Microplastic pollution in rivers of the Adriatic Sea basin in Montenegro: Impact on pollution of the Montenegrin coastline.

Concern regarding microplastic (MP) pollution in aquatic ecosystems has increased in recent years with growing awareness of the environmental harm that it causes. While most studies have focused on seas and oceans, knowledge of MP occurrence in freshwater sediments is limited. This study investigated MP concentrations at shore sediments of the Zeta, Moraca, and Bojana rivers in Montenegro. The MP concentration in the studied samples varied depending on the river, location, and sampling season. MP abundance in river shore sediments varied between mean values of 145 ± 110 MPs/kg for the Zeta, 169 ± 113 MPs/kg for the Moraca, and 180 ± 53.5 MPs/kg dry sediment for the Bojana. In comparison, the mean MP abundance in the three rivers combined was 163.6 ± 96.1 MPs/kg of dry sediment. The identified MPs were mainly fibres and fragments of blue, red and clear color, 0.5-1 mm in size, and mainly composed of polyethylene, polypropylene, polyamide and polyethylene terephthalate. The main contribution of this study is that it provides new insight into MP abundance in freshwater sediments of rivers, where the studied rivers were identified as a potential important sink and source of MP on the Montenegrin coast.

Self-Heating Flower-like Nanoconstructs with Limited Incorporation of Yttrium in Maghemite: Effect of Chemical Composition on Heating Efficiency, Cytotoxicity and Genotoxicity.

Partial cation substitution can significantly change the physical properties of parent compounds. By controlling the chemical composition and knowing the mutual relationship between composition and physical properties, it is possible to tailor the properties of materials to those that are superior for desired technological application. Using the polyol synthesis procedure, a series of yttrium-substituted iron oxide nanoconstructs, γ-Fe2-xYxO3 (YIONs), was prepared. It was found that Y3+ could substitute Fe3+ in the crystal structures of maghemite (γ-Fe2O3) up to a limited concentration of ~1.5% (γ-Fe1.969Y0.031O3). Analysis of TEM micrographs showed that crystallites or particles were aggregated in flower-like structures with diameters from 53.7 ± 6.2 nm to 97.3 ± 37.0 nm, depending on yttrium concentration. To be investigated for potential applications as magnetic hyperthermia agents, YIONs were tested twice: their heating efficiency was tested and their toxicity was investigated. The Specific Absorption Rate (SAR) values were in the range of 32.6 W/g to 513 W/g and significantly decreased with increased yttrium concentration in the samples. Intrinsic loss power (ILP) for γ-Fe2O3 and γ-Fe1.995Y0.005O3 were ~8-9 nH·m2/Kg, which pointed to their excellent heating efficiency. IC50 values of investigated samples against cancer (HeLa) and normal (MRC-5) cells decreased with increased yttrium concentration and were higher than ~300 µg/mL. The samples of γ-Fe2-xYxO3 did not show a genotoxic effect. The results of toxicity studies show that YIONs are suitable for further in vitro/in vivo studies toward to their potential medical applications, while results of heat generation point to their potential use in magnetic hyperthermia cancer treatment or use as self-heating systems for other technological applications such as catalysis.

Utilisation of waste Cu-, Mn- and Fe-loaded zeolites generated after wastewater treatment as catalysts for air treatment.

Disposal of copper, manganese and iron is particularly problematic in wastewater of metallurgical and galvanization plants, the electronics industry and agriculture. On the other hand, volatile organic compounds (VOCs), emitted from industrial processes, transportation and consumer products are the main class of air pollutants. The study revealed the potential of waste metal-loaded zeolite, generated through wastewater treatment procedures, to be utilised as an effective VOC removal catalyst for air treatment. In the first step, we have evaluated the sorption performance of natural zeolite clinoptilolite (HEU type), and synthetic zeolite 4A (LTA type) for the simultaneous removal of Cu2+, Mn2+ and Fe3+ species from aqueous solution. By a detailed sorption study, we determined the optimum sorption conditions and maximum metal concentrations in wastewater that can be after treatment disposed of in rivers or municipal plants. The efficiency of both zeolites for metal immobilization was demonstrated for concentrations up to 5 mg metals/1 g zeolite. These waste Cu-, Mn- and Fe-loaded zeolites were thermally treated at 540 °C before the second step, where we evaluated their catalytic performance in removing VOC. The thermally treated waste Cu-, Mn- and Fe-loaded natural zeolite clinoptilolite showed good catalytic performance in total toluene oxidation as a model VOC (conversion rate up to 96% at 510°C) and cycling stability (less than 15% drop in conversion rate in 4 h). In contrast, this is not the case for thermally treated waste Cu-, Mn- and Fe-loaded synthetic zeolite 4A.

