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Vol.2, No.1, 2012
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Table of Contents
Articles Uric Acid Inhibition Activity of Annona muricata L Leave Extract in Hyperuricemia induced Wistar Rat
Sri-Wahjuni, Putra-Manuaba, I. B., Rahayu-Artini, N. P., and Wahyu-Dwijani, S.
Chemistry Department, Faculty of Math and Science, Udayana University, Bali-Indonesia 81 - 90 Kinetics of Organic Dyes Degradation in Water Using Vacuum Ultra Violet Radiation
Khaled M. Elsousy Alaqsa University, Gaza, Gaza strip, Palestinian Territories 91 - 97 Occurrence and prevalence of four viruses infecting tomatoes in Northern districts of West Bank, Palestinian Territories
Hazem Sawalha Department of Biology and Biotechnology, Faculty of Arts and Sciences, Arab American University of Jenin, Palestine 98-101 Study of Liquefied Petroleum Gas Heating Value A Thermodynamics Approach
Niaz Bahar Chowdhury, 1Dr. Md. Iqbal Hossain Chemical Engineering Department, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh 102-105 Advances in Pure and Applied Chemistry (APAC) 86 Vol. 2, No. 1, 2012, ISSN 2167-0854 Copyright © World Science Publisher, United States www.worldsciencepublisher.org
Uric Acid Inhibition Activity of Annona muricata L Leave Extract in Hyperuricemia induced Wistar Rat
Sri-Wahjuni, Putra-Manuaba, I. B., Rahayu-Artini, N. P., and Wahyu-Dwijani, S.
Chemistry Department, Faculty of Math and Science, Udayana University, Bali-Indonesia
Abstract-This research aims to find a cure of gout, base on the utilization of Annona muricata. The research was started with descriptive study to explore active components of Annona muricata leaf and followed by an experimental study to investigate uric acid inhibition activity of the leaf extract in hyperuricemia induced wistar rat. We observed three dominant components, i.e. 2,3-dihidrobenzofuran; 3-ethoxy-1,4,4a,5,6,7,8,8a-octahydroisoquinoline; 2- cyclohexen-1-one, 4-hydroxy-3,5,6-trimethyl-4-(3-oxo-1-butenyl) which were probably active to inhibit uric acid formation in hyperuricemic induced wistar rat. In this study, n-buthnol was applied for partitioning the relatively pure compound. The n-buthanol extract obtained was then applied to cure hyperuricemic rat induced by a mixture of chicken livers and Gnetum gnemon a high purine diet. It was obtained, that the highest extract dose of 400 mg/kgBW was able to inhibit the formation of uric acid in hyperuricemic rat. It can be concluded that Annona muricata leaf extracted with n-buthanol in a dose of 400 mg/kg BW has an ability to inhibit further formation uric acid in hyperuricemic rat. Therefore, this natural plant is potent to develop for hyperuricemic medicine.
Keywords: gout, Annona muricata, hyperuricemic rat, active components
Introduction often used in treating this condition, as it possesses many anti-inflammatory compounds. Other helpful herbs Uric acid is a metabolic product of exogenous include turmeric, boswellia, cayenne, colchicum and (brought in with food) or endogenous purine bases. This hyssop were also potent to treat hyperurisemia. acid in most physiologic fluids is an end product of Clearly, uric acid is produced by purine nucleoside purine degradation. The serum urate level in a given metabolism through hipoxanthin, xanthin, and guanin patient is determined by the amount of purines basic purine. Distortion of this metabolism leads to synthesized and ingested, the amount of urate produced elevate level of uric acid and known as hyperuricemia.5 from purines, and the amount of uric acid excreted by the Annona muricata L is a traditional plant in Bali known kidney (and, to a lesser degree, from the gastrointestinal as sirsak, empirically in Balinese traditional medicine tract).1,2 Gout is an inflammatory arthritis caused by the was proven as a cure of hyperuricemia. This study was deposition of monosodium urate crystals in tissues.1 This carried in order to investigate the component active of the condition typically occurs after years of sustained plant that have an ability to inhibit further uric acid hyperuricemia. It is estimated to affect 5.1 million people formation in the hyperuricemia wistar rat. in the United States according to the most recent National Health and Nutrition Examination Survey (NHANES Methods III).2 Gout affects approximately 2% of men older than This study employs two research methods, i.e. 30 years and 2% of women older than 50 years, and is the descriptive explorative to determine the active most common form of inflammatory joint disease in men components of Annona muricata L leaf extracted with n- older than 40 years. Serum uric levels are, on average, buthanol and followed by experimental study to observed 0.5 to 1.0 mg/dL higher in men than women, making their hyperuricemia activity. male sex a risk factor for hyperurisemia and gout. Lower Leaf extract was obtained through maseration process serum uric levels in women are associated with the using methanol and followed by partition using n- presence of estrogen, which is thought to act as an buthanol. Crude extract obtained was the identified by antihyperuricemic.3 In Indonesia, based on Health Survey applying GS-MS instrument. in the year of 2005, there were around 10-20% men and Post only control group design was applied for postmonopause women have a higher levels of uric acids experimental study, in which a number of 20 Wistar Rat than normal person.4 It was proven that, celery seed is 1.5 month age and 70-75 g of weight recruited in this
Sri-Wahjuni et al, APAC, Vol. 2, No. 1, pp. 86-90, 2012 87
study and devided into 5 groups. First group is a negative (2,4,6-tribromo-3-hydroxybenzoic acid) was then added control group in which rat fed with a mixture of 4 g/kg to the serum obtained. The mixture was then incubated BW of Gnetum gnemon and 50 mL/kg BW of chicken- for 10 minutes at a temperature of 370C. Then, optical liver juice in ad libitum manner. The second group is density of the mixture was determined using simillar to first group instead of delivering an anti- sphectrophotometer at 546 nm of wave number. hyperuricemia medicine, allopurinol in a dose of 10 ANOVA was performed to determine the different mg/kg BW oraly. The third group is simillar to the first effect amongst treatment with p<0.05 was consider group instead of delivering Annona muricata L extract in significant. a dose of 100 mg/kg BW oraly. The fourth and five groups have similar treatment to the first group, instead Results of have extract of Annona muricata L in dose of 200 mg/kgBW and 400 mg/kgBW, respectively. Descriptive study Animal ethical clearance was obtained from a local authority body at Veterinary Faculty Udayana University, Around 1,200 g of Annona muricata L. leaf powder Bali-Indonesia. Around 1 mL of blood was taken from was macerated with methanol for overnight. From this, a rat heart aorta which was anesthesia before proceeding. number of 158 g crude extract was obtained. This crude The blood was then centrifuged for 15 minutes at the rate extract was then tested for its antioxidant activity using of 3.000-3.500 rpm. Uric acid reagent, FS TBHBA DPPH test. The tes results was presented in Table 1.
Table 1. Antiozidant Activity Test of Annona muricata L Crude Extract Absorbance Sampl Time A % Test 497 517 537 e (minutes) 517 nm inhibition nm nm nm Crude 5 DPPH 0.714 0.785 0.698 0.0790 77.22 extract Sampl 0.635 0.593 0.515 0.0180 % e 60 DPPH 0.651 0.704 0.613 0.0720 85.42 Sampl 0.527 0.508 0.468 0.0105 % e
The crude extract was the purified by applying anti-oxidant ativity indicates by their DPPH test. partition using petroleum ether, chlroform, n-buthanol, Therefore, the n-buthanol extract was then identified and water. Amongst them, in this research, it was Phythochemically using a number of reagent as indicated obtained that partiton with n-buhanol produce the highest in Table 2.
Table 2. Phythochemical Test of n-Buthanol Extract N Compounds Reagent Coloue Changes Resul o. ts 1 Alkaloid Meyer Yellow - orange - . (without white Wagner precipitate) - Yellow - chocolate (without chocolate precipitate) 2 Flavonoid Wilstatter Yellow - crimson + . NaOH 10 % Yellow - chocolate + H2SO4 concentrated Yellow - crimson + Bate Smith-Metacalf Yellow - red + 3 Triterpenoid Lieberman-Burchard Yellow - chocolate + . H2SO4 10 % Yellow - chocolate + 4 Saponin Hot water + HCl No foam formation - . 5 Phenolate Hot water + FeCl3 Yellow – greenish black + . (tannin) 6 Steroid Lieberman-Burchard Yellow - chocolate - . H2SO4 10 % Yellow - chocolate Remarks: (+) = containing compound tested (-) = not containing compound tested
Sri-Wahjuni et al, APAC, Vol. 2, No. 1, pp. 86-90, 2012 88
The most active extract was then identified by applying GC-MS, the chromatogram obtained was presented in Figure 1.
