Manganese tolerance in Verbascum olympicum Boiss. affecting elemental uptake and distribution: changes in nicotinic acid levels under stress conditions.

A multielemental determination methodology in conjunction with an organic acid analysis that were supplemented with other stress parameters and an ultrastructural analysis used herein to study Verbascum olympicum Boiss. (Scrophulariaceae) under Mn stress. Uptake and accumulation characteristics of B, Cu, Fe, Mn, Mo, and Zn were evaluated in 8-week-old seedlings grown in Hoagland's nutrient solution and exposed to 5 (CK), 50, and 200 µM MnSO4 for 7 days. Hydrogen peroxide levels were determined to evaluate oxidative stress, and changes in compatible substance levels (total phenolic contents, glutathione and glutathione disulfide levels) were determined to assess antioxidant defense mechanisms. The distribution of manganese on the root surface was characterized by scanning electron microscopy images and energy-dispersive X-ray spectroscopy analysis. The levels of nicotinic acid, which is involved in nicotinamide adenine dinucleotide biosynthesis, were determined in roots and leaves to assess tolerance mechanisms. V. olympicum exhibited the ability to cope with oxidative stress originating from excessive Mn, while increased Mn concentrations were observed in both roots and leaves. The translocation factor of B was the most affected among other studied elements under the experimental conditions. Total nicotinic acid levels exhibited a trend of reduction in the roots and leaves, which could be attributed to the appropriate metabolic progress associated with oxidative stress based on the nicotinamide adenine dinucleotide cycle that may reach glutathione in response to manganese stress during plant growth.

Correlation of lithium bioaccessibility from tea (Camellia sinensis L.) with tea type and consumption habits.

In this study, the total contents, leachability into tea infusions, and bioaccessibility of lithium from black, Earl Grey, and green teas were evaluated by inductively coupled plasma mass spectrometry. Leachabilities were evaluated after infusion for 2, 5, or 10min. Bioaccessibility was determined in vitro under simulated stomach and intestinal digestion conditions. Addition of lemon juice, sugar, or milk for consumption, and calcium, tannic acid, and citric acid as additives were evaluated to determine if they affected bioaccessibility of lithium from black tea. The bioaccessible lithium contributed to 0.01%, 0.02%, and 0.03% of the recommended dietary allowances of lithium for black, Earl Grey, and green tea samples, respectively. These contributions may increase up to 4.4 times or decrease up to seven times with certain additives.

Elemental Composition of Plant Species from an Abandoned Tungsten Mining Area: Are They Useful for Biogeochemical Exploration and/or Phytoremediation Purposes?

We aimed to evaluate the elemental (W, Mo, Zn, Fe, Cu, Co, Bi, Mn, Cd, Cr, As) composition of some plant species spread around the abandoned tungsten mining area of Uludag Mountain. The plant species tested were Anthemis cretica and Trisetum flavescens which are grown in this area and they are pioneer species on these contaminated sites. W levels in soils were found up to 1378.6 ± 672.3 mg/kg dry weight in contaminated areas. The leaf W contents of the selected plant species were found 41.1 ± 24.4 and 31.1 ± 15.5 mg/kg dry weight for A. cretica and T. flavescens, respectively. Our results indicate that the elemental composition of species changed by the increased tungsten and some element concentrations in soil without detrimental effect. So, these species can be useful tungsten removal and some elements from contaminated sites.

Elemental composition of Marrubium astracanicum Jacq. growing in tungsten-contaminated sites.

This study evaluates the elemental (W, Mo, Zn, Fe, Cu, Cd, Mn, Pb, Cr, Co, B, and Bi) composition of Marrubium astracanicum Jacq. (Lamiaceae), around the abandoned tungsten mine on Uludag Mountain, Turkey, to determine if it is an appropriate candidate for phytomonitoring and/or phytoremediation purposes. Three sample sites were selected around the mine for soil and plant sampling. Two sites approximately 500 m from the mine were assumed to be unpolluted sites. The other site was selected from a waste removal pool (WRP) and was assumed to be a polluted site. The soil and different organs (roots, leaves, and flowers) of plant samples were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) to determine the elemental content. The classic open wet digestion procedure was applied to the samples with 5 mL HNO3 and 3 mL H2O2 in a borosilicate glass vessel for the roots, leaves, and the flowers of the plants. Kjeldahl digestion was used for the soil samples. The W, Zn, Fe, Cu, Cd, Mn, Pb, B, and Bi contents were found to be higher in the soil samples from the waste removal pools compared with the samples from the unpolluted sites. We also found that the elemental composition of M. astracanicum has generally been increased by the activity of the tungsten mine, and there were significant correlations between the elemental contents of the soil samples and plant parts, except for Mo and Cr. The high level of many elements in the soil samples indicates the presence of contamination related to tungsten-mining activity on Uludag Mountain. Assessing the elemental contents of M. astracanicum, we can suggest this species as a candidate for phytoremediation purposes of W-contaminated sites due to its high W-accumulation capacity.

