Fresenius Environmental Bulletin

Publications
Potentially paramagnetic elements such as Fe, Cu, and Mn, did not affect NMR sensitivity and T1p(H) values of humic materials from volcanic soils, despite a large ash content in the extracts. T1p(H) values increased with increasing C/H ratios, thereby confirming a relationship between the number of protons bound to carbons and process of relaxation in solid humic materials. Differences in T1p(H) values were explained by molecular composition of the samples. Few carbon-bound protons and high molecular rigidity in highly aromatic humic matter reduced the efficiency of the relaxation. Humic samples richer in polar carbons showed variable T1p(H) values due to different molecular rigidity conferred by intermolecular hydrogen bonds. Not only the number, but also the distribution of protons in humic molecules appeared to affect T1p(H) values.
 
This paper presents results of trace metal monitoring in the coastal waters of the eastern Adriatic (Croatian coast), during the 2001-2005 period, using the Mediterranean blue mussel (Mytilus galloprovincialis) as indicator species. Levels of essential (Cu, Zn) and non-essential (Cd, Cr, THg, Pb) metals were determined in a whole soft tissue of mussels collected from 20 locations along the eastern Adriatic coast. Examination of the spatial pattern of contaminants revealed two types of metal distribution. Lead, chromium, copper, zinc and total mercury were significantly elevated in the urban and industrial areas. Concentrations of Cr and Cd were more uniformly distributed across all sites. Elevated concentrations of Cd were also found in mussels from rural areas located far away from known anthropogenic sources of contamination. Although elevated concentrations of all trace metals were recorded in the areas with high input of industrial, harbor and urban wastes, the obtained data provide no proof of the significant pollution along the eastern Adriatic coast. Analysis of temporal trends showed that metal concentrations had not changed with time during the monitoring period. With few exceptions, 98% of values were well below the permissible limits for fresh seafood.
 
This study deals with the development of thermally modified bentonite as an effective adsorbent for the removal of imazapyr herbicide from aqueous solution. XRD, SEM, and TGA analyses were used to characterize the material. Bentonite was calcined at 350-550°C for 3 and 12 h. Calcination at 350-500°C for 12 h increased the specific surface area strongly. Sample calcined at 500°C shows the highest surface area of 43.6 m 2/g (BET) and 750 m 2/g (BM). The calcined bentonite-500°C adsorbed approximately 65 % of imazapyr at an initial concentration of 30 mg/L, while bentonite adsorbed only 33 % under the same conditions. The effects of various factors on the adsorption, such as contact time, pH of the solution and amount of adsorbent, were studied. For both bentonite and bentonite-500°C the adsorption isotherm has been determined and data have been analysed according to the Freundlich model and found to be favourable.
 
Agricultural areas in Northern Greece were subjected to cloud seeding with AgI over a period of 12 years in order to suppress hailstone formation and protect crops from damage. Potential soil pollution due to the Ag used and Ag mobility were investigated. Soil samples taken from undisturbed surface soils and from three soil depths were analysed. Average Ag concentrations at soil depths of 0-10, 10-20 and 20-30 cm were 87, 51 and 43 ppb, respectively. Silver mobility through various soil substrates and into plants was investigated in a two-year pot experiment. Silver iodide or AgNO3 were applied to the pot soil surface and grass species seeded were periodically watered, simulating a natural rainfall pattern. Silver was quantified in water leachates, in grass shoots, and in the pot soil profile at the end of the experiment. Silver was not detected in water leachates, exhibiting a very slow motion through the soil columns. Plants absorbed Ag, but in minute quantities, when supplied in the form of AgI, whereas appreciable amounts of Ag were absorbed from the much more soluble AgNO3 form.
 
The Hellenic Organization of Agricultural Insurance carried out cloud seeding with silver iodide (AgI) over two agricultural regions in Northern Greece, Hemathia-Pella (200000 Ha) and Serres (100000 Ha), for 12 years in the former and 13 years in the latter, in order to suppress hailstone formation. The possibility of soil pollution due to Ag input was investigated by analyzing 2500 soil samples. A spectrophotometric method capable of detecting Ag in ppb quantities in soil samples was developed, reflecting the low total amount of AgI used in cloud seeding in the two regions (469 and 361 kg, respectively). Average Ag concentrations in soils of Hemathia-Pella (45 ppb) and Serres (37 ppb) were found to be within the range of those in control areas and comparable to those reported in the literature for unpolluted soils.
 
Microorganisms respond rapidly to changing environ-mental conditions. Therefore microbes are generally con-sidered as sensitive indicators of soil health. The aim of this study was to assess the biological fertility status and sustainability of three differently managed agricultural soils by using microbial indicators. Management practices in-volved a soil with minimum treatment (biodynamic); a soil characterized by periodic application of manure and chemi-cal fertilizer (manure); and a soil characterized by depu-rated and stabilized organic sludge amendment (sludge). Samples were taken four times during a year, at two depths: 0-15 and 15-30 cm. An extensive characterization of soil organic matter was carried out. Biochemical parameters in-cluded metabolic quotient, mineralization quotient and kinetic parameters of microbial decomposition of soil or-ganic matter. Community level physiological profile analy-sis (CLPP) was used to investigate soil microbial energetic strategies adopted in differently managed soils. Total amounts of fungi and bacteria were determined by direct microscopy. Indicators related to labile and humic organic matter fractions suggest significantly lower soil fertility and lower sustainability in the sludge amended treatment. Differences between the biodynamic treatment and Manure treatment were less consistent. Eco-physiological quotients and kinetic parameters of C-mineralization indicated a steady state in the biodynamic treatment and stressed con-ditions in the sludge treatment. Microbial communities seem to adopt a typically K-strategy (persistent) in the bio-dynamic treatment and a typically r-strategy (opportunists) in the sludge treatment. Manure management shows an in-termediate result: the superficial layer is characterized by r-strategists and the deeper layer by K-strategists.
 