Figure 1. GC-MS Chromatogram of The Most Active Extract of Leaf Annona muricata L
Based on library data base of the GC-MS instrument, there were three compound detected as indicated in Table 3.
Table 3. Compound Identified Based on GC-MS Chromatogram Retentiom % Peaks Time Compounds identified Area (tR) Peak 1 11.29 minutes 31.4 benzofuran,2,3-dihidro 8 Peak 2 18.07 minutes 11.7 3-ethoxy-1,4,4a,5,6,7,8,8a- 1 octahydroisoquinoline Peak 3 18.70 minutes 30.8 2-cyclohexen-1-one, 4-hydroxy-3,5,6- 9 trimethyl-4-(3-oxo-1-butenyl
Experimental study hyperuricemia condition was achieved, the rat then was fed with varies dose of leaf Annona muricata L extract, i.e In this study, increase uric acid in wistar rat was 100 me/kgBW, 200 mg/kgBW, and 400 mg/kgBW. Other achieved by intake of high purine diet. Rat were fed with treatments are positive control using allopurinol and a mixture of 4 g/kg BW of Gnetum gnemon with 50 negative control. The uric acid concentration of mL/kg BW of chicken liver ad libitum. After hyperurisemia rat were presented in Table 4.
Table 4. Uric Acid Levels of Hyperurisemia Wistar Rat Tratrment group Uric acid concentration (mg/dL) Day-6 Day-9 Day-14 Day-18 Hyperurisemia Control (H)1 3.48 4.05 4.35 4.98 Control (H)2 5.54 5.65 5.87 6.07 Control (H)3 4.48 4.62 5.97 6.23 Control (H)4 4.25 4.65 5.03 5.67 Average 4.44 4.74 5.31 5.74 Allopurinol dose 10 mg/kg BW Control positive 1 3.81 4.39 3.46 3.42 Control positive 2 3.50 6.23 4.35 3.88 Control positive 3 3.96 6.88 5.77 5.34 Control positive 4 4.38 8.19 4.50 3.08
Sri-Wahjuni et al, APAC, Vol. 2, No. 1, pp. 86-90, 2012 89
Average 3.91 6.42 4.52 3.93 Extract dose of 100 mg/kg BW Treatment I1 4.81 7.18 3.35 3.08 Treatment I2 4.19 6.11 3.00 2.65 Treatment I3 4.50 5.73 4.19 3.96 Treatment I4 4.92 6.04 3.77 3.50 Average 4.61 6.27 3.58 3.30 Extract dose of 200 mg/kg BW Treatment II1 3.00 3,38 2,31 1,61 Treatment II2 3.27 3,57 3,00 1,69 Treatment II3 4.11 4,35 2,61 1,69 Treatment II4 3.73 4,11 3,04 2,73 Average 3.53 3,85 2,74 1,93 Extract dose of 400 mg/kg BW Treatment III1 3.69 4.69 3.00 3.00 Treatment III2 3.81 5.15 3.77 3.00 Treatment III3 3.77 4.19 2.73 2.31 Treatment III4 4.04 7.69 5.19 3.96 Average 3.83 5.43 3.67 3.09
Anova test indicates there was a significant different determined. In this study, uric acid levels of normal rats between treatment and control groups, indicate by p < were in the range of 1.7 – 3.0. After induction with high 0.05. purine diet the uric acid levels of the rat was increase roughly, in which all rats have uric acid levels above 3 Discusions mg/dL, on average of 4.74 0.665 mg/dL. It can be said, that all experimental rats are in hyperuricemia condition. Discriptive study Rats induced hyperuricemia were achieved during 9 days after feeding with high purine diet. Then, on day-10 As can be seen in Table 2, n-buthanol fraction based all experimental rats receive treatment for decreasing uric on phytochemical test was positively containing acid levels. Five groups of experiment were carried out as flavonoid, triterpenoid, and phenolate indicates by the mentioned on the method. The treatment was stopped on colour changes for all compounds type tested. This is the day-18 and uric acid leves were detrmined for all because of n-buthanol is a polar solvent with 3.9 of experimental rats. polarity index.6 Generally, the present of glucose bind to In this study we obtain that for positive control group flavonoid group results in the compound easier to solve treated with allopurinol, there is a 51.93% decrease of 7 on water and polar solvent. Tannin group is a phenolate uric acid levels, their uric acid levels become 3.93 0.995 compound, that has a tendency to solve in water and polar mg/dL. For the varies extract treatment, i.e. dose of 100, solvent. On the other hand, triterpenoid group of 200, and 400 mg/kg BW, the uric acid decrease levels compound is a pentacyclic compound tend to solve in obtained are 63.98%, 86.29%, and 61.50%, respectively. nonpolar solvent. GC-MS analysis confirms three Therefore, the optimum dose of 200 mg/kg BW produces important compounds observed as indicates on Table 3. the highest decrease. All of these compounds are benzofuran,2,3-dihidro, 3- Allopurinol was applied in this study as a positive ethoxy-1,4,4a,5,6,7,8,8a-octahydroisoquinoline, and 2- control, since this medicine is a cure for hyperuricemia cyclohexen-1-one, 4-hydroxy-3,5,6-trimethyl-4-(3-oxo-1- case. In low dose this compound has an ability to inhibit butenyl. The present of triterpenoid is probably due to the the formation of xanthine oxidase enzyme.8 Allopurinol present of hydroxide group on the structure. The extract dose of 10 mg/kg BW applied is on the basis of Zhao et that contain all these thee compound was then tested for al, (2005), they obtain this dose was effective to decrease their anti-hyperurisemia activity. uric acid levels until 125.59 1.49 on their mice experimental study.9 Experimental study Conclusion A number of 20 wistar rat were adapted in a laboratory condition. Then, all of these rats were fed with high This study investigates the application of natural plant, purine diet, i.e. a mixture of 4 g/kg BW of Gnetum Annona muricata L as a cure of hyperuricemia on gnemon and 50 mL/kg BW of chicken liver and mix with experimental rat. The rat was induced to become 100 g pelete a standard diet for rat. On day-6 and day-9, hyperuricemia by feeding the animal with high purine about 1 mL of blood were taken from the heart aorta of diet. Traditionally, in Bali this plant was applied to cure the rat to determine the increase of uric acid. Before hyperurucemia, therefore, we would like to collect treatment uric acid serum level of the rats were scientific data of this plant. In this study, three
Sri-Wahjuni et al, APAC, Vol. 2, No. 1, pp. 86-90, 2012 90
compounds, i.e. benzofuran,2,3-dihidro, 3-ethoxy- 2. Mandell, B. F. 2008. Clinical manifestations of 1,4,4a,5,6,7,8,8a-octahydroisoquinoline, and 2- hyperuricemia and gout. Cleveland Clinic Journal of cyclohexen-1-one, 4-hydroxy-3,5,6-trimethyl-4-(3-oxo-1- Medicine Volume 75, Supplements 5 July 2008. butenyl) were identified. However, this still need to be 3. Luk AJ, Simkin PA. Epidemiology of further investigated. Our study also gained that the extract hyperuricemia and gout. Am J Manag Care. 2005;11 (15 leaf of this plant is potent to develop as a cure for Suppl):S435-S442; quiz S465-S468 [Review]. hyperuricemia, since we obtain that the dose of 200 4. Saraswati-Sylvia. 2009. Diet Sehat Untuk mg/kg BW of rat is effective to decrease uric acid levels. penyakit Asam Urat, Diabetes, Hipertensi, dan Stroke, This also need to be investigaed further, whether that will Yogyakarta, A-Plus Books. give simmilar effect on human. 5. Harn-Shen, C. 2011. Clinical implications of the metabolic syndrome and hyperuricemia. Journal of the Akcnowledgment Chinese Medical Association 74 (2011) 527-528. 6. Snyder, C. R., et al, 1997. Practical HPLC The authors would like to thank Staff of UPT Lab. Method Development, Second Edition. New York:John Analitik Udayana University for access and aid of their Wiley and Sons, Lnc, Hal 722-723. fasilities for managing the research. Thanks also to Mr. 7. Markham, K. R., 1988, Cara Mengidentifikasi Priono from Kristallindo for providing reagents for uric Flavonoid, ITB, Bandung, Hal 15-17. analysis, Mr. Rudy at Forensic Laboratory Police 8. Tjay, T.H., dan Raharja., 2002, Obat-Obat Department for help in assessing the GC-MS data. And penting, Khasiat, Penggunaan dan Efek-Efek sampingnya, special thank to Vetinery Board for providing rat for this Edisi V, Cetakan ke-2, Penerbit PT. Eleks Media experiment. Komputindo Kelompok Gramedia, Jakarta. 9. Zhao, X., Zhu, X. dan Pan, Y., 2005, Effects Of References Cassia Oil On Serum and Hepatic Uric Acid Levels In Oksonate-Induced Mice and Xantine Dehiydrogenase and 1. Stankov, M., Predrag, D., and Stankov, D. 2003. Xantin Oksidase Aktivities In Mouse Liver, Journal Of Determination of uric acid in human serum by an Ethnopharmacology, (http:/ enzymatic method using N-methyl-N-(4-aminophenyl)-3- www.elsevier.com/locate/jethpharm, diakses 15 Agustus methoxyaniline reagent. J.Serb.Chem.Soc. 68(8–9)691– 2005 698.
