Research Journal of Recent Sciences ______ ______________________________ ______ ____ ___ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J. Recent .Sci. International Science Congress Association 261 Comparative Study on Phytoremediation of Synthetic and Industrial E ffluent Sharma H.K., Dogra P., Sharma N. and Sharma S. M.M University, Mullana, Ambala, INDIA Available online at: www.isca.in Received 30 th Nov ember 201 2 , revised 18 th January 201 3 , accepted 23 rd January 201 3 Abstract The effectiveness of Eichhornea Crassipes in removing metal ions was investigated. Results obtained indicate that plant was very effective in removing Cu +2 and Ni + ions. After one week, the percentage removal efficiency of copper and Nickel in industrial effluent was 14.4% and 13.5% respectively, which increased to 73.5% for copper and 92.2% for Nickel. After five weeks, the plant was able to remove the metal successfully without any phys ical sign of being affected by it. Results showed that conductance, total dissolved solids, dissolved oxygen and CO 2 values have decreased after phytoremediation. Whereas relative growth was increased after phytoremediation. The value of total suspended s olids in effluent, after first week was 1990mg/l and in last week it was reduced to 1940mg/l while pH of effluent was increased from 6.85 - 7.01. Overall results indicate that Eichhornea Crassipes can be used for phytoremediation of industrial effluent. K ey w ords : pH, EC, TDS, TSS, DO etc . Introduction The 20th century can be characterized as a time of increasing environmental awareness. Phytoremediation is an emerging technology that uses various plants to degrade, extract and immobilize contaminants fr om soil and water. This technology has been receiving attention lately as an innovative, cost - effective alternative to the more established treatment methods used at hazardous waste sites 1, 2 . Many hazardous waste sites are contaminated with salts, organi cs, heavy metals, trace elements, and radioactive compounds 3 - 5 . The simultaneous clean - up of multiple, mixed contaminants using conventional chemical and thermal methods are both technically difficult and expensive; these methods also destroy the biotic co mponent of soils. Phytoremediation of a site contaminated with heavy metals or radionuclides involves "farming" the soil with selected plants to "biomine" the inorganic contaminants, which are concentrated in the plant biomass 6,7 . For soils contaminated wi th toxic organics, the approach is similar, but the plant may take up or assist in the degradation of the organic compounds 8. Phytoremediation actually benefits the soil, leaving an improved, functional, soil ecosystem at costs estimated at approximately o ne - tenth of those currently adopted technologies. Phytoremediation includes Rhizofiltration 9,10 , Phytostabilization 11,12 , Phytovolatization 13 - 15 , and Phytodegredation 16 - 18 . In this study aquatic plant, water hyacinth ( Eichhornia crassipes ) was employed a s a plant model for the removal of heavy metals from industrial effluent. Material and methods Plant materials : Eichhornia crassipes were collected from a pond, near M.M. University Mullana. This aquatic plant was put in hydroponic system containing tap water, for a two – week acclimatization period, before being exposed to heavy metal contaminants. Preparation of copper and nickel contaminated solution : Synthetic solution of nickel and copper of 2.0 ppm and 4.0 ppm were prepared using copper and nickel st andard solution of 1000ppm using deionised water. Industrial Effluent : Industrial effluent was collected from electroplating waste water industry, Karnal. Experimental Set up : Approximately 10 liters of raw effluent from factory was brought to the labora tory and experiment was set up in plastic craits. Industrial effluent was diluted 50, 40 and 30 times and then transferred to the plastic craits. For each experiment set up, three controls were maintained with 5.0 litres each of effluent, tap water, Cu 2+ and nickel synthetic solutions [19] . Approximately 500g of Eichhornia crassipes was used for study. 