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Soil certified reference material (CRM), UME EnvCRM 03 was produced by a collaborative approach among national metrology institutes, designated institutes and university research laboratories within the scope of the EMPIR project: Matrix Reference Materials for Environmental Analysis. This paper presents the sampling and processing methodology, homogeneity, stability, characterization campaign, the assignment of property values and their associated uncertainties in compliance with ISO 17034:2016. The material processing methodology involves blending a natural soil sample with a contaminated soil sample obtained by spiking elemental solutions for 8 elements (Cd, Co, Cu, Hg, Ni, Pb, Sb and Zn) to reach the level of warning risk monitoring values specified for metals and metalloids of soils in Europe. Comparative homogeneity and stability test data were obtained by two different institutes, ensuring the reliability and back up of the data. The certified values and associated expanded uncertainties for the total mass fractions of thirteen elements (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V and Zn) are established. The developed CRM can be used for the development and validation of measurement procedures for the determination of the total mass fractions of elements in soil and also for quality control/assurance purposes. The developed CRM is the first example of a soil material originating from Türkiye.
In this study, we demonstrate the applicability of nitrogen microwave inductively coupled atmospheric pressure mass spectrometry (MICAP-MS) for Ca, Fe, and Se quantification in human serum using isotope dilution (ID) analysis. The matrix tolerance of MICAP-MS in Na matrix was investigated, uncovering that high Na levels can suppress the signal intensity. This suppression is likely due to the plasma loading and the space charge effect. Moreover, 40Ca and 44Ca isotopic fractionation was noted at elevated Na concentration. Nine certified serum samples were analyzed using both external calibration and ID analysis. Overestimation of Cr, Zn, As, and Se was found in the results of external calibration, which might be resulted from C-induced polyatomic interference and signal enhancement, respectively. Further investigations performed with methanol showed a similar enhancement effect for Zn, As, and Se, potentially supporting this assumption. The mass concentrations determined with ID analysis show metrological compatibility with the reference values, indicating that MICAP-MS combined with ID analysis can be a promising method for precise Ca, Fe, and Se determination. Moreover, this combination reduces the influences of matrix effects, broadening the applicability of MICAP-MS for samples with complex matrix.
Capillary electrophoresis (CE) is a powerful and sensitive tool for speciation analysis when combined with inductively coupled plasma mass spectrometry (ICP-MS); however, the performance of this technique can be limited by the nature of pneumatic nebulizers. This study compares two commercially available pneumatic nebulizers to a newly introduced vibrating capillary nebulizer (VCN) for on-line coupling of CE with ICP-MS. The VCN is a low-cost, non-pneumatic nebulizer that is based on the design of capillary vibrating sharp-edge spray ionization. As a piezoelectrically driven nebulization source, the VCN creates an aerosol independent of gas flows and does not produce a low-pressure region at the nebulizer orifice.
To compare the systems, we performed replicate analyses of sulfate in river water with each nebulizer and the same CE and ICP-MS instruments and determined the figures of merit of each setup. With the CE-VCN-ICP-MS setup, we achieved around 2–4 times lower sensitivity compared to the commercial setups. However, the VCN-based setup provided lower noise levels and better linear correlation from the analysis of calibration standards, which resulted in indistinguishable LOD and LOQ values from the in-house-built VCN-based and commercial setups for CE-ICP-MS analysis. The VCN is found to have the highest baseline stability with a standard deviation of 3500 cts s−1, corresponding to an RSD of 2.7%. High reproducibility is found with the VCN with a peak area RSD of 4.1% between 3 replicate measurements.
We report an analytical methodology for the quantification of sulfur in biological molecules via a speciesunspecific postcolumn isotope dilution (online ID) approach using capillary electrophoresis (CE) coupled online with inductively coupled plasma−mass spectrometry (online ID CE/ICP−MS).
The method was optimized using a mixture of standard compounds including sulfate, methionine, cysteine, cystine, and albumin, yielding compound recoveries between 98 and 105%. The quantity of sulfur is further converted to the quantity of the compounds owing to the prior knowledge of the sulfur content in the molecules. The limit of detection and limit of quantification of sulfur in the compounds were 1.3−2.6 and 4.1−8.4 mg L−1, respectively, with a correlation coefficient of 0.99 within the concentration range of sulfur of 5−100 mg L−1. The capability of the method was extended to quantify albumin in its native matrix (i.e., in serum) using experimentally prepared serum spiked with a pure albumin standard for validation. The relative expanded uncertainty of the method for the quantification of albumin was 6.7% (k = 2). Finally, we tested the applicability of the method on real samples by the analysis of albumin in bovine and human sera. For automated data assessment, a software application (IsoCor) which was developed by us in a previous work was developed further for handling of online ID data. The method has several improvements compared to previously published setups: (i) reduced adsorption of proteins onto the capillary wall owing to a special capillary-coating procedure, (ii) baseline separation of the compounds in less than 30 min via CE, (iii) quantification of several sulfur species within one run by means of the online setup, (iv) SI traceability of the quantification results through online ID, and (v) facilitated data processing of the transient signals using the IsoCor application. Our method can be used as an accurate approach for quantification of proteins and other biological molecules via sulfur analysis in complex matrices for various fields, such as environmental, biological, and pharmaceutical studies as well as clinical diagnosis.
Sulfur is an essential element in living organisms, where it plays important roles in various biological processes, such as protein synthesis, enzyme activity, and antioxidant defense. However, the biological effects of different sulfur species can vary widely, and imbalances in sulfur speciation have been observed in a range of diseases, including cancer, Alzheimer’s disease, and diabetes.1−3 The accurate quantification of sulfur and its species in biological samples requires sensitive and selective analytical techniques. In recent years, separation techniques coupled online with inductively coupled plasma−mass spectrometry (ICP−MS) have emerged as powerful online analytical tools complementary to molecular spectrometric methods for speciation analysis of biological compounds.
External calibration4−9 and isotope dilution (ID)10−15 are common calibration approaches applied for online quantification of sulfur species in complex samples. The ID analysis is advantageous over.
Trace element (TE) analysis of pyrite via LA-ICP-MS can be used to reconstruct the conditions of pyrite formation in complex mineral systems. The Carpentaria province in northern Australia is host to some of the world’s highest value Zn-Pb (+Ag, Cu) deposits. The genesis of many of these deposits is controversial, with competing models of single-vs. multi-stage ore formation. In this study, LA-ICP-MS data of paragenetically constrained pyrite from the George Fisher Zn-Pb-Ag deposit has been analysed to investigate the chemistry of different stages of ore formation. Pyrite from correlative unmineralized host rocks has also been analysed to investigate evidence of distal hydrothermal anomalism. All LA-ICP-MS data have been statistically evaluated (principal component analysis) and interpreted together with whole rock lithogeochemical data of the same samples. Pre-ore diagenetic pyrite is compositionally similar to other Proterozoic diagenetic pyrite, with some evidence of minor hydrothermal anomalism that with further analysis could help define distal alteration. Pyrite from the different ore stages are compositionally distinct, consistent with a multi-stage system. Ore stage 1 pyrite exceeds background contents of Co, Cu, Zn, As, Ag, Sb, Tl, and Pb and has elevated Co/Ni ratios, whereas only Ni and Co are above background abundances in ore stage 2 and 3 pyrite, of which only ore stage 3 pyrite has high Co/Ni ratios. Ore stage 1 pyrite has a similar composition to hydrothermal pyrite in the undeformed northern Carpentaria CD-type deposits and was likely syn-diagenesis. Ore stage 2 was syn-deformation, and resulted in replacement and recrystallization of pre-existing pyrite, and the expulsion of incompatible TEs. Ore stage 3 formed via a later Cu-Zn-Pb mineralizing event that resulted in a new geochemically distinct generation of Co-rich pyrite. Overall, this study demonstrates the value of paragenetically-constrained pyrite TE data for refining genetic models in complex sediment hosted mineral systems.
