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Book of Abtracts Erem 6th
Book of Abtracts Erem 6th
Book of Abstracts
Editors: Claudio Cameselle Fernndez M Angeles Sanromn Braga Marta Mara Pazos Currs
University of Vigo Dept. of Chemical Engineering Building Isaac Newton 36310 Vigo. Spain
Scientific Committee
Lisbeth Ottosen Technical University of Denmark. Lyngby, Denmark. Sibel Pamucku Lehigh University. Lehigh, Pennsylvania, USA. Ji Won Yang Korean Advanced Institute of Science and Technology. Daejeon, Korea. Henrik K. Hansen Technical University Federico Santa Mara. Valparaso, Chile. Achille De Battisti University of Ferrara. Ferrara, Italy. Roman Zorn Karlsruhe University. Karlsruhe, Germany. Djamal Akretche USTHB. Algiers, Algeria. M Angeles Sanromn Braga University of Vigo. Vigo, Spain. Claudio Cameselle Fernndez University of Vigo. Vigo, Spain. Marta Mara Pazos Currs University of Vigo. Vigo, Spain.
Organizing Committee
Claudio Cameselle Fernndez (Coordinator of the organizing committee) M ngeles Sanromn Braga Marta M Pazos Currs M Teresa Ricart Ricart M Teresa Alcntara Lpez Jos Gmez Sieiro Susana Ferreira de Gouveia Ftima Moscoso Daz Iria Vazquez Rodrguez Mara Barreiro Miranda Francisco Javier Deive Herva Arstides Huerga Vzquez Mara Rivera Sobrado
EREM 2007 Secretariat University of Vigo Dept. of Chemical Engineering Building Isaac Newton 36310 Vigo. Spain e-mail: erem2007@uvigo.es phone: +34 986 812318 fax: +34 986 812380
Conference Venue
The conference will be held in "Centro Social Caixanova". The organizers appreciate very much the help of CAIXANOVA in the organization of EREM 2007.
Sponsors
Caixanova
University of Vigo
City of Vigo
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Programme
12th JUNE 2007 17:00-20:00 Registration and Poster set-up. 13th JUNE 2007 9:00-9:30 9:30-10:00 Conference Opening Plenary Lecture Sustainable soil remediation. The use of combined technologies. M.C. Lobo (IMIDRA, Spain) Session 1: Electrokinetic Barriers Coffee Break - Poster Session Plenary Lecture Utilization of electromigration in civil and environmental engineering. Lisbeth M. Ottosen (DTU, Denmark) Session 2: Metal Removal Lunch - Poster Session Session 3: New Applications Inorganic Pollutants Reception and cocktail in the gardens of the Museum "Quiones de Len" 14th JUNE 2007 8:30-10:30 10:30-11:00 11:00-11:30 Session 4: New Applications Bioremediation Coffee Break - Poster Session Plenary Lecture Electrokinetic delivery of nanoscale iron particles for remediation of pentachlorophenol in clayey soil Krishna R. Reddy (Univ. of Illinois at Chicago, USA) Session 5: Organic Pollutants Lunch Plenary Lecture Electroremediation Where do we go now? Henrik K. Hansen (Univ. Tcnica Federico Santa Mara, Chile) Session 6: Modelling and other Applications Coffee Break - Poster Session Session 7: Electrokinetic and Electrochemical Degradation Conference Closure Social Dinner 15th JUNE 2007 10:30-19:00 Guided Tour to the Cies Islands
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Session 1: Electrokinetic Barriers 10:00-10:20 In-situ electrokinetic permeable reactive barrier: field investigation in the vicinity of unregulated landfill site. MyungHo Lee and Ha-Ik Chung 10:20-10:40 Chromate adsorbtion in a transformed red mud permeable reactive barrier using electrokinesis. Giorgia De Gioannis, Aldo Muntoni, Romano Ruggeri, Hans Zijlstra and Matteo Floris 10:40-11:00 Electrokinetic permeable reactive barrier for the removal of heavy metal and organic substance in contaminated soil and groundwater. Ha Ik Chung, Yong Soo Lee 11:00-11:20 Use of a pulsed electric field for resisting groundwater pollution. J Reeve and R J Lynch 11:20-11:50 11:50-12:20 Coffee Break - Poster Session Plenary Lecture Utilization of electromigration in civil and environmental engineering. Lisbeth M. Ottosen, Iben V. Christensen, Inge Rrig-Dalgrd, Pernille E. Jensen
