Photochemical reactions of musk ketone

The photolysis of musk ketone in cyclohexane and methanol afforded several cyclization products while the product spectrum in cyclohexene and squalene was characterized by an amino derivative and a ring expansion product, respectively. On cellulose stearate layers the photochemical reactions of musk ketone proceeded readily both under sun simulator and in natural sunlight and several photoproducts identified in solvent experiments were detected. Photoproducts were isolated by preparative HPLC and TLC and analyzed by means of HPLC, GC/MS, MS, LC/MS, ¹H‐ and ¹³C‐NMR.     

Radon as a naturally occurring tracer for the assessment of residual NAPL contamination of aquifers

The noble gas radon has a strong affinity to non-aqueous phase-liquids (NAPLs). That property makes it applicable as naturally occurring partitioning tracer for assessing residual NAPL contamination of aquifers. In a NAPL contaminated aquifer, radon dissolved in the groundwater partitions preferably into the NAPL. The magnitude of the resulting radon deficit in the groundwater depends on the NAPL-specific radon partition coefficient and on the NAPL saturation of the pore space. Hence, if the partition coefficient is known, the NAPL saturation is attainable by determination of the radon deficit. After a concise discussion of theoretical aspects regarding radon partitioning into NAPL, related experimental data and results of a field investigation are presented. Aim of the laboratory experiments was the determination of radon partition coefficients of multi-component NAPLs of environmental concern. The on-site activities were carried out in order to confirm the applicability of the "radon method" under field conditions.     

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia Usneoides (L.) in an industrialized area in Rio de Janeiro state, south east Brazil--Part I: PCDD and PCDF

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic Bromeliad species as biomonitor and measuring total deposition rates on funnels covered with polyurethane foams. Samples were collected during 78 days in V.R. and 95 days in PNI in winter (dry season, June-August 2003) and during 114 days in both areas in summer (rainy season, December 2003-February 2004). The PCDD/PCDF deposition rates ranged from 0.10 to 1.9 pg WHO-TEQ/(m2 day) in winter and from 0.11 to 2.2 pg WHO-TEQ/(m2 day) in summer. Deposition rates found in V.R. in summer were four- to ninefold higher than those measured in PNI, while in winter deposition rates in both regions were in the same range. Deposition rates in V.R. in summer were about five fold lower than those measured in 1996. PCDD/PCDF levels in biomonitor samples were between 0.95 and 14.6 ng WHO-TEQ/kg d.m. in winter and between 2.2 and 5.2 ng WHO-TEQ/kg d.m. in summer. In winter, concentrations found in V.R. were up to 11 times higher than those found in PNI, while in summer the levels measured in both areas were comparable. The homologue and isomer profiles found in the deposition as well as in the biomonitor samples from V.R. indicate that steel production is the main source of contamination in the region, whereas in PNI, the long range transport of these pollutants is the predominant contamination pathway.     

High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

Altitude profiles of total chlorinated paraffins in humus and spruce needles from the Alps (MONARPOP)

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. CPs were analyzed in humus and needle samples, which were taken within the Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants (MONARPOP) at sampling sites of 7 different altitude profiles in the Alps. Gas chromatography combined with electron ionization tandem mass spectrometry (EI-MS/MS) was used for the determination of total CPs (sum of short, medium and long chain CPs). CPs were found in all samples; the concentrations varied between 7 and 199 ng g⁻¹ dry weight (dw) and within 26 and 460 ng g⁻¹ dw in humus and needle samples, respectively. A clear vertical tendency within the individual altitude profiles could not be ascertained. Within all altitude profiles, elevated concentrations were observed in humus samples taken between 700 and 900 m and between 1300 and 1500 m. In the needle samples no similar correlation could be observed due to higher variation of the data.     

Fetal surgery for cardiac lesions

Intrauterine dilation of critical fetal aortic stenosis (AS) and pulmonary stenosis or atresia has the potential to change the natural course of these congenital heart defects preventing progression to a single ventricle circulation. This article reviews the world experience in fetal cardiac interventions. In carefully selected cases, fetal cardiac surgery can reverse end-stage heart failure and can provide biventricular outcome postnatally in about two thirds of the cases with successful interventions. Copyright © 2011 John Wiley & Sons, Ltd.     

Ontogenetic data and the evolutionary origin of the mammalian scapula

One of the most useful diagnostic therian features is the division of the lateral surface of the scapula into two fossae separated by a scapular spine. A new model to describe this evolutionary innovation based on ontogenetic data is provided, consistent with information provided by recent fossil discoveries. The development of the scapula in three didelphid and one dasyurid marsupials using histological sections was studied. Only the ventral, acromial portion of the scapular spine, which originates from the anterior margin of the scapular blade, is preformed in cartilage. The major dorsal portion is formed at a later stage by appositional bone, which expands from the perichondral ossification of the scapula into an intermuscular aponeurosis between the supra-and infraspinatus muscles. This intermuscular aponeurosis inserts more or less in the middle of the lateral surface of the developing scapula. Thus, the floor of the supraspinous fossa is already present at the beginning of scapular development, simultaneous with the infraspinous fossa. The portion of the scapular spine that is situated dorsal to the acromial process is hypothesized to be a neomorphic structure of therians. The dorsal portion of the scapular spine evolved as additional attachment for powerful supraspinatus and infraspinatus muscles meeting near the middle of the lateral scapula.     

Femtosecond time-resolved spectroscopy of elementary molecular dynamics

Femtosecond time-resolved coherent anti-Stokes Raman spectroscopy (CARS) is applied in order to prepare and monitor laser-induced vibrational coherences (wave packets) of different samples mainly in its electronic ground state but also in excited states. The time evolution of these wave packets gives information on the dynamics of molecular vibrations. In a first example the femtosecond (fs) CARS transients of iodine are investigated. By changing the relative delay between the applied laser pulses of this non-degenerated four-wave mixing technique, both the wavepacket motion on the electronically excited and the ground states can be detected as oscillations in the coherent anti-Stokes signal. Second we report on selective excitation of the vibrational modes in the electronic ground state of polymers of diacetylene by means of a femtosecond time-resolved CARS scheme. This selectivity is achieved by varying the phase shape (chirp) and the relative delay between the exciting laser pulses.