Evaluation of X-ray fluorescence for analysing critical elements in three electronic waste matrices: A comprehensive comparison of analytical techniques.

As the drive towards recycling electronic waste increases, demand for rapid and reliable analytical methodology to analyse the metal content of the waste is increasing, e.g. to assess the value of the waste and to decide the correct recycling routes. Here, we comprehensively assess the suitability of different x-ray fluorescence spectroscopy (XRF)-based techniques as rapid analytical tools for the determination of critical raw materials, such as Al, Ti, Mn, Fe, Co, Ni, Cu, Zn, Nb, Pd and Au, in three electronic waste matrices: printed circuit boards (PCB), light emitting diodes (LED), and lithium (Li)-ion batteries. As validated reference methods and materials to establish metrological traceability are lacking, several laboratories measured test samples of each matrix using XRF as well as other independent complementary techniques (instrumental neutron activation analysis (INAA), inductively coupled plasma mass spectrometry (ICP-MS) and ICP optical emission spectrometry (OES)) as an inter-laboratory comparison (ILC). Results highlighted key aspects of sample preparation, limits of detection, and spectral interferences that affect the reliability of XRF, while additionally highlighting that XRF can provide more reliable data for certain elements compared to digestion-based approaches followed by ICP-MS analysis (e.g. group 4 and 5 metals). A clear distinction was observed in data processing methodologies for wavelength dispersive XRF, highlighting that considering the metals present as elements (rather than oxides) induces overestimations of the mass fractions when compared to other techniques. Eventually, the effect of sample particle size was studied and indicated that smaller particle size (<200 µm) is essential for reliable determinations.

Evaluating Source Complexity in Blended Milk Cheese: Integrated Strontium Isotope and Multi-Elemental Approach to PDO Graviera Naxos.

Graviera Naxos, a renowned cheese with Protected Designation of Origin status, is crafted from a blend of cow, goat, and sheep milk. This study focused on assessing the Sr isotopic and multi-elemental composition of both the processed cheese and its ingredients, as well as the environmental context of Naxos Island, including samples of milk, water, soil, and feed. The objective was to delineate the geochemical signature of Graviera Naxos cheese and to explore the utility of Sr isotopes as indicators of geographic origin. The 87Sr/86Sr values for Graviera Naxos samples ranged from 0.70891 to 0.70952, indicating a relatively narrow range. However, the Sr isotopic signature of milk, heavily influenced by the feed, which originates from geologically distinct areas, does not always accurately reflect the local breeding environment. Multi-elemental analysis revealed variations in milk composition based on type and season; yet, no notable differences were found between raw and pasteurized milk. A mixing model evaluating the contributions of milk, sea salt, and rennet to the cheese's Sr isotopic signature suggested a significant average contribution of 73.1% from sea salt. This study highlights the complexities of linking dairy products with their geographical origins and emphasizes the need for sophisticated geochemical authentication methods.

Compost amendment in urban gardens: elemental and isotopic analysis of soils and vegetable tissues.

Urban horticulture poses a sustainable form of food production, fosters community engagement and mitigates the impacts of climate change on cities. Yet, it can also be tied to health challenges related to soil contamination. This work builds on a previous study conducted on eleven urban gardens in the city of Vienna, Austria. Following the findings of elevated Pb levels in some soil and plant samples within that project, the present study investigates the elemental composition of soil and plants from two affected gardens 1 year after compost amendment. Inductively coupled plasma mass spectrometry (ICP-MS) analysis of skin, pulp and seeds of tomato fruits revealed minor variations in elemental composition which are unlikely to have an impact on food safety. In turn, a tendency of contaminant accumulation in root tips and leaves of radishes was found. Washing of lettuce led to a significant reduction in the contents of potentially toxic elements such as Be, Al, V, Ni, Ga and Tl, underscoring the significance of washing garden products before consumption. Furthermore, compost amendments led to promising results, with reduced Zn, Cd and Pb levels in radish bulbs. Pb isotope ratios in soil and spinach leaf samples taken in the previous study were assessed by multi-collector (MC-) ICP-MS to trace Pb uptake from soils into food. A direct linkage between the Pb isotopic signatures in soil and those in spinach leaves was observed, underscoring their effectiveness as tracers of Pb sources in the environment.

Green and blue infrastructure as model system for emissions of technology-critical elements.

