Age of Jurassic continental tholeiites of French Guyana, Surinam and Guinea: Implications for the initial opening of the Central Atlantic Ocean

A detailed ⁴⁰Ar/³⁹Ar study, of mineral separates from the Jurassic Atlantic Continental Tholeiites (JACT) of Guyana (French Guyana and Surinam, South America), and Guinea (West Africa) related to the initial opening of the Central Atlantic, has been carried out. In French Guyana, plateau ages of 196.0 ± 5.7 Ma and 196.1 ± 7.5 Ma were obtained on single, small amphibole grains from NNW—SSE trending dykes. In Guinea, single biotite grains from intrusive formations from the Kakoulima and Fouta Djalon areas yielded plateau ages of 200.4 ± 0.2 Ma and 194.8 ± 0.5 Ma, concordant with high temperature apparent ages on other biotites. The bulk plagioclase samples display disturbed age spectra due to alteration and excess argon. However, intermediate temperature, weighted mean plagioclase ages are similar in both regions of Guyana and Guinea, ranging from 200.2 ± 2.4 Ma to 188.7 ± 1.9 Ma, partly in agreement with the amphibole and biotite data.

These data, combined with previous ⁴⁰Ar/³⁹Ar and U/Pb results from the northern part of the Central Atlantic margins, indicate intense magmatic activity distributed over a large area from Iberia to Liberia (ca. 4500 km long) for a short period of time (204-195 Ma, perhaps less for the bulk of the magmatism) during the initial break-up of Pangea continent. These data do not support an initiation of the magmatism from a radial volcano-tectonic system centred in the south of the region, as suggested by May [1], and the initial break-up seems to affect the whole Central Atlantic during a period of 9 Ma.     

Long-term climate policy: international legal aspects of sector-based approaches

Abstract

The aim of this article is to discuss the international legal implications of a sector-based approach to long-term climate policy. Sector-based approaches have emerged as a possible way of engaging all the major emitters of greenhouse gases into the system. The article divides sectoral approaches into two main categories based on their legal relevance. Substantive sectoral models focus on ways of defining emission levels for global industry sectors. From the point of view of international law, substantive sectoral models could be integrated into the existing climate change regime if the Parties so agree. Procedural sectoral models focus on actors. Some procedural sectoral models envisage treaty regimes involving non-State actors, such as organizations representing global industry sectors undertaking to reduce emissions of greenhouse gases. The main focus of the article is on these models.     

Arsenic redox transformation by humic substances and Fe minerals

The toxicity and mobility of the redox-active metalloid As strongly depends on its oxidation state, with As(III) (arsenite) being more toxic and mobile than As(V) (arsenate). It is, therefore, necessary to know the biogeochemical processes potentially influencing As redox state to understand and predict its environmental behavior. The first part of this presentation will discuss the quantification of As redox changes by pH-neutral mineral suspensions of goethite [α-Fe^IIIOOH] amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis (Amstaetter et al., 2010). First, it was found that goethite itself did not oxidize As(III). Second, in contrast to thermodynamic predictions, Fe(II)–goethite systems did not reduce As(V). However, surprisingly, rapid oxidation of As(III) to As(V) was observed in Fe(II)–goethite systems. Iron speciation and mineral analysis by Mössbauer spectroscopy showed rapid formation of ⁵⁷Fe–goethite after ⁵⁷Fe(II) addition and the formation of a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer spectroscopy, EXAFS, scanning electron microscopy, X-ray diffraction or high-resolution transmission electron microscopy. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite.The second part of the presentation will show that semiquinone radicals produced during microbial or chemical reduction of a humic substance model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) can react with As and change its redox state (Jiang et al., 2009). The results of these experiments showed that these semiquinone radicals are strong oxidants and oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. The oxidation of As(III) depended strongly on pH. More arsenite (up to 67.3%) was oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction, reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In an attempt to understand the observed redox reactions between As and reduced/oxidized quinones present in humic substances, the radical content in reduced AQDS solutions was quantified and Eh-pH diagrams were constructed. Both the radical quantification and the Eh-pH diagram allowed explaining the observed redox reactions between the reduced AQDS solutions and the As.In summary these studies indicate that in the simultaneous presence of Fe(III) oxyhydroxides, Fe(II), and humic substances as commonly observed in environments inhabited by Fe-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.     

Mineralisation and structural changes during the initial phase of microbial degradation of pyrogenic plant residues in soil

The microbial recalcitrance of char accumulated after vegetation fires was studied using pyrogenic organic material (PyOM) with increasing degrees of charring, produced from rye grass (Lolium perenne) and pine wood (Pinus sylvestris) at 350 °C under oxic conditions. Solid state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy confirmed increasing aromaticity and the formation of heterocyclic N with prolonged charring. After mixing with a mineral soil, the PyOM was aerobically incubated for 48 days at 30 °C. To account for the input of fresh litter after a fire event, unburnt rye grass residue was added as a co-substrate. The grass-derived PyOM showed the greatest extent of C mineralisation. After 48 days incubation, up to 3.2% of the organic C (OC) was converted to CO₂. More severe thermal alteration resulted in a decrease in the total C mineralisation to 2.5% of OC. In the pine-derived PyOM, only 0.7% and 0.5% of the initial C were mineralised. The co-substrate additions did not enhance PyOM mineralisation during initial degradation. ¹³C NMR spectroscopic analysis indicated structural changes during microbial degradation of the PyOM. Concomitant with a decrease in O-alkyl/alkyl-C, carboxyl/carbonyl C content increased, pointing to oxidation. Only the strongly thermally altered pine PyOM showed a reduction in aromaticity. The small C losses during the experiment indicated conversion of aryl C into other C groups. As revealed by the increase in carboxyl/carbonyl C, this conversion must have included the opening and partial oxidation of aromatic ring structures. Our study demonstrates that plant PyOM can be microbially attacked and mineralised at rates comparable to those for soil organic matter (SOM), so its role as a highly refractory SOM constituent may need re-evaluation.     

