Lenz, Markus

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Lenz
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Markus
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Lenz, Markus

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  • Vorschaubild
    Publikation
    From trace to pure. Pilot-scale scandium recovery from TiO2 acid waste
    (American Chemical Society, 06.04.2023) Hedwig, Sebastian; Yagmurlu, Bengi; Peters, Edward Michael; Misev, Victor; Hengevoss, Dirk; Dittrich, Carsten; Forsberg, Kerstin; Constable, Edwin C.; Lenz, Markus [in: ACS Sustainable Chemistry & Engineering]
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild nicht verfügbar
    Publikation
    Organic solvent free PbI2 recycling from perovskite solar cells using hot water
    (Elsevier, 05.04.2023) Schmidt, Felix; Amrein, Meret; Hedwig, Sebastian; Kober-Czerny, Manuel; Paracchino, Adriana; Holappa, Ville; Suhonen, Riikka; Schäffer, Andreas; Constable, Edwin C.; Snaith, Henry J.; Lenz, Markus [in: Journal of Hazardous Materials]
    Perovskite solar cells represent an emerging and highly promising renewable energy technology. However, the most efficient perovskite solar cells critically depend on the use of lead. This represents a possible environmental concern potentially limiting the technologies’ commercialization. Here, we demonstrate a facile recycling process for PbI2, the most common lead-based precursor in perovskite absorber material. The process uses only hot water to effectively extract lead from synthetic precursor mixes, plastic- and glass-based perovskites (92.6 – 100% efficiency after two extractions). When the hot extractant is cooled, crystalline PbI2 in high purity (> 95.9%) precipitated with a high yield: from glass-based perovskites, the first cycle of extraction / precipitation was sufficient to recover 94.4 ± 5.6% of Pb, whereas a second cycle yielded another 10.0 ± 5.2% Pb, making the recovery quantitative. The solid extraction residue remaining is consequently deprived of metals and may thus be disposed as non-hazardous waste. Therefore, exploiting the highly temperature-dependent solubility of PbI2 in water provides a straightforward, easy to implement way to efficiently extract lead from PSC at the end-of-life and deposit the extraction residues in a cost-effective manner, mitigating the potential risk of lead leaching at the perovskites’ end-of-life.
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Ecotoxicity attenuation by acid-resistant nanofiltration in scandium recovery from TiO2 production waste
    (Elsevier, 2023) Fekete-Kertész, Ildikó; Stirling, Tamás; Vaszita, Emese; Berkl, Zsófia; Farkas, Éva; Hedwig, Sebastian; Remmen, Kirsten; Lenz, Markus; Molnár, Mónika; Feigl, Viktória [in: Heliyon]
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Environmental selenium volatilization is possibly conferred by promiscuous reactions of the sulfur metabolism
    (Elsevier, 2023) Liu, Ying; Schäffer, Andreas; Martinez, Mathieu; Lenz, Markus [in: Chemosphere]
    Selenium deficiency affects many million people worldwide and volatilization of biogenically methylated selenium species to the atmosphere may limit Se entering the food chain. However, there is very little systematic data on volatilization at nanomolar concentrations prevalent in pristine natural environments. Pseudomonas tolaasii cultures efficiently methylated Se at these concentrations. Nearly perfect linear correlations between the spiked Se concentrations and Dimethylselenide, Dimethyldiselenide, Dimethylselenylsulfide and 2-hydroxy-3-(methylselanyl)propanoic acid were observed up to 80 nM. The efficiency of methylation increased linearly with increasing initial Se concentration, arguing that the enzymes involved are not constitutive, but methylation proceeds promiscuously via pathways of S methylation. From the ratio of all methylated Se and S species, one can conclude that between 0.30% and 3.48% of atoms were Se promiscuously methylated at such low concentrations. At concentrations higher than 640 nM (∼50 μg/L) a steep increase in methylation and volatilization was observed, which suggested the induction of specific enzymes. Promiscuous methylation at low environmental concentrations calls into question that view that methylated Se in the atmosphere is a result of a purposeful Se metabolism serving detoxification. Rather, the concentrations of methylated Se in the atmosphere may be “coincidental” i.e., determined by the activity of S cycling microorganisms. Further, a steep increase in methylation efficiency when surpassing a certain threshold concentration (here ∼50 μg/L) calls into question that natural methylation can be estimated from high Se spikes in laboratory systems, yet highlights the possibility of using bacterial methylation as an effective remediation strategy for media higher concentrated in Se. © 2023 The Authors
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Rapid sequestration of perovskite solar cell-derived lead in soil
    (Elsevier, 08/2022) Schmidt, Felix; Ledermann, Luca; Schäffer, Andreas; Snaith, Henry J.; Lenz, Markus [in: Journal of Hazardous Materials]
    Efficient and stable perovskite solar cells rely on the use of Pb species potentially challenging the technologies’ commercialisation. In this study, the fate of Pb derived from two common perovskite precursors is compared to cationic lead in soil-water microcosm experiments under various biogeochemical conditions. The rapid and efficient removal of Pb from the aqueous phase is demonstrated by inductively coupled plasma mass spectrometry. Sequential soil extraction results reveal that a substantial amount of Pb is associated with immobile fractions, whereas a minor proportion of Pb may become available again in the long term, when oxygen is depleted (e.g. during water logging). X-ray absorption spectroscopy results reveal that the sorption of Pb on mineral phases represents the most likely sequestration mechanism. The obtained results suggest that the availability of leached Pb from perovskite solar cells is naturally limited in soils and that its adverse effects on soil biota are possibly negligible in oxic soils. All three Pb sources used behaved very similar in the experiments, wherefore we conclude that perovskite derived Pb will have a similar fate compared to cationic Pb, so that established risk assessment considerations for Pb remain legitimate.
