1.1 Anorganische Spurenanalytik
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Paper des Monats
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Nine gravimetrically prepared 206Pb/208Pb mixtures spanning R = 0.461 to 9.937 mol mol−1 were measured on eight ICP-MS instruments at PTB and BAM to assess whether the mass bias correction factor remains independent of isotopic composition. The investigated MC-ICP-MS, ICP-SF-MS, ICP-Q-MS, and ICP-QQQ-MS configurations showed no reproducible directional trend in Knorm across the studied mixture series. This supports practical composition independence of K206/208 for these platforms under the tested conditions and is consistent with the validity of conventional K-factor correction and standard-sample bracketing for natural Pb isotope-ratio measurements when sample and calibration material are measured under comparable conditions. Among the investigated platforms, MC-ICP-MS remained the most suitable for high-accuracy GIM-based Pb isotope-ratio metrology because it showed the smallest correction-factor variability. The non-ToF single-collector platforms may be applicable for GIM-type measurements where moderate target uncertainties are acceptable, provided that the relevant isotope-composition interval is experimentally validated and the correction-factor variability is included in the uncertainty budget. In contrast, the investigated ICP-ToF-MS configuration showed a systematic decrease of Knorm,206/208 with increasing R206/208, indicating a signal-distribution-dependent response. Under the conditions of this study, ICP-ToF-MS is therefore not suitable for composition-independent GIM-based isotope-ratio determination with enriched mixtures.
Regulatory testing of cannabis and hemp commonly prioritizes As, Cd, Pb, and Hg, yet inductively coupled plasma mass spectrometry (ICP‐MS) workflows often require extensive tuning and method setup that can be difficult to implement in resource‐limited laboratories. Although general guidance exists, quantitative ranges for critical settings are still sparsely documented for cannabis matrices, and “one‐set” conditions may not transfer well across instruments. To address this gap, we developed a resource‐efficient, low‐run screening strategy intended to reduce trial‐and‐error, reagent consumption, and instrument time when only a limited number of runs is feasible, using two linked 12‐run, resolution‐III Plackett–Burman designs generated in R. First, key ICP‐MS parameters were screened under QC conditions to define a stable operating region. Second, digestion factors (acid composition/volumes, temperature program, sample mass, and predigestion) were assessed using spiked inflorescence samples. Apparent effects were identified using standard screening diagnostics and supported by two‐factor trend visualizations. The screening highlighted three underreported practical contributors—RF power, peristaltic‐pump speed, and operation without inrun dilution—as dominant drivers of robustness, together with element‐dependent recovery drivers: As was mainly governed by HCl level; Cd and Hg by coupled HCl volume × sample mass trends; and Pb by combined heating‐ramp/HNO₃ and temperature/predigestion patterns. Because resolution‐III designs alias main effects with specific two‐factor interactions, the numerical effects should be interpreted as first‐pass screening estimates rather than definitive optima and require higher resolution confirmation. Overall, the study provides a quantitative map of factor relevance for cannabis metal digestion and narrows the experimental space for subsequent optimization and validation.
Multiple sclerosis is an autoimmune-mediated neurodegenerative disease of the central nervous system and is characterized by physical disability, cognitive impairment, and other symptoms. Gadolinium-enhanced magnetic resonance imaging is the most common tool for diagnosing multiple sclerosis and monitoring treatment. Numerous studies in recent years suggest that linear gadolinium-based contrast agents (GBCAs) in particular accumulate in various body tissues, including the brain. In our study, we investigated whether neuroinflammation promotes Gd deposition in the brain after repeated administration of linear and macrocyclic GBCAs. For this purpose, the experimental autoimmune encephalomyelitis (EAE) mouse model frequently used for studies on multiple sclerosis was employed. Healthy control mice (HC) and EAE mice were injected with GBCAs at different time points. On day 1, 10 or 40 after the last GBCA administration, the mice were sacrificed and cryosections were prepared from different brain regions. A laser ablation system coupled to an inductively coupled plasma time-of-flight mass spectrometer (LA-ICP-ToF-MS) was used for elemental mapping. Gd was detected in both HC and EAE mice, however EAE brains showed significantly higher Gd levels compared to HC. Inflammation thus promotes long-term retention after GBCA administration.
