Heavy metal and nitrogen concentrations in mosses are declining across Europe whilst some "hotspots" remain in 2010.

In recent decades, naturally growing mosses have been used successfully as biomonitors of atmospheric deposition of heavy metals and nitrogen. Since 1990, the European moss survey has been repeated at five-yearly intervals. In 2010, the lowest concentrations of metals and nitrogen in mosses were generally found in northern Europe, whereas the highest concentrations were observed in (south-)eastern Europe for metals and the central belt for nitrogen. Averaged across Europe, since 1990, the median concentration in mosses has declined the most for lead (77%), followed by vanadium (55%), cadmium (51%), chromium (43%), zinc (34%), nickel (33%), iron (27%), arsenic (21%, since 1995), mercury (14%, since 1995) and copper (11%). Between 2005 and 2010, the decline ranged from 6% for copper to 36% for lead; for nitrogen the decline was 5%. Despite the Europe-wide decline, no changes or increases have been observed between 2005 and 2010 in some (regions of) countries.

Bioaccumulation of heavy metals by endemic Viola species from the soil in the vicinity of the As-Sb-Tl mine "allchar' Republic of Macedonia.

Allchar mine is an abandoned arsenic-antimony-thallium deposit located on the northwestern part of Kozuf Mt., Republic of Macedonia. Allchar is a unique deposit within the world, due to the variety of its mineral composition especially and in the high content of thallium. The aim of this work was to assess the level of contamination at this post-mining area as well as to determine the intensity of accumulation of various elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Sr, Tl, V, and Zn) with focus on As, Sb and Tl, in two endemic Viola species from this locality (Viola allcharensis G. Beck, Viola arsenica G. Beck) and one Balkan endemic species (Viola macedonica Boiss. & Heldr.). Samples of different plant parts and soil were digested and then analysed by ICP-AES. It was found that the accumulation of As, Sb, and Tl in these endemic species is significantly high. In this study a systematic investigation of the As-Sb-Tl contamination of soils and their bioavailability was carried out using the extraction procedure in order to explore the mobility and potential bioavailability of the As, Sb, and Tl.

Country-specific correlations across Europe between modelled atmospheric cadmium and lead deposition and concentrations in mosses.

Previous analyses at the European scale have shown that cadmium and lead concentrations in mosses are primarily determined by the total deposition of these metals. Further analyses in the current study show that Spearman rank correlations between the concentration in mosses and the deposition modelled by the European Monitoring and Evaluation Programme (EMEP) are country and metal-specific. Significant positive correlations were found for about two thirds or more of the participating countries in 1990, 1995, 2000 and 2005 (except for Cd in 1990). Correlations were often not significant and sometimes negative in countries where mosses were only sampled in a relatively small number of EMEP grids. Correlations frequently improved when only data for EMEP grids with at least three moss sampling sites per grid were included. It was concluded that spatial patterns and temporal trends agree reasonably well between lead and cadmium concentrations in mosses and modelled atmospheric deposition.

Determination of trace elements in some copper minerals by k0-neutron activation analysis.

Trace element contents in two copper minerals [brochantite [Cu(4)SO(4)(OH)(6)] and native Cu] using k(0)-NAA were determined before and after quantitative removal of copper. The distribution of 44 elements in the studied minerals was investigated. An important advantage of the proposed method is the possibility to determine the content of several elements (Al, Dy, Mg, Mn and V) via their short-lived nuclides after the electrolytic removal of Cu due to the elimination of matrix interferences.

Microbiological and chemical characteristics of water and sediment from Vrelo Cave, Republic of Macedonia.

Vrelo Cave is the deepest cave in Macedonia, located in the canyon Matka which is home to many endemic species not found anywhere else in Europe. Until now, Vrelo Cave has not been investigated in terms of its composition and biodiversity. The purpose of this study was to offer some preliminary data for physical and chemical parameters of water and sediments from Vrelo Cave, as well as its microbiological diversity. Samples were taken from 5 locations. They were analysed for a wide array of physico-chemical parameters, macro- and microelements and concentration of selected organic pollutants. All samples were investigated for several groups of bacteria, yeasts and moulds by a conventional selective media approach. Molecular identification of the isolated bacterial species was done by sequencing of the bacterial 16S ribosomal RNA gene. Regarding the total dry components, total hardness, dissolved oxygen, biochemical and chemical consumption of oxygen, water from Vrelo Cave belongs to Class I. All of the investigated groups of microorganisms except anaerobic sporogenic bacteria were present in water and sediment samples. Notably, a large number of coliformic bacteria (total and faecal) were isolated from all of the investigated samples which classify this water in Class IV, as ecologically unsuitable drinking water. Most of the identified non-coliformic bacteria belonged to the genus Bacillus. We have also identified representatives from Staphylococcus, Proteus, Brevundimonas and Enterobacter. Overall findings suggest a possible connection between the water from the cave and surface waters. Further investigation should be performed to determine the origin of these waters.