Bioaccessibility of Copper in Turkish Hazelnuts (Corylus avellana L.) by Chemical Fractionation and In Vitro Methods.

Copper is known as either an essential or toxic trace element in foods to living organisms at sufficient or excess intake levels, respectively. In this study, in vitro simulated gastric and intestinal digestion methods combined with n-octanol extraction and activated carbon adsorption were applied to Turkish hazelnuts (Corylus avellana L.) to evaluate the bioaccessibility of copper. Additionally, analytical fractionation procedures based on water, diethyl ether, n-hexane, and methanol extractions were applied to identify copper-related matrix structures. The macrochemical compositions of the samples were determined to be associated with the fractionation results. The total contents of copper in the samples, digests, and fractions were determined by inductively coupled plasma mass spectrometry after microwave-assisted digestion, and additional validation was performed using atomic absorption spectroscopy. The limits of detection and quantification were 0.016 and 0.053 mg kg(-1), respectively. The bioaccessibility of copper was found to be in the range from 16 to 31 % for hazelnut samples. The recommended dietary allowance of copper for adults is 0.9 mg daily, and considering this value, 100 g of hazelnuts supplies 33-44 % of daily copper intake.

Ni-induced Changes in Nitrate Assimilation and Antioxidant Metabolism of Verbascum olympicum Boiss.: Could the Plant be Useful for Phytoremediation or/and Restoration Purposes?

Verbascum olympicum Boiss. (Scrophulariaceae) were studied as a candidate plant for remediating the Ni polluted soils. The metabolic responses, such as nitrate assimilation (nitrate reductase and glutamine synthetase activity) and antioxidant system activity [superoxide dismutase (SOD), catalase (CAT) and ascorbate peroxidase (APX) activity], of this species exposed to nickel in Hoagland's nutrient medium were investigated as remediation performance parameters. The accumulation of nickel and the variations in the content of some elements (B, Cu, Fe, Mg, Mn, Mo and Zn) and some growth parameters, such as the water content, biomass production, and contents of chlorophyll and soluble protein, were also examined. The accumulation of Ni in both the roots and leaves varied depending on the exposure times and doses. Increased oxidative stress was suggested by the increases in the activities of SOD, CAT and APX. Although some element contents were inhibited by Ni treatments, these inhibitory effects was decreased depending on the time, and even these elements are accumulated in roots. These results are the novelties in the use of this species in biotechnology.

Diethyl phthalate removal from aqueous phase using poly(EGDMA-MATrp) beads: kinetic, isothermal and thermodynamic studies.

In this study, poly(ethylene glycol dimethacrylate-N-methacryloyl-L-tryptophan methyl ester) [poly(EGDMA-MATrp)] beads (average diameter=106-300 µm), which were synthesized by co-polymerizing of N-methacryloyl-L-tryptophan methyl ester (MATrp) with ethylene glycol dimethacrylate (EGDMA), were used for diethyl phthalate (DEP) adsorption. The various factors affecting the adsorption of DEP from aqueous solutions such as pH, initial concentration, contact time and temperature were analysed. Adsorption behaviour of DEP on the poly(EGDMA-MATrp) beads was investigated by varying pH values of solution, contact time, initial concentration and temperature. An optimum adsorption capacity of 590.7 mg/g for DEP was obtained at 25 °C. The present adsorption process obeyed a pseudo-second-order kinetic model. All the isotherm data can be fitted with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. Thermodynamic parameters ΔH=7.745 kJ/mol, ΔS=81.92 J/K/mol and ΔG=-16.69 kJ/mol to -18.31 kJ/mol with the rise in temperature from 25 °C to 45 °C indicated that the adsorption process was endothermic and spontaneous.

Fractionation analysis of manganese in Turkish hazelnuts (Corylus avellana L.) by inductively coupled plasma-mass spectrometry.

In this study, an analytical fractionation scheme based on water, diethyl ether, n-hexane, and methanol extractions has been developed to identify manganese-bound fractions. Additionally, in vitro simulated gastric and intestinal digestion, n-octanol extraction, and activated carbon adsorption were used to interpret the manganese-bound structures in hazelnuts in terms of bioaccessibility. The total content of manganese in the samples was determined by inductively coupled plasma-mass spectrometry after microwave-assisted digestion, and additional validation was performed using atomic absorption spectroscopy. Water fractions were further evaluated by high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry for the identification of water-soluble manganese fractions in hazelnut samples. The limits of detection and quantification were 3.6 and 12.0 µg L(-1), respectively, based on peak height.

Removal of diethyl phthalate from aqueous phase using magnetic poly(EGDMA-VP) beads.

The barium hexaferrite (BaFe(12)O(19)) containing magnetic poly(ethylene glycol dimethacrylate-vinyl pyridine), (mag-poly(EGDMA-VP)) beads (average diameter=53-212 µm) were synthesized and characterized. Their use as an adsorbent in the removal of diethyl phthalate (DEP) from an aqueous solution was investigated. The mag-poly(EGDMA-VP) beads were prepared by copolymerizing of 4-vinyl pyridine (VP) with ethylene glycol dimethacrylate (EGDMA). The mag-poly(EGDMA-VP) beads were characterized by N(2) adsorption/desorption isotherms (BET), vibrating sample magnetometer (VSM), X-ray powder diffraction (XRD), elemental analysis, scanning electron microscope (SEM) and swelling studies. At a fixed solid/solution ratio, the various factors affecting the adsorption of DEP from aqueous solutions such as pH, initial concentration, contact time and temperature were analyzed. The maximum DEP adsorption capacity of the mag-poly(EGDMA-VP) beads was determined as 98.9 mg/g at pH 3.0, 25°C. All the isotherm data can be fitted with both the Langmuir and the Dubinin-Radushkevich isotherm models. The pseudo first-order, pseudo-second-order, Ritch-second-order and intraparticle diffusion models were used to describe the adsorption kinetics. The thermodynamic parameters obtained indicated the exothermic nature of the adsorption. The DEP adsorption capacity did not change after 10 batch successive reactions, demonstrating the usefulness of the magnetic beads in applications.

Assesment of dimethyl phthalate removal from aqueous phase using barium hexaferrite containing magnetic beads.

The barium hexaferrite (BaFe(12)O(19)) containing magnetic poly (ethylene glycol dimethacrylate-vinyl pyridine; mag-poly [EGDMA-VP]) beads (average diameter=53-212 µm) were synthesized and characterized. Their use as an adsorbent in the removal of dimethyl phthalate (DMP) from an aqueous solution was investigated. The mag-poly (EGDMA-VP) beads were prepared by copolymerizing of 4-vinyl pyridine (VP) with ethylene glycol dimethacrylate (EGDMA). The mag-poly (EGDMA-VP) beads were characterized by N(2) adsorption/desorption isotherms (BET), vibrating sample magnetometer (VSM), X-ray powder diffraction (XRD), elemental analysis, scanning electron microscope (SEM), and swelling studies. At a fixed solid/solution ratio, the various factors affecting the adsorption of DMP from aqueous solutions such as pH, initial concentration, contact time, and temperature were analyzed. The maximum DMP adsorption capacity of the mag-poly (EGDMA-VP) beads was determined as 96.2 mg/g at pH 3.0, 25 °C. All the isotherm data can be fitted with both the Langmuir and the Dubinin-Radushkevich isotherm models. The pseudo-first-order, pseudo-second-order, Ritch-second-order, and intraparticle diffusion models were used to describe the adsorption kinetics. The thermodynamic parameters obtained indicated the exothermic nature of the adsorption. The DMP adsorption capacity did not change after 10 batch successive reactions, demonstrating the usefulness of the magnetic beads in applications.

Common vetch (Vicia sativa L.) germplasm: correlations of crude protein and mineral content to seed traits.

In order to increase knowledge of seed nutritive value and to demonstrate its relationship in common vetch (Vicia sativa L.) germplasm, 388 common vetch accessions were grown under field conditions in 2008-2009 growing season in Bursa province of Turkey. Seeds were analyzed for seed minerals (Ca, Cu, Mg, Mn, P, S, Zn and K) and crude protein (CP) content. The accessions were grouped according to testa and cotyledon color and seed size, and the results were evaluated by analysis of variance to determine relationships between minerals and CP content, testa and cotyledon colors, and seed weight. In general, there was no significant difference between testa colors or cotyledon colors in minerals and CP content. However, seed weight was closely associated with minerals and CP contents in this study. Analysis of variance and correlation analysis showed that seed weight was closely associated with some minerals and CP content. The small seeds had significantly higher Ca, Cu, Mg, Mn, S, Zn and CP contents than medium and large seeds.

Determination of some phthalate acid esters in artificial saliva by gas chromatography-mass spectrometry after activated carbon enrichment.

