Determination of Background Concentrations of Ag, Pd, Pt and Au in Highly Mineralized Ground Waters at Sub-ng L–1 Concentrations by Online Matrix Separation/Pre-Concentration Coupled to ICP-SFMS

Though not regulated in directives such as the Water Framework Directive of the European Union, the investigation of geogenic background concentrations of certain elements such as precious metals is of increasing interest, in particular for the early detection of a potential environmental pollution due to the increased use in various industrial and technological applications and in medicine. However, the precise and accurate quantification of precious metals in natural waters is challenging due to the complex matrices and the ultra-low concentrations in the (sub-) ng L−1 range. A methodological approach, based on matrix separation and pre-concentration on the strong anion exchange resin TEVA® Resin in an online mode directly coupled to ICP-SFMS, has been developed for the determination of Ag, Pt, Pd and Au in ground water. Membrane desolvation sample introduction was used to reduce oxide-based spectral interferences, which complicate the quantification of these metals with high accuracy. To overcome errors arising from matrix effects—in particular, the highly varying major ion composition of the investigated ground water samples—an isotope dilution analysis and quantification based on standard additions, respectively, were performed. The method allowed to process four samples per hour in a fully automated mode. With a sample volume of only 8 mL, enrichment factors of 6–9 could be achieved, yielding detection limits <1 ng L−1. Validation of the trueness was performed based on the reference samples. This method has been used for the analysis of the total concentrations of Ag, Pt, Pd and Au in highly mineralized ground waters collected from springs located in important geological fault zones of Austria’s territory. Concentrations ranges of 0.21–64.2 ng L−1 for Ag, 0.65–6.26 ng L−1 for Pd, 0.07–1.55 ng L−1 for Pt and 0.26–1.95 ng L−1 for Au were found.

Multielemental Determination of Rare Earth Elements in Seawater by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) After Matrix Separation and Pre-concentration With Crab Shell Particles

Considering the unique characteristics of rare earth elements (REEs), the presence of REEs beyond specific limits will adversely affect the environment and it can be employed as a powerful probe for investigating hydrogeochemical processes. This requires sensitive determination of REEs in natural seawater. A matrix separation and pre-concentration technique using the mini-column packed with crab shell particles (CSPs) by inductively coupled plasma mass spectrometry (ICP-MS) as a means of determination has been developed. The aim of the proposed method was to simultaneously determine 16 REEs (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) at trace or ultra-trace concentrations in seawater. The biosorption capacity of CSPs was found to achieve 1.246–1.250 mg g−1 for all elements. In order to optimize performance of the method, the effects of analytical parameters concerning oscillation time, solution pH, salt concentration and eluent concentration were explored. Under the optimal conditions, the detection limits of REEs ranged 0.0006–0.0088 μg L−1, and relative standard deviations (n = 7) varied between 0.55 and 1.39%. The accuracy of developed method was evidenced by applying it to the analysis of REEs in seawater samples, with the overall recoveries at a level of 95.3 and 104.4%. Together, this work provides a promising and cost-effective CSPs-based pretreatment approach for REEs detection in sea environment.

Assessing the potential of online ICP–MS analysis to optimize Ca/matrix separation using DGA Resin for subsequent isotopic analysis

Ca isotopes have gained increasing interest as a diagnostic tool for bone diseases due to the variations in abundances as a consequence of changes in bone-mineral balance. Optimized Ca/matrix separation prior to analysis is a prerequisite for reliable isotope ratio measurements in complex biological matrices such as blood, serum, or urine. The online analysis of analyte/matrix separation by ICP-MS enables direct assessment of elution profiles supporting the optimization process. The integration of transient signals and signal suppression challenge the quantification and interpretation of the elution profiles. Mn and Co remain unretained by the DGA Resin (TrisKem International) from nitric acid. Hence, in the present study, these elements were investigated for their application as standards to monitor signal suppression. Successful analyte quantification was accomplished using a dynamic correction strategy applying a linear gradient of a suppression factor based on Mn and Co intensities. An optimized Ca/matrix separation procedure using DGA Resin is proposed based on the results during online ICP-MS analysis. Graphic abstract

A Force-Balanced Fiber Retardation Model to Predict Fiber-Matrix-Separation during Polymer Processing

The use of discontinuous fiber reinforced composites in injection and compression molding faces a number of challenges regarding process-induced changes in microstructure, which have a significant influence on the mechanical properties of the final component. The changes in final microstructure are caused by complex fiber movements, such as fiber orientation, attrition and accumulation during flow. While there are existing phenomenological prediction models for both fiber orientation and attrition, the prediction of fiber accumulation due to fiber-matrix separation is currently only possible with a complex mechanistic particle simulation, which is not applicable in industrial simulations. A simplified phenomenological model, the fiber retardation model (FRM), for the prediction of fiber-matrix separation in commercially available software tools is presented in this paper. The model applies a force balance onto an interacting two phase flow of polymer melt and fiber phase and applies a retardation factor Κ to calculate the slowing and accumulation of the fiber phase. The general model is successfully applied to a simple compression molding simulation.