Over the recent decades, technological advancements have led to a rise in the use of so-called technology-critical elements (TCEs). Environmental monitoring of TCEs forms the base to assess whether this leads to increased anthropogenic release and to public health implications. This study employs an exploratory approach to investigate the distribution of the TCEs Li, Be, V, Ga, Ge, Nb, Sb, Te, Ta, Tl, Bi and the REYs (rare-earth elements including yttrium) in urban aerosol in the city of Vienna, Austria. Leaf samples (n = 292) from 8 plant species and two green facades and water samples (n = 18) from the Wienfluss river were examined using inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). Surface dust contributions were assessed by washing one replicate of each leaf sample and analysing the washing water (n = 146). The impacts of sampling month, plant species and storey level on elemental distribution were assessed by statistical tools and generative deep neural network modelling. Higher TCE levels, including Li, V, Ga, Ge, Tl, Bi, and the REYs, were found in the winter months, likely due to the use of de-icing materials and fossil fuel combustion. A. millefolium and S. heufleriana displayed the highest levels of Li and Ge, respectively. In addition, increased elemental accumulation at lower storeys was observed, including Be, Sb, Bi and the REYs, indicating greater atmospheric dust deposition and recirculation closer to ground level. The results suggest a broad association of TCE levels with urban dust. This study enhances the current understanding of TCE distribution in urban settings and underscores the importance of their inclusion in pollution monitoring. It highlights the complex interplay of human activities, urban infrastructure, and environmental factors, offering valuable insights for managing urban environmental health risks and underlining the need for comprehensive urban ecosystem studies.

Elucidating the Role of Honey Bees as Biomonitors in Environmental Health Research.

Recently, the One Health concept, which recognizes the interconnectedness of environmental, animal, and human health, has gained popularity. To collect data on environmental pollutants potentially harmful to human health over time, researchers often turn to natural organisms known as biomonitors. Honey bees, in particular, prove to be exceptionally valuable biomonitors due to their capacity to accumulate pollutants from the air, soil, and water within a specific radius during their foraging trips. This systematic literature review summarizes the previous application of the bee species Apis mellifera in pollutant monitoring in articles published during the period of 2010-2020. Nineteen studies were included in this systematic literature review. Of these studies, the majority (n = 15) focused on the detection of heavy metals in honey bees and beehive products, while 4 studies focused on air pollution by polycyclic aromatic hydrocarbons or particulate matter. The matrix most often applied was the whole honey bee. The included studies demonstrated that honey bees and hive products deliver quantitative and qualitative information about specific pollutants. In this regard, the whole honey bee was found to be the most reliable biomonitor. We found that the included studies differed in design and the methods used. Standardized studies could foster a more consistent interpretation of the levels detected in beehive matrices from an environmental health perspective.

Characterisation of gas cell reactions for 70+ elements using N2O for ICP tandem mass spectrometry measurements.

One widely utilised method to reduce spectral interferences for measurements using inductively coupled plasma mass spectrometry (ICP-MS) is to employ the use of a reaction cell gas. Nitrous oxide (N2O) is a highly reactive gas typically used for mass-shifting only target analytes to a higher mass-to-charge ratio with increased sensitivity (e.g. +16, +32, +48 amu for monoxide, dioxide, and trioxide product ions respectively). Traditionally, the use of N2O was limited to selected applications due to the creation of new interferences that also interfere with the detected masses of interest. However, with the advent of inductively coupled plasma tandem mass spectrometry (ICP-MS/MS), the use of N2O has gained more traction, with a growing number of publications in recent years. Here, a comprehensive study of the use of N2O for the determination of 73 elements has been conducted, with a comparison to the most widely used mass-shift method using oxygen (O2) as a reaction gas. In total, 59 elements showed improved sensitivity when performing mass-shift with N2O compared to O2, with 8 elements showing no reaction with either gas. Additionally, N2O demonstrated a collisional focusing effect for 36 elements when measuring on-mass. This effect was not observed using O2. Monitoring asymmetric charge transfer reactions with N2O highlighted 14 elements, primarily non-metals and semi-metals, that enter the gas cell as metastable ions and could be used as an alternative mass-shift option. The results from this study highlight the high versatility of N2O as a reaction cell gas for routine ICP-MS/MS measurements.

