The cohesive energy of superheavy element copernicium determined from accurate relativistic coupled-cluster theory.

The cohesive energy of bulk copernicium is accurately determined using the incremental method within a relativistic coupled-cluster approach. For the lowest energy structure of hexagonal close-packed (hcp) symmetry, we obtain a cohesive energy of -36.3 kJ mol (inclusion of uncertainties leads to a lower bound of -39.

Co-adsorption of acetic acid and nitrous acid on ice.

The co-adsorption of acetic and nitrous acids was investigated in a packed ice bed flow tube at atmospheric pressure in the temperature range of 213-243 K. The uptake of acetic acid (CH3COOH) on ice was probed by means of a chemical ionisation quadrupole mass spectrometer. For the interaction of HONO with ice, molecules labelled with the short-lived radioisotope 13N (t1/2 = 10 min) were used.

Post 17th-century changes of European PAH emissions recorded in high-altitude Alpine snow and ice.

The occurrence of organic pollutants in European Alpine snow/ice has been reconstructed over the past three centuries using a new online extraction method for polycyclic aromatic hydrocarbons (PAH) followed by liquid chromatographic determination. The meltwater flow from a continuous ice core melting system was split into two aliquots, with one aliquot directed to an inductively coupled plasma quadrupole mass spectrometer for continuous trace elements determinations and the second introduced into a solid phase C18 (SPE) cartridge for semicontinuous PAH extraction. The depth resolution for PAH extractions ranged from 40 to 70 cm, and corresponds to 0.

Thallium as a tracer for preindustrial volcanic eruptions in an ice core record from Illimani, Bolivia.

Trace element records from glacier and ice sheet archives provide insights into biogeochemical cycles, atmospheric circulation changes, and anthropogenic pollution history. We present the first continuous high-resolution thallium (Tl) record, derived from an accurately dated ice core from tropical South America, and discuss Tl as a tracer for volcanic eruptions. We identify four prominent Tl peaks and propose that they represent signals from the massive explosive eruptions of the "unknown 1258" A.

Uptake of NO2 to deliquesced dihydroxybenzoate aerosol particles.

The uptake of nitrogen dioxide (NO2), a major trace gas in the atmosphere, to deliquesced particles containing the sodium salts of hydroquinone (1,4-dihydroxybenzene) or gentisic (2,5-dihydroxybenzoic) acid was investigated at 40% relative humidity and 23 degrees C in an aerosol flow tube. The experiments were performed using the short-lived radioactive tracer 13N and a denuder technique. The observed uptake coefficient for NO2 was up to approximately 6 x 10(-3) for the hydroquinone disodium salt aerosol, which exceeds previously reported data in the range 10(-4) to 10(-3).

Kinetics of the heterogeneous reaction of nitric acid with mineral dust particles: an aerosol flowtube study.

The heterogeneous reaction of HNO3 with mineral dust aerosol (Arizona Test Dust) was studied in an aerosol flow tube at atmospherically relevant conditions (298 K, approximately 1 atm, 6-60% RH) and using radioactively labelled HNO3. The uptake of nitric acid was found to depend on HNO3 and H2O concentrations in the gas phase. A reaction mechanism is suggested to describe the heterogeneous interaction, involving Langmuir type adsorption and surface reaction.

Chemical characterization of element 112.

The heaviest elements to have been chemically characterized are seaborgium (element 106), bohrium (element 107) and hassium (element 108). All three behave according to their respective positions in groups 6, 7 and 8 of the periodic table, which arranges elements according to their outermost electrons and hence their chemical properties. However, the chemical characterization results are not trivial: relativistic effects on the electronic structure of the heaviest elements can strongly influence chemical properties.

Estimate of European 129I releases supported by 129I analysis in an Alpine ice core.

129I in the European environment originates predominantly from the industrial nuclear fuel reprocessing plants Sellafield (Great Britain), Marcoule, and La Hague (both France). While reliable data on 129I releases from La Hague exist for the whole period of operation, less is known about the contributions from Sellafield and Marcoule. For those periods where no data are available, i.

Atmospheric pressure coated-wall flow-tube study of acetone adsorption on ice.

An atmospheric pressure variant of the coated-wall flow-tube technique in combination with a Monte Carlo simulation is presented. In a performance test of simple first-order wall loss, the Monte Carlo simulation, which uses a simplified model of transport in laminar flow, reproduced results of an analytical solution of the transport equations in a flow tube. This technique was then used to investigate the reversible adsorption of acetone on ice films between 203 and 223 K and a surface coverage of below 5% of a formal monolayer.

Plutonium from global fallout recorded in an ice core from the Belukha glacier, Siberian Altai.

