Bibadsorptive Removal of concentration range 2mg / L for same biomass (60g /

L ) concentration.
Chromium and Lead by Aquatic
Macrophyte Key words: Bioremediation, Chromium, Lead,
water lettuce, hydroponic culture
Rupa Chakraborty
Research Scholar* INTRODUCTION
Environmental Engineering division Management of water quality in the
Civil Engineering Department hydrosphere is a big challenge throughout the world
Jadavpur University, Kolkata- 700032
because of different anthropogel.ic pollution. The
rupachakra@yahoo.co.in removal of heavy metals from contaminated water
is of great importance in terms of protection of the
Somnath Mukherjee "..
environment and human health. Heavy metals may
Professor
Environmental Engineering division build up various physiological effects in biological
Civil Engineering Department, systems and cause serious health hazards like skin
Jadavpur University, Kolkata- 700032 diseases, lung cancer, liver dysfunction, kidney
snmJu@yahoo.co.in damage, permanent damage in nervous system etc.
The conventional removal methods like chemical
ABSTRACT Jecipitation, coagulation, lime-softening etc. are
The accumulation of heavy metals in the water generally expensive and require frequent
environment receives increasing attention because monitoring apart from high chemical cost and
of the indiscriminate adverse public health effect by disposal problem of chemical sludge, though such
the respective elements. For removal of such toxic process are attenuative. . Biosorption is one of the
metals from the aqueous phase in a more innocuous most important biological methods which has been
way, biosorption is emerged as a potential option recommended as cheaper, eco-friendly and effective
for heavy metal removal as reported in various techniques for removal of heavy metals from
literatures. The accumulation of heavy metals using aqueous environment (Miretzky et aI, 20041;
living photosynthetic species such as aquatic weeds Odjegba and Fasidi, 20042). Aquatic macrophytes
and plants are applied for the purpose to establish such as water lettuce, duckweeds etc. are one of
an alternative method to different existing physico- the biological components as being used in recent
chemical method for such purposes. The years as functional intent to prevent the hazards of
bioremediation as utilizing some aquatic plants for toxic metal pollution successfully (Suhag et al.,201P,
removal of toxic metals from water environment Maine et al.,2006,4). The treatment responses in an
unveils to be a plausible alternative. The present aquatic macrophyte treatment system are due to
- paper discusses on laboratory investigation as direct uptake of material by plants' root under
carried out in Environmental Engineering division, favorable environmental conditions. This uptake
Civil Engineering Department, Jadavpur University capacity of aquatic plants along with other
to explore chromium and lead uptake capacity of one influencing factors has also been reported as
of the common aquatic macrophytes normally grown phytoremediation technology (Pilon-Smiths, 20055).
abundantly in Indian subcontinent such as water This technology involves several sub-mechanistic
lettuce (Pistia stratiotes). The plants were collected processes like rhizofiltration, phytostimulation,
from a nearby pond and hydroponically cultured in phytostabilization, phytoextraction, phytodegra-
the laboratory condition using Hoagland solution. dation, phytomining and phytovolatilization. The
The sample water was prepared with Cr (VI) and Pb phytoremediation process involves the introduction
(II) -spiked synthetic solution with varied initial of plants into an ecosystem and allowing them to
concentrations as single substrate respectively in assimilate rather hyperaccumulate the
several test cases. The plants of different quantities contaminants in their roots and associated parts.
(biomass) were exposed to spiked solutions in Some earlier studies have shown the
separate containers batch wise for a specific periods. hyperaccumulation potential for metals like Pb, Hg,
it was observed that for an initial concentration Cd,.etc. (Alam et al., 19946; Baharudin et al., 20087).
range of 1-5mg / L of Cr (VI), about 99-72% In certain cases the rate of metal uptake has been
corresponding removal took place after a contact reported to go up to even 90-95% depending on the
period of9 days. In case of lead, about 82% removal plant species concerned, its biomass, metal
was achieved after 9 days contact period for an initial concentration and environmental factors like pH,
temperature, etc. (Baharudin et al., 20087, Mishra
*Corresponding Author and Tripathi, 20088).

