Sebastian Szopa

Application of Ion Chromatography with ICP-MS or MS Detection to the Determination of Selected Halides and Metal/Metalloids Species

Speciation analytics as determination of various forms of elements is becoming more and more popular and valuable in areas such as environmental protection, biochemistry, geology, medicine, pharmaceuticals, and food product quality control. Its growing importance is related to the fact that what often decides the toxicological properties of a given element or compound is not its total content but the presence of its various forms, especially ionic. Determination of low concentrations of analytes requires complex and sophisticated analytical methods and techniques. The latest trends in this area concern the so-called “hyphenated techniques,” in which the separation and various detection methods are combined. This article is a review of possible uses of ion chromatography in combination with ICP-MS and MS detectors for the speciation analytics of selected halides as well as metals and metalloids species.

PM2.5 in the central part of Upper Silesia, Poland: concentrations, elemental composition, and mobility of components

The paper discusses ambient concentrations of PM2.5 (ambient fine particles) and of 29 PM2.5-related elements in Zabrze and Katowice, Poland, in 2007. The elemental composition of PM2.5 was determined using energy dispersive X-ray fluorescence (EDXRF). The mobility (cumulative percentage of the water-soluble and exchangeable fractions of an element in its total concentration) of 18 PM2.5-related elements in Zabrze and Katowice was computed by using sequential extraction and EDXRF combined into a simple method. The samples were extracted twice: in deionized water and in ammonium acetate. In general, the mobility and the concentrations of the majority of the elements were the same in both cities. S, Cl, K, Ca, Zn, Br, Ba, and Pb in both cities, Ti and Se in Katowice, and Sr in Zabrze had the mobility greater than 70%. Mobility of typical crustal elements, Al, Si, and Ti, because of high proportion of their exchangeable fractions in PM, was from 40 to 66%. Mobility of Fe and Cu was lower than 30%. Probable sources of PM2.5 were determined by applying principal component analysis and multiple regression analysis and computing enrichment factors. Great part of PM2.5 (78% in Katowice and 36% in Zabrze) originated from combustion of fuels in domestic furnaces (fossil fuels, biomass and wastes, etc.) and liquid fuels in car engines. Other identified sources were: power plants, soil, and roads in Zabrze and in Katowice an industrial source, probably a non-ferrous smelter or/and a steelwork, and power plants.

A Study on the Seasonal Mass Closure of Ambient Fine and Coarse Dusts in Zabrze, Poland

Diurnal samples of PM2.5 and PM2.5–10 were taken in an urban background area in Zabrze (Upper Silesia in southern Poland) in the winter (January–March) and summer (July–September) of 2009. The samples were analyzed for carbon (organic and elemental), water soluble ions (Na+, NH4+, K+, Mg2+, Ca2+, F−, Cl−, NO3−, PO43−, SO42−) and concentrations of 27 elements by using, respectively, a Behr C50 IRF carbon analyzer, a Herisau Metrohm AG ion chromatograph, and a PANalitycal EPSILON 5 X-ray fluorescence spectrometer. To perform the mass closure calculations for both dust fractions in the two periods, the particulate matter (PM) chemical components were categorized into organic matter, elemental carbon, secondary inorganic aerosol, crustal matter, marine components and unidentified matter. The chemical composition of the two dust fractions and the element enrichment coefficients in the two seasons, referred to proper emission profiles, proved about 80% of PM2.5 and more than 50% (in winter 65%) of PM2.5–10 mass coming from anthropogenic sources, mainly from fuel combustion and specific municipal emission shaping the winter emission of ambient dust in the area.

Development and validation of HPLC–ICP-MS method for the determination inorganic Cr, As and Sb speciation forms and its application for Pławniowice reservoir (Poland) water and bottom sediments variability study

The optimization of methodology for determination and extraction of inorganic ionic As(III)/As(V), Cr(III)/Cr(VI) and Sb(III)/Sb(V) forms in water and easily-leached fractions of bottom sediments by HPLC-ICP-MS were studied. In paper total concentration of As, Cr, Sb, pH and redox potential were determined. Ions were successfully separated on Dionex IonPac AS7: As(III), As(V), Sb(III), Sb(V) and Dionex IonPac AG7: Cr(III), Cr(VI) with LOD 0.18 μg/L, 0.22 μg/L, 0.009 μg/L, 0.012 μg/L 0.11 μg/L, 0.17 μg/L, respectively. Water and bottom sediments samples were collected monthly from Pławniowice Reservoir, in three-point transects between March and December 2012. In the bottom water predominated As(III) and Cr(III) forms and the highest content of Cr(III) was in the water flowing into the Pławniowice Reservoir. Concentration of Cr(VI) increased in the bottom water in the spring and summer (April-July), while decreasing of the Cr(III) content was associated with the release of Cr(VI) from sediment into the water. Studies have shown that antimony accumulates in reservoir sediments and its reduced form was predominated except May and October-November period when high concentrations of Sb(V) was present. In contrast As(V) was the predominant arsenic form in bottom sediments.