Ice cores from glaciers situated near anthropogenic sources of air pollution provide important archives of the emissions of species with short atmospheric lifetimes. Here we present the history of atmospheric Pu fallout reconstructed from an ice core from the Belukha glacier in the Siberian Altai. Fourteen ice core samples covering the time period 1941-1986 were selected for Pu analysis, chemically processed, and measured using accelerator mass spectrometry.

Historical record of European emissions of heavy metals to the atmosphere since the 1650s from alpine snow/ice cores drilled near Monte Rosa.

Cr, Cu, Zn, Co, Ni, Mo, Rh, Pd, Ag, Cd, Sb, Pt, Au, and U have been determined in clean room conditions by inductively coupled plasma sector field mass spectrometry and other analytical techniques, in various sections of two dated snow/ice cores from the high-altitude (4450 m asl) glacier saddle Colle Gnifetti, Monte Rosa massif, located in the Swiss-Italian Alps. These cores cover a 350-year time period, from 1650 to 1994. The results show highly enhanced concentrations for most metals in snow/ice dated from the second half of the 20th century, compared with concentrations in ancient ice dated from the 17th and 18th centuries.

Accuracy of continuous ice-core trace-element analysis by inductively coupled plasma sector field mass spectrometry.

Trace elements trapped in glaciers are important indicators for the characterization of past biogeochemical cycles, the identification of numerous sources and their varying strength, and thus indirectly provide insight into past climate variations. However, this necessitates highly resolved and continuous records of trace elements in ice. To obtain records corresponding to these requirements, a continuous ice-core melting (CIM) device was coupled to an inductively coupled plasma sector field mass spectrometer (ICP-SFMS).

Precision measurement of the 7Be(p,gamma)8B cross section with an implanted 7Be target.

The 7Be(p,gamma)8B reaction plays a central role in the evaluation of solar neutrino fluxes. We report on a new precision measurement of the cross section of this reaction, following our previous experiment with an implanted 7Be target, a raster-scanned beam, and the elimination of the backscattering loss. The new measurement incorporates a more abundant 7Be target and a number of improvements in design and procedure.

Chemical investigation of hassium (element 108).

The periodic table provides a classification of the chemical properties of the elements. But for the heaviest elements, the transactinides, this role of the periodic table reaches its limits because increasingly strong relativistic effects on the valence electron shells can induce deviations from known trends in chemical properties. In the case of the first two transactinides, elements 104 and 105, relativistic effects do indeed influence their chemical properties, whereas elements 106 and 107 both behave as expected from their position within the periodic table.

Significance of semivolatile diesel exhaust organics for secondary HONO formation.

The atmospheric origin of nitrous acid (HONO) is largely unknown despite its estimated importance as an OH source during daytime due to its rapid photolysis. Recently, primary HONO contained in automobile exhaust as well as secondary HONO formation on soot particles have been invoked as possible HONO sources, but none of them is able to account for the observed HONO to NOx ratios of up to 0.04 in the atmosphere.

Heterogeneous reaction of NO2 on diesel soot particles.

Soot particles were collected from a diesel engine using a procedure that realistically mimics exhaust gas conditions in tailpipes and during dilution at room temperature. After being sampled, the particles were exposed to NO2 concentrations and relative humidity in ranges relevant for the troposphere using 13N as tracer. Gas-phase nitrous acid(HONO) and irreversibly bound (i.

Chemical characterization of bohrium (element 107).

The arrangement of the chemical elements in the periodic table highlights resemblances in chemical properties, which reflect the elements' electronic structure. For the heaviest elements, however, deviations in the periodicity of chemical properties are expected: electrons in orbitals with a high probability density near the nucleus are accelerated by the large nuclear charges to relativistic velocities, which increase their binding energies and cause orbital contraction. This leads to more efficient screening of the nuclear charge and corresponding destabilization of the outer d and f orbitals: it is these changes that can give rise to unexpected chemical properties.

Analysis of size-classified ice crystals by capillary electrophoresis.

In order to analyse the main inorganic cations (NH4+, K+, Na+, Ca2+, Mg2+) and anions (Cl-, NO3-, SO4(2-)) as well as carboxylic and dicarboxylic acids in ice crystals by capillary electrophoresis, electrolyte systems were developed and optimised with respect to limits of detection, resolution, reproducibility and analysis time. We applied indirect UV detection, which enables the simultaneous detection of multiple components. Salicylic acid and 4-methylaminophenolsulfate were used as UV-active co-ions for analysis of anions and cations, respectively.

First Measurement of a Thermochemical Property of a Seaborgium Compound.

With only a few atoms of seaborgium (Sg, element 106), in the form of volatile SgO(2)Cl(2), it was possible to determine the sublimation enthalpy of this compound using gas chromatography. Furthermore, it was demonstrated that in Group 6 Sg is chemically more similar to W than to Mo.