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1 Korean Journal of Environmental Agriculture Korean J Environ Agric (11) Online ISSN: Vol. 3, No. 3, pp Print ISSN: 폐미역을이용한생물흡착시스템별중금속제거효율평가 최익원, 1 서동철, 1 김성은, 1 강세원, 1 이준배, 2 임병진, 2 강석진, 3 전원태, 4 허종수, 5 조주식 1* 1 순천대학교생물환경학과, 2 영산강물환경연구소, 3 농촌진흥청국립축산과학원, 4 농촌진흥청국립식량과학원, 5 경상대학교응용생명과학부 Evaluation of Removal Efficiencies of Heavy Metals Using Brown Seaweed Biosorbent Under Different Biosorption Systems Ik-Won Choi, 1 Dong-Cheol Seo, 1 Sung-Un Kim, 1 Se-Won Kang, 1 Jun-Bae Lee, 2 Byung-Jin Lim, 2 Seok-Jin Kang, 3 Weon-Tai Jeon, 4 Jong-Soo Heo 5 and Ju-Sik Cho 1* ( 1 Department of Bio-Environmental Sciences, Sunchon National University, 2 Yeongsan River Environmental Research Center, 3 National Institute of Animal Science, Rural Development Administration, 4 National Institute of Crop Science, Rural Development Administration, 5 Division of Applied Life Science, Gyeongsang National University) Received: 16 September 11 / Accepted: 23 September 11 c 11 The Korean Society of Environmental Agriculture Abstract BACKGROUND: Heavy-metal pollution represents an important environmental problem due to the toxic effects of metals, and their accumulation throughout the food chain leads to serious ecological and health problems. METHODS AND RESULTS: Optimum conditions in continuous-flow stirred tank reactor (CSTR) and packedbed column contactor (PBCC) using brown seaweed biosorbent were investigated. Under optimum conditions from both lab-scale biosorbent systems, removal efficiency of copper (Cu) in a large-scale PBCC system was investigated. Removal capacity of Cu using brown seaweed biosorbent in a lab-scale CSTR system was higher than that in a lab-scale PBCC system. On the other hand, over 48 L/day of flow rate in Cu solution, removal efficiency of Cu in a lab-scale PBCC system was higher than that in a lab-scale CSTR system. Optimum flow rate of Cu was 24 L/day, optimum Cu solution concentration was mg/l. Removal capacity of Cu at different stages was higher in the order of double column biosorption system > single column * 교신저자 (Corresponding author), Phone: ; Fax: ; chojs@sunchon.ac.kr 공동제 1 저자 biosorption system. Under different heavy metals, removal capacities of heavy metal were higher in the order of Pb > Cr > Ni > Mn Cu Cd Zn Co. Removal capacity of Cu was 138 L in a large-scale PBCC system. Removal capacity of Cu a large-scale PBCC system was similar with in a lab-scale PBCC system. CONCLUSION(s): Therefore, PBCC system using brown seaweed biosorbent was suitable for treating heavy metal wastewater. Key Words: Biosorption, Biosorbent, Copper, Heavy metal, Breakthrough curve 서론 산업화도시화에따른생태계와인간을해치는중금속오염은심각한환경오염문제를야기시키고있다. 