Environmental diagnosis of supra-littoral and semi-intensive shrimp farm systems (SCS) in the northwestern part of Mexico had been developed for a 10-years period (1993 to 2003). The activities in the construction, operation and abandonment phases were evaluated by an environmental impact diagnosis analysis, causal diagrams, complex analysis systems, relevant environmental criteria analysis, and fuzzy logic impact assessment. The SCS, divided in Natural and Socioeconomic subsystems, showed important negative impact in the construction phase affecting the flora and fauna because of vegetation removal, but as positively was detected the employment because of the number of people hired. During the operation phase, positive impacts in the Socio-economic subsystem (SEC) were produced by high-educated employments offers, and increase of life quality. Opposite, the most important negative effect was caused by pollutant-enriched water discharges. In the abandonment phase, negative effects were identified by soil salinization, acidification, erosion increase, or the ecologic barriers' role that ponds play. The combination of the methods applied in this work help to identify in an ordinal way the magnitude of the environmental impacts on shrimp cultures in any region and different conditions.
 
We analyzed PCBs in sediment cores from Osaka Bay (an industrial area), Lake Biwa (both suburban and rural areas), and a background sampling area in Japan. The historical trends in PCB levels nearly matched the trends in Japanese PCB production. The deposition flux of PCBs was in the order of Osaka Bay > Lake Biwa > background sampling area. Principal component analysis was applied to profiles of dioxin-like PCB congeners. Two principal components were interpreted as the degree of chlorination and the contribution of incineration by-product, respectively.
 
Chemical composition of oil polluted with PCB. 
Effects of PCB congeners chosen for biodegradation under aerobic conditions. 
Commercial biological mixtures of microorganisms, especially suitable for the utilisation of hydrocarbons in polluted soil and water, and one PCB-degrading strain were used for biodegradation of PCB-containing waste transformer oil. High degradation effects of low chlorinated PCB congeners, 2-CB and 3-CB, were observed during aerobic process. Under these conditions also the higher chlorinated congeners, 6-CB and 7-CB, were degraded. The PCB biodegradation effects in the solution of hydrocarbons were observed for congeners with six or seven chlorine atoms. The non-specific enzymes could provide PCB biodegradation in a way different to the via dioxygenase attack.
 
Teaching organic chemistry should be a compulsory element in university education in the field of chemistry and related subjects. However, most curricula are still based on traditional laboratory classes in chemistry. They focus on teaching basic experimental techniques for synthesis and analysis and demonstrate potential chemical hazards. The efficiency of a chemical transformation is usually only measured by the chemical yield of the product obtained. Students do not learn how to determine the overall efficiency of a reaction, which directly correlates with its sustainability. The aspect of the efficiency and sustainability of a reaction must be added to the content of teaching courses in organic chemistry. Within this considerably wider scope students learn how to plan, set up, and analyse organic reactions taking their effects on man and the environment into account. Within an inter-university research project of nine institutes from seven universities we develop a free accessible internet database, which provides all necessary material, amongst others covering experimental procedures, toxicity data, alternative reaction procedures to discuss and assess a chemical reaction in a much wider sense. The provided information can be individually adapted to a specific course.
 
We discuss the effect of long-term elevated CO2 on quality and decomposability of litter from mature trees, and its influence on soil organic matter (SOM) dynamics by evaluating the available data from mineral CO2 springs in Central Italy. Results from the vegetation around these natural CO2 springs demonstrate that elevated CO2 did not affect litter quality. Consequently, C and N mineralization rates remained unaffected by CO2 level. However, there were significant differences in litter quality and decomposition between species. Results from soil analysis indicate that elevated CO2 increased the total organic C content and C pool sizes in the F layer, but not in HA and 0-10 cm layers. Neither were soil N, C/N ratio and the decomposition of SOM affected by elevated CO2. Soil N mineralization in the forest floor seems to be enhanced by CO2 enrichment.
 
In this paper the binding ability of functional groups present in the cell walls of an ubiquitous soil fungus, Trichoderma viride Pers.: Fr., towards some divalent heavy metals, Cd, Co, Cu, Pb and Zn, was studied. Processing the data from potentiometric titrations of T. viride by the McCallum, Midgley and Gran’s combined methods, the surface of the cell wall was characterised in terms of functional group total acidity, distinguishing among strong, weak and very weak acidity. The dissociation constant values of weak and very weak acid, pKa1 and pKa2, respectively, were graphically determined using the Henderson-Hasselbach equation. Titration data of T. viride in the presence of metal were processed with the Bjerrum’s method as adapted by Gregor for determining the conditional stability constants of metal complexes with synthetic polyelectrolytes in terms of log K1 and log K2. Here has been used for 1:1 and 1:2 metal- T. viride complexes, respectively.
 
