Barbara Feist

Adsorption of divalent metal ions from aqueous solutions using graphene oxide

The adsorptive properties of graphene oxide (GO) towards divalent metal ions (copper, zinc, cadmium and lead) were investigated. GO prepared through the oxidation of graphite using potassium dichromate was characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FT-IR). The results of batch experiments and measurements by flame atomic absorption spectrometry (F-AAS) indicate that maximum adsorption can be achieved in broad pH ranges: 3-7 for Cu(II), 5-8 for Zn(II), 4-8 for Cd(II), 3-7 for Pb(II). The maximum adsorption capacities of Cu(II), Zn(II), Cd(II) and Pb(II) on GO at pH = 5 are 294, 345, 530, 1119 mg g(-1), respectively. The competitive adsorption experiments showed the affinity in the order of Pb(II) > Cu(II) ≫ Cd(II) > Zn(II). Adsorption isotherms and kinetic studies suggest that sorption of metal ions on GO nanosheets is monolayer coverage and adsorption is controlled by chemical adsorption involving the strong surface complexation of metal ions with the oxygen-containing groups on the surface of GO. Chemisorption was confirmed by XPS (binding energy and shape of O1s and C1s peaks) of GO with adsorbed metal ions. The adsorption experiments show that the dispersibility of GO in water changes remarkably after complexation of metal ions. After adsorption, the tendency to agglomerate and precipitate is observed. Excellent dispersibility of GO and strong tendency of GO-Me(II) to precipitate open the path to removal of heavy metals from water solution. Potential application of GO in analytical chemistry as a solid sorbent for preconcentration of trace elements and in heavy metal ion pollution cleanup results from its maximum adsorption capacities that are much higher than those of any of the currently reported sorbents.

Determination of rare earth elements by spectroscopic techniques: a review

An overview of publications focussed on the period since 2000 and outlining modern methods of sample preparation as well as advanced techniques for determination of rare earth elements (REE) in various matrices is presented in this paper. The review discusses the problems of REE determination in diverse samples i.e. from biological through environmental and geological to advanced materials. The preferable procedure of sample digestion and the most frequently applied methods of sample preparation for determination of trace elements are discussed in this paper. The case of direct analysis of samples for REE determination is also discussed. The review outlines determination of REE employing many techniques such as, inter alia, flame or graphite furnace atomic absorption spectrometry, atomic absorption with chemical vapor generation, X-ray fluorescence spectrometry, inductively coupled plasma optical emission spectrometry, inductively coupled plasma mass spectrometry and neutron activation analysis. This article summarizes and classifies materials in which rare earth elements are present, main places of their occurrence and the methods of their analysis.

Preconcentration of heavy metals on activated carbon and their determination in fruits by inductively coupled plasma optical emission spectrometry

A method of separation and preconcentration of cadmium, cobalt, copper, nickel, lead, and zinc at trace level using activated carbon is proposed. Activated carbon with the adsorbed trace metals was mineralised using a high-pressure microwave mineraliser. The heavy metals were determined after preconcentration by inductively coupled plasma optical emission spectrometry (ICP-OES). The influence of several parameters, such as pH, sorbent mass, shaking time was examined. Moreover, effects of inorganic matrix on recovery of the determined elements were studied. The experiment shows that foreign ions did not influence recovery of the determined elements. The detection limits (DL) of Cd, Co, Cu, Ni, Pb, and Zn were 0.17, 0.19, 1.60, 2.60, 0.92 and 1.50 μg L(-)(1), respectively. The recovery of the method for the determined elements was better than 95% with relative standard deviation from 1.3% to 3.7%. The preconcentration factor was 80. The proposed method was applied for determination of Cd, Co, Cu, Ni, Pb, and Zn in fruits materials. Accuracy of the proposed method was verified using certified reference material (NCS ZC85006 Tomato).

Suspended aminosilanized graphene oxide nanosheets for selective preconcentration of lead ions and ultrasensitive determination by electrothermal atomic absorption spectrometry.

The aminosilanized graphene oxide (GO-NH2) was prepared for selective adsorption of Pb(II) ions. Graphene oxide (GO) and GO-NH2 prepared through the amino-silanization of GO with 3-aminopropyltriethoxysilane were characterized by scanning electron microscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy. The batch experiments show that GO-NH2 is characterized by high selectivity toward Pb(II) ions. Adsorption isotherms suggest that sorption of Pb(II) on GO-NH2 nanosheets is monolayer coverage, and adsorption is controlled by a chemical process involving the surface complexation of Pb(II) ions with the nitrogen-containing groups on the surface of GO-NH2. Pb(II) ions can be quantitatively adsorbed at pH 6 with maximum adsorption capacity of 96 mg g(-1). The GO-NH2 was used for selective and sensitive determination of Pb(II) ions by electrothermal atomic absorption spectrometry (ET-AAS). The preconcentration of Pb(II) ions is based on dispersive micro solid-phase extraction in which the suspended GO-NH2 is rapidly injected into analyzed water sample. Such features of GO-NH2 nanosheets as wrinkled structure, softness, flexibility, and excellent dispersibility in water allow achieving very good contact with analyzed solution, and adsorption of Pb(II) ions is very fast. The experiment shows that after separation of the solid phase, the suspension of GO-NH2 with adsorbed Pb(II) ions can be directly injected into the graphite tube and analyzed by ET-AAS. The GO-NH2 is characterized by high selectivity toward Pb(II) ions and can be successfully used for analysis of various water samples with excellent enrichment factors of 100 and detection limits of 9.4 ng L(-1).