Session 2: Metal Removal 12:20-12:40 Phosphation of bottom-ash from MSWI by means of electrokinetics. G. Traina, S. Ferro, A. De Battisti 12:40-13:00 Electrodialytic removal of toxic elements from sediments of eutrophic fresh waters. Pernille E. Jensen, Lisbeth M. Ottosen, Arne Villumsen 13:00-13:20 Enhanced electrokinetic treatment of different marine sediments contaminated by heavy metals. De Gioannis Giorgia, Muntoni Aldo, Polettini Alessandra, Pomi Raffaella 13:20-13:40 Electroremediation of an industrial area contaminated by chromium. O. Merdoud and D. E. Akretche 13:40-14:00 Bench scale evaluation of hexavalent chromium reduction and containment using firs (ferric iron remediation and stabilisation) technology. Anne Hansen, Laurence Hopkinson, Andrew Cundy, Ross Pollock 14:00-16:00 Lunch - Poster Session
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Session 6: Modelling and other Applications 15:30-15:50 Prediction of the performance of EKR based on speciation analysis and mathematical modeling. C. Vereda-Alonso, A. Garca-Rubio, C. Gmez-Lahoz, J. M. RodrguezMaroto and F. Garca-Herruzo 15:50-16:10 Electrokinetic remediation model: electric resistivity heating with dc electric fields. Zorn, R., & Steger, H. 16:10-16:30 Strengthening of soft clay with electrokinetic stabilization method. Dilek Turer, Ayten Genc 16:30-16:50 Induced electrical gradients by hyperfiltration in clays. J.P. Gustav Loch and Katja Heister 16:50-17:20 Coffee break Poster Session
Session 7: Electrokinetic and Electrochemical Degradation 17:20-17:40 Electrochemical treatment of pharmaceutical wastewater by combining electrochemical oxidation with ozonation. Menapace, Hannes; Daz, Nicols 17:40-18:00 Soil remediation by electro synthesis of oxidants and their electrokinetic distribution. Heidi Mikkola, Wolfgang Wesner, Julia Schmale, Slagjana Petkovska 18:00-18:20 On site and in situ production of oxidants for soil remediation. W. Wesner, A. Diamant, B. Schrammel, M. Unterberger, H. Mikkola 18:20-18:30 Conference Closure
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New Posters
P47 Dewatering of Tunnelling Slurry Waste using Electrokinetic Geosynthetics Denis Kalumba1,*, Stephanie Glendinning1, Chris D. F. Rogers2, David I. Boardman2, Mark Tyrer3 and Alan Atkinson3 1 Newcastle University, 2University of Birmingham and 3Imperial College, London (*Correspondence: denis.kalumba@ncl.ac.uk ) P48 Speciation Of Heavy Metals In Sludge, Dewatered By Electrokinetik Process, Using VISUAL MINTEQ Abdoli H.1, Esmaeily A.1, Elektorowicz M.1, Oleszkiewicz J.2 1 Department of Building, Civil and Environmental Engineering, Concordia University. 2 Department of Civil Engineering, University of Manitoba.
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List of Participants
Dr Hassan Aboughalma Institute of Environmental Technology, FHOOW Emden, Germany e-mail: aboughalma@fho-emden.de Ms. Anna Abyzova Geological Faculty of MSU Moscow, Russia e-mail: anna_abyzova@mail.ru Mr. Kieran Agnew School of the Environment, Civil Engineering Division, University of Brighton Brighton, UK
Prof. Djamal E. Akretche U.S.T.H.B. Algiers, Algeria e-mail: dakretche@hotmail.com Ms. Teresa Alcntara Lpez University of Vigo Vigo, Spain e-mail: talopez@uvigo.es Mr. Ahmet Altin Zonguldak Karaelmas University Zonguldak, Turkey e-mail: aaltin@karaelmas.edu.tr Mr. Tobias Augenstein Water Technology Center Karlsruhe, Germany e-mail: Mr. Jeong-Hyo Bae Korea Electrotechnology Research Institute Korea e-mail: jhbae@keri.re.kr A. Prof. Kitae Baek Kumoh National Institute of Technology Gumi, Korea e-mail: kbaek@kumoh.ac.kr Ms. Mara Barreiro Miranda University of Vigo Vigo, Spain e-mail: mariabarreiro@uvigo.es
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Mr. Dirk Becker DECHEMA, Karl-Winnacker-Institut Frankfurt, Germany e-mail: dbecker@dechema.de Miss Ran Bi University of Applied Sciences (FHOOW) Emden, Germany e-mail: ran.bi@fho-emden.de Mr. Claudio Cameselle Fernndez University of Vigo Vigo, Spain e-mail: claudio@uvigo.es Dr. Henry Cardenas Louisiana Tech University Ruston, LA, USA e-mail: cardenas@latech.edu Mr. Jeong-Hee Choi Korea Electrotechnology Research Institute Korea e-mail: dodgers@keri.re.kr Mr. Jong-Young Choi Korea Advanced Institute of Science and Technology (KAIST) Daejeon, Korea e-mail: jy_choi@kaist.ac.kr Dr. Mohamed M. I. Darwish Shell International E&P Rijswijk, The Netherlands e-mail: Mohamed.IM.Darwish@shell.com Mr. Francisco Javier Deive Herva University of Vigo Vigo, Spain e-mail: deive@uvigo.es Ms. Belen Daz Fernndez E.T.S.E.I. Universidad de Vigo Spain e-mail: belenchi@uvigo.es Dr. Maria Elektorowicz Concordia University Montreal, QC, Canada e-mail: mariae@civil.concordia.ca Ms. Celia Ferreira Escola Superior Agrria Coimbra, Portugal e-mail: celia@esac.pt