The inhibitory effect of some pyrazole ligands and their Cu(II) complexes on the growth of Escherichia coli, Klebsiella-Enterobacter spp., and Staphylococcus aureus.

The aim of this study was to evaluate the inhibitory activity of chemistry products against the growth of Escherichia coli, Klebsiella-Enterobacter spp., and Staphylococcus aureus. Pyrazole derivatives (4-bromo-2-(1H-pyrazol-3-yl)phenol, 4-nitro-3-pyrazolecarboxylic acid, N-(benzyloxycarbonyl)-1H-pyrazole-1-carboxamidine), 3-amino-5-hydroxypyrazole, 3,5-pyrazoledicarboxylic acid monohydrate, and selected complexes of Cu(II) with the mentioned pyrazoles as ligands were used as chemistry bioactives for antibacterial activity. The testing method was carried out according to the disc diffusion method. Some compounds have shown inhibitory effects against the growth of E. coli. A small number of compounds have shown inhibitory effects against the growth of Klebsiella-Enterobacter spp. but did not show inhibitory effects on Staphylococcus aureus compared to amoxicillin as a standard.

First crystal structures of metal complexes with a 4-nitropyrazole-3-carboxylic acid ligand and the third crystal form of the ligand.

Pyrazole (pz)-derived ligands can, besides exhibiting a strong coordination ability toward different metal ions, exhibit a great diversity in their coordination geometry and nuclearity, which can be achieved by varying the type and position of the pz substituents. The present study reports the synthesis and crystal structure of two binuclear complexes, namely bis(µ-4-nitro-1H-imidazol-1-ide-5-carboxylato)-κ3N1,O:N2;κ3N2:N1,O-bis[aqua(dimethylformamide-κO)copper(II)], [Cu2(C4HN3O4)2(C3H7NO)2(H2O)2], (II), and bis(µ-4-nitro-1H-imidazol-1-ide-5-carboxylato)-κ2N1,O:N2;κ2N2:N1,O-bis[triaquacobalt(II)] dihydrate, [Co2(C4HN3O4)2(H2O)6]·2H2O, (III). These compounds represent rare examples of metal complexes comprising 3,4-substituted pz derivatives as a bridging ligand and also the first crystal structures of transition-metal complexes with ligands derived from 4-nitropyrazole-3-carboxylic acid. Recently, the crystal structures of the same ligand in the neutral and mixed neutral/anionic forms have been reported. We present here the third form of this ligand, where it is present in a fully deprotonated anionic form within a salt, i.e. ammonium 4-nitropyrazole-3-carboxylate, NH4+·C4H2N3O4-, (I). Single-crystal X-ray diffraction revealed that in the present complexes, the CuII and CoII centres adopt distorted square-pyramidal and octahedral geometries, respectively. In both cases, the N,N',O-coordinated pz ligand shows simultaneously chelating and bridging coordination modes, leading to the formation of a nearly planar six-membered M2N4 metallocycle. In all three crystal structures, the supramolecular arrangement is controlled by strong hydrogen bonds which primarily engage the carboxylate O atoms as acceptors, while the nitro group adopts the role of an acceptor only in structures with an increased number of donors, as is the case with CoII complex (III). The electrostatic potential, as a descriptor of reactivity, was also calculated in order to examine the changes in ligand electrostatic preferences upon coordination to metal ions.

Levels and distribution of cobalt and nickel in the aquatic macrophytes found in Skadar Lake, Montenegro.