Determination of 48 elements in 7 plant CRMs by ICP-MS/MS with a focus on technology-critical elements.

Seven plant certified reference materials (NIST SRM1515 Apple Leaves, NIST SRM1547 Peach Leaves, BCR-129 Hay Powder, BCR-670 Aquatic Plant, GBW07603 Bush Twigs and Leaves, GBW10015 Spinach Leaves and NCS ZC73036a Green Tea) were analysed for their mass fractions of 48 elements by inductively coupled plasma tandem-mass spectrometry (ICP-MS/MS): Li, Be, Na, Mg, Al, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Nb, Mo, Ag, Cd, Sb, Te, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ta, Tl, Pb, Bi, Th, U. Special focus was put on the determination of technology-critical elements (TCEs), to which, e.g. Li, Be, Ga, Ge, Nb, Sb, Ta, Tl, Bi, and the rare-earth elements (REEs, lanthanides and Y) are counted. Closed-vessel microwave digestion was performed using HNO3, H2O2 and HBF4. The average bias for certified values is - 1% ± 13% (SD). Limits of detection (xL) in the measured solutions lie between 13 fg g-1 (Tb) and 52 ng g-1 (Ca). This article seeks to provide an optimised measurement procedure for the determination of element mass fractions of emerging importance in environmental samples, which are challenging to analyse with more traditional techniques such as single-quad ICP-MS. In addition, it aims to improve the characterisation of commonly used plant reference materials by providing mass fraction data for rarely studied elements.

Enriched stable 204Pb as tracer at ultra-low levels in clinical investigations.

The potential of enriched Pb (204Pb) was assessed to monitor pathways of trace levels of Pb in the pg range within the human body via isotope pattern variation in situations where natural lead cannot be used as a tracer due to regulatory limitations. Isotope ratio measurements were accomplished by means of (multi-collector) inductively coupled plasma mass spectrometry including a comparison of single and multi-collector ICP-MS for low-level 204Pb assessment. Isotopic pattern results from a blend of a large quantity of the element with a natural isotopic composition and an enriched stable isotope at orders of magnitude lower levels pose a nontrivial analytical problem. Isotope pattern deconvolution was successfully applied as mathematical tool based on multiple linear regressions. The method allowed for deconvolving the isotope pattern from measured isotope ratios without knowing the quantities of different isotope sources incorporated and mixed into the sample at levels of < 1 pg 204Pb/g blood. The objective of this manuscript is to evaluate and summarize the analytical aspects for Pb isotope pattern deconvolution based on the results of a clinical trial, where a 204Pb-enriched isotope tracer was applied to investigate the bioavailability of orally applied Pb along with purified clinoptilolite tuff as potential supplement. This unique approach allows to reduce tracer amounts to harmless levels to human health, which are in accordance with the legal regulative to study enrichment levels of < 0.01% in human blood.

Microchemical provenancing of prey remains in cormorant pellets reveals the use of diverse foraging grounds.

Piscivorous birds in aquatic ecosystems exert predation pressure on fish populations. But the site-specific impact on fish populations, including stocked and commercially used fish species, remains disputed. One of the key questions for the management of piscivorous birds and fish is determining the origin of prey and thus which fish populations are targeted by the birds. We addressed this question by provenancing otoliths (earstones) of fish obtained from regurgitated pellets of piscivorous birds by otolith microchemistry analysis. We retrieved otoliths from regurgitated pellets of great cormorants (Phalacrocorax carbo sinensis) collected every 2 weeks for 2 years from breeding and roosting colonies at Chiemsee in Bavaria, Germany, and classified them according to family or species. We collected water samples from Chiemsee and potential surrounding foraging grounds. We measured the strontium (Sr) 87Sr/86Sr isotope ratio and Sr mass fraction of water and otoliths using (laser ablation) inductively coupled plasma-mass spectrometry. We assigned otoliths from regurgitated pellets to habitat clusters of origin by comparing the Sr isotopic and elemental composition of otoliths and waterbodies. In 36% of cormorant pellets collected at Chiemsee, prey was assigned to waterbodies distinct from Chiemsee. Furthermore, cormorants used different foraging sites during 1 day. Microchemical provenancing of prey remains can contribute to identifying foraging sites of piscivorous birds and to what extend the birds switched among foraging sites.