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Nanofiltration-enhanced solvent extraction of scandium from TiO acid waste
    (American Chemical Society, 27.04.2022) Yagmurlu, Bengi; Huang, Danyu; von Arx, Oliver; Dittrich, Carsten; Constable, Edwin; Friedrich, Bernd; Hedwig, Sebastian; Lenz, Markus [in: ACS Sustainable Chemistry & Engineering]
    Scandium is a critical raw material with a technological potential to reduce transportation costs and CO2 emissions. However, global supply and market adoption are crucially impaired by the lack of high-grade Sc ores and recovery strategies. A tandem nanofiltration solvent extraction route is demonstrated to enable effective Sc recovery from real-world acid waste from the chloride TiO2 production route. The process involving several filtration stages, solvent extraction, and precipitation was optimized, ultimately producing >97% pure (NH4)3ScF6.
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Magnesium sensing via LFA-1 regulates CD8+ T cell effector function
    (Cell Press, 2022) Lötscher, Jonas; Martí i Líndez, Adrià-Arnau; Kirchhammer, Nicole; Cribioli, Elisabetta; Giordano Attianese, Greta Maria Paola; Trefny, Marcel P.; Rothschild, Sacha I.; Strati, Paolo; Künzli, Marco; Lotter, Claudia; Schenk, Susanne H.; Dehio, Philippe; Löliger, Jordan; Litzler, Ludivine; Schreiner, David; Koch, Victoria; Page, Nicolas; Lee, Dahye; Grählert, Jasmin; Kuzmin, Dmitry; Burgener, Anne-Valérie; Merkler, Doron; Pless, Miklos; Balmer, Maria L.; Reith, Walter; Huwyler, Jörg; Irving, Melita; King, Carolyn G.; Zippelius, Alfred; Hess, Christoph; Lenz, Markus [in: Cell]
    The relevance of extracellular magnesium in cellular immunity remains largely unknown. Here, we show that the co-stimulatory cell-surface molecule LFA-1 requires magnesium to adopt its active conformation on CD8+ T cells, thereby augmenting calcium flux, signal transduction, metabolic reprogramming, immune synapse formation, and, as a consequence, specific cytotoxicity. Accordingly, magnesium-sufficiency sensed via LFA-1 translated to the superior performance of pathogen- and tumor-specific T cells, enhanced effectiveness of bi-specific T cell engaging antibodies, and improved CAR T cell function. Clinically, low serum magnesium levels were associated with more rapid disease progression and shorter overall survival in CAR T cell and immune checkpoint antibody-treated patients. LFA-1 thus directly incorporates information on the composition of the microenvironment as a determinant of outside-in signaling activity. These findings conceptually link co-stimulation and nutrient sensing and point to the magnesium-LFA-1 axis as a therapeutically amenable biologic system.
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Recovery of scandium from acidic waste solutions by means of polymer inclusion membranes
    (Elsevier, 2022) Hedwig, Sebastian; Kraus, Manuel; Amrein, Meret; Stiehm, Johannes; Constable, Edwin C.; Lenz, Markus [in: Hydrometallurgy]
    Scandium is a raw material with properties that promise considerable potential for application in alloys to enable aviation fuel savings and as dopants for use in sustainable energy production using solid oxide fuel cells. Despite these attractive properties, scandium is rarely used due to its scarcity and unreliable supply. Therefore, new strategies for scandium recovery are of economic priority. In this study, polymer inclusion membranes (PIMs) consisting of PVDF-HFP, 2-NPOE and DEHPA, were optimised for selective scandium separation from real TiO2 production waste. With the optimised system, >60% of the scandium was recovered with high selectivity, resulting in scandium mole fraction at more than two orders of magnitude higher in the receiving phase than in the original waste. This suggests PIMs may be an effective way to recover scandium from bulk waste, thus easing the scarcity and insecurity that currently limit its bulk application.