특히도금폐수중에존재하는중금속처리방법으로는침전법, 이온교환법, 막분리법, 용매추출법, 흡착법및증발법등이있다 (Stephen et al., 1986; Suh et al., 1). 이러한기존의공정들은전처리가필요하거나 2차오염을발생시키고 (Thomas and Drew, 1989), 처리비용이과다하여대부분의영세규모인국내도금업계의실정으로는적용하기어려운문제점들이있다 (Ahn and Suh, 1995; Say et al., 1). 이러한문제점을해결하기위한방법중에서친환경적인생물흡착기술에대한연구가활발하게이루어지고있다 (Davis et al., 3; 31
2 Evaluation of Removal Efficiencies of Heavy Metals Using Brown Seaweed Biosorbent Under Different Biosorption Systems 311 Choi et al., 5). 중금속제거가가능하다고알려진생물흡착제로는균류, 박테리아및조류등이있다. 그중에서갈색해조류의일종인미역은우리나라해조류생산중최대량을차지하고비교적가격이저렴하며쉽게구할수있고, 생산량은 8년기준으로약 38만톤이었다. 이는 년에비해서 15% 증가한양이다 (Shim et al., 1). 그러나매년생산된미역의 % 이상인 14만톤에서 21만톤에이르는양이식용으로이용되지못하고바다에투기되고있는실정이다 (Cho et al., 4; Ahn et al., 4). 이에본연구진의선행연구 (Cho et al., 4) 에의해개발된미역폐기물을이용한생물흡착제를이용하여 lab-scale 생물흡착시스템과 lab-scale의최적조건을 scale-up한 Packedbed column contactor (PBCC) 시스템을제작하였다. Labscale 생물흡착시스템에서최적조건을구명하기위해서중금속생물흡착시스템별, 유입속도별및농도별중금속제거능력을각각조사하였고, 최적조건인 PBCC 시스템의처리단계별및중금속종류별로중금속제거능력을각각조사하였다. 또한상기 lab-scale 생물흡착시스템의최적조건하에서실제시스템의적용성을검토하기위해 PBCC 시스템을 scale-up한다음중금속제거능력을조사하였다. 재료및방법 공시시료본연구에사용된중금속시약은 Sigma-Aldlich사의특급시약을사용하였으며, 중금속용액은 Pb(NO 3) 2, CuSO 4, CdSO 4, ZnSO 4, CoSO 4, MnSO 4, CrCl 3 및 NiSO 4 를사용하여각중금속농도가 1, mg/l 되게조제한후일정한농도로희석하여사용하였다. 실험장치 Lab-scale 생물흡착시스템과 lab-scale의최적조건을 scale-up한 PBCC 시스템으로실험장치를제작하였다. Lab-scale 생물흡착시스템설계및제작은 Fig. 1과같은구조의 Continuous-flow stirred-tank reactor (CSTR) 및 PBCC 두가지형태의생물흡착시스템을제작하였다. PBCC 시스템 (Fig. 1A) 은고정식흡착시스템으로단일컬럼또는연속식결합컬럼으로이용가능하도록제작하였다. PBCC 시스템의사양은직경이 46 mm, 충전높이가 mm인투명아크릴 ( 두께 1 mm) 로제작하였고, 충진된흡착제는 67 g( 수분 96.5±.5%) 이었다. CSTR 시스템 (Fig. 1B) 은직경이 142 mm, 높이가 125 mm인투명아크릴 ( 두께 1 mm) 로제작하였으며교반기를부착하여회전속도를조절할수있게하였고, 충진된흡착제의무게는 67 g( 수분 96.5±.5%) 이었으며반응조의유효부피는약 2 L이었다. CSTR 시스템의교반속도는반응조에흡착제를채운후생물흡착제가파쇄되지않는범위내에서최적의접촉빈도를가질수있도록하기위해예비실험을거쳐분당회전속도 (rpm) 를 46 rpm으로하였다. (A) Packed-bed column contactor (B) Continuous-flow stirred tank reactor Fig. 1. Schematic diagrams of various biosorption systems using biosorbent. Lab-scale의최적조건하에서실제시스템의적용성을검토하기위해 scale-up한 PBCC 시스템은상기 Fig. 1A와동일한시스템으로제작하되흡착제용량을 27배로증가시켰다. Scale-up한 PBCC 시스템의크기는직경 195 mm, 높이 9 mm로제작하였고, column에충진된흡착제는 18,1 g( 수분 96.5±.5%) 이었고, 유효부피는약 27 L이었다. 실험방법 Lab-scale의생물흡착시스템에서최적조건을구명하기위해서생물흡착시스템별, 유입속도별및농도별중금속제거능력을각각조사하였고, 최적조건인 PBCC 시스템의처리단계별및중금속종류별로중금속제거능력을각각조사하였다. 폐미역을이용한생물흡착제를제조하기위하여전남완도에서채취된미역을사용하였다. 채취된미역의중금속함량은약.1 mg/kg으로본연구에큰영향을미치지않을것으로판단되었다. 그리고채취된미역의염분제거를위해증류수로세척한뒤믹서기로균일하게분쇄하여시료로사용하였다. 생물흡착제제조는본연구진이개발한시스템 (Fig. 2) 을이용하여균일하게분쇄한미역을 2% CaCl 2 용액에떨어뜨려 bead 형태로제조하였다. Cu용액의유입속도별 Cu 제거능력은 Cu용액유입속도를각각 48 L/day, 24 L/day 및 12 L/day로달리하고 Cu용액을 mg/l로제조하여연속
