Wiesław Żyrnicki

Metal Concentrations in Deciduous Tree Leaves from Urban Areas in Poland

Accumulation of metals in deciduous tree foliage fromurban areas in western-south Poland was monitored duringthe vegetation season of 2000 year. Concentrations of Al,Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sr, Ti and Znwere measured in birch, willow, linden and maple leavesusing the ICP-AES method. Seasonal variations of metalconcentrations and their relations with sampling sitewere investigated. The most dynamic accumulation of Al,Cd, Cr, Ni and Pb was observed for examined species. Thehighest differences in element concentrations forinvestigated sites were found for Ba, Cd, Mn and Ni.Interelement correlations were investigated. In allfoliar samples synergistic relationships between Al–Crand Ca-Sr were found. Statistically significant negativecorrelations were observed only for Cd and Ti in birch leaves.

Determination of toxic and other trace elements in calcium-rich materials using cloud point extraction and inductively coupled plasma emission spectrometry.

A cloud point extraction (CPE) procedure for the simultaneous separation and preconcentration of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn from materials rich in calcium prior to trace element analysis by inductively coupled plasma optical emission spectrometry (ICP OES) was developed. The method is based on the formation of hydrophobic complexes of the metal ions with PAN or 5-Br-PADAP, followed by their extraction into a surfactant-rich phase using Triton X-114 as the surfactant. The main variables affecting the extraction process, such as pH, concentration of surfactant and chelating agent were optimised. Under the optimum conditions the obtained limits of detection for Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn were of 4.0, 4.3, 2.1, 1.9, 0.3, 5.6, 40 and 2.0 microg L(-1), respectively. The RSD values for 10 replicates were from 1.5% for Mn to 11% for Pb. The accuracy of the procedure was verified by analysis of certified reference material NIST 1400 (Bone Ash) and by recovery tests. The optimised method was successfully applied for the simultaneous determination of trace elements in dolomites used by different fertiliser factories.

Atmospheric Pressure Glow Discharges Generated in Contact with Flowing Liquid Cathode: Production of Active Species and Application in Wastewater Purification Processes

Miniaturized atmospheric pressure glow discharges (APGDs) were generated in contact with small sized flowing liquid cathode systems. As anodes a solid pin electrode or a miniature flow Ar microjet were applied. Both discharge systems were operated in the open to air atmosphere. Hydrogen peroxide (H2O2) as well as ammonium (NH4+), nitrate (NO3−), and nitrite (NO2−) ions were quantified in solutions treated by studied discharge systems. Additionally, an increase in the acidification of these solutions was noted in each case. Emission spectra of the near cathode zone of both systems were measured in order to elucidate mechanisms that lead to the formation of active species in gas and liquid phases of the discharge. Additionally, the concentration of active species in the liquid phase (H2O2, NH4+, NO3− and NO2−) was monitored as a function of the solution uptake rate and the flow rate of Ar. The suitability of investigated discharge systems in the water treatment was tested on artificial wastewaters containing an organic dye (methyl red), hardly removable by classical methods non-ionic surfactants (light Triton x-45 and heavy Triton x-405) and very toxic Cr(VI) ions. Preliminary results presented here indicate that both investigated flow-through APGD systems may successfully be applied for the efficient and fast on-line continuous flow chemical degradation of toxic and hazardous organic and inorganic species in wastewater solutions.

An analytical performance of atmospheric pressure glow discharge generated in contact with flowing small size liquid cathode

A dc atmospheric pressure glow discharge (APGD) operated in open air atmosphere was applied as a miniaturized excitation source in analytical optical emission spectrometry. The discharge was generated in contact with a small size liquid cathode of a novel design and stably operated at a low current (20 mA) and solution uptake rate (0.6 mL min−1). The volume of the discharge was estimated to be ∼6 mm3, while the power density was ∼5 kW cm−3. For the selected elements, i.e., Ca, Cd, Cu, K, Li, Mg, Mn, Na, Rb and Zn, the detection limits, the dynamic linearity ranges and the precisions were determined to ascertain the analytical performance of this miniaturized excitation source. The concentrations of some elements (Ca, K, Mg, Mn, Na and Zn) were determined in the samples of tea and its infusions and mineral water. These results were compared to those obtained by flame atomic absorption spectrometry (FAAS) and flame atomic emission spectrometry (FAES) and a good agreement between the results was established. Additionally, the effect of the easily ionizable elements (EIEs) on the relative intensities and the signal to background ratios (SBRs) of the measured emission lines as well as the Mg II/Mg I ratio and electron number density were investigated.

Determination of metal concentrations in animal hair by the ICP method

Concentrations of minor and trace elements (Mg, Ca, Fe, Ba, Cu, Zn, Cd, Ni, Al, Mn, Cr, Ti, and V) in the hair of three races of dogs (fox terrier, schnauzer, and mini schnauzer) were analyzed by the inductively coupled plasma-atomic emission spectrometry method. The influence of five washing solutions, deionized water, acetone, methanol, EDTA, and Triton X-100, on the concentrations measured in hair was investigated. Triton X-100 was found to be suitable to use for the removal of exogenous elements in multielemental hair analysis. Additionally, the results indicated that the concentration of the elements measured in the dogs’ hair were similar to those reported for human hair. The relation between the element content in the dog hair and its color were similar to those found for human hair.

Influence of chemical vapor generation conditions on spectroscopic and analytical characteristics of a hyphenated CVG-ICP system

Excitation conditions of inductively coupled plasma hyphenated with chemical vapor generation with the use of borane reducing agents (NaBH4, C(CH3)3NH2–BH3 and (CH3)2NH–BH3) and acids (HCl and CH3COOH) were investigated. The electron number density, the Mg II/Mg I intensity ratio as well as the Ar, B, Bi, Sb and H excitation temperatures were measured at various concentrations of the reductants and acids. Some analytical figures of merit were also determined. The plasma parameters were affected if NaBH4 was applied. Influence of other borane reductants was not so significant. Hydrogen produced due to chemical vapor generation was responsible for changes in the ICP characteristics, while a role of other products transported simultaneously to plasma was negligible. The Ar, B, Bi and Sb excitation temperatures were independent or slightly dependent on chemical vapor generation conditions. The electron number density increased with NaBH4 concentration, from 0.7 × 1015 cm−3 for “dry” argon plasma to 1.5 × 1015 cm−3 while the Mg II/Mg I intensity ratio varied from 5 to 11. At low concentrations of the reductants and acids, the plasma was not in robust conditions. If the NaBH4 was the reductant, the H temperature varied more significantly, from 3100 to 2100 K.

Spectroscopic evaluation of a low power atmospheric pressure mixed argon–helium microwave induced plasma combined with the chemical generation of volatile species for the optical emission spectrometric determination of arsenic, antimony and mercury

Spectroscopic and analytical characteristics of a low power atmospheric pressure mixed argon–helium microwave induced plasma were examined for its usefulness in the determination of As, Sb and Hg by optical emission spectrometry and using a continuous flow chemical vapor generation of these elements (AsH3, SbH3, Hg0) in the reaction with sodium tetrahydroborate. The effect of the concentration of helium in the plasma gas on excitation, vibrational and rotational temperatures and the electron number density in the discharge obtained from argon and mixtures of argon with helium was studied to evaluate changes in excitation conditions and their impact on the analytical performance of the plasma. It was found that the presence of 10–20% v/v of helium in the carrier/plasma gas is very convenient for the excitation of As, Sb and Hg introduced to the plasma via the volatile species generation reaction. In reference to limits of detection of 4.1 (As), 1.8 (Sb) and 1.4 (Hg) ng ml−1, such a plasma has a considerably better analytical performance as compared to the plasma generated only in an argon atmosphere.

Major and Trace Elements in Spruce Needles from Urban Areas: Some Aspects of Analysis in Environmental Studies

Main and trace elements in samples of spruce needles from urban areas in Poland and Norway were analysed using the ICP-AES method. Concentrations of Al, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, P, Sr, Ti, V and Zn were measured in needles from conifer trees growing in different locations. Two different procedures of laboratory sample preparation were compared and discussed. Different washing procedures were examined and compared. For quality control of analytical measurements, Standard Reference Material BCR CRM 101 (spruce needles from Europe) was used. Synergistic and antagonistic relationships between elements in spruce needles were investigated. Applicability of spruce needles in biomonitoring of environmental metal pollution was discussed.

Multielemental Analysis of Yew, Pine and Spruce Needles by ICP-AES

Abstract Concentrations of 22 trace and nutritional elements in yew, pine and spruce needles collected from urban and industrial areas were determined by inductively coupled plasma atomic emission spectrometry. Dependence of concentrations of trace elements in conifers species on sampling site was investigated. Various procedures of sample digestion (different acids, conventional hot plate and microwave digestion methods, dry ashing) were examined and discussed.

Inorganic micronutrients in food products of plant origin used for breakfast in Poland

The mineral compositions and nutritional properties of 22 breakfast cereals available at the local market in the Wroclaw agglomeration were studied. Products of popular brands widely distributed to the international market were selected for the investigation. The total concentrations of micronutrients were measured using the ICP-OES method in samples mineralised in a microwave system. The macroelement contents ranged from 0.02 to 4.60, 0.07 to 0.82 and 0.22 to 1.81 mg g−1 for Ca, Mg, and P, respectively. The contents of the Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Ti, V and Zn were found to be 0.08 to 1.73, 0.07 to 0.38, 0.12 to 0.24, 0.10 to 3.67, 1.67 to 167, 0.34 to 15.8, 0.19 to 2.30, 1.10 to 2.02, 0.03 to 4.01, 0.03 to 0.38, 0.05 to 7.28 and 0.21 to 14.4 µg g−1, respectively. The mineral contents in breakfast cereals based on wheat, rice, oats and barley, multigrain cereals and ready-to-eat breakfast cereals with taste additives were higher than in corn-based breakfast cereals, with the Ca, Mg and P concentrations being 3/4, 1/2 and 1 times higher, respectively, on average. The contents of the essential minerals were compared to the human nutritional requirements and daily permissible doses. The results are discussed in terms of the utility of breakfast cereals as a source of indispensable minerals for proper human function.