AbstractThe minor and trace element composition of minerals provides critical insights into a variety of geological processes. Multi-element mapping by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is an important technique applied for this purpose and although the method is rapidly advancing, there remains a fundamental compromise between spatial resolution, detection limit, and experiment duration when using sequential mass analyzers. To address the limitation of limited analyte selection for high spatial resolution maps imposed by the sequential nature of typical quadrupole (Q)-ICP-MS, we tested the Aerosol Rapid Introduction System (ARIS) for repeat mapping of the same area. The ARIS is a high-speed transfer tubing system that reduces aerosol washout times, permitting resolution of individual pulses at 40–60 Hz. Here, the ARIS was tested not for pulse resolution but with novel operating conditions optimized to perform fast, high spatial resolution mapping of minor and trace element distribution in pyrite and marcasite. For this purpose, ablation was conducted with a 5 µm beam aperture, a repetition rate of 50 Hz, and a continuous stage scan speed of 40 µm s−1. For each LA-Q-ICP-MS map, data were acquired for six elements with an acquisition time of 20 ms per element. This deliberately reduced the individual pulse resolution of the ARIS but instead exploited the spatial resolution and sensitivity gains afforded by the high-laser repetition rate combined with efficient aerosol transfer. The new method successfully mapped trace elements at single to double-digit parts per million levels, and the maps reveal fine-scale zoning of trace elements with an effective x and y resolution of 5 µm, while white light interferometry showed that for each experiment, only ca. 1 µm of the sample was removed. Repeated mapping of the same area showed excellent correspondence not only between element concentrations in successive experiments but also in the shape, dimension, and location of regions of interest defined by concentration criteria. The very good repeatability of the elemental maps indicates that for studies requiring more analytes, successive mapping of additional elements is possible. By contrast with conventional very small spot (i.e., 5 µm) analysis, fast repetition rate and stage scan speed mapping avoids down-hole fractionation effects and minimizes accidental analysis of buried invisible inclusions. Compared to conventional LA-ICP-MS mapping, the method reduces the experiment time by 4–8 times.
Molten sulfur is found in various subaerial volcanoes. However, limited records of the pools and flows of molten sulfur have been reported: therefore, questions remain regarding the physicochemical processes behind this phenomenon. A suite of new sulfur flows, some of which active, was identified at the Lastarria volcano (northern Chile) and studied using satellite imagery, in situ probing, and temperature and video recording. This finding provides a unique opportunity to better understand the emplacement mechanisms and mineral and chemical compositions of molten sulfur, in addition to gaining insight into its origin. Molten sulfur presented temperatures of 124–158°C, with the most prolonged sulfur flow reaching 12 m from the source. Photogrammetric tools permitted the identification of levees and channel structures, with an estimated average flow speed of 0.069 m/s. Field measurements yielded a total volume of 1.45 ± 0.29 m3 of sulfur (equivalent to ∼2.07 tons) mobilized during the January 2019 event for at least 408 min. Solidified sulfur was composed of native sulfur with minor galena and arsenic- and iodine-bearing minerals. Trace element analysis indicated substantial enrichment of Bi, Sb, Sn, Cd, as well as a very high concentration of As (>40.000 ppm). The January 2019 molten sulfur manifestations in Lastarria appear to be more enriched in As compared to the worldwide known volcanoes with molten sulfur records, such as the Shiretoko-Iozan and Poás volcanoes. Furthermore, their rheological properties suggest that the “time of activity” in events such as this could be underestimated as flows in Lastarria have moved significantly slower than previously thought. The origin of molten sulfur is ascribed to the favorable S-rich chemistry of fumarolic gases and changes in host rock permeability (fracture opening). Molten sulfur in Lastarria correlates with a peak in activity characterized by high emissions of SO2 and other acid species, such as HF and HCl, in addition to ground deformation. Consequently, molten sulfur was framed within a period of volcanic unrest in Lastarria, triggered by changes in the magmatic-hydrothermal system. The appearance of molten sulfur is related to physicochemical perturbations inside the volcanic system and is perhaps a precursor of eruptive activity, as observed in the Poás and Turrialba volcanoes.
AbstractIn this study, we present a screening method based on molecular absorption spectrometry to study PFAS uptake and fate in plants. To evaluate the suitability of this method we analyzed plant extracts with molecular absorption spectrometry (MAS) as well as liquid chromatography–tandem mass spectrometry (LC–MS/MS) for mass balance studies (w(F)). French bean plants (Phaseolus vulgaris) were grown on soil spiked using eight PFAS substances that vary in chain length and functional group composition. Specifically, these include three short-chained (C4–C5), five long-chained (C7–C10) carboxylic acids, one sulfonic acid and one sulfonic amide moieties. To investigate substance-specific PFAS uptake systematically, PFAS were spiked as single substance spike. Additionally, we studied one mixture of the investigated substances in equal proportions regarding w(F) and four PFAS mixtures of unknown composition. After 6 weeks, the plants were separated into four compartments. We analyzed the four compartments as well as the soil for extractable organically bound fluorine (EOF) by high resolution-continuum source-graphite furnace-molecular absorption spectrometry (HR-CS-GFMAS) as well as for sum of ten target-PFAS by LC–MS/MS. All three short-chained PFAS perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS) and perfluoropentanoic acid (PFPeA) were determined in high concentrations mainly in the fruits of the investigated plants while long-chained PFAS perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA) were mainly determined in roots. PFBS was determined in remarkably high concentrations in leaves compartment by both quantification methods. Overall, comprehensive results of single substance spikes were in good agreement for both methods except for a few cases. Hence, two phenomena were identified: for mixed PFAS spikes of unknown composition huge differences between EOF and sum of target PFAS were observed with systematically higher EOF values. Overall, both methods indicate comparable results with MS being more reliable for known PFAS contamination and MAS being more valuable to identify PFAS exposure of unknown composition.
Graphical Abstract
Solid wastewater-based fertilizers were screened for per- and polyfluoroalkyl substances (PFAS) by the extractable organic fluorine (EOF) sum parameter method. The EOF values for ten sewage sludges from Germany and Switzerland range from 154 to 7209 mg kg−1. For thermal treated sewage sludge and struvite the EOF were lower with values up to 121 mg kg−1. Moreover, the application of PFAS targeted
and suspect screening analysis of selected sewage sludge samples showed that only a small part of the EOF sum parameter values can be explained by the usually screened legacy PFAS. The hitherto unknown part of EOF sum parameter contains also fluorinated pesticides, pharmaceutical and aromatic compounds. Because these partly fluorinated compounds can degrade to (ultra-)short PFAS in wastewater treatment plants they should be considered as significant sources of organic fluorine in the environment. The combined results of sum parameter analysis and suspect screening reveal the need to update current regulations, such as the German fertilizer ordinance, to focus not solely on a few selected PFAS such as perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) but
consider an additional sum parameter approach as a more holistic alternative. Moreover, diffusion gradient in thin-films (DGT) passive samplers were utilized as an alternative simplified extraction method for PFAS in solid wastewater-based fertilizers and subsequently quantified via combustion ion chromatography. However, the DGT method was less sensitive and only comparable to the EOF values
of the fertilizers in samples with >150 mg kg−1, because of different diffusion properties for various PFAS, but also kinetic exchange limitations.
The performance of second generation ICP-TOFMS, equipped with a micro-channel plate (MCP) enabling multi-isotope detection, in terms of isotope ratio precision and instrumental isotopic fractionation (IIF) for (multi-)isotope ratio analysis was thoroughly assessed for B, Sr and Pb. Experimental isotope ratio precision of 0.14 % for 11B/10B intensity ratio, 0.15 % for 87Sr/86Sr intensity ratio and 0.07% for 208Pb/206Pb intensity ratio were obtained at high signal levels ($500 mg L−1) which is comparable to first generation ICP-TOFMS. The long-term stability of isotope ratios, measured over several hours and expressed as repeatability, is between 0.05 % and 1.8 % for B, Sr and Pb. The observed IIF per mass unit is negative for B (i.e., −11 % for 11B/10B) which is in accordance with measurements using sector field (MC) ICP-MS. But the observed IIF per mass unit is positive for Sr (i.e., 2 % for 87Sr/86Sr) and Pb (i.e., 4.5 % for 208Pb/206Pb) which is not in accordance with measurements using sector field (MC) ICP-MS. Furthermore, different IIFs per mass unit were observed for different isotope pairs of the same isotopic system (i.e., Sr, Pb) and adjacent isotopic systems (i.e., Pb vs. Tl). This and the observations from three-isotope plots for Sr and Pb show that ion formation, ion extraction, ion transmission, ion separation and ion detection in second generation ICP-TOFMS is subject to IIF that does not follow the known mass dependent fractionation laws and is possibly caused by mass independent fractionation and/or multiple (contradictory) fractionation processes with varying contributions. The non-mass dependent IIF behavior observed for second generation ICP TOFMS has profound consequences for the IIF correction of isotope raw data, including application of multi-isotope dilution mass spectrometry (IDMS) using ICP-TOFMS. Hence, only IIF correction models that correct also for mass independent fractionation are applicable to calculate reliable isotope ratios using second generation ICP-TOFMS. In the present study, reliable d11B values, and absolute B, Sr and Pb isotope ratios could be determined using the SSB approach in single-element solutions as well as in a mixture of B, Sr and Pb, where the isotopes were measured simultaneously.