3 312 CHOI et al. Table 1. Breakthrough point in copper solution under different flow rates and Cu concentrations Breakthrough point (ml/g-biosorbent) Type Packed-bed column contactor system Continuous-flow stirred tank reactor system Flow rate (L/day) Cu concentration (mg/l) > > Fig. 2. Schematic diagram of apparatus for preparing biosorbent using brown seaweed. 적으로처리하면서일정시간간격으로시료를채취하여분석하였다. Cu용액의유입농도별 Cu 제거능력은 Cu용액의농도를각각 1, 5 및 mg/l로제조하여유입속도를 24 L/day인조건하에서연속적으로처리하면서일정시간간격으로시료를채취하여분석하였다. 중금속흡착시스템에서처리단계별 Cu 제거능력은 PBCC 시스템을단일컬럼및연속식결합컬럼으로설치하여제조된 Cu용액의농도를 mg/l로하고유입속도를 144 L/day로처리하면서일정한간격으로시료를채취하여분석하였다. 생물흡착시스템에서중금속종류별중금속제거능력은각각의중금속에대하여 mg/l로제조된용액을 144 L/day의속도로 PBCC 시스템에유입하여처리후유출수중의중금속 (Pb, Cu, Cd, Zn, Mn, Co, Cr 및 Ni) 함량에대해서각각조사하였다. Lab-scale의생물흡착시스템의최적조건하에서실제시스템의적용성을검토하기위해 scale-up한 PBCC 시스템의 Cu 제거능력은 Cu용액의농도를 mg/l로하고유입속도를 144 L/day로처리하면서일정한간격으로시료를채취하여분석하였다. 중금속분석방법중금속분석은수질오염공정시험법 (Choi et al., 4) 및 APHA의 standard method(apha, 1995) 에준하여용액중에남아있는중금속잔존량을플라즈마분광광도법 (ICP, Optima 33DV, Perkin-Elmer, Waltham, MA, U.S.A.) 으로각각분석하였다. 결과및고찰 Lab-scale 생물흡착시스템의최적조건구명 Cu용액의처리시스템별 Cu 제거능력 Cu용액의농도및유입속도에따른생물흡착시스템별파과점 (C/Co=5%) 은 Table 1에서보는바와같다. 용액의농도변화에따른두시스템의 Cu처리효율을보면두시스템간의파과점차이는크게나타나지않았지만, 파과점까지의 Cu 용액처리량을비교하였을때미세한차이로 CSTR이고농도폐수를처리하는데적합하였다. 또한유입속도에따른 PBCC 와 CSTR에서 Cu용액을처리하면서파과점을비교한결과유입속도가 48 L/day로빠른경우는 PBCC에비하여 CSTR의파과점이빨리나타났으나유입속도가 24 L/day 이하로줄어들면 CSTR의파과점이 PBCC에비하여늦게나타났다. 이러한결과는 CSTR의규모가작을경우는빠른유입속도로인하여완전혼합상태를유지하지못하고유입수일부가바이패스되는이상흐름이생기기때문에흡착효율이떨어진다 (Hashimoto, 1993). 따라서실제중금속폐수를처리하기위해서는 PBCC의경우가적합할것으로판단된다. Cu용액의유입속도별 Cu 제거능력 PBCC 에서 Cu용액유입속도에따른파과곡선을조사한결과는 Fig. 3A에나타내었다. 시스템의유입속도가 12 L/day일때 24 L/day에비해서 Cu를완전히처리할수있는능력이약 15-% 정도향상되는것으로나타났었고, 48 L/day의유속에서 Cu용액처리량이가장적은것으로나타났다. Cu용액처리량은유입속도가 12 L/day일경우가 24 L/day 및 48 L/day에비하여각각약 8 L 및 3 L정도증가하였다. CSTR에서유입속도에따른파과곡선은 Fig. 3B 에서보는바와같다. 유입속도가 12 L/day의경우 24 L/day에비해서 Cu용액의처리능력이약 15-% 정도향상되었고, 48 L/day의유입속도에서 Cu용액처리량이가장적은것으로나타났다. 이결과는 PBCC의결과 (Fig. 3A) 와매우유사하였다. Cu용액처리량은유입속도가 12 L/day일경우가 24 L/day 및 48 L/day에비하여각각약 12 L 및 19 L 증가하였다. 따라서 column에충진된생물흡착제의최대흡착량은동일하지만유입속도를늦출경우흡착제의사용가능시간이더연장됨을알수있었다. 하지만 Cu용액의처리능력을완전히상실하는지점은유입속도 48 L/day가다른폐수유입속도에비해가장늦게나타나서, 실제적인총처리능력은거의차이가없는것으로나타났다. 본연구결과에서 Cu용액의유입속도가 12 L/day일경우가가장유리한것으로나타났지만, 시간당처리량이너무작아서효율적인면이나경제적인면을고려해본다면 24 L/day이상의유입속도가적합할것으로판단되었다.