Advances in Pure and Applied Chemistry (APAC) 91 Vol. 2, No. 1, 2012, ISSN 2167-0854 Copyright © World Science Publisher, United States www.worldsciencepublisher.org
Kinetics of Organic Dyes Degradation in Water Using Vacuum Ultra Violet Radiation
Khaled M. Elsousy
Alaqsa University, Gaza, Gaza strip, Palestinian Territories
Corresponding: Dr. Khaled M. Elsousy, [email protected]
Abstaract: In this study vacuum ultraviolet (VUV) radiation (185 nm wave length) was used in the presence of atmospheric oxygen as an advanced oxidation technique. Six organic dyes were examined as model pollutants (methyl violet, methyl blue, brilliant green, malachite-green, Remazole blue B and picric acid). Picric acid as the most persistent one was selected for more detailed kinetic investigations. The influence of each of the related main parameters was studied, Radiation time, salinity, pH, temperature and radiation intensity. Kinetics of the oxidation reaction was studied. COD was also followed up. It follows from the results that vacuum-UV radiation of 185 nm in the presence of atmospheric oxygen is an efficient method for the oxidation process. Four of sex examined dyes were degraded in different rates according to persistency of each pollutant dye. The reaction rates were in the order of: (methyl violet > methyl blue >brilliant green > remazole > malachite green> picric acid). In the case of picric acid; the reaction was promoted by rising the temperature, raising or lowering pH above and below pH 7.0, increasing radiation dosage. The rate was inhibited by increasing salinity and buffering. The present technique was found promising in the elimination of the persistent organic pollutants out of the treated water.
Keywords: Advanced oxidation process - Vacuum ultraviolet - Wastewater treatment, Radiochemistry, Organic pollutants.
1. Introduction the solution such as H2O2 or with a catalyst surface such as TiO2. (US.EPA 1998; Bakardjieva et al 2005; During recent years the Advanced Oxidation Bakardjieva et al 2004). Processes (AOPs) have become an important group of techniques to the treatment of hazardous water Peroxone is another technique including the oxidation contaminants, with an increasing number of feasible of organic pollutants using ozone with H2O2 was also applications. (Ahmed et al. 2011) Normally, the main reported. (Ben Abdelmelek et al. 2011; Ben Abdelmelek reason for the use of AOPs is the resistivity and/or the et al. 2010; Chu et al. 2022) Many studies were toxicity of pollutants that makes unfeasible the biological conducted concerning the elimination of the hardly- treatment. Although AOPs use different reacting systems, oxidized water pollutants by different catalytic methods using hydrogen peroxide as the main source of OH free all are characterized by the same chemical feature: production of OH free radicals. These radicals are radicals. Persisting pollutants such as phenol derivatives, extraordinarily reactive species. (Ahmed et al. 2010) (Ben Abdelmelek et al. 2011; Ben Abdelmelek et al. The oxidation reactions involving hydroxyl radical and 2010) aromatic pesticides, (Chu et al. 2011; Chu et al. organic substrates in aqueous solution may be classified 2010) fuel additives, dyes, and some other with respect to their character to: (Bossmann et. al. 1998) pharmaceutical drugs has been treated. (Radjenovic et al. a. Abstraction of hydrogen: .OH +RH 2009; Gaya et al. 2008) . To date, there are many evidences supporting the idea R + H2O . b) Addition reactions: .OH + PhX that hydroxyl radical ( OH) are the main oxidizing HOPhX. species responsible for photo-oxidation of the majority of c) Electron transfer: .OH +RH the studied organic compounds. (Ollis et al. 1991; Dodd [+R-H] + HO- et al. 2009; Benites et al. 2009; Prevot et al. 1999) Vacuum-UV irradiation of wavelength <190nm, initiates AOPs are characterized by a free radical mechanism reactions that produce hydroxyl radicals, hydrogen initiated by the interactions of photons of a proper energy atoms, and aqueous electrons which play important roles level with the molecules of chemical species present in during degradation of organic substrates in water. Depletion rate of organic contaminants depends on the
Khaled M. Elsousy, APAC, Vol. 2, No. 1, pp. 91-97, 2012 92
reaction rate of compounds of interest with hydroxyl Spectrophotometer (Spectrum-900-USA) has been radicals. Aqueous electrons are powerful reducing agents used for the spectroscopic measurements. A Hanna pH and act as nucleophiles. They react with substrates with meter was used to adjust the pH of different solutions. one-electron transfer process. One of the most important reactions of aqueous electrons is with halogenated 2.3 Methodology organic compounds resulting elimination of halide anions. The reaction kinetic study was conducted to compare . . + - . H2O (L) + h (< 190 nm) H + OH H + e + OH similar samples of different pollutants; the samples have Carbon centered radicals, formed by their reaction been treated identically under the same conditions of with hydroxyl radicals, may result in the formation of pollutant concentration (mg/l), circulating rate (0.65 dm3/ higher molecular weight compounds hindering min), aeration rate (6.0 watt pump), working temperature mineralization and TOC (Total Organic Carbon) (25.0 Co) and reaction volume (2500 ml). reduction. This problem may be surmounted by bubbling Substrates depletion rates were followed oxygen gas. (Oppenländer 2003b) spectrophotometrically. For each pollutant separately It was reported that (VUV) radiation produced by an substrate concentration through the reaction term was immersed Xe-excimer light source (172 nm) was determined. Each dye was followed at the proper max investigated for the oxidative degradation of organic (picric acid at 355 nm, remazole at 570 nm, methyl blue pollutants in aqueous systems. ( Hashem et al. 1997; at 665 nm, methyl violet at 590 nm and malachite green Oppenländer and Gliese 1997; Chong et al. 2010) It was at 625 nm). Absorption bands max were obtained shown that the rates of degradation of the substrate practically, Calibration curves of concentration against decrease in the order of the applied processes, VUV/O3 > absorbance were obtained for the six dyes. O3 > VUV. Kinetic investigation was performed such that: in each Influence of the oxygen concentration on the rate and experimental run, reaction vessels were prepared with the reaction pathway of the degradation of organic proper volume (500 to 2500ml) of the reaction solution. compounds in aqueous solution by VUV-irradiation (Xe- The (observed reaction half-life) t1/2 was obtained for excimer: 172 nm) was reported. (Heering 2004) The each run. The half-life was approved because of the reaction rate was found to be strongly influenced by the ignorance of the exact reaction order since many concentration of dissolved molecular oxygen in the reactions are expected to proceed on the same time. volume of primary reactions. Samples of picric acid were read spectrophotometrically In the present research; 185 nm, VUV, radiation from with 0.02 mg/L detection limit at 355 nm max which was a low pressure mercury lamp in the presence of determined experimentally. Reaction parameters such as atmospheric oxygen will be studied as advanced salinity (ionic strength), temperature, light intensity and oxidation technique, the process is thought to be simple, reaction pH) were investigated and the resultant half- cheap and clean where no chemicals are to be used. Six lives were plotted against readings (or values) of each organic dyes will be tested as model pollutants, the parameter to clarify the relation graphically. Phosphoric method efficiency and the oxidation kinetic parameters acid (0.1M; H3PO4), and (0.1M; NaOH) were used to will be investigated on the most persisting one of them. adjust the reaction pH at the values of (5, 6, 7, 8 and 9).
