HEMIĈARA, TEHNOLOGA I EKOLOGA · BOSNA I HERCEGOVINA DECEMBAR, 2016. Glasnik hem. teh. i ek. RS GHTERS 12 1-45 . Glasnik hemiĉara, tehnologa i ekologa Republike Srpske Gazette of

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G L A S N I K HEMIĈARA, TEHNOLOGA I EKOLOGA

REPUBLIKE SRPSKE

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BANJALUKA

BOSNA I HERCEGOVINA

DECEMBAR, 2016.

Glasnik hem. teh. i ek. RS GHTERS 12 1-45

UDK: 54+66+502/504 ISSN 2232-755X

G L A S N I K HEMIĈARA, TEHNOLOGA I EKOLOGA

REPUBLIKE SRPSKE

12

BANJALUKA

BOSNA I HERCEGOVINA

DECEMBAR, 2016.

Glasnik hem. teh. i ek. RS GHTERS 12 1-45

Glasnik hemiĉara, tehnologa i ekologa Republike Srpske Gazette of Chemists, Technologists and Environmentalists of

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SADRŢAJ TABLE OF CONTENTS

I. Milanović , A. Rašković, S. Vukmirović, N. Stilinović, M. Mikov

THE INFLUENCE OF ROSEMARY ESSENTIAL OIL APPLIED PER OS ON THE PHARMACODYNAMIC AND PHARMACOKINETIC PROPERTIES OF PARACETAMOL

UTICAJ ETARSKOG ULJA RUZMARINA PRIMENJENOG per os NA FARMAKODINAMSKA I FARMAKINETSKA SVOJSTVA PARACETAMOLA

1

D. Drljaĉa, B. Dalmacija, Lj. Vukić, S. Zorić

BIOLOŠKO UKLANJANJE AMONIJUM JONA IZ VODE ZA PIĆE

BIOLOGICAL REMOVAL OF AMMONIUM IONS FROM DRINKING WATER 9

T. Botić, D. Drljaĉa, A. Šinik

ANALIZA UTICAJA SASTAVA SIROVINE NA ENERGETSKU VRIJEDNOST DRVNOG PELETA NA PROSTORU BOSNE I HERCEGOVINE

ANALYSIS OF THE INFLUENCE OF RAW MATERIALS COMPOSITION ON THE ENERGY VALUE OF WOOD PELLETS ON THE TERRITORY OF B&H

17

J. Filipović, V. Filipović, M. Košutić

FUNKCIONALNE OSOBINE HLEBA OBOGAĆENOG MODIFIKOVANIM VLAKNIMA

FUNCTIONAL CHARACTERISTICS OF BREAD ENRICHED WITH MODIFIED FIBERS 25

J. Filipović, V. Filipović, M. Košutić

SPELT PASTA ENRICHED WITH ω-3 FATTY ACIDS

TESTENINA OD SPELTE OBOGAĆENA ω-3 MASNIM KISELINAMA 31

Ţ. Pavlović, S. Dedijer, M. Pál, I. Tomić, I. Juriĉ

READABILITY OF SCREEN PRINTED QR CODES DEPENDING ON THEIR DIMENSION, ENCODED CONTENT AND TYPE OF PRINTING SUBSTRATE USING SCREEN PRINTING TECHNIQUE

ĈITLJIVOST SITO ŠTAMPANIH QR KODOVA U ZAVISNOSTI OD NJIHOVIH DIMENZIJA, KODIRANOG SADRŢAJA I VRSTE ŠTAMPARSKE PODLOGE

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Glasnik hemiĉara, tehnologa i ekologa Republike Srpske, 12 (2016) 1-8

1

THE INFLUENCE OF ROSEMARY ESSENTIAL OIL APPLIED PER OS ON THE PHARMACODYNAMIC AND PHARMACOKINETIC

PROPERTIES OF PARACETAMOL

Isidora Milanović1*, Aleksandar Rašković2 , Saša Vukmirović2, Nebojša Stilinović2, Momir Mikov2

1Higher Education School of Professional Health Studies, Zemun, Serbia 2Medical Faculty of University of Novi Sad, Novi Sad, Serbia

ISSN 2232-755X UDC: 615.276.03:582.282.123 DOI: 10.7251/GHTE1612001M Original scientific paper

Introduction: Rosemary essential oil can be used for treating dyspepsia, mild spasmodic disorders of the gastrointestinal tract, externally as analgetic in muscular and articular pain and minor peripheral circulatory disorders. It is important to explore its analgesic potential and its influence on the pharmacodynamic and pharmacokinetic properties of paracetamol. Methodology: Rosemary essential oil was applied to mice orally (doses: 10 and 20 mg/kg b.w.) for pharmacodynamic tests for seven days. Rats treated with rosemary essential oil for seven days orally (5 and 10 mg/kg b.w.) were used for the examination of the influence of essential oil on the pharmacokinetic properties of paracetamol (applied on the 7th day p.o. or i.v.). Pharmacokinetic parameters were analyzed in blood samples obtained from rats' tail veins, with the HPLC method. Results: The essential oil of rosemary shows analgetic properties. The rosemary essential oil increases pharmacological effects of paracetamol and does not change paracetamol bioavailability. Conclusion: The herbal drugs could change the pharmacodynamic and the pharmacokinetic properties of classical drugs and they could also change the safety of classical drugs use in human population.

Key words: Rosemary, Herb-Drugs Interactions, Paracetamol

INTRODUCTION

The use of herbal medicinal products to relieve pain has been increasing in recent years because they are often perceived as being natural and therefore harmless [1,2]. Herbal medicines are often taken in combination with conventional drug therapies and some of their pharmacologically active ingredients might interact with synthetic drugs [3]. Drugs that are substrates for metabolism mediated by cytochrome P450 (CYP) enzymes are particularly subject to herb-drug interactions, which can be attributed to the ability of many herbal compounds to induce or inhibit these enzymes [4].

Rosemary (Rosmarinus officinalis L., Lamiaceae) is widely cultivated all over the world as an ornamental and aromatic plant, and has been commonly used for flavoring food, but also for different medicinal purposes. In traditional medicine, rosemary was used as mild analgesic, for relieving renal colic pain, dysmenorrhea, respiratory disorders, due to its antispasmodic properties [5,6]. Recently, essential oil isolated from rosemary and monoterpenes as its main active compounds have been of great interest due to their various health benefits and therapeutic effects. According to the recommendation of European Medicines Agency (EMA) from 2010, rosemary essential oil (REO) can be used for treating dyspepsia and mild spasmodic disorders of the gastrointestinal tract, as well as an adjuvant in the relief of minor muscular and articular pain and in minor peripheral circulatory disorders [7]. Besides, the experiments conducted with REO have demonstrated some of its notable pharmacological effects, such as antioxidant and antimicrobial [8], anti-inflammatory and antinociceptive [9], among others.

On the other hand, there are several well-established interactions of rosemary preparations with different drugs, such as antibiotics, anxiolytics and anticoagulant medicines, in terms of potentiating of their activity [3,10]. Given that REO was found to exert analgesic effects in different experimental models of nociception, its potential interactions with analgesics may be assumed. Besides, it was demonstrated that REO and its main components induce catalytic activities of microsomal enzymes, and therefore may interact with drugs metabolized by cytochromes or UGT [11,12].

Paracetamol (acetaminophen) is one of the most widely used drugs for the treatment of pain in both acute and chronic settings. It has a unique position among analgesic drugs, having a spectrum of action similar to that of NSAIDs, but with negligible anti-inflammatory and antirheumatic activities. The mode of action of paracetamol has still not been fully elucidated, but there is some evidence supporting a central analgesic effect. It is now generally accepted that it inhibits COX-1 and particularly COX-2 through metabolism by the peroxidase function of these isoenzymes [13,14]. Recently, it was discovered that paracetamol may act as a prodrug by triggering the CB1 receptor - mediated effects of the cannabinoid system. At therapeutic doses, the greater part of paracetamol is conjugated with glucuronic acid and, to a lesser extent, with sulphate or cysteine. A fraction usually ranging from 5 to 15% is oxidized by CYP2E1, CYP1A2,

* Coresponding author: Isidora Milanović, Higher Education School of Professional Health Studies, Cara Dušana st. No

254, Zemun, Serbia, e-mail: [email protected]. Rad je izloţen na meĊunarodnom nauĉnom skupu XI Savjetovanje hemiĉara, tehnologa i ekologa Republike Srpske, novembar 2016.


I. Milanović et al.: THE INFLUENCE OF ROSEMARY ESSENTIAL OIL APPLIED...

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CYP3A4, and CYP2A6 subfamilies of cytochromes P450, resulting in the formation of the highly reactive and hepatotoxic N-acetyl-p-benzoquinoneimine (NAPQI), which is quickly conjugated with glutathione to form non-toxic cysteine and mercapturic acid conjugates [15]. Hepatic enzymes induction may increase paracetamol hepatotoxicity, and therefore the potential for interactions of paracetamol with herbal medicinal products should be carefully considered.

Based on the above-mentioned facts, the aim of our study was to examine the analgesic effects of REO and its pharmacodynamic interactions with paracetamol in mice, as well as pharmacokinetic interactions in rats.

MATERIAL AND METHODS OF WORK

Plant material and chemicals

Aerial parts of cultivated plants of rosemary were obtained from the Institute for Medicinal Plants Studies, Dr Josif Panĉić, Belgrade. A voucher specimen of the plant (Rosmarinus officinalis L. 1753 subsp. officinalis No 2-1746, det.: Goran Anaĉkov) was confirmed and deposited in the Herbarium of the Biology and Ecology Department, Faculty of Natural Sciences, University of Novi Sad. The essential oil, used in our experiments, was isolated from the obtained plant material.

Paracetamol was purchased from Sigma-Aldrich (St Louis, MO, USA).

Isolation and analysis of essential oil

The essential oil was isolated from air-dried aerial parts of rosemary by hydrodistillation, according to the procedure of the European Pharmacopoeia 4 [16]. N-hexane was used as a collecting solvent, which was afterwards removed under vacuum from the obtained essential oil.

The identification and quantification of chemical constituents of the essential oil were carried out by gas chromatography coupled with flame ionization detection (GC/FID) and mass spectrometric detection (GC/MS). GC/FID analysis was performed using a Hewlett-Packard HP 5890 series II chromatograph equipped with an auto sampler and a split/splitless injection system. The capillary column used in this study was HP-5 (25 m × 0.32 mm; film thickness of 0.52 μm), coupled to the flame ionization detector (FID). The injector and detector temperatures were set at 250°C and 300°C, respectively, and the column temperature was programmed from 40 to 260°C at a rate of 4°C/min. The flow rate of hydrogen as a carrier gas was 1 ml/min. A sample of 1% solution of the oil in ethanol (1 μl) was injected in split mode (split ratio, 1:30). GC/MS analysis was carried out using a Hewlett-Packard HP G1800C series II GCD system under the same analytical conditions as in GC/FID. The column HP-5MS (30 m × 0.25 mm; film thickness 0.25 μm) and helium as a carrier gas were used in this analysis. The system was operated in electron ionization (EI) mode at 70 eV, in the mass (m/z) range 40-450 Da.

The identification of essential oil constituents was performed by comparison of the obtained mass spectra and retention indexes with those of reference compounds or those from mass spectra libraries and literature data. The quantitative analysis provided the percentage composition of the essential oil components, calculated by FID peak area normalization method.

Animals and treatment

Experiments were carried out on adult, sexually mature NMRI mice of both sexes, weighing 25-35 g, which were obtained from the Veterinary Institute Novi Sad, Serbia, and on adult, sexually mature Wistar rats of both sexes, weighing 250-300 g, which were obtained from Vojnotehniĉki institut VMA, Belgrade. Animals were housed in standard laboratory cages at a controlled temperature (23 ± 1 ºC) and humidity (55 ± 1.5 %) under standard circadial rhythm (day/night), with free access to pelleted food and water. Animal care and experimental procedures were conducted in accordance with the Guide for the Care and Use of Laboratory Animals edited by Commission of Life Sciences, National Research Council (USA). The experimental procedures were approved by Ethical Committee for Animal Use in Experiments of the University of Novi Sad (No. 01-153/6-2).

The mice for pharmacodinamic tests were divided into 5 experimental groups, each containing 6 individuals, and treated as follows:

ConS: control group, saline solution p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.p. administration of saline solution

REO: REO (20 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.p. administration of REO

Par: saline solution p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.p. administration of paracetamol

ParR10: REO (10 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.p. administration of paracetamol


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ParR20: REO (20 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before

i.p. administration of paracetamol

Applied daily doses of REO for mice were 10 mg/kg and 20 mg/kg, and those for rats were 5 mg/kg and 10 mg/kg. Recommended human daily dose of REO of 40 mg/day for a male of approximately 70 kg weight [7,17] was adapted for the experimentation on mice. Each mouse received appropriate dose of REO in the volume of 10 ml of solution per kg of body weight, by per os gavage and each rat received dose of REO in the volume of 1 ml of solution per kg of body weight, by per os gavage. The tested drug, paracetamol (60 mg/kg for mice and 20 mg/kg for rats), was administered intraperitoneally (i.p.) for mice and p.o. and i.v. for rats, 30 min after the last REO intake. The control group of animals received an equivalent volume of saline solution.

The rats for pharmacokinetic examination were divided into 6 experimental groups, each containing 6 animals, and treated as follows:

Con7+PARp.o., control group, saline solution p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before p.o. administration of paracetamol;

Con7+PARi.v., control group, saline solution p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.v. administration of paracetamol;

Reo57+PARp.o.; REO (5 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes

before p.o. administration of paracetamol;

Reo57+PARi.v, REO (5 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.v. administration of paracetamol;

Reo107+PARp.o.; REO (10 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before p.o. administration of paracetamol;

Reo107+PARi.v., REO (10 mg/kg) p.o. for 7 days, where the last dose on the 7th day was applied 30 minutes before i.v. administration of paracetamol.

Hot plate test

Hot plate test was performed by placing mice individually on a hot plate and assessing their response to the thermal stimulus. The temperature of the metal plate enclosed by plexiglas walls was maintained at 52.5 ⁰C. The response

time was measured in seconds at which the animal licked or flinched one of the hind paws, or jumped off the plate. To prevent tissue damage, a cut-off time was used as a double value of latencies measured before drug application. Response latencies were first determined two times before the application of the tested compound, in order to determine a pre-treatment response for each mouse, and then 5, 10, 15, 20, 30, 40, 50, 60 minutes following the drug administration. After responding or reaching the cut-off time, mice were removed from the plate. Analgesic effect determined in seconds was expressed as percentage of prolongation of measured reaction time compared to control reaction time [18].

(А−В)/В*100 = % of analgesic effect

А – measured reaction time (sec)

В – control average reaction time

Pharmacokinetic tests

From all experimental groups a blood sample was taken from tail veins, before paracetamol was given. The paracetamol was applied 30 min after last dose of REO. The samples were taken at 0, at 15th, 30th, 45th, 60th, 90th, 120th, 180th, 240 and 300th minute after paracetamol was applied per os or I.V.. The animals were imobilised and their tails were washed with hot water. Then they were given massage to produce hyperemia. The perforation of skin was done 1 cm from the top of the tail and 200 microliters of blood was taken. Those samples were centrifugated for 10 minutes on 6000 o/min.

The water solutions were prepared with water HPLC degree –JT Baker.

Stock solution was made in concentration 1 mg/ml.

The sample analysis was done on the Dionex HPLC with UV detector. The system for chromatography detecting of paracetamol was made from the following elements: column ZORBAX Extend C-18 Narrow-Bore 2.1 mm x 150 mm 5-Micron; subcolumn ZORBAX Eclipse Plus-C 18, Analytical Guard Column 4.6 m x12.5 mm 5-Micron.

In the examination, isocratic elution was used, with constant flow of mobile phase of 0.4 ml/min. The mobile phases were made of water and acetonitrile w/w: H2O : ACN = 88 : 12.

The samples were injected by using autosampler ASI 100 autosampler plus. The volume of injection was 20 μl. The part with column was at the temperature of 20°C. The paracetamol was detected by detector UV at the wave of λ=254 nm. The time of retention of paracetamol in biological samples was 2.2 minutes, and the duration of analysis was 8 minutes.


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The control of the chromatographic system was done by the programme CHROMELEON v.6.70, Chromatography management system, Dionex, 2005.

The concentration of paracetamol was calculated from the area under the curve of different concentration of external standards.

The pharmacokinetic parameters were analyzed in blood samples obtained from rats' tail veins. The HPLC method was used for measurement of paracetamol concentration in blood samples. Those concentrations were used for calculation of the pharmacokinetic parameters.

Statistical analysis

The level of significance between the groups was assessed with the Student’s t-test for small independent samples using MedCalc 9.2.0.1 software. All data are expressed as a mean ± standard deviation (SD). A value of p < 0.05 was considered to be statistically significant.

RESULTS AND DISCUSSION

The essential oil obtained from rosemary had a pale yellow color and a strong odor, and the obtained yield of the

essential oil was 1.03% (v/w in dry matter). The total number of identified chemical constituents was 29, representing 99.87% of the total oil content. As presented in Table 1., the isolated essential oil contains a complex mixture of 95.10%, of monoterpenes and 4.77% of sesquiterpenes. It was found to be composed mainly of oxygenated monoterpenes (63.88%), followed by monoterpene hydrocarbons (31.22%) and sesquiterpene hydrocarbons (4.77%). The major compounds that were identified and quantitated by GC-FID and GC-MS were 1,8-cineole (43.77%), camphor (12.53%), α-pinene (11.51%), β-pinene (8.16%), camphene (4.55%), and β-caryophyllene (3.93%).

In our study, REO (20 mg/kg) significantly increased the latency time of animal response to heat-induced pain between 20th and 50th minute of the test (Table 2), when compared to saline-treated group. We showed that analgesic effect of REO was slightly higher than that of paracetamol.

Table 1. Total amount of identificated compounds in the examined sample of essential oil of rosemary (% m/m)

Compounds The number of identificated compounds

Total amount, percent %(m/m)

Monoterpenes 14 31.22

Oxygenated monoterpenes 9 63.88

Sesquiterpenes 6 4.77

Total number/amounts of identificated compounds

29 99.87

Amount of non-identificated

Compounds 0.13

Table 2. The reaction of mice on hot stimulus during hot-plate test

Interval of measurement [min]

0 5 10 15 20 30 40 50 60

Group of animals

ConS 11.63±

2.57 11.11±

4.52 9.87± 2.17

12.47± 3.27

10.06± 1.84

10.91± 2.87

10.27± 1.91

11.58± 1.64

11.88± 2.70

REO 10.91±

2.80 12.92± 3.30#

13.85± 7.70

15.21± 3.00

14.17± 3.20*#

14.66± 7.50

14.24± 6.50

15.58± 3.10*#

14.44± 3.90

Par 10.91±

2.61 10.34±

1.05 12.38±

3.97 11.73±

2.32 11.08±

3.85 11.56±

2.92 12.42± 1.80*

13.32± 2.28

12.10± 5.08

ParR10 10.91±

2.61 10.91±

2.61 11.97±

2.55 13.08±

4.00 12.63± 2.26*

12.20± 3.15

13.68± 2.04*

11.93± 1.40*

13.41± 3.85

ParR20 10.91±

2.61 13.17± 3.18#

11.53± 7.59

14.45± 8.80

13.25± 4.19*

16.53± 5.35#*

15.48± 5.57*

18.50± 6.40*

12.78± 3.25

(*) statistically different value from group ConS, p˂0,05;

(#) statistically different value from group Par, p˂0,05.


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Figure 1. Analgesic effect of essential oil of rosemary compared with those of paracetamol

We demonstrated that percent of analgesic effect of REO was comparable to those of paracetamol, alone and in combinations with REO (Table 2 and Figure 1). The administration of REO in the dose of 20 mg/kg with paracetamol significantly prolonged the reaction time of animals provoked by heat stimuli, when compared to both saline- and paracetamol-treated group, with a maximal response observed between the 30th and 50th minute of the test.

Two main chemotypes of essential oils isolated from rosemary have been reported considering the chemical composition. The main component of the Tunisian, Turkish, Moroccan and Italian oils is 1,8-cineole with usually over 40%, whereas most Spanish, French and Greek oils have 1,8-cineole, α-pinene and camphor with approximately equal ratios (20-30%) [8]. The main constituents in the rosemary essential oil investigated in our study were 1,8-cineole (43.77%), camphor (12.53%), and α-pinene (11.51%), and therefore it can be categorized in the Morocco/Tunisian type. It should be noted that there are several factors that contribute to significant variations in the chemical composition of rosemary essential oils, including the geographic origin, part of the plant, season of harvesting, hence

the stage of the plant growth, and also the essential oil isolation method [19]. All effects of REO should be therefore carefully examined, considering the chemical composition of the examined oil.

In hot plate assay, 7-day treatment with REO (20 mg/kg) induced significant analgesic effects in mice, which is in accordance with the results of previous studies. Analgesic activity of REO was confirmed in different nociceptive experimental models. Analgesic effect of REO was confirmed for different monoterpenes that constitute more than 90% of the essential oils [20], but also for the ethanol extract of rosemary [21] and its major constituent carnosol [22], and triterpenes fractionated from the rosemary extract [23].

The observed analgesic effect of REO in hot plate test in our study indicates its central mechanism of analgesia, since both paw licking and jumping are supraspinally integrated responses [24]. Serotonergic and opioid endogenous systems were suggested to be involved in the mechanism of action as an antinociceptive of the essential oil isolated from rosemary[25]. Furthermore, the GABAergic system may be another possible route involved in the pharmacological activity of rosemary [21].

Several studies using different nociceptive in vivo models demonstrated analgesic activity of many monoterpenes [26]. The mechanisms of antinociceptive effects of monoterpenes are still to be elucidated, but are suggested to involve different members of the TRP channel family, as confirmed for camphor [27]. It is generally assumed that acyclic monoterpenes modulate the opioid system, while monocyclic and bicyclic monoterpenes produce analgesic effects mostly by peripheral pathways [20]. The potent analgesic and anti-inflammatory activity of 1,8-cineole, as a dominant component of REO, was shown to be mediated through the inhibition of COX enzymes and suppression of cytokines (TNF-α and IL-1β) production as well [28].