Using compost in agriculture can cause environmental problems because it may contain toxic substances. Particular attention should be paid to the possible presence of heavy metals in compost. However, in these cases the severity of pollution depends on the chemical form of the heavy metals. Studies on the environmental effects of heavy metal levels in compost showed that the amount of pollution varies according to soil type, plant species and compost quality. Experiments have therefore been carried out with lettuce ( Lactuca sativa ) grown in soils amended with different types of compost (leaves of beached Posidonia oceanica were used as a matrix), which had high concentrations of heavy metals. The total concentrations of Pb, Zn, Cd, Cr, Ni and Cu were determined in soils samples, leaves and lettuce roots. Finally, a sequential extraction of heavy metals in soil samples was carried out. Comparisons were made with non-amended soil. In the compost-amended soil samples, there was an increase in the total heavy metal concentration. The percentage of metals extracted by H<sub>2</sub>O was low in all the soil samples. The percentage of metals extracted by Ca(NO<sub>3</sub>)<sub>2</sub> and EDTA was variable, depending on the metals analysed. There was no significant difference in the heavy metal concentrations between leaves and roots in all the plants examined. Finally, the results showed that the use of compost obtained from leaves of beached P. oceanica as a matrix did not cause accumulation of heavy metals in lettuce plants.
 
In an environmental pollution research some wild animals, deceased due to accidental causes, were collected from all over Sardinia. In order to detect the possible residues of unknown pollutants the isolated livers of these animals, previously lyophilized, were analyzed. First, by a GC-MS method, we identified the p,p<sup>1</sup>-DDE and some PCBs belonging to 5, 6, 7, 8 series PCBs. Later we set up a method for quantification of these compounds, using chicken liver as a model, by GC-ECD. The spiked chicken liver, free from p,p<sup>1</sup>-DDE and PCBs, was lyophilized and extracted by supercritical fluid extraction (SFE), subsequently the solutions obtained were subjected to cleanup by solid phase extraction (SPE). Finally, this method was employed to quantify p,p<sup>1</sup>-DDE and PCBs in the samples of the specimens collected.
 
This paper discusses the pros and cons of economic instruments for environmental management. The theoretical discussion highlights the importance of economic concepts for the design of a rational environmental policy. However, the application of economic instruments may be limited by the prevailing technical, economic and ecological conditions. Therefore, a three-step approach towards policy design is recommended which takes into account these conditions. Such an approach can significantly enhance the practical relevance of economic instruments.
 
Owing to extensive practical applications and fundamental importance, the controllable synthesis of well-faceted anatase TiO2 crystals with a high percentage of reactive facets has attracted increasing attention. Here, a novel visible light responsive graphene (GR)-CuO/TiO2 photocatalyst was successfully synthesized by a simple hydrothermal method. The morphology, structural properties, and photocatalytic performance of GR-CuO/TiO2 were investigated and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse reflectance spectroscopy. In particular, the new photocatalyst GR-CuO/TiO2 exhibited a better performance for the photocatalytic degradation of methylene blue (MO) under visible-light irradiation than pure TiO2 and P25, which may be attributed to efficient reduction of electron-hole pair recombination and an extended spectral response from the UV to the visible region. This work is expected to open up new possibilities for the simple remediation of environmental pollution.
 
An indigenously isolated basidiomycete Pleurotus ostreatus IBL-02 was used for decolorization of reactive textile dye Drimarene Blue K2RL (C.I. Reactive Blue 209). In initial time course trial P. ostreatus caused 69.2% decolorization of 0.01% Drimarene Blue K2RL synthetic solution after 5 days using Kirk's basal nutrient medium in shake flask cultures. Effect of varying pH, temperature, carbon and nitrogen sources and initial dye concentration on dye decolorization was investigated. By optimization of decolorization parameters, % decolorization of Drimarene Blue K2RL solution could be enhanced to 97.86 % in 3 days at pH 3 and 30 °C by the addition of 1% glucose (carbon source) and 1% ammonium sulphate (nitrogen source). The optimally de-colorized culture filtrates were analyzed for lignolytic enzymes. Ligninase assays showed that the fungus synthesized all ligninases. Lacasse (460 U/mL) was the major enzyme involved in dye degradation, followed by manganese peroxidase (443 U/mL) and lignin peroxidase (157 U/mL).
 
White rot fungi (WRF) are suitable microorganisms for treating a broad range of organic pollutants and synthetic textile dyes because of their non-specific extracellular enzyme system. An indigenous novel strain, Pleurotus ostreatus IBL-02, was screened for its ability to decolorize four reactive dyes (Drimarene Brilliant Red K-4BL, Drimarene Golden Yellow K-2R, Drimarene Orange KGL and Drimarene Blue K-2RL). Samples were removed after 10 days, centrifuged and supernatants were analyzed for determination of enzyme activities and percent dye decolorization. Flasks containing Drimarene Brilliant Red K-4BL showed 73% dye color removal after ten days with lacease production of 64 IU/ml, followed by 42 IU/ml manganese peroxidase (MnP) and only 1.0 IU/ml lignin peroxidase activity. The fungus also caused 53% decolorization of Drimarene Orange K-GL with 49 IU/ml, 18 IU/ml of lacease and MnP, respectively, but no LiP was detected. The maximally decolorized dye Drimarene Brilliant Red K-4BL was selected for subsequent enhanced lacease production and dye decolorization studies. Using modified medium IV (pH 5; temperature, 35 °C) supplemented with glucose (2 g/100 ml) as carbon source, ammonium nitrate (0.06g/100 ml) as nitrogen source, copper (1 mM) as metal activator and ABTS (2 ml of 10 mM) as mediator, Pleurotus ostreatus produced 321 IU/ml of laccase to completely decolorize the Drimarene Brilliant Red K-4BL within 24hours.
 
