Phytoremediation of cyanophos insecticide by Plantago major L. in water
© Romeh; licensee BioMed Central Ltd. 2014
Received: 4 October 2012
Accepted: 14 January 2014
Published: 21 January 2014
Cyanophos is commonly used in Egypt to control various agricultural and horticultural pests. It is not easily hydrolyzed and thus they are highly persistent and accumulate in various aquatic compartments such as rivers and lakes. Such issues may be solved by phytoremediation, which is the use of plants for the cleanup of pollutants. Here, we tested Plantago major L. to clean water polluted with cyanophos insecticide under laboratory conditions.The biosorption capacity (KF) of cyanophos were 76.91, 26.18 and 21.09 μg/g for dry roots, fruit (seeds with shells) and leaves of the Plantago major L., respectively. Viable Plantago major L. in water significantly reduced cyanophos by 11.0% & 94.7% during 2 hours & 9 days of exposure as compared with 0.8% & 36.9% in water without the plantain. In water with plantain, cyanophos significantly accumulated in plantain roots and leaves to reach maximum levels after two and four hours of treatment, respectively. After 1 day, the concentration of cyanophos decreased in roots and shoots until the end of testing. Three major degradation products were detected at roots and leaf samples. Here we demonstrate that plantago major L. removes efficiently cyanophos residue in water and has a potential activity for pesticide phytoremediation.
Cyanophos (O, O-dimethyl O-4-cyanophenyl phosphorothioate) is an organophosphorus insecticide with a commercial name of Cyanox . Cyanox is commonly used in Egypt to control various agricultural and horticultural insect pests such as Hemiptera of Aphididae, Coccidae, Diaspididae, Lepidoptera, etc. in various fruits and vegetables . Cyanophos used in Africa to control quelea and other granivorous species that are considered pests of cereal crops . Mobile ground spraying with cyanophos control quelea, as routinely practiced in Senegal during the 1995/1996 cropping season, was found to be hazardous to the environment . The toxicological effect of cyanophos is the inhibition of acetylcholine esterase activity . Cyanophos is not easily hydrolyzed and highly persistent and accumulate in various aquatic compartments such as rivers and lakes . Desmethyl-cyanophos, 4-Cyanophenol and desmethyl-cyanophos oxon are degradation products of cyanophos in soil . All conventional methods for the removal of pesticides are found to be either uneconomical or insufficient . Therefore, it becomes essential to search for effective and economical alternative method to overcome the constraints of convention methods. Biological method such as biosorption is an attractive and promising alternative which accumulate organic and inorganic matter including metal, dyes, phenols and pesticides and offers potential advantages such as low operating cost, minimization of chemical or biological sludge . Several researchers reported on biosorption uptake of phenols, dyes and pesticides by biosorption .
Phytoremediation is an accumulation of plant-associated processes which include biotransformation, phytoaccumulation, phytoextraction, phytovolatilization, and rhizodegradation from enhanced microbial activity in plant rhizospheres  and plant transformation, conjugation, and sequestration are vital tools in waste management . There have been several studies focused on the phytoremediation of pesticides [11, 12]. Plant remediation of soils, sediments, and water is a cost-effective and resource-conservative approach for clean-up of contaminated sites . Biosorption is one of the effective alternative methods for the removal of pesticides in contaminated water samples. Plants can accumulate or metabolize a variety of organic compounds, including, imidacloprid , triazophos , chlorpyrifos [12, 15], methyl parathion , and atrazine .
The common broad leaved plantain (Plantago major L.) is a very familiar perennial weed found anywhere by roadsides, and in meadows, cultivated fields, waste areas, and canal water. The seed and husks are in fiber expanding to become highly gelatinous when soaked in water. The methanol, ethanol and aqueous extract of Plantago major L. contained antibacterial activity against some gram negative and positive bacteria besides a weak anti-narcotic activity . The encouraging results of previous studies regarding phytoremediation gained the attention of researcher to continue studies in this field. Therefore, the objective of this work was to evaluate phytoremediation by living broadleaf plantain (Plantago major L.) and non- living material from plants as cleanup methods for water contaminated with the insecticide cyanophos.
