Jerzy Golimowski

Nanoparticles: their potential toxicity, waste and environmental management.

This literature review discusses specific issues related to handling of waste containing nanomaterials. The aims are (1) to highlight problems related to uncontrolled release of nanoparticles to the environment through waste disposal, and (2) to introduce the topics of nanowaste and nanotoxicology to the waste management community. Many nanoparticles used by industry contain heavy metals, thus toxicity and bioaccumulation of heavy metals contained in nanoparticles may become important environmental issues. Although bioavailability of heavy metals contained in nanoparticles can be lower than those present in soluble form, the toxicity resulting from their intrinsic nature (e.g. their size, shape or density) may be significant. An approach to the treatment of nanowaste requires understanding of all its properties--not only chemical, but also physical and biological. Progress in nanowaste management also requires studies of the environmental impact of the new materials. The authors believe Amaras law is applicable to the impact of nanotechnologies, and society might overestimate the short-term effects of these technologies, while underestimating the long-term effects. It is necessary to have basic information from companies about the level and nature of nanomaterials produced or emitted and about the expectation of the life cycle time of nanoproducts as a basis to estimate the level of nanowaste in the future. Without knowing how companies plan to use and store recycled and nonrecycled nanomaterials, development of regulations is difficult. Tagging of nanoproducts is proposed as a means to facilitate separation and recovery of nanomaterials.

UV-photooxidation as pretreatment step in inorganic analysis of environmental samples

Many laboratories deal with the determination of heavy metals, carbon, nitrogen and phosphorus. The first step in chemical analysis is a proper preparation of the investigated samples. The presence of organic substances can cause problems in many analytical methods. This paper describes the application of UV irradiation as a method of destruction of organic matter in the investigated samples.

Trace determination of chromium in various water types by adsorption differential pulse voltammetry

ZusammenfassungEine neue voltammetrische Methode zur Spurenbestimmung von Chrom [als Summe von Cr(III) und Cr(VI)] in natürlichen Gewässern wurde entwickelt. Die Methode beruht auf einer Anreicherung des Cr(III)-DTPA-Komplexes durch Adsorption an der hängenden Queck-silbertropfenelektrode beim Potential −1.0 V. Der adsorbierte Komplex wird anschließend im differentiellen Pulsmodus reduziert und die Peakhöhe beim Peakpotential −1.22 V gemessen. Die katalytische Wirkung von Nitrat- und Bromationen auf die Cr(III)-DTPA-Reduktion wurde mit der cyclischen Voltammetrie geklärt. Die Adsorption der Cr-Komplexe wurde zusätzlich mit der a.c.-Voltammetrie (kapazitive Komponente) untersucht und der Potentialbereich der Adsorption ermittelt. Aufgrund der Untersuchungen wurden die optimalen Bedingungen zur Chrombestimmung im Konzentrationsbereich 20–2000 ng/l festgelegt. Die Bestimmungsgrenze liegt bei 20 ng/l und die relative Standardabweichung beträgt 5% für Konzentrationen ⩾200 ng/l. Die weite Anwendbarkeit der Methode für die zuverlässige und hochempfindliche Analyse von Chromspuren bis zu den natürlichen Ultraspurengehalten in verschiedenen Typen natürlicher Wässer wird an Beispielen der Analyse des gelösten Gesamtgehaltes von Chrom in Flußwasser, Seewasser, Meerwasser und Regenwasser aufgezeigt.SummaryA new sensitive voltammetric method is presented for the determination of trace amounts of total chromium [Cr(III) and Cr(VI)] in natural waters. The method is based on the preconcentration of the Cr(III)-DTPA complex by adsorption at the HMDE at the potential of −1.0 V. The adsorbed complex is then reduced producing a response with a peak potential of −1.22 V and the peak height of the Cr(III) reduction is measured. The catalytic action of nitrate and bromate ions on the Cr(III)-DTPA reduction has been elucidated using cyclic voltammetry. The adsorption of chromium complexes at the HMDE was investigated using out-of-phase a. c. voltammetry and the potential range of adsorption was determined. Based on these investigations optimal conditions for the determination of the total chromium concentration in the range 20–2,000 ng/l have been established. The determination limit is 20 ng/l and the RSD is 5% for chromium concentrations ⩾200 ng/l.The usefulness and wide scope of this new voltammetric method for reliable and highly sensitive chromium analysis down to the natural ultra trace levels existing in various types of natural waters is demonstrated by determinations of the total dissolved chromium content in river, lake, sea and rain water.