Volume 2012-13 e Number 2 eJuly2012 43

 (
Rupa UhakralJOny, i:>OrrUtUtl
"'"""H'<-'J~~ '1.

Chromium (VI) rarely occurs naturally, but is sessilis (grown on settling ponds of a sewage I
usually produced from anthropogenic sources. It is treatment works) can accumulate Pb in leaves in I
used in various industries such as chrome higher amount than in the roots and stems
tanneries, plating, cooling tower water treatment combined. In contrary to the above, Sharma and I
etc. The hexavalent form of chromium is of Dubey ,200520 reported lead accumulation in root
particuLar concern because of its great toxicity jn hjgher as compared to other parts of plants.
resulting from its powerful oxidation properties. It Verma et al., 200521 detected that water hyacinth
is classified as a group A carcinogen and poses other could remove lead to a higher percentage 80.3%
health risks such as liver damage, dermatitis and from industrial wastewater with Pb 1.39 mg / L.).
gastrointestinal ulcers (Dokken et al.,19999). Shao-Wei Liao, 200422 exhibited water hyacinth can
Reduction of hexavalent chromium to trivalent with be an useful macrophytes for absorption of lead
subsequent immobililation as the hydroxide is and storing it in root tissue along with other heavy
considered as one of the main strategies for metals.
chromium removal from waster water (Lazardis and The present investigation was carried out to
Asouhidou, 200310). In a separate study Lytle et al., explore the potential use of water-lettuce (Pistia
199811 found that water hyacinth could accumulate sp.), a floating aquatic plant to remove toxic heavy
hexavalent chromium from contaminated water. metals like chromium (VI) and lead (II) from a
Under X-ray spectroscopy, the plants had converted laboratory prepared spiked solution in presence of
hexavalent chromium to trivalent chromium in the hydroponic solution.
lateral roots of the plant, thus detoxifying the water
significantly. Keith et al., 200612 also showed that MATERIALS AND METHODS
the water hyacinth can hyper accumulate chromium
in the tune of72.3, 21, and 19% chromium( Cr VI) Designing of the Experiment: The present
removal for 7,14 and 28 mg/L respectively. Espinoza experiments were carried out in multicells aquarium
Quinones et al., 200613 observed that for a range of made of Perspex sheet in the laboratory in
2-3 mg / L initial Cr (VI) concentration, Salvinia Environmental Engineering division, J adavpur
auriculata could remove 90 percent of Cr(VI) , much University, Kolkata, West Bengal, India. The young
higher than Pistia stratiotes (70 percent) and plants were collected from a nearby pond and
Eichhornia crassipes (50 percent) after 35 days of acclimatized hydroponically in flat bottom HDPE
uptake experiment. Aquatic fern (Azolla) has been tray. Plants harvested from this tray were
demonstrated as an important candidate for subsequently washed in single distilled water,
polishing wastewateT containing Cr (VI). Arora et O.OlM NH4-EDTA solutions respectively and finally
al., 200614 detected the high tolerance of Azolla sp in deionised distilled water. They were grown
for a wide range ofCr(VI) [up to 10 mg / L] as well hydroponically in Hoagland solution (1950)23 as a
as to bioconcentrate [BCF i.e. Bio concentration nutritional supplement at pH 7 :t 0.2 in
factor ( ratio of metal concentration in the dry approximately 10000 lux/m2 light intensity. The
biomass to the initial concentration of metal ion in experiment was carried out at ambient temperature
-
feed solution) ranged between 243 4617 for three (250 :t 50 C). For treatment purpose, culture medium
sp of Azolla] them. Toxicity in treated tannery was prepared with Cr (VI) and Pb (II) -spiked
effluent has been reduced using alga Nostoc synthetic solutions separately. The different
muscorum and bacterium Photobacterium synthetic solutions of varied concentration levels
phosphorium [Chandra et al., 200415] were prepared by diluting stock solution with
Lead [Pb (II)] contamination of the environment nutrient solution in required quantity to get the
has resulted from mining and smelting activities, desired concentration of metallic solutions. Stock
leads based paints, gasoline, storage battery potassium dichromate solution of the strength of
manufacturing plants and explosives as well as from 1000mg of Cr (VI)/L was prepared by dissolving 2.82g
municipal sewage sludges enriched in Pb (II) in K Cr 0 (oven dried) in lL of double distilled water.
water environment (Chaney and Ryan, 199416).Lead A2set2of intermediate stock chromium of different
attributes to its toxic ability to interfere with several diluted strength solution were made by adding
enzymes like CAT, POD, SOD (Odjegba and deionised distilled water plus nutrient solution to
Fasidi,200717). As lead causes a large variety oftoxic stock in such quantity that finally solution volume
effects, including gastrointestinal, muscular, in each container became lL. Approximate 60g of
reproductive, neurological, behavioral and genetic biomass were placed in the aquarium with
malfunctions [Johnson ,199818], the fate oflead in predetermined volume (lL) and allowed to retain
the aquatic environment is of great concern. in the solutions with supplement of Hoagland
Moodley et al., 200719 found that Alternanthera solution. Volume of solution was adjusted after

