Thermal erosion of cratonic lithosphere as a potential trigger for mass-extinction.

The temporal coincidence between large igneous provinces (LIPs) and mass extinctions has led many to pose a causal relationship between the two. However, there is still no consensus on a mechanistic model that explains how magmatism leads to the turnover of terrestrial and marine plants, invertebrates and vertebrates. Here we present a synthesis of ammonite biostratigraphy, isotopic data and high precision U-Pb zircon dates from the Triassic-Jurassic (T-J) and Pliensbachian-Toarcian (Pl-To) boundaries demonstrating that these biotic crises are both associated with rapid change from an initial cool period to greenhouse conditions. We explain these transitions as a result of changing gas species emitted during the progressive thermal erosion of cratonic lithosphere by plume activity or internal heating of the lithosphere. Our petrological model for LIP magmatism argues that initial gas emission was dominated by sulfur liberated from sulfide-bearing cratonic lithosphere before CO2 became the dominant gas. This model offers an explanation of why LIPs erupted through oceanic lithosphere are not associated with climatic and biotic crises comparable to LIPs emitted through cratonic lithosphere.

Bronze Age volcanic event recorded in stalagmites by combined isotope and trace element studies.

Stable isotope analyses of speleothems (carbonate deposits formed in caves) have been widely used to reconstruct paleoenvironmental conditions. Recent improvements in geochemical techniques have enabled us to analyze climate-influenced deposits at high temporal resolution so that hitherto unrecognized environmental conditions may be identified. Stable H, C and O isotope analyses on carbonate and inclusion water have been combined with multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) age dating and laser-ablation ICP-MS trace element analyses on a stalagmite from southern Hungary. The study reveals significant changes in chemical and isotopic compositions of the speleothem between approx. 3800 and 3500 years BP ('Before Present') indicating coupled changes in the temperature and precipitation regime under which the speleothem formed. Stable isotopic and trace element correlations within this time period correlate with similar studies of stalagmites of comparable age from the Alpine-Mediterranean region. Our studies suggest that traces of deposition of volcanic dust, possibly related to the Thera eruption of Santorini (Greece) ca. 1650 BC (approximately 3650 BP), and environmental changes can be detected at a distance of several thousand kilometers.

Metasomatized lithosphere and the origin of alkaline lavas.

Recycled oceanic crust, with or without sediment, is often invoked as a source component of continental and oceanic alkaline magmas to account for their trace-element and isotopic characteristics. Alternatively, these features have been attributed to sources containing veined, metasomatized lithosphere. In melting experiments on natural amphibole-rich veins at 1.5 gigapascals, we found that partial melts of metasomatic veins can reproduce key major- and trace-element features of oceanic and continental alkaline magmas. Moreover, experiments with hornblendite plus lherzolite showed that reaction of melts of amphibole-rich veins with surrounding lherzolite can explain observed compositional trends from nephelinites to alkali olivine basalts. We conclude that melting of metasomatized lithosphere is a viable alternative to models of alkaline basalt formation by melting of recycled oceanic crust with or without sediment.

Synthesis and characterization of platinum(IV) anticancer drugs with functionalized aromatic carboxylate ligands: influence of the ligands on drug efficacies and uptake.

A series of trans-platinum(IV) complexes with functionalized aromatic carboxylate ligands, cis,cis,trans-Pt(NH3)2Cl2(CO2C6H4R)2 (R = H (3), p-vinyl (4), p-methoxy (5), p-iodo (6), p-cyano (7), or o-carboxyl (8)) was synthesized and characterized by spectroscopic methods. Crystal structures of 3, 4, 7, and 8 were obtained, which revealed that their structural conformations were influenced by intramolecular H-bonding interactions. The complexes were evaluated for cellular uptake and inhibition of cell proliferation against a panel of lung, colon, and breast carcinoma cell lines. The functionalization of the aromatic carboxylate ligand was found to have a profound influence on the uptake, and hence, efficacy, of this class of complex.