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Approximately 13% of the waste generated in Germany (2023) is processed in municipal solid waste incinerators (MSWI). MSWI in Europe operate under strict regulatory requirements defined by the Industrial Emissions Directive (IED), resulting in very low overall emissions, including PCDD/F. A more recent and widely discussed group of pollutants are per‐ and polyfluoroalkyl substances (PFAS), which are thermally degraded to hydrogen fluoride (HF), carbon dioxide (CO 2 ) and other thermodynamic end point compounds depending on elemental composition under complete combustion conditions. This study investigates the completeness of PFAS degradation in laboratory‐ and pilot‐scale incinerators. The conversion of PFAS to HF is assessed using several analytical techniques for detecting fluorine‐containing species in flue gas, liquids and solids, and their impact on establishing a consistent fluorine balance (F‐balance). Depending on the analytical method employed, the achieved F‐balance ranges from 59 to 100 wt% when ‘products of incomplete combustion’ (PICs) are not considered.
Algae from the Viridiplantae lineage grow on glaciers and semi-permanent snow patches globally. These algal taxa have adapted to extreme environmental conditions, such as freezing temperatures, high light, and oligotrophic nutrient availability. However, how cryosphere algae balance their cellular nutrients to deal with these conditions is not fully known. To address this knowledge gap, we used single-cell inductively coupled plasma-mass spectrometry to quantify the single-cell ionomes (Phosphorus, Magnesium, Calcium, Copper, Iron, Manganese, and Zinc) of cryosphere chlorophyte algae, Microglena sp ., Raphidonema sempervirens , and Deuterostichococcus sp ., and compared them to mesophile chlorophyte algae, Acutodesmus obliquus and Chlamydomonas reinhardtii . We validated our results through mass spectrometric analyses of digested cultures. When corrected to average cell biovolume, cryosphere algae had lower Phosphorus, Magnesium, and Calcium, consistent with slow cellular metabolism adapted to cold life. Under Phosphorus-starvation, Raphidonema showed no impact of extracellular Phosphorus loss on its single-cell ionome, however, Microglena had a correlative loss of Phosphorus and Magnesium, and an increase in Copper, indicating Phosphorus mobilisation via polyphosphate hydrolysis. Our results provide a comprehensive insight into the single-cell ionomes of ryosphere and mesophile hlorophyte algae and reveal insights into nutrient homeostasis in algal cells adapted to the cryosphere.
Elastomers commonly used as sealing materials are highly networked rubbery polymers. They may contain different pollutants such as fluorinated compounds like per- and polyfluoroalkyl substances (PFAS), for example used as additives to enhance the performance of the elastomer under a variety of chemical and mechanical stresses. As of now, no reliable recycling strategy for elastomers is available and they are consequentially disposed of by incineration or in landfills. Due to the potential wash out of additives or other pollutants into landfill leachates, elastomers present a possible source of continuous environmental pollution. A processing protocol for elastomers is required as a basis to enable the reliable determination of extractable fluorine: Here, we describe a quick and robust sample preparation protocol to determine extractable fluorine in various sealing materials. The optimization was aimed for time efficiency and robustness of results; sample preparation was conducted for fluorine sum parameter analysis via high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). Samples were first roughly shredded to 2 mm and then further milled and sieved to defined particle size fractions. Different size fractions were tested and the extraction of the size fraction between 125 and 250 µm was found to be the best trade-off between extraction efficiency, time efficiency and sample loss. Subsequent methanolic or aqueous extraction and HR-CS-GFMAS analysis of various polymer samples revealed quantifiable extractable fluorine content for most samples. In the future, the sample processing method developed could make a valuable contribution as a standard operating procedure (SOP) for a time-efficient sample preparation for subsequent extraction and screening of sealing materials in prospect of the strict regulation on PFAS proposed by the European Chemicals Agency (ECHA).
