Ionic Liquid Modified Polymer Gel for Arsenic Speciation.

A new ionic liquid modified polymer gel containing methylimidazolium groups (poly(MIA)) is proposed as a sorbent for the separation and enrichment of trace inorganic and organic arsenic species in surface waters. The poly(MIA) was synthesized by chemical modification of polymeric precursor using post-polymerization modification of poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate). The composition, structure, morphology, and surface properties of the prepared particles were characterized using elemental analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption-desorption measurements. Optimization experiments showed that at pH 8, monomethylarsonic acid (MMAs), dimethylarsinic acid (DMAs), and As(V) were completely retained on the poly(MIA), while the sorption of As(III) was insignificant. The desorption experiments revealed that due to the weaker binding of organic arsenic species, selective elution with 1 mol/L acetic acid for MMAs + DMAs, followed by elution with 2 mol/L hydrochloric acid for As(V), ensured their quantitative separation. The adsorption kinetic and mechanism were defined. The analytical procedure for As(III), As(V), MMAs, and DMAs determination in surface waters was developed and validated through the analysis of certified reference material.

Polymeric Materials in Speciation Analysis Based on Solid-Phase Extraction.

Speciation analysis is a relevant topic since the (eco)toxicity, bioavailability, bio (geo)chemical cycles, and mobility of a given element depend on its chemical forms (oxidation state, organic ligands, etc.). The reliability of analytical results for chemical species of elements depends mostly on the maintaining of their stability during the sample pretreatment step and on the selectivity of further separation step. Solid-phase extraction (SPE) is a matter of choice as the most suitable and widely used procedure for both enrichment of chemical species of elements and their separation. The features of sorbent material are of great importance to ensure extraction efficiency from one side and selectivity from the other side of the SPE procedure. This review presents an update on the application of polymeric materials in solid-phase extraction used in nonchromatographic methods for speciation analysis.

Cr(III) Ion-Imprinted Hydrogel Membrane for Chromium Speciation Analysis in Water Samples.

Novel Cr(III)-imprinted poly(vinyl alcohol)/sodium alginate/AuNPs hydrogel membranes (Cr(III)-IIMs) were obtained and characterized and further applied as a sorbent for chromium speciation in waters. Cr(III)-IIMs were prepared via solution blending method using blends of poly(vinyl alcohol) and sodium alginate as film-forming materials, poly(ethylene glycol) as a porogen agent, sodium alginate stabilized gold nanoparticles (SA-AuNPs) as a crosslinking and mechanically stabilizing component, and Cr(III) ions as a template species. The physicochemical characteristics of pre-synthesized AuNPs and obtained hydrogel membranes Cr(III)-IIM were studied by UV-vis and FTIR spectroscopy, TEM and SEM observations, N2 adsorption-desorption measurements, and XRD analysis. The mechanism of the adsorption process toward Cr(III) was best described by pseudo-first-order kinetic and Langmuir models. Experiments performed showed that quantitative retention of Cr(III) is attained in 20 h at pH 6 and temperature 40 °C. Under the same conditions, the adsorption of Cr(VI) is below 5%. A simple and sensitive analytical procedure was developed for the speciation of Cr in an aquatic environment using dispersive solid phase extraction of Cr(III) by Cr(III)-IIM prior to selective Cr(VI) measurement by ETAAS in the supernatants. The detection limits and reproducibility achieved for the Cr speciation analysis fulfill the requirements for their monitoring in waters under the demand of the Water Framework Directive.

Uranium Determination in Waters, Wine and Honey by Solid Phase Extraction with New Ion Imprinted Polymer.

An analytical method for uranium determination in waters, wine and honey was developed based on solid phase extraction (SPE) with new ion imprinted polymer. The sorbent was synthesized using 4-(2-Pyridylazo)resorcinol (PAR) as a ligand via dispersion polymerization and characterized by SEM for morphology and shape of polymer particles and nitrogen adsorption-desorption studies for their surface area and total pore volume. The kinetic experiments performed showed that the rate limiting step is the complexation between U(VI) ions and chelating ligand PAR incorporated in the polymer matrix. Investigations by Freundlich and Langmuir adsorption isotherm models showed that sorption process occurs as a surface monolayer on homogeneous sites. The high extraction efficiency of synthesized sorbent toward U(VI) allows its application for SPE determination of U(VI) in wine and honey without preliminary sample digestion using ICP-OES as measurement method. The recoveries achieved varied: (i) between 88 to 95% for surface and ground waters, (ii) between 90-96% for 5% aqueous solution of honey, (iii) between 86-93% for different types of wine. The validity and versatility of proposed analytical methods were confirmed by parallel measurement of U in water samples using Alpha spectrometry and U analysis in wine and honey after sample digestion and ICP-MS measurement. The analytical procedure proposed for U determination in surface waters is characterized with low limits of detection/quantification and good reproducibility ensuring its application for routine control in national monitoring of surface waters. The application of proposed method for honey and wine samples analysis provides data for U content in traditional Bulgarian products.

Pollen and Chemical Content of Beebreads from Serpentine Areas in Albania and Bulgaria.

Beebread from serpentine localities in Albania and Bulgaria were characterized based on their pollen and chemical element content (macroelements K, Ca, Mg, P and microelements Cd, Co, Cr, Cu, Fe, Mn, Na, Ni, Pb, Zn) aiming to (1) evaluate the effect of serpentine soil on the quality of beebread; (2) compare elemental concentrations in samples from serpentine areas in Albania and Bulgaria; and (3) compare the differences in pollen spectra. Chemical element content was determined using microwave digestion of beebread samples followed by ICP-OES measurements. The analytical procedure developed was validated by added/found method. Analytical figures of merit of analytical method proposed were presented. The melissopalynological analysis was applied for pollen characterization. The results demonstrate clear difference in the pollen spectra between the two sets of samples, confirming differences in local serpentine flora in both countries, but specific pollen type is difficult to be suggested. The pollen content is related to the flowering period, climatic conditions, and bees forage preferences. The samples vary in their elemental concentrations depending on the pollen type and year of collection. The highest average concentrations found for K, Ca, Mg, and P are close to values reported in the literature. However, elevated concentrations observed for Ni, Cr, Mn, and Fe in beebread, especially from Albania, are in line with the serpentine characteristics of studied areas. The concentrations of Cd and Pb for all beebread samples are below permissible limits. The results should be taken into consideration in future specific food safety regulations at national and international level.

Raffinose Capped Silver Nanoparticles: A New Localized Surface Plasmon Resonance Based Sensor for Selective Quantification of Cr(VI) in Waste Waters.

In this study, a new method for selective determination of Cr(VI) in water samples at pH 4 is presented using raffinose capped silver nanoparticles (Ag/Raff NPs) as an optical sensor. The method is based on the variation of LSPR absorption band intensity as a result of electrostatic interaction between the negatively charged Ag/Raff NPs and positive Cr(III) ions, in-situ produced by chemical reduction of Cr(VI) with ascorbic acid, combined with the fast kinetics of Cr(III) coordination to the -OH groups of the capping agent on the nanoparticle surface, further causing the nanoparticle aggregation. The calibration curve for Cr(VI) is linear in the range 2.5-7.5 µmol L-1, the limit of quantification achieved is 1.9 µmol L-1, and values of relative standard deviation vary from 3 to 5% for concentration level 1.9-7.5 µmol L-1. The interference studies performed in the presence of various metal ions show very good selectivity of Ag/Raff NPs toward Cr(VI) species. The added-found method is used to confirm the accuracy and precision of developed analytical approach.

Chitosan film loaded with silver nanoparticles-sorbent for solid phase extraction of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II).

The present study describes the ecofriendly method for the preparation of chitosan film loaded with silver nanoparticles (CS-AgNPs) and application of this film as efficient sorbent for separation and enrichment of Al(III), Cd(II), Cu(II), Co(II), Fe(III), Ni(II), Pb(II) and Zn(II). The stable CS-AgNPs colloid was prepared by dispersing the AgNPs sol in chitosan solution at appropriate ratio and further used to obtain a cast film with very good stability under storage and good mechanical strength for easy handling in aqueous medium. The incorporation of AgNPs in the structure of CS film and interaction between the polymer matrix and nanoparticles were confirmed by UV-vis and FTIR spectroscopy. The homogeneously embedded AgNPs (average diameter 29nm, TEM analysis) were clearly observed throughout the film by SEM. The CS-AgNPs nanocomposite film shows high sorption activity toward trace metals under optimized chemical conditions. The results suggest that the CS-AgNPs nanocomposite film can be feasibly used as a novel sorbent material for solid-phase extraction of metal pollutants from surface waters.

Submicron silica spheres decorated with silver nanoparticles as a new effective sorbent for inorganic mercury in surface waters.

An analytical method using silica supported silver nanoparticles as a novel sorbent for the enrichment and determination of inorganic mercury (iHg) in surface water samples has been developed. Silver nanoparticles (AgNPs) were synthesized by a completely green procedure and were deposited onto the amine functionalized surface of silica submicrospheres (SiO2-NH2). The prepared nanocomposite material (SiO2/AgNPs) was characterized by transmission electron microscopy, UV-vis spectroscopy, X-ray diffraction and atomic force microscopy. The sorption and desorption characteristics of the nanosorbent SiO2/AgNPs toward Hg species were investigated by a batch method. An excellent separation of iHg and methylHg was achieved in 20 minutes at pH 2. The high selectivity of the SiO2/AgNPs toward iHg was explained by Hg(ii) reduction and subsequent silver-mercury amalgam formation. The analytical procedure for the enrichment and determination of inorganic mercury in surface waters was developed based on solid phase extraction and ICP-MS measurements. The total Hg content was determined after water sample mineralization. The recoveries reached for iHg in different surface waters e.g. river and Black sea water samples varied from 96-101%. The limits of quantification are 0.002 µg L(-1) and 0.004 µg L(-1) for iHg and total Hg, respectively; the relative standard deviations varied in the ranges of 5-9% and 6-11% for iHg and total Hg, respectively, for Hg content from 0.005 to 0.2 µg L(-1). The accuracy of the procedure developed for total Hg determination was confirmed by a comparative analysis of surface river (ICP-MS) and sea (CV AFS) waters.

Toxic element profiles in selected medicinal plants growing on serpentines in Bulgaria.

Populations of medicinal plants growing on serpentines and their respective soils were analyzed for Fe, Ni, Mn, Cr, Co, Cd, Cu, Zn, and Pb using inductively coupled plasma atomic emission spectrometry. Aqua regia extraction and 0.43 M acetic acid extraction were used for the quantification of pseudototal and bioavailable fractions, respectively, of elements in soil and nitric acid digestion for determination of total element content in plants. Screening was performed to (1) document levels of toxic metals in herbs extensively used in preparation of products and standardized extracts, (2) compare accumulation abilities of ferns and seed plants, and (3) estimate correlations between metal content in plants and their soils. The toxic element content of plants varied from site to site on a large scale. The concentrations of Fe and Ni were elevated while those of Cu, Zn, and Pb were close to average values usually found in plants. The highest concentrations for almost all elements were measured in both Teucrium species. Specific differences in metal accumulation between ferns and seed plants were not recorded. The investigated species are not hyperaccumulators but can accumulate toxic elements, in some cases exceeding permissible levels proposed by the World Health Organization and European Pharmacopoeia. The harvesting of medicinal plants from serpentines could be hazardous to humans.

Synthesis and application of vinylpyridine containing ion-imprinted copolymer gel microbeads for Cu(II) solid-phase extraction.

The influence of polymer matrix on the extraction efficiency for Cu(II) and selectivity against metal ions such as Ni(II), Cd(II), Pb(II) of Cu(II) imprinted copolymer gels was described. The functional monomers investigated include the weakly basic 4-vinylpyridine (4-VP) and its mixure with the acidic and hydrogen binding methacrylic acid. Copolymer gels were prepared by dispersion cross-linking copolymerization using Cu(II)-4-(2-pyridylazo)resorcinol complex, Cu(II), or 4-(2-pyridylazo)resorcinol as templates. The chemical structure and morphology of the Cu(II)-imprinted microbeads are defined using elemental analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy. Extraction efficiencies of newly synthesized sorbents were studied by batch procedure. The prepared copolymer gel with 4-VP as monomer and Cu(II)-4-(2-pyridylazo)resorcinol complex has higher capacity and selectivity toward Cu(II) than the copolymer gels prepared using the mixture of methacrylic acid and 4-VP. This new sorbent can be used as an effective SPE material for the highly selective preconcentration and separation of Cu(II) in sea water samples. It shows high mechanical and chemical stability.

Non-chromatographic mercury speciation and determination in wine by new core-shell ion-imprinted sorbents.

In this study new Hg(II) core-shell imprinted sorbents (Hg(II)-IIPs) were prepared and tested for speciation and determination of Hg in wine. The silica gel, chemically modified with 3-(trimethoxysilyl)propyl methacrylate (TSPM) was used as supporting material. The Hg(II)-imprinted polymer layer was grafted by copolymerization of methacrylic acid and trimethylolpropane trimethacrylate in the presence of Hg(II) complexes with two different chelating agents: 1-pyrrolidinedithiocarboxylic acid (P(PDC-Hg)/SiG) and 1-(2-thiazolylazo)-2-naphthol (P(TAN-Hg)/SiG). High selectivity and fast kinetics of processes of sorption and desorption for Hg(II) were found by using P(PDC-Hg)/SiG. Recovery experiments performed for selective determination of inorganic mercury in wines showed that the interfering organic matrix did not influence the extraction efficiency. Column solid phase extraction scheme was developed for the determination and speciation of Hg in wines. The limit of detection (LOD) achieved for inorganic mercury determination in wine samples is 0.02 µg L(-1) (3σ), measured by CV AAS. The relative standard deviation varied in the range 6-11% at 0.05-2 µg L(-1) Hg levels. The sorbents showed high mechanical and chemical stability and extraction efficiency has not changed after more than 50 sorption/desorption cycles.

Solid-phase extraction in the determination of gold, palladium, and platinum.

A simple classification of various sorbents and solid-phase extraction procedures used for preconcentration of trace levels of Au, Pd, and Pt from different sample types is proposed in this review article. The large variety of available sorbents/procedures has been organized according to expected mechanisms of sorption process (complex formation; ion exchange; adsorption; ion-imprinted or molecularly imprinted polymers); according to the kind of monomeric units of the polymer matrix as well as on the basis of the kind of functional group responsible for main performance characteristics (selectivity, capacity) of the sorbent. Advantages of chemically modified sorbents, sulfur-containing sorbent extractants, and ion-imprinted polymers, together with rational pretreatment by means of microwave treatments, scaling down of enrichment, and quantification by means of flow and flow injection approaches are given. Preferred instrumental techniques for quantification of ppb levels of Au, Pd, and Pt in prepared concentrates/column eluates are multielement instrumental techniques: inductively coupled plasma optical emission spectrometry (ICP-OES), and inductively coupled plasma mass spectrometry (ICPMS). Excellent limits of detection at picogram levels of these analytes are provided by electrothermal atomic absorption spectrometry (ETAAS), generally in single-element mode and the neutron activation analysis (NAA), while X-ray fluorescence spectrometry and flame AAS are rarely applied because of lack of sensitivity at sub-ppm levels of Au, Pd, and Pt. Some problems of atomic spectrometric quantification techniques and their representative limits of detection are given. Recent applications to geological, industrial, pharmaceutical, biological, and other materials are tabulated. References have been selected mostly from the period 1995 to 2010.

Chitosan membranes as sorbents for trace elements determination in surface waters: chitosan membranes as sorbents for trace elements.

