Marcin Frankowski

New method for speciation analysis of aluminium fluoride complexes by HPLC-FAAS hyphenated technique.

Speciation analysis of aluminium in the presented system of HPLC-FAAS hyphenated technique lasts 4min. Using the bifunctional column in model analysis and using the calculation methods for modelling using the Mineql program enabled the authors to presume that particular forms will be subjected to elution in the following order: (1) AlF(2)(+) and AlF(4)(-), (2) AlF(2+) and AlF(3)(0) and (3) Al(3+). Based on the obtained results for model solutions, the presented method enables the determination of aluminium fluoride complexes and Al(3+) speciation form. The study compares the tendency of occurrence variability of aluminium fluoride complexes and Al(3+) form, determined based on the results obtained using the HPLC-FAAS hyphenated technique with the trend defined based on the Mineql program calculation method. The method was successfully applied to soil samples.

Development of a new analytical method for online simultaneous qualitative determination of aluminium (free aluminium ion, aluminium-fluoride complexes) by HPLC-FAAS.

The paper presents a novel method for simultaneous online examination of inorganic forms of aluminium: AlF(2)(+), AlF(2+,) and Al(3+) by means of the high performance liquid chromatography hyphenated with a detection by the atomic absorption spectrometry with flame atomization (HPLC-FAAS) without post-column reaction. The application of optimization procedure conditions of chromatographic separation of inorganic forms of aluminium was achieved by the analytical column IonPac CS5A (Dionex) with guard column IonPac CG5A (Dionex) and an aqueous ammonium chloride mobile phase, at pH about 3 with gradient elution. The separation of Al forms with nominal charge of 1+, 2+, 3+ required a run time of less than 8 min during a single analysis. The proposed method has been successfully used for the examination of aluminium forms formation AlF(n)((3-n)+) in environmental samples.

Aluminium dynamics from soil to tea plant (Camellia sinensis L.): is it enhanced by municipal solid waste compost application?

Application of municipal solid waste compost (MSWC) in tea (Camellia sinensis L.) cultivation can increase the fertility status of soils and thus enhance the plant growth. The present study attempts at application of MSWC in tea (TV1 and TV23 clones) cultivation to assess the effect of different doses of MSWC on growth and translocation potential of Al on this plant as well as fate of Al in soil, through the calculation of a risk assessment code (RAC). The sequential extraction of Al in MSWC amended soils showed that the fractionation of Al in soil changed after compost application, with an overall increase of the fractions associated to with Fe-Mn oxides, organic and of the residual fraction. The accumulation of Al in different parts ofC. sinensisL., grown on MSWC amended soil effected an overall increased growth of the plant with increasing doses of MSWC. According to RAC, Al falls in medium to high risk, though no adverse effect on plant health was observed. Tea plants were found to adapt well to MSWC amended soils. However, long term field trials are necessary to completely assess the risk of Al accumulation in soils upon MSWC application. Hierarchical cluster analysis was applied aiming to check for the presence of homogenous groups among different treatments. It was found that in both TV1 and TV23, treatments formed two different groups.

Speciation analysis of aluminium and aluminium fluoride complexes by HPIC-UVVIS.

The study presents a new analytical method for speciation analysis in fractionation of aluminium fluoride complexes and free Al(3+) in soil samples. Aluminium speciation was studied in model solutions and soil extract samples by means of high performance ion chromatography (HPIC) with UV-VIS detection using post-column reaction with tiron for the separation and detection of aluminium fluoride complex and Al(3+) forms during one analysis. The paper presents particular stages of the chromatographic process optimization involving selecting the appropriate eluent strength, type of elution or concentration and quantity of derivatization reagent. HPIC was performed on a bifunctional analytical column Dionex IonPac CS5A. The use of gradient elution and the eluents A: 1M NH(4)Cl and B: water acidified to pH of eluent phase, enabled full separation of fluoride aluminium forms as AlF(2)(+), AlF(3)(0), AlF(4)(-) (first signal), AlF(2+) (second signal) and form Al(3+) in a single analytical procedure. The proposed new method HPIC-UVVIS was applied successfully in the quantitative and qualitative analysis of soil samples.