An automated and straightforward detection and data treatment strategy for the determination of the protein relative concentration in individual human cells by single cell–inductively coupled plasma–time-of-flight mass spectrometry (sc-ICP-ToF-MS) is proposed. Metal nanocluster (NC)-labeled specific antibodies for the target proteins were employed, and ruthenium red (RR) staining, which binds to the cells surface, was used to determine the number of cell events as well as to evaluate the relative volume of the cells. As a proof of concept, the expression of hepcidin, metallothionein-2, and ferroportin employing specific antibodies labeled with IrNCs, PtNCs, and AuNCs, respectively, was investigated by sc-ICP-ToF-MS in human ARPE-19 cells. Taking into account that ARPE-19 cells are spherical in suspension and RR binds to the surface of the cells, the Ru intensity was related to the cell volume (i.e., the cell volume is directly proportional to (Ru intensity)3/2), making it possible to determine not only the mass of the target proteins in each individual cell but also the relative concentration. The proposed approach is of particular interest in comparing cell cultures subjected to different supplementations. ARPE-19 cell cultures under two stress conditions were compared: a hyperglycemic model and an oxidative stress model. The comparison of the control with treated cells shows not only the mass of analyzed species but also the relative changes in the cell volume and concentration of target proteins, clearly allowing the identification of subpopulations under the respective treatment.
Accurate and precise isotope ratio measurements of heavy elements are playing an increasinglyimportant role in modern analytical sciences and have numerous applications. Today, isotope ratio measurements are typically performed with two principal techniques: thermal ionization mass spectrometry (TIMS) and multiple collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). To obtain accurate results by mass spectrometry, isotopic certified reference materials (iCRMs) are needed for mass bias correction and for the validation of the method used for analysis.Thus, it is of paramount importance to achieve measurement comparability of all data reported, and to assess measurement capability of each CRM producer/National Metrology Institute (NMI). Therefore, the international comparison (CCQM-P213) was performed to assess the analytical capabilities of NMIs for the accurate determination of copper isotope ratio delta values in high purity materials. The study was proposed by the coordinating laboratories, National Research Council Canada (NRC), National Institute of Standards and Technology (NIST), Bundesanstalt für Materialforschung und -prüfung (BAM) and Physikalisch-Technische Bundesanstalt (PTB), as an activity of the Isotope Ratio Working Group (IRWG) of the Consultative Committee for Amount of Substance - Metrology in Chemistry and Biology (CCQM). Participants included six NMIs and one designated institute (DI) from the six countries. Although no measurement method was prescribed by the coordinating laboratories, MC-ICP-MS with either standard-sample bracketing (SSB) or combined SSB with internal normalization (C-SSBIN) models for mass bias correction were recommended. Results obtained from the six NMIs and one DI were in good agreement.
This study describes an interlaboratory comparison (ILC) among nine (9) laboratories to evaluate and validate the standard operation procedure (SOP) for single-particle (sp) ICP-TOFMS developed within the context of the Horizon 2020 project ACEnano. The ILC was based on the characterization of two different Pt nanoparticle (NP) suspensions in terms of particle mass, particle number concentration, and isotopic composition. The two Pt NP suspensions were measured using icpTOF instruments (TOFWERK AG, Switzerland).
Two Pt NP samples were characterized and mass equivalent spherical sizes (MESSs) of 40.4 ± 7 nm and 58.8 ± 8 nm were obtained, respectively. MESSs showed <16% relative standard deviation (RSD) among all participating labs and <4% RSD after exclusion of the two outliers. A good agreement was achieved between the different participating laboratories regarding particle mass, but the particle number concentration results were more scattered, with <53% RSD among all laboratories, which is consistent with results from previous ILC studies conducted using ICP-MS instrumentation equipped with a sequential mass spectrometer. Additionally, the capabilities of sp-ICP-TOFMS to determine masses on a particle basis are discussed with respect to the potential for particle density determination. Finally, because quasi-simultaneous multi-isotope and multielement determinations are a strength of ICP-TOFMS instrumentation, the precision and trueness of isotope ratio determinations were assessed. The average of 1000 measured particles yielded a precision of below ±1% for intensity ratios of the most abundant Pt isotopes, i.e. 194Pt and 195Pt, while the accuracy of isotope ratios with the lower abundant isotopes was limited by counting statistics.
Per- and polyfuoroalkyl substances (PFAS) are emerging organic pollutants and can occur in surface and groundwater. To identify the degree of pollution in surface water with PFAS, often targeted HPLC–ESI–MS/MS has been employed in which commonly 30–40 compounds are analyzed. However, other PFAS and organofuorines remain undetected. We sampled surface water of the river Spree and the Teltow Canal in Berlin, Germany, which are afected by the efuent discharge of wastewater treatment plants. Here, we employed high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) for measuring extractable organofuorines (EOF) and compared in a mass balance approach the total fuorine to the identifed and quantifed PFAS from the targeted analysis. The analysis highlights that the EOF are in the range expected for an urban river system (Winchell et al. in Sci Total Environ 774, 2021). However, downstream of an efuent discharge, the EOF increased by one order of magnitude, e.g., 40.3 to 574 ng F L−1, along the Teltow Canal. From our target analytes, mostly short-chained perfuorinated carboxylic acids and sulfonates occur in the water, which however makes up less than 10% of the EOF. The increase in EOF in the Teltow Canal correlates well with the increase of perfuorohexanoic acid (PFHxA), indicating that PFHxA is characteristic for the discharged EOF but not responsible for the increase. Hence, it points to PFHxA precursor discharge. The study highlights that EOF screening using HR-CS-GFMAS is necessary to identify the full scale of pollution with regard to PFAS and other organofuorines such as pharmaceutical compounds from the efuent of WWTPs.
An interlaboratory comparison (ILC)was organised to characterise 87Sr/86Sr isotope ratios in geological and industrial reference materials by applying the so-called conventional method for determining 87Sr/86Sr isotope ratios. Four cements (VDZ 100a,VDZ 200a, VDZ 300a, IAG OPC-1), one limestone (IAG CGL ML-3) and one slate (IAG OU-6) reference materials were selected, covering a wide range of naturally occurring Sr isotopic signatures. Thirteen laboratories received aliquots of these six reference materials together with a detailed technical protocol. The consensus values for the six reference materials and their associated measurement uncertainties were obtained by applying a Gaussian, linear mixed effects model fitted to all the measurement results. By combining the consensus values and their uncertainties with an uncertainty contribution for potential heterogeneity, reference values ranging from 0.708134 mol mol-1 to 0.729778 mol mol-1 were obtained with relative expanded uncertainties of ≤ 0.007 %. This study represents an ILC on conventional 87Sr/86Sr isotope ratios, within which metrological principles were considered and the compatibility of measurement results obtained by MC-ICP-MS and by MC-TIMS is demonstrated. The materials characterised in this study can be used as reference materials for validation and quality control purposes and to estimate measurement uncertainties in conventional 87Sr/86Sr isotope ratio measurement.
This study uses conventional 87Sr/86Sr and 143Nd/144Nd isotope and interelement ratios of Ca, Sr, K, Mn, Mg and Ti as fingerprints for provenancing ordinary Portland cements (OPC). Herein, the first database of Sr and Nd isotope ratios investigated in OPCs, stemming from 29 cement plants located worldwide, was created. The results show that the Sr isotope ratios of OPCs are higher than those of seawater from the observed geological period. The spread of 143Nd/144Nd in OPCs is not as large as the spread for 87Sr/86Sr isotope ratios. However, the combination of both Sr and Nd isotope ratios provides the potential for distinguishing between cements of different production sites. Most of the OPCs investigated have measurable differences in their 87Sr/86Sr and 143Nd/144Nd isotope ratios, which can be employed as a valuable analytical fingerprinting tool. In the case of equivocal results, divisive hierarchical clustering was employed to help overcome this issue. The construction of geochemical profiles allowed the computing of suitably defined distances between cements and clustering them according to their chemical similarity. By applying this methodology, successful fingerprinting was achieved in 27 out of the 29 ordinary Portland cements that were analysed.
Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from <LOQ to over ~1000 mg F/kg after oxidation/hydrolysis and <LOQ to over 2000 mg F/kg for TF, while EOF and target PFAS in extracts were detected at much lower concentrations (up to ~ 60 mg F/kg) (amount of fluorine in the order: extraction << EOF << oxidation/hydrolysis ≤ TF). Perfluoroalkyl carboxylic acids (PFCAs) and fluorotelomer alcohols (FTOHs) from THP and PhotoTOP both represented the chain-length distribution in the textiles showing that long-chain SFPs are still used in current textiles. Further advantages and disadvantages of the applied methods are discussed.
