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The increasing need for water remediation due to water scarcity and the accumulation of persistent pollutants in water cycles requires innovative materials and their more sustainable synthesis processes. The aim of this work was therefore to develop an approach for the bottom-up synthesis of colloidal Fe/C composites. It was tested whether the composites fulfill the main criteria for use as injectable adsorbents and reducing agents for the removal of chlorinated pollutants in in-situ groundwater remediation. After screening different Fe and C precursors, the bottom-up synthesis of a particulate and reactive Fe/C composite was developed via hydrothermal carbonization (HTC) of mixtures of ferrous and sodium gluconate in a one-pot HTC and subsequent carbothermal reduction at 800 °C. The produced particles show good dispersibility with particle diameters in the range of d10 ≥ 2 µm, d50 ≈ 11 µm and d90 ≤ 40 µm in aqueous suspensions. By varying the molar ratio of Fe to gluconate in the HTC process, the final content of zero-valent iron equivalents (ZVI) in the composite could be adjusted between (24 ± 12) and (49 ± 15) wt.-%. The chemical reactivity of the composite was tested by reductive dechlorination of chloroform (CF) as a test reaction. The characterization of the composites before and after reductive dechlorination with X-ray diffraction (XRD) shows that not only pristine Fe0 but also Fe3C is active in the reductive dechlorination reaction. Palladization of the composite material shifts the product selectivity from dichloromethane as the main product to the non-chlorinated products methane (up to 77 mol-%) and ethane (up to 9 mol-%) without any external H2 feed. The dispersiblity and intrinsic reactivity of the synthesized composites meet the requirements for application in water remediation where contaminants need to be retained and degrad

MnO2 can be used in advanced oxidation processes to activate peroxydisulfate (PS) and generate reactive species such as sulfate radicals (SO4•-), hydroxyl radicals (•OH) and singlet oxygen (1O2) for the abatement of organic water contaminants. Alternatively, one can use MnO2 as particulate oxidant which, in contrast to PS, is active already at low temperatures. This low-temperature activity is particularly attractive for in situ groundwater treatment. The roles of PS and MnO2 as oxidant and catalyst, respectively, may invert: MnO2 functions as primary oxidant and PS works as re-oxidant of reduced Mn-oxides. In this way, the limited oxidation capacity of particulate MnO2 can be overcome. So far, such reaction systems have not been extensively explored. In the present study, the degradation of 4-hydroxybenzoic acid (HBA) by PS + MnO2 was studied under various experimental conditions, by varying reaction temperature (15–45 °C), reagent concentrations, and water matrix. Both PS and MnO2 alone have the ability to effect the oxidation of HBA. In the co-presence of PS and MnO2, a fast removal of HBA from water was achieved even at low temperatures (half-life of HBA about 0.5 h with 2.4 g/L MnO2 at 25 °C), owing to a synergic effect between the two components.Quenching experiments indicate that the primary HBA oxidation step is a heterogeneous reaction on the MnO2 surface rather than a homogeneous reaction driven by SO4•- or 1O2, as frequently reported in literature. This is in line with results from the PS driven oxidation of perfluorooctanoic acid which is not significantly enhanced in the presence of MnO2.

Nitroaromatic compounds (NACs) are prominent explosives. In this context, these toxic substances were released into the environment and cause long-lasting groundwater contamination. In preparation of a possible in-situ remediation, colloidal Fe-zeolites were investigated for their capabilities as adsorbents and oxidation catalysts. It was shown that the Fe-zeolites FeBEA35 and FeFAU55 are potent inorganic adsorbents for NACs and simultaneously capable of activating H2O2 as Fenton-like oxidation catalysts. Adsorption isotherms of 15 NACs on both zeolites were measured to evaluate the option of coupling adsorptive contaminant enrichment with oxidative degradation. The faujasite-type zeolite FeFAU55 showed a distinct S-type adsorption behaviour and reached significantly higher NAC loadings of > 20 wt%. For FeBEA35, L-type adsorption isotherms and maximum loadings qmax of about 4 wt% were obtained. Degradation of all NACs, monitored by nitrate formation, was observed. Apparent rate constants of the NACs with hydroxyl radicals in a homogeneous, stoichiometric Fenton reaction were related to the heterogeneous system to examine the role of adsorption on the oxidative degradation. Beneficial influence of the adsorption on the oxidation rates was identified. The results of this work open up promising prospects for future application of Fe-zeolites for the in-situ remediation of NAC-contaminated groundwater.

Recent innovative adsorption technologies for water purification rely on micrometer-sized activated carbon (AC) for ultrafast adsorption or in situ remediation. In this study, the bottom-up synthesis of tailored activated carbon spheres (aCS) from sucrose as renewable feedstock is demonstrated. The synthesis is based on a hydrothermal carbonization step followed by a targeted thermal activation of the raw material. This preserves its excellent colloid properties, i.e., narrow particle size distribution around 1 µm, ideal spherical shape and excellent aqueous dispersibility. We investigated the ageing of the freshly synthesized, highly de-functionalized AC surface in air and aqueous media under conditions relevant to the practice. A slow but significant ageing due to hydrolysis and oxidation reactions was observed for all carbon samples, leading to an increase of the oxygen contents with storage time. In this study, a tailored aCS product was generated within a single pyrolysis step with 3 vol.-% H2O in N2 in order to obtain the desired pore diameters and surface properties. Adsorption characteristics, including sorption isotherms and kinetics, were investigated with monochlorobenzene (MCB) and perfluorooctanoic acid (PFOA) as adsorbates. The product showed high sorption affinities up to log (KD/[L/kg]) of 7.3 ± 0.1 for MCB and 6.2 ± 0.1 for PFOA, respectively.

Functional colloidal carbon materials find various applications, including the remediation of contaminated water and soil in so-called particle-based in-situ remediation processes. In this study, uniform and highly dispersible micro-sized carbonaceous spheres (CS) were generated by hydrothermal carbonization (HTC) of sucrose in the presence of carboxymethyl cellulose (CMC) as environmentally friendly polyelectrolyte stabilizer. In order to ensure their optimal subsurface delivery and formation of a self-contained treatment zone, a narrow size distribution and low agglomeration tendency of the particles is desired. Therefore, the obtained CS were thoroughly characterized and optimized with respect to their colloidal properties which are a crucial factor for their application as quasi-liquid sorbent. The as-prepared uniform CS are readily dispersible into single particles in water as confirmed by digital microscopy and form stable suspensions. Due to their perfectly spherical shape, particle sedimentation in aqueous suspensions is well predicted by Stokes’ law. High sorption coefficients on the synthesized CS KD,CS were determined for phenanthrene (up to log (KD,CS/[L kg−1]) = 5) and other hydrophobic groundwater contaminants. This confirms the application potential of the CS, which were prepared by an economic low-temperature process using sucrose as bio-based precursor, for generating in-situ sorption barriers for groundwater and soil remediation.