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Dr. Violetta Ferri Ferrara University Ferrara, Italy e-mail: violetta.ferri@unife.it Dr. Rafael A. Garca-Delgado Instituto Geolgico y Minero de Espaa (IGME) Madrid, Spain e-mail: r.garcia@igme.es Mr. David B. Gent USACE Engineer Research and Development Center Vicksburg, MS, USA e-mail: David.B.Gent@erdc.usace.army.mil Mr. Jos Gmez Sieiro University of Vigo Vigo, Spain e-mail: josegomez@uvigo.es Ms. Susana Gouveia University of Vigo Vigo, Spain e-mail: sm.teixeira@netcabo.pt Mr. Yoon-Cheol Ha Korea Electrotechnology Research Institute Korea e-mail: ycha@keri.re.kr Dr. Boualem Hamdi U.S.T.H.B. Algiers, Algeria
Prof. Jung-Geun Han Chung-Ang University Seoul, Korea e-mail: jghan@cau.ac.kr Dr. Anne Hansen Churngold Remediation Limited Bristol, UK e-mail: anne.hansen@churngold.com Dr. Henrik K. Hansen Universidad Tcnica Federico Santa Mara Valparaiso, Chile e-mail: henrik.hansen@usm.cl Dr. Laurence Hopkinson University of Brighton Brighton, UK e-mail: L.Hopkinson@brighton.ac.uk
Mr. Arstides Huerga Vzquez University of Vigo Vigo, Spain e-mail: arishv_2@yahoo.es Ms. Pernille E. Jensen Technical University of Denmark Lyngby, Denmark e-mail: pej@byg.dtu.dk Mr. Do-Hyung Kim Kumoh National Institute of Technology Gumi, Korea e-mail: dhkim@kumoh.ac.kr Dr. Jae-Young Lee Korea Railroad Research Institute (KRRI) Uiwang, Korea e-mail: iyoung@krri.re.kr Dr. MyungHo Lee Hanyang University Seoul, Korea e-mail: mhleecok@paran.com Mr. You-Jin Lee Korea Advanced Institute of Science and Technology Daejeon, Korea e-mail: jiny@kaist.ac.kr Dr. Christina Liaki University of Birmingham Birmingham, UK e-mail: c.liaki@bham.ac.uk Ms. Ana T. Lima Universidade Nova de Lisboa Caparica, Portugal e-mail: lima.at@gmail.com Ms. M Carmen Lobo Bedmar IMIDRA Madrid, Spain e-mail: carmen.lobo@madrid.org Dr. J.P. Gustav Loch Utrecht University The Netherlands e-mail: jpgl@geo.uu.nl Ms. Svenja T. Lohner Water Technology Center Karlsruhe, Germany e-mail: lohner@tzw.de
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Dr. Rod Lynch Cambridge University Cambridge, UK e-mail: rjl1@eng.cam.ac.uk Ms. Hannes Menapace University of Leoben Leoben, Austria e-mail: hannes.menapace@mu-leoben.at Dr. Heidi Mikkola University of Leoben Leoben, Austria e-mail: heidi.mikkola@mu-leoben.at Ms. Ftima Moscoso Daz University of Vigo Vigo, Spain e-mail: fatimamoscoso@yahoo.es Ms. Ana M. Nieto Castillo Instituto Geolgico y Minero de Espaa (IGME) Madrid, Spain e-mail: a.nieto@igme.es Mr. Patricio Nuez Universidad Tcnica Federico Santa Mara Valparaiso, Chile e-mail: patricio.nunez@usm.cl Ms. Anshy Oonnittan University of Kuopio Mikkeli, Finland e-mail: plamthot@uku.fi Ms. Lisbeth Ottosen Technical University of Denmark Lyngby, Denmark e-mail: lo@byg.dtu.dk Ms. Marta Pazos Currs University of Vigo Vigo, Spain e-mail: mcurras@uvigo.es Prof. Krishna R. Reddy University of Illinois at Chicago Chicago, Illinois, USA e-mail: kreddy@uic.edu Miss Jo Reeve Cambridge University Cambridge, UK
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Ms. Mara Teresa Ricart Ricart University of Vigo Vigo, Spain e-mail: ricart@uvigo.es Ms. Mara Rivera Sobrado University of Vigo Vigo, Spain e-mail: mrivera@uvigo.es Prof. Jos Miguel Rodrguez-Maroto University of Mlaga Mlaga, Spain e-mail: maroto@uma.es Prof. Christopher Rogers University of Birmingham Birmingham, UK e-mail: c.d.f.rogers@bham.ac.uk Mr. Adrin Rojo Universidad Tcnica Federico Santa Mara Valparaiso, Chile e-mail: adrian.rojo@usm.cl Ing. Valeria Silvia Sala Snamprogetti S.p.A. Milano, Italy e-mail: valeria.sala@snamprogetti.eni.it Prof. M Angeles Sanromn Braga University of Vigo Vigo, Spain e-mail: sanroman@uvigo.es Ms. Lei Shi UFZ Helmholtz-Center for Environmental Research Leipzig, Germany e-mail: lei.shi@ufz.de Mr. Mika Sillanp University of Kuopio Mikkeli, Finland e-mail: mika.sillanpaa@uku.fi Dr. Hagen Steger University of Karlsruhe Karlsruhe, Germany e-mail: steger@agk.uka.de Ing. Giombattista Traina Istituto Giordano S.p.A. Bellaria, Italy e-mail: ing_traina@yahoo.it