Macrophytes react to changes in the quality of the environment in which they live (water/sediment), and they are good bioindicators of surface water conditions. In the present study, the content of the metals cobalt (Co) and nickel (Ni) was determined in the sediment, the water, and different organs of macrophytes from six localities around Lake Skadar, across four different seasons of year. The aquatic macrophytes that have been used as bioindicator species in this study are Phragmites australis (an emerged species), Ceratophyllum demersum (a submerged species), and Lemna minor (a floating species). The aim of this study was to determine the distribution of metals in macrophyte tissues and also to discover the degree of bioaccumulation of the investigated metals, depending both on the location and on the season. The content of Co and Ni in the examined parts of the macrophytes was in the range of 0.04-8.78 and 0.30-28.5 ppm, respectively. The greatest content of the investigated metal in the organs of P. australis and C. demersum was recorded at the beginning of and during the growing season. Greater concentrations of metals in the tissue of L. minor were observed at the end of the growing season.

Soil pollution fingerprints of children playgrounds in Sarajevo city, Bosnia and Herzegovina.

This is the first study, 10 years after the war activities, to report about the content of heavy metals and metalloids, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs) found in samples of soils from selected playgrounds in Sarajevo. Due to the fact that children are in direct contact with surface soils, it has been recommended that children's playgrounds should be given special consideration in this respect. Basic properties (pH in H2O, pH in 1 mol dm-3 KCl, humus, and CaCO3) of the examined soils were determined. Samples for the determination of heavy metals and metalloids were prepared by microwave-assisted acid digestion and determined by using an inductively coupled plasma optical emission spectrometer. Fluorine was determined potentiometrically. Gas chromatography with mass spectrometry was used for determination of PAHs and PCBs. Determined contents (mg kg-1) for Cd, Pb, Hg, Cr, Ni, Cu, Zn, Co, Mo, Fe, Se, As, B, and F were in the ranges from: 0.031 ± 0.03 to 0.52 ± 0.05; 26.1 ± 2.5 to 47.7 ± 4.5; 0.07 ± 0.01 to 0.50 ± 0.08; 26.2 to 50; 19.5 ± 1.6 to 33.3 ± 2.7; 12.8 ± 1.8 to 31.9 ± 4.5; 56.0 ± 4.0 to 89.0 ± 6.5; 6.7 ± 0.6 to10.6 ± 1.0; <0.8; 3.05 to 7.35; 1.98 to 2.60; 6.5 ± 0.8 to 17.2 ± 2.0; 0.4 to 3.6, and 286 to 575, respectively. The total PAHs ranged between 0.184 ± 0.32 mg kg-1 and 7.983 ± 1.389 mg kg-1. The total PCBs was <0.002 mg kg-1. Our preliminary results may contribute to more accurate health risk assessments of the soils, and may be included in projects planning children's health risk assessments and adopting environmental legislation which has not been sufficiently regulated in Bosnia and Herzegovina so far.

Environmental Status and geochemical assessment Sediments of Lake Skadar, Montenegro.

The environmental mobility and geochemical partitioning of ten metals were examined in sediments collected from the six locations around Lake Skadar in Montenegro. A three-step sequential extraction procedure was used to determine the distribution of the metals in various substrates of lacustrine sediments, and the concentrations were measured in the liquid extract by ICP-OES. The largest portion of the total amount of cadmium, strontium and manganese can be found in sediment bound to the hydrated iron and manganese oxides; cobalt, lead, copper and nickel in the oxidizable fraction and the highest portion of chromium, vanadium and zinc are in the residual fraction. The most mobilized and potentially mobile metals are strontium, cadmium and cobalt while the most immobilized metals are chromium, vanadium and zinc. Based on geochemical parameters, an assessment of sediment contamination by the investigated metals was performed and the results showed potential risks ranging from "no risk" to "low risk" to the environment.

Herbicide and pesticide occurrence in the soils of children's playgrounds in Sarajevo, Bosnia and Herzegovina.

