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.

A tool to assure the geographical origin of local food products (glasshouse tomatoes) using labeling with rare earth elements.

BACKGROUND: Trace element fingerprinting has been widely used for identification of provenance of regional food. In the case of products from conventional agriculture, it is expected that the elemental composition will comply with that of the commercially available substrate of the plants. Therefore, for products without a direct relationship with the regional soil the region-specific differences in elemental composition are no longer recognizable. The idea of this work is the labeling of tomatoes with rare earth elements (REE) in the ultra-trace range for food authentication. RESULTS: Labeling of tomatoes was carried out either by watering the soil with Nd- and Er-spiked water or by adding these elements as solid oxides to the soil. In both cases enrichment of Nd and Er relative to the control group was detected in tomato fruits and leaves using inductively coupled plasma-mass spectrometry. Tomato plants rapidly absorb the dissolved REE from the irrigation water, and watering for a short period just before ripeness is sufficient to induce REE labels. CONCLUSION: Labeling with trace amounts of REE could potentially be used to assure the provenance of tomatoes of local origin and separate these from products of foreign origin. © 2018 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

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.

Characterization of Zr-Containing Dispersoids in Al-Zn-Mg-Cu Alloys by Small-Angle Scattering.

The characterization of Zr-containing dispersoids in aluminum alloys is challenging due to their broad size distribution, low volume fraction, and heterogeneous distribution within the grains. In this work, small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) were compared to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) regarding their capability to characterize Zr-containing dispersoids in aluminum alloys. It was demonstrated that both scattering techniques are suitable tools to characterize dispersoids in a multi-phase industrial 7xxx series aluminum alloy. While SAXS is more sensitive than SANS due to the high electron density of Zr-containing dispersoids, SANS has the advantage of being able to probe a much larger sample volume. The combination of both scattering techniques allows for the verification that the contribution from dispersoids can be separated from that of other precipitate phases such as the S-phase or GP-zones. The size distributions obtained from SAXS, SANS and TEM showed good agreement. The SEM-derived size distributions were, however, found to significantly deviate from those of the other techniques, which can be explained by considering the resolution-limited restrictions of the different techniques.

To Waste or Not to Waste: Questioning Potential Health Risks of Micro- and Nanoplastics with a Focus on Their Ingestion and Potential Carcinogenicity.

Micro- and nanoplastics (MNPs) are recognized as emerging contaminants, especially in food, with unknown health significance. MNPs passing through the gastrointestinal tract have been brought in context with disruption of the gut microbiome. Several molecular mechanisms have been described to facilitate tissue uptake of MNPs, which then are involved in local inflammatory and immune responses. Furthermore, MNPs can act as potential transporters ("vectors") of contaminants and as chemosensitizers for toxic substances ("Trojan Horse effect"). In this review, we summarize current multidisciplinary knowledge of ingested MNPs and their potential adverse health effects. We discuss new insights into analytical and molecular modeling tools to help us better understand the local deposition and uptake of MNPs that might drive carcinogenic signaling. We present bioethical insights to basically re-consider the "culture of consumerism." Finally, we map out prominent research questions in accordance with the Sustainable Development Goals of the United Nations.

Authentication of meat and dairy products using rare earth element labeling and detection by solution based and laser ablation ICP-MS.

In order to meet the increasing customer demand for local food products, various methods for verification of food origin by means of region specific trace element fingerprinting have been developed. However, for products from conventional agriculture, without a close relationship to the local soil, other methods for food authentication are required. In an alternative approach, foodstuffs produced in a certain region, by a specific producer or under certain conditions can be safeguarded against imitation by chemical labeling. The objective of the present study was to develop a method for labeling lamb meat and goat milk by selective enrichment of terbium and thulium in the feed for the animals. Therefore, a distinctive rare earth element (REE) pattern is artificially introduced which can be determined in labeled food products. Detection of REE labels was carried out using inductively coupled plasma mass spectrometry (ICP-MS) after acid digestion. Alternatively, laser ablation ICP-MS (LA-ICP-MS) was applied, allowing direct analysis of bone samples and analysis of meat and milk samples after dry ashing and pressing pellets. After three weeks of administering 1000-fold terbium and thulium enriched feed to lambs, terbium and thulium enrichment was detected in all sample types except blood, following the trend bones > kidney > liver > heart > meat > kidney fat. Similarly, goat milk was successfully labeled after three weeks of feeding 500-fold terbium and thulium enriched feed. Hence, the present method allows discrimination of labeled from unlabeled animal products, while REE contents in all labeled products remained low enough to avoid any health risk for the consumer.

