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.
KeywordsPhytoremediation Plantago major L Water Cyanophos insecticide
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.
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