Analysis of polycyclic aromatic hydrocarbons (PAHs) in airborne particles by direct sample introduction thermal desorption GC/MS

The technique of thermal desorption (TD)–GC/MS was evaluated for measuring airborne, 4–6 ring polycyclic aromatic hydrocarbons (PAHs) collected onto quartz filters. TD provides a more readily automated and sensitive alternative to traditional solvent extraction, decreasing the time/cost of analysis and reducing the risk of analyte loss or sample contamination. The developed method was successfully applied to the analysis of PAH standard solutions loaded on sorbent tubes packed with quartz wool and the graphitized carbon black sorbent Carbograph2. The optimized method showed high desorption efficiency over the whole range of target PAHs with good precision, linearity and sensitivity. The proposed method was verified on an urban dust Standard Reference Material (SRM 1649a); the experimentally determined concentrations agreed with the certified ranges (95% confidence limit) for all target compounds except benzo[a]anthracene, which fell just outside the narrow certified range. The desorption efficiency and the reproducibility of the method was evaluated by analysing pieces of real sample filters sampled from urban air for a period of 24 h. The results confirmed the homogeneity of the filter and showed high recovery efficiencies for all target PAHs.     

Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil: results of the IAEA–UNESCO SGD project

Results of groundwater and seawater analyses for radioactive (³H, ²²²Rn, ²²³Ra, ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra) and stable (D and ¹⁸O) isotopes are presented together with in situ spatial mapping and time series ²²²Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d⁻¹ to 360 cm d⁻¹; the unit represents cm³/cm²/day), as well as during a few hours (from 0 cm d⁻¹ to 110 cm d⁻¹), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous ²²²Rn measurements is 17 ± 10 cm d⁻¹. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7 × 10³ m³ d⁻¹ per km of the coast. The isotopic composition (δD and δ¹⁸O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time series measurements of ²²²Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1–2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.     

Chemically mediated interactions between the red algaPlocamium hamatum (Rhodophyta) and the octocoralSinularia cruciata (Alcyonacea)

Interactions between the red algaPlocamium hamatum J. Agardh (Rhodophyta) and other benthic organisms including the alcyonacean soft coralSinularia cruciata (Tixier-Durivault) were investigated on an inshore fringing reef environment in whichP. hamatum was the dominant large fleshy alga. Field observations of sessile reef organisms including octocorals and sponges living in close proximity toP. hamatum revealed that varying degrees of tissue necrosis were suffered by the invertebrates when in physical contact with the alga. In order to establish whether the chemical constituents of the alga, especially chloromertensene, played a role in this necrosis, manipulative field experiments were carried out in the Pelorus Channel, Palm Island group (18°34S; 146°29E), North Queensland, Australia, in November and December 1988. The first experiment involved the relocation of healthy plants and soft corals into contact and non-contact situations on a mesh grid. In all cases of contact betweenP. hamatum andS. cruciata, the soft coral suffered tissue necrosis (n=6,p=0.0022). The second experiment had the same design, but involved the use of artificial plants both uncoated and coated with natural levels of chloromertensene, in contact withS. cruciata. In all cases of contact with coated treatments, necrosis was observed inS. cruciata (n=4,p=0.025). In cases where uncoated artificial fronds were placed in contact with soft corals,S. cruciata showed minor abrasion effects, but no appreciable necrosis. Coated treatments were not fouled by epiphytes during the experiment and were not consumed by predators. Uncoated treatments were rapidly reduced in size by predation and any remaining material was biofouled. These experiments thus demonstrated that the deleterious effects observed in soft corals in the field were caused by contact with the algaP. hamatum, that these effects were indeed chemically mediated by chloromertensene, and that physical contact without chemical intervention caused no such deleterious effects. This is the first experimental evidence which conclusively demonstrates allelopathy between an alga and other marine organisms and identifies the compound responsible for the observed allelopathic effects.     

