Preliminary exploration of direct mercury speciation in solid samples by using thermal release coupled to electrothermal atomic absorption spectrometry.

It is known that monitoring of mercury and notably its species is very important to assess their impact and distribution in the environment. In this regard, the development of a methodology for mercury speciation in natural and man-made media is of particular importance. There are a variety of studies in this area associated with the application of thermal release in combination with electrothermal atomic absorption detection for direct mercury speciation in solid samples without preliminary extraction of analytes. Nevertheless, a number of issues remain that hinder its practical application as a reliable analytical method. However, in order to achieve progress in this field, it is necessary to understand the features of the evaporation process itself. The goal of this work is to study the thermal behavior of the most common mercury species in order to eliminate the gaps in this approach. At this stage, studies were carried out using pure substances and their mixtures as a starting point for a subsequent transition to real natural samples. For this the installation scheme was modernized by introducing a module that provides programmable heating of the sample and variation of the heating rate. As a result of the experiments it was shown that the transformation of studied compounds with the examples of mercury chloride, methylmercury chloride, mercury sulfide and mercury sulfate occurs under thermal exposure, which leads to a change in their physicochemical characteristics, but, nevertheless, does not prevent their baseline separation for 30 min using programmable heating mode, which includes a continuous increase in temperature with a subsequent stop until the thermal peak is formed.

Metal-organic framework application for mercury speciation using solid phase extraction followed by direct thermal release-electrothermal atomization atomic absorption spectrophotometric detection (ETA AAS).

Metal-organic frameworks (MOFs) are increasingly used in analytical chemistry for pre-concentration of trace elements followed by their determination using modern analytical techniques. However, there are a limited number of publications concerning the use of MOFs for speciation purposes, while their structural and functional features are perspective for the element species selective extraction and pre-concentration. It is known that mercury refers to the most hazardous elements which species demonstrate different toxicity, migration routes and bioavailability as well. Consequently the development of new approaches for mercury speciation in environments remains an actual objective of analytical chemistry. In present work a new methodology for inorganic and organic mercury speciation in water was proposed. This approach is based on pre-concentration using solid phase extraction (SPE) followed by their determination directly from the solid phase with the application of the thermal release - electrothermal-atomic-absorption technique (TR-ETA-AAS). An original SPE-procedure based on the use of UIO-66 [Zr6O4(OH)4(bdc)6] in two different modes (non-modified and modified with cysteine) as a sorbent was designed. As a result of SPE as well as TR-ETA-AAS optimization the detection limits (LOD) for all listed species at the level of 0.06 µg L-1 have been achieved. It was also shown that the presence of the other elements (K, Na, Ca, Mg at the level of 100 µg L-1, and Mn, Fe, Cr, Al, Zn, Cd, Pb - of 25 µg L-1) does not affect the results obtained. The developed assay demonstrates a high efficiency, low LODs, wide linear range and admissible analysis duration. The reliability of the data obtained was confirmed by the standard addition approach and by a comparison with the results of independent analytical methods.

Capillary zone electrophoresis as a simple approach for the study of p-arsanilic acid transformation in the process of photolytic degradation.

Arsenic aromatic compounds including p-arsanylic acid (pASA) are still widely used in a number of countries as the feed additives in animal breeding resulting in its entering the environment. Under the influence of oxidizing agents or UV radiation, pASA undergoes transformations leading to generation of inorganic arsenic species that are more mobile and toxic than organic ones. On the one hand, an approach based on the treatment of contaminated waters by UV irradiation seems perspective for their detoxification, but the feasibility of this approach depends on the composition of the products forming as a result of photodegradation. In the present work, a CZE was applied for the study of the pASA degradation process during stationary (308 nm) photolysis in the presence of Fe(III)-oxalate complex. A developed assay allowed controlling the parent compounds and also As-containing products of pASA degradation, presented mainly by arsenate and arsenite ions. It was found that the main inorganic derivatives of the pASA photolytic conversions are presented by arsenate and arsenite ions whose ratio depends on the initial amount of pASA and reaction conditions.

Rh(III) hydroxocomplexes speciation using HPLC-ESI-MS.

