A natural analogue of high-pH cement pore waters from the Maqarin area of northern Jordan: Comparison of predicted and observed trace-element chemistry of uranium and selenium

Current design concepts for low-/intermediate-level radioactive waste disposal in many countries involve emplacement underground in a cementitious repository. The highly alkaline groundwaters at Maqarin, Jordan, are a good analogue for the cementitious pore waters that will be present within such a repository. A geochemical modelling study of these groundwaters has been carried out in order to test the applicability of equilibrium models in geochemical programs and their associated thermodynamic databases in such hyperalkaline conditions. This was achieved by comparison of elemental solubilities and speciations predicted by the programs with observations in the natural system. Five organisations took part in the study: AEA Technology, U.K.; Chalmers University of Technology, Sweden; MBT Tecnología Ambiental, Spain; Nagra, Switzerland; and SKB, Sweden. The modelling study was coordinated by the University of Berne.The results of the study showed good agreement between the predictions of the programs employed. Comparison of the observed solids with those predicted by the models has allowed limited validation of the databases. The results for U and Se are presented here.     

Surfactant solubilization of hydrophobic compounds in soil and water

The soil/water partition coefficient (K_d) of hexachlorobenzene (HCB) ranged from 220 1/kg to 1800 1/kg for eight soils having a wide range of physico-chemical properties. K_d normalised to soil organic carbon (K_oc) was found to be 28000 ± 4800 1/kg. Anionic surfactant dodecylsulphate (DS) present at concentrations above the critical micellar concentration (CMC) caused reductions in the apparent soil/water partition coefficient (K_d ^*) in the range of 3–26 times for most soils and up to 36–91 times for sandy soils. Below CMC, at environmentally relevant surfactant concentrations, K_d ^* was reduced by a factor of 1–13. For clay and calcareous soils significant adsorption/complexation/precipitation of DS occurred. At the lowest DS concentration this produced a two-fold increase in K_d ^*. At increasing DS concentrations this effect was shielded by the solubihzing effect from DS. Monomer (K_mn) and micellar (K_mc) surfactant/water partition coefficients for HCB were determined to be, 980 ± 190 1/kg and 21000 ± 1600 1/kg, respectively.     

Cadmium concentration in tobacco (Nicotiana tabacum L.) from different countries and its relationship with other elements

Cadmium accumulation in crop plants, such as tobacco (Nicotiana tabacum L.), can lead to human exposure to this carcinogenic metal. To better define actual Cd distribution in cured or processed tobacco leaves from chief tobacco-producing regions, we analyzed 755 leaf samples of three major types (Flue-cured, Burley, and Oriental) obtained from 13 countries during 2001-2003. This survey may help identify regions with low- or high-Cd concentrations in tobacco to obtain insight into the cause of the concentration extremes and to assist in defining strategies to reduce Cd in tobacco. Cadmium concentrations in the samples ranged from 0 to 6.78 microg g(-1), as determined by ICP-MS. Significant differences were found among types and among countries, but significant interactions between type and country were found. Variations in Cd concentrations were also found in all countries. Our results suggest an important contribution of the field (e.g., bioavailable Cd in soil, other soil characteristics) to the Cd concentration in tobacco. Finally, the correlation between the concentration of Cd and that of other elements differed among the types, which could be effectively discriminated based on the concentrations of 20 elements.     

Characterization of trace organic contaminants in marine sediment from Yeongil Bay, Korea: 2. Dioxin-like and estrogenic activities

This study employed mechanism-specific in vitro bioassays to help characterize the occurrence and distribution of dioxin-like and estrogenic contaminants in sediment from Yeongil Bay, Korea. Approximately 85% of the sediments tested induced significant dioxin-like activity in the H4IIE-luc bioassay, while approximately 50% induced significant estrogenic activity in the MVLN bioassay. Instrumentally-derived estimates of 2,3,7,8-tetrachlorodibenzo-p-dioxin and 17beta-estradiol equivalents tended to underestimate the magnitude of response observed in the bioassays, suggesting that compounds detected by chemical analysis did not account for all the activity associated with Yeongil Bay sediments, or that non-additive interactions were occurring. The greatest dioxin-like and estrogenic activity was associated with the mid-polarity Florisil fractions (F2) expected to contain polycyclic aromatic hydrocarbons (PAHs) as well as chlorinated dioxins and furans. As in previous studies of Korean coastal sediment, more polar fractions (F3) generated more modest responses both in terms of magnitude and the number of samples responding.     