Pesticide and plant
Cyanophos (Cyanox 50% EC) 0,0-dimethyl 0-(4-cyanophenyl) phosphorothioate was obtained from the Central Agriculture Pesticide Laboratory, Agriculture Research Center, Dokki, Gaiza, Egypt.
The common broadleaf plantain (Plantago major L.) used as seedlings in Phytoremediation experimentals and adult plants in biosorption assays from meadow-land in Zagazig University, Zagazig, Sharkia governorate, Egypt.
Raw agricultural solid wastes have been used as adsorbents. These materials are available in large quantities and may have potential as adsorbents due to their physico-chemical characteristics and low-cost . So, Low cost materials (leaves, roots and fruits of Plantago major L.) have been tested for their ability to quickly sorb cyanophos. Adults Plantago major L. were collected with the help of fine jet of water causing minimum damage to the roots washed thoroughly with distilled water and blotted dry. Different plant parts separated manually to leaves, roots and fruits (seeds plus shells). The plantain leaves, roots and fruits (seeds plus shells) dried naturally on laboratory benches at room temperature (28–30°C) for 5 days until crisp. Sorption was measured using 0.5 g of (powder) leaves, roots and fruits (seeds plus shells), each of the broad-leaved plantain in centrifuge tube was shaken with 10 ml of the aqueous adsorbate for four hours (equilibrium concentration). Five initial concentrations (CB) were used in each case, ranging 1, 5, 10, 20 and 40 μg/mL plus water blank. After centrifugation at 2000 r.p.m. for 15 minutes, the concentrations of cyanophos in the supernatant (Ce) were determined. Aliquot (4 mL) of the supernatant was analyzed. All adsorption studies were conducted at room temperature 30°C ± 2°C and three replicated were used. The amount adsorbed (μg/g) calculated . Author aimed at plotting the adsorption isotherms due to which it is possible to compare the sorption capacity of cyanophos on different adsorbents (leaves, roots and fruits of Plantago major L.). Freundlich sorption isotherm assumes that the uptake of sorbate occurs on a heterogeneous surface by multilayer sorption and can be described by the following equation: Y = KF Ce (n-1) where, KF is a Freundlich constant related to the adsorption capacity (μg/g), and n-1 is the intensity of adsorption. The values of KF and n-1can be determined from the intercept and slope, respectively of the linear plot of log y versus log Ce. The empirical Freundlich isotherm often satisfactory model of experimental data .
Whole Plantago major L. uptake experiment was performed in nutrient solution in Erlenmeyer flasks during test period from 2 h to 9 days. A whole Plantago major L. were grown in 250 ml of Hogland solution , containing 10 μg/ml of cyanophs in each 18 Erlenmeyer (6-periods × 3-replicates) flask 500 mL. The same number of flasks with pesticide only solution (10 μg/mL) was prepared. Three flasks were prepared as a control with a plant alone. After 2 and 4 hours, 1, 3, 6, and 9 days, three exposed and three control plants were collected. The experiment was studied at the room temperature (30 ± 2°C). Plant roots were rinsed in running tap water for 2 minutes and were blotted dry. The plants dissected into individual leaves and roots then 4 g of leaves and 2 g of roots were analyzed for the pesticide.
Water samples were extracted with methylene chloride without clean up using a continuous liquid-liquid extraction . Cyanophos was extracted from the root and leaf samples with acetone or water–acetone and then extracting with petroleum ether and dichloromethane. The organic phase was separated, dried, and concentrated just to dryness . The organic phase was dissolved in 5 mL of hexane then cleaned up via passing through a column prewashed with 50 ml of hexane + acetone (9: 1 v/v). The column was filled with acidic alumina (5 g) + sodium sulphate (2 mg) and was eluate with 100 mL of a mixture of hexane + acetone, 9: 1 v/v . The elute was evaporated to dryness and the residue was dissolved in 1.0 mL methanol and then analyzed by high-performance liquid chromatography (HPLC) with a UV-detector at 236 nm. A C18 column was used, and the mobile phase was a mixture of methanol and water (70:30, v/v). The flow rate was 1.0 mL/min. The retention time of cyanophos was 3.46 min. The metabolite 4-cyanophenol synthesized in our laboratory by hydrolyzing cyanophos with methanolic sodium hydroxide  and identified by HPLC with the same condition of cyanophos. Under these conditions, the retention time of 4-cyanophenol was 1.33 min.