Rare Earth Element Labeling as a Tool for Assuring the Origin of Eggs and Poultry Products.

Laying hens were fed terbium and thulium supplemented feed in order to introduce a distinctive rare earth element pattern that allows discrimination of labeled from unlabeled poultry products. Samples of egg yolk, egg shells, meat, bones, liver, blood, and feces were analyzed using either conventional or laser ablation inductively coupled plasma mass spectrometry. Already after a short time of administering supplemented feed, terbium and thulium enrichment could be unambiguously detected in the products, while absolute terbium and thulium contents remained low enough to ensure safety for the customer. This method could potentially be applied to specifically label foodstuffs produced in certain regions or under certain conditions, in order to ensure food authenticity.

The potential impact of municipal solid waste incinerators ashes on the anthropogenic osmium budget.

Osmium release from Municipal Solid Waste Incinerators (MSWI), even if acknowledged to occur at least over the last fifteen years, remains overlooked in the majority of recent studies. We present the osmium concentration and (187)Os/(188)Os isotopic measurements of different kinds of bottom and fly ash samples from MSWI plants and reference materials of incinerator fly ash (BCR176 and BCR176R). The analysis of the unknown ash samples shows a relatively wide range of (187)Os/(188)Os ratios (0.24-0.70) and Os concentrations (from 0.026 ng/g to 1.65 ng/g). Osmium concentrations and isotopic signatures differ from those of other known Os sources, either natural or manmade, suggesting a mixture of both contributions in the MSWI feedstock material. Furthermore, the comparison between the BCR176 and the renewed BCR176R indicates a decrease in Os concentration of one order of magnitude over the years (from 1 to 0.1 ng/g) due to improved recycling efficiency of Os-bearing waste. The estimated annual amount of Os from a typical incinerator (using average Os values and MSWI mass balance) is 13.4 g/a. The osmium potentially released from MSWI smokestacks is predicted to be from 16 to 38 ng Os/m(2)/a, considering a medium size country having 50 MSWI facilities; therefore much higher than the naturally transported osmium from continental dust in the atmosphere (about 1 pg Os/m(2)/a). MSWI systems are considered one of the best options for municipal solid waste management in industrialised countries, but their contribution to the Os budget can be significant.

The rare earth elements in municipal solid waste incinerators ash and promising tools for their prospecting.

Bottom and fly ashes from Municipal Solid Waste Incinerators (MSWI) are hazardous products that present concern for their safe management. An attractive option to reduce their impact both on the environment and the financial commitment is turning MSWI ashes into secondary raw materials. In this study we present the REE content and distribution of bottom and fly ashes from MSWI after a highly effective digestion method and samples analysis by ICP-MS. The chondrite-normalised REE patterns of MSWI bottom and fly ash are comparable with that of crustal averages, suggesting a main geogenic source. Deviations from typical crustal pattern (e.g., Eu, Tb) disclose a contribution of likely anthropogenic provenance. The correlation with major elements indicates possible sources for REE and facilitates a preliminary resource assessment. Moreover, magnetic susceptibility measurements can be a useful prospecting method in urban ores made of MSWI ashes. The relationship between REE and some influencing parameters (e.g., Pricing Influence Factor) emphasises the importance of MSWI ash as alternative source of REE and the need of further efforts for REE recovery and purification from low concentrations but high flows waste.

Active biomonitoring of palladium, platinum, and rhodium emissions from road traffic using transplanted moss.

The use of transplanted moss (Pleurozium schreberi) in active biomonitoring of traffic-related emissions of Pd, Pt, and Rh was studied. Moss mats were transplanted to three locations along highway E75 (in Oulu, Finland) at three different distances from the highway. Five samples were collected from a background site after the same exposure period. Mass fractions of Pd, Pt, and Rh as well as mass fractions of 18 other elements were determined in these samples. The results indicated that P. schreberi is well suited for active biomonitoring of Pd, Pt, and Rh. Mass fractions above the background values were observed in the samples exposed to traffic-related emissions. When the results were compared with those of the other elements, high correlations of Pd, Pt, and Rh with commonly traffic-related elements (e.g., Cu, Ni, Sb, Zn, etc.) were found. It was also found that the amounts of Pd, Pt, and Rh in moss samples decreased when the distance to the highway increased. This trend gives evidence for the suitability of P. schreberi for active biomonitoring of Pd, Pt, and Rh. Furthermore, it can be concluded that the mass fractions determined in this study provide valuable evidence about the current state of Pd, Pt, and Rh emissions in Oulu, Finland.

