Suitability of using diffusive gradients in thin films (DGT) to study metal bioavailability in mine tailings: possibilities and constraints

Background, aim, and scope  

Diffusive gradients in thin films (DGT) have been recognized as a suitable tool to assess in situ metal bioavailability in soils. Mine tailings have some singular characteristics such as high heavy-metal concentrations, low pH, or absence of water retention capacity that may compromise the correct application of this technique whose applicability is known to be pH dependent. The goal of this study was to determine the response of DGT devices in heavy-metal-polluted mine tailings with different pH. In addition some experiments were performed in order to determine the effect of acidic pH and dissolved ions on the binding properties of the chelating resin.     

Influence of the initial state of carbon nanotubes on their colloidal stability under natural conditions

The colloidal stability of dry and suspended carbon nanotubes (CNTs) in the presence of amphiphilic compounds (i.e. natural organic matter or surfactants) at environmentally realistic concentrations was investigated over several days. The suspensions were analyzed for CNT concentration (UV-vis spectroscopy), particle size (nanoparticle tracking analysis), and CNT length and dispersion quality (TEM). When added in dry form, around 1% of the added CNTs remained suspended. Pre-dispersion in organic solvent or anionic detergent stabilized up to 65% of the added CNTs after 20 days of mild shaking and 5 days of settling. The initial state of the CNTs (dry vs. suspended) and the medium composition hence are critical determinants for the partitioning of CNTs between sediment and the water column. TEM analysis revealed that single suspended CNTs were present in all suspensions and that shaking and settling resulted in a fractionation of the CNTs with shorter CNTs remaining predominantly in suspension.     

Bioindication of atmospheric trace metals--with special references to megacities

After considering the particular problems of atmospheric pollution in megacities, i.e. agglomerations larger than 5 mio. inhabitants, with urbanization of World's population going on steadily, possibilities of active biomonitoring by means of green plants are discussed. Based on specific definitions of active and passive bioindication the chances of monitoring heavy metals in Sao Paulo megacity were demonstrated (first results published before). This is to show that there is need for increased use of bioindication to tackle the particular problems of megacities concerning environmental "health", the data to be processed according to the Multi-Markered-Bioindication-Concept (MMBC). Comparison to other work shows this approach to be reasonable.     

Crystal structure of δ-isobutoxypentabromo-cyclododecanes, kinetics and selectivity of their isomerization during thermal treatment of flame-proofed polystyrenes

Hexabromocyclododecanes (HBCDs) are persistent organic pollutants now ubiquitous in the environment. Technical HBCD mixtures and with it flame-proofed polystyrenes (FP-PS) also contain isobutoxypentabromocyclododecanes (iBPBCDs) as minor constituents, which are possibly released together with HBCDs. So far, eight diastereomeric pairs of enantiomers named as α-, β-, γ-, δ-, ?-, ξ-, η-, and θ-iBPBCDs with proportions of 10%, 5%, 2%, 21%, 11%, 11%, 12% and 28% were found in technical HBCD. Herein the crystal structure of racemic δ-iBPBCD, the second most prominent diastereomer, is presented and assigned to (1S)-1-isobutoxy-(2R,5R,6S,9S,10S)-2,5,6,9,10-pentabromocyclododecane and its enantiomer. During thermal treatment of FP-PS, e.g. the production of extruded polystyrenes (XPS), proportions of δ-iBPBCDs decrease and those of other stereoisomers increase. Evidence was found that δ-iBPBCDs isomerize stereo- and regioselectively to β-iBPBCDs. Based on structural and kinetic data, a transformation mechanism was proposed. Apparent first-order rate constants (k_iso) of 0.0019, 0.0050, and 0.012 min⁻¹ are found for the δ- to β-iBPBCD isomerization at 120, 130, and 140 °C, respectively, corresponding to half-lives of 360, 140, and 56 min. These transformations also occur during the production of XPS, which predominantly contain β-iBPBCDs, whereas δ-iBPBCDs dominate in materials experiencing lower thermal stress, e.g. expanded polystyrenes (EPS). The relative configurations of δ- and θ-iBPBCDs are TtCtCt, like the one of γ-HBCDs. γ-HBCDs are the kinetically and α-HBCDs with a TcCtCc configuration the thermodynamically favored products. In analogy, β-iBPBCDs are assumed to have a TcCtCc configuration like α-HBCDs because they are formed from δ-iBPBCDs under thermodynamic control. In conclusion, HBCD- and iBPBCD-patterns in flame-proofed polystyrenes vary substantially, reflecting the thermal stress these materials have experienced. When released to the environment, these patterns might further change, as observed for HBCDs.     

Aqueous solubility, effects of salts on aqueous solubility, and partitioning behavior of hexafluorobenzene: experimental results and COSMO-RS predictions

The aqueous solubility of hexafluorobenzene has been determined, at 298.15 K, using a shake-flask method with a spectrophotometric quantification technique. Furthermore, the solubility of hexafluorobenzene in saline aqueous solutions, at distinct salt concentrations, has been measured. Both salting-in and salting-out effects were observed and found to be dependent on the nature of the cationic/anionic composition of the salt. COSMO-RS, the Conductor-like Screening Model for Real Solvents, has been used to predict the corresponding aqueous solubilities at conditions similar to those used experimentally. The prediction results showed that the COSMO-RS approach is suitable for the prediction of salting-in/-out effects. The salting-in/-out phenomena have been rationalized with the support of COSMO-RS σ-profiles. The prediction potential of COSMO-RS regarding aqueous solubilities and octanol-water partition coefficients has been compared with typically used QSPR-based methods. Up to now, the absence of accurate solubility data for hexafluorobenzene hampered the calculation of the respective partition coefficients. Combining available accurate vapor pressure data with the experimentally determined water solubility, a novel air-water partition coefficient has been derived.     

