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International Review of Chemical Engineering (I.RE.CH.E.), Vol. 2, N. l,76ze January 2010

Special Section on I st Conference on Chemical Engineering and Advanced Materials (CE tlltf)VIRTUAL FORUM

Algal Biorefinery: a Road towards Energy Independence andSustainable Future

Shakeel A. Khanl. Rashmi2

Abstract - The most important renewable resource on this planet is biomass. As the value ofbiomass content is related to the chemical and physical properties of large molecules, thechallenges for the future are to be found in a combination of the biological, physical and chemicalsciences, to replicate an oil refnery with a biorefnery thus replacing finite non-renewable fossitresources with biorenewable biomass resources for the production offood, feed, fertilizer, fuel,energ), medicinal products, industrial chemical and related consumer product through the use ofclean and green bioprocess technologies. Algal biorefineries offer significant potential for futuiesupply ofoils, protein, and carbohydratesforfuels and chemicals without impactingfood supplies.The residual biomass from biodiesel production processes can be used potentialty as animal andfisheries feed and after anaerobic digestion can be used as fertilizers in the form of compost. Evenit could solve the problem of huge carbon emission from thermal power plant by recycling thecarbon. The simple, direct method of greenhouse gas (GHG) mitigation is the removat of COrfromstack gases, followed by long term sequestration of CO2by microalgae ponds. Thus the micrialgalbiodiesel proiects can qualifu as clean development mechanism (CDM) projects anct bring inadditional income through the sale of certified emission reductions (CER). Microalgal biorefineryconcept could become a highly distributed source of fuel oil, energt, feed, fertilizer and medicinalmetabolites and perhaps make this world pollutionfree and leap towards sustainable development.Copyright A 2U0 Praise lltorthy Prize S.r.L - All rights reserved

Keywords: Algae, Biodiesel, Biomass, Biorefinery, Carbon Sequestration, Fuel

L Introduction

A need of sustainable energy resources currentlythreatens the survival of an increasingly globalized worldeconomy. Continued use of petroleum-based fuels is nowwidely recognized as unsustainable because of depletingsupplies and contribution of these fuels to pollute theenvironment. Steady increases in the price of rawmaterials such as crude oil are forecast, due to risingdemand from developing countries and escalatingscarcity of reserves. Also, the increasing accumulation ofCO2 in the atmosphere and its impact on climate changehas provided a significant driver for change. Amidgrowing concern, global agreements to limit greenhousegas (GHGs) emissions have been formed such as theKyoto Protocol. Directly resulting from such agreements,many developed countries have adopted 'cap-and-trade,

carbon trading schemes in efforts to curb emissions. Thusprojects which capture CO2 and prevent it being releasedinto the atmosphere will play a significant role incombating climate change. While the 20th century sawthe emergence and establishment of an organic chemicalmanufacturing industry based on petroleum refining, the2l't century will see the development of a new organicsindustry based on biomass refining. In both scenarios thedriver is energy. The enormous demand for petroleum as

a cheap, single-use fuel gave chemical manufacturing alarge volume, low cost and continuous supply ofhydrocarbons from which the petrochemical industry wasbuilt; chemical and engineering technology for cracking,separating, rearranging, polymerizing and functionalizingallowed us to take complex mixtures of simple chemicalsand transform them into a multitude of higher valuemolecules with a seemingly never-ending range ofapplications from high volume, low cost plastics to smallvolume but highly expensive drugs. We are now at thebeginning of an era where new, renewable sources ofenergy are sought with increasing vigor; biomass,renewable carbon, is guaranteed a place in the newenergy portfolio for the foreseeable future t!-t31.