4 Evaluation of Removal Efficiencies of Heavy Metals Using Brown Seaweed Biosorbent Under Different Biosorption Systems 313 (A) (A) Remaining Cu in solution (%) (B) 48 L/day 24 L/day 12 L/day 48 L/day 24 L/day 12 L/day Amount of treated waste water (L) Fig. 3. Effects of flow rate on the removal (%) of Cu in PBCC (A) and CSTR (B) systems with biosorbent. Cu용액의유입농도별 Cu 제거능력 PBCC에서 Cu용액의농도에따른처리효율을조사한결과는 Fig. 4A에나타내었다. Cu용액의농도가 1 > 5 > mg/l순으로 Cu용액의처리가능용량이큰것을볼수있었다. 그중에서가장처리량이많은 1 mg/l Cu용액은 L이상처리가가능한것으로나타났다. Cu용액의농도가 5 mg/l인경우의처리능력은약 7 L 이었고, Cu 농도 mg/l에서는약 L까지처리가가능하였다. CSTR에서 Cu용액의농도에따른처리효율을조사한결과는 Fig. 4B 에나타내었다. Cu용액의농도가 5 및 mg/l의경우에비하여 1 mg/l일경우처리용량이상당히큰것으로나타났다. Cu용액의농도가 1 mg/l인경우는 L이상처리가가능한것으로나타났다. 이에비해 Cu용액의농도가 5 및 mg/l인경우에는 25 L 및 18 L까지처리되는것으로나타났다. 이와같은결과는 PBCC의결과 (Fig. 4A) 와유사한경향이었다. 그러므로 Cu용액의농도가높을수록처리용량은상당히낮아지는것으로나타났다. 그러나처리된 Cu이온의양으로비교하였을경우는 Cu폐수농도가 mg/l인폐수가 Cu폐수농도 5 mg/l인폐수에비해서 Cu 이온의양이약 15-3% 가량많은것으로나타났다. PBCC와 CSTR의 Cu용액의처리능력을비교하면전반적으로 PBCC 시스템의처리능력이 CSTR 시스템의처리능력에비해높았다. 이는생물흡착제의반응성이높아서 PBCC 에서도충분한흡착이이루어진것으로판단되어진다. 따라서본생물흡착제에는 CSTR 보다 PBCC를이용하는것이반응기체적축소및시스템의운영적인면에서도유리할것으로판단된다 (Hashimoto, 1993). Remaining Cu in solution (%) 1 mg/l 5 mg/l mg/l 1 19 (B) 1 mg/l 5 mg/l mg/l Fig. 4. Effects of Cu concentration on the removal (%) of Cu at flow rate of 24 L/day of PBCC (A) and CSTR (B) systems with biosorbent. 생물흡착시스템에서처리단계별 Cu 제거능력단일컬럼과연속식결합컬럼으로구성한두종류의 PBCC 시스템에서폐수의 Cu농도를 mg/l으로하고유입속도를 144 L/day로처리하여비교한결과는 Fig. 5에서보는바와같다. 단일컬럼 PBCC와결합컬럼 PBCC로구성된시스템의각각의파과곡선은유사한형태를나타내었다. 유입속도를 144 L/day로빠르게설정하였기에단일컬럼의파과점은 5 L/day인데비해서, 결합컬럼의파과점은 38 L/day로파과점에이르는시간이단일컬럼에비해서상당히늦춰졌다. 이러한컬럼의연속적구성에따른파과곡선과 Kratochvil RemainingCuinsolution(%) Single column biosorption system Double column biosorption system Fig. 5. Removal (%) of Cu in different stages of PBCC system. Cu concentration and its flow rate were operated at mg/l and 144 L/day.