The rate of degradation (K) and half-life (t 1/2) was obtained from the following Equation: The rate of degradation (K) = 2.303 × slope. Half-life (t 1/2) = 0.693/K .
In this study, all statistical analyses were performed with CoStat 6.311 CoHort Software. Significant differences between controls and contaminated samples were determined by the one-way ANOVA test.
Calibration curve was obtained by plotting peak areas in ‘y’ axis against concentrations of the pesticide in ‘x’ axis within the investigated range (0.18 to 12.5 μg/ml) of concentrations. Each solution was injected in triplicate. The linearity was significant with an excellent correlation coefficient of R2 = 0.994. The Limit of Detection (LOD) and Quantification (LOQ) of cyanophos were evaluated using the following equations: LOD = 3.3S0/b (3) and LOQ= 10S0/b (4) . Where S0 is the standard deviation of the calibration line and b is the slope. The Limit of Detection LOD and Quantification LOQ of cyanophos in this study were found to be 0.34 μg/mL corresponding to 0.08 μg/g and 1.02 μg/mL corresponding to 0.26 μg/g, respectively. The extraction efficiency of the analytical procedure was evaluated via recovery experiments conducted in triplicate using the fortified blank Plantago major L. samples at two different concentrations, 0.2 and 0.5 μg/g. The average percentage recoveries obtained were between 93.1± 5.3%, 90.9± 4.5% and 88.3± 3.6% in water, leaves and roots, respectively.
Results and discussion
Biosorption of cyanophos by plantago major L. on a dry weight basis after 4 hours exposure
Concentrations in water (μg/mL) ±*S.D.
Concentrations in water (μg/mL) and adsorption on a dry weight basis
Fruits (seeds with shells)
34.07 ± 1.0(a)
15.17 ± 0.67(b)
12.12 ± 0.39(c)
8.43 ± o.45(b)
4.47 ± 0 .13
2.23 ± .05(b)
0.092 ± 0.01(c)
0.074 ± 0.002(c)
Uptake and distribution
Concentrations of cyanophs uptake during plantago major L
Days after application
In water solution
μg/mL ± *S.D
In water solution with plantain
μg/mL ± *S.D
In plantain roots
μg/g ± S.D
In plantain leaves
μg/g ± *S.D
The use of plants to detoxify contaminated water is a potentially cost-effective alternative to traditional remediation technologies. From the results of this study, it can be ended that the existence of plants increased the removal t1/2 of cyanophos in water system. Plantago major L. is able to take up cyanophos from water by roots as well as by leaves, so Plantago major L. may be used for phytoremediation of water contaminated with cyanophos insecticide.
The author is most grateful to the laboratory staff of pesticides analysis and environmental pollution Laboratory, Plant Production Department, Faculty of Technology and Development, Zagazig University, Zagazig, Egypt for their collaboration in this research.
