Sample preparation - A crucial step to distinguish metallic and ionic platinum forms and their mobility in soil.

The study is focused on one of the technology-critical elements (TCEs), Pt in the context of distinguishing ionic from metallic forms and assessing sorption capacity of soil. Solid-liquid extraction, cross-comparison of the results of two determination techniques and two decomposition methods enable quantitative determination of the ionic form and, indirectly, NPs in soil and plants. Information about ionic form is obtained after sample digestion with conc. HNO3 and AdSV determination, and total Pt content is determined after digestion using mixture of conc. HNO3 and conc. HCl. The recovery of Pt was in the range 99-110 % for both forms. The mobility (0.43 mol L-1 HAc) of Pt-NPs and Pt (II) was below 1 % even in the presence of citrates (after 2 month incubation). The long-term sorption study indicated that Pt retention (both forms) in the organic soil is related to formation of organic complexes, and the equilibrium is achieved after 2 days. When the soil is enriched in Fe2O3, stronger sorption is observed up to 2 days for both Pt forms (the mobility is 9-14 pp. lower), to finally achieve similar sorption as without modification, reaching 89/90 % for incubation with DI water, and 81/85 % with citrates. The addition of biocarbon/biochar does not play an important role in immobilization of Pt (II) and Pt-NPs.

On site separation of inorganic forms of thallium and arsenic in sea water systems followed by ICP-MS determination.

Reduction of Tl(III) and oxidation of As(III), which are unstable speciation forms, start just after sampling as a result of disturbed chemical equilibrium. Separation of inorganic Tl and As species, unchanged, is thus crucial for reliable results of speciation analysis in water systems. Presented here a simple and fast sample pretreatment, based on ion exchange cartridges, which gives the possibility to separate Tl and As species already on the sampling site. Note the reduction of Tl(III) (15%) is in the range of losses typical for standard procedures based on Tl(III) fixation. The use of SCX-3 allows for Tl(III) and SAX for As(III) separation, which are then quantitated in the effluent by ICP-MS. Determination of non-retained species was done after reduction of the sample volume to 2 mL (50-fold preconcentration), which allowed for detection of As concentrations <0.1 ppb and Tl <0.01 ppb. For As, a collision chamber is required. The possibility of direct determination is very important for the forms being in trace amounts in sea water in the vicinity of harbors.

Corrosion process of stainless steel in natural brine as a source of chromium and iron - the need for routine analysis.

The corrosion of the installations carrying high salinity water is particularly important in the case of utility and therapeutic waters, such as natural brine. The analysis of such complex systems is challenging in the context of routine analysis of Fe and Cr. Both elements can be determined by UV-Vis spectrophotometry after only 1 : 100 dilution and liquid-liquid extraction (LODFe = 0.03 mg L-1) or thermal chloride stripping (LODCr = 0.02 mg L-1). The corrosion process was characterized. Electrochemically accelerated corrosion showed uneven decomposition of the steel components - Cr is less easily released to the solution than Fe. Iron comprises 53% of the dissolved part, and Cr comprises 8.6%, while the steel originally contained 62% of Fe and 18% of Cr. During the short-term (one week) contact of the brine with stainless steel, the amounts of Fe and Cr released to the brine were insignificant from the perspective of its therapeutic value.

Sinapis alba as a useful plant in bioremediation - studies of defense mechanisms and accumulation of As, Tl and PGEs.

Pollution of the soils with toxic elements is a serious problem all over the world. One of environmentally friendly techniques of their removal is phytoremediation. This paper is a summary of literature data and the results of own studies about the potential of Sinapis alba for bioaccumulation of Tl, As and PGEs, and its usefulness in remediation of polluted environment. S. alba is characterized with low living requirements, BFs ≫ 1 and high TFs, especially for Tl (up to 3). The influence of different forms of studied elements on plants was discussed based on biomass production, morphological changes and the impact on photosynthesis activity. The plants were cultivated in hydroponics and solid media of various composition, for example, in soil supplemented with MnO2, which resulted in BFs lower 6-7 times for leaves, and about 3-4 times for stems, as well as twice lower leaf development. Application of advanced analytical techniques was presented in studies of the detoxification mechanisms, identification of particular chemical forms of the elements and the presence of phytochelatins and their complexes with the investigated elements.Novelty StatementThe paper summarizes both literature and original data on Sinapis alba exposed to such elements as thallium, arsenic and platinum group metals. The influence of different forms of studied elements on white mustard was discussed based on biomass production and morphological changes, as well as the impact on photosynthesis activity. The study covers such aspects as bioaccumulation, phytotoxicity as well as the usefulness of white mustard in remediation of polluted environment.

Statistical evaluation of the effect of sample preparation procedure on the results of determinations of selected elements in environmental samples. Honey bees as a case study.

Honey bees became a frequently studied environmental research object due to the fact that they are considered as indicators of the environmental contamination with metals. Such studies require reliable methods of sample preparation that allow comparison of the results obtained in different laboratories. In this paper, different variants of sample preparation were examined, including washing, milling and mineralization. Determination of total contents of Cd, Pb, Co, Cr, Cu, and Zn was performed using ICP MS. Each procedure of the sample preparation was characterized in terms of repeatability and recovery and the resulting combined standard uncertainty was evaluated. The relative UNC ranges for the treatment procedures examined are: 11-16% (washing, open digestion), 13-14% (open digestion), 13-51% (washing, closed digestion), 12-37% (washing, milling, closed digestion), 13-68% (closed digestion), and 12-51% (milling, closed digestion). In almost all cases the lower limits of these ranges correspond to Zn determinations while the upper limits to Pb. Analytical results of metal determination obtained for samples prepared according to six different procedures do not differ significantly when compared within the expanded uncertainty (±2×u(c¯M)). The procedures were compared statistically using one-factor analysis of variance (ANOVA) and chemometrically on the basis of Principal Component Analysis (PCA), which allowed to demonstrate some general recommendations regarding environmental monitoring for matrices other than honey bees.

Search for effective eluent for Pd separation on ion-exchange sorbent before voltammetric determination.

Determination of Pd traces in environmental samples is still a challenging analytical task. The aim of this study was to propose an efficient system (i.e. ion-exchange resin and eluent) for Pd elution from SPE column after the analyte preconcentration. Moreover, the search was focused on solvents that would not interfere voltammetric determination of Pd, as well as ICP-MS analysis. Five ion-exchange sorbents were compared in terms of effective Pd separation from matrix components when using different eluents. The highest recovery (up to 91%) of palladium was obtained for Dowex 1 and ammonium buffer as the eluent. This solution not only provides relatively high palladium elution efficiency but also allows both voltammetric and ICP-MS determinations, without any additional sample preparation. It was proven that the proposed procedure including SPE separation and determination with AdSV and/or ICP-MS could be used for quantitative Pd measurement in environmental samples, such as quartz sand used for the monitoring of Pd emission in the areas of high traffic density.

A chemical speciation insight into the palladium(ii) uptake and metabolism by Sinapis alba. Exposure to Pd induces the synthesis of a Pd-histidine complex.

Palladium is recognized as a technologically critical element (TCE) because of its massive use in automobile exhaust gas catalytic converters. The release of Pd into the environment in the form of nanoparticles of various size and chemical composition requires an understanding of their metabolism by leaving organisms. We provide here for the first time a chemical speciation insight into the identity of the ligands produced or used by a plant Sinapis alba L. exposed in hydropony to Pd nanoparticles and soluble Pd (nitrate). The analytical method developed was based on the concept of 2D HPLC with parallel inductively coupled plasma mass spectrometry (ICP MS) and electrospray MS detection. Size exclusion chromatography - ICP MS of the plant extracts showed no difference between the speciation of Pd after the exposure to nanoparticles and after that to Pd2+ which indicated the reactivity and dissolution of Pd nanoparticles. A comparative investigation of the Pd speciation in a control plant extract spiked with Pd2+ and of an extract of a plant having metabolized palladium indicated the response of the Sinapis alba by the formation of a Pd-histidine complex. The complex was identified via Orbitrap MS; the HPLC-MS chromatogram produced two peaks at m/z 415.0341 each corresponding to a Pd-His2 complex. An investigation by ion-mobility MS revealed a difference in their collision cross section indicating that the complexes present varied in terms of spatial conformation. A number of other Pd complexes with different ligands (including nicotianamine) circulating in the plant were detected but these ligands were already observed in a control plant and their concentrations were not affected by the exposure to Pd.

