Elevated Urbanization-Driven Plant Accumulation of Metal(loid)s Including Arsenic Species and Assessment of the Klodnica River Sediment Contamination.

The impact of water and bottom sediment pollution of a river subjected to a strong industrial anthropogenic pressure of metal(loid) (including arsenic and its species) accumulation in riverbank plants such as Solidago virgaurea L., Phragmites L. and Urtica dioica L. was investigated. The high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) technique was used to study organic and inorganic arsenic species in selected plants and their response to heavy metal and arsenic contamination. The modified BCR extraction results showed that arsenic was mainly bound to the mobile reducible and organic-sulfide fractions in the Klodnica River bottom sediments. Research has shown that the bottom sediments of the Klodnica River are contaminated with metals, including Pb, Zn, Ni, As, and among arsenic species, the As(V) form dominated quantitatively, with its highest concentration being 49.3 mg kg-1 and the organic species occurred extremely rarely. The highest concentration of arsenic, among the tested plants, occurred in Phragmites communis L. The evaluation of the bottom sediment pollution was performed using Sb/As factor, geoaccumulation index (Igeo), enrichment factor (EF) and pollution load index (PLI). The ability of the plant to assimilate metals from the substrate was studied by calculation of the bioaccumulation factor (BAF). Values of the Igeo change in a wide range from class 1 (uncontaminated to moderately polluted for Cu and Zn) at the first sampling point, to 5 (highly to extremely polluted for Ba and Fe) at the K4 sampling point. The Igeo results show an increase in the contamination with elements toward the runoff of the Klodnica River.

Selected technology-critical elements as indicators of anthropogenic contamination of surface water and suspended solids on the example of the Biala Przemsza River (Poland).

Pollution of surface waters from anthropogenic activities is a global problem, affecting natural ecosystems, having a large impact on the life and health of living organisms. The development of mining and metallurgic industries of Pb and Zn ores in the Biala Przemsza cachment area has had a strong influence on the surface waters and suspended solids. This paper proposes the use of selected critical elements such as Tl, Te, Ga, Ge and In as indicators of anthropogenic pollution of surface waters and suspended solids on the example of the Biala Przemsza River. The impact of strongly anthropogenic urban-industrial catchment on the temporal and spatial distribution of the selected TCEs content in the water and suspension of the Biala Przemsza River depending on the oxygen, pH and Eh conditions is presented. Research has shown that selected critical elements such as Te, Ge, and In can be indicators of anthropogenic pollution of surface waters. In the case of the Biala Przemsza River, elements such as Ga and Tl cannot be indicators of anthropogenic pollution due to their presence in the zinc and lead ore deposits occurring in the river basin. Correlation matrices showed significant relationships between the selected TCEs and other water parameters. The calculated water pollution indices confirmed that the Biala Przemsza River is the most polluted in the last three sampling points.

Studies on the Content of Selected Technology Critical Elements (Germanium, Tellurium and Thallium) in Electronic Waste.

The article draws attention to the problem of the presence of metals: germanium (Ge), tellurium (Te), thallium (Tl), and others (Cd, Ba, Co, Mn, Cr, Cu, Ni, Pb, Sr, and Zn) in selected waste of electrical and electronic equipment (WEEE). As a result of the growing demand for new technologies, the global consumption of TECs has also been increasing. Thus, the amount of metals in circulation, of which the impacts on the environment have not yet been fully understood, is constantly increasing. Due to the low content of these metals in WEEE, they are usually ignored during e-waste analyses. The main aim of this study was to determine the distribution of Ge, Te, and Tl (and other elements) in ground sieve fractions (1.0, 0.5, 0.2, and 0.1 mm) of selected electronic components (solar lamps, solar cell, LED TV screens, LCD screens, photoresistors, photodiodes, phototransistors) and to determine the possible tendency of the concentrations of these metals in fractions. This problem is particularly important because WEEE recycling processes (crushing, grinding, and even collection and transport operations) can lead to dispersion and migration of TCE pollutants into the environment. The quantitative composition of e-waste was identified and confirmed by ICP-MS, ICP-OES and SEM-EDS, and XRD analyses. It was found that Ge, Te, and Tl are concentrated in the finest fractions of ground e-waste, together with Cd and Cr, which may favor the migration of these pollutants in the form of dust during storage and processing of e-waste.