A mixture of rhodium(iii) hydroxocomplexes formed during the polycondensation process in alkaline media has been fully characterized by the hyphenated high performance liquid chromatography with electrospray ionization mass spectrometry (HPLC-ESI-MS). The baseline separation was achieved using reverse phase ion-pair chromatography (RP-IP-HPLC) in gradient elution mode. When using SDS as the ion pair, the formation of all types of its associates with the molecules of acetonitrile, as well as oligomers of rhodium aquahydroxocomplexes, etc. was taken into consideration. As a result, it was shown that the test mixture is presented by [Rh(H2O)6]3+, [Rh2(µ-OH)2(H2O)8]4+, [Rh3(µ-OH)4(H2O)10]5+, [Rh4(µ-OH)6(H2O)12]6+.

Photodegradation of para-arsanilic acid mediated by photolysis of iron(III) oxalate complexes.

Organic arsenicals are important environment pollutants due to wide use in livestock and toxicity of degradation products. In this work we report about the efficient photodegradation of the p-arsanilic acid (p-ASA) and its decomposition products in the Fe(III)-oxalate assisted approach under nature-relevant conditions. At neutral pH under near-visible UV irradiation the Fe(III) oxalate complexes generate the primary oxidizing intermediate, OH radical (the quantum yield of ϕOH âˆ¼ 0.06), which rapidly reacts with p-ASA with high rate constant, (8.6 ± 0.5) × 109 M-1s-1. Subsequent radical reactions result in the complete photooxidation of both p-ASA and basic aromatic photoproducts with the predominant formation of inorganic arsenic species, mainly As(V), under optimal conditions. Comparing with the direct UV photolysis, the presented Fe(III)-oxalate mediated degradation of p-ASA has several advantages: higher efficiency at low p-ASA concentration and complete degradation of organic arsenic by-products without use of short-wavelength UV radiation. The obtained results illustrate that the Fe(III)-oxalate complexes are promising natural photosensitizers for the removal of arsenic pollutants from contaminated waters.

The study of Rh(iii) hydroxocomplexes using capillary zone electrophoresis with a UV-Vis detector: the development of the method.

The expediency of capillary zone electrophoresis application in the study of a mixture of rhodium(iii) hydroxocomplexes is shown for the species formed during the thermal treatment of [Rh(OH)6]3- at 60 °C in alkaline media. As these compounds are unstable in solution because of polycondensation at pH > 10 and the formation of insoluble rhodium(iii) hydroxides at pH 5-10, their acidic derivatives with terminal aqua ligands acted as the objects of the study. Optimal separation conditions were achieved using sodium perchlorate as a background electrolyte, a voltage of +20 kV and pH 2.6. Rhodium(iii) species with different nuclearities were identified in accordance with their UV spectra and the regularities of electrophoretic migration in the capillary. The presence of a dimer was also verified by the spiking of the mixture under investigation with a previously synthesised complex [Rh2(µ-OH)2(H2O)8](NO3)4, which confirms the correct identification.

Mechanisms of low-temperature vapor-gas streams formation from sulfide mine waste.

This paper presents experimental data that revealed the potential for chemical element transport by low-temperature vapor-gas streams. The study was conducted on sulfide waste heap sites located in the Kemerovo region, Russia. Condensates of vapor-gas streams were collected and analyzed in the air above the waste heaps and during laboratory experiments using samplers specially designed for this purpose. The gas streams from a waste heaps are complex mixtures consisting of water vapor, sulfur- and selenium-containing compounds (sulfur dioxide SO2, dimethyl sulfide C2H6S, carbon disulfide CS2, dimethyl disulfide C2H6S2, dimethyl selenide C2H6Se, and dimethyl diselenide C2H6Se2), elemental sulfur (S6, S7, and S8) and various chemical elements, including rock-forming elements (Ca, Mg, Na, K, Si, Fe, Al, and Mn), metals (Cu, Zn, Pb, Ni, and Sn), and metalloids (As, Te, and Sb). The main sources of chemical elements in the gas streams are unstable secondary minerals associated with crystalline hydrates: gypsum CaSO4 × 0.5H2O, sideronatrite Na2Fe(SO4)2(OH) × 3H2O, serpierite CaCu3Zn(SO4)2(OH)6 × 3H2O, and copiapite (Mg,Zn,Fe2+Fe3+)4(SO4)6(OH)2 × 20H2O that formed during the oxidation of sulfide minerals. Some of the elements come from pore waters that are acidic, highly mineralized solutions. The mechanism of element migration from the pore waters is as follow: the water vapor phase transports elements in the form of aqueous ions, but complexed species (such as MeSO4(aq), MeCl(aq), Me(OH)+, etc.) remain in the salt residue. A significant contribution to the processes of transformation and transport of elements is made by biochemical methylation reactions, which occur in the presence of bacteria producers of methyl groups and are accompanied by the formation of volatile compounds of arsenic, selenium, sulfur, and tellurium.