In situ spatiotemporal solute imaging of metal corrosion on the example of magnesium.

Visualization and quantification of corrosion processes is essential in materials research. Here we present a new approach for 2D spatiotemporal imaging of metal corrosion dynamics in situ. The approach combines time-integrated Mg2+ flux imaging by diffusive gradients in thin films laser ablation inductively coupled plasma mass spectrometry (DGT LA-ICP-MS) and near real-time pH imaging by planar optodes. The parallel assessment of Mg2+ flux and pH distributions on a fine-structured, bare Mg alloy (b-WE43) showed intense Mg dissolution with Mg2+ flux maxima up to 11.9 ng cm-2 s-1 and pH increase >9 during initial corrosion (≤15 min) in aqueous NaNO3 solution (c = 0.01 mol L-1). The techniques visualized the lower initial corrosion rate in buffered synthetic body fluid (Hank's balanced salt solution; pH 7.6) compared to unbuffered NaNO3 (pH 6.0), but precise localization of Mg corrosion remains challenging under these conditions. To further demonstrate the capability of DGT LA-ICP-MS for spatiotemporal metal flux imaging at the microscale, a coated Mg alloy (c-WE43) with lower reactivity was deployed for ≤120 min. The high spatial resolution (∼10 µm × 80 µm) and low limits of detection (≤0.04 ng cm-2 s-1, t = 60 min) enabled accurate in situ localization and quantification (Urel = 20%, k = 2) of distinct Mg2+ flux increase, showing micro-confined release of Mg2+ from surface coating defects on c-WE43 samples. The presented approach can be extended to other metal species and applied to other materials to better understand corrosion processes and improve material design in technological engineering.

Low-level 40Ca determinations using nitrous oxide with reaction cell inductively coupled plasma-tandem mass spectrometry.

In inductively coupled plasma mass spectrometry, the most abundant Ca isotope (40Ca) suffers from isobaric interference with argon, hindering the potential for low detection limits of Ca. A powerful approach is to remove the interference by using a reaction gas in a reaction cell. Ammonia (NH3) has proven to be an effective reaction gas by process of a charge transfer reaction. However, NH3 is highly corrosive and toxic and cannot remove isobaric 40 K. Therefore, this work proposes the use of nitrous oxide (N2O) to mass shift the target analyte 40Ca to 40Ca16O+ as a non-corrosive and non-toxic alternative. Instrument performance testing demonstrated that N2O was capable of reaching equivalent detection limits (0.015 ng g-1) and background equivalence concentrations (0.041 ng g-1) to that of NH3 and limited by the blank only. Further investigation of matrix interferences with synthetic standards highlighted that the N2O approach supports the separation of potassium (K) and magnesium (Mg)-based interferences at tested concentrations of more than 600 times and almost 800 times higher than Ca respectively, whereas NH3 was found to only support the removal of Mg. This work highlights a clear advantage of N2O for low-level Ca determinations with high matrix loads, as well as compatibility with other instrumentation sensitive to corrosion that supports reaction cell technology.

Selective Diffusive Gradients in Thin Films (DGT) for the Simultaneous Assessment of Labile Sr and Pb Concentrations and Isotope Ratios in Soils.

A method using diffusive gradients in thin films (DGT) for the accurate quantification of trace-level (µg L-1) Sr and Pb concentrations and isotope ratios [δSRM 987(87Sr/86Sr) and δSRM 981(207Pb/206Pb)] in labile, bioavailable element fractions in soils is reported. The method is based on a novel poly(tetrafluoroethylene) (PTFE) membrane binding layer with combined di(2-ethyl-hexyl)phosphoric acid (HDEHP) and 4,4'(5')-bis-t-butylcyclohexano-18-crown-6 (crown-ether) functionality with high selectivity for Sr and Pb (TK100 membrane). Laboratory evaluation of the TK100 DGT showed linear uptake of Sr over time (2-24 h) up to very high Sr mass loadings on TK100 membranes (288 µg cm-2) and effective performance in the range of pH (3.9-8.2), ionic strength (0.001-0.1 mol L-1), and cation competition (50-160 mg L-1 Ca in a synthetic soil solution matrix) of environmental interest. Selective three-step elution of TK100 membranes using hydrochloric acid allowed us to obtain purified Sr and Pb fractions with adequate (≥75%) recovery and quantitative (≥96%) matrix reduction. Neither DGT-based sampling itself nor selective elution or mass loading effects caused significant isotopic fractionation. Application of TK100 DGT in natural soils and comparison with conventional approaches of bioavailability assessment demonstrated the method's unique capability to obtain information on Sr and Pb resupply dynamics and isotopic variations with low combined uncertainty within a single sampling step.