A new white rot fungus Ganoderma lucidum IBL-05 was used to decolorize the reactive textile dye Cibacron Turquoise P-GR in shake flask cultures. In an initial time course study of 10 days the fungus showed maximum decolourization (58.5%) of the dye in 7 days. The decolorizing ability of the fungus could be substantially improved by optimizing the operational conditions such as medium composition, initial pH, incubation temperature, additional carbon and nitrogen sources and, initial dyestuff concentration. Media composition and, type of carbon and nitrogen sources played a significant role. The results showed that modified Kirk's nutrient medium M-II was the best at pH 4.5 and 30°C temperature for dye decolourization; 85 % decolourization was observed after 3 days when the medium was supplemented with molasses (0.1%) as a carbon source. The enzyme profile of G. lucidum IBL-05 was also studied and manganese peroxidase was the dominant enzyme activity involved in biodegradation of Cibacron Turquoise P-GR by G. lucidum IBL-05 with minor activities of lignin peroxidase and laccase.
 
A bacterial strain D-B was isolated from aerobic activated sludge. Based on the biochemical test results, the strain was identified as a gram-negative bacterium, Alcaligenes sp., which could grow on 1,1-dichloroethylene (1,1-DCE) as the sole carbon and energy source. Moreover, 1,1-DCE degradation characteristics of strain D-B were investigated , and it was found that biological removal rate of 1,1-DCE increased at first, but then decreased with increasing of 1,1-DCE, and degradation mainly took place within 3-5 h after adding 1,1-DCE. Removal rate of 1,1DCE attained the maximum value of 85.32% when its initial concentration was 300 ug/L. The Monod equation was used to describe the kinetics of 1,1-DCE degradation (kinetic parameters were as follows: K s= 21.96 mg/L, Vmax=50.76 mg/(L-h)).
 
Solvent removal procedures (rotary evaporation or blowing down) may be accompanied with the loss of volatile organochlorines. Loss will most likely happen to compounds with a high vapor pressure, and therefore particularly to α-HCH. A new internal standard to monitor recoveries in sample preconcentration procedure was found with perdeuterated α-HCH (α-PDHCH). α-PDHCH and α-HCH show identical behaviour in the sample clean-up but are easily separated by gas chromatography. Recoveries of α-HCH in solvent removal procedures by blowing down with nitrogen and rotary evaporation were compared with those of ε-HCH and α-PDHCH. Careful solvent removal yielded high recoveries for all compounds. Significant losses of α-HCH and α-PDHCH were obtained when blowing down and rotary evaporation were continued after dryness was achieved. The loss of α-PDHCH and α-HCH was identically but the less volatile ε-HCH yielded higher recoveries than α-HCH and α-PDHCH. Thus, α-PDHCH is much better suitable as internal standard than ε-HCH to monitor presumable losses of volatile compounds.
 
We investigated in preliminary studies the removal of 3(5)-amino-1,2,4-triazole in aqueous solution by the photo degradation processes in the presence of titranium dioxide (TiO2) at different ratios of herbicide/TiO2 (weight/ weight) coupled with simulated sunlight. This photocatalytic degradation was evaluated at pH values 5, 6 and 7. Irradiation was carried out with polychromatic light using heraeus apparatus equipped with xenon lamp having a spectral energy distribution similar to solar irradiation (> 290 nm). The concentration of remaining herbicide was monitored using a high pressure liquid chromatograph (HPLC) equipped with UV detector at 205 nm. The presence of TiO2, induced an increase of the photodegradation of the pesticide with respect to pure water solution. By varying the pH in the range 5-7, no effect on rate of photodegradation of 3-amino-1,2,4-triazole with TiO2 (ratio 1/5) was observed.
 
Klebsiella species are excellent 1,3-propanediol (1,3 PDO) producers. Klebsiella pneumoniae is a well-studied microorganism and, therefore, its metabolic pathway is known. Accordingly, a number of by-products are simultaneously produced together with 1,3 PDO. Optimization of medium composition significantly decreased these byproducts' concentrations. Optimization of culture media concentrations on 1,3 PDO production by K pneumoniae was studied using statistical experimental designs and analysis, namely, Taguchi Orthogonal Array (TOA) and BoxBehnken design (BBD). The optimal composition of the fermentation medium for maximum 1,3 PDO yield, with a L18 (2∧1 × 3∧7) design using TOA, and after that, a threelevel three-factor BBD, was obtained. The most significant chemicals were found to be glycerol (p<0.0001) and K 2HPO 4 (p<0.05). MgSO 4.7H 2O, which is the third significant factor obtained from TOA, was not found to be significant (p>0.05) from BBD. A maximum 1,3 PDO concentration of 23.6 g/L was obtained which is higher compared to that foreseen by the statistical model (9.3 g/L).
 