- Mullie W, Diallo A, Gadji B, Ndiaye M: Environmental hazards of mobile ground spraying with cyanophos and fenthion for Quelea control in Senegal. Ecotoxicol Environ Saf 1999, 43: 1–10. 10.1006/eesa.1998.1744View ArticleGoogle Scholar
- Tomlin C: The e- pesticide Manual. A world Compendium. 13 2004 edition. United kingdom: British Crop Protection Council: Farniham, surey; 2004:184.Google Scholar
- Bruggers RL, Elliott CCH: quelea, Africa1s Bird Pest. Oxford: Oxford University Press; 1989.Google Scholar
- Floesser-Mueller H, Swack W: Photochemistry of organophosphorus insecticides. Rev Environ Contam Toxicol 2001, 172: 129–228.Google Scholar
- Chiba M, Shlgeru K, Izuru Y: Metabolism of cyanox and surecide in bean plants and degradation in soil. J Pesticide Sci 1976, 1: 179–191. 10.1584/jpestics.1.179View ArticleGoogle Scholar
- Kiso Y, Sugiura Y, Kitao T, Nishimura K: Effects of hydrophobicity and molecular size onrejection of aromatic pesticides with nanofiltration membranes. J Mem Sci 2001, 92: 1–10.View ArticleGoogle Scholar
- Rahman MA, Hasegawa H: Aquatic arsenic: Phytoremediation using floating macrophytes. Chemosphere 2011, 83: 633–646. 10.1016/j.chemosphere.2011.02.045View ArticleGoogle Scholar
- Yadamari T, Kalyan Y, Gangadhar B, Ramakrishna N: Biosorption of malathion from aqueous solutions using herbal leaves powder. AJAC 2011, 2: 37–45. 10.4236/ajac.2011.228122View ArticleGoogle Scholar
- Susarla S, Medina VF, McCutcheon SC: Phytoremediation: an ecological solution to organic chemical contamination. Ecol Eng 2002, 18: 647–658. 10.1016/S0925-8574(02)00026-5View ArticleGoogle Scholar
- McCutcheon SC, Schnoor JL: Phytoremediation, Transformation and Control of Contaminants. Hoboken, New Jersey: John Wiley and Sons; 2003:1–58.Google Scholar
- Romeh A: Phytoremediation of water and soil contaminated with imidacloprid pesticide by plantago major , L. Int J Phytoremediation 2010, 12: 188–199.View ArticleGoogle Scholar
- Prasertsup P, Naiyanan A: Removal of chlorpyrifos by water lettuce ( Pistia stratiotes l.) and duckweed ( Lemna minor l.). Int J Phytoremediation 2011, 13: 383–395. 10.1080/15226514.2010.495145View ArticleGoogle Scholar
- Byrne FJ, Toscano NC: Uptake and persistence of imidacloprid in grapevines treated by chemigation. Crop Prot 2006, 25: 831–834. 10.1016/j.cropro.2005.11.004View ArticleGoogle Scholar
- Cheng S, Jin X, Huiping X, Liping Z, Zhenbin W: Phytoremediation of triazophos by canna indicalinn. in a hydroponic system. Int J Phytoremediation 2007, 9: 453–463. 10.1080/15226510701709531View ArticleGoogle Scholar
- Romeh AA, Hendawi MY: Chlorpyrifos insecticide uptake by plantain from polluted water and soil. Environ Chem Lett 2013, 11: 163–170. 10.1007/s10311-012-0392-0View ArticleGoogle Scholar
- Khan NU, Bhavya V, Nazeeb I, Paddu KS: Phytoremediation using an indigenous crop plant (wheat): the uptake of methyl parathion and metabolism of p-nitrophenol. Indian J Sci Technol 2011, 4: 1661–1667.Google Scholar
- Wang Q, Wei Z, Cui. Bo X: Phytoremediation of atrazine by three emergent hydrophytes in a hydroponic system. Water Sci Technol 2012, 66: 282–1288.Google Scholar
- Sharifa AA, Neoh YL, Iswadi MI, Khairul O, Abdul Halim MM, Jamaludin Mohamed A, Hing HL: Effects of methanol, ethanol and aqueous extract of plantago major on gram positive bacteria, gram negative bacteria and yeast. Ann Microsc 2008, 8: 42–44.Google Scholar