Although it possesses analgesic activity, REO can also influence catalytic activities of cytochromes and thus efficacy of other analgesic drugs. REO rich in 1,8-cineole was found to induce catalytic activities of microsomal enzymes, particularly CYP2B, but also slightly the activity of UDP-glucuronosyltransferase (UGT), and therefore may interact with codeine and paracetamol [12]. The main REO component 1,8-cineole also increased the levels of cytochromes CYP2B1 and 3A2 [11]. It was demonstrated that water extracts of rosemary significantly increased activity of CYP2E1, 1A2 and 3A, which are involved in the formation of hepatotoxic metabolite of paracetamol [29,30]. As shown in Figure 1, the administration of REO in combination with paracetamol exerted distinct effects when applied in different doses. REO in the dose of 20 mg/kg was shown to be more efficient than in the dose of 10 mg/kg, in combinations with paracetamol, which suggests that dose determines whether REO will predominantly induce cytochromes or act as analgesic and


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have additive effect with administered antinociceptive drugs. This is in agreement with previous findings that many monoterpenes do not exhibit dose-dependent effects and that it is necessary to find the most appropriate dose range that shows effectiveness [31].

Table 3. The influence of essential oil of rosemary applied per os, during seven days, 5 i 10 µg/kg, on the pharmacokinetic parameters of paracetamol used intravenously, 20 mg/kg, on white laboratory rats (m±Sd)

Pharmacokinetic parameter

Con7+PARi.v. Reo57+PARi.v. Reo107+PARi.v.

K (1/min) 15.92x10-3 ±3.28x10-3 19.80x10-3±11.52x10-3 16.88x10-3± 2.82x10-3

t ½

min 45.42±11.53 43.55±19.69 42.16±8.48

C0

μg /ml 47.65±18.39 24.25±11.34* 27.63±12.81

AUC 0-t

min*ug/ml 1256.69±441.40 1001.36±428.62 982.58±502.44

Table 4. The influence of essential oil of rosemary applied per os, during seven days, 5 i 10 µg/kg, on the pharmacokinetic parameters of paracetamol used also per os, 20 mg/kg, on white laboratory rats (m±Sd)

Pharmacokinetic parameter

Con7+PARp.o. Reo57+PARp.o. Reo107+PARp.o.

K (1/min) 9.10x10-3± 4.19x10-3 7.32x10-3 1.87x10-3 10.13x10-3± 4.43x10-3

t 1/2

min 89.77±39.58 101.65±34.49 78.13±28.28

t max

min 41.25±18.87 36.00±8.22 35.00±12.25

Cmax

ug/ml 3.20±0.44 2.38±0.86 2.80±0.74

AUC 0-t

min*ug/ml 354.12±102.00 262.11±68.72 272.06±72.10

The influence of REO applied orally was seen through the changes of pharmacokinetic parameters within experimental groups on one side and control group which received paracetamol by intravenous route (Table 3.).

The constants of elimination were increased in both experimental groups and half-life was decreased in both experimental groups. The first measured concetration was statistically lower than in control group.

In the control group where paracetamol was applied orally (Table 4.), the changes of parameteres are different in association with dose which was applied.

In the group treated with 10 mg of REO the elimination was faster, and in the group treated with 5 mg the elimination of drug is lower than in the control group. The same was seen in the parameteres of half-life of drug.

There is no statisticaly significant difference beetween bioavailability of paracetamol, but it is still lower in the group treated with 5 mg of REO (only 2% lower then in control group. This result can’t be taken as significant but it should

be taken as a reason for precaution when classical drugs and herbal drugs are used together).

CONCLUSIONS

These results could be caused with presistemic metabolism of paracetamol and of influence of REO at the resorption of paracetamol. The paracetamol is the P-glycoprotein substrate, and the extract of rosemary shows influence to this tansport proteine [32].

The decrease of bioavailability of paracetamol after REO use could be explaned with the influence of monoterpene,8-cineole, which is most present in our sample of REO. This monoterpene could interact with microsomal enzymes, sulfur transferase, UDP-glucuronyl transferase and cytochromes CYP3A4, CYP1A2, CYP2D6, CYP2E1, which are used in biotransformation of paracetamol [7,22,33,34].


7

In summary, it can be concluded that REO possesses centrally acting analgesic properties, as determined in hot plate assay, although a more in-depth evaluation of the mechanisms involved should be performed. Our findings support the folkloric use of rosemary in the management of pain, but also indicate a therapeutic potential of REO in combination with analgesic drugs. Considering nonlinear dose-response relationship of most monoterpenes, the appropriate dose of REO has to be determined in order to obtain an improved therapeutic effect without adverse reactions due to interactions.

Acknowledgements

This study was funded by Ministry of Education, Science and Technological Development, Republic of Serbia (grant No 41012) and by Provincial Secretariat for Science and Technological Development, Autonomous Province of Vojvodina (grant No 114-451-3551/2013-02). The authors are grateful to Mr. Goran Anaĉkov, Department of Biology and Ecology, Faculty of Sciences, University of Novi Sad, for determination of plant material.

Conflict of Interest

The Authors declare that they have no conflict of interests.

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8. Ojeda-Sana, A.M., van Baren, C.M., Elechosa, M.A., Juarez, M.A., Moreno, S.: New insights into antibacterial and antioxidant activities of rosemary essential oils and their main components. Food Control, 31(1) (2013), 189-195.

9. Takaki, I., Bersani-Amado, L.E., Vendruscolo, A., Sartoretto, S.M., Diniz, S.P., Bersani-Amado, C.A., Cuman, R.K.: Anti-inflammatory and antinociceptive effects of Rosmarinus officinalis L. essential oil in experimental animal models. J Med Food, 11(4) (2008), 741-746.

10. Ulbricht, C., Abrams, T.R., Brigham, A., Ceurvels, J., Clubb, J., Curtiss, W., Kirkwood, C.D., Giese, N., Hoehn, K., Iovin, R., Isaac, R., Rusie, E., Serrano, J.M., Varghese, M., Weissner, W., Windsor, R.C.: An evidence-based systematic review of rosemary (Rosmarinus officinalis) by the Natural Standard Research Collaboration. J Diet Suppl, 7(4) (2010), 351-413.

11. Hiroi, T., Miyazaki, Y., Kobayashi, Y., Imaoka, S., Funae, Y.: Induction of hepatic P450s in rat by essential wood and leaf oils. Xenobiotica, 25(5) (1995), 457-467.

12. Debersac, P., Heydel, J.M., Amiot, M.J., Goudonnet, H., Artur, Y., Suschetet, M., Siess, M.H.: Induction of cytochrome P450 and/or detoxication enzymes by various extracts of rosemary: description of specific patterns. Food Chem Toxicol, 39(9) (2001), 907-918.

13. Mikus, G., Weiss, J.: Influence of CYP2D6 genetics on opioid kinetics, metabolism and response. Curr Pharmacogenomics, 3 (2005), 43-52.

14. Bibi, Z.: Role of cytochrome P450 in drug interactions. Nutr Metab, 5 (2008), 27. 15. Bertolini, A., Ferrari, A., Ottani, A., Guerzoni, S., Tacchi, R., Leone, S.: Paracetamol: new vistas of an old drug.

CNS Drug Rev, 12 (2006), 250-275. 16. European Pharmacopeia (4th edition). Council of Europe: Strasbourg Cedex, France. 2002; pp. 183-184. 17. Blumenthal, M., Goldberg, A., Brinckmann, J., editors: Herbal Medicine: Expanded Commission E Monographs.

Boston (MA): Integrative Medicine Communications; 2000. 18. Horvat, O., Raskovic, A., Jakovljevic, V., Sabo, J., Berenji, J.: Interaction of alcoholic extracts of hops with

cocaine and paracetamol in mice. Eur J Drug Metab Pharmacokinet, 32(1) (2007), 39-44. 19. Teixeira, B., Marques, A., Ramos, C., Neng, N.R., Nogueira, J.M.F., Saraiva, J.A., Nunes, M.L.: Chemical

composition and antibacterial and antioxidant properties of commercial essential oils. Ind Crop Prod, 43 (2013), 587-595.


8

20. de Faria, L.R.D., Lima, C.S., Perazzo, F.F., Carvalho, J.C.T.: Anti-inflammatory and antinociceptive activities of the essential oil from Rosmarinus officinalis L. (Lamiaceae). Int J Pharm Sci Rev Res, 7 (2011), 1-8.

21. Martínez, A.L., González-Trujano, M.E., Pellicer, F., López-Muñoz, F.J., Navarrete, A.: Antinociceptive effect and GC/MS analysis of Rosmarinus officinalis L. essential oil from its aerial parts. Planta Med, 75(5) (2009), 508-511.

22. Guimarães, A.G., Quintans, J.S., Quintans, L.J. Jr.: Monoterpenes with analgesic activity--a systematic review. Phytother Res, 27(1) (2013) 1-15.

23. González-Trujano, M.E., Peña, E.I., Martínez, A.L., Moreno, J., Guevara-Fefer, P., Déciga-Campos, M., López-Muñoz, F.J.: Evaluation of the antinociceptive effect of Rosmarinus officinalis L. using three different experimental models in rodents. J Ethnopharmacol, 111(3) (2007) 476-482.

24. Le Bars, D., Gozariu, M., Cadden, S.W.: Animal models of nociception. Pharmacol Rev, 53(4) (2001), 597-652. 25. Martínez, A.L., González-Trujano, M.E., Chávez, M., Pellicer, F.: Antinociceptive effectiveness of triterpenes from

rosemary in visceral nociception. J Ethnopharmacol, 142 (2012), 28-34. 26. de Sousa, D.P.: Analgesic-like activity of essential oils constituents. Molecules, 16(3) (2011), 2233-2252. 27. Radulović, N.S., Randjelović, P.J., Stojanović, N.M., Blagojević, P.D., Stojanović-Radić, Z.Z., Ilić, I.R., Djordjević,

V.B.: Toxic essential oils. Part II: chemical, toxicological, pharmacological and microbiological profiles of Artemisia annua L. volatiles. Food Chem Toxicol, 58 (2013), 37-49.

28. Xu, H., Blair, N.T., Clapham, D.E.: Camphor activates and strongly desensitizes the transient receptor potential vanilloid subtype 1 channel in a vanilloid-independent mechanism. J Neurosci, 25 (2005), 8924-8937.

29. Santos, F.A., Rao, V.S.: Antiinflammatory and antinociceptive effects of 1,8-cineole a terpenoid oxide present in many plant essential oils. Phytother Res, 14 (2000), 240-244.

30. Debersac, P., Vernevaut, M.F., Amiot, M.J., Suschetet, M., Siess, M.H.: Effects of a water-soluble extract of rosemary and its purified component rosmarinic acid on xenobiotic-metabolizing enzymes in rat liver. Food Chem Toxicol, 39(2) (2001) 109-117.

31. Metwally, N.S., Hamed, M.A., Ahmed, S.A.: Association between efficiency of certain medicinal plants and severity of renal disorders in rats. Int J Pharm Pharm Sci, 4 (2012), 432-438.

32. Plouzek, C.A., Ciolino, H.P.: Inhibition of P-Glycoprotein activity and reversal of multidrug resistance in vitro by rosemary extract. Eur J Cancer, 35(10) (1999), 1541-45.

33. Tanikawa, K., Torimura, T.: Studies on oxidative stress in liver diseases: important future trends in liver research. Medical Molecular Morphology, 39 (2006), 22-27.

34. Zhu, R., Wang, Y., Zhang, L., Guo, Q.: Oxidative stress and liver disease. Hepatology Research, 42 (2012), 741-749.

UTICAJ ETARSKOG ULJA RUZMARINA PRIMENJENOG per os NA FARMAKODINAMSKA I FARMAKINETSKA SVOJSTVA

PARACETAMOLA

Isidora Milanović1* , Aleksandar Rašković2 , Saša Vukmirović2, Nebojša Stilinović2, Momir Mikov2

1Visoka zdravstvena škola strukovnih studija u Beogradu, Zemun, Srbija 2Medicinski fakultet Novi Sad, Novi Sad, Srbija

Uvod: Etarsko ulje ruzmarina se koristi za tretman dispepsije, blagih spazama gastrointestinalnog trakta; spolja kao analgetik za leĉenje blaţih mijalgija i bolova u zglobovima, i za poboljšanje periferne cirkulacije. Stoga je vaţno ispitati analgetski potencijal etarskog ulja ruzmarina i njegov uticaj na farmakokinetske i farmakodinamske osobine drugih analgetika, odnosno u našem sluĉaju paracetamola. Metodologija: Etarsko ulje ruzmarina je primenjivano oralno (10 i 20 mg/kg TM) tokom sedam dana za potrebe farmakodinamskih testova. Pacovi su tretirani etarskim uljem ruzmarina per os sedam dana (5 i 10 mg/kg TM). Na njima je ispitivan uticaj etarskog ulja ruzmarina na farmakokinetske osobine paracetamola (primenjenog sedmog dana per os ili intravenski). Farmakokinetski parametri su ispitivani u uzorcima krvi pacova dobijenim iz repne vene HPLC metodom. Rezultati: Etarsko ulje ruzmarina je pokazalo analgetski efekat. Etarsko ulje ruzmarina je pojaĉalo analgetski efekat paracetamola i ne utiĉe na biološku raspoloţivost paracetamola. Zakljuĉak: Biljni lekovi mogu uticati na farmakodinamiku i farmakokinetiku klasiĉnih lekova, a time i na bezbednost primene tih lekova u humanoj populaciji.

Kljuĉne reĉi: Ruzmarin, interakcije lekovi-lekovite biiljke, paracetamol

Rad primljen: 28. 11. 2016. Rad prihvaćen: 16. 12. 2016.


9

BIOLOŠKO UKLANJANJE AMONIJUM JONA IZ VODE ZA PIĆE

Dijana Drljaĉa1*, Boţo Dalmacija2, Ljiljana Vukić1, Slobodanka Zorić3 1Univerzitet u Banjoj Luci, Tehnološki fakultet, Banja Luka, B&H

2Univerzitet u Novom Sadu, Prirodno-matematiĉki fakultet, Novi Sad, Republika Srbija 3a.d. „Vodovod‖ Banja Luka, B&H

ISSN 2232-755X UDC: 628.161.2/.3:669.245.087

DOI10.7251/GHTE1612009D Originalni nauĉni rad

Biološki procesi uklanjanja amonijum jona iz vode za piće, poput biofiltracije, zauzimaju sve više paţnje, s obzirom da se primjenom ovih procesa mogu izbjeći toksiĉni nusproizvodi dezinfekcije, ali i problemi koji se pojavljuju u distribucionom sistemu. Istraţivanja su sprovedena na poluindustrijskom postrojenju („Pilot―) u a.d. „Vodovod― Banja Luka projektovanom za ispitivanje i optimizaciju procesa pripreme vode za piće iz površinske vode (rijeka Vrbas). Ciklus istraţivanja biološkog uklanjanja amonijum jona na filterima proveden je u ljetnom, jesenjem i zimskom periodu pri hidrauliĉkom opterećenju sirove vode od 1,2–2 m3/h. Biološka filtracije na poluindustrijskom postrojenju, praćena je na jedno- i dvo-medijumskim filterima uz promjenu brzine filtracije i temperature ulazne vode. Pri brzini filtracije od 3,3 m/h nije postignuta potpuna nitrifikacija. Nepotpunost nitrifikacije ogleda se u nepotpunosti njene druge faze – nitratifikacije, dok je proces nitritifikacije konstantan na oba filtera (pijesak; pijesak+antracit), za sve primijenjene inicijalne koncentracije amonijum jona (γ = 0,6-1,3 mg NH4+- N/L). Pri brzini filtracije od 0,8 m/h postiţe se potpuna nitrifikacija ĉak i pri sniţavanju temperature sa 11,1° na 8,8°C.

Kljuĉne rijeĉi: pilot postrojenje, voda za piće, nitrifikacija, brzina filtracije

UVOD

Amonijum jon koji je prisutan u površinskim vodama zajedno sa otpadnim vodama, koje su takoĊe nosioci amonijum jona u visokim koncentracijama, troši veliku koliĉinu kiseonika za svoju oksidaciju do nitrita ili nitrata. Svi oblici azota smatraju se nepoţeljnim u vodi za piće, i u klasiĉnoj higijensko-hemijskoj analizi vode za piće NO3

-, NO2-, i NH4

+

smatraju se indikatorima fekalnog zagaĊenja.

Prema Pravilniku o higijenskoj ispravnosti vode za piće [1] maksimalno dopuštene koncentracije za specije azota iznose:

– amonijak 0,1 mg NH3/L, odnosno 0,08 mg NH4+- N/L,

– nitrati 50 mg NO3/L, odnosno 11,3 mg NO3-- N/L,

– nitriti 0,03 mg NO2/L, odnosno 0,009 mg NO2-- N/L.

Uklanjanje amonijum jona iz vode za piće

U cilju oĉuvanja kvaliteta vode za piće, amonijum jon je ĉesto potrebno ukloniti u postrojenjima za pripremu vode za piće, jer njegova prisutnost moţe uzrokovati probleme vezane za kvalitet vode i distribuciju, npr. ponovni bakterijski rast, stvaranje nitrita nepotpunom oksidacijom i pojavu nepoţeljnog mirisa i ukusa [2-3].

Za uklanjanje amonijum jona prisutnog u vodi za piće mogu se primjenjivati fiziĉko-hemijski i biološki postupci. U fiziĉko-hemijske postupke ubrajaju se izmjena jona i hemijska oksidacija, pri ĉemu je najĉešće primjenjivana metoda hlorisanje preko prevojne taĉke. Uvjerenje, da metoda hlorisanja preko prevojne taĉke, predstavlja potpuno siguran postupak uklanjanja i sigurnu dezinfekciju, polako se dovodi u pitanje radovima u kojima se govori o nalaţenju sporednih proizvoda, štetnih po zdravlje ljudi, poput halosirćetnih kiselina, kao i N-nitrozodimetilamina, koji je klasifikovan kao vjerovatni kancerogen [4-5].

Biološki procesi uklanjanja amonijum jona, poput biofiltracije, zauzimaju sve više paţnje, s obzirom da se primjenom ovih procesa mogu izbjeći toksiĉni nusproizvodi dezinfekcije, ali i problemi koji se pojavljuju u distribucionom sistemu. Nitrifikacija predstavlja mikrobiološki proces pri kojem se redukovana azotna jedinjenja (prije svega amonijum jon) uzastopno oksiduju do nitrita i nitrata. Vinogradski je još 1892. godine utvrdio da postoje dvije grupe nitrifikatora:

jedna vrši oksidaciju amonijum jona do nitritne kiseline ( ) – nitritifikacija, a druga – oksidaciju nitritne

kiseline do nitratne ( ) – nitratifikacia. Do danas nije pronaĊena ni jedna grupa bakterija koja moţe izvršiti direktnu oksidaciju amonijum jona do nitratnog jona [6-7].

* Korespondentni autor: Dijana Drljaĉa, Univerzitet u Banjaluci, Tehnološki fakultet, Vojvode Stepe Stepanovića 73,

Banja Luka, RS, BiH, e-mail: [email protected]. Rad je izloţen na meĊunarodnom nauĉnom skupu XI Savjetovanje hemiĉara, tehnologa i ekologa Republike Srpske, novembar 2016.


D. Drljaĉa i sar.: BIOLOŠKO UKLANJANJE AMONIJUM JONA IZ VODE ZA PIĆE

10

Nitritifikacija

Oksidacija amonijum jona se odvija preko intermedijarnog jedinjenja hidroksilamina (NH2OH) uz enzim amonijum monooksigenazu (AMO), a oksidacija hidroksilamina do nitrita uz enzim hidroksilamin oksidoreduktazu (HAO), prema jednaĉinama:

pa se zbirna reakcija nastajanja nitrita moţe prikazati:

Nitratifikacija

Formirani nitriti u prethodnoj jednaĉini oksiduju se do nitrata pomoću enzima nitrit-oksidoreduktaza prema reakciji:

Sumirajući prethodne reakcije proces nitrifikacije predstavlja se poznatom jednaĉinom:

Nitrifikacione bakterije se razvijaju na pH=6,0–8,6 sa optimumom sredine 7,5–8,0. Pri vrijednostima niţim od pH=6 i višim od pH=9,2 bakterije se ne razvijaju, odnosno stopa rasta nitrificirajućih bakterija se smanjuje za 50% [8]. Optimalna temperatura za razvoj nitrifikatora je T=25–30ºC [8-9].

Nitrifikacija se, u okviru prerade sirove vode u vodu za piće, odvija na filterima sa imobilisanom mikroflorom. Granulovani medijum koji podrţava bakteriološko priĉvršćivanje je pijesak i/ili granulovani ugalj.

Efikasan rad filtera za uklanjanje amonijum jona zahtijeva sljedeće uslove:

dovoljan sadrţaj kiseonika,

prisustvo (ili dodatak) fosfora u cilju podrţavanja bakterijskog rasta,

odgovarajuću pH vrijednost ( >7,5),

dovoljno visoku temperaturu; ispod 8–10ºC bakterijski metabolizam naglo opada, oksidacija amonijum jona se znaĉajno usporava (pojava nitrita), a na temperaturi ispod 4–5ºC dolazi do potpune inhibicije, i

potpuno odsustvo dezinfekcionih reziduala.

Pored toga potrebno je omogućiti period od 1 – 3 mjeseca inokulacije filtera, kako bi proces bio što efikasniji uz konstantno prisustvo amonijum jona [9].

MATERIJAL I METODE RADA

Istraţivanja su provedena na poluindustrijskom postrojenju („Pilot―) u a.d. „Vodovod― Banja Luka projektovanom za ispitivanje i optimizaciju procesa pripreme vode za piće iz površinske vode (rijeka Vrbas).

Na slici 1. prikazana je šema poluindustrijskog postrojenja sa mjestima uzorkovanja.

Postupak uklanjanja amonijum jona je podrazumijevao koagulaciju, flokulaciju, sedimentaciju i filtraciju. Kao koagulant korišten je 10% rastvor Al2(SO4)3 doziran u optimalnim koliĉinama u zavisnosti od mutnoće ulazne vode, a za flokulaciju 0,025% rastvor polielektrolita A110, takoĊe doziran u optimalnoj koliĉini. Filtracija je vršena kroz jednomedijumski (kvarcni pijesak) i dvomedijumski filter (pijesak+antracit), a nakon njihovog zasićenja, filteri su prani iskljuĉivo vodom proizvedenom na poluindustrijskom postrojenju, kako rezidualni hlor u vodi iz glavnog postrojenja (0,3 mg/L), ne bi uništio formiranu mikrofloru na filterima.

Filteri su izvedeni kao kolone sa filtracionim slojem od kvarcnog pijeska (jednomedijumski filtar) i kombinacijom antracita i pijeska (dvomedijumski filtar), a karakteristike filtera date su u tabeli 1. Visina vodenog stuba iznad filtracionog sloja bila je 1,5 m. Zapremina filtracionog medijuma je 0,146 m3.


