Journal of Applied Science Studies

Journal of Applied Science

Volume 2, Issue 1 Studies March 2009

Influence of nitrogen and boron nutrition on nutrient balance A Study of Surface Durability of Polymer Sheets Exposed to and Sugar beet yield UV, Heat And grown in calcareous Soil Combined Condition of Water Effects Hellal, F.A., Taalab, A. S. and Safaa, A. M. Hale Gezer, Murat Eric

The Effects of Different Additives on Silage Gas Production, Fermantation Kinetics The Petrographic Properties of the Epiclastites in Neogen and Silage Quality Volcanic Succession B. Zehra Sariçiçek and Ünal KILIÇ and Usage as Admixture in Pozzolanic Cement Production (Çemisgezek/Tunceli, Numerical Solution of One-Dimensional Stefan-Like Problems Turkey) Using Three Sevcan Kürüm, Dicle Bal Akkoca Time-Level Method Vildan Gülkaç A New Species of the Genus Psephellus (Asteraceae) From North-East Anatolia, Turkey A numerical application of the semi-implicit pseudo-spectral Ahmet Duran, Meryem Öztürk & Bekir Dogan method for the Korteweg-de Vries Equation V. Gulkac, T. Ozis A Study into Organizational Commitment and Job Establishing Conditions for Determination of Inorganic Involvement: Arsenic By Using Flotation and An Application Towards the Personnel in the Central Preconcentration Techniques Organization for Ministry of Safiye Atar and Ümit Ay Health in Turkey Akyay UYGUR Computer Aided Power Control for Wound Rotor Induction Generator Fluid Inclusion Studies in the Different Origin Quartzs Fevzi Kentli Associated with Cu-Pb-Zn Mineralizations at Kizildag and Köprücük-Harput, East Kernel Smoothing Function and Choosing Bandwidth for Anatolian District, Turkey Non-Parametric Leyla Kalender, Ahmet Sagiroglu and Sumru Kisman Regression Methods Murat Kayri and Gürol Zırhlıoglu

Globalization and its Effects on the Banking System performance in Egypt Ezzat Molouk Kenawy

Influence of Potassium Humate on Growth and Chemical constituents of Thuja Orientalis L seedlings. Sahar, M. Zaghloul, E.M. Fatma, El-Quesni and Azza A.M.Mazhar

OZEAN JOURNAL of APPLIED SCIENCE A PEER REVIEVED INTERNATIONAL JOURNAL

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Volume 2, Issue 1, MArch 2009

ONLINE ISSN 1943-2542 PRINTED ISSN: 1943-2429

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Managing Editor Ali Ozel, Dumlupinar University

Publication Coordinator Taskin Inan, Dumlupinar University

Editorial Board

Gerald S. Greenberg, Ohio State University, USA Mihai Maxim, Bucharest University, Romania

Hakki Yazici, Afyon Kocatepe University, Turkey Ibrahim Atalay, Dokuz Eylul University, Turkey

Hayati Akyol, Gazi University, Turkey Ibrahim S. Rahim, National Research Center, Egypt

Hayati Doganay, Ataturk University, Turkey Janet Rivera, NOVA University, USA

Laurie Katz, Ohio State University, USA Ramazan Ozey, Marmara University, Turkey

Lisandra Pedraza, University of Puerto Rico in Samara Madrid, Northern Illinois University, USA Rio Piedras, Puerto Rico Samia Abdel Aziz-Ahmed Sayed, National Research Lutfi Ozav, Usak University, Turkey Center, Egypt

OZEAN JOURNAL of APPLIED SCIENCE A PEER REVIEVED INTERNATIONAL JOURNAL

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Volume 2, Issue 1, March 2009

ONLINE ISSN 1943-2542 PRINTED ISSN: 1943-2429

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Influence of nitrogen and boron nutrition on nutrient balance and Sugar beet yield grown in calcareous Soil Hellal, F.A., Taalab, A. S. and Safaa, A. M.

The Effects of Different Additives on Silage Gas Production, Fermantation Kinetics and Silage Quality B. Zehra Sariçiçek and Ünal KILIÇ

Numerical Solution of One-Dimensional Stefan-Like Problems Using Three Time-Level Method Vildan Gülkaç

A numerical application of the semi-implicit pseudo-spectral method for the Korteweg-de Vries Equation V. Gulkac, T. Ozis

Establishing Conditions for Determination of Inorganic Arsenic By Using Flotation and Preconcentration Techniques Safiye Atar and Ümit Ay

Computer Aided Power Control for Wound Rotor Induction Generator Fevzi Kentli

Kernel Smoothing Function and Choosing Bandwidth for Non-Parametric Regression Methods Murat Kayri and Gürol Zırhlıoglu

Globalization and its Effects on the Banking System performance in Egypt Ezzat Molouk Kenawy

Influence of Potassium Humate on Growth and Chemical constituents of Thuja Orientalis L seedlings. Sahar, M. Zaghloul, E.M. Fatma, El-Quesni and Azza A.M.Mazhar

A Study of Surface Durability of Polymer Sheets Exposed to UV, Heat And Combined Condition of Water Effects Hale Gezer, Murat Eric

The Petrographic Properties of the Epiclastites in Neogen Volcanic Succession and Usage as Admixture in Pozzolanic Cement Production (Çemisgezek/Tunceli, Turkey) Sevcan Kürüm, Dicle Bal Akkoca

Journal of Applied Sciences 2(3), 2009

A New Species of the Genus Psephellus (Asteraceae) From North-East Anatolia, Turkey Ahmet Duran, Meryem Öztürk & Bekir Dogan

A Study into Organizational Commitment and Job Involvement: An Application Towards the Personnel in the Central Organization for Ministry of Health in Turkey Akyay UYGUR

Fluid Inclusion Studies in the Different Origin Quartzs Associated with Cu-Pb-Zn Mineralizations at Kizildag and Köprücük-Harput, East Anatolian District, Turkey Leyla Kalender, Ahmet Sagiroglu and Sumru Kisman

A peer revieved international journal ONLINE ISSN 1943-2542 PRINTED ISSN: 1943-2429

http://ozelacademy.com/ojas.htm

Ozean Journal of Applied Sciences 2(1), 2009

Influence of nitrogen and boron nutrition on nutrient balance and Sugar beet yield grown in calcareous Soil

Hellal, F.A., Taalab, A. S. and Safaa, A. M. Plant Nutrition Dept., National Research Centre, Dokki, Egypt Email: [email protected]

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Abstract: In a greenhouse experiment, plant of sugar beet (Beta vulgaris L.) cv. Pamela were grown in calcareous soil with different N and B levels, in order to investigate the effect of applied nitrogen and boron as well as their interactions on yield and nutrient distribution and ratios in shoots and roots of sugar beet plants. This study included nine treatments three mineral nitrogen fertilizer levels (60, 80 and 100 mg N kg -1 soil) as soil application of ammonium sulphate and four boron treatments (0, 25, 50 and 100 ppm) as boric acid foliar spray. The obtained results showed that increasing N level up to 80 mg N kg -1 significantly increased root and shoot yield and P, K and Fe. Application of 50 ppm Boron significantly improved the parameters of the yield of roots and above ground growth and nutrient contents and balance ratio of sugar beet. The combined application of N-B treatments at the rate of 100 mg N kg -1 + 50 ppm B gave the maximum shoot and root yield and nutrient balance whereas increasing the B application until 100 ppm appeared to have a toxic effect on plant growth. The results concluded that B found also to interact positively with nitrogen to affect yield components of sugar beet. The interaction from the applied N and B increased N, K and Fe distribution between root and shoot. The yield of sugar beet was highly and positively correlated with N, K and B content in root and shoot.

Keywords: boron content, root yield, nutrient ratio, foliar fertilization ______

INTRODUCTION

Sugar beet is considered the second sugar crop for sugar production in Egypt after sugar cane. Recently, sugar beet crop has been an important position in Egyptian crop rotation as a winter crop not only in fertile soils, but also in poor, saline, alkaline and calcareous soils. Sugar beet is one of the most important sugar crops worldwide. Allen and Pilbeam (2007) stated that sugar beet crop has high requirements for boron (B). Boron is required for all plant growth. Adequate B nutrition is critical for high yields and quality of crops. Boron increases the rate of transport of sugars (which are produced by photosynthesis in mature plant leaves) to actively growing regions and also in developing fruits. Boron is essential for providing sugars which are needed for root growth in all plants and also for normal development of root nodules in legumes such as alfalfa, soybeans and peanuts

Boron is by far the most important of the trace elements needed sugar beet because, without an adequate supply, the yield and quality of roots is very depressed [Cooke and Scott, 1993]. Soil application, as well as, a foliar spray of boron is equally effective, hence the root fresh weight, sucrose %, root and top yields significantly increased by increasing boron levels [Jaszczolt, 1998].

The effects of nitrogen on the boron nutrition of plants have consistently shown that nitrogen reduces boron toxicity but there have been conflicting reports on the effects of nitrogen on boron deficiency. In cotton

1 Ozean Journal of Applied Sciences 2(1), 2009

boron deficiency may have been involved in yield reductions caused by high rates of nitrogen (Gupta, 1979), but with sugar beets nitrogen fertilizers decreased boron deficiency symptoms (Hemphill , 1982).

The addition of nitrogen was shown to depress boron uptake by lucerne and it is probable that the death of the lucerne in the nil boron treatments was caused by severe boron deficiency. The effect appears to be due to a physiological interference in the plant rather than an effect of the nitrogen on the availability of boron in the soil. However, it was not possible to determine whether the nitrogen affected the distribution of boron between the roots and shoots as well as its entry to the roots Willett et al. (1985).

Bonilla et al (1980) studied the effects of deficient and toxic levels of boron on various aspects of nitrogen metabolism in sugar beet are studied. Plant analysis shows a nitrate ion accumulation, a decrease in the activity of the nitrate reductase enzyme and lower molybdenum absorption. Pospišil et al. (2005) concluded that, the application of 50 l/ha of Fertina B (3% N + 4% B) increased the root and sugar yields by 16.7 %. Further increase of Fertina B rates reduced the root and sugar yields and lowered the technological quality of sugar beet roots.

Kristek et al. (2006) studied the effect of foliar fertilization with Fertina B element (1.0 kg B/ha) on sugar beet root yield and quality was investigated compared to the control variant, root yield is higher by 13.86 t/ha (19.4%), sugar concentration higher by 1.46% (relative 10.8%) and sugar yield higher by 3.15 t/ha (39.5%). Based upon these results, foliar fertilization with 1.0 kg B/ha is suggested for soils characterized by insufficient boron supply. It should be added through two top dressings, first prior leaves formation and second 10 -14 days later.

Ouda (2007) studied the effect of chemical and bio-fertilizer of N and boron as well as their interactions on yield and quality of sugar beet. The results of interaction effects showed that significant interactions of application of nitrogen and serialine + boron, but most of them did not give additional information except root yield and sugar yield ton/ fed. Therefore, the objective of this work aims to investigate the effect of nitrogen on the boron nutrition of sugar beet in a calcareous soil with low boron availability.

MATERIALS AND METHODS

A pot experiment was conducted in the green house of National Research Centre, Dokki, Cairo, Egypt in order to investigate application of nitrogen and boron rates on root yield and nutrient contents of sugar beet (Beta vulgaris L.) cv. pamela grown in calcareous soil conditions. Physical and chemical properties of soil site are shown in Table 1 according to methods described by Jackson, 1973.

Polyethylene pots (50 x 35 cm) were filled with 15 kg soil. Each pot received 2.0 g calcium super phosphate (15.5 % P 2O5) and 4.0 g potassium sulphate (48.0% K 2O) before sowing. Five uniform seeds of sugar beet were sown and thinned after 30 days to one plants per pot. Sugar beet plants were harvested after 170 days from sowing date. The fresh weights of leaves and tubers were recorded. All samples were dried at 70 0C oven for 48 hr. The dried plant samples were finely grinded and analyzed for N, P, K, B and Fe according the methods described by (Cottenie et al. 1982).

The experiments were set up in a two factor-completely randomized design with three replicates. Nitrogen levels as 60, 80 and 100 mg N kg -1 soil in the form of ammonium sulphate (20.6 % N) were arranged in the main treatments and applied in three equal doses (25, 50 and 120 Days. While the boron rates as 0, 25, 50 and 100 ppm B in the form of Boric acid (17.0 %) were applied as foliar spray in two sprays (40 and 80 days) and randomly distributed in sub treatments. The obtained data of yield and nutrient analysis were statistically analyzed according to (Snedecor and Cochran 1980).

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Table 1. Physical and chemical characteristics of the soil used

Characters Values and evaluation Characters Values and evaluation Sand (%) 82.84 Macronutrients mg kg -1 soil Silt (%) 4.73 N 52.11 L Clay (%) 12.50 P 4.32 L Texture Loamy sand K 173.10 M Micronutrients (ppm) pH (1:2.5) 8.35 H Fe 2.66 L -1 EC (1:5) dS m 2.26 H Mn 1.71 M CaCO 3 (%) 11.82 H Zn 0.42 L OM (%) 1.15 M Cu 0.33 M B 0.28 L L: low, M: Marginal, H: high

RESULTS AND DISCUSSION Shoot and Root yield Data in Table (2) showed that either nitrogen or boron has a significant positive effect on shoot and root yield of sugar beet crop grown in calcareous soil. Application of 100 mg N kg -1 soil gave the highest fresh shoot and root weight (94.2 and 425.5 g/pot), respectively. However the dose of 60 mg N kg -1 soil gave the lowest values of fresh shoot and root yield 80.3 and 312.7 g/pot. Positive effect of increasing N doses on shoot and root weight may be due to the role of nitrogen in development and survival of new tillers, through synthesis of nucleic acids and other organelles (Allam, 2003). Amin (2005) reported that increasing N levels significantly increased root length and its diameter, root fresh weight, top, root and sugar yield.

Table 2. Effect of Nitrogen and Boron interaction on fresh and dry weight of sugar beet

Nitrogen Boron Shoot yield (g plant -1) Root yield (g plant -1) -1 (mg N kg ) (ppm) Fresh weight Dry weight Fresh weight Dry weight 0 80.3 28.1 312.7 64.1 25 92.9 30.7 339.6 71.9 60 50 98.5 34.8 432.3 96.3 100 94.0 31.4 401.5 88.9 0 89.2 29.4 377.9 89.3 25 104.1 36.8 414.7 97.3 80 50 116.8 39.5 475.6 105.3 100 105.4 37.3 421.3 98.4 0 94.2 32.7 425.5 97.7 25 105.7 38.4 500.7 111.5 100 50 127.7 43.1 565.8 135.4 100 108.1 38.0 511.2 118.9 LSD (1%) N 4.6 0.8 10.6 2.0 B 5.3 0.9 12.3 2.3 N x B NS 1.5 21.2 4.1

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N: Nitrogen, B: Boron, NS: Not Significant

All boron doses found to give a significant increase in the shoot and root yield of sugar beet as compared to the untreated plants. Application of 50 ppm B was the best for achieving maximum fresh shoot and root yield as compare to other boron treatments. However, positive effect of Boron may be due to the boron role in cell elongation and turgidity where, in case of boron deficiency, plant leaves were reported to be smaller, stiff and thick (Brown and Hu, 1996). High boron doses above 50 ppm appeared to have toxic effects on the plant growth.

Boron found also to interact positively with nitrogen to affect yield and yield components of sugar beet. Combination of 50 ppm B plus 100 mg N kg -1 soil led to the highest values of shoot and root yield of sugar beet (127.7 and 565.8 g/pot), respectively. Boron encourages proper nutrient balance and assimilation as well as synthesizes transport. It is also reported that boron contributes in cell wall stability and proper binding of nitrogenous synthesizes (Allen and Pilbeam, 2007). Thus the interaction between B and N has a positive effect on yield quantity. Similar trend found by Azzazy (2004) who found that the combined B-N treatments at the rate of 100 kg + 5 kg borax are recommended to maximize quality and yield of sugar beet under the new reclaimed soil of El-Fayoum Governorate.

Nitrogen content The obtained results in Table 3 show that, the nitrogen and boron application significantly increased the N contents in root and shoot of sugar beet grown in calcareous soil. Application significantly increased nitrogen content in shoot and root of sugar beet than those of control plants. The highest values of nitrogen percentage (2.72 and 0.74 %) in shoot and root were found with 100 mg N kg -1 soil + 50 ppm B. While the lowest values (2.12 and 0.37 %) of nitrogen percentages were determined at the low N levels (60 mg N kg -1 soil) with no B applied. The increment in nitrogen percentage may be due to fixed nitrogen by N fixers used as a source of nitrogen. As well as the increase of root size, this led to augmentations in nitrogen uptake from the soil. Foliar application of B significantly increased the N content of sugar beet root and it has no significant effect on shoot N. Table 3. Effect of Nitrogen and Boron interaction on N and P content of sugar beet Nitrogen Boron N (%) P (%) -1 (mg N kg ) (ppm) Shoot Root R/S Shoot Root R/S 0 2.12 0.38 0.18 0.17 0.19 1.12 25 2.22 0.43 0.19 0.19 0.23 1.21 60 50 2.28 0.46 0.20 0.27 0.25 0.93 100 2.16 0.51 0.24 0.21 0.20 0.95 0 2.40 0.42 0.18 0.20 0.22 1.10 25 2.52 0.50 0.20 0.26 0.28 1.08 80 50 2.70 0.66 0.24 0.28 0.29 1.04 100 2.60 0.63 0.24 0.25 0.24 0.96 0 2.47 0.44 0.18 0.21 0.24 1.14 25 2.53 0.53 0.21 0.28 0.35 1.25 100 50 2.72 0.74 0.27 0.29 0.30 1.03 100 2.71 0.56 0.21 0.23 0.28 1.22 LSD (1%) N 0.35 0.09 NS 0.05 B NS 0.10 NS NS N x B NS NS NS NS R: root, S: shoot, N: Nitrogen, B: Boron, P: Phosphorus, NS: Not Significant

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The synergetic effect found between B and N acting increase in N contents in root and shoot tissues. This can be explained by the integration in nutrient uptake and the balance created by plant regulation mechanisms in the presence of sufficient concentrations of the two elements (Shaaban and El-fouly, 2001). The root /shoot ratio or the N distribution registered highest at 50 ppm of applied B with application of 100 mg N kg -1 soil. Significant effect was found from the application of N on P content of sugar beet root (Tabale 3) Whereas, the B foliar spray has none significant effect on p content in shoot or root of sugar beet grown in calcareous soil. Chatterjee et al., (1990) observed that P deficiency causes increase in protein solubility, ribonuclease, acid phosphatase, and polyphenol oxidase activities which were intensified by a combined deficiency of B and P. On the other hand, decrease in scratch, sugar content, DNA, RNA and ribonuclease, activity were aggravated by a combined excess of B and P. The P distribution decreased due to N and B application but it was highest at the highest dose of N and P applied.

Potassium content Foliar application of B significantly increased K content in root and shoot of sugar beet crop (Fig. 1). The best effect was obtained with the spray 50 ppm B and the K content in the shoot and root was 5.16 and 1.26 % respectively at the lower level of N applied (60 mg N kg -1 soil). This may be attributed to best amendment of K nutrient as a result of B foliar feeding due to improve the physiological performance of the plants.

4 Shoot Root 3

K contentK (%) R/S 2

0 0 0 0 25 50 25 50 25 50 100 100 100

60 80 100 N level (ppm)

Figure 1. Effect of Nitrogen and Boron application on potassium content of sugar beet

The combined from the application of 100 mg N kg -1 soil + 50 ppm B led to the highest K content (1.65 %) in sugar beet roots. Takkar et al., (1989) reported that the application of K and B significantly increased each other’s concentration in rice plants grown in sand. Also, the interactive effect of K and B was significant and synergistic in increasing green gram yield grown on highly calcareous soils of Dholi in Bihar. Morsey and Taha (1986) reported that applied soil B and foliar application increased the concentration and uptake of N, P, K, Mn and B in both tops and roots of sugar plants. The K distribution

5 Ozean Journal of Applied Sciences 2(1), 2009

from root to shoot was increased by N and B application. The highest level of B and N application registered the high distribution of K between root and shoot over other treatment.

Iron content Iron content in shoot and root of sugar beet were found to be significantly affected by the application of both N and B to the plants in Table (4). Nitrogen application significantly increased iron content of sugar beet. The pots receiving 100 mg N kg -1 soil recorded significantly higher iron content in shoot (166.3 ppm) and root (59.4 ppm)

High pH values in addition to high CaCO3 content of the soil induce Fe deficiency which resulted in lower values of shoot and root of the control plants and plant treated with lower doses. Similar results were obtained by Asad and Rafique (2000). Shaaban et al., (2004) found that B foliar application lead to significant increase in both concentrations and uptake of Ca, K, Fe, Mn, Zn and Cu in wheat shoots. Significant interaction effects between N and B on Iron content were also found. So, the highest iron content was recorded by the application of 100 mg N kg -1 soil + 50 ppm B to sugar beet grown in calcareous soil.

Table 4. Effect of Nitrogen and Boron interaction on iron and boron of sugar beet Nitrogen Boron Fe (ppm) B (ppm) -1 ( mg N kg ) (ppm) Shoot Root R/S Shoot Root R/S 0 60.51 18.01 0.30 52.51 28.00 0.53 25 83.11 29.52 0.36 67.20 37.81 0.56 60 50 92.60 39.20 0.42 75.43 43.31 0.57 100 86.72 31.44 0.36 85.62 45.92 0.54 0 73.40 34.11 0.46 58.50 36.24 0.62 25 85.64 57.30 0.67 72.90 42.81 0.59 80 50 118.81 66.13 0.56 85.11 51.60 0.61 100 90.33 60.72 0.67 88.72 58.22 0.66 0 88.01 52.10 0.59 62.22 39.71 0.64 25 117.94 56.04 0.48 79.03 48.63 0.62 100 50 166.32 59.41 0.36 89.51 59.73 0.67 100 142.40 63.50 0.45 91.40 60.80 0.67 LSD (1%) N 2.01 1.97 2.17 2.16 B 2.32 2.28 2.51 2.49 N x B 4.02 3.95 NS 4.31 R: root, S: shoot, N: Nitrogen, B: Boron, Fe: iron, NS: Not Significant

Boron content The effect of applied N levels significantly increased the boron content in the plant grown in calcareous soil (Tables 4). It was observed in the present study that, application of 100 mg N kg -1 soil treatment recorded the highest boron content (62.2 and 39.7 ppm) irrespective of B foliar spray followed by 58.5 and 36.2 ppm at 80 mg N kg -1 soil and 52.5 and 28.0 ppm at 60 mg N kg -1 soil in shoot and root of sugar beet, respectively. This could be due to more vegetative growth and root growth, which release root exudates resulted in increased boron availability in soil. The results of the investigation are in consonance with the findings of Diab (1992) found a positive relationship between B and the concentration of B, N, P and K in wheat plants.

6 Ozean Journal of Applied Sciences 2(1), 2009

Among boron levels, addition of 100 ppm B as foliar spray recorded the highest increase of iron content in shoot and root (91.4 and 60.8 ppm) as compared to 50 ppm B (89.5 and 59.7 ppm ) and 25 ppm B (79.0 and 48.6 ppm) at the highest N levels, respectively. The lowest B content registered in the control treatment (no B applied). Since B was hypotheses to work on the level of plasma membrane in the root system, its deficiency caused a dramatic decrease in all nutrient contents of the plant tissues (Zude et al ., 1997). Significant interaction effects were found between N and B on Boron content in root of sugar beet grown in calcareous soil. The Fe distribution decreased with increasing the applied N and B while B distribution increased with increasing the N applied at 50 ppm of applied B.

Nutrient ratio Balance ratios among the essential elements are one of the most important criteria in plant nutrition and if this balance becomes upset due to the variation of any essential element, the crop yield is sometimes considerably reduced and shows nutrient disorder symptoms. Nutrient ratios of sugar beet were significantly influenced by N and B application. In roots, the B/Fe ratio varied between 0.7 to 1.5, B/K between 30.8 and 45.5 and B/N between 75.7 up to 97.9. At the highest level of applied B, B: Fe decreased whereas B:K and B/N increased (Fig. 2). B/N ratio in treatment received 50 ppm B increased to over 80 at the higher level of Nitrogen application, whereas 100 ppm B increased B/N ratio up to 97.9. These results suggest that the degree of N accumulation was higher at 100 ppm B. Bonilla et al., (1980) observed that B deficiency and toxicity resulted in more NO3-N accumulation in the sap of sugar beet due to the decrease of the activity of the N-Rase enzyme, suggesting a specific effect of B on N-Rase activity.

120

100 B/Fe 80 B/K 60 B/N

40 Nutrientsratios 20

0 0 0 0 25 50 25 50 25 50 100 100 100 B levels (ppm) 60 80 100 N levels(ppm)

Figure 2. Nutrient ratios in sugar beet root as affected by N and B application

The B/Fe ratio in shoot in Figure 3 was increased due to the foliar spray of 100 ppm B up to 1.0 and B/K increased to 18.4 whereas B/N increased up to 39.6 at the lower rate of the applied N (60 mg N kg -1 soil). The evidence suggests that the deficiency or excess of B not only affects the relative values of individual elements, but it is also affect the balance among certain nutrient elements within the plants causing either an increase or decrease of dry matter production. Increasing the rate of applied N and B up to the highest dose decreased the B/Fe in sugar beet shoot. It appears that B may be concerned with the oxidation-

7 Ozean Journal of Applied Sciences 2(1), 2009

reduction equilibrium of iron in cells. Alvarez-Tinaut et al., (1980) observed that the Mn/Fe ratio in the shoots of tomato plants decreased when B level increased, reaching its minimal value at that B level producing the maximum yield.

45 40 35 30 25 B/Fe 20 B/K 15 B/N Nurientsratios 10 5 0 0 0 0 25 50 25 50 25 50 100 100 100 B levels (ppm) 60 80 100 N levels (ppm)

Figure 3. Nutrient ratios in sugar beet shoot as affected by N and B application

Correlation analysis The yield of sugar beet was highly and positively correlated with N and B content in root and shoot. The B content in root was highly correlated with N, K and Fe content. Significant negative correlation was found between root B and B/Fe ratio (Table 5). This result shows that the sugar beet yield was paralleled with the changes of the applied Band N. The N content also showed significant correlation with B (0.920**), K (0.864**) and Fe (0.768**) in sugar beet roots and negatively correlated with B/Fe. The total N, P, K and B found negatively correlated with B/Fe content in sugar beet root. Highly and significant positive correlations were found between root K and total N and B content of sugar beet. Shorrocks (1990) reported that effects of B and membrane permeability could lead to association between B and K. The stimulation of K accumulation by the ATP-ase proton pump which may account for positive correlations between K and B.

Data in Table 6 indicated highly significant positive correlation between shoot B and shoot yield (0.784**), N (0.629**), K (0.863**) and Fe (0.758**) in sugar beet shoots suggested that the differential absorption of these nutrients could be governed by B through a large or small nutrient absorption or distribution. The B/Fe ratio was declared a negative correlation with N, K, B and shoot yield.

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Table 5. Correlation between root yield and nutrient content and ratio of sugar beet Root yield Root B Root N Root K Root Fe Root B/N Root B/K Root B 0.838** Root N 0.824** 0.920** Root K 0.938** 0.895** 0.864** Root Fe 0.809** 0.816** 0.768** 0.748** Root B/N 0.198 0.343* -0.045 0.224 0.256 Root B/K 0.159 0.572** 0.442** 0.151 0.436** 0.392* Root B/Fe -0.611** -0.492** -0.439** -0.462** -0.882** -0.257 -0.268 **Significant at 1%, *Significant at 5%

Table 6. Correlation between shoot yield and nutrient content and ratio of sugar beet Shoot yield Shoot B Shoot N Shoot K Shoot Fe Shoot B/N Shoot B/K Shoot B 0.784** Shoot N 0.854** 0.629** Shoot K 0.924** 0.863** 0.741** Shoot Fe 0.898** 0.758** 0.760** 0.850** Shoot B/N 0.419** 0.843** 0.118 0.595** 0.435** Shoot B/K 0.276 0.762** 0.194 0.333* 0.314 0.838** Shoot B/Fe -0.592** -0.184 -0.592** -0.464** -0.765** 0.179 0.268 **Significant at 1%, *Significant at 5%

CONCLUSION

As result of Boron supply, the N, K, Fe distribution in root and shoot and their balanced ratio increased significantly. Boron has synergetic effect on nitrogen and other nutrient uptake and utilization by sugar beet plants. In calcareous soil were high level of calcium carbonate are present, boron should be applied to improve the yield and nutrient balance of sugar beet. Increasing the applied B up o 100 ppm appeared to have a toxic effect on sugar beet growth. Application of 50 ppm boron as foliar spray solution twice sprayed in combination with 100 mg N kg -1 soil was satisfactory to achieve a balanced nutrient status and getting a better yield of sugar beet under calcareous soil condition.

ACKNOWLEDGMENT

Authors wish to thank Prof Dr Mohammad Abou-Seeda, Plant Nutrition Department, Dokki, Egypt for his kind support and advice to achieve this research work.

REFERENCES

Allam, A. Y. (2003). Response of three wheat cultivars to split application of nitrogen fertilization rates in sandy soil. Assiut J of Agric. Sci., 34 (1): 1-14. Allen V. Barker, David J. Pilbeam. Ed. (2007). Handbook of plant nutrition. (Books in soils, plants and the environment). Boron by Umesh C. Gupta. Pp 241-278) Alvarez-Tinaut, M.C., A. Leal and L. Recalde-Martinez (1980). Iron-Manganese interaction and its relation to Boron levels in tomato plants. Plant and Soil, 55: 377-388. Amin, Gehan , A.M. (2005). Study of some agricultural practices on sugar beet. M.Sc.Thesis, Fac. of Agric., Zagazig Univ. Asad, A., and Rafique, R. (2000). Effect of zinc, copper, iron, manganese and boron on the yield and yield components of wheat crop in Tehsil Peshawar. Pakistan J of Biological Sci., 3 (10): 1615-1620.

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Azzazy, N.B. (2004). Effect of nitrogen and Boron fertilization on yield and quality of sugar beet under new reclaimed soil conditions. Egypt J. Appl. Sci., 19 (8): 230-238. Bonilla, C. Cadahia, O. Carpena and V. Hernando (1980). Effects of boron on nitrogen metabolism and sugar levels of sugar beet. Plant and Soil 57, 3-9. Cooke, D.A. and R.K. Scott, (1993). The Sugar Beet Crop. Chapman and Hall London, pp. 262 -265. Brown, P.H. and Hu, H. (1996). Phloem mobility of boron in species dependent: Evidence for phloem mobility in sorbitol-rice species. Ann. Botany, 77: 497-505. Chatterjee ,C., P. Sinha and S.C. Agrawala (1990). Interactive effect of boron and phosphorus on growth and metabolism of maize grown in refined sand. Can. J. Plant Sci., 70: 455-460. Cottenie, A.; M. Verloo; M. Velghe and R. Camerlynck (1982). Chemical Analysis of Plant and Soil. Laboratory of Analytical and Agrochemistry. State Univ. Ghent, Belgium. Diab, M. (1992). Boron requirement of wheat and effect on the growth and nutrients B, N, P and K content. Egypt J. Appl. Sci., 7 (8): 412-421. Gupta, U. C. ( 1979 ). Adv. In Agron. 31, 273-307. Hemphill, D. D. (1982). Soil Sci. Soc. Am. J. 46, 1190-1192. Jackson, M. I. (1973). Soil chemical Analysis. Printice Hall Inc., N. J., U. D. A. Jaszczolt, E. (1998). Effect of two methods of fertilizing sugar beet with trace elements on the yields of roots and sugar. Gazeta-Cukrownicza, 106: 232-234. Kristek A., Biserka Stoji ć, Suzana Kristek (2006). Effect of the foliar boron fertilization on sugar beet root yield and quality. Agriculture-Scientific and Professional Review. 12 (1). Morsey, M.A and E.M. Taha (1986). Effect of Boron, manganese and their interaction on sugar beet under El-Minia conditions. 2: Concentration and uptake of N, P, K, B and Mn. Ann. Agric. Sci. Ain Shams University, 31:1241-1259. Ouda, Sohier M. M. (2007). Effect of chemical and bio-fertilizer of nitrogen and boron on yield and quality of sugar beet. Zagazig Journal of Agricultural Research. 34 (1), 1-11. Pospišil, M., Pospišil, A., Sito, S (2005). Foliar application of liquid fertilizer Fertina B to sugar beet. Listy Cukrovarnické a Reparské,121:(5/6), 174-177. Shaaban, M. M., and El-Fouly, M.M. (2001). Boron foliar fertilization improves zinc and other nutrient staus in cotton plants grown under low or high calcium carbonate level in soil. Proc. of the Int. Workshop (Boron 2001) Bonn, Germany, June 23-28. Shaaban, M. M., El-Fouly, M.M. and Abdel-Maguid, A. A. (2004). Zinc-boron relationship in wheat plants grown under low or high calcium carbonate levels in soil. Pakistan J of biological Sci., 7 (4): 633-639. Shorrocks, V. M. (1990). Behavior, function and significance of boron in agriculture. Report on an international workshop at St. Johns College, Oxford, England. 23-25 July. Published by Borax consolidated Limited, London. Snedecor, G.W. and W.G. Cochran (1980). Statistical Methods 7th Ed., Iowa State Univ. Press., Ames . Iowa, U.S.A. Takkar, P. N., I. M. Chhibba and S. K. Mehta (1989). Bull No. I. Indian Institute of Soil Science ( IISS ), Bhopal, MP (India). Willett, R., P. Jakobsen and B. A. Zarcinas (1985). Nitrogen-induced boron deficiency in Lucerne. Pant and Soil 86,443-446. Zude, M.; Alexander , A. and Luedders, P. (1997). Influence of boron spray on boron concentration, fruit set and calcium related disorders in apple. In: Boron in soils and Plants, R. W. Beli and B. Rerkasem, pp. 139-143.

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The Effects of Different Additives on Silage Gas Production, Fermantation Kinetics and Silage Quality

B. Zehra Sariçiçek and Ünal KILIÇ Department of Animal Science of Agricultural Faculty of Ondokuzmayıs University, Samsun, Turkey E-mail address:[email protected]

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Abstract: The objective of study was to explain the effects of differ additives on the nutrient, energy content, gas production and parameters, fermentation kinetics and silage quality of corn silage. Test silages from fresh material, wilted for 6 hours were conserved into 1.5-litre jars and opened for analysis in 60 days. Additives (additive ratio) were wheat ground (5%), formic acid (2.5 l/ton), urea (1%), chemical material, (Artturi Imarın Virtanen; AIV) (8%), biological material (L. Plantarum + P.acidilactici + L.salivarus) (10 g/ton). Gas production (GP) and its parameters were studied by using in in vitro gas production technique with ruminally fistulated Sakız x Karayaka rams. Silage treated with wheat ground had significantly greater OM, CP content, TE and GP compared with other groubs (P<0.01). Ash content of silage was the highest in silage treated with AIV (P<0.01). The pH value after 96 h. of incubation was lewer in silage treated with inoculant compared with AIV (P<0.05). The silage added AIV decreased the ME, NE L and OMD (P<0.01). While lactic acid concentration were the highest in silage treated with wheat and inoculant, it was the lowest in silage treated with urea (P<0.01). Silage NH 3-N and butyric acid concentration were significantly higher in silage treated with urea (P<0.01). The highest flieg point was obtained from treatment with AIV.

Keywords: corn silage, additives, gas production, silage quality ______

INTRODUCTION Considering the real climate conditions, silage is the best method for preserving fresh forage with minimal losses. Silage quality and nutritional value are influenced by numerous biological and technological factors, When the proper ensilage techniques are used, silage will have a high nutritive value and hygienic quality. However, the results in practice indicate that the quality of silage is often poor or even unsatisfactory. These results are usually achieved when the fermentation condition are difficult. (Lattemae et al., 2006). Factors which influence fermentation include degree of gren fodder wilting, length of cut, ensiling technology type, and amount of an additive used (Haigh, 1988). Silage additives include feedstuffs, urea, inoculants and acids. (Weiss and Underwood, 2006). The major goal in silage making is to preserve silage material with minimum nutrient loss. In order to achieve this goal, growth of lactic acid bacteria should be stimulated. Especially, formic acid is widely used to accomplish this target. While wheat is commonly used to provide readily available energy for lactic acid fermentation, bacterial inoculant is used to establish a desirable microbial flora in silage.

Corn has low concentrations of protein and some minerals, but high concentrations of fermentable carbohydrates. Nutritional additives such as urea however, are benefical. The justifications for using non protein nitrogen (NPN) have been prolonged aerobic stability during the feedout phase and the addition of an economical nitrogen source to low protein crops, such as corn (Weiss and Underwood, 2006).

Feed evaluation for ruminant is often based on an estimate of rumen digestibility, even though such measurements alone cannot predict how ruminants will utilise feed nutrients. However, in vivo digestibility depends on a range of factors, including potential digestibility, rate of digestion, fractional rumen outflow

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and efficiency of microbial production. Gas production techniques are used in many laboratories to study fermentation kinetics of ruminant feeds. In vitro gas production system (Menke et al., 1979; Mauricio et al., 2001) provide and estimate of dry matter (DM) and OM digestion anda re an indicator of the end products produced. (Bueno et al., 2005). Maize silage is an important component of ruminant diets and its energy value is widely estimated from chemical composition and in vitro organic matter digestibility (OMD) (DeBoever et al., 2005). In this study, the effect of different silage additive added during ensiling period was investigated on the nutrient, the silages quality, gas production, gas production parameters, energy values, organic matter digestibility of maize silage.

MATERIALS AND METHODS Maize (Arifiye) as a silage material was used in this study. As additives; wheat ground, urea (contains 46% N), formic acid, AIV solution (composed 1 part H 2SO 4, 1 part H2SO4, 1 part HCl and 6 part water), microbial inoculant (Maize-All® GS obtained from Alltech-Pioneer). Maize-all GS is formulated with three lactic acid-producing bacteria ( Lactobacillus plantarum , Pediococcus acidilactici and Lactobacillus salivarus ) and high level amylase.

In this study, maize (arifiye) crop was grown at the Agricultural Faculty Experimental Farm of Ondokuzmayıs University, Samsun. It was harvested by a one row forage harvester at dough stage of kernel maturuty. The fresh material which will be ensilaged was chopped to about 2 cm length and were ensiled in laboratory type 2.0-l glass jars, equipped with a lid that enable gas release only. The maize from dough stage was wilted for 24 h in the field, to about 35%DM, before ensiling. Six different silages were prepared (quadriplicate) form chopped forage. Silage treatments included control (no additives) (CS). 5% wheat ground (WGS), 2.5 lt/ton formic acid (FS), 10 g/t microbial inoculant (Maize-All® GS). As recommend by the manufacturer, inoculant was added at 1.0x1011 cfu/g of fresh forage (MAS), 1% urea (US) and 8% AIV (AIVS). They were stored for 60 d in the dark room with a temparature ranging between 20 to 25 oC. At the end of the ensiling period (60 d), the silages were opened. Representative samples were dried at 48 ˚C in a forced-air oven for 72 hours.

After drying, silage samples were ground through a 1-mm screen for chemical analysis. The dry matter (DM) (105 oC), ash (550 oC), crude protein (CP)(Kjeldahl Nx6.25), ether extract (EE), crude fiber (CF) of the silages were determined by the methods described by AOAC (1990). Volatile fatty acid and NH 3-N contents in rumen fluid were determined using Markham Steam Distillation procedure (Markham, 1942) (Table 1).

All silage organic acids analysis was accomplished by using gas chromatograph (Shimadzu, GC-14B) as described by Leventini et al. (1990). Furthermore, quality analysis (Kilic, 1986), were made in silages, and nitrogen free extract (NFE) was determined by calculation. All cemical analysis was carried out in triplicate.

Table 1. pH, TVFA and NH 3-N content of rumen fluid pH TVFA (mmol/l) NH 3-N (mg/l) Average 6.20 119 310 Lowest 5.92 90 280 Highest 6.29 136 427 TVFA:Total volatile fat acid

The pH of each sample was determined in triplicate using approximately 25 g wet ensilage added to 100 ml of distilied water. After hydration for 10 min using blender, pH was determined using digital pH meter. Flieg points were calculated in silages according to Kılıc (1986) (Flieg Point = 220+(2 x % Dry Matter - 15) – 40 x pH).