The banded iron formation (BIF) of the Saksaganska Formation within the Kryvyi Rih belt in Ukraine hosts one of the largest Fe ore resources in Europe. The multistage genesis of Fe ores involves gas-bearing fluids of complex and unresolved origins. This study aims to identify sources of these gases and their generation mechanisms within evolving fluid systems, which were responsible for Fe ore formation, upgrading, and alteration, as this is crucial for refining ore genetic models. Trace element geochemistry and stable C-N isotopes of fluid inclusion gases are used to determine multiple generations of iron oxides and associated gangue minerals, reflecting mineral transformations that fostered the development of large-scale gas-bearing fluid systems during high-temperature metamorphic and metasomatic-hydrothermal reactions. The C-N isotope compositions of quartz-hosted fluid inclusion gases from various sites within the Kryvyi Rih belt record high carbon fluxes and progressive evolution of CO2( ± N2-CH4)-bearing fluid systems during the late Paleoproterozoic. The dynamic large-scale fluid migration encompassing multiple fluid flow pulses played a pivotal role in the upgrading of Fe quartzites into high-grade hypogene Fe ores of the Saksagansk type. The δ13C(CO2) and δ15N values of fluid inclusion gases hosted in quartz within schists, ferruginous horizons, and shear zones suggest different carbon sources, including graphite-rich schists, metamorphic decarbonation reactions, devolatilization of greenstone belt sequences, metasomatic-hydrothermal decomposition of Fe carbonates, and igneous sources. Unique trace element compositions observed in specular hematite and magnetite indicate selective alteration by Nb-Ta-rare earth element + Y (REY)-bearing hydrothermal fluids likely originating from a deep alkaline magmatic source.
Tropical rainforests have often been considered marginal environments for Pleistocene hunter-gatherers, yet archaeological research in Sri Lanka demonstrates long-term occupation of these habitats from ~48,000 years ago (ka). Material evidence indicates specialized hunting of arboreal mammals, as well as the use of plant resources, but plant consumption is often difficult to detect because organic remains preserve poorly in rainforest settings. Here we present zinc isotope data (δ66Zn) from Late Pleistocene to Late Holocene human (n = 24) and faunal tooth (n = 57) enamel, spanning ~20–3 ka of rainforest occupation in Sri Lanka. Our results show that humans consistently occupied an intermediate trophic position, indicating mixed diets of animal and plant foods. Over time, human δ66Zn values shift towards those typical of herbivores, suggesting an increasing reliance on plant resources. This pattern predates the regional introduction of crop agriculture and indicates that rainforest foragers were intensifying plant use long before farming emerged.
Elastomers commonly used as sealing materials are highly networked rubbery polymers. They are often produced using per- and polyfluoroalkyl substances (PFAS) either during manufacturing or as additives to enhance their performance during applications in harsh environments. Due to the lack of reliable recycling strategies without compromising the resulting polymer-quality, sealing materials are often disposed of in landfills. Thus, they represent a possible source of continuous PFAS contamination of both the immediate environment and surrounding ground water reservoirs through landfill leachates. To assess the scope of fluorine content, we developed a potential Standard Operating Protocol (SOP) to allow for subsequent fluorine/PFAS determination in various blends of sealing materials. Optimizations were aimed for time efficiency and robustness of results. The SOP entails a shredding sequence from roughly cutting to sieving. Optimal results were obtained for the fraction size between 125 250 µm. Extractions performed with either acidified methanol or ultra-pure water proved reproducibility of results and revealed high extractable fluorine concentrations for most sealing materials investigated. The high fluorine concentrations extracted by water further puts emphasis on the risks associated with leaching from microplastics generated by material abrasion during their lifetime and within landfills. The SOP can easily be expedited by implementation of additional sample preparation steps such as Solid Phase Extraction to explicitly measure extractable organofluorides. In prospect of the broad ban of PFAS proposed by the European Chemical Agency (ECHA), it will be imperative to reliably screen products for fluorine and PFAS and scan for future compliance. Regarding the derogations discussed for certain applications such as NafionTM in Proton Exchange Membranes and sealants in industrial sites, the SOP will allow for the fast screening of fluorine leaching to help advance the development of materials safe and sustainable by design.