Oxidation of trichloroethene over metal oxide catalysts: kinetic studies and correlation with adsorption properties

The performance of bulk chromium oxide is compared with that of a Mn commercial catalyst for the deep oxidation of trichloroethene (1000-2500ppmv, 55h(-1) space velocity) in air, in dry and wet (20000ppm of H(2)O) conditions, in terms of activity, selectivity and stability. Chromium oxide was found to be more active (on a catalyst weight basis), however its activity decreases continuously with time on stream. The presence of water increases its stability, the Mn catalyst showing the opposite behaviour. The effect of water on the Cr catalyst can be explained according to the Deacon equilibrium, as the presence of water tends to decrease the Cl(2) concentration, assumed to be responsible of the catalyst deactivation. Regarding to the selectivity, the Mn catalyst yields C(2)Cl(4), CCl(4) and CHCl(3) as organochlorinated by-products, whereas chromium oxide produces only trace amounts of CCl(4). Simple power-law kinetics expressions (first-order for Mn and zero-order for Cr) provide fairly good fits for the evolution of the conversion with the temperature. Furthermore, the kinetic behaviour of chromium oxide can be represented with a Langmuir-Hinshelwood model taking into account the chlorine inhibitory effect.     

Sorption and desorption behavior of benzidine in different solvent-sediment systems

The sorption and desorption behavior of benzidine in eight solvent-sediment systems were studied using a batch method. The solvents tested included deionized water (DI), calcium chloride solution (CaCl2), sodium hydroxide solution (NaOH), acetonitrile (ACN), a mixture of acetonitrile and ammonium acetate solution (ACN-NH4OAc), methanol (MeOH), ammonium acetate solution (NH4OAc) and hydrochloric acid solution (HCl). Three sets of sorption isotherm experiments were conducted separately in these eight solvents with seven days, three weeks, and two months of contact times, respectively. The results demonstrated nonlinear benzidine sorption phenomena in all eight solvents with higher sorption affinities for sediment sites in the aqueous solvents than in the organic solvents. The results from the desorption experiments revealed that the benzidine desorption efficiencies in the solvents decreased in an order, which was approximately the reverse order of its sorption affinity. Results also suggested that hydrophobic partitioning and covalent binding processes dominated in the desorption experiments, while cation exchange process had little effect on desorption of benzidine. A three-stage model was subsequently applied to simulate the desorption data in the selected solvents of ACN, ACN-NH4OAc and NaOH, respectively. The rapidly desorbing initial fractions were about 0.13-0.20, 0.15-0.26, and 0.18-0.25 for ACN, ACN-NH4OAc and NaOH, respectively. Finally, the sorbed concentrations of benzidine in slowly and very slowly desorbing domains in the selected solvents were correlated with the maximum sorption capacities obtained from the Langmuir sorption isotherm model. The maximum sorption capacities of benzidine were found to be comparable to the amount of benzidine residing in the slowly and very slowly desorbing domains.     

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain)

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.     

Algal-bacterial interactions in metal contaminated floodplain sediments

The aim of the present study was to investigate algal-bacterial interactions in a gradient of metal contaminated natural sediments. By means of multivariate techniques, we related the genetic structure (denaturing gradient gel electrophoresis, DGGE) and the physiological structure (community-level physiological profiling, CLPP) of the bacterial communities to the species composition of the algal communities and to the abiotic environmental variables, including metal contamination. The results revealed that genetic and physiological structure of the bacterial communities correlated with the species composition of the algal community, but hardly to the level of metal pollution. This must be interpreted as an indication for a strong and species-specific linkage of algal and bacterial species in floodplain sediments. Metals were, however, not proven to affect either the algal or the bacterial communities of the Dutch river floodplains.     

Lichen biomonitoring of ammonia emission and nitrogen deposition around a pig stockfarm

Effects of high ammonia emissions and nitrogen deposition were investigated on lichens around a pig stockfarm (ca. 7,000 animals) in central Italy. Four sites were selected along a transect at 200, 400, 1000 and 2500 m from the stockfarm, the diversity of epiphytic lichens was measured and transplanted thalli of Xanthoria parietina and Flavoparmelia caperata exposed, together with passive NH3 (diffusion tubes) samplers. Ammonia dramatically decreased from the centre of the stockfarm to the sampled sites, where it was correlated with bark pH. Total lichen diversity was not associated with either NH3 concentrations or bark pH, but the diversity of strictly nitrophytic species was highly correlated with both parameters. Physconia grisea was the best indicator species for NH3 pollution. Total N accumulated in X. parietina and F. caperata was correlated with NH3 concentrations.     

Bioaccumulation of lead, mercury, and cadmium in the greater white-toothed shrew, Crocidura russula, from the Ebro Delta (NE Spain): sex- and age-dependent variation

We quantified bioaccumulation of lead, mercury, and cadmium in bones from 105 greater white-toothed shrews (Crocidura russula) collected at the Ebro Delta, a polluted area, and the Medas Islands, a control site. Lead and mercury levels varied with site, age, and sex, although statistical significances depended on each factor. Globally, shrews from the polluted area exhibited significantly higher concentrations of Pb and Hg. Increment of Pb with age was particularly remarkable in wetland animals and was interpreted in relation to human activities, namely hunting. Unlike males, females from the Ebro Delta maintained low Hg levels, which were associated with gestation and lactation. Cadmium levels did not differ between sites, sexes, or ages. This study provides the first data on heavy metals in mammals from this wetland and suggests that C. russula is a good bioindicator of metal pollution. We concluded that sex and age may represent an important source of variation in the bioaccumulation of these metals in wild populations.     