2. Experimental 3. Results and Discussion
2.1 Materials. 3.1 Influence of the organic pollutant resistivity.
Picric acid; (2,4,6-trinitrophenol) was locally prepared Six organic pollutant were tested with respect to by the nitration of phenol, (Brewster et al. 1977) conversion or degradative oxidation, as shown in (Table Remazole blue B commercial grade was purchased from 1), it can be observed that the rate of depletion was in the (Brilliant Blue Daystar-LP, India), methyl blue, methyl order of (methyl violet > methyl blue > brilliant green > violet and malachite green, Solid sodium hydroxide and malachite green> picric acid). This order may be due to Phosphoric acid 85% ~15M were analytical grade of different persistency of the various functional groups of (Merck-Germany). Distilled water of (TDS 60 ppm) was each pollutant dye or the ease of oxidation. The used in all the experimental activities. experimental oxidation process was disturbed in two cases: the first was remazole case where a suspensional 2.2 Instruments colloid appeared after some time (15-30 minutes) of the degradation process and the second was the case of The main kinetic investigation system was a semi- malachite green where polymerization is thought to continuous system as shown in (fig. 1, a low pressure interfere the degradation process since highly viscous mercury, VUV, 185 nm lamp (S415 ROL-Rcan- USA) is green product was adhering the reaction vessel internal contained inside of a sealed stainless steel cell (S300- wall. Trinitrophenol (picric acid) was selected for more S2R,OZAP-USA) which is protecting the electrical detailed kinetic study. It was the most persistent pollutant components of the system. The system also includes air among the six dyes. pump for the continuous aeration of the reaction media, a thermo-statated water bath, and a circulation system for the treated water.
Khaled M. Elsousy, APAC, Vol. 2, No. 1, pp. 91-97, 2012 93
0 Table 1: Organic pollutants degradation Half-lives (t1/2), (2500 ml total volume, T= 25±0.5 C, circulating rate, 6.5 dm3/min).
Pollutant Methyl Methyl Brilliant Malachite Remazole Picric die violet blue green green blue B acid max , nm 590 665 523 625 570 355 t1/2 , hrs 1.5 1.83 1.7 3.11 Colloid 4.73 mechanisms. Comparison of t1/2 in buffered and non- 3.2 Effect of salinity buffered pH 7 reactions which were respectively (14.73 and 4.71 hours) implies that the presence of ions in the The influence of the treated water salinity on the treated water again has a retarding influence on the observed reaction half-life was studied. Salinity of degradation rate. course is mainly proportional to ionic strength. The The last results show that the treatment of basic reaction was conducted under fixed conditions of polluted water is easier and faster than the treatment of temperature, circulating power and reaction total volume. neutral and acidic polluted water under the same In the studied range of [NaCl] the reaction half-life was conditions. It is not recommended of course to increase increasing by increasing [NaCl], direct relation was the basicity of the treated water to get a faster process but observed up to 6000 mg/l sodium chloride concentration at least it should be known that if the treated water was as shown in (fig. 2), the optimum oxidation rate can be basic by chance the process is expected to be faster. achieved in desalinized treated water. In practical water 3.6 COD follow up. treatment processes; water salinity is expected to have a Degradation was followed by measuring chemical negative influence on the rate of degradation. The oxygen demand COD at different time intervals. One influence of aqueous NaCl is not clear, wither it is up to model run was performed. Picric acid oxidation free radical scavenging or simply the loss of UV photons derivatives are thought to go further oxidation by time. by scattering with ions. After the breakage of aromaticity, ketones, aldehydes and carboxylic acids are thought to precede oxidation (Qian- 3.3 Effect of the volume of the treated water Rong L. 2006). The final expected products are mostly CO2 and H2O. Degradation conditions were (250mg o 3 Degradation rate was lowered by increasing the picric acid in 2500 ml, distilled water, 25 C, 6.5 dm /min treated water volume. Reaction half-life was followed. It circulating rate). (Fig. 6) insures the degradation process, was increasing directly by increasing the volume of the t1/2 of the COD depletion was 6.5 where the oxidation treated water in the studied range, the relation is plotted process is continuous for the derivatives as well as in (fig. 3). The conversion rate is decreasing by the starting compound picric acid. decreasing the radiation intensity per unit volume of the treated water in the studied range (3.0 to 30.0 Watt per 4. Conclusion liter). The primary goal of this project was to investigate the 3.4 Influence of temperature VUV degradative oxidation of persistent industrial organic pollutants. The method was found efficient for Increasing temperature has a promotional influence on four per six examined pollutants. As expected, the the oxidation reaction in the range of (25-60 0C). It is present method is more efficient at higher temperatures clear in (Fig. 4) that an inverse relationship was obtained and higher intensity of VUV radiation. The present between ln 1/(t1/2) and 1/T, where a straight-line was technique can be preferable over other techniques in two obtained. The result means that the process has an overall ways: it is simple and clean method where no chemicals Arrhenius type behavior. It was expected according to are needed; only atmospheric oxygen. It can be suggested post studies (Oppenländer et al 2005) that: the radiation for practical applications after case study is conducted intensity is affected by changing the environment concerning the real pollutant/s specifically beside the temperature. In that case it may affect the UV light other treated water conditions. intensity and so the reaction kinetics, Arrhenius type relation has been observed in this case, which means a very weak influence of temperature on the radiation References: intensity under the present reaction conditions. R. Palaniappan, C. Eswaran, Using genetic algorithm to 3.5 Effect of pH select the presentation order of training patterns that improves simplified fuzzy ARTMAP classification Effect of pH on the oxidation reaction was examined performance, Applied Soft Computing, 9 (2009) 100-106 in the pH range (4 to 10). (Fig. 5) shows the values of S. Ahmed, M.G. Rasul, W.N. Martens, R. Brown, M.A.
