New Evidence for the presence of arsenocholine in shrimps (Pandalus borealis) by use of pyrolysis gas chromatography — atomic absorption spectrometry/mass spectrometry

An analytical method for the structure elucidation of quarternary organoarsenic compounds in trace amounts in fish and crustaceans has been developed in this laboratory. The two major organoarsenicals found in shrimps have been separated by ion-exchange chromatography and their stucture has been studied by the use of pyrolysis gas chromatography. Their degradation in the pyrolyzer unit has been studied by the use of atomic absorption spectrophotometer or mass spectrometer as detectors. A comparison of the analytical data of these substances and data from synthetic reference substances show complete agreement. The structures of reference compounds have been confirmed by use of nuclear magnetic resonance spectrometry and fast atom bombardment (FAB) mass spectrometry. It is demonstrated that both of the organoarsenic compounds in shrimps have a trimethylarsonio moiety e.g. the compounds have a quarternary structure. Furthermore, the more basic organoarsenic compound has a mass spectrometric fragmentation pattern similar to synthetic arsenocholine and acetylarsenocholine. Treatment of arsenobetaine with hot base produces trimethylarsineoxide in a high yield (96%). Arsenocholine, however, remains unchanged during this treatment. Treatment with sodium benzenethiolate does not result in chemical demethylation, which shows that this method together with gas chromatography-mass spectrometry is not feasible for confirmation of its structure.     

Element immobilization in refuse incinerator ashes by solidification in glass, ceramic or cement

Incineration of municipal refuse results in the production of massive quantities of fly ash and bottom ash. Toxic elements in the original refuse may be concentrated up to 40-fold in the resultant ash. There is concern that burial of such ash in landfills could result in leaching of these elements downward into groundwater. In this study, refuse ashes were incorporated into glass, ceramic and cement composites to immobilize such toxic elements. The EP Toxicity Test (1986) was used to show that extraction of such elements by simulated acid rain is effectively blocked in these new solid materials.     

The fate of chlorobenzenes and permethrins during anaerobic sewage sludge digestion

Mixed primary sewage sludge was incubated anaerobically with and without azide addition to prevent biological activity. The behaviour of 1,3-, 1,4- and 1,2-dichlorobenzene, 1,3,5-, 1,2,4- and 1,2,3-trichlorobenzene, 1,2,3,4- and 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, and cis- and trans-permethrin was examined to determine their potential removal during anaerobic digestion. All the chlorobenzenes were removed to varying extents over 32 days of incubation, ranging from 25% removal for 1,3,5-trichlorobenzene to 80% removal for 1,4-dichlorobenzene. Biodegradation may have been responsible for the reductions in 1,3- and 1,4-dichlorobenzene and 1,2,4- and 1,2,3-trichlorobenzene as there was no significant removal of these compounds in azide treated sludge. The removal over 32 days of cis- and transpermethrin was 87% and 96% respectively. These removals were attributed to a chemical or physical process.     

Concentrations of cadmium and other metals in Fucus vesiculosus L. and Fontinalis dalecarlica Br. Eur. from the northern Baltic Sea and the southern Bothnian Sea

Concentrations of Cd and ten other metals (Al, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn) were determined in the brown seaweed Fucus vesiculosus L. and the aquatic moss, Fontinalis dalecarlica Br. Eur. from the northern Baltic Sea and the southern Bothnian Sea. Elevated concentrations of metals were found in samples taken close to densely populated areas, such as Stockholm and Nyn?shamn. Very high concentrations of especially Zn were found in both Fucus and Fontinalis samples taken from the area south of the Gulf of G?vle. The results indicate that mining and industrial activities along the river Dal?lven are the main sources of Zn and several other metals. Cd concentrations in Fucus plants reached maximum values (24.5 mg kg(-1)) at the northern site. The gradual increase of Cd concentrations in Fucus plants northward could not be totally explained by the salinity gradient in the Baltic Sea; reasons for this are discussed in this paper.     

Distribution of metals in grassland soils following surface applications of sewage sludge

In order to decide on a suitable sampling depth for grassland soil treated with sewage sludge and to assess implications for grazing animals, a field trial on two soils was designed to estimate the distribution of metals in grassland soil profiles following surface applications of sludge. Thus the sites represented permanent grassland where no form of cultivation had taken place. Soil cores were taken using specialised equipment to 30 cm depth and divided into seven sections. Movement from the soil surface to a depth of 10 cm was observed for all of the seven metals, Cd, Cr, Cu, Mo, Ni, Pb and Zn, but most of the metal (60%-100%, mean 87%) remained in the upper 5 cm of soil. It was concluded that sampling to a depth of 5 or 7.5 cm would be most suitable for monitoring long-term grassland treated with surface applications of sludge.     