500ml of each of effluent and synthetic solutions were collected periodically for analyzing the physico - chemical characteristics subsequently with an interv al of 7 days up to 35 days. Estimation of physico - chemical parameters: Major parameters analyzed include pH, total solid, TDS, TSS, free CO 2 , Salinity, Cu 2+ , Ni 2+ , DO and conductivity. Relative Growth : Relative growth of control and treated plant was calculated as follows; Relative growth = Final weight / Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ________ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J.Recent.Sci International Scien ce Congress Association 262 Initial fresh weight Metal remained in residual solution: The quantification of the metal ions in the industrial effluent has been performed on AAS (AAS, 630, shimadzu, Japan). Results are given in t able no. (a). Estimation of nickel ions : In 2 ml of the sample slight excess of 0.1M EDTA solution was added. Solution was diluted by adding 20ml distilled water and 1ml of buffer of pH 10 was added to the solution. Few drops of Eriochrome Black T were ad ded as an indicator. Excess of EDTAwas titrated with 0.1 M ZnSO 4 solution until colour changes from blue to wine red. Estimation of copper ions : 2.0ml of sample was diluted by adding 3.0ml of distilled water. 3 ml of buffer of pH 10 was added followed by 2 drops of Eriochrome black T as an indicator. This solution was titrated against standard EDTA solution until colour changes from red to blue. pH measurement: pH of each sample was noted after every seven days by pH meter ( pH - microprocessor based, the E E - 013 series, Tanko). Conductance Measurement : Conductance was measured by using conductometer (Digital conductometer, the EE - 014 series, Tanko). Dissolved oxygen : Dissolved oxygen was measured using Winkler’s Method. Dissolved carbon di - oxide: 2 - 3 dr ops of phenolphthalein was added to each 100 ml of sample. Sample was titrated against NaOH, pink colour appeared, indicates the presence of CO 2 . CO 2 , mg/l = Ax N NaOH x1000 x 44/2x Vc.c. , A= Volume of NaOH used, V= Volume of sample taken Suspended impurit ies : 3ml of filtered water sample was kept in oven set at temperature 600 0 C for the evaporation of water sample. After evaporation, crucible was kept in desiccators for a while to prevent impurities, and then weighed. Same procedure was repeated with unfil tered water sample. The process was repeated with each sample. Results and Discussion In the present study an attempt has been made to have a comparative assessment of the efficiency of aquatic plant like Eichhornea Crassipes to treat the industrial eff luent and synthetic solution. The effluent sample and the synthetic solution were analyzed periodically with a view to find out the changes in physiochemical properties brought about by the Eichhornea Crassipes. It was observed that plants survive only in 50% effluent; therefore, the further studies were carried out only with this concentration. Metal Removal Efficiency: It was calculated as (C i - C f /C i ) × 100 % where C i is the initial concentration and C f is the remaining heavy metal concentration in the so lution. Figure - 1 and table - 1 shows percentage removal efficiency of copper and nickel ions in effluent and synthetic solution. After one week, the percentage removal of copper in effluent was 14.4% and it and after last week percentage suddenly increased t o 73.5%. The percentage removal of nickel in effluent after one week was 13.5% and in last week percentage removal nickel has greatly increased to 92.2%. This result shows that phytoremidiation has occurred in the effluent. The percentage removal of copper in synthetic solution was 12.5% during first week and in last week its value was reached to 31%. Same result was observed in case of nickel synthetic solution. Its value was 25% after one week and in last day it was increased up to 57.1%. It is clear from the trend that after certain time period the saturation point is reached, this is due to the loading effect where sorption sites were saturated by copper and nickel ions. The removal efficiency was also due to the utilization of Cu and Ni for the developm ent of the plant. A similar trend was reported by Felix and Mokhtar 20,21 , where the Pistia stratiotes, Asiattica and Spirodela polyrrhiza performed extremely well in removing the chromium and zinc from their solution and