Asymmetrical Flow Field-Flow Fractionation (AF4), as a cleaning technique, was combined on-line with the multielemental analytical capabilities of an Inductively Coupled Plasma-Time of Flight-Mass Spectrometer (ICP-ToF-MS). In that manner, the heavy ionic matrix effect of untreated cells' samples can be significantly reduced. As a proof of concept, commercial baker's yeast cells were analysed.
Immobilized metal affinity chromatography (IMAC) is a widely used technique for purifying polyhistidine-tagged recombinant proteins. However, it often has practical limitations that require complex optimizations and additional steps for purification. In this study, we introduce functionalized corundum particles as a novel, efficient, and economical method for purifying recombinant proteins in a column-free format. The corundum surface is modified with amino silane APTES, followed by EDTA dianhydride, and then loaded with nickel ions. We used the Kaiser test to monitor the modification process and ICP-MS to quantify the metal-binding capacity. To evaluate the system, we used His-tagged protein A/G (PAG) mixed with bovine serum albumin (BSA). The corundum particles exhibited a binding capacity of approximately 3 mg of protein per gram of corundum or 2.4 mg per 1 mL of corundum suspension. We also examined cytoplasm obtained from different E. coli strains as an example of a complex matrix. Varying the imidazole concentration in the loading and washing buffers showed that higher concentrations during loading improved purity. Even with sample volumes as large as one liter, we successfully isolated recombinant proteins down to a concentration of 1 µg/mL. We found higher purity levels with corundum when comparing the corundum material to standard Ni–NTA agarose beads. We successfully purified His6-MBP-mSA2, a fusion protein comprising monomeric streptavidin and maltose-binding protein, from E. coli cytoplasm, demonstrating the method's applicability. We also purified SARS-CoV-2-S-RBD-His8 expressed in human Expi293F cells, confirming its suitability for mammalian cell culture supernatants. The material cost of the nickel-loaded corundum material (without regeneration) is estimated to be less than 30 cents per gram of functionalized support or 10 cents per milligram of isolated protein. Another advantage of this system is the exceptional physical and chemical stability of corundum particles. Overall, we have demonstrated that this novel material offers an efficient, robust, and cost-effective purification platform for His-tagged proteins, even in challenging, complex matrices and large sample volumes with low product concentrations. This method has potential applications in both small laboratories and large-scale industrial settings.
Per- und polyfluorierte Alkylverbindungen (PFAS) sind eine Substanzklasse bestehend aus mehreren tausenden Einzelverbindungen. Unter PFAS zählen alle Verbindungen, die mindestens eine perfluorierte Methyl- (-CF3) oder Methylen-Gruppe (-CF2-) besitzen. Somit zählt auch ein großer Teil der fluorierten Medikamente, Pflanzenschutzmittel oder Biozide in die PFAS-Substanzklasse. Aufgrund der Persistenz, Bioakkumulation in Nahrungsketten, Toxizität und der ubiquitären Verbreitung von PFAS zählen sie zu den „emerging pollutants“. Die PFAS-Analytik ist wegen ihrer vielfältigen physikalisch-chemischen Eigenschaften und der sehr hohen Anzahl an PFAS eine große Herausforderung. Da es für viele Anwendungen noch ungewiss ist, welche PFAS verwendet werden, wie sie in die Umwelt gelangen und welche Transformations- bzw. Abbauprodukte entstehen, stoßen analytische Ansätze, die nur auf Einzelsubstanzen abzielen, hier an ihre Grenzen. PFAS-Summenparameter-Methoden, die darauf abzielen ein möglichst vollständiges Abbild der PFAS-Belastungssituation widerzuspiegeln, werden daher immer wichtiger.
In this study, we compare analytical methods for PFAS determination–target analysis, non-target screening (NTS), direct total oxidizable precursor assay (dTOPA) and extractable organically bound fluorine (EOF). Therefore, suspended particulate matter (SPM) samples from German rivers at different locations in time series from2005 to 2020 were analyzed to investigate temporal and spatially resolved trends. In this study 3 PFAS mass balances approaches were utilized: (i) PFAA target vs. PFAS dTOPA, (ii) PFAS target vs. EOF and (iii) PFAS target vs. PFAS dTOPA vs. organofluorines NTS vs. EOF. Mass balance approach (i) revealed high proportions of precursor substances in SPM samples. For the time resolved analysis an increase from 94% (2005) to 97% in 2019 was observable. Also for the spatial resolved analysis precursor proportions were high with >84% at all sampling sites. Mass balance approach (ii) showed that the unidentified EOF (uEOF) fraction increased over time from82% (2005) to 99% (2019). Furthermore, along the river courses the uEOF increased. In the combined mass balance approach (iii) using 4 different analytical approaches EOF fractions were further unraveled. The EOF pattern was fully explainable at the sampling sites at Saar and Elbe rivers. For the time resolved analysis, an increased proportion of the EOF was now explainable. However, still 27% of the EOF for the time resolved analysis and 25% of the EOF for the spatial resolved analysis remained unknown. Therefore, in a complementary approach, both the EOF and dTOPA reveal unknown gaps in the PFAS mass balance and are valuable contributions to PFAS risk assessment. Further research is needed to identify organofluorines summarized in the EOF parameter.
During its 25 years of existence, the Inorganic Analysis Working Group of the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology (CCQM IAWG) has achieved much in establishing comparability of measurement results. Impressive work has been done on comparison exercises related to real-world problems in fields such as ecology, food, or health. In more recent attempts, measurements and comparisons were focused on calibration solutions which are the basis of most inorganic chemical measurements. This contribution deals with the question of how to achieve full and transparent SI traceability for the values carried by such solutions. Within this framework, the use of classical primary methods (CPMs) is compared to the use of a primary difference method (PDM). PDM is a method with a dual character, namely a metrological method with a primary character, based on the bundling of many measurement methods for individual impurities, which lead to materials with certified content of the main component. As in classical methods, where small corrections for interferences are accepted, in PDM, many small corrections are bundled. In contrast to classical methods, the PDM is universally applicable to all elements in principle. Both approaches can be used to certify the purity (expressed as mass fraction of the main element) of a high-purity material. This is where the metrological need of National Metrology Institutes (NMIs) for analytical methods meet the challenges of analytical methods. In terms of methods, glow discharge mass spectrometry (GMDS) with sufficient uncertainties for sufficiently small impurity contents is particularly noteworthy for the certification of primary transfer standards (PTS), and isotope dilution mass spectrometry (IDMS), which particularly benefits from PTS (back-spikes) with small uncertainties, is particularly noteworthy for the application. The corresponding relative uncertainty which can be achieved using the PDM is very low (< 10−4). Acting as PTS, they represent the link between the material aspect of the primary calibration solutions and the immaterial world of the International System of Units (SI). The underlying concepts are discussed, the current status of implementation is summarised, and a roadmap of the necessary future activities in inorganic analytical chemistry is sketched. It has to be noted that smaller measurement uncertainties of the purity of high-purity materials not only have a positive effect on chemical measurements, but also trigger new developments and findings in other disciplines such as thermometry or materials science.
The 18O/16O ratio of cherts (δ18Ochert) increases nearly monotonically by ~15‰ from the Archean to present. Two end-member explanations have emerged: cooling seawater temperature (TSW) and increasing seawater δ18O (δ18Osw). Yet despite decades of work, there is no consensus, leading some to view the δ18Ochert record as pervasively altered.
Here, we demonstrate that cherts are a robust archive of diagenetic temperatures, despite metamorphism and exposure to meteoric fluids, and show that the timing and temperature of quartz precipitation and thus δ18Ochert are determined by the kinetics of silica diagenesis. A diagenetic model shows that δ18Ochert is influenced by heat flow through the sediment column. Heat flow has decreased over time as planetary heat is dissipated, and reasonable Archean-modern heat flow changes account for ~5‰ of the increase in δ18Ochert, obviating the need for extreme TSW or δ18Osw reconstructions. The seawater oxygen isotope budget is also influenced by solid Earth cooling, with a recent reconstruction placing Archean δ18OSW 5 to 10‰ lower than today. Together, this provides an internally consistent view of the δ18Ochert record as driven by solid Earth cooling over billion-year timescales that is compatible with Precambrian glaciations and biological.
The need for quality assessment of anthropogenic impact on environmental pollution is increasing due to discharge from various industries, the use of chemicals in agriculture and the consumption of fossil fuels. Diminishing resources such as natural waters used for the cultivation of agricultural products, plant and animal habitats are under severe pollution pressure and are at constant risk. Several parameters, such as Pb, Cd, Ni, Hg were listed by Water Framework Directive in Directive(2008/105/EC) in the priority substances. Cadmium and Hg were identified as priority hazardous substances whereas As is an important contaminant for its potential toxicological and carcinogenic effects. An inter-comparison study is organised in EURAMET TC-MC in order to demonstrate the capability participants for measuring five elements in river water. The participants carried out measurements for analytes: Pb, Cd, Ni and As as mandatory elements, and Se as an optional one. Participants were asked to perform the measurements with respect to the protocol provided. To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database https://www.bipm.org/kcdb/.
The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).
The most profound consequences of the presence of Ca–Mg carbonates (CaCO3–MgCO3) in the Earth’s upper mantle may be to lower the melting temperatures of the mantle and control the melt composition.
Low-degree partial melting of a carbonate-bearing mantle produces CO2-rich, silica-poor melts compositionally imposed by the melting relations of carbonates. Thus, understanding the melting relations in the CaCO3–MgCO3 system facilitates the interpretation of natural carbonate-bearing silicate systems.
We report the melting relations of the CaCO3–MgCO3 system and the partition coefficient of trace elements between carbonates and carbonate melt from experiments at high pressure (6 and 9 GPa) and temperature (1300–1800 ◦C) using a rocking multi-anvil press. In the absence of water, Ca–Mg carbonates are stable along geothermal gradients typical of subducting slabs. Ca–Mg carbonates (∼ Mg0.1–0.9Ca0.9–0.1CO3) partially melt beneath mid-ocean ridges and in plume settings. Ca–Mg carbonates melt incongruently, forming periclase crystals and carbonate melt between 4 and 9 GPa. Furthermore, we show that the rare earth element (REE) signature of Group-I kimberlites, namely strong REE fractionation and depletion of heavy REE relative to the primitive mantle, is resembled by carbonate melt in equilibrium with Ca-bearing magnesite and periclase at 6 and 9 GPa. This suggests that the dolomite–magnesite join of the CaCO3–MgCO3 system might be useful to approximate the REE signature of carbonate-rich melts parental to kimberlites.
The environmental fate of the frequently used broad-spectrum β-lactam antibiotic amoxicillin (AMX) is of high concern regarding the potential evolution of antimicrobial resistance (AMR). Moreover, it is known that AMX is prone to hydrolysis, yielding a variety of hydrolysis products (HPs) with yet unknown effects. Studies to identify those HPs and investigate their formation mechanisms have been reported but a long-term study on their stability in real water samples was missing. In this regard, we investigated the hydrolysis of AMX at two concentration levels in four distinct water types under three different storage conditions over two months. Concentrations of AMX and four relevant HPs were monitored by an LC-MS/MS method revealing pronounced differences in the hydrolysis rate of AMX in tap water and mineral water on the one hand (fast) and surface water on the other(slow). In this context, the occurrence, relative intensities, and stability of certain HPs are more dependent on the water type than on the storage condition. As clarified by ICP-MS, the main difference between the water types was the content of the metals copper and zinc which are supposed to catalyze AMX hydrolysis demonstrating an effective method to degrade AMX at ambient conditions.
ADAMTS4-specific MR-probe to assess aortic aneurysms in vivo using synthetic peptide libraries
(2022)
The incidence of abdominal aortic aneurysms (AAAs) has substantially increased during the last 20 years and their rupture remains the third most common cause of sudden death in the cardiovascular field after myocardial infarction and stroke. The only established clinical parameter to assess AAAs is based on the aneurysm size. Novel biomarkers are needed to improve the assessment of the risk of rupture. ADAMTS4 (A Disintegrin And Metalloproteinase with ThromboSpondin motifs 4) is a strongly upregulated proteoglycan cleaving enzyme in the unstable course of AAAs. In the screening of a one-bead-one-compound library against ADAMTS4, a low-molecular-weight cyclic peptide is discovered with favorable properties for in vivo molecular magnetic resonance imaging applications. After identification and characterization, it’s potential is evaluated in an AAA mouse model. The ADAMTS4-specific probe enables the in vivo imaging-based prediction of aneurysm expansion and rupture.
Despite numerous advantages offered by hyphenation of chromatography and electrokinetic separation methods with multicollector (MC) ICP-MS for isotope analysis, the main limitation of such systems is the decrease in precision and increase in uncertainty due to generation of short transient signals. To minimize this limitation, most authors compare several isotope ratio calculation methods and establish a multi-step data processing routine based on the precision and accuracy of the methods. However, to the best of our knowledge, there is no universal data processing tool available that incorporates all important steps of the treatment of the transient signals. Thus, we introduce a data processing application (App) IsoCor that facilitates automatic calculation of isotope ratios from transient signals and eases selection of the most suitable method. The IsoCor App performs baseline subtraction, peak detection, mass bias correction, isotope ratio calculation and delta calculation. The feasibility and reliability of the App was proven by reproducing the results from isotope analysis of three elements (neodymium, mercury and sulfur) measured on-line via hyphenated systems. The IsoCor App provides trackability of the results to ensure quality control of the analysis.
Isotope ratio applications are on the increase and a major part of which are delta measurements, because they are easier to perform than the determination of absolute isotope ratios while offering lower measurement uncertainties. Delta measurements use artefact-based scales and therefore scale conversions are required due to the lack of the scale defining standards. Such scale conversions often form the basis for comparing data being generated in numerous projects andtherefore need to be as accurate as possible. In practice, users are tempted to apply linear approximations, which are not sufficiently exact, because delta values are defined by nonlinear relationships. The bias of such approximations often is beyond typical measurement uncertainties and its extent can hardly be predicted. Therefore, exact calculations are advised. Here, the exact equations and the bias of the approximations are presented, and calculations are illustrated by real-world examples. Measurement uncertainty is indispensable in this context and therefore, its calculation is described as well for determining delta values but also for scale conversions. Approaches for obtaining a single delta measurement and for repeated measurements are presented. For the latter case, a new approach for calculating the measurement uncertainty is presented, which considers covariances between the isotope ratios.
Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials.
This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences.
However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences.
The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials.
Inflammatory bowel diseases (IBD) comprise mainly ulcerative colitis (UC) and Crohn´s disease (CD). Both forms present with a chronic inflammation of the (gastro) intestinal tract, which induces excessive changes in the composition of the associated extracellular matrix (ECM). In UC, the inflammation is limited to the colon, whereas it can occur throughout the entire gastrointestinal tract in CD. Tools for early diagnosis of IBD are still very limited and highly invasive and measures for standardized evaluation of structural changes are scarce. To investigate an efficient non-invasive way of diagnosing intestinal inflammation and early changes of the ECM, very small superparamagnetic iron oxide nanoparticles (VSOPs) in magnetic resonance imaging (MRI) were applied in two mouse models of experimental colitis: the dextran sulfate sodium (DSS)-induced colitis and the transfer model of colitis. For further validation of ECM changes and inflammation, tissue sections were analyzed by immunohistochemistry. For in depth ex-vivo investigation of VSOPs localization within the tissue, Europium-doped VSOPs served to visualize the contrast agent by imaging mass cytometry (IMC). VSOPs accumulation in the inflamed colon wall of DSS-induced colitis mice was visualized in T2* weighted MRI scans. Components of the ECM, especially the hyaluronic acid content, were found to influence VSOPs binding. Using IMC, colocalization of VSOPs with macrophages and endothelial cells in colon tissue was shown. In contrast to the DSS model, colonic inflammation could not be visualized with VSOP-enhanced MRI in transfer colitis. VSOPs present a potential contrast agent for contrast-enhanced MRI to detect intestinal inflammation in mice at an early stage and in a less invasive manner depending on hyaluronic acid content.
Lithium and boron are trace components of magmas, released during exsolution of a gas phase during volcanic activity. In this study, we determine the difusivity and isotopic fractionation of Li and B in hydrous silicate melts. Two glasses were synthesized with the same rhyolitic composition (4.2 wt% water), having diferent Li and B contents; these were studied in difusion-couple experiments that were performed using an internally heated pressure vessel, operated at 300 MPa in the temperature range 700–1250 °C for durations from 0 s to 24 h. From this we determined activation energies for Li and B difusion of 57±4 kJ/mol and 152±15 kJ/mol with pre-exponential factors of 1.53 × 10–7 m2/s and 3.80× 10–8 m2 /s, respectively. Lithium isotopic fractionation during difusion gave β values between 0.15 and 0.20, whereas B showed no clear isotopic fractionation. Our Li difusivities and isotopic fractionation results difer somewhat from earlier published values, but overall confrm that Li difusivity increases with water content. Our results on B difusion show that similarly to Li, B mobility increases in the presence of water. By applying the Eyring relation, we confrm that B difusivity is limited by viscous fow in silicate melts. Our results on Li and B difusion present a new tool for understanding degassing-related processes, ofering a potential geospeedometer to measure volcanic ascent rates.
Within this work, the combination of a microdroplet generator and an ICP-ToF-MS for nanoparticle analysis is presented. For the size determination of platinum nanoparticles an on-line isotope dilution analysis approach was developed. The 194Pt/195Pt isotopic ratio was used for the characterization of the particles, while the 182W/183W isotopic ratio was monitored simultaneously for mass bias correction. The on-line ID-MDG-sp-ICP-ToF-MS approach was deployed for the size determination of three platinum nanoparticle samples (50 nm, 63 nm, 70 nm); for validation, complementary size characterization techniques (sp-ICP-ToF-MS and TEM) were used. The robustness of this technique was evidenced, by using sodium chloride concentrations up to 100 mg L−1 as a matrix component. Our new on-line ID MDG-sp-ICP-ToF-MS approach is a promising tool for the fast and reliable determination of nanoparticles' size in severe matrix concentrations, e.g., environmental samples.
The present Table of Standard Atomic Weights (TSAW) of the elements is perhaps one of the most familiar data sets in science. Unlike most parameters in physical science whose values and uncertainties are evaluated using the “Guide to the Expression of Uncertainty in Measurement” (GUM), the majority of standard atomic weight values and their uncertainties are consensus values, not GUM-evaluated values. The Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) regularly evaluates the literature for new isotopic-abundance measurements that can lead to revised standard atomic-weight values, Ar(E) for element E.
The Commission strives to provide utmost clarity in products it disseminates, namely the TSAW and the Table of Isotopic Compositions of the Elements (TICE). In 2016, the Commission recognized that a guideline recommending the expression of uncertainty listed in parentheses following the standard atomic-weight value, for example, Ar(Se) = 78.971(8), did not agree with the GUM, which suggests that this parenthetic notation be reserved to express standard uncertainty, not the expanded uncertainty used in the TSAW and TICE. In 2017, to eliminate this noncompliance with the GUM, a new format was adopted in which the uncertainty value is specified by the “±” symbol, for example, Ar(Se) = 78.971 ± 0.008. To clarify the definition of uncertainty, a new footnote has been added to the TSAW. This footnote emphasizes that an atomic-weight uncertainty is a consensus (decisional) uncertainty. Not only has the Commission shielded users of the TSAW and TICE from unreliable measurements that appear in the literature as a result of unduly small uncertainties, but the aim of IUPAC has been fulfilled by which any scientist, taking any natural sample from commerce or research, can expect the sample atomic weight to lie within Ar(E) ± its uncertainty almost all of the time.
Boron isotope fractionation in soil-plant systems and its influence on biogeochemical cycling
(2022)
Boron (B) is an essential mineral nutrient for higher plants. Although B plant nutrition is well studied, the B isotope fractionation at the soil-plant interface, within plant metabolism, and its influence on biogeochemical cycling is not fully understood. Boron concentrations and isotope variations (δ11B) of the dicotyledonous plants of Chenopodium album and Brassica napus and their growing soils along a climatic gradient were analyzed to decipher these unresolved issues of the B behavior. The boron concentrations and δ11B values show an increasing trend from roots to leaves for both plants, while a decreasing trend from flower to shell and to seed for Brassica napus. A large boron isotope fractionation occurs within the plants with median Δ11Bleaf-root ≈ +20‰, which is related to different boron transporters and transportation ways. Formation of borate dimerized rhamnogalacturonan II in cell and B(OH)3 transportation in xylem lead to heavier δ11B values from root to stem and leaf while B(OH)4 transportation in phloem lead to lighter δ11B values from flower to shell and seed. Although samples cover a distinct transect with systematically different climatic conditions, Δδ11B within the individual plant compartments and between the bulk plants and the soil available B do not show any systematic variation.
This suggests that B uptake from the soil into Chenopodium album and Brassica napus occurs without a distinct isotope fractionation at the soil-plant interface (median Δ11Bbulkplant-soil = 0.2‰) and plants are able to regulate boron uptake. Both the observed large B fractionation within plant and low or absent B isotope fractionation at the soil-plant interface may have profound implications for the biological and geological B cycle. If this observed boron behavior also exists in other plants, their litters would be an important source for exporting 11B-rich biological material from continental ecosystems via rivers to the global oceans. This may be helpful for the explanation of ocean B cycle and the increasing δ11B values over the Cenozoic.
Prostate cancer (PCa) is one of the most common cancers in men. For detection and diagnosis of PCa, non-invasive methods, including magnetic resonance imaging (MRI), can reduce the risk potential of surgical intervention. To explore the molecular characteristics of the tumor, we investigated the applicability of ferumoxytol in PCa in a xenograft mouse model in two different tumor volumes, 500 mm3 and 1000 mm3. Macrophages play a key role in tumor progression, and they are able to internalize iron-oxide particles, such as ferumoxytol. When evaluating T2*-weighted sequences on MRI, a significant decrease of signal intensity between pre- and post-contrast images for each tumor volume (n = 14; p < 0.001) was measured. We, furthermore, observed a higher signal loss for a tumor volume of 500 mm3 than for 1000 mm3. These findings were confirmed by histological examinations and laser ablation inductively coupled plasma-mass spectrometry. The 500 mm3 tumors had 1.5% iron content (n = 14; sigma = 1.1), while the 1000 mm3 tumors contained only 0.4% iron (n = 14; sigma = 0.2). In vivo MRI data demonstrated a correlation with the ex vivo data (R2 = 0.75). The results of elemental analysis by inductively coupled plasma-mass spectrometry correlated strongly with the MRI data (R2 = 0.83) (n = 4). Due to its long retention time in the blood, biodegradability, and low toxicity to patients, ferumoxytol has great potential as a contrast agent for visualization PCa.
Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol Ar(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated Ar(E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances:
Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963]
Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006
Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002
Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94]
Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010
The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of Ar(Ar) and Ar(Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). Ar of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021:
Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003
Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004
Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003
F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005
(Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007)
Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005
Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002
Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01
Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01
Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01
Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02
Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004
(Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008)
Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007
(Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006)
Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005
(Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01)
Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.000 002
Objectives: Using a murine model of multiple sclerosis, we previously showed that repeated administration of gadopentetate dimeglumine led to retention of gadolinium (Gd) within cerebellar structures and that this process was enhanced with inflammation. This study aimed to compare the kinetics and retention profiles of Gd in inflamed and healthy brains after application of the macrocyclic Gd-based contrast agent (GBCA) gadobutrol or the linear GBCA gadopentetate. Moreover, potential Gd-induced neurotoxicity was investigated in living hippocampal slices ex vivo.
Materials and Methods: Mice at peak of experimental autoimmune encephalomyelitis (EAE; n = 29) and healthy control mice (HC; n = 24) were exposed to a cumulative dose of 20 mmol/kg bodyweight of either gadopentetate dimeglumine or gadobutrol (8 injections of 2.5 mmol/kg over 10 days). Magnetic resonance imaging (7 T) was performed at baseline as well as at day 1, 10, and 40 post final injection (pfi) of GBCAs. Mice were sacrificed after magnetic resonance imaging and brain and blood Gd content was assessed by laser ablation-inductively coupled plasma (ICP)-mass spectrometry (MS) and ICP-MS, respectively. In addition, using chronic organotypic hippocampal slice cultures, Gd-induced neurotoxicity was addressed in living brain tissue ex vivo, both under control or inflammatory (tumor necrosis factor α [TNF-α] at 50 ng/μL) conditions.
Results: Neuroinflammation promoted a significant decrease in T1 relaxation times after multiple injections of both GBCAs as shown by quantitative T1 mapping of EAE brains compared with HC. This corresponded to higher Gd retention within the EAE brains at 1, 10, and 40 days pfi as determined by laser ablation-ICP-MS. In inflamed cerebellum, in particular in the deep cerebellar nuclei (CN), elevated Gd retention was observed until day 40 after last gadopentetate application (CN: EAE vs HC, 55.06 ± 0.16 μM vs 30.44 ± 4.43 μM). In contrast, gadobutrol application led to a rather diffuse Gd content in the inflamed brains, which strongly diminished until day 40 (CN: EAE vs HC, 0.38 ± 0.08 μM vs 0.17 ± 0.03 μM). The analysis of cytotoxic effects of both GBCAs using living brain tissue revealed an elevated cell death rate after incubation with gadopentetate but not gadobutrol at 50 mM. The cytotoxic effect due to gadopentetate increased in the presence of the inflammatory mediator TNF-α (with vs without TNF-α, 3.15% ± 1.18% vs 2.17% ± 1.14%; P = 0.0345).
Conclusions: In the EAE model, neuroinflammation promoted increased Gd retention in the brain for both GBCAs. Whereas in the inflamed brains, efficient clearance of macrocyclic gadobutrol during the investigated time period was observed, the Gd retention after application of linear gadopentetate persisted over the entire observational period. Gadopentetate but not gadubutrol appeared to be neurotoxic in an ex vivo paradigm of neuronal inflammation.
The study, dedicated to Beautiful Pietàs conserved in South Tyrol (Northern Italy), aims to establish, for the first time, a connection between Austroalpine raw materials and the high-fired gypsum mortars constituting the Gothic figure groups in question. The origin and chronology of this stylistically and qualitatively differing ensemble have been subject of art historical debate for nearly a century. The discourse is dominated by three main hypotheses: itinerary of an Austrian artist versus itinerary of the work of art created in an artist’s workshop in Austria versus itinerary of the stylistic vocabulary via graphical or three-dimensional models. The comparison of the δ34S values and the 87Sr/86Sr ratios of the gypsum mortars and Austroalpine sulphate deposits (in a compilation of own reference samples and literature data) points to the exploitation of sediments in the Salzkammergut and possibly also in the evaporite district of the Eastern Calcareous Alps, thus evidencing the import of the sculptures and not the activities of local South Tyrolean or itinerant artists. Two geochronological units are distinguishable: The Pietà in the Church St. Martin in Göflan can be assigned to Upper Permian raw material, whereas the metrologically consistent sculptures in the Church of Our Lady of the Benedictine Abbey Marienberg and in the Chapel St. Ann in Mölten correlate with deposits of the Early Triassic (or the Lower-Middle Triassic transition). The medieval gypsum mortars also differ in their mineralogical characteristics, i.e. in their geologically related minor components, as in the first case, characterised by a significant proportion of primary anhydrite, natural carbonate impurities mainly consist of calcite (partly converted to lime-lump-like aggregates), whereas in the second group dolomite (or rather its hydration products after pyrometamorphic decomposition) predominates, accompanied by celestine, quartz and potassium feldspar. The Pietà in the Cathedral Maria Himmelfahrt in Bozen turned out to be made of Breitenbrunn calcareous sandstone (Leitha Mountains, Burgenland, Austria), which is why the sample is not considered in the geochemical analysis.
Quantitative proteomics is a growing research area and one of the most important tools in the life sciences. Well-characterized and quantified protein standards are needed to achieve accurate and reliable results. However, only a limited number of sufficiently characterized protein standards are currently available. To fill this gap, a method for traceable protein quantification using sulfur isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) was developed in this study.
Gel filtration and membrane filtration were tested for the separation of non-protein-bound sulfur in the protein solution.
Membrane filtration demonstrated a better performance due to the lower workload and the very low sulfur blanks of 11 ng, making it well suited for high-purity proteins such as NIST SRM 927, a bovine serum albumin (BSA). The method development was accomplished with NIST SRM 927e and a commercial avidin. The quantified mass fraction of NIST SRM 927e agreed very well with the certified value and showed similar uncertainties (3.6%) as established methods while requiring less sample preparation and no species-specific standards. Finally, the developed procedure was applied to the tau protein, which is a biomarker for a group of neurodegenerative diseases denoted “tauopathies” including, e.g., Alzheimer’s disease and frontotemporal dementia. For the absolute quantification of tau in the brain of transgenic mice overexpressing human tau, a well-defined calibration standard was needed. Therefore, a pure tau solution was quantified, yielding a protein mass fraction of (0.328 ± 0.036) g/kg, which was confirmed by amino acid analysis.
Per- und polyfluorierte Alkylsubstanzen (PFAS) bilden eine sehr komplexe Schadstoffgruppe mit über 6300 Einzelsubstanzen, die in vielfältiger Form in die Umwelt eingetragen werden. Für ein effektives Monitoring dieser Schadstoffklasse benötigt es ein Zusammenspiel aus Summenparameter-Analytik zur hot-spot-Identifizierung und Klassifizierung von Belastungssituationen sowie einer nachgeschalteten target-Analytik zur Identifizierung von Eintragswegen, die zugleich ein tieferes Verständnis von Transformationsprozessen ermöglicht. In diesem Beitrag präsentieren wir eine optimierte Extraktions-Methode für die PFAS-Summenparameteranalytik. Mit Hilfe dieser können bisher verwendete zeit- und kostenintensive Festphasenextraktionen (SPE) umgangen und PFAS-Extraktionseffizienzen gesteigert werden. Die methodische Bestimmungsgrenze (LOQ) war mit 10,30 μg/kg (Fluor pro Bodenprobe) ausreichend für alle 9 untersuchten Realbodenproben.
Here, we describe an optimized fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) in soils utilizing high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR–CS–GFMAS). To omit the bias of the solid phase extraction (SPE) step commonly used during the analysis of extractable organically bound fluorine (EOF) we optimized a fast and simple SPE-free extraction method. The developed extraction method consists of a liquid-solid extraction using acidified methanol without any additional SPE. Four extraction steps were representative to determine a high proportion of the EOF (>80% of eight extractions). Comparison of the optimized method with and without an additional SPE clean-up step revealed a drastic underestimation of EOF concentrations using SPE. Differences of up to 94% were observed which were not explainable by coextracted inorganic fluoride. Therefore, not only a more accurate but also a more economic as well as ecologic method (bypassing of unnecessary SPE) was developed. The procedural limit of quantification (LOQ) of the developed method was 10.30 μg/kg which was sufficient for quantifying EOF concentrations in all tested samples. For future PFAS monitoring and potential regulative decisions the herein presented optimized extraction method can offer a valuable contribution.
Imaging Keratan Sulfate in Ocular Tissue Sections by Immunofluorescence Microscopy and LA-ICP-MS
(2022)
Carbohydrate-specific antibodies can serve as valuable tools to monitor alterations in the extracellular matrix resulting from pathologies. Here, the keratan sulfate-specific monoclonal antibody MZ15 was characterized in more detail by immunofluorescence microscopy as well as laser ablation ICP-MS using tissue cryosections and paraffin-embedded samples. Pretreatment with keratanase II prevented staining of samples and therefore demonstrated efficient enzymatic keratan sulfate degradation. Random fluorescent labeling and site-directed introduction of a metal cage into MZ15 were successful and allowed for a highly sensitive detection of the keratan sulfate landscape in the corneal stroma from rats and human tissue.
The 87Sr/86Sr isotope ratio can, in principle, be used for provenancing of cement. However, while commercial cements consist of multiple components, no detailed investigation into their individual 87Sr/86Sr isotope ratios or their influence on the integral 87Sr/86Sr isotope ratio of the resulting cement was conducted previously. Therefore, the present study aimed at determining and comparing the conventional 87Sr/86Sr isotope ratios of a diverse set of Portland cements and their corresponding Portland clinkers, the major component of these cements. Two approaches to remove the additives from the cements, i.e. to measure the conventional 87Sr/86Sr isotopic fingerprint of the clinker only, were tested, namely, treatment with a potassium hydroxide/sucrose solution and sieving on a 11-µm sieve. Dissolution in concentrated hydrochloric acid/nitric acid and in diluted nitric acid was employed to determine the 87Sr/86Sr isotope ratios of the cements and the individual clinkers. The aim was to find the most appropriate sample preparation procedure for cement provenancing, and the selection was realised by comparing the 87Sr/86Sr isotope ratios of differently treated cements with those of the corresponding clinkers. None of the methods to separate the clinkers from the cements proved to be satisfactory. However, it was found that the 87Sr/86Sr isotope ratios of clinker and cement generally corresponded, meaning that the latter can be used as a proxy for the clinker 87Sr/86Sr isotope ratio. Finally, the concentrated hydrochloric acid/nitric acid dissolution method was found to be the most suitable sample preparation method for the cements; it is thus recommended for 87Sr/86Sr isotope analyses for cement provenancing.