IL World's Fuel Scenario

Over 1.5 trillion barrels of oil equivalent have beenproduced since Edwin Drake drilled the world's first oilwell in 1859. The world will need that same amount tomeet demand in the next 25 years alone. TheIntemational Energy Agency (IEA) has reported in thereference scenario that the world's primary energy needis projected to grow by 55% befween 2008 and 2030, atan average annual rate of 1.8 Yo per year. Demand

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Shakeel A. Khan, Rashmi

reaches 17.7 billion tonnes of oil equivalent, comparedwith 12.4 billion tonnes in 2008. Energy and Capitalhave reported that, by 2025, the world's demand for oilwill shoot 60%, while production capacity would bethrown back to 1985 levels. According to the EnergyInformation Agency (EIA) report, petroleumconsumption falls by 90,000 barrels per day in 2008-2009. China's annual oil consumption growth rate is of7.5Vo and India's of 5.5%o and both are expected to takequantum leap over the next decade t4]. If thegovernments around the world stick to current policies,the world will need almost 607o more energy in 2030than today, of this 45% will be accounted by China andIndia together. Transportation is one of the fastestgrowing sectors using2T%o of the primary energy. At thepresent staggering rates of consumption, the world fossiloil reserve will be exhausted in less than 45 years [10].

Renewable and carbon neutral biofuel utre necessaryfor environmental and economic sustainability. Biofuelssuch as biodiesel and bioethanol have been proposed aspossible altemative renewable fuels. Unfortunatelybiofuel produced from oil crop, waste cooking oil andanimal fats are not able to replace fossil fuel. Theviability of the first generation biofuels production ishowever questionable because of the conflict with foodsupply. Production of biofuel using microalgae biomassappears to be a viable alternative and algal biorefineryapproach give us a feasible economy and endow withfuel for sustainable future.

nI. BiorefineryConctirpt

The biorefinery concept is analogous to today'spetroleum refinery, which produce multiple fuels andproducts from petroleum. A Biorefinery is collection ofprocesses that utilizes a renewable biological source toproduce an end product, that is a zero-waste producing,and whereby each component of the renewable biologicalor bio-based source, or a product there from, is convertedor utilized in a manner to add value. and hencesustainability to the plant. By producing multipleproducts, a biorefinery takes advantage of the variouscomponents in biomass and their intermediates thereforemaximizing the value derived from the biomassfeedstock. Algal biorefinery is a facility that integratesbiomass conversion processes and equipment to producefuels, power, and value added chemicals from algalbiomass. Algal biorefinery could, for example, produceone or several low volume, but high value, chemical ornutraceutical products and a low value, but high volumeliquid transportation fuel such as biodiesel or bioethanol.At the same time generating electricity and process heat,through combined heat and power (CFIP) technology, forits own use and perhaps enough for sale of electricity tothe local utility. Multidisciplinary collaborative researchprogram has emerged in order to develop innovativetechnologies for the economical and sustainableproduction of biofuels and other bioproducts frommicroalgae. Fast growing microalgae are efficient

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converters of solar energy and carbon dioxide, therebyproducing many times the biomass per unit area of landwhen compared to terrestrial plants. Thesephotosynthetic microorganisms have great potential to bethe solution to the growing energy and environmentalchallenges, as a more efficient method for bioenergyproduction and a practical and environmentallyresponsible method for carbon dioxide sequestration [4].

IV. Algae as Best Feedstock for Biorefinery

Algae having ability to synthesize triacylglycerols(TAGs) consider as a second generation feedstock forproduction of biofuels. The potential value of microalgalphotosynthesis to produce biofuels is widely recognizedt4l-t71.

The advantages of microalgae over any other biomassas a source of transportation biofuels are numerous:l. Microalgae synthesize and accumulate large

quantities of neutral lipids/oil (20-50% dry cellweight) and grow at high rates (e.g. I 3 doublingsper day).

2. Oil yield per area of microalgae cultures could greatlyexceed the yield ofbest oilseed crops.

3. Microalgae can be cultivated in saline/brackishwater/coastal seawater on non arable land, and do notcompete for resources with conventional agriculture.

4. Microalgae tolerate marginal lands (e.g. desert, arid-and semi-arid lands) that are not suitable forconventional agriculture.

5. Microalgae utilize nitrogen and phosphorus from avariety of wastewater sources (e.g. agricultural run-ofl concentrated animal feed operations, andindustrial and municipal wastewaters), providing theadditional benefi t of wastewater bioremediation.

6. Microalgae sequester carbon dioxide from flue gasesemitted from fossil fuel-fired power plants and othersources, thereby reducing emissions of a majorgreenhouse gas. I kg ofalgal biomass requiring about1.8 kg of CO, [9].

