The occurrence of health-relevant contaminants in water has become a severe global problem. For treating heavy-metal-polluted water, the use of zeolite materials has been extended over the last decades, due to their excellent features of high ion exchange capacity and absorbency. The aim of this study was to assess the effect of heavy metal uptake of one purified (PCT) and two non-purified clinoptilolite tuffs (NPCT1 and NPCT2) in aqueous solutions on monovalent ions Ni+, Cd+, Cs+, Ba+, Tl+, and Pb+. Experiments were furthermore carried out in artificial gastric and intestinal fluids to mimic human digestion and compare removal efficiencies of the adsorbent materials as well as release characteristics in synthetic gastric (SGF) and intestinal fluids (SIF). Batch experiments show low sorption capacities for Ni+ and Cd+ for all studied materials; highest affinities were found for Ba+ (99–100%), Pb+ (98–100%), Cs+ (97–98%), and Tl+ (96%), depending on the experimental setup for the PCT. For the adsorption experiments with SGF, highest adsorption was observed for the PCT for Pb+, with an uptake of 99% of the lead content. During artificial digestion, it was proven that the PCT did not release Ba+ cations into solution, whereas 13,574 ng·g−1 and 4839 ng·g−1 of Ba+ were measured in the solutions with NPCT1 and NPCT2, respectively. It was demonstrated that the purified clinoptilolite tuff is most effective in remediating heavy-metal-polluted water, particularly during artificial digestion (99% of Pb+, 95% of Tl+, 93% of Ba+). In addition, it was shown that the released amount of bound heavy metal ions (e.g., barium) from the non-purified clinoptilolite tuffs into the intestinal fluids was significantly higher compared to the purified product.
Iron deficiency-induced chlorosis is a widespread horti-/agricultural problem that can lead to massive crop failures, especially for plants growing on calcareous soils. The most effective agronomical practice to prevent plants from iron deficiency is to apply synthetic Fe-(chelate)-fertilizers to the soil. Because these compounds are usually not biodegradable and, therefore, may become soil contaminants, efficient and environmentally friendly solutions are needed. The present study investigates a novel approach to tackle chlorosis in plants using clinoptilolite-tuff as a carrier substrate for the natural Fe-siderophore ‘coprogen’. The combination of the two substances promises economic and ecological potential to be used as a fertilizer to prevent crop failures triggered by micro-nutritional shortages. Sorption and release experiments were performed in batch and column setups in order to understand the binding characteristics; analyses were carried out using ICP-MS, HPLC, XRD, and SEM, respectively. Results show the highest sorption capacity of coprogen (92.8%) and corresponding Fe (90.2%) on clinoptilolite-tuff at pH 4 within 30 min as well as the efficient release of coprogen at pH 8, mimicking alkaline soil conditions (88% of the sorbed coprogen is released from the tuff). The gained data suggest that coprogen is bound onto the clinoptilolite-tuff through surface-mediated sorption based on electrostatic interactions.
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