Sorption of polycyclic aromatic hydrocarbons (PAHs) to carbonaceous materials in a river floodplain soil

We report on sorption isotherm of phenanthrene (Phe) for river floodplain soil associated with carbonaceous materials, with particular attention being devoted to the natural loading of Phe. Our sorption experiments with original soil samples, size, and density sub-fractions showed that the light fraction had the highest sorption capacity comparable to low rank coals. In addition, the light fraction contributed most for the sorption of Phe in total soil samples. K_oc values for all fractions were in the same range, thus indicating that coal and coal-derived particles in all samples are responsible for the enhanced sorption for Phe. Sorption was strongly nonlinear and the combined partitioning and pore-filling model gave a better fit than the Freundlich sorption model. In addition, the spiked PAHs did not show the same behavior as the naturally aged ones, therefore the accessibility of indigenous background organic contaminants was reduced when coal and coal-derived particles are associated with the soils.     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Concentration of heavy metals in various children's herbal tea types and their correlations

This investigation was undertaken to determine the concentrations of cadmium, lead, mercury, zinc, copper and magnesium in six tea types used as children's tea. Six types of tea of different herbal composition used for children's consumption (T1, T2, T3, T4, T5 and T6) were analyzed in three subsequent collections. The analysis of cadmium showed that the concentration was very similar in all types of children's tea, ranging from 0.233 to 0.369 mg/kg. Lead concentrations were in the range of 0.340-1.564 mg/kg without any significant differences. The analysis of mercury detected very low concentration of this metal in all samples (0.002-0.004 mg/kg). In zinc, the values ranged from 36.633 to 71.711 mg/kg, with significant differences (p < 0.001) according to tea type. Copper concentration was 10.089-30.178 mg/kg with the highest value in T4. The concentration of magnesium was significantly higher in tea T1 and T2 (102.311 and 129.422 mg/kg) in comparison with other tea types where the level was 19.811-37.411 mg/kg. The maximum tolerable limit determined by Codex Alimentarius was not exceeded in any sample. In general, correlation analysis detected high positive correlation between cadmium and lead (r = 0.89), cadmium and mercury (r = 0.92) and between lead and mercury (r = 0.77).     

Field scale characterization and modeling of contaminant release from a coal tar source zone

A coal tar contaminated site was characterized using traditional and innovative investigation methods. A careful interpretation of hydrogeological and hydrogeochemical data allowed for the conceptualization of the heterogeneous coal tar distribution in the subsurface. Past and future contaminant release from the source zone was calculated using a modeling framework consisting of a three-dimensional steady-state groundwater flow model (MODFLOW) and two hydrogeochemical models (MIN3P). Computational time of long-term simulations was reduced by simplifying the coal tar composition using 3 composite and 2 individual constituents and sequential application of a 2D centerline model (for calibration and predictions) and a 3D model (only for predictions). Predictions were carried out for a period of 1000 years. The results reveal that contaminant mass flux is governed by the geometry of zones containing residual coal tar, amount of coal tar, its composition and the physicochemical properties of the constituents. The long-term predictions made using the 2D model show that even after 1000 years, source depletion will be small with respect to phenanthrene, 89% of initial mass will be still available, and for the moderately and sparingly soluble composite constituents, 60% and 98%, respectively.     

Characteristics of residual organochlorine pesticides in soils under different land-use types on a coastal plain of the Yellow River Delta

The residual levels of organochlorine pesticides (OCPs) were examined in soils covering five types of land use along a salinity gradient on the Yellow River Delta. The most prominent OCPs were dichlorodiphenyltrichloroethane (∑DDT, arithmetic mean = 5.11 μg kg^?1), hexachlorocyclohexane (∑HCH, 1.69 μg kg^?1) and ∑endosulfan (10.4 μg kg^?1). The spatial variability of OCPs composition shifted from γ-HCH and o,p′-DDT dominated pesticides in coastal soils to p,p′-DDE dominated pesticides in inland soils. In different land-use types, the percentages of β-HCH and p,p′-DDE are characterized by more recalcitrant components in decreasing order of vegetable fields, cereal fields, cotton fields, wetlands and tidal flats with increasing soil salinity. However, the less recalcitrant components, γ-HCH and o,p′-DDT, showed an opposite trend. Endosulfan sulfate predominated in all land-use types. Residual levels of β-HCH were affected by soil organic matter. The correlations between γ-HCH and clay content and between p,p′-DDE, o,p′-DDT and salinity might associate with the influence of sediment cotransport by the Yellow River and the density of anthropogenic activities in coastal region. Depth distribution of the OCPs in typical soil profiles also implied that local historical usage and sediment transport by the Yellow River both affected the OCPs residual in this region.     

Sex or Food? Appetetive Learning of Sex Odors in a Male Moth

Moths learn to associate a flower odor with a food reward after a few learning trials. Can a hungry, male moth learn to associate a sex attractant with food instead of with sex? We provided a hungry male with odors of single female sex pheromone components, of the full sex pheromone blend or of a flower odor component as cues in an appetitive learning assay. The male learned the single pheromone components just as well as the flower odor. Learning was, however, severely impaired when the full sex pheromone blend was used as conditioning stimulus. The "hard-wiring" between pheromone odor and sex thus seems to be restricted to those circumstances when the male moth experiences the full blend.