5 314 CHOI et al. 등 (1997) 이보고한생물흡착컬럼을이용한 Cu 제거실험에서컬럼의길이에따른파과곡선은유사한패턴을보여주었다. 따라서생물흡착제의교환주기를늘리기위해서는컬럼의길이를길게하거나컬럼을연속식으로배열하는결합컬럼이유리할것으로판단된다. 생물흡착시스템에서중금속종류별중금속제거능력 PBCC에서중금속용액의성상별처리효율은 PBCC에서중금속오염폐수농도를 mg/l로하고유입속도를 144 L/day로처리하여유출수중의중금속농도에대하여조사한결과를 Fig. 6에서보는바와같다. 각각의중금속은생물흡착제와모두선택적인반응을하였고, 유입속도를 144 L/day로빠르게설정하였기때문에중금속처리효율은다소떨어지는결과를나타내었다. PBCC 에서중금속처리효율은 Cu용액이외의다른중금속용액에서도동등한수준이상의처리효율을나타내었다. 그중에서도 Pb용액의처리효율이상당히높게나타났고, 그다음으로 Cr용액의처리효율이높게나타났다. 이결과는본연구진이 Batch 상태에서수행한중금속흡착실험의결과 (Cho et al., 4; Choi et al., 5) 와반응시간이상대적으로짧은 PBCC 시스템에서의결과와상당부분일치하는것은본연구에서사용된생물흡착제가상당히짧은시간에흡착이이루어졌기때문이다 (Choi, 4). 이상의결과를미루어볼때, 폐미역을이용한생물흡착제를이용한생물흡착시스템에 PBCC 시스템에적용시키는것이적절한것으로판단되어 PBCC 시스템을 lab-scale의 27배로 scale-up하여중금속제거능력을조사하였다. Scale-up 한 PBCC 생물흡착시스템에의한 Cu 제거효율평가 Lab-scale PBCC와 large-scale PBCC에서 mg/l 농도의 Cu용액을 144 L/day의유입속도로처리한결과는 Fig. 7과같다. Cu용액을처리한 lab-scale PBCC와 large- Remaining heavy metals in solution (%) Pb Cu Cd Zn Mn Co Cr Ni 1 1 Fig. 6. Removal (%) of heavy metals in PBCC systems. Heavy metals concentrations and flow rate were operated at mg/l and 144 L/day. Remaining Cu in solution (%) Large-scale PBCC system Lab-scale PBCC system Fig. 7. Removal (%) of Cu in large-scale PBCC systems. Cu concentration and flow rate were operated at mg/l and 144 L/day. scale PBCC의파과곡선의유형은거의유사하였다. 파과점은 lab-scale PBCC의경우는약 5 L 이었고, large-scale PBCC의경우는 138 L로나타났다. lab-scale PBCC와 large-scale PBCC의처리용량의확대정도가약 27배인데파과점도거의같은배수의차이를나타내었다. 본연구에사용된 PBCC은대용량의폐수를대상으로할경우처리효율에유리한것으로알려져있어서 (Vilar et al., 8; Hashimoto, 1993), PBCC 시스템을 scale-up시처리효율이상승할것으로예상하였으나 lab-scale PBCC와 large-scale PBCC가같은수준의처리효율을보여주었다. 이결과는 large-scale PBCC 제작시 column 내의흡착제의표면적은같은비율로확대되었지만높이대지름의비가 lab-scale PBCC는 13인데비해서 large-scale PBCC는 4.6으로작아서전체적인처리효율이상승하지못하고동등한수준을유지한것으로판단된다. 요약 폐미역을이용한생물흡착제의중금속제거능력을조사하기위해 lab-scale의생물흡착시스템에서최적조건을구명하고, lab-scale의생물흡착시스템의최적조건하에서 large-scale PBCC 시스템의중금속제거능력을조사하였다. Lab-scale 생물흡착시스템별중금속제거능력은 PBCC보다 CSTR이뛰어났지만 CSTR은폐수유입속도가 48 L/day이상에서완전혼합상태를유지하지못하여안정적인운전이가능한 PBCC 가적합하였다. Cu용액의유입속도및농도별 Cu 제거능력은유입속도 12 L/day 및유입농도 1 mg/l일때 Cu용액처리량이가장뛰어났으나경제적인부분을검토한결과유입속도 24 L/day 및유입농도 mg/l가적절할것으로판단되었다. 처리단계별 Cu 제거능력은컬럼을연속식으로배열하는것이 Cu 제거효율이높았다. 중금속종류별제거능력은 Pb, Cr의처리효율이높았고 Cu용액이외의다른중금속용액들도 Cu와동등한수준이상의처리효율을나타내었다. Lab-scale의 PBCC 시스템을 27배규모로 scale-up한