Removal of PCB-DNAPL from a rough-walled fracture using alcohol/polymer flooding

Phase behaviour experiments employing PCB (Aroclor 1242)/alcohol/water systems were conducted with ethanol (EtOH) and n-propanol (nPA). Both exhibited an affinity for the aqueous phase within the entire two-phase region. As much as 88% by volume (88% vol.) EtOH and 80% vol. nPA were necessary to achieve full miscibility of the PCB in the aqueous phase. DNAPL-water interfacial tension (IFT) was reduced from 38.9 dyn/cm to 4.7 dyn/cm and 2.4 dyn/cm with 80% vol. EtOH and 76% vol. nPA. The addition of alcohol brought about 41% and 54% reductions in DNAPL viscosity at maximal concentrations of EtOH and nPA. Density of the PCB-DNAPL was relatively unaffected by the presence of alcohol. A series of seven experiments were conducted where successive slugs of nPA and xanthan gum polymer solutions were injected into a fractured shale sample. A 30% vol. nPA solution injected under a hydraulic gradient of 0.36 allowed enhanced PCB removal primarily through reduction of IFT and resulted in 72% DNAPL recovery. Several pore volumes of alcohol solution were necessary to displace all the potentially mobile non-wetting phase since the high-viscosity DNAPL was mobilized at a lower flow rate than the overall fluid velocity, illustrating non-piston displacement. The injection of a 95% vol. nPA alcohol solution, theoretically at a sufficient concentration to produce fully miscible displacement of the residual DNAPL at equilibrium, resulted in non-equilibrium partitioning of the PCB into the flushing solution, likely due to the high fluid velocities in the fracture. The injection of 200 pore volumes of 95% vol. nPA solution resulted in 94% DNAPL recovery. Alcohol floods operated below the miscibility envelope appear to be a valuable source zone remedial alternative where the objective is to reduce DNAPL mobility to zero, but it should be noted that DNAPL mobility is increased during the application of the technology and steps may need to be taken to prevent unwanted vertical mobilization.     

In situ and laboratory bioassays using Poecilia reticulata Peters, 1859 in the biomonitoring of an acidic lake at Camaçari, BA, Brazil

The suitability and viability of acute in situ bioassays were investigated in the biomonitoring program of an acidic lake contaminated with sulphur residues. Responses of organisms observed in laboratory and in situ bioassays were also assessed to determine whether or not they were similar and comparable, regarding accuracy and precision. Newborn Poecilia reticulata were employed as test organisms and exposed to the same water samples under in situ and laboratory conditions. Mortality/immobility was the endpoint assessed and dead/immobile organisms were counted at various time intervals during exposure. The mean calculated LT50 values and 95% confidence intervals were 1.61 (1.36-1.87) h in the laboratory bioassays and 0.72 (0.55-0.89) h in the in situ bioassays. Statistical comparison of these values revealed a significant difference (p<0.05). In situ bioassays were more accurate than those carried out in the laboratory, demonstrating higher sensitivity and better reproduction of what occurs in nature, while laboratory bioassays were more precise.     

Genotypic variations in the accumulation of Cd, Cu, Pb and Zn exhibited by six commonly grown vegetables

Metal contaminants in garden and allotment soils could possibly affect human health through a variety of pathways. This study focused on the potential pathway of consumption of vegetables grown on contaminated soil. Five cultivars each of six common vegetables were grown in a control and in a soil spiked with Cd, Cu, Pb and Zn. Highly significant differences in metal content were evident between cultivars of a number of vegetables for several of the contaminants. Carrot and pea cultivars exhibited significant differences in accumulated concentrations of Cd and Cu with carrot cultivars also exhibiting significant differences in Zn. Distinctive differences were also identified when comparing one vegetable to another, legumes (Leguminosae) tending to be low accumulators, root vegetables (Umbelliferae and Liliaceae) tending to be moderate accumulators and leafy vegetables (Compositae and Chenopodiaceae) being high accumulators.     

Effect of farmyard manure application on boron adsorption-desorption characteristics of some soils

Boron (B) availability to crop plants depends on soil properties as well as management practices like liming, fertilization and use of organic manures. To assess the effect of farmyard manure (FYM) application on availability of added B, adsorption-desorption of B was investigated in five different soils receiving varying doses of FYM (0, 5 and 10 g FYM kg(-1) soil). Two surfaces Freundlich model was found best to account for B adsorption-desorption data of all soils. Application of FYM increased B adsorption capacities pertaining to low (K1) and high (K2) concentration ranges in all soils, except Soil C (Alfisol) having a pH of 9.8, in which the higher rate of FYM decreased the value of K2. Application of FYM did not change B desorption capacities of soils corresponding to low B concentration range (K(1)(1)) significantly, however, it increased B desorption capacity pertaining to high B concentration (K(1)(2)) in all soils, except Soils C (Alfisol) and E (Entisol) having pH of 9.8 and 5.1, respectively. Application of FYM increased the desorption slope factor applicable to low concentration range (1/n(1)(1)) in Soil A (Inceptisol), but decreased it in Soil E (Entisol). The 1/n(1)(2) (desorption slope factor applicable to high concentration range) decreased with FYM application in all soils except Soil E (Entisol), where it was increased. Boron desorption index (slope(ads)/slope(des)) decreased with FYM application in low B concentration range, but increased in high concentration range for all soils except soil E (Entisol, pH 5.1), in which a reverse trend was observed. Application of FYM increased the retention of added B in soils and may help reducing the leaching losses.