Three Sakız x Karayaka rams aged 2 with ruminal cannulas were used in gas production technique. Rumen fluid was obtained from three fistulated sheep fed twice daily (08.30-16.30) with a diet containing grass hay (%60) and concentrate (%40) (Table 2). The samples (milled through a 1-mm sieve) were incubated in

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vitro rumen fluid in calibrated glass syringes following the procedures of Menke et al. (1979), Menke and Steingass (1988) and Blümmel and Ørskov (1993). Approximately 200 mg dry weight of sample was weighed in triplicate into calibrated glass syringes of 100 ml. Rumen fluid was collected before the morning feeding. The syringes were prewarmed at 39 ºC before the injection of 30 ml Rumen-buffer mixture consisting of 10 ml rumen fluid and 20 ml digestion medium into each syringe followed by incubation in a water bath at 39 ºC. Triplicates of each sample were used in two separate runs. Readings of gas production recorded before incubation and 3, 6, 9, 12, 24, 48, 72 and 96 h after incubation. Total gas values corrected for blank incubation. Cumulative gas production data were fitted to the model of Ørskov and McDonald (1979) by NEWAY computer package programme. y = a+b(1-e-ct )

Table 2. Chemical composition of silages (% DM) Feed E E Ash CP CF NFE Control Mean 2,09 ab 6,93 b 7,05 b 22,07 a 61,85 b Wheat Mean 1,65 ab 5,18 c 8,32 a 19,49 b 65,37 a Formic acid Mean 2,25 a 5,65 bc 7,22 b 21,03 a 63,84 ab Maize-all Mean 2,20 ab 5,64 bc 7,16 b 22,24 a 62,76 b Urea Mean 2,07 ab 6,57 bc 12,10 a 22,78 a 56,48 c AIV Mean 1,60 b 10,22 a 7,19 b 22,19 a 58,81 b SEM 0,083 0,361 0,1 10 0,254 0,449 Significant ** ** ** ** ** EE: Eter extract, CP:crude protein, CF:Crude fiber, NFE:Nitrogen free extract a,b,..:Means with different superscript within same column significantly differ (P<0.05). ** (P<0.01), * (P<0.05)

Where; a: the gas production from the immediately soluble fraction (ml), b: the gas production from the insoluble fraction (ml), c: the gas production rate constant for the insoluble fraction (ml/h), a+b: potential gas production (ml), t: incubation time (h), y: gas produced at time “t”. Oganic matter digestibility (OMD), metabolisable energy (ME) (Menke et al. 1979) and NE L (Menke and Steingass,1988) contents of forages were estimated using equations given below:

OMD, % = 14.88+ 0.889 GP + 0.45 CP + 0.065 A, Where; GP:24 h net gas production (ml/200mg DM), CP:Crude protein (%), A:Ash content (%)

ME, (MJ/kg DM) = 2.20+0.136 GP + 0.0574 CP NE L, (MJ/kg DM) = 0.101 GP + 0.051 CP + 0.112 EE Where; GP: 24 h net gas production (ml/200mg DM), CP: g/kg DM, EE: g/kg DM

One-way analysis of variance (ANOVA) was carried out to compare gas production, gas production parameters, Energy values, DMD and OMD values using General Linear Model (GLM) of SPSS 12.0 package programs. Significance between individual means were identified using the Duncan’s multiple range test.

RESULTS AND DISCUSSION Total volatile fat acids (TVFA), pH and NH3-N of rumen liquid were given Table 1. Chemical composition of silages are presented in Table 2. Results of gas production and gas production parameters, organic matters digestibility (OMD), ME and NE L were given in Table 3. Organic acids concentration, pH, NH 3-N and Flieg point of silages were given Table 4.

According to the results of this study, the TVFA, pH and NH 3-N content of rumen liquid for in vitro gas production technique were normal level (McDonald et al.,1996; Menke and Steingass,1988) The highest DM content was found for silage treated with wheat and the lowest was obtained from silage treated with AIV.

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Table 3. Gas production and gas production parameters, estimated energy content and organic matter digestibility of silages Gas Control Wheat Formic Maize Urea Aiv SEM Sig production acid all 3 7,99 9,81 7,05 8,22 7,27 10,12 0,468 NS 6 13,06 16,01 12,31 13,39 11,75 12,82 0,617 NS 9 17,64 21,44 16,99 17,97 15,75a 15,24 0,800 NS 12 21,77 ab 26,18 a 21,16 ab 22,01 ab 19,30 ab 17,40 b 0,970 ** 24 34,61 ab 39,91 a 33,78 bc 34,11 ab 30,03 bc 24,10 c 1,427 ** 48 48,78 ab 52,86 a 46,95 ab 46,38 ab 41,05 b 31,49 c 1,742 ** 72 55,08 a 57,55 a 52,45 ab 51,33 ab 45,43 b 35,01 c 1,793 ** 96 57,91 a 59,30 a 54,80 a 53,40 ab 47,19 b 36,80 c 1,787 ** pH 6,73 ab 6,61 ab 6,70 ab 6,59 b 6,69 ab 6,74 a 0,019 * Gas production parameters a, ml 2,36 b 2,69 b 1,13 b 2,38 b 2,23 b 7,11 a 0,491 ** b, ml 57,94 a 57,71 a 55,51 a 52,67 a 46,14 b 32,44 c 1,982 ** c, ml/h 0,04 0,05 0,04 0,04 0,04 0,04 0,001 NS RSD 2,04 2,40 1,67 1,52 1,45 1,34 0.219 NS Energy and OMD ME, MJ/kg DM 7,31 a 8,10 a 7,21 a 7,25 a 6,98 ab 5,89 b 1.193 ** NE L, MJ/kgDM 4,09 a 4,64 a 4,03 a 4,06 a 3,88 a 2,98 b 1.145 ** OMD, % 49,27 a 54,44 a 48,53 a 48,79 a 47,45 ab 40,21 b 1. 253 ** a,b,..:Means with different superscript within same column significantly differ (P<0.05). ** (P<0.01), * (P<0.05) NS:Not significant

Table 4. Organic acid, pH, NH 3-N concentration and estimated Flieg point of silage Control Wheat Formic Maize- Urea AIV SEM Significant acid all pH 3.55a 3.45a 3.70aa 3.55a 3.65a 1.55b 0.35 ** DM, % 26.17b 28.74a 25.17d 26.22b 26.08c 17.69e 0.64 ** Laktic 2.97b 3.60a 3.09b 3.46a 1.66d 2.09c 0.44 ** acid Acetic 1.28b 1.05b 2.19a 1.68b 1.26b 2.12a 0.48 ** acid Butyric - 0.004 - 0.003 0.05 - 0.43 * acid NH 3-N 0.90b 1.26ab 0.78b 0.90b 2.55a 1.83ab 0.38 ** g/kgDM Flieg 115.36 124.48 107.30 115.41 111.15 178.38 point Quality Very Very Very Very Very Very good good good good good good a,b,..:Means with different superscript within same column significantly differ (P<0.05). ** (P<0.01), * (P<0.05)

There were significant differences between the AIV and WGS (P<0.01). Weiss and Underwood (2006) reported that addition of wheat into silage increased DM content of wet silage, which underlines our result. The highest EE was found for FAS (P<0.01) and the lowest was obtained from AIVS (P<0.01).

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While addition of AIV into silage increased, addition of wheat ground decreased crude ash content of silage. There were significant differences between the AIV and WGS treatments (P<0.01). The results obtained in the present experiment are supported by Olt et al. (2005), who reported that AIV is a rich mineral acid source.

CP content of silage were the significantly improved by treatment with urea and wheat ground (P<0.01). The highest increase was obtained with addition urea. Bolsen et al. (1996) reported that urea is an economical nitrogen source to low protein crops, such as corn. Many researchers have reported that the urea addition increased the CP content of silage (Bolsen et al., 1992).

The lowest cellulose content of silage was found for silage treated with AIV. The differences between the AIVS and the other groups were significant (P<0.01). This decrease in cellulose concentration may have resulted from increased cell wall degradability due to increased silage fermentation caused by addition of chemical additive AIV. This result is consistent with Olt et al. (2006), who reported that cellulose content declined in silage treated with AIV. Cellulose content of silage were not affected by the other additives. While the highest N free extract (NFE) content was obtained from silage treated with WG, and the lowest for the silage treated with urea. The differences between the WGS and the other groubs (CS, MAS, US and AIVS) were significant (P<0.01). This increase in NFE content for WS could be explained with the fact, that wheal is a rich carbohydrate source. This statement was in agreement with the reporting of Weiss and Underwood (2006). On the other hand, decrease in NFE for US may has resulted of a rich nitrogen source of urea.

As seen in Table 3, gas production of silages were not affected by treatments for incubation after the first 3, 6 and 9 hour, but silage treated with wheat ground for 12, 24, 48, 72 and 96 h. incubation were numerically higher than that of control silage. This could be due to the fact that the grain (wheat) is a relatively rich source of easily fermentable carbohydrate. The lowest gas production were obtained from AIV and urea treatment for 72 and 96 h incubation. The differences between the AIV and the other groups were significant (P<0.01). Gas production values of CS were in agreement with the findings of Kılıç and Sarıçiçek (2005) and Mould et al. (2000) reported that gas production for 96 h. was 53.-56.0 ml/200ml OM, what also supports our result.

The highest rumen pH value was found for AIVS after 96 h and the lowest for silage treated with Maize-all (MAS). AIVS was significantly different from the MAS (P<0.01). The pH value of AIVS in present study was higher than the findings of Mertens et al. (1997). The highest “a” value was obtained from silage treated with AIV and the lowest for FAS, but the other additives did not affect the a value. While decrease in formic acid treated group can be explained with limited degradability coused by formic acid; on the other hand, an increase can also be explained with increased degradability in the AIV treated group due to the very strong acid content of AIV. A value obtained in the present experiment was higher than the finding(1.68 ml) reported by Kılıç and Sarıçiçek (2005), contrary, the a value for corn silage in this study was lower than findings (7.4 ml) of Compos et al. (2000). These discrepancies may be attributed to differences in varieties of these corn silages and differences in sample preparation prior to incubation among the studies.

The highest “b” value was found for CS (untreated), but the lowest “b” value were obtained from AIVS and US. The AIVS group were significantly different from the other groups (P<0.01). There were no differences between the silages in terms of “c” value (rate of gas production). The result obtained in the present experiment are supported by Compos et al. (2000), who reported that c value of corn silage was 0.04 ml.

The lowest ME, NE L and OMD between the silages were obtained from the silage treated with AIV. AIVS group were significantly different from control and the other groups (P<0.01). Olt et al. (2005) suggested that OMD of silage could be affected by chemical acids such as AIV treatments. The ME, NE L and OMD of silage treated with wheat ground was numerically higher than the control group.

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The current study showed similarities with the reports of Hamilton (2005) in that ME for corn silage was between 5-13 MJ/kg DM. The ME of corn silage in this study was lower than the findings reported by Getachew et al. (2002) (8.0-9.35 MJ/kg DM), which is near result to silage treated with wheat ground. In this study, the NE L of corn silage (untreated) are in accordance with those (4.72 MJ/kg DM) reported by Kılıç and Sarıçiçek (2005).

While OMD value of CS was obtained by Lee et al. (2000) as 79.60%, by Getachew et al. (2002) as 53.55- 62.35% and by Sarıçiçek and Çayıro ğlu (2001) as 53.70 %. The result of WGS were close to the finding of Getachew et al. (2002). Nocek and Tamminga (1991) reported that, ruminal starch degradability of wheat was higher than barley, sorghum and corn, and that wheat and corn starch degradability were 80-90 % and 55-70 %, respectively.

The lowest pH value was found for AIVS. The differences between the AIVS and the other groups were significant (P<0.01). The decrease in pH could be attributed to the strong mineral acid content of AIV. Ludenmark (2005) reported that AIV additive into silage decreased the pH value, and the best silages qualities were achieved with the additive AIV.

The highest lactic acid content were found for WGS and MAS (P<0.01). This could be due to the fact that the wheats are relatively rich source of carbohydrate, which is easily fermentable. On the other hand, many rearchers reported that bacterial inoculants have positive effects on pH and lactic acid levels, an indication of goal fermentation (Bolsen et al., 1992; Handerson, 1993; Weiss and Underwood, 2006).

The lowest lactic acid concentration was found for US. Lactic acid content for US were significantly different from the WGS, MAS and the other groubs (P<0.01). Urea is a rich nitrogen source. This could be due to the fact the urea is a rich source of nitrogen. Silage treated with formic acid showed numerically greater lactic acid concentrations compared with control. Kennedy (1990) has reported that addition of formic acid into silage decreased silage lactic acid content by limiting silage fermentation, but also Charmly et al. (1990) reported that formic acid increased silage lactic acid concentration.

While addition of wheat ground into silage numerically decreased, addition of formic acid and AIV increased silage acetic acid concentration (P<0.01). Some researchers reported a decrease; other reported no changes in concentrations of acetic acid with addition of formic acid and AIV into silage (O’Kiely et al., 1990; Kennedy, 1990).

While addition of urea into silage increased butyric acid concentration (P<0.05), but were not affected by the other treatments. The highest NH 3-N cocentration was found for US. The differences between the urea treated group and formic acid, maize-all groub were significant (P<0.01). These results are consistent with Bolsen et al. (1996), who reported that N content of silage increased treatment with urea.

In this study, the flieg point of silages ranged from 107.3 to 178.38. Although no statistical analysis of silage flieg point was conducted, the following trends were apparent. The AIVS and WGS had the highest point among the silages. The pH value of silage decreased by AIV treatment and DM content of silage increased by wheat treatment. This leads to the increase in the flieg point.

The effect of AIV, formic acid, urea, inoculant and wheat ground treatments on corn silage were investigated in this study. The results showed, that silage additives had positive and/or negative effect on nutrient, silage fermentation, OMD, energy content, gas production and gas production parameters and quality of silage. However, effects of these additives on silage fermentation, gas production, gas production parameters, OMD and silage quality should further be studied to determine proper silage additive.

REFERENCES A.O.A.C. 1990. Association of Official Analytical Chemists. Official Methods of analysis, 15th (Ed.), Vol.1. AOAC, Washington, DC, pp. 69-79.

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Blümmel, M., E. R. Orskov. 1993. Comparison of in vitro gas production and nylon bag degradability of roughages in prediction of feed intake in cattle. Anim. Feed Sci. Technol. 40:109-119. Bolsen, K. K., G. Ashbell, Z. G. Weinberg. 1996. Silage fermentation and silage additives. Asian- Australasian J. Anim.Sci.5:483-493. Bolsen, K. K., D. G. Tlemann, R.N. Sanon, A. Hart, B. Dalke, T. Dickerson, C. Lin. 1992. Evaluation of inoculant-treated corn silage. In:Kansas Agric.Exp.Sta.Rpt.of Prog. Kansas State Univers. Manhattan, pp103-106 Bueno, I. C. S., S. L. S. Cabral Filo, S. P. Gobbo, D. M. S. S. Vitti, A. L. Abdalla. 2005. Influence of inoculum source in a gas production method. Anim.Feed Sci. And Technol.xxx(2005)xxx-xxx. Charmley, E., M. Gill, C. Thomas. 1990. The effect of formic acid treatment and the duration of the wilting period on the digestion of silage by young steers. Anim.Prod., 51:497-504. Compos, F. P., M. L. V. Bose, C. Boin, D. P. D. Lanna, J. P. G. Morals. 2000. Evaluation of the in vitro digestion computerized monitoring system. 3. Dry Matter and/or Neutral Detergent Fiber Disappearence by Gas Production. Rev.Bras. Zootec.,29(2)537-544. De Boever, J. L., J. M. Aerts, J. M. Vanacker, D. L. De Brabander. 2005. Evaluation of the nutritive value of maize silages using a gas production technique. Anim. Feed Sci. And Technol. 123-124:255-265. Getachew, G., G. M. Crovetto, M. Fondevila, B. Singh, M. Spanghero, H. Steingass, P. H. Robinson, M. M. Kailas. 2002. Laboratory variation of 24h in vitro gas production and estimated metabolisable energy values of ruminant feeds. Anim.Feed Sci. And Technol., 102:169-180. Haigh, P.M. 1988. The effect of wilting and silage additives on the fermentation of autmn made grass silage ensiled in bunkers on commercial farms in South wales. Grass Forage Sci., 43:337-345. Hamilton, D. 2005. Nutritive characteristics of supplementary feeds used in the Victorian Dairy Industry non-forage supplements. http://www.dpi.vic.gov.au/dpi/nrenfa.nsf Handerson, M. A. 1993. Aerobic stability and in vitro fiber digestibility of microbially inoculated corn and sorghum silages. J. Anim. Sci. 71:505-514. Kennedy, S. J. 1990. Comparison of the fermentation quality and nutritive value of sulphuric and formic acid treated silage feed to beef cattle. Grass Forage Sci., 45:17-28. Kılıç, A. 1986. Silo Feed . Bilgehan Publ. İzmir. pp327. Kılıç, U., B. Z. Sarıçiçek. 2005. Determination of Some Fermentation Products and Energy Contents of Some Feedstuffs Using In vitro Gas Production Technique. Ondokuz Mayıs University, Sci. Enstitute, Samsun (Doctora Thesis), pp160. Lee, M. J, S.Y. Hwang, P.W. S. Chiou. 2000. Metabolisable energy of roughages in Taiwan. Small Rum. Res., 36:251-259. Lattemae, P., A. Laats, U. Tamm. 2006. The technological factors affecting the quality of big bale silage. www.eria,ee/public/files/summary_1.8_2006./link/ Leventini, M. W, C. V. Hunt, R. E. Roffler, D. G. Casebolt. 1990. Effects of dietary levels of barley-based supplements and ruminal buffer on digestion and growth by beef cattle. J. Anim. Sci. 68:4334-4344. Lundmark, C. 2005. Ensiling experiment in bagged silage with 3 silage additives.Examensarbete/Sveriges lantbruksuniversitet, Institutionen för, 217: 18. http://ex-epsilon.slu.se/archive/00000870/ Markham, R. 1942. A steam distilation apparatus suitable for micro-kjeldahl analysis. Biochem. J., pp.36:790. Mauricio, R. O., E. Owen, F. L. Mould, I. Givens, M. K. Theodorou, J. France, D. R. Davies, M. S. Dhanoa. 2001. Comparison of bovine rumen liquor and bovine faeces as inokulum for an in vitro gas production technique for evaluating forages. Anim. Feed Sci. And Technol. 89:33-48. Menke, K. H., H. Steingass. 1988. Estimation of the energetic feed value obtained from chemical analysis and gas production using rumen fluid. Anim. Res. Develop. 28:7-55. Menke, K. H., L. Raab, A. Salewski, H. Steingass, D. Fritz, W. Schneider. 1979. The estimation of the digestibility and metabolisable energy content of ruminant feedingstuffs from the gas production when they are incubated with rumen liquor in vitro. J. Agric. Sci. Camb. 93:217-222. Mertens, D. R., P. J. Weimer, G. C. Waghorn. 1997. Inocula differences affect in vitro gas production kinetics. USA Dairy Forage Research Center, 1997 Research Summaries.pp.53-54. Mould, F. L., D. Colombatto, E. Owen. 2000. The impact of particle size on the rate and extent of in vitro fermentation investigated using the reading pressure technique. Proceeding of the British Society of Animal Science. Pp.61. Nocek, J. E., S. Tamminga. 1991. Site of digestion of starch in the gastrointestinal tract of dairy cows and its effect on milk yield and composition. J.Dairy Sci. 74:3598-3629.

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O’Kiely, P. 1990. Influence of a partially neutralised blend of aliphatic organic acid on fermentation, effluent production and aerobic stability of autmn grass silage. Irish J. Agric. Food Res., 32:13-26. Olt, A, O. Kart, H. Kaldmae, M. Ots, E. Songisepp, I. Smidt. 2005. The effect of additive and dry matter content on silage protein degradability and biogenic amine content. www.eau.ee/~aps/pdf/ 2005 2/ Olt _i.pdf , Estonian University of Life Sciences, 117-123. Orskov, E. R., I. McDonald. 1979. The estimation of protein degradability in the rumen from incubation measurements weighted according to rate of passage. J.Agric. Sci. Camb. 92:499-503. Sarıçiçek, B. Z., H. Çayıro ğlu. 2001. Determining in vitro digestibilities and energy values of some forages and dairy compound feeds treated with fat, tannic acid. J.of Fac of Agric. OMÜ, 16(3):22-26. Weiss, B., J. Underwood. 2006. Silage Additives. Ohio State University Extension department of Horticulture and Crop Science 2021 Coffey Road, Colombus, Ohio 43210-1044, AGF-018-92.

18 Ozean Journal of Applied Sciences 2(1), 2009

Numerical Solution of One-Dimensional Stefan-Like Problems Using Three Time-Level Method

Vildan Gülkaç Department of Mathematics, Faculty of Science and Arts, Kocaeli University, Kocaeli, Turkey. [email protected]

______

Abstract: We introduce formulation based on three time- level finite- difference method for one- dimensional Stefan- like problems. Matrix method stability analysis of equations is also investigated. The computational results obtained by the present method are in excellent agreement with the results reported previously by the other authors.

Keywords: numericalsolution, three time-level method ______

INTRODUCTION Problems in which the solution of a differential equation has to satisfy certain conditions on the boundary of a prescribed domain are referred to as boundary-value problems. In many important cases, however, the boundary of the domain is not known in progress but has to be assigned as part of solution. The term free- boundary problem is frequently used when the boundary is stationary and a steady- state problem exists. Moving boundary, on the other hand, is connected with time- dependent problems and the position of the boundary has to be described as a function of time and space.

In all cases, two conditions are wanted on the free or moving boundary, one to describe the boundary itself and the other to mature the definition of the solution of the differential equation. Convenient conditions on the fixed boundaries and, where favorable, an initial condition is also prescribed as usual. Moving boundary problems are often called Stefan problems, with reference to the early work of J. Stefan who, around 1890, was interested in the melting of the polar ice cap Crank (1987).

Many transient problems arising in science, engineering and industry involve a domain whose boundary changes its shape and size in time. Such problems have become well known as moving boundary problems or free boundary problems and such problems are often referred to as Stefan problems after Stefan, see Crank (1987), Furzeland (1977), Hill (1987). These problems are naturally nonlinear since the moving boundary is not known a priori and must be determined as a part of the solution. Numerical treatments of Stefan problems have been commonly based on finite- difference and finite- elements. Owing to do the nonlinearity of the moving interface, it is difficult obtain analytical solutions of these type problems excepting a restricted number of special cases Hill and Carslaw (1987, 1959). A perfect examine of these techniques and other various methods can be found in Crank (1957), Crank & Özi ş (1980), Özi ş & Gülkaç (2003), Gülkaç & Özi ş (2004), Gülkaç (2005), Radhey et al (1985), Crank & Gupta (1975), Sparrow & Hsu (1981), Smith (1987), Landau (1950), Furzeland (1980), Fasano & Primicerio (1979), Muehlbauer (1965).

In this paper, three time-level method based on the implicit finite- difference are applied to the one- dimensional Stefan-like problems. The computational results obtained by the present method are in excellent agreement with the results reported previously by other researchers.

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Problem Description We consider a Stefan problem for which the exact solutions has been obtained by Cho (2002). Referring to Kutluay (2005), U(x ,t) is the phase- change temperature and s(t) is the position of the moving boundary, a dimensionless model of the one-phase Stefan Problem with a forcing term in a semi- infinite slab of material that is initially at its melt temperature is as follows:

The temperature U(x, t) satisfies the heat conduction equation

∂U ∂ 2U = + f (x,t) , 0 < x < s(t ,) t > 0 (1) ∂t ∂x 2 subject to the boundary and initial conditions.

U ,0( t) = ,0 t > 0 (2) U (s(t), t) = ,0 t > 0 (3) U (x )0, = g(x), 0 ≤ x ≤ 1 (4) where f(x, t) and g(x) are described functions which are sufficiently smooth and nonnegative.

The moving interface s(t) satisfies the energy balance equation known as Stefan condition

ds ∂U = − , x = s(t), t > 0 (5) dt ∂x subject to s(t)=1, t=0. Problem a: Referring to Kutluay (2005), for this problem we first consider F(x, t) = x exp(t)+2 g(x) = x (1-x) referring to Muehlbauer (1965), this problem has the following exact solution for U(x,t) and s(t), respectively: U(x, t) = x (exp(t)-x), 0 ≤ x ≤ s(t) s(t)=exp(t), t ≥ 0 .

Problem b: In this problem, we consider

h& (t) h& (t)  h&& (t) h& 2 (t)   h& 2 (t) h&& (t)  2   3   f (x,t) = −2 + 6x 2 + x  − 2  + x 2 3 − 2  h(t) h (t)  h(t) h (t)   h (t) h (t) 

g(x) = 5.0 πx 2 1( − x) where h(t) = 1+ 5.0 Sin (πt) . Referring to Cho (2002) this problem has the following exact solution for U(x, t) and s(t), respectively:

5.0 πx 2Cos (πt)( 1+ 5.0 Sin (πt − x) U (x,t) = , 0 ≤ x ≤ s(t) 1( + 5.0 Sin (πt)) 2

s(t) = 1+ 5.0 Sin (πt), t ≥ 0 .

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Three time level finite- difference regularization

By using the three time- level finite-difference, we can get the equation (1):

1 3 1  5 3 1   (u − u ) − (u − u ) +  (u − u ) − (u − u ) 12 k 2 i+ ,1 j+1 i+ ,1 j 2 i+ ,1 j i+ ,1 j−1  6k 2 i, j+1 i, j 2 i, j i, j−1 

1 3 1  1 +  (u − u ) − (u − u ) − (u − 2u + u ) = f (x,t) 12 k 2 i− ,1 j+1 i− ,1 j 2 i− ,1 j i− ,1 j−1  h 2 i+ ,1 j+1 i, j i− ,1 j+1

(6) and truncation error of equation (6) is (0 k 2 ) + (0 h 4 ) . And equation (6) can be written as

 3   3  1  −12 r u + 15( + 24 r)u +  −12 r u = 2u + 20 u + 2u − u  2  i− ,1 j+1 i, j+1  2  i+ ,1 j+1 i− ,1 j i, j i+ ,1 j 2 i− ,1 j−1

1 − 5u − u +12 kf (x ,t ) (7) i, j−1 2 i+ ,1 j−1 i, j j where r = k . h 2

For known boundary values they can be written as

u ,0 j = 0

u N , j = 0

Hence, the equation (7) can be written matrix form as:

Au j+1 = Bu j − Cu j−1 + D j (8)

−1 −1 −1 u j+1 = A Bu j − A Cu j−1 + A D (9) where D is a vector of know f(x, t) values and

 3  15 + 24 r −12 r  2  3 3   −12 r 15 + 24 r −12 r  A =  2 2   . . .   3   −12 r 15 + 24 r  2 

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 1  5  20 2  2   1 1   2 20 2   5  B = and C = 2 2 are of order (N-1).  . . .       . . .   2 20   1   5  2 

Equation (9) can be written as

 u  A−1B | − A−1C  u   A−1D   j+1     j    − − − =  − | −  − − − + − − −          u j   I | 0   u j−1   0 

' i.e. v j+1 = Pv j + C , A has distinct eigenvalues and all the sub matrices of P commute with each other so ε ξ  k − k the eigenvalues λ of P are the eigenvalues of   where ε is the kth eigenvalue of B, ξ is µk µk  k k  1 0  the kth eigenvalue of C and µk is the kth eigenvalue of A.As     2 ε k ξ k det( P − λI) = 0 = λ −  λ +    µk   µk  sπ sπ sπ where ε = 20 + 4Cos , ξ = 5 + Cos and µ = 15 + 24 r + 3( − 24 r)Cos k N +1 k N +1 k N +1

2 and λ = {ε k ± ε k − 4ξ k µk } 2/ µk .

Hence, λ ≤ 1for all r. Therefore the equations are unconditionally stable. It is shown in Richtmyer & Morton (1967) that same equations are also stable for all r>0 as mesh lengths tend to zero.

CONCLUSION In this paper, we presented an implicit finite- difference method for one dimensional Stefan-like problem. All the computational results obtained by using the schemes outlined in the previous section show good agreement with the exact solution. As a conclusion the three time-level finite-difference method is accurate and efficient to solve Stefan-like problems. Note that the results obtained by the present method are excellent agreement with the exact results of Cho (2002) and are superior to the results obtained by Kutluay (2005).

Table 1. shows the values of the temperature distribution of problem (a) for the indicated values of t obtained by the present method, along with the corresponding results of the other authors. Table 2. shows the values of the temperature distribution of problem (b) for the indicated values of t obtained by the present method, along with the corresponding results of the other authors.

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Table 1. Values of the temperature distribution of problem (a) at t f = 0.1 , h=0.0125. Values of the

interface movement at t f = 0.1 2.718280, exact solution 2.718282 .

Numerical solution h=0.005 Exact solution t Present Kutluay [19] [18]

0.1 0.665024 0.665109 0.665015 0.2 1.182251 1.182432 1.182249 0.3 1.551709 1.551959 1.551702 0.4 1.773377 1.773684 1.773373 0.5 1.847269 1.847601 1.847264 0.6 1.773380 1.773709 1.773373 0.7 1.551705 1.552004 1.551702 0.8 1.182249 1.182485 1.182249 0.9 0.665015 0.665150 0.665015

Table 2. Values of the temperature distribution of problem (b) at t f = 0.1 , h=0.0125. Values of the

interface movement at t f = 0.1 1.475520, exact solution 1.475528 .

Numerical solution h=0.005 Exact solution t [18] Present Kutluay [19]

0.1 0.006440 0.006416 0.006446 0.022915 0.022836 0.022919 0.2 0.3 0.045118 0.044974 0.045122 0.4 0.068753 0.068542 0.068758 0.5 0.089522 0.089252 0.089528 0.6 0.103130 0.102820 0.103136 0.7 0.105279 0.104960 0.105285 0.091670 0.091390 0.091677 0.8 0.9 0.058009 0.057829 0.058014

ACKNOWLEDGEMENT I would like to thank to my supervisor Prof. Dr. Turgut Özi ş for all contributions he has made for my academic improvements and guiding me with his suggestions.

REFERENCES Carslaw, H. S. & Jeager, J. C., (1959) Conduction of heat in solids, second ed., Clarendon press, Oxford. Cho, C. K., (2002), A new approach for numerical identification of free boundary, Appl. Math. Comput. 133, 131-145. Crank, J., (1957), Two methods for the numerical solution of moving boundary problems in diffusion and heat flow, Quart. J. Mech. Appl. Math. X (2), 220-231. Crank, J., (1987) Free and moving boundary problems, Clarendon press, Oxford. Crank, J., & Gupta, R. S., (1975), Isotherm migration method in two-dimensions, Int. J. Heat Mass Transfer 18, 1101-1107. Crank, J. & Özis, T., (1980), Numerical solution of free boundary problem by interchanging dependent and independent variables, J. Ins. Math. Appl. 26, 77-85.

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Fasano, A. & Primicerio, M., (1979), Free boundary problems for non-linear parabolic equations with nonlinear free boundary conditions, J. Math. Anal. Appl. 72, 247-273. Furzeland, R. M., (1977),A survey of the formulation and solution of free and moving boundary (Stefan) problems, Technical report TR/76,Brunel University, Uxbridge, United Kingdom. Gülkaç, V., & Özi ş, T., (2004), On a Lod method for solution of two-dimensional fusion problem with convective boundary conditions, Int. Comm. Heat Mass Transfer, 31 597-606. Gülkaç, V., (2005), On the finite differences schemes for the numerical solution of two-dimensional moving boundary problem, Appl. Math. and Comput. 168, 549-556. Hill, J., (1987),One-dimensional Stefan problem: An Introduction, Longman Scientific and Technical, Essex. Kutluay, S., (2005), Numerical schemes for one-dimensional Stefan-like problems with a forcing term, Appl. Math. and Comput. 168 (2005) 1159-1168. Landau, H. G., (1950), Heat conduction in a melting solid, Quart. Appl. Math. 8, 81-94. Muehlbauer, J. C., & Sunderland, J. E., (1965), Heat conduction with freezing or melting, Appl. Mech. Rev. 18 (12), 951-959. Özi ş, T., & Gülkaç, V., (2003),Application of variable interchange method for solution of two dimensional fusion problem with convective boundary conditions, Numerical Heat and Mass Transfer A 44, 85- 95. Radhey, R. S., & Gupta, S., & Kumar, A., (1985) Treatment of multi-dimensional moving boundary problems by co-ordinate transformation, Int. J. Heat Mass Transfer 8, 1355-1366. Richtmyer, R. D., & Morton, K. W., (1967), Difference methods for initial-value problems, Interscience Publishers, New York. Smith, G. D., (1987), Numerical Solution of partial differential equations: Finite difference Methods, Clarendon press, Oxford, 1987. Sparrow, E. M., & Hsu, C. F. (1981), Analysis of two-dimensional freezing an outside of an the outside of a coolant carrying tube, Int. J. Heat Mass Transfer 24, 1345-1357.

24 Ozean Journal of Applied Sciences 2(1), 2009

A numerical application of the semi-implicit pseudo-spectral method for the Korteweg-de Vries Equation

V. Gulkac 1, T. Ozis 2

1Faculty of Arts and Science, Department of Mathematics, Kocaeli University, Kocaeli, Turkey 2Faculty of Science, Department of Mathematics, Ege University, Bornova-Izmir, Turkey E-mail: [email protected]

______

Abstract: In this paper, we present a numerical method for solving KdV-equation. The KdV-equation is one of the nonlinear partial equations which combines the effect of nonlinearity ( єuu x) and dissipation (µuxxx). In this paper the semi-implicit pseudo-spectral method used to develop a numerical solution of the KdV equation. Numerical simulations under taken proved that the scheme can model the KdV equation faithfully. The semi-implicit pseudo-spectral method for the KdV equation obtains and numerical results demonstrate that the method is efficient and reliable.

Keywords: KdV equation, pseudo-spectral method ______

INTRODUCTION

The first documented observation of the solitary wave was made in 1834 by the John Scott Russell. Whilst observing the movement of a canal barge, Scott Russell noticed a novel type of water wave on the surface of the canal (Dod et al 1998). The study of the soliton as a stable particle-like state of nonlinear systems has so caught the imagination of physicists and mathematicians of all descriptions that it can genuinely claim to be one of the few interdisciplinary subjects of modern day mathematical physics. The study of solitons is a good example of an area of research which has brought together workers indifferent areas ranging from experimental physics to pure mathematics.

KdV-equation has several connections to physical problems. In addition to being the governing equation of the string in the Fermi-Pasta-Ulam problem in the continuum limit , approximately describes the evolution of long, one-dimensional waves in many physical settings, including shallow-water waves with weakly non-linear restoring forces, long interval waves in a density-stratified ocean, ion-acoustic waves in plasma, acoustic waves on a crystal lattice, and more.

One- dimensional non-linear KdV-equation was originally first derived by Korteweg –de Vries (Dod et al, 1998) to describe the behavior of one-dimensional shallow water solitary waves to be called solitons with small but finite amplitude. In fact, the Korteweg-de Vries equations are most known ones because of their large applications in the nonlinear integrable wave equations and of the KdV type has received little attention. The KdV-equation has been studied analytically by Zabusky (1967), Gardner et al (1974) and Fomberg & Witham, (1978). The KdV-equation has motivated considerable research into numerical solution methods by several authors.

The KdV-equation has been solved numerically based on finite-difference schemes by Vliegenhart, (1971), Petrov-Galerkin finite element methods by Sanz-Serna & Christie, (1981) and Greig & Morris, (1976) proposed and alternative algorithm to the Zabusky-Kruskal method, Alexander & Morris, (1979) extended previous numerical work on KdV and RLW equations. Recently, the study of the solitons has been focus of

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many research groups (Barros & Cardenas, 2001, Ceniceros, 2002, Kim & Ishimaru, 1999, Pasquetti, 2006, Triki, 2007). In this paper we have applied the semi implicit pseudo-spectral method to the one- dimensional KdV-equation with a set of initial and boundary conditions in order to obtain its numerical solutions.

2. Governing Equation

In this paper our main focus for governing is given by the KdV equation:

U t + εUU x + µU xxx = ,0 a ≤ x ≤ b, t > 0 (1) where ε and µ are positive constants and a, b are real constants.

Test problem (1): First, we consider the KdV-equation (1) subject to the boundary conditions U(0, t) = 0, t>0

(2) U(2, t) = 0, t>0

Initial condition: U(x, 0) =3csech 2(Ax+D), 0 ≤ x ≤ 2 (3)

The exact solution is given by Alexander and Morris (1979).

U(x, t) = 3csech 2(Ax-Bt+D), 0 ≤ x ≤ 2 (4) where D, c constants and A and B defined by A1/2 εc/ µ , B= ε cA. This problem representing a single soliton moving with unchanged amplitude from left to right at a steady velocity ε c.

Test problem (2): Second, we consider the KdV- equation (1) with the boundary conditions U(0, t) = 0, t>0 (5) U(4, t) = 0 t>0 and the initial condition shall be derived from the exact solution (Taha & Ablowitz, 1984). This problem represents the interaction of two solitons.

3. Semi-implicit pseudo-spectral method Semi-implicit and fully-implicit pseudo-spectral methods has been well studied in the literature (Fournier et al, 2005, Tse & Chasnow 1998, Yee & Shinn 1986), including, for instance thermal convection in rotating ax symmetric container, hyperbolic conservation laws with stiff source terms, penetrative convection, Sturm Liouville problems, and more.

Nouri and Sloan (1985) studied Fourier pseudo-spectral methods for solve the KdV equation. Here, we extend the (Chan & Kerkhoven, 1985) scheme for equation (1). Equation (1) is integrated in time by the leap frog finite-difference scheme in the spectral space. The infinite interval is replaced by –L

U(-L, t) = U(L, t) =0.

When we apply the (Chan-Kerkhoven, 1985) scheme “noise” propagation problem due to the numerical scheme does not appear to be serious when L is large enough and the proper time step ∆ t is chosen.

By introducing ξ = sx + π where s= π / L

26 Ozean Journal of Applied Sciences 2(1), 2009

We will transform U(x, t) into V ( ξ , t). Thus equation (1) will be transformed into 3 Vt + εsVV ξ + µs Vξξξ = 0 (6) sV 2 Let W( ξ t), = , then the nonlinear term εsVV can be written as W to gives 2 ξ ξ 3 (7) Vt + εWξ + µs Vξξξ = 0 For the numerical solution of equation (6), we discreet the interval [0,2 π] by N+1 equidistant points. We let

ξ0 =0, ξ1 , ξ2, …, ξn =2 π so that ∆ξ =2 π/N.

In this case, N will always be even and is to be a power of 2. So we let m=N/2. The discrete ∧ Fourier Transform (DFT) of V( ξj, t) for j=0,1, 2,…,N-1 is denoted by V( p,t) is given by 2πjp ∧ N −1 −( )i 1 N V( p,t) = ∑ V( ξ j ,t)e N j=0 Where p=-m,-m+1,…,m-1. ∧ The inverse Fourier Transform of V( p,t) for p=-m,-m+1,…, m-1 is denoted by V( ξ j ,t) written as m−1 ∧ 1 2( πjp / N )i V( ξ j ,t) = ∑V( p,t)e N p=−m where j=0,1,2,…,N-1 and i is the imaginary number.

The DTF of equation (3) with respect to ξ gives

∧ ∧ ∧ V( p,t) + εip W ( p,t) − iµp 3 s 3 V( p,t) = 0 (8) By using leap frog approximation ∧ ∧ ∧ V()()p,t + ∆t − V p, t- ∆, V( p,t) = 2t and ∧  ∧ ∧ ∧  p 3 V()p,t = p 3 − 3V( p,t + ∆t) − 4 V( p,t) + V( p,t − ∆t)   ∧ ∧ ∧ ∧ ∧ ∧ and denote V( p,t + ∆t) by V pt , V( p,t − ∆t) by V mt and V( p,t) by V t , where ∧ ∧ ∧ 4 V t = 2V pt + 2V mt then ∧ ∧ ∧ 3 3   p V( p,t) = p − 5V pt − V mt  

And then equation (4) can be written as; ∧ ∧ ∧ ∧ ∧ V pt − V mt 1 3 3 3   + εip W ( p,t) + µi p s − 5V pt − V mt = 0 2t 2   (9) by multiplying the above equation (9) with 2 ∆ t ,

27 Ozean Journal of Applied Sciences 2(1), 2009

we get, ∧ ∧ ∧ ∧ ∧  1 3 3 3   V pt = 2∆t− εip W ( p,t) − µi p s − 5V pt − V mt  + V mt (10)  2   So equation (11) will be our forward scheme, ∧ ∧ ∧ 1  3 3  V pt = − 2∆tip W ( p,t) + 1( − ∆tµip s )V mt 1+ 5∆tµi 3 p 3 s 3   (11)

4. Numerical results and discussion We use the semi-implicit pseudo-spectral method to solve the KdV equation. The numerical results obtained by the present method are compared with those obtained by the exact values in (Alexander & Morris, 1979, Taha & Ablowitz, 1984). The numerical results obtained by the two schemes have been compared with the exact solutions and are found to be in good agreement with each other. It is shown that the numerical solutions exhibit the expected convergence to the exact one as the mesh size is reduced. All working out were done for the parameters µ= 4.84x10 -4 , ε= 1.0, D= -6, c= 0.3. The numerical results obtained by the present method ( ∆t= 0.00001, ∆t= 0.005, ∆t= 0.01, N= 100) for the test problems at different times are distinguished with exact values in Tables 1-2. Therefore, we can say that the semi- implicit pseudo- spectral method can solve the KdV equation powerfully. The outstanding accuracy due to the spectral type discretization has been demonstrated by comparisons with (Alexander & Morris, 1976, Taha & Ablowitz, 1984). In order to show how good the present scheme demonstrates the physical behavior of each test problem we only give the figures in Fig. 1 and 2. Both results for each problem are designed on the same figure, but the curves cannot be distinguishable since they are very close to each other. We have presented a semi-implicit pseudo-spectral method allowing for the KdV-equation. The method is based discrete Fourier Transform (DTF). The KdV-equation is integrated in time by the leap-frog finite-difference scheme in the spectral space. It has been shown that due to its semi-implicitness the approach features fairly good stability properties and that it is superior to corresponding explicit methods. While we have focused our considerations on the KdV-equation, due to the inherent flexibility of the semi- implicit pseudo-spectral scheme, the applicability of the proposed solution procedure is not limited to such kind of problems.