Simplification of organic matter before voltammetric determination of Tl(I) and Tl(III) in water using nanostructured photocatalyst and solar light.

The crucial point of this study was to verify the hypothesis that both thallium species are not affected by the procedure of photolysis when it is applied as a method of simplification of sample matrix containing surfactants, and that this method of sample pretreatment leads to reliable results of Tl speciation analysis. It is important especially because of high instability of Tl(III), which makes partial reduction of Tl(III)DTPA complex unavoidable. After conservation of Tl speciation by addition of DTPA the photolysis assisted with nanostructured hierarchically organized film was performed using "solar lamp" (Fe2O3/WO3/Fe2O3 film, pH 6, 380-800 nm). The results imply that under proposed photolysis conditions Tl(I) is not oxidized in the presence of water matrix, SDS nor DTPA. Also, even 100-fold excess of Fe(III) ions over Tl(I) ions does not accelerate the oxidation of Tl(I) to Tl(III), and already 2 h of heterogeneous photolysis allow to limit the interferences caused by SDS and obtain reliable results. The data obtained by anodic stripping voltammetry (ASV) were verified using an inter-method comparison with SEC ICP MS. Moreover, after 2 h irradiation the reduction rate of Tl(III)DTPA standard solution increased only slightly from 2-3% to 4-6%. The presence of river water matrix causes a slightly higher (9%) reduction of the trivalent form. These changes are irrelevant in the context of instability of Tl(III) compounds. This study indicates that "soft decomposition" can be applied in speciation analysis of thallium in water matrix.

Comparison of the contents of selected elements and pesticides in honey bees with regard to their habitat.

The inspiration for this study was the anxiety of Warsaw beekeepers, who raised the question whether location of hives in large urban agglomerations results in changes in concentrations of xenobiotics, toxic elements, and micronutrients in honey bees. Preliminary studies required elaboration of the research methodology, as the studied object is characterized by a low degree of homogeneity and the method of sample preparation affects obtained results. From many tested approaches, the use of washed and milled abdomens of the bees is recommended. Results obtained for such prepared samples are slightly lower than for whole bees, but their repeatability is higher, which enables easier interpretation of the trends and comparison of different locations. The contents of selected elements (As, Al, Cd, Co, Cr, Cu, Mn, Pb, and Zn) were compared in bees from urban and rural areas. The studies were supported by pesticides analysis. Also, it was checked whether these substances are accumulated on the surface or inside the bee's body. The research indicates the markers of contamination: Al, As, and Cr on the surface and Cd inside the bodies of honey bees. The location of the hives does not influence significantly the content of "toxic," nutrient metals and metalloids in bees (slightly higher levels of As, Al, Pb, and Cd were found in bees from urban areas). In terms of exposure to these elements and pesticides, the large city environment is not harmful for honey bees.

Study of the uptake and bioaccumulation of palladium nanoparticles by Sinapis alba using single particle ICP-MS.

In recent years, increased palladium content has been found in the environment, due to its wide use in various fields, especially as catalytic converters. Palladium can be emitted as a range of soluble and insoluble compounds and in the form of palladium nanoparticles (PdNPs). The level of toxicity is equally dependent on concentration and form of palladium and hence, it is important to determine not only the total content of this element, but also its forms of occurrence. This study for the first time investigates the uptake degree and distribution of PdNPs by model plant Sinapis alba, in comparison with a platinum salt (Pd(NO3)2). An enzymatic digestion method which allows the extraction of PdNPs from the different plant tissues without altering their properties was applied. After extraction, samples were analysed by single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) to provide information about the presences of palladium in nanoparticulated or dissolved form, the nanoparticle size and the nanoparticle number concentration. Significant amounts of PdNPs were found even in aboveground organs, but no significant changes in plant morphology were observed. Size distributions of PdNPs found in all tissues presented lower diameters than size distribution of the PdNPs stock suspension, suggesting that bigger nanoparticles are not taken up by the plant. The average size found is in good agreement between the different organs. Moreover, dissolved palladium was found in all samples, with the biggest contribution, in relative terms, observed in leaves followed by stems and roots.