Development of a Tellurium Speciation Study Using IC-ICP-MS on Soil Samples Taken from an Area Associated with the Storage, Processing, and Recovery of Electrowaste.

The optimization and validation of a methodology for determining and extracting inorganic ionic Te(VI) and Te(IV) forms in easily-leached fractions of soil by Ion Chromatography-Inductively Coupled Plasma-Mass Spectrometry (IC-ICP-MS) were studied. In this paper, the total concentration of Te, pH, and red-ox potential were determined. Ions were successfully separated in 4 min on a Hamilton PRPX100 column with 0.002 mg/kg and 0.004 mg/kg limits of detection for Te(VI) and Te(IV), respectively. Soil samples were collected from areas subjected to the influence of an electrowaste processing and sorting plant. Sequential chemical extraction of soils showed that tellurium was bound mainly with sulphides, organic matter, and silicates. Optimization of soil extraction allowed 20% average extraction efficiency to be obtained, using 100 mM citric acid as the extractant. In the tested soil samples, both tellurium species were present. In most cases, the soils contained a reduced Te form, or the concentrations of both species were similar.

Impact of River Water and Bottom Sediment Pollution on Accumulation of Metal(loid)s and Arsenic Species in the Coastal Plants Stuckenia pectinata L., Galium aparine L., and Urtica dioica L.: A Chemometric and Environmental Study.

The role of water and bottom sediment pollution of a river subjected to a strong industrial anthropo-pressure in coastal plants was investigated. The work presented the influence of polluted environment on accumulation of metal(loid)s (including arsenic and its species) in Stuckenia pectinata L., Galium aparine L., and Urtica dioica L. The study provided important information on the contents of organic and inorganic arsenic species in selected plants and their response to heavy metal and arsenic contamination. The As(III), As(V), AB (arsenobetaine), MMA (monomethylarsonic acid), and DMA (dimethylarsinic acid) ions were successfully separated on the Hamilton PRP-X100 column with high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) techniques. The Pollution Load Index and geo-accumulation Index (Igeo) values clearly indicate significant pollution of the examined ecosystem with heavy metals. The chemometric analysis with the concepts of (Dis)similarity Analysis, Cluster Analysis, and Principal Component Analysis helped to visualize the variability of the As species concentrations and to analyse correlations between sampling point locations and analyte contents.

Spatial and temporal variability of metal(loid)s concentration as well as simultaneous determination of five arsenic and antimony species using HPLC-ICP-MS technique in the study of water and bottom sediments of the shallow, lowland, dam reservoir in Poland.

The optimization of new methodology for simultaneous determination of arsenic [As(III), As(V)] and antimony [Sb(III), Sb(V), SbMe3] species using high-performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) in water and bottom sediment samples collected from the dam Kozlowa Góra Reservoir (Poland) was studied. Samples were collected monthly from May to September 2018 in four-point (water) and fifth-point (sediment) transects. The contents of Mn, Co, Ni, Cu, Zn, As, Cr, Rb, Sr, Cd, Sb, Ba, Tl, Pb, and Sb were studied in water and bottom sediments using ICP-MS techniques. Additionally, arsenic and antimony fractions were determined in sediments with the BCR method. Pollution Load Index (PLI), Geoaccumulation Index (Igeo), LAWA classification, and Sb/As ratio indicated the presence of extreme sediment pollution for Zn, Cd, Pb, and Cr from anthropogenic sources. Research has shown that the easy-leached bottom sediment fraction contained in most cases more As(V) and Sb(V). But often Sb(V) concentration was equal as Sb(III), which can be released into the pelagic zone under favorable conditions. Even though As(V) and Sb(V) prevail in the reservoir bottom sediments, they can be transformed into As(III) and Sb(III) as a result of drastic changes in pH or redox potential. The Kozlowa Góra sediments are heavily polluted with Pb, Zn, Cd, and As, Cu, and Ni. The highest concentrations of the heavy metals were recorded in the middle of the tank and there was a small spatial variability. The migration of metals along the reservoir transect was closely related to its morphometry.

Time and spatial variability in concentrations of selected metals and their species in water and bottom sediments of Dzierzno Duze (Poland).

