Investigation of anthropogenic gadolinium in tap water of polish cities: Gdansk, Kraków, Warszawa, and Wroclaw.

In urban areas where tap water is often produced by a purification of water supplied from a river bank filtration, a significant fraction of gadolinium (Gd) total pool is of an anthropogenic origin. It happens because Gd-based contrast agents used in Magnetic Resonance Imaging (MRI) are not removed during wastewater treatment and they are discharged to the environment and returned to the water cycle. Despite the growing number of MRI examinations worldwide, little is known about the anthropogenic Gd in Polish surface water as well as drinking water. The aim of this pilot study was to gain information about the occurrence of emergent pollution as Gd in potable water available for inhabitants of Polish municipal areas. Tap water samples from Gdansk, Kraków, Wroclaw and Warszawa were analyzed by an inductively coupled plasma quadrupole mass spectrometry after their preconcentration by a seaFAST-pico chromatographic system. In this study, the sum of REE was in the range registered in the drinking waters of European urban regions (usually below 100 ng/L). The highest values of the sum of REE total concentrations were observed in the tap water samples collected in Warszawa (37.7 ng/L) and Wroclaw (35.9 ng/L and 32.9 ng/L), where water supplies originate from the Wisla River and Olawa River, respectively. The highest total Gd concentration was observed in the tap water of Warszawa city where the anthropogenic Gd fraction represented about 90% of the total Gd. The lowest values of the sum REE were registered in tap waters of Gdansk (sum of REE below 2.2 ng/L) with up to 17% of the anthropogenic Gd. Thus, our study showed the occurrence of the anthropogenic Gd in all analyzed tap waters.

A novel simultaneous isotope dilution strategy as a powerful tool in the two-track certification process of trace metal mass fractions: a case study of mercury, cadmium and lead in soil and sediment materials.

An analytical methodology based on isotope dilution (ID) principles was developed to establish the reference procedure for the simultaneous assignation of aqua regia extractable and total mass fractions of Hg, Cd, and Pb in soil and sediment matrix samples. The 'twin sample-spike blends' were prepared under close to the exact matching conditions, resulting in almost identical mass ratios of the spike to the sample in the blends, which followed either the aqua regia extraction method or total digestion procedure. The isotope ratios in 'twin-blends' were measured by inductively coupled plasma mass spectrometry (ICP-MS). The two-track IDMS strategy proposed in this work was successfully applied to three certified reference materials (CRMs): ERM-CC141 loam soil, EnvCRM 03 soil, and MODAS-2 bottom sediment. This ensured an adequate method validation. For two CRMs (EnvCRM 03 and MODAS-2) it was found that the isotope ratio values in 'twin-blends' for Hg, Cd, and Pb were almost identical with a variability of less than 2.4%. This confirmed that there is no measurable difference between the aqua regia extractable and the total mass fractions within the uncertainty ranges. Therefore, aqua regia mass fractions assigned in this study were found to be equal to certified element contents. For ERM-CC141 loam soil, the Hg isotope ratio values measured in the 'twin-blends' were found to be identical within their measurement uncertainties, and thus, it was concluded that the aqua regia extractable Hg content is identical to the total Hg content. However, in the case of Cd and Pb isotope ratio values in 'twin-blends' varied around 24% or 16%, respectively and because this significant difference was noticed, for both elements it is necessary to calculate the aqua regia content and the total content separately. Because this significant difference was noticed for both elements, it is necessary to calculate the aqua regia content and the total content separately. A detailed comparison of the isotope ratio values between the 'twin-blends' provided unambiguous information about aqua regia extractability of metals and it is a strong indicator for making decisions related to the assignment of either a single mass fraction valid for both procedures or two separate element mass fraction values. To our knowledge and based on the relevant literature survey, this is a novel strategy based on IDMS, and such studies have not been undertaken and presented so far.

Development and validation of seaFAST-ICP-QMS method for determination of rare earth elements total concentrations in natural mineral waters.