7. Microalgae produce value-added co-products or by-products (e.g. biopolymers, proteins, polysaccharides,pigments, animal feed and fertilizer) and do not needherbicide and pesticide.

8. Microalgae grow in suitable culture vessels (photo-bioreactors) throughout the year with higher annualbiomass productivity on an area basis.

The oil productivity of many microalgae exceeds thebest producing oil crops.

Microalgae are photosynthetic microorganism whichconverts sunlight, water and COz to sugars, from whichmacromolecules, such as lipids and triacylglycerols(TAGs) can be obtained. These TAGs are the promisingand sustainable feedstock for biodiesel production [4].However, cultivating algae only for biodiesel is noteconomically viable in the current environment becauseit provides higher costs when comparing withconventional fuels [8]. There are four stages involved inmicroalgal biodiesel production system includes

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Shakeel A. Khan, Rashmi

crritiuution, dewatering, extraction and transesterification.Each ofthe stages requires higher energy that need to beconsumed thus contributes in higher production cost.Microalgal biorefinery approach can be used to reduce

V. Microalgal Biomass Production

Conventional open pond algal production systems arevery old and now some recent closed photobioreactorshave been developed for continuous and increasedbiomass production. The vast bulk of microalgaecultivated today are grown in open ponds. Open pondscan be built and operated very economically and henceoffer many advantages as long as the species forcultivation can be maintained. Producing microalgalbiomass is generally more costly than growing crops. Tominimize expense, biodiesel production must rely onfreely available sunlight, despite daily and seasonalvariations in light levels which are easily available inIndia. ln open pond method, fresh culture medium is fedat a constant rate and the same quantity of microalgalbroth is withdrawn continuously. Feeding ceases duringthe night, but the mixing of broth continue to preventsettling of the biomass [1 1 ]. There are three potential andvery common methods of large-scale production ofmicroalgae:. Open ponds/Raceway ponds

Open ponds have a variety ofshapes and sizes but themost commonly used design is the raceway pond. It is aclosed loop of rectangular grid with recirculationchannel. They usually operate at water depths of 15-20cm, as at these depths biomass concentrations of I g dryweight/L and productivities of 60-100 mglLlday can beobtained [12]. There is a paddlewheel, which mix andcirculate the algal biomass as shown in figure 2. Flow isguided around bends by baffles positioned in the flow

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the cost of making microalgal biodiesel. Microalgal-based carbon sequestration technologies cover the cost ofcarbon capture and sequestration. The general concept ofthe proposed system is illustrated in (see Fig. l).

BiodieselT

Glycerol

Animal FeedOther Products

channel. Raceway channels are built in concrete orcompacted earth, it can be of different length anddiameter and generally lined with white plastic. Duringdaylight, the culture is fed continuously in front of thepaddlewheel where the flow begins. Broth is harvestedbehind the paddlewheel, on completion of the circulationloop. The paddlewheel operates all the time to preventsedimentation. The main disadvantage of open systems isthat by being open to the atmosphere, they loose water byevaporation at a rute similar to land crops and are alsosusceptible to contamination by unwanted species. Inpractice open ponds are usually reported to be dominatedby two to six species with a range of evolutionaryadvantages; rapid growth, resistance to predators,tolerance to high levels ofdissolved oxygen, etc.

Water + Nutrients

Power to Biomass

Powerto grid

Effluent)X'ertilizer) I rrigation

Fig. l. A conceptual process ofAlgal Biorefinery for better economy

Ba'b

Raceways arephotobioreactors,

Fr6n Baltb

Fig.2. A Raceway Pond

perceived to be less expensive thanbecause they cost less to build and

International Review ofChemical Engineering, Vol. 2, N. 1Special Section on Ist Conference on Chemical Engineering and

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\ilnfer *Algal Biomass

Extraction

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Shakeel A. Khan, Rashmi

operate. Economically, open pond system of biomassproduction is 10 time less costly in comparison tophotobioreactors [13]. Although raceways are low-cost,they have a low biomass productivity compared withphotobioreactors. There is need to approve the racewaypond system of biomass culture to achieve high andsustained growth rates and oil yields that is essential todeveloping an algal-based biofuel industry.t Closed biorcactors

Closed bioreactors support up to fivefold higherproductivity with respect to reactor volume andconsequently have a smaller "footprinf' on a yield basis.Besides saving water, energy and chemicals, closedbioreactors have many other advantages which areincreasingly making them the reactor of choice forbiofuel production, as their costs are reduced [14].Closed bioreactors permit essentially single-speciesculture of microalgae for prolonged durations. Mostclosed bioreactors are designed as fubular reactors, platereactors, or bubble column reactors. Other less commondesigns like semi-hollow-spheres have been reported torun successfully.

The most common type of closed bioreactor is tubularphotobioreactor. Tubular photobioreactor consists of anarray of straight transparent tubes that are usually madeofplastic or glass. The solar collector tubes are generally0.1 meter diameter or less in diameter because light doesnot penetrate too deeply in the dense culture broth that isnecessary for ensuring a high biomass productivity of thephotobioreactor. Microalgal broth is circulated from areservoir (i.e. the degassing column in Fig. 3) to the solarcollector and back to the reservoir [5].

ExhaustHarvesl

col urfin

Freshrn€dium

unwanted species. Therefore to minimize contaminationissues, cleaning or flushing the ponds should be part ofthe aquaculture routine, and as such, open ponds can beconsidered as batch cultures. This process has beendemonstrated by Aquasearch (Ilawaii, USA) cultivatingHaematococcus pluvialis for the production ofastaxanthin. Half of the Aquasearch facility was devotedto photobioreactors and half to open ponds. H. pluvialisis grown continuously in photobioreactors under nutrientsufficient conditions and then a portion is transferred tonutrient-limited open ponds to induce astaxanthinproduction [4].

VI. Products of Algal Biorefinery

The main components of algal biomass are protein,carbohydrate, lipids and valuable compounds. Algalproteins comprise all the 20 amino acids and constituteup to 50% of dry weight in growing cultures. Algaecould be the good source of ethanol as its storageproducts are 6-(l-4)-glucans, B-(l-3)-glucans, fructans,sugar and glycerol while the cellulose content is very lowin the algae. The lipids of the algae can be classified intwo groups namely storage lipids and membrane lipids.Storage lipids are mainly TAGs and add up to 50% ofdry weight. These TAGs could be extractable from thewet biomass with the help of organic solvent and furtherutilize as biodiesel after transesterihcation. Up to 40% ofmembrane lipids are polyunsaturated fatty acids (PUFAs)such as o-linolenic, eicosapentaenoic and docosaesaenoicacids, belongs to the co-3 groups. We could also get thevaluable compounds from the algal biorefrnery such aspigments, antioxidants, essential fatfy acids, vitamins,sterols, anti-fungal microbial, anti-viral toxins etc. A listof valuable compounds from algal biomass is given inTable I. An assortment of scenario for exploitation ofalgal biomass in an algal refinery is given in Fig. 4. Afterextraction of TAGs and valuable components the residualbiomass of algae is subjected to anaerobic digestion forbiogas generation.

Another important aspect of algal biorefinery isbiofixation of carbon dioxide. Microalgae have theadvantages of efficient photosynthesis superior to C4plants (those plants that form four carbon stableintermediates in the photosynthetic process; generallyassociated with agricultural and large terrestrial plants),fast proliferation rates, wide tolerance to extremeenvironments, and potential for intensive cultures. Theseadvantages promise high performance in the reduction ofcarbon dioxide. Therefore once harvested, microalgaecan serve as a product to offset the costs that have beenincurred.

VII. Conclusion

The rapidly escalating costs of petroleum andpetrochemicals are likely to accelerate the shift towardschemical products derived from renewable, biological

International Review ofChemical Engineering, VoL 2, N. IspeciatsectiononlstConferen*";f#"::i"LY:;:;:r;;E;Xi,

Ccolingwsiet S6far snay

FumpAir

Fig. 3. A tubular photobioreactor with parallel run horizontal tubes

. H)tbrid systemsIn this case both open ponds as well as closed

bioreactor system used in combination to get the betterresults. Open ponds are a very proficient and lucrativemethod of cultivating algae, but they becomecontaminated with superfluous species very quickly. Acombination of both systems is probably the most logicalchoice for cost-effective cultivation of high yieldingstrains for biofuels. Open ponds are inoculated with adesired strain that was invariably cultivated in abioreactor, whether it be as simple as a plastic bag or ahigh tech fiber optic bioreactor. Importantly, the size ofthe inoculums needs to be large enough for the desiredspecies to establish in the open system before an