Table 1. Comparison between present and exact solution of the problem (1).

t= 0.00001 t= 0.005 t= 0.01 X Present Exact Present Exact Present Exact Method Solution Method Solution Method Solution 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.00026664 0.00026663 0.00026664 0.00025688 0.00026664 0.00024746 0.2 0.00320970 0.00320953 0.00320971 0.00309232 0.00320970 0.00297915 0.3 0.03794668 0.03794496 0.03794669 0.03658529 0.03794791 0.03527077 0.4 0.36617770 0.36615672 0.36617900 0.35574611 0.36618033 0.34551636 0.5 0.85626487 0.85627907 0.85626790 0.86305601 0.85627101 0.86931944 0.6 0.17201067 0.17202234 0.17201139 0.17787423 0.17201117 0.18391219 0.7 0.01567985 0.01568113 0.01568003 0.01627119 0.01568001 0.01688449 0.8 0.00131101 0.00131108 0.00135099 0.00136083 0.00136054 0.00141257 0.9 0.00010880 0.00010881 0.00010884 0.00011294 0.00011294 0.00011724 1.0 0.00000900 0.00000903 0.00000912 0.00000937 0.00000913 0.00000972 1.1 0.00000075 0.00000075 0.00000076 0.00000078 0.00000079 0.00000081 1.2 0.00000006 0.00000006 0.00000006 0.00000006 0.00000007 0.00000007 1.3 0.00000001 0.00000001 0.00000001 0.00000001 0.00000001 0.00000001 1.4 0.0 0.0 0.0 0.0 0.0 0.0

28 Ozean Journal of Applied Sciences 2(1), 2009

2.0 0.0 0.0 0.0 0.0 0.0 0.0 Table 2. Comparison between present and exact solution of the problem (2).

t= 0.00001 t= 0.005 t= 0.01 x Present Exact Present Exact Present Exact Method Solution Method Solution Method Solution 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.2 0.00146228 0.00146220 0.00145930 0.00140886 0.00145931 0.00135737 0.4 0.16469769 0.16468845 0.16408647 0.16006747 0.16008647 0.15552281 0.6 0.07126427 0.07126799 0.07126445 0.07370500 0.07236427 0.07622045 0.8 0.00130930 0.00130936 0.00130930 0.00135498 0.00130930 0.00140230 1.0 0.01295397 0.01295441 0.01296469 0.01335669 0.01296469 0.01377158 1.2 0.11258667 0.11258826 0.11258767 0.11389579 0.11258776 0.11516847 1.4 0.05012460 0.05012214 0.05012350 0.04886617 0.05012350 0.04762990 1.6 0.00350790 0.00350778 0.00350790 0.00339791 0.00350791 0.00329122 1.8 0.00020050 0.00020050 0.00020050 0.00019414 0.00020050 0.00018797 2.0 0.00001132 0.00001132 0.00001130 0.00001096 0.00001130 0.00001061 2.2 0.00000064 0.00000064 0.00000064 0.00000064 0.00000064 0.00000060 2.4 0.00000004 0.00000004 0.00000004 0.00000003 0.00000004 0.00000003 2.6 0.00000001 0.00000001 0.00000001 0.00000001 0.00000001 0.00000001 2.8 0.0 0.0 0.0 0.0 0.0 0.0

4.0 0.0 0.0 0.0 0.0 0.0 0.0

1,0

0,9

0,8

0,7

0,6 U 0,5

0,4

0,3

0,2

0,1

0,0 0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 x

Fig. 1. Present method and exact solution of the problem (1) at t= 0.00001, t= 0.005 and t= 0.01.

29 Ozean Journal of Applied Sciences 2(1), 2009

0,18

0,16

0,14

0,12

U 0,10

0,08

0,06

0,04

0,02

0,00 0,0 0,4 0,8 1,2 1,6 2,0 2,4 2,8 3,2 3,6 4,0 x

Fig. 2. Present method and exact solution of the problem (2) at t= 0.00001, t= 0.005 and t= 0.01.

REFERENCES

Alexander, M. E., & Morris, J. L. L., (1979), Galerkin methods for some model equations for nonlinear dispersive waves, J. Comp. Phys. 30, 428-451. Barros, S. R., & Cardenas, J. W., (2001), A nonlinear Galerkin method for the shallow-water equations on periodic domains, J. Comp. Phys. 172, 592-608. Ceniceros, H. D., (2002), A semi-implicit moving mesh method for the focusing nonlinear Schrödinger equation, Comm. on Pure and Appl. Anals. 1, 1-14. Chan, T. F. & Kerkhoven, T., (1985), Fourier method with extended stability intervals for the Korteweg-de Vries equation, Siam J. Numer. Analys. 22, 441-454. Dod, R. K et al, (1998), Solitons and non linear wave equations, Academic Press, New York. Fornberg, B., & Whitham, G. B., (1978), A numerical and theoretical study of certain nonlinear wave phenomena. Phil. Trans. R. Soc. Lond., 289, pp., 374-404. Fournier, A., & Bunge, H. P. & Hollerbach, R., & Violette, J. P., (2005),A Fourier-spectral element algorithm for thermal convection in rotating axisymmetric containers, J. Comp. Phys. 204 462-489. Gardner, C. S. et al., (1974). Korteweg-de Vries equation and generalizations. VI. Method of exact solutions. Comm. Pure Appl. Math., 27, pp., 97-133. Greig, L. S. & Morris, J. L. L., (1976), A hopscotch method for the Korteweg-de Vries equation, J. Comput. Phys. 20, 64-80. Kim, A. D., & Ishimaru, A., (1999), A Chebyshev spectral method for radiative transfer equations applied to electromagnetic wave propagation and scattering in a discrete random medium, J. Comp. Phys. 152, 264-280. Nouri, F. Z., & Sloan, D. M., (1985), A comparison of Fourier pseudo-spectral methods for the solution of the Korteweg-de Vries equation, J. Comp. Phys. 83, 324-344.

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Pasquetti, R., (2006), Spectral vanishing viscosity method for large-eddy simulation of turbulent flows, Journal of Scientific Computing . Sanz-Serna, J. M., & Christie, I., (1981), Petrov- Galerkin methods for nonlinear dispersive waves. J. Comp. Phys. 39, pp., 94-102. Taha, T. R., & Ablowitz, M. J., (1984), Analytic and numerical aspects of certain nonlinear evolution equations III. Numerical KdV Equation, J. Comp. Phys. 55, 231-253. Triki, H., (2007), Energy transfer in a dispersion-managed Korteweg-de Vries system, Mathematics and Computer in Simulation , article in press. Tse, K. L. & Chasnov, J. R., (1998), A Fourier- Hermit pseudospectral method for penetrative convection, J. Comp. Phys. 142, 489-505. Vliegenthard, A. C., (1971), on finite-difference methods for the KdV equation. J. Engrg. Math., 51, 137- 155. Yee, H. C. & Shinn, J. L., (1986), Semi-implicit and fully-implicit shock-capturing methods for hyperbolic conservation laws with stiff source terms, Nasa Technical Memorandum 98415, December. Zabusky, N. J., (1967), A synergetic approach to problem of nonlinear dispersive wave propagation and interaction, in: W. Ames (Ed.), Proceedings of the symposium on nonlinear Partial Differential Equations, Academic Press, New York, pp. 223-258.

Establishing Conditions for Determination of Inorganic Arsenic By Using Flotation and Preconcentration Techniques

Safiye Atar and Ümit Ay* *Department of Chemistry, Kocaeli University, Izmit, TURKEY E-mail: [email protected] or [email protected]

______

Abstract: Colloid precipitate flotation of arsenic from fresh water is applied for preconcentration and separation. Optimal conditions using iron (III) hexamethylenedithiocarbamate as collectors were investigated. Various factors affecting the arsenic recovery, including collector mass, pH of the working medium, electrokinetic potential of the collector particle surfaces, type of surfactant, induction time etc., were checked. Within the optimal pH range (2.5-3.0) arsenic was separated quantitatively (100.0% - 90.0%) with 5mg Fe (III) as collector. The content of arsenic was determined by graphite furnace atomic absorption spectrometry. The detection limit of arsenic by the method described is 0.035mg/L.

Keywords: arsenic, flotation, preconcentration, atomic absorption spectrometry ______

INTRODUCTION The determination of arsenic and its compounds in environmental samples is growing interest of its high toxicity and abundance in the environment. Arsenic contamination in water causes severe health risk and impacts negatively in the environment. So it is highly important to know the actual arsenic species in millions of water samples. Both pure arsenic and arsenic combined with other mineral ores are common in nature and it can be easily transmitted to water and plants therefore to foodstuffs. Arsenic used for medical purposes as well as several fields such as agriculture, farm animals, electronics, industry and metallurgy. Today, it is known that consumption of arsenic even in small amounts has carcinogenic impacts (Mandal and Suzuki, 2002). Determining arsenic and arsenic components on environmental samples has become more and more important due to high levels of toxicity and presence on environment. (Rupasinghe et al., 2001). Arsenic contamination in water leads to severe health conditions and negative impact on environment (Sigrist and Beldomenico, 2004). Arsenite (As III), Arsenate (As V), mono-methyl arsenic acid (MMA), di-methyl arsenic acid (DMA), arsenobetaine, arsenocholine etc. are the main arsenic types found in natural water samples. The toxicity levels and metabolic rate of these arsenic types are different (Arabinda, 2001). The toxicity of arsenic found in natural water does not only depend on its concentration but also depends on the chemical formula. Composition of inorganic forms is more poisonous than organic forms (Cabon and Cabon, 2000). Atomic absorption spectroscopy (AAS) provides accurate and fast determination of several heavy metals on water matrix. However, determining heavy metals of very small concentrations in water samples can not performed directly. First of all, step of pre-concentration and separation is required for this (Cundeva et al., 2002).

Generally, there are traces of arsenic types in natural waters. There are a few sensitive and selective enough analytic methods available for determining types of arsenic traces in natural waters. Hence, sensitive and accurate methods must be improved for separation and de-concentration of traces of As (III) and As (V) (Zhang et al., 2004). Flotation is a process that brings dispersed solid or liquid particles, sediments, colloidal particles and substances dissolved in water to the surface of aqueous phase via the increase of gas bubbles. Flotation is often used for concentration of these elements once trace elements are precipitated together on appropriate collectors (Zolotov and Kuzmin, 1990). Advantages of flotation technique compared to other techniques can be listed as follows; the method is fast, perfectness in recovery of examined elements, simplicity and reasonable prices of the equipments required for pre-concentration, using lesser amounts of surfactant, eliminating certain severe risk to occur on high blank volumes due to small air bubbles necessary for providing appropriate flotation, ability to analyze high volume sample solutions.

In most cases, the separation and preconcentration techniques are generally required to determine arsenic at low concentration levels in natural waters. For the purpose of this study, flotation method is applied for preconcentration of arsenic present in natural waters in small concentrations. Availability of Fe (HMDTC)3 as flotation collector for the purpose of collection arsenic has been examined. Graphite furnace atomic absorption spectrometry device is used for determining the experimental conditions.

EXPERIMENTAL

Apparatus All atomic absorption spectrometric measurements were made with a Perkin-Elmer AAnalyst 800 atomic absorption spectrometer with THGA graphite furnace. A arsenic Perkin-Elmer hollow cathode lamp was applied as a radiation source. Instrumental parameters (temperature and time) for the GFAAS determination were established by extensive testing and were 110 °C and 20 s (for drying), 1200 °C and 30 s (for pyrolysis), 2000 °C and 5s (for atomizing) and 2700 °C and 3 s (for cleaning).The flotation separations were carried out in a cylindrical glass cell (4x105 cm) with a sintered glass disc (porosity No.4) at its bottom to produce air bubbling. A combined glass electrode and the pH meter (Hanna pH 211) were used to monitor the pH of the solutions during the step of incorporation of arsenic traces in the collector mixture.

Reagents and standards The aqueous solutions were prepared by deionized redistilled water. All chemicals used for the preparation of solutions were of an analytical-reagent grade (Merck). Fe (III) stock solution (10 mg / ml) is prepared by dissolving appropriate amount of Fe (NO 3)3.9H 2O ( Merck, Darmstadt, Germany). Arsenic (III) stock solution is prepared as 1000 µg /ml by taking out of suitable salt. Then, the standard arsenic of 25 µg / ml used for the experiment is prepared by taking appropriate amount from this stock solvent. 0.1M HMDTC - anion solution is prepared by dissolving appropriate amount of HMA-HMDTC crystal in 96 % ethanol solution. As HMDTC solution does not last for a long period of time, it must be prepared freshly. Hence, the solutions of 25 ml are prepared. Furthermore, the HMA-HMDTC used is synthesized under laboratory conditions (Busev et al., 1970). Triton X-100 and NaDDS, surface active agents used for creating foam are prepared as 0.5 % solutions; Triton X-100 in deionized water, NaDDS in 96 % ethanol solution. KOH solutions of 2.5 % and 10 % and 0.1 M HNO 3 solutions are used for regulating pH. Saturated KNO 3 solution is prepared for regulating the ion intensity. 0.1M NH 4NO 3 solution is prepared and used for taking the precipitate remaining on the glass electrode and in beakers at the end of collective precipitate. 4M HNO 3 and concentrated HNO 3 are used for dissolving the precipitate created during flotation process. Ethanol and distillate water are used for colon cleaning at the end flotation.

Separation procedure The separation procedure applied in this work consisted of coprecipitation and flotation. During the coprecipitation, carried out in the beaker, trace of arsenic was incorporated in the collector particles of Fe (HMDTC) 3. During the flotation, performed in the flotation cell, they were separated from the water phase by air bubbles together with the collector precipitate.

Coprecipitation pH meter is calibrated and then glass electrode is immersed in 1 l of deionized water poured in beakers. Beaker is mixed on magnetic mixer. Solution’s pH has become 2-3 with 0.1M HNO 3. 6 ml saturated KNO 3 solution is added and 5 mg Fe(III) is introduced by adding 0.5 ml of 10 mg/ml Fe(III) solution. Then, 1 ml of 25 ppm arsenic solution is added to the solution. pH value is carefully adjusted to 6 via 2.5 % and 10 % KOH solutions. 3 ml 0.1M HMA-HMDTC is added and mixed for 15 minutes to achieve reaction. Meanwhile, formation of brown-black precipitate is observed. The formation of Fe (HMDTC) 3 precipitate is illustrated on Figure 1. The pH level is kept approximately 6-6.5 pH during all these processes. The necessary pH is kept at a fixed level by adding required acid or base solutions when there is a deviation from the pH value. Following the pH optimization performed, it is confirmed that the optimum pH value for arsenic is 2.5. Hence, entire study is made on the basis of pH 2.5. After mixing for a period of 15 minutes, 1 ml of 0.5 % NaDDS solution is added to the solution and magnetic mixer is closed. Surface of pH electrode is washed with a small amount of 0.1 M NH 4NO 3 solution and the solution in the beaker is carefully emptied from the top of flotation colon without dropping the magnet into the colon. Beaker is washed with a certain amount of 0.1M NH 4NO 3 solution for the purpose of cleaning the complex remaining in the beaker after the solution is emptied.

Ozean Journal of Applied Sciences 2(1), 2009

Fig.1. Iron (III) hexamethylenedithiocarbamate, applied as a collector for trace elements flotation preconcentration

Procedure for flotation A stream of numerous air bubbles is passed through the solution for 1 min. Gas bubbles raised the black precipitate flakes to the water phase surface. There a frothy layer is formed and the water in the cell became completely clear and free of solid particles. Then, the glass pipette-tube is immersed into the cell through the layer on the liquid surface (a mixture of coagulated precipitate and surfactant foam) and the water phase is sucked off. The solid phase remained in the cell is decomposed by 5 ml hot concentrated HNO 3. When the liquid in the cell becomes clear yellow, it is sucked off through the bottom of the cell and collected in a volumetric bottle of 25 ml. The cell and the pipette-tube are washed with 4 mol/l HNO 3 solution. The flask is filled up to the mark with 4mol/l HNO 3 and the sample is ready for GFAAS measurements.

RESULTS AND DISCUSSION The influence of pH on the arsenic flotation The separation procedure employed in this work consists of two steps: formation of a sublate in a beaker and flotation by air bubbles in a flotation cell. Those two processes depend on medium pH. The formation of sublate begins by formation of solid collector precipitate. Then the collector interacts with analyte ionic species from matrix incorporating them in its structure. During air bubble flotation separation, pH had to be the same, since variations can induce a decomposition of solid sublate and, consequently, a loss of analytes. Therefore, the optimization of pH must be performed with special care (Ay et al., 2004, 2005).

The influence of pH on the arsenic flotation recovery (R) was studied within the range 2.5 to 9.5. Standard solutions ( 1l ) containing 25 µg of arsenic was floated with constant iron mass ( 5mg ) and 3ml of 0.1M HMDTC – at constant ionic strength by addition of 1ml 0.5% alcoholic solution NaDDS. The R/pH curves (Fig.2) illustrate the arsenic recovery dependence on medium pH.

35 Ozean Journal of Applied Sciences 2(1), 2009

140

120

100

Recovery (%) Recovery 40

0 0 2 4 6 8 10 pH

Fig.2. Influence of pH on arsenic flotation recoveries (5mg Fe, 3ml of 0.1M HMDTC -, NaDDS as surfactant)

Iron mass Arsenic flotation recoveries depend on iron mass. This effect was investigated by changing the mass of iron added to test solutions (1l) containing 25 µg of arsenic from 2.5-100 mg. During the preconcentration all other experimental parameters, i.e., pH = 2.5, ionic strength, 3ml of 0.1M HMDTC -, were kept constant. The data presented in Fig.3 show that arsenic flotation can be performed correctly with 5 mg iron. Therefore, 5mg of iron per liter of solution was selected as the most appropriate for the procedure.

120

100

40 Recovery (%) Recovery 20

0 20 40 60 80 100 Fe (mg)

Fig.3. Influence of iron mass on arsenic recovery (R) (at constant pH = 2.5, 3 ml of 0.1M HMDTC -, NaDDS as surfactant)

Amount of HMDTC - This influence was studied by varying the HMDTC - amount, while iron mass, pH (2.5) and ionic strength were kept constant. The effect of HMDTC - quantity on flotation capacity is examined on a flotation series formed by used different amounts of 0.1M HMDTC - solution (1, 2, 3, 4, 5 and 6 ml) while all other experimental parameters are kept steady. During pre-concentration process, pH 2.5, ionic intensity shall be fixed and the amount of added iron will be 5 mg. 1l of each solution includes 25µg arsenic. Maximum recovery for arsenic determination is achieved when 3 ml 0.1M HMDTC is added during the optimization studies performed. Hence, this value is used for subsequent studies.

36 Ozean Journal of Applied Sciences 2(1), 2009

ζ potential of the collector particle surfaces The electro-kinetic potential of collectors used is an important parameter for selection of surface active agents. Hence, the potential of collector particle surfaces must be known. Experimental results show that potential of Fe 2O3 x H 2O particles is 25.2 – 28.0 mV whereas the potential of second collector Fe (HMDTC) 3 is 68,4 – 69,0 mV. The positive values on these two collector potentials show that anionic surface active agents can be appropriate for flotation. (Cundeva et al., 2000). Negative charged groups of NaDDS anion incline towards the positive surface of Fe(HMDTC) 3 particles and a better separation technique is achieved thanks to steady-state micelles. The reason of better hydrophobicity is the larger HMDTC – hydrocarbon ring (Stafilov et al., 2000). Hence, Fe(HMDTC) 3 is used as collector for the purpose of this study.

Selection of surfactant

The potential value (68.4 – 69.0 mV) of Fe(HMDTC) 3 shows that cationic surfactants can not be effective during flotation. Positive charge on the collector’s surface will alienate the cationic surfactants. Anionic surfactants attract each other since they are charged opposite to the collector particle surfaces and flotation is formed by means of micelle.

For the purpose of experiments, anionic surfactant NaDDS is used as surface active substance and arsenic is successfully floated. It is confirmed that this surfactant is not effective for flotation process performed by using non-ionic triton X-100. There were plenty of foam on the top of aqueous phase however Fe (HMDTC) 3 precipitate could not separated with flotation and remained in water.

CONCLUSIONS

In this study, conditions for determination of arsenic when Fe (HMDTC) 3 is used as collector are investigated. Inorganic arsenic has gone under flotation process with this collector for the first time. Arsenic is collected with a complex created as pH 2.5 with 5 mg iron and 3 ml 0.1M HMDTC, and it can be floated on flotation colon with sodium dodecyl sulfate surface active agent. Results are achieved with approximately 95 % recovery on atomic absorption spectrometry. 40 times concentration of arsenic is succeeded under these conditions. The determination limit of arsenic determined by this method is 0.035 mg/l. Our opinion here is that arsenic forms a complex with HMDTC as a reaction mechanism and the mechanism formed is absorbed in Fe (HMDTC) 3.

ACKNOWLEDGEMENTS The authors wish to thank the Research Fund of the Kocaeli University for providing financial support (Project no.2381).

REFERENCES Arabinda, K. (2001). Literature survey of on-line elemental speciation in aqeous solution. Talanta , Vol.55, 1-217. Ay, Ü., Koyuncu, İ., Bundalevska, J.M., Cundeva, K., Stafilov, T., and Akçin, G. (2004). Atomic absorption spectrometry determination of Cd, Cu, Fe, Ni, Pb, Zn and Tl traces in seawater following flotation separation. Separation Science and Technology , 39(11), 2751-2765. Ay, Ü., Bundalevska, J.M., Koyuncu, İ., Cundeva, K., Akçin, G., and Stafilov, T. (2005). Separation of Tl (I) and Tl(III) from environmental water samples by flotation method coupled with zeeman ETAAS determination. Journal Of Environmental Science and Health, Part A 40, 1045-1054. Busev, A.I., By’rko, V.M., Tereshchenko, A.P., Novikavo, N.N., Nadina, V.P. and Terentiev, P.B. (1970). Atomic absorption and spectrographic determination of traces of heavy metals after their concentration by extraction hexamethileneammonium hexamethylene-ditiocarbamates. Zh. Anal. Khim. 25, 665-669.

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Cabon, J.Y., and Cabon, N. (2000). Determination of arsenic species in seawater by injection hydride generation in situ collection followed by graphite furnace atomic absorption spectrometry stability of As(III). Analytica Chimica Acta . 418, 19-31. Cundeva, K., Stafilov, T., and Pavlovska, G. (2000). Flotation separation of Cobalt and Copper from fresh waters and their determination by electrothermal atomic absorption spectrometry. Microchemical Journal . 65, 165-175. Cundeva, K., Stafilov, T., Zendelovska, D. and Pavlovska, G. (2002). Application of coprecipitate flotation as a method for selective separation of traces of Co, Cu, Ni and Pb in dolamite and gypsum and their determination by ETAAS. Bulletin of The Chemists Technologists of Macedonia. Vol. 21, No.1, 43-52. Mandal, B.K. and Suzuki, K.T. (2002). Arsenic round the World: A Review. Talanta . 58 (1), 201-235. Rupasinghe, T., Cardwell, T.J., Cattrall, R.W. and Lugue de Castro, M.D. (2001). Pervaporation-flow injection determination of arsenic based on hydride generation and the molybdenum blue reaction. Analytica Chimica Acta . 445(2), 229-238. Sigrist, M.E., and Beldomenico, H.R. (2004). Determination of inorganic arsenic species by flow injection hydride generation atomic absorption spectrometry with variable sodium tetrahydroborate concentrations. Spectrochimica Acta Part B 59, 1041-1045. Stafilov, T., Pavlovska, G. and Cundeva, K. (2000). Electrothermal atomic absorption spectrometric determination of nickel after its flotation enrichment by Iron(III) Hexamethylenedithiocarbamate. Turk J Chem 24, 303-310, Tübitak. Zhang, Q., Minami, H., Inoue, S., and Atsuya, I. (2004). Differential determination of trace amounts of arsenic(III) and arsenic(V) in seawater by solid sampling atomic absorption spectrometry after preconcentration by coprecipitation with a Nickel-Pyrrolidine Dithiocarbamate complex. Analytica Chimica Acta . 508 (1), 99-105. Zolotov, Y.A., and Kuzmin, N.M. (1990). Preconcentration of trace elements. Elsevier, Amsterdam.

38 Ozean Journal of Applied Sciences 2(1), 2009

Kernel Smoothing Function and Choosing Bandwidth for Non-Parametric Regression Methods 1

Murat Kayri and Gürol Zırhlıo ğlu Yuzuncu Yil University, Faculty of Education, Van/Turkey

______

Abstract: It is possible to get detailed results between independent and dependent variables in non- parametric regression methods. By using non-parametric regression methods, the estimation of curve may have complexity. This is a crucial problem to read and interpret the regression curve. To solve this problem, some smoothing functions were developed. Kernel function is one of the smoothing techniques. Kernel function choices the optimal bandwidth value (h) to get a readable curve. Also the distribution type is important for Kernel smoothing function. The Kernel function obtains the different curves according to distribution type (Gaussian, Uniform, Quartic, etc). To show Kernel smoothing process, internet dependency levels of intermediate students’ were evaluated. The relation between internet dependency point (dependent variable) and daily hours of internet use (independent variable) were examined and scatter plot with curve was obtained. In this study, in terms of different bandwidth values, some curves have been obtained and the differences of these curves have been argued.

Keywords: curve estimation, bandwidth, non-parametric distribution ______

INTRODUCTION It is known that regression model is too crucial process for estimation of future. Essentially, regression methods are gathered in three main topics. These are parametric, non-parametric and semi-parametric regression methods (Härdle, Müler, Sperlich & Werwatz, 2004; Kaki, 2004). In estimation of curve methods, parametric methods are not always capable of obtaining information sufficiently. For all that, it is difficult to get detailed information about population with using non-parametric methods (Härdle ve Tsybakov, 1997). Although parametric and linear equation (y = f(x)) can make possible to conclude any estimation for each person, non-linear function can’t conclude regression equation for each one. Generalized Linear Model (GLM) was developed to estimate parameters robustly because of parametric linear regression method can’t explain variance sources efficiently. But, GLM is vulnerable to explain a non-linear situation which can not interpret attitude of individual in distribution curve (Kaki 2004; Muller, 2001). In case of interpreting any one’s situation in population, non-parametric methods can be used as an alternative to GLM. It must also considered that non-parametric methods are not enough powerful to analyze plenty of discontinuous variables. And it will be difficult to get a regression curve (Pinkse, 1994). In literature, curse of dimensionality is too crucial problem and it leads unreadable curve for population. Some smoothing methods are used to solve the unreadable curve. By this way, it will be possible to reduce curse of dimensionality. Especially, using semi-parametric methods can obtain the most clarity curves with using partial linear models. Also, it can rescue the complexity by using Kernel smoothing method (Pinkse, 1994; Muller, 2001). The other smoothing method is Spline methods which has different process from Kernel. Kernel smoothing method is so appropriate for distribution types such as Gaussian, uniform and Quartic. Spline smoothing is preferred for two or more level polynomial cases. Purpose of Kernel and Spline methods are to control the error of variance. Controling variance error can make easy the readable of curves.

1 This study was presented in X.Biostatistic Congress as a summary oral paper.

49 Ozean Journal of Applied Sciences 2(1), 2009

In this study, Kernel which is one of the smoothing methods was investigated with its mathematical features. It was also aimed to show Kernel’s capabilities on reading and understanding distribution curves. The choicing of bandwidth was also underlined to get optimal distribution.

MATERIAL AND METHOD To show Kernel smoothing process, internet dependency levels of intermediate students’ were evaluated. Data set was obtained for determining the regression curve. This data set was consisted by Gunuc & Kayri (2009) to develop an Internet Addiction Scale. The aim of using this data set is not identify the dependency level. The single aim of using this data set is just to present how Kernel function is capable of reducing the curve complexity according as choosing appropriate bandwidth. The relation between internet dependency point (dependent variable) and daily hours of internet use (independent variable) were examined and scatter plot with curve was obtained. In this study, the bandwidth (h) value was chosen as 0.01, 0.10, 0.50 and 1.00. According to these values, the differences of regression curves were compared with each other. Also with same bandwidth value, Normal, Uniform and Epanechnikov distribution curves were compared. SPSS was used for all analysis.

Kernel Method Kernel function estimates choosing of origin point a bin grid on curve. To make estimation, it calculates f(x) function: ^ 1 f h(x) = {, Xi ∈[x − h, x + h)} (1) 2hn

Here, 2hn interval length and [x-h, x+h) are handled for distribution type (Härdle, Müler, Sperlich & Werwatz, 2004). Kernel function has alteration according to distribution type. If distribution is uniform Kernel function will change. Taking account of uniform distribution, Kernel function is:

1 K(u) = I ()u <= 1 (2) 2

Here, u=(X-Xi)/h and I is an identity matrix. In case of examining equation 2, it will be seen that ½ weighted additions will be added for each observed values in uniform distribution. Kernel smoothing process for a uniform distribution will carry out a probability density function. This density function can be showed in equation 3.

^ 1 n  X − Xi  1 n 1  X − Xi  f h(x) = ∑ K  = ∑ I  <= 1 (3) nh i=1  h  nh i=1 2  h 

The different types of Kernel smoothing functions were summarized in Table 1 (Härdle, Müler, Sperlich & Werwatz, 2004). In general, a probability density function of Kernel can be calculated in equation 4 (Härdle, Müler, Sperlich & Werwatz, 2004):

^ 1 n f h(x) = ∑ Kn ()X − Xi (4) n i=1

1 Here, Kh (•) = K(•/ h) . K (•) is one of Kernel function which has been showed in Table 1. h

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Table1. Kernel smoothing function related to the distribution types (Härdle, Müler, Sperlich & Werwatz, 2004).

Kernel K(u)

Uniform 1 I()u <= 1 2 Triangle (1-|u|) I(|u|<=1) Epanechnikov ¾(1-u2)I(|u|<=1) Quartic (Biweight) 15/16(1-u2)2I(|u|<=1) Triweight 35/32(1-u2)3I(|u|<=1) Gaussian 1  1  exp − u 2  2π  2  Cosine π  π  cos  uI()| u |<= 1 4  2 

Value of h shows the bandwidth of curve. Choosing of optimal bandwidth is too important topic for Kernel smoothing parameter (Rice, 1984; Sheather & Jones, 1991; Hall & Marron, 1991). According to bandwidth (h) value, the distribution curve shows changeability. Kernel function is capable of obtaining more readable and more interpretable curve if choosing of distribution (Gaussian, Quartic, Uniform) is appropriate. The main aim of optimal choosing of bandwidth is to reduce the mean square error (Doksum, Peterson & Samarov, 2000; Kaki, 2004). Choosing of optimal bandwidth can be obtained by two methods. These methods are “Plug-in” and “Cross-Validation” (Jones, Marron & Sheather, 1996). It is known that common method of bandwidth choosing is Cross-Validation (Rice & Silverman, 1991). The purposes of Cross- Validation method is to reduce mean square error and to examine transformation of smoothing function in a reliability border. For having more sensitive examination, Generalized Cross-Validation was developed. Generalized Cross-Validation method was showed in equation 5.

RRS (h) GCV (h) = n−1 (5) 1{ − n−1trA (h)} 2

In equation 5, RRS shows sum of error, n show sample size. It is known that RRS is calculated as equation 6: n 2 RRS = ∑()Yi − m(xi ) (6) i=1

In equation 6, m(x i)shows the smoothing function and Yi means the observation values.

RESULTS Readable and interpretable regression curves are obtained with using different bandwidth values and Kernel density estimation was showed in Figure 1.

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h = 0.01 h = 0.10

3,00

5,00

2,50

4,00

r u

u 2,00 o

o 3,00

h h

1,50 2,00

1,00 1,00 50,00 75,00 100,00 125,00 150,00 50,00 75,00 100,00 125,00 150,00 dependency level internet dependency

h = 0.50 h = 1.00 (Normal)

4,00

2,50

s s

r 3,00

r 2,00

h h

2,00 1,50

1,00 1,00 50,00 75,00 100,00 125,00 150,00 50,00 75,00 100,00 125,00 150,00 internet dependency internet dependency

Figure 1. Kernel density estimation for h = 0.01, 0.10 and h = 0.50 and h = 1.00

In case of scrutinizing Figure 1, if h value has a low bandwidth value, the curve is unreadable and the regression curve is so roughly. In the event of Increasing h value, the distribution has more readable and smooth. But choosing inappropriate high bandwidth value, the variance of population will be hidden. Because of all these reasons, Kernel density function smooth at an optimal value of bandwidth. Contrast to high level value of h, the small value can produce curse of dimensionality. So that choosing of bandwidth value is considered too crucial. Considering distribution type, Cross-Validation algorithm can determine optimal bandwidth value. According to distribution type such as Gaussian, Uniform, Epanechnikov and Quartic, it will be obtained different regression curve. Each distribution has different curve and mathematical equation which has been showed in Table 1. In this study, It was also proved that Uniform, Normal and Epanechnikov distribution types have different curves. And this result has been showed in Figure 2.

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h = 1.00 (Normal) h = 1.00 (Uniform)

2,50 2,50

s r

r 2,00 2,00

h h

1,50 1,50

1,00 1,00 50,00 75,00 100,00 125,00 150,00 50,00 75,00 100,00 125,00 150,00 internet dependency internet dependency

h = 1.00 (Uniform)

2,50 s

r 2,00

o h

1,50

1,00 50,00 75,00 100,00 125,00 150,00 internet dependency

Figure 2. Normal, Epanichnikov and Uniform curves with same bandwidth (h = 1.00).

Although bandwidth value is same for each distribution the regression curves are obtained different. In researches, the type of distribution must be considered and it must be determined before analyzing or getting any curve.

DISCUSSION Although parametric regression methods are insufficient for parameter estimation non-parametric methods are detailed information about population unnecessarily. So that regression curves which belong to non- parametric methods are too roughly and it makes it difficult the readability and interpretability of curves (Pinkse, 1994; Müler, 2001).This problem is called as “curse of dimensionality”. Solving this problem depends on some smoothing methods which enhance the readability of curves (Härdle, Müler, Sperlich & Werwatz, 2004). Besides, determining distribution type of population and choosing of bandwidth must be taken account of process. It must be considered that smoothing function varies according to distribution type. Kernel function is one of the smoothing methods. Kernel function is capable of creating optimal curves according to appropriate distribution types. In this study, curse dimensionality was focused and Kernel function was scrutinized to fix this problem.

REFERENCES Doksum, K., Peterson, D.& Samarov, A. (2000). On Variable Bandwidth Selection in Local Polynomial Regression. Journal of the Royal Statistical Society, Series B , 62: 432-448.

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Härdle, W., Müler, M., Sperlich, S. & Werwatz, A. (2004). Nonparametric and Semiparametric Models. Springer Series in Statistics. Springer press, Germany. Härdle, w. & Tsybakov, A.B. (1997). Local Polynomial Estimators of the Volatility Function in Nonparametric Auto-regression, Journal of Econometrics 81(1): 223-242. Hall, P. & Marron, J.S. (1991).Local Minima in Cross-Validation Functions. Journal of the Royal Statistical Society, Series B 53: 245-252. Jones, M.C., Marron, J.S. & Sheather, S.J. (1996). Progress in Data-Based Bandwidth Selection for Kernel Density Estimation. Computational Statistics 11(3): 337-381. Kaki, B. (2004). Yarı Parametrik Regresyon Yönteminin Hayvancılıkta Kullanımı. Yüzüncü Yıl Üniversitesi Fen Bilimleri Enstitüsü, Yayınlanmamı ş Yüksek Lisans Tezi, VAN. Muller, M. (2001). Estimation and Testing in Generalized Partial Linear m-a Comparative Study, Statistics and Computing 11: 299-309. Pinkse, C.A.P. (1994). Nonparametric and Semiparametric Estimation and Testing. Unpublished doctorate thesis, London School of Economics and Politicial Science, London. Rice, J. (1984). Bandwidth Choice of Nonparametric Regression. The Annals of Statistics , 12(4): 1215- 1230. Rice, J. & Silverman, B.W. (1991). Estimating the Mean and Covariance Structure Nonparametrically When the Data are Curves. Journal of the royal Statistical society, Series B, 53(1): 233-243. Sheather, S.J. & Jones, M.C. (1991). A Reliable Data-Based Bandwidth Selection Method for Kernel Density. Journal of the Royal Statistical Society, Series B 53: 683-690.

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Globalization and its Effects on the Banking System performance in Egypt

Ezzat Molouk Kenawy Faculty of Commerce-Department of Economic, Kafr Elsheikh University, Egypt E-Mail: [email protected]

______

Abstract: Since the implementation of the Economic Reform Program in Egypt in the early 1990s, Egypt has paid great attention to the reform of the banking system through merging and possession to face banking competition within the framework of financial globalization,expanding the capital base of corporate banks and restructuring banks to keep up with international developments. To activate this, Egypt issued the United Bank Law No. 88 for the year 2003 with the aim of activating and enhancing the banking system and increasing the merging process in order to form strong banks with high financial positions. Despite the measures Egypt took to reform and enhance and restructure the banking system, the profits achieved by banks are still low. Also, the contribution of the financial sector in the gross domestic product remained low (8.3% in 2007). This may be attributed to the increased value of default loans and the slow procedures followed to adjust and handle them, in addition to other factors that clearly affect the efficiency of the banking system. The present research aims to explain the Effect of Globalization on the Banking System performance in Egypt and identifying the performance of the Egyptian banking system and the challenges facing that performance in achieving more effective contribution in moving the economic development wheel .Finally, the research presents the most important results it has reached, making some recommendations which will enable Egyptian Banking System to play an active and effective role in raising the level of the quality of banking services.

Keywords: egypt, banking globalization, banking mergers, governance, basel committee, economic effects ______

INTRODUCTION

The banking sector is one of the most important economic sectors and the most influential and responsive to changes, whether international or domestic. The most important of those changes include technological developments, the internationality of money markets, and freedom from the constraints that hinder all banking activities, the removal of barriers that prevent some financial institutions from working in certain sectors, and the trend to develop and manage the risks of lending in light of the increase in international competition in this sector while seeking to attract foreign capital with the emergence of giant banking entities.

The Egyptian banking system is one of the important channels for mobilizing savings in the form of credit or investment tools and working to direct them to more effective and more profitable productive sectors and activities. Added to this is the role which the banking system plays in activating and enhancing privatization and attracting investments to get the financial resources required for developmental needs.

Since the implementation of the Economic Reform Program in Egypt in the early 1990s, Egypt has paid great attention to the reform of the banking system through merging and possession to face banking competition within the framework of financial globalization(Tarek,H.2002),expanding the capital base of corporate banks and restructuring banks to keep up with international developments. To activate this, Egypt issued the United Bank Law No. 88 for the year 2003 with the aim of activating and enhancing the banking

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system and increasing the merging process in order to form strong banks with high financial positions(Farag A.,2005).

The severe competition among commercial banks in the past two decades led to an urgent need to study the impact of the elements of the quality of the banking services provided for the clientele on the competitive position of banks and, therefore, their profitability. (Schwartz, M, 1989) identified four basic dimensions for measuring the quality of banking services. These are: banking service, consumer service, physical and electronic resources and method of providing service to customers. (Bergman and Klefsjo, 1994) noted that quality has become a strategic weapon in the conflict taking place to gain market shares and promote profitability.

Problem of the Research: Despite the measures Egypt took to reform and enhance and restructure the banking system, the profits achieved by banks are still low. Also, the contribution of the financial sector in the gross domestic product remained low (8.3% in 2007). This may be attributed to the increased value of default loans and the slow procedures followed to adjust and handle them, in addition to other factors that clearly affect the efficiency of the banking system(Moustafa, M.,2000).Within this framework, the present study attempts to answer the following questions: What is the Effect of Globalization on the Banking System performance in Egypt?, What is the role of banking systems in contributing to financing economic sectors after the implementation of monetary and financial reforms?, What is the position of the Egyptian banking system in the world banking industry circle?