Near-UV photooxidation of As(III) by iron species in the presence of fulvic acid.

Photooxidation of As(III) in ternary As(III) - Fe(III) - Fulvic acid system at pH 4 was investigated by optical spectroscopy, steady-state photolysis (365 nm) and atomic-emission spectrometry with inductively coupled plasma techniques. It was found that at all values of [FA]/[Fe] ratio the main photoactive species is OH radical formed by photolysis of Fe(III) hydroxocomplexes. Addition of fulvic acid leads to mainly negative effect on As(III) photooxidation due to the following reasons: (i) slow dark reduction of photoactive Fe(III) species with formation of scattering particles and photoinert Fe(II) species; (ii) formation of photoreductive Fe(III)-FA complexes incapable to oxidize As(III), (iii) competition of both FA and Fe(III)-FA complexes for UVA quanta with FeOH2+ complex and for OH radicals with As(III). Aging of ternary system is also very important parameter leading to one order decrease of quantum yields of both Fe(II) formation and As(III) photooxidation.

Phytoremediation-biorefinery tandem for effective clean-up of metal contaminated soil and biomass valorisation.

During the last few decades, phytoremediation process has attracted much attention because of the growing concerns about the deteriorating quality of soil caused by anthropogenic activities. Here, a tandem phytoremediation/biorefinery process was proposed as a way to turn phytoremediation into a viable commercial method by producing valuable chemicals in addition to cleaned soil. Two agricultural plants (Sinapis alba and Helianthus annuus) were grown in moderately contaminated soil with ca. 100 ppm of Ni and further degraded by a fungal lignin degrader-Phanerochaete chrysosporium. Several parameters have been studied, including the viability of plants, biomass yield, and their accumulating and remediating potentials. Further, downstream processing showed that up to 80% of Ni can be easily extracted from contaminated biomass by aqueous extraction at mild conditions. Finally, it was demonstrated that the growth of plants on the contaminated soil could be degraded by P. chrysosporium, and the effect of nickel and biomass pretreatment on the solid-state fermentation was studied. The proposed and studied methodology in this work could pave the way for successful commercialization of the phytoremediation process in the near future.

Phytoextraction of trace elements by water hyacinth in contaminated area of gold mine tailing.

The ability of water hyacinth (Eichhornia crassipes) to uptake Ag, Ba, Cd, Mo, and Pb from waters in gold mine tailing area was studied. All experiments were carried out in the field conditions without using of model system. Bioconcentration (BCF) and translocation factors (TF) as well as elements accumulation by plant in different points of tailings-impacted area were evaluated. It has been shown that water hyacinth demonstrates high ability to accumulate Mo, Pb, and Ba with BCF values 24,360 ± 3600, 18,800 ± 2800 and 10,040 ± 1400, respectively and is efficient in translocation of Mo and Cd. The general trend of the plant accumulation ability in relation to the studied elements corresponds to their concentration in the medium. As the distance from tailings increases, concentration of Ag, Ba and Pb in plant decreases more clearly than that of Cd, while the amount of Mo accumulated by plant doesn't drop significantly in accordance with its concentration in water. Under the conditions of the confluence of river Ur and drainage stream Ba and Ag can be considered as potential candidates for phytomining.

The study of polyoxometalates formation using capillary zone electrophoresis.

