Miloslav Pouzar

Determination of metals in lubricating oils by X-ray fluorescence spectrometry

The determination of common wear metals, namely iron, chromium, copper, zinc and lead, in a wide range of lubricating oil samples was investigated for the use of a low-cost, wavelength-dispersive X-ray fluorescence spectrometer. The procedure provided results in satisfactory agreement with inductively coupled plasma spectrometry used as reference method after microwave digestion of the samples in concentrated nitric acid. Statistical tests following extensive regression analyses of the data indicated that interelement effects were not statistically significant and that a simple linear regression was adequate for the calibration of individual metals.

LIBS analysis of crop plants

A fast and cheap method for the analysis of macronutrients (K, P, Mg and Ca) in leaves of crop plants (wheat, poppy, barley and rape) using double pulse laser induced breakdown spectrometry (LIBS) is suggested. A commercially available LIBS spectrometer was calibrated with the aid of authentic plant samples previously analysed by AAS and ICP-OES after microwave digestion. The concentration ranges of K, P, Mg and Ca in the calibration standards were 30–66; 2.8–6.6; 1.0–5.6 and 6–24 g kg−1, respectively. Cryogenic grinding and powder pressing to pellets were used as sample preparation steps. Obtained LIBS/ICP-OES recovery values for authentic crop plant samples were 93–109% (K); 93–114% (P); 89–109% (Mg) and 94–110% (Ca). Six certified reference materials (CRMs) of plant tissues were used for the LIBS method validation. Recovery values of 96–101% were obtained for K and P, when the certified concentration of the element in the CRM was inside the concentration range of the used calibration standards. Substantial matrix differences of the CRMs and LIBS calibration standards seem to be a probable reason for the worse recovery results (58–99%) obtained for Mg and Ca.

Quantitative LIBS analysis of vanadium in samples of hexagonal mesoporous silica catalysts.

The method for the analysis of vanadium in hexagonal mesoporous silica (V-HMS) catalysts using Laser Induced Breakdown Spectrometry (LIBS) was suggested. Commercially available LIBS spectrometer was calibrated with the aid of authentic V-HMS samples previously analyzed by ICP OES after microwave digestion. Deposition of the sample on the surface of adhesive tape was adopted as a sample preparation method. Strong matrix effect connected with the catalyst preparation technique (1st vanadium added in the process of HMS synthesis, 2nd already synthesised silica matrix was impregnated by vanadium) was observed. The concentration range of V in the set of nine calibration standards was 1.3-4.5% (w/w). Limit of detection was 0.13% (w/w) and it was calculated as a triple standard deviation from five replicated determinations of vanadium in the real sample with a very low vanadium concentration. Comparable results of LIBS and ED XRF were obtained if the same set of standards was used for calibration of both methods and vanadium was measured in the same type of real samples. LIBS calibration constructed using V-HMS-impregnated samples failed for measuring of V-HMS-synthesized samples. LIBS measurements seem to be strongly influenced with different chemical forms of vanadium in impregnated and synthesised samples. The combination of LIBS and ED XRF is able to provide new information about measured samples (in our case for example about procedure of catalyst preparation).

Serpentine ecotypic differentiation in a polyploid plant complex: shared tolerance to Mg and Ni stress among di- and tetraploid serpentine populations of Knautia arvensis (Dipsacaceae)

Background and aimsSerpentine soils impose limits on plant growth and survival and thus provide an ideal model for studying plant adaptation under environmental stress. Despite the increasing amount of data on serpentine ecotypic differentiation, no study has assessed the potential role of polyploidy. We tested for links between polyploidy and the response to serpentine stress in Knautia arvensis, a diploid-tetraploid, edaphically differentiated complex.MethodsVariation in growth, biomass yield and tissue Mg and Ni accumulation in response to high Mg and Ni concentrations were experimentally tested using hydroponic cultivation of seedlings from eight populations of different ploidy and edaphic origin.ResultsRegardless of ploidy level, serpentine populations exhibited higher tolerance to both Mg and Ni stress than their non-serpentine counterparts, suggesting an adaptive character of these traits in K. arvensis. The effect of ploidy was rather weak and confined to a slightly better response of serpentine tetraploids to Mg stress and to higher biomass yields in tetraploids from both soil types.ConclusionsThe similar response of diploid and tetraploid serpentine populations to edaphic stress corresponded with their previously described genetic proximity. This suggests that serpentine tolerance might have been transmitted during the local autopolyploid origin of serpentine tetraploids.

Late Pleistocene-early Holocene transition recorded in the sediments of a former shallow lake in the Czech Republic.

Quaternary limnic sediments from Velanská Cesta, a former lake in the Czech Republic, were investigated to document the response of an aquatic environment to global climatic shifts during the late Pleistocene–early Holocene transition. The obtained multi-proxy record, including subfossil diatoms, diatom-inferred variables (index of trophic state, halobic index, TP, and pH), plant macrofossils, and geochemical data, was compared with the δ18O GISP2 curve. Diatom accumulation zones and subzones established on the basis of a ConSLink cluster analysis corresponded well with the boundaries of the Bölling, Older Dryas, Alleröd, Younger Dryas, and Preboreal periods. The diatom-inferred trophic state and salinity data showed increased values during the colder epochs, which were supported by the findings of low-temperature macrofossil indicators in the corresponding samples. The results of this study document a long-term forcing of a shallow lacustrine ecosystem in central Europe by climatic events of a global scale.