LES validation of urban flow,part I: flow statistics and frequency distributions

Essential prerequisites for a thorough model evaluation are the availability of problem-specific, quality-controlled reference data and the use of model-specific comparison methods. The work presented here is motivated by the striking lack of proportion between the increasing use of large-eddy simulation (LES) as a standard technique in micro-meteorology and wind engineering and the level of scrutiny that is commonly applied to assess the quality of results obtained. We propose and apply an in-depth, multi-level validation concept that is specifically targeted at the time-dependency of mechanically induced shear-layer turbulence. Near-surface isothermal turbulent flow in a densely built-up city serves as the test scenario for the approach. High-resolution LES data are evaluated based on a comprehensive database of boundary-layer wind-tunnel measurements. From an exploratory data analysis of mean flow and turbulence statistics, a high level of agreement between simulation and experiment is apparent. Inspecting frequency distributions of the underlying instantaneous data proves to be necessary for a more rigorous assessment of the overall prediction quality. From velocity histograms local accuracy limitations due to a comparatively coarse building representation as well as particular strengths of the model to capture complex urban flow features with sufficient accuracy are readily determined. However, the analysis shows that further crucial information about the physical validity of the LES needs to be obtained through the comparison of eddy statistics, which is focused on in part II. Compared with methods that rely on single figures of merit, the multi-level validation strategy presented here supports conclusions about the simulation quality and the model’s fitness for its intended range of application through a deeper understanding of the unsteady structure of the flow.     

Medical radioisotopes in the environment – following the pathway from patient to river sediment

Motivated by the detection of ¹³¹I in river sediment in routine long-term surveillance samples, a systematic short-term study of the wastewater treatment chain was planned and conducted. Inflow, effluent and primary sludge were collected on a daily basis during two weeks at a regional wastewater treatment plant. Samples were investigated by gamma spectroscopy. Four medically used isotopes could be identified (¹³¹I and ^99mTc regularly, ¹⁵³Sm and ¹²³I sporadically). The concentration levels coincide well with literature data for ¹³¹I, and with our own long-term data for ¹³¹I and ^99mTc for the same plant. Cosmogenic ⁷Be activity in primary sludge correlated well with rainfall intensity. Surface sediment was sampled at low tide at both shores of the river, up- and downstream of the plant. ¹³¹I was identified in all samples, with a sharp maximum (about 100 Bq kg⁻¹ d.m.) at the discharge point of the plant and lower levels elsewhere, decreasing monotonically in downstream direction. ⁷Be and ¹³⁷Cs showed the same behaviour, but no peak at the discharge point. Predictions from simple equilibrium models for the transport and sedimentation of ¹³¹I show good agreement with the experimental data and suggest that the wastewater treatment plant is the main source for this isotope.     

Factors controlling the biodegradation of 17beta-estradiol, estrone and 17alpha-ethinylestradiol in different natural soils

We conducted a series of laboratory microcosm incubations with [(14)C]-labeled 17beta-estradiol (E2), estrone (E1) and 17alpha-ethinylestradiol (EE2) in 17 different natural soils to characterize hormone mineralization. A significantly higher mineralization was observed for E1 (2.0-37.6%) and E2 (4.2-50.2%) than for EE2 (0.5-2.6%) in all test soils after 21 days. Soil physical or chemical parameters were not related to estrogen mineralization. Although sorption parameters varied greatly for E2 (K(F)=21.9-317.5 mL g(-1)), for E1 (K(F)=46.0-517.5 mL g(-1)) and for EE2 (K(F)=29.9-326.1 mL g(-1)) this apparently did not control estrogen bioavailability since it showed no effects on hormone mineralization. In order to elucidate the controlling factors, experiments with combined additions of radiolabeled estrogens and different substrates were conducted. Additions of ammonium nitrate or alanine to soil samples generally increased EE2 mineralization, thus indicating N-limitation. Additions of glucose induced higher E2 and EE2 degradation in comparison to control samples which is attributed to co-metabolism. Additions of saw dust, catechol or streptomycin influenced the microbial population in the test soils and affected the mineralization of E2 and EE2. Thus, we clearly demonstrate that different microbial communities are responsible for E2 and EE2 degradation in soils. We suggest that EE2 is mineralized by white-rot fungi and E2 by bacteria.     

Determination of heavy metals and halogens in plastics from electric and electronic waste

The presence of hazardous substances and preparations in small waste electrical and electronic equipment (sWEEE) found in the residual household waste stream of the city of Dresden, Germany has been investigated. The content of sWEEE plastics in heavy metals and halogens is determined using handheld X-ray fluorescence analysis (HXRF), elemental analysis by means of atomic absorption spectrometry (AAS) and ion exchange chromatography (IEC). Mean value of results for heavy metals in samples (n = 51) by AAS are 17.4 mg/kg for Pb, 5.7 mg/kg for Cd, 8.4 mg/kg for Cr. The mass fraction of an additive as shown by HXRF (n = 161) can vary over a wide range. Precise deductions as regards sWEEE plastics content in hazardous substances and preparations cannot be made. Additional research would be expedient regarding the influence of hazardous substances to recycling processes, in particular regarding the contamination of clean fractions in the exit streams of a WEEE treatment plant. Suitable standards for calibrating HXRF for use on EEE plastics or complex electr(on)ic components do not exist and should be developed.