Granulometry and the content of toxic and potentially toxic elements in vacuum-cleaner collected, indoor dusts of the city of Warsaw

Twenty-seven sites, together with 23 household dust sample sites, representing the home environment, and four public room dust sample sites, representing working environment (mainly offices) have been described in this paper. The latter were examined to obtain an approximate reference to the home environment data. All the samples were collected between May and July 1997 by a vacuum-cleaner method, in the city of Warsaw, Poland. The granulometry of the dusts was determined by their separation into seven fractions in the range 8-500 microm. The concentrations of Cr, Ni, Cu, Zn, Pb, Br and Fe in the samples were investigated in fractions 8-32, 32-63 and 63-125 microm by the EDXRF technique. The results showed higher concentrations of these elements in finer fractions (8-32 microm). The Pb content in the household dusts was found to be unexpectedly low, ranging from 120 microg g(-1) for the 63-125 microm fraction, up to 210 microg g(-1) for the 8-32 microm fraction. Car exhausts could not be determined clearly as the main source of Pb in the indoor household dusts due to the lack of a Pb-Br intercorrelation. In these dusts, only Cr and Zn showed a remarkably high content of 90-100 and 1020-1070 (microg g(-1)), respectively. In the household dusts, strong intercorrelations were present in the three analysed fractions for the metal pairs: Pb-Zn, Pb-Cu, Fe-Cr, and Cu-Cr (weaker). The working environment rooms showed a higher degree of dustiness by 300%, as compared to the dwellings. The dusts collected in the working environment rooms showed slightly higher concentrations of Ni and by 50-100% higher concentrations of: Cu, Zn, Pb, Br than the analysed household dusts.

Speciation analysis of arsenic in terrestrial plants from arsenic contaminated area

Arsenic speciation analysis was carried out in plants collected from arsenic contaminated area. Two plant species were chosen for the investigation: Reed Grass (Calamagrostis arundinacea) and Lady Fern (Athyrium filix-femina). To characterize arsenic species several different extraction procedures were applied including enzymatic extraction and extraction using surfactant solution (SDS). Two-step sequential extraction (water+SDS) that assures the highest extraction efficiency was applied to extract arsenic species from plant material. HPLC with anion-exchange column was used to separate extracted arsenic compounds and ICP-MS was applied for quantitative arsenic determination after species separation.

Determination of thallium forms in plant extracts by anion exchange chromatography with inductively coupled plasma mass spectrometry detection (IC-ICP-MS)

The speciation of thallium was investigated in the Indian mustard plant (Sinapis alba L.), hydroponically cultivated and in moss (Entondon schreberi) used as a bioindicator. The separation of thallium species was done using anion exchange chromatography coupled with on-line ICP-MS detection with 100 mmol L−1 ammonium acetate containing 5 mmol L−1 DTPA as a mobile phase. The study indicated that Tl(I) is the dominating form in plant extracts; Tl(III) was not detected. Three species of Tl were found in the leaves, two of them remained unidentified. Additionally, the fractionation study of Tl in organs of the Indian mustard plant using water, ammonium acetate containing DTPA and sodium dodecyl sulfate solutions was performed. The highest leaching efficiency was reached using an ammonium acetate/DTPA solution. Next, the efficiency of Tl transport from roots to stems and leaves and the accumulation factors were estimated. 80% of uptaken Tl was found in above-ground plant organs.

Miniaturized back-side contact transducer for potentiometric sensors

A novel type of a miniature transducer for potentiometric sensors was designed and tested. The transducer is made from an ordinary printed circuit board using a typical technology. As a result, a back-side contact structure was obtained, which can be mounted in flow systems. The advantage of the fabrication process is its cheapness and flexibility in designing modified structures. The measurement properties of the transducer were tested as a chloride sensor. Then the structure was covered with polyHEMA and a potassium-selective membrane and tested as a potassium sensor. The performance and the long-term stability of the sensors with plasticized PVC and Siloprene based potassium-selective membranes were compared.