Volume2012-13. Number 2. July 2012 44

 ("
Rupa Chakraborty, Somnath Mukherjee

aliquots of solution were taken for analysis and to to an equilibrium concentration level after a period
make up the loss due to evaporation with deionised of 9 days. It is also revealed that the sorption by
w:ater. The total retention period for each set of the plants was maximum at lower initial
experiment was nine days. In each case 'control' concentration (1 mg/L) and started declining at
set was kept without any metal solution. higher initial concentrations which could be due to
imposition of toxic effects to the plant metabolism.
Estimation of Cr(VI) and Pb(II): The sample was Lead is not an essential element for the plants
digested with a sui ph uric-nitric acid mixture and but it gets easily absorbed and accumulated in
followed by oxidation with potassium permanganate different parts of the plant unless it reaches a
[for total conversion of all chromium species to Cr threshold inhibitory limit. This uptake is controlled
(VI) ]. Dissolved hexawalent chromium was by pH, particle size and other physico-chemical
estimated colorimetrically by reaction with parameters. The uptake oflead at pH (7.0) for the
diphenylcarbazide in acid solution to form a red- removal percentage with time, the different initial
purple chromium 1, 5-diphenyl-carbohydrazine lead concentrations are shown in Table 2. It is
complex that is measured at 540 nm in accordance evident from the data set that like Cr (VI) uptake
with Standard Methods (APHA 1985)24 in UV-VIS initially the adsorption rates are faster and then
Spectrophotometer (Varian, USA make, model Cary found to be decreased gradually to reach an
50). equilibrium level between the time period after
For lead treatment, a stock (lOOmg/L) lead 7days. It is noted that about 82% removal took place
solution was prepared by dissolving lead nitrate salt after same retention period (9 days) for an initial
in double distilled water. Spike sample solution of lead concentration range 2mg/L for same biomass
2mg/L was prepared by diluting the stock 50 times concentration (60g/L ). However, in the field
with double distilled water. Lead concentration was condition it can be achieved more by adopting
determined using Flame Atomic Absorption continuous harvesting technique with more
Spectrophotometer (Perkin Elmer Analyst 200 exposure to sunlight or better photosynthesis since
model) it is expected that cells may be vibrant within the
All reagents were used of AR grade ofE-Merck, plant regime by photosynthetic action. The increase
India make. in initial rate of removal with subsequent increase
All the tests were conducted with three of initial lead concentration may be due to the
replicates. The experiment was performed as batch difference in concentration potential between the
mode kinetic. Sixty gm ofihitial biomass (laboratory solution and root system. The rapid uptake perhaps
cultured samples) was next placed equally in the due to an initial phase of exchange phenomenon
different cells of the multicells aquarium containing followed by a slow phase due to metabolic regulation
the mixture of chromium and nutrient solution. The and more flux intrusion through root system.
solution was buffered to a pH of 6.8:!::O.2.Samples Percent removal data of Cr (VI) and Pb (II) by
were pipetted out from each cell after 1,2,3,4,5,6,7,8 water lettuce (Pistia) from 0 to 9 days of culture
and 9 days from the start of the experiment and has been plotted in Figure 1. In each treatment,
analysed for residual chromium and lead the results showed a rapid removal at initial phase
concentration as described above. which ultimately reached at equilibrium after 6 to
For each initial concentration set, the same 7 days. Among two metals tested, highest removal
procedure was repeated three times with fresh (82%) was observed in case ofPb (II) followed by Cr
laboratory cultured samples. All the above tests (VI) (79.5%) at an initial concentration of 2 mg/L
have been carried out as batch kinetic studies. after 9 days of culture as shown in Table 3.