Objective of Research: The present research aims to explain the Effect of Globalization on the Banking System performance in Egypt and identifying the performance of the Egyptian banking system and the challenges facing that performance in achieving more effective contribution in moving the economic development wheel . Finally, the research presents the most important results it has reached, making some recommendations and suggestions which will enable Egyptian banks to play an active and effective role in raising the level of the quality of banking services.

Research Hypotheses: The present Research draws on the following hypotheses: The implementation of the Economic Reform Program has a positive effect on the performance of the banking system. Banking Mergers leads to the achievement of economies of scale and increases the volume of activity and savings and reduce the costs of the activity. With increasing globalization, banking work became exposed to risks whether external or internal factors.

Research Method: The present research uses the descriptive quantitative analysis method, using data and Informations which are published in the reports of the Central Bank of Egypt, besides the books and scientific periodicals in this field.

Research Plan: The Research falls into sixth main Parts as follows: First: The Concept of Banking Globalization .Second: The Concept and Motives of Banking Mergers. Third: Basel Committee for the development of banking supervision .Fourth: Governance and its Role in the Egyptian Banking System .Fifth: The Challenges Facing Banking System under Financial Globalization. Sixth: Results and Recommendations.

The Concept of Banking Globalization and its Economic Effects on the Banking System.

The concept of banking globalization: The phenomenon of globalization has become one of phenomena that are most associated with economic activity. Globalization is also linked to banking activity as part of economic globalization. Globalization has taken banking dimensions and contents of a new, made the banks tend to the fields and activities unprecedented, and led to the transition from the attitudes and perceptions of activities and extended range, in order to maximize the opportunities and increased gains, and look to the future(Abdel-Bar,S.,2006) .

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As the banks and banks manufactured identity and personality through orientation, which charted throughout its history, since its inception, the bank has made globalization futuristic vision of a new dimension to enter the new world of cosmic, a world of enormous economic opportunity.

In light of globalization and the restructuring of the banking services industry trend banks and commercial banks in particular, the shift towards universal banks. Are those banking entities that seek always behind the diversification of sources of funding and employment, and mobilization of the greatest possible savings from all sectors, and employ their resources in more than one activity in several diverse areas. It opens and gives credit to all sectors. As well as working to provide all the miscellaneous services and renewable which may not based on the balance of knowledge. In light of globalization become banks innovate and create distinct clients, and provide them with future richer and richer more at the level of banking service (El-Dabie, A., 1999). And the future of this innovative technology is owned and used by banks, which are only common denominator in all the work of trying to progress and to the growth and prosperity.

Hence the concept of globalization has been associated with the concept of abundance and availability of the services provided by banks. The accurate view to provide banking services, whether related to deposits, loans, or bonds (as traditional services), or to the contracts of complex derivatives or other innovative advanced services, leads banks to exist effectively in all fields of economic activity.

At the same time, the organic link with banking groupings and blocs is the basis for the bank to reach the large economic size, which allows economies of scale and amplitude banking. This has led to the integration association of the World Bank, which is based on specialization and the division of labor, which maximizes the quality of performance and the ability to upgrade the level of saturation.

It can be argued that the changes reflected in the banking world of globalization on the performance of bank, is the emergence and growth of new banking entities, which are clearly a coup in the world of banks. The giant banking entities, by virtue of the enormous economic power relations and the large economic size, and high economic performance, has become a high capability to influence the form and market trends banking growing global growth and accelerating the proliferation and expanding through a presence in all parts of the world(El-Naggar,F.2000).

Banking globalization never means abandoning what exists and is directed towards the national domestic market, but it means gaining new momentum, and moving to provide banking services from the inside to outside, keeping the national position more effective and more capable and active to ensure banking extension and expansion(Hefny,A.,&Abu-Qahf,A.2000).

Globalization is not a framework for action in so much as it is a motivator of work too. Thus, banking globalization draws on several reasons that must be identified and, at the same time, must be linked with the pillars driving the growth of the bank and its expansion and enhancing its capabilities.

Economic Effects of Globalization on the Banking System: Many changes and developments, studies and events and repercussions of globalization indicate that it has a large-scale impact on the banking system in any country in the world, including the Egyptian banking system. It must be noted that the economic effects of globalization on the banking system may be positive or negative; the task of those in charge of the management of the Egyptian banking system is to maximize the positive effects and minimize the negative ones. Therefore, reference may be made to a number of serious economic effects of globalization on the banking system, through the following analysis:

Restructuring the banking service industry: A significant change occurred in the work of banks and the size and scope of their banking services whether at the local or international level expanded. All banks are going to perform banking and financial services that they have not provided before. This is clearly reflected in the structure of bank budgets. On the other hand, declined relative share of deposits in total liabilities to banks. The liabilities are trading in the share relative to the total liabilities of banks due to the increasing activity of banks in activities other than lending, and led to a decline in the share of loans and increase the relative share of other assets, in particular the issuance of bonds. The effects of globalization on the banking system did not stand on the restructuring of the banking services industry, has been extended in an

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indirect entry to non-bank financial institutions such as insurance companies and pension funds, a strong rival of the commercial banks in the area of financial services, which led to the retreat of the role of commercial banks especially in the field of financial intermediation(Mohamed S., 2003).

Diversification of banking activity and the tendency towards dealing in financial derivatives: This includes the diversification of banking services at the level of funding sources, the issuance of marketable deposit certificates and long-term loans from outside the banking system and at the level of expenditure and banking investments, and then the diversification of loans granted and the establishment of banking and securitizing holding companies. In other words, this means transferring banking debts to contributions in the form of securities and engaging in new investment areas such as attribution and performance of investment banking and the financing of the privatization at the income level to engage in non-banking areas, then the tendency towards leasing and trafficking in currency and deepening the activity of issuing securities, the establishment of investment funds, and insurance activity through sister insurance companies involved in holding companies management of investments for the benefit of customers.

The necessity of adhering to the decisions of the Basel Committee: With increasing globalization, banking work became exposed to risks whether external or internal factors and banks had to be causation about risks using several means, the most significant of which is strengthening capital. The criterion of capital adequacy became increasingly important since it was approved by the Basel Committee in 1988, and it became necessary for banks to abide by it as a global criterion, and thus banks were affected but this criterion as the ratio of their capital to total at-risk assets after weighting them against credit risks must reach at least 8% by the end of 1999(National Bank of Egypt, 2001).

The amendments with respect to such decisions, and these came to be known as Basel Decisions II, and this new framework for capital adequacy must be in line with current developments in the global banking market. Here the Basel Committee seeks to develop a new and comprehensive framework for capital adequacy to focus on the following regulatory objectives (Shalaby, M., 2005):Continue to enhance the safety and soundness of the financial system, Continue to support competitive equality, and Creating comprehensive way for coping with risks.

The new framework proposed by the Basel Committee for capital adequacy is expected to be the cornerstone of the international financial engineering process currently under way. The main objective is to promote the safety and integrity of the international financial system, based on the composition of that capital is sufficient to meet the financial risks diverse and growing. Believes the Basel Committee that new framework must be maintained at a minimum at the current level of capital in the banking sector.

The focus of the new framework proposed to absorb the risks inherent in each banking group, at the same time must work this framework to provide security and safety independently of each institution within the group. To this end, the Basel Committee proposed to be expanded to include the old framework on the basis of compound all companies Holding group, which includes banking, which in turn engage in banking activities. In some States, the banking group can be recorded sink, and in addition to that we must emphasize regulatory authorities on the issue that every bank in the group enjoys adequate capital (Zayed, H., 2003).

Banks have expanded increasingly towards new fields within the financial activity, particularly the fields of securities and insurance. Therefore, the Basel Committee is working to clarify how to treat bank investment operations in these fields. With regard to diverse financial groups, the Committee recognizes the need for follow-up work with the regulatory authorities supervising insurance companies and securities in order to determine the criteria for capital adequacy.

Intensified competition in the banking market after the agreement on the liberation of the banking services trade: With the increase of financial globalization, services liberation agreement was liberated from the constraints that came out in the GATT in Uruguay round in 1994. Competition within the framework of the Banking Services Agreement took three major manifestations of trends (Tawfik, H., 2001):

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First trend: competition among commercial banks whether in the local banking market, or the global market.

Second trend: competition between banks and other financial institutions.

The third trend: competition among banks and other non-financial institutions to provide banking services. These trends led to the intensification of competition in the banking market in light of the removal of geographic barriers to meet the needs of clients so that financial institutions other than banks may enter the banking market, particularly financial services markets. Competition is expected to continue with the entry of insurance companies, securities firms, financial institutions and financial intermediation institutions in the light of the increasing desire to provide financial services related to banking activity.

Importance and characteristics of modern banking services: Banking services represent one of the important activities in any country. If we look at the banking services as an economic activity, we find that it has a number of characteristics, the most important of which are the following (World Bank, 2001:) Complexity and multiplicity of banking service and its relation to all other economic and social activities in the country.

The demand for banking services is an indication of the degree of the economic progress of the country, since the banking service is a productive activity of a particular nature and is related to different development issues. The supply of banking services is an indication of the level of economic prosperity in the country, as well as the different characteristics of population, in addition to its political and economic ties to other countries of the world. The demand for many banking services is characterized by repetition. Banking services are considered an industry as they have all the requirements and elements of any productive activity.

There is no doubt that the availability of features means the need to keep up with the former banking activity to the requirements of development in all aspects of economic and social activity in any country regardless of the nature of its economic or political philosophy.

In short, the banking services, like other aspects of economic activities, went through several stages of development, with a mere shift of activity from conducting lending and deposit within the borders of the State concerned for the banks to enter into the fields of investment and owned for many industrial projects, service trade, as well as exporting services outside the State border and the spread of the branches of many banks in most countries around the world and the emergence of multinational banks ... Etc.. There is no doubt that this major transformation in the remarkable diversity of banking services in the industry or banks in general was a necessity imposed by the reality of evolution and rapid growth in various economic activities in the various countries of the world. This is what makes many of the writers and practitioners in the industry believe banks that the real problem facing men banks lies in the face of how to manage change and the rapid growth in economic and social areas successfully, in addition to the change and evolution in the market for the banking industry, which has become characterized by severe competition.

The Concept and Motives of Banking Mergers The Concept of Banking Mergers: One of the economic impacts of globalization is what happened in the present time of the wave & Majat bank between big banks and small banks and large and each other. The process of integration of numerous banking and speed become a global phenomenon affected by all the banks in the world. Mergers and banking in general is the Union Bank in more than one bank or melting bankers or more entities into one entity, and the most important of many mergers motives(Robert,A.&Manmoban,S.1995): to achieve economies of scale and defended expansion and improve profitability in the context of Liberation of banking services.

The banking mergers is the process whereby financial cornering bank or more by other banking institution where the bank abandon integrated usually give up on the smaller bank license and take a new name on behalf of the institution Aldamjh as add-nuclear assets and liabilities of the bank integrated to the assets and liabilities of the merger bank.

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Motives behind Merging and Acquisition: There are many reasons and motives for mergers and acquisition is different from the banking sector and any other companies differ from one activity to another or from one sector to another sector of the national economy. These motives and reasons can be divided into (Shehata, I., 2001):

Motives for maximizing the value of the business (the bank): International capital markets are adopting free competition and market mechanisms and motivation, the primary goal of its activity is to maximize revenue and market value of the shares, however, shows that although the maximization of value is important elements when deciding whether sale or merger but there are other considerations that must be taken into account, in particular, For mergers Egyptian banking system, the value of any bank is determined by the discounted present value of expected future profits, as mergers and acquisition lead to increased profits for the current discounted expected future profits due to lower costs or increase revenue projected or both. The truth is that mergers and acquisition lead to lower costs due to (Tarek, H.2002):

A. Merging leads to the achievement of economies of scale and increases the volume of activity and savings and reduce the costs of the activity and mergers and acquisition leads to a change in bank management and the selection of leaders to pursue more efficient and modern management methods which leads to lower costs and increase profits application of the economics area to the lower unit cost due to integration The overlap when the institution produces many products lead geographical spread and diversification of risk to reduce risks and increase the activity and profits may also lead to a reduction in tax liabilities lead to increased merger monopoly power of the bank, which puts it in a better position when buying production requirements or determine the price and then exceptional profits for the lead as large scale to increase the ability to penetrate markets and increase the credit itself as leading mergers and acquisition to increase profits: As mergers lead to the large volume of the bank and increased geographical spread and increasing potential clients and provide better services leading to increased profits as lead the multiplicity and diversity of products to increase the share of the bank in the banking market and attract new clients and the monopoly power of the bank unable to control the prices of services and increase its profits, therefore, increase.

B. Motives of merging and acquisition not related to the maximization of the value of the bank : These are the motives related to the achievement of the objectives of the bank that the decisions of the bank may not always aim to maximize the value especially when there is a separation between management and ownership, the management has taken some decisions for personal goals and not to serve Valmderin owners who run banks, large companies or large rate a high degree of conviction and complacency result of the increase in the degree of safety in their jobs and their income and thus distinguished may resort to mergers to increase the size of the bank, even if it did not lead to the maximization of the value of the bank accounts of any other institution to fear the establishment of an institution to greater absorption institution which defines possession defensive As mergers and acquisition may build on factors are not intended to maximize the value of the bank and it does not lead to the hoped-for results of the integration process and therefore been many studies to determine the best methods for reducing the degree of probability that managers merger-related operations to maximize the value of the bank and that are incompatible with the interests of shareholders. Among the most important suggestions in this regard are the following (Ibrahim M., 1999):

Managers should own an acceptable percentage of the bank's capital, which makes their work to increase the value of the bank and not to resort to mergers inconsistent with that.

The need to focus property owners so that the bank can effectively influence the actions of managers in the opposite case when there is a break in the property in this case managers the opportunity to be more of the movement and decision-making.

The need for independent external members of the Board of directors, which makes it easy to control the behavior of managers.

Motives and external factors of merging and acquisition : There are many external factors that led to the proliferation of mergers and acquisition between both banks or companies and institutions - for the banks

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there are certain circumstances led to the adoption of banks to mergers and acquisition as one of the methods of restructuring after his many banks to financial crises and there are many obvious international experience of the phenomenon during the nineties, where the Japanese monetary authorities and possession of integrating operations of financial institutions in the framework of the program of restructuring and capitalization of financial institutions and banks faltering. The motives and external factors of merging and acquisition is not linked to a certain period of time such as times of financial crises. The factors which have contributed to widening the spread of the phenomenon of merging and acquisition since the early 1990s include (El-Said, H., 2004): technological development, getting rid of restrictions, and globalization of financial markets. Banking services witnessed tremendous development and radical changes as a result of technological progress which changed job competitiveness both for the production, distribution and marketing methods and then create new products and thus the process of restructuring aimed at increasing competitiveness of the banking system has led to the creation of the appropriate environment for the process of merging and acquisition.

Determinants of merging and acquisition in the banking system: When it is necessary to prepare plans for mergers and acquisition knowledge of the banking system parameters and considerations necessary for the success of the integration process and achieve its objectives and to identify financial institutions that will be merged. These determinants are as follows (Tarek, H.2002):

Setting the goals to be achieved during the long time where it is necessary to identify each bank's long-term objectives it seeks to achieve, it is necessary to estimate the extent of future improvement in revenues due to the depreciation of the competition as a result of the merger determine the impact of mergers on financial risk management in reducing the degree the risks posed to the banking system following the mergers to reduce financing costs Will lead to decreasing the cost of banking services following the merger on the competitiveness of the banking system and its ability to depletion of the international markets and through those factors and parameters can be determined target growth rates of the bank and whether this growth horizon Through horizontal merger with Bank or institution working in different activity.

The need for sound and appropriate banking policies for the newly merged entity: Banking merging supports capital and reduce the cost and increase the effectiveness of the activity merged banks increase their competitiveness and thereby increase their ability to deal with international developments and changes and the accompanying risks can be achieved only if the units are strong while banking Some believe that the strongest banks is not only big banks, but it is very important to the existence of sound policies and banking systems appropriate and what was the size of the bank even if the small banks resulting from heart banking mergers can grow healthy growth and apply sound policies leading to increased competitiveness and face the risks, however, to achieve those goals will depend on a sound policies and practices of the new entity, and that the process of integration needed for the delay and inaction to re-evaluate each of:-the level of performance and management policies of both liquidity and credit and deposits and investments as well as capital structure and dividend policies and structure of operating costs and other expenses to ensure their compatibility with the objectives and characteristics of the institution new banking and this requires a certain period of time(Gomaa,F., 2000).

The need to identify the appropriate structure of employment and the attitude of workers towards merging: Important factors that must be taken into account when conducting mergers include employment structure before and after the merger, the position of management and workers unity bank target of the process of integration where integration process to restructure labor and management the two institutions and, therefore, may oppose the merger and it is therefore necessary to identify the sites responsible for administrative functions new banking unit in order for the new administration to perform its work efficiently and to eliminate duplication of work in certain departments and the dismissal of labor unproductive and therefore it is necessary to determine the structure of the new employment before the merger.

The need to work to continue competition in the banking system after merging: Since merging may lead to decline in the number of banks, the banking system, which may lead to the elimination of competition must prevail banking market also believes that some people might accompany the merger capture a limited number of banks to Britain ratio of the banking market and control through oligopoly This does not only

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lead to the elimination of competitive advantages and mechanisms of supply and demand and competition among many banking units to obtain appropriate share in the banking market, which reflected the negative performance of the banks and their role in the development process efficiently, but also for the economic, social and political accumulation of capital in a limited number of the banks control the market probably in the national economy.

Sources of financing the merging and acquisition: Where implementation of mergers either purchase the assets of the bank integrated or purchase shares from the stock market.

Financing the merging by purchasing assets: According to this method, the Bank Merger purchase all or some of the assets of bank suffered in cash or shares will be distributed in cash and shares to shareholders in the form of share liquidation and thus solve the bank targeted in some cases may continue business in the sale of assets and operating as a separate but each smaller.

Financing the merging by purchasing shares: According to this method, the merged banking unit disappears the merger bank buys all assets and liabilities, while money is used to finance other forms of integration that the rules only require the bank to pay the value of the merged unit through the issuance of the Unit bank obsession to additional shares This method is not subject to tax(Gomaa,F., 2000) . The merging process also requires long-term financing, and the issuance of additional shares is considered the best way as the banking unit using proceeds from the sale of additional shares to buy banking unit target or sell new shares to shareholders in the unit by changing the target shares. Unity Aldamjh particular exchange rate or borrowing funding is remarkably such methods lead to an increase in the debts of the merger banking unit(El-Said, H.,2004).

Basel Committee for the development of banking supervision: In light of the trend towards greater globalization, the financial stability is a major priority in the framework of macroeconomic policies, it is not the impact of the problems faced by the financial system in the country is limited to the border country, but has approved this influence extends to the foreign markets in the world.

Efforts of the Basel Committee for the development of banking supervision: The theme of bank capital adequacy has acquired major importance in recent years in light of the financial and banking developments and the rapid opening of markets in industrialized countries, which served to consolidate control regimes and the development of the minimum capital of banks in an attempt to curb unfair competition in the global banking market by the Japanese banks to European and American banks because of the low proportion of their capital assets. These developments have been accompanied by the desire of industrial nations in the transition to avoid the risks of banking work either from each other or from other States as we have already stated after escalating risks arising from credit operations and the worsening of the external debt crisis and the decline of some developing nations to meet the burden of those debts, which in effect negative on the bank borrowings at the international level and instability in the global banking system.

The Basel Committee issued for the control of the banks many of the recommendations that contribute to the improvement of technical methods for the control of the banks so that banking commensurate with the twenty-first century is what these recommendations issued by the Commission in 1999 m on the requirements to be met for effective banking supervision and the basic principles for the exercise of such control Many of the issues on the management of credit risks, and recently issued standards on Basel(National Bank of Egypt,2001).

These recommendations will create significant challenges for financial institutions and banking, rating agencies and regulators, and global capital markets, and the level of organization, operation and risk management. These challenges are summarized as follows (National Bank of Egypt, 2001):

Banks must apply an institutional framework for a comprehensive risk management links between regulatory capital and economic capital.

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The challenges imposed by the new agreement will not include non-banking financial institutions, but they may be forced to apply the criteria and guidance so as to maintain their competitiveness in the market.

Dealers with banks will need to collect, and disclose new information, and this may lead to increased transparency deal to create new formulations of the risks to these clients.

Rating agencies will face new challenges in light of the criteria set out in the new agreement and the importance addressed by these agencies.

Organizers should adhere to a certain level of regulatory practices and policies are equal to those used by legislators in different countries according to the recommendations of the Basel Committee.

Comprehensive banks may shift to securitization in the financial institutions in response to the requirements of Basel.

The complexities imposed by the new agreement, and local regulatory frameworks in different countries made the application of the Basel a highly complex task. The process of applying the new standards by banks will depend on the restructuring of its risk management as strategies and means to identify the minimum requirements for capital and information requirements of clients and market participants, and information technology systems and through alternatives disciplined and vehicles, banks can begin to benefit from improved risk management and reduced requirements for the top money, that these changes in turn will affect the strategies of banks, and the relationship with clients, in the long run, will affect the business models banks in general. The minimum requirements for capital will be the effects on the implicit risk management and thus on the institutional governance in the banks, and therefore the focus of banking institutions at all aspects of the agreement vested benefit from the opportunities offered by important for securing global banking environment safe and secure(Shalaby, M.,2005).

Basic requirements to be met for the exercise of effective banking Control: The Basel Committee indicated that banking control is part of an integrated system that helps to achieve financial stability. This system consists of the following five elements (Shalaby, M., 2005): Stable and sound macroeconomic policies, A developed infrastructure that includes: Laws regulating companies, and consumer protection and private property, Internationally recognized accounting rules and principles, An independent system for reviewing the budgets of companies with significant size, Effective banking control, as will be discussed in detail later on, Specific rules for regulating the work of financial institutions other than banks, and A system for settling payments. Effective Market Discipline, which depends on the flow of information from borrowers to investors and creditors. The lack of government intervention in industry decisions of the parties and in particular the granting of credit. Validity of the regulatory authority to take corrective action to remove the defaulting banks or restructuring / liquidation of these banks in critical situations. A mechanism for providing an appropriate level of government intervention aimed at protecting the banking system when exposed to systemic obstacles.

Principles of the Basel Committee for Effective Banking Control: The Basel Committee has prepared two documents: one is a comprehensive set of basic principles for effective banking supervision (Basel Core Principles Basle Core Principles of Banking Supervision) which can be applied in the Group of Ten and other countries, and the second contains the summary of recommendations and standards frameworks Committee already in place. The basic principles of the Basel Committee include 25 principles, covering all aspects of banking supervision and fall of these principles in 7 major groups. They are (Zayed, H., 2003): The conditions to be met for the application of effective banking control system: Every institution subject to this system must have: Specific and clear responsibilities and goals, Autonomous administration, as well as availability of adequate financial resources, The existence of a legal framework for banking supervision, and An information exchange system (based on trust) between the institution and controllers.

Granting the licenses and infrastructure required for banks: The activities allowed for the institutions which are subject to the regulatory system must be determined, and institution must not be called a bank unless it already practices banking work. Licensure authorities have the right to approve the bank or reject any requests for the establishment of banks, if they do not comply with the standards set. Banking controllers

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must have sufficient authority to review and reject any proposals to transfer ownership of the bank. Banking controllers must be given to the authority to set standards for reviewing acquisitions and investments in banks, and to make sure that they do not represent risks to the bank or impede effective control.

Control and effective requirements (Zayed, H., 2003): Banking controllers must define the minimum requirements of the bank's capital and its components and its ability to absorb losses, given that these requirements must not be less than is specified in accordance with the capital adequacy standard. Autonomy of the control system in its assessment of the bank's policies and procedures associated with the granting and management of loan and investment portfolios and implementation. Controllers must make sure that banks adopt adequate policies and effective measures to assess the quality of assets, as well as the existence of adequate provisions to offset default loans as well as the availability of adequate reserves.

Methods of continuous banking control (MisrBank, ResearchCenter, 2002): Effective banking control must combine internal control and external control. The ability of controllers to monitor the banking system as a whole is a fundamental element of banking control.

Information needs (availability of information): Controllers must make sure that every bank keeps adequate records of accounting policies and applications which can be controlled to obtain insight of the financial situation of the bank and the results of its work they must also make sure that the bank deploys budgets that reflect its financial position on a regular basis.

Official authorities of controllers: Controllers must have official authorities to enable them to take adequate corrective actions to review the bank failed to abide by one of the control measures such as the availability of minimum capital adequacy, or when violations occur on a regular basis, or in the event of a threat to depositors funds in any way.

Banking operations across borders: Controllers must apply unified global control, and use prudent regulatory models for all matters relating to banking work on a global scale, and in particular for the branches of foreign banks (Hefny,A.,&Abu-Qahf,A.2000).Unified control requires the presence of communication channels and exchanging information with various controllers involved in the controlling process, mainly in the host country. Controllers must ask foreign banks operating in the host country to perform their work with the same high levels of performance required by local banks and force them to provide the information required to have unified control.

There is no doubt that the presence of a strong banking system requires effective control of its units, and as comprehensive in the basic principles outlined above. The safety of the banking system supports the economic environment in general, the banking system plays a key role Seville implementation of payments for all transactions in the mobilization and allocation of national savings and the importance of banking supervision is to ensure that banking units operate properly and to reduce health risks and that their property rights (capital and reserves) and Apportionment (Provisions) adequate to cover the risks it faces. With the overall control of the effective macro-economic policies and effective. There is a basis for financial stability effectively. On the other hand, it is important to supervise the banking risk assessment of each bank individually and to ensure that devices based on the supervision of their human resources required for this evaluation and implementation of procedures required for any repairs required, the most important of the existence of an adequate level of capital, and management of strong banking system and an effective internal control and accounting records sound prepared to international accounting standards. This has been the Basel Committee announced that it would follow up the application of those principles by various countries, especially in emerging economies, as announced by the International Monetary Fund to maintain the integrity of the banking system must come at the forefront of the objectives of the banking authorities in the world (Zayed,H.,2003).

Governance and its Role in the Egyptian Banking System: Governance in the banking system means monitoring performance by the board of directors and top management of the bank and protect the rights of shareholders and depositors, in addition to interest relationship these external actors, as determined by the regulatory framework and powers of the regulatory body, apply governance in the banking system to public

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banks and private banks and joint, and is key elements in the process of governance in the two groups, the first group of internal actors who are shareholders and the Board of Directors and Executive Management, observers and internal auditors, and the second group is to players outside representatives to the depositors, and the deposit insurance fund, the media and companies classification and credit evaluation, in addition to the legal framework the regulatory and supervisory, and the fundamental pillars that must be met to complete the provisions of effective control over bank performance summarized in transparency and the availability of information and the application of international accounting standards and to upgrade human skills through training(Abul-Eyoun,M.2003).

The success of governance in the banking system does not only depend on setting regulatory rule, but it also needs to be applied correctly and this depends on the Central Bank and control on the one hand and on the bank and its management on the other, which must be convinced of the importance of the bank such rules and controls, which help to implement. This reveals the role of the Board of directors executive and non-executive committees that provide follow him the necessary data on the performance of the bank and the inspection departments in the banking system, which presented their reports to the Board of directors and the shareholders who must do their part in monitoring the performance of the bank by contributing to the provision capital Bank in the event of need, and the proper exercise of public governance lead to the support and safety of the banking system, through the standards set by the "Basel Committee" for the control of banks and the regulation and control of the banking industry, of which the most important are the following(Abul-Eyoun,M.2003):The announcement of the strategic objectives of the banking system and to define the responsibilities of bank management. Checking the efficiency of the members of the board of directors and the full understanding of the concept of governance, and the absence of deliberate errors by top management. Ensuring the effectiveness of the role of controllers and their awareness of the importance of their controlling role. The need for transparency and disclosure in all the work and activities of the bank and management.

We note that the Central Bank has taken a number of actions in the light of the basic rules approved by the Basel Committee. The legal, regulatory and controlling framework of the work of the Central Bank of Egypt includes the setting of rules for the prudent control of the work of banks, including determining the size and area of activity of each bank and the ratios of its liquidity and reserve and controlling the application of the capital adequacy criterion. The CBE decided to increase this ratio from 8% to 10%, asking banks to comply with it by no later than March, 30 2003. In this context, the CBE paid attention to the method of classifying assets and determining appropriate provisions for each category of them as banking safety is achieved when the classification is done in a proper way. It also paid attention to the criterion of the concentration of loans to one client or one currency to protect the bank from the fluctuations that can occur in any of these categories. It also paid attention to lending to related and relevant parties, who could cause crises to the banking system. In this connection, the CBE, in November 2002, made a decision requiring dealing with this type of lending cautiously, and success of governance in the banking system requires the existence of some sort of punishment when a mistake is made and the existence of a mechanism for correcting errors (Adib, Emad, 2003).

The Challenges Facing Banking System under Financial Globalization: It is expected during the next few years that banks will face significant changes, as well as a number of strategic issues as a result of the increasing influence of the following main strong forces(Ibrahim M.,1999):

Tendency for internationalization: Internationalization mean increased cooperation among nations and different institutions located those States in the economic sphere, and notes that the internationalization has three important implications in a number of states, and those three effects led to the following(Ibrahim M.,1999): Increased importance of assets and liabilities in foreign and domestic banks. Increased number of banks and financial institutions operating in foreign markets, banking locally. Increased assets of foreign banks operating in the local banking markets. At present, there are a number of indications that foreign banks will pose a threat to local banking markets, in Europe, for example, in the next few years, it is expected that large foreign banks will only constitute the main threat competitive in the market for retail banking ( Retail Banking Market) as long as the opportunity is available, and the foreign banks have the ability to monopolize (Acquire) for financial institutions with large clients (Large Customers Bases).

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internationalization: This is a major banking development that emerged in Europe, then in many countries of the world during the past two decades, since banks in those countries started to keep away from specialization in banking and reduce the emphasis on traditional forms of lending and investment. Thus the bank came to provide a comprehensive mix of financial services (Abdel-Hafez, M.,2001). Accordingly, in all parts of Europe now, banks are moving towards global banking systems, which enable them to exercise their activity in the markets had previously been prohibited, as the pace of erosion commas between traditional banking work and other services is a reflection of the erosion that coincided commas in the international capital markets, particularly markets banking and finance markets financing through bonds, in addition to the phenomenon of securitization will continuously feed the decay and collapse of the demarcation lines between banking and capital markets and exchange markets(Abdel-Hafez,M., 2001).

Securitization: This phenomenon emerged in the seventies and eighties, and now constitutes one of the most important features of international capital markets, and that the term "securitization" mainly refers to the transfer of assets or change the format to the external financial assets and so can be re-sold to investors in the money markets(Rady, A., 2003), and this has created the phenomenon of "securitization" in the banks that have lost their comparative advantage compared with the stock markets, in the area of financial intermediation in the international credits also bore "securitization" with a meaningful change in the role played by Bankers since profitability is now transformed from being dependent on the conduct of studies and research regarding the interest rate margin, to focus towards income from commissions on activities for the provision of debt instruments) to investors.

Globalization: Globalization refers to the unification and integration of global markets for both capital and money markets, i.e., unification and integration of financial markets globally, through the swaps mechanism and arbitraging accompanying for differences in international prices that have led globalization the possibility that banks and other financial institutions management Governor international investments (Global Investment Portfolios), as well as the full and comprehensive series of products and new methods become available now, so that the main players in the market (international financial institutions) carry out their activities in the various financial markets throughout the world, at the same time, i.e., simultaneously(world bank,2001).

Conglomeration: Due to a number of factors and variables in each of the market of financial services as well as global economic environment, it is expected in the future that provide financial services through four major types of institutions: the groupings (conglomerates), and specialists, and agents (Agents), and institutions that operate under the umbrella of privilege from another institution (Franchisers)(world bank,2001).Conglomeration is perhaps the most important trend appropriate for banking work in many countries around the world and probably the "assembly and integration features identified and acquired the distinctive characteristics and attributes through the desire of banks, which operate on a large scale to maintain its presence globally. It is noted that a large number of mergers (Mergers), as well as operations control (Takeovers) in the European financial services market was in 1986, and this can be said that most of the main reasons that explain the occurrence of mergers and control, due to the motives Strategy (Strategic Motives), and associated with diversification (Diversification), as well as economic motives related to synergy and growth.

Concentration: Concentration in banking markets is also one of the important features of the structural changes in the world of banks, and concentration is not in any way a recent phenomenon, since the banking systems in many countries in the world, dominated and controlled by a few big banks, since at least half a century. Banking systems differ in competitive degree of concentration (El-Naggar, F. 2000).

As for the most common way to measure the concentration banking is dependent on the calculation of the proportion of assets or deposits in the banking sector and State-controlled and managed by the three largest banks, or five, but it should be noted that there is difficulty in accurately assess both the effectiveness and extent of concentration within systems bank alone, and it also became difficult to measure the concentration significantly banking contemporary measures, because of lack of clear lines between labor markets banking and financial markets other, and yet it is clear that there is a tendency to prefer the large size of many banks a large number of the world's countries.

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In the end we can summary these Challenges as following (El-Alem, M., 2004):

Global Changes: Global changes occurred successively in the form of shocks that had a significant impact on banks and other institutions. Among the most important of these changes are the electronics revolution, and economic blocs, and the emergence of the new world order, and control of the market economy, the information revolution, and the Liberation of world trade, and increased competition, and the spread of the phenomenon of privatization, mergers between banks and the Basel agreement issued in 1988 on the banks. Information and Communications Technology: Computers have become available and their speed and potential increased, and they entered into networks that can connect with one another in audio, image and movement. The use of computer systems to summon immediate decisions and upgrade management skills with the availability of information. The computer systems are also used in external oversight of performance in different locations.

Through modern communication technology traders and staff in the banks could work through their e-mail and thus can be contacted and complete the work without the personal presence at the headquarters of the bank. Become driven by the banks to go global because of the serious financial accumulation negotiable move from one State to another as soon as the light effective global communications technology that allows the transfer of funds and investment anywhere in the world in minutes.

Competition and the Global Market: Global changes forced banks and other institutions to compete with one another. At the same time, large blocks appeared to expand the scope of the market before and reduce cost and maximize profit through service, speed, innovation and meet the needs of the consumer. In order to achieve these objectives, the value of knowledge as an important factor of production (El-Alem, M., 2004). In order to be competitive and put in a data base available for use in banks and institutions in the light of fierce competition require conversion strategies to expand geographically and to open new markets and the challenge of competitors.

The change in the operating style: Now banks look at the human element on the basis of providing self- commitment and the alleviation of restrictions and a regulation imposed on workers and has become a focus on self-directed work teams in achieving goals. It was necessary to have leadership that rely on human allow shared vision among all workers, believes decentralization to achieve accomplishments and drive material and intended merit systems through the development of operating systems quick and disciplined(Hefny,A.,&Abu-Qahf, A.2000).

Basel Accord on the banking blanket: The agreement mainly aims to achieve this kind of international consensus regarding the regulations on the adequacy of bank regulatory capital, which leads to the safety and stability of the international banking system by hand, and to achieve justice in the international banking arena of competition on the other. This agreement is based on the application of a set of standards for the provision of capital adequacy of banks and making capital to reach assets and liabilities weighted by risk to 8 %( Zayed, H., 2003).

In accordance with decisions of the Basel Committee, countries of the world have been classified into countries with low risks including the industrialized member countries of the Organization for Economic Cooperation and Development plus Switzerland and Saudi Arabia, and countries with high risks including the rest of the world.

The resolutions issued by the Basel Committee drew attention to the future of the banking system in Egypt and other Arab countries and to the actions to be taken to adapt to developments on the international scene. Local changes: The economic reform program: Since the mid-seventies Egypt has witnessed a comprehensive movement of restructuring of its economy, particularly the adoption of economic reform programs aimed at deregulation of economic activities that impede their growth through free rein to market forces to play their role, and was one of the most important reform measures Liberation of the national currency, the abolition of exchange controls, The Liberation of interest rates, the Liberation of foreign trade, Liberation of prices for goods and services, especially agricultural commodities, the application of tax reform and the development of financial markets, and reducing the role of the state in economic activity

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through a policy of reform and the privatization of the public sector, in addition to actions aimed at improving the investment climate and attract national and foreign investments.

The effect of all this and its implications on the banking system in various forms and images of increased responsibilities in implementing and supporting economic reform programs, which also requests liberates the development and management functions and providing high efficiency is also taking into account the impact of global changes mentioned above(Kassem, M.,1998).

The privatization of the public sector: The privatization process aimed at enhancing the efficiency of the national economy through management style approach the private sector in its activity, which achieve a greater financial resources available to the government due to conduct a sale in some units owned and lead to the retreat of the responsibility the state budget for financing investments, and increase productivity the quantity and quality of the availability of better methods of management(Gomaa,F., 2000).The methods of privatization range from offering all or part of the shares for sale to the public, which is known as "public tender", or presentation to a group of investors and this method is defined as " private tender" Privatization may be through increased capital established by the State with retaining majority ownership. Having sold parts of the company, or are leasing the business or some of its assets to others. There is no doubt that the promotion and organization dealing in the stock market is an important factor that will help the success of the privatization program. The banks played important roles in the success of the privatization program through (Capriog. and C., 2000):

Solving the problems of the debts of the public sector companies by granting grace periods and / or capitalizing debt and interest in companies, rescheduling debt and / or granting loans to support them. The contribution of banks in reviving the capital market through the financing of the purchase of shares and grant funding under its guarantee, the provision of information and data required for Corporations sale and promotion at home and abroad.

Playing the role of the seller of the shares which he has in companies, and / or acting as the buyer of certain stocks of companies sold for different objectives. Bank and Credit Laws : Taking into account the global and local variables were the most important legislation multiple comprehensive law of the Central Bank and the banking system, monetary contains many rules and requirements that entailed(Abu Gahf, A.,2005):

Examining the conditions of banks to take necessary update on the capital adequacy requirements of the standard of banks and thus to re-examine the structure of assets for the benefit of lower-risk, the resort to increase capital to meet the minimum requirement in accordance with the law. The application of safety standards designed financial positions of banks and the development of systems and accounting rules in line with the requirements of the Central Bank.

Paying attention to the various aspects of the qualitative development of the banking law and the emphasis on the need to upgrade the management of the banks, and the level of human cadres, and accommodate modern banking techniques, so that they can keep up with what used by the financial markets and banking institutions from financial instruments at attracting funds and employment, according to the latest methods of harmonizing considerations security, liquidity and profitability.

Management of credit risk, taking into account the fact that the non-observance of standards of the Basel Committee will adversely affect the external lines of credit and hinders the flow of investments and financial resources into the countries that ignore their application, which in turn leads to obstruct development plans and economic reform programs.

Change of banking and credit policies : The developments undergone by the Egyptian economy affected the course of the banking sector, and as a result considerations required by economic liberation emerged, according to which it was seen banks have the right to determine debit and credit interest rate and the need arose to increase credit to finance private investment. Banks had to go to areas they were allowed to go before when they were forced to exercise the functions of investment banks, and then enter the retail operations to expand the market(El-Antary, S., 2001).

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Meeting global and local challenges: Through a review of the most important global and local changes and their impact on the banks, we can say that the most important challenges facing the banks are as follows (Abdel-Hafez,M.,2001): First: Assessing the risks related to the change of product mix with increased competition. Second: Obtaining the resources needed, especially human resources for the exercise of outstanding jobs and new roles and the requirements of the application of banking legislation.

Third: Obtaining better operational results so that profitability may be the basic element for measuring the efficiency of performance. To achieve these broad objectives, we must consider the following (El-Baz, H., 2003):

Identifying the banking strategy which should seek for sectors in which the bank has a comparative advantage, and those in which these advantages may develop so that they become relative later on.

Expanding the product mix and banking services continuously so that they may become integrated and convenient to customers, rather than relying on traditional financial services that achieve profit margins narrow. Effective control of costs through more effective control. Restructuring banks, taking into account the rapid development of technology, so management can approach the levels of marketing banking, and focus on the promotion of banking services is the principal challenge in the future. Managing risks in lending operations to meet the rapid changes in positions of debtors with emphasis on the importance of policies for the management of assets and liabilities.

The strategy for facing challenges is based on the following (El-Alem, M., 2004): Providing minimum capital of the bank in accordance with the criteria set. Restructuring public sector banks, Adjusting bad loans, Merging small banks in strong banks, Disseminating the culture of risk management developed between banks, and expanding and deepening banking and financing services (comprehensive banks , Contributing to the development of the financial market ,and Support control systems and procedures for monitoring and evaluation of performance.

Results and Recommendations: In the light of the foregoing, the researcher can conclude some results, the most important of which are the following:

The banking sector is one of the most important economic sectors and the most influential and responsive to changes, whether international or domestic, those changes include technological developments, the internationality of money markets, and freedom from the constraints that hinder all banking activities.