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Dr. Dilek Turer Hacettepe University Ankara, Turkey e-mail: dturer@hacettepe.edu.tr Dr. Mario V. Vzquez University of Antioquia Medelln, Colombia e-mail: mariovictorv@gmail.com Ms. Iria Vazquez Rodrguez University of Vigo Vigo, Spain e-mail: iriavazquez7@yahoo.es Mr. Wolfgang Wesner Echem Wiener Neustadt, Austria e-mail: Wolfgang.Wesner@echem.at Dr. Lukas Wick UFZ Helmholtz-Center for Environmental Research Leipzig, Germany e-mail: lukas.wick@ufz.de Mr. J. Kenneth Wittle Electropetroleum Inc Wayne, PA, USA e-mail: kwittle@electropetroleum.com Prof. Gordon C. C. Yang National Sun Yat-Sen University Kaohsiung, Taiwan e-mail: gordon@mail.nsysu.edu.tw Prof. Ji-Won Yang Korea Advanced Institute of Science and Technology Daejeon, Korea e-mail: jwyang@kaist.ac.kr Dr. Hans Zijlstra University of Cagliari Cagliari, Italy
Dr. Roman Zorn EIfER, Karlsruhe University Karlsruhe, Germany e-mail: roman.zorn@eifer.uni-karlsruhe.de
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INDEX
Plenary Lectures
PL1 Sustainable soil remediation. The use of combined technologies. Lobo, M.C, ...........................................................................................................................3 PL2 Utilization of electromigration in civil and environmental engineering. Lisbeth M. Ottosen, Iben V. Christensen, Inge Rrig-Dalgrd, Pernille E. Jensen.............5 PL3 Electrokinetic delivery of nanoscale iron particles for remediation of pentachlorophenol in clayey soil. Krishna R. Reddy, Amid P. Khodadoust and Madhusudhana R. Karri ...............................7 PL4 Electroremediation Where do we go now? Henrik K. Hansen ................................................................................................................9
Oral Presentations
Session 1: Electrokinetic Barriers S11 In-situ electrokinetic permeable reactive barrier: field investigation in the vicinity of unregulated landfill site. MyungHo Lee and Ha-Ik Chung........................................................................................13 S12 Chromate adsorbtion in a transformed red mud permeable reactive barrier using electrokinesis. Giorgia De Gioannis, Aldo Muntoni, Romano Ruggeri, Hans Zijlstra and Matteo Floris ..................................................................................................................................15 S13 Electrokinetic permeable reactive barrier for the removal of heavy metal and organic substance in contaminated soil and groundwater. Ha Ik Chung, Yong Soo Lee..............................................................................................17 S14 Use of a pulsed electric field for resisting groundwater pollution. J Reeve and R J Lynch .....................................................................................................19 Session 2: Metal Removal S21 Phosphation of bottom-ash from MSWI by means of electrokinetics. G. Traina, S. Ferro, A. De Battisti......................................................................................23 S22 Electrodialytic removal of toxic elements from sediments of eutrophic fresh waters. Pernille E. Jensen, Lisbeth M. Ottosen, Arne Villumsen...................................................25 S23 Enhanced electrokinetic treatment of different marine sediments contaminated by heavy metals. De Gioannis Giorgia, Muntoni Aldo, Polettini Alessandra, Pomi Raffaella .......................27 S24 Electroremediation of an industrial area contaminated by chromium. O. Merdoud and D. E. Akretche ........................................................................................29 S25 Bench scale evaluation of hexavalent chromium reduction and containment using firs (ferric iron remediation and stabilisation) technology. Anne Hansen, Laurