Thio arsenosugars in freshwater mussels from the Danube in Hungary

In contrast to the large body of data on naturally-occurring arsenic compounds in marine organisms, relatively little is known about arsenic speciation in freshwater biota. We report an investigation using HPLC-ICPMS into the arsenic compounds in five species of freshwater mussels collected from five sites from the Danube in Hungary. Total arsenic concentrations in the mussels ranged from 3.8-12.8 mg As kg(-1). The arsenic speciation patterns were broadly similar for mussels representing each of the five species and five sites, but quite different from those reported for marine mussels. The major extractable arsenicals were two oxo arsenosugars (glycerol sugar and phosphate sugar), and their thio analogues (thio glycerol sugar and thio phosphate sugar). Arsenobetaine, usually the major arsenical in marine organisms, was not a significant compound in the freshwater mussels and was detected in only three of the 11 samples. This is the first report of thio arsenosugars in freshwater biota and suggests that these compounds may be common and widespread naturally-occurring arsenicals.     

Changes in wet meadow vegetation after 20 years of different management in a field experiment (North-West Germany)

Conservation and restoration of semi-natural wet grasslands often suffer from poor knowledge on successional pathways of respective habitats under different mowing treatments to derive profound management concepts. In this study, we present the results of a 20-year experiment in six semi-natural wet grassland sites in NW Germany including mowing with and without fertilizer addition and fallow. Succession was recorded by permanent plots. The studied wet grassland communities responded quite similar under equal management. Fallow resulted in the most significant changes in floristic and functional composition facilitating highly competitive rushes and tall forbs. The changes were more pronounced the more the experimental management treatment differed from the former use. For all mowing treatments without fertilizer application, we still observed directed changes in the floristic composition even after 20 years. In particular mowing twice led to a shift in floristic composition towards stress-tolerant plants with low nutrient demands, which was paralleled by decreasing productivity and strongly diminishing Ellenberg nutrient values. Our results documented that restoration of low-yielding target communities by regular mowing is possible – even in an area with high atmospheric nitrogen inputs. However, our results also show that succession did not come to an end even after 20 years, most obviously due to the continuous but very slow immigration and spread of new species.     

Higher Cd adsorption on biogenic elemental selenium nanoparticles

Cadmium (Cd) is a carcinogenic metal contaminating the environment and ending up in wastewaters. There is therefore a need for improved methods to remove Cd by adsorption. Biogenic elemental selenium nanoparticles have been shown to adsorb Zn, Cu and Hg, but these nanoparticles have not been tested for Cd removal. Here we studied the time-dependency and adsorption isotherm of Cd onto biogenic elemental selenium nanoparticles using batch adsorption experiments. We measured ζ-potential values to assess the stability of nanoparticles loaded with Cd. Results show that the maximum Cd adsorption capacity amounts to 176.8 mg of Cd adsorbed per g of biogenic elemental selenium nanoparticles. The ζ-potential of Cd-loaded nanoparticles became less negative from ?32.7 to ?11.7 mV when exposing nanoparticles to an initial Cd concentration of 92.7 mg L^?1. This is the first study that demonstrates the high Cd uptake capacity of biogenic elemental selenium nanoparticles, of 176.8 mg g^?1, when compared to that of traditional adsorbents such as carboxyl-functionalized activated carbon, of 13.5 mg g^?1. An additional benefit is the easy solid–liquid separation by gravity settling due to coagulation of Cd-loaded biogenic elemental selenium nanoparticles.     

Variations in the elemental compositions of plants,and computer‐aided sampling in ecosystems∗

To obtain comparable results of multi‐element analysis of plant materials by different laboratories, a harmonized sampling procedure for terrestrial and marine ecosystems is essential. The heterogeneous distribution of chemical elements in living organisms is influenced by different biological parameters. These parameters are mainly characterized by genetic predetermination, seasonal changes, edaphic and climatic conditions, and delocalization processes of chemical substances by metabolic activities.

The biological variations of the element content in plants were divided into 5 systematic levels, which are: 1. the plant species; 2. the population; 3. the stand (within an ecosystem); 4. the individual; and 5. the plant compartment. Each of these systematic levels can be related to: 1. genetic variabilities; 2. different climatic, edaphic and anthropogenic influences; 3. microclimatic or microedaphic conditions; 4. age of plants (stage of development), exposure to environmental influences (light, wind, pollution etc.), seasonal changes; and 5. transport and deposition of substances within the different plant compartments (organs, tissues, cells, organelles).

An expert system for random and systematic sampling for multi‐element analysis of environmental materials, such as plants, soils and precipitation is presented. After statistical division of the research area, the program provides advice for contamination‐free collection of environmental samples.     

Pilot study of personal, indoor and outdoor exposure to benzene, formaldehyde and acetaldehyde

There is a lack of data for health risk assessment of long term personal exposure to certain ubiquitous air pollutants present particularly in urban atmospheres. The relationship between ambient background concentrations and personal exposure is often unknown. A pilot campaign to measure indoor concentrations, outdoor concentrations and personal exposure to benzene, formaldehyde and acetaldehyde was conducted in a medium sized French town. A strong contribution to total personal exposure was observed from indoor sources, especially for formaldehyde and acetaldehyde, suggesting that indoor sources are dominant for these compounds. For benzene, the average personal exposure exceeded a 10 μgm^?3 limit value, although this was not the case for the ambient background concentration. For formaldehyde, the limit level was also exceeded. Observations suggest that true personal exposure cannot be determined directly from measurements pertaining from fixed ambient background monitoring stations. It is hoped that this will be taken into consideration by the bodies responsible for monitoring air pollution and the future European Air Quality Directive.     

Atmospheric Volatile Organic Compound Monitoring. Ozone Induced Artefact Formation

Assessment of population exposure to VOC in ambient atmospheres is receiving heightened interest as the adverse health effects of chronic exposure to certain of these compounds are identified. Active (pumped) and passive samplers are the most commonly used devices for this type of monitoring. It has been shown, however, that these devices, along with all other preconcentration techniques, are susceptible to ozone interference. It is demonstrated that this interference occurs even at low ozone concentrations and that it may result in the under-estimation of population exposure. A convenient and effective ozone scrubbing method is identified and successfully applied and validated for both active and passive samplers for a range of VOC.     

2,5,6,9,10-Pentabromocyclododecanols (PBCDOHs): a new class of HBCD transformation products

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C₁₈-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials.