A new method for highly efficient separation and determination of arsenic species in natural water using silica modified with polyamines.

A simple and highly efficient method for the determination of highly toxic arsenic species using non-covalently aminated silica is proposed. The polyamines including poly(hexamethyleneguanidine), poly(4,9-dioxadodecane-1,12-guanidine), hexadimethrine, and poly(diallyldimethylammonium) were tested as silica modifiers. The prepared adsorbents allow effective preconcentration of anionic species of arsenic from aqueous solutions. It was found that As(V) can be quantitatively extracted from solutions at pH 4.5-7.0 by the anion exchange mechanism in less than 5 min, while neutral at this pH As(III) was not adsorbed at these conditions. A reaction with 2,3-dimercapto-1-propanesulphonic acid, which resulted in the formation of the negatively charged complex of As(III) with adsorbents was used for its quantitative extraction from solutions with a pH of 3.5-6.5. A system of two cartridges filled with poly(diallyldimethylammonium) modified silica and the on-line reaction of As(III) with 2,3-dimercapto-1-propanesulphonic acid proceeding between the cartridges was used for separate preconcentration and determination of As(V) and As(III) at pH 5. The proposed method was used for four-year monitoring of natural water pollution by arsenic in the area of residence of the indigenous peoples of Tyva Republic (Russia).

Effective separation of chromium species in technological solutions using amino-immobilized silica prior to their determination.

Amino-immobilized (poly(4,9-dioxadodecane-1,12-guanidine, polydiallyldimethylammonium, hexadimethrin bromide, polyhexamethylene guanidine) silicas were proposed for chromium speciation for the first time. Adsorbents surface was characterized by TGA-DSC, FT-IR, CHN, XRD and SEM analysis. Polyamines were strongly fixed on the silica surface and were not washed off with solutions of 3М HNO3 and 20 g L-1 NaCl. Аmino-immobilized silica quantitatively removed (R ≥ 99%) Cr(VI) from solutions at pH 4-7. Cr(III) was not recovered in this pH range, which makes it possible to separate Cr(VI) from Cr(III). The separation factor (КCr(VI)/Cr(III)) was ≥ 1∙104. Silica-based adsorbents layer-by-layer immobilized with polyamines and 2-(1,8-dihydroxy-3,6-disulfo-2-naphthylazo)benzenearsonic acid were proposed for quantitative removal of Cr(III) from aqueous solutions with pH 4-6 at 90 °C. A system of sequentially connected columns filled with selective adsorbents was used to separate the chromium species in stream at рН= 5 and a flow rate of 1 mL min-1. Chromium was determined after its elution with 5 mL of 2 M HNO3 at a flow rate of 1 mL min-1 using ICP-OES or ICP-MS. The pre-concentration factors for Cr(VI) and Cr(III) was 60. A two-column system was used for chromium speciation in technological solutions. The efficiency of chromium speciation was confirmed by state standard procedure.

Biosilica layer-by-layer modified with polyamines and carboxyarsenazo for REE preconcentration prior to ICP-MS determination in lignites and volcanic fumarole sediment.

Biosilica-based adsorbents prepared from rice husk, sequentially modified with polymeric polyamines and carboxyarsenazo were proposed for the preconcentration of 13 lanthanides, La, Sc, and Y. It is shown that the proposed adsorbent quantitatively extracted rare earth elements (REEs) from solutions with pH 3.5-6.5. Carrying out adsorption at pH 3.5-4.5 allows the quantitative separation of rare earth elements from accompanying ions of non-ferrous, alkaline and alkaline-earth metals. A procedure for solid-phase extraction followed by mass spectrometric determination (SPE-ICP-MS) of REEs has been developed, which includes passing of 100 mL of the analyzed solution (pH 4) through a column with the adsorbent at a flow rate of 1 mL min-1, elution of REEs with 5 mL 1 M HNO3 (a preconcentration factor of 20) and subsequent determination of elements in the eluate by inductively coupled plasma mass spectrometry (ICP-MS). The accuracy of the results was confirmed by the recovery test of spiked samples and by analysis of a Certified Reference Material. The limit of detection was 0.04-10.9 ng L-1. The procedure was used for determination of REEs in lignites from Krasnoyarsk Krai (Russia) and fumarole sediment from Kudryavy volcano of the Greater Kuril Chain (Sakhalin Oblast, Russia).

Determination of Metals in Natural Waters by Inductively Coupled Plasma Optical Emission Spectroscopy after Preconcentration on Silica Sequentially Coated with Layers of Polyhexamethylene Guanidinium and Sulphonated Nitrosonaphthols.

A series of complexing adsorbents is prepared by coating silica particles with linear polyhexamethylene guanidinium (PHMG) chloride followed by saturation with a number of sulphonated nitrosonaphthols reagents electrostatically retained by positively charged polymer layer. PHMG coated silica is hydrolytically stable even during treatment with 6 M HCl heated up to 50 °C. The adsorption of 1-nitroso-2-naphthol-3,6-disulfonic acid (nitroso-R-salt), 2-nitroso-1-naphthol-4-sulfonic acid (nitroso-N-salt), and 2-nitroso-1-naphthol-3,6-disulfonic acid (nitroso-K-salt) on PHMG modified silica was studied. The effective immobilisation of sulphonated nitrosonaphthols was achieved in the range of pH of 3 - 8, while the adsorption of the monosulphonated reagent (nitroso-N-salt) is twice as high as the disulphonated analogues (nitroso-R-salt and nitroso-K-salt). The adsorption of Cu(II), Fe(III), Co(II), Ni(II), Al(III), Zn(II), Pb(II), Mn(II), and Cr(III) on prepared complexing adsorbents under static and dynamic conditions was studied as a function of time, pH, sample volume, and presence of interfering ions. Metal ions can be desorbed by using 1 M HCl or 1 M HNO3. The preconcentration factors of metals under optimized conditions are varied from 20 to 80. The developed method was used for the preconcentration of trace metals from natural waters followed by ICP-OES determination. The sub-ppb limits of detection of metals are achieved.