Directing nanoparticles to the nucleus by attachment of nuclear localization sequences (NLS) is an aim in many applications. Gold nanoparticles modified with two different NLS were studied while crossing barriers of intact cells, including uptake, endosomal escape, and nuclear translocation. By imaging of the nanoparticles and by characterization of their molecular interactions with surface-enhanced Raman scattering (SERS), it is shown that nuclear translocation strongly depends on the particular incubation conditions. After an 1 h of incubation followed by a 24 h chase time, 14 nm gold particles carrying an adenoviral NLS are localized in endosomes, in the cytoplasm, and in the nucleus of fibroblast cells. In contrast, the cells display no nanoparticles in the cytoplasm or nucleus when continuously incubated with the nanoparticles for 24 h. The ultrastructural and spectroscopic data indicate different processing of NLS-functionalized particles in endosomes compared to unmodified particles. NLS functionalized nanoparticles form larger intraendosomal aggregates than unmodified gold nanoparticles. SERS spectra of cells with NLS-functionalized gold nanoparticles contain bands assigned to DNA and were clearly different from those with unmodified gold nanoparticles. The different processing in the presence of an NLS is influenced by a continuous exposure of the cells to nanoparticles and an ongoing nanoparticle uptake. This is supported by mass-spectrometry-based quantification that indicates enhanced uptake of NLS-functionalized nanoparticles compared to unmodified particles under the same conditions. The results contribute to the optimization of nanoparticle analysis in cells in a variety of applications, e.g., in theranostics, biotechnology, and bioanalytics.
One of the most commonly diagnosed cancers in men is prostate cancer (PCa). Understanding tumor progression can help diagnose and treat the disease at an early stage. Components of the extracellular matrix (ECM) play a key role in the development and progression of PCa. Elastin is an essential component of the ECM and constantly changes during tumor development. This article visualizes and quantifies elastin in magnetic resonance imaging (MRI) using a small molecule probe. Results were correlated with histological examinations. Using an elastin-specific molecular probe, we were able to make predictions about the cellular structure in relation to elastin and thus draw conclusions about the size of the tumor, with smaller tumors having a higher elastin content than larger tumors.
Human prostate cancer (PCa) is a type of malignancy and one of the most frequently diagnosed cancers in men. Elastin is an important component of the extracellular matrix and is involved in the structure and organization of prostate tissue. The present study examined prostate cancer in a xenograft mouse model using an elastin-specific molecular probe for magnetic resonance molecular imaging. Two different tumor sizes (500 mm3 and 1000 mm3) were compared and analyzed by MRI in vivo and histologically and analytically ex vivo. The T1-weighted sequence was used in a clinical 3-T scanner to calculate the relative contrast enhancement before and after probe administration. Our results show that the use of an elastin-specific probe enables better discrimination between tumors and surrounding healthy tissue. Furthermore, specific binding of the probe to elastin fibers was confirmed by histological examination and laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS). Smaller tumors showed significantly higher signal intensity (p > 0.001), which correlates with the higher proportion of elastin fibers in the histological evaluation than in larger tumors. A strong correlation was seen between relative enhancement (RE) and Elastica–van Gieson staining (R2 = 0.88). RE was related to inductively coupled plasma–mass spectrometry data for Gd and showed a correlation (R2 = 0.78). Thus, molecular MRI could become a novel quantitative tool for the early evaluation and detection of PCa.
Metal-containing nanoparticles (NP) can be characterized with inductively coupled plasma mass spectrometers (ICP-MS) in terms of their size and number concentration by using the single-particle mode of the instrument (spICP-MS). The accuracy of measurement depends on the setup, operational conditions of the instrument and specific parameters that are set by the user. The transport efficiency of the ICP-MS is crucial for the quantification of the NP and usually requires a reference material with homogenous size distribution and a known particle number concentration.
Currently, NP reference materials are available for only a few metals and in limited sizes. If particles are characterized without a reference standard, the results of both size and particle number may be biased. Therefore, a dual-inlet Setup for characterizing nanoparticles with spICP-MS was developed to overcome this problem. This setup is based on a conventional introduction system consisting of a pneumatic nebulizer (PN) for nanoparticle solutions and a microdroplet Generator (μDG) for ionic calibration solutions. A new and flexible interface was developed to facilitate the coupling of μDG, PN and the ICP-MS system. The interface consists of available laboratory components and allows for the calibration, nanoparticle (NP) characterization and cleaning of the arrangement, while the ICP-MS instrument is still running.
Three independent analysis modes are available for determining particle size and number concentration. Each mode is based on a different calibration principle.
While mode I (counting) and mode III (μDG) are known from the literature, mode II (sensitivity), is used to determine the transport efficiency by inorganic ionic Standard solutions only. It is independent of NP reference materials. The μDG based inlet system described here guarantees superior analyte sensitivities and, therefore, lower detection limits (LOD). The size dependent LODs achieved are less than 15 nm for all NP (Au, Ag, CeO2) investigated.
The quantification of the sulphur mass fraction in pure copper and copper alloys by GDMS and LA-ICP-MS revealed a lack of traceability mainly due to a lack of suitable certified reference materials for calibrating the instruments. Within this study GDMS and LA-ICP-MS were applied as routine analytical tools to quantify sulphur in copper samples by applying reference materials as calibrators, which were characterized for their sulphur mass fraction by IDMS beforehand. Different external calibration strategies were applied including a matrix cross type calibration. Both techniques with all calibration strategies were validated by using certified reference materials (others than those used for calibration) and good agreement with the reference values was achieved except for the matrix cross type calibration, for which the agreement was slightly worse. All measurement results were accompanied by an uncertainty statement. For GDMS, the relative expanded (k = 2) measurement uncertainty ranged from 3% to 7%, while for LA-ICP-MS it ranged from 11% to 33% when applying matrix-matched calibration in the sulphur mass fraction range between 25 mg kg-1 and 1300 mg kg-1. For cross-type calibration the relative expanded (k = 2) measurement uncertainty need to be increased to at least 12% for GDMS and to at least 54% for LA-ICP-MS to yield metrological compatibility with the reference values. The so obtained measurement results are traceable to the international system of units (SI) via IDMS reference values, which is clearly illustrated by the unbroken chain of calibrations in the metrological traceability scheme.
Annexin A5 (anxA5) is a marker for apoptosis, but has also therapeutic potential in cardiovascular diseases, cancer, and, due to apoptotic mimicry, against dangerous viruses, which is limited by the short blood circulation. An 864-amino-acid XTEN polypeptide was fused to anxA5. XTEN864-anxA5 was expressed in Escherichia coli and purified using XTEN as tag.
XTEN864-anxA5 was coupled with DTPA and indium-111. After intravenous or subcutaneous injection of 111In-XTEN864-anxA5, mouse blood samples were collected for blood half-life determination and organ samples for biodistribution using a gamma counter. XTEN864-anxA5 was labeled with 6S-IDCC to confirm binding to apoptotic cells using flow cytometry.
To demonstrate targeting of atherosclerotic plaques, XTEN864-anxA5 was labeled with MeCAT(Ho) and administered intravenously to atherosclerotic ApoE−/−mice. MeCAT(Ho)-XTEN864-anxA5 was detected together with MeCAT(Tm)-MAC-2 macrophage antibodies by imaging mass cytometry (CyTOF) of aortic root sections. The ability of anxA5 to bind apoptotic cells was not affected by XTEN864. The blood half-life of XTEN864-anxA5 was 13 h in mice after IV injection, markedly longer than the 7-min half-life of anxA5. 96 h after injection, highest amounts of XTEN864-anxA5 were found in liver, spleen, and kidney. XTEN864-anxA5 was found to target the adventitia adjacent to atherosclerotic plaques. XTEN864-anxA5 is a long-circulating fusion protein that can be efficiently produced in E. coli and potentially circulates in humans for several days, making it a promising therapeutic drug.
With the aim of identifying the origin and the manufacturer of a cement, a reliable procedure that provides unambiguous results is needed. Such procedure could resolve practical issues in damage research, liability issues and forensic investigations. A substantial number of attempts for fingerprinting of building materials, including cement, has already been carried out during the last decades. Most of them were based on concentration analysis of the main elements/components. This review provides an overview of provenance studies of cement and the main approaches commonly used. Provenance studies of cement via isotope techniques are also presented and discussed as representatives of the state-of-the-art in the field. Due to the characteristic properties and the occurrence of carefully selected isotope ratios, unique fingerprints of different kinds of materials can be provided by these methods. This property has largely been explored in various scientific fields such as geo- and cosmochemistry, food forensics, archaeology, geochronology, biomedical studies, and climate change processes. However, the potential of isotope techniques in cement and concrete research for provenance studies has barely been investigated.
Therefore, the review outlines a suitable approach using isotope ratios, which could lead to reliable provenancing of cementitious materials in the future.