And attracting investments to get the financial resources required for developmental needs. Egypt has paid great attention to the reform of the banking system through merging and possession to face banking competition within the framework of financial globalization, expanding the capital base of corporate banks and restructuring banks to keep up with international developments. Despite the measures Egypt took to reform and enhance and restructure the banking system, the profits achieved by banks are still low. Also, the contribution of the financial sector in the gross domestic product remained low (8.3% in 2007). With increasing globalization, banking work became exposed to risks whether external or internal factors and banks had to be causation about risks using several means, the most significant of which is strengthening capital. Merging leads to the achievement of economies of scale and increases the volume of activity and savings and reduce the costs of the activity and mergers and acquisition leads to a change in bank management and the selection of leaders to pursue more efficient and modern management methods which leads to lower costs and increase profits. The success of governance in the banking system does not only depend on setting regulatory rule, but it also needs to be applied correctly and this depends on the Central Bank and control on the one hand and on the bank and its management on the other. It is expected during the next few years that banks will face significant changes, as well as a number of strategic issues as a result of the increasing influence of the different strong forces under financial globaliziation. In the light of the above results, the study recommends the following:

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Benefiting by the models of central banks which are highly autonomous through information communication, on-going training, participation in international banking conferences, and increasing overseas missions and scholarships to get acquainted with new developments in banking systems.

Developing the skills of those in charge of credit and selecting the best of them from among those who are efficient, well-reputed and highly experienced in the field of banking, and stopping political appointments in the banking sector, taking into consideration on-going training of banking cadres to get acquainted with the latest developments in banking work, especially in the field of credit, through seeking the assistance of specialized experts whether from Egypt or abroad, and activating the overseas training scholarship system to benefit by international experiences.

To face international competition, commercial banks in Egypt must work to know all details about the banking market needs in such a way as to not to conflict with the goals of the banks. They must also know the nature of competition which banks face. Reinforcing the financial resources of Egyptian commercial banks through increasing capital and merging small and weak banks to form more effective units in order to achieve the required reduction in costs and benefit by larger economies. Working to develop human resources through rehabilitation and training in such a way as to fit with the developmental process and the requirements of modern banking technology. Implementing a modern banking technology and introducing modern services and products to deliver those services to clients in the local market.

REFERENCES Abdel-Bar, S., 2006: Restructuring the Banking System and How to Increase its Competitiveness: A Study Based on International Experiences. Contemporary Egypt Magazine, Egyptian Association of Political Economics, Statistics and Legislation, No. 483, Cairo. Abdel-Hafez, M., 2001: The Importance of Establishing a Crisis Management Department in Banks in the Light of International Changes. The 6 th Annual Conference on Managing Economic Crises in Egypt and the Arab World (Faculty of Commerce, Ain Shams University), Cairo. Abu Gahf, A., 2005: Organization of Bank Management, Alexandria: El-Nahda Egyptian Bookstore. Abul-Eyoun, M.2003: Workshopon:"Governance from a banking perspective, 05/02/2003, in: Link seminar series, Egyptian Banking Institute-Central bank of Egypt. Issue 3. Adib, Emad, 2003: Workshop on: "Governance from a banking perspective, 05/02/2003 in: Link seminar series, Egyptian banking institute – Central bank of Egypt, issue 3. Bergman and Klefsjo, 1994: "Quality from Customer Needs to Customer Satisfaction”, London: Mcgraw- Hill book. Capriog.,and C.,2000 : Bank privatization and regulation in Egypt, Distiguished lectur series, the Egyptian Center for Economic Studies (ECES), No 15. El-Alem, M., 2004: The Effect of Modern International Changes on Egyptian Public Sector Commercial Banks. Unpublished M. Com. Thesis, Faculty of Commerce in El-Ismailia, Suez Canal University. El-Antary, S., 2001: Credit Problems: Causes and Ways of Confrontation. Economic Dialogue Forum, Developing Countries Studies and Research Center, Faculty of Economics and Political Science, Cairo University. El-Baz, H., 2003: International Developments and their Effect on Banking Work and the Strategy Adopted by Banks to Face Them with Special Reference to Egypt. M. Com. Thesis, Faculty of Commerce, Ain Shams University. El-Dabie, A., 1999. Privatization of Banks and Development in Egypt. El-Ahram Economic Book, No. 153. El-Naggar, F.2000: Management of Credit and Defaulting banks Loans: Threats Facing Banks in the Twenty-First Century. University Youths Institution, Cairo. El-Said, H., 2004: Merging of Banks, Finance Journal. Farag A., 2005: Local Credit and its Impact on some Total Economic Variables under Law 88 for the Year 2003. The 24 th Annual Scientific Conference of Egyptian Economists on "Activating and Enhancing the Role of Monetary Policy in Egyptian Economy," Egyptian Association of Political Economics, 5-7 May.

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Gomaa, F., 2000: Financial Performance of Business Organizations: Current Challenges. El-Marikh Publishing House. Hefny, A., &Abu-Qahf, A.2000, Bank Organization and Management. Modern Arab Office. Ibrahim M., 1999, Banking Finance as an Approach to Decision-Making, Egyptian Anglo Bookstore. Kassem, M., 1998: Economic Reform in Egypt: the Role of Banks in Privatization and the Most Important International Experiences. Egyptian-Lebanese House, Cairo. MisrBank, ResearchCenter, 2002: Banking Handling of Default loans: Causes and Effects. Misr Bank Research Papers, No. 12, Cairo. Mohamed S., 2003, Bank Management between Theory and Practice, Mansoura: El-Galaa Bookstore. Moustafa, M., 2000: Evaluation of the Economic Reform Program in Egypt Focusing on the Economic Stagnation Phase. Contemporary Egypt Magazine, Egyptian Association of Political Economics, Statistics and Legislation, No. 457-458, Cairo. National Bank of Egypt, 2001: the New Suggested Framework of Basel Committee: Capital Sufficiency. Economic Bulletin, Vol. 54, No. 1 & 2. Rady, A., 2003: Default loans in Egyptian Banks. A Study Submitted to the Economic Research Council, Academy of Scientific Research and Technology, Cairo. Robert,A.& Manmoban,S.1995 , Emerging Egypt Markets , Growth Benefits , and Policy Concerns, World Bank Research Observer, Vol. 10, No.2. Schwartz, M, 1989: "A Quality Issue: Bank Product and Service" Bank Administration. Shalaby, M., 2005: Bank Control and Risk Management under Basel Criteria and Requirements of the Development of Institutional Governance. The 24th Annual Scientific Conference of Egyptian Economists on "Activating and Enhancing the Role of Monetary Policy in Egyptian Economy," Egyptian Association of Political Economics, 5-7 May. Shehata, I., 2001: Restructuring and Merging Banks: Individual Cases and Sector Reform. El-Ahram Economic Book, No. 132. Tarek, H.2002, Merging and Privatization of Banks, Alexandria: University Press. Tawfik, H., 2001: Modern Methods of Credit Management. Central Bank of Egypt, the Egyptian Banking Institute, Cairo, 2002. World Bank, 2001: Global experience in Restructuring banking, IMF Stuff paper. Zayed, H., 2003: What is Basel II? Financial Info issue (1) - Egyptian Banking Institut- Central Bank of Egypt.

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Influence of Potassium Humate on Growth and Chemical constituents of Thuja Orientalis L seedlings.

Sahar, M. Zaghloul, 1E.M. Fatma, El-Quesni 1 and 2 Azza A.M.Mazhar 1Plant Nutrition Dept., 2Ornamental Plants and Woody Trees Dept., National Research Centre, Egypt [email protected]

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Abstract: A pot experiment was conducted during 2006-2007 seasons at National Research Centre (Research and Production Station, Nubaria). The aim of this work is to study the effect of foliar spray with potassium humate (0.0, 0.5, 1.0, 1.5, 2.0 and 2.5 % K-humate ) on vegetative growth and some chemical constituents of Thuja orientalis L plants. Most criteria of vegetative growth expressed plant height, stem diameter, root length, fresh and dry weights of shoots and roots were significantly affected by application of aforementioned concentrations of K-humate under study, as well as chemical constituents content i.e. total soluble sugar content, (N, P, and K percentage content), essential oil % and essential oil yield/plant. All growth parameters and chemical constituents were increased by increasing humic acid concentrations compared with untreated control. Therefore, humic acid may recommended for promoted growth parameters and possessed the best oil percentage in Thuja orientalis L plants

Keywords: Thuja orientalis L plants, potassium humate , chemical constituent ______

INTRODUCTION Thuja orientalis L plants, Family Cupressaceae, the genus have five species, two one native to North America and three native to eastern Asia, they are commonly known as arbovitea. It has been widly cultivated as an ornamental timber tree for its source of wood, shade in different kind of soils, it can be grown as dense hedge, Vines (1987). Medicinal and windy resistance trees, prefers a sunny shetterd positions, Bown (1995). This species is known to have antipyretic, aperient, ostringent, diuretic, emollient, expectrant, lenitive, sedative, a yellow dye is obtained from young branches Grieve (1984). In addition wood is durable and used for construction, cabinet making and cooperage, Gamble (1972). Thuja orientalis L plants is a small sized evergreen trees, its length reached 10 m., with a conic crown, and the foliage grows in dense sprays, dark green colour.

Humic substances are organic compounds that result from the decomposition of plant and animal materials. Humic acid and their salts which derived from coal and other sources may provide a viable alternative to liming, to ameliorate soil acidity and improve soil structurel stability. Research has shown it is the humic fractions (humic acid, fulvic acid and humin) of the soil organic matter that are responsible for the generic improvement of soil fertility and improved productivity (Kononova 1966 and Fortun et al 1989), the same author added that humic acids are known to posses many beneficial agricultural properties, they participate actively in the decomposition of organic matter, rocks and mineral, improve soil structure and change physical properties of soil, promote the chelation of many elements and make these available to plants, aid in in correcting plant chlorisis, enhancement of photosynthesis density and plant root respiration has resulted in greater plant growth with humate application (Smidova, 1960 and Chen and Avid, 1990). Increase the permeability of plant membranes due to humate application resulted in improve growth of various groups of beneficial microorganisms, accelerate cell division, increased root growth and all plant organs for a number of horticultural crops and turfgrasses, as well as, the growth of some trees, Russo and

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Berlyn (1990), Sanders et al (1990) and Poincelot (1993). The aim of the present work is enhancing the vegetative growth of Thuja orientalis L plant by application of potassium humate, as well as, chemical constituents, and essencial oil content at Nubaria region, Egypt.

MATERILAS AND METHODS Two pot experiments were carried out at National Research Centre (Research and Production Station, Nubaria), during two successive seasons 2006 and 2007 to study the effect of potassium humate on growth, chemical constituents, and essential oil of Thuja orientalis L.

Six months old seedling of thuja were obtained from nercery of Forestry Department, Horticultural Research Institute, the seedlings were planted on the last week of march at the two seasons 2006 and 2007, in plastic pots 30 cm in diameter, filled with 10 kg of sandy soil , one plant /pot, the average heights of seedlings were 15-20 cm. The investigated soil characterized by sand 68.33%,silt 4.43%,clay 27.24% with pH 7.81,EC 2.18 dS/m,CaCO 3 22.50 %,OM 1.55%,Ca 11.61, Mg 4.80, Na 4.64, K 1.59,Cl 1.80,HCO 3 1.4,SO 4 8.5 meq/L ,N 19.60,P 65.80,K 165.64 meq/100g . The available commercially fertilizer used through this experimental work was kristalon (NPK 19:19:19) produced by Phayzon Company, Holand. The fertilizers rates (5.0 g/pot) used in four equal doses after 4, 8, 16 and 20 weeks from transplanting. The potassium humate used in this study is produced by alkaline treatment of Victoria brown coal and is commercially available in Australia (18 % k-humate) . Plants were sprayed with twice freshly prepared solution of potassium humate at ( 0.5, 1.0, 1.5, 2.0 and 2.5 %)in addition to the untreated plants (control) which were sprayed with tap water. The plants treated with K-humate two times of 30 days intervals starting on the 20 th May in both seasons. At last week of November of 2006 and 2007, the following data were recorded: plant height (cm), stem diameter (mm), root length (cm), fresh and dry weights of shoots and roots (g), and calculating shoots fresh weight / root fresh weight and shoots dry weight / root dry weight ratios. The experiment was sit in a completely randomized design with six treatments and six replicates of each treatment. The data were statistically analyzed according to Snedcor and Cochran (1980) using the least significant differences (LSD) at 5% level. The following chemical analyses were determined: total soluble sugars percentage was determined according to the method of Dubois et al (1956). Essential oil was determined in the shoots of each treatment according to Badawy et al (1991), and essential oil yield /plant were determined by multiplying essential oil percentage X average of dry shoot weight/plant. Nitrogen, phosphorus, and potassium were determined according to the method described by Cottenie et al (1982).

RESULTS AND DISCUSSIONS Vegetative growth: Effect of foliar application of potassium humate on the vegetative growth: The results in Table (1) show that plant growth is a function of nutrients supply providing, there were clear significantly positive trend in increasing plant height, stem diameter and root length by increasing the concentration of potassium humate. The highest significant increases were recorded in the treatments of 2.0 and 25 % potassium humate to a formentioned characters. Application by 0.5 to 2.5 % of K-humate were increased fresh weight of shoot and roots, it ranged from 13.14 to 47.64 % and 19.96 to 75.93 %, respectively than the corresponding values of the control plants. Similar results were reported by Brown and Lilleland (1946) who indicated that spraying tomato plants with humic acid increased growth compared with control plants due to the direct effect of humic acid on solubilization and transport of nutrients. Application by 0.5 to 2.5 % of K-humate were increased dry weight of shoots and roots, it ranged from 3.07 to 76.07 and 12.93 to 117.66 %, respectively than the corresponding values of the control plants. These results are in accordance with those obtained by Norman et al (2004) on marigolds and peppers and number of fruits of strawberries. Chen and Avaid (1990) added that humic substances have a very pronounced influence on the growth of plant roots and enhance root initiation and increased root growth which known root stimulator. Humic acid improve growth of plant foliage and roots. Vaughan (1974) proposed that humic acids may primarily increase root growth by increasing cell elongation or root cell membrane permeability, therefore increased water uptake by increased plant roots, and added that it

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can produce root systems with increased branching and number of fine roots, as a result potentially increase nutrients uptake by increase root surface area (Rauthan and Schnitzer, 1981).

Table 1. The influence of potassium humate on growth parameters of the Thuja orientalis L plant (means of the two seasons 2006 and 2007).

Shoots Roots Stem Shoots Roots Shoots dry dry Shoots Treatments Plant Roots diamet fresh fresh FW/R weight weight DW/R (%) height length er weight weight oots oots K-humate (cm) (cm) (mm) FW DW (g) (g) Zero 35.33 5.33 31.00 49.83 10.72 4.65 21.44 4.02 5.33 0.5 41.00 6.00 34.67 56.38 12.86 4.38 22.10 4.54 4.87 1.0 43.33 6.67 39.00 66.84 13.75 4.86 26.26 4.80 5.47 1.5 45.67 7.67 42.67 69.73 13.87 5.03 29.57 5.47 5.41 2.0 48.67 8.33 44.33 70.82 15.64 4.53 32.21 6.80 4.74 2.5 49.67 9.67 50.00 73.57 18.86 3.90 37.75 8.75 4.31 LSD 5% 3.80 1.46 4.58 5.02 1.74 ns 1.74 0.69 ns

Effect of potassium humate on chemical constituents: Soluble sugar content: Data presented in Table (2) show that foliar application of K-humate affected soluble sugar content of shoots of Thuya orientalis L . plant compared with control plant. Data emphasized that soluble sugar contents increased when plants treated with K-humate, the highest values of these parameters were obtained in plants treated with 2.0 and 2.5% compared with control plants. These results were in accordance with those obtained by Sladky (1959) . Chen and Avaid (1990) added that humic acid aid in correcting plant chlorisis, thus enhancement of photosynthesis density. These increments lead to positive effects on growth parameters and increased total soluble sugars content of Thuja orientalis L. plants

2- Minerals content: It is evident from the data in Table (2) that all minerals content (N, P and K %) under investigation were gradually increased by increasing humic acid concentrations. The increased in nitrogen content of shoots of Thuja oreintalis L. plants, due to humic acid application, these increments might have influenced plant growth directly through its effects on ion uptake or by the effects on plant growth regulators. These results were in line with those obtained by Satish Kumar (1997) and Sivakumar and Devarajan (2005). These increments led to positive effect on growth parameters and increased nitrogen and phosphorus percent. In relation to the effect of K-humate on the previous minerals in the shoots were gradually increased by increasing K-humate level, these increments due to enhancing effect of K-humate on the absorption or translocation of those minerals. Such phenomenon may due to its effect on enhancing plant metabolism. In addition humic acid maintained high level of acid phosphate activity led to increase phosphate activity holds for increased phosphorus uptake by plants (Malcm and Vanghan , 1979). However the increase in potassium content might be the reason for the increase in K % when increased humic acid doses (Siva Kumar and Devarajan, 2005).

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Table 2. The influence of potassium humate on chemical constituents of the Thuja orientalis L plant (means of the two seasons 2006 and 2007).

Soluble Essential Nitrogen % Phosphorus % Potassium % Treatments sugars % Essenti oil % al oil % yield/pla Shoots Roots Shoots Roots Shoots Roots Shoots Roots nt (ml) Zero 1.51 1.05 0.34 0.31 0.78 0.48 3.67 2.73 0.42 0.09 0.5 1.61 1.16 0.39 0.36 0.90 0.53 4.73 3.41 0.54 0.12 1.0 1.72 1.45 0.46 0.47 1.04 0.64 5.27 3.82 0.57 0.15 1.5 1.77 1.61 0.57 0.53 1.18 0.70 5.83 4.35 0.68 0.20 2.0 1.83 1.68 0.69 0.62 1.34 0.78 6.09 4.79 1.21 0.37 2.5 2.15 1.74 0.81 0.77 1.68 0.86 6.53 5.15 1.67 0.63 LSD 5% 0.07 0.02

Oil content : Total oil percent in Thuja orientalis L. shoots were significantly affected as a result of foliar application with different concentrations of K-humate. The highest recorded oil % recorded in plants treated with 2.5 % K-humate, it produced 1.67%, whereas the lowest value was 0.42 %, it produced from untreated control plants. In addition, all concentrations of K-humate caused an increases in the essential oil yield content in shoots of Thuja orientalis L. plant, Russo and Berlyn (1990), Sanders et al (1990) and Pioncelot et al (1993) reported that humate application lead to quantitative and qualitative changes in proteins content which acted positively in cell division resulting in addition to vegetative growth.This led to increase oil content. From the obove mentioned results, it could be concluded that foliar application of K-humate promoted growth parameters and possessed the best oil percentage in Thuja oreintalis plant.

Correlation study : The results of simple correlation coefficients between the essential oil% and soluble sugars % as well as minerals content are presented in Table(3).

Table 3. Simple correlation coefficients between essential oil% and some minerals content as well under the used sugars content under the used Potassium humate.

K N S NR Ps Pr Ks Kr Sug s Sug r EssO K 1 N S 0.946988 1 NR 0.968955 0.871731 1 Ps 0.988307 0.955896 0.93049 1 Pr 0.988351 0.978639 0.93903 0.991497 1 Ks 0.979147 0.987598 0.911116 0.990125 0.996096 1 Kr 0.997003 0.947714 0.97377 0.986199 0.991322 0.978124 1 Sug s 0.975589 0.90205 0.973895 0.932615 0.942024 0.927512 0.966422 1 Sug r 0.99571 0.925338 0.974297 0.972568 0.971478 0.960341 0.988477 0.989715 1 EssO 0.917036 0.944527 0.798107 0.959146 0.948845 0.964186 0.913388 0.82541 0.886873 1

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It is clear that both essential oil% and soluble sugars % in roots and shoots showed positive and significant correlation in most cases with the other characters , mainly phosphorus % in roots and shoots , nitrogen in roots and shoots as well as both potassium% in roots and shoots. Such results might be indicated that humic acid could play an active role in plant constituents via they might be had a promotive effects ,as mentioned before(including cell elongation or root cell membrane permeability as well as more produce root systems) are reflected on nitrogen % ,phosphorus % , potassium % as well as essential oil and soluble sugars %.

Essential oil % 2.0 Essential oil yield/plant % 1.8 1.6 1.4 1.2 1.0

Value Value % 0.8 0.6 0.4 0.2 0.0 Zero 0.5 1 1.5 2 2.5 K-Humate %

Figure 1. Effect of potassium humate on essential oil % and essential oil yield/plant(ml).

8 y = 1.0823x + 4.0005 R 2 = 0.9519** 7

5 Sug s

4 EssO Value 3

2 y = 0.4783x + 0.2505 R 2 = 0.8408** 1

0 0 0.5 1 1.5 2 2.5 3 K- Humate

Regression analysis was carried out between K-Humate from side and Sug s and Ess O

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REFERENCES Badawy, A.M. Morsi, S.S. Sakr, El-Bahr and H.S. Taha 1991. Production of essential oil obtained from callus of different organs of chamomile plant in vitro. Bull. Fac. Agric., Cairo Univ., 42: 1485-1500. Bown, D. Encyclopaedia of Herbs and their Uses. Darling Kindersly, London. 1995. ISBNo- 7513-020- 31. A very well presented and informative book on herbs from around the globe. Plenty in it for both the casual reader and the serious students. Just one main quibble is the silly way of having two separate entries of each plant. Brown, J.D. and I. Lilleland, 1946. Rapid determination of potassium and sodium in plant material and soil extracts by flame photometry. Proc.Amer.Soc.Hort.Sci., 48: 341-346. Chen, Y. and T. Avaid. 1990. effect of humic substances on plant growth. Pp. 161-186. In: American Society of Agronomy and Soil Science Society of America (eds.), Humic substances in soil and crop science; selected Readings. American Society of Agronomy, Madison, WI. Cottenie, A., M.Verloo, L. Kikens, G. Velghe and R. Camerlynck. 1982. Chemical Analysis of Plant and Soil. Laboratory of Analytical and Agrochemistry. Sate Univ. Ghent, Belguim, pp:100-129. Dubios, M., A. Giolles, Hamelton, P.A. Robers and P.A. Smith. 1956. A clorimetric for determination of sugar and related substances. Anal Chin., 28: 350-356. Fortun, C., A. Fortun and G. Almendros. 1989. the effect of organic materials and their humified fractions on the formation and stabilization of soil aggergates. The Science of the Total Environment, 81/82: 561-568. Gamble, J.S. 1972. A manual of Indian Timbers. Bishen Singh Mahendra Pal Singh, giving a lot of information on the uses and habitals of Indian trees. Grieve. 1984. A modern Herbal. Penguin ISBN 0140464409, have lots of information, mainly temperate plants. Kononova, M.M. 1966. Soil organic matter. Its role in soil formation and in soil fertility. Pergamon Press, Oxford. Malcom, R.L. and D. Vaughan. 1999. Humic substances and phosphatase activities in plant tissues. Soil Biochem., 11:253-259. Norman, Q. Arancona, Stephenlesa, Clive. A. Edwardsa and Rola Atiyeha. 2004. Effect of humic acid derived from cattle, food and paper –waste vermiconiposts on growth of greenhouse plants. The Soil Ecology Laboratory. The Ohio State Univ., 1735 Neil Avenue, Columbus, OH 43210, USA. Pioncelot, R.P. 1993. The use of a commerical organic biostimulant for bedding plant production J. Sustainable Agriculture 3:99-110. Rauthan, B.S. and M. Schnitzer. 1981. Effects of a fulvic acid on the growth and nutrient content of cucumber ( Cucumis sativus) plants. Plants and Soil 63:491-495. Russo, R.O. and G.P. Berlyn. 1990. The use of organic biostimulants to help low input sustainable agriculture. J. Sustainable Agriculture, 1:19-42. Sanders, D.C., J.A. Ricotta and L. Hodges. 1990. Improvement of carrot stands with plant biostimulants and fluid drilling. Hortscience 25:181-183. Satishkumar, B. 1997. Extraction and characterization of humic acids and their effect on the performance of soybean. M.Sc (Ag.). Thesis submitted to and approved by Annamalai Univ. Tamil NAdu. Sivakumar and L. Devarajan. 2005. Introgen of K-humate on the yield and nutrient uptake of Rice. Madras Agric. J. 92: 718-721. Sladky, Z. 1959. The effect of extracted humus substances on the growth of tomato plants. Biol Plant, 1: 142-150. Smidova, M. 1960. The influence of humus acid on the respiration of plant roots. Biol. Plant 2: 154-164. Snedecor, G.W. and W.G. Cochran. 1980. Statistical Method. 7 th Edition. Iowa State Univ. Press. Amer, Iowa, USA. Vaughan, D. 1974. A possible mechanism for humic acid action on cell elongations in root segments of Pisum sativum L.under aseptic conditions. Soil Biol. Biochem. 6: 241-247. Vines, R.A. 1987. Trees of Central Texas. University of Texases ISBN 0292780206. A readable quite to the area, it contains descriptions of the plants and their habitats with quite a bit of information on plant uses.

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A Study of Surface Durability of Polymer Sheets Exposed to UV, Heat And Combined Condition of Water Effects

Hale Gezer*, Murat Eric** *Maltepe University, Faculty of Architecture, Ba şıbuyuk-Istanbul, 34857, Turkey E-mail: [email protected] , ** Mimar Sinan Fine Art University, Faculty of Architecture, Fındıklı-Istanbul, 34427, Turkey, Istanbul E-mail: [email protected]

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Abstract: ‘Polymer material’ is the most preferable exterior coating material. However before applications, materials should be checked whether they are suitable to use and their performance should be evaluated as well. Thus, this study is intended; i. to show how rigid polyurethane (PU) and Polyvinyl Chloride (PVC) sheets materials, which are increasingly used in Turkey, are suitable for building physics ii. to determine their performance and durability changes in different climate in Turkey conditions. iii. to determine whether the materials suitable or not for these climates. It has been observed that there has been no scientific research on the durability of PU and PVC material in UV and heat conditions of Turkey, all standards of polymer material has been examined and after the evaluations it has been seen that standards have different conditions and are not adequate to get a result in the study and thus, specific test conditions have been prepared. Both materials with two different colours were conditioned in standard atmosphere conditions and strength tests were applied on their aged conditions done in 4 different test conditions. The results of these tests showed that mechanical and material properties of PU and PVC materials changed in Mediterranean-South Region .

Keywords: polymer materials, accelerated tests, surface strength. ______

INTRODUCTION

Production-consumption opportunities of building products are increasing day by day. The variability of polymer material makes it difficult to choose the most appropriate one. In recent years, PU and PVC based sheets are applied very often in all climates. However, due to ultraviolet (UV) radiation effect, some discolouration and deformation has been seen.

On PU coating deformations, there have been some studies in which UV rays effects on the material have been examined by changing the power and duration of the rays (Yang et al., 2001; Yang et al., 2002; Zhang et al., 2001), in which heat transfer mechanisms and performance are evaluated, in which Elasticity Modulus changes under heat and UV effects is evaluated and in which coating surface deformations due to the exposure to water is examined.

There have been also studies in which PVC deformations due to UV effect are determined, in which how chlorine decompose into its ions due to exposure level to light, heat and ion radiation, polyenes shapes of affect colour properties (Birer, 1999; Troitskii and Troitskaya, 1999; Tudôs, 1979), also the material’s strength decreases because of radiation and in which starting reactions are examined. PVC material deformation when exposed to heat, has been discussed by Mohamed, et al., (2003). The deformations due to HCl departure, mechanical and physical property loss in coloured polymer, deformations due to high temperature, the beginning and spreading phases of chain reactions due to heat, mathematical models of

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these phases have been examined by Simon et al., (1989), Troitskii and Troitskaya, (1999). Various types of rays and deformations due to oxygen, water effect mechanisms have been mentioned in various but similar studies by Carenza, (1984).

The results we gained in the studies, when evaluated independent from the literature, present invaluable data on the performance of the material. In standards and literature, no connection between aging conditions and radial time and natural conditions is stated. There is a lack of knowledge on radial time due to the fact that the strength and quality of sun rays change according to place and time because of the regional differences of natural UV radiation figures, humidity, heat, dirtiness and other factors.

The content and method of this study which contains the results of specific test conditions, is based on material performance research conditions of ASTM E 632-82 ‘Standard Practice for Developing Accelerated Tests to Aid Prediction of the Service Life of Building Components and Materials’.

EXPERIMENTAL SECTION Specimen Preparation In the test, rigid thermoset PU and thermoplastic PVC exterior sheet materials were used. PU material was taken from MD and PVC material was taken from Paksiding producers. Their dimensions were prepared in accordance with test standards and for each test conditions 5 samples were prepared (Gezer, 2005).

Standard Atmosphere Conditions “1 st class standard atmosphere conditions” were used on the materials. Both materials were conditioned at 23 °C, at 50% relative humidity without rays for 88 hours which based on TS 720 EN ISO 291 / April 1999. The values on this test conditions are identified as “S” in Figures.

Accelerated Test Conditions In this research, sun radiation, heat and water are used as physical environmental effects. A mechanism was prepared without dependence to general standards. Present standards are based on general conditions, so it is not possible to make a relationship between Turkey’s climatic conditions and these standards. Because of this; Turkey’s general annual radiation values are based on references from Dilmac, et al., (1996) and TS 825 Standards and rainfall and temperature values are based on meteorological information . In this study in order to determine the ray source effect time, the UV ray figures in northern and southern parts of Turkey have been used.

Lacking of standards for the experiment, special measurement machine was created by me for obtaining different climate conditions for each experiment. The machine produces special test conditions by creating rain, heat and radiation conditions which can be adjusted to each climate values in different conditions of Turkey.

In order to determine radiation values, the annual total global radiation values of 1.Region-South and 2. Region-North have been used. TS 825 has indicated these values (p.58). However, in test mechanism, (in the experiment the light source is in right angle to material) considering the fact that the lamp illuminates perpendicular, the radial time applied must be half as it was documented by Schmid, (1988). The ray source chosen for accelerated tests was 400 W/D Osram-Powerstar HQI-E UV lamp and was not switched off during the test. It was changed after its service life which is 1000 hours. The lamp was used with Tridonic- ignitor 2RM 6-Es/B 220/240 V and Philips BHL 400 L-220 V transformer.

In the tests, as it would not be realistic to evaluate the material performance at a high temperature, the temperature was kept at max. 45 °C for A and C Test Conditions, and at max. 55°C for B and D Test Conditions. In order to fix the heat in this climatic machine, a thermostat system connected to a heat detector was installed and with the help of a ‘fan’, the increasing heat was decreased. The thermostat operated with ‘lae-electronic’ heat detector and with a transformer fixing which decreases 220 Volt to 12 Volt.

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Spray-up cycle was 90 minutes dry, 15 minutes raining period for A and C Test Conditions, and 60 minutes dry, 15 minutes raining period for B and D Test Conditions. The water used was within the standards as 16 ±5 °C. In the test, % 50 ±2 °C relative humidity was used. The measurement was done using humidity measuring instrument Lae HT 2W Humidity Transmitter. Table 1 has shown that the time series and test conditions.

Temp. Test Conditions Time (hr) Water cycle (°C) A Test Condition 500 UV + 45 °C 90 min. dry 15 min. rain B Test Condition 900 UV + 55 °C 60 min. dry 15 min. rain C Test Condition 1000 UV + 45 °C 90 min. dry 15 min. rain D Test Condition 1800 UV + 55 °C 60 min. dry 15 min. rain

Mechanisms Used In this study; For Colour, Brightness Values Measurement Mechanism : Colorgene, Altair, light source: CIE-65, Geometry: d/8°, sight angle 2°.Charlestown MA. USA, For Hardness Measurement Test Mechanism : Shore D, brand: Bareiss, serial no: DTAA 5054/01, For Tensile Test Machine : Zwick / Roell, type: BZ250/SN5A, serial number: 156275/2002 devices were used.

Measurement Standards Used standards were; Standard atmosphere conditions; have been prepared in accordance with TS 720 EN ISO 291/April 1999 . For accelerated test conditions ; ASTM G 90-98 Standard Practice for Performing Accelerated Outdoor Weathering of Non-metallic Materials Using, ASTM G 151, G 152, ASTM G 153, G 154, ASTM G 155 Standard Practice For Exposure, ASTM G 23,G 53 Practice for Exposing Non-metallic Materials in Accelerated Test Devices The Laboratory Light Sources (Carbon-arc, Xenon-arc, fluorescent UV), ISO 4892-1-2-3: 2001 Plastics-Methods of Exposure to Laboratory Light Sources, TS 2826-1986 Polymeric Materials-Flexible Textured-Accelerated Aging Test, TS 8106-1-2-3-1998 Plastics Methods of Exposing to Laboratory Ray Sources, TS 10261-1992 Determination of Colour and Property Changes in Plastics when Exposed to Daily Light, Normal Weather Conditions and Sun Light under Glass, TS 10733-1993 Determination Standards of Hot and Humid Environment and Water Spray and Salty Water Spray Effect- Plastics have been examined.

Test method’s in all these standards, methods qualitative assessments of weathering effects has simulated in short time at high temperature and there aren’t any values of radiation for correlation of real time. These standards’ situations are not suitable for natural climate conditions usage and determining of the real durability of plastic materials. Because of this, new accelerated conditions of were prepared by TS conditions and Turkey’s meteorological values.

Colour measurements ; have been done in accordance with CIE Colorimetric 15.2, brightness measurements, DIN 67 530 and ASTM D 523-89 Standards.

Hardness measurement, have been done in accordance with ASTM D 2240-91 Durometer Hardness, EN ISO 868, TS 1181 (Shore Hardness) standards.

Tensile test measurements, have been done in accordance with the rules in ASTM D 638-91 Standard Test Method for Tensile Properties of Plastics - EN 10002, TS 1398-

2 EN ISO 527-2 April 1997 ‘Plastics– Determination of Tensile Properties– Section II: Test Conditions for Moulding and Extrusion Plastics Standards.

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Each test has been done on 5 materials and the values used in Figures have been reached [45].

MEASUREMENT RESULTS

The Measurements of Colour and Brightness (Light Source – CIE-D 65)

Test Condition Sample ∆a*b* ∆C* ∆L* PU, be 2.52 -0.15 -0.25 A Test Condition PU, bl 1.27 -0.50 0.92 PVC, be 2.77 2.23 1.64 PVC, bl 0.61 0.51 0.26 PU, be 1.44 1.24 0.23 B Test Condition PU, bl 1.90 -0.27 1.81 PVC, be 0.87 0.46 -0.73 PVC, bl 0.89 0.81 0.37 PU, be 1.47 1.39 -2.50 C Test Condition PU, bl 4.47 -1.70 -0.66 PVC, be 1.05 0.60 -0.84 PVC, bl. 0.09 0.02 0.01 PU, be 1.66 -0.63 -1.39 D Test Condition PU, bl 2.18 0.13 0.88 PVC, be 1.29 1.03 -0.73 PVC, bl 1.32 0.85 0.96

Table 2. Value Differences of Colour and Brightness of PVC and PU Material (be; beige, bl; blue)

By using these values of Table 2, the figures can be provided. It can be easily seen the relationships among the values . Lightness-Darkness Values (L*) Lightness-Darkness Values (L*) PU Material Colour Beige PU Material Colour Blue 90 87,7 87,45 87,94 90 85,21 86,31

80 77,07 77,96 77,03 80 76,15 75,49 L* L* 70 70

60 60 S A B C D S A B C D

Figure 1. Lightness-darkness Values of beige and blue PU material (L*)

For beige PU material, there is a slight lightening in B Test Condition whereas a slight darkening in other conditions, for blue material there is a lightening in all conditions except C Test Condition.

Lightness-Darkness Value (L*) Lightness-Darkness Value (L*) PVC Material Colour Beige PVC Material Colour Blue 90 90

80 77,77 80 76,13 75,4 75,29 75,4 L* L* 70 70 62,74 63 63,11 62,75 61,7 9 60 60 S A B C D S A B C D

84 Ozean Journal of Applied Sciences 2(1), 2009

Figure 2. Lightness-darkness values of beige and blue PVC material (L*)

It is seen that; there is a lightening for both beige and blue PVC material in A Test Condition, whereas a darkening for beige colour in B, C and D Test Conditions, no change in blue colour, and it turns to its original in C Test Condition.

(a*) Value (a*) Value PU Material Colour Beige PU Material Colour Blue 1 -8 0,51 0,5 -9 0,06 a* a* 0 -10 -9,81 -10,1 -10,12 -0,18 -0,5 -11 -0,58 -11,45 -1 -0,82 -12 -11,71 S A B C D S A B C D

Figure 3. (a*) values of beige and blue PU material

For beige PU material a* value goes to red nuances in A and B Test Conditions and to green in C and D Test Conditions. Blue colour turns into green in C and D Test Conditions.

(a*) Value (a*) Value PVC Material Colour Beige PVC Material Colour Blue 1,5 1,34 -2 1,18 1,12 1,1 -2,2 0,96 1 -2,4 a* a* -2,35 -2,43 -2,6 0,5 -2,56 -2,8 -2,75 -2,81 0 -3 S A B C D S A B C D

Figure 4. (a*) values of beige and blue PVC material

It is seen that; for beige PVC material there is a turning into red, for blue colour; there is a turning into red in A and B Test Conditions and into original nuance in C and D Test Conditions.

(b*) Value (b*) Value PU Material Colour Blue PU Material Colour Beige 0 30 22,65 22,8 21,41 21,26 20,76 -5 20 b* b* -10 10 -10,01

-13,18 -12,87 -15 -14,01 -13,51 0 S A B C D S A B C D

Figure 5. (b*) values of beige and blue PU material

Beige PU material turns into its original yellow colour in B and C Test Conditions. Blue colour turns into yellow especially in C Test Conditions.

85 Ozean Journal of Applied Sciences 2(1), 2009

(b*) Value (b*) Value PVC Material Colour Beige PVC Material Colour Blue 15 0 12,67 11,4 10,45 10,9 11,03 -1 10 -2 b* b* -3 5 -3,37 -3,34 -4 -3,67 -4,08 -4,25 0 -5 S A B C D S A B C D

Figure 6. (b*) values of beige and blue PVC materialBeige PVC material turns into yellow within the limits in all test conditions.

Blue colour becomes more blue in A, B and D Test Conditions, but goes back to its original colour in C Test Condition.

(C*) Value (C*) Value PU Material Colour Beige PU Material Colour Blue

22,65 22,08 21,41 21,26 20,78 20 20 17,1 16,6 16,88 17,23 15,4 C C 10 10

0 0 S A B C D S A B C D

Figure 7. (C*) values of beige and blue PU material

Beige PU material has a little brightness loss in A and D Test Conditions whereas it has no brightness loss in B and C Test Conditions. Blue PU material has a little brightness loss in A and B Test Conditions, whereas loosing in C Test Condition. There is a little increase in brightness in D Test Condition.

(C*) Value (C*) Value PVC Material Colour Beige PVC Material Colour Blue

20 20 12,72 C 10,49 10,96 11,1 11,52 C 10 10 4,11 4,62 4,92 4,13 4,96

0 0 S A B C D S A B C D

Figure 8. (C*) values of beige and blue PVC material

The brightness of beige PVC material increases in all test conditions. In blue material there is also a little increase in brightness.

The Results of Hardness Measurements The surface hardness of PU material decreases in all test conditions except B Test Condition. The surface hardness of PVC material increases in all test conditions.

86 Ozean Journal of Applied Sciences 2(1), 2009

Surface Hardness Surface Hardness PU Material PVC Material 78,02 76,62 76,98 80 80 72,5 73,93 60 60

40 40

Shore Shore D 23,7 24,06 Shore D 19,34 18,6 20 15,98 20

0 0 S A B C D S A B C D

Figure 9. The values of surface hardness of PU and PVC material

The Measurement Values of Tensile Test

Elasticity Modulus Elasticity Modulus PU Material PVC Material

50 850 38,37 809,32

40 800 780,45 770,91 775,63 30

750 721,91 20 E N / mm2 E N / E N / mm2 E N / 6,47 9,25 6,5 700 10 4,9 0 650 S A B C D S A B C D

Figure 10. Elasticity Modulus (E) of PU and PVC material

There are sharp decreases in PU material elasticity modulus in all test conditions. In C test Condition an increase is seen comparing to other periods which is not considerable. There is an increase in PVC material elasticity modulus especially in D Test Condition.

Tensile Strength Strain Tensile Strength Strain PU Material PVC Material 3 2,81 55,06 60 52,04 48,85 50,64

38,66 2 1,77 1,75 1,67 40 1,53

m N / mm2 m N 1 / mm2 m N 20 σ σ

0 0 S A B C D S A B C D

Figure 11. PU and PVC material tensile strength strain values

There is a decrease in tensile strength strain for PU material, an increase for PVC material, and the highest value is in D Test Condition.

Tensile Strength Stretching % Values Tensile Strength Stretching % Values PU Material PVC Material 40 40 35,5 34,02

30 26,15 25,76 30

20,36 20 20 F max % % F max F max % max F ε ε % max 8,6 8,91 8,78 8,92 9,32 10 10

0 0

S A B C D S A B C D Figure 12. PU and PVC material tensile strength stretching values as %

87 Ozean Journal of Applied Sciences 2(1), 2009

There is an increase in PU material tensile strength stretching values especially in A and B Test Conditions, and also an increase PVC material tensile strength stretching values especially in all test conditions.

