Bioavailability of metals occurring in polluted soil and its accumulation in plant food

Bioavailability of metals occurring in soil is the basic source of its accumulation in plant food. The impact of soil pollution (due to urban and mining areas) on the food chain presents a challenge for many investigations. Bioavailability of metals in a potentially polluted soil and their possible transfer and bioaccumulation in several vegetable species and herbs was examined. Three extraction methods were implemented for determination of bioavailable metals in the soil. Microwave digestion was applied for total digestion of the plant tissues, while on the soil samples open wet digestion with a mixture of acids was applied. Atomic emission spectrometry with inductively coupled plasma was used for determination of total elements contents. Significant enrichments in agricultural soil for As, Pb and Zn (in urban area), Cd, Cu and Ni (in a copper mine area), compared with the respective values from European standards were detected. On the basis of three different extraction methods, higher availability was assumed for both lithogenic and anthropogenic elements. Translocation factors higher than 1 were obtained for As, Cd, Cu, Ni, Pb and Zn. Higher root to shoot translocation of these metals indicated that plants species have vital characteristics to be used for phytoextraction of these metals. The obtained data also suggested that S. oleracea and R. acetosa were singled out to have a phytostabilization potential for Cd, Cu, Ni and Pb, while U. dioica only for Cu. Rumex acetosa has a potential for phytoextraction of Cd in urban and copper polluted areas

Determination of Thallium Traces from Aqueous Solutions Using Iron(III) Hexamethylenedithiocarbamate as a Flotation Collector and Subsequent Electrothermal Atomic Absorption Spectrometry

Hexamethyleneammonium hexamethylenedithiocarbamate (HMA-HMDTC) was used as a new flotation reagent for enrichment and separation of thallium traces from aqueous Solutions. HMA-HMDTC added to the first precipitate collector of hydrated iron(III) oxide (Fe2O3 ⋅ xH2O) gives the second precipitate collector of iron(III) hexamethylenedithiocarbamate (Fe(HMDTC)3). During the coprecipitation step, thallium ions are incorporated in the structure of the collector particles forming a sublate, which is separated from the processed water phase by flotation. After the preconcentration and separation step, a quantitative analysis is performed by electrothermal atomic absorption spectrometry (ETAAS). The diverse experimental parameters affecting the flotation efficiency were determined and optimized. It was ascertained by a proposed procedure that total thallium can be separated quantitatively by addition of 10 mg FeIII and 3 mL 0.1 mol/L HMDTC- to the sample at pH = 6.0. The applicability of the proposed new procedure has been verified by the analysis of natural water samples by the method of standard additions and by inductively coupled plasma - atomic emission spectrometry (ICP-AES), as an independent comparative method. The limit of detection for thallium in this method is 0.024 μg/L

Priprava uzoraka i određivanje diuretika u tjelesnim tekućinama čovjeka pomoću RPHPLC

This article described reverse phase high-performance liquid chromatography (RPHPLC) methods for determination of diuretics in different human body fluids (whole blood, plasma, serum or urine). Sample preparation procedures including solid-phase extraction, liquid-liquid extraction, dilution, precipitation as well as automated RPHPLC procedures were discussed in order to give advantages and disadvantages of each type of sample preparation. Also, values for analytical recovery of each procedure used for sample preparation are summarized. The most important RPHPLC parameters (detection mode, stationary phase, mobile phase, sensitivity, etc.) are also summarized and discussed.U članku se opisuje metoda određivanja diuretika u različitim tjelesnim tekućinama čovjeka (punoj krvi, plazmi, serumu ili urinu) inverzno-faznom visokotlačnom tekućinskom kromatografijom (RPHPLC). Priprava uzoraka uključuje postupke čvrsto-tekuće ili tekuće-tekuće ekstrakcije, razrijeđivanje, taloženje ili automatizirani RPHPLC postupak. Diskutiraju se prednosti i nedostaci različitih priprava uzoraka. Sažete su vrijednosti za analitički povrat svakog pojedinog postupka. Također se sumiraju i diskutiraju najvažniji RPHPLC parametri (način detekcije, stacionarna faza, mobilna faza, osjetljivost, itd.)