Removal of phosphate from water by lanthanum-modified zeolites obtained from fly ash

The possibility and effectiveness of removal of phosphate from aqueous solutions with the use of new low-cost synthetic zeolites obtained from fly ash and modified with lanthanum, was studied. Physicochemical properties of the zeolites were characterized by different techniques such as X-ray diffraction, low-temperature nitrogen sorption and scanning electron microscopy. It has been established that lanthanum is preferentially located in the zeolites channels and cages, which is related to the ion-exchange method of modification. Introduction of lanthanum cations leads to a reduction in BET surface area, mainly due to a decrease in the area of micropores and reduction in the pore volume. The key element of the study was a series of tests of phosphate adsorption from aqueous solutions. The efficiency of adsorption process was found to depend on the concentration of adsorbate, pH of its solution and temperature. The sorption capacity of zeolites obtained from fly ashes (La-P1, La-A) towards phosphate was compared with that of a natural zeolite - clinoptilolite, modified with lanthanum (La-CLP). The sorption capacities of the particular samples were as follows: La-P1 - 58.2 mg/g, La-A - 44.0 mg/g and La-CLP - 24.6 mg/g. The experimental data were well fitted by the Langmuir isotherm model. The sorption capacities of all samples towards phosphate increased with temperature increasing from 25 to 60 °C. The values of the thermodynamic parameters ΔH0 and ΔG0 revealed that the adsorption was spontaneous and endothermic.

Carbon Dynamics in a Hardwater Lake: Effect of Charophyte Biomass on Carbonate Deposition

ABSTRACT: The photosynthetic activity of phytoplankton (in pelagial) and macrophytes (in littoral) is considered to be one of the main factors affecting the carbon cycle in lakes. This concerns in particular hardwater ecosystems, where most of the carbon is available in the form of Ca- or Mg-bicarbonates. In such ecosystems charophytes (macroscopic green algae, forming dense meadows) are regarded as the most effective carbonate producer due to the HCO3 — utilization and the formation of thick CaCO3 encrustations. Calcium carbonate and biomass production of charophytes were studied in a small and shallow charophyte-dominated Lake Jasne (Western Poland). Fresh and dry weight of plants, percentage contribution of calcium carbonate and production of CaCO3 per 1 m2 were studied at three depths (1, 3 and 5 m) in three sample sites (each sampled area — 0.04 m2). Additionally, physical-chemical parameters of water samples were studied. It was found that the dry weight of charophytes and the values of calcium carbonate were similar for all sites but varied for depth of sampling. The dry weight exceeded 2000 g m-2 (average 1165 g m-2) at the most shallow sample sites. CaCO3 encrustations constituted from 39.5% at the depth of 5m, to over 82% of the charophyte dry weight at the depth of 1m. The maximum and average values of carbonates precipitated by charophytes were 1696 g m-2 and 891 g m-2, respectively, and exceeded results reported so far. The results of physical-chemical analyses revealed no statistically significant differences between all the sample sites. Nevertheless, distinct correlations were found between dry weight of charophytes, carbonates precipitated by charophytes and some physical-chemical properties of water from the sample sites. The results highlight the habitat engineering role of charophytes, evidenced in particular by great amounts of biomass influencing sedimentary processes and biogeochemical cycle within littoral zone.

Aluminum uptake and migration from the soil compartment into Betula pendula for two different environments: a polluted and environmentally protected area of Poland

This paper presents the impact of soil contamination on aluminum (Al) concentrations in plant parts of Betula pendula and a possible way of migration and transformation of Al in the soil-root-stem-twig-leaf system. A new procedure of Al fractionation based on extraction in water phase was applied to obtain and measure the most available forms of Al in soils and B. pendula samples. In addition, total Al content was determined in biological samples and pseudo total Al content in soil samples collected under plant saplings, using atomic absorption spectrometry with flame atomization. A number of relations concerning the occurrence of Al and Ca in soils and plant parts of B. pendula (tap roots, lateral roots, stem, twigs, and leaves) were observed. Based on the research findings, the mechanism of Al migration from soil to the leaves of B. pendula can be presented. It was found that aluminum uptake may be limited in roots by high calcium concentration. The application of a new procedure based on the simple sequential extraction of water-soluble fractions (the most available and exchangeable fractions of Al) can be used as an effective tool for the estimation of aluminum toxicity in soils and plants.