RESULTS AND DISCUSSION CONCLUSION

The residual Cr (VI) concentrations in the Phytoremediation technology is gaining the
solutions were determined from the culture solution status of a major scientific progress in ecological
after every 24h interval up to 9 days contact period and environmental engineering application and has
continuously for different initial Cr (VI) immense contemporary relevance for potential use
concentrations. From the residual Cr (VI) to decontaminate or to render harm less
concentration left in the culture media after environmental ecosystem. Plant species such as
treatment with the test plant, the removal water lettuce (Pistia sp,) has been successfully
percentage was calculated at specified time intervals. explored to examine the sorption potential for
The results are shown in the Table 1. It reveals chromium and lead separation from the spiked
that the uptake took place in two phases with rapid solution. So this plant can be used as low cost
initial uptake up to 4 days which gradually reached treatment material for scavenging heavy metal from

Volume 2012-13 - Number 2- July 2012 45

 (i.
Rupa Chakraborty, Somnath Mukherjee

Table: 1 Batch Kinetic Results of Cr (VI) Removal by Water lettuce Biomass cone. 60gIL

81 No. InHial cone. of Time (Days) Residual cone. of Percent

Cr (mg/L) Cr (mg/L) removal
0 1.0 0
1 0.75 25.0
2 0.55 45.0
3 0.45 55.0
1. 1 4 0.30 70.0
".. 5 0.26 74.0
6 0.08 92.0
7 0.04 96.0
8 0.02 98.0
9 0.01 99.0
0 2.0 0
1 1.65 17.5
2 1.31 34.5
3 1.05 47.5
2. 2 4 0.71 64.5
5 0.62 69.0
6 0.51 74.5
7 0.46 77.0
8 0.43 78.5
9 0.41 79.5
0 30.0 0
1 2.50 16.7
2 2.06 31.3
1.84 38.7
3. . 3
3
4 1.45 51.7
5 1.21 59.7
6 1.08 64.0
7 0.88 70.7
8 0.79 73.7
9 0.76 74.67
0 4.0 0
1 3.15 21.3
2 2.59 35.3
3 2.31 42.3
4. 4 4 1.82 54.5
5 i.70 57.5
6 1.45 63.8
7 1.25 68.8
8 1.18 70.5
9 1.13 71.7
0 5.0 0
1 3.95 21.0
. 2 3.25 35.0
3 2.87 42.6
1. 1 4 2.38 52.4
5 2.05 59.0
6 1.70 66.0
7 1.53 69.4
8 1.44 71.2-
9 1.40 72.0

Volume2012-13. Number 2. July 2012 46

 ('. Rupa Chakraborty, Somnath Mukherjee

Table 2. Batch kinetic Results of Pb(lI) technology can be used in real life technology in
Removal by Water lettuce near future.
In connection with this, it must be mentioned that
Time Residua Percent
there are certain hazards associated with the use
(Day) Conc. of Removal
of water lettuce as a means for bioremediation.
Pb (mglI)
Sometimes this plant produces a nuisance when it
0 2 0 finds entry in natural water bodies and decrease
1 1.6 20 dissolved oxygen level in water. After harvesting,
2 1.36 32 proper disposal will also pose a problem to
:3 1.12 44 environment. Dissociation of soluble matters in
4 0.84 58 water bodies from the plant will increase the
5 0.6 69 pollutant levels. This is a serious limitation for
6 0.52 74 using plants for heavy metal and metalloid removal
7 0.46 77 from wastewater.
8 0.38 81 A list showing the common names of aquatic
9 0.36 82 plants against their scientific names is enclosed.