LIBS analysis of chromium in samples of dyed wool fabric

A method for the analysis of chromium in wool fabric samples was developed. It is fast and cheap with no sample preparation. This method involved the use of double pulse Laser Induced Breakdown Spectrometry (LIBS) for the wool fabric samples dyed by two types of metal complex dyes (C.I. Acid Orange 173 and C.I. Acid Black 60). A commercially available LIBS spectrometer was calibrated with the aid of authentic wool fabric samples previously analysed by F-AAS after microwave digestion. Comparable results can be obtained using this unique procedure if the same set of standards is used for XRF and LIBS calibration. Limits of detection for chromium achieved by suggested LIBS methods (from 5 to 10 mg kg−1) are comparable with the WD XRF ones (from 4 to 5 mg kg−1).

The cryogenic grinding as the important homogenization step in analysis of inconsistent food samples

Some homogenisation approaches have been investigated to make easier and overcome troublesome preparation of inconsistent food samples. Contents of Na, Ca, Mg, P, Fe, Mn and Zn in muesli, seed and instant food samples were determined by inductively coupled plasma optical emission spectrometry after their grinding with an agate mortar, a kitchen coffee grinder and a cryogenic mill. The efficiency of a grinding step was evaluated using RSDs and homogeneity factors (H-factor). For cryogenically grinded samples, RSDs were detected about 4% and H-factors on 10, what is acceptable for the analytical purpose. The results for grinding with an agate mortar as well as a coffee grinder were quite unsatisfactory (RSDs in tens percent). Differences between RSDs and H-factors for the procedures tested were detected to be statistically significant. Different element contents were observed in differently treated samples which is probably a result of an unevenly element distribution in inhomogeneous components forming sample.

Toxicity of zinc oxide nanoparticles to the annelid Enchytraeus crypticus in agar-based exposure media

Toxicity of zinc oxide nanoparticle (ZnO-NPs) powder and water soluble salt of Zn (ZnCl2) to the annelid Enchytraeus crypticus was tested in agarose gel. Influence of the spiking method on the resulting size of nanoparticles and on E. crypticus mortality was studied. Two methods of ZnO-NPs powder (mean particle size diameter of 10 nm) introduction into the exposure media were used. In the first method, the nano-powder was initially cryogenically ground with dry agar followed by an addition of water. The second procedure began with re-suspension of nanoparticles in demineralized water containing a dispersant (sodium pyrophosphate decahydrate). The obtained colloid was subsequently mixed with hot agar gel. Relative mortality in worms observed after 96 h of their exposure to the ZnO-NPs concentrations (all in mg of ZnO-NPs per kg of agar) of 50, 100, 200, 500 and 1000 in the cryogenically ground medium ranged between 28.9 % and 34.4 % and it did not exhibit any concentration dependence. When the second method of exposure media preparation was applied, the relative mortality ranged from 0 % to 66.6 % in the same concentration region depending on the concentration. Scanning electron microscopy (SEM) revealed the presence of large agglomerates (1–10 µm in diameter) in the media prepared by cryogenic grinding with the highest concentration of ZnO-NPs. Neither the cryogenically ground media with lower ZnO-NPs concentrations nor any media prepared from colloidal solutions contained agglomerates exceeding 100 nm, detectable by SEM. Hydrodynamic diameters of particles in the colloids used in the second method of agar preparation were measured using dynamic light scattering (DLS) and ranged between 164 nm and 240 nm. The observed toxicity was thus clearly dependent on the size of ZnO-NPs agglomerates and the technique of exposure media preparation. Experimentally detected LC50 value for dissolved Zn2+ was 37.2 mg kg−1 in agar. The same concentration of Zn induced an approximately 30 % mortality of E. crypticus when administered in form of cryogenically ground ZnO-NPs with agar. No observable effects were found at this ZnO-NPs concentration when the exposure medium was prepared from the colloid solution.

Fast determination of the surface density of titanium in ultrathin layers using LIBS spectrometry

This work deals with the use of laser-induced breakdown spectroscopy (LIBS) for determining the surface density of titanium in ultrathin layers, particularly in ultrathin layers on a steel sheet. The results obtained by LIBS spectroscopy were compared with those obtained by wavelength dispersive X-ray fluorescence spectroscopy (WDXRF), X-ray photoelectron spectroscopy (XPS) and laser ablation inductively coupled plasma time of flight mass spectrometry (LA-ICP-TOF-MS). A simple, cheap and efficient method for the determination of the surface density of titanium in thin layers has been developed.

Cryogenic grinding of electrospun poly-ε-caprolactone mesh submerged in liquid media.

In this paper, the treatment of poly-ε-caprolactone (PCL) nano/micro-mesh system by cryogenic grinding and subsequent characterization of obtained product is described. The PCL nano/micro-mesh layer submerged in appropriate liquid was cryogenically ground and obtained particles were characterized employing mainly laser diffraction and scanning electron microscopy (SEM). In the ground sample, different types of particles (fibrous particles, fibrous fragments, agglomerates with and without an internal fibrous structure, lamellae and nanoparticles) were identified, described and quantified. Parameters of cryogenic grinding (weight of sample, type of liquid medium, and influence of sample storage) were optimized to maximize the yield of particles with desired features. The potential of the system for cell scaffolding was demonstrated by cultivation of 3T3 fibroblasts on the produced microparticles.