T1/2 corresponding to each pH value. The oxidation rate is Hashib, Heterogeneous photo catalytic degradation of increasing by increasing each of OH- and H+ phenols in wastewater: A review on current status and concentrations. It means that there are two accelerating developments. Desalination 261 (2010) 3-18. roles for each of H+ and OH- according to various
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S. Ahmed, M.G. Rasul, W.N. Martens, R. Brown, M.A. photolysis of aqueous reaction systems using one VUV Hashib, Advances in heterogeneous photocatalytic light source, Water Science and Technology, 35. 4 (1997) degradation of phenols and dyes in wastewaters: A 25–30. Review. Water, Air and Soil pollution 215 (2011) 3-29. W. Heering, UV bources-basics, properties and S. Bakardjieva, J. Subrt, V. Stengl, M. J. Dianez, M. J. applications, International ultra violet association, 6. 4 Sayagues, Photoactivity of anatase-rutile (2004) 7-13. TiO2nanocrystalline mixtures obtained by heat treatment D. F. Ollis, E. Pelizzetti, N. Serpone, Destruction of of homogeneously precipitated anatase. Applied water contaminants. Environ. Sci. Technol. 25. 9 (1991) Catalysis B: Environmental 58 (2005) 193-202. 1523-1529. S. Bekkouche, M. Bouhelassa, N.H. Salah, T. Oppenländer, Photochemical Purification of water and F.Z.Meghlaoui, Study of adsorption of phenol on air, advanced oxidation processes (AOPs): Principles, titanium oxide (TiO2). Desalination 166 (2004) 355-362. reaction mechanisms, and reactor concepts. Wiley-VCH, F. J. Benitez, J. L. Acero, F. J. Real, G. Roldan, Germany (2003b) 73-91. Ozonation of pharmaceutical compounds: Rate constants T. Oppenländer., S. Gliese, Mineralization of organic and elimination in various water matrices. Chemosphere micropollutants (homologous alcohols and phenols) in 77.1 (2009) 53-59. water by vacuum-UV-oxidation (H2O-VUV) with an F. L. Ben Abdelmelek, E. C. Wert, S. A. Snyder, incoherent xenon-excimer lamp at 172 nm. Evaluation of UV/H2O2 treatment for the oxidation of Chemosphere, 40. 1(2000) 15-21 pharmaceuticals in wastewater. Water Research 44.5 T. Oppenländer, J. Burgbacher, M. Kiermeier, K. (2010) 1440-1448. Lachner, H.Weinschrottin, Improved vacuum-UV S. Ben Abdelmelek, J. Greaves, K. P. Ishida, W. J. (VUV)-initiated photomineralization of organic Cooper, W. Song, Removal of pharmaceutical and compounds in water with a xenon excimer flow-through personal care products from reverse osmosis retentate photoreactor (Xe2* lamp, 172 nm) containing an axially using advanced oxidation processes. Environmental centered ceramic oxygenator. Chemosphere 60.3 (2005) Science & Technology 45.8 (2011) 3665-3671. 302-9. S. H. Bossmann, E. Oliveros, S. Gob, S. Siegwart, E. A. B. Prevot, M. Vincenti, A. Bianciotto, E. Pramauro, Dahlen, L. Payawan, M. Straub, M. Worner, A. Braun, Photocatalytic and photolytic transformation in aqueous New evidence against hydroxyl radicals as reactive solutions. App. Catal. B: Environ; 22 (1999) 149-158. intermediates in the thermal and photochemically L. Qian-Rong, G. Cheng-Zhi, D. Yan, y. Hao, Z. Jun- enhanced Fenton reactions. J. Phys. Chem 102 (1998) Ying, Photo-degradation of nitrobenzene using 172 nm 5542-5550. excimer UV lamp. Materials, 133, Issue: 1. 3 (2006) 68- R.Q. Brewster, C.A. Vanderwarvf , W.E. Mcewen, 74 Unitized experiments in organic chemistry, 4th edition, J. Radjenovic, M. Godehardt, M. Petrovic, A. Hein, M. 1977, PP 394. Farre, M. Jekel, D. Barcelo, Evidencing Generation of M.N. Chong, B. Jin, C.W.K. Chow, C. Saint, Recent Persistent Ozonation Products of Antibiotics developments in photocatalytic water treatment Roxithromycin and Trimethoprim. Environmental technology: A review. Water Research 44 (2010) 2997- Science & Technology 43.17 (2009) 6808-6815. 3027 T.Chu, S.K. Umamaheshwar, A. Mumper, Removal of Vitae sulfadiazine, sulfamethizole, sulfamethoxazole, and sulfathiazole from aqueous solution by ozonation. Dr. Khaled M. Elsousy, was born in Gaza/ Chemosphere 79.8 (2010) 814-820. Palestinian territories in 1962. He obtained a Bs.C. in W. Chu, Y.R. Wang, H.F. Leung, Synergy of sulfate and chemistry/ physics in 1985, Msc. in physical hydroxyl radicals in UV/S2O8-/H2O2 oxidation of chemistry from METU-Ankara-Turkey 1988 and iodinated X-ray contrast medium iopromide. Chemical Ph.D. degree from ainshams Uni. Cairo Egypt in Engineering Journal 178 (2011) 154-160. 2001. M.C. Dodd, H.P.E. Kohler, U. Von Gunten, Oxidation He worked as a chemistry instructor in Alaqsa of Antibacterial compounds by ozone and hydroxyl University/Gaza. His research interest includes radical: Elimination of biological activity during aqueous Physical chemistry fields such as kinetics, ozonation processes. Environmental Science & heterogeneous catalysis, advanced oxidation Technology 43.7: 2498-2504. technology, adsorption methods of purification and Gaya UI, Abdullaha AH. 2008. Heterogeneous water treatment methods in general. photocatalytic degradation of organic contaminants over He is the peer reviewer of XX. He is a member of titanium dioxide: A review of fundamentals, progress and Arabian journal of chemistry and Tenside detergents problems. Journal of Photochemistry and Photobiology and surfactants. C: Photochemistry Reviews.9 (2009) 1-12. T.M. Hashem, M. Zirlewagen, A.M. Braun Simultaneous photochemical generation of ozone in the gas phase and
Khaled M. Elsousy, APAC, Vol. 2, No. 1, pp. 91-97, 2012 95
Fig. 1. kinetic installation system.
35
30
25
20 , hrs ,
1/2 15 t
10
5
0 01234567 [NaCl] x 1000, mg/ L
0 Fig. 2. Effect of [NaCl] on the degradation half-life of picric acid using vacuum UV. (25±0.5 C, [picric acid]0=100 mg/l, reaction volume 2500ml, 6.5 dm3/min circulating rate).
6
5
4
3 t1/2, hrs.
2
1
0 012345 Reaction volume, L
Fig. 3. The relation between degradation half-life of picric acid and the amount of the treated water, (25±0.5 0C, 3 [picric acid]o 100 mg/l, circulating rate, 6.5 dm /min).
Khaled M. Elsousy, APAC, Vol. 2, No. 1, pp. 91-97, 2012 96
-1
-1.2 -1 -1.4 ), s 1/2
-1.6 ln 1/(t
-1.8
-2 2.8 2.9 3 3.1 3.2 3.3 3.4
1/T x 10-3, K-1
Fig. 4. Effect of temperature change on the VUV oxidative degradation of picric acid, (reaction volume = 2500ml, 3 [picric acid]0=100 mg/l, 0.65 dm /min circulating rate).
Fig. 5. 0 Influence of changing pH on picric acid degradation Half-live (t1/2), (2500ml total volume, T= 25±0.5 C, 6.5 3 dm /min circulating rate, H3PO4/NaOH pH control).
Khaled M. Elsousy, APAC, Vol. 2, No. 1, pp. 91-97, 2012 97
Fig. 6. COD decay with process time, (2500mL total volume, T= 25±0.50C, circulating rate, 6.5 L/min). [picric acid]0=100 mg/L, pH=7.0.
Advances in Pure and Applied Chemistry (APAC) 98 Vol. 2, No. 1, 2012, ISSN 2167-0854 Copyright © World Science Publisher, United States www.worldsciencepublisher.org
Occurrence and prevalence of four viruses infecting tomatoes in Northern districts of West Bank, Palestinian Territories
Hazem Sawalha
Department of Biology and Biotechnology, Faculty of Arts and Sciences, Arab American University of Jenin, Palestine
Email: [email protected]
Abstract – Studying tomato viruses during 2003/2004 using immunosorbent assays revealed that tomato yellow leaf curl virus (TYLCV) was the most dominant disease infecting tomato plants in the northern districts of the West Bank particularly Jenin and Tobas as its incidence ranged from 28-93%. The maximum disease incidence of 90-93% was recorded in Al-Far'a region of Tobas district. Cucumber mosaic virus (CMV) was the second most prevalent virus of tomato in the studied regions as its incidence ranged from 15-51%. Tomato infection with tomato mosaic virus (TMV) and potato virus Y (PVY) was considered insignificant as these viruses were detected in very few tomato samples.
Keywords – Tomato; Viruses; Palestine.