Lifetime mobility of an Arctic woolly mammoth.

Little is known about woolly mammoth (Mammuthus primigenius) mobility and range. Here we use high temporal resolution sequential analyses of strontium isotope ratios along an entire 1.7-meter-long tusk to reconstruct the movements of an Arctic woolly mammoth that lived 17,100 years ago, during the last ice age. We use an isotope-guided random walk approach to compare the tusk's strontium and oxygen isotope profiles to isotopic maps. Our modeling reveals patterns of movement across a geographically extensive range during the animal's ~28-year life span that varied with life stages. Maintenance of this level of mobility by megafaunal species such as mammoth would have been increasingly difficult as the ice age ended and the environment changed at high latitudes.

Concomitant oral intake of purified clinoptilolite tuff (G-PUR) reduces enteral lead uptake in healthy humans.

Lead exposure can cause substantial organ damage. Enteral lead absorption may be reduced by concomitant intake of clinoptilolite tuff, a zeolite from natural sources. This study aimed to assess the effect of purified clinoptilolite tuff (G-PUR) on enteral lead uptake in adults using stable lead isotope 204Pb as a tracer. In this randomized, placebo-controlled, double-blind, parallel-group study, 42 healthy participants were randomized to receive oral G-PUR 2.0 g, 2 * 2.0 g, or placebo, together with 2.5 µg of 204Pb in water. The enrichment of 204Pb caused by the tracer in blood and urine was measured by mass spectrometry. G-PUR was well tolerated. The mean maximum 204Pb enrichment of 0.505% of total blood lead was significantly higher (p < 0.0001) in the placebo group compared to G-PUR 2.0 g (0.073%) or G-PUR 2 * 2.0 g (0.057%) group. Normalized 204Pb AUC0-192 was 86.5, 11.9, and 8.5% * h without and with G-PUR 2.0 g, and G-PUR 2 * 2.0 g, respectively (p < 0.0001 vs. placebo). This smaller 204Pb exposure was paralleled by a reduced urinary excretion in subjects receiving G-PUR. Concomitant oral intake of purified clinoptilolite tuff reduced enteral uptake of 204Pb in healthy humans by approximately 90%. The reduced bioavailability is demonstrable by a decrease of 204Pb tracer enrichment in blood and urine.Trial registration: clinicaltrials.gov identifier: NCT04138693, registered 24/10/2019.

Ancient DNA reveals monozygotic newborn twins from the Upper Palaeolithic.

The Upper Palaeolithic double burial of newborns and the single burial of a ca. 3-month-old infant uncovered at the Gravettian site of Krems-Wachtberg, Austria, are of paramount importance given the rarity of immature human remains from this time. Genome-wide ancient DNA shows that the male infants of the double grave are the earliest reported case of monozygotic twins, while the single grave´s individual was their 3rd-degree male relative. We assessed the individuals´ age at death by applying histological and µCT inspection of the maxillary second incisors (i2) in conjunction with C- and N-isotope ratios and Barium (Ba) intake as biomarker for breastfeeding. The results show that the twins were full-term newborns, and that while individual 2 died at birth, individual 1 survived for about 50 days. The findings show that Gravettian mortuary behaviour also included re-opening of a grave and manipulation of its layout and content.

Sub-millimeter distribution of labile trace element fluxes in the rhizosphere explains differential effects of soil liming on cadmium and zinc uptake in maize.