The determination of six phthalate acid esters was achieved in artificial saliva using gas chromatography-mass spectrometry following activated carbon enrichment of samples. Central composite experimental design was applied to optimize method parameters, such as pH, adsorption time and amount of activated carbon. The best compromise of analytical conditions for the simultaneous determination of analytes from spiked artificial saliva were found to be: pH (3), adsorption time (30 min), activated carbon amount (1.8 g L(-1)) and elution solvent (chloroform). These conditions were applied to study the migration of phthalate acid esters from different children's toys into saliva. A horizontal agitation method was applied to extract the analytes from plastic toys into saliva for 2h at 37°C. The detection limits of the method were in the range of 1.3-5.1 µg L(-1), while the relative standard deviation (%) values for the analysis of 100 µg L(-1) of the analytes were below 3.0% (n=5). Di-2-ethylhexyl phthalate was the main analyte found in these samples.

Occupational lead exposure: blood lead levels of apprentices in Bursa, Turkey.

The aim of this cross-sectional study was to compare the blood lead levels of apprentices working in lead-related industries with those of non-apprentice controls and to evaluate the influence of such occupational exposure. The study was conducted between October 2004 and June 2005 in Bursa, Turkey. Subjects included 231 apprentices and 252 male controls, age ranging from 14-19 yr old. Inductively coupled plasma mass spectrometry (ICP-MS) was used to analyze blood lead levels. The overall mean blood lead level was 3.62 microg/dl (95% CI 3.39-3.85), the apprentice mean was 4.99 microg/dl (95% CI 4.60-5.38), and the control group mean was 2.37 microg/dl (95% CI 2.22-2.51). The blood lead level of apprentices was significantly higher than that of controls (p<0.05). Results show that occupational exposure increases the blood lead levels of apprentices, although the impact on their immediate health is low. Measurement of blood lead levels of apprentices should be taken periodically, and a regular medical surveillance program should be established.

Photocatalytic degradation of Congo Red by hydrothermally synthesized nanocrystalline TiO2 and identification of degradation products by LC-MS.

Degradation of Congo Red (CR) dye in aqueous solutions was investigated by means of photocatalysis of TiO2 which was hydrothermally synthesized at 200 degrees C in 2 h, in anatase phase with 8 nm crystallite size. Efficiency of TiO2 in photocatalytic degradation under visible irradiation was studied by investigating the effects of amount of TiO2, irradiation time, initial CR concentration and pH. It was found that complete decolorization is achieved within 30 min of irradiation. Effects of nitrate and sulphate ions and humic acid on the degradation were also tested. The results were compared with Degussa P-25 TiO2 at the same degradation conditions. Degradation products were detected using LC-MS technique. The probable pathways for the formation of degradation products were proposed.

Element content (Cu, Fe, Mn, Ni, Pb, and Zn) of the ruderal plant Verbascum olympicum Boiss. from East Mediterranean.

In this study, heavy metal content (Cu, Fe, Mn, Ni, Pb, Zn) was determined in soils and different organs of Verbascum olympicum Boiss. This species is endemic to Uludag and spreads on destroyed areas such as: roadsides, developed building areas, ski lift stations and sheep folds. Soils and different organs (roots, stems, leaves and flowers) of plant samples were analyzed using an atomic absorption spectrophotometer for determining the element content. Heavy metal contents in soils and different organs in this species were highly correlated (P < 0.05). However, the contribution of plant organs to the accumulation capacity varied according to the metal. These results suggest that this species may be useful as a bioindicator for heavy metals.

Selective determination of aluminum bound with tannin in tea infusion.

In this study, an analytical method for indirect measurement of Al bound with tannin in tea infusion was studied. This method utilizes the ability of the tannins to precipitate with protein. Separation conditions were investigated using model solutions. This method is uncomplicated, inexpensive and suitable for real samples. About 34% of the total Al in brew extracted from commercially available teas was bound to condensed and hydrolyzable tannins.

Blood lead levels of traffic policemen in Bursa, Turkey.

This study was conducted in January 2001, in Bursa, Turkey. Of the 99 traffic policemen who were included in the study, 21 were office workers. Blood lead levels were determined by using an electro-thermal atomic absorption spectrometer (ET-AAS). Average blood lead levels were 9.4 +/- 1.6 micrograms/l and 8.7 +/- 1.7 micrograms/l for policemen working outdoors and indoors, respectively. The difference between the two groups was statistically insignificant (P > 0.05). When policemen less than 15 years on duty were taken into account (n = 48) the difference between the outdoors and indoors working groups was significant (9.3 +/- 1.3 and 8.2 +/- 1.8 micrograms/l, P < 0.05). In order to prevent the negative effects of tetraethyl lead on humans and the environment the use of lead in petrol must be prohibited.