- Ahmaruzzaman MD: Adsorption of phenolic compounds on low-cost adsorbents: a review. Adv Colloid Interface Sci 2008, 143: 48–67. 10.1016/j.cis.2008.07.002View ArticleGoogle Scholar
- Felsot A, Dahm A: Sorption of organophosphorus and carbamate insecticides by soil. J Agric Foods Chem 1979, 27: 557–563. 10.1021/jf60223a013View ArticleGoogle Scholar
- Tebbutt THY: Principles of Water Quality Control. 3rd edition. Oxford, England: Pergamon Press; 1991:219–220.Google Scholar
- Wang W: Toxicity tests of aquatic pollutants by using common duckweed. Environ Poll 1986, 11: 1–14.View ArticleGoogle Scholar
- EL-Sheamy MK, Hussein MZ, El-Sheak AA, Khater AA: Residue behavior of certain organophosphorus and Carbamate insecticides in water and fish. Egypt J Appl Sci 1991, 6: 94–102.Google Scholar
- Luke MA, Froberg JE, Doose GM, Masumato HT: Improved multiresidue gas chromatographic determination of orgonophosphorus, orgononitrogen and orgonohalogene pesticides in procedure, using flame photometric and electrolytic conductivity detectors. Journal of AOAC 1981, 64: 1187–1195.Google Scholar
- Zaalok A, Sherif A: Combined effect of applied equipment and formulation of pesticide on spray and dust drift in relation to harmful effects for some non-target organisms. Agric Biol J N Am 2011, 2: 1059–1065.View ArticleGoogle Scholar
- Gomaa EA, Belal MH: Determination of dimethoate residues in some vegetables and cotton plant. Zagazig J Agric Res 1975, 2: 215–221.Google Scholar
- Thomsen V, Schatzlein D, Mercuro D: Limits of detection in spectroscopy. Spectroscopy 2003, 18: 112–114.Google Scholar
- Kang F, Dongsheng C, Yanzheng G, Yi Z: Distribution of polycyclic aromatic hydrocarbons in subcellular root tissues of ryegrass ( Lolium multiflorum Lam.). BMC Plant Biol 2010, 10: 210. 10.1186/1471-2229-10-210View ArticleGoogle Scholar
- Mohamed AE, Rashed MN: Assessment of essential and toxic elements in some kinds of vegetables. Ecotoxicol Environ Saf, Environ Res 2003, 55: 251–260. 10.1016/S0147-6513(03)00026-5View ArticleGoogle Scholar
- Ghaly AE, Snow Kamal AM: Kinetics of manganese uptake by wetland plants. American Appl Sci 2008, 5: 1415–1423. 10.3844/ajassp.2008.1415.1423View ArticleGoogle Scholar
- Naghizadeh A, Nasseri S, Nazmara S: Removal of trichloroethylene from water by adsorption on to multiwall carbon nanotubes. Iran J Environ Health Sci Eng 2011, 8: 317–324.Google Scholar
- Rengaraj S, Seuny H, Sivabalan MR: Agricultural solid waste for the removal of organics: adsorption of phenol from water and wastewater by Palm seed coat activated carbon. Waste Manag 2002, 22: 543–548. 10.1016/S0956-053X(01)00016-2View ArticleGoogle Scholar
- Mahvi AH: Application of agricultural fibers in pollution removal from aqueous solution. Int J Environ Sci, Tech 2008, 5: 275–285. 10.1007/BF03326022View ArticleGoogle Scholar
- Hiller E, Fargas A, Zemanova L, Barta M: Influence of wheat Ash on the MCPA immobilization in agricultural soils. Bull Environ Contam Toxicol 2008, 81: 285–288. 10.1007/s00128-008-9400-2View ArticleGoogle Scholar
- Ofomaja AE: Kinetic study and sorption mechanism of methylene blue and methyl violet onto mansonia wood sawdust. Chem Eng J 2008, 143: 85–95. 10.1016/j.cej.2007.12.019View ArticleGoogle Scholar
- Senthilkumaar S, Krishna SK, Kalaamani P, Subburamaan CV, Ganapathi N: Adsorption of organophosphorous pesticide from aqueous solution using “waste” jute fiber carbon. Mod Appl Sci 2010, 4: 67–83.View ArticleGoogle Scholar
