Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

Seasonal and Inter-Annual Variations in Methyl Mercury Concentrations in Zooplankton from Boreal Lakes Impacted by Deforestation or Natural Forest Fires

We compared the effects of natural and anthropogenic watershed disturbances on methyl mercury (MeHg) concentration in bulk zooplankton from boreal Shield lakes. MeHg in zooplankton was monitored for three years in nine lakes impacted by deforestation, in nine lakes impacted by wildfire, and in twenty lakes with undisturbed catchments. Lakes were sampled during spring, mid- and late summer. MeHg in zooplankton showed a seasonal trend: concentrations were the lowest in spring, then peaked in mid-summer and decreased in late summer. Over the three study years, MeHg concentrations observed in mid-summer in zooplankton from forest harvested lakes were significantly higher than in reference and fire-impacted lakes, whereas differences between these two groups of lakes were not significant. The pattern of distribution of MeHg in zooplankton during the different seasons paralleled that of dissolved organic carbon (DOC), which is known as a vector of Hg from watershed soils to lake water. Besides DOC, MeHg in zooplankton also showed a positive significant correlation with epilimnetic temperature and sulfate concentrations. An inter-annual decreasing trend in MeHg was observed in zooplankton from reference and fire-impacted lakes. In forest harvested lakes, however, MeHg concentrations remained higher and nearly constant over three years following the impact. Overall these results indicate that the MeHg pulse observed in zooplankton following deforestation by harvesting is relatively long-lived, and may have repercussions to the accumulation of MeHg along the food chain. Therefore, potential effects of deforestation on the Hg contamination of fish should be taken into account in forest management practices.     

Desorption of arsenic from drinking water distribution system solids

Previous work has shown that arsenic can accumulate in drinking water distribution system (DWDS) solids (Lytle et~al., 2004) when arsenic is present in the water. The release of arsenic back into the water through particulate transport and/or chemical release (e.g. desorption, dissolution) could result in elevated arsenic levels at the consumers' tap. The primary objective of this work was to examine the impact of pH and orthophosphate on the chemical release (i.e. desorption) of arsenic from nine DWDS solids collected from utilities located in the Midwest. Arsenic release comparisons were based on the examination of arsenic and other water quality parameters in leach water after contact with the solids over the course of 168~hours. Results showed that arsenic was released from solids and suggested that arsenic release was a result of desorption rather than dissolution. Arsenic release generally increased with increasing initial arsenic concentration in the solid and increasing pH levels (in the test range of 7 to 9). Finally, orthophosphate (3 and 5 mg PO₄/L) increased arsenic release at all pH values examined. Based on the study results, utilities with measurable levels of arsenic present in their water should be aware that some water quality changes can cause arsenic release in the DWDS potentially resulting in elevated levels at the consumer's tap.     

Monitoring the formation of trihalomethanes in the effluents from a shrimp hatchery

Formation of trihalomethanes (THM) was monitored at the Laboratório de Camarões Marinhos (LCM) from the Universidade Federal de Santa Catarina. THM could be present because chlorinated effluents from disinfection are discharged from the different hatchery rooms. THM quantification was done through an analytical methodology using Purge&;Trap coupled with a gas chromatograph equipped with an electron capture detector. Relative standard deviation (RSD), limit of detection (LOD) and limit of quantification (LOQ) for the methodology corresponded to the ranges of 8–17%; 0.01–0.03 μg L^?1 and 0.03–0.08 μg L^?1, respectively. Linear working range was of 0.1–8.0 μg L^?1 for all compounds. Enrichment and recovery method was applied to evaluate possible matrix effects and the results varied from 71.2% to 107.9%. LCM was monitored between August and December, 2004. This study showed that THM did not increase with the increase in postlarvae production and also that the aquatic life and the surrounding environment were not affected.     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Modeling the impact of direct phototransformation on predicted environmental concentrations (PECs) of propranolol hydrochloride in UK and US rivers

There is currently uncertainty on the persistence of active pharmaceutical ingredients (APIs) and on their depletion mechanisms in natural surface waters such as rivers, and hence predictions of their fate are often poor. In this study, a beta-adrenergic receptor, propranolol hydrochloride, was selected as a model API to explore the relative significance of direct phototransformation as a potential removal process of hydrophilic APIs in rivers. Phototransformation kinetics of propranolol was measured under simulated solar irradiation in the laboratory, which were then converted to the kinetics applicable in UK and US rivers. The effects of light intensity, light penetration, river size and flow were examined. The extrapolated phototransformation half-lives were applied in the river catchment models of GREAT-ER and PhATE. Results demonstrated that direct phototransformation significantly reduced the predicted environmental concentrations of propranolol in the water phase. Predicted reductions of mean concentrations in the River Aire (UK) were 27% in summer and 3% in winter; and for the US rivers simulated, reductions were 28-68% in summer and 11-41% in winter. The highest reductions were predicted for long rivers with low turbidity and low flow conditions.     

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.     

The influence of radical architecture on cadmium bioaccumulation in the black mangrove, Avicennia germinans L

Two groups of Avicennia germinans plants with differences in the radical architecture were exposed under hydroponic conditions to 95ppm of cadmium (Cd) for a period of 24h. Later, Cd concentration in roots, stems and leaves was determined by graphite furnace atomic absorption spectrophotometry. Our results showed that, for both groups of plants, the roots accumulated higher concentration of Cd as compared to stems and leaves, though, the plants of group B displayed enhanced radical architecture, better growth performance, and lower Cd concentration as compared to plants of group A. In contrast, low values of leaves/roots Cd transportation index, and bioaccumulation factor were found in plants of group B. These results suggest that the higher radical architecture developed in plants of group B might better adjust the uptake of Cd as a result of an integrated network of multiple response processes for instances, production of organic acids, antioxidative replay, cell-wall lignification and/or suberization. Further studies will be focused in understanding the role of the radical system in mangrove plants with the rhizosphere activation and root adsorption to soil Cd under natural conditions.     

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.     

Zinc and cadmium accumulation and tolerance in populations of Sedum alfredii

To investigate the variation of Zn and Cd accumulation and tolerance of Sedum alfredii (a newly reported Zn/Cd hyperaccumulator), field surveys and hydroponic experiments were conducted among three populations of this species: two originating from old Pb/Zn mines in Zhejiang (ZJ) and Hunan (HN) Provinces and one from a "clean" site in Guangdong (GD) Province, China. Under field conditions, up to 12,524 and 12,253 mg kg(-1) Zn, and 1400 and 97 mg kg(-1) Cd in shoots of ZJ and HN plants were recorded respectively. Under hydroponic conditions, ZJ and HN plants accumulated significantly higher Zn and Cd in their leaves and stems, and possessed significantly higher Zn and Cd tolerance than GD plants. Among the two contaminated populations, ZJ plants showed higher Cd tolerance and accumulation (in leaves) than HN plants. The present results indicate that significant differences in Zn and Cd accumulation and tolerance exist in populations of S. alfredii.