Priprava uzoraka i određivanje diuretika u tjelesnim tekućinama čovjeka pomoću RPHPLC

This article described reverse phase high-performance liquid chromatography (RPHPLC) methods for determination of diuretics in different human body fluids (whole blood, plasma, serum or urine). Sample preparation procedures including solid-phase extraction, liquid-liquid extraction, dilution, precipitation as well as automated RPHPLC procedures were discussed in order to give advantages and disadvantages of each type of sample preparation. Also, values for analytical recovery of each procedure used for sample preparation are summarized. The most important RPHPLC parameters (detection mode, stationary phase, mobile phase, sensitivity, etc.) are also summarized and discussed.U članku se opisuje metoda određivanja diuretika u različitim tjelesnim tekućinama čovjeka (punoj krvi, plazmi, serumu ili urinu) inverzno-faznom visokotlačnom tekućinskom kromatografijom (RPHPLC). Priprava uzoraka uključuje postupke čvrsto-tekuće ili tekuće-tekuće ekstrakcije, razrijeđivanje, taloženje ili automatizirani RPHPLC postupak. Diskutiraju se prednosti i nedostaci različitih priprava uzoraka. Sažete su vrijednosti za analitički povrat svakog pojedinog postupka. Također se sumiraju i diskutiraju najvažniji RPHPLC parametri (način detekcije, stacionarna faza, mobilna faza, osjetljivost, itd.)

Heavy metals air pollution study in mines environments. Case study Bregalnica river basin, Republic of Macedonia

Application of several moss species and attic dust for monitoring of anthropogenic impact on heavy metals air pollution in Bregalnica River Basin, Republic of Macedonia, was studied. Moss samples were reviewed for their potential to reflect heavy metals air pollution. The attention was focused on their quantification ability, underlying the metal accumulation within moss plant tissue and attic dust “historical archiving”. Potential “hot spots” were selected in areas of copper mine (Bučim mine) and lead and zinc mines (Zletovo mine and Sasa mine) as main metal pollution sources in the Eastern part of the Republic of Macedonia. Continuously, dust distribution from ore and flotation tailings occurs. This results with air-introduction and deposition of higher contents of certain metals. Several moss species (Hypnum cupressiforme, Homalothecium lutescens and Scleropodium purum) were used as plant sampling media. Determination of chemical elements was conducted by using both instrumental techniques: atomic emission spectrometry with inductively coupled plasma (ICP-AES) and mass spectrometry with inductively coupled plasma (ICP-MS). Combination of multivariate techniques (PCA, FA and CA) was applied for data processing and identification of elements association with lithogenic or anthropogenic origin. Spatial distribution maps were constructed for determination and localizing of narrower areas with higher contents of certain anthropogenic elements. In this way influences of selected human activities in local (small scale) air pollution can be determined. Summarized data reveal real quantification of the elements distribution not only in order determination of hazardously elements distribution, but also present complete characterization for elements deposition in mines environs

General features of some pollymetalic ore deposits in the Republic North Macedonia

The general features of several important mineral deposits of polymetallic character in the Republic of Northern Macedonia that have been actively exploited in the past are described. These include the Buchim copper mine and Sasa, Zletovo and Toranica lead-zinc mines, as well as some ore prospects that have been extensively explored for years. In addition, sites with known ore reserves, but which are not yet at the exploitation stage are presented, including Plavica, Ilovica, Kadiica, Borov Dol and others. The elaborated RIS-RESERVES program is used to affirm numerous parameters related to the definition of ore reserves in the deposits, and has now provided the opportunity for preparation of an overview which shows the major metallogenetic characteristics of the deposits with their techno-economic parameters. This approach enables affirmation of the potential of the polymetallic ore deposits in the Republic of Northern Macedonia

Determination of Thallium Traces from Aqueous Solutions Using Iron(III) Hexamethylenedithiocarbamate as a Flotation Collector and Subsequent Electrothermal Atomic Absorption Spectrometry

Hexamethyleneammonium hexamethylenedithiocarbamate (HMA-HMDTC) was used as a new flotation reagent for enrichment and separation of thallium traces from aqueous Solutions. HMA-HMDTC added to the first precipitate collector of hydrated iron(III) oxide (Fe2O3 ⋅ xH2O) gives the second precipitate collector of iron(III) hexamethylenedithiocarbamate (Fe(HMDTC)3). During the coprecipitation step, thallium ions are incorporated in the structure of the collector particles forming a sublate, which is separated from the processed water phase by flotation. After the preconcentration and separation step, a quantitative analysis is performed by electrothermal atomic absorption spectrometry (ETAAS). The diverse experimental parameters affecting the flotation efficiency were determined and optimized. It was ascertained by a proposed procedure that total thallium can be separated quantitatively by addition of 10 mg FeIII and 3 mL 0.1 mol/L HMDTC- to the sample at pH = 6.0. The applicability of the proposed new procedure has been verified by the analysis of natural water samples by the method of standard additions and by inductively coupled plasma - atomic emission spectrometry (ICP-AES), as an independent comparative method. The limit of detection for thallium in this method is 0.024 μg/L