PURPOSE: Chitosan membranes (non-crosslinked, crosslinked, and modified with L-cysteine) were evaluated as sorbents prior to electrothermal atomic absorption spectrometry (ETAAS) determination of total dissolved metal content in surface water samples. METHODS: Different types of chitosan membranes were prepared in the presence or absence of L-cysteine. Chemical parameters for quantitative sorption/desorption of trace analytes have been optimized. RESULTS: The optimal pH for Cd(II), Cu(II), Ni(II), and Pb(II) sorption using L-cysteine-modified membrane is between 7 and 8.5 and coincides with typical surface water pH, allowing in situ preconcentration of analytes without any additional water sample pretreatments. Non-crosslinked chitosan membrane could be used for simultaneous sampling, transportation, and laboratory determination of Hg(II). Determination limits (calculated as 10σ) achieved for total dissolved metal contents are: Cd 0.001 µg/L, Cu 0.02 µg/L, Ni and Pb 0.05 µg/L, and relative standard deviations were 10-15% for all elements at concentration level of 0.05-2 µg/L. The determination limit achieved for Hg(II) was 0.012 µg/L and relative standard deviations at concentration levels 0.015-2 µg/L were within 9% and 15%. CONCLUSIONS: Non-crosslinked chitosan membrane was proposed as an efficient sorbent for Hg(II) preconcentration and determination in river and lake waters; L: -cysteine modified chitosan membrane was recommended for solid phase extraction of Cd(II), Cu(II), Ni(II), and Pb(II) from surface (lake, river, and sea) waters. The application of chitosan membranes as adsorbents for in situ field preconcentration of the analytes and their subsequent determination by CVAAS and ETAAS in water samples has been demonstrated.

Trace metal speciation and bioavailability in surface waters of the Black Sea coastal area evaluated by HF-PLM and DGT.

Trace metal speciation in seawater from the Bulgarian Black Sea coast was studied in situ by hollow fiber permeation liquid membrane (HF-PLM) and by diffusion gradients in thin-film gels (DGT). The concentrations of Cd, Cu, Ni, and Pb determined by HF-PLM were lower than those measured by DGT, in agreement with their analytical windows, e.g., free metal ions provided by the HF-PLM and dynamic (mobile and labile) species by the DGT. The obtained suite of data was further used to evaluate the bioavailability of these metals to the microorganisms, which was then compared with experimental results of metal uptake to green microalga Chlorella salina. Uptake fluxes of the Cd, Cu, Ni, and Pb to C. salina, were predicted from the measured HF-PLM concentrations and laboratory experimentation in artificial seawater, in agreement with theoretical considerations. The HF-PLM and DGT appear to be promising analytical techniques for speciation and bioavailability studies in complex environmental media and allow improved understanding of the role of different chemical species in metal bioavailability (and impact) in seawaters.

Ion-imprinted polymethacrylic microbeads as new sorbent for preconcentration and speciation of mercury.

Metal ion-imprinted polymer particles have been prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as cross-linking agent and 2,2'-azobisisobutyronitrile as initiator, in the presence of Hg(II)-1-(2-thiazolylazo)-2-naphthol complex. The separation and preconcentration characteristics of the Hg-ion-imprinted microbeads for inorganic mercury have been investigated by batch procedure. The optimal pH value for the quantitative sorption is 7. The adsorbed inorganic mercury is easily eluted by 2 mL 4M HNO(3). The adsorption capacity of the newly synthesized Hg ion-imprinted microbeads is 32.0 micromol g(-1) for dry copolymer. The selectivity of the copolymer toward inorganic mercury (Hg(II)) ion is confirmed through the comparison of the competitive adsorptions of Cd(II), Co(II), Cu(II), Ni(II), Pb(II), Zn(II)) and high values of the selectivity and distribution coefficients have been calculated. Experiments performed for selective determination of inorganic mercury in mineral and sea waters showed that the interfering matrix does not influence the extraction efficiency of Hg ion-imprinted microbeads. The detection limit for inorganic mercury is 0.006 microg L(-1) (3 sigma), determined by cold vapor atomic adsorption spectrometry. The relative standard deviation varied in the range 5-9 % at 0.02-1 microg L(-1) Hg levels. The new Hg-ion-imprinted microbeads have been tested and applied for the speciation of Hg in river and mineral waters: inorganic mercury has been determined selectively in nondigested sample, while total mercury e.g. sum of inorganic and methylmercury, has been determined in digested sample.

The biouptake and toxicity of arsenic species on the green microalga Chlorella salina in seawater.