Solid residues from Italian municipal solid waste incinerators: A source for "critical" raw materials.

The incineration of municipal solid wastes is an important part of the waste management system along with recycling and waste disposal, and the solid residues produced after the thermal process have received attention for environmental concerns and the recovery of valuable metals. This study focuses on the Critical Raw Materials (CRM) content in solid residues from two Italian municipal waste incinerator (MSWI) plants. We sampled untreated bottom ash and fly ash residues, i.e. the two main outputs of common grate-furnace incinerators, and determined their total elemental composition with sensitive analytical techniques such as XRF and ICP-MS. After the removal of a few coarse metallic objects from bottom ashes, the corresponding ICP solutions were obtained using strong digestion methods, to ensure the dissolution of the most refractory components that could host significant amounts of precious metals and CRM. The integration of accurate chemical data with a substance flow analysis, which takes into account the mass balance and uncertainties assessment, indicates that bottom and fly ashes can be considered as a low concentration stream of precious and high-tech metals. The magnesium, copper, antimony and zinc contents are close to the corresponding values of a low-grade ore. The distribution of the elements flow between bottom and fly ash, and within different grain size fractions of bottom ash, is appraised. Most elements are enriched in the bottom ash flow, especially in the fine grained fractions. However, the calculated transfer coefficients indicate that Sb and Zn strongly partition into the fly ashes. The comparison with available studies indicates that the CRM concentrations in the untreated solid residues are comparable with those residues that undergo post-treatment beneficiations, e.g. separation between ferrous and non-ferrous fractions. The suggested separate collection of "fresh" bottom ash, which could be processed for further mineral upgrading, can constitute an attractive option of the waste management system, when physical-mechanical devices are not available or could not be implemented in old MSWI systems. The suggested procedure may lead to the improvement of recovery efficiency up to 83% for CRM and 94% for other valuable metals.

Determination of anthropogenic input of Ru, Rh, Pd, Re, Os, Ir and Pt in soils along Austrian motorways by isotope dilution ICP-MS.

A joint study with the Federal Environment Agency of Austria was carried out to determine the distribution of Ru, Rh, Pd, Os, Ir and Pt (PGE) and Re in soils along major motorways. Emphasis was put on Ir as to date little is known about its anthropogenic input as this metal is now also used in automobile catalytic converters. Soil samples were analysed by ICP-MS through online-coupling of a chromatographic column to separate the PGEs from interfering matrix constituents. At all sampled sites not only Rh, Pd and Pt but also Ir and Re significantly exceed natural background values; concentrations reached 13 ng/g, 25 ng/g, 134 ng/g, 1.1 ng/g and 9.8 ng/g, respectively. The analytical procedure proved to be very selective and sensitive and, therefore applicable to routine soil analysis.

Suitability of elemental fingerprinting for assessing the geographic origin of pumpkin (Cucurbita pepo var. styriaca) seed oil.

An analytical method was developed and validated for the classification of the geographical origin of pumpkin seeds and oil from Austria, China and Russia. The distribution of element traces in pumpkin seed and pumpkin seed oils in relation to the geographical origin of soils of several agricultural farms in Austria was studied in detail. Samples from several geographic origins were taken from parts of the pumpkin, pumpkin flesh, seeds, the oil extracted from the seeds and the oil-extraction cake as well as the topsoil on which the plants were grown. Plants from different geographical origin show variations of the elemental patterns that are significantly large, reproducible over the years and ripeness period and show no significant influence of oil production procedure, to allow to a discrimination of geographical origin. A successful differentiation of oils from different regions in Austria, China and Russia classified with multivariate data analysis is demonstrated.

Antimony speciation in soil samples along two Austrian motorways by HPLC-ID-ICP-MS.