Review of effects of radiation damage on the luminescence emission of minerals, and the example of He-irradiated CePO4

The accumulation of structural damage that is created in minerals upon corpuscular irradiation, has two apparently contrarious effects on their luminescence behaviour. First, irradiation may cause the generation of luminescent defect centres, which typically results in broad-band emissions. Such defect emissions are characteristic of low levels of radiation damage. Second, radiation damage depletes in general the luminescence of minerals, which is associated with broadenings and intensity losses of individual emission lines. Minerals that have suffered elevated levels of irradiation hence tend to be virtually non-luminescent. This review paper aims at giving an overview of the possible correlations of radiation damage and emission characteristics of minerals. After a brief, introductory summary of the damage-accumulation process and its causal corpuscular radiation, an array of examples is presented for how internal and/or external irradiation may change appreciably the emission of rock-forming and accessory minerals. As a detailed example for the complexity of changes of emissions upon damage accumulation, preliminary results of a case study of the photoluminescence (PL) of synthetic CePO₄ irradiated with 8.8 MeV He ions are presented. Irradiation-induced spectral changes include (i) the initial creation, and subsequent depletion, of a broad-band, defect-related PL emission of orange colour, and (ii) gradual broadenings and intensity losses of PL lines related to electronic transitions of rare-earth elements, eventually leading to gradual loss of their splitting into multiple Stark levels (shown for the ⁴F_3/2 → ⁴I_9/2 transition of Nd³⁺).     

Influence of a Xenobiotic Mixture (PCB and TBT) Compared to Single Substances on Swimming Behavior or Reproduction of Daphnia magna

Aroclor 1254, a technical PCB mixture (polychlorinated biphenyls) and TBT (tributyltinchloride) are environmental pollutants that cause a broad spectrum of acute toxic and chronic effects in aquatic animals. In this paper, the sensitivity of Daphnia magna to chronic exposure to mixed xenobiotics was evaluated under laboratory conditions. The results show that xenobiotic mixtures (50 % each of the single compounds) were more toxic than individual xenobiotics alone. By measuring behavioral parameters of animals, it becomes evident that exposure to single xenobiotics significantly affects daphnids: exposure led finally to a rapid decrease in mean swimming activity and also caused changes in preferred swimming depth, with daphnids preferring the upper layers of aquaria. The mixture altered the swimming behavior even more strongly compared to the group stressed by single chemicals. Finally, all daphnids sank to the bottom of the aquaria, still alive, but inactive at the end of the exposure period. In addition, we investigated the reproductive capacity (number of newborn per female and day). PCB did not affect the number of newborn significantly, TBT‐stress led to an evidently decreased number of young daphnids and the xenobiotic mixture decreased reproduction even more. In conclusion, we found significant effects of the single compounds as well as approximately additive (swimming behavior) and synergistic (reproduction) effects of the chemical mixture on daphnids indicating the possibility of dramatic ecological consequences of the occurrence of mixed xenobiotic substances in the aquatic environment.     

Indices for the assessment of environmental pollution of the Baltic Sea coasts: integrated assessment of a multi-biomarker approach

Two mathematical methods to assess the "health status" of flounder (Platichthys flesus), eelpout (Zoarces viviparus) and blue mussel (Mytilus spp.) populations of the Baltic Sea were applied on selected biomarker data collected during the EU project "BEEP" (Biological Effects of Environmental Pollution on Marine Coastal Ecosystems). The Bioeffect Assessment Index (BAI) and the Integrated Biomarker Index (IBR) combine different biomarkers to single values, which can be used to describe the toxically-induced stress level of populations in different areas. Both indices determined here produced essentially similar results, which in most cases agreed with the known contamination levels in the different study areas. Advantages and limitations of index applications and interpretations are critically discussed. The use of indices provides comprehensive information about biological effects of pollution in marine organisms and may therefore serve as a useful tool for environmental management by ranking the pollution status of marine coastal areas.     

Multi-isotope (Ba,C, O) partitioning during experimental carbonatization of a hyper-alkaline solution

Carbonates formed from hyperalkaline aqueous solutions at the Earth?s surface are known to bear the most extreme disequilibrium isotope signatures reported so far in nature. We present here the results for stable carbon (C), oxygen (O), and barium (Ba) isotope fractionation during the precipitation of witherite (BaCO₃) induced by the chemical absorption of atmospheric carbon dioxide (CO₂) into an aqueous hyper-alkaline solution (at 4° and 21?°C; 1?atm total pressure). Independent from temperature, the barium carbonate formation was associated with a substantial enrichment of the lighter C and O isotopes in the solid compared to the atmosphere (C, O), close to previous results found in experiments and nature. A new approach is introduced to explain oxygen isotope fractionation upon hydroxylation of CO₂. With Ba isotope enrichment factors between ?0.45 and ?0.53‰ (^138/134ε) or ?0.34 and ?0.40‰ (^137/134ε), respectively, the synthesized BaCO₃ displays the highest kinetic enrichment of the light Ba isotope in the carbonate solid reported so far.