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Ce contenu n'est pas disponible en français.Scientific Highlights
in the Laboratory of Environmental Chemistry (LUC)
Coexistence of Physisorbed and Solvated HCl at Warm Ice Surfaces
The interfacial ionization of strong acids is an essential factor of multiphase and heterogeneous chemistry in environmental science, cryospheric science, catalysis research and material science. Using Near Ambient Pressure X-ray Photoelectron (NAPP) spectroscopy, we directly detected a low surface coverage of adsorbed HCl at 253 K in both molecular and dissociated states and interpret the results as physisorbed molecular HCl at the outermost ice surface and dissociation occurring upon solvation deeper in the interfacial region. This study gives clear evidence for nonuniformity across the air−ice interface and questions the use of acid−base concepts in interfacial processes.
Ice-core evidence of earliest extensive copper metallurgy in the Andes 2700 years ago
Although copper (Cu) was essential for the wealth of pre- and post-colonial societies in the Andes, the onset of extensive Cu metallurgy in South America is still debated. Based on a 6500 year ice-core Cu record from Illimani glacier in Bolivia we provide the first complete history of large-scale Cu smelting activities in South America. Earliest anthropogenic Cu pollution was found during the Early Horizon period ~700-50 BC. We attribute the onset of intensified Cu smelting in South America to the activities of the central Andean Chiripa and Chavin cultures ~2700 years ago. This study provides for the first time substantial evidence for extensive Cu metallurgy already during these early cultures.
Organic Nitrate Contribution to New Particle Formation and Growth in Secondary Organic Aerosols from α-Pinene Ozonolysis
The chemical kinetics of organic nitrate production during new particle formation and growth of secondary organic aerosols (SOA) were investigated using the short-lived radioactive tracer 13N in flow-reactor studies of α-pinene oxidation with ozone. Direct and quantitative measurements of the nitrogen content indicate that organic nitrates accounted for ∼40% of SOA mass during initial particle formation, decreasing to ∼15% upon particle growth to the accumulation-mode size range (>100 nm). Experiments with OH scavengers and kinetic model results suggest that organic peroxy radicals formed by α-pinene reacting with secondary OH from ozonolysis are key intermediates in the organic nitrate formation process
Pb pollution from leaded gasoline in South America in the context of a 2000-year metallurgical history
Exploitation of the extensive polymetallic deposits of the Andean Altiplano in South America since precolonial times has caused substantial emissions of neurotoxic lead (Pb) into the atmosphere; however, its historical significance compared to recent Pb pollution from leaded gasoline is not yet resolved. We present a comprehensive Pb emission history for the last two millennia for South America, based on a continuous, high-resolution, ice core record from Illimani glacier. Illimani is the highest mountain of the eastern Bolivian Andes and is located at the northeastern margin of the Andean Altiplano.
Polychlorinated biphenyls in glaciers
We present a highly time-resolved historical record of polychlorinated biphenyls (PCBs) from an Alpine ice core (Fiescherhorn glacier, Switzerland). Introduced in the 1940s, PCBs were widely used industrial chemicals. Because of their persistence they are still found in the environment, long after their production phase-out. The Fiescherhorn ice core record covers the entire time period of industrial use of PCBs, that is, 1940?2002. The total concentration of six PCBs varies from 0.5 to 5 ng/L and reveals a temporal trend, with an 8-fold increase from the early 1940s to the peak value in the 1970s.
Ice-core based assessment of historical anthropogenic heavy metal (Cd, Cu, Sb, Zn) emissions in the Soviet Union
The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist.
Effect of surface charge density on the affinity of oxide nanoparticles for the vapor–water interface
Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups by counterions in the condensed ion layer.
Chemistry: Ten things we need to know about ice and snow
Understanding the molecular behaviour of frozen water is essential for predicting the future of our planet, says Thorsten Bartels-Rausch.
Variations in diesel soot reactivity along the exhaust after-treatment system, based on the morphology and nanostructure of primary soot particles
The reactivity of soot at different sites of the exhaust after-treatment system of a diesel engine (upstream and downstream of the diesel oxidation catalyst (DOC), downstream of the diesel particulate filter (DPF), as well as inside the DPF) was investigated on the basis of morphology and structure of primary soot particles by high resolution transmission electron microscopy (HRTEM). The results indicate that combustion-formed soot particles are susceptible to further transformations of their morphology within the exhaust system.