Elongation at Break % Values Elongation at Break % Values PU Material PVC Material

124,6 122,25 120 120 111,09 107,39

80 80

B B %

B % ε ε 40,5 41,48 35,68 33,59 40 40 21,56 18,77 0 0 S A B C D S A B C D

Figure 13. PU and PVC material elongation at break values as %

There is an increase in PU material elongation at break values in A and B Test Conditions. They decrease a little bit in C and D Test Conditions having he same performance. PVC material elongation at break values increase in high proportions in all test conditions.

SUMMARY The Result on Surface Durability of Rigid PU Material Colour and Brightness Values It is seen that beige PU material darkens a little bit in long periods, colour changes go back to original and some slight brightness changes occur. It has been determined that blue colour darkens only in C Test Condition, deviates from the original colour, and as the period lasts longer it turns into yellow and also tends to turn into green. No considerable change in brightness is observed but the colour changes its originality.

Surface Hardness Values The surface hardness values of PU material increase in B Test Condition, but decrease in all other tests.

Tensile Test Values The elasticity modulus values of PU material decrease and the shape change of the material in ‘Elastic Region’ increase. The shape change also increases in ‘Plastic region’.

The Result on Surface Durability of PVC Material Colour and Brightness It is seen that in beige PVC material, the original colour darkens and it turns into yellow and then into red nuances. The brightness increases. There is a deviation from the original colour. However, in D Test Condition the change in colour is limited. In blue colour a slight lightening is seen in A and B Test Conditions. In D Test Conditions the colour darkens a little bit comparing to its original and a slight brightness increase occurs. Colour change occurs towards blue and green regions. It is more likely to be in the blue region.

Surface Hardness The surface hardness of PVC material reaches high values in A, B, C and D Test Conditions.

88 Ozean Journal of Applied Sciences 2(1), 2009

Tensile Test It is seen that; in PVC when material elasticity modulus increases, the material shows a smaller elastic shape change, there are considerable increases in elongation at break, and shape change in ‘Plastic Region’ increases in high proportions except C Test Condition in which the change is minimum.

RESULTS Estimation of the performance exterior durability of coating system is important in buildings’ material development. To retain their physical properties and their appearance depend on their used area. Weathering data for tests done under different condition can be related by a Turkey’s climatic data of different region. The relationship between the temperature and total UV values used in test conditions and the temperature and total UV values in Turkey according to regions which based on TS.825:

A Test Condition; Istanbul-North Region (5 years)....635.03 x 5=3175.15 W/m 2 B Test Condition; Mediterranean-South Region (5 years)....996.34 x 5=4900.81 W/m 2 C Test Condition; Istanbul-North Region (10 years)....6350.3 W/m 2 D Test Condition; Mediterranean -South Region (10 years)....9963.40 W/m 2

Evaluating the results in general in this respect, it is obvious that both materials are applicable for Istanbul- North Region considering the fact that rigid PU material should be applied by hanging method and if enough screw nut expansion space is given instead of using adhesive in order to prevent the discoloration in blue colour.

PVC material gains ductility in Mediterranean-South Region. Important properties such as thermal stability, flexibility, surface characteristics are changed in Mediterranean-South Region. In addition, due to changes in blue colour, It is not suitable to use in both regions. When the usage period increases in this region, the stability of PVC material decreases, because of the increase in percent of elongation in PVC. Also colour changes are determined. In applications, proper solutions must be investigated in hanging systems by considering expansion ratios.

The colour changes detected in test results show us that, the type of degradation is also chemical. This situation should be discussed another future research because it is caused by chemical degradation. In addition to these results also there is no correlation between realistic use and accelerated test standard data for polymer material. Especially a need of acceleration shift factor when aging a polymer material is determined in this study.

REFERENCES Birer, O. (1999). Spectroscopic Investigation of Polyvinyl Chloride Photodegration in Blends with Basic Traps , M. S. in Chemistry, Bilkent University, Ankara. Carenza, M., Gligo, N., Palma, G. and Busulini, L. (1984). Contributions to Radiation Crosslinking and Degradation of PVC-Based Mixtures. Eur. Polym. J . vol.20: 915-922. Dilmac, S.,Topcu, S. and Akman, M,S. (1996). A Study of Solar Ultraviolet Radiation at Istanbul, Energy, vol.21(3): 189-195. Gezer H. (2005). A Study of Surface Durability of Polymer Based Exterior Coating Material Exposed to UV, Heat and Combined Condition of Water Effects , PhD Thesis, Mimar Sinan Fine Art University; Faculty of Architecture. Istanbul. Mohamed, N.A., Sabaa, M. W., Oraby, E. H. and Yassin, A. A. (2003). Organic Thermal Stabilizers Polymer For Rigid Poly (Vinyl cloride). Degradation and Stability , vol.79(3): 495-501.

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Schmid, E.V. (1988). Exterior Durability of Organic Coatings , Fmj International Publications Limited, England. Simon, P., Cernay, P. and Valko, L. (1989). MINDO/3 Study of HCI Elimination from PVC Model Compounds. Eur. Polym, J ., vol.25: 245-249. Troitskii, B. B. and Troitskaya, L. S. (1999). Degenerated Branching of Chain in Poly (vinyl chloride) Thermal Degradation. Eur. Polym. J. vol.35: 2215-2224. Tudôs, F., Kelen, T. Naggy, T. T. and Turcsayi, B. (1979). Radiation Effects on The Thermal Degradation of Polyvinyl. Developments in Polymer Degr. Chapter 7, vol.2: 187. Yang, X. F., Tallman, D. E., Croll, S. G. and Bierwagen, G. P. (2002). Morphological Changes in Polyurethane Coating on Exposure to Water. Polym. Degrad. and Stabil, vol.77:391-396. Yang, X. F., Vang, C., Tallman, D.E., Bierwagen, G. P., Croll, S. G. and Rohlik, S. (2001). Weathering Degradation of a Polyurethane Coathing. Polym. Degrad. and Stability , vol.74:341-351. Zhang, R., Chen, H., Cao, H., Huang, C.M, Mallon, P. E, Li, Y. Sandreczki, T. C., Jean, Y.C., Suzuki, R. and Ohdaira, T. (2001). Degradation of polymer coating systems studied by positron annihilation spectroscopy IV Oxygen effect of UV irradiation. J. Polymer Science ; vol.39, issue.17: 2035 -2047.

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The Petrographic Properties of the Epiclastites in Neogen Volcanic Succession and Usage as Admixture in Pozzolanic Cement Production (Çemi şgezek/Tunceli, Turkey)

Sevcan Kürüm, Dicle Bal Akkoca Department of Geological Engineering Engineering Faculty, Fırat University, 23119, Elazığ, Turkey E-mail: [email protected]

______

Abstract: In this study, the epiclastic rocks in Neogene volcano-sedimanter succession, composed of volcanics and fluvial-lacustrine sediments, in Bölmebölen and Vi şneli villages near the Çemi şgezek district have been studied for examining their use as admixture in pozzalanic cements. The aim is to determine the mineralogical, petrographical, chemical, mechanic and physical properties of these rocks and discuss their use as admixture cement.The Neogene succession petrographically consists of conglomerate, limestone, dolomite, sanded claystone, sandstone, carbonated claystone, carbonated sandstone and tuffaceous sandstone. XRD examination of the rock samples shows that they include feldspar, quartz, crystobalite, calcite, dolomite and clay minerals. The XRD mineral identiciation is also supported with SEM analysis. The physical and mechanical tests carried out are specific weight, fraction of 90 and 200 micron sieve grains, moisture, Blaine (in cm 2/gr), loss on ignition (LOI), total 2 SO 3 content and pozzolanic activity values (N/mm ). It was observed that the pozzolanic activity was lower than normal level in the samples which include high amount of clay and carbonate. However, pozzolanic activity, fineness, and chemical compositions of tuffaceous sandstone samples having low content of clay and some carbonate together with amorphous silica and volcanic glass are within the required values suggested by TSE standard.

Keywords: Epiclastite, Cement, Admixture, SEM, Çemi şgezek, Tunceli ______

INTRODUCTION Epiclastic rocks are formed by the sedimantation in normal surface conditions where the decomposition and erosion of the previously formed volcaniclastic rocks are effective. These kinds of rocks are used as admixture in pozzolanic cement production. As is known, natural pozzolans include high amount of silica or silica + aluminum components (Massazza, 1997) and although they do not have binding property on their own, when they are grinded into very small particles they combine with lime in moist environment and form stable and hydraulic compounds that does not dissolve in water.

Generally a good pozzolanic material (or tuff) is preferred to include low amount of clay or alkaline feldspar. However tuff, which is an important pozzolanic material, is used in cement industry, such as various silica minerals together clay, different silica minerals and glassy matix.

It has been mentioned in various studies that the epiclastites within the Neogene volcanic sequence that widely crop out in the study area and surrounds, include tuffs in various properties (Sungurlu et al., 1985; Ercan et al., 1990). However, while subjects of some of these studies are petrographic properties of Neogene volcanites (Ercan and Asutay, 1993; Alparslan and Terzio ğlu, 1996; Kürüm and Bingöl, 1996), others examined the general stratigraphic properties of Neogene units that are intermediate contributory with these volcanites around Elazı ğ (Turan and Bingöl, 1991). Again Akkoca and Sa ğıro ğlu (2002, 2003, 2005) examined the mineralogy and petrography of fluvial-lacustrine sediments in the Çayba ğı (east of Elazı ğ) and Ağın (north east of Elazı ğ) and around Elazı ğ, and determined clay minerals. However neither in mentioned basins, nor in the study area, no evaluation has been made until today about the usage of these rocks including tuff and clay in cement industry.

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The purpose of this study is to determine the mineralogy and petrography of the epiclastites around Çemi şgezek and usage of these sediments including tuff and clay, as admixture in cement industry. The data that obtained, will allow mineralogical and petrographical comparison of these sediments with other Neogene sediments around Elazı ğ, also the usage properties of suitable samples as cement raw material will be determined so that it will be understood if these kind of sediments are worth examining in means of their usage as cement raw material.

GEOLOGICAL SETTING In the area of study, Keban metamorphites (Jurassic-Createse) which is one of the three different lithologic units within the mapping area are surfaced in a narrow area (Fig. 1). The unit shows the best and widest extension around Keban. The other unit, Alibonca formation (Lower Miocene) is represented by marl, limestone with sand and limestone in the area of study (Kürüm and Bingöl, 1996).

Epiclastic rocks which are the essential subject of study are located in volcanic rock seria which is considered as a continuance of Neogene volcanites which show a wide spreading in East Anatolia and are described as Karabakır formation by Naz (1979) or Tunceli volcanites (Ercan and Asutay, 1993). This volcanic seria which consists of pyroclastic, epiclastic and lava flows with basaltic composition (Kürüm and Bingöl, 1996; Kürüm et al., 1999) (Fig. 1) is completely represented by terrestrial environment sediments and terrestrial volcanism products.

Epiclastites, are widespread around Bölmebölen and Vi şneli villages (Fig. 1) and are represented with conglomerate, limestone, dolomite, sanded claystone, sandstone, carbonated claystone and tuffaceous sandstone composition rocks (Figs. 2a-d). Especially around Çemi şgezek road splitting, the conglomerates are with bad landed and gradation with matrix support. The blocks are generally located in the softer material below. The sandstones that are consecutive to conglomerates have light gray and beige color, include volcanic material and are almost horizontal. There are pebbles scattered in massive sandstones and their composition is andesitic and basaltic. The matrix between the grains is formed of material with clay. Sandstones, in which gradual and parallel laminated structures are seen, sometimes have planer cross bedded and trough cross bedded (Figs. 2b-c). Türkmen and Aksoy (1998) in the sedimentologic studies they made on this Neogene units, they stated that braided-stream sediments and that the transfers on these rivers are from east to west. Carbonates seen in these sequences are non- resistant, cracked, secondary calcite filled and micritic. While they do not show any lamination, they show oolite-like sedimentary structure (Kürüm and Bingöl 1996). Manganese dendrites are seen along the layering surfaces. Epiclastic materials being with mud and sand matrix and including blocks in various dimensions show that they develop as mud flow.

Pyroclastites are widespread in the east of the study area, around Sinsor and Yünlü villages. Normally tuffs with big and small particles are composed of well circled and equally sized lappilistones and bad landed and non-homogenous coarse graded agglomerates. (Kürüm and Bingöl, 1996). In this series, sometimes thin lava flows, interbedded tuffs or thin lava flows are observed.

Lava flows, are in basaltic composition and form the highest level of the stack. The lava flows seen in the study area, Karayazı and Kurugöl hills, (Fig. 1), are generally dark colored, hard, in different dimensions and have dense gas gaps. There are column shaped cracks on Kurugöl hill due to cooling cracks.

STUDY METHOD This study is conducted in 2 stages, field and laboratory. In the field studies, in two different locations around Bölmebölen (B) and Vi şneli (V) villages, sampling was made from fluvial-lacustrine sediments composed of conglomerate, limestone, dolomite, sanded claystone, sandstone, carbonated claystone and tuffaceous sandstone composition together with lava flows (Vk) in the upper levels of the succession. The locations around Bölmebölen and Vişneli villages from where the samples were taken are shown in Figure 1 and 2a. Epiclastic rocks (tuffacous sandstone, limestone with clay and limestone) and lava flow samples were examined in a James Swift polarising microscope for the determination of their mineralogical and petrographic properties. For the purpose of determining the mineralogical composition of the rocks, X-ray diffraction was applied in 20 samples. For this purpose powder samples were placed in Rigaku D-MAXIII model X-Ray Diffractometer (Cu K α, Ni filter, 30 mA current, 40 kV voltage) in MTA (General Directorate of Mineral Research and Exploration, Turkey) Mineral Analysis and Technology Department.

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91 93 95 97 99 101 103 Cemisgezek

Karayazi H. 20 Sinsor Caybagi Visneli Bolmebolen Kurugol H.

18 Yunlu Bölmebölen Saribalta

16 Urik

14 Dogankoy

12 Vaskovan

Hastek

8 Konaklar

K E B A N D A M L A K E N 6 0 1km

Cemisgezek Alluvium Keban Dam Lake

Tunceli volcanites Pertek Upper Miyocene-Pliyocene Keban Study Epiclastites area ELAZIG Lava flows

Pyroclastices Diyarbakir

Alibonca formation N N Upper Miyocene Ankara 39o 0 10km C T E Keban methamorphites Jurasic-Creatase 36o

150 km

o 36o 39o 42

Figure 1. The geological and location maps of the study area (simplified from Kürüm and Bingöl 1996). E: Elazig, T: Tunceli, C: Cemisgezek.

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Figure 2. (a) field and location section of the samples views of the Bölmebölen (1) and Vi şneli (2) villages; (b) top of location of the Bölmebölen section; (c) cross bedded tuffaceous sandstone in the Bölmebölen section; (d) views of the tuffaceous sandstone in the Vi şneli section.

The seven samples, whose mineral compositions were determined, were examined in Scanning Electron Microscope in İnönü University Research Center Laboratories (Malatya) and the morphologic properties of the minerals that form these rocks, such as shapes and dimensions, possible mineral changes and the textural relation with other components were determined. For this purpose, the natural surface of the samples (nearly 0.5 cm 3) was covered with gold and they were examined with a LEO brand Evo 40 VP model Scanning Electron Microscope with 3 nm separation power and 0.2-30 KV accelerating voltage interval. 5 samples whose mineralogy and petrography were determined were applied a chemical analysis (main oxide, heating loss and SO 3) in order to understand if they are suitable for using as cement admixture (trass / natural pozallanic) and tests to determine physical and mechanical properties were made according to TSE-24 and TSE-25 (Turkish Standards Institue) standards in Elazı ğ Cement Factory. In this aspect, the specific weight (gr/cm 3), percentage remains on 90 micron sieve, percentage remains on 2 200 micron sieve, moisture, Blaine (specific surface) (cm /gr), heating loss, total SO 3 amounts and pozzolanic activity values (N/mm 2) which is the most important property for usage as a cement admixture were determined. The pozzolanic activity test was made with trass, slaked lime [(Ca (OH) 2)] and standard sand. For the mixture, 150 gr slaked lime and 1350 gr standard sand was used. In the tras mixture, Trass = 2 x 150 (Trass Specific Weight / Slaked Lime Specific Weight) Water= 0,5 (150+T) Pozzolanic activity experiment was prepared according to Rilem Cembureau method mentioned in TS-24. The necessary material amounts for preparing 3 samples are calculated according to above. Each experiment is prepared with at least 3 samples. The samples were kept in room temperature (23 ± 2 oC) for 24 hours and after the end of 24 hours, they were kept in an incubator for 6 days at 55± 2 oC without removing the molds. The samples were taken out of the incubator 4 hours before breaking and pressure resistance determination was made according to TS-24.

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RESULTS Petrography The petrographic studies made on epiclastites in the study area were made on samples taken along the sections in Bölmebölen and Vi şneli villages (Figs. 1, 2a). In this study, it was determined that the rocks are properties sandstone, carbonated sandstone, claystone, limestone and tuffaceous sandstone (Fig. 2). However as thin cross section is hard to obtain in dense clay composition, the petrographic studies were mainly made with limestone and sandstone.

The general texture of the carbonated rocks is micritic. Petrographic datas conform to dolomite (V2, V6), limestone (B12, 15) and claystone (B9, 18) compositions at the end of XRD examinations (Table 1). According to Folk (1962) classification, these micrit rocks are formed of intraclast, litoclast formed of volcanic rock pieces and extraclasts formed of quartz, plagioclases and biotitic minerals.

Quart z Crist. Clay Calcite Dolomite Feldspar B1 5 3 8 23 61 B4 ------5 95 --- B6 1 --- 50 3 41 5 B7 2 2 19 2 3 72 B8 3 7 26 11 --- 53 B9 7 5 72 6 --- 10 B10 3 -- - 56 3 --- 38 B11 2 1 31 12 --- 54 B12 ------100 ------B13 2 --- 51 8 26 13 B14 3 --- 27 40 --- 30 B15 ------100 ------B17 2 4 57 23 --- 14 B18 3 --- 75 16 --- 6 V1 3 --- 21 2 --- 74 V2 ------100 V3 4 3 52 10 9 22 V4 1 --- 58 4 6 31 V5 4 2 16 2 3 72 V6 ------100 --- Dist. freq. 75 35 75 90 45 75 Arit. aver. 3 3,42 42,4 20,55 43 35,86 Gen. aver. 2,25 1,2 31,8 18,5 19,35 26,9 Dist. freq; distribution frequence, Arit. aver; arithmetic average, Gen. aver; general average, Crist; cristobalite

Table 1. Whole rock minerals and averages according to the XRD.

In the sanded tuff samples, mostly andesitic, basaltic and sometimes dasitic rock pieces together with quartz and feldspar minerals are found. In these rocks biotitic and opaque minerals were also seen as accessory mineral. Again in these rocks, in the feldspar minerals claying occurs due to dense alterations and generally Fe-oxidation is also prevalent. All these components are occupied with carbonated micritic matrix and it is named according to Schmid (1981) classification, as tuffaceous sandstone or vitric and litic tuff (Figs. 3a,b). In the lithic tuffs are contained rocks pieces with andesitic-basaltic composition are seen vesicular texture. However in the vitric tuffs are seen plagioclase laths in the glassy matrix. The optic-microscope data of these rocks that are examined petrographically, also conform with XRD data (Table 1).

Lava flows observed in Kurugöl and Karayazı hills (Fig. 1) are in basalt composition and are composed of primary minerals such as plagioclase, pyroxene, olivine and as accessory nefeline and as well as

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secondary formations developing around gas gaps such as zeolite and carbonate. (Figs. 3c,d). In these rocks, vesicular-amygdale textures together with flow texture and intesertal-intergranular textures are observed.

Figure 3. Thin section photomicrographs of epiclastite and lava flows showing. (a) plagioclase, pyroxene and vesicles in the basalts with the intersertal texture; (b) zeolite minerals in the vesicles of the basalts; (c) the pieces of rock, plagioclase latas, vesicles in the tuffaceous sandstone; (d) plagioclase latas in the dark color glasses, clayed matrix in the tuffaceous sandstone. Rf; rock fragment, Plg; plagioklase, Prx; pyroxene, Zeo; zeolite.

XRD Examinations In the clay and carbonated rocks, X-ray dissolvations were made in the whole rock, minerals were determined, half 001 peak heights were measured (mm) and their quantitative percentage was calculated. According to this, the main minerals found in rocks are respectively, clay, feldspar, dolomite, calcite, quartz, crystobalyte (Table 1). In the tuffaceous sandstones, little amount of hornblende and biotite was observed. In whole rock examinations the minerals were identified with the following peaks. Feldspar 3.18-3.22A°, dolomite 2.89-2.91A°, calcite 3.2-3.03A°, quartz 3.35-3.36A°, crystobalite 4.00-4.05A°. The d(104) values of carbonate minerals are between 3.025-3.032 and evaluated as low Mg-calcite (Milliman, 1974). Besides in samples B7, B11, B17, V3, V4 and V5, a few peaks combined and Mg-calcite mineral peaks whose reflection values were observed between 2.94-2.96 A o. For the crystallite degree of dolomite, the reflection values of dolomite d(104) in XRD profiles are found out to be between 2.882-2.891 and that their composition is suitable for ideal dolomite (Goldsmith and Graf, 1958). In the X-ray difractograms of all rock samples, the surface rising from 2Ө-15 A° in V1, V3, V4, B8, B9, B10, B13 samples, determines the existence of volcanic glass with amorphous characteristics (Jones and Segnit, 1971).

Scanning Electron Microscope (SEM) Examinations In the SEM studies made in the 7 samples in the study area the morphological properties of the minerals such as shape and dimension, possible mineral changes and textural relations with other components were determined.

Dolomite, from the carbonate minerals, is mostly observed as groups within smectite and matrix or individually as single euhedral spherulites (Fig. 4a). It was seen that these spherulites have smooth surfaces, their dimensions vary between 3-6 µm and the ones that grew in pores are bigger. They are euhedral because they are in ideal composition. Although rarely, in some regions, a dolomitic rose-like structure with sharp edges was also observed. Tucker (2001), states that the dolomites that show this kind of morphological and textural characteristics form from the primary sedimentation. In B15 sample, calcite crystals, that can be recognized easily with its typical trigonal symmetry between 1-3

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µm in carbonated rock gaps or / and matrix and which is found generally adjacent and also sometimes separately were observed (Fig. 4b). These euhedral calcite crystals indicate meniscus cement developed in vadose environment (Strong et al., 1992). In the chalk-like calcite stacks in calcitic mud characteristic were found as big crystals and small hexagonal plates together with smectite formations between sharp authigenic calcite crystals (Fig. 4c). Again in all samples, there are smectites, shapes that grew on volcanic glass with gap and splinter (Figs. 4d,e). In some samples while spherical alteration and volcanic glass splinters are observed, smectite formations developed on crystobalite groups and conversions from smectite to illite and illite fringes were seen in B8 sample (Fig. 4f).

Figure 4. Scanning elektron photomicrographs. (a) dolomite slabs, euhedral quartz and small dolomite crystals (Sample B6), (b) trigonale textured calcite crystals (Sample B15), (c) sharp authigeniccalcite crystals between bird-feather smectite (Sample B17), (d) smectites on the vesicular volcanic glasses material (Sample B8), (e) authigenicsmectites and volcanic glass splinters formed together vesicular volcanic glasses (Sample B8), (f) well formed bird-feather, vesicles authigenicsmectites and weblike- vesicles smectites, authigenicillite-flamentes formed around volcanic glass (Sample B8). Q; quartz, Do; dolomite, Ca; calcite, Sm; smectite, Vg; volkanic glass, I; illite

Chemical Composition After the mineralogy and petrography of the rocks in the study area were determined, the result of the chemical analysis made on 5 samples to determine their usage possibility as cement material (trass/natural pozzalan) are given in Table 2. As seen in the table the SiO 2 ratios of the samples varies between 53-63% while Fe 2O3 distribution which is average 4.1%, can be considered high. Fe 2O3 being high in the samples can be explained as presence of opaque phases such as hematite or clay minerals formed by the transformation of mafic phases in the main rock paste material of Fe element. The CaO in the rocks is relatively high with an average amount of 4.7%. This result may be due to calcite prevalence in the rocks which can not be seen much in optical microscope data but can be understood according Scanning Electron Microscope dates (Fig. 4, Table 1). While the K 2O content in the rocks varied between 1.5–2.7%, Na 2O value is 1.1-4.2 % which is higher than K2O and change interval is

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also wider. The Na excess in rocks can be explained with the presence plagioclases (especially the ones with rich Na content) which can also be intensively observed in petrographic examinations.

% B7 B8 B9 V1 V5

SiO 2 59.59 63.15 53.05 58.03 61.47 Al 2O3 16.83 16.83 14.31 17.34 17.39

Fe 2O3 3.94 3.06 5.44 3.96 3.97 CaO 5.00 4.19 4.84 4.79 4.65 MgO 2.92 1.98 3.32 2.67 2.26

Na 2O 3.74 3.87 1.06 3.38 4.16 K2O 1.74 2.70 2.02 1.47 2.26

SO 3 0.18 0.34 0.62 0.20 0.25 LOI 4.7 4.2 5.3 4.8 3.5 S+A+F 80.36 83.04 72.8 79.33 82.83

S+A+F: SiO 2+Al 2O3+Fe 2O3, LOI:Loss on ignition

Table 2. Results of major element analysis of samples (%).

When the chemical analysis results given in Table 2 are compared with standard values mentioned in ASTM C-618 and TS-25 (Turkish Standards Institute) (Table 3), SiO 2 + Al 2O3 + Fe 2O3 total of all samples is more than 70% which is important for the formation of pozzolanic reaction. Also, it can be seen that other chemical data such as MgO, SO 3 and heating loss which are important for the formation of this reaction, are exactly compatible with the standards.

Table 3. TS-25 standard requirements and Çemi şgezek samples.

SiO 2+Al 2O3 Al 2O3 Fe 2O MgO CaO SO 3 LOI +Fe 2O3 Turkish >%70 > %15 > %4 > %5 ~%10 <%3 <%10 Standard Studied samples 79.67 16.54 4.07 2.63 4.69 0.32 4.5 (Avr %)

MECHANICAL AND PHYSICAL PROPERTIES In the determination stage of the samples in the study area in means of conformity to raw material, physical properties should also be determined as well as chemical properties. Accordingly the mechanical and physical properties of the samples taken from the area of study are shown in Table 4 and the physical property comparison of trass, used in this aspect are shown in Table 5 (Binici and Bodur, 2005).

In concretes containing an admixture, the main factors that effect concrete durability are the main cement composition percentages, additive amount, thinness of cement, heating loss amount, undissolved residue and air amount (Şahin, 1995). The specific surface which is one of the most important mechanical and physical properties of the admixture is the relative surface that 1 gr of substance in dust form covers. The trass used in the cement industry is preferred with high Blaine value. After the trass with high specific surface is grinded, they fill the gaps in concrete plaster phase. This increases the endurance. According to TS-24, the minimum desired Blaine value is 3000 cm 3/gr. These values of the samples in the study area, being suitable to the values shown in Table 5, shows that the samples can easily be grinded and they are in required standards. In the XRD examinations, the presence of the amorphous phased volcanic glass was determined. In the SEM examinations, glassy phases were observed in samples. The increase of glassy phase increases the pozzolanic activity of the rock (Türkmeno ğlu and Tankut, 2002).

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Table 4. Important mechanic and physical properties of the samples.

V1 V5 B7 B8 B9 Water amount (%) 25.8 26 24.8 24.3 25.3 Specific weight (gr/cm 3) 2.69 2.67 2.62 2.55 2.7 Blaine (cm 2/gr) 4400 4610 4500 4560 4800 200 micron sieve (%) 6.3 6.5 6 7.6 4.9 90 micron sieve (%) 14.10 13.9 13.6 15.2 10.6 Pozzollanic ac tiv ite (N/mm 2) 5.1 6.1 4.8 10.8 3.6 moisture (%) 7.8 9.2 9.2 8.9 8.6

SO 3 (%) 0.2 0.18 0.5 0.6 0.6 Loss on Ignition (%) 4.8 4.7 5.2 3.3 5.3 Room temperature (20 oC)

Table 5. General physical properties of trass c omparison with Çemi şgezek samples.

Trass/Natural pozallanic Çemi şgezek samples

200 micron sieve >% 0.6 % 4.9 – 7.6 90 micron sieve >% 8.0 % 10.6 - 15.2 Blaine (cm 2/gr) 3000 4400 - 4800 Pozzollanic activite (N/mm 2) <4N/mm 2 % 3.6 - 10.8 (7th day compressive strength) Loss on Ignition >% 5.0 % 3.3 - 5.3

The pozzolanic activity is required to be over 4N/mm 2 according to TS-25. In B8 sample, the pozzolanic activity is maximum (Table 4). The presence of crystobalite and glass phases in this rock and the porous formations in glassy phase observed in SEM examinations should be the factors that affect the pozzolanic activity. It is considered that, high amount of clay phase observed in sample B9 (Table 1) and the absence of a reactive silica such as crystobalite decreases the pozzolanic activity. According to the studies, the not enough clay content is not a required situation (Türkmeno ğlu and Tankut, 2002). The pozzolanic activity is small in B9 sample with clay content and this sample is not suitable for usage as admixture. Increasing clay mineral formations decreased the reactivity of glass phase and caused the pozzolanic activity to occur below the limit.

DISCUSSION

The chemical properties that form the basis of the admixture (SiO 2+Al 2O3+Fe 2O3 ratio, MgO, SO 3, moisture and heating loss) are suitable to the properties of trass raw material used in the production of cement with admixture (TS-24) and cement with trass (TS 25). Besides, all properties of the samples except the low pozzolanic activity in sample B9 are in conformity with the specific weight, Blaine and pozzolanic activity properties specified in TS-25. The amorphous silica in these rocks played an important role of volcanic glass amount and geochemical results being in conformity with the specified standards. However, the pozzolanic activity may be low due to the high clay content in the lacustrine rocks. For this reason, it is understood that using tufaceous sandstones, which includes these components less and whose petrography and geochemistry are within the standards, as cement admixture (trass) seems more suitable. As mentioned before, the Neogene volcanites in Eastern Anatolia starts from Malatya and continue to east and northeast with widening surfaces. In the fluvial and lacustrine sediments which are found together with these volcanites, tufaceous sandstone is present as widespread surfaces around Elazı ğ and are also present in Çayba ğı (east of Elazı ğ), A ğın, Çemi şgezek, Arguvan-Arapgir (northwest of Elazı ğ) and these formations offer similar mineralogy and geochemical properties. These rocks should also be examined in this aspect in order to understand if

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these kinds of sediments are worth examining in means of usage as cement admixture. This is very important for the economy of the region and the country.

ACKNOWLEDGEMENT The authors are grateful to Scientific Research Projects Section of the Fırat University (FÜBAP-Project number-1423) for the financial support.

REFERENCES Akkoca, D.B., Sa ğıro ğlu A. (2002). Çayba ğı (Elazı ğ) havzası kil minerallerinin incelenmesi, Yerbilimleri/Geosound, 40/41, 39-50. Akkoca, D.B., Sa ğıro ğlu A. (2003). Çayba ğı havzası mineralojik verilerinin istatistiksel yöntemlerle değerlendirilmesi, Yerbilimleri/Geosound, 42, 193-203. Akkoca, D.B. ve Sa ğıro ğlu A. (2005). The Authigenic dolomite and smectite formations in the Neogene lacustrine-fluvial Çayba ğı basin (Elazı ğ, Eastern Turkey), Geologica Carpathica, 56/6, 531-543. Alpaslan, M., Terzio ğlu, N. (1996). Arguvan (Malatya Kuzeyi) yöresinde Üst Miyosen ve Pliyosen ya şlı volkaniklerin kar şıla ştırılmalı jeokimyasal özellikleri, Türkiye Jeoloji Bülteni, 39, 2, 75-86. ASTM C618-03. (1995). Standard specification for coal fly ash and raw or calcined natural pozzolan for use as a mineral admixture in Portland cement concrete, American Society of Testing and Materials, pp. 305-308. Binici, H., Bodur, M.N. (2005). Çimento katkı maddesi olarak pomzaların aktiviteleri, Türkiye Pomza Sempozyumu ve Sergisi, Isparta, Türkiye. Ercan, T., Fujitani, T., Matsuda, J.I., Notsu, K., Tokel,S. ve Ui,T. (1990). Do ğu ve Güneydo ğu Anadolu Neojen-Kuvaterner volkanitlerine ili şkin yeni jeokimyasal, radyometrik ve izotopik verilerin yorumu. MTA Derg., 110, 143- 163. Ercan,T., Asutay, H.J. (1993). Malata-Elazı ğ-Tunceli-Bingöl-Diyarbakır dolaylarındaki Neojen- Kuvaterner ya şlı volkanitlerin petrolojisi. A. Suat Erk Jeoloji Simpozyumu Bildirileri, 291-302. Folk, R.L. (1962). Spectal subdivision of limestone types. In:Classtification of Carbonate Rocks, Am. Assoc. Petrol. Geologists, Mem., 1, 62-84. Goldsmith, J. R. and Graf, D. L. (1958). Relation between lattice constants and composition of the Ca-Mg carbonates. Am. Mineral. 43, 84-101. Jones, J.B. and Segnit, E.R. (1971). The Nature of opal: I. Nomenclature and Constituent Phases. Journal of The Geological Society of Australia, 18, 57-68. Kürüm S. ve Bingöl, A.F. (1996). Elazı ğ yakın kuzeybatısındaki volkanitlerin petrolojik özellikleri. F.Ü. Fen ve Müh. Bil. Derg., 8/2, 83-98. Kürüm, S., Akgül, B., Erdem, E. (1999). Eskiarapkir-Şıhlar köyleri (Malatya-Elazı ğ) çevresindeki volkanitlerin petrografik ve jeokimyasal özellikleri. Geosound / Yerbilimleri. 34, 187-201. Massazza, F. (1997). Pozzolanas and durability of concrete. Çimento ve Beton Dünyası, Journal of TÇMB, Ankara. Milliman, J.D. (1974). Marine carbonates. Recent Sedimentary Carbonates, part 1, Springer Verlag, Newyork, 375p. Naz, H. (1979). Elazı ğ-Palu dolayının jeolojisi. TPAO Ar şivi Rap. No 1360 yayınlanmamı ş). Schmid, R. (1981). Descriptive Nomenclature And Classification Of Pyroclastic Deposits And Fragments: Recommendations Of The Iugs Subcommision On The Systematics Of Igneous Rocks, Geology, 9, 41-3. Strong, G.E.; Giles, J.R.A. ve Vright, V.P. (1992). A Holocene Calcrete From North Yorshire, England: Calcretes, Sedimentology, 39, 333-347. Sungurlu, O., Perinçek, D., Kurt, G., Tunç, E., Dulger, S., Çelikdemir, E., Naz, H. (1985). Geology of Elaz ğ-Hazar-Palu area. General Directorate Of Petroleum, 9, 83-100. Şahin, A. (1995). Ergani yöresinde mevcut puzolanik katkı maddelerinin çimento ve beton üretiminde kullanılabilirli ğinin ara ştırılması. Yüksek Lisans Tezi, F.Ü. Fen Bil.Enst. TS-25, (1975). Trass, UDK 666.95, Turkish Standards Institute, Ankara, Turkey TS-24, (1985). Physical and Mechanical Testing Methods of Cement. UDK 666.94.06, Turkish Standards Institute, Ankara, Turkey Tucker, M. E. (2001). Sedimentary Petrology, 3rd ed., 262pp., Oxford: Blackwell Science.

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Turan, M. ve Bingöl, A.F. (1991). Kovancılar-Baskil (Elazı ğ) arası bölgenin tektonostratigrafik özellikleri. Çukurova Üniversitesi Ahmet Acar Sempozyumu Bildiriler Kitabı, Adana, 213- 227. Türkmen, İ., Aksoy, E. (1998). Arapgir (Malatya), Çemi şgezek (Tunceli), Elazı ğ dolaylarındaki Neojen birimlerinin stratigrafik-sedmantolojik incelenmesi ve bölgesel korelasyonu, Türkiye Petrol Jeologları Derne ği Bülteni, 10(1). Türkmeno ğlu, A.G. And Tankut, A. (2002). Use of tuffs from Central Turkey as admixture in pozzolanic cements. Assessment of their petrographic properties. Cement and Concrete Research, 32, 629-637.

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A New Species of the Genus Psephellus (Asteraceae) From North-East Anatolia, Turkey

Ahmet Duran 1, Meryem Öztürk 1* & Bekir Do ğan 2 1Selçuk University, Education Faculty, Department of Biology Education, 42090 Meram-Konya, Turkey 2Selçuk University, Education Faculty, Department of Science Education, 42090 Meram-Konya, Turkey *E-mail: [email protected]

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Abstract: A new species, in sect. Hyalinella (Tzvelev) Wagenitz & Hellwig Psephellus coruhensis A.Duran & M.Öztürk (Asteraceae), is described and illustrated from Anatolia, Turkey. The species grows on eroded serpentine stony slopes in Çoruh Valley (A8 Artvin province) in North-East Anatolia. An endemic confined to Yusufeli district (Artvin), it is closely related to Psephellus simplicicaulis (Boiss. & Huet) Wagenitz. Diagnostic morphological characters from closely similar taxa are discussed, and arranged in a key of Turkish similar Psephellus Cass. Ecology, conservation status, biogeography of the species is also presented. Achene surface morphology of P. coruhensis is examined by SEM. The geographical distribution of the new species and other related species is mapped.

Keywords: Cardueae, Compositae, Hyalinella, Psephellus, Turkey ______

INTRODUCTION Recently, Centaurea L. has been divided into four genera (Wagenitz & Hellwig, 2000; Greuter, 2003a, b). According to the revised system these genera are Centaurea , Rhaponticoides Vaill., Psephellus Cass. and Cyanus Mill. One of these is Psephellus that has 75–80 species and a distribution with a centre in East Anatolia, Caucasian and northwest Iran; only few species occur outside this area (Wagenitz & Hellwig, 2000).

The genus Centaurea was previously revised by Wagenitz (1975) for the Flora of Turkey. In the Flora of Turkey, 172 plus six imperfectly known species of Centaurea were accepted (Wagenitz, 1975). Since then, following species have been described C. nydeggeri Hub.-Mor., C. mykalea Hub.-Mor., C. rechingeri Phitos, C. iconiensis Hub.-Mor., C. cariensiformis Hub.-Mor., C. yozgatensis Wagenitz, C. hadimensis Wagenitz, Ertu ğrul & Dural (Davis et al. 1988; Güner et al . 2000). C. amplifolia Boiss. & Heldr. was added as a new record for Turkey (Davis et al. 1988).

In addition to these, thirteen new species have been identified as C. cankiriense and C. antalyense (Duran & Duman 2002), C. yildizii (Türko ğlu et al. 2003), C. goeksunense (Aytaç & Duman 2005), C. marashica (Uzunhisarcıklı et al. 2005), C. tuzgoluensis (Vural et al . 2006), C. ulrichiorum and C. werneri (Wagenitz et al. 2006), C. glabro-auriculata (Uysal et al. 2007), C. kizildaghensis (Uzunhisarcıklı et al. 2007), C. elazigensis (Kaya & Vural 2007), C. ertugruliana (Uysal 2008) and C. yaltirikii (Aksoy et al . 2008).

C. amplifolia , C. iconiensis and C. mykalea species are transferred to genus Rhaponticoides (Greuter, 2003b) . C. hadimensis , C. yildizii Civelek et al . and C. goeksunense Aytaç & H.Duman are transferred to

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genus Psephellus (Greuter 2003a, Greuter & Raab-Straube 2006). P. turcicus A.Duran & E.Hamzao ğlu was described according to new revised system by Wagenitz and Hellwig (2000) from the genus Psephellus (Duran & Hamzao ğlu 2005).

In Wagenitz & Hellwig (2000), 12 sections that had been included in the genus Centaurea were transferred to the genus Psephellus . The former sections of the genus Centaurea were: Sect. Psephelloideae, Psephellus, Hyalinella, Aetheopappus, Odontolophus, Xanthopsis, Amblyopogon, Heterolophus, Czerniakovskya, Odontolophoideae, Uralepis and Sosnovskya. New combinations under the genus Psephellus are provided for these sections and 35 species, especially from Turkey and Iran. Some of these species occur only in Turkey. In this article, we have preferred the latest system in generic classification.