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Shakeel A. Khan, Rashmt

feedstocks. While biofuel from edible and non edible oilcrops are being produced in increasing amounts asrenewable biofuels, but their production in largequantities is not sustainable. Carbon neutral renewableIiquid fuels are needed to eventually totally displacepetroleum-derived transport fuels that contribute toglobal warming. An alternative is offered by microalgaebut it appears that the production of microalgal biodieselis not economically viable in current environmentbecause it costs more than conventional fuels. Therefore,a new concept of algal biorefinery is required as an

option to reduce the total production cost of microalgalbiodiesel. Combination of wastewater treatment andmicroalgal CO2 fixation provides additional economicincentives due to the savings from chemicals (thenutrients) and the environment benefits. It provides apathway for removing nitrogen, phosphorus, and metalfrom wastewater, and producing algal biomass, whichcan further be exploited for biofuel production, withoutusing freshwater. Use of the biorefrnery concept andadvances in raceway ponds engineering will furtherlower the cost of production.

TABLEI

Pigments/Carotenoid

LISTOFVALUABLE

Vitamins AntioxidantsFRoM TI€ MICRoAIGAE

PUFAs Pharmaceutical s/Others

B-CaroteneAstaxanthinLuteinZeaxanthinCanthaxanthinChlorophyllPhycocyaninPhycoery.thrinFucoxanthin

A, BI ,86, B12,C,EBiotineRiboflavinNicotinic acidPantothenateFolic acid

Superoxid DismutasePolyphenolsCatalasesTocopherols

DHA(C22:6)EPA (C20:s)ARA (C20:4)GAL (C18:3)

AntifungalAntimicrobialAntiviralToxinsAmino acids, proteinsSterolsMAAs as light protectant

AqqeullsFPouttry bFSi.€

gitundisrt bundin! btoc*sa{idcn1#hoJ*

Dir:elKetugselillflhamSlrngas

Fatty acidsitipid:PigfenbftramitrgAntioxidrdGHufacr6i€ls

Fig. 4. Utilization of algal biomass in an Algal refinery

We can expect more and more biorefinery-typefacilities where some combination of chemical, energyand food processing are used to add value to biomassfeeds.

The more use we can make of food and bioenergy by-products to make chemicals, the lower the cost of thosechemicals and the quicker we can expect their successfulmarket entry.

It is vital to the future of sustainable chemicalproduction that we employ only low environmentalimpact chemistry to convert these by-products intovaluable chemicals and materials.

Therefore, in present scenario algal biorefinery is away to link between energy, local environment andclimate change and give us energy independence andsustainable future.

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References

J. Bozell and M. K- Patel, Feedstoclcs for the Future, ed., ACS,New York (2006).C. V. Stevens and R V. Yerhe, Renewable Resources, ed. l{ilev.Chichester, (2004).A- J- Ragauskas et al., Science, (2006), 311, 484S.A Khan, Rashmi, M. Z. Hussain S. Prasad and U. C. Baner.]ee,Prospects of biodiesel production from microalgae in India,Renewable and Sustainable Energy Reviews, 13, (2009), 2361_2372.Y. Chisti Biodieselfrom microalgae. Biotechnol Adv (2007),25:294,306.Q. Hu, M. Sommerfeld, E, Jarvis, M. Ghirardi, M. posewiE, M.Seibert et al. Microalgal triacylglycerols as feedstocks for biofiielproduction: perspectfues and advances, plant J (2008), 54: 621-639.S.A. Khan, Raslrlmi. Algae: A novel source of renewable energltan.d carbon sequestration. Renewable energy . Sept-Oct (200C),2(2\, r4-18.K. Dimitrov,. GreenFuel Technologies: A case study for

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t3lt4l

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Shakeel A. Khan. Rashmi

industrial photosynthetic energ) capture (2007).http :linrlrl'. nanostrine. net/al eaelCase Studj/. pdf

t9l L. Rodolfi, C.G. Zittelli, N. Bassi, G. Padovani, N. Biondi, G.Biondi et al., Microalgae for oil: strain selection, induction oflipid synthesis and outdoor ma.ss cultivation in a low costphotobioreactor Biotechnol Bioengineering. ( 2009) ; 1 02 (l) : 1 00-I 12.