Pesticide pollution in Sarajevo public playgrounds is an important health and environmental issue, and the lack of information about it is causing concerns amongst the general population as well as researchers. Since children are in direct contact with surface soils on children's playgrounds, such soils should be much more carefully examined. Furthermore, herbicides and pesticides get transmitted from soil surfaces brought from outside the urban areas, or they get dispersed following their direct applications in urban areas. Infants' and children's health can be directly affected by polluted soils because of the inherent toxicity and widespread use of the different pesticides in urban environments such as playgrounds. In addition to that, the presence of chromated copper arsenate (CCA) wood preservative pesticide found as soil pollutant in playing equipment was also documented. Soil samples from playgrounds were collected and analyzed for triazines, carbamates, dithiocarbamates, phenolic herbicides and organochlorine pesticides. Samples for the determination of heavy metals Cu, Cr and As were prepared by microwave-assisted acid digestion, and the findings were determined by using an inductively coupled plasma optical emission spectrometer. Triazines, carbamates, dithiocarbamates, chlorphenoxy compounds, phenolic herbicides, organochlorine pesticides and organotin compounds were detected in playground soils and their determined concentrations (mg/kg) were respectively found as follows: <0.005, <0.05, <0.5, < 0.4, <0.1, <0.001 and <0.004. The determined contents (mg/kg) of Cu, Cr and As were in the ranges from 16.77 to 80.21, from 7.14 to 15.45 and from 3.31 to 4.43, respectively. Our preliminary results raise concerns about potential adverse effects of herbicides and pesticides on human health, which strengthens the case for a more preventative and protective approach to the uncontrolled presence of herbicides and pesticides in Sarajevo's playground soils.

4-Di-chloro-methyl-4-methyl-5-(nitro-meth-yl)cyclo-hex-2-enone.

In the title compound, C9H11Cl2NO3, the six-membered ring adopts a screw-chair conformation. In the crystal, two different C-H⋯O hydrogen bonds involving the same acceptor atom connect the mol-ecules into a chain extending along the c-axis direction.

Transition metal complexes with pyrazole-based ligands. XXII. Part XXI: Mészáros Szécsényi, Leovac, Kovacs, Pokol & Jacimovic (2005). Di-mu-thiocyanato-bis[(3,5-dimethyl-1H-pyrazole-1-carboxamidine-kappa2N,N')(thiocyanato-kappaN)copper(II)] and a redetermination of bis(3,5-dimethyl-1H-pyrazole-1-carboxamidine-kappa2N,N')bis(nitrato-kappaO)copper(II).

The title Cu(II) complex, [Cu2(NCS)4(C6H10N4)2], represents the first crystal structure of a polynuclear transition metal complex with the 3,5-dimethyl-1H-pyrazole-1-carboxamidine ligand (HL). It is compared with previously reported crystal structures of metal complexes with the same HL ligand. The molecule contains an eight-membered binuclear Cu2(NCS)2 ring, which is centrosymmetric and in a chair conformation. The Cu atom has a distorted square-pyramidal geometry with a very elongated Cu-S bond of 2.993 (2) A. The crystal structure redetermination of the bis(3,5-dimethyl-1H-pyrazole-1-carboxamidine-kappa(2)N,N')bis(nitrato-kappaO)copper(II)complex, [Cu(NO3)2(C6H10N4)2], and analysis of its hydrogen bonds confirm the significance of the NO3 groups in the formation of a three-dimensional hydrogen-bonding network. Both complexes are centrosymmetric, the inversion centre being located at the mid-point of the Cu...Cu line in (I) and the Cu atom being located at the inversion centre in (II).

Tris(3,5-dimethyl-1H-pyrazole-1-thiocarboxamidato-kappa(2)N(2),N)cobalt(III).

In the crystal structure of the title complex, [Co(C(6)H(8)N(3)S)(3)], the Co(III) atom is octahedrally coordinated by three monodeprotonated bidentate 3,5-dimethyl-1H-pyrazole-1-thiocarboxamide ligands with two thiocarboxamide N atoms in axial positions. The asymmetric unit contains two molecules (A and B) and these molecules are arranged in chains in an alternating fashion connected by N-H...S interactions.