Atmospheric deposition of trace element pollutants in Macedonia studied by the moss biomonitoring technique.

For the first time the atmospheric deposition of trace metals was studied over the entire territory of the Republic of Macedonia. Samples of the terrestrial mosses Hypnum cupressiforme, Camptothecium lutescens, and Homalothecium sericeum were collected in September-October 2002 at 73 sites evenly distributed over the country, and a total of 43 elements were determined by instrumental neutron activation analysis and atomic absorption spectrometry. Principal component factor analysis was used to identify the most polluted areas and characterize different pollution sources. The most important sources of trace metal deposition are ferrous and non-ferrous smelters, oil refineries, fertilizer production plants, and central heating stations. Four areas appear to be particularly exposed to metal pollution: Veles, Skopje, Tetovo, and Kavadarci-Negotino, whereas the predominantly agricultural regions in the south, southwest, and southeast show levels closer to European median values for most elements of mainly pollution origin.

Nickel and strontium nitrates as modifiers for the determination of selenium in wine by Zeeman electrothermal atomic absorption spectrometry.

A mixed matrix modifier of nickel and strontium nitrates was used as a chemical modifier for the determination of selenium in wines by Zeeman electrothermal atomic absorption spectrometry. Wine samples were heated on a boiling water bath with small amounts of nitric acid and hydrogen peroxide. For complete elimination of interference, especially from sulfates and phosphates, selenium is complexed with ammonium pyrolidinedithiocarbamate (APDTC), extracted into methyl isobutyl ketone (MIBK), and measured by ETAAS. The graphite furnace temperature program was optimized for both aqueous and organic solutions. Pyrolysis temperatures of 1300 degrees C and 800 degrees C were chosen for aqueous and organic solutions, respectively; 2700 degrees C and 2100 degrees C were used as optimum atomization temperatures for aqueous and organic solutions, respectively. The optimum modifier mass established is markedly lower than those presented in the literature. The platform atomization ensures pretreatment stabilization up to 1100 degrees C and 1600 degrees C, respectively, for organic and aqueous selenium solutions. The procedure was verified by the method of standard addition. The investigated wine samples originated from the different regions of the Republic of Macedonia. The selenium concentration varied from not detectable to 0.93 microg L(-1).

Separation, preconcentration, and determination of cadmium in drinking waters.

A fast method for separation, preconcentration and determination of cadmium in drinking (source, well, tap) and water for irrigation is described. Iron(III) hexamethylenedithiocarbamate, Fe(HMDTC)3, has the role of colloid precipitate flotation collector. The determination of cadmium in final water solutions preconcentrated by flotation can be performed by flame (FAAS) or electrothermal atomic absorption spectrometry (ETAAS). The method applied, either FAAS or ETAAS, depends of the concentration level of analyte in the water sample investigating. The AAS results are compared with inductively coupled plasma-atomic emission spectrometric measurements (ICP-AES) as an independent method. The ETAAS detection limit of cadmium is 0.002 microgram/L.

Preconcentration and separation of cadmium by use of cobalt(III) hexamethylenedithiocarbamate as a collector prior to its determination by atomic absorption spectrometry.

Co(III) hexamethylenedithiocarbamate has been applied as a collector in colloid flotation preconcentration of Cd from water prior to electrothermal atomic absorption spectrometry (ETAAS). All experimental parameters necessary for successful flotation have been studied and optimized. The ETAAS results were compared with those obtained by inductive coupled plasma-atomic emission spectrometry (ICP-AES). The ETAAS detection limit was found to be 0.003 microg L(-1) Cd.

Electrothermal atomic absorption spectrometric determination of cobalt, copper, lead and nickel traces in aragonite following flotation and extraction separation.

