Importance of arsenic bioaccessibility in health risk assessment based on iron "Minette" rocks and related soils.

Total element concentrations by themselves are not always good predictors of toxicity and are therefore not suitable for eco- and/or human toxicological risk determination. In addition, despite the growing call for harmonization, countries show significant variation in risk assessment tools, screening/background values, protocols and legal management of soils. By incorporating mobility and bioaccessibility/availability into soil risk assessments, location-specific physico-chemical and geological conditions can be considered in routinely applied general risk assessment methodologies. Minette soils and rocks are a great case in point since they often are associated with high geogenic As concentrations and consequently potential risks. Minette iron ores form the world largest Fe ore deposits since the "great oxidation". For the first time, oral bioaccessibility during direct ingestion was assessed on Minettes from Luxembourg by applying the in vitro Solubility/Bioavailability Research Consortium (SBRC) method. Out of > 180 samples, 25 representative samples were selected providing a unique dataset which showed an average gastric bioaccessibility of ∼10% (7.8 ± 4.0 mg/kg) of the total As-concentration, with a maximum of 45% (17.9 mg/kg). Of importance is that bioaccessibility of As in Minette rocks and soils are controlled by, and can be estimated from, lithology, mineralogy and total Ca content. Soils and ooid grainstones with an iron oxide or clayey matrix, are characterized by average gastric bioaccessible As concentrations < 6 mg/kg. Gastric As bioaccessibility is highest in Fe-bearing calcite-cemented bioclastic grainstones (∼12 mg/kg). Importantly, for all samples the maximal bioaccessible As concentrations remain below the threshold from which significant adverse non-carcinogenic and/or carcinogenic health effects are expected. These new results are in strong contrast with what total As concentrations might suggest. Considering bioaccessibilities, consequently, can help to avoid disproportionate, costly and environmentally impacting risk management strategies. Furthermore, this study illustrates the importance of cross-disciplinary collaboration between geo- and health scientists.

The ecotoxic potential of a new zero-valent iron nanomaterial, designed for the elimination of halogenated pollutants, and its effect on reductive dechlorinating microbial communities.

The purpose of this study was to assess the ecotoxic potential of a new zero-valent iron nanomaterial produced for the elimination of chlorinated pollutants at contaminated sites. Abiotic dechlorination through the newly developed nanoscale zero-valent iron material and its effects on dechlorinating bacteria were investigated in anaerobic batch and column experiments. The aged, i.e. oxidized, iron material was characterization with dynamic light scattering, transmission electron microscopy and energy dispersive x-ray analysis, x-ray diffractometry and cell-free reactive oxygen measurements. Furthermore, it was evaluated in aerobic ecotoxicological test systems with algae, crustacean, and fish, and also applied in a mechanism specific test for mutagenicity. The anaerobic column experiments showed co-occurrence of abiotic and biological dechlorination of the common groundwater contaminant perchloroethene. No prolonged toxicity of the nanomaterial (measured for up to 300 days) towards the investigated dechlorinating microorganism was observed. The nanomaterial has a flake like appearance and an inhomogeneous size distribution. The toxicity to crustacean and fish was calculated and the obtained EC50 values were 163 mg/L and 458 mg/L, respectively. The nanomaterial showed no mutagenicity. It physically interacted with algae, which had implications for further testing and the evaluation of the results. Thus, the newly developed iron nanomaterial was slightly toxic in its reduced state but no prolonged toxicity was recorded. The aquatic tests revealed a low toxicity with EC50 values ≥ 163 mg/L. These concentrations are unlikely to be reached in the aquatic environment. Hence, this nanomaterial is probably of no environmental concern not prohibiting its application for groundwater remediation.

Development of diffuse double layers in column-wicking experiments: implications for pH-dependent contact angles on quartz.

The pH dependence of contact angles in quartz powder beds was studied by column wicking. The rate of capillary penetration was found to be highest at the isoelectric point of quartz which, by applying the classical Washburn equation, results in a minimum contact angle at the isoelectric point. Direct contact angle measurements however show that the contact angle is at a maximum at the point of zero charge (see e.g. [1-6]). By measuring the permeability of powder columns with aqueous solutions of varying pH, it is shown that the permeability reaches a maximum at the isoelectric point. This suggests that the rate of capillary penetration is influenced by the permeability of the powder columns towards respective aqueous solutions. The difference in permeability can be explained by the notion of an electroosmotic counter-pressure which was already recognized by Klinkenberg. An approach is presented that involves the calculation of capillary constants from permeability measurements of the corresponding aqueous solutions. An equation is derived that takes direct account for the electroosmotic counter-pressure. Application of this equation combined with capillary constants calculated from permeabilities of the corresponding aqueous solutions results in the expected contact angle-pH relationship.

Reactivity of alkaline lignite fly ashes towards CO2 in water.

The reaction kinetics between alkaline lignite fly ashes and CO2 (pCO2 = 0.01--0.03 MPa)were studied in a laboratory CO2 flow-through reactor at 25--75 degrees C. The reaction is characterized by three phases that can be separated according to the predominating buffering systems and the rates of CO2 uptake. Phase I (pH > 12, < 30 min) is characterized by the dissolution of lime, the onset of calcite precipitation and a maximum uptake, the rate of which seems to be limited by dissolution of CO2. Phase II (pH < 10.5, 10--60 min) is dominated by the carbonation reaction. CO2 uptake in phase III (pH < 8.3) is controlled by the dissolution of periclase (MgO) leading to the formation of dissolved magnesium-bicarbonate. Phase I could be significantly extended by increasing the solid-liquid ratios and temperature, respectively. At 75 degrees C the rate of calcite precipitation was doubled leading to the neutralization of approximately 0.23 kg CO2 per kg fly ash within 4.5 h, which corresponds to nearly 90% of the total acid neutralizing capacity.