Poland is an industrialized country in which industries (especially the heavy ones) have had a tremendous influence on the environment. It is particularly visible in the Upper Silesia region, where the observed air, soil and water pollution levels are the most highest. The aim of this study was to determine the time and spatial variability in: concentrations of selected metals (Co, Ni, Zn, Cr, Mn, Pb, Cd), and, to a limited extent, of Cu, V, Al and Sr; concentrations of inorganic ions (Cl-, SO42-, Na+, K+, Ca2+ and Mg2+) and values of pH, conductivity and redox potential. The enlisted parameters were determined for the water and bottom sediments of Dzierzno Duze, a water reservoir located in Poland (Upper Silesia region). Additionally, fractions of a few characteristic metals were determined in the bottom sediments of the discussed reservoir with the BCR method. The investigation was carried out in 2017. It showed that the reservoir surface water was not polluted with the determined metal contents. However, it was highly polluted with the inorganic ions. The metal contents determined in the bottom sediments were high. If the conditions for releasing them from the bottom sediments had been favorable, this situation could have posed a potentially considerable environmental threat.

Metal(loid) speciation in a river subjected to industrial anthropopressure: chemometric and environmental studies.

High-performance liquid chromatography (HPLC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was applied to the speciation of arsenic [As(III), As(V), and AsB (arsenobetaine)], MMA (monomethylarsonic acid), DMA (dimethylarsinic acid), antimony [Sb(III) and Sb(V)], and chromium [Cr(III) and Cr(VI)] in water and bottom sediment samples collected from the urban Bytomka River (Poland). The main objective of the study was the research of As, Cr and Sb species in the Bytomka River, as well as the simplified three-stage sequential chemical extraction of bottom sediments according to the Institute for Reference Materials and Measurements (BCR). The contents of V, Mn, Co, Ni, Cu, Zn, Rb, Sr, Ag, Cd, Te, Ba, Tl, Pb, Fe, Ga, and U in the water and bottom sediments were tested using the ICP-MS technique. The risk assessment code (RAC) indicated a medium risk for As and a high risk for Sb to the environment. Sequential chemical extraction of bottom sediments showed that As and Cr were strongly demobilized. Sb was mainly bound with the ion-exchange fraction and posed a serious threat to the environment. Chemometric analysis with the (dis)similarity analysis and principal component analysis (PCA) allowed for visualization of the variability and correlations of the analyzed elements.

Time and spatial variability in the concentrations of selected metals in water and bottom sediments of Plawniowice and Dzierzno Male reservoirs (Poland).

The migration of metals and metalloids between bottom sediments and water and the other way round is a complex process. Understanding those mechanisms is essential for recognizing transformations taking place in water reservoir ecosystems. The objective behind the following study was to define time and spatial correlations in the changes in total concentrations of selected elements (Cr, Zn, Co, Mn, Cu, Ni, Pb, As, Ba, Sb, Sr and V) in waters and bottom sediments from two water reservoirs located in Upper Silesia (Poland), i.e., Plawniowice and Dzierzno Male. The research was carried out to demonstrate whether the bottom sediments deposited in the discussed reservoirs could pose an environmental threat due to the possible release of toxic metals and metalloids into the pelagic zone. The obtained results constitute material helping to describe the bioavailability of particular elements. They also expose the existing environmental threats for such water reservoirs and their users.

Alterations of Hair and Nail Content of Selected Trace Elements in Nonoccupationally Exposed Patients with Chronic Depression from Different Geographical Regions.

The aim of this study was to determine if altered levels of selected trace elements manifest themselves during chronic depression. To identify elements strongly associated with chronic depression, relationships between the elemental contents of hair and nails and the interelement correlations were checked. Inductively coupled plasma mass spectrometry and ion chromatography were used to evaluate the contents of Zn, Cu, Co, Pb, Mn, and Fe in hair and nail samples from a total of 415 subjects (295 patients and 120 healthy volunteers). The study included logistic regression models to predict the probability of chronic depression. To investigate possible intercorrelations among the studied elements, the scaled principal component analysis was used. The research has revealed differences in TE levels in the group of depressed men and women in comparison to the healthy subjects. Statistically significant differences in both hair and nails contents of several elements were observed. Our study also provides strong evidence that the intermediary metabolism of certain elements is age- and gender-dependent. Zn, Mn, Pb, and Fe contents in hair/nails seem to be strongly associated with chronic depression. We found no statistically significant residence-related differences in the contents of studied elements in nonoccupationally exposed patients and healthy subjects.