Introduction extent that viruses have spread during the planting of the crop (Walkey 1985). Like many other developing countries, Palestine has an important agricultural sector, which has been Tomato production in Palestine, however, has not yet considered the backbone of its economy. This was reached its full potential due to many factors related to particularly true in the years after instituting its autonomy climate and poor management, and above all, due to the with the establishment of the National Palestinian high level of pests and diseases (PCBS 2008). In regard Authority in 1994. Since then the agriculture became the to diseases, viral diseases may be considered an largest contributor to the country’s gross product and important factor responsible for the recurrent crop failure provided employment to the economically active in the country forcing many farmers to switch their population (Palestinian Central Bureau of Statistics choice of crop production from tomato to other (PCBS) 2008). vegetables (Sawalha 2010, Ministry of Agriculture, personal communication). Vegetables are the most important crops grown in the country, occupying 18734.4 hectares, with an annual As tomato is the most important vegetable crop in the production of 645157 metric tons. More than 31% of country, this research aims to study and identify the those vegetables are tomatoes, and the remainder include viruses affecting this crop and to shed light on their thirty-five other vegetable crops, of which cucumbers are occurrence and prevalence. Northern districts including the most important. Tomato is the main greenhouse crop Jenin and Tobas were selected for this study because but it is also cultivated in low tunnels and in open fields, tomato production in those regions is 48250 metric tons comprising a total annual production of 203999 metric and they occupy about 47% of the total tomato tons (PCBS 2008). Several viruses are known worldwide production in the West Bank part of Palestine (PCBS to attack tomatoes causing serious damage and yield 2008). reduction. TMV, TYLCV, CMV and PVY are of the ten most viruses affecting the crop elsewhere (Oetting and Materials and Methods Yunis, 2004, Agrios, 1997, Pico et. al. 1996, Sawalha. (2009a, 2009b, 2010). Regions of study
Viral diseases of tomatoes occasionally cause serious The research was carried out during the summer damages and large economic losses. The amount of loss growing seasons of 2003 and 2004. Tomato fields were depends on the viral disease involved, the strain of the selected randomly in the regions with intensive tomato virus, the variety of tomato, the age of the plant at cultivation to represent all possible conditions of tomato infection time, the presence of other diseases, and the production in these districts. The major tomato producing Hazem Sawalha., APAC, Vol. 2, No. 1, pp. 98-101, 2012 99 fields located in Jenin were selected in Al-Zababdeih, Al- results of the ELISA tests were recorded one hour after Jededeih, and Qabatyya regions. Two fields were selected the substrate incubation took place using the automated in Tobas; one of them was in Kashda village and the ELISA-Reader. The light absorbance was measured for other was selected in Al-Far’a region a few hundred ELISA wells at 405 nanometer (Sawalha (2009c) meters away from the town’s midpoint (Fig 1). Statistical analysis Growing season Statistical analysis of the data was done using the The experiments were carried out during the summer Two-Sample Tests of Proportions (TSTP) to compare growing season because this season is considered the virus occurrence in the studied regions. The results were main planting one of tomato in the regions of study analysed using a level of significance when = 0.05 throughout the year. In this season, seeds are sown (Lind et. al. 2005). during April and May and the seedlings are transplanted from the middle of May until the middle of June. Results
The pattern of tomato cultivation in the regions Virus identification and incidence of study ELISA tests showed that the TYLCV, CMV, TMV Tomato is planted in the studied area in rows with a and PVY parasitize tomato fields in different percentages. width of about 1 to 1.2m. The lands are first prepared by ELISA readings recorded for the virus-infected samples hoeing twice and then adding manure. Chemical were at least eight times greater than the readings fertilizers are added in three equal doses; the first when recorded for the virus-free samples (Fig 1). preparing the land, the second after transplanting and the third at fruit set. Fig 1: ELISA detection of tomato viruses showing the difference between positive and negative control samples Field visits and sample collection 1.4
1.2
Field visits in the studied regions began in July and 1 continued until the end September. Samples were 0.8 collected at least one month after the transplanting of Pos itiv e s ample 0.6 tomato seedlings to ensure that tomato had become Negative sample infected after being exposed for a sufficient period to the 0.4 Absorbance at 405 nm 405 at Absorbance viral source. The selected fields were visited weekly in a 0.2 regular manner and leaf samples were collected randomly 0 from top parts of plants. The samples were labelled and TYLCV CMV TMV PVY kept frozen for laboratory testing. Tomato virus
Virus identification and incidence The four viruses are found in tomato planted in Kashda, Al-Far’a and Al-Jededeih regions. TYLCV is the Virus identification was done serologically using most dominant virus affecting tomato fields in all regions virus-specific antibodies purchased from international as its occurrence rate ranges from 28-93% in the tested companies. Thus, indirect enzyme-linked immunosorbent tomato fields. In addition, the maximum TYLCV assay (I-ELISA) adopted by Clark et. al (1986) was used infection (93%) is recorded for tomato fields planted in to test the plant samples for CMV, PVY and TMV. With Al-Far'a region. CMV is the second-most dominant respect to the other case, the triple-antibody sandwich tomato virus in all tested fields as it infects tomato fields enzyme-linked immunosorbent assay (TAS-ELISA) was with an occurrence rate ranging from 15-51%. The used to test the TYLCV infection. TAS-ELISA was used maximum occurrence of CMV is found in Qabatyya according to Macintosh et. al. (1992), Muniyappa et. al. followed by Al-Far'a and Kashda regions. The minimum (1991), Sawalha et. al. (2000: 339) and Sawalha (2000: percentage of CMV infection is recorded for Al- 24-89). The antibodies of CMV, PVY and TMV and the Zababdeih and Al-Jededeih regions. Both TMV and PVY goat anti-rabbit conjugate were purchased from Bioreba, are present in minute samples collected from the studied Inc. The polyclonal and monoclonal antibodies of regions, while most of the other samples were free from TYLCV, along with the rabbit anti-mouse conjugate, these viruses (Table 1) (Fig 2). were purchased from Adgen Ltd (Scotland, UK.). The Hazem Sawalha., APAC, Vol. 2, No. 1, pp. 98-101, 2012 100
Table 1: Number of samples collected from the studied region and the percentages of infection with TYLCV, CMV, TMV and PVY. Region TYLCV CMV TMV PVY Total samples 2003 2004 2003 2004 2003 2004 2003 2004 collected 2003 2004
NS PI NS PI NS PI NS PI NS PI NS PI NS PI NS PI Kashda 33 70 35 69 11 23 11 21 3 6 0 0 1 2 0 0 47 51 Al-Far’a 43 45 1 46 50 93 90 14 30 17 34 5 10 3 6 2 4 2
Qabatyya 23 0 45 44 51 23 52 23 51 22 50 4 8 4 9 0 0 0
Al-Zababdeih 16 0 51 49 31 16 33 10 20 9 18 2 4 2 4 0 0 0
Al-Jededeih 17 0 50 54 34 15 28 11 22 8 15 1 2 2 3 1 2 0 TOTAL 132 1 239 248 55 134 54 69 29 67 27 15 6 11 4 4 2 0.004
NS: Number of infected samples, PI: Percentage of infection
Fig 2: Average incidence of tomato viruses in the study regions in 2003/2004 Discussion 100 90 80 Tomato viruses were identified serologically using I- 70 60 ELISA for CMV, and TMV, PVY, and TAS-ELISA for 50 40 TYLCV. TYLCV is the most prevalent virus threatening TYLCV 30 CMV tomato fields in the studied regions. The higher incidence 20 Percentage of infection TMV 10 of TYLCV (31-93%) is attributed to the abundance of PV Y 0 Kashda Al-Far'a Qabatyya Al-Zababdeih Al-Jededeih whiteflies (Bemisia tabaci) and the overlapping that Re gion occurs between tomato growing seasons in the regions (Sawalha 2010). The 93% incidence of the virus in Al-