-Proposed reaction scheme / mechanisms for one-pot MC reductive dechlorination of 1,3,5-TCB to benzene employing magnesium and n-butylamine (n-BuNH2). It shows three consecutive coupled Grignard formation and Zerewitinoff reactions.
-Postulated detailed reaction scheme for the protonation of intermediary 3,5-dichlorophenylmagnesium chloride by n-butylamine yielding 1,3-DCB (adapted from the literature [31-33]). Because the amine is applied in excess in this work, the overall protonation step is assumed to be of pseudo first-order regarding the concentration of the Grignard compound (see rate equations 2, 4 and 6 below).
1,3,5-Trichlorobenzene (TCB) is completely dechlorinated to benzene when treated with magnesium and nbutylamine at room temperature in a ball mill. A full mass balance is observed for its stepwise reductive dechlorination via the intermediates 1,3-dichlorobenzene (DCB) and monochlorobenzene (MCB). This mechanochemical (MC) reaction occurs due to ongoing, simultaneous comminution and mechanical activation of small particle size magnesium during milling. The base metal is utilized as the actual dechlorinating agent whereas n-butylamine as a hydrogen donor. A kinetic study reveals that consecutive and coupled one-pot Grignard-Zerewitinoff reactions occur: MC activated formations of intermediary Grignard components from 1,3,5-TCB, 1,3-DCB and MCB, take place each first, and then stepwise their protonation to DCB, MCB and benzene, respectively, by the amine, which reacts as a (weak) acid towards strong bases such as Grignard reagents. An appropriate reaction model comprising a corresponding set of rate equations (ordinary differential equations (ODEs) representing an initial value problem) could successfully be fitted to two data sets recorded for a representative model degradation reaction of 1,3,5-TCB at two different initial concentrations. The rate constants for the formation of the postulated intermediary Grignard components were computed, hence this method can readily be extended to determine Grignard formation rate constants in general as well. Results are in very good accordance to data recently reported for an analogous MC reductive dechlorination reaction of 1,3-DCB and correspond well, too, to other data previously reported elsewhere. In conclusion, MC reductive dechlorination employing base metals in combination with hydrogen donors can be applied as a promising non-combustion method to the environmentally friendly, defined and well characterized destruction of persistent organic pollutants (POPs) at room temperature.
 
Control Group, seminiferous tubules, germ cells and interstitial area, Masson's trichrome, X 40
Body weight with Paired Samples T Test
The purpose of the study is to investigate the damage caused by iron (Fe) and zinc (Zn) heavy metals in the testis tissue of rats and the protective impact of juglone-an antioxidant in preventing this damage-with the help of histological and immunohistochemical methods. Adult, male Wistar-Albino rats raised in Suleyman Demirel University Experimental Animals Production and Experimental Research Laboratory (HADYEK) were used in this study. Subjects were randomly grouped into 5. Group I; iron (Fe) (iron from 0.3 ml stock solution/600 ppm. + 0.7 ml. water), Group II; zinc (Zn) (zinc from 0.2 ml stock solution/400 ppm + 0.8 ml. water), Group III; iron (iron from 0.3 ml stock solution /600 ppm.) + Antioxidant (juglone (5-hidroxy-1,4-naphthoquinone)/200 ppm- 0.7 ml.), Group IV; zinc (zinc from 0.2 ml stock solution/400 ppm.)+Antioxidant (juglone (5-hidroxy-1,4-naphthoquinone)/200 ppm-0.7 ml.+ 0.1 ml. water), Group V; Control (1 ml. Water); gavage was applied to each group once a day throughout 30 days. At the end of the experiment, rats were decapitated and their testis tissues removed, then histological staining and TUNEL method were applied following the routine histological follow-ups. Based on the histopathological examinations, significant damage was observed in the testis tissue of the groups administered with Fe and relatively Fe+Juglone. The most explicit findings were; partly ruptures in seminiferous tubules epithelium and decrease in thickness of epithelium, dissociation in basal lamina of the seminiferous tubules, decrease in the number of germ cells, intense edema and congestion in the interstitial area, and vacuolization in the seminiferous tubules epithelium. The damage associated with the Zn and Zn+Juglone was determined to be less significant than the damage by Fe and Fe+Juglone group. Based on the TUNEL method, a significant increase was observed in the number of apoptotic cells in Fe, Fe+Juglone and Zn groups compared to the control group (p<0.05). No significant difference was observed between the Zn, Zn+Juglone group and control group.
 
The principle aim of this study was to evaluate the anti-biofilm activity of newly synthesized hexahydroimidazo [1,5-a] pyridinium bromides with varying benzyl substituents to test as biofilm eradication agents against 10 opportunistic pathogens. To our knowledge this important aspect of their anti-biofilm and antioxidant activity has not yet been discussed in the literature. Anti-biofilm activity of benzyl substituted hexahydroimidazo[1,5-a]pyridinium bromide salts (B1-B9) was tested accoriding to microtitre plate method. Additionally, the best biofilm production of E.coli ATCC 8739 was monitoring with SEM (Scanning Electron Microscopy). The antioxidant activity of these salts were studied by the method of ABTS (2,2 azinobis( 3-ethylbenzothiazoline-6-sulfonic acid)) radical cation. In this study we have shown that these compounds possess excellent, broad spectrum antibiofilm activity against opportunistic microorganisms: The bacteria Staphylococcus aureus, Staphylococcus epidermidis, Bacillus cereus, Micrococcus luteus, Proteus vulgaris, Escherichia coli, Salmonella typhimurium, Klebsiella pneumoniae and the yeasts Candida albicans, Candida krusei. All of these compounds inhibited bacterial and fungal biofilm formation at concentrations ranging from 0.78 to 400 μg/mL, 3.12 to 50 μg/mL, respectively (biofilm inhibitory concentration=BIC). Additionally, these compounds have been found to possess antioxidant potential with the highest inhibitory percentage of 92.4% using ABTS radical cation assay. The obtained results revealed that all the salts displayed anti-biofilm and antioxidant activity against the tested microorganisms, indicating that these salts could use in the design of new therapeutics and more effective antimicrobials for the control and prevention of biofilm infections caused by the spread of pathogenic microorganisms to the environment.
 
