely magnetized. Two other sites yield well defined intermediate polarities. The mean direction, supported by a positive reversal test is in reasonably good agreement with the expected paleodirection for Early Cretaceous stable South America and in disagreement with a 10° clockwise rotation found in the previous studies. On the other hand, paleomagnetic poles are significantly different from the pole position suggested by hotspot reconstructions, which may be due to true polar wander or the hotspot motion. Our data suggest a different style of secular variation during (and just before) the Cretaceous Normal Superchron and the last 5 Ma, supporting a link between paleosecular variation and reversal frequency.