Inland waters are of great importance for scientists as well as authorities since they are essential ecosystems and well known for their biodiversity. When monitoring their respective water quality, in situ measurements of water quality parameters are spatially limited, costly and time-consuming. In this paper, we propose a combination of hyperspectral data and machine learning methods to estimate and therefore to monitor different parameters for water quality. In contrast to commonly-applied techniques such as band ratios, this approach is data-driven and does not rely on any domain knowledge. We focus on CDOM, chlorophyll a and turbidity as well as the concentrations of the two algae types, diatoms and green algae. In order to investigate the potential of our proposal, we rely on measured data, which we sampled with three different sensors on the river Elbe in Germany from 24 June–12 July 2017. The measurement setup with two probe sensors and a hyperspectral sensor is described in detail. To estimate the five mentioned variables, we present an appropriate regression framework involving ten machine learning models and two preprocessing methods. This allows the regression performance of each model and variable to be evaluated. The best performing model for each variable results in a coefficient of determination R2 in the range of 89.9% to 94.6%. That clearly reveals the potential of the machine learning approaches with hyperspectral data. In further investigations, we focus on the generalization of the regression framework to prepare its application to different types of inland waters.

Se is an essential nutrient at trace levels, but also a toxic environmental contaminant at higher concentrations. The mobility of the trace element Se in natural environments is mainly controlled by the occurrence of the highly soluble Se oxyanions-selenite [Se(IV)] and selenate [Se(VI)]-and their interaction with geological materials. Since iron oxides are ubiquitous in nature, many previous studies investigated Se retention by adsorption onto iron oxides. However, little is known about the retention of Se oxyanions during the formation process of iron oxides. In this paper, we therefore studied the immobilization of Se oxyanions during the crystallization of hematite from ferrihydrite. In coprecipitation studies, hematite was synthesized by the precipitation and aging of ferrihydrite in an oxidized Se(IV)-or Se(VI)-containing system (pH 7.5). Hydrochemical data of these batch experiments revealed the complete uptake of all available Se(IV) up to initial concentrations of c(Se) 0 = 10-3 mol/L (m/V ratio = 9.0 g/L), while the retention of Se(VI) was low (max. 15 % of c(Se) 0). In case of high initial Se(IV) concentrations, the results also demonstrated that the interaction of Se with ferrihydrite can affect the type of the final transformation product. Comparative adsorption studies, performed at identical conditions, allowed a distinction between pure adsorption and coprecipitation and showed a significantly higher Se retention by coprecipitation than by 2 adsorption. Desorption studies indicated that Se coprecipitation leads to the occurrence of a resistant, non-desorbable Se fraction. According to time-resolved studies of Se(IV) or Se(VI) retention during the hematite formation and detailed spectroscopic analyses (XPS, XAS), this fraction is the result of an incorporation process, which is not attributable to Fe-for-Se substitution or the Se occupation of vacancies. Se initially adsorbs to the ferrihydrite surface, but after the transformation of ferrihydrite into hematite, it is mostly incorporated by hematite. In systems without mineral transformation, however, Se remains as a sorption complex. In case of Se(VI), an outer-sphere complex forms, while Se(IV) forms a mixture of bidentate mononuclear edge-sharing and bidentate binuclear corner-sharing inner-sphere complexes. The results of this study demonstrate that incorporation of Se oxyanions by hematite is an important retention mechanism in addition to pure adsorption, which may affect the migration and immobilization of Se oxyanions in natural systems or polluted environments.

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Environmental and health hazards associated with the trace element selenium are mainly related to the presence of the highly mobile selenium oxyanions selenite and selenate (oxidation states IV and VI). In this study, we investigated the immobilization of dissolved selenite and selenate during the formation of magnetite in coprecipitation experiments based on the progressive oxidation of an alkaline, anoxic Fe2+ system (pH 9.2). Up to initial selenium concentrations of 10-3 mol L-1 (mass/volume ratio = 3.4 g L-1), distribution coefficient values (log Kd) of 3.7 to 5.1 L kg-1 demonstrate high retention of selenium oxyanions during the mineral formation process. This immobilization is due to the reduction of selenite or selenate, resulting in the precipitation of sparingly soluble selenium compounds. By X-ray diffraction analysis, these selenium compounds were identified as trigonal elemental selenium that formed in all coprecipitation products following magnetite formation. Time-resolved analysis of selenium speciation during magnetite formation and detailed spectroscopic analyses of the solid phases showed that selenium reduction occurred under anoxic conditions during the early phase of the coprecipitation process via interaction with iron(ii) hydroxide and green rust. Both minerals are the initial Fe(ii)-bearing precipitation products and represent the precursor phases of the later formed magnetite. Spectroscopic and electron microscopic analysis showed that this early selenium interaction leads to the formation of a nanoparticulate iron selenide phase [FeSe], which is oxidized and transformed into gray trigonal elemental selenium during the progressive oxidation of the aquatic system. Selenium is retained regardless of whether the oxidation of the unstable iron oxides leads to the formation of pure magnetite or other iron oxide phases, e.g. goethite. This reductive precipitation of selenium induced by interaction with metastable Fe(ii)-containing iron oxide minerals has the potential to influence the mobility of selenium oxyanions in contaminated environments, including the behavior of 79Se in the near-field of nuclear waste repositories.

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