6 Evaluation of Removal Efficiencies of Heavy Metals Using Brown Seaweed Biosorbent Under Different Biosorption Systems 315 large-scale PBCC 시스템의 Cu 제거능력은 138 L 로 lab-scale 의 5 L 와비교하였을때동등한수준을유지하였다. 따라서중금속처리를위한최적폐미역활용생물흡착시스템은 PBCC 시스템인것으로판단되나, 실제중금속폐수에본최적시스템을적용하기위해서는중금속폐수특성에따른적용성연구가추가로진행되어야할것으로판단된다. 감사의글 This paper was supported by Sunchon National University Rescarch Fund in 1. This research was supported by a fellowship from the Yeongsan & Sumjin River Watershed Management Fund of South Korea. 참고문헌 Ahn, K.H., Suh, K.H., Biosorption of heavy metals by Saccharomyces uvarum, J. Korean Environ. Sci. Soc. 4, Ahn, S.J., Kim, Y.S., Park, K.P., 4. Storage of waste-brown seaweed and degradation of alginate using microorganism, J. Environ. Sci. 13, APHA, AWWA, WCF, Standard methods for the examination of water and wastewater, 19th ed. American Public Health Association, Washington, DC, USA. Cho, J.S., Park, I.N., Heo, J.S., Lee, Y.S., 4. Biosorption and desorption of heavy metals using Undaria sp., Korean J. Environ. Agric. 23, Choi, I.W., 4. Biosorption of heavy metals and development of biosorbent by using seaweeds. Master Science Thesis. Sunchon National University, Korea. Choi, I.W., Kim, S.U., Seo, D.C., Kang, B.H., Sohn, B.K., Rim, Y.S., Heo, J.S., Cho, J.S., 5. Biosoroption of heavy metals by biomass of seaweeds, Laminaria species, Ecklonia stolonifera, Gelidium amansii and Undaria pinnatifida, Korean J. Envirion. Agric. 24, Choi, K.C., Kwan, O.U., Kim, Y.D., Kim, Y.H., Lee, W.S., Lee, J.Y., jun, S.J., Jung, S.K., 4. Annotation for standard methods of water quality. printed in Dong Hwa Technology Publishing Co. Korea. Davis, T.A., Volesky, B., Mucci, A., 3. A review of the biochemistry of heavy metal biosorption by brown algae, Water Research 37, Hashimoto, K Chemical reaction engineering. Baifukan, Japan. Kratochvil, D., Volesky, B., Demopoulos, G., Optimizing Cu removal / recovery in a biosorption column, Water Research. 31, Say, R., Denizli, A., Arica, M.Y., 1. Biosorption of cadmium(ii), lead(ii), and copper(ii) with the filamentous fungus Phanerochaete chrysosporium, Bioresour. Technol. 76, Shim, J.H., Hwang, J.R., Lee, J.S., Kim, J.H., Kim, S.S., 1. Variations in nutrients and CO 2 uptake with growth of Undaria pinnatifida from the south coast of korea, Kor. J. Fish Aquat. Sci. 43, Stephen, B., Normal, S.W., Removal of heavy metals from wastewaters, B.&L. Information Service, Canada. Suh, K.H., Ahn, K.H., Cho, M.C., Cho, J.K., Jin, H.J., Hong, Y.K., 1. Sargassum Confusum for biosorption of Pb and Cr, J. Korean Fish. Soc. 34, 1-6. Thomas, E.H., Drew. P.O., Metal finishing and processing, WPCF 61, Vilar, V.J.P., Cidalia, B.M.S., Loureiro, J.M., Boaventura, R.A.R., 8. Biosorption of copper by marine algae Gelidium and algal composite material in a packed bed column, Bioresource Technology 99,
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