Application of hyphenated techniques in speciation analysis of arsenic, antimony, and thallium.

Due to the fact that metals and metalloids have a strong impact on the environment, the methods of their determination and speciation have received special attention in recent years. Arsenic, antimony, and thallium are important examples of such toxic elements. Their speciation is especially important in the environmental and biomedical fields because of their toxicity, bioavailability, and reactivity. Recently, speciation analytics has been playing a unique role in the studies of biogeochemical cycles of chemical compounds, determination of toxicity and ecotoxicity of selected elements, quality control of food products, control of medicines and pharmaceutical products, technological process control, research on the impact of technological installation on the environment, examination of occupational exposure, and clinical analysis. Conventional methods are usually labor intensive, time consuming, and susceptible to interferences. The hyphenated techniques, in which separation method is coupled with multidimensional detectors, have become useful alternatives. The main advantages of those techniques consist in extremely low detection and quantification limits, insignificant interference, influence as well as high precision and repeatability of the determinations. In view of their importance, the present work overviews and discusses different hyphenated techniques used for arsenic, antimony, and thallium species analysis, in different clinical, environmental and food matrices.

Impact of Mining Dump on the Accumulation and Mobility of Metals in the Bytomka River Sediments

Abstract The research aim was to determine the long-term impact of the mine waste stored at the coal waste dump Hałda Ruda on the content of heavy metals in the bottom sediments of the Bytomka River. It is a watercourse flowing along this coal waste dump and has been under its influence for over fifty years. The research also attempted to determine the seasonality of changes (2 years) and mobility of selected elements. The article presents total contents of Cr, Mn, Ni, Cu, Zn, As, Cd and Pb in the bottom sediments collected from the Bytomka River. It also focuses on the distribution of these elements in particular geochemical fractions determined with the Tessiers sequential chemical extraction procedure. Total element contents were determined with an EDPXRF (Energy Dispersive X-ray Fluorescence) technique. The extractants of particular Tessiers fractions were determined quantitatively with an ICP-MS (Inductively Coupled Plasma Mass Spectrometry) spectrometer. The research results show that the stored waste significantly influences the contents of heavy metals in the Bytomka River bottom sediments. The lowest concentration of heavy metals was observed at the B1 spot (above the dump), while the highest one was measured at the B3 spot (below the dump). Sequential chemical extraction of the bottom sediments indicates that the Zn content in the ion-exchange and carbonate fractions diminished within a year. Nevertheless, Zn bound to Fe and Mn oxides acted in the opposite way. Mn, Zn and Pb are the most dangerous elements from the viewpoint of environmental hazards, as their total concentrations were high. Moreover, their high contents were observed in the most mobile (ion-exchange and carbonate) fractions. Extremely toxic Cd was bound to the oxide fraction to the largest extent. Cu was mainly bound to the organic fraction while environmentally hazardous Cr was bound to the residual fraction.

Variability in different antimony, arsenic and chromium species in waters and bottom sediments of three water reservoirs in Upper Silesia (Poland): a comparative study

ABSTRACT Migration of metals/metalloids and their inorganic forms from bottom sediments into waters and from waters into bottom sediments is a complex process. Understanding this mechanism is essential for recognising transformations that occur in water reservoir ecosystems. The following research was conducted in 2012–2014. The aim was to define the time and spatial correlations in the changes of total and ionic antimony, arsenic and chromium concentrations in waters and bottom sediments of three water reservoirs located in Upper Silesia (Poland), i.e. Pławniowice, Rybnik and Goczałkowice. The ionic form contents were determined with high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The research was carried out to verify whether the bottom sediments deposited in the discussed reservoirs could have posed an environmental threat due to the possible release of toxic ionic forms (i.e. As(III), Sb(III) and Cr(VI)) into the pelagic zone. The comparison of the research results obtained for three reservoirs (being under different anthropopressure influence) enabled the researchers to describe the bioavailability of specific elements and their species. It also helped to discern the existing environmental threats for such water reservoirs and their users.

Variability in inorganic As, Sb and Tl species concentrations in waters and bottom sediments of the Kłodnica River (Poland)

ABSTRACT The study describes the application of new methodologies for the simultaneous determination of As(III)/As(V), Sb(III)/Sb(V) and Tl(I)/Tl(III) ions in waters and bottom sediments of the Kłodnica River (Poland) with the hyphenated technique of high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) . Time and spatial correlations were determined in the changes of total and speciation concentrations of the above-mentioned analytes in Kłodnica river in 2012. The developed methodologies demonstrate high selectivity and limits of quantification at the level of 0.009–0.120 µg/L. Their repeatability, precision and recovery are appropriate for trace analyses of environmental samples. Time and spatial correlations, and concentrations of inorganic As, Sb and Tl ions demonstrated high variability both in water and bottom sediments.