Spherical silica particles decorated with graphene oxide nanosheets as a new sorbent in inorganic trace analysis.

Graphene oxide (GO) is a novel material with excellent adsorptive properties. However, the very small particles of GO can cause serious problems is solid-phase extraction (SPE) such as the high pressure in SPE system and the adsorbent loss through pores of frit. These problems can be overcome by covalently binding GO nanosheets to a support. In this paper, GO was covalently bonded to spherical silica by coupling the amino groups of spherical aminosilica and the carboxyl groups of GO (GO@SiO2). The successful immobilization of GO nanosheets on the aminosilica was confirmed by scanning electron microscopy and X-ray photoelectron spectroscopy. The spherical particle covered by GO with crumpled silk wave-like carbon sheets are an ideal sorbent for SPE of metal ions. The wrinkled structure of the coating results in large surface area and a high extractive capacity. The adsorption bath experiment shows that Cu(II) and Pb(II) can be quantitatively adsorbed at pH 5.5 with maximum adsorption capacity of 6.0 and 13.6 mg g(-1), respectively. Such features of GO nanosheets as softness and flexibility allow achieving excellent contact with analyzed solution in flow-rate conditions. In consequence, the metal ions can be quantitatively preconcentrated from high volume of aqueous samples with excellent flow-rate. SPE column is very stable and several adsorption-elution cycles can be performed without any loss of adsorptive properties. The GO@SiO2 was used for analysis of various water samples by flame atomic absorption spectrometry with excellent enrichment factors (200-250) and detection limits (0.084 and 0.27 ng mL(-1) for Cu(II) and Pb(II), respectively).

Preconcentration of some metal ions with lanthanum-8-hydroxyquinoline co-precipitation system

A method of separation and preconcentration of cadmium, copper, nickel, lead and zinc at trace level using 8-hydroxyquinoline as a chelating agent and lanthanum(III) as a carrier element is proposed. The heavy metals were determined after preconcentration by inductively coupled plasma optical emission spectrometry (ICP-OES). The results were compared with those obtained using flame atomic absorption spectrometry (F-AAS). The influence of several parameters such as pH, amount of lanthanum(III) as a carrier element, amount of 8-hydroxyquinoline, duration of co-precipitation was examined. Moreover, effects of inorganic matrix on recovery of the determined elements were studied. The detection limits (DL) for ICP-OES were 0.31, 2.9, 1.4, 3.2 and 1.2 μg L(-1) for Cd, Cu, Ni, Pb and Zn, respectively, whereas for F-AAS DL were 0.63, 1.1, 3.2, 2.7 and 0.74 μg L(-1). The recovery of the method for the determined elements was better than 94% with relative standard deviation between 0.63% and 2.9%. The preconcentration factor was 60. The proposed method was successfully applied for determination of Cd, Cu, Ni, Pb, and Zn in plant materials. Accuracy of the proposed method was verified using certified reference material (NCS ZC85006 Tomato).

Liquid-phase microextraction as an attractive tool for multielement trace analysis in combination with X-ray fluorescence spectrometry: an example of simultaneous determination of Fe, Co, Zn, Ga, Se and Pb in water samples

In recent years, liquid-phase microextraction (LPME) has become one of the most valuable techniques for the preconcentration and separation of trace and ultratrace elements. LPME can be combined with an atomic technique which requires only a few microlitres of liquid to perform a measurement, e.g. electrothermal atomic absorption spectrometry. In this study, combining LPME with X-ray fluorescence spectrometry (XRF), a dried-spot technique is proposed. Since the X-ray beam can be focused on a small spot size and simultaneously LPME produces a very small drop of a volume ranging from 2 to 30 μL, the combination of these two techniques is a very promising tool for multielement trace and ultratrace analyses. The present research was performed using dispersive liquid–liquid microextraction (DLLME) with APDC as a chelating agent. Nevertheless, any LPME technique, e.g. single-drop microextraction (SDME), can be applied in combination with XRF. Because XRF measurement follows the microextraction, deposition and drying of the small drop, the influence of the diameter of the dried residue on the intensity of fluorescent radiation is discussed in detail. Pipetting and spray-on techniques are proposed for the deposition of the small drop onto the substrate (membrane filter or Mylar foil). Under the optimized conditions, the detection limits were 2.8, 1.6, 2.5, 1.7, 2.1 and 4.1 ng mL−1 for Fe, Co, Zn, Ga, Se and Pb, respectively, with a preconcentration factor of 250 for 5 mL of the water sample.