A method of determination of Co, Cu, Pb and Ni in nanogram quantities from aragonite is presented. Flotation and extraction of Co, Cu, Pb and Ni is suggested as methods for elimination matrix interferences of calcium. The method of flotation is performed by iron(III) hexamethylenedithiocarbamate, Fe(HMDTC)(3), as a colloid precipitate collector. The liquid-liquid extraction of Co, Cu, Pb and Ni is carried out by sodium diethyldithiocarbamate, NaDDTC, as complexing reagent into methylisobutyl ketone, MIBK. The electrothermal atomic absorption spectrometry (ETAAS) is used for determination of analytes. The detection limits of ETAAS followed by flotation are: 7.8 ng.g(-1) for Co, 17.1 ng.g(-1) for Cu, 7.2 ng.g(-1) for Pb and 9.0 mug.g(-1) for Ni. The detection limits of ETAAS followed by extraction are found to be: 12.0 ng.g(-1) for Co, 51.0 ng.g(-1) for Cu, 24.0 ng.g(-1) for Pb and 21.0 ng.g(-1) for Ni.

Determination of total thallium in fresh water by electrothermal atomic absorption spectrometry after colloid precipitate flotation.

Tl(I) and Tl(III) are preconcentrated simultaneously from aqueous solutions by colloid precipitate flotation using two collectors: hydrated iron(III) oxide (Fe(2)O(3).xH(2)O) and iron(III) tetramethylenedithiocarbamate (Fe(TMDTC)(3)). After the coprecipitation step and the addition of foaming agents, Tl(I) and Tl(III) were separated from the water by a stream of air bubbles. Various factors affecting Tl(I) and Tl(III) recoveries during the separation from water, including the collector mass, the nature of the supporting electrolyte, pH, zeta potential of the collector particle surfaces, type of tenside, etc., were investigated. Within the optimal pH range (6-6.5), establishing by a recommended procedure, Tl(I) and Tl(III) were separated quantitatively (94.9-100.0%) with 30 mg Fe(III). Both Tl ions were simultaneously separated without any previous conversion of one type of Tl ion to the other. Total Tl determination was performed by electrothermal atomic absorption spectrometry by previous matrix modification of the concentrated samples. The determination limit of Tl by this method is 0.108 mug l(-1).

Flame atomic absorption spectrometric determination of zinc after colloid precipitate flotation with hydrated iron(III) oxide and iron(III) tetramethylenedithiocarbamate as collectors.

Colloid flotation of zinc from fresh water with a combination of two collectors, hydrated iron(III) oxide (Fe(2)O(3).xH(2)O) and iron(III) tetramethylenedithiocarbamate (Fe(TMDTC)(3)), permits rapid separation of the precipitate before its atomic absorption spectrometric (AAS) analysis. All important parameters necessary for the successful flotation like optimal mass of collectors, pH of the medium, electrokinetic potential of the collector particle surfaces, type of tenside, induction time etc., were checked. At the optimal pH value of medium (5.5) establishing by recommended procedure, zinc was separated quantitatively (97.4-98.8%) with 5 mg Fe(III) as constitutive element of the two collectors used. The content of zinc was determined by flame atomic absorption spectrometry (FAAS). These results were compared with the results obtained by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The FAAS detection limit for zinc is 9.4 mug 1(-1). The proposed method is simple, rapid and applicable to the zinc separation at mug 1(-1) levels from a large volume of water.

Spectrophotometric determination of thallium in zinc and zinc-base alloys with iodoacetic acid and hexamethylenetetramine.

Thallium(III) forms a ternary complex of yellow colour with iodoacetic acid and organic bases, especially hexamethylenetetramine. The complex is soluble in water and various organic solvents. Zinc, copper, cadmium and iron do not form complexes with these reagents, so that a spectrophotometric determination of thallium in zinc and its alloys is possible. The limit of detection is 15 microg g(-1), the molar absorption coefficient about 2000 mol(-1) l(-1) cm(-1).

Composition of the essential oil from Thymus moesiacus from Macedonia.

Composition of the essential oil of Thymus moesiacus Velen. from Macedonia was examined by GC and GC-MS methods. The main constituents of the oil were geraniol, linalool, geranyl acetate, and terpenyl acetate.