Assessment of atmospheric metallic pollution in the metropolitan region of São Paulo, Brazil, employing Tillandsia usneoides L. as biomonitor

Tillandsia usneoides L. is an epiphytic bromeliad plant able to absorb water and nutrients directly from the air. For this reason this species was selected to carry out a monitoring study of air pollution in the metropolitan region of S?o Paulo, Brazil. Five consecutive transplantation experiments (8 weeks each) were performed in 10 sites of the city, submitted to different sources of air pollution (industrial, vehicular), using plants collected from an unpolluted area. After exposure, trace metals were analyzed in the plant by instrumental neutron activation analysis. Traffic-related elements such as Zn and Ba presented high concentrations in exposure sites near to heavy traffic avenues (cars, buses and trucks) and may be associated to vehicular sources. For Zn and Co the highest contents were related to industrial zones and can be associated to the presence of anthropogenic emission sources. The rare earth elements, Fe and Rb, probably have soil particles as main source.     

Size-related aspects of arm damage, tissue mechanics, and autotomy in the starfish Asterias rubens

 Arm damage is a widely reported but superficially investigated aspect of the biology of the starfish Asterias rubens L. In the present study, the incidence of arm damage was surveyed in populations of A.  rubens at two sites in the Firth of Clyde, Scotland, and three sites in Gullmarsfjorden, Sweden. The mean (±SD) incidence across all sites of individuals with basal arm damage (resulting from detachment at the basal autotomy plane) was 19.69 ± 8.86%, the incidence of those with distal arm damage (resulting from amputation at more distal levels) was 7.74 ± 10.01%. The mean incidence of arms with basal damage was 5.28 ± 4.12%, of those with distal damage 1.83 ± 2.45%. There was a significant negative correlation between size and the incidence of basal damage at all but one site, but no significant correlation between size and distal damage at any site. Mechanical tests on specimens of the aboral body wall from the basal region of the arm (which included the autotomy plane) and from a more distal region revealed that with increasing body size there was a significant increase in yield stress, ultimate stress and Young's modulus (stiffness) but no significant change in yield strain and ultimate strain. There was no significant difference between the relationships for basal and distal specimens. It is hypothesised that in larger individuals increased mechanical toughness replaces autotomy as an effective antipredator strategy. Using two methods to induce autotomy, a significant positive correlation between size and the delay between the onset of stimulation and arm detachment was found; this may represent a size-related decline in the efficiency of the autotomy mechanism through the relaxation of selection pressure. Since size is an unreliable indicator of age in A.  rubens, the trends identified herein can be interpreted only tentatively as age-associated phenomena. Received: 4 September 1999 / Accepted: 17 February 2000     

Humoral opsonin from the colonial ascidian Botryllus schlosseri as a member of the galectin family

The synthesis and secretion of the humoral opsonin from the colonial ascidian Botryllus schlosseri was studied by using specific polyclonal antibodies that recognise both of the bands obtained after SDS-PAGE of the purified lectin. The agglutinin was revealed on the surface of agglutinated yeast and red blood cells and in the cytoplasm of the phagocytes, either uniformly distributed or localised inside the cytoplasmic projections. A previous incubation of haemocytes with the agglutinin resulted in intense labelling of the surface that disappeared in the presence of D-galactose, whereas it was not affected by treatment with proteases. These results, together with the already published data, suggest that our molecule is a new member of the galectin family. Received: 16 July 1999 / Accepted: 7 February 2000     

Spatial and temporal patterns of predation on seeds of the surfgrass Phyllospadix torreyi

Spatial and temporal patterns of predation on seeds of the seagrass Phyllospadix torreyi S. Watson were quantified at four sites near Santa Barbara, California, USA. Over a period of four flowering seasons during 1995 to 1998, monthly patterns of seed fall and intensity of seed predation were similar among sites, but were temporally quite variable. Abundance of dispersed seeds varied greatly both among seasons and years. Within any one year, seeds were present in the environment every month, but they peaked in abundance during the fall months following the annual flowering period. Seeds were more abundant during the earlier years of the study. The intensity of predation steadily increased throughout the study period, from a low of ≤10% seeds consumed during 1995 to ∼50% consumption by 1997, and it was not correlated with abundance of seeds in the environment. Pre-dispersal seed loss also was estimated in two flowering seasons by counting the numbers of seeds consumed prior to release from the plant, and was relatively low (<15%). No differences were detected among the four study sites in patterns of pre-dispersal loss. Field surveys were done at two sites to identify potential seed predators. Three of the most abundant species identified in these surveys were tested in the laboratory to determine size-specific patterns of feeding activity and to assess which early life stages of P. torreyi (fruits within spadices, dehisced fruits, seedlings) were most vulnerable to predation. All three of the early life stages were consumed. The crabs Pugettiaproducta (Randall) and Pachygrapsus crassipes Randall were much more voracious predators than the isopod Idotea resecata Stimpson. Received: 8 June 1999 / Accepted: 2 February 2000