The estimation of persistence and range belongs to the most urgent tasks with regard to the environmental assessment of chemicals which have the potential to distribute ubiquitously. The most direct proof for the ubiquitous occurrence of anthropogenic chemicals is their analytical detection in remote areas; this is not practicable, however, due to the great number of chemicals in question. For a preselection, multimedia models of differing complexity seem to be suitable. The most powerful model with regard to resolution in time and space is based on a global circulation model. This model has been tested with a set of model compounds. The work done by the authors, aimed at testing simpler models with the same set of substances in order to find out, whether the results give at least the same tendency compared to the complex model. The models chosen for this purpose include Chemrange 1.0 + 2.1 and SimpleBox 2.0. The results presented here are restricted to a comparison between the two evaluative models and to persistence under different use pattern scenarios. The model compounds include α-HCH, γ-HCH, atrazine, DDT, PCB-28, -52,-101 and benzo[a]pyren (BaP). The results agree well for the first four compounds, but much less so for the PCBs and BaP.
 
-Characteristics of the ion exchange resin.
In this study, removal of copper and zinc in wastewater was studied by using Purolite C-104. The removal efficiencies as a function of initial heavy metal concentrations, contact time, and resin dosage were investigated over experimental periods lasting 30 to 180 min. Adsorption isotherms were calculated according to the linear form of the Langmuir and Freundlich isotherms. The result showed that the Freundlich adsorption capacities of Zn+2 and Cu2 on Purolite C-104 were calculated as 2.96 mg g-1 and 1.803 mg g-1. Langmuir adsorption capacities for Zn+2 and Cu+2 were calculated as 7.92 and 1.218 for Purolite C-104. The experimental data were well fitted to the Langmuir isotherm model with a reasonable R2 value.
 
Boron is known as a trace element for animals and humans. Sodium borates are used in some cosmetics, detergents, and chemicals of photography, adhesives and textile compounds. It was aimed to evaluate the antioxidant potentials and genotoxic risk of sodium borate (Na(2)B4O(7)center dot 10H(2)O) on human whole blood cultures in the extent of this study (n=5). Na(2)B4O(7)center dot 10H(2)O was administrated at wide range concentrations (0-1280 mu g/ml) to cultured human whole blood samples. The sister chromatid exchange (SCE), micronucleus (MN) and 8-oxo-2-deoxyguanosine (8-OH-dG) assays were performed to determine genotoxic effect. In addition, total antioxidant capacity (TAC) and total oxidative stress (TOS) levels were measured as biochemical parameters. Our results clearly demonstrated that all tested concentrations of Na(2)B4O(7)center dot 10H(2)O were not mutagenic. Moreover, Na(2)B4O(7)center dot 10H(2)O showed antioxidant activities especially at low concentrations (<40 mg/L) and the determined TOS levels did not change at all the concentrations of Na(2)B4O(7)center dot 10H(2)O. As a result, our data clearly demonstrated that Na(2)B4O(7)center dot 10H(2)O is non-genotoxic and it has a remarkable antioxidant potential in vitro.
 
The influence of cyfluthrin-degrader, a novel Lysinibacillus sphaericus strain, FLQ-11-1, with respect to biodegradation effectiveness and its effects on soil microbial community simulating in situ, was evaluated. Two 4-kg soil samples containing 100 mg/L of cyfluthrin were set up, one without cyfluthrin degrader inoculation and one inoculated with degrader. The results showed that the cyfluthrin concentration in the inoculated soil declined by 99.45% within 28 days, whereas in strain-free samples, this concentration decreased by 29.1%. The amount of culturable bacteria in the inoculated soil grew faster in the 7 days after inoculation than in the strain-free sample, although it was low in both samples. PLFA profiles of soil after inoculating strain FLQ-11-1 displayed significant difference, with the character of biomark 18:0 negative related to cyfluthrin residue content. microrganisms L. sphaericus and P. amygdali, were only detected in the the soil inoculated with FLQ-11-1, while R. leguminosarum and Nitrosospira sp., were special microbes in the free soil, and twelve bacterium were in common. And strain FLQ-11-1 were the advantage organism in the 28 day, accomplying with the microbial diversity recovery. These results showed that strain FLQ-11-1 could well colonized in the cyfluthrin-polluted soil, although change the indigenous microorganism community diversity in its earlier bioremediation action, but contribute to recover the indigenous microorganisms community with decreasing of cyfluthrin in the soil.
 
-Effects of Cd on the contents of soluble protein in leaves of Populus 118 exposed to Cd stress for 40 days. Vertical bars denote SE (n = 5). Values with different letters are significantly different from each other (p < 0.05) according to t-test.  
-TEM micrographs of chloroplasts from control and Cd-treated Populus 118 for 40 days (a. chloroplasts with a well-developed lamellar system and the grana layers in control cell; b-c. slightly changed chloroplast in the plant exposed to 50 µM Cd. Note slightly disintegrated thylakoid membranes and disrupted chloroplast grana (arrows); d. strongly swollen thylakoids and dissolved grana in the plant treated with 100 µM Cd (arrows); e-f. disorganization of grana, increased number of plastoglobuli, breakdown of chloroplast membrane and irregular chloroplast shapes (rounded in shape) at 500 µM Cd; abbreviations: C, cytoplasm; Ch, chloroplast; CM, chloroplast membrane; CW, cell wall; DCM, damaged chloroplast membrane; G, grana stack; M, mitochondria; P, plastoglobuli;, S, starch grain).  
Photosynthetic parameters (chlorophyll pigment, soluble protein and chlorophyll fluorescence) and ultrastructural changes in leaves of Populus 118 {Populus nigra × Populus ussuriensi) grown in the presence of different concentrations of Cd were investigated. The results from photosynthetic parameters indicated that soluble protein contents in leaves, exposed to 100 and 500 μmol/L Cd, increased significantly at 20th day but declined at 40th day. At the end of the experiment, the contents in leaves exposed to all Cd treatments were significantly lower. The contents of leaf pigments exposed to Cd for 40 days decreased significantly. Decrease tendency in photochemical efficiency of PSII (Fv′/Fm′), actual photochemical efficiency of PSII (ΦPSII), electronic transfer rate (ETR) and photochemical quenching (qP) were observed, whereas qN had an increasing tendency. The results from ultrastructural effects induced by Cd showed that a 100 umol/L Cd treatment resulted in variable degrees of structure disruption/damage of chloroplasts within the thy-Iakoid membrane system. At high Cd levels (500 μmol/L), the toxicity symptoms in chloroplasts were mainly the disorganization of grana, increased number of plastoglobuli, breakdown of chloroplast membrane, and changes of chloroplasts (rounded in shape and irregular in outline).
 