Psephellus specimen did not have flowers when it was first collected in 2002. The specimens with flowers were collected from the same locality in 2003. The specimens were not referable to any known Psephellus species. Studying the specific descriptions of Psephellus in Wagenitz (1975), Dostal (1976), Davis et al. (1988), Wagenitz et al . (1998), Wagenitz & Hellwig (2000), Güner (2000), Türko ğlu et al . (2003) and Duran & Hamzao ğlu (2005) as well as comparison with specimens in the Herbaria KNYA, ANK, GAZI, GOET, HUB, E, K and BM, showed that the specimens represent a species new to science. The specimens of P. coruhensis were examined and compared with specimens of the related species P. simplicicaulis in Turkey. Examined representative specimens of P. simplicicaulis from two localities and P. aucherianus (DC.) Boiss . five localities are cited below. The authors of plant names were checked from Brummitt & Powell (1992).

The molecular studies were made on the genus Centaurea (Psephellus, Cyanus , Rhaponticoides incl.). There is not yet a very clear picture of the evolution of the tribe Cardueae. Formal cladistic analyses published so far are based on few molecular markers Font et al . (2002) and Hellwig (2004). According to the new molecular technologies the taxonomic complexity of genus Centaurea is trying to solve, but needs further study. Only P. dealbatus (Willd.) C.Koch (Susanna et al . 1995), P. hedgei Wagenitz, P. bellus (Trautv.) Wagenitz and P. trinervius (Willd.) Wagenitz (Hellwig, 1996) have been included in phylogenetic analyses using molecular markers (Wagenitz & Hellwig, 2000). In these studies the ITS regions of the nuclear ribosomal repeat were sequenced. P. hedgei and P. bellus were also included in RFLP analysis of the chloroplast DNA (Hellwig, 1996). In both cases Psephellus proved to be monophyletic (Hellwig, 1996; Wagenitz & Hellwig, 2000).

Description of the New Species Psephellus coruhensis A.Duran & M.Öztürk sp. nov. (Figs. 1 and 2) Sect. Hyalinella (Tzvelev) Wagenitz & Hellwig

Affinis P. simplicicaulis , sed caulibus saturate ramosis (nec simplicibus), foliis terminalibus segmentatis 2– 8 mm latis (nec 7–15 mm latis), involucris 9–12 x 5–8 mm (nec 14–19 x 9–14 mm), appendicibus marginatis 5–8 ciliatis ac 0.8–1.3 mm longis (nec marginatis hyalinis dilute dentatis, dentibus usque 0.5 mm longis), pappis 1.5–2 mm longis (nec 5–10 mm longis) differt.

Type : Turkey. A8 Artvin: between Yusufeli-Sarıgöl, 2 th km, 630 m, 31.v.2003, stony slopes, 40°50.820'N, 41°32.339'E, A.Duran 6174 (holotype: KNYA, isotypes: GAZI, ANK, HUB, E).

Perennial with woody rootstock, many-stemmed, forming tufts. Stem slightly ascending to erect, remains of stems and basal leaves of the previous year present, ± sparsely floccose-tomentose, 5-striate, 25–35(–40) cm tall, 0.7–1.5 mm diameter at base, very rich branched in lower ¼ part of the stem, branches mostly fertile, some branches sterile or undeveloped, branches subequal to equal. Leaves mostly half of the stem, distinctly bi-coloured, green and sparsely tomentose above, densely adpressed grey-tomentose below, decreasing in number and size to capitula; basal and lower cauline leaves pinnatisect to lyrate with 1–2(–3) pairs of oblong to lanceolate lateral segments and conspicuously larger lanceolate or oblanceolate terminal segment, or rarely entire, oblanceolate or ± linear, variable in outline, terminal segment 2–8 mm wide, leaves to 7 x 1(–1.6) cm (incl. petiole), apex obtuse or acute; median and upper cauline leaves linear to

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linear-lanceolate, mostly entire or rarely one toothed per side, ± sessile, apex acute to acuminate. Capitula solitary, 14–17 x 5–8 mm (incl. flowers), erect. Involucre 9–12 x 5–8 mm, obovate to cup-shaped. Phyllaries imbricate, with scarious margins, glabrous; outer phyllaries broadly ovate, 1.5–2 x 1.5–2 mm, appendages 1.5–2 x 1.3–2 mm; median phyllaries oblong, 3.5–5 x 2–2.5 mm, appendages 2–2.2 x 2.5–3 mm; inner phyllaries narrowly oblong to linear, 7–8.5 x 0.8–1.5 mm, appendages 3 x 1.5–2 mm. Appendages medium-sized, concealing basal part of phyllaries, ± not decurrent, triangular to orbicular, ± hyaline, straw-colored to entirely brownish or in center, phyllaries appendages with cilia, 0.8–1.3 mm long, 5–8 cilia on each side, ending in a triangular 0.4–1 mm spinule, slightly longer than the closest cilia or ± equal. Corolla pink. Marginal florets longer than central florets and radiant, 15–16 mm long, with staminode, infundibular limb and 5–6 narrowly linear-lanceolate lobes, lobes 4–4.5 mm long; central flowers hermaphrodite, 11–12.5 m long, with 5 lobes, lobes c. 2.5 mm long, anthers of central florets equal to corolla, with yellow to slightly pinkish; style longer than corolla. Achenes 4.5–5.5 mm long, straw- colored to brownish, smooth and shiny, glabrous or few hairs; pappus 1.5–2 mm, barbellate, straw-colored to brownish, biseriate, inner series indistinctly differentiated, ± equal to outer series.

Phenology : Fl. May-June & fr. June-July.

Figure 1 . Psephellus coruhensis A.Duran & M.Öztürk sp. nov. (from isotype). A: habit. B: basal and lower cauline leaves. C: median and upper cauline leaves.

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Figure 2. Psephellus coruhensis . A. Habit and general view of type locality, B. Capitula, C. Flowers, D- E. SEM images of the general shape and surface of achene, F-G. General aspect of achenes and the detachment area (Photographs by A.Duran).

Distribution and suggested conservational status: The Çoruh Valley (Artvin province) is a very interesting area for plant diversity because of microclimatic conditions (Fig. 3). Elements of the Mediterranean phytogeographical region and a number of local endemic species grow there (see ‘Ecology’). This species belongs to Europe-Siberian phytogeographic region. Psephellus coruhensis is an endemic species known from four localities only in Yusufeli district (Artvin province); therefore, it is considered as ‘Endangered’ (criterion B1 a). The reduction of population size 80% because of the construction of the Yusufeli Dam on the Çoruh River (criterion A3). Only one locality will be outside of the level of dam after Yusufeli Dam project completely finished in nine years. This locality is “Artvin: Yusufeli, exit of Balaban village”. Because of this it could also be categorized as ‘Critically Endangered’ (criterion B2) for its known ‘area of occupancy’ of less than 2 km 2, population size estimated to be fewer than 250 mature individuals (criterion C) (IUCN, 2001).

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Figure 3. Distribution map of Psephellus coruhensis (), P. simplicicaulis (), P. aucherianus () and Centaurea dichroa () in Turkey.

Representative specimens examined : — Psephellus coruhensis (Paratypes): Turkey. A8 Artvin: between Yusufeli-Sarıgöl, 1–2 km, 650 m, 27.vii.2002, stony slopes, A.Duran 6042 (KNYA); Artvin: Yusufeli, the road of Barhal, 730 m, 17.v.2004, stony places, H.Duman 9394 & Z.Aytaç (GAZI); Artvin: Yusufeli, exit of Balaban village, 1600 m, 6.vi.2008, Hamzao ğlu 5087 (KNYA, Bozok Univ. herb.); Artvin: Yusufeli, around of Havuzlu village, 560 m, stony places, in shrubby, 6.vi.2008, Hamzao ğlu 5069 (KNYA, Bozok Univ. herb.). — Psephellus simplicicaulis: [Turkey ] A8 Erzurum: Armenia prope Ispir, vi 1853, Huet du Pavillon (iso. GOET! Photo BM!); A8 Artvin: Yusufeli, south of İçhan village, 1200–1350 m, steppe, 13.vi.2004, 73°20.302'E, 45°20.671'N, Z.Aytaç 8675 & H.Duman (GAZI!). — Psephellus aucherianus : [Turkey B7? ] in Cappadocia ad Euphratem, 1834, Aucher 3144 (iso. K, photo!); B7 Erzincan: Baschtasch ad Euphratem, 1890, Sint. 2925 (K, photo!); Erzincan: Egin (Kemaliye) Baschtasch ad Euphratem, 26.vi.1889, Sint. 961, 962 (K, photo!); Erzincan: between Erzincan-Kemaliye 128 th km, 1170 m, 15.vi.2004, calcareous rocks, A.Duran 6529 & Hamzao ğlu (S.Ü. E ğt. Fak. Herb.); Erzincan: between Erzincan-İliç, 15 th km, 1400 m, 15.vi.2004, serpentine slopes, A.Duran 6541 & Hamzao ğlu (S.Ü. E ğt. Fak. Herb.).

Ecology : Psephellus coruhensis grows in Mediterranean microclimate on eroded serpentine stony slopes with Acer divergens Pox var. divergens (local endemic), Paliurus spina-christii Mill., Juniperus oxycedrus L., Rhus coriaria L., Cotinus coggyria Scop., Ferula szowitsiana DC., Verbascum gracilescens Hub.-Mor. (local endemic), Caragana grandiflora (M.Bieb.) DC., Isatis erzurumica P.H.Davis (local endemic), Ephedra major Host, Alyssum artvinense Busch (local endemic), Asphodeline tenuior (Fisch.) Ledeb. ssp. tenuiflora (C.Koch) Tuzlaci, Atraphaxsis billardieri Jaub. & Spach. var. tournefortii (Jaub. & Spach) Cullen, Chesneya elegans Fomin L. (local endemic), Centaurea straminicephala Hub.-Mor. (local endemic), Clypeola raddeana Albov (local endemic), Micromeria elliptica C.Koch (local endemic), Stipa caragana Trin., Erodium oxyrrhynchum M.Bieb., and Seseli andronakii Woron. (local endemic), Ferula mervynii M.Sa ğıro ğlu & H.Duman (Sa ğıro ğlu & Duman, 2007).

Achene surface characteristics : Achenes surface of Psephellus coruhensis was studied by SEM. The surface ornamentation is reticulate, with cells in rectangular shape. There is rarely few distances between the some of cells of P. coruhensis (specimen no: A.Duran 6174) (Fig. 4).

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Figure 4. SEM images of the achene of the Psephellus coruhensis . A: general shape. B: achene surface.

DISCUSSION AND CONCLUSION Psephellus coruhensis is between sect. Hyalinella (Tzvelev) Wagenitz & Hellwig and sect. Odontolophoidei (Tzvelev) Wagenitz & Hellwig. The species placed in sect. Hyalinella (Tzvelev) Wagenitz & Hellwig according to the diagnostic characters of which determined by Wagenitz (1975), Wagenitz & Hellwig (2000).

The characters of the sect. Odontolophoidei (Tzvelev) Wagenitz & Hellwig similar with some morphological characters of sect. Hyalinella . It mainly differs from sect. Odontolophoidei because it has simple stem or with few branches (not several branches); leaves arachnoid and glabrescent above, densely appressed-tomentose below (not floccose or appressed tomentose); the lower pinnatisect to lyrate (not only lyrate); involucre 12–19 x 6–14 mm, ovoid (not 10–20 x 6–22 mm, ovoid to nearly globose); appendages denticulate or ciliate margin, not or very slightly decurrent (not only ciliate, not decurrent); pappus 5–8 mm, inner row short, scaly (not 1–4.5 mm, inner row short).

The sect. Hyalinella has three species which are P. simplicicaulis (Boiss. & Huet) Wagenitz, P. bellus (Trautv.) Wagenitz, P. pecho (Albov) Wagenitz. These taxa are placed into this section from Turkey and Caucasus region (Wagenitz 1975, Wagenitz & Hellwig, 2000). The morphological characters of P. coruhensis are very similar with Hyalinella section, but the length and inner row of pappus are differentiated from section Hyalinella . P. coruhensis needs much more investigation and molecular studies to solve problem related with section.

Psephellus coruhensis is closely related to P. simplicicaulis in sect. Hyalinella. It mainly differs from P. simplicicaulis because it has very rich branched stem (not simple stem), lateral segments of leaves 1–2, oblong to lanceolate (not with 1–4 pairs of elliptic to circular), terminal segment 2–8 mm wide (not 7–15 mm wide). In addition, it differs P. simplicicaulis from involucres 9–12 x 5–8 mm (not 14–19 x 9–14 mm), appendages small, 1.3–3 mm wide, margin distinctly 5–8 cilia and 0.8–1.3 mm long (not 2.5–5 mm, hyaline slightly toothed, teeth up to 0.5 mm), marginal florets radiant (not strongly radiant), pappus 1.5–2 mm (not 5–10 mm). P. simplicicaulis is very similar to P. pecho Albow which placed into same section Hyalinella (Table 1).

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Table 1. A comparison diagnostic characters of Psephellus coruhensis with P. simplicicaulis

Diagnostic Psephellus coruhensis Psephellus simplicicaulis characters Plant without sterile shoots with numerous sterile shoots Stem with remains of stems of the previous year without remains of the stems of the present, very rich branched previous year present, unbranched Basal leaves with 1–2 pairs of oblong to lanceolate 1–4 pairs of elliptic to circular lateral lateral segments and terminal segment 2–8 segments and terminal segment 7–15 mm wide mm wide Involucre 9–12 x 5–8 mm 14–19 x 9–14 mm Appendages 1.3–3 mm wide, margin distinctly 5–8 cilia 2.5–5 mm wide, margin hyaline slightly and 0.8–1.3 mm long toothed, teeth up to 0.5 mm long Marginal flowers slightly radiant strongly radiant Pappus 1.5–2 mm long and shorter than achene 5–10 mm long and longer than achene

In sect. Odontolophoidei, Psephellus aucherianus (DC.) Boiss. is distinguished from P. coruhensis , by its stem with almost entirely leaves; leaves firm, floccose-tomentose; lower leaves lyrate with large lanceolate to rhomboid, mostly irregularly toothed terminal segment; involucre 10–14 x 6–11 mm, ovoid to nearly globose, appendage rather large concealing most of basal part of phyllaries, ovate to broadly rhomboid or triangular, with 7–10 cilia on each side.

In addition, the general aspect of the new species is related to Centaurea dichroa Boiss. & Heldr. It mainly differs from Psephellus coruhensis because it has leaves white-tomentose or glabrescent (not distinctly bicoloured), involucre 4–6 mm wide oblong to cylindrical (not 5–8 mm wide, obovate to cup-shaped), appendages with cilia and 0.5–0.8 mm long (not 0.8–1.3 mm long), appendages decurrent (not decurrent), flowers without staminodes (not staminodes), corolla yellowish (not pink), anther-tube clearly pink to violet (yellow to slightly pink), inner row of pappus short (not ± equal). Both of these species grow in areas which have similar ecological conditions, and Centaurea dichroa distributed in Mediterranean phytogeographic region in Antalya and Mu ğla provinces, and Psephellus coruhensis occur in Mediterranean microclimate in Artvin province (Fig. 3).

Key to closely related Psephellus species 1. Stem very rich branched, involucre 5–8 mm wide, appendages margin with cilia, pappus 1.5–2 mm and shorter than achene …………… …………………...….… …...….……...….……...….…P. coruhensis 1. Stem simple, involucre 9–14 mm wide, appendages margin with toothed, pappus 5–10 mm and longer than achene …………….………………….……………….... …...….……...….…….. P. simplicicaulis

Biogeography: Palaeopalynological data show that Anatolia had a dense vegetation cover in the last interglacial period. The topography of Turkey has been changed many times, introducing many microclimates in tectonic valleys (Gemici, 1993). Psephellus coruhensis grow in areas distant from the Mediterranean phytogeographic region. There is a fairly very large area of Mediterranean vegetation in the Çoruh valley (Artvin) that is formed from vertical rocks, and the rivers pass through into the valley. Zohary (1973) considered that he traced vegetation patches all along the valley. As other hot and protected valley or eroded gorges, the Çoruh valley displaced patches of mixed vegetation made up of Euxinian and Mediterranean elements. In the last glacial period, some species from Mediterranean origin migrated into the tectonic valleys. These species in the last glacial period were prevented in these valleys on slopes, exposed to the south, from the effects of cold climate (Duran & Hamzao ğlu, 2002). The area is very rich endemic plants. Lately some new endemic species are described from the Çoruh Valley. These are Astragalus olurensis Podlech (Podlech, 2001), Astragalus khokhrjakovii Sytin & Podlech (Podlech & Sytin, 2002) and Ferula mervynii M.Sa ğıro ğlu & H.Duman (Sa ğıro ğlu & Duman, 2007).

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ACKNOWLEDGEMENTS The authors would like to thank to the Curators of Herbaria who send us to study their Psephellus specimens and pictures, also would like to thank to Selçuk University (Project no: 08701036) for financial support.

REFERENCES Aksoy, N., Duman, H. & Efe, A. 2008: Centaurea yaltirikii sp. nov. (Asteraceae, C. sect. Pseudoseridia ) from Turkey. – Nordic Journal of Botany 25: ..-.. (in press). Aytaç, Z. & Duman, H. 2005: A new species of Centaurea L. (Compositae) from Turkey. – Pakistan Journal of Botany 37(3): 563-566. Brummitt, R. K. & Powell, C. E. 1992: Authors of Plant Names . – Kew: Royal Botanic Gardens, Kew. Davis, P. H., Mill, R. R. & Tan, K. 1988: Centaurea L. – In: Davis, P. H., Mill, R. R. & Tan, K., (eds.), Flora of Turkey and the East Aegean Islands . Vol. 10 (Suppl. 1): 165-169. – Edinburgh University Press, Edinburgh. Dostal, J. 1976: Centaurea L. – In: Tutin, T. G., Heywood, H. V., Walters, S. M. & Webb, D. A. (eds.) Flora Europaea . Vol. 4: 254-3001. – Cambridge University Press, Cambridge. Duran, A. & Duman, H. 2002: Two new species of Centaurea (Asteraceae) from Turkey. – Annales Botanici Fennici 39: 43-48. Duran, A. & Hamzao ğlu, E. 2002: Flora of Kazankaya Canyon (Yozgat-Çorum). – Turkish Journal of Botany 26: 351-369. Duran, A. & Hamzao ğlu, E. 2005: Psephellus turcicus sp. nov. (Asteraceae), a new chasmophyte species from Central Anatolia, Turkey. – Botanical Journal of the Linnean Society 148: 495-500. Font, M., Garnatje, T., Garcia-Jacas, N. & Susanna, A. 2002: Delineation and phylogeny of the Centaurea sect. Acrocentron based on DNA sequences: a restoration of the genus Crocodylium and indirect evidence of introgression. – Plant Systematics Evolution 234: 15-26. Gemici, Y. 1993: Tersiyerden günümüze Türkiye’nin flora ve vejetasyonu. – Turkish Journal of Botany 17: 221-226. Greuter, W. 2003a: The Euro+Med treatment of Cardueae (Compositae) – generic concepts and required new names. – Willdenowia 33: 49-61. Greuter, W. 2003b: The Euro+Med treatment Senecioneae and the minor Compositae tribes-generic concepts and required new names, with an addentum to Cardueae . – Willdenowia 33: 245-250. Greuter, W. & Raab-Straube, E. Von 2006: Euro+Med Notulae, 2. – Willdenowia 36: 707-717. Güner, A. 2000 : Centaurea L. – In: Güner, A., Özhatay, N., Ekim, T. & Ba şer, K. H. C. (eds.) Flora of Turkey and the East Aegean Islands. Vol. 11 (Suppl. 2): 163-164. – Edinburgh University Press, Edinburgh. Hellwig, F. H. 1996: Untersuchungen zur Phylogenie der Cardueae-Centaureinae (Compositae) unter verwendung molekularer und morphologich-anatomischer Merkmale. – Habilitations-schrift Univ. Göttingen, Göttingen. Hellwig, F. H. 2004: Centaureinae (Asteraceae) in the Mediterranean-history of ecogeographical radiation. – Plant Systematics Evolution 246: 137 -162. IUCN. 2001: IUCN red list categories , Version 3.1 . – Gland and Cambridge: IUCN Species Survival Commission. Kaya, Z. & Vural, M. 2007: A new species of Centaurea Sect. Acrocentron (Asteraceae) from Turkey. – Novon: A Journal for Botanical Nomenclature 17(2): 198 -201. Podlech, D. 2001: Contributions to the knowledge of the genus Astragalus L. (Leguminosae) VII-X. – Sendtnera 7: 163 -201. Podlech, D. & Sytin, A. 2002: New species of Astragalus L. (Leguminosae) sect. Hololeuce , Onobrychoidei , O rnithopodium and Synochreati and a new section Baldaccia. – Sendtnera 8: 155 -166. Sa ğıro ğlu, M. & Duman, H. 2007: Ferula mervynii (Apiaceae), a distinct new species from north-east Anatolia, Turkey. – Botanical Journal of the Linnean Society 153: 357 -362. Susanna, A., Garcia Jacas, N., Soltis, D. E. & Soltis, P. S. 1995: Phylogenetic relationships in tribe Cardueae (Asteraceae) based on ITS sequences . – American Journal of Botany 82: 1056 -1068. Türko ğlu, İ., Akan, H. & Civelek, Ş. 2003: A new species of Centaurea (Asteraceae: Sect. Psephelloideae ) from Turkey . – Botanical Journal of the Linnean Society 143: 207-212.

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Uysal, T., Demirelma, H., Ertu ğrul, K., Garcia-Jacas, N. & Susanna, A. 2007: Centaurea glabra- auriculata (Asteraceae), a new species from Turkey. – Annales Botanici Fennici 44: 219-222. Uysal, T. 2008: Centaurea ertugriliana (Asteraceae) a new species from Turkey . – Annales Botanici Fennici 45: 137-140. Uzunhisarcıklı, M. E., Tek şen, M. & Do ğan, E. 2005: Centaurea marashica (Asteraceae) a new species from Turkey. – Annales Botanici Fennici 42: 309-312. Uzunhisarcıklı, M. E., Do ğan, E. & Duman, H. 2007: A new species of Centaurea (Cardueae: Asteraceae ) from Turkey. – Botanical Journal of the Linnean Society 153: 61 -66. Vural, M., Duman, H., Aytaç, Z. & Adıgüzel, N. 2006: Saponaria Karapınarensis , Senecio salsuginea and Centaurea tuzgoluensis , Three New Species From Central Anatolia, Turkey. – Belgian Journal of Botany 139 (2): 252 -260. Wagenitz, G. 1975: Centaurea L. – In Davis P. H. (ed.) Flora of Turkey and the East Aegean Islands . Vol. 5: 465 -585. – Edinburgh University Press, Edinburgh. Wagenitz, G., Ertu ğrul, K. & Dural, H. 1998: A new species of Centaurea Sect. Psephelloideae (Compositae) from SW Turkey. – Willdenowia 28: 157 -161. Wagenitz, G. & Hellwig F. H. 2000: Psephellus Cass. (Compositae, Cardueae ) revisited with a broadened concept. – Willdenowia 30: 29 -44. Wagenitz, G., Hellwig, F. H., Parolly, G. & Martins, L. 2006: Two new species of Centaurea (Compositae: Cardueae ) from Turkey. – Willdenowia 36: 423 -435. Zohary, M. 1973: Geobotanical Foundations of the Middle East . Vol 1 -2. – Gustav Fischer Verlag, Stuttgart.

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A Study into Organizational Commitment and Job Involvement: An Application Towards the Personnel in the Central Organization for Ministry of Health in Turkey

Akyay UYGUR Gazi University, Commercial and Tourism Educational Faculty, Ankara, Turkey E-mail:[email protected]

Gonca KILIC Duzce University, Tourism Business Vocational School, Düzce, Turkey E-mail:[email protected]

______

Abstract: The investigation studied the level of organizational commitment and the job involvement of the personnel at Central Organization of Ministry of Health in Turkey. 210 subjects, selected randomly, were distributed the questionnaire forms. Of the questionnaires, 180 of them (86%) returned and 168 of them were regarded valid and acceptable and analyzed. A moderate positive correlation was found out between organizational commitment and job involvement (r=0,44). In the light of this, there is a significant correlation between organizational commitment and job involvement, though not very strong.

Keywords: organizational commitment, job involvement, an application for ministry of health in Turkey ______

INTRODUCTION Organizational commitment is defined as the overall strength of an employee’s identification and involvement in an organization. Hence, paving the way for employees to be satisfied with the organization in which they work can be said to be as crucial as providing goods and services (Çöl, 2004). In this regard, taking into the positive effects of organizational commitment into account, the significance involved augments. Organizational commitment has become an issue of great importance to be dealt with, because it helps to increase employee performance (Shore & Martin, 1989; Meyer et al., 1989; Meyer et al., 1993; Meyer et al., 2002; Siders et al., 2001; Jaramillo et al., 2005) and helps to minimize turning up late to work, absenteeism, and leaving..

The concept of organizational commitment has become a major focus of a number of studies; however, no comprehensive definition to cover all disciplines has yet been rendered (Morrow, 1983). The foremost reason for it is that researches from different field of study such as sociology, social psychology and organizational behaviour have dealt with the topic based on their field of study. Hence, it is no surprise that the literature accommodates a variety of different definitions related to organizational commitment (Çöl, 2004).

Organizational commitment has been defined by the researchers as the level of involvement and identification with a given organization. In the context of this definition, organizational commitment embraces the following three elements. These are (a) the acceptance of organizational goals and a strong belief in these goals (b) willingness to perform substantial efforts on behalf of the organization (c) having a definite desire to maintain organizational membership (Chen et al., 2002; Allen & Meyer, 1990; Agarwal et al., 1999; Nijhof et al., 1998; Uygur, 2004).

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Employees with high level of organizational commitment have significant contributions to the achievement of the organization under competitive conditions (Feldman & Moore, 1982). Commitment of employees to the organization and using all his/her skills and expertise for the advancement of the organization concerned is a significance issue. Establishment may have a preference to work with those with high level of organizational commitment. The reason fort his is the belief that challenges encountered on the way to reaching goals may be overcome with such employees. Attributes of employees in terms of organizational commitment is the key guide for the success of the business.

JOB INVOLVEMENT There are many definitions of job involvement. Job involvement is defined as the degree to which a person psychologically identifies with. Job involvement is related with the work motivation that a person has with a job (Bashaw & Grant, 1994; Hackett et al., 2001; McElroy et al., 1995; Blau, 1986; Blau & Boal, 1987; Balay, 2000).

Job involvement is the internalization of values about the work or the importance of work according to the individual. Job involvement may appraise the ease with which a person can be further socialized by an organization. Organizational socialization is the process by which an individual understands the values, abilities, behaviors, and social knowledge indispensable for an organizational role and for taking part in as a member (Ramsey et al., 1995).

It is a belief about one’s current job and is a function of how much the job can satisfy one’s wishes. Highly job involved individuals make the job a central part of their personal character. Besides, people with high job involvement focus most of their attention on their job (Hackett et al., 2001).

Job involvement is grouped into four diverse categories. These categories: 1) work as a central life interest, 2) active participation in the job, 3) performance as central to self-esteem, and 4) performance compatible with self-concept. In work as a central life interest, job involvement is thought of as the degree to which a person regards the work situation as important and as central to his/her identity because of the opportunity to satisfy main needs. In active participation in the job, high job involvement hints the opportunity to make job decisions, to make an important contribution to company goals, and self-determination. Active participation in the job is thought to ease the achievement of such needs as prestige, self-respect, autonomy, and self-regard. In performance as central to self-esteem, job involvement implies that performance on the job is central to his/her sense of worth. (Ramsey et al., 1995; Blau & Boal, 1987; Balay, 2000).

Job involvement is a function of individual difference and the work situation. Thus demographic and work experience variables are expected to relate to job involvement. Positive relationships are expected with age, tenure, years in occupation, education, having children, and gender. There is no evidence for a strong relationship between job involvement and performance (Cohen, 1999).

Job involvement is negatively associated with intentions to quit and positively related to job satisfaction and organizational climate perceptions (McElroy et al.,1995; McElroy et al., 1999). In the same way, Blau and Ryan put forward that (1997: 437) job involvement and organizational commitment are negatively related to absence, withdrawal intentions and turnover as well as lateness and leaving work early and job involvement is positively related to work effort and performance.

Individuals with high levels of both job involvement and organizational commitment should be the most motivated to go to work and to go on time. Individuals with low levels of job involvement and organizational commitment should be the least motivated. Both highly motivated and non-motivated employees may miss work or come late for excusable reasons (e.g., illness, religious holiday, vacation time, transportation problems). However, highly motivated employees cannot be thought as non-motivated employees to miss work or come late for inexcusable reasons. Individuals with higher levels of job involvement and organizational commitment are likely to exhibit less unexcused lateness and unexcused absence than individuals with lower levels of job involvement and organizational commitment (Blau, 1986; Blau & Boal, 1987).

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Blau and Boal (1989) portray four different groups to classify employees by: (a) high job involvement - high organizational commitment; (b) high job involvement – low organizational commitment; (c) low job involvement – high organizational commitment; and (d) low job involvement – low organizational commitment. Employees in the first group are labeled “institutionalized stars”, in the second group “lone wolves”, in the third group “corporate citizens” and in the fourth group “apathetic employees”.

There has also been some research into organizational commitment and job involvement especially related to the health-care workers and nurses (Brewer & Lok, 1995; Brooks & Swailes, 2002; Örs et al, 2003; Özsoy et al, 2004; Sjöberg & Sverke, 2000; Blau & Boal, 1989). In a study conducted by Sjöberg and Sverke in Swedish Emergency Hospital (2000), it was found out that organizational commitment and job involvement had a variety of consequences on turnover. Blau and Boal (1989) found that nurses with higher levels of job involvement and organizational commitment had significantly less unexcused absences than nurses with lower levels of job involvement and organizational commitment. Yet, no study into organizational commitment and job involvement of the state employees at Ministry of Health has been performed.

METHODS

Data and Sample The research employed a questionnaire survey as the main tool to gather data. The questionnaire form is comprised of three parts and the questionnaire was administered to the employees at Central Organization of Ministry of Health. The first part of the questionnaire contained the questions related to the demographic attributes of the employees. The second part employs a 15-item scale (Mowday et al., 1979; Mowday et al., 1982) to determine the level of organizational commitment. In the third part, a job involvement scale, designed by Kanungo (1982) and developed by Karacao ğlu (2005), was employed to find out the level of job involvement. Likert’s five-point scale was employed. Data obtained, for the first part on demographic information, were analyzed through percentage and frequency tables. For the second and the third part, percentage, frequency, arithmetical average and standard deviation was calculated. The relation between organizational commitment and job involvement level was calculated using Pearson correlation coefficient. Besides, parametric tests to find out difference by demographic attributes were used, to measure relationship and independent samples t-test and one-factor variance analysis was employed. Reliability coefficient for organizational commitment scale was found to be (Cronbach’s Alpha) α=0,78 and as for job involvement α=0,83. The population of the study is comprised of the personnel employed at Central Organization of Ministry of Healthy. The total number of the personnel at the ministry is 420, according to the data obtained by the Ministry of Health. 210 people were selected randomly and they were administered the questionnaires. Of the questionnaires administered, 168 of them were found to be acceptable and analyzed.

Hypothesis The hypothesis of the study is H1: “There is a relation between the organizational commitment and job involvement levels of the employees working for the Central Organization of the Ministry of Health” the sub-goals of the study are; • To determine the level of organizational commitment • To determine the level of job involvement • To determine the relation between organizational commitment and job involvement • To compare the levels of organizational commitment and job involvement

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• To find out whether there is a significant difference by the level of organizational commitment and job involvement according to demographic attributes. Findings obtained through the realization of the sub-goals may be of great importance both in contributing to the literature and in terms of the organizations concerned.

RESULTS and DISCUSSION This study has revealed that there is a moderate positive correlation between the organizational commitment and job involvement levels of the employees working for the Central Organization of the Ministry of Health. This finding has verified the hypothesis of the study, which is H1: “There is a relation between the organizational commitment and job involvement levels of the employees working for the Central Organization of the Ministry of Health” (r=0,44). However, there has been found a significant difference between the organizational commitment and job involvement levels at a 0,005 significance level. This comes down to the fact that the job involvement level of the employees working for the Central Organization of the Ministry of Health is higher than that of the organizational commitment.

The questionnaire, intended for the identification of the organizational commitment level, has revealed that while 80% of the subjects have responded positively to the statement whether they cast importance upon the future of the organization, 71,5% have stated that they are ready to show an extraordinary effort for the success of the organization and nearly 50% have stated that they are proud to say that they work for the organization. In addition to this, most of the subjects have stated that their organizational commitment level is not low. Most of the subjects have responded positively to the statements which have also been mentioned in the studies conducted by Sökmen (2000) and Uygur (2004).

However, almost 50% of the subjects have responded negatively to the statement that the organization is highly effective in motivating the employees in terms of working performance and to the statement concerning the willingness to undertake any task to continue working for the organization. The subjects in the study conducted by Uygur (2004), however, responded to the above mentioned statements positively.

According to the data collected, in this study the organizational commitment level does not significantly vary according to gender. According to the studies conducted to reveal the relationship between gender and organizational commitment, no consensus has been reached in terms of the difference between organizational commitment levels of men and women. Some studies (Fry & Grenfeld, 1980; Cromie, 1981; Bruning & Snyder, 1983) have revealed that organizational commitment do not vary according to gender. Some other studies, on the other hand, (Hrebiniak & Alutto, 1972; Angle & Perry, 1981) have pointed out that women have a higher level of organizational commitment. Still, in another study, conducted by (Chusmir, 1982; Graddick & Farr, 1983), it has been argued that women have a lower level of organizational commitment compared with men. Nevertheless, it has been found that the organizational commitment levels of the employees working in the Central Organization of the Ministry of Health vary according to gender and that male employees have a higher level of organizational commitment than female employees. Some studies conducted to identify the organizational commitment level (Sager, 1991; Özsoy et al., 2004) have concluded that organizational commitment level does not vary according to the marital status of individuals. This supports the results of the study implemented on the employees working in the Central Organization of the Ministry of Health.

Some studies concerning the question whether the age and rank of the employees vary according to organizational commitment level (Angle & Perry, 1981; Hunt et al., 1985; Pierce & Dunham, 1987; Cohen, 1993; Zeffane, 1994; Linz, 2004), have revealed that organizational commitment level increases as the age and rank increase. However, in a study they conducted on sales assistants, Sager & Johnston (1989) have stated that there is no significant relationship between age and organizational commitment.

There are studies claiming that there is a negative correlation between educational status and organizational commitment and job involvement (Angle & Perry, 1981; Sommer et al., 1996). In addition, as a result of a study they conducted, Mathieu & Zajac (1990) have pointed that there is no strong correlation between

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educational status and organizational commitment. The data collected in this study, too, concludes that organizational commitment and job involvement levels do not significantly vary according to educational status.

The study has shown that the organizational commitment and job involvement levels of the employees do not significantly differentiate according to their status and the number of children they have. In the study conducted by Cohen (1992), it was stated that the number of children they have do not have an impact on the organizational commitment level of the employees and in another study conducted by Örs et al. (2003), it was stated that the employees’ ideas / perception of organizational commitment do not significantly vary according to the title of the employee.

TABLES Table I illustrates the data on the demographic features of the subjects working in the Central Organization of the Ministry of Health. Table 1. Frequency and Percentage Distributions on The Demographic Features of The Subjects (n=168)

Total Variables f % f % Male 89 53,0 Sex 168 100 Female 79 47,0 30 and below 25 14,9 31-35 33 19,6 Age 168 100 36-45 81 48,2 46 and above 29 17,3 High School 40 23,8 Two-year Degree 40 23,8 Educational Status 168 100 University 59 35,1 Post-graduate 29 17,3 Married 124 73,8 Marital Status 168 100 Single 44 26,2 The Spouse’s Employed 89 71,8 124 100 Employment Status Unemployed 35 28,2 No 5 4,2 One 33 27,7 Number of Children 119 100 Two 66 55,5 Three and more 15 12,6 0-5 years 19 11,3 The Length of Time of 6-11 years 26 15,5 Employment in a Public 12-17 years 38 22,6 168 100 Institution 18-23 years 60 35,7 24 years and more 25 14,9 0-5 years 46 27,4 The Length of Time of 6-11 years 42 25,0 Employment in The 12-17 years 25 14,9 164 97,6 Ministry of Health 18-23 years 40 23,8 24 years and more 11 6,5 Senior/Top echelon 12 7,1 The Position in the Middle-echelon official 13 7,7 168 100 Institution Lower-echelon official 24 14,3 Other Personnel 119 70,8 Province 92 54,8 Where he/she spent County 48 28,6 168 100 childhood Village 28 16,7

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According to the data on Table I, 53% of the subjects in the study are male and 47% are female. When the distribution of the study population by age is considered, the majority of the subjects are between 36 and 45, at a 48,2% rate; the76,2 % of the subjects hold a university degree, ranging from a two-year degree to a post-graduate degree. The 73,8% of the subjects are married and of all these married subjects, the 71,8% have employed spouses. When the distribution of the subjects according to the length of time they have been employed by the Ministry of Health is analyzed, it has been identified that the 11,3% of the subjects have been employed in governmental institutions for 0-5 years, the 5,5% for 6-11 years, the 22,6% for 12-17 years, the 35,7% for 18-23 years and the 14,9% for 24 and more years. On the other hand, 27,4% of the subjects have been working in the Ministry of Health for 0-5 years, 25% for 6-11 years, 14,9% for 12-17years, 23,8% for 18- 23 years and 6,5% for 24 and more years. In addition to this, it can be observed from the data that 29,2% of the subjects work at a senior/top echelon position, middle echelon staff position and lower echelon staff position and 70,8% of the subjects are employed as personnel. And finally, it has been found that 54,8% of the subjects spent their childhood in provinces, 28,6% in counties or small towns and 16,7% in villages. Table 2. The Frequency and Percentage Distribution of The Opinions of The Employees Working in The Central Organization of The Ministry of Health on Organizational Commitment Levels

sure zagree

I agree I’m not I’m not disagree I strongly I strongly STATEMENTS I disagree f % f % f % f % f % Χ S.S. I am willing to make more efforts than normally expected of me to contribute to 14 8,3 22 13,1 12 7,1 92 54,8 28 16,7 3,58 1,16 the success of the institution. I can comfortably tell people that the 28 16,7 41 24,4 50 29,8 43 25,6 6 3,6 2,75 1,12 institution is a great place to work in. My commitment level to this organization 44 26,2 81 48,2 18 10,7 18 10,7 7 4,2 2,18 1,07 is low. I would accept to undertake any responsibility to go on working in the 38 22,6 76 45,2 24 14,3 16 9,5 14 8,3 2,35 1,17 institution. I can see that my values are very similar 24 14,3 61 36,3 43 25,6 37 22,0 3 1,8 2,60 1,03 to those of the institution. I am proud to tell people that I am part of 10 6,0 35 20,8 30 17,9 80 47,6 13 7,7 3,30 1,07 this institution. I can work for some other institution as 10 6,0 38 22,6 29 17,3 73 43,5 18 10,7 3,30 1,11 long as I serve the same duty. The institution I am working in has motivated me in the best way possible in 25 14,9 52 31,0 39 23,2 45 26,8 7 4,2 2,74 1,13 terms of job performance. Even a slight change that may occur in the present conditions can cause me to quit 29 17,3 71 42,3 36 21,4 25 14,9 7 4,2 2,46 1,07 work. I am really content with working in this 16 9,5 36 21,4 56 33,3 44 26,2 16 9,5 3,04 1,11 institution instead of other institutions. I don’t think there is much to earn by committing yourself to the institution for 15 8,9 33 19,6 47 28,0 57 33,9 16 9,5 3,15 1,12 good. It is mostly hard to agree with the policies 9 5,4 28 16,7 43 25,6 70 41,7 18 10,7 3,35 1,05 of the institution towards employees. I do care about the future of the 8 4,8 10 6,0 17 10,1 95 56,5 38 22,6 3,86 0,99 institution. I am of the opinion that this institution is the best of the other possible institutions 17 10,1 42 25,0 61 36,3 40 23,8 8 4,8 2,88 1,03 to work in. It was certainly a mistake to have decided to work in this institution in the first 32 19,0 72 42,9 40 23,8 18 10,7 6 3,6 2,36 1,02 place.

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According to the results on Table II, to the statement that “I am willing to make more efforts than normally expected of me to contribute to the success of the institution. ”, the 8,3% of the subjects responded as “I strongly disagree”; 13,1% as “I disagree”, 7,1% as “I’m not sure”, 54,8% as “I agree” and 16,7% as “I strongly agree”. The arithmetical mean of this statement is 3,58. According to this data, the majority of the employees (71,5%) have positively expressed that they are willing to work more to contribute to the success of the institution. . To the statement that “I can comfortably tell people that the institution is a great place to work in.”, 41,1% 0f the subjects responded as ‘I strongly disagree’ and ‘I disagree’, while 29,2% of the subjects have responded positively as ‘I strongly agree’ and ‘I agree’. The percentage of the subjects who have responded as ‘I’m not sure’ is 29,8 (X=2,75). The majority of the subjects (74,4%) have responded negatively to the statement that “My commitment level to this organization is low”, which has indicated that the employees are highly committed to the institution (X=2,18).

