Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.     

Column studies on transport of deicing additive benzotriazole in a sandy aquifer and a zerovalent iron barrier

Benzotriazole (BTA), a chemical with wide industrial applications, is a typical additive in deicer/anti-icer used at airport. To achieve a better understanding of the transport behaviour and environmental fate of BTA, laboratory column studies have been performed on subsoil samples from Oslo Airport, Gardermoen. To explore possibilities for aquifer remediation, BTA behaviour was also studied in a column of granular zerovalent iron (Fe(0)). The subsoil column study demonstrates a very limited retardation of BTA. Consecutive loadings of BTA of the subsoil column showed no change of the break-through curve (BTC) and complete desorption was observed. The sorption behaviour of BTA to metallic iron (Fe(0)) was rather complex. Considerable retardation was observed in the Fe(0) column and repeated BTA loading resulted in an earlier break-through. Between 20% and 50% of the input concentration was retained permanently in the iron (Fe(0)) column. The BTA sorption to metallic iron was found to be enhanced by chloride which lowered the break-through concentration (i.e the C/C(0) plateau). The fraction of BTA remaining in the iron column was found to vary with the flow rate, indicating a time dependant multilayer sorption mechanism. The steady increase in the amount of adsorbed BTA to the iron column during loading corresponds to a rather strong bonding of 4-15 BTA layers to the iron surface. A very slow desorption of BTA was observed; even after flushing with 753 pore volumes of BTA free water, 7.5% of the BTA remained in the column. A geochemical model was developed based on PHREEQC-2 to simulate the sorption and transport of BTA in the tested materials. The BTA sorption was modelled with Freundlich sorption isotherms, as earlier determined in batch experiments. A slight adjustment of the Freundlich parameters was required to fit the observed column break-through. However, our model was not able to simulate the long-term retainment of BTA in the granular iron columns. The simulations confirm the high mobility of BTA in groundwater aquifers and suggest that zerovalent iron could be used to retain a BTA plume, although oxidation of the sorbent might reduce the long-term performance of such a remediation scheme and slow desorption has been observed.     

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.     

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.     

Influence of urbanization and tourist activities on the water quality of the Potrero de los Funes River (San Luis – Argentina)

A study of the water quality of the Potrero de los Funes River (San Luis – Argentina) was carried out in order to evaluate the possible effect of the anthropogenic activities on the river developed in the homonymous town. Samples were collected during the period March 2000–November 2005 at three selected sampling sites (RP₁, RP₂ and RP₃). Different physicochemical and bacteriological parameters (turbidity, pH, conductivity, suspended solids, alkalinity, potassium, sodium, calcium, magnesium, chlorides, nitrates, phosphates, sulphates, chemical oxygen demand (COD), 5-day biological oxygen demand (BOD₅), dissolved oxygen, total coliforms, Escherichia coli and total heterotrophic bacteria) were analysed according to the Standard Method for the Examination of Water and Wastewater. When comparing the values of total coliforms, E. coli, total heterotrophic bacteria, COD, BOD₅ and phosphates from the zone without anthropogenic influence (RP₁) and the urban zones (RP₂ and RP₃) an important variation in the parameters was observed. These results indicate that the urban activity produces a serious and negative effect on the water quality, thus constituting a sanitary risk and may have a major impact on the trophic status of the Potrero de los Funes dam. As case study, we report on the use of General Quality Index (GQI) to evaluate spatial and seasonal changes in the water quality of Potrero de los Funes River. Results revealed a significant degradation of the water quality at RP₂ and RP₃.     

Testing the use of juvenile Salmo trutta L. as biomonitors of heavy metal pollution in freshwater

Individual specimens of Salmo trutta were captured, from four sampling sites in Galician rivers (NW Spain) affected by different types of contamination: diffuse urban waste, run-off from an unrestored dump at a copper mine and waste from a fish farm. The ages of the captured trouts were established and only those belonging to the 1+ age class were selected for study. The liver and kidney were removed from each fish and analysed to determine the tissue concentrations of Cu, Fe and Zn. The results obtained showed that: (i) the use of 1+ individuals allowed differentiation of contamination scenarios on the basis of the tissue concentrations of metal; (ii) the use of 1+ individuals allowed standardization of the time of exposure, which was sufficiently long for differential uptake to have taken place; (iii) liver tissue provided the best results as, less effort was required than for processing kidney tissue, and significant differences between sampling sites were detected because the intrapopulational variability in metal levels was lower than for kidney, and (iv) the levels of elements detected were not affected by basal tissue concentrations or residual concentrations due to past contamination, which older trouts may have been exposed to. In addition, the use of 1+ trout may provide better results in annual environmental sampling surveys.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

A field trial for an ex-situ bioremediation of a drilling mud-polluted site

The remediation of drilling mud-polluted sites in the Southeast of Mexico is a top priority for Mexican oil industry. The objective of this work was to find a technology to remediate these sites. A field trial was performed by composting in biopiles, where four 1ton soil-biopiles were established, one treatment in triplicate and one unamended biopile. Amended biopiles were added with nutrients to get a C/N/P ratio of 100/3/0.5 plus a bulking agent (straw) at a soil/straw ratio of 97/3. Moisture content was maintained around 30-35%. Results showed that, after 180 d, total petroleum hydrocarbon (TPH) concentrations decreased from 99300+/-23000mgTPHkg(-1) soil to 5500+/-770mgTPHkg(-1) for amended biopiles and to 22900+/-7800mgTPHkg(-1) for unamended biopile. An undisturbed soil control showed no change in TPH concentrations. Gas chromatographic analysis showed residual alkyl dibenzothiophene type compounds. Highest bacterial counts were observed during the first 30 d which correlated with highest TPH removal, whereas fungal count increased at the end of the experimentation period. Results suggested an important role of the straw, nutrient addition and water content in stimulating aerobic microbial activity and thus hydrocarbon removal. This finding opens an opportunity to remediate old polluted sites with recalcitrant and high TPH concentration.     

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.     

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.