In the present study, Pistacia atlantica seed extract ability in a batch system to remove Reactive Red-120 from aqueous solutions was investigated. The effects of major operating variables, such as coagulant dose (0.05-4 ml L -1), initial dye concentration (20,40, 80,100,150 and 200 mg/L) and pH (2-12), were investigated. The optimum pH for Reactive Red-120 removal by coagulation using Pistacia atlantica seed extract was 12 with a coagulant dose 0.1 ml/L, and the highest removal was found to be 58.2, 60.17, 59.89, 62.31, 69.26 and 70.04% at initial dye concentrations of 20, 40, 80, 100, 150 and 200 mg/L, respectively, as a result of precipitation, co-precipitation and adsorption mechanisms. Also, turbidity addition to samples with various dye concentrations improved dye removal efficiency. According to the achieved results, it was defined that Pistacia atlantica seed extract not only is an inexpensive coagulant, but also a quite effective factor in removal of Reactive red-120 from aqueous environments.
 
In the present study, activated carbon obtained from cumin herb wastes was used as an adsorbent for the removal of Reactive Red-120 (RR-120) textile dye from aqueous solutions. The influence of parameters including concentration of dye (10-200 mg L-1), contact time (5-180 min), adsorbent dosage (0.1-1.4 g L-1) and initial pH (2-12) has been investigated in order to find the optimum adsorption conditions. Optimum pH for removing of RR-120 dye was found to be 2, and for this condition maximum adsorption capacity was obtained to be 47.88 mg g-1. Experimental results have shown that by increasing the adsorbent dosage, dye removal rate was increased but amount of adsorbed dye per mass unit of adsorbent was decreased. Also, the equilibrium data were fitted to the Langmuir, Freundlich and BET equilibrium isotherms. It was found that the data fitted to BET (R2=0.9864) better than Langmuir (R2= 0.9761) and Freundlich (R2=0.9308) models.
 
A preconcentration technique, which includes Amberlite IR-120 cation exchange resin, was applied for the determination of thallium traces in river water. Analysis of synthetic thallium solutions consistently yielded >95% recovery with negligible cross contamination. The certified reference material was used to test the accuracy of the method described. Water samples collected from selected stations of Lower Sakarya River were analyzed for dissolved thallium concentrations were found to be 120 ± 8 ng L-1 for Sakarya köprüsü and 110 ± 6 ng L-1 for Adliye köprüsü. The preconcentration factor for thallium ion was found as 100. As a result, simple, accurate, highly sensitive, and efficient solid phase extraction method was developed for preconcentration trace thallium species prior to determination by ICP-MS. Thus, the experimental results showed that Amberlite IR-120 cation exchange resin can be used for thallium determination.
 
Dye wastewater pose high pH and strong color to the environment. Single process for treatment of dye wastewater would be inefficient. Large amount of dosages for neutralization and chemical treatment are required, leading to the rapid increase of the cost of treatment. In this study, a combined adsorption/coagulation process was studied by using magnesia as an adsorbent and polyaluminum chloride (PAC1) as a coagulant. The removal of C.I. Reactive Red 120 was optimized using response surface methodology (RSM). The effect of treatment sequence, pH, dosages and initial dye concentration were investigated. It was indicated that dosing magnesia before PACI was more efficient than dosing PAC1 before magnesia. The optimal conditions obtained were as follows: magnesia dosage 2.5 gl-1, PACI dosage 15×10-3 gl-1 and pH 12.0. Under the optimal conditions, more than 80% of dye removal efficiency was achieved as the initial dye concentration increased from 0.1 to 2 gl-1. Based on these results, low-cost materials were applied and the dosages were optimized. The adsorption/coagulation process was considered to be cost-effective. The disadvantages of a single process were overcome and significant dye removal efficiency was obtained in the alkaline pH range. Therefore, alkaline dye waste was quite suitable to be treated with the process without neutralization.
 
Application of ultraviolet activated persulfate for degradation of Reactive Orange 122 (RO122) as a model organic pollutant in water was studied. Almost no dye degradation is achieved by UV and persulfate alone. However, 97% of the dye content is eliminated using UV illumination and peroxydisuifate simultaneously within 30 min. The effect of different parameters, such as UV irradiation, peroxydisuifate concentration, dye concentration, light intensity and temperature on the removal of RO122 was investigated. Influence of temperature on UV/S2O82- process was examined in the range of 10-70 °C, and a simple kinetic power law model joint with Arrhenius equation was introduced for prediction of the degradation rate. The degradation rate of RO122 is described by a pseudo first order kinetic model, including temperature parameter.
 
