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.

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.

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.

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.

Rapid Determination of Per- and Polyfluoroalkyl Substances (PFAS) in Harbour Porpoise Liver Tissue by HybridSPE®-UPLC®-MS/MS.

A rapid hybrid solid phase extraction (HybridSPE®) protocol tailored to ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry (UPLC®-ESI-MS/MS) analysis was developed for the determination of 15 per- and polyfluoroalkyl substances (PFAS) in liver tissue from harbour porpoises (Phocoena phocoena). The HybridSPE® technique has been applied in trace concentration bioanalysis, but it was mainly used for liquid biological media until now. In this study, the protocol was applied on tissue matrix, and it demonstrated acceptable absolute recoveries (%) ranging from 44.4 to 89.4%. The chromatographic separation was carried out using a gradient elution program with a total run time of 4 min. The inter-day method precision ranged from 2.15 to 15.4%, and the method limits of detection (LODs) ranged from 0.003 to 0.30 ng/g wet weight (w.w.). A total of 20 liver samples were analyzed to demonstrate the applicability of the developed method in liver tissue from a wildlife species.

NMR resonance assignments of the pathogenesis-related peach allergen Pru p 1.0101.

In Europe, Northern America, and China a large number of individuals are suffering from peach (Prunus persica) allergy caused by the protein Pru p 1. Immunologic reactions against this 17.5 kDa protein result from initial sensitization to the birch (Betula verrucosa) pollen allergen Bet v 1 and subsequent immunologic cross-reactivity of Bet v 1 specific antibodies. Allergic symptoms typically include severe itching, scratching of the throat, and rhino conjunctivitis. So far, experimental structural data for the peach allergen Pru p 1 are not available. In a first step towards the elucidation of the structure of this protein we assigned backbone and side chain 1H, 13C, and 15N chemical shifts of the naturally occurring isoform Pru p 1.0101 by solution NMR spectroscopy. Our chemical shift data indicate that this protein fold consists of seven ß-strands separated by two short α-helices and a long C-terminal α-helix, which is in accordance with the reported crystal structure of Bet v 1. Our data provide the basis for determining the three-dimensional solution structure of this protein and to characterize its immunologic cross-reactivity on a structural basis.