- Derbalaha AS, Belalb EB: Biodegradation kinetics of cymoxanil in aquatic system. Chem Ecol 2008, 24: 169–180. 10.1080/02757540802032173View ArticleGoogle Scholar
- Al-Makkawy HK, Madbouly MD: Persistence and accumulation of some organic insecticides in Nile water and fish. Resour Conserv Recycl 1999, 27: 105–115. 10.1016/S0921-3449(98)00090-1View ArticleGoogle Scholar
- Mikami N, Ohkawa H, Miyamoto J: Photodecomposition of surecide (O-ethyl O-4-cyanophenyl phenylphophonothioate) and Cyanox (O, O-dimethyl O-4-cyanophenyl phosphorothioate). J Pestic Sci 1976, 1: 273–281. 10.1584/jpestics.1.273View ArticleGoogle Scholar
- Azmat R, Haider S, Riaz M: An inverse relation between Pb 2+ and Ca 2+ ions accumulation in Phaseolus mungo and Lens culinaris under Pb stress. Pak J Bot 2009, 41: 2289–2295.Google Scholar
- Turgut C: Uptake and modeling of pesticides by roots and shoots of parrot feather ( myriophyllum aquaticum ). Environ Sci Pollut Res 2005, 12: 342–346. 10.1065/espr2005.05.256View ArticleGoogle Scholar
- Bouldin JL, Farris JL, Moore MT, Smith SJ, Cooper M: Hydroponic uptake of atrazine and lambda-cyhalothrin in Juncus effusus and Ludwigia peploides . Chemosphere 2006, 65: 1049–1057. 10.1016/j.chemosphere.2006.03.031View ArticleGoogle Scholar
- Wang MJ, Jones KC: Behaviour and fate of chlorobenzenes (CBs) introduced into soil–plant systems by sewage sludge application: a review. Chemosphere 1994, 28: 1325–1360. 10.1016/0045-6535(94)90077-9View ArticleGoogle Scholar
- Chefetz B: Sorption of phenathrene and atrazine by plant cuticular fractions. Environ Toxicol Chem 2003, 22(10):2492–2498. 10.1897/02-461View ArticleGoogle Scholar
- Karthikeyan R, Lawrence D, Larry E, Kassim A, Peter A, Philip L, Stacy L, Asil A: Potential for plant-based remediation of pesticide-contaminated soil and water using nontarget plants such as trees, shrubs, and grasses. Crit Rev Plant Sci 2004, 23: 91–101. 10.1080/07352680490273518View ArticleGoogle Scholar
- Chuluun B, Janjit I, Jae Seong R: Phytoremediation of organophosphorus and organochlorine pesticides by acorus gramineus . Environ Eng Res 2009, 14: 226–236. 10.4491/eer.2009.14.4.226View ArticleGoogle Scholar
- Ibrahim S, Abdel Lateef M, Khalifa H, Abdel Monem A: Phytoremediation of atrazine-contaminated soil using Zea mays (maize). Ann Agric Sci 2013, 58: 69–75. 10.1016/j.aoas.2013.01.010Google Scholar
- Rankins A, Shaw R, Boyette M: Perennial grass filter strips for reducing herbicide losses in runoff. Weed Sci 2001, 49: 647–651. 10.1614/0043-1745(2001)049[0647:PGFSFR]2.0.CO;2View ArticleGoogle Scholar
- Angier T, McCarty W, Rice P, Bialek K: Influence of a riparian wetland on nitrate and herbicides exported from an agricultural field. J Agric Food Chem 2002, 50: 4424–4429. 10.1021/jf011057nView ArticleGoogle Scholar
- Zhao S, Arthur L, Coats R: The use of native prairie grasses to degrade atrazine and metolachlor in soil. In Environmental Fate and Effects of Pesticides. Edited by: Coats JR, Yamamoto H. Washington, DC: ACS Symposium Series 853, ACS; 2003:157–167.View ArticleGoogle Scholar
- Kodaka R, Sugano T, Katagi T, Takimoto Y: Comparative metabolism of organophosphorus pesticides in water-sediment systems. J Pestic Sci 2003, 28: 175–182. 10.1584/jpestics.28.175View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.