was capable of removing zinc, Coppe r and chromium during 12 days incubation period. pH: pH of effluent was noted 6.85 - 7.01 after phytoremediation. pH of the synthetic solution was also increased after the culture (t able - 2). Das had also recorded increase in pH of municipal sewage on expo sure of macrophytes after seven days. Percentage increase in pH value was 0.72 - 2.28% in the effluent, Cu 2+ solution and in Ni 2+ solution. An increase in pH value supports the growth of aquatic plant 22 . Conductance: EC value had ranged from 2.51 - 0.49 mh o/cm in industrial effluent. Results are given in f ig ure - 2 and t able - 3. In the synthetic Ni 2+ solution and in Cu 2+ solution, EC values are 1.25 - 0.13 mho/cm and 1.21 - 0.158 mho/cm respectively. EC value was lowered after the culture due to absorption of diss olved solids by E. Crassipes during Phytoremediation. Moorheed (1986) 2 3 recorded 48% reduction in EC value during 22 days of culture of aquatic plant. TDS: TDS value was observed to be decreasing after phytoremediation with Eichhornea Crassipes TDS and EC were closely related hence, exhibits the same trend of variation in value i.e 1377 - 1161mg/l in effluent. Values of TDS in copper synthetic solution vary from 1209 - 507mg/l and that nickel synthetic solution is 1013 - 304 mg/l. Reduction in the values is due to evaporation and absorption of dissolved solids by the plant. Dissolved Oxygen: Dissolved oxygen values were recorded 6.8 - 5.7 ppm during phytoremediation of the effluent. The value of D.O. was found to be 6.9 - 4.7 ppm in Ni +2 solution and in case of Cu +2 synthetic solution it was 7.9 - 5.9 ppm. From the observations, it was concluded that demand of oxygen has greatly increased in each plant for growth and phytoremediation has occurred in each plant. Results are given in f igure - 3 and f igure - 4. Patel and Kanungo also observed the decrease in DO Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ________ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J.Recent.Sci International Scien ce Congress Association 263 after the culture of aquatic plant 24 . Suspended solid: The value of suspended impurities has decreasing trend shown in f ig ure - 4. The value of TSS in effluent after first week was 1990mg/l and in las t week, it was reduced to 1940mg/l. similar trend was observed in synthetic solution of Cu +2 , it was 1400mg/l, after first week and in last week, it was reduced to 1355mg/l ( f ig ure - 6). Similarly in case of Ni +2 synthetic solutions, its value was 1255mg/l a fter first week and in last week; it was reduced to 1220mg/l ( f ig ure - 5). Highest reduction value was observed in last week. Phytoremediation generally reduced turbidity. Relative Growth: The effect of Cu 2+ and Ni 2+ on the relative growth of Eichhornea Cra ssipes was shown in Figure 7. The relative growth of plants grown in the effluent as well as synthetic solution significantly increased with the passage of time. Highest value of relative growth was observed in effluent i.e. 1.21591%. In case of Cu and Ni synthetic solution value of relative growth was 1.21311% and 1.07229 % respectively. Dissolved CO 2 : The value of total CO 2 was ranging from 150.0 - 79.0 ppm in the effluent during the phytoremedation. Dissolved CO 2 value was significantly reduced because of successful photosynthetic activity by the aquatic plant Conclusion Results obtained indicate that plant was very effective in removing Cu +2 and Ni 2+ ions. After one week, the percentage removal efficiency of copper and Nickel in industrial effluent was 14.4% and 13.5% respectively, which increased to 73.5% for copper and 92.2% for Nickel. It is clear from the trend that after certain time period the saturation point is reached, this is due to the loading effect where sorption sites were saturated by co pper and nickel ions. The removal efficiency was also due to the utilization of Cu and Ni for the development of the plant. Dissolved oxygen and CO 2 values have decreased after phytoremediation. It was concluded that demand of oxygen has greatly increased in each plant for growth. Dissolved CO 2 value was significantly reduced because of successful photosynthetic activity by the aquatic plant. The relative growth of plants, grown in the effluent as