Disappearance of bromopropylate residues in artichokes, strawberries and beans

Residues of Bromopropylate were determine in artichokes, strawberries and beans after foliar spray of acaricide at two rates. The rates used were 1 g/l formulated product (normal recommended) and 1.5 g/l. The residue levels of bromopropylate in the three crops after 14 days were lower than 0.7 ppm and did not exceed the Maximum Residual Level (MRL) recommended by FAO. In the artichokes and strawberries, the total concentration of residues decreased by 50% of the initial level after 2-3 days. Only trace levels of the bromopropylate residues (less than 0.01 ppm) were detected in the "hearts" of the artichokes. Bromopropylate residues in the green beans were also less than 0.8 ppm after the first day of foliar spraying. The kinetic of degradation occurred in two different steps. In the first step (4-6 days) the dissipation of bromopropylate was faster whereas in the second step (7-14 days) the loss of residues was much slower.     

A modular approach to Integrated Assessment modeling

In this paper, we present a new approach to model coupling that probably forms the methodological basis of a new generation of Integrated Assessment models. This approach respects the knowledge and expertise that is embodied in existing models and encourages their gradual evolution. Modularity is the guiding principle. Our approach is distinguished by the way modules are coupled which is based on an interplay of a job control module, a numerical coupling module, and a couple of stand-alone functional modules. The numerical coupling module - the core component - serves to treat the feedbacks between the functional modules. A first implemented example that couples an economic and a climate module by means of a two-phase meta-optimization is presented here. The algorithm and mathematical structure behind are discussed as well as important features such as convergence behavior and reliability.     

Sequential extractions of selenium soils from Stewart Lake: total selenium and speciation measurements with ICP-MS detection

Different techniques have been employed in order to evaluate the most efficient procedure for the extraction of selenium from soil as required for speciation. Selenium contaminated sediments from Stewart Lake Wetland, California were used. A strong acid mineralization of the samples gives quantitative total selenium, which is then used to estimate recoveries for the milder extraction methods. The different extraction methodologies involve the sequential use of water, buffer (phosphate, pH 7) and either acid solution (e.g. HNO3 or HCl) or basic solutions (e.g. ammonium acetate, NaOH or TMAH). Pyrophosphate extraction was also evaluated and showed that selenium was not associated with humic acids. The extractants were subsequently analyzed by size exclusion chromatography (SEC) with UV (254 and 400 nm) and on-line ICP-MS detection; anion exchange chromatography, and ion-pair reversed phase chromatography with ICP-MS detection. For sequential extractions the extraction efficiencies showed that the basic extractions were more efficient than the acidic. The difference between the acidic and the basic extraction efficiency is carried to the sulfite extraction, suggesting that whatever is not extracted by the acid is subsequently extracted by the sulfite. The species identified with the different chromatographies were selenate, selenite, elemental selenium and some organic selenium.     

The modern theory of biological evolution: an expanded synthesis

In 1858, two naturalists, Charles Darwin and Alfred Russel Wallace, independently proposed natural selection as the basic mechanism responsible for the origin of new phenotypic variants and, ultimately, new species. A large body of evidence for this hypothesis was published in Darwins Origin of Species one year later, the appearance of which provoked other leading scientists like August Weismann to adopt and amplify Darwins perspective. Weismanns neo-Darwinian theory of evolution was further elaborated, most notably in a series of books by Theodosius Dobzhansky, Ernst Mayr, Julian Huxley and others. In this article we first summarize the history of life on Earth and provide recent evidence demonstrating that Darwins dilemma (the apparent missing Precambrian record of life) has been resolved. Next, the historical development and structure of the modern synthesis is described within the context of the following topics: paleobiology and rates of evolution, mass extinctions and species selection, macroevolution and punctuated equilibrium, sexual reproduction and recombination, sexual selection and altruism, endosymbiosis and eukaryotic cell evolution, evolutionary developmental biology, phenotypic plasticity, epigenetic inheritance and molecular evolution, experimental bacterial evolution, and computer simulations (in silico evolution of digital organisms). In addition, we discuss the expansion of the modern synthesis, embracing all branches of scientific disciplines. It is concluded that the basic tenets of the synthetic theory have survived, but in modified form. These sub-theories require continued elaboration, particularly in light of molecular biology, to answer open-ended questions concerning the mechanisms of evolution in all five kingdoms of life.Dedicated to Prof. Dr. Dr. hc mult. Ernst Mayr on the occasion of his 100th birthdayThis revised version was published online in March 2004, with corrections to the caption of Figure 6.     

Energie-Speicherung und Methoden des Energie-Transports

The Science of Nature - Because of the sudden rise in primary-energy costs and the rapid inflation of plants which are used for the conversion of primary to secondary energy, the storage of energy,...