Levels and potential health risks of mercury in prescription, non-prescription medicines and dietary supplements in Poland.

Determination of mercury is important in the case of pharmaceuticals for which the European Union regulations have not defined the maximum permissible concentration of this metal. The aim of the study was to determine the levels of mercury in the following groups of drugs (n = 119): analgesics, diuretics, cardiacs, antihypertensives, anti-influenza, antibiotics, anti-allergics, tranquilizers, antibacterials and in dietary supplements (n = 33) available on the Polish market. Mercury was analyzed using cold vapor atomic fluorescence spectrometry CV-AFS. Its content in the samples varied in the range of 0.9-476.1 ng g(-1). Higher mercury concentrations were reported for prescription drugs (Rx): 0.9-476.1 ng g(-1) (median: 7.4 ng g(-1)), lower--for non-prescription medicines (OTC): 1.2-45.8 ng g(-1) (median: 6.0 ng g(-1)). In the analyzed dietary supplements the concentrations were: 0.9-16.7 ng g(-1) (median: 5.9 ng g(-1)). On the basis of the information contained in the leaflet accompanying the medicine, a daily dose of mercury taken into the body with an analyzed medicament was estimated and the health risk posed by using such medicines was assessed. The study indicates that it is justified to carry out measurements of mercury in pharmaceuticals due to its high, potentially harmful.

Seasonality of Water Chemistry, Carbonate Production, and Biometric Features of Two Species of Chara in a Shallow Clear Water Lake

The objective of this study was to analyze the temporal variability of biometric features and the carbonate production of two charophytes: Chara polyacantha A. Braun and Chara rudis A. Braun against the background of the physical-chemical properties of water. The investigation was carried out in a small, mid-forest Lake Jasne (western Poland). It is a polymictic, mesotrophic, hardwater ecosystem dominated by charophyte vegetation. Each month, 10 individuals of each species were characterized in terms of morphometric features, fresh and dry weight, and the percentage of calcium carbonate. Additionally, physical-chemical parameters of the water were studied. The results of physical-chemical analyses indicated similar habitat conditions for both species. Despite smaller dry weight C. polyacantha was characterized by greater morphological variability and higher rates of growth and percentage share of calcium carbonate in dry mass than C. rudis. The percentage of calcium carbonates in dry mass did not differ significantly between the species and exceeded 60%, reaching the maximum (76% in C. polyacantha) in July and August. For both species, distinct correlations between the structure of biomass and morphological features were found. The obtained results show the great importance of charophyte vegetation in carbon cycling and functioning of lake ecosystems.

Factors affecting the aluminium content of human femoral head and neck

Tissues for the study were obtained intraoperatively during hip replacement procedures from 96 patients. In all the cases, the indication for this treatment was primary or secondary degenerative changes in the hip joint. The subject of the study was the head and neck of the femur, resected in situ. Aluminium concentrations measured in femoral head and neck samples from patients aged between 25 and 91 were varied. Statistical methods were applied to determine the variations in relation to the parameters from the background survey. Significant differences in the aluminium content of femoral head samples were observed between patients under and over 60 years of age. Based on the results, it was confirmed that the aluminium accumulates in bones over a lifetime. The study showed that the content of aluminium in the head and neck of the femur depends on the factors such as: type of medicines taken, contact with chemicals at work, differences in body anatomy and sex. The study on the levels of aluminium in bones and the factors affecting its concentration is a valuable source of information for further research on the role of aluminium in bone diseases. Based on the investigations, it was found that the GF-AAS technique is the best analytical tool for routine analysis of aluminium in complex matrix samples. The use of femoral heads in the investigations was approved by the Bioethics Committee of the University of Medical Sciences in Poznań (Poland).