A strain TR-13 capable of highly degrading triclopyr was isolated from soil. The strain TR-13 was identified as Bacillus cereus based on 16S rRNA and analysis of morphology, physiological and biochemical characters. The optimal pH value and temperature were 7.0-7.5 and 30-35C. The 7d degradation rate of 100 mg/L triclopyr by strain TR-13 could reach about 98.5% in inorganic salt medium. The strain TR-13 could hydrolyze triclopyr to 3,5,6-trichloro- 2-pyridinol(TCP) ,but could not degrade TCP as the sole carbon source for its growth. The combined applications of the strain TR-13 and the strain CM-Z6 was considered an effective means for degrading triclopyr, because the strain CM-Z6 could degrade TCP. The degradation rate of triclopyr (100mg/L) by the strain TR-13 and the strain CM-Z6 could reach about 99% in 6d. In addition, the strain TR-13 could tolerate 800 mg/L of triclopyr and showed a high tolerance to triclopyr.
 
Stable isotope is a powerful method for characterizing flows of energy through ecosystems. The power of this method, however, may be affected by preservation methods of the samples. We investigated the effects of four common preservatives (salt, formalin, and ethanol and freezing [control] and preservation duration (six and three months) on delta N-15 and delta C-13 values of two freshwater fish species, Perca fluviatilis (perch) and Blicca bjoerkna (silver bream). Six-month preservation caused little enrichment in delta N-15 of both species compared to three month but had almost the same effects on delta C-13 values of both species as in three-month preservation. All methods caused significant shifts (enrichment) in delta N-15 of both species, and the effects in general were greater in perch (range: 0.28 parts per thousand-2.19 parts per thousand) than in bream (range: 0.31 parts per thousand-1.29 parts per thousand), which suggested that preservative induced shifts in delta N-15 was species-specific. The methods caused little enrichment (ethanol-range: 0.03 parts per thousand - 0.26 parts per thousand bream and 0.30 parts per thousand-0.48 parts per thousand perch and salt: 0.18 parts per thousand perch three month) and depletion (salt-range: 0.03 parts per thousand-0.13 parts per thousand bream and 0.13 parts per thousand perch six month) in delta C-13. Of the preservatives, however formalin had significant but consistent effects on delta C-13 in both species (-1.27 parts per thousand and -1.25 parts per thousand) for the entire preservation duration. Preservation-induced shifts in delta C-13 were consistent in direction and magnitude for both species. The results suggested that ethanol and salt could be used without correction factor and formalin with correction factor for preservation of samples solely in delta C-13 studies.. For the studies requiring use of carbon and nitrogen together, however, ethanol at least six month in preservation may be suitable for storing samples when considering detection of changes less than 2 parts per thousand is required in ecological applications.
 
Feta the most common cheese in Greece, was produced from sheep milk by a procedure normally used in Greece. The effect of artificially added I-131 on the ripening of feta cheese was studied. The contamination was introduced directly to milk (25 KBq/Kg milk). The rate of ripening was evaluated up to two months by determining the pH, moisture, fat, total N, non protein N, brine concentration, ash, free fatty acids, ripening and salt coefficients. Microflora evaluation during ripening was also studied. It was found that the radioisotope I-131 decreased the viability of Lactobacillus bulgaricus and Streptococcus thermophilus, had no critical effect on pH, had mininal effect on proteins, fats, total solids, free fatty acids and caused little change on ripening and salt coefficients.
 
Yoghurt, a cultured milk product, routinely consumed in Greece, was prepared from cow milk and sheep milk by a procedure normally used in Greece. The behavior of artificially added 131I on lactic acid microflora was studied. The lactic acid bacteria (LAB) counts decreased by 45% in the "set style" or "Strained style" yoghurt due to the presence of 131I.
 
The effect of artificially added I-131 on lactic acid bacteria (LAB) in cheese butter and their by-products, cheese whey and buttermilk, was studied. The radioisotope was introduced directly to cow milk and cream in doses equivalent to 10,000 Bq/Kg. After homogenization and cooling, milk and cream were inoculated with 1.5% mixed activated cultures (Streptococcus thermophilus-Lactobacillus bulgaricus and Streptococcus lactis-Streptococcus diacetylactis,1 :1 in ratio). The results demonstrate that the radioisotope I-131 decreased the LAB counts by 29.5% and 25.8% in cheese and butter and by 33.3% and 29.0% in cheese-whey and buttermilk. The presence of I-131 had minimal or no effect on the gross composition and percent yield of both products, but Lactobacillus bulgaricus was more sensitive to I-131 than Streptococcus thermophilus.
 
In this paper, a low-cost combustion system was developed to effectively destruct HFC-134a. Meanwhile, a series of experiments were carried out in the combustion system. The effects of operation parameters such as excess air ratio, type of flame (Premixed flame and Premixeddiffusive flame) and HFC-134a/LPG on the HFC-134a decomposition efficiency were also investigated. The experimental results indicated that a maximum HFC-134a decomposition efficiency of 99.98% was achieved when excess air ratio was above 0.9 and HFC-134/LPG was below 0.8 in the premixed diffusive flame. Meanwhile, the excess air ratio and HFC-134a/LPG ratio had a significant impact on the HFC-134a destruction efficiency. Moreover, the premixed flame was better than the premixed-diffusive flame for decomposing HFC-134a. Although HFC-134a decomposition efficiency was as high as 98.5%, there were still some byproducts such as C2H2F 2, CHF3 and C2H3F in the flue gas, which was proven by gas chromatography mass spectrometry analyzer (GC-MS).
 
Top-cited authors
Mustafa Soylak
  • Erciyes Üniversitesi
Mustafa Sevindik
  • Osmaniye Korkut Ata university
Ayman El Sabagh
  • Siirt Üniversitesi
Hasan Akgül
  • Akdeniz University
Hossam El-Beltagi
  • King Faisal University