The method for determination of rare earth elements (REE: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) total concentrations in mineral waters was developed and validated. The proposed method comprised inductively coupled plasma mass spectrometry (ICP-MS) detection and the 10-fold off-line REE preconcentration. To improve the method sensitivity and selectivity, the major matrix components and elements causing severe spectral interferences (Ba and Sr) were removed by the seaFAST-pico chromatographic system. The assessed method performance characteristics showed low detection limits (0.02 ng/L-0.3 ng/L), high elements recoveries (98% ± 4%), good repeatability (3%-5%), and satisfactory uncertainties (8%-16%). The method usability was confirmed via analysis of available reference materials with different water matrices (SLRS-5, SLRS-6, CASS-5, SERMIN1, and VIDAC18) and natural mineral waters originated either directly from wells or bottles sold in supermarkets.

Determination of rare earth elements concentrations in natural waters - A review of ICP-MS measurement approaches.

Since the rare earth elements (REEs) determination in waters is still not a routine procedure, different analytical protocols have been developed to deal with complexity and variability of sample matrices, problems caused by spectral and non-spectral interferences, insufficient instruments sensitivity, potential contamination and lack of certified reference materials. The aim of this work is to review the current measurement approaches given for REEs total concentrations in natural water samples, including surface and groundwaters as well as rain water and Antarctic ice. As inductively coupled plasma mass spectrometry (ICP-MS) has become the most widely employed technique for analysis of trace concentrations of REEs in aqueous samples it has been intended to present the common issues affecting the measurement results. Apart from a sample preparation step, various configurations of mass spectrometers and sample introduction systems, means of interferences elimination or correction, and calibration strategies used in analytical approaches for REEs analysis are discussed and compared.

Baseline study on trace and rare earth elements in marine sediments collected along the Namibian coast.

Namibia is a fast-growing country with extensive mineral extraction activities used in diamond, fluorspar, uranium, and metals production. To assess the impact of land based human activities on the Namibian coastal marine environment, 25 elements were analyzed in 22 surface sediments samples collected along the coast. After applying a variety of pollution assessment indices (Enrichment Factor, Igeo and Pollution Load Indexes) was concluded that As, Cd and Sb were considerably enriched in the sediments from several sites, while Cu, Pb and Zn showed very high enrichment near the Walvis Bay harbor. Pearson's correlation and Principal Component Analysis were used to investigate common metal sources. Additionally, the determination of Pb isotope ratios confirmed the contribution of land based human activities at Walvis Bay and Lüderitz as sources of pollution. The analysis of REEs did not reveal any important enrichment due to anthropogenic activities, but provides a needed baseline for further investigations.

Determination of ultra-trace level of 232Th in seawater by ICP-SFMS after matrix separation and preconcentration.

This article describes the development and validation of an analytical procedure for the matrix separation, preconcentration and determination of sub-ng kg-1 levels 232Th in a small volume (20 mL) of seawater samples. The matrix separation and Th preconcentration was carried out using a commercially available ion-chelation system seaFAST-pico. The acidified to pH < 2 seawater samples were mixed on-line with the ammonium acetate buffer (pH of 6.0 ± 0.2) before loading on the column containing resin with iminodiacetic and ethylenediaminetriacetic functional groups. At this pH, 232Th was quantitatively retained on the resin, demonstrating a good affinity (selectivity) for Th in seawater matrix. The element retained on the resin was eluted using only 0.2 mL of 1.8 M HNO3 enabling to achieve high preconcentration factor. The pretreatment procedure, with two sample loading cycles (each one 10 mL), was accomplished in about 25 min. Determining 232Th mass fraction in seawater samples was based on isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS) method, which was considered as the most accurate calibration strategy for precise quantification of 232Th mass fraction in seawater samples. ISO/IEC17025 and Eurachem guidelines were followed to perform the validation of the developed in this study procedure. In the case of seawater samples with natural level of thorium the major contributions to the expanded uncertainty arose from the uncertainty associated with isotopic ratio measurements in the isotopically spiked sample, followed by the correction for procedural blank and the correction for mass discrimination effect. The estimated method detection limit for 232Th was 0.005 ng kg-1. The developed method was successfully applied to the determination of 232Th mass fraction in seawater reference samples: IAEA-443, SLEW-3, NASS-4, NASS-6, and CASS-5. Although 232Th is not certified in any of the seawater reference materials, a good agreement was obtained between the results in this study and data published elsewhere.