Trace element concentrations in the rhizosphere were quantified to better understand why soil liming often fails to reduce cadmium (Cd) uptake by plants. Maize seedlings were grown on a soil with natural background levels of Cd and zinc (Zn). Soil liming increased soil pH from 4.9 to 6.5 and lowered the soil solution free ion activities by factor 7 (Cd) and 9 (Zn). In contrast, shoot Cd concentrations were unaffected by liming while shoot Zn concentrations were lowered by factor 1.9. Mapping of labile soil trace elements using diffusive gradients in thin films (DGT) in combination with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) revealed an almost complete depletion of Cd in the rhizosphere in all soil treatments, showing that Cd uptake is controlled by diffusion. The flux of Cd from soil to the DGT, with direct contact between the soil and the binding gel, was unaffected by liming whereas it decreased by factor 3 for Zn, closely mimicking the contrasting effects of liming on Cd and Zn bioavailability. This evidence, combined with additional flux data of freshly spiked Cd and Zn isotopes in soil and with modelling, suggests that the diffusive transport of Cd in unsaturated soil is more strongly controlled by the labile adsorbed metal concentration than by its concentration in solution. This is less the case for Zn because of its inherently slower desorption compared to Cd.

Characterization of alloying components in galvanic anodes as potential environmental tracers for heavy metal emissions from offshore wind structures.

The impact of offshore constructions on the marine environment is unknown in many aspects. The application of Al- and Zn-based galvanic anodes as corrosion protection results in the continuous emission of inorganic matter (e.g. >80 kg Al-anode material per monopile foundation and year) into the marine environment. To identify tracers for emissions from offshore wind structures, anode materials (Al-based and Zn-based) were characterized for their elemental and isotopic composition. An acid digestion and analysis method for Al and Zn alloys was adapted and validated using the alloy CRMs ERM®-EB317 (AlZn6CuMgZr) and ERM®-EB602 (ZnAl4Cu1). Digests were measured for their elemental composition by ICP-MS/MS and for their Pb isotope ratios by MC ICP-MS. Ga and In were identified as potential tracers. Moreover, a combined tracer approach of the elements Al, Zn, Ga, Cd, In and Pb together with Pb isotope ratios is suggested for a reliable identification of offshore-wind-farm-induced emissions. In the Al anodes, the mass fractions were found to be >94.4% of Al, >26200 mg kg-1 of Zn, >78.5 mg kg-1 of Ga, >0.255 mg kg-1 of Cd, >143 mg kg-1 of In and >6.7 mg kg-1 of Pb. The Zn anodes showed mass fractions of >2160 mg kg-1 of Al, >94.5% of Zn, >1.31 mg kg-1 of Ga, >254 mg kg-1 of Cd, >0.019 mg kg-1 of In and >14.1 mg kg-1 of Pb. The n(208Pb)/n(206Pb) isotope ratios in Al anodes range from 2.0619 to 2.0723, whereas Zn anodes feature n(208Pb)/n(206Pb) isotope ratios ranging from 2.0927 to 2.1263.

Extreme spatial variation of Sr, Nd and Pb isotopic signatures and 48 element mass fractions in surface sediment of the Elbe River Estuary - Suitable tracers for processes in dynamic environments?

The Elbe River has been long considered as one of the most anthropogenically impacted rivers in Europe. Its estuary is characterized by strong tidal effects, continuous dredging and dumping of sediment, and intense ship traffic between the North Sea and the Port of Hamburg. The aim of this study was to elucidate if a combined multi-element fingerprinting and isotopic tracer approach represented a suitable tool to investigate transport and mixing processes of inorganic contaminants within a complex and highly dynamic estuarine environment. A total of 37 surface sediment samples from the tidal Elbe were characterized in a comprehensive survey by determining the mass fractions of 48 elements and the isotopic signatures of stable Sr, Nd and Pb. Statistical data analysis resolved four discrete clusters of sampling locations in the estuary: One cluster upstream of the city of Hamburg, two clusters within the mixing zone between Hamburg and the mouth of the Elbe Estuary and one cluster in the mouth of the Estuary. River sediment entering the estuary carry significantly higher loads of metals (e.g. Cu, Zn, Sb, Cd and Pb), which are rapidly "diluted" by lower elemental mass fractions in marine sediment on a remarkably small regional scale. The cluster within the mouth of the estuary is mainly characterized by extreme isotopic variations of n(208Pb)/n(204Pb) ranging from 38.67 ±â€¯0.15 to 73.86 ±â€¯0.29, beside high mass fractions of U, Th, and some rare-earth elements. Determined Pb isotope ratios are among the highest reported values for terrestrial materials. This study indicates the general potential of combined element fingerprinting and isotope tracer approaches to elucidate processes in complex river systems. Furthermore, it represents an initial characterization of the catchment area of the Elbe River as basis for future studies on river and harbor management.