U0l B P Statistical Review of the world enerry, June (2008).

[11] E. Molina Grima, F.G. Aci6n Femiindez, F. Garcia Camacho, Y.Chisti. Photobioreactors: light regime, mass transfer, and scaleup. J Biotechnol (1999), 70: 23 I-47.

[12] O. Pulz, Photobioreactors: production systems for phototrophicmicroorganisms. Appl Microbiol Biotechnol (2001), 57:287- 293.

[13] J. Sheehan, T. Dunahay, J. Benemann, P. Roessler". A look backat the U.S. Deparflnent of Energt's Aquatic Species Program-biodiesel from algae. National Renewable Energ)) Laboratory,Golden, CO: National renewable energy laboratory Q998). USReport NREUTP-S8|| 24 I 90.

[4] P.M. Schenk, S.R. Thomas-Hall, E. Stephens, U.C. Marx, J.H.Mussgnug, C. Posten et al., Second Generation Biofuels: High-Efficiency Microalgae for Biodiesel Production. Bioenerg Res(2008), 1 2F43.

Authors' information' Division of Environmental Sciences, Indian Agricultural ResearchInstitute, New Delhi 1 100i2. India.

2Department of Biotechnology, Indian Institute of Petroleum, Dehradun-248005. India.

Shakeel Ahmad Khan was bom in Gorakhpur,U.P.. India the16ft March i973Educational Qualification: Ph. D. (1999-2003)Division of Environmental Sciences, I.A.RI.Pusa, New Delhi - 110012- Major field :Environmental Sciences. Minor field: Remote

Sensing, GIS (Ag. Physics), Water Science & Technology.Title of thethesis'."Calibration and validation of Info Crop model Jor water-balance of rice-wheat cropping system in the Indo-Gangetic allwialplains"Post Graduation: (1) 2001 - 02 P. G. Diploma inEnvironmental Law, (part time), Indian Law Institute, New Delhi -

i 10001; (2) 1994 - 96l:Nl. Sc. (Environmental Sciences) Department ofEnv. Sciences, Dr. R. M. L. Avadh University, Faizabad. (Division:First);(3)1994-97 P. G. Diploma in Ecology & Environment,Indian Institute of Ecology & Environment, New Delhi. (Division:First) (Correspondence Course). Graduation (1990-93-94) :B. Sc. withChemistry, Botany & Zoology from Gorakhpur university, Gorakhpur.(Division: First); Dissertation (During M. Sc.) '7 case study of TandaThermal Power Station, Faizabad" Project (During M. Sc.)"Analysisof Captainganj Distillery spent wash (waste Water) and its utilizationin agriculture." Project (During P.G. Diploma)"^ltudy of Biogas Plantand how to improve ft efrtciency."After post graduation, he worked for Indian Institute of RuralManagement (IIRM) as Fellow and in 1999 joins the Indian AgricultureResearch Institute (IARI), New Delhi, India as Ph.D. Scholar. He hasawarded with the Senior Research Fellowship liom IARI andcompleted his Ph.D. in environmental sciences from IARI in 2003. Hehas got the First rank in merit for Agricultural Research Service (ARS)in Environmental Sciences discipline (200i) and also qualified theNational Eligibility Test (NET) twice frorn UGC and ICAR. Since2003, he is working in the Division of Environmental Sciences, IARI asScientist. He is the revierver of many national and intemational joumalsand has published more than 30 papers. IIe worked on heavy metalpollution problems of peri-urban agriculture of Delhi and Impactassessment of Bt cotton on soil microbiology. Now he is uorking onthe phycoremediation of ra'aste rvater and microalgal biodiesel. Alongwith the research, he also teaches the M.Sc and Ph.D. students of theIARI.Dr. Shakeel A. Khan is the senior member of Intemational Associationof computer Science arrd Infonnation Technology [ACSIT).Intemational Society for Environmental Information Sciences (ISEIS),Canada and Intemational Sociery- for Agicultural Metrology.

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