11

5b

FILTRACIJA

2

SEDIMENTACIJA

5a

OZONIZACIJA

Al2(SO4)3 Polielektrolit A110

1

NH4Cl (1,2 mgN/L)

Ko

nta

kt s

a A

UP

Ko

agu

laci

ja

Ko

nta

kt s

a P

M

Flo

kula

cija

Slika 1. Šema poluindustrijskog postrojenja sa mjestima uzorkovanja vode (1 - sirova voda; 2- nakon doziranja NH4Cl; 5a i 5b-nakon filtracije)

Figure 1. Scheme of pilot plant with water sampling points (1 - raw water ; 2- after the addition of NH4Cl; 5a,5b- after filtration)

Tabela 1. Karakteristike jednomedijumskog i dvomedijumskog filtera Table 1. Characteristics of one-medium and two-medium filters

Vrsta filtera

Filter type

5a 5b

Pijesak

Sand

Antracit

Anthracite

Pijesak

Sand

Visina filterske ispune (cm)

Filtering filling height (cm) 120 40 80

Granulacija (mm)

Granulation (mm) 0,7 - 1,2 1,6 - 2,5 0,7 - 1,2

Istraţivanje biološkog uklanjanja amonijum jona provedeno je u ljetnom, jesenjem i zimskom periodu uz kontinuirano doziranje rastvora NH4Cl (~1,2 mg NH4-N/L), pri hidrauliĉkom opterećenju sirove vode od 1,2 – 2 m3/h. Brzina filtracije varirala je u granicama 0,8 – 5,0 m/h u zavisnosti od ispitivane varijante.

Koncentracija amonijum jona odreĊena je kolorimetrijskom komparativnom metodom sa Nessler-ovim reagensom. Koncentracija nitritnog jona odreĊena je kolorimetrijskom komparativnom metodom sa sulfanilnom kiselinom, dok je koncentracija nitratnog jona odreĊena UV spektrofotometrijskom metodom primjenom UV–VIS.

REZULTATI I DISKUSIJA

U zavisnosti od protoka sirove vode i brzine filtracije, rezultati istraţivanja na poluindustrijskom istraţivaĉkom postrojenju predstavljeni su sljedećim fazama:

formiranje mikroflore,

nepotpuna nitrifikacija,

potpuna nitrifikacija,


12

Formiranje mikroflore

Ova faza ispitivanja provoĊena je konstantnim doziranjem amonijum jona u koliĉini od 1,2 mg NH4+-N/L pri protoku

sirove vode od 2 m3/h i brzini filtracije od 5 m/h. Navedeni uslovi voĊenja procesa odrţavani su mjesec dana. Za to vrijeme nije došlo do procesa nitrifikacije, odnosno do formiranja, za taj proces, potrebne mikroflore. Rastvoreni kiseonik u sirovoj vodi, kao i kiseonik nakon filtracije kretao se od 9,5 do 10,5 mg O2/L, temperatura ulazne vode od 17 do 18ºC, a pH vrijednost oko 8.

Nepotpuna nitrifikacija

Smanjivanjem protoka sirove vode na 1,2 m3/h i brzine filtracije na 3,3 m/h dolazi do nepotpune nitrifikacije. Nepotpunost nitrifikacije ogleda se u nepotpunosti njene druge faze, tj. nitratifikacije, koja se manifestuje povećavanjem koncentracije nitrita u filtriranoj vodi. Pješĉani filter je nešto ranije otpoĉeo sa procesom nepotpune nitrifikacije, što se manifestuje povećanjem koncentracija nitrita iza ovog filtera (slika 2).

(a) (b)

Slika 2. Rad filtera prvog(a) i drugog (b) dana procesa nitrifikacije Figure 2. The work of filters on the first (a) and second (b) day of the process of nitrification

Procenat uklanjanja amonijum jona veći je na pješĉanom filteru i iznosi prvog dana 80%, drugog dana 99%, dok su ovi procenti na dvomedijumskom filteru, 70% i 83% respektivno. Trećeg dana nitrifikacije (slika 3.) oba filtera rade ujednaĉeno, a procenat uklanjanja amonijum jona je isti na oba filtera i iznosi oko 97,9%.

Slika 3. Rad filtera trećeg dana procesa nitrifikacije Figure 3. The work of filters on the third day of the process of nitrification

Male razlike u ponašanju filtera na poĉetku procesa nitrifikacije vjerovatno su uslovljene razliĉitom specifiĉnom površinom granulovanog medijuma na koji se priĉvršćuju nitrifikacione bakterije.

Prema istraţivanjima sprovedenim u Kanadi o vertikalnoj distribuciji nitrifikacionih bakterija na filterima sa aktivnim ugljem, ustanovljeno je da nitrifikaciona biomasa perzistira u gornjim slojevima filtera, tako da se kompletna nitrifikacija odvija u prvih 25 cm filtera [10]. Na osnovu toga moţe se ustanoviti da se dvomedijumski filter (antracit+pijesak), tokom procesa nitrifikacije, ponaša kao jednomedijumski antracitni filter, s obzirom da je visina filterske ispune antracita 40 cm.


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Najniţa izmjerena temperatura sirove vode tokom procesa nepotpune nitrifikacije je 10,8ºC, a najviša 18,0ºC, što nije u granicama optimalnog temperaturnog intervala (25–30ºC), ali je prema mnogim autorima dovoljna za potpunu nitrifikaciju, koja se moţe ostvariti i na temperaturama od 10–15ºC [11-12].

pH-vrijednost sirove vode varirala je izmeĊu 8,14–8,37 što je u optimalnim granicama za izvoĊenje procesa nitrifikacije u vodi za piće i prema literaturnim podacima iznosi 7,2–8,5.

Za potpunu oksidaciju 1 mg NH4+-N potrebno je 4,27–4,57 mg O2 prema [10]. U nedostatku kiseonika dolazi do

inhibicije nitratifikacije, odnosno nakupljanja nitrita, jer je proces nitratifikacije osjetljiviji na nedostatak kiseonika od procesa nitritifikacije [13-14]. MeĊutim, za ovaj eksperiment ovakva razmatranja nisu primjenjiva jer je sadrţaj kiseonika u vodi i nakon filtracije bio ĉak veći od potrebnog, što se moţe vidjeti na slici 4.

Slika 4. Odnos maksimalne rastvorljivosti kiseonika i rastvorenog kiseonika u ispitivanim uzorcima tokom

nepotpune nitrifikacije Figure 4. The ratio of the maximum solubility of oxygen and dissolved oxygen in the analyzed samples during the

incomplete nitrification

Uklanjanje amonijum jona, tokom ovog perioda, konstantno je na oba filtera, bez obzira na variranje ulaznih

koncentracija NH4Cl (0,6–1,3 mg NH4+-N/L). Za formiranje nitrifikacionih bakterija potrebno je duţe vrijeme, ali kad se

formiraju, manje su osjetljive na promjenu ulazne koncentracije amonijum jona, što je u skladu sa saznanjima drugih autora [15]. Na slici 5, prikazana je redukcija amonijum jona promjenom ulazne koncentracije NH4Cl. Procenat uklanjanja amonijum jona je dosta visok na oba filtera i kreće se od 97,2–98,8%.

Slika 5. Redukcija amonijum jona na 5a uz promjenu ulazne koncentracije NH4Cl Figure 5. The reduction of ammonium ions on 5a with a change in the input concentration of NH4Cl

Bez obriza na tako dug vremenski period (oko dva mjeseca) odrţavanja pomenutih uslova eksperimenta (protok sirove vode 1,2 m3/h i brzine filtracije 3,3 m/h), nije došlo do procesa potpune nitrifikacije, iako spora pješĉana biofiltracija ima veću brzinu filtracije (1–4 m/h) [16]. Nasuprot tome, hidrauliĉko vrijeme zadrţavanja u biofilteru kreće se izmeĊu 0,7–1,5 h [17]. Hidrauliĉko vrijeme zadrţavanja vode u filterima u predstavljenom eksperimentu, s obzirom na visinu filtracionog medijuma od 120 cm i brzinu filtracije od 3,3 m/h, iznosi 0,36h, što je suviše kratko za realizaciju procesa potpune nitrifikacije.


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Potpuna nitrifikacija

Smanjivanjem brzine filtracije na 0,8 m/h, a time i povećanja hidrauliĉkog vremena zadrţavanja vode na filterima od 0,36 h na 1,5 h dolazi do potpune nitrifikacije na oba filtera (pijesak; pijesak + antracit), što je u skladu sa [17].

Grafiĉki prikaz prvog i zadnjeg dana praćenja potpune nitrifikacije prikazan je na slici 6.

(a) (b)

Slika 6. Prvi (a) i zadnji (b) dan potpune nitrifikacije Figure 6. The first (a) and the last (b) day of complete nitrification

Sa slike je vidljivo da je gotovo cjelokupna koliĉina amonijum jona procesom potpune nitrifikacije prevedena u nitratni jon. Varijacije u koncentraciji nitratnog jona uslovljene su promjenom inicijalne koncentracije amonijaĉnog jona (1,10 – 1,50 mg NH4

+-N/L).

Sadrţaj kiseonika u filtriranoj vodi se znatno smanjuje u odnosu na sirovu vodu, što je i oĉekivano (slika 7). Taĉnije, najmanja izmjerena vrijednost rastvorenog kiseonika nakon filtracije, neposredno nakon smanjivanja brzine filtracije, iznosila je 4,37 mg O2/L, a potom je ona u porastu i kretala se u prosjeku oko 5,50 mg O2/L.

Slika 7. Odnos maksimalne rastvorljivosti kiseonika i rastvorenog kiseonika u ispitivanim uzorcima tokom potpune nitrifikacije

Figure 7. The ratio of the maximum solubility of oxygen and dissolved oxygen in the analyzed samples during the complete nitrification

Potpuna nitrifikacija pri navedenim uslovima voĊenja procesa izvedena je i pri temperaturi sirove vode od 8,8ºC (to je i najniţa izmjerena vrijednost temperature sirove vode pri kojoj dolazi do potpune nitrifikacije), iako je temperatura filtrirane vode za stepen viša i iznosi 9,9ºC [18].

Sumirajući naprijed navedene rezultate istraţivanja, mogu se postaviti sljedeće zavisnosti prosjeĉnih koncentracija amonijum, nitritnog i nitratnog jona od brzine filtracije, koje su prikazane na slici 8.


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a) b)

c)

Slika 8. Prosjeĉne vrijednosti amonijum (a), nitritnog (b) i nitratnog (c) jona u zavisnosti od brzine filtracije Figure 8. Average values of ammonium (a), nitrite (b) and nitrate (c) ions depending on the filtration rate

ZAKLJUĈAK

Provedena ispitivanja su pokazala, da se konvencionalnim postupcima obrade vode, amonijum jon moţe ukloniti biološkom filtracijom, preciznije procesima nitrifikacije. Za odvijanje ovih proseca veoma je vaţna brzina filtracije:

– Naime, pri brzini filtracije od 3,3 m/h nije postignuta potpuna nitrifikacija, unatoĉ ĉinjenici da su svi uslovi za izvoĊenje ovog procesa bili u optimalnim granicama ( pH = 8,14 – 8,37; t°C = 10,8 – 18,0; mg O2/L = 8,8 – 11,2).

Nepotpunost nitrifikacije ogleda se u nepotpunosti procesa nitratifikacije. Dokaz za to je porast koncentracije nitrita u filtriranoj vodi, dok je proces nitritifikacije konstantan na oba filtera (pijesak; pijesak+antracit), bez obzira na variranje inicijalne koncentracije amonijum jona (0,6 – 1,3 mg NH4-N/L). Pri pomenutoj brzini filtracije koncentracija amonijum jona nakon filtracije iznosi oko 0,024 mg NH3/L, i ne prelazi MDK propisanu za vodu za piće (0,1 mg NH3/L). Nasuprot tome, koncentracija nitrita ( 0,99 – 1,60 mg NO2/L), zbog nepotpunosti nitratifikacije, znatno prelazi MDK propisane za vodu za piće ().

– Pri brzini filtracije od 0,8 m/h postiţe se gotovo potpuna nitrifikacija. Koncentracije amonijum jona (oko 0,024 - MDK=0,1 mg NH3/L ) i nitrita (oko 0,003 mg NO2/L - MDK = 0,03 mg NO2/L) tokom procesa potpune nitrifikacije su veoma niske, i nalaze se u dopuštenim granicama. Provedena ispitivanja su pokazala da ukupni sadrţaj nitrata u sirovoj vodi, ali i nitrata nastalih tokom procesa nitrifikacije (4,78 - 11,38 mg NO3/L), ne prelazi MDK propisane za

vodu za piće (50 mg NO3 /L).

– Efikasnost rada oba filtera (pijesak; pijesak+antracit) u toku procesa nitrifikacije je skoro identiĉna. Male razlike u njihovom ponašanju registrovanom na poĉetku procesa nitrifikacije mogu biti izazvane razliĉitim granulometrijskim sastavom filtarske ispune, odnosno neujednaĉenošću aktivne specifiĉne površine na kojoj se razvijaju nitrifikacione bakterije.

LITERATURA

1. Pravilnik o higijenskoj ispravnosti vode za piće. Sluţbeni Glasnik Republike Srpske 40/2003. 2. Yang J., G.W.Harrington, D.R.Noguera, K.K.Fleming, Risk analysis of nitrification occurrence in pilot-scale

chloraminated distribution systems, J. Water Supply: Res. and Technol.-Aqua, 56 (5) (2007).


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3. Yang J., G.W.Harrington, D.R.Noguera, Nitrification Modeling in Pilot-Scale Chloraminated Drinking Water Distribution Systems, J. Environ. Eng. 134 (9) (2008) 731-742.

4. Qi Y., C.Shang, I.M.C.Lo, Formation of haloacetic acids during monochlo-ramination, Water Res. 38 (2004) 2375-2383.

5. Charrois J.W.A., J.M.Boyd, K.L.Froose, S.E.Hrudey, Occurrence of N-nitrosamines in Alberta public drinking-water distribution systems, J. Environ. Eng. Sci. 6 (2007) 103-114.

6. Lipponen M.T.T, P.J.Martikainen, R.E.Vasara, K.Servomaa, O.Zacheus, M.H.Kontro, Occurrence of nitrifiers and diversity of ammonia-oxidizing bacteria in developing drinking water biofilms, Water Res. 38 (2004):4424–4434.

7. Peng Y., G.Zhu, Biological nitrogen removal with nitrification and denitrifikation via nitrite partway, Appl. Microbiol. Biotechnol. – Mini review, 73 (2006) 15-26.

8. Bhaskar K.V, P.B.B.N.Charyulu, Effect of environmental factors on nitrifying bacteria izolated from the rhizosphere of Setaria italica (L.) Beauv, African J. Biotechnol. 4 (10) (2005) 1145-1146.

9. Dalmacija B., J.Agbaba, M.Klašnja: Savremene metode u pripremi vode za piće, PMF – Departman za hemiju, Univerzitet u Novom Sadu, Novi Sad (2009).

10. Kihn A., P. Laurent, P. Servais, Measurement of potential activity of fixed nitrifyng bacteria in biological filters used drinkind water production, J. Industr. Microbiol. Biotechnol. 24 (2000) 161-166.

11. Zhang Y., N.Love, M.Edwards, Nitrifikation in Drinking Water Systems, Critical Reviews in Environ. Sci. and Technol., 39 (2009) 153-208.

12. Hwang J.H. & J.A.Oleszkiewicz, Effect of cold-temperature shock on nitrification, Water Environ. Res., 79 (9) (2007) 964-968.

13. Sliekers A.O., S.C.M.Haaijer, M.H.Stafsnes, J.G.Kuenen, M.S.M.Jetten, Competition and coexistence of aerobic ammonium and nitrite-oxidizing bacteria at low oxygen concentrations, Appl. Microbiol. Biotechnol. 68 (2005) 808-817.

14. Bernet N., P.Dangcong, J-P.Delgenès, R.Moletta, Nitrification at Low Oxygen Concentration in Biofilm Reactor, J. Environ. Eng., MARCH (2001) 226-271.

15. Hu Y-Y., L-L.Wang, Effect of media heights on the performance of biological aerated filter, J. Environ. Sci., 17(2) (2005) 281-284.

16. Kubare M., J.Haarhoff, Rational design of domestic biosand filters, J. Water Supply: Res. and Technol.-AQUA, 59 (1) (2010) 1-15.

17. Vigne E., J-M.Choubert, J-P.Canler, A.Heduit, K.H.Srrensen, P.Lessard, The role of loading rate, backwashing, water and air velocities in an up-flow nitrifying tertiary filter, Biores. Technol. 102 (2011) 904-912.

18. Drljaĉa D., Primjena fiziĉko-hemijskih postupaka kod uklanjanja lindana I amonijaka iz vode u sluĉaju akcidentnih zagaĊenja, Magistarski rad, Univerzitet u Banjoj Luci, Tehnološki fakultet, Banja Luka, 2011.

BIOLOGICAL REMOVAL OF AMMONIUM IONS FROM DRINKING

WATER

Dijana Drljaĉa1*, Boţo Dalmacija2, Ljiljana Vukić1, Slobodanka Zorić3 1 University of Banja Luka, Faculty of technology, Banja Luka, B&H

2 University of Novi Sad, Faculty of sciences, Novi Sad, The Republic of Serbia

3 a.d. „Vodovod‖ Banja Luka, B&H

Biological processes for ammonium ion removal from drinking water, such as bio-filtration, take up more and more attention, due to the fact that by application of these processes the toxic by-products of disinfection may be avoided, and also the problems that occur in the distribution system. The study was conducted at the pilot plant facility ("Pilot") in the a.d. "Vodovod" Banja Luka, designed for testing and optimization of the process of preparation of drinking water from surface water (the Vrbas river). Cycle Research of biological removal of ammonium ion on the filters was carried out in summer, autumn and winter period when the hydraulic load of raw water from ranges from 1,2 – 2,0 m3/h. Biological filtration at the pilot plant facility was followed on the one-mode and two-mode filters, with the change of filtration rate and the temperature of incoming water. At the filtration rate of 3,3 m/h, complete nitrification was not achieved. Incompleteness of nitrification is reflected in the incompleteness of its second phase - nitratification, while the nitritification process is constant on both filters (sand, sand + anthracite), for all the applied initial concentrations of ammonium ions (γ=0,6 – 1,3 mgNH4-N/L). In the filtration rate of 0,8 m/h, complete nitrification takes place, even at lowering temperature from 11,1° to 8,8°C.

Key words: pilot plant, drinking water, nitrification, filtration rate



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ANALIZA UTICAJA SASTAVA SIROVINE NA ENERGETSKU VRIJEDNOST DRVNOG PELETA NA PROSTORU BOSNE I

HERCEGOVINE

Tatjana Botić 1*, Dijana Drljaĉa 1, Aleksandra Šinik 1 1Univerzitet u Banjoj Luci, Tehnološki fakultet, Banja Luka, RS, BiH

ISSN 2232-755X UDC: 674.093.6

DOI: 10.7251/GHTE1612017B Originalni nauĉni rad

Šume i šumska zemljišta se prostiru na preko 50% ukupne površine Bosne i Hercegovine. Srazmjerno šumskom fondu razvijena je drvna industrija, posebno primarna prerada drveta, zbog ĉega BiH raspolaţe velikim koliĉinama, još uvijek nedovoljno iskorišćene, otpadne drvne biomase. U skladu sa postavljenim ciljem pribliţavanja zahtjevima EU podsticanja proizvodnje i korišćenja obnovljivih izvora energije, BiH moţe ostvariti velike poslovne aktivnosti vezane za preradu drvne biomase u drvni pelet. Cilj istraţivanja u ovom radu je bio ispitati uticaj hemijskog sastava i oblika sirovine najzastupljenijih vrsta drveća na prostoru BiH na kvalitet peleta od drvne biomase kao goriva.

Kljuĉne rijeĉi: šuma, kvalitet peleta, biomasa, pelet, obnovljiva energija

UVOD

Sveopšta zabrinutost zbog prevelike potrošnje fosilnih goriva, narušavanja postojeće prirodne ravnoteţe i problematike globalnog zagrijavanja planete, podstakla je mnoge zemlje da se u svojim energetskim strategijama okrenu domaćim energetskim resursima i pobudila veće interesovanje za iznalaţenje mogućnosti pretvaranja svih oblika biomase u goriva. Iskorišćavanje drvnog i poljoprivrednog otpada u svrhu proizvodnje energetskih peleta, u posljednjoj deceniji privuklo je veliku paţnju u inostranstvu, ali i na prostoru BiH. Prema procjenama MeĊunarodne agencije za energiju (IEA) uz povećanje energetske efikasnosti i postojeći trend porasta doprinosa obnovljivih izvora energije ukupnoj potrošnji energije, do 2040. godine potraţnja za naftom bi se smanjila za gotovo 40%. Najveći dio obnovljivih izvora energije (55,1%) potiĉe iz biogoriva i otpada. Pri tome ĉvrsta biogoriva, ukljuĉujući drvo, drveni otpad, ostali ĉvrsti otpad i drveni ugalj, ĉine najveći udio od 37,4% [1]. Drvo je sirovina koja se od davnina koristi kao energent i sirovina koja se preraĊuje razliĉitim mehaniĉkim i hemijskim postupcima. Pri tome nastaju razliĉiti oblici drvnog otpada kao što su: grane, sjeĉka, kora koja ĉini 15% mase stabla drveta, strugotina i piljevina, a pri hemijskoj preradi i lignin i smole. Analizom nastalih otpadaka dolazi se do podataka da u primarnoj preradi drveta nastaje 35-40% otpada od ukupne mase drveta, a u finalnoj preradi drveta taj udio se kreće oko 70% [2,3]. Trenutno, ova velika koliĉina drvnog otpada

najvećim dijelom ostaje neiskorišćena.

Uvaţavajući trenutni asortiman drvnih proizvoda u BiH, za proizvodnju energenata na bazi drveta identifikovane su sljedeće sirovine: prostorno drvo, otpaci pri sjeĉi, sitna granjevina, pilanski otpad od proizvodnje rezane graĊe, otpad od izrade furnira i namještaja, a njihov godišnji potencijal u BiH prikazan je na slici 1.

Slika 1. Godišnji energetski potencijal drvne biomase u B&H [4]

Figure 1. Annual energy potential of wood biomass

Iz ove jednostavne ilustracije vidljiv je smisao promovisanja i razvoja proizvodnje i korišćenja drvog peleta kao energenta i proizvoda kojim se moţe trgovati na prostoru BiH i u svijetu. Trenutno, najveći dio proizvedenih peleta u

* Korespondentni autor: Tatjana Botić, Tehnološki fakultet, Univerzitet u Banjaluci, Vojvode Stepe Stepanovića 73,

Banja Luka, RS, BiH, e-mail:[email protected]. Rad je izloţen na meĊunarodnom nauĉnom skupu XI Savjetovanje hemiĉara, tehnologa i ekologa Republike Srpske, novembar 2016.