Table 3. Comparative Results of Cr (VI) and Scientific Name Common Name

Pb (II) Removal (%) by Water Lettuce after 9 Pistia stratiotes water lettuce
Days of Culture
Eichhornia crassipes water hyacinth
Biomall concentration - 60g/L
Azollasp Aquatic fern
Initial Cr (VI) Pb (II)
Lemna sp. spirodela sp Duckweeds
concentration
Salvinia auriculata Kariba weed, water
2mg/L 79.50 82.00
velvet, water fern,
water spangles
90
80 REFERENCES
70 1. Miretzky, P., Saralegui, A., Ferna'ndez Cirelli,
-.. 60 A., (2004). Aquatic macrophytes potential
~ 50 Biomass conc.- 60g/L for the simultaneous removal of heavy metals
E Soiution \Olume-1 L
~ 40 (Buenos Aires, Argentina)". Chemosphere, Vol-
~ Initial conc.2mg/L
0 30 57(8), PP-997-1005.
I
20 1-- CreVI) 2. Odjegba, V.J. and Fasidi, 1.0. (2004).
10 ~ . --"'111!LJ "Accumulation of Trace Elements by Pistia
0 ~-~
stratiotes: Implications for Phytoremediation".
0 2 4 6 8 10
Ecotoxicology, Vol-13, PP-637-646.
Time (days) 3. Suhag, A., Gupta,.R., Tiwari, A. (2011),
Figure 1: Percent removal of Cr (VI) and "Biosorptive removal of heavy metals from
Pb (II) by Water lettuce wastewater using duckweeds". Int J of
Biomedical and Advance Res. Vol-2(8),PP-281-
290
waste water. For chromium (VI) treatment, 99-72%
removal was obtained at 1-5mg/L initial Cr (VI) 4. Maine, M.A., Sune, N., Hadad, H., Sanchez,
concentration after a contact period of 9 days. In G. and Bonetto, C. (2006), "Nutrient and metal
removal in a constructed wetland for
case of lead, about 82% removal was obtained for
an initial concentration of 2mg/L for same biomass wastewater treatment from a metallurgic
concentration (60g/L). industry". Ecological Engineering, Vol- 26, PP-
341-347.
The present study is a prospective one,
however, it also suggests that in future some 5. Pilon-Smits,E .(2005)," Phytoremediation".
metabolic factors on growth parameters of the plant Annu. Rev, Plant. BioI. Vol- 56, PP-15-39.
and associated plant physiological stress should be 6. Alam, B., Chatterjee, A.K. and Dattagupta, S.,
investigated in details to explain the metals hyper (1994), "Bio accumulation of Cd (In by water
accumulation behavior by the plants and also to lettuce (Pistia stratiotes L.)", Poll. Research,
Vol-14(1), PP-59-64.
assess the stress response to various heavy metal
concentration level in the solution so that this 7. Baharudin B Shahrel Mohd. (2008), "Lead and