Far’a may be attributed also to the warm climate which Statistical analysis revealed that the proportions of helps the whiteflies to appear earlier and to reproduce TYLCV in the studied regions were greater than CMV, more compared with the other regions (PCBS 2005, TMV and PVY. The maximum computed Z values ( = Sawalha 2010). In this regards, Nava-Camberos et. al. 0.05) for the TYLCV compared with the other viruses (2001) reported that the warm climate is the best were recorded in Al-Far'a region followed by Kashda, condition for the whitefly development, fecundity and Qabatyya, Al-Zababdeih and Al-Jededeih. No significant survival. Similar results were recorded in Jordan where difference was recorded between TYLCV and CMV Al-Musa and Mansour (1983) reported that TYLCV was infecting tomato fields in Qabatyya region as the the predominant virus affecting tomatoes in the Jordan computed Z value was much less than the critical one Valley. CMV was detected to be the second-most (Table 2) prevalent virus affecting tomato fields in the studied
Table 2: Statistical analyses and the Z value of the TSTP. The Z regions. This infection with CMV may be attributed to table = 1.65 allate aphid species which are usually ample in the Region Virus combination Computed Z value Decision region, especially the green peach aphid (Myzus persicae Kashda TYLCV/CMV 6.74 S Sulzer) and the melon aphid (Aphis gossypii Glover). The TYLCV/TMV 9.80 S virus has a wide host range (800 species) from which it TYLCV/PVY 10.16 S can be acquired by aphids and transmitted in a non- Al-Far'a TYLCV/CMV 8.66 S persistent manner and can also be mechanically TYLCV/TMV 11.81 S TYLCV/PVY 12.54 S transmitted (Oetting and Yunis, 2004, Trigiano et. al. Qabatyya TYLCV/CMV 0.14 NS 2004). Another reason for the wide spread occurrence of TYLCV/TMV 6.63 S CMV in the studied regions may be attributed to the TYLCV/PVY 8.30 S intensive and annual culturing of cucurbits including Al-Zababdeih TYLCV/CMV 2.10 S cucumber, squash and melon in the region. According to TYLCV/TMV 5.15 S TYLCV/PVY 6.17 S PCBS (2008), these crops are planted in a wide area with Al-Jededeih TYLCV/CMV 2.20 S an annual production of 15376 and 9250 metric tons in TYLCV/TMV 5.55 S Jenin and Tobas districts, respectively. These crops are TYLCV/PVY 5.83 S the most suitable hosts for CMV, so their presence in the S: Significant, NS: Non significant tomato growing sites makes them the viral source from which the allate aphids transmit the disease to tomato (Oetting and Yunis 2004, Sacristian et. al. 2004). The Hazem Sawalha., APAC, Vol. 2, No. 1, pp. 98-101, 2012 101 high rate of tomato infection with CMV in Qabatyya tabaci, transmission, and field study of virus association region may be attributed to the extensive culturing of with the vector and non-vector nsects, An Najah tobacco in the village Plains, which are situated very University for Research, 23 (2009a) 93-115. close to tomato growing sites. The plains are the major [10]. H. Sawalha, Purification, Antiserum Production, culturing sites of tobacco in Jenin district. The rare Biological and Molecular Studies of Tomato Yellow Leaf infection of tomato plants with TMV and PVY may be Curl Virus, PhD. dissertation, University of Jordan, attributed to the scarcity of the viral source in the region Amman, Jordan, 2000, pp. 24-89 at that time. [11]. H. Sawalha, The use of PCR, IC-PCR, TAS-ELISA, TBIA, and biological methods to determine the time As the results above indicate, it can be concluded that needed to detect TYLCV in inoculated jimsonweeds, The TYLCV was the key virus affecting tomato fields in the First Conference on Biotechnology Research and region. Therefore, efforts must be directed towards the Application in Palestine, Furno Hall, Bethlehem control of the disease. Furthermore, because CMV infects University, Bethlehem, Palestine, 3-4 April, 2009c, pp. tomato fields in much lower percentages, it is of the 28. utmost importance that efforts towards the prevention of [12]. M. Clark, R. Lister, M. Bar-Joseph, ELISA further outbreaks must take place. TMV and PVY, on the Techniques, Methods in Enzymology, 115 (1986) 771- other hand, play a very insignificant role in tomato 773 production as their occurrence was very low in tomato [13]. Palestinian Central Bureau of Statistics, Agricultural fields. Statistics, Ramallah; Palestine, 2008, pp. 77-110. [14]. Palestinian Central Bureau of Statistics, References Meteorological Conditions in the Palestinian Territories Annual Report, Ramallah; Palestine, 2005, pp. 39-49. [1]. A. Al-Musa, A. Mansour, Plant Viruses Affecting [15]. R. Oetting, H. Yunis, Field Guide to Common Tomato in Jordan. Identification and Prevalence, Insects, Mites, and Diseases of Greenhouse Grown Sweet Phytopath. Z, 106, (1983) 186-190. Peppers, Cucumbers and Tomatoes, Hakohav Press; Kfar [2]. B. Pico, M. Diez, F. Muez, Viral disease causing the Qari, 2004, pp. 58-79. largest economic losses to tomato crop. II. The tomato [16]. R. Trigiano, M. Windham, A. Windham Plant yellow leaf curl virus-a review, Scientia Horticulturae, 67 Pathology, Concepts and Laboratory Exercises, CRC (1996) 151-196. Press; London, 2004, pp. 28-29. [3]. D. Lind, W. Marchal, S. Wathen, Statistical [17]. S. Macintosh, D. Robinson, B. Harrison, Detection Techniques in Business & Economics, Twelfth Edition, of three whitefly-transmitted gemini viruses occurring in McGraw-Hill Irwin, New York, 2005, pp. 262-263 Europe by testing with heterologous monoclonal [4]. D. Walkey, Applied Plant Virology, Heinemann; antibodies, Annals of Applied Biology, (1992) 279-303. London, 1985, pp. 6-92. [18]. U. Nava-Camberos, D. Riley, M. Harris, Camberos, [5]. G. Agrios, Plant Pathology, Fourth Edition, U., Riley, D., and Harris, M. (2001). "Temperature and Academic Press; London, 1997, pp. 479-554. host plant effects on development, survival, and fecundity [6]. H. Sawalha, A. Mansour, M. El-Khateeb, Serological of Bemisia tabaci (Homoptera: Aleyrodidae), and PCR detection of tomato yellow leaf curl virus from Environmental Entomology, 30 (2001) 55-63. infected plant tissues and whiteflies, Seventh Arab [19]. V. Muniyappa, M. Swanson, G. Duncan, B. Congress of Plant Protection, Amman-Jordan, 22-26 Harrison, Particle purification, properties and epitope October, (2000). variability of Indian tomato yellow leaf curl gemini virus, [7]. H. Sawalha, Whitefly population and incidence of Annual of Applied Biology, 118 (1991) 595-604. tomato yellow leaf curl virus in tomato fields grown in the northern regions of the West Bank, Al-Aqsa Vitae University Journal (Natural Sciences Series), 13 (2010) 7-24. Dr. Sawalha was born in Palestine. He obtained a [8]. H. Sawalha, Occurrence of tomato yellow leaf curl Ph.D. degree in Horticulture and Plant Protection virus on volunteer tomato, jimsonweed and tobacco in from the University of Jordan in 2000. North West Bank: Distribution of the virus natural He worked as an associate professor at the Arab reservoirs in summer season, An Najah University for American University/ Jenin-Palestine in 2010. His Research, 23 (2009b) 73-91. research interest includes the fields of [9]. H. Sawalha, Palestinian isolate of tomato yellow leaf Phytopathology, Virology, and Microbiology. curl virus: capsid and nucleic acid retention in Bemisia
. Advances in Pure and Applied Chemistry (APAC) 102 Vol. 2, No. 1, 2012, ISSN 2167-0854 Copyright © World Science Publisher, United States www.worldsciencepublisher.org
Study of Liquefied Petroleum Gas Heating Value A Thermodynamics Approach
1Niaz Bahar Chowdhury, 1Dr. Md. Iqbal Hossain
1Chemical Engineering Department, Bangladesh University of Engineering and Technology, Dhaka, Bangladesh
Email: [email protected]
Abstract – The heating value of liquefied petroleum gas (LPG) is an important characteristic implying LPG fuel- quality. Nevertheless, the quantitative and detail study on the heating value of LPG is still in high scarcity. Hence, the heating value of LPG is analyzed extensively in the present study. A combustion reactor simulated employing Aspen- Hysys simulator is used to determine the heating value. The separate effects of the presences of additives or foreign components (e.g., ethane, hydrogen sulfide, moisture, and mercaptan), the proportion of primary LPG components (e.g., propane and butane), and the combustion temperature and pressure on the heating value of LPG are studied. Explanations of the observed effects are also provided. The present study would help the researchers, manufacturers, bottlers, and distributors of LPG immensely.
Keywords –Heating value; LPG; Aspen-Hysys process simulator; Fuel.
