Sorption of Iron on Surfaces: Modelling,Data Evaluation,and Measurement Uncertainty

Assessment of the likely outcome of engineered invention strategies in acid mine drainage often involves complex geochemical modelling activities. Geochemical modelling is based on chemical thermodynamic data. In addition sorption models, kinetical reaction rates and transport tools are included into the modelling codes because the interactions between solution components and surfaces, reaction time and transport are considered important features characterising the site‐specific situation. In the determination of both thermodynamic data and sorption coefficients, speciation calculations play an important role. By applying the probabilistic speciation code Ljungskile to some simplified acid mine drainage scenarios, the strong impact of chemical speciation on the complete measurement uncertainty budget of geochemical modelling predictions is shown. The complete measurement uncertainty budget in combination with other metrological concepts like traceability is an essential element of quality assurance for experimental data. The elements of quality assurance are provided by international agreements and normative documents on national and international levels. The following discussion will focus on some metrological issues of sorption data.     

The Analysis of the Seasonal,Spatial, and Compositional Distribution of Humic Substances in a Subtropical Shallow Lake

The spatial and temporal distribution of humic substances in aquatic ecosystems can have important effects on ecosystem productivity, negatively impacting primary productivity while positively impacting secondary productivity. In the present investigation, a large shallow lake ecosystem was studied to determine the spatial and seasonal variation of the composition and concentration of humic substances. Concentrations of total dissolved organic matter, humic acid, and fulvic acid were found to display significant spatial distributions (1.3…13.5 mg/L, DOM; 0.1…5.4 mg/L, HA). The distribution is described by using mapping techniques and the analysis of the spatial distribution of the lake. An analysis of the seasonal variations also indicated the dependence of the occurrence of these compounds on meteorological and hydrological conditions. To identify the potential sources of these organic materials, an analysis was made of the ratio of humic and fulvic acid fractions and total DOM. It was found that areas of high DOM concentration coincided with the areas of highest HA percentage of total DOM. Furthermore using the ratio of the normalised concentrations of HA, FA, and residual DOM (< 5000 g/mol) it was found that areas dominated by each are spatially distinct. This confirms the hypothesis that in these shallow lakes, photodegradation and bacterioplankton activity will create a residence time dependent zonation of each component of the total DOM.     

Applicability of Single and Sequential Extractions for Assessing the Potential Mobility of Heavy Metals in Contaminated Soils

Heavy metal polluted sites are bearing an acute hazardous risk for the groundwater, but also a potential one. While the acute risk can be assessed directly via seepage water measurements, determination of the potential risk is much more complex. It results from the sum of all reactions that are capable to mobilize heavy metals under worst case environ-mental conditions. Using a fourfold sequential extraction (SE₄) such a worst case was simulated for four soils highly contaminated with Pb, Zn, and Cu. The resulting potential mobilizable amounts ϕ_pm have been compared with those derived from 6 single extractions. By means of variance analyses, it is shown that ϕ_pm of lead can be represented by a single extraction with NH₂OH. In contrary, ϕ_pm of zinc can be represented using the pH_stat test or an extraction with aqua regia, while ϕ_pm of copper can be represented only by aqua regia extraction. The water-soluble amounts deriving from the DEV-S4 test do not correlate with the potential mobilizable amounts of any metal. Therefore, an assessment of contaminated sites should include an aqua regia extraction additionally to the seepage water analysis.     

Factors Controlling Total Concentration and Aqueous Speciation of Aluminium in an Acidic Headwater Stream of the Bavarian Forest National Park: a Modelling Approach

The purpose of the present paper is to analyse factors controlling total concentration and aqueous speciation of aluminium in the Große Ohe River, using a thermodynamic equilibrium model and a mixing approach. A model compound for humic substances is derived on the basis of the relation between anion deficit and the organic carbon content in the river as well as literature data. An equilibrium speciation model for aluminium is set up, considering this model compound and relevant inorganic solutes. Although the model cannot be verified directly, its results may be viewed as qualitatively correct. Applying the model to measured stream water samples highlights that aqueous speciation of aluminium is mainly controlled by the pH value and discharge and that free aluminium concentrations reach clearly toxic levels during acidic episodes. Comparing measured concentrations of sulfate and H⁺ and calculated concentrations of Al³⁺ with solubility curves of gibbsite like minerals and jurbanite clearly shows that total aluminium concentrations are not controlled by equilibria with these mineral phases alone. The observed relationship can be better explained from a mixture of two distinct waters, representing lowflow and highflow chemistry, and the resulting equilibrium concentrations. This indicates that total aluminium concentration, in particular during high discharge events, is mainly controlled by the mixture of waters with differing chemistry and flowpaths.     

Occurrence of an Algal Mass Development in an Acidic (pH 2.5):, Iron and Aluminium‐rich Coal Mining Pond

A bloom of Chlamydomonas botryopara was observed in an extremely acid coal mining pond (pH 2.5) with high concentrations of iron and aluminium (1160...3760 mg L^–1 Fe, 133...387 mg L^–1 Al). Cell density of algae was counted as 6.45 · 10⁶ mL^–1 corresponding to 700 mg L^–1 fresh weight and 2660 μg L^–1 chlorophyll‐a. The nutrient concentrations were 3.5 mg L^–1 soluble reactive phosphorus and 0.15 mg L^–1 dissolved inorganic nitrogen. This observation supports the hypothesis that a low nutrient availability rather than extreme conditions (e.g. high acidity and low pH) limit the development of phytoplankton in many acidified lakes.     

Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part I: Drug Residues and other Polar Contaminants in Berlin Surface and Groundwater

Several polar contaminants were found in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. Residues of pharmaceuticals and N-(phenylsulfonyl)-sarcosine originating from various sewage treatment plants effluents were found at concentrations up to the μg/L-level in the surface water, whereas the concentrations of polar pesticides such as dichlorprop and mecoprop were always below 0.1 μg/L. The pharmaceuticals most frequently detected in the surface water samples include clofibric acid, diclofenac, ibuprofen, propiphenazone, and two other drug metabolites. Additional investigations of groundwater wells of a drinking water plant have shown that polar contaminants such as drug residues or N-(phenylsulfonyl)-sarcosine easily leach through the subsoil into the groundwater aquifers when contaminated surface water is used for groundwater recharge in drinking water production.