Impact of the Pb and Zn ore mining industry on the pollution of the Biala Przemsza River, Poland.

The development of mining and metallurgic industries of Pb and Zn ores in the Biala Przemsza catchment area has had a strong influence on the condition of the surface water and bottom sediments. In the following study, total contents of metals and metalloids were researched in the water and bottom sediment samples from the Biala Przemsza River. The samples were collected monthly in 2014 at five sampling points along the river. The research helped to determine correlations between the parameters and components of the water environment (metals/metalloids, cations/anions, pH, Eh, conductivity, carbon (TOC, IC, TC), and suspension). The contents of metals and metalloids were determined with inductively coupled plasma-mass spectrometry (ICP-MS), whereas anions and cations were investigated with ion chromatography (IC). The simplified Community Bureau of Reference (BCR) three-step sequential chemical extraction was performed on Biala Przemsza River bottom sediments collected in April, July, and October. At its lower course, the Biala Przemsza River water did not meet the Polish surface water quality standards. The Biala Przemsza River water is mainly loaded with metals. Toxic concentrations of Cd, Pb, and Zn were observed at sampling points in Okradzionów and Slawków. The toxic Tl concentration was exceeded (2-6 µg/L) at three sampling points. The Biala Przemsza River bottom sediments were composed mostly of medium and fine sand. The BCR extraction of the bottom sediments demonstrated that Cd and Zn were bound to cations/anions and carbonates loosely adsorbed on the bottom sediments in spring and summer. Such a situation was observed at all the sampling points, except for BP3 in Okradzionów. The organic carbon concentration increased along the river course.

Chemometric and environmental assessment of arsenic, antimony, and chromium speciation form occurrence in a water reservoir subjected to thermal anthropopressure.

In the study, arsenic, antimony, and chromium concentrations and selected physicochemical parameters in water and sediment samples from the thermal anthroporessure subjected Rybnik Reservoir (Poland) were determined. As(III), As(V), Sb(III), and Sb(V) ions were successfully separated on Dionex IonPac AS7 column, and Cr(III) and Cr(VI) on Dionex IonPac AG7 column. The obtained limits of detection were 0.18, 0.22, 0.009, 0.012, 0.11, and 0.17 µg/L, respectively. Water and bottom sediment samples were collected monthly at three-point transect between January and November 2013. The As(III) and Sb(III) speciation forms dominated in the bottom water, and Cr(VI) concentration in the bottom water was twice as high as the value measured for the surface water. The oxidized arsenic, antimony, and chromium forms dominated in the bottom sediments in the heated water discharge zone of the Rybnik Power Plant. The location of sampling point had a significant influence on the observed transformations and contents of the analyzed speciation forms. The chemometric analysis coupled with the dissimilarity analysis and principal component analysis helped to visualize the variability in the concentrations of the element speciation forms within the researched period and analyzing correlations.

Antimony, Arsenic and Chromium Speciation Studies in Biala Przemsza River (Upper Silesia, Poland) Water by HPLC-ICP-MS.

In this paper the total concentration of As, Cr, Sb, pH and the red-ox potential of water and sediment samples of the Biala Przemsza River were determined. The arsenic (AB, MMA, DMA, As(III), As(V)), chromium (Cr(III), Cr(VI)) and antimony (Sb(III), Sb(V)) forms were studied by HPLC-ICP-MS. Ions were successfully separated on Hamilton PRP-X100: (AB, MMA, DMA, As(III), As(V)), Dionex Ion Pac AS-7 (Sb(III), Sb(V)) and Dionex IonPac AG7 columns: Cr(III), Cr(VI) with LOD 0.16 µg/L, 0.08 µg/L, 0.09 µg/L, 0.012 µg/L, 0.08 µg/L, 0.12 µg/L, 0.009 µg/L, 0.012 µg/L, 0.19 µg/L, 0.37 µg/L, respectively. The simplified BCR three-step sequential chemical extraction was performed on the bottom sediment samples. The samples were collected monthly, between April and December 2014, at five sampling points. Large contents of manganese, lead, cadmium and zinc were found in the Biala Przemsza River water. In December 2014, the lead content in the bottom sediment in Slawków was nearly 6000 mg/kg. In the river water, only the inorganic arsenic speciation forms were found. Sb(V), As(V) and Cr(III) were dominant. Studies have shown that arsenic, antimony and chromium were mainly bound to oxides, organic matter and sulphides in the bottom sediments.

Arsenic, Antimony, Chromium, and Thallium Speciation in Water and Sediment Samples with the LC-ICP-MS Technique.

Chemical speciation is a very important subject in the environmental protection, toxicology, and chemical analytics due to the fact that toxicity, availability, and reactivity of trace elements depend on the chemical forms in which these elements occur. Research on low analyte levels, particularly in complex matrix samples, requires more and more advanced and sophisticated analytical methods and techniques. The latest trends in this field concern the so-called hyphenated techniques. Arsenic, antimony, chromium, and (underestimated) thallium attract the closest attention of toxicologists and analysts. The properties of those elements depend on the oxidation state in which they occur. The aim of the following paper is to answer the question why the speciation analytics is so important. The paper also provides numerous examples of the hyphenated technique usage (e.g., the LC-ICP-MS application in the speciation analysis of chromium, antimony, arsenic, or thallium in water and bottom sediment samples). An important issue addressed is the preparation of environmental samples for speciation analysis.

H/D isotopic recognition and temperature effects in IR spectra of hydrogen-bonded cyclic dimers in crystals: 3-methylcinnamic acid and 4-phenylbutyric acid.

In the present work, the experimental and theoretical study of the nature of the inter-hydrogen bond interactions in two different carboxylic acids, 3-methylcinnamic acid (3MCA) and 4-phenylbutyric acid (4PBA), were reported. The polarized IR spectra of 3MCA and 4PBA crystals were recorded at the frequency ranges of the νO-H and νO-D bands. The spectral properties of 3MCA and 4PBA interpreted with the aid of the calculations based on the "strong-coupling" model. The differences in the spectral properties of the two different dimeric systems in the crystals provide a valuable information about the existence of a direct relationship between the crystal spectral properties in IR and the electronic structure of the molecular systems. In 3MCA crystals strong vibrational exciton interactions favor a "tail-to-head" (TH)-type Davydov coupling widespread via the π-electrons, whereas in 4PBA crystals a weak "through-space" (SS) exciton coupling is responsible for a "side-to-side"-type coupling. The relative contribution of each individual exciton coupling mechanism in IR spectra generation strongly depends on temperature and molecular electronic structure. The H/D isotopic recognition effect, depending on a non-random distribution of protons and deuterons in the crystal hydrogen bridges, was also analyzed.

Development and validation of HPLC-ICP-MS method for the determination inorganic Cr, As and Sb speciation forms and its application for Plawniowice 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 Plawniowice 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 Plawniowice 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.

Levels of selected carcinogens and toxicants in vapour from electronic cigarettes.

SIGNIFICANCE: Electronic cigarettes, also known as e-cigarettes, are devices designed to imitate regular cigarettes and deliver nicotine via inhalation without combusting tobacco. They are purported to deliver nicotine without other toxicants and to be a safer alternative to regular cigarettes. However, little toxicity testing has been performed to evaluate the chemical nature of vapour generated from e-cigarettes. The aim of this study was to screen e-cigarette vapours for content of four groups of potentially toxic and carcinogenic compounds: carbonyls, volatile organic compounds, nitrosamines and heavy metals. MATERIALS AND METHODS: Vapours were generated from 12 brands of e-cigarettes and the reference product, the medicinal nicotine inhaler, in controlled conditions using a modified smoking machine. The selected toxic compounds were extracted from vapours into a solid or liquid phase and analysed with chromatographic and spectroscopy methods. RESULTS: We found that the e-cigarette vapours contained some toxic substances. The levels of the toxicants were 9-450 times lower than in cigarette smoke and were, in many cases, comparable with trace amounts found in the reference product. CONCLUSIONS: Our findings are consistent with the idea that substituting tobacco cigarettes with e-cigarettes may substantially reduce exposure to selected tobacco-specific toxicants. E-cigarettes as a harm reduction strategy among smokers unwilling to quit, warrants further study. (To view this abstract in Polish and German, please see the supplementary files online.).