1. Introduction simulator is used in this study to determine the heating value at various conditions. On the basis of reserve and uses, natural gas is the main energy resource in Bangladesh. Since it is being 2. Methodology used in the sectors of power, industrial, commercial, domestic, automobile, etc largely, the reserve of Heating value is normally defined as the amount of natural gas is depleting rapidly. As exploration of heat obtained from the complete combustion of one new gas fields in Bangladesh is not going as unit of fuel (e.g., LPG). The pure experimental setup expected, it will not be possible for natural gas to to determine this heating value especially for LPG is fulfill the demand solely after a decade [1]. From this rarely available. Hence the simulation method is scenario the necessity of energy-diversification is felt. adopted to determine the heating value. A combustion Liquefied petroleum gas, LPG is a mixture primarily of reactor is created in AspenHYSYS 7.1 process propane and butane. It has already been proved as an simulator as shown in Fig.1. The simulation and efficient alternative domestic fuel in Bangladesh. It can heating value determination are briefly stated below: also used as a fuel in heating appliances and vehicles. To A new file in Aspen-HYSYS is opened and a popularize and enhance the uses of LPG also require package unit (e.g., SI unit) is chosen from preference fundamentals research at various aspects. Heating value tab. The various components (e. g. ethane, propane, is a very important character of any combustion-fuel butane, mercaptan, hydrogen sulfide, water, indicating the fuel quality or value. It is expected that the methanol, ethanol, oxygen, and nitrogen, etc.) are heating value of LPG is affected by the parameters like selected from the component tab. Subsequently, an presences of additives or foreign components, proportion appropriate fluid package (i.e., Peng Robinson) is of primary LPG components, and combustion pressure selected from the fluid package tab. The specific and temperature, etc. Unfortunately, no quantitative and reactions are also defined in the reaction tab and the detail study on the effect of the important parameters selected fluid package is assigned to each reaction. stated above on the heating value of LPG is available in After entering into the simulation environment the the literature. Therefore, the objective of the present reactor (i.e., conversion type) is taken from object study is to the study of the separate effects of the pellet. A 100 % conversion of each LPG component presences of additives or foreign components (e.g., is added to the reactor as a parameter. Then the LPG ethane, hydrogen sulfide, moisture, and mercaptan) in and air streams at a given condition are finally added LPG, the proportion of primary LPG components (e.g., to the reactor [2]. An energy stream (E, in Fig. 1) is propane and butane), and the LPG combustion also added to the reactor to represent the heat temperature and pressure. The Aspen-HYSYS process generated by the combustion reactions. With the run
Niaz Bahar Chowdhury, et al., APAC, Vol. 2, No. 1, pp. 102-105, 2012 103 of the simulation, the reactions are completed and the heating value is obtained from the energy stream, E.
Figure1. Combustion reactor and associated streams Figure2. Effect of ethane on the heating value of LPG in Aspen HYSYS simulator
3. Results and Discussion
The effects of various parameters on the heating value of LPG are presented and discussed in the following sub-sections.
3.1. Effect of additives or foreign components
During the manufacture of LPG, ethane can come into it. Similarly, H2S and moisture can also be present in LPG. In addition, mercaptan is deliberately added to commercial grade LPG to identify the leakage of LPG from cylinder or bottle. Therefore, it Figure3. Effect of hydrogen sulphide on the is required to know the effect of these additives or heating value of LPG foreign components on the heating value of LPG. Fig. 2 clearly shows that the heating value decreases monotonically if the proportion of ethane increases. This is because the heating value of ethane is lower than that of LPG primary components (i.e., propane and butane). Fig. 3 also indicates that the heating value decreases monotonically with the increases in the proportion of H2S in LPG. This also happen due to the fact that the heating value of H2S is much lower than that of propane and butane. Finally, Figs. 4 and 5 also show the same effect that is the heating value of LPG decreases with the increases in the proportions of moisture and mercaptan [3]. In addition, here the decreasing effect is severe than that Figure4. Effect of hydrogen sulphide on the heating value of LPG of ethane and H2S. This is because both the moisture and mercaptan are non-combustible. Therefore, it is desirable to suppress the proportions of additives or 3.2. Effect of Primary Component foreign components in LPG as much as possible. The propane and butane are the primary components of LPG. Fig. 6 shows that with the increase in the proportion of propane, the heating value per unit volume of LPG also decreases substantially. This is because the heating value of pure propane is lower than that of pure butane in volume basis units. The actual reason behind the lower heating value of propane is that, in a unit volume, propane has the lower number of carbon atom (C) than butane, which are converted into C-O bond upon combustion generating lower amount of heat than butane [4]. Same qualitative trend is observed if the heating value is considered per unit mole and mass of LPG. Hence, it is
Niaz Bahar Chowdhury, et al., APAC, Vol. 2, No. 1, pp. 102-105, 2012 104 desirable to have more butane in LPG to yield higher that the first region becomes shorter with the increase heating value of the mixture. of pressure. The increase on heating value with the increase in temperature would be due to the change of energy level of reacting molecules with the increase in combustion temperature.
Figure5. Effect of mercaptan (M) on the heating value of LPG
Figure7. Effect of combustion temperature on the heating value of LPG
Figure6. Effect of primary component composition
3.3. Effect of combustion temperature and pressure
Having the same pressure different geographical regions utilizing LPG as cooking and heating fuel can be at different temperatures. Similarly, having the Figure8. Effect of combustion pressure on the heating same temperature the geographical regions can value of LPG hypothetically be under different pressures too. In addition, numerous industrial and mechanical units The effect of combustion pressure on heating employing LPG as a combustion fuel can be under value of LPG is studied over a pressure range of 0 to different temperatures and pressures. Therefore, LPG 4 atm under three separate temperatures of 0, 25, and with a particular quality can give different heating 70oC. Fig. 8 shows that, regardless of combustion values upon combustion at different temperatures and temperature considered, the heating value initially pressures. As a result, it is also very important to decreases to a minimum level and then increases know the effect of combustion temperature and [5] abruptly with the increase in pressure. This complex pressure on the heating value of LPG . behavior of heating value with combustion pressure is The effect of combustion temperature on heating expected to involve multiple contributing factors, value is studied over a temperature range of -50 to o which are still under research. 200 C under three separate pressures of 1, 5, and 10 atm. Fig. 7 clearly indicates that the heating value increases monotonically with the increase in 4. Conclusions combustion temperature at all pressures. However, three distinct regions along temperature can be The separate effects of additives or foreign observed, which have different rate of the increase of components present in LPG, proportion of primary heating value with temperature. The first and last LPG components, and combustion temperature and regions have nearly the same rate of increase of the pressure on the heating value of LPG are studied in heating value with temperature while the middle this study. It is found that the presences of additives region has abruptly faster rate [6]. Fig.7 also shows or foreign components (e.g., ethane, hydrogen
Niaz Bahar Chowdhury, et al., APAC, Vol. 2, No. 1, pp. 102-105, 2012 105 sulfide, moisture, and mercaptan) always decrease the [6] J. M. Moran, Howard N. Sapiro, Fundamentals of heating value. Hence, it is required to minimize the Engineering Thermodynamics, 6th edition, John amount of the additives if the high heating value is Wiley & Sons, New York, 2010, pp. 33-48 desired. It is also found that the heating value of LPG decreases if the proportion of propane is increased Vitae through the decrease in the proportion of butane. Hence, it is required to have more proportion of Include a short biography for each author along with a butane in the LPG to ensure a higher heating value. frontal photograph. Analysis shows that the heating value always increases with the increase in combustion temperature. Three distinct regions with different rates of increase can clearly be observed in the curve of heating value vs. combustion temperature. However, regardless of combustion temperature, the effect of combustion pressure on the heating value is complex. The heating value decreases with the increase in pressure initially up to a critical pressure level; once the pressure level is exceeded, the heating value increases with increasing pressure. Those who are involved with the research, manufacturer, bottling, and distribution of LPG are expected to be Mr. Niaz Bahar Chowdhury was born in Chittagong, benefited immensely by the results of this study. Bangladesh. He obtained a B. Sc degree in 2012 in Chemical Engineering department from Bangladesh Acknowledgements University of Engineering in Technology. He worked as a Research Assistant in the above The supports from the Department of Chemical department. His research interest includes LPG, Engineering, Bangladesh University of Engineering and Process Engineering, Coal Gasification, and Thermal Technology are gratefully acknowledged. Engineering.
References Photo not Available
[1] www.lpgbangladesh.com. Dr. Md. Iqbal Hossain was born in Dhaka, [2] www.aspentech.com Bangladesh. He obtained a Ph. D. degree in 2010 [3] Smith, J.M., H.C. Van Ness and M.M. Abbott, from School of Chemical and Biomedical Introduction to Chemical Engineering Engineering, Nanyang Technical University, Thermodynamics, 6th edition, Singapore: McGraw- Singapore. Hill, (2001) [4] Y. A. Cengel, M. A. Boles, Thermodynamics an His research interest includes LPG, Process Engineering Approach, 5th edition, McGraw-Hill, Engineering, Coal Gasification, Diagnostic Singapore, 2007, pp. 313 Technologies, Fossil & synthetic Fuels , Gas to [5] C. Borgnakke, Richard E. Sonntag, Fundamentals of Liquid Technology
Thermodynamics, 1st edition, Apprentice Hall, India, Link: http://teacher.buet.ac.bd/teacher/iqbalhossain 2008, pp. 123-134