well as synthetic solution significantly increased with the passage of time which indicates that plant was very effective in removing Cu +2 and Ni 2+ ions without any physical sign of being affected by it. EC value was lowered after the culture due to absorption of dissolved solids by E. Crassipes during Phytoremedi ation. Highest reduction value of the turbidity was observed in last week because phytoremediation generally reduces turbidity. All results indicate that Eichhornea Crassipes can be used for phytoremediation of industrial effluent. Acknowledgement My hea rtiest felt gratitude is due to the management of M. M. University, Mullana(Ambala) especially chancellor for granting me necessary permission. Table - a Concentaration of Cu 2+ , Ni 2+ and Fe 2+ ions in industrial effluent S.No. Metal ion Concentration (ppm) 1. Cu 2+ 115.52 2. Ni 2+ 135.40 3. Fe 2+ 90.23 Table - 1 Variation in percentage removal efficiency of metal ions in synthetic solution and effluent during Phytoremediation Time Period (days) % removal of Cu 2+ in effluent % removal of Ni 2+ in efflue nt % removal of Ni 2+ in synthetic sol % removal of Cu 2+ in synthetic sol 7 th 14.43 13.59 25.0 12.50 14 th 39.08 50.60 37.5 18.75 21 th 49.64 75.57 45.0 25.00 28 th 52.64 91.65 51.25 28.12 35 th 73.59 92.20. 57.12 31.00 Table - 2 Variation in pH value of synthetic solution and industrial effluent during Phytoremidiation Time Period (days) pH of Effluent ( 50%) pH of Tap Water pH of Ni 2+ synthetic Solution pH of Cu 2+ synthetic Solution 1st 6.85 7.0 6.90 6.02 7 th 6.90 7.0 6.93 6.94 14 th 6.93 7.0 6.95 6 .96 21 th 6.95 7.0 6.97 6.97 28 th 6.98 7.0 6.99 7.02 35 th 7.01 7.0 7.05 7.04 Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ________ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J.Recent.Sci International Scien ce Congress Association 264 Figure - 1 Percentage removal efficiency of metal ions in synthetic solution and industrial effluent d uring Phytoreme diation Table - 3 Variation in conductance values of synth etic solution and industrial effluent during phytoremediation Time Period (days) Effluent (50%)(mhos/c m) Ni 2+ synthetic Solution(mho s/cm) Cu 2+ synth etic Solution (mhos/cm) 1st 2.51 1.25 1.21 7 th 2.49 1.17 1.15 14 th 2.47 1.15 1.30 21 th 0.845 0.360 0.336 28 th 0.525 0.350 0.178 35 th 0.490 0.139 0.158 Table - 4 Variation in dissolved oxygen of synthetic solution and industrial Effluent during phytoremediation Time Period (days) Effluent (50%) ppm Ni 2+ synthetic solution (ppm) Cu 2+ syntheti c solution (ppm) Tap Water (ppm) 1st 6.8 6.9 7.9 6.7 7 th 7.4 5.9 6.9 6.5 14 th 5.6 4.8 5.8 6.4 21 th 5.9 4.3 5.5 5.8 28 th 5.3 4.6 5.7 5.4 35 th 5.7 4.7 5.9 5.9 Table - 5 Variation in total suspended solids in synthetic solution and industrial effluent d uring Phytoremediation Time Period Effluent (50%) Ni 2+ synthetic solution Cu 2+ synthetic solution Tap Water 1st 1990 1255 1400 1600 7 th 1982 1250 1390 1590 14 th 1974 1240 1381 1589 21 th 1964 1235 1372 1580 28 th 1950 1230 1365 1570 35 th 1940 1220 13 55 1565 Figure - 2 Variation in conductance values of synthetic solution and industrial effluent during phytoremediation Table - 6 Variation in relative growth of the plants in synthetic solution and industrial effluent during phytoremediation Time Peri od Relative growth in effluent Plant Control Cu 2+ synthetic solution Ni 2+ synthetic solution 7 th 1.06818 1.01282 1.01667 1.01205 14 th 1.09091 1.02564 1.03279 1.02413 21 th 1.13636 1.05128 1.09836 1.04217 28 th 1.18182 1.06838 1.18033 1.05422 35 t h 1.21591 1.09402 1.21311 1.07229 Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ________ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J.Recent.Sci International Scien ce Congress Association 265 Figure - 3 Variation in values of dissolved oxygen of synthetic solution and effluent during phytoremediation Figure - 4 Variation in total suspended solids in industrial effluent during phytoremidiation Figure - 5 V ariation in total suspended solids in nickel synthetic solution during phytoremediation Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ________ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J.Recent.Sci International Scien ce Congress Association 266 Figure - 6 Variation in total suspended solids in copper