Ryszard Dobrowolski

Application of laboratory prepared and commercially available biochars to adsorption of cadmium, copper and zinc ions from water.

The goal of the presented work was the evaluation and comparison of two biochars (produced from Sida hermaphrodita - BCSH/laboratory produced and from wheatstraw - BCS/commercial available) to adsorb heavy metal ions (Cd(II), Cu(II) and Zn(II)) from water. Kinetics of the sorption as well as sorption isotherms, the influence of solution pH and interfering ions were investigated. Different physico-chemical properties of biochars had the great influence on adsorption capacity. The greater adsorption efficiency was observed for BCSH than for BCS in the case of all investigated metals. The adsorption efficiency of BCSH was correlated with higher content of carbon and oxygen, what is equal with higher content of polar-groups on the BCSH surface e.g., -COOH. Furthermore, the molar ratio of O/C as well as polarity index (which was higher for BCSH) was also important parameters.

Determination of Ni and Cr in soils by slurry graphite furnace atomic absorption spectrometry

The analytical conditions for chromium and nickel determination in soils by slurry sampling graphite furnace atomic absorption spectrometry (GFAAS) are presented. Stability tests for slurries have been carried out. The ratio of the amount of the analyte found in the liquid phase to the total amount is investigated. The influence of the soil matrix on the background is described. Less sensitive resonance lines of chromium rather than an internal gas flow through the graphite furnace are recommended for some soil samples with high contents of chromium.

Slurry sampling hydride generation atomic absorption spectrometry for the determination of extractable/soluble As in sediment samples

Abstract A method combining the sampling of slurry pretreated by ultrasonic agitation and microwave assisted extraction with hydride generation atomic absorption spectrometry (HGAAS) for the determination of arsenic in sediment samples is proposed and evaluated. The pretreatment of slurried samples by ultrasonication enabled the extraction of (approximately) up to 85% of arsenic from the studied sediment samples. The further (slight) improvement of the efficiency of extraction was accomplished by the introduction of a short microwave-accelerated treatment. l -cysteine was used as an efficient pre-reduction reagent. The accuracy and precision of the slurry sampling HGAAS method were studied using the certified reference materials: Sediment GBW 30043 (NRCCRM, Peoples Republic of China), Sediment NIST 2704 (NIST, USA) and Marine Sediment BCSS-1 (NRCC, Canada). The relative standard deviation of the full (overall) analytical procedure was 8.5% and an absolute limit of detection of 2.75 ng was achieved. Factors which influence the reliability of this method are, for example, the choice of slurry liquid phase (extraction medium), sample homogeneity and, in particular, very effective mixing of slurries.

Determination of trace elements in plant materials by slurry sampling graphite furnace AAS — some analytical problems

SummaryThe analytical conditions of cadmium, lead, nickel and cobalt determination in plant material by slurry sampling graphite furnace atomic absorption spectrometry (GFAAS) are presented. The results of stability tests for slurries prepared in different ways are also shown. The ratio of the amount of analyte found in the liquid phase to the total amount of analyte in the slurries is investigated. The determination results are calculated from aqueous standard calibration graphs (cobalt and nickel) or by the standard addition method (cadmium and lead). Statistical evaluation of the results from the certified materials indicate that the slurry method is both accurate and comparable in precision to the conventional wet-ashing procedure.

Determination of gold in geological materials by carbon slurry sampling graphite furnace atomic absorption spectrometry

A simple and cost effective preconcentration method on modified activated carbons is described for the determination of traces of gold (Au) in geological samples by carbon slurry sampling graphite furnace atomic absorption spectrometry (GFAAS). The basic parameters affecting the adsorption capacity of Au(III) ions on modified activated carbons were studied in detail and the effect of activated carbons modification has been determined by studying the initial runs of adsorption isotherms. The influence of chlorides and nitrates on adsorption ability of Au(III) ions onto the modified activated carbons for diluted aqueous solution was also studied in detail in respect to the determination of gold in solid materials after digestion steps in the analytical procedure, which usually involves the application of aqua regia. SEM-EDX and XPS studies confirmed that the surface reduction of Au(III) ions to Au(0) is the main gold adsorption mechanism on the activated carbon. Determination of gold after its preconcentration on the modified activated carbon was validated by applying certified reference materials. The experimental results are in good agreement with the certified values. The proposed method has been successfully applied for the determination of Au in real samples using aqueous standards.

Comparison of action of mixed permanent chemical modifiers for cadmium and lead determination in sediments and soils by slurry sampling graphite furnace atomic absorption spectrometry

Slurry sampling atomic absorption spectrometry with electrothermal atomization was used to the determination of cadmium (Cd) and lead (Pb) in soils and sediments using permanent modifiers. Comparison of action of mixed permanent modifiers niobium (Nb)/iridium (Ir) and tungsten (W)/iridium (Ir) were studied in detail. The effect of amount of Ir, W and Nb on analytical signals of Cd and Pb was examined. The optimal amounts of modifiers for Cd and Pb determination were stated. Niobium carbide formation on graphite surface was studied for different pyrolysis temperatures. Finally for Cd determination in sediments and soils 200 microg of Nb mixed with 5 microg of Ir was used as permanent modifiers and 15 microg of Nb mixed with 200 microg of Ir for Pb determination. Suspensions were prepared in 5% HNO(3). The analytical procedure was optimized carefully basing on data from pyrolysis and atomization curves studies. Ammonium dihydrogen phosphate was used additionally as matrix modifier during Cd determination in samples in order to prevent interferences coming from matrix components. The analysis of CRMs confirmed the reliability of the proposed approach. The precision and accuracy of Cd and Pb determination by the described method for soils and sediments were acceptable.

Study of Chromium(VI) Adsorption from Aqueous Solution on to Activated Carbon

The adsorption of chromium(VI) from dilute aqueous solutions on to activated carbons at natural pH values was investigated. The activated carbons were modified to obtain materials with a well-defined surface containing inorganic impurities at ppb or ppm level. Measurements of the adsorption kinetics relative to the degree of granulation were undertaken. It was found that the reaction rate of the ions on the surface of the activated carbon rather than diffusion was the major process influencing the equilibrium. Surface reduction of CrVI to CrIII appeared to be the principal mechanism for the adsorption of chromium on the activated carbons studied. It was demonstrated experimentally that the presence of oxidizing agents dramatically changed the adsorption capacity of CrVI on the studied carbons. The influence of the ionic strength (controlled by the addition of NaCl) on the adsorption capacity was also studied. Variable and complex influences of the ionic strength on the adsorption capacity were observed.

Investigations on the adsorption properties and porosity of natural and thermally treated dolomite samples

Abstract Adsorption properties with respect to certain toxic substances as well as porosity investigations of raw and thermally modified dolomite are presented. After the partial decomposition of dolomite at 800°C a new so-called ‘dolomitic’ adsorbent of the calcium carbonate skeleton and pumice structure was obtained. Its physicochemical properties are significantly different from those of the raw material, e.g. the specific surface area increases 37 times and the adsorption capacity for SO2 increases approximately 15 times, which makes the new adsorbent useful in the protection of the environment.

Preparation and evaluation of Fe-loaded activated carbon for enrichment of selenium for analytical and environmental purposes

The adsorbent, based on the thermal modification of activated carbon impregnated by iron(III) nitrate(V), has been prepared and applied for selenium enrichment from aqueous solution. Various ratios of the impregnating agent to carbon mass were carefully examined with respect to selenium adsorption capacity and selectivity. The basic Se(VI) ions adsorption parameters affecting the adsorption ability onto the prepared activated carbons were studied. The carbon impregnated by 10% Fe(NO(3))(2) and thermally treated at 200 °C possessed the highest adsorption capacity and selectivity towards selenium ions. The physico-chemical characterization of the prepared adsorbents before and after selenium uptake were carried out using scanning electron microscopy (SEM) equipped with an energy dispersive X-ray detector (EDX) and X-ray photoelectron spectroscopy (XPS). The studies confirmed the surface complexation reactions of iron species and selenium on the Fe-loaded activated carbon. Due to its high adsorption capacity enrichment of selenium on the studied adsorbent has been successfully applied for its determination in the complementary feeds, using the carbon slurry sampling graphite furnace atomic absorption spectrometry technique (GFAAS) and standard calibration method.

Determination of vanadium in soils and sediments by the slurry sampling graphite furnace atomic absorption spectrometry using permanent modifiers

A new analytical procedure for vanadium (V) determination in soils and sediments by the slurry sampling graphite furnace atomic absorption spectrometry (slurry sampling GFAAS) using the mixed permanent modifiers is described. Moreover, the comparison of action of the modifiers based on the iridium (Ir) and carbide-forming elements: tungsten (W) and niobium (Nb) deposited on the graphite tubes is studied, especially in terms of their analytical utility and determination sensitivity. The mechanism of their action was investigated using an X-ray diffraction technique (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive X-ray detector (EDX). Finally, the mixture of 0.3 μg of Ir and 0.04 μg of Nb was used for the graphite tube permanent modification. The analytical procedure was optimized on the basis of the data from pyrolysis and atomization temperature curves studies. The results obtained for the four certified reference materials (marine sediments: PACS-1 and MESS-1, lake sediment: SL-1, soil: San Joaquin Soil SRM 2709), using the slurry sampling GFAAS and the standard calibration method, were in good agreement with the certified values. The detection and quantification limits and characteristic mass calculated for the proposed procedure were 0.04 µg/g, 0.16 µg/g and 11.9 pg, respectively. The precision (RSD% less than 8%) and the accuracy of vanadium determination in the soil and sediment samples were acceptable.