Organic matter decomposition before arsenic speciation analysis of water sample - "Soft decomposition" using nano-photocatalysts.

The applicability of photolysis in the speciation analysis of arsenic is investigated. The use of nano scale semiconductors (Fe2O3/WO3/Fe2O3 at pH 6) as an active film during solar light irradiation of a water sample, containing some surfactants (SDS), results in the simplification of the organic matter and gives no speciation change in the arsenic. The reproducibility of active layer is shown to be high and the surface roughness of each photoactive sample and photocurrent do not differ by more than 6 and less than 8%, respectively. The procedure of sample pretreatment caused a minimum (8-10%) amount of speciation change, whilst the irradiation is no longer that 2 h. The study indicates that "soft decomposition" can be performed for as long as 4 h, and still give photostable arsenates (III) and methylarsenate species. However, the saturation of the water sample with Ar is required (to reduce the oxygen content) for the longer the decomposition time being applied.

Selective and sensitive electrochemical device for direct VB2 determination in real products.

The developed by us electrochemical device for vitamin B2 (VB2; riboflavin) determination, without preconcentration step, in real products exhibits high sensitivity, selectivity, stability and low detection limit compared to those described in the literature. The determination procedure was based on the monitoring of the reduction current signal of VB2 bound with dsDNA anchored to the electrode surface through intermediary - carboxyphenyl layer. The application of such intermediary layer formed during electroreduction of appropriate diazonium salt at CV peak potential guarantees high efficiency of hybridization process and thus fully available places for VB2 interaction. Moreover, such intermediary layer provides good electrical contact, what is very important in the case of electrochemical sensors. The analytical range of work of the proposed VB2 sensor was between 0.08-1µM (30-377µgL-1) of riboflavin concentration. The obtained detection (LOD) and quantification limits (LOQ) were 24±2 and 55±5µgL-1, respectively. The proposed VB2 detection method was used for determination of riboflavin content in commercially available dietary supplements and yolk of hen egg samples. The accuracy of the obtained data was proved using comparison with an independent method (HPLC FLD).

Overlapping toxic effect of long term thallium exposure on white mustard (Sinapis alba L.) photosynthetic activity.

BACKGROUND: Heavy metal exposure affect plant productivity by interfering, directly and indirectly, with photosynthetic reactions. The toxic effect of heavy metals on photosynthetic reactions has been reported in wide-ranging studies, however there is paucity of data in the literature concerning thallium (Tl) toxicity. Thallium is ubiquitous natural trace element and is considered the most toxic of heavy metals; however, some plant species, such as white mustard (Sinapis alba L.) are able to accumulate thallium at very high concentrations. In this study we identified the main sites of the photosynthetic process inhibited either directly or indirectly by thallium, and elucidated possible detoxification mechanisms in S. alba. RESULTS: We studied the toxicity of thallium in white mustard (S. alba) growing plants and demonstrated that tolerance of plants to thallium (the root test) decreased with the increasing Tl(I) ions concentration in culture media. The root growth of plants exposed to Tl at 100 µg L(-1) for 4 weeks was similar to that in control plants, while in plants grown with Tl at 1,000 µg L(-1) root growth was strongly inhibited. In leaves, toxic effect became gradually visible in response to increasing concentration of Tl (100 - 1,000 µg L(-1)) with discoloration spreading around main vascular bundles of the leaf blade; whereas leaf margins remained green. Subsequent structural analyses using chlorophyll fluorescence, microscopy, and pigment and protein analysis have revealed different effects of varying Tl concentrations on leaf tissue. At lower concentration partial rearrangement of the photosynthetic complexes was observed without significant changes in the chloroplast structure and the pigment and protein levels. At higher concentrations, the decrease of PSI and PSII quantum yields and massive oxidation of pigments was observed in discolored leaf areas, which contained high amount of Tl. Substantial decline of the photosystem core proteins and disorder of the photosynthetic complexes were responsible for disappearance of the chloroplast grana. CONCLUSIONS: Based on the presented results we postulate two phases of thallium toxicity on photosynthesis: the non-destructive phase at early stages of toxicant accumulation and the destructive phase that is restricted to the discolored leaf areas containing high toxicant content. There was no distinct border between the two phases of thallium toxicity in leaves and the degree of toxicity was proportional to the migration rate of the toxicant outside the vascular bundles. The three-fold (nearly linear) increase of Tl(I) concentration was observed in damaged tissue and the damage appears to be associated with the presence of the oxidized form of thallium - Tl(III).