According to Table II, the subjects have expressed their negative attitude towards some statements in the questionnaire. The percentages according to statements are as follows: 67,8% to the statement that they would accept to undertake any responsibility to go on working in the institution, 50,6 % to the statement that their values are very similar to those of the institution, 45,9% to the statement that the institution has motivated them in the best way possible in terms of job performance. On the other hand, while 54,2% of the subjects have expressed that they can work for some other institution as long as they serve the same duty, 52,4% of the subjects have expressed that it is mostly hard to agree with the policies of the institution towards employees. However, 55,3% of the subjects have responded positively to the statement that “I am proud to tell people that I am part of this institution.”, and 79,1% have stated that they do care about the future of the institution.

Moreover, 59,6% of the subjects have stated that a slight change in the conditions at work would not make it necessary for them to quit, and 62,8% have stated that they do not consider it a mistake to have started to work in the institution in the first place.

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Table 3. The Frequency and Percentage Distribution of The Opinions of The Employees Working in The Central Organization of The Ministry of Health on Job Involvement Levels

sure sure

STATEMENTS agree I I agree I’m not disagree I strongly I strongly I I strongly I I disagree f % f % f % f % f % Χ S.S. I like to spend most of my time 21 12,5 48 28,6 12 7,1 78 46,4 9 5,4 3,03 1,21 at work. Most of my personal goals are 16 9,5 79 47,0 25 14,9 41 24,4 7 4,2 2,66 1,07 related with my job. I get the most satisfaction in life 21 12,5 76 45,2 23 13,7 41 24,4 7 4,2 2,62 1,10 from my job. Every morning I go to work 12 7,1 27 16,1 38 22,6 77 45,8 14 8,3 3,32 1,06 enthusiastically. I would go on working even if I 28 16,7 51 30,4 40 23,8 46 27,4 3 1,8 2,67 1,10 did not need to earn money. My job and my personality 23 13,7 50 29,8 43 25,6 49 29,2 3 1,8 2,75 1,07 completely fit/overlap. Most of my interests are related 24 14,3 68 40,5 30 17,9 42 25,0 4 2,4 2,60 1,08 with my job. My job to me is no different from eating, drinking or 22 13,1 71 42,3 31 18,5 37 22,0 7 4,2 2,61 1,09 breathing. My commitment to my job is 16 9,5 45 26,8 28 16,7 69 41,1 9 5,4 3,05 1,13 hard to be broken. I mostly feel uninterested in my 33 19,6 95 56,5 20 11,9 17 10,1 2 1,2 2,16 0,90 job. I was more enthusiastic about 16 9,5 59 35,1 24 14,3 45 26,8 21 12,5 2,97 1,23 my job in the old days. Many things in my life matter 13 7,7 62 36,9 25 14,9 46 27,4 20 11,9 2,98 1,20 more than my job. I sometimes feel like punishing myself for mistakes I make 18 10,7 75 44,6 25 14,9 43 25,6 5 3,0 2,65 1,07 about my job. Frequently enough, I would rather stay home than go to 12 7,1 60 35,7 32 19,0 56 33,3 6 3,6 2,90 1,06 work. I would avoid undertaking extra duties and responsibilities 35 20,8 84 50,0 20 11,9 21 12,5 5 3,0 2,25 1,02 related with my job. I am perfectionist in my job. 6 3,6 15 8,9 26 15,5 81 48,2 37 22,0 3,77 1,01 It is a significant reason for me to fulfill the requirements of my 6 3,6 5 3,0 9 5,4 95 56,5 48 28,6 4,06 0,89 job I am personally quite committed 6 3,6 8 4,8 12 7,1 98 58,3 42 25,0 3,97 0,92 to my job. When there are things to do, I leave home earlier to go to 7 4,2 15 8,9 9 5,4 88 52,4 42 25,0 3,88 1,03 work. I can overwork to finish things even if I don’t have the 8 4,8 16 9,5 21 12,5 85 50,6 34 20,2 3,73 1,05 necessary time. I am sometimes preoccupied 10 6,0 15 8,9 14 8,3 92 54,8 33 19,6 3,75 1,07 with the following day’s work. I feel uneasy/uncomfortable 11 6,5 4 2,4 7 4,2 99 58,9 44 26,2 3,97 1,00 when things go bad at work. I have other concerns more 7 4,2 39 23,2 21 12,5 67 39,9 30 17,9 3,45 1,16 important than my job.

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According to the data illustrated in Table III, to the statement that I like to spend most of my time at work, 12,5% of the subjects have responded as ‘I strongly disagree’, 28,6% as ‘I disagree’, 7,1% as ‘I’m not sure’, 46,4% as ‘I agree’ and 5,4% as ‘I strongly agree’. The arithmetical mean of the responses to this statement is 3,03. This concludes that the majority of the employees (51,8) have expressed a positive attitude, stating that they like spending most of their time at work.

To the statement that “Most of my personal goals are related with my job.”, 56,5% of the subjects have responded negatively, opting for ‘I strongly disagree’ and ‘I disagree’, while 28,6% of them have responded positively opting for ‘I strongly agree’ and ‘I agree’. 14,9% of the subjects have responded as ‘I’m not sure’ (X=2,66). To the statement that “I get the most satisfaction in life from my job”, the majority of the subjects have responded negatively, which indicates that it is not their job they get the most satisfaction from.

54% of the subjects have responded positively to the statement that “Every morning I go to work enthusiastically”, which concludes that the employees like going to work. However, to the statement that “I would go on working even if I did not need to earn money” only 29,2% of the subjects have responded positively and they stated , this way, they would probably prefer not to work provided they had a high level of income.

According to the data illustrated in Table III, 55,4% of the subjects have responded negatively to the statement about one’s job being as important as satisfying one’s fundamental needs (such as eating, drinking etc.), 54,8% of the subjects have responded negatively to the statement that most of my interests are related with my job, 55,3% to the statement that they sometimes feel like punishing themselves for mistakes they make about their job. On the other hand, most of the subjects (70%) stated that they do their best to fulfill the requirements of their job, 85,1% have stated that it is important to fulfill the requirements of one’s job, 70% have stated that they leave home earlier if they have things to do at work, 70,8% have stated that they can overwork and 75,4% have stated that they are sometimes preoccupied with the following day’s work.

Most of the subjects (70,8%) have expressed that they would not avoid undertaking extra duties and responsibilities related with their job; 76,1% have expressed that they feel responsible for the tasks and duties they undertake at work; and 75,1% have expressed that it de-motivates them when things go bad or wrong at work. In addition, most of the employees (83,3%) have stated that they are personally committed to their job.

Table 4. The Correlation Analysis for The Relation between Organizational Commitment and Job Involvement

Variables Job Involvement

r = 0,444 Organizational R2= 0,20 Commitment p= 0,000* *p<0,001

According to the data in Table IV, there is a significant correlation between organizational commitment and job involvement (p<0,01). A moderate positive correlation has been identified between variables (r=0,44). This indicates that there is a significant, though not very strong, level of correlation between job involvement and organizational commitment. This finding has verified the hypothesis of the study, which is H1: “There is a relation between the organizational commitment and job involvement levels of the employees working for the Central Organization of the Ministry of Health” (r=0,44). The fact that determination coefficient is R 2= 0,20 indicate that 20 % of the change in organizational commitment can be

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explained by job involvement or 20 % of the change in job involvement can be explained by organizational commitment.

Table 5. A Comparison of the Organizational Commitment and Job Involvement Levels of the Subjects (T- Test Results)

Variables N Χ s.s. t p Organizational Commitment 168 3,08 0,51 2,17 0,031* Job Involvement 168 3,17 0,45 *p<0,05

According to the data in Table V, there has been found a significant difference between the organizational commitment and job involvement levels at a 0,005 significance level (p<0,05). This comes down to the fact that the job involvement level of the employees working for the Central Organization of the Ministry of Health is higher than that of the organizational commitment.

Table 6. The Contrastive Analysis of The Subjects’ Level of Organizational Commitment and Job Involvement According to Sex, Employment Status of The Spouse and Marital Status (Independent T-test Results)

Organizational Commitment Job Involvement Variables N Χ s.s. t p N Χ s.s. t p Male 89 3,12 0,51 89 3,23 0,44 Sex 1,14 0,254 2,48 0,014* Female 79 3,03 0,49 79 3,06 0,42 Married 124 3,06 0,50 124 3,17 0,41 Marital Status 0,96 0,335 1,12 0,261 Single 44 3,15 0,51 44 3,09 0,52 Employment Employed 89 3,03 0,51 89 3,14 0,41 Status of the 1,17 0,244 1,58 0,117 Unemployed Spouse 35 3,14 0,46 35 3,27 0,39 *p<0,05

According to Table VI, the job involvement levels of the employees working in the Central Organization of the Ministry of Health varies significantly according to gender (t=2,48; p<0,05). Given the means in Table VI, we can conclude that the job involvement levels of male employees ( Χ =3,23) are higher than those of female employees ( Χ =3,06). However, the organizational commitment level does not significantly vary according to gender (p>0,05). In addition to this, organizational commitment and job involvement levels of the subjects do not significantly vary according to the marital status and the employment status of the spouses (p>0,05).

According to the data in Table VII, the organizational commitment and job involvement levels of the employees working in the Central Organization of the Ministry of Health do not significantly vary according to age, number of children, educational status, the length of time being employed in a governmental institution, the length of time being employed in the Ministry of Health, position and the place where they spent their childhood (p>0,05). The organizational commitment and job involvement levels of the sub-groups concerning the set variables are close to each other.

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Table 7. The Comparison of The Opinions of The Employers Working in The Central Organization of The Ministry of Health on The Statements According to Demographic and Some Other Features (Variance Analysis Results)

Organizational Commitment Job Involvement Variables N Χ s.s. F p N Χ s.s. F p 30 and less 25 3,28 0,57 25 3,05 0,60 31-35 33 2,95 0,51 33 3,12 0,44 Age 2,46 0,065 1,48 0,220 36-45 81 3,04 0,49 81 3,14 0,41 46 and above 29 3,16 0,41 29 3,29 0,32 High School 40 3,21 0,52 40 3,18 0,41 Educational Two year degree 40 2,95 0,46 40 3,10 0,50 2,29 0,080 0,27 0,844 Status University 59 3,13 0,46 59 3,15 0,45 Post-graduate 29 2,99 0,56 29 3,17 0,37 No 5 3,32 0,36 5 3,49 0,41 Number of One 33 2,95 0,50 33 3,03 0,43 2,53 0,060 2,76 0,045 Children Two 66 3,08 0,47 66 3,21 0,38 Three and more 15 3,32 0,42 15 3,24 0,35 The Length of 0-5 years 19 3,20 0,60 19 3,10 0,59 time of 6-11 years 26 2,95 0,54 26 3,04 0,48 employment in 12- 17 years 38 3,13 0,50 0,95 0,432 38 3,09 0,38 1,33 0,259 a public 18-23 years 60 3,04 0,48 60 3,20 0,41 institution 24 years and more 25 3,15 0,41 25 3,28 0,39 The Length of 0-5 years 46 3,10 0,58 46 3,11 0,47 time of 6-11 years 42 3,01 0,52 42 3,12 0,41 employment in 12- 17 years 25 3,19 0,47 0,47 0,756 25 3,17 0,48 0,42 0,787 the Ministry 18-23 years 40 3,08 0,44 40 3,22 0,41 of Health 24 years and more 11 3,07 0,34 11 3,12 0,36 Senior/Top echelon 12 3,03 0,58 12 3,25 0,36 Middle-echelon official 13 3,08 0,39 13 3,20 0,29 Position 0,11 0,953 0,30 0,819 Lower-echelon official 24 3,05 0,46 24 3,15 0,37 Other Personnel 119 3,09 0,51 119 3,13 0,47 Where he/she Province 92 3,03 0,51 92 3,10 0,43 spent County 48 3,14 0,50 1,25 0,289 48 3,15 0,47 2,81 0,063 childhood Village 28 3,17 0,47 28 3,32 0,36 *p<0,05

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Meyer, J.P., Paunonen, S.V., Gellaty, I.R., Goffin, R.D., & Jackson, D.N. (1989). Organizational commitment and job performance: it’s the nature of the commitment that counts. Journal of Applied Psychology, 74: 152-156. Meyer, J.P., Stanley, D.J., Herscovitch, L., & Topolnytsky, L. (2002). Affective, continuance, and normative commitment to the organization:A meta-analysis of antecedents, correlates, and consequences. Journal of Vocational Behavior, 61: 20 –52. Morrow, P. (1983). Concept redundancy in organizational research: the case of work commitment. Academy of Management Review , 8(3): 486–500. Mowday, R.T., Porter, L.W., & Steers, R.M. (1982). Employee-organization linkages: The psychology of commitment, absenteeism and turnover . San Diego,CA: Academic Press. Mowday, R.T., Steers, R.M.,& Porter, L.W. (1979). The measurement of organizational commitment. Journal of Vocational Behavior, 14: 224 –247. Nijhof, W.J., De Jong, M.J., & Beukhof, G. (1998). Employee commitment in changing organizations: an exploration. Journal of European Industrial Training, 22, 243-248. Örs, M., Acuner, A.M., Sarp, N., & Önder, Ö. R. (2003). Antalya Tıp Fakültesi Hastanesi’nde, Antalya Sosyal Sigortalar Kurumu Hastanesi’nde ve Antalya Devlet Hastanesi’nde çalı şan hekimler ile hem şirelerin örgütlerine ba ğlılıklarına ili şkin görü şlerinin de ğerlendirilmesi. Ankara Üniversitesi Tıp Fakültesi Mecmuası, 56(4): 217-224. Özsoy, S. A., Ergül, Ş. & Bayık, A. (2004). Bir yüksekokul çalı şanlarının kuruma ba ğlılık durumlarının incelenmesi. İş , Güç Endüstri İli şkileri ve İnsan Kaynakları Dergisi, 6(2): 56 - 75. Pierce, J.L., & Dunham, R.B. (1987). Organizational commitment: Pre-employment propensity and initial work experiences. Journal of Management, 12 (Spring): 163-178. Ramsey, R., Lassk, F.G., & Marshall, G.W. (1995). A critical evaluation of a measure of job involvement: The use of the Lodahl and Kejner (1965) scale with salespeople. Journal of Personal Selling & Sales Management , 15 (3): 65-74. Sager, J.K. (1991). Recruiting and retaining committed salespeople. Industrial Marketing Management, 20: 99- 103. Sager, J.K. and Johnston, M.W. (1989). Antecedents and outcomes of organizational commitment: A study of salespeople. Journal of Personal Selling and Sales Management, 9 (Spring) : 30-41. Shore, L. M., & Martin, H. J. (1989). Job satisfaction and organizational commitment in relation to work performance and turnover intentions. Human Relations, 42(7): 625-638. Siders, M.A., George, G., & Dharwadkar, R. (2001). The Relationship of internal and external commitment foci to objective job performance measures, Academy of Management Journal, 44(3): 570-579. Sjöberg, A., & Sverke, M. (2000). The interactive effect of job involvement and organizational commitment on job turnover revisited: A note on the mediating role of turnover intention. Scandinavian Journal of Psychology , 41: 247-252. Sommer, S.M., Bae, S.H., & Luthans, F. (1996). Organizational commitment across cultures: the impact of antecedents on Korean employees. Human Relations, 49(7): 977-989. Sökmen, A. (2000). Ankarada’ki be ş yıldızlı konaklama i şletmelerinde örgütsel ba ğlılık ile i şgören performansı arasındaki ili şkinin belirlenmesine yönelik ampirik bir ara ştırma. Yayımlanmamı ş Yüksek Lisans Tezi. Gazi Üniversitesi, Sosyal Bilimler Enstitüsü. Uygur, A. (2004). Örgütsel ba ğlılık ve i şgören performansı. Türkiye Vakıflar Bankası Ankara, İstanbul ve İzmir ili şubelerine yönelik alan ara ştırması. Yayımlanmamı ş Doktora Tezi. Hacettepe Üniversitesi, Sosyal Bilimler Enstitüsü. Zeffane, R. (1994). Patterns of organizational commitment and perceived management style: A comparison of public and private sector employees. Human Relations. 47 (8): 977-1007.

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Fluid Inclusion Studies in the Different Origin Quartzs Associated with Cu-Pb-Zn Mineralizations at Kizildag and Köprücük-Harput, East Anatolian District, Turkey

Leyla Kalender, Ahmet Sa ğiro ğlu and Sumru Ki şman University of Firat, Department of Geology, 23119 Elazig, Turkey E-mail: [email protected]

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Abstract: The Kızılda ğ Cu-Pb-Zn mineralizations are located in the north of Harput (Elazı ğ) in Eastern Turkey. This study includes fluid inclusion studies in quartzs of quartz veinlets and of biotite porphyries from Elazı ğ magmatits (80-82 Ma) associated with the mineralizations. The different salinity and homogenization temperature values were determined in the primary and the secondary fluid inclusions in quartzs. The data obtained here indicate that four major types of fluids were involved during the formation of the mineralizations. They are type I liquid-rich, type II vapor-rich, type III halite-bearing inclusions within the H 2O–NaCl–KCl–CaCl 2 system and type IV liquid-vapor-halite-daughter minerals-rich. The high salinity fluids represented by type III inclusions, being unusual to the distal part of an intrusion-centered ore-forming system such as Kızılda ğ and Köprücük, have been interpreted as the product of direct exsolution of a crystallizing magma, rather than a result of fluid immiscibility from a low salinity fluid. Trapping conditions for type I inclusions were estimated to be around 320 °C, while type III- type IV inclusions were constrained to be > 500 °C. The formation temperatures for type II inclusions range from 440 to 677 °C. Fluid inclusion study are higher than natural conditions, as result of the potential fluid mixing and tectonism are supposed to have played an important role in triggering the precipitation of ore minerals from the hydrothermal solution and geotectonic environments are taken into account.

Keywords: alteration, Cu, Pb, Zn mineralization, fluid inclusion, Kızılda ğ-Köprücük, Turkey ______

INTRODUCTION Fluid inclusion study has proven to be an important tool for constraining the physico-chemical conditions of hydrothermal mineralization and arounded alteration processes. At Kızılda ğ–Harput, numerous crosscutting quartz veins and micro-veins that formed during various stages of alteration and mineralization provide suitable material for an analysis of fluid inclusions. These veins bear a striking similarity to the Keban Pb-Zn ores in terms of mineral paragenesis, age of the ore, and in particular the nature of Ag- bearing phases (Kine ş, 1971; Kumbasar, 1974). Sa ğıro ğlu (1986; 1987) reported that mineralization and wallrock alteration is abundant because of the deep nature of fault zones within the area of Kızıldag mineralization; therefore, it is possible that a porphyry deposit underlies the mineralization. The Kizildag Cu-Pb-Zn veins are uneconomic because of the small volume of reserves.

The present fluid inclusion study is the second to recognize Kızıldag mineralisation in eastern Turkey. The first such study involved an analysis of fluid inclusions in chalcopyrite-related quartz within Keban Cu-Pb- Zn mineralization in the East Anatolian district (Kalender and Hanelçi, 2000).

Fluid inclusion studies have shown many common features on fluid inclusion characteristics (Roedder, 1962; Roedder, 1963; Swanenberg, 1980; Bodnar and Sterner, 1987; Bodnar, 1992; Bodnar, 1993; Bodnar and Vityk, 1994; Bakker and Thiéry, 1994; Bakker et al.1996; Bakker, 1997; Bakker, 1998; Bakker, 1999). The flow of fluids may be focused through preferrentially orientated fractures, faults, or shear zones within rock, where they may be preserved in vein-forming minerals. Our approach is to determining the genetic

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evolution of forming mineralization hydrothermal solutions by fluid inclusion data for quartz from granitic rocks and quartz veins.

Geologic Setting Turkey takes place in the Alpinde Orogenic belts, are thought to constitute a normal facet of calc-alkaline magmatisim. Calc-alkaline volcanic and plutonic rocks which represent magmatic arc products built up partly on continental crust, partly on oceanic crust (Baskil-Elazig arc) and occur by partial melting of oceanic crustal rocks on underlying subduction zones at the elongate compressive junctures between litospheric plates. The Elazı ğ Magmatics outcropping largely in the Elazig region contain plutonic rocks composed of diorites, monzodiorites, quartzdiorites, and tonalites, volcanic rocks that are composed of basaltic pillow-lavas, andesitic lavas, and andesitic pyroclastics. Granitic and dasitic rocks cut all of these units. The geohemical data indicate that the Elazı ğ Magmatitcs belong generally to calc-alkaline series and they are product of an island-arc formed on the supra-subduction ophiolite (Kömürhan ophiolite) during late Cretaceous by a northward dipping subduction of the southern brance of Neotethys which began spreading in late Triassic. The Elazı ğ Magmatic rocks cover large areas in the Elazig region. The granitic rocks are cut by older dioritic rocks of the complex, and are of Coniacian-Campanian age (80-82 Ma) (Perinçek, 1979; 1980; Bingöl, 1984; 1988; Yazgan, 1983; Yazgan, 1984; Sa ğıro ğlu, 1986; K/Ar age by Yazgan and Chessex, 1991, Bingöl and Beyarslan, 1996). The Elazig Magmatic rocks are overlied as inconformibility by the Kirkgecit Formation (Middle Eocene-Upper Oligocene) and the Karabakir Formation (Miocene-Lower Pliocene) in the study area. The Kızılda ğ mineralizations occur within the tonalites and granites of the Elazig Magmatic rocks and related to the faultings what generally E-W and dip to North (Fig. 1).

The Kızılda ğ-Köprücük Cu-Pb-Zn mineralizations are located in the eastern Anatolian district. Its geographic position is embedded in the Elazig Magmatic Rocks of a Late Cretaceous volcanic arc that was intrudded by the Elazı ğ Magmatits. The Kızılda ğ porphyr has been derived as late-stage quartz rich differentiates of a more asidic granitic magma from Elazı ğ Magmatits and have migrated upward along and close to the contacts of larger, earlier acidic intrusions.

Thereby, Turkey seem to be likely are as for porphyries associated with mineralizations discovery, a detail analysis of Alpine-Mediterranian orogen in terms of the new global tectonics would provide a cogent tool in the search for different type deposits.

Hydrothermal alteration and mineralization The mineralizations are either disseminated or as fillings of the fault zones and the type of mineralizations are specularite, pyrite, chalcopyrite, galena, and sphalerite and fahlerz or tetrahedrite group minerals. The secondary minerals are: smithsonite, limonite, cerussite-anglesite and covellite-chalcosite. Galena almost always bears minute inclusions (15-20µm) of sulphosalts. Arsenopyrite grains (20-50µm or higher grain sized) are also enclosed by galena. Galena is altered to cerusite-anglesite along the grain boundaries and the cleavage planes. Sphalerite is not as common as galena and often bears dense chalcopyrite inclusions. Its grain size is medium (1-2 mm) and the grains are subhedral. Sphalerite is altered to smithsonite along the grain boundaries. The tetrahedrites are appropriate to call Kızılda ğ tetrahedrites "Freibergites". Specularite mineralizations are observed in the oxidation zones along the fault zones. Straight deep is passed to the specularite-pyrite and pyrite-chalcopyrite mineralizations that magnetite change in to pyrite at the location, in which is important sericitic alteration. The Kızılda ğ Cu-Pb-Zn mineralizations show microscopic textures, which is cataclastic texture. Cataclastic texture predominated during main deformational stages during early stages. This texture is common in polycrystalline, and coarser-grained pyrite and chalcopyrite. Little or no cataclastic texture is observed in single, fine-grained chalcopyrite and coarse-grained tetrahedrite and tennandite crystals (Fig. 2). Cataclastic deformation texture is likely to have formed at about 400 0C to 500 0C and at 1 kb to 3 kb pressures (Cox et al. 1981; McClay and Ellis 1983). Alterations have been observed as kaolinization, silicification and carbonization in the wallrocks. However, sericite and quartz are the most abundant alteration minerals. Two district types of the hydrothermal alteration and mineralizations were recognized at Kizildag and Köprücük. One of them is the hypogene alteration, which is developed as phyllic alteration which is restricted to enrichment caolene argilic type

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alteration. Moreover, biotite porphyries have insituted within pyrite and chalcopyrite mineralization, and altereted as chloritizations at Kızılda ğ.. The other is the supergene alteration zones are recognized at Kizildag and Köprücük, and oxidized and leached zone, which is characterized specularites at specially Kızılda ğ. Oxidized minerals derived from the various sulfide minerals found in disseminated Kızılda ğ and Köprücük mineralizations.

Figure 1. Geology map of the study area (reproduced from Şaşmaz and Sa ğıro ğlu 1999)

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Figure 2. Cataclastic texture in the chalcopyrite bearing quartz veins. Th: Tetrahedrite; Tn: Tennandite, Cpy: Chalcopyrite.

ANALYTICAL METHODS Fluid inclusion studies were carried out using Linkham THMS 600 heating–freezing stage and HFS 92 system attached to Nikon lobophotpol microscope at Research Institute for Technical Physics and Materials Science. Calibration against standards of known melting points was indicated at the accuracy of beter than ± 0.5 0C for freezing point depression. The system has a temperature range between -180 0C and +700 0C. Doubly polished sections, approximately 200 µm thick, were prepared for microthermometric determination. Reproducibility of the homogenization temperature is within 3 °C and of the temperature of final ice melting within 0.4 °C. A total of 36 samples, representative of all mineralization types encountered at Kızılda ğ, were used for reconnaissance survey of fluid inclusions. However, suitable fluid inclusions were only found in 10 samples. Of these, 3 samples are biotite-quartz porphyries, 3 samples are halite bearring quartz veins, 2 samples are pyrite-bearing quartz veins, and 2 samples is chalcopyrit-bearing granitic rock. Thermometric analyses were performed principally on fluid inclusions which were relatively large (>5 µm) and preferably polygonal and bi-poligonal-shaped. The freezing and heating were employed to determine the approximate salinity (wt%NaCl equivalent) and homogenization temperature (T H), respectively. Freezing was carried out mainly for non-halite bearing liquid-rich inclusions, and the temperature of the first melting values were corelated with eutectic point of NaCl-H2O sytem and found composition of salt in the fluid inclusions (eutectic point for NaCl-H2O, NaCl-KCl-H2O and NaCl-KCl- CaCl 2-H2O system), (Shepherd et al., 1985). In the primary multi phases fluid inclusions were measured solid saline crystal melting point before lose of the bubble. Thus salinity of the hydrothermal fluid was estimated from the temperature (Roedder, 1972; Bodnar, 1993; 1996).

Fluid inclusion Fluid inclusions suitable for microthermometric study were mainly found in quartz. Quartz grains hosting

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fluid inclusions are either clear phenocrysts in quartz porphyries or subhedral crystals interstitial to other metallic minerals in veins, such as chalcopyrite, pyrite and sphalerite. The primary, secondary and psuedosecondary criteria suggested by Roedder (1984) were used as a standard for distinguishing the origin of inclusions but microthermometric measurements were mainly carried out on inclusions with a primary or most likely primary origin and some secondary origin. In terms of the number and the volumetric proportions of phases present in the fluid inclusion at room temperature, four major types of inclusions can be recognized at Kızılda ğ and Köprücük. They are designated as liquid-rich (type I), vapor-rich (type II), halite-bearing multiphase (type III) and liquid-vapor-halite-daughter minerals-rich (type IV) inclusions. A detailed discussion of each type of inclusion is presented below.

Type I

Type I inclusions are dominated by low than 30 vol % (typically around 20%) of H 2O-CO 2 at room temperature and were locally observed in the examined samples (Fig. 3a). Fluid inclusions of this type usually occur as isolated individuals with rare occasions which can be attributed to specific growth zones in vein crystals, and hence bear an unambiguous primary origin. Fluid inclusions within this group are generally between 4 and 50 µm in size and show ellipsoidal to rounded morphologies. Type I inclusions are found in the quartz grains in mineralization and in quartz from biotite porphyries (H8; H34; H35), halite- bearing quartz veins (H13; H7; H5), pyrite-bearing quartz veins (H32; H50) and chalcopyrite-bearing quartz veins (H51; H52). Salinities determined by last ice melting temperatures (Bodnar, 1993) were 30.95 to 42.51 weight percent NaCl equivalent (size of inclusions between 2.5 and 45µm) for inclusions trapped in whole quartz samples. Homogenization temperature values change with between 357 and 653°C. Homogenization temperature exists for different types of fluid inclusion-containing materials at Kızılda ğ- Köprücük, which, combined with the salinities, may indicate repeated episodes of hydrothermal activities with similar physicochemical properties throughout the veining and mineralization history.

Type II Type II inclusions, characterized by much more gas bubble within an aqueous liquid are commonly found in all selected samples (Fig. 3b). Type II inclusions are dominated by more than 60 vol % H 2O-CO 2 at room temperature. This is the rearly inclusion type and accounts for 15% of all fluid inclusions observed during this study. In most cases, such inclusions are relatively small in size (5–10 µm) with ellipsoidal and regular shapes. At room temperature, a variable vapor to liquid ratio can be seen for this type of inclusions with a majority ranging from 60% to 90%. The distribution of these inclusions in the host quartz varies from random isolations, clusters and trials along microfractures, giving rise to a complex origin embracing primary, pseudosecondary and secondary according to the criteria suggested by Roedder (1984). 26 heating–freezing measurements were carried out. Fluid inclusions of this type freeze to ice up to cooling aproximately − 70 °C. Final ice melting occurred at temperatures above − 28 °C, indicating a consistently high salinity (from 29.56 to 44.34 wt% NaCl equiv.). Upon heating, all type II inclusions measured showed homogenization via the expansion of vapor phase. Homogenization temperature values are between 236 and 376 0C in samples. Salinity values change with between 33.17 and 35.22 % NaCl equiv.

Type III Fluid inclusions of this type consist, at room temperature, of aqueous liquid, a vapor bubble and a halite crystal, and in some circumstances, additional solid phases such as sylvite (Fig. 3c). Inclusions with halite occur in quartz grains in mineralized veins. Inclusions of this type exhibit ellipsoidal to irregular shapes and are 5 to 25 µm in diameter. In most cases, such inclusions are relatively ellipsoidal and irregular shapes. Most of such inclusions probably bear a primary origin as demonstrated by their isolated distribution pattern though some inclusions do occur as planar trails crosscutting grain boundaries and hence show an apparent secondary nature. Halite exhibits a light grey color in all of these inclusions and has been identified based on its cubic crystal shape and absence of birefringence in sample H13. During warming, first ice melting temperature (e.g. eutectic point) was observed for a few inclusions between − 10 and − 22 °C, indicating an H 2O–NaCl–KCl–CaCl 2 system for the fluids trapped Shepherd (1993). Commonly, H 2O–NaCl system was observed much more fluid inclusion. As mentioned above, fluid inclusions of this type usually contain a NaCl crystal (halite). Salinites

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determined from dissolution temperature of halite (range of from 153 to 374 °C) in some samples and estimated wt% NaCl equivalent range of (from 29.56 to 44.34) for quartz phenocrysts.

a c Halite H2O Type I CO 2 Taype II

CO 2 H2O 0 0.1 mm

CO d b 2 Halite Type II sylvite

H2O

CO 2 H2O Cpry? 0 0.1 mm 0 0.1 mm

Figure 3. a: photomicrographs of inclusions from aqueous liquid-rich inclusion without daughter minerals (type I); b: inclusions from low-density vapor-rich inclusion (type II); c: inclusions of the halit bearing guartz veins (type III); d: halite and daughter mineral bearing inclusion (chalcopyrite?) (type IV).

Type IV The inclusion, which is contain well-formed cubic halite and generally other daughter minerals in Figure 3d. Overall, fluid inclusions with two or more solid phases are commonly found in the quartz phenocrysts from pyrite-bearing, quartz veins and chalcopyrite-bearing biotite porphyries. They are interpreted to be true daughters rather than accidental crystals trapped during the formation of fluid inclusions according to their consistent phase ratios (ca. 20 vol %) when present. Inclusions of this type exhibit ellipsoidal are 2.5 to 37.5 µm in diameter. Opaque minerals are characteristically observed in igneous quartz of the porphyries and many quartz sulfide veins. A second isotropic daughter mineral, sylvite, comonly is present; it has rounded edges, lower relief, and a higher thermal coefficient of solubility than halite. A number of birefringent daughter minerals occur in these inclusions. Some of the opaque phases have been identified with certainty mineralogical study, e.g. chalcopyrite, pyrite, sphalerite, tetrahedrite-tennandite in quartz (Fig. 2).

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Upon heating, vapor disappearance normally occurs at a temperature of 6 °C to 267 °C, prior to complete homogenization which was exclusively achieved via the dissolution of salt crystals at range from 180 to 374 °C. Opaque phases, assumed to be chalcopyrite, remain undissolved until 700 °C in this study. A total of 41 measurements on type IV inclusions of primary or most likely primary origin show a wide range of homogenization temperatures of 389 to 677 °C for quartz phenocrysts in quartz porphyries samples and quartz veins. Salinity values are change from 40.35 to 44.7 wt % NaCl equivalent for type VI inclusions. The formation temperatures for type VI inclusions were determined at 389–>600 °C. The secondary fluid inclusions were commonly trapped in quartz from late halite quartz veinlets. These fluid inclusions are characteristic necking down of long tabular inclusions (199-214 0C and salinity values are between 5 and 15 equiv. wt % NaCl).

DISCUSSION Petrographical studies indicate that four different type quartz veins were observed in the study area, which were biotite-quartz granite porphyries, halite quartz veins, pyrite-bearing quartz veins, chalcopyrit-bearing quartz including biotite porphyries. The pyrite late quartz veins occured spatially in phyllitic and argilic type alteration zones and chloritizations at Kizilda ğ. However, the Kızılda ğ biotite-granite porphyries have insituted within pyrite and chalcopyrite mineralization at dept. Specularite mineralizations in the fault zones; according to Davies and Lutha (1978), the presence of hematite in the pink albite-quartz zone probably indicates a higher fO 2 than that present in the surrounding quartz-albite-sericite-carbonate assemblage where hematite is absent. The mineralizing hydrotermal solutions were probably low sulfur content with the result that pyrit is almost totally absent from the central parts of the mineral bodies.

Caolinization, silicification, carbonization are clearly observed in the wallrocks. Besides, sericite and quartz are comonly alteration minerals at Kızılda ğ. Two district types of the hydrothermal alteration and mineralizations were determined at Kızıldag and Köprücük. One of them is the hypogene alteration, which is developed as phyllitic which is restricted to enrichment caolene argilic type alteration especiallity at Kızılda ğ. Nash and Cunningham (1974) indicated that sericitic alteration mineral assemblages include sericite, quartz, sulfides, variable amounts of kaolinite. According to these reporters, plagioclase is the mineral most susceptible to sericitic alteration; biotite in the lamporphyritic porphry has been affected to lesser extent. Heberlein and Godwin (1984), indicated that botite-anhydrite alteration near the stocks implies high temperatures (> 400 0C), but chloritization of biotite and gradiation in to a fringing zone of propylitic alteration suggests dilute fluids and lower temperature (160 to 400 0C). Fluid inclusions investigated in this study indicate that a relatively wide variation in temperature and fluid composition in the binary system of H 2O–NaCl had occurred during the formation of the Kızılda ğ and Köprücük mineralizations. Figure 4 shows distribution of salinity and homogenization temperature values of all fluid inclusion samples. Primary inclusions have salinities of 30 to 44 wt % NaCl equivalent and vapor to liquid homogenization at temperatures from 250 °C to 677 °C (Fig. 4a; 4b). Some of the fluid inclusions data, which are halite-bearing inclusions, are plotted in Fig. 5, according to homogenization temperatures and salinity values. There are many halite-bearing fluid inclusions whose data points lie below the halite saturation curve (Fig. 5). Therefore, these inclusions may be trapped an undersaturated (with respect to NaCl) homogeneous fluid at very high pressure and temperatures, as suggested by Roedder (1984). By accepting this premise, the inclusions began trapping mixed fluid and halite crystals when the ambient temperature was interval 240-388 °C. At temperatures >350 °C, apparently no halite-bearing inclusions trapped free suspended halite crystals, because the fluid was undersaturated with respect to NaCl at the prevailing pressure. Thereby, field studies at Kızılda ğ and Köprücük indicate that the maximum thickness of the overlying rocks for the orebodies is approximately 500 m, giving rise to a lithostatic pressure estimate of 125 bars, known "geobare Tiefenstufe" of 1 atmosphere per 4 meter, which apparently differed greatly from the pressure of the fluid. Such a difference in lithostatic pressure estimated from the thickness of overlying rocks and fluid pressure determined from fluid inclusion study implies that the mineralizing system at Kızılda ğ and Köprücük was overpressured, which is supported by the development of implosive brecciation along mineralization zones of quartz and granitic porphyries (Zhang et al., 1997). On the other hand, previous studies have indicated that the salinities of aqueous fluids exsolved from crystallizing magmas are a function of system pressure and crystallization degree and the increase or decrease of the salinities of the exsolved fluids mainly rests with the pressure or depth at which magmas crystallize

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(Candela, 1991, Cline and Bodnar, 1991 and Webster, 1992). Calagary (2004) had interpreted that the high salinity values measured in inclusions having do not reflect the actual salinty of the fluid at the time of entrapment and the variation of salinity values in the solid phase might depend mainly on the size of the trapped suspended halite crystals. According to Bouzary and Clark (2006), salinity was related to deph and pressure. It is therefore deduced that the halite-bearing could be caused by halite meta-satbility, and the final fluids exsolved from such a silicate melt are characterized by very high salinity, which attests to the interpretation that halite-bearing and doughter minerals included inclusions were trapped from the late exsolved magmatic fluids rather than formed by fluid immiscibility.

Figure 4. Histograms of salinity (a) and homogenization temperature data (b).

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According to Kalender and Ki şman (2008), two physico-chemically distinct fluids circulated at different times in granitic rocks as the hydrothermal system evolved: an early hypersaline and hot brine and later more dilute fluids. Initial ore mineralizations, granitic rocks and quartz formations were produced by early hypersaline hydrothermal solutions and meteoric water diluted hydrothermal solutions formed kaolinitic wallrock alteration and secondary inclusions. High salinity values have been depended on porphyry type mineralizations but in this study has been proved that inclusions have been trapped an undersaturated by the potential fluid mixing in high temperature. Our study indicates that tectonic and hydrothermal proceses at Kızılda ğ-Köprücük mineralizations are intimately linked and that they directly influence fluid-flow paths.

Figure 5. The distribution pattern of the data relative to the NaCl saturation and critical curves (NaCl saturation and critical curves from Ahmed and Rose (1980)); dashed lines reffering to vapour pressures of NaCl solutions at the indicated temperatures and salinity from Roedder (1984)).

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RESULTS A broad range of fluid compositions and physical conditions are recorded in inclusions at Kızılda ğ and Köprücük. Physical conditions, such as temperature is effectively determined from fluid inclusions. The character of the ore and alteration of wallrocks is highly variable. Fluid inclusion types and abundances also are highly variable and are an aid to undestanding the physical-chemical environment of ore emplacement and distribution in wallrocks. However, chemical characteristic was determined from fluid inclusions. The fluid inclusion data presented that a multi-staged fluid entrapment with variable composition in the H 2O–NaCl system occurred during the formation of the Kızılda ğ and Köprücük minaralizations. Petrographic examination indicates that type II vapor-rich inclusions are the earliest inclusions trapped mainly in the first stage without significant sulfide minerals associated under microscopic scale. Whereas type III and type IV halite and doughter mineral bearing inclusions tend to be trapped within the second stage of fine-grained quartz accompanied by certain ore mineral precipitation within biotite porphyries. Type II liquid-rich inclusions were observed in early and late stages of quartzs. The early fluids exsolved from such silicate melts will have a very low salinity due to the low pressure conditions, being represented by type II inclusions in this study. Such a dilute hot fluid is mainly responsible for the development of early halite and possibly some chalcopyrite-bearing quartz veins. With continued crystallization saline fluids were then exsolved from the crystallizing magmas. Sealing of the fractures by precipitation of minerals may have been led to increase in pressure and the system became overpressured. Secondary inclusion forming fluids, together with part of the saline fluids, may have been responsible for the deposition of ore minerals at Kızılda ğ and Köprücük. As deduced from fluid inclusion data plus decreases in salinity and temperature as result of the potential fluid mixing are supposed to have played an important role in triggering the precipitation of ore minerals from the hydrothermal solution. It is concluded that early to intermediate fluids responsible for all the halite, pyrite and chalcopyrite-bearing veins are magmatic in origin. However, late fluids related to galena, sphalerite veins may be a mixed product of magmatic and meteoric waters wihin a shallow depth and the lastest fluids related to specularite formations within oxidation zones.

ACKNOWLEDGEMENTS We would like to thanks Firat University (Science Research and Projects Unit) for providing financial support (Project Number: 1160).

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