Effects of ozone, acid mist and soil characteristics on clonal Norway spruce (Picea abies (L.) Karst.)--an introduction to the joint 14 month tree exposure experiment in closed chambers

This paper introduces a series of publications referring to a single 14-month laboratory study testing the hypothesis that the recent decline of Norway spruce (Picea abies (L.) Karst.) at higher elevations of the Bavarian Forest and comparable forests in medium-range mountains and in the calcareous Alps is caused by an interaction of elevated ozone concentrations, acid mist and site-specific soil (nutritional) characteristics. The effect of climatic extremes, a further important factor, was not included as an experimental variable but was considered by testing of the frost resistance of the experimental plants. Results of these individual studies are presented and discussed in the following 14 papers. Plants from six pre-selected clones of 3-year-old Norway spruce (Picea abies (L.) Karst.) were planted in April 1985 in an acidic soil from the Bavarian Forest, or a calcareous soil from the Bavarian Alps. After a transition period, plants were transferred, in July 1986, into four large environmental chambers and exposed for 14 months to an artificial climate and air pollutant regime based on long-term monitoring in the Inner Bavarian Forest. The climatic exposure protocol followed realistic seasonal and diurnal cycles (summer maximum temperature, 26 degrees C; total mean temperature, 9.8 degrees C; winter minimum, -14 degrees C; mean relative humidity, 70%; maximum irradiance, 500 W m(-2); daylength summer maximum, 17 h; winter minimum, 8 h). Plants were fumigated with ozone, generated from pure oxygen (control: annual mean of 50 microg m(-3); pollution treatment: annual mean of 100 microg m(-3) with 68 episodes of 130-360 microg m(-3) lasting 4-24 h), and background concentrations of SO(2) (22 microg m(-3)) and NO(2) (20 microg m(-3)); windspeed was set at a constant 0.6 m s(-1). Plants were additionally exposed to prolonged episodes of misting at pH 5.6 (control) and pH 3.0 (treatment). Simulation of the target climatic and fumigation conditions was highly reliable and reproducible (temperature +/-0.5 degrees C; rh+/-10%; ozone+/-10 microg m(-3);SO(2) and NO(2)+/-15 microg m(-3)).     

Nutrient accumulation in trees and soil following irrigation with municipal effluent in Australia

Irrigation of tree crops is being evaluated as a method of land disposal of municipal effluent in Australia. A study was carried out from 1980-84 in which seven tree species were sprinkler-irrigated with effluent at an annual rate of 1191-1752 mm. Effective weed control and frequent irrigation resulted in good survival of all species (range 83-100%) at 12 months. Total productivity was estimated at age 4 years by measuring biomass of each species inclusive of litter and roots to a soil depth of 80 cm. Biomass production of the high-yielding species, flooded gum (Eucalyptus grandis) and Sydney blue gum (E. saligna), was around 10 kg m(-2). Percentage leaf mass of these species was small (8-9%) compared with 25% and 29% for the relatively slow-growing river she-oak (Casuarina cunninghamiana) and radiata pine (Pinus radiata). Accumulation of nutrients in the total biomass differed significantly between species and ranged from 34-54 g m(-2) for nitrogen, 4.0-10.4 g m(-2) for phosphorus, 2.1-12.2 g m(-2) for sodium, 22-34 g m(-2) for potassium, 12-61 g m(-2) for calcium and 4.7-9.3 g m(-2) for magnesium. River she-oak and river red gum (E. camaldulensis), because of their relatively large crown and litter masses, accumulated more nitrogen, phosphorus, potassium and calcium than flooded gum or Sydney blue gum. Chemical properties of soils (0-150 cm) were measured in 1980 and again in 1984. Irrigation significantly increased pH (by around 1 unit), throughout the profile. Concentrations of total phosphorus, and exchangeable sodium, calcium and magnesium were increased in the upper profile. Overall, soil chemical properties were not adversely affected by effluent irrigation over the 4-year period, though there was a trend towards more sodic conditions in the soil profile. Nutrient accumulation in soil occurred mainly in the 0-35 cm depth, coinciding with the main root zone of the trees. Renovation of the effluent was therefore estimated as the amount of each nutrient accumulated in the biomass (averaged over the seven species) plus soil (0-35 cm), expressed as a percentage of amount applied in irrigation over the 4 years; that is, nitrogen, 29%; phosphorus, 78%; sodium, 15%; potassium, 26%; calcium, 98% and magnesium, 54%.