T. Botić i sar.: ANALIZA UTICAJA SASTAVA SIROVINE NA ENERGETSKU VRIJEDNOST DRVNOG PELETA...

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BiH i regionu izvozi se na trţište razvijenih zemalja. Drvni pelet bi mogao da ima visoku energetsku vrijednost za energetski sektor BiH i mogao bi znaĉajno smanjiti upotrebu i zavisnost o fosilnim gorivima.

Peleti predstavljaju oblik prethodno pripremljene ĉvrste biomase koji se koriste u procesima sagorijevanja, kako u malim, savremenim pećima i kotlovima za grijanje domaćinstva, tako i u industrijskim kotlovima i energetskim postrojenjima za proizvodnju elektriĉne i toplotne energije. Pelet izraĊen od ostataka primarne ili sekundarne prerade drveta postali su vaţan obnovljiv izvor energije, a trţište peleta se naglo razvilo. Od svih oblika ĉvrste biomase drvni pelet je doţivio najveći porast u meĊunarodnoj trgovini [5]. Jedna od prednosti ovog ĉvrstog biogoriva jeste da se proizvodi od obnovljivih sirovina dostupni u izobilju po relativno niskoj cijeni. U poreĊenju sa drugim neobraĊenim oblicima ĉvrste biomase, osnovna prednost je u višestruko većoj gustoći biomase ĉime se povećava neto toplotna vrijednost po jedinici zapremine peleta, olakšava pakovanje, transport i skladištenje, i smanjuju ukupni troškovi rukovanja i prevoza. Peletiranjem se povećava gustoća biomase ĉak do tri puta, dobija gorivo homogenog sastava, gustine, kvaliteta i praktiĉnog oblika. U poreĊenju sa ĉvrstim fosilnim gorivima, peleti od biomase imaju znatno manji sadrţaj pepela i vlage, homogenog su oblika i veliĉine, imaju veliku energetsku gustinu i toplotnu vrijednost na nivou mrkog uglja [6,7].

Pored primijenjenih tehnologija za pripremu i preradu drvne biomase, izbor vrste drveta i oblika drvnog otpada predstavljaju najznaĉajnije faktore koji utiĉu na karakteristike peleta koji će se dobiti njihovom preradom. Za proizvodnju drvnih peleta koristi se otpadni drvni materijal veoma raznovrsnih fiziĉko-hemijskih karakteristika, zbog

ĉega ponekad dolazi do velike varijabilnosti u kvalitetu peleta. Razlike u strukturi i graĊi izmeĊu kore i jezgra ĉetinarskog i listopadnog drveta, izmeĊu tvrdog i mekog drveta, rezultuju razlikama u kvalitetu peleta.

Da bi se osigurao definisan i ujednaĉen kvalitet peleta na trţištu, olakšala trgovina i pruţila garancija trgovcima i krajnjim korisnicima u kvalitet peleta pojedine evropske zemlje, meĊu prvima Austrija (ÖNORM M 7135), Švedska (SS 187120) i Njemaĉka (DINplus), su usvojile nacionalne standarde kvaliteta za pelete od biomase koji se koriste i u drugim zemljama EU. Da bi se u cijeloj Evropi obezbjedio isti kvalitet drvnog peleta Evropski komitet za standarde (CEN/ TC335) je donio jedinstven standard oznaĉen kao EN 14961-2 [8].

Danas najvaţniji sertifikat kvaliteta za drvne pelete prihvaćen širom svijeta je novi evropski standard ENplus. Taĉnije, ovaj standard je kreirao njemaĉki institut za pelet (DEPI - Deutsches Pelletinstitut), a Evropsko vijeće za pelete (EPC - European Pellet Council) nakon uvoĊenja sistema sljedivosti i sertifikovanja ga je implementiralo u ENplus standard. Novi evropski standard za energetske pelete ENplus je definisao tri klase peleta. One su zasnovane na meĊunarodnom standardu ISO 17225-2, koji je zamijenio evropski standard EN 14961-2, i nazvane su: ENplus A1, ENplus A2 i ENplus B. U tabeli 1 dat je pregled graniĉnih vrijednosti najvaţnijih parametara kvaliteta drvnih peleta prema ENplus standardu.

Tabela 1. Graniĉne vrijednosti najvaţnijih parametara za pelete [9] Table 1. Threshold values of the most important pellet parameters

Karakteristika

Property

Jedinica

Junit EBplus-A1 EBplus-A2 Enplus-B

Standardna metoda

Testing standard

Preĉnik / Diameter mm 6 – 8 (± 1) ISO 17829

Duţina / Length mm 3,15 < L ≤ 40

Sadrţaj vlage / Moisture %m/m ≤ 10 ISO 18134

Pepeo / Ash %m/m ≤ 0,7 ≤ 1,5 ≤ 2,0 ISO 18122

Toplotna vrijednost

Heat Value MJ/kg ≥ 16,5 ISO 18125

Sadrţaj aditiva / Additives %m/m < 2 -

Sadrţaj hlora

Chlorine contetnt %m/m ≤ 0,02 ≤ 0,03 ISO 16994

Taĉka topljenja pepela

Ash Deformation Temperature °C ≥ 1200 ≥ 1100 CEN/TC 15370-1

Teški metali

Heavy metals %m/m definisan ISO 16968

A1: stablo drveta; hemijski ne tretirani ostaci drveta (tree trunk; chemically untreated wood residues) A2: cijela stabla bez korijena; stabljike drva; ostaci od sjeĉe drveta; kora; hemijski ne tretirani ostaci drveta (the whole trees without roots; stem wood; residues from harvesting of timber; bark; chemically untreated wood residues) B: Plantaţna šuma i drugo sirovo drvo; nusproizvodi i ostaci iz drvne industrije; korišćeno drvo. (Plantation woods and other raw wood; by-products and residues from the wood industry; used wood).


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Drvni peleti analizirani za potrebe ovog rada su industrijski proizvedeni u pogonu za peletiranje u Srpcu. Kao polazna sirovina za proizvodnju drvnog peleta korišćeni su razliĉiti oblici drvnih ostataka primarne prerade drveta, a to su: sjeĉka pilanskog ostatka bez kore, sjeĉka od okrajaka sa većim udjelom kore, piljevina i piljevina iz pilane bez kore, koji su sakupljeni širom BiH. Peleti se rijetko proizvode od jedne vrste drveta. Tako su i peleti koji su bili predmet ispitivanja proizvedeni miješanjem razliĉitih vrsta crnogoriĉnog i bjelogoriĉnog drveta, i to: jele, smreke, bukve, hrasta i lipe, kao što je opisano u tabeli 2. Drvna masa je prethodno osušena na 10 – 12% relativne vlaţnosti i samljevena u mlinu ĉekićaru na granulaciju 3 – 5 mm. Za mjerenje fiziĉkih i hemijskih svojstava nasumiĉno su odabrani uzorci peleta iz svake serije i hermetiĉki zatvoreni u staklenu posudu.

Tabela 2. Sirovinski sastav drvnih peleta Table 2. The composition of wood pellets

Oblik drvne biomase

Biomass specific

Vrsta drveta

Type of wood

Oblik drvne biomase

Biomass specific

Vrsta drveta

Type of wood

P1 30% sjeĉka 70% piljevina

75% jela/smreka 25% bukva






70% jela/smreka 20% bukva 10% lipa


100% jela/smreka (bez kore)




100% jela/smreka P12 100% piljevina 50% bukva 50% hrast


100% jela/smreka P13 100% sjeĉka (okorci sa korom)

100% bukva


100% jela/smreka (bez kore)

P14 100% piljevina 100% jela/smreka

P7 100% sjeĉka 100% jela/smreka (bez kore)


100% bukva

P8 100% sjeĉka 100% jela/smreka (sa više kore)

P16 100% sjeĉka 100% bukva (sa više kore)

(Sjeĉka - chips ; piljevina - sawdust; jela - fir; smreka - spruce; bukva - beech; lipa - linden; hrast - oak; bez kore - without bark; sa korom - with bark; okorci sa korom - pieces of bark with bark; sa više kore - with more bark)

OdreĊivanje sadrţaja vlage u uzorcima peleta izvršeno je prema postupku opisanom u standardnoj metodi za odreĊivanje vlage u ĉvrstim biogorivima EN ISO 18134. Jedan gram peleta usitnjenog na veliĉinu ĉestica 0,2 mm sušen je u sušioniku na 105 ± 2°C u atmosferi vazduha dok se ne postigne konstantna masa. Gubitak mase uzorka izraţava se kao sadrţaj vlage u masenim procentima u odnosu na masu vlaţnog uzorka.

Sadrţaj pepela u uzorcima peleta odreĊen je mjerenjem mase ostatka nakon potpunog sagorijevanja usitnjenog uzorka peleta na temperaturi 550 ± 10°C, u strogo kontrolisanim uslovima u skladu sa procedurom opisanom u standardnoj metodi ISO 18122. Prethodno osušeni uzorak je ţaren jedan sat na 250°C, a zatim dva sata na 550°C.

Prije odreĊivanja sadrţaja lignina iz uzoraka drvnih peleta odstranjene su druge ekstraktivne materije (smole, masti,

terpeni i sl.) da bi se izbjeglo stvaranje kondenzacionih produkata sa ligninom tokom postupka izdvajanja. Izdvajanje smola i masti vršeno je u standardnoj aparaturi za ekstrakciju po Soxhlet-u. Metoda je pogodna za ekstrakciju masti iz ĉvrstih, organskih uzoraka koji se mogu ravnomjerno usitniti i kod kojih mast nije blokirana sastojcima koji sprjeĉavaju ekstrakciju. Ekstrakcija je vršena 6 ĉasova, a kao ekstrakciono sredstvo upotrijebljena je smjesa metanol-benzen (1:3). Za hidrolizu holoceluloza i izdvajanje lignina korišćena je 72%-tna sumporna kiselina u trajanju 150 minuta na temperaturi 25°C. Uzorak se zatim prelije sa vodom i zagrijava jedan sat na povratnom hladilu. Izdvojeni lignin se istaloţi, profiltrira, ispere vrelom vodom, suši i vaţe [10].

OdreĊivanje gornje toplotne vrijednosti peleta (Qg) uraĊeno je pomoću adijabatskog kalorimetra Parr, Model 6200. Za spaljivanje je korišćen ĉisti kiseonik (>99,95%) pod pritiskom 3,0±0,2 MPa prema EN 14918. Kalibracija kalorimetra vršena je pomoću benzojeve kiseline. Poznajući gornju toplotnu vrijednost i sadrţaj vlage moţe se izraĉunati donja toplotna vrijednost (Qd). Za sva ispitivanja uraĊena su najmanje tri mjerenja, a zatim izraĉunata srednja vrijednost.


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Toplotna vrijednost drvnog peleta je jedan od najbitnijih podataka analize koja odluĉuje o mogućnosti njegove upotrebe kao biogoriva. Parametri koji imaju znaĉajan uticaj na toplotnu vrijednost drvnih peleta su: vrsta drveta, oblik otpadne drvne sirovine, primijenjeni tehnološki postupak peletiranja i hemijski sastav drveta, prvenstveno sadrţaj vlage. Uticaj hemijskog sastava na toplotnu vrijednost peleta prikazan je dijagramima na slikama 2 – 5.

Na slici 2 je prikazana funkcionalna zavisnost toplotne vrijednosti od sadrţaja vlage. Izraĉunati koeficijent korelacije R potvrĊuje linearnu funkcionalnu zavisnost toplotne vrijednosti od sadrţaja vlage, odnosno toplotna vrijednost opada linearno sa porastom sadrţaja vlage.

Slika 2. Korelacija izmeĊu toplotne vrijednosti i sadrţaja vlage u drvnom peletu Figure 2. Correlation between calorific value and water content of wood pellets

Sadrţaj vlage kreće se u rasponu od 4,63 do 24,15 %m/m i kod tri uzorka peleta prekoraĉuje propisanu graniĉnu vrijednost (≤10 %m/m) što se odrazilo i na toplotnu vrijednost istih koja je ispod minimalno propisane vrijednosti 16,5 MJ/kg. Dio energije koji se otpušta tokom procesa sagorijevanja troši se na isparavanje vode te se iz tog razloga smatra gubitkom toplote. Za isparavanje vode troši se 2,44 MJ po kilogramu vode.

Osim što smanjuje toplotnu vrijednost, preveliki sadrţaj vlage utiĉe na neekonomiĉnost procesa sagorijevanja, što dovodi do pada vrijednosti energetskih peleta na trţištu. Pored toga, sadrţaj vlage ima veliki uticaj na stepen biološke aktivnosti (truljenja), na fiziĉka svojstva peleta i stabilnost peleta tokom duţeg skladištenja. Peleti izraĊeni sa većim sadrţajem vlaţnosti su krtiji, porozni, neujednaĉenih dimenzija, površina im nije glatka i lakše se osipaju [11].

Sadrţaj ekstraktivnih materija je vaţan parametar koji utiĉe na toplotnu vrijednost drvnih peleta. U tkivu drveta prisutne su varijacije u pogledu sadrţaja ekstraktivnih materija, u zavisnosti od starosti i dijela stabla sa kojeg je uzet uzorak. Prema literaturnim podacima toplotna vrijednost ekstraktivnih materija se kreće od 35,6 do 38,1 MJ/kg [12] tako da je visok sadrţaj ovih materija poţeljan jer povećava energetsku vrijednost drvnih peleta. U radu je ispitan uticaj sadrţaja lignina (predstavnika iz grupe fenolnih organskih ekstraktiva) i sadrţaj smola i masti (predstavnika iz grupe alifatskih jedinjenja) na toplotnu vrijednost drvnih peleta.

Iz literature je poznato da se meko (crnogoriĉno) i tvrdo (bjelogoriĉno) drvo meĊusobno razlikuju po sadrţaju i sastavu lignina. Crnogoriĉno drvo ima veće uĉešće lignina i on se, zavisno od vrste drveta, kreće 27-32 %m/m [13]. Varijacije u sadrţaju lignina dovode do varijacija u toplotnoj vrijednosti, ali porast sadrţaja lignina ne prati obavezno porast toplotne vrijednosti. Zbog visokog energetskog potencijala lignina, koji se zavisno od vrste drveta kreće izmeĊu 23,26 MJ/kg i 26,58 MJ/kg [14], oĉekivan je veći uticaj sirovinskog sastava na toplotnu vrijednost drvnih peleta.


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Slika 3. PoreĊenje toplotne vrijednosti i sadrţaja lignina peleta razliĉitog sirovinskog sastava Figure 3. Comparison of calorific value and lignin content of different types of wood biomass

Pretpostavka je da je vlaga imala veći uticaj na toplotnu vrijednost od tipa drveta. Zato je ispitan uticaj sadrţaja lignina i vlage na toplotnu vrijednost na uzorcima drvnih peleta proizvedenih od 100% crnogoriĉnog drveta. Iz dobijenih rezultata prikazanih na slici 4 moţe se uvidjeti da povećanje sadrţaja lignina od 26,33 do 29,15 %m/m nije znaĉajno uticalo na toplotnu vrijednost peleta. PotvrĊeno je da vlaga ima veći uticaj na toplotnu vrijednost, što je naroĉito uoĉljivo kod uzoraka P7 i P8 koji imaju najveći procenat lignina, ali i najveću vlaţnost, dok je toplotna vrijednost najniţa.

Postoje i druge dobre osobine lignina zbog kojih je poţeljna komponenta u drvnom peletu. Prema autorima Kaliyan i Morey, lignin doprinosi boljoj povezanosti usitnjenog drveta bez potrebe dodavanja vezujućih agensa kao što su: škrob, melasa, proteini, bentonit, modifikovana celuloza ili sporedni proizvodi industrije papira i celuloze. Na povišenoj temperaturi, iznad >140°C, lignin omekšava, postaje ljepljiv, jaĉe prijanja u strukturu drveta, što smanjuje troškove peletiranja i doprinosi većoj mehaniĉkoj ĉvrstoći peleta [15]. Visok sadrţaj lignina je naroĉito poţeljan ukoliko je pelet namijenjen za izvoz u zemlje EU u kojima je zabranjeno ili ograniĉeno dodavanje hemijskih ili bioloških veziva [16].

Slika 4. Zavisnost toplotne vrijednosti drvnog peleta od sadrţaja lignina Figure 4. Dependence of the calorific value of wood pellets on lignin content

Na osnovu rezultata prikazanih na slici 5 uoĉava se da je kod uzoraka peleta u ĉijem sastavu je veći udio crnogoriĉnog drveta izolovan veći procenat masti i smola. MeĊutim, ne moţe se uoĉiti opšta zavisnost izmeĊu toplotne vrijednosti peleta i koliĉine izolovanih masti i smola iz istih. Po strukturi crnogoriĉno drvo je mekše i jednostavnije anatomske graĊe sa većim sadrţajem smola, dok su bjelogoriĉne vrste tvrĊe sa većim sadrţajem tanina. Mekše drvo se lakše


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usitnjava što olakšava proces ekstrakcije. Zbog toga je i rastvorljivost u organskim rastvaraĉima veća kod ĉetinarskog drveta nego kod lišićara. Uprkos visokoj toplotnoj vrijednosti, preveliki sadrţaj masti i smola u peletu nije poţeljan jer su one podloţne procesima razgradnje putem autooksidacije što rezultuje gubitkom suve materije, spontanim zagrijavanjem koje u kombinaciji sa prisutnom drvnom prašinom moţe dovesti do poţara [17].

Slika 5. PoreĊenje toplotne vrijednosti i sadrţaja masti peleta razliĉitog sirovinskog sastava Figure 5. Comparison of calorific value and resin content of different types of wood biomass

Pepeo biogoriva predstavlja jednu od najvećih smetnji za voĊenje procesa sagorijevanja. Poznavanje sadrţaja i sastava pepela su vaţni parametri na osnovu kojih se moţe predvidjeti ponašanje drvnog peleta prilikom sagorijevanja. Pri sagorijevanju peleta sa visokim sadrţajem pepela mora se osigurati efikasno uklanjanje pepela. Pepeo se lijepi na površinama loţišta i dimnim kanalima i u sluĉaju niske taĉke topljenja prijanja za loţište obrazujući poroznu i ĉvrstu šljaku koja moţe dovesti do ozbiljnih oštećenja postrojenja za sagorijevanje. Osim problema adhezivnog efekta i sinterovanja pepela u postrojenju za sagorijevanje, pepeo je uglavnom jako alkalan sa pH≈12. Alkalni oksidi pepela imaju agresivno dejstvo na materijal od kojeg je napravljeno loţište. Prema literaturnim podacima, drvo i kora imaju relativno visoku taĉku topljenja pepela (1300 – 1400 °C), npr. za pepeo od smreke ona iznosi 1430°C što zadovoljava zahtjeve standarda ENplus (≥1200°C) [18,19]. Zavisnost koliĉine pepela od sastava materijala od kojeg je proizveden pelet je ispitana i prikazana dijagramom na slici 6.

Iz rezultata prikazanih na slici 6 vidljivo je da sadrţaj pepela raste sa porastom udjela sjeĉke u peletu. TakoĊe, primjetan je veći procenat pepela kod uzoraka sa većim uĉešćem kore. Sjeĉka je oblik drvne biomase koji nastaje usitnjavanjem krupnih i sitnih ostatka drveta iz šume, parkova i sl. ili kao otpad u drvnoj industriji, tako da prilikom sjeĉe, obrade i transporta moţe biti kontaminirana razliĉitim neorganskim primjesama, kao što su zemlja ili pijesak, koje povećavaju sadrţaj pepela. Za razliku od sjeĉke, piljevina nastaje u procesima mehaniĉke obrade otkorenog drveta u drvnoj industriji i mogućnost njene kontaminacije neorganskim primjesama je veoma mala.

Slika 6. Zavisnost sadrţaja pepela od oblika otpadne drvne sirovine Figure 6. Correlation between biomass specific and ash content of wood pellets


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Sadrţaj pepela samo ĉetiri ispitana uzorka drvnih peleta proizvedenih od drveta bez kore je u propisanim vrijednostima

(≤1,2%) ENplus A2 standarda. Dok, sedam uzoraka peleta sa većim uĉešćem kore ispunjava zahtjev standarda ENplus B (≤ 2,0%). Ĉetiri uzorka peleta sa većim uĉešćem kore ne zadovoljava ni jednu klasu ENplus standarda. Veći sadrţaj pepela u kori drveta (2-5%) uzrokuje povećani sadrţaj pepela u peletu od kore drveta. Ovo ukazuje da uzorci peleta pripremljeni od drveta bez kore ispunjavaju minimalne uslove standarda ENplus A1 ili A2, dok peleti sa uĉešćem kore u najboljem sluĉaju mogu zadovoljiti zahtjev kvaliteta peleta za klasu ENplus B. Visoka vrijednost pepela, kao što je 3,49 i 4,27%, moţe se objasniti samo prisustvom mineralnih neĉistoća.

ZAKLJUĈAK

Kao sirovina za proizvodnju drvnih energetskih peleta u B&H najviše se koristi drvni otpad od drveta jele, smreke, bukve i hrasta, a koji potiĉe od sjeĉe drveta u šumi ili iz pilana.

Svi drveni peleti imaju pribliţno istu gornju toplotnu vrijednost, ali donja toplotna vrijednost varira u odnosu na sadrţaj vode. Postoji izraţena zavisnost toplotne vrijednosti od sadrţaja vlage u peletu, dok vrsta drveta i oblik otpadne drvne mase imaju mnogo manji uticaj na toplotnu vrijednost. Najveća toplotna vrijednost je izmjerena kod peleta P6 proizveden od pilanske sjeĉke i piljevine bez kore jele/smreke, a najniţa kod peleta P8 , koji ujedno ima i najveću

vlaţnost, a proizveden je od šumske sjeĉke jele/smreke sa većim udjelom kore.

Sadrţaj lignina se kretao u širokim granicama od 6,35% do 44,83%, meĊutim, nije dobijena opšta zavisnost izmeĊu njegovog sadrţaja i toplotne vrijednosti peleta. Ĉinjenica je da masti i smole imaju visoku toplotnu vrijednost, ali su prisutne u malim koliĉinama, od 1,55% do 8,19%, i nemaju veliki uticaj na toplotnu vrijednost peleta.

PoreĊenjem dobijenih rezultata analize kljuĉnih parametara kvaliteta kao što su: sadrţaj vlage, pepela i donja toplotna vrijednost, te graniĉnih vrijednosti definisanih ENplus standardom za drvne pelete dolazi se do zakljuĉka da svi ispitani uzorci ne zadovoljavaju standardom propisane vrijednosti. Samo dva uzorka peleta, P1 i P6, ispunjavaju zahtjeve za klasu A2, osam uzoraka ispunjava zahtjeve za klasu B, dok šest uzoraka ne ispunjava jedan od zahtjeva standarda.