Volume2012-13. Number 2. July 2012 47

 (, Rupa Chakraborty, Somnath Mukherjee

cadmium removal in synthetic wastewater Microbiology & Biotechnology. Vol-22, PP- 97-
using constructed wetland". EngD thesis. 100.
Faculty of Chemical & Natural 15. Chandra, R, Pandey, P.K, and Srivastava, A.,
Resources
Engineering University, Malaysia Pahang (2004), "Comparative toxicological evaluation
8. Mishra, V.K and Tripathi, B. D. (2008). of untreated and treated tannery effluent with
"Concurrent removal and accumulation of
Nostoc muscorum L. (algal bioassay) and
heavy metals by the three aquaticMicrotox bioassay". Environ. Monit.o Assess.,
macrophytes". Bioresource Technology, V01-99 Vol-95, PP-287-294.
. (15), PP- 7091-7097. 16. Chaney, RL. and Ryan, J.A(1994), "Risk based
9. Do k ken, K. ; G am e z , G. ; Her r era, I . ; standards for arsenic, lead and cadmium in
Tienman,KJ.; Pingitore,N.E.; Chianelli, RR urban soils". DECHEMA, Frankfurt, Germany
and Torresday, J:L.G. (1999), "Characterization 17. Odjegba,V.J. and Fasidi,I.O. (2007), "Changes
of chromium (VI) bioreduction and chromium in antioxidant activities in Eichhornia crassipes
(III) b~nding to alfalfa biomass". Proceedings (Pontederiaceae) and Pistia stratiotes (Araceae)
of the conference on Hazardous Waste under heavy metal stress".Rev. BioI.Trop.(Int.
Research. University ofTexas.101-113. . J. Trop. BioI.) Vol-55(3-4), PP- 815-823.
10. Lazaridis, N.K and Asouhidou, D.D.(2003), 18. Johnson, F.M. (1998), "The genetic effects of
"Kinetics of sorptive removal of Chromium(VI) environmental lead". Mutation Research, Vol-
from aqueous solutions by calcined Mg-AI-COa, 410, PP-123-140. .

hydrotalcite". Water Research, Vol- 37,PP-
2875-2882.
11. Lytle, C.M ; Lytle, F.W; Yang, N; Qian, J;
Hansen, D; Zayed, A. and Terry, N (1998)
"Reduction of Cr (VI) to Cr (III) by wetland
plants: Potential for in situ heavy metal
Detoxification". Environ Sci Technol, Vol- 20. Sharma, P. and Dubey, RS.(2005), "Lead
32,PP- 3087-3093.
12. Keith, C; Borazjani, H: Diehl, S.V; Su, Y and
Baldwin, B.S. (2006), "Removal of Copper,
Chromium and Arsenic by Water Hyacinth".
Proceedings fo~36th Annual Mississippi Water
Resources Conference
13. Espinoza Quinones, F.R, Silva, E.A, Palacio,
S.M., Modenes, A.N., Rizzutto, M.A., Rossi, 22. Shao-Wei Liao and Wen-Lian Chang, (2004),
F.L., Szymanski, N., Costa Jr., I.L., Thome,
L.P. and. Castro, J.KD.(2006), "Removal of
chromium ions by three aquatic macrophytes
from an aqueous solution". Brazilian
Synchrotron Light Laboratory. LNLS, Activity
Report: 1-2
14. Arora, A., Saxena, S. and Sharma, D.K(2006),
"Tolerance and phytoaccumulation
Chromium by three Azolla species". World J of
19. Moodley, KG; Baijnath, H.; Southway-Ajulu,
F.A.; Maharaj, S. and Chetty, S.R (2007)
"Determination of Cr,Pb and Ni in water,
sludge and plants from settling ponds of a
sewage treatment works". Water SAVol-33(5),
PP-723-727.
toxicity in plants". Braz. J of Plant Physiol, Vol-
17(1), PP-35-52.
21. Verma, V.K, Gupta, RK and Rai, J.P.N.
(2005)."Biosorption ofPb and Zn from pulp and
paper industry effluent by water hyacinth
(Eichhornia crassipes)". J. Sci. Ind. Res. 64:
778-781.
"Heavy Metal Phytoremediation by Water
Hyacinth at Constructed Wetlands in Taiwan".
J. Aquat. Plant Manage, 42: 60-68
23. Hoagland, D.R and Arnon, D.L. (1950), "The
water culture method of growing plants without
soil". Calif. Agri. Expt. Cir., 34
24. APHA, AWWA and WPCF, (1985), Standard
of methods for the Examination of Water and
Wastewater, 15th edn (New York).

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