Toxic trace metals in food

ZusammenfassungEin neues durch besonders hohe Empfindlichkeit und Zuverlässigkeit gekennzeichnetes Analyseverfahren zur präzisen Bestimmung der toxischen Spurenmetalle Cadmium, Blei und Kupfer wird dargelegt. Es besteht in einer einfachen und bequemen Probenvorbehandlung durch UV-Bestrahlung (1,5 Std, 500-W-Hg-Lampe) zur Freisetzung des durch organische Substanzen gebundenen Spurenmetallanteiles und nachfolgender Bestimmung mit der differentiellen anodischen Pulsinversvoltammetrie (DPASV). Hierbei wird für die Simultanbestimmung von Cadmium und Blei die in situ auf einen Glaskohleträger gebildete Quecksilberfilmelektrode (MFE) und für Kupfer die Goldelektrode eingesetzt.Die beschriebene Verfahrensweise führt zu einer weitgehenden Ausschaltung von kontaminationsfelern. Nur spezielle Weine mit einem Zuckergehalt über 10% erfordern eine Substitution der UV-Bestrahlung durch einen ebenfalls beschriebenen Naßaufschluß. Das Verfahren ist leicht auf die Bestimmung weiterer Spurenmetalle, z. B. Quecksilber und Zink, ausdehnbar.SummaryA new highly sensitive and particularly reliable analytical procedure for the precise determination of the most relevant toxic trace metals cadmium, lead and copper in wine is presented. It consists of a simple and convenient sample pretreatment by UV irradiation (1,5 h, 500-W-H g-lamp) to release the toxic trace metals bound by organic substances and subsequent voltammetry (DPASV) of cadmium and lead simultaneously at a mercury film electrode (MFE) formed in situ on a vitreous carbon carrier and of copper on a gold electrode. Particular emphasis has been placed on the efficient exclusion of interference due to contamination. Only special wines, with more than 10% of sugar, require substitution of UV irradiation by a wet digestion also described. The procedure may be easily expanded to include the determination of mercury and zinc.

Determination of cobalt in blood using cathodic stripping voltammetry

A method was developed to determine low levels of cobalt in whole blood, serum and plasma. Samples of blood (0.2 ml) were mineralized at 160 degrees C in the presence of concentrated nitric acid. Residual organic matter was destroyed by digestion using ultraviolet irradiation after dilution with water. The cobalt concentration was determined by catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of cobalt complexed with diphenylglyoxime (DPG). The optimized analytical conditions for the CSV analysis included a DPG concentration of 0.5 mumol l-1, 0.05 mol l-1 ammonium chloride buffer (pH 9.3), 0.15 mol l-1 nitrite, a deposition potential of -0.75 V, an adsorption time of 30-120 s and a negative potential scan using the differential-pulse modulation. The limit of detection was 40 pg of cobalt in 0.2 ml of blood, which was limited by the blank level of cobalt in the reagents after purification.

Voltammetric methods for the determination of heavy metals in domestic waste and compost produced from it

Methods of sampling an preparation of waste and compost samples for analysis are described. A voltammetric method has been used for the determination of the contents of toxic heavy metals (one of the most important criterion for compost quality evaluation) in domestic waste and in compost produced from it. A novel method was proposed for the UV mineralisation of water extracts obtained during leaching of waste and compost samples. Copper, lead, zinc and cadmium were determined in wet-digested samples of domestic waste, compost and its extracts by anodic stripping voltammetry. Nickel and cobalt were determined by adsorption voltammetry. The determination of five metals in one sample over a wide range of concentrations and the low cost of the apparatus used are the main advantages of the analytical method described. This has been shown by the determination of the metals in fractions of domestic waste, in compost produced of that waste and in compost mixed with sewage sludge. Special attention has been paid to investigations of the mobilisation of metals from waste and compost during the leaching test.