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Sulfur amino acid status controls selenium methylation in pseudomonas tolaasii. Identification of a novel metabolite from promiscuous enzyme reactions
    (American Society for Microbiology, 26.05.2021) Liu, Ying; Hedwig, Sebastian; Schäffer, Andreas; Lenz, Markus; Martinez, Mathieu [in: Applied and Environmental Microbiology]
    Selenium (Se) deficiency affects many millions of people worldwide, and the volatilization of methylated Se species to the atmosphere may prevent Se from entering the food chain. Despite the extent of Se deficiency, little is known about fluxes in volatile Se species and their temporal and spatial variation in the environment, giving rise to uncertainty in atmospheric transport models. To systematically determine fluxes, one can rely on laboratory microcosm experiments to quantify Se volatilization in different conditions. Here, it is demonstrated that the sulfur (S) status of bacteria crucially determines the amount of Se volatilized. Solid-phase microextraction gas chromatography mass spectrometry showed that Pseudomonas tolaasii efficiently and rapidly (92% in 18 h) volatilized Se to dimethyl diselenide and dimethyl selenyl sulfide through promiscuous enzymatic reactions with the S metabolism. However, when the cells were supplemented with cystine (but not methionine), a major proportion of the Se (∼48%) was channeled to thus-far-unknown, nonvolatile Se compounds at the expense of the previously formed dimethyl diselenide and dimethyl selenyl sulfide (accounting for <4% of total Se). Ion chromatography and solid-phase extraction were used to isolate unknowns, and electrospray ionization ion trap mass spectrometry, electrospray ionization quadrupole time-of-flight mass spectrometry, and microprobe nuclear magnetic resonance spectrometry were used to identify the major unknown as a novel Se metabolite, 2-hydroxy-3-(methylselanyl)propanoic acid. Environmental S concentrations often exceed Se concentrations by orders of magnitude. This suggests that in fact S status may be a major control of selenium fluxes to the atmosphere. IMPORTANCE Volatilization from soil to the atmosphere is a major driver for Se deficiency. “Bottom-up” models for atmospheric Se transport are based on laboratory experiments quantifying volatile Se compounds. The high Se and low S concentrations in such studies poorly represent the environment. Here, we show that S amino acid status has in fact a decisive effect on the production of volatile Se species in Pseudomonas tolaasii. When the strain was supplemented with S amino acids, a major proportion of the Se was channeled to thus-far-unknown, nonvolatile Se compounds at the expense of volatile compounds. This hierarchical control of the microbial S amino acid status on Se cycling has been thus far neglected. Understanding these interactions—if they occur in the environment—will help to improve atmospheric Se models and thus predict drivers of Se deficiency.
    01A - Beitrag in wissenschaftlicher Zeitschrift
  • Vorschaubild
    Publikation
    Analysis of bioavailability and induction of glutathione peroxidase by dietary nanoelemental, organic and inorganic selenium
    (MDPI, 15.03.2021) Lenz, Markus; Ringuet, Mitchell; Hunne, Billie; Bravo, David; Furness, John [in: Nutrients]
    Dietary organic selenium (Se) is commonly utilized to increase formation of selenoproteins, including the major antioxidant protein, glutathione peroxidase (GPx). Inorganic Se salts, such as sodium selenite, are also incorporated into selenoproteins, and there is evidence that nanoelemental Se added to the diet may also be effective. We conducted two trials, the first investigated inorganic Se (selenite), organic Se (L-selenomethionine) and nanoelemental Se, in conventional mice. Their bioavailability and effectiveness to increase GPx activity were examined. The second trial focused on determining the mechanism by which dietary Se is incorporated into tissue, utilising both conventional and germ-free (GF) mice. Mice were fed a diet with minimal Se, 0.018 parts per million (ppm), and diets with Se supplementation, to achieve 0.07, 0.15, 0.3 and 1.7 ppm Se, for 5 weeks (first trial). Mass spectrometry, Western blotting and enzymatic assays were used to investigate bioavailability, protein levels and GPx activity in fresh frozen tissue (liver, ileum, plasma, muscle and feces) from the Se fed animals. Inorganic, organic and nanoelemental Se were all effectively incorporated into tissues. The high Se diet (1.7 ppm) resulted in the highest Se levels in all tissues and plasma, independent of the Se source. Interestingly, despite being ~11 to ~25 times less concentrated than the high Se, the lower Se diets (0.07; 0.15) resulted in comparably high Se levels in liver, ileum and plasma for all Se sources. GPx protein levels and enzyme activity were significantly increased by each diet, relative to control. We hypothesised that bacteria may be a vector for the conversion of nanoelemental Se, perhaps in exchange for S in sulphate metabolising bacteria. We therefore investigated Se incorporation from low sulphate diets and in GF mice. All forms of selenium were bioavailable and similarly significantly increased the antioxidant capability of GPx in the intestine and liver of GF mice and mice with sulphate free diets. Se from nanoelemental Se resulted in similar tissue levels to inorganic and organic sources in germ free mice. Thus, endogenous mechanisms, not dependent on bacteria, reduce nanoelemental Se to the metabolite selenide that is then converted to selenophosphate, synthesised to selenocysteine, and incorporated into selenoproteins. In particular, the similar efficacy of nanoelemental Se in comparison to organic Se in both trials is important in the view of the currently limited cheap sources of Se.
    01A - Beitrag in wissenschaftlicher Zeitschrift