The present study focuses on the biouptake, biotransformations, and toxicity of arsenic species on the marine green alga Chlorella salina in seawater from the Bulgarian Black Sea coast. Exposure to equal concentrations of As(III) or As(V) led to equivalent levels of toxicity and total intracellular arsenic content. Biouptake and toxicity of methylated arsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA), were approximately three orders of magnitude lower than those for inorganic arsenic species. Seawater enrichment with phosphate (up to 1.3 mg P L(-1)) resulted in a significant reduction of both intracellular As content and toxicity due to As(III) and As(V). In contrast, the toxicity and intracellular content of MMA and DMA were unaffected by the presence of phosphate. We measured the distribution and excretion of intracellular arsenic species, and demonstrated that the release of As(V) and/or As(III), together with the bio-reduction of As(V) and the subsequent methylation of As(III) may be a detoxification mechanism for these algae. The implications of the results with respect to arsenic species bioavailability and toxicity in marine water are further discussed.

Determination of lead in wine by hydride generation atomic fluorescence spectrometry in the presence of hexacyanoferrate(III).

A rapid, accurate, and precise method is described for the determination of Pb in wine using continuous-flow hydride generation atomic fluorescence spectrometry (CF-HGAFS). Sample pretreatment consists of ten-fold dilution of wine followed by direct plumbane generation in the presence of 0.1 mol L(-1) HCl and 1% m/v K(3)[Fe(CN)(6)] with 1% m/v NaBH(4) as reducing agent. An aqueous standard calibration curve is recommended for Pb quantification in wine sample. The method provides a limit of detection and a limit of quantification of 0.3 microg L(-1) and 1 microg L(-1), respectively. The relative standard deviation varies between 2-6% (within-run) and 4-11% (between-run) at 3-30 microg L(-1) Pb levels in wine. Good agreement has been demonstrated between results obtained by CF-HGAFS and direct electrothermal atomic absorption spectrometry in analyses of red and white wines within the concentration range of 9.2-25.8 microg L(-1) Pb.

Solid phase selective separation and preconcentration of Cu(II) by Cu(II)-imprinted polymethacrylic microbeads.

Ion-imprinted polymer (IIP) particles are prepared by copolymerization of methacrylic acid as monomer, trimethylolpropane trimethacrylate as crosslinking agent and 2,2'-azo-bis-isobutyronitrile as initiator in the presence of Cu(II), a Cu(II)-4-(2-pyridylazo)resorcinol (Cu(II)-PAR) complex, and PAR only. A batch procedure is used for the determination of the characteristics of the Cu(II) solid phase extraction from the IIP produced. The results obtained show that the Cu(II)-PAR IIP has the greatest adsorption capacity (37.4 micromol g(-1) of dry copolymer) among the IIPs investigated. The optimal pH value for the quantitative preconcentration is 7, and full desorption is achieved by 1 M HNO(3). The selectivity coefficients (S(Cu/Me)) for Me=Ni(II), Co(II) are 45.0 and 38.5, respectively. It is established that Cu(II)-PAR IIPs can be used repeatedly without a considerable adsorption capacity loss. The determination of Cu(II) ions in seawater shows that the interfering matrix does not influence the preconcentration and selectivity values of the Cu(II)-PAR IIPs. The detection and quantification limits are 0.001 micromol L(-1) (3sigma) and 0.003 micromol L(-1) (6sigma), respectively.

Determination of cadmium in wine by electrothermal atomic absorption spectrometry.

A method is described for direct electrothermal atomic absorption spectrometric (ETAAS) determination of cadmium in untreated samples of wine. Pyrolytic graphite tubes and graphite tubes with standard L'vov pyrolytic platforms were tested as atomizers. The detection limit achieved was 0.08 microg L(-1) Cd in wine. The relative standard deviation for the concentration range from 0.2 to 10 microg L(-1) Cd ranged from 1 to 7%. The accuracy of the method was confirmed by comparing the current results with those found for wet digested wine samples and by the analysis of spiked samples. By applying the proposed method it was found that the cadmium concentration in Macedonian wines ranges from 0.10 to 0.90 microg L(-1).

Properties of the copper(II)-histidine complex obtained after dialysis of human plasma with histidine.

The copper(II)-histidine complex obtained following dialysis of human plasma with histidine was investigated using various types of extraction systems and ion exchange resins. According to the results obtained, the Cu(II)-histidine complex formed under the dialysis conditions has one positive charge. Preconcentration of copper from the dialysis solution was achieved by its extraction as a dithiocarbamate complex and by sorption on cation-exchange resin or onto chelate sorbent.