Direct speciation analysis of thallium based on solid phase extraction and specific retention of a Tl(III) complex on alumina coated with sodium dodecyl sulfate.

Alumina (Al2O3) with an average particle size of 63 µm was modified with the anionic surfactant sodium dodecyl sulfate (SDS) and then applied to (i) solid phase extraction and separation of both thallium(I) and thallium(III), and (ii) preconcentration of Tl(III) from waste water samples. Only Tl(III), in the form of its complex with diethylenetriaminepentaacetate (DTPA), was retained on the sorbent, from where it can be eluted with 40 % nitric acid. Thallium species were then quantified by ICP MS. The method was characterized by a LOD of 25 pg of Tl(I) and 160 pg of Tl(III) in 10 mL samples. A large excesses of Tl(I) over Tl(III) was tolerated, and relatively high levels of other metal ions, such as a 500-fold excess of Pb(II) and Cd(II), and a 2000-fold excess of Zn(II), respectively, do not interfere. The sorbent was easily prepared and possesses a high loading capacity, and these properties make it an attractive material for rapid and efficient extraction and speciation of Tl. Graphical abstract:Schematic of the SPE procedure for separation (with preconcentration) of Tl(III) from Tl(I) was developed and applied to direct speciation analysis of thallium in wastewater. Self-made columns packed with alumina coated with SDS were used. The method is resistant to interferences from Pb, Cd, Zn and tolerates a large excess of Tl(I) over Tl(III).

Stability of Tl(III) in the context of speciation analysis of thallium in plants.

The paper presents both "good" and "bad" results obtained during speciation analysis of thallium in plant tissues of a hyperaccumulator of this metal. The object was white mustard - Sinapis alba L. In this plant there were found traces of trivalent thallium. The crucial point of this study (especially in the case of so unstable thallium form as Tl(III)) was to prove that the presence of Tl(III) was not caused by the procedure of sample preparation itself, and that the whole analytical method provides reliable results. Choice of the method for conservation of the initial speciation, extraction with the highest efficiency and proving the correctness of the obtained data were the most difficult parts of the presented study. It was found that: both freezing and drying cause significant changes in the speciation of thallium; quantitative analysis could be performed only with fresh tissues of mustard plants; only short-term storage of an extract from fresh plant tissues is possible; the methodology is not the source of thallium (III); only the presence of DTPA can greatly limit the reduction of TI(III) to TI(I) (up to 1-3%); the UV irradiation results in disintegration of TI(III)DTPA in the presence of plant matrix (reduction up to 90%).

Thallium in spawn, juveniles, and adult common toads (Bufo bufo) living in the vicinity of a zinc-mining complex, Poland.

A breeding population of the common toad Bufo bufo living in the vicinity of a Zn-Pb smelting works in Bukowno, Poland was studied for the presence of thallium. Tl concentration was measured in the bottom sediments of the spawning pond, in the laid eggs, in juveniles after metamorphosis, and in the selected tissues of the adult individuals. A very high concentration of Tl was detected in the spawn (13.97 ± 8.90 mg/kg d.w.). In 50% of the spawn samples, levels exceeded 20 mgTl/kg d.w. The issue of maternal transfer of thallium from females to oocytes is discussed. Due to a significant accumulation of thallium, spawn analysis can be used as a sensitive indicator of the presence of this element in the environment and may replace more invasive methods that involve the killing of adult animals. In those regions that are abundant in Zn-Pb ores, the spawn of amphibians may be a very important source of thallium contamination for predators. From among all tissues of the Bukowno adult toads, the livers have shown the highest accumulation of thallium (mean 3.98 mg/kg d.w. and maximum value--18.63). For as many as 96.5% of livers, concentrations exceeded 1.0 mgTl/kg d.w. which is treated as indicative of poisoning.

Mobility of toxic elements in carbonate sediments from a mining area in Poland.

The Boleslaw-Bukowno mining area in Poland is highly polluted by elements such as Zn, Pb, Cd and As. The reactivity and mobility of toxic elements such as Tl are poorly known. Here, we studied by sequential extraction the mobility of As, Cd, Co, Cr, Cu, Mn, Mo, Pb, Tl and Zn in sediments from two water reservoirs near Bukowno. Results show that available As, Co, Mn, Pb and Zn are found in carbonate minerals. Available Cd, Cu and Tl are found in sulphides and organic matter. The extractability of As, Cr, Mo and Tl was rather poor. By contrast, 85 % of total Cd, Pb and Zn was mobile. We discuss Tl and Mo association in carbonate sediments from ore deposits.

Determination of traces of Pt and Rh in soil and quartz samples contaminated by automobile exhaust after an ion-exchange matrix separation.

Monitoring of PGEs content in the natural samples is a crucial point in the environment science since catalytic car converters have been introduced. In the presented paper application of a very sensitive voltammetric method for determination of traces of Pt and Rh in the environmental samples contaminated by automobile exhausts is discussed. Voltammetric measurements were carried out in the supporting electrolyte containing formaldehyde and semicarbazide. PGEs were separated from the digested solutions of soils or quartz samples, collected from monitoring plots-by applying an ion-exchange resin Cellex-T. Pt was very effectively separated from the matrix approaching nearly 100% recovery after its elution by hydrochloric acid. Moreover the conditions of soil and quartz samples digestion were discussed. To validate the obtained result an independent analytical method-ICP MS was applied and analysis of certified reference material road dust 723-was completed.

Thallium (III) determination in the Baltic seawater samples by ICP MS after preconcentration on SGX C18 modified with DDTC.

The main difficulty of speciation analysis of thallium lies in extremely low concentrations of Tl(III) in comparison to Tl(I), which is the dominating form of thallium in environmental samples. In this study, a sensitive method is presented for separation of trace amounts of Tl(III) from Tl(I) and preconcentration of Tl(III) using octadecyl silica gel modified with diethyldithiocarbamate (DDTC). Under optimal conditions, only Tl(III) is retained on the sorbent, and then eluted with 96% ethanol. After chemical decomposition of Tl(III)-DDTC complex, thallium is determined by inductively coupled plasma mass spectrometry. High performance liquid chromatography with ICP MS detection was used to control the correctness of the obtained results. Parameters affecting solid phase extraction (SPE) such as pH, type, concentration and volume of eluent, breakthrough volume, and the impact of sample salinity (chlorides) and other interfering ions (Cd(II), Zn(II), Pb(II), Cu(II), Sn(II)) were investigated. The limit of detection (LOD), evaluated for 2 mL of sample solution, was 0.10 ng for Tl(I) and 0.43 ng for Tl(III). The method was applied to the determination of Tl(I) and Tl(III) in the Baltic seawater samples enriched in both thallium species.

Voltammetric and electrochemical gravimetric selective detection of interactions between Tl(I) and guanine and the influence on activity of DNA drug-intercalators.

The interactions of Tl(I), a well known toxic species, with selected oligonucleotides were examined. The oligonucleotide sequences selected for the investigation were taken from gene hOGG1 responsible for repairing of DNA damage. Cyclic voltammetry was particularly useful, since nitrogen N-7 in guanine can be electrooxidized while its binding with Tl(I) leads to the loss of electroactivity. So, this selected interaction could be quantitatively used in drawing Scatchard's plot and calculating the binding constants and the number of active sites in guanine molecules occupied by one metal ion. Further, we have shown that the presence of Tl(I) leads to a decrease in activity of doxorubicin (DOX), a popular anticancer drug, vs. DNA. The obtained circular dichroism (CD) spectra and the measurements with an electrochemical quartz crystal microbalance (EQCM) led to a conclusion that in the presence of monovalent thallium cations the DNA double helix was neither damaged/oxidized nor its conformation changed substantially.