Distribution of antimony and its inorganic species in soil samples along two traffic routes (A14, Rankweil and S36, Knittelfeld) in Austria was determined, since vehicle emissions are an important anthropogenic source of Sb in soil. The samples were taken along three parallel lines at about 0.2, 2 and 10 m distances from the edge of the road and in two depths range (0-5 and 5-10 cm from the soil surface). The optimized extraction was carried out using 100 mmol L(-1) citric acid at pH 2.08 applying an ultrasonic bath for 45 min at room temperature. Speciation analyses were done using on-line isotope dilution after a chromatographic separation of Sb species. Results of the two traffic routes confirmed significant accumulations of Sb at surface (0-5 cm depth) exceeding the natural background values by more than ten times at the S36 or four times at the A14. Concentrations of the extractable inorganic species decreased to natural background levels within a few meters from the edge of the traffic lane. The predominant Sb species was Sb(V). The Sb(III) concentrations at 5-10 cm depths range are nearly constant with distance from the edges of the two roads. Magnetic susceptibility data of all soil samples show the same distribution pattern as Sb and Sb(V) concentrations along the two traffic roads with an excellent correlation. This is an evidence for an anthropogenic source of Sb such as abrasions of motor vehicles surfaces or braking linings. The input of Sb and its inorganic species at one of the sampling sites (Knittelfeld) in samples taken in 2002 and in those taken recently (2005) was monitored. An increase in Sb (>or=30%), Sb(v)(>or=51%) and Sb(iii)(>or=10%) concentrations was only observed near the edge (

Speciation analysis of inorganic antimony in soil using HPLC-ID-ICP-MS.

Speciation analysis of Sb(III) and Sb(V) in a soil sample was performed through extraction and on-line isotope dilution concentration determination after a chromatographic separation. The total Sb concentration found in a through traffic contaminated soil sample was (4.17 microg g(-1), 0.3 microg g(-1) SD, n=6). It was determined using ICP-MS after soil digestion using the sodium peroxide sintering method. The optimized extraction procedure for speciation analysis was carried out using 100 mmol L(-1) citric acid at pH 2.08 by applying an ultrasonic bath for 45 min at room temperature. The effects of citric acid concentration (0-500 mmol L(-1)), pH (1-6), and temperature (30-60 degrees C) on inorganic antimony species distribution in the examined sample were studied and optimized. The separation of Sb(III) and Sb(V) was achieved using an anion exchange column (PRP-X100) and 10 mmol L(-1) EDTA and 1 mmol L(-1) phthalic acid at pH 4.5 as a mobile phase. The eluent from the HPLC was mixed with an enriched (94.2%) (123)Sb spike solution that was pumped by a peristaltic pump with a constant flow rate (0.5 mL min(-1)) in a three-way valve. The blend passed directly to the Conikal nebulizer of the ICP-MS. By using the above extraction procedure and methodology, 43.2% Sb(V) (2.9% RSD, n=3) and 6.0% Sb(III) (1.3% RSD, n=3) of total Sb found in the sample could be detected. The detection limits achieved by the proposed method were 20 ng L(-1) and 65 ng L(-1) for Sb(V) and Sb(III), respectively. The precision, evaluated by using RSD with 100 ng L(-1) calibration solutions, was 2.7% and 3.2% (n=6) for Sb(V) and Sb(III), respectively, in aqueous solutions.

Combined chemical separation of Lu, Hf, Sm, Nd, and Rees from a single rock digest: precise and accurate isotope determinations of Lu-Hf and Sm-Nd using multicollector-ICPMS.

A combined procedure for separating Lu, Hf, Sm, Nd, and rare earth elements (REEs) from a single sample digest is presented. The procedure consists of the following five steps: (1) sample dissolution via sodium peroxide sintering; (2) separation of the high field strength elements from the REEs and other matrix elements by a HF-free anion-exchange column procedure; (3) purification of Hf on a cation-exchange resin; (4) separation of REEs from other matrix elements by cation exchange; (5) Lu, Sm, and Nd separation from the other REEs by reversed-phase ion chromatography. Analytical reproducibilities of Sm-Nd and Lu-Hf isotope systematics are demonstrated for standard solutions and international rock reference materials. Results show overall good reproducibilities for Sm-Nd systematics independent of the rock type analyzed. For the Lu-Hf systematics, the reproducibility of the parent/daughter ratio is much better for JB-1 (basalt) than for two analyzed felsic crustal rocks (DR-N and an Archaean granitoid). It is demonstrated that this poorer reproducibility of the Lu/Hf ratio is truly caused by sample heterogeneity; thus, results are geologically reasonable.