Najveće odstupanje od zahtjeva standarda je zabiljeţeno kod pepela. Tri uzorka peleta, koji su proizvedeni od otpadne drvne sirovine sa velikim uĉešćem kore, imali su jako visoku vrijednost pepela koja ne zadovoljava nijednu klasu ENplus standarda. To se moţe objasniti samo prisustvom mineralnih neĉistoća koje sa sobom donosi kora.

Za uspješnu primjenu drvnih peleta od izuzetnog je znaĉaja standardizacija kvaliteta i pridrţavanje usvojenih standarda u proizvodnji. Standarde kvaliteta moguće je provjeriti na osnovu metoda za ispitivanje definisanih parametara kvaliteta. Neophodno je što prije donijeti domaće standarde i metode ispitivanja za definisanje kvaliteta drvnih peleta.

LITERATURA

1. Shen, Y., Wang, J., Ge, X., Chen, M.: By-products recycling for syngas cleanup in biomass pyrolysis – An overview, Renewable and Sustainable Energy Reviews, 59 (2016), 1246-1268.

2. Nikolić, S.: Bio-masa kao znaĉajna komponenta u rješavanju globalne energetske krize, Sagorijevanje biomase u energetske svrhe, Zbornik radova, JDT, Nauĉna knjiga, Beograd, 1992, str. 45-61.

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6. Mahapatra K., Harris D. L., Durham D. L., Lucas S., Terrill T. H., Kouakou B., Kannan G.: Effects of moisture change on the physical and thermal properties of sericea lespedeza pellets, International Agricultural Engineering Journal, 19(3) (2010), 23-29.

7. Manić, N.: Optimizacija i modeliranje sagorijevanja peleta od biomase u pećima za domaćinstvo, Doktorska disertacija, Univerzitet u Beogradu, Mašinski fakultet, Beograd, 2011.

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12. Popović, J.: Efekti nekih predtretmana na hemijski sastav juvenilnog i zrelog drveta poljskog jasena (Fraxinus angustifolia Vahl. ssp. Pannonica Soó & Simon) i mogućnost primene tako modifikovanog drveta, Doktorska disertacija, Univetzitet u Beogradu, Šumarski fakultete, Beograd, 2015.

13. Đikanović Golubović D.: Strukturna ispitivanja ćelijskog zida i lignina razliĉitog porekla, Doktorska disertacija, Univerzitet u Beogradu, Fakultet za Fiziĉku hemiju, Beograd, 2013.

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ANALYSIS OF THE INFLUENCE OF RAW MATERIALS COMPOSITION ON THE ENERGY VALUE OF WOOD PELLETS ON THE TERRITORY

OF B&H

Tatjana Botić1*, Dijana Drljaĉa1, Aleksandra Šinik1

1Faculty of Technology University of Banja Luka, [email protected]

Forest and forest lands spread on over 50% of the total area of Bosnia and Herzegovina. Forest industry was developed in proportion to the forest fund, especially primary wood processing. Because of that there are large amounts of waste wood biomass, still underutilized. In accordance with set goals of approaching EU requirements, incentives for production and use of renewable energy sources, B&H can achieve big business activities related to processing wood biomass. The aim of the research in this work was to examine the impact of the chemical composition and the shape of the raw material of the most common wood types in the area of B&H on the quality of wood biomass pellets as a fuel. The impact of moisture resins and fats content, lignin, and also the impact of the shape of raw material, on calorific value of pellets are tested. Wood pellets analyzed for this study are industrially produced in the plant for pelletization in Srbac. As a starting material for the production of wood pellets, various forms of wood waste remains of primary wood processing were used. Those are: chips from sawmill residues without bark, chips with higher percentage of bark, sawdust and chips from sawmill without bark, which were collected across Bosnia and Herzegovina. By analysing key quality parameters, such as moisture content, ash content and lower heating value, and threshold values defined by ENplus standard for wood pellets, it was concluded that all tested samples do not meet the prescribed standards. For the successful use of wood pellets it is very important to standardize quality and adherence to adapted standards in production.

Key words: wood, pellet quality, biomass pellets, renewable energy



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FUNKCIONALNE OSOBINE HLEBA OBOGAĆENOG MODIFIKOVANIM VLAKNIMA

Jelena Filipović1, Vladimir Filipović2, Milenko Košutić1 2Univerzitet u Novom Sadu, Nauĉni institute za prehrambene tehnologije, Novi Sad, Srbija

2Univerzitet u Novom Sadu, Tehnološki fakultet, Novi Sad, Srbija

ISSN 2232-755X UDC: 664.66.016/.019 DOI: 10.7251/GHTE1612025F Originalni nauĉni rad

U razvijenijim zemljama hleb sa visokim sadrţajem prehrambenih vlakana se nalazi na trţištu i sve je veće interesovanje proizvoĊaĉa za plasiranjem ovakvih proizvoda. Svakim danom povećava se i broj potrošaĉa zainteresovanih za konzumiranje hleba obogaćenog vlaknima. Za izradu hleba sa povećanim i visokim sadrţajem vlakana, korišćena su hemijski modifikovana prehrambena vlakna iz ekstrahovanih rezanaca šećerne repe, usitnjena i frakcionisana. Uticaj vlakana na tehnološke parametre proizvodnje hleba praćen je promenom reoloških i pecivnih osobina testa. Razliĉit udeo vlakana (0%, 5%, 10% i 15%) dodavan je u osnovne sirovine za izradu testa kao zamena za deo brašna i zapaţeno je da vlakna u testu negativno utiĉu na formiranje glutenskog matriksa, tako da je bilo neophodno dodavati vitalni gluten za ojaĉavanje glutenske strukture. Pri istoj koliĉini vode dodate za zames testa, kao i u testu bez dodataka, modifikovana vlakna utiĉu na povećanje parametara: konzistencije testa u 5. minutu, maksimalne konzistencije i vremena potrebnog za postizanje maksimalne konzistencije. Pravilnom korekcijom sirovinskog sastava i tehnoloških parametara proizvodnje, moţe se dobiti hleb sa 10 i 15% modifikovanih vlakana iz šećerne repe koja ne sadrţe fitinsku kiselinu, po senzornim osobinama sliĉan je belom hlebu na koga su potrošaĉi navikli. Hleb sa vlaknima, ima promenjen nutritivni sastav i smanjenu energetsku vrednost, odnosno ima sve osobine funkcionalnog proizvoda.

Kljuĉne rijeĉi: modifikovana vlakna, reologija testa, kvalitet hleba, nutritivna vrednost, energetska vrednost

UVOD

Sagledavajući nedostatke u ishrani ljudi u visokorazvijenim zemljama, već duţe vreme nutricionisti istiĉu vaţnost prehrambenih vlakana u postizanju, odrţavanju i poboljšanju zdravlja ljudi. Uticaj ishrane na zdravlje i prevenciju bolesti mora se uskladiti sa ţeljama i individualnim potrebama potrošaĉa, jer se samo na taj naĉin moţe ostvariti najbolje delovanje prehrambenih vlakana [1].

Funkcionalna hrana će biti pre prihvaćena ako su potrošaĉi spremni da pravilnim naĉinom ishrane preuzmu odgovornost za odrţavanje zdravlja, a pogotovo ako pozitivni zdravstveni efekti konzumiranja takve hrane ne zahtevaju promenu naĉina ţivota. Najvaţnije je da nov proizvod ima dobar ukus i da je veoma sliĉan proizvodima na koje su potrošaĉi navikli, odnosno proizvodima koje treba da zameni. Potrošaĉi će bolje prihvatiti onu vrstu hrane ĉijim konzumiranjem će moći brţe da zapaze pozitivno delovanje kao što je: hrana sa sniţenim sadrţajem energije i hrana koja se brzo vari, a teţe prihvataju onu hranu ĉijim konzumiranjem će se ostvariti pozitivni efekti tek u trećem dobu [1, 2].

Savremeni stav nutricionista je da proizvodi od ţita treba u najvećoj koliĉini da su zastupljeni u dnevnom obroku [3]. Hleb se smatra vrlo vaţnom nutritivnom namirnicom jer je izvor ugljenih hidrata, proteina, vitamina, mikronutritienata i antioksidanasa [4]. Ukoliko je potrebno ishranu obogatiti prehrambenim vlaknima pekarski proizvodi su veoma pogodne namirnice, jer su svakodnevno prisutne u dnevnim obrocima. U razvijenijim zemljama hleb sa visokim sadrţajem prehrambenih vlakana se nalazi na trţištu i sve je veće interesovanje proizvoĊaĉa za plasiranjem ovakvih proizvoda. Na trţištu još uvek nema dovoljno komercijalnih preparata vlakana koji zadovoljavaju sve potrebe proizvoĊaĉa pekarskih proizvoda i ukus potrošaĉa [5-8].

Cilj ovog rada je da se ispita uticaj dodatka modifikovanih vlakana na reološke osobine testa i tehnološki kvalitet hleba, odnosno da se hleb obogati sa što većim udelom modifikovanih prehrambenih vlakana iz šećerne repe, koji ne sadrţe fitinsku kiselinu, a sve radi poboljšanja funkcionalnih i nutritivnih osobina hleba, uz oĉuvanje originalnih senzornih osobina hleba.


U eksperimentalnom radu korišćene su sledeće sirovine: suvi ekstrahovani rezanci šećerne repe iz fabrike šećera "Šajkaška" u Ţablju, i komercijalni proizvodi: brašno T 500 A.D. ‖Danubius‖ iz Novog Sada (sadrţaj pepela max. 0,55%, moć upijanja vode 63,5%), pekarski kvasac (proizvoĊaĉ ‖Alltech-Fermin‖ Senta), suvi vitalni gluten, proizvoĊaĉ (A.D. ‖Fidelinka‖ Subotica, sadrţaj proteina min. 77%), kuhinjska so - komercijalni proizvod.

Korespondentni autor: Jelena Filipović, Univerzitet u Novom Sadu, Nauĉni Institut za prehrambene tehnologije,

Bulevar cara Lazara 1, Novi Sad, Srbija, e-mail: [email protected]


J. Filipović i sar.: FUNKCIONALNE OSOBINE HLEBA OBOGAĆENOG MODIFIKOVANIM VLAKNIMA

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Vlakna izmenjene strukture su hemijski modifikovana tako što su suvi ekstrahovani rezanci hidratisani stajanjem u vodi 24 h na sobnoj temperaturi, pri ĉemu je odnos mase vlakana i voda 1:9. Ovako pripremljena vlakna su nakon hidratacije tretirana rastvorom vodonik peroksida tako da koncentracija bude 10 g H2O2 po 1 litru, zatim je dodat 10 M rastvor natrijum hidroksida a pH je pH-metrom podešen na 11. Tretman rezanaca je trajao 12 h uz povremeno mešanje, zatim su neutralisana rastvorom hlorovodoniĉne kiseline do pH=6-7 isprana vodovodskom i destilovanom vodom do uklanjanja hloridnih jona. Voda iz vlakana je uklonjena presovanjem na laboratorijskoj presi, a zatim sušenjem u konvektivnoj sušnici. Vlakna dobijena iz ekstrahovanih rezanaca i zatim hemijski modifikovana, u laboratorijskim uslovima su grubo usitnjena, a zatim fino samlevena na mlinu sa piruetom (tip WZ – 1 "Spolem", proizvoĊaĉ ZBPP, Bydgoszoz, Poljska). Za eksperiment su korišćena vlakna sa ĉesticama manjim od 150 µm prosejana na planskom situ (tip SZ-1, proizvoĊaĉ ZBPP, Bydgoszoz Poljska).

Reološke osobine testa su ispitane Brabenderovim farinografom sa 50 g-skom mesilicom [9]. Modifikovanim vlaknima šećerne repe je supstituisano od 0%, 5% i 10% brašna. Gluten je dodavan u koliĉini od 0%, 5% i 10% na ukupnu masu brašna i vlakana šećerne repe.

Kvalitet hleba je odreĊen po metodi mikro peĉenja [10]. Sastav hlebnog testa: brašno 100%, 95%, 90% i 85%; modifikovana vlakna šećerne repe 0%, 5%, 10% i 15%; kuhinjska so 2,0%, pekarski kvasac 2,5%, gluten 0%, 5%, 10% i 15% (raĉunato na masu brašna i vlakana). Kvalitet hleba je izraţen zapreminom hleba i vrednosnim brojem sredine koji se dobija kvantifikovanjem senzornih ocena za elastiĉnost sredine i finoću pora. Ocenu je radila grupa od 5

obuĉenih ocenjivaĉa. Maksimalna ocena je 7, a minimalna 0 [9].

Sadrţaj svarljivih i nesvarljivih ugljenih hidrata je odreĊen na osnovnu hemijskog sastava hleba. U sadrţaj svarljivih ugljenih hidrata ulazi sadrţaj skroba i redukujućih šećera, a nesvarljivi ugljeni hidarti hleba predstavljaju sadrţaj prehrambenih vlakana. Osnovni hemijski sastav (sadrţaj proteina, skroba, redukujućih šećera i lipida) odreĊen je po statandarnoj AOAC metodi [11], a sadrţaj prehrambenih vlakana po AOAC metodi [12].

Rezultati uticaja modifikovanih vlakana na reološke osobine testa, kvalitet hleba i nutritivne osobine su obraĊeni statistiĉkom analizom varijanse ANOVA, a znaĉajnost razlike je testirana Tukey–evim testom pomoću statistiĉkog programa StartSoft Statistica 10.


Pri dodatku prehrambenih vlakana u testo oteţano je formiranje glutenskog matriksa koji je osnovni nosilac strukture testa, jer molekuli vlakana ometaju lance proteina da doĊu u kontakt i da formiraju trodimenzionalnu strukturu glutena [13-15].

Tabela 1. Uticaj udela vlakana na farinografske pokazatelje testa

Table 1. The influence of fiber on farinograph date

koliĉina modifikovanih prehrambenih vlakana (% u brašnu)

modified fiber quantity (% of fluor or supplementation)

0 (%) 5 (%) 10 (%) 15(%)

koliĉina dodatog vitalnog glutena (% na masu brašna i vlakana)

quantity of added vital gluten (% on flour and fiber mass)

0 (%) 5 (%) 10 (%) 15 (%)

konzistencija testa u 5 minutu (Fj) dough consistency in 5 min mixing (Fj)

490±0,21a 820±0,13b 770±0,19c 750±0,23c

maksimalna konzistencija (Fj) peak consistency (Fj)

500±0,20a 830±0,25b 890±0,16c 930±0,21d

vreme potrebno za postizanje maksimalne konzistencije (min) peak time consistency (min)

2,50±0,05a 5,50±0,01b 12,00±0,10c 15±0,14d

stepen omekšanja (Fj) drop (Fj)

60±0,15a 130±0,16b 0±0c 0±0c

abc Razliĉita slova u eksponentu u istom redu tabele ukazuju na statistiĉki znaĉajnu razliku izmeĊu vrednosti, pri nivou znaĉajnosti od p<0,05 (na osnovu post-hoc Tukey-evog HSD testa)

abc Different letters in the superscript in the same row of the table indicate statistically significant difference between values at the level of significance of p<0.05 (based on post-hoc Tukey HSD test)

Kada se veća koliĉina modifikovanih vlakana ugraĊuje u testo, neophodano je pravilno obrazovanje glutenskog matriksa i kao ojaĉivaĉ glutenske strukture moţe se dodavati vitalni gluten [13, 16]. Uticaj udela vlakana u brašnu na reološke osobine testa praćen je na testu napravljenom od uzorka brašna koga karakteriše velika moć upijanja vode i proseĉan stepen omekšanja. Pri istoj dodatoj koliĉini vode u brašno od 63,5%, dodatkom vlakana u koliĉini od 5% do 15% dolazi do statistiĉki znaĉajnog povećanja maksimalne konzistencije testa, što ukazuje na osobine vlakana da


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produţeno vezuju vodu. Tokom zamesa testa gluten brţe hidratiše, a vlakna prvo površinski vezuju slobodnu vodu i naknadno hidratišu tako što oduzimaju vodu glutenu i menjaju mu reološke osobine. Ova pojava se na farinogramu sa 10% vlakana prepoznaje kao znaĉajno veća konzistencija testa (tabela 1), a što je u skladu sa ispitivanjima koja je obavio Cadden [17]. Nepovezani delovi farinografske krive pokazuju koliko su vlakna narušila glutensku strukturu (slika1.). Farinofram sa 15% vlakana je veoma sliĉan krivoj sa 10% vlakana, te stoga nije prikazan. Modifikovana vlakna se ugraĊuju u trodimenzionalnu glutensku strukturu testa i što je veći njihov udeo više se smanjuje mogućnost obrazovanja inter- i intramolekularnih veza izmeĊu glutenskih lanaca, što su neki autori objasnili efektom "razreĊenja" [18].

Dodatkom 5% i 10% vlakana u brašnu, statistiĉki znaĉajno se povećava maksimalna konzistencija testa kao i vreme potrebno za postizanje maksimalne konzistencije, te dodatak sirovina bogatih vlaknima zahteva produţenje faze mešenja da bi se omogućila potpuna hidratacija i da se poveţu glutenski lanci oko unetih vlakana, ili da gluten potpuno obavije ĉestice vlakana, (slika 2.) [19].

0 (%) vlakana 5 (%) vlakana 10 (%) vlakana

Slika 1. Farinografske krive sa razliĉitom koliĉinom vlakana u testu

Figure 1. Farinograms of the dough with different fiber quantity

Pri dodatku 5% vlakana u brašno, dolazi do statistiĉki znaĉajnog povećanja razvoja testa, maksimalne konzistencije testa i povećanog stepena omekšanja u odnosu na testo sa 0% vlakana, što je verovatno posledica manje sposobnosti vlakana da zadrţavaju vodu (tabela 1). Testo koje sadrţi 10% vlakana ima statistiĉki znaĉnajno veću maksimalnu konzistenciju testa od testa sa 5% i 0% vlakana. Konzistencija testa se povećava do kraja mešenja, što ukazuje na sposobnost produţene hidratacije vlakana. Ovakvo ponašanje vlakana navodi na pretpostavku da bi, pre dodatka, u

testo bila opravdana njihova prethodna hidratacija. Dodatkom 10% vlakana u brašno, vreme potrebno za postizanje maksimalne konzistencije je statistiĉki znaĉajno veće u odnosu na testo sa 0% vlakana, jer veći udeo vlakana u testu usporava i oteţava formiranje glutenske strukture. Testo sa 10% vlakana u brašnu ne omekšava u toku 15 minuta, jer vlakna sporo hidratišu (tabela 1).

Slika 2. Vlakna u glutenskom matriksu testa [19]

Figure 2. Fibers in dough gluten matrix

Dodatkom 5% modifikovanih vlakna statistiĉki se znaĉajno produţava završna fermentacija hlebnog testa (tabela 2), smanjuje se zapremina hleba, povećava se prinos testa i hleba i narušava se kvalitet sredine što je u skladu se tvrĊenjem, Nelson-a [18]. Slika 1 i 2, potvrĊuju da primenjena modifikovana vlakna i njihova koliĉina negativno utiĉu na homogenost glutenskog matriksa, a samim tim i na mogućnost zadrţavanja gasa unutar testane strukture. Hleb sa vlaknima je male zapremine i nerazvijene sredine, stoga se preporuĉuje dodavanje vitalnog glutena koji povećava udeo gradivnih komponenata testa i smanjuje negativne efekte vlakana na kvalitet gotovog proizvoda, što potvrĊuju i podaci iz ovih istraţivanja [6, 15, 20].


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Kao rezultat sposobnosti vlakana da vezuju vodu, uz dodatak glutena u zames, moguće je dodati veću koliĉinu vode u zames, te se stoga statistiĉki znaĉjano povećava prinos hleba. Kvalitet sredine hleba izraţen vrednosnim brojem (VBS) je najmanji kada se u hlebno testo ugraĊuje 5% vlakana, jer se narušava finoća struktura pora (tabela 2), a dodatak male koliĉine (5%) vitalnog glutena nije dovoljan da ublaţi negativan uticaj vlakana na kvalitet hleba. Dodatkom 5% modifikovanih vlakana statistiĉki je znĉajno niţi prinos zapremine i vrednosni broj sredine u odnosu na hleb sa 0%, 10% i 15% vlakana. Dodatkom 15% vlakana i 15% glutena (tabela 2) nema statistiĉki znaĉajne razlike u vrednosnom broju sredine hleba u poreĊenju sa 0% vlakana, odnosno kvalitet hleba sa 15% vlakana i 15% glutena je na nivou kvaliteta hleba sa 0% vlakana. Dodatak vitalnog glutena u koliĉini od 10% i 15% ojaĉava glutensku strukturu i eliminiše negativan uticaj vlakana na glutenski matriks brašna što se ogleda u visokim ocenama za kvalitet sredine hleba, (tabela 2.).

Tabela 2. Uticaj udela vlakana na farinografske pokazatelje testa Table 2. The influence of fiber on farinograph date

koliĉina modifikovanih prehrambenih vlakana (% u brašnu)

modified fiber quantity (% of flour supplementation )

0 (%) 5 (%) 10 (%) 15 (%)

koliĉina dodatog vitalnog glutena (% na masu brašna i vlakana)

quantity of added vital gluten (% on flour and fiber mass)

0 (%) 5 (%) 10 (%) 15 (%)

Bread quality

Završna fermentacija (min) Proof Time (min) 57±0,13a 68±0,21b 91±0,09c 95±0,14d

Prinos hleba (g) Yield of Bread (g) 137,6±0,56a 136,6±0,17a 149,6±0,74b 161,2±0,21c

Prinos zapremine (ml) Yield of Volume (ml) 332,4±0,54a 324,8±0,30b 343,3±0,41c 334±,0,29d

Vrednosni broj sredine Bread Crumb Quality 4,5±0,05a 3,9±0,14b 5,1±0,17c 4,8±0,09ac

Nutritivna vrednost hleba

Nutritive value of bread

Sadrţaj proteina (% s.m.) Protein content (% d.m.) 11,2±0,05a 13,7±0,18b 16,1±0,21c 18,3±0,11d

Sadrţaj masti (% s.m.) Lipid content (% d.m.) 0,7±0,2a 0,7±0,2a 0,7±0,2a 0,7±0,2a

Sadrţaj svarljivih ugljenih hidrata (% s.m.) Content of digestible carbohydrates (% d.m.)

77,3±0,59a 69,5±0,48b 63,3±0,36c 57,1±0,40d

Sadrţaj nesvarljivih ugljenih hidrata (% s.m.) Content of non-digestible carbohydrates (% d.m.)

0,2±0,02a 5,2±0,19b 10,1±0,54c 15,1±0,49d

Smanjenje svarljivih ugljenih hidrata (%) Decrease of digestible carbohydrates (%)

- 10,1±0,16a 18,1±0,12b 26,1±0,11c

Sadrţaj nesvarljivih ugljenih hidrata (g) u 250 g hleba Content of non-digestible carbohydrates (g) in 250 g of bread

0,1±0,01a 3,20,13b 6,2±0,41c 10,1±0,17d

Smanjenje energije hleba (%) Decreasing energy of bread (%) - 5,9±0,51a 10,1±0,73b 14,6±0,81c

abcd Razliĉita slova u eksponentu u istom redu tabele ukazuju na statistiĉki znaĉajnu razliku izmeĊu vrednosti, pri nivou znaĉajnosti od p<0,05 (na osnovu post-hoc Tukey-evog HSD testa) abcd Different letters in the superscript in the same row of the table indicate statistically significant difference between values at the level of significance of p<0.05 (based on post-hoc Tukey HSD test)


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Imajući u vidu da je hleb pogodna namirnica za korigovanje ishrane s obzirom da se svakodnevno konzumira u svim reţimima ishrane, od posebnog su znaĉaja informacije o njegovim nutitivnim karakteristikama [1, 4]. Iz tabele 2 se vidi da dodatkom vitalnog glutena zajedno sa vlaknima u hlebu se znaĉajno povećava sadrţaj proteina i nesvarljivih ugljenih hidrata što doprinosi novim funkcionalnim osobinama hleba. Hleb sa 10% i 15% vlakana se prema vaţećem Pravilniku o kvalitetu ţita, mlinskih i pekarskih proizvoda, testenina i brzo smrznutih testa [21] moţe deklarisati kao hleb obogaćen proteinima. S obzirom da su proteini pšeniĉnog glutena deficitarni u lizinu ova vrsta hleba u dnevnom obroku u kombinaciji sa proteinima ţivotinjskog porekla ili mahunarki doprinosi povećanju biološke vrednosti hrane. Znaĉajan udeo nesvarljivih ugljenih hidrata u hlebu prikaznom u tabeli 2, smanjuje energiju i povećava funkcionalnost proizvoda. Proseĉnom dnevnom potrošnjom hleba sa 15% vlakana od 250 g unosi se 10 g vlakana dnevno, tako da ova vrsta hleba moţe da ima pozitivne dugoroĉne efekte u prevenciji masovnih nezaraznih bolesti nastalih usled nepravilne ishrane u razvijenom društvu [8, 22]. Dodatkom glutena i modifikovanih vlakana ostvaruje se znaĉajn pad svarljivih ugljenih hidrata i energetske vrednosti proizvoda, pri ĉemu se dobija hleb koji ima funkcionalne osobine, a u skladu je sa navikama potrošaĉa, jer je nepromenjenog ukusa, mirisa, boje i kvaliteta sredine.

ZAKLJUĈAK

Na osnovu rezultata ispitivanja uticaja koliĉine modifikovanih vlakana na reološke osobine testa, kvaliteta i nutritivnih

osobina hleba moţe se zakljuĉiti da obradivost testa sa dodatkom vlakana zavisi od sposobnosti vlakana da se inkorporiraju u glutenski matriks. Dodatkom vlakana povećavaju se konzistencija testa, menjaju se reološke osobine i vreme potrebno za postizanje maksimalne konzistencije, smanjuju se zapremina i kvaliteta sredine hleba, te je neizbeţno ojaĉavanje strukture testa vitalnim glutenom. Dodatak razliĉitog udela vlakana uz ojaĉavanje glutenske strukture testa vitalnim glutenom dovodi do povećanja prinosa hleba i prinosa zapremine. Modifikovana vlakana u hlebnom testu u koliĉini od 15% ne smanjuju zapreminu, a kvalitet sredine hleba je sliĉan hlebu sa 0% vlakana. Dodatkom 10% i 15% glutena i iste koliĉine nesvarljivih vlakana dobija se hleb sa znaĉajim padom svarljivih ugljenih hidrata, obogaćen proteinima, tako da se dobija proizvod smanjene energetske vrednosti, a poboljšanog nutritivnog sastava sa osobinama funkcionalne hrane.

Zahvalnica

Rezultati prikazani u ovom istraţivanju su deo Nacionalnog projekta III 46005 i TR 31029, finansiranog od strane Ministarstva prosvete, nauke i tehnološkog razvoja Republike Srbije

LITERATURA

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food and feed, Eds. van der Kamp, J.W., Asp, N-G., Miller Jones, J, and Schaafsma, G., Wageningen academic Publisher, Wageningen, The Netherlands (2004) p. 74.

3. Novaković, B., i M. Mirosavljev: Higijena ishrane, Univerzitet u Novom Sadu, Medicinski fakultet, Novi Sad, (2002) pp. 54-59.

4. Rubel, I. A., E. E. Pe´rez, G. D. Manrique, D. B. Genovese: Fibre enrichment of wheat bread with Jerusalem artichoke inulin: Effect on dough rheology and bread quality. Foodstructure. 3 (2015) 21-29.

5. Filipović, N., G., KaluĊerski, M. Šarić: Priprema pšenice za proizvodnju hleba od celog zrna. Acta Periodica Technologica, 31 (2000) 273-280.

6. Filipović, N., J. Gyura, J. Filipović: Quality of bread enriched with dietary fiber proceedings, 1st International Symposium "Food in the 21st century", Proceedings, Subotica, 14-17 novembar, 2001, pp. 566 – 569.

7. Filipović, J., S. Popov, N. Filipović: Behavior of different fibers at bread dough freezing. Chemical Industry & Chemical Engineering Quartery, 14 (4) (2008) 257-259.

8. Filipović, J., L. Pezo, V. Filipović, G. Ludajić: Spelt pasta with inulin as a functional food. Acta Periodica Technologica, 6 (2015) 37-44.

9. KaluĊerski, G., N. Filipović: Metode ispitivanja kvaliteta ţita, brašna i gotovih proizvoda, Tehnološki fakultet, Zavod za tehnologiju ţita i brašna, Novi Sad, (1998) p. 264.

10. Filipović, N., J. Filipović, D. Šoronja Simović: Metoda mikropeĉenja hleba – mogućnosti, prednosti i nedostaci. Ĉasopis za procesnu tehniku i energetiku u poljoprivredi, 9 (1-2) (2005) 42-45.

11. AOAC, Official methods of analysis. 17ed. Washington Association of Official Analytical Chemists, 2000. 12. AOAC, Official Methods of Analysis of the Association of Official Analytical Chemists, Vol. II, 15th ed. Sec. 985.29.

The Association Arlington, VA, 1990. 13. Stauffer, C.E.: Dietary Fiber: Analisis, Physiology and Calorie Reduction, Chapt. 14 in Advances in Baking

Technology, Eds. Kamel, B. S., Stauffer C.E., Blackie Academic & Proffesional, London (1993) p. 105.


30

14. Marquart, L., N. G. Asp, D. P. Richardson: Whole grain health claims in United States, United Kingdom and Sweden, Chapt. 1 in Dietary Fibre bio-active carbohydrates for food and feed, Eds van der Kamp, J.W., Asp. N-G., Miller Jones J., Schaafsma G., Wageningen academic Publisher, Wageningen, The Netherlands (2004).

15. Yangilar F.: The Application of Dietary Fibre in Food Industry: Structural Features, Effects on Health and Definition, Obtaining and Analysis of Dietary Fibre: A Review, Journal of Food and Nutrition Research, 1 (3) (2013) 13-23.

16. Wisker, E., W. Feldheim, Y. Pomeranz, F. Meuser: Dietary Fiber in Cereals, Chapt 4 in Advances in Cereal Science and Technology, Vol VII, AACC, St. Paul Minn (1985) p. 85.

17. Cadden A. M.: Comparative effects of particle size reduction on physical structure and water binding properties of several plant fiber. Journal of Food Science, 52 (6) (1987) 1595-1599.

18. Nelson, A. High-Fiber Ingredients, Eagan Press, St. Paul Minn. (2001). 19. Filipović J.: Prehrambena vlakna iz šećerne repe za pekarsku industriju, Magistarski rad, Univerzitet u Nobom

Sadu, Tehnološki fakultet, Novi Sad, 2005. 20. Asp, N-G. (2004): Definition and analysis of dietary fibre in context of food carbohydrates, Chapt. 1 in Dietary

Fibre bio-active carbohydrates for food and feed, Eds van der Kamp, J.W., Asp. N-G., Miller Jones J., Schaafsma G., Wageningen academic Publisher, Wageningen, The Netherlands, (2004).

21. Pravilnik o kvalitetu ţita, mlinskih i pekarskih proizvoda, testenina i brzo smrznutih testa, Sluţbeni list SRJ 52/1995.

22. World Health Organization, WHO Diet, Nutrition and Prevantion of Chronic Disease, Report of a Jint WHO/FAO Expert Consultation, WHO Technical Report Series, No. 894, Geneva, (2003).

FUNCTIONAL CHARACTERISTICS OF BREAD ENRICHED WITH MODIFIED FIBERS

Jelena Filipović1*, Vladimir Filipović2, Milenko Košutić1 2University of Novi Sad, Institute fo Food Technology, Novi Sad, Serbia

2University of Novi Sad, Faculty of Technology, Novi Sad, Serbia

In highly developed societies inappropriate nutrition is very frequent. Dietary fibers have high importance in preventing mass non-infectious diseases by achieving, maintaining and improving the health of people. Bread is suitable for enhancement of eating plan because it is quick and easy to prepare, it is easily digestible food as well as a good source of carbohydrates, and it is one of the most widely consumed foods in the world. More and more consumers are interested in fiber enriched bakery products, particularly bread. However, market is lacking commercial fibers that are meeting needs of bakery industry and consumer taste. For the preparation of fiber enriched or high fiber bread sugar beet fibers were chemically treated. Modified fibers were grinded and fractionated. Contrary to cereal brean, sugar beet fibers are free of phytic acid. The influence of modifed fiber on technological bread processing parameters is followed by dough rheology and bread characteristics. In the lean dough formula, modifeid fibers supplemented different quantities of flour (5%, 10% and 15%). At all levels of supplementation the structure of gluten matrix was interrupted. It was inevitable to reinforce gluten structure. Modified fibers, due to the application of the same quantity of water in dough mixing, increase dough consistency after 5 min mixing, increase peak consistency and peak time. By adequate formula and processing parameters correction it is possible to make bread with 10 and 15% of modified fibers with sensory characteristics similar to the white bread which suits consumer taste. Bread with modified fiber is attributed with altered nutritive value and reduced energy. As such it refers to the concept of functional food. The term functional food refers to the concept of the science of nutrition and includes all foods that, except for basic functions, have a positive physiological effect and contribute to a reduced risk of disease and show no negative side effects when consuming.

Keywords: modified fiber, dough rheology, bread quality, nutritive value, energy value



31

SPELT PASTA ENRICHED WITH ω-3 FATTY ACIDS

Jelena Filipović1*, Vladimir Filipović2, Milenko Košutić1 2University of Novi Sad, Institute fo Food Technology, Novi Sad, Serbia

2University of Novi Sad, Faculty of Technology, Novi Sad, Serbia

ISSN 2232-755X DC: 664.69.016.3

DOI: 10.7251/GHTE1612031F Original scientific paper

In this paper the quality of spelt pasta with the addition of ω-3 fatty acid, which is positively contributing to the functional and technological changes of the product is investigated.ω-3 fatty acids are added in the quantity of 0%, 0.2%, 0.4% and 0.6% based on farina. Concerning pasta quality addition of ω-3 fatty acids is related to increased cooking time and cooking loss, as well as reduced pasta stickiness. Gas chromatography with mass spectrometry was used for carrying out a quantitative analysis of the liposoluble pasta extract. Pasta with 0.6% ω-3 fatty acids contains 0.6048 g /100 fatty acids, which positively contributes to ω-6/ω-3 fatty acid ratio in daily meal, thus meeting values recommended by nutritionists. This type of pasta is a new product with good technological quality, improved fatty acids profile and sensory characteristics with consumer acceptability range.

Key words: pasta, technological quality, sensory quality, fatty acids, ω-6/ω-3 ratio.

INTRODUCTION

Pasta quality mainly depends on the properties of raw material, especially flour protein content and gluten quality [1]. Pasta is suitable for correcting eating plan because it is quick and easy to prepare, easily digestible food and it is one of the widespread foods in many countries around the world [2, 4, 5]. Due to its handling, storage and preparation properties and popularity with consumers’ pasta is an excellent choice for incorporating "nutraceuticals". Nutritional and functional properties of pasta can be improved by using whole meal spelt as basic raw material for pasta preparation and by adding raw materials such as ω-3 fatty acids [4, 6]. Normal and balanced diet recommended by nutritionists for prevention of mass non-infectious diseases consider intake of essential fatty acids and decrease of ω-6/ω-3 fatty acids ratio [7]. Enriched pasta and other cereal products could be a good source of ω-3 fatty acids and can

contribute to achieving the recommended daily intake. ω-3 fatty acids are polyunsaturated fatty acids (PUFA) that are widely distributed in animal tissues and plants [8]. ω-3 fatty acids are becoming more familiar to consumers due to the increasing amount of research demonstrating their health benefits. New studies are identifying potential benefits for a wide range of conditions including cancer, inflammatory bowel disease and other autoimmune diseases such as lupus and rheumatoid arthritis [9,10]. The main challenges of food producers is to produce food enriched with ω-3 fatty acids that does not reduce their current quality despite the added active ingredient [11-13]. Spelt wheat grown without use of pesticides was suitable as an organic material. Spelt cultivars have higher concentration of mineral elements Fe, Zn, Cu, Mg and P compared to Triticum Aestivum and Triticum Durum [4, 9].

The aim of this study is to produce spelt pasta enriched with ω-3 fatty acids in order to enhance fatty acids profile of pasta, and also to quantify and inspect the effect of ω-3 fatty acids on the technological and sensory quality of pasta.

MATERIAL AND METHODS

Spelt wheat "Nirvana" cultivar, grown in the year 2013 in Serbia at Baĉko Gradište location, is used for pasta production, with the following characteristics tested: moisture, starch, protein, lipids and cellulose content of 13.0 %, 69.6% d.m., 13.1 % d.m. 2.33% d.m. and 1.3% d.m., respectively [14]. Stone milled spelt whole meal flour with particle size ranged between 200 and 300 μm was supplied by a local producer "Jeftić"-Baĉko Gradište. ω-3 fatty acids are added during mixing, and were produced by Pharmanova, Obrenovac, Serbia. Pasta was made using the device "La Parmigiana D45" MAC 60. In a paddle mixer wholemeal moisture was adjusted to 31.5% by adding water, then the ω-3 fatty acids are added in quantity of 0%, 0.2%, 0.4% or 0.6% based on farina and mixed for 15 min [15] into a homogeneous mass. Hydrated whole meal entered an extrusion worm which moved the loose dough forward and simultaneously compressed it into a homogeneous plastic mass prior to extrusion through a die with 1.4 mm diameter used for spaghetti. Quality of pasta was evaluated in terms of cooking characteristics (cooking time, volume increase, cooking loss and stickiness), by applying the method described by KaluĊerski and Filipović [15].

Sensory analysis was conducted according to SRPS ISO 4121:2002 [16], by panel of six trained evaluators. Evaluators identified descriptors and scored taste using 6 point scale (0 – not detected, 5 – strong). Sensory analysis of cooked pasta included determination of colour (yellow, red, whiteness, of different colouration), taste (characteristic, non-characteristic, fatty taste, fish taste) and odour (characteristic, non-characteristic, fatty taste, fish taste). Fatty acids

content was determined on dry pasta by using gas chromatography with mass spectrometry (Agilent Technologies, Palo Alto, CA, USA), according to Vujić et al. [17].

* Korespondentni autor: Jelena Filipović, Univerzitet u Novom Sadu, Nauĉni Institut za prehrambene tehnologije, Bulevar cara Lazara 1, Novi Sad, Srbija, e-mail: [email protected]


J. Filipović et al.: SPELT PASTA ENRICHED WITH ω-3 FATTY ACIDS

32

Descriptive statistical analyses for all the obtained technological parameters were expressed as the mean values ± standard deviation (SD). Collected data were subjected to analysis of variance (ANOVA) for the comparison of means and significant differences are calculated according to post-hoc Tukey’s HSD (honestly significant differences) test at p<0.05 significant level, 95% confidence limit, using StatSoft Statistica 10.0® software.


Quality is the primary criterion for evaluating a food product and it has a dominant influence on the acceptance by consumers. Related to pasta quality, the addition of 0.4% and 0.6% of ω-3 fatty acids statistically significantly increases cooking time of pasta (Table 1). Volume increase of pasta represents the ability of starch to swell, and this parameter indicates that there were no statistically significant differences in volume increase between pastas with higher amounts of ω-3 fatty acids (0.4% and 0.6%) compared to pasta with 0% ω-3 fatty acids. Cooking loss is also a useful parameter for cooked pasta quality evaluation. Cooking loss significantly increases with addition of ω-3 fatty acid, which indicates that this small quantity of fatty acids does not strengthen the gluten structure of the product. Stickiness of pasta showed a significant decrease with increased ω-3 fatty acids addition (Table 1), and the maximum was observed in pasta with 0% ω-3 fatty acids (8.7±0.5) while the minimum stickiness of 7.2±0.4, was observed with 0.6% ω-3 fatty acids, as confirmed by Filipović et al. [3].

Table 1. Quality of pasta with ω-3 fatty acids Tabela 1. Kvalitet testenine sa ω-3 masnim kiselinama

Quantity of ω-3 fatty acids Koliĉina ω-3 masnih kiselina

0% 0.2% 0.4% 0.6%

Cooking time, CT (s) vreme kuvanja (s)

212±12a 239±8a 270±14b 298±10b

Volume increase,

povećanje zapremine 3.57±0.03a 3.42±0.05b 3.55±0.05ab 3.57±0.07a

Cooking loss, (% d.m.) procenat raskuvavanja, (% s.m)

5.98±0.07a 6.32±0.03ab 6.75±0.03b 7.00±0.08b

Stickiness* Lepljivost

8.7±0.5a 8.3±0.4ab 7.8±0.3ab 7.2±0.4b

*Sensor testing, minimum score is 1, maximum score is 10 (non sticky) * senzorna ocena, minimalna vrednost 1, maksimalna vrednost 10 (ne lepljiva) The results are presented as mean±SD (standard deviation); Rezultati predstavljaju srednju vrednost±SD (standardna devijacija)

a,b Different letters within the same row indicate statistically significant differences (p<0.05), according to Tukey’s test, number of repetitions: n=6, a,b Razliĉita slova u eksponentu vrednosti u istim redovima ukazuju na statistiĉki znaĉajne razlike pri nivou znaĉajnosti od p<0,05 po Tukey, broj ponavljanja: n=6

On Figure 1 changes of descriptive sensory characteristics of pasta with different quantities of ω-3 fatty acids are shown.

0

1

2

3

4

5Yellow

Red

Whitness

Difference of colouration 0

1

2

3

4

5Characteristic

Fatty taste

Fish taste

01

2

3

4

5

Characteristic

Fatty odour

Fish odour

0 0.2

Non-characteristic

Non-characteristic

a) b) c)

0.4 0.6

Figure 1.a-c Sensory analysis of pasta with different quantity of ω-3 fatty acids Slika 1.a-c Senzorna ocena testenine sa ω-3 masnim kiselinama

The data point out that the adding of ω-3 fatty acids positively contributes to the increase of yellow colour and decrease of red colour (Figure 1a). ω-3 fatty acids contribute to increased differences of colouration (the highest


33

descriptor, 3, was in pasta with 0.6% fatty acids and the lowest descriptor, 1, was in pasta with 0% and 0.2% fatty acids). The highest whiteness of pastas was experienced with 0% fatty acids and it was decreasing with addition of ω-3 fatty acids. Pasta with 0% ω–3 fatty acids had characteristic taste (descriptor was 5), while the addition of ω-3 fatty acids (Figure 1b) had negative impact on pasta taste. Non-characteristic and fatty tastes were increased with addition of ω-3 fatty acids. Descriptor values for fish taste, as negative component of taste, had increased with addition of ω–3 fatty acids. The influence of different quantities (0.2%, 0.4% and 0.6%) of ω–3 fatty acids used in pasta production had shown that ω-3 fatty acids (Figure 1c) had negative influence on odour descriptors of pasta. Pasta sample with addition of 0.2 % of ω-3 fatty acids had descriptor values of 1 for non-characteristic and fatty odour, while pasta samples with addition of 0.4 % and 0.6 % of ω-3 fatty acids had descriptor values of 2 for non-characteristic and fatty odours.

The distribution of saturated, monounsaturated and polyunsaturated fatty acidin in spelt pasta with 0%, 0.2%, 0.4% and 0.6% ω-3 fatty acids are given in table 2. Gas hromatography with mass spectrometry was used for performing a qualitative analysis of saturated, monounsaturated and polyunsaturated fatty acids. The addition of ω-3 fatty acids in spelt pasta in the quantities of 0.2%, 0.4% and 0.6% statistically significantly increased the total fatty acid content. The addition of 0.4% and 0.6% ω-3 fatty acids in spelt pasta statistically significantly decreased the share of palmitic

and stearic acids (Table 2). There were no significant statistical differences in values of oleic acid content of pasta with different content of ω-3 fatty acids. The spelt pasta contains 0.16 mg/100 g of total fatty acids with the shares of linoleic acid and linolenic acid of 0.096 mg/100 g and 0.0048 mg/100 g, respectively (Table 2). In pasta without addition of ω-3 fatty acids, ω-6 fatty acids make a share of 60% while the ω-3 fatty acids make a share of only 3%, which is consistent with findings of Abdel et al [18] and the essential ω-6/ω-3 ratio is 20:1. The addition of ω-3 fatty acids in spelt pasta causes statistically significant increase in share of linolenic acid, which results with improved ω-6/ω-3 ratio of 1:2, 1:4 and 1:6 for pasta with 0.2%, 0.4% and 0.6% ω-3 fatty acids, respectively.

By consuming 100 g of pasta with 0.6% ω-3 fatty acids the ω-3 fatty acids intake is around 0.6048 g, which contributes to the improvement of ω-6/ω-3 fatty acids ratio in the daily diet (1:6) (Table 2). Daily needs in ω-3 fatty acids recommended by the International Society for the Study of Fatty acids and Lipid’s (ISSFAL) [12,13] could be met by consuming 160 g pasta with 0.4% ω-3 fatty acids, 317 g pasta with 0.2% ω-3 fatty acids and 13541 g with 0% ω-3 fatty acids, with recommended dietary intake of 0.65 g/day of EPA (eicosapentaenoic) and DHA (docosahexanoic) [12,13].