Application of solid phase extraction procedures for rare earth elements determination in environmental samples.

Determination of rare earth elements in environmental samples requires often pre-concentration and separation step due to a low metal content and high concentration of the interfering matrix components. A solid phase extraction technique with different kind of solid sorbents offers a high enrichment factor, rapid phase separation and the possibility of its combination with various detection techniques used either in on-line or off-line mode. The recent developments in this area published over the last five years are presented and discussed in this paper.

In vivo investigation of the distribution and the local speciation of selenium in Allium cepa L. by means of microscopic X-ray absorption near-edge structure spectroscopy and confocal microscopic X-ray fluorescence analysis.

In this work, microscopic X-ray absorption near-edge structure spectroscopy (mu-XANES) and confocal microscopic X-ray fluorescence analysis (mu-XRF) were used for the in vivo determination of the distribution of total selenium and for the local speciation of selenium in roots and leaves of onion. Selected Allium cepa L. plants were grown hydroponically in a standard medium containing inorganic selenium compounds (selenite or selenate). The measurements were performed in vivo, that is, on living plants without the need for any form of sampling or sample pretreatment and without the necessity for cutting plant tissues into pieces. Distinct energy differences of the XANES spectra of various selenium reference compounds having different oxidation states allow adjusting the excitation energies used for mu-XRF mapping in such a manner that the distribution of selenium in various oxidation states is obtained with a spatial resolution of a few tens of micrometers within the virtual cross section of the onion tissues. We find that the ratio of inorganic to amino acid selenium compounds differs in various subparts of the plant. Detailed in vivo investigation of the distribution of various selenium species in virtual cross sections of root tips and green leaf shows that the selenium transport takes place via different mechanisms, depending on the nature of the selenium compounds originally taken up.

Assessment of selenium bioavailability from high-selenium spirulina subfractions in selenium-deficient rats.

It was previously found that the bioavailability of Se from Se-rich spirulina (SeSp) was lower than that from selenite or selenomethionine when fed to Se-deficient rats. The present study examined the bioavailability of Se from SeSp subfractions: a pellet (P) issuing from the centrifugation of a suspension of broken SeSp and a retentate (R) resulting from ultrafiltration of the supernatant through a 30 kDa exclusion membrane. Animals were fed a torula yeast based diet with no Se (deficients) or supplemented with 75 microg of Se/kg of diet as sodium selenite (controls) for 42 days. Se-deficient rats were then repleted for 56 days with Se (75 microg/kg of diet) supplied as sodium selenite, SeSp, P, or R. During this period, controls continued to receive sodium selenite. Speciation of Se in subfractions showed that the majority was present in the form of high molecular weight compounds; free selenomethionine was only a minor constituent. Gross absorption of Se from sodium selenite, P, and R was not different and was higher than from SeSp. Only retentate allowed full replenishment of Se concentration in liver and kidney (as did sodium selenite) and glutathione peroxidase (GSHPx) activity in liver, kidney, plasma, and erythrocytes. The bioavailabilities of Se in retentate, as assessed by slope ratio analysis using selenite as a reference Se, were 89 and 112% in the tissue Se content and 106-133% in the GSHPx activities. SeSp and P exhibited a gross bioavailability of <100%. These results indicate that Se in retentate is highly bioavailable and represents an interesting source of Se for food supplementation.