Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

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.     

Aerobic degradation of di- and trichlorobenzenes by two bacteria isolated from polluted tropical soils

Two polychlorinated biphenyl (PCBs)-degrading bacteria were isolated by traditional enrichment technique from electrical transformer fluid (Askarel)-contaminated soils in Lagos, Nigeria. They were classified and identified as Enterobacter sp. SA-2 and Pseudomonas sp. SA-6 on the basis of 16S rRNA gene analysis, in addition to standard cultural and biochemical techniques. The strains were able to grow extensively on dichloro- and trichlorobenzenes. Although they failed to grow on tetrachlorobenzenes, monochloro- and dichlorobenzoic acids, they were able to utilize all monochlorobiphenyls, and some dichlorobiphenyls as sole sources of carbon and energy. The effect of incubation with axenic cultures on the degradation of 0.9 mM 1,4-dichlorobenzene, 0.44 mM 1,2,3- and 0.43 mM 1,3,5-trichlorobenzene in mineral salts medium was studied. Approximately, 80-90% of these xenobiotics were degraded in 200 h, concomitant with cell increase of up to three orders of magnitude, while generation times ranged significantly (P<0.05) from 17-32 h. Catechol 1,2-dioxygenase and catechol 2,3-dioxygenase activities were detected in crude cell-free extracts of cultures pre-grown with benzoate, with the latter enzyme exhibiting a slightly higher activity (0.15-0.17 micromolmin(-1) mg of protein(-1)) with catechol, suggesting that the meta-cleavage pathway is the most readily available catabolic route in the SA strains. The wider substrate specificity of these tropical isolates may help in assessing natural detoxification processes and in designing bioremediation and bioaugmentation methods.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

The impact of UV-B and sulphur- or copper-containing solutions in acidic conditions on chlorophyll fluorescence in selected Ramalina species

Ramalina maciformis and Ramalina lacera were exposed to different solutions and UV-B to seek for alterations in the PSII photosynthetic quantum yield (F(v)/F(m)), in response to chemicals and radiation. For R. maciformis, significant alterations of the F(v)/F(m) ratio occurred only in response to different bisulphite solutions. The F(v)/F(m) ratio decreased most in R. maciformis and R. lacera following exposure to 5 and 1 mM bisulphite, respectively. Significant differences in F(v)/F(m) ratios were observed for R. lacera in response to different solutions and light at different wavelengths, this being synergistic. The PSII system was unaffected by simulated acid rain in both lichens. R. maciformis, in particular, may survive limited acid rain exposure owing to high Ca oxalate accumulation. The F(v)/F(m) ratio decreased most in R. lacera following short-term exposures to CuSO(4), suggesting that this species is more sensitive to Cu ions under acidic conditions.     

Essential and non-essential element concentrations in two sleeper shark species collected in arctic waters

A number of elements/metals have increased in arctic biota and are of concern due to their potential toxicity. Most studies on elements in the Arctic have focused on marine mammals and seabirds, but concentrations in the Greenland shark (Somniosus microcephalus) and Pacific sleeper shark (Somniosus pacificus), the only two shark species known to regularly inhabit arctic waters, have never been reported. To address this data gap, concentrations and patterns of 25 elements were analyzed in liver of Greenland sharks collected about Cumberland Sound (n=24) and Pacific sleeper sharks collected about Prince William Sound (n=14). Several non-essential elements differed between species/locations, which could suggest geographical exposure differences or ecological (e.g., diet) differences between the species. Certain essential elements also differed between the two sleeper sharks, which may indicate different physiological requirements between these closely related shark species, although information on such relationships are lacking for sharks and fish.     

Pentachlorophenol association with fulvic acids from recycled wastes

The apparent water solubility of pentachlorophenol was measured at pH=6 and at 25 degrees C in pure water, aqueous solutions of three salts (NaCl, KNO(3) and CaCl(2) at 0.010, 0.10 and 1.0M) and in aqueous solutions of three fulvic acids samples extracted from a natural soil (sFA), composted sewage sludge (csFA) and composted livestock's material (lsFA). A solubility enhancement method was developed for the measurement of partition coefficients (K(oc), L/kg organic carbon). Pentachlorophenol associates strongly with the fulvic acid samples and the calculated K(oc) were the following (averages and standard deviations): (sFA) (211+/-22) x 10(2), (csFA) (253+/-26) x 10(2), (lsFA) (235+/-10) x 10(2). For comparison purposes the K(oc) for pyrene were also calculated for the three FA samples and were the following: (sFA) (119+/-10) x 10(2), (csFA) (239+/-21) x 10(2), (lsFA) (92+/-10) x 10(2). The analysis of variance (one-way ANOVA) of the effect of the type of FA sample on the solubilization of pentachlorophenol and pyrene shows that this factor causes significant differences on the aqueous solubilization of these two organic substances.     

Estrogenic activity associated with organochlorine compounds in fish extracts from European mountain lakes

Fish muscle extracts from ten European mountain lakes were analyzed for organochlorine compounds (OCs) and estrogenic activity, the latter by a recombinant yeast assay based on the human estrogen receptor. Seventy percent of the samples showed estrogenic activity above detection limits and a subset of five samples showed estrogenic activities, equivalent to more than 10,000 pg/g of estradiol. These highly estrogenic samples occurred in two lakes, Velké Hin?ovo in the Tatra Mountains and Redon in the Pyrenees. Principal component analysis correlated estrogenic activity of muscle extracts to fish age and concentrations of the more chlorinated polychlorobiphenyls (PCBs). This is consistent with previously observed correlations of these PCBs with fish age. In addition, most fish with high estrogenic activity were found in lakes containing high OC levels in the sediments, which gives further ground to atmospheric deposition of anthropogenic pollutants as main process leading to the observed endocrine disruption effects.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Use of (15)N-labelled nitrogen deposition to quantify the source of nitrogen in runoff at a coniferous-forested catchment at Gårdsjön, Sweden

To determine the source of dissolved inorganic nitrogen (N) in runoff, approx. 35kg N enriched with the stable isotope (15)N (2110 per thousand delta(15)N) was added to a mature coniferous forested catchment for one whole year. The total N input was approx. 50kg ha(-1) year(-1). The enrichment study was part of a long-term whole-catchment ammonium nitrate addition experiment at G?rdsj?n, Sweden. The (15)N concentrations in precipitation, throughfall, runoff and upper forest floor were measured prior to, during, and 3-9years following the (15)N addition. During the year of the (15)N addition the delta(15)N level in runoff largely reflected the level in incoming N, indicating that the leached NO(3)(-) came predominantly from precipitation. Only 1.1% of the incoming N was lost during the year of the tracer addition. The cumulative loss of tracer N over a 10-year period was only 3.9% as DIN and 1.1% as DON.