Table 2. Content of fatty acids in pasta with ω-3 fatty acids Tabela 2. Sastav masnih kiselina u testenini sa ω-3 masnim kiselinama

Quantity of added ω-3 fatty acids Koliĉina dodatih ω-3 masnih kiselina

0% 0.2% 0.4% 0.6%

FAC (g/100g) Masne kiseline

TFAC(g/100g) Ukupne masne kiseline

0.16±0.02a 0.30±0.03b 0.54±0.03c 0.70±0.04d

SAFA Zasićene masne kiseline

C 16:0 (g/100g) 0.028±0.002a 0.025±0.001ab 0.022±0.002b 0.020±0.003b

C 18:0 (g/100g) 0.002±0.0001a 0.002±0.0002a 0.001±0.0001b 0.001±0.0001b

MUFA Mononezasićene masne kiseline

C 1:18 (g/100g) 0.023±0.002a 0.022±0.001a 0.023±0.003a 0.021±0.002a

PUFA Polinezasićene masne kiseline

C 18:2N (g/100g) 0.096±0.010a 0.096±0.009a 0.095±0.008a 0.094±0.010a

C 18:3N (g/100g) 0.0048±0.001a 0.2048±0.009b 0.4048±0.011c 0.6048±0.015d

Ratio ω-6/ω-3 Odnos ω-6/ω-3

20:1 1:2 1:4 1:6

The results are presented as mean±SD (standard deviation); Rezultati predstavljaju srednju vrednost±SD (standardna devijacija);

a,b,c Different letters within the same row indicate statistically significant differences (p<0.05): according to Tukey’s test, number of repetitions: n=6. FAC-fatty acid content, TFAC-total fatty acid content SAFA-saturated fatty acids, MUFA-monounsaturated fatty acids, PUFA-polyunsaturated fatty acids, C16:0- palmitic acid, C18:0-stearic acid, C1:18-oleic acid, C18:2N-linoleic acid ω-6,C18:3N-linolenic acid ω-3. a,b,c Razliĉita slova u eksponentu vrednosti u istim redovima ukazuju na statistiĉki znaĉajne razlike pri nivou znaĉajnosti od p<0,05 po Tukey, broj ponavljanja: n=6. C16:0-palmitinska kiselina, C18:0-stearinska kiselina, C1:18-oleinska kiselina, C18:2N-linolna kiselina ω-6,C18:3N-linoleinska kiselina ω-3.

J. Filipović et al.: SPELT PASTA ENRICHED WITH ω-3 FATTY ACIDS

34

CONCLUSION

Based on the obtained results of the effects of ω-3 fatty acids addition on pasta properties, it can be concluded that added ω-3 fatty acids increase cooking time and cooking loss. Volume is not significantly affected, while stickiness of cooked pasta is reduced.

The addition of ω-3 fatty acids contributes to decreasing characteristic taste and increasing non-characteristic taste, fatty taste and fish taste. This research points to pasta with ω-3 fatty acids used for production of functional pasta product, stressing that sensory characteristics are within consumer acceptability range. The addition of ω-3 fatty acids in spelt pasta in quantities of 0.2% significantly increases the share of ω-3 fatty acids, which results in improved ratio of ω-6/ω-3 to 1:2. Consumption of 100 g of pasta with 0.6% ω- 3 fatty acids means the intake of 0.6048 g of essential fatty acids per day. Pasta enriched with ω-3 fatty acids represents a new functional product with good technological quality and improved fatty acids profile.

Acknowledgement

These results are part of the project supported by the Ministry of Education and Science of the Republic of Serbia, III 46005, TR 31029.

REFERENCES

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2. Dziki, D., J. Laskowski: Evaluation of the cooking quality of spaghetti. Polish Jounal of Food and Nutrition Sciences, 2 (2005) 153–158.

3. Filipović, J., L. Pezo, V. Filipović, J. Brkljaĉa, J. Krulj: The effects of ω-3 fatty acids and inulin addition to spelt pasta quality. LWT – food Science and Technology (Lebensmitte-Wissenschaft und Technologie), 63 (2015) 43-51.

4. Filipović, J., L. Pezo, N. Filipović, V. Filipović, J. Brkljaĉa, J. Jevtić-Vukmirović: Optimization of Spelt Pasta

Composition, Regarding Inulin HPX Content and Eggs Quantity. Jouranl Food of Nutritional Research, 2 (2014) 167-173.

5. Villeneuve, S., L. P. Des Marchais, V. Gauvreau, S. Mercier, C. B. Do, Y. Arcand: Effect of flaxseed processing on engineering properties and fatty acids profiles of pasta. Food and bioproducts processing, 91 (2013)183–191.

6. Simonato, B., A. Curioni, G. Pasin: Digestibility of pasta made with three wheat types: A preliminary study. Food Chemistry, 17 (2015) 4219–225.

7. Verardo, V., F. Ferioli, Y. Riciputi, G. Iafelice, E. Marconi, M. F. Caboni: Evaluation of lipid oxidation in spaghetti pasta enriched with long chain n-3 polyunsaturated fatty acids under different storage conditions. Food Chemistry, 114 (2009) 472-477.

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9. Filipović, J., L. Pezo, N. Filipović, V. Filipović, M. Bodroţa-Solarov, M. Planĉak: Mathematical approach to assessing spelt cultivars (Triticumaestivum subsp. spelt) for pasta making. Journal of Food and Nutrition Research, 48 (2013) 195-203.

10. Kolanowski, W.: Bioavailability of ω-3 PUFA from foods enriched with fish oil. A mini review. Journal of Food and

Nutrition Science, 4 (2005) 335-340. 11. Drusch, S., S. Mannino: Patent-based review on industrial approaches for the microencapsulation of oils rich in

polyunsaturated fatty acids. Trends Food Science and technology, 20 (2009) 237-244. 12. Babuskin, S., K. R. Krishnan, P. P. A. Babu, M. Sivarajan, M. Sukumar: Functional Food Enriched with Marine

Microalga Nannochloropsis oculata as a source of ω-3 Fatty Acids. Food Techology and Biotechnology, 52 (2014) 292-299.

13. http://www.eufic.org/article/en/artid/The-importance-of-omega-3-and-omega-6-fatty-acids/ 14. AOAC, Official methods of analysis (15th ed.). Arlington, VA: Association of Official Analytical Chemists, 1990. 15. KaluĊerski, G., N. Filipović: Methods for the investigation of cereals, flour and final product quality,Faculty of

Technology, Novi Sad, (1998), p. 71. 16. SRPS ISO 4121: 2002 Sensory analyses – Methodology – Evaluation of Food Products by Methods using scales,

(2002). 17. Vujić, Đ., M. Aĉanski, M. Bodroţa-Solarov, N. Hristov, M. Krunić: Performance of GC-MS analysis for

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18. Abdel-Aal, E. S. M., P. Hucl, F. W. Sosulski: Compositional and Nutritional Characteristics of Spring Einkorn and Spelt Wheats, Cereal Chemistry, 72 (1995) 621-624.


35

TESTENINA OD SPELTE OBOGAĆENA Ω-3 MASNIM KISELINAMA

Jelena Filipović1*, Vladimir Filipović2, Milenko Košutić1 2Univerzitet u Novom Sadu, Nauĉni institute za prehrambene tehnologije, Novi Sad, Srbija

2Univerzitet u Novom Sadu, Tehnološki fakultet, Novi Sad, Srbija

U ovom radu je ispitan uticaj dodatka ω-3 masne kiseline na kvalitet testenine od spelte i poboljšanje funkcionalnih osobina testenine. ω-3 masne kiseline su dodavane u uzorke testenine u koliĉini 0%, 0,2%, 0,4% i 0,6%. Dodatak ω-3 masne kiseline utiĉe na povećanje vremena kuvanja i procenta raskuvavanja, zapremina se ne menja znaĉajno, dok se smanjuje lepljivost. Za kvantitativno odreĊivanje sadrţaja masnih kiselina korišĉena je gasna hromatografija sa masenom spektroskopijom. Testenina sa dodatkom 0,6% ω-3 masnih kiselina sadrţi 0,6048 g ω-3 masnih kiselina što doprinosi poboljšanju odnosa ω-6/ω-3 masnih kiselina u dnevnom obroku, što se preporuĉuje od strane nutricionista. Konzumiranjem 100 g testenine sa dodatkom 0,6% ω- 3 masnih kiselina dnevno, unosi se 0,6048 g esencijalnih masnih kiselina dnevno. Testenina obogaćena sa ω-3 masnim kiselinama je nov proizvod sa dobrim tehnološkim karakteristikama, poboljšanim sastavom masnih kiselina i prihvatljivim senzornim ocenama za potrošaĉe.

Kljuĉne reĉi: kvalitet testenine, senzorne osobine, masne kiseline, odnos ω-6/ω-3

Rad primljen: 07. 04. 2016.

Rad prihvaćen: 17. 06. 2016.


37

READABILITY OF SCREEN PRINTED QR CODES DEPENDING ON THEIR DIMENSION, ENCODED CONTENT AND TYPE OF PRINTING

SUBSTRATE USING SCREEN PRINTING TECHNIQUE

Ţivko Pavlović*, Sandra Dedijer, Magdolna Pál, Ivana Tomić, Ivana Juriĉ University of Novi Sad, Faculty of Technical Sciences, Graphic engineering and design,

Novi Sad, Serbia ISSN 2232-755X UDC: 655.228:659.127 DOI: 10.7251/GHTE1612037P Original scientific paper

QR (Quick Response) code is a two-dimensional code consisting of white and black squares as information carriers. The main advantages of a two-dimensional or matrix code is the possibility of various and extensive content in the given area, wherein the amount of encoded data is limited to about 7000 numbers and about 1800 symbols. The above-mentioned codes have become an inevitable part of any industrial product. The aim of this experiment was to test readability of different QR codes printed with screen printing with different mesh tread densities (140 threads/cm and 180 threads/cm). The QR codes were prepared in six different dimensions (1 cm2, 1.3 cm2, 1.6 cm2, 1.9 cm2, 2.2 cm2 and 2.5 cm2) with three different types of content (textual message-SMS with 160 characters, short URL and long URL) on seven different substrates (paper 170g/m2, self-adhesive paper, PVC foil, white and yellow cotton cloth/fabric, aluminium sheet and glass plate). During the experiment D65 light source was used as a simulation of daylight. We have used Neo Reader software for QR code reading on HTC Desire phone, using the 5-megapixel camera and possibility of autofocus. The results show improved readability with QR codes printed with screen mesh of 140 threads/cm and with the reduction of carried information, i.e. the number of characters that QR codes consist of. Also, the problem with readability decreases when using substrates such as aluminium sheet or glass plate.

Key words: QR code, screen printing, ink, substrate

INTRODUCTION

Quick Response Code, (QR code®), is a two-dimensional matrix encoding consisting of black and white squares, called modules. These modules form a machine-readable barcode to tag information onto products. It was originally designed by a Japanese company Denso Wave in 1994 for the automotive industry. In accordance with the intent of developers it could be used by as many people as possible. Under this circumstance, QR Code can grow into ―public code‖ used by individuals and enterprises without any cost or worry about a potential problem. QR is the abbreviation of quick response, expressing the development notion of QR code, which means emphasizing the high-speed reading. QR code has quickly been adapted as a fast and effective way to embed digital content and is extensively used in diverse fields including manufacturing, marketing, etc. [1, 2, 3]

At present, QR Code is becoming an increasingly standard way when communicating with potential customers via print media in most countries. QR Code is being located on e.g. stickers, booths, business cards and advertisement vehicle. The reason why to use QR Code is that QR Code is new and unique. QR Code can immediately connect people to the virtual environment of information and entertainment. In addition, convenient and fast features of QR code also attract people to use it. Besides, QR code can send information to the mobile phone instantly, regardless of someone's physical location [4].

QR Code Architecture

Each QR Code symbol shall be constructed of nominally square modules set out in a regular square array and shall consist of an encoding region and function patterns: finder, separator, timing patterns, and alignment patterns. Function patterns shall not be used for the encoding of data. The symbol shall be surrounded on all four sides by a quiet zone border. This zone is the spacing provided to distinguish between QR code and its surroundings. It is important for the scanning program [5].

Three common structures on the three corners of QR code symbol are called finder patterns. Finder pattern is used for deciding the correct orientation of the symbol. Timing patterns are used by the decoder software to find the side of the pattern. Alignment patterns are used in the case of image distortion to correctly decode the symbol by decoder software. The rest of the region i.e. other than function pattern, is the encoded region where data code words and error-correcting code words are stored (Fig. 1) [6].

* Korespondentni autor: Ţivko Pavlović, Univerzitet u Novom Sadu, Fakultet tehniĉkih nauka, Trg Dositeja Obradovića

6, Novi Sad, Srbija, e-mail: [email protected]. Rad je izloţen na meĊunarodnom nauĉnom skupu XI Savjetovanje hemiĉara, tehnologa i ekologa Republike Srpske, novembar 2016.

mailto:


Ţ. Pavlović et al.: READABILITY OF SCREEN PRINTED QR CODES DEPENDING ON THEIR DIMENSION...

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Figure 1. QR code structure (ISO/IEC18004)

MATERIAL AND METHODS

As a first step, before generating and printing QR codes, an Adobe Illustrator SC5 program has been used to simulate the actual size of the future QR code. Simulation of screen printing mesh with the drawn lines has been done with the aim to predict possible problems which can occur in the printing process. Similar screen mesh has been drawn that simulates an actual size of the screen printing mesh, width, and thickness of the threads. An example is presented in Fig. 2. where the actual size of the mesh count, with 120 threads/cm, is unsuitable for printing in this experiment.

Figure 2. Simulation of QR code for screen printing with mesh count of 120 threads/cm

The simulation showed that the loss of QR code elements with lower thread density could be greater, and QR code might be completely unreadable after the printing process. Thus, screen meshes with a larger mesh count – higher thread density (140 threads/cm and 180 threads/cm) have been used in the experiment.

For generating QR codes we have used an on-line generator – Kerem Erkan [7]. This program is written in PHP language and it is capable of generating two-dimensional codes. Generation of QR code for this experiment was done with three different contents of QR codes:

textual message -SMS (160 characters, maximum for text message (Fig. 3a),

long URL address (http://flashzourtattoo.com/blog/wpcontent/uploads/2010/05/da vidbollt.jpg) (Fig. 3b) and

short URL address (http://www.grid.uns.ac.rs/) (Fig. 3c)

a) b) c)

Figure 3. Generated QR codes with:

a) textual message -SMS, b) long URL address, c) short URL address

http://flashzourtattoo.com/blog/wpcontent/uploads/2010/05/da%20vidbollt.jpg


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In order to determine the minimum dimensions that can be printed with screen printing and thereby to remain readable, these three QR codes were generated in six different dimensions: 1 cm2, 1.3 cm2, 1.6 cm2, 1.9 cm2, 2.2 cm2 and 2.5 cm2.

Seven different printing substrates have been used: paper 170g/m2, self-adhesive paper, PVC foil, white and yellow cotton fabric, aluminium sheet and glass plates..

Depending on the substrate, two different types of black screen printing inks have been used: Sericol Trichromatic Plastijet TG004 and SericolTexopaque Classic OP004. Plastijet ink is designed for high-speed printing of self-adhesive vinyls, rigid PVC, and polystyrenes, while Texopaque Classic is designed for printing on textile. The semiautomatic screen printing machine S550 TSH Print Swiss was used for the printing process. Printing speed was 15 cm/sec; squeegee hardness was 80 Shore Type A, printing pressure 275.8 x 103 Pa and 4 mm snap-off distance. Each substrate was printed five times, which in summary gave ten QR codes on each substrate.

For the simulation of daylight conditions, Agile Radiant Controlled Light 5 box has been used with a light emission of D65 (colour temperature of 6500 K) that represents the average spectral power distribution of daylight.

Reading of printed QR codes has been done with Neo Reader software, using HTC Desire mobile phone with a 5-megapixel camera and possibility of autofocus.

Before the measuring procedure, printed samples of QR codes were fixed at the wall of the background of a light box. For the scanning procedure, a model with an aperture of 25 mm x 25 mm has been made, in order to provide an easier selection of QR code that has to be scanned.

The scanning procedure has been done as follows: The phone has been placed at a distance of 15 cm from printed QR code sample, scanning time was limited to maximum 5 seconds, in order to simulate everyday use.

The test results were given as average values for every analyzed printed sample.


QR codes printed on paper

The first substrate that has been analyzed was paper printed with a screen mesh count of 140 threads/cm and 180 threads/cm.

One can see (Fig. 4 a) that readability of codes with text content, for samples printed with lower mesh count, was successful starting from QR code size 1,6 cm2 and for the samples with higher screen mesh count, (Fig 4b) from the size 1,9 cm2. Smaller sizes of QR codes were unreadable and the possible reason could be an extensive number of the details in the code, which cannot be readable on the smaller sizes of the QR codes.

a) b)

Figure 4. Number of successful readings of QR codes with text content, Substrate: paper 170g/m2,a) 140 threads/cm, b) 180 threads/cm

Readability of QR codes with long URL address (Fig 5a, b) printed on paper was very similar for both resolutions of the screen threads (140 and 180 threads/cm). Very small number of QR codes could not be read on sample 4 due to a great number of small details and minor damages of the QR codes content caused by the printing process.


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a) b)

Figure 5. Number of successful readings of QR codes with long URL address, Substrate: paper 170 g/m2, a) 140 threads/cm, b) 180 threads/cm

a) b)

Figure 6. Number of successful readings of QR codes with short URL address, Substrate: paper 170g/m2, a) 140 threads/cm, b) 180 threads/cm

Best results, as it was expected, were obtained in scanning process of QR codes with short URL address. Analyzed QR codes gave identical values of 100% readability of printed samples (Fig. 6) on paper printed with both meshes, 140 and 180 threads/cm.

QR codes printed on self-adhesive paper

From the Figure 7a, it can be seen that the readability of QR codes with text content, printed on self-adhesive paper using screen with140 threads/cm, was successful, starting with the size of 1,6 cm2 and 1,9 cm2 with minor readability problems on sample 4 and 5.

a) b)

Figure 7. Number of successful readings of QR codes with text content, Substrate: self-adhesive paper, a) 140 threads/cm, b) 180 threads/cm


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Similar situation with readability was with QR codes printed using the screen of 180 threads/cm. In this case, the possibility of QR reading starts with the size of 1,9 cm2 and small problems are also viewed on sample 1, 3 and 4 within the same size of QR codes. With the size of 2,2 cm2 readability gets better with minor problems on samples 2, 3 and 5. The reason for these results could be rough matte surface of the self-adhesive paper, larger resolution of screen fabric and a number of small details, as it was the case in the previously analyzed samples printed on paper (Fig 4 a, b).

a) b)

Figure 8. Number of successful readings of QR codes with long URL address Substrate: self-adhesive paper, a) 140 threads/cm, b) 180 threads/cm

Scanned samples of QR codes with long URL address (Fig. 8), printed on self-adhesive paper with both screen thread resolution gave almost identical results of complete readability of all size of printed QR codes.

The same results were obtained from the scanned QR codes with short URL address. The readability was 100% successful for all sizes of QR codes with both screen thread resolution.

QR codes printed on PVC FOIL

From the Figure 9a. one can see that readability of QR codes with text content, printed on PVC substrate, begins with the size of 2,2 cm2, for a screen resolution of 140 threads/cm. Readability of these QR codes has been problematic on PVC (Fig. 9 a), especially in sample 2 and 5 for the size of 2,2 cm2.

a) b)

Figure 9. Number of successful readings of QR codes with text content Substrate: PVC, a) 140 threads/cm, b) 180 threads/cm

Comparing these results with the results of readability of printed samples with a screen of 180 threads/cm (Fig. 9b), it can be noticed that the similarity is connected to the size of readable QR code. The cause of these results could be the different surface of the PVC samples as well as a large number of details of text QR codes.

Results gained from a reading of QR codes with long and short URL address are identical, for both screen threads. For all sizes of the printed QR codes, they are readable 100%.


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QR codes printed on Cotton FaBRIC (WHITE AND yellow)

Results of QR codes printed on white cotton samples using 140 thread/cm (Fig. 10 a) show that QR code readability starts from the printed size of 1,9 cm2 , and for the 180 thread/cm screen mesh readability was possible only for QR codes size of 2,5 cm2 (Fig. 10b).

a) b)

Figure 10. Number of successful readings of QR codes with text content Substrate: white cotton, a) 140 threads/cm, b) 180 threads/cm

Results of printed QR codes with text content on yellow cotton shows that readability, for both resolutions (140 and 180) was not possible and therefore results were not presented. The reason for these results could be due to different texture of the textile material and lower contrast of the printed substrate as well as greater screen mesh resolution of 180 threads/cm (yellow cotton).

Readability of QR codes with long URL address printed on white cotton was almost perfect for both screen resolutions.

Minor problems with reading were observed with the smallest codes (1 cm2), but they were 90% successful for 140 threads/cm (Fig. 11a) and 80 % for 180 threads/cm (Fig. 11b).

a) b)

Figure 11. Number of successful readings of QR codes with long URL address Substrate: white cotton, a) 140 threads/cm, b) 180 threads/cm

The results for yellow cotton for the same QR codes with long URL address exhibit differently comparing with the ones printed on the white cotton substrate (Fig. 12). For the screen resolution of 140 threads/cm, readability of samples starts from size 1, 6 cm2. The sample 3 was unreadable for all sizes of QR codes with the exception of the size of 2.2 cm2 with a 20% of readability. Sample 5 was also problematic for reading for the QR code size of 2,2 cm2 (readability of 10%). For other sizes readability was more than 60% (Fig. 12 a).


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a) b)

Figure 12. Number of successful reading of QR codes with long URL address Substrate: yellow cotton, a) 140 threads/cm, b) 180 threads/cm

Printed samples with screen mesh with 180 threads/cm became readable from the size of 1,3 cm2 on certain samples, such as sample 2 (readability of 80%) and 4 (readability of 40%). For greater QR codes sizes, readability was successful for all samples (Fig. 12 b).

QR codes with short URL address printed on white and yellow cotton were 100 % readable.

QR codes printed on ALUMINIUM

All the QR codes, printed on aluminium, with the screen resolution of 140 threads/cm were 100% unreadable, regardless of the encoded content. Results of readability of QR codes with text content for the screen resolution 180 threads/cm are shown in Figure 13. For most of the samples, successful readability starts with the QR codes size of 1,6 cm2 except for the sample 3, which was unreadable until the size of 1,9 cm2.

Figure 13. Number of successful readings of QR codes with text content Substrate: aluminium, screen resolution 180 threads/cm

From the Figure 14 (a, b) one can see that readability of QR codes with longer URL printed on aluminium, for both screen resolutions, is almost identical.

Figure 14. Number of successful readings of QR with long URL address Substrate: aluminium, a) 140 threads/cm b) 180 threads/cm


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Results obtained from the scanning process on QR codes with short URL address, printed with a screen resolution of 180 threads/cm on aluminium substrate, were 100% readable, for all sizes and therefore were not presented.