synthetic solution a fter phytoremediation Figure - 7 Variation in relative growth of the plants in synthetic s olution and industrial effluent during phytoremediation References 1. Smith R.D and Salt D.E., Phytoremediation of metals: using plants to remove pollutants from the environment, Current Op inion in Biotechnology , 8, 221 - 226 (1997 ) 2. Lee A.N., Sharon L., Katrina L., Paul E., Induluis M., Tanya Q., Sarah T., Stuart E., Xiaoping W., Angela M. and Milton P, Contaminants: A Review of Phytoremediation Research at the University of Washington, Soil and Sediment Contamination: An International Journal , 7 , 531 – 542 (1998) 3. Adams N., Carroll D., Kelly M., Steve R., Wilson T. and Pivetz B., United States Protection Agency Reports Introduction to Phytoremediation – EPA., 600(99) , 107 (2000) 4. Adriano D.C., Trace elements in the terrestrial environment – Springer - Verlag, 533 - 545 (1986) 5. Alloway B.J. In Heavy Metals in Soils. Blackie Glasgow, 354 - 362 (1990) 6. Henry J.R. In An Overview of Phytoremediation of Lead and Mercury, NNEMS Report, 3 - 9 (2000) 7. Ross A. and Ross S., Toxic Metals in Soil - Plant Systems, Biotechnology (N Y), (1994) 8. Salt D.E . , Blaylock M . , Kumar N.P . , Dushenkov V . , Ensley B.D . , Chet I . and Raskin I ., P hytoremediation: a novel strategy for the removal of toxic metals from the environment using plants , Biotechnology (NY) , 13, 68 - 74 (1995) 9. McCutcheon S.C. and Jørgensen S.E., Phytoremediation , Encyclopedia of Ecology , 2751 - 2766 (2008) 10. Ghosh M., Singh S.P. and Devi Ahilya, A Review on Phytoremedia tion of Heavy Metals and Utilization of Its Byproducts, Applied Ecology and Environmental Research, 3, 1 - 18 (2005) 11. Salt D.E., Smith R.D. and Raskin I., Phytoremediation, Annu. Rev , Plant Physiol , Plant Mol. Biol., 49, 643 - 668 (1998) Research Journal of Recent Sciences ______ _ _ _______________________________ ______________ _ ________ ISSN 2277 - 2502 Vol. 2 ( ISC - 2012 ), 261 - 267 (201 3 ) Res.J.Recent.Sci International Scien ce Congress Association 267 12. Suresh B . and Ravishankar G.A ., Phytoremediation: a novel and promising approach for environmental clean - up , Crit Rev Biotechnol , 24, 97 - 124 (2004) 13. Negri C. and Hinchman R., Plants that remove contaminants from the environment , Lab Med , 27, 3 6 - 40 (1996) 14. Ernst. WHO Bioavailability of heavy metals and decontamination of soils by plants, Appl Geochem , 11, 163 - 167 (1996) 15. Bouwman L.A., Bloem J., Romkens PFAM, Boon GT. And Vangronsveld J., Beneficial effects of the growth of metal tolerant grass on b iological and chemical parameters in copper and zinc - contaminated sandy soils, Minerva Biotechnological , 13, 19 - 26 (2001) 16. Schnoor J., Licht L., Mccutcheon S., Wolfe N. and Carreira L., Phytoremediation of organic and nutrient contaminants , Environ Sci Tech nol . , 29, A318 - A323 ( 1995) 17. Hinchman R. and Negri C., The Grass Can Be Cleaner on the Other Side of the Fence, Argonne National Laboratory , 12, 8 - 11 (1994) 18. Marseille F., Tiffreau C., Laboudigue A. and Lecomte P., Impact of vegetation on the mobility and bio availability of trace elements in a dredged sediment deposit: a greenhouse study. Agronomie , 20, 547 – 556 (2000) 19. Laxami C., Kruatrachue M., Pokethitiyoo K., Upatham E.S. and Soonthornsarathool, Toxicity and accumulation of lead and cadium in the filament gr rrn alga cladophora fracta, A laboratory study, Science asia, 31 , 121 - 127 (2005) 20. Hamizah M., Mmorad N. and Fizri F.F.A. phytoaccumulation of copper and aqueous solution using Eichhornia Crassipes and Centella asiatica, Int. J. Environ. Sci. Development , 2, 3 (2011) 21. Aisein F. A., Faleye O. and Tina E., Phytoremediation of Heavy Metals in Aqueous Solutions. Leonardo J. Sci., (2010). 22. Vermaat J. E. and Hanif K.M., Performance of common duckweed species (Lemnaceae) and the water fern Azolla filiculoides on diff erent types of wastewater , Water Res ., 32 , 2569 - 2576 (1998) 23. Moorhead K.K. and Reddy K.R., Oxygen transport through selected aquatic macrophytes, J. Environ. Qual. , 17(1) , 138 - 142 (1988) 24. Patel D.K. and Kanungo V.K., Ecological efficiency of ceratophyllum De mersum L. in phytoremediation of nutrient from domestic waste, The Ecoscan , 4, 257 - 262 (2010)