Selective dispersive micro solid-phase extraction using oxidized multiwalled carbon nanotubes modified with 1,10-phenanthroline for preconcentration of lead ions.

A dispersive micro solid phase extraction (DMSPE) method for the selective preconcentration of trace lead ions on oxidized multiwalled carbon nanotubes (ox-MWCNTs) with complexing reagent 1,10-phenanthroline is presented. Flame and electrothermal atomic absorption spectrometry (F-AAS, ET-AAS) were used for detection. The influence of several parameters such as pH, amount of sorbent and 1,10-phenanthroline, stirring time, concentration and volume of eluent, sample flow rate and sample volume was examined using batch procedures. Moreover, effects of inorganic matrix on recovery of the determined elements were studied. The experiment shows that foreign ions did not influence on recovery of the determined element. The method characterized by high selectivity toward Pb(II) ions. Lead ions can be quantitatively retained at pH 7 from sample volume up to 400mL and then eluent completely with 2mL of 0.5molL(-1)HNO3. The detection limits of Pb was 0.26μgL(-1) for F-AAS and 6.4ngL(-1) for ET-AAS. The recovery of the method for the determined lead was better than 97% with relative standard deviation lower than 3.0%. The preconcentration factor was 200 for F-AAS and 100 for ET-AAS. The maximum adsorption capacity of the adsorbent was found to be about 350mgg(-1). The method was applied for determination of Pb in fish samples with good results. Accuracy of the method was verified using certified reference material DOLT-3 and ERM-BB186.

Ultrasound-assisted solid-phase extraction using multiwalled carbon nanotubes for determination of cadmium by flame atomic absorption spectrometry

Ultrasound-assisted solid-phase extraction (SPE) with multiwalled carbon nanotubes (MWCNTs) as a solid sorbent and 1-(2-pyridylazo)-2-naphthol (PAN) as a chelating agent was developed for the determination of trace and ultratrace amounts of Cd(II) ions in aqueous samples. The solution containing Cd(II) complexed with PAN was passed through the syringe filter with a PVDF membrane loaded with 25 mg of MWCNTs. The elution process was performed with 2.0 mL of 2.0 mol L−1 HNO3 with assistance of sonication. In order to obtain the high recovery of the Cd(II) ions, the proposed procedure was optimized for various analytical parameters such as pH, amounts of PAN, sample volume, and elution conditions such as volume and concentration of eluent and influence of sonication and temperature. The investigation shows that sonication considerably improves the recovery, whereas temperature does not influence the elution process. Under optimized conditions Cd(II) ions can be determined with very good recovery (99 ± 3%), precision (RSD = 3.2%) and detection limit (0.3 ng mL−1) for an enrichment factor of 50. The effect of common coexisting ions was also investigated. Cd(II) can be determined in the presence of heavy metal ions and alkali metals. The proposed ultrasound-assisted SPE was applied for the determination of Cd(II) in water samples and biological samples (Lobster Hepatopancreas).

The use of Chromazurol S in the presence of a mixture of cationic and non-ionic surfactants for the spectrophotometric determination of iron in cereals

Simple and sensitive methods for the spectrophotometric determination of iron(III) in food, based on the formation of coloured complexes of Fe(III) with Chromazurol S (CAS) in the presence of tetradecyltrimethylammonium bromide (TTA) or octadecyltrimethylammonium chloride (ODTA) and Triton X-100 (TX100), have been developed. Optimum pH and the concentrations of CAS, TTA, ODTA, and TX100 ensuring maximum absorbance have been determined. For the Fe-CAS-TTA-TX100 system the molar absorptivity is 1.12 × 105 L/(mol cm) at 650 nm; for Fe-CAS-ODTA-TX100 it is 1.35 × 105 L/(mol cm) at 659.5 nm. Beer’s law was obeyed for iron concentration in the range 0.08–0.56 μg/mL for the complex Fe-CAS-TTA-TX100 and 0.08–0.64 μg/mL for Fe-CAS-ODTA-TX100. The influence of several interfering ions has been discussed. The stoichiometry of the complexes was established by applying Job’s method. The more sensitive method, based on the Fe-CAS-ODTA-TX100 system, has been applied to the determination of iron in cereals. To evaluate the accuracy of the elaborated method, the determined content of Fe was compared to the declared value as well as to the result obtained by the reference ICP-OES method.