DISTRIBUTION OF CHEMICAL ELEMENTS IN SEDIMENTS AND ALLUVIUM SOILS FROM THE PČINJA RIVER BASIN, NORTH MACEDONIA

In this work, the distribution of chemical elements in sediment and alluvial soil samples from the Pčinja river basin was investigated. For this purpose, samples of sediments and natural and anthropogenic alluvium soils from the river and lake plains were collected along the course of the Pčinja river in the period from June to July 2017, according to a previously established sampling network with 10 sites on the rivers and 4 sites on the Glažnja and Lipkovo lakes. In addition to five sites on the Pčinja river, two samples were collected from the river of Tabanovska and one sample from the each tributaries of Kumanovsk, Konjarska and Kriva rivers. At each site, the following samples were collected: river sediment, lake sediment and natural alluvium (topsoil sample, 0–5 cm, and subsoil sample, 20–30 cm). In all samples collected, 22 macro- and trace elements (Аg, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, P, Ni, Pb, Sr, V and Zn) were analyzed by inductively coupled plasma – atomic emission spectrometry (ICP-AES). The contents of almost all the analyzed elements are within the expected values and are consistent with the lithology of the area studied. A multivariate factor analysis was applied to analyze the relationships between the number of variables. The method includes processing information from a large number of original variables and processing them into a smaller set (factor) with minimal loss of information from the original variables. From the obtained results, spatial distribution maps of the factors for each group and distribution maps the analyzed elements were created. It was found that the distribution of most elements follows the lithology of the study area, with the exception of some elements (As, Cu, P) whose increased contents are to urban, industrial and agricultural activities

ENRICHMENT OF SOME POTENTIALLY TOXIC ELEMENTS IN SOILS AFFECTED BY Pb-Zn MINING AND METALLURGICAL PROCESSING IN THE MITROVICA REGION, KOSOVO

The results of a study on the presence and enrichment of potentially toxic elements in surface soil in the Mitrovica region, Kosovo, are reported. The investigated region (301.5 km2) was covered by a sampling grid of 1.4×1.4 km and a total of 156 soil samples were collected. Inductively coupled plasma - mass spectrometry (ICP-MS) was applied for the determination of anthropogenic association of 12 elements: Ag, As, Au, Bi, Cd, Cu, Hg, Pb, Mo, Sb, Tl and Zn. For data evaluation, parametric and non-parametric statistics methods were used. Soil contamination is assessed on the basis of enrichment factor (EF). The average content of Pb was 19.6-fold; Cd 11-fold; Hg 5-fold; Zn 4.5-fold; As 4.3-fold; Sb 3.8-fold; Cu 3.2-fold and Ag 1.6-fold higher that European average values. Increased levels of the content of these metals showed that mining and smelter processing activities strongly affected in soils of the towns of Zveçan and Mitrovica and their environs. In the close vicinity of the cities of Zveçan and Mitrovica, the contents of the As, Cd, Cu, Pb and Zn were even higher than the corresponding intervention values according to the New Dutch list and were exceed in 122 km2 of the investigated area. Key words: soil pollution; potentially toxic elements; Mitrovica; Republic of Kosov

Geological characteristics of the Republic of North Macedonia

Detailed description of the geological characteristics of the Republic of North Macedonia is given. The characteristics of the six major tectonic units are described: the Vardar zone (VZ) in Central Region, the Pelagonian massif (PM), the West-Macedonian zone (WMZ) and a small part of the Cukali-Krasta zone (CKZ) in the west, and the Serbo-Macedonian massif (SMM) and the Kraishtide zone (KZ) in the east. The geological map with these units is also shown, including the most presented lithological units: Quaternary alluvial and deluvial/proluvial sediments, Neogene, Paleogene and Mesozoic clastic rocks, Mesozoic, Paleozoic and Proterozoic carbonate rocks, Paleozoic and Proterozoic metamorphic rocks from Pelagonian and Serbo-Macedonian massif and Neogene, Paleogene, Mesozoic and Paleozoic magmatic rocks. Additionally, special attention is given to the Neogene and the Quaternary in North Macedonia