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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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