QR codes printed on glass

Scanning process on QR codes with long and short URL, printed with a screen resolution of 140 and 180 threads/cm on a glass substrate, were 100% successful, for all sizes, and were, therefore, not presented.

From the Figure 15, it can be seen that readability of QR codes with text content, printed on glass, using a screen with140 threads/cm, starts with the QR codes size of 1.9 cm2. For sample 4, it starts with the size of 2.2 cm2.

Figure 15. Number of successful readings of QR codes with text content Substrate: glass, screen resolution 140 threads/cm

CONCLUSIONS

Printed QR codes with a text content, and thus with the largest number of information - squares, were the most problematic for reading. For most of the substrates, excluding aluminum and glass, readability starts from the size of 1.6 cm2 with the screen resolution of 140 threads/cm. With the higher screen resolution (180 threads/cm), readability of printed QR codes with a text content was variable, depending on the used substrate. For aluminium, readability starts from the QR code size of 1.6 cm2. For the paper, self-adhesive paper and glass, readability starts from QR code size of 1.9 cm2. For PVC, readability can be expected from size of 2.2 cm2 and for the white and yellow cotton readability was possible only on the size of 2.5 cm2.

In most cases, (for both screen resolutions and for all substrates), QR codes with a long URL address were readable, with almost 100% of success. Only yellow cotton showed a lower readability success for this type of QR codes content.

All materials show perfect readability results for QR codes with less details containing short URL address.

Based on the results it can be concluded that different QR code size, the complexity of information coded, screen mesh tread count, surface and texture of substrate have a significant impact on the readability results. Usage of a compatible printing inks and materials is recommended in order to achieve good quality print and readability of QR codes.

REFERENCES

1. History of QR code, Available on: http://www.qrcode.com/en/history/(12.07.2016.) 2. Li L., Jinxia Q., Jianfeng L., Chin-Chen C: An aesthetic QR code solution based on error correction mechanism,

The Journal of Systems and Software, 116 (2016) 85–94. 3. Hung-Kuo C., Chia-Sheng C., Ruen-Rone L., Niloy J. M: Halftone QR Codes, ACM Transactions on Graphics

(Proc. of SIGGRAPH Asia 2013), Available on: http://cgv.cs.nthu.edu.tw/Projects/Recreational_Graphics/Halftone_QRCodes/ (12.07.2016.)

4. Winter, M., 2010. Scan me-everybody‟s guide to the magical world of QR Codes. The United States: Westsong Publishing. Available on: https://books.google.com.hk/books?id=s5ZxqwwYKk8C&printsec=frontcover&dq=What+is+QR+code&hl=zh-CN&sa=X&ei=4HoyVKGrJcq7ygPR7oGoCQ&ved=0CCsQ6AEwAQ#v=onepage&q=What%20is%20QR%20code&f=false (12.07.2016.)

5. ISO/IEC18004 - Information technology — Automatic identification and data capture techniques — Bar code

symbology — QR Code, 6. Sangeeta S: QR Code Analysis, International Journal of Advanced Research in Computer Science and

Software Engineering, 6(5), (2016), 89 – 92. 7. Kerem Erkan, Available on: http://keremerkan.net/ (20.05.2016.)


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ĈITLJIVOST SITO ŠTAMPANIH QR KODOVA U ZAVISNOSTI OD NJIHOVIH DIMENZIJA, KODIRANOG SADRŢAJA I VRSTE

ŠTAMPARSKE PODLOGE

Ţivko Pavlović*, Sandra Dedijer, Magdolna Pál, Ivana Tomić, Ivana Juriĉ Univerzitet u Novom Sadu, Fakultet tehniĉkih nauka, Grafiĉko inţenjerstvo i dizajn,

Novi Sad, Srbija [email protected]

QR (Quick Response) kod je dvo-dimenzionalni kod koji se sastoji od crno belih kvadrata kao nosioca informacija. Glavna prednost dvo-dimenzionalnog ili matriĉnog koda je mogućnost razliĉitog i opseţnog sadrţaja na odreĊenom podruĉju, gde je koliĉina kodiranih podataka ograniĉena na oko 7000 brojeva i oko 1800 znakova. Pomenuti kodovi su postali neizostavan deo svakog industrijskog proizvoda. Cilj ovog istraţivanja bio je ispitati ĉitljivost razliĉitih QR kodova štampanih sito štampom razliĉitom gustinom tkanja niti sita (140 niti/cm i 180 niti/cm). QR kodovi su pripremljeni u šest razliĉitih dimenzija (1 cm2, 1.3 cm2, 1.6 cm2, 1.9 cm2, 2.2 cm2 i 2.5 cm2) sa tri razliĉita tipa sadrţaja (tekstualna poruka-SMS sa 160 znakova, kratki URL i dugaĉki URL) na sedam razliĉitih štamparskih podloga (papir, samolepljivi papir, PVC folija, bela i ţuta pamuĉna odeća/tkanina, aluminijumska folija i staklena ploĉa). Tokom eksperimenta D65 svetlosni izvor je korišten kao simulacija dnevne svetlosti. Za oĉitavanje QR kodova korišten je Neo Reader program na HTC Desire telefonu, koristeći 5 megapikselnu kameru sa mogućnošću autofokusa. Rezultati pokazuju povećanu ĉitljivost QR kodova štampanih linijaturom tkanja mreţe sita od 140 niti/cm i sa smanjenjem nosećih informacija, tj. broja znakova od kojih se sastoji QR kod. TakoĊe, problem ĉitljivosti se smanjuje u sluĉaju korištenja podloga kao što su aluminijumska folija ili staklena ploĉa.

Kljuĉne reĉi: QR kod, sito štampa, boja, podloga

Rad primljen: 29. 11. 2016.

Rad prihvaćen: 14. 12. 2016.

UPUTSTVO AUTORIMA

1. Glasnik hemiĉara, tehnologa i ekologa RS objavljuje radove koji podlijeţu recenziji i svrstavaju se u sljedeće kategorije:

- originalni nauĉni radovi - kratka saopštenja - prethodna saopštenja - pregledni radovi - struĉni radovi - izlaganja sa nauĉnih skupova

Autori predlaţu kategoriju svojih radova, ali konaĉnu odluku o tome donosi Uredništvo na osnovu mišljenja recenzenata.

Originalni nauĉni radovi sadrţe rezultate izvornih istraţivanja. Nauĉne informacije u radu moraju biti obraĊene i izloţene tako da se mogu eksperimenti ponoviti i provjeriti analize i zakljuĉci na kojima se rezultati zasnivaju. Kratka saopštenja sadrţe rezultate kratkih ali završenih istraţivanja ili opise izvornih laboratorijskih tehnika. (metoda, aparata itd) Prethodno saopštenje sadrţi nauĉne rezultate ĉiji karakter zahtijeva hitno objavljivanje, ali ne mora da omogući provjeru i ponavljanje iznesenih rezultata. Pregledni rad predstavlja cjelovit pregled nekog podruĉja ili problema na osnovu već publikovanih materijala koji je u pregledu sakupljen, analiziran i raspravljen Struĉni rad predstavlja koristan prilog iz podruĉja struke, a ĉija problematika nije vezana za izvorna istraţivanja. Struĉni rad se odnosi na provjeru ili reprodukciju poznatih istraţivanja i predstavlja koristan materijal u smislu širenja znanja i prilagoĊavanja izvornih istraţivanja potrebama nauke i prakse.

Kategorizacija nauĉnih i struĉnih radova data je prema preporukama UNESKO-a Radovi svrstani u ove kategorije podlijeţu ocjenjivanju dvaju recenzenata. Recenzije su dvosmjerno anonimne, odnosno recenzentima se ne otkriva identitet autora i obratno. Rad će se objaviti jedino na osnovu pozitivnih

recenzija , o ĉemu će Uredništvo obavjestiti autora. Recenzenti se biraju meĊu struĉnjacima u neposrednom podruĉju istraţivanja na koja se odnosi rad predloţen za objavljivanje. U pravilu recenzent ne moţe biti autorov saradnik niti pretpostavljeni.

2. Glasnik hemiĉara, tehnologa i ekologa RS objavljuje radove koji ne podlijeţu recenziji:

- mišljenja i komentari - prikazi i saopštenja iz prakse u obliku dopisa ili prevoda stranih ĉlanaka -

3. Glasnik hemiĉara, tehnologa i ekologa RS moţe ukljuĉivati dodatke sa kongresa, savjetovanja ili simpozijuma. 4. Autor je u potpunosti odgovoran za sadrţaj rada. Uredništvo pretpostavlja da su autori prije podnošenja rada regulisali pitanje objavljivanja sadrţaja rada saglasno pravilima ustanove ili preduzeća u kojem rade. 5. Brzina kojom će se rad objaviti zavisiće o tome koliko rukopis (tekst) odgovara uputama. Radovi koji zahtijevaju veće prepravke ili dopune biće vraćeni autoru na preradu prije recenzije.

UPUTSTVO ZA PISANJE RADOVA

1. Rad se dostavlja Uredništvu ĉasopisa elektronski (e-mailom ili na CD-u poštom) s tekstom pripremljenim iskljuĉivo pomoću programa za obradu teksta Microsoft Word.

2. Ukoliko se rad šalje poštom, ispis rada zajedno sa CD-om poslati na adresu: Uredništvo "Glasnika hemiĉara, tehnologa i ekologa RS" Tehnološki fakultet, Vojvode Stepe Stepanovića 73, 51000 Banjaluka.

3. Rad treba da ima najviše 10 strana i da sadrţi sljedeće dijelove na jednom od jezika Bosne i Hercegovine ili na nekom od priznatih evropskih jezika: naslov, spisak autora i ustanova, saţetak, uvod, materijal i metode rada, rezultati i diskusija, zakljuĉak, literatura, naslov na engleskom jeziku, spisak autora i rezime na engleskom jeziku.

4. Naslov rada pisati centrirano i velikim slovima (Times New Roman, 14 pt, bold, Caps Lock), autore pisati centrirano bez titule i sa nazivom ustanove (Times New Roman, 10 pt, normal). Podnaslove pisati centrirano, (Times New Roman, 12 pt, bold). Ostale dijelove rada treba pisati sa obostranim ravnanjem redova (Times New Roman, 12 pt), jednostranim proredom sa jednim praznim redom iznad, izmeĊu podnaslova i izmeĊu pasusa, sa marginama od 2.54 cm (1"). Poĉetak pasusa kucati od poĉetka reda.

5. Saţetak treba da ima 100-250 rijeĉi, a stoji izmeĊu zaglavlja rada (koji ĉini naslov rada, i podaci o autorima) i kljuĉnih rijeĉi, nakon kojih slijedi tekst rada.

6. Ukoliko je rad napisan na maternjem jeziku, saţetak na engleskom jeziku se daje u proširenom obliku, kao tzv. rezime i treba da sadrţi do 500 rijeĉi.

7. Tabele uraditi u WORD-u, a grafike u EXCEL-u izuzev posebnih sluĉajeva kada to tehniĉki nije moguće, i treba da budu jasne, što jednostavnije i pregledne. Naslov, zaglavlja (tekst) i podtekst u tabelama i grafikama treba da budu napisani fontom Times New Roman – normal, Font Size 10 pt. Tabele se stavljaju na odreĊeno mjesto u tekstu. Tabele ne bi smjele sadrţavati više od deset okomitih kolona i više od petnaest vodoravnih redova. Ukoliko autor ocjenjuje da podatke mora prikazati u većem broju kolona i redova, potrebno je sadrţaj tabele podijeliti u dvije ili više manjih tabela ili je dostaviti u posebnom prilogu. Moraju se izraditi prema kompjutorskom predlošku (Insert Table), a ne pomoću razmaka, taĉki i tabulatora.

8. Jednaĉine pisati u grafiĉkom editoru za jednaĉine, iskljuĉivo u Microsoft Equation i postaviti je na poĉetak teksta. Na desnom rubu teksta, u redu na kojem je pisana jednaĉina, u zagradi treba naznaĉiti njen broj, poĉevši od broja 1.

9. Fotografije moraju biti pripremljene za crno-bijelu štampu tj. ako je izvorna slika u bojama koje se u crno bijeloj štampi ne razlikuju, boje se moraju zamijeniti ―rasterom‖ tj. razliĉitim grafiĉkim znakovima koje je potrebno objasniti u legendi. U slike se unosi samo najnuţniji tekst potreban za razumijevanje kao što su mjerne varijable s njihovim dimenzijama, kratko objašnjenje na krivuljama i sl. Ostalo se navodi u legendi ispod slike. Maksimalna veliĉina slike je 13 cm x 17 cm. Fotografije, crteţe, sheme (izvorni format faila - TIF, JPG sa 300 dpi, ili vektorski format sa slovima pretvorenim u krive – CDR) i grafikone, osim u tekstu na predviĊenom mjestu, dati i u posebnom prilogu.

10. Radi uspješnog ukljuĉivanja radova objavljenim na jednom od jezika Bosne i Hercegovine u meĊunarodne informacione tokove, dijelove rukopisa treba pisati na jeziku autora i na engleskom jeziku, i to: tekst u tablicama , slikama, dijagramima i crteţima , njihove naslove i oznake.

11. Pri slanju rada navesti i punu sluţbenu adresu, telefon i e-mail svih autora i naglasiti autora s kojim će Uredništvo saraĊivati. Ove obavjesti priloţiti na posebnom listu.

12. Eksperimentalna tehnika i ureĊaji opisuju se detaljno samo onda ako znatno odstupaju od opisa već objavljenih u literaturi. Ukoliko su tehnike i ureĊaji poznati navodi se samo izvor potrebnih obavjesti.

13. Simbole fiziĉkih veliĉina treba pisati kurzivom (Times New Roman, 12 pt. – italik), a mjerne jedinice uspravnim slovma, npr. V, m, p, t, T, ali m3, kg, Pa, 0C, K.

14. Veliĉine i mjerne jedinice se moraju upotrebljavati u skladu sa MeĊunarodnim sistemom jedinica (SI). 15. Literaturne citate numerisati onim redom kojim se pojavljuju u tekstu. Citati se u tekstu oznaĉavaju

arapskim brojevima u uglastoj zagradi [ ]. Kratice za ĉasopise moraju biti strogo u skladu sa kraticama kako ih navodi Chemical Abstract. Literaturu treba citirati na sljedeći naĉin:

Primjer citiranja nauĉnog ĉasopisa:

Moreno, S., Scheyer, T., Romano, C.S., Vojnov, A.A.: Antioxidant and antimicrobial activities of rosemary extracts linked to their polyphenol composition. Free Radical Research, 40 (2) (2006) 223–231.

Primjer citiranja knjige:

Banks, W. and Greenwood, C.T.: Starch and its Components, Edinburgh University Press, Edinburgh (1975) p. 98.

Primjer citiranja poglavlja u knjizi:

Fogarty, W. and Kelly, C.: Pectic enzymes, in Microbial Enzyme and Biotechnology. Eds. Fogarty, W. Applied Science Publishers, London (1983) pp. 131-182.

Primjer citiranja rada u zborniku:

Ţabić, M. i Kukrić, Z.: : Inhibicija aktivnosti tripsina ferocenom i njegovim derivatima, VIII Savjetovanje hemiĉara i tehnologa Republike Srpske, zbornik radova, Banjaluka, 27. i 28. novembar 2008., str. 75-84.

Primjer citiranja magistarskih radova i disertacija:

Petrović, R.: Dehidratacija etera na mordenitnim katalizatorima. Magistraski rad, Univerzitet u Banjaluci, Tehnološki fakultet, Banja Luka, 2001.

Primjer citiranja patenta:

Ehrenfreund J.: (Ciba Geigy A.–G.): Eur.Pat.Appl. 22748, 21 Jan (1981) 7078 Primjer citiranja web stranice: Environment Agency: Leachte Treatment (Online). Dostupno na:

http://www.environment-agency.gov.uk/business/sectors/37063.aspx

(19. 09. 2011.)

Obavezno navesti datum citiranog podatka

Neobjavljeni rezultati:

Citiraju se sa jednim od sljedećih komentara "u štampi"; "neobjavljen rad"; "liĉna komunikacija"

Radovi, koji nisu napisani striktno po ovom uputstvu, neće biti prihvaćeni za štampu

http://www.environment-agency.gov.uk/business/sectors/37063.aspx

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ANALITIĈKA OBRADA ĈASOPISA

GLASNIK HEMIĈARA, TEHNOLOGA I EKOLOGA REPUBLIKE SRPSKE

God. 7, br. 11 (2015)

1 ANALIZA osetljivosti procesa osmotske dehidratacije mesa srebrnog karaša (carassius gibelio) u tri razliĉita osmotska rastvora / Biljana Lonĉar, Vladimir Filipović, Milica Nićetin, Violeta Kneţević, Lato Pezo, Marijana Aĉanski. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511041L.

U:. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 41-47. 597.551.2:66.047.3 COBISS.RS-ID 5803288

2 CHEMOMETRIC Approach to Determination of the Authenticity of Different Types of Serbian and Macedonian Brandy / Sanja O. Podunavac-Kuzmanović, Lidija R. Jevrić, Strahinja Z. Kovaĉević, Biljana V. Marošanović, Maja M. Lojović. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511011K. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 11-17. 543.51:546.791.027 COBISS.RS-ID 5802264

3 ĐUĐIĆ, Radana Uticaj koncentracije rastvora cefaleksina na sorpciju na modifikovano celulozno vlakno / Radana ĐuĊić, Pero Sailović, Branka Rodić Grabovac, Boro Rudić. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511019Dj. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 19-23. 615.33.012:661.728.7.094.94 COBISS.RS-ID 5802520

4 POREĐENJE kinetike prenosa mase isto-strujnog i protiv-strujnog procesa osmotske dehidratacije svinjskog mesa / Vladimir Filipović, Biljana Lonĉar, Milica Nićetin, Violeta Kneţević, Marijana Aĉanski. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511033F.

U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 33-40. 637.5`64:66.047.3 COBISS.RS-ID 5803032

http://dx.doi.org/10.7251/GHTE1511041L

http://www.rs.cobiss.net/scripts/cobiss?command=DISPLAY&base=COBIB&RID=5803288

http://dx.doi.org/10.7251/GHTE1511011K


http://dx.doi.org/10.7251/GHTE1511019Dj


http://dx.doi.org/10.7251/GHTE1511033F




• централа: 051 / 215 859, 215 866 • е-пошта: [email protected] • директор / секретарица: (тел) 051 / 215 894, (факс) 051 / 217 040 • секретар: 051 / 215 822

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JИБ: 4401722970003 • жиро рачун: 562-099- 00001695-65

5 SIMURDIĆ, Ljiljana Primjena razliĉitih metoda za odreĊivanje koncentracije / Ljiljana Simurdić, Mirjana Dragoljić, Vesna Matić. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511057S. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 57-64. 613.81/.83:616-056.8 COBISS.RS-ID 5803800

6 SULJKANOVIĆ, Mersiha Odabir organskog rastvaraĉa kao teĉne membrane tokom transporta metalnih kationa / Mersiha Suljkanović, Ţeljka Nikolić, Edita Nurković. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511025S. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 25-32. 553.611.66.061.18 COBISS.RS-ID 5802776

7 TREND razvoja primjene superkritiĉnih fluida u industriji / Vladan Miĉić, Suzana Yusup, Sabina Begić, Pero Dugić, Zoran Petrović, Yi Herng Chan. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511065M. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 65-71. 621.643:532.54 COBISS.RS-ID 5804056

8 UTICAJ toplotnog dejstva i karakteristika sita na kvalitet otisaka dobijenih crnom bojom na tekstilnim materijalima / Mladen Stanĉić, Nemanja Kašiković, Branka Ruţiĉić, Dragoljub Novaković, Dragana Grujić, Rastko Milošević. - Naĉin dostupa (URL): http://dx.doi.org/10.7251/GHTE1511049S. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 49-56. 677.1/.5:667.2 COBISS.RS-ID 5803544

9 ŢABIĆ, Mirjana Antioksidativna aktivnost biljaka iz familije Polygonaceae / Mirjana Ţabić. - Naĉin dostupa (URL):http://dx.doi.org/10.7251/GHTE1511001Z. U: Glasnik hemiĉara, tehnologa i ekologa Republike Srpske. - ISSN 1840-054X. - God. 7, br. 11 (2015), str. 1-9. 582.665.11:635.89 COBISS.RS-ID 5802008

http://dx.doi.org/10.7251/GHTE1511057S




http://dx.doi.org/10.7251/GHTE1511065M




http://dx.doi.org/10.7251/GHTE1511001Z




• централа: 051 / 215 859, 215 866 • е-пошта: [email protected]

• директор / секретарица: (тел) 051 / 215 894, (факс) 051 / 217 040 • секретар: 051 / 215 822 • помоћник директора / матична служба: 051 / 215 750

JИБ: 4401722970003 • жиро рачун: 562-099- 00001695-65

REGISTAR NASLOVA

Analiza osetljivosti procesa osmotske dehidratacije mesa srebrnog karaša (carassius gibelio) u tri razliĉita osmotska rastvora 1

Antioksidativna aktivnost biljaka iz familije Polygonaceae 9

Chemometric Approach to Determination of the Authenticity of Different Types of Serbian and Macedonian Brandy 2

Odabir organskog rastvaraĉa kao teĉne membrane tokom transporta metalnih kationa 6

PoreĊenje kinetike prenosa mase isto-strujnog i protiv-strujnog procesa osmotske dehidratacije svinjskog mesa 4

Primjena razliĉitih metoda za odreĊivanje koncentracije 5

Trend razvoja primjene superkritiĉnih fluida u industriji 7

Uticaj koncentracije rastvora cefaleksina na sorpciju na modifikovano celulozno vlakno 3

Uticaj toplotnog dejstva i karakteristika sita na kvalitet otisaka dobijenih crnom bojom na tekstilnim materijalima 8

IMENSKI REGISTAR

Dragoljić, Mirjana (autor) 5

ĐuĊić, Radana 3

Filipović, Vladimir (autor) 4

Lonĉar, Biljana (autor) 1

Matić, Vesna (autor) 5

Miĉić, Vladan (autor) 7

Nikolić, Ţeljka (autor) 6

Nurković, Edita (autor) 6

Podunavac-Kuzmanović, Sanja O. (autor) 2

Rodić Grabovac, Branka (autor) 3

Rudić, Boro (autor) 3

Sailović, Pero (autor) 3

Simurdić, Ljiljana 5

Stanĉić, Mladen (autor) 8

Suljkanović, Mersiha 6

Ţabić, Mirjana 9

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HEMIĈARA, TEHNOLOGA I EKOLOGA · BOSNA I HERCEGOVINA DECEMBAR, 2016. Glasnik hem. teh. i ek. RS GHTERS 12 1-45 . Glasnik hemiĉara, tehnologa i ekologa Republike Srpske Gazette of