The formation process of polyoxometalates [PMo12 O40 ](3-) and [PMo12 - x Vx O40 ](-3-x) has been studied in aqueous solutions of 0.1 M malonate buffer at pH 2.8-3.0 using CZE. Two different approaches, pre-capillary and in-capillary, were examined and compared. In precapillary mode, the reaction mixture of the reactants and reaction products was injected into the capillary followed by the separation procedure. In in-capillary mode, the sequential input of the reagents and running electrolyte into the capillary and the species separation occurs simultaneously. The optimal parameters of in-capillary separation were established as functions of applied voltage and the length of the intermediate buffer zone between the reagents in the capillary. As a result the best-compromise conditions for the separation of the mixtures containing the reactants, intermediates, and reaction products, in order to achieve the best efficiency, symmetry, and peak areas, were achieved at -18 kV and the input parameter of 900 mbar·s. It was also shown that in-capillary mode is more informative than pre-capillary mode for studying the complex compound formation process.

Comparison of sustained low-efficiency dialysis with acetate-free and acetate-containing bicarbonate dialysate in unstable patients.

This work is focused on the problem of maintenance of intradialytic hemodynamic safety in unstable patients with acute kidney injury (AKI). A hypothesis that "small" quantities of acetate in standard bicarbonate dialysate can cause pronounced acetatemia and exacerbate cardiovascular instability was tested. In this prospective randomized study, a group of patients with AKI after cardiac surgery was treated with sustained low-efficiency dialysis with either acetate-containing bicarbonate dialysate or acetate-free dialysate, where acetate is replaced by hydrochloric acid. It was demonstrated that application of acetate-containing bicarbonate dialysate results in blood acetate levels up to 12 times the normal level. Additionally, it is associated with a 3.8-fold-increased risk of hemodynamic complications in comparison with acetate-free dialysate. The choice of acetate-free or acetate-containing bicarbonate dialysate does not influence adequacy of correction of the acid-base and electrolyte content of blood.

Studies on cadmium accumulation by some selected floating macrophytes.

The results of investigation of the process of cadmium accumulation by floating plants of Eichhornia crassipes and Pistia stratiotes are discussed. The main specialty of this study is that it puts more emphasis on the mechanism of penetration of pollutant within the plant and its fate during accumulation act. As a result it was shown that at the first stage of cadmium uptake the sorption of the metal on the surface of the roots due to the presence of carboxylic groups takes place. At the root of the plant cadmium mainly localized in the cortex and rhizodermis, then the pollutant penetrates into the tissues of the stem according to its translocation factor. It has been also assumed that flavonoids perform an intermediate role in the accumulation of cadmium by the plant, taking part in the transport and combat an oxidative stress.

Arsenic speciation in natural and contaminated waters using CZE with in situ derivatization by molybdate and direct UV-detection.

A simple and sensitive procedure for simultaneous determination of arsenate, arsenite, monomethylarsonate and dimethylarsinate (DMA) ions in waters using CZE with chemical derivatization in situ and UV-detection at 250 nm was developed. The separation was performed in a fused-silica capillary using solution containing sodium molybdate and sodium perchlorate as electrolyte. Molybdate forms heteropolycomplexes with arsenic species in low acidic media, while sodium perchlorate masks silicate ion. The analysis conditions were optimized; the best results were achieved with the electrolyte consisting of 10 mM Na(2)MoO(4) and 10 mM NaClO(4) at pH 3.0 using negative voltage and pneumatic injection of the sample. Nevertheless, the signal of arsenite ion was not detected, probably because of its instability. Arsenite ion was quantified as a difference between arsenate ion contents after and before oxidation by bromine water. The detection limits for the fresh water at the level of 5.0 microg/L for As(III) and As(V), 16 microg/L for DMA and 20 microg/L for MMA were achieved. The reproducibility varied in the range of 0.06-0.25 relative units. To reduce the interferences of the sample salinity an addition of organic substances and isotachophoretic effect were used.

Mercury speciation in environmental solid samples using thermal release technique with atomic absorption detection.

A sensitive and very simple method for determination of mercury species in solid samples has been developed involving thermal release analysis in combination with atomic absorption (AAS) detection. The method allows determination of mercury(II) chloride, methylmercury and mercury sulfide at the level of 0.70, 0.35 and 0.20ng with a reproducibility of the results of 14, 25 and 18%, respectively. The accuracy of the developed assay has been estimated using certified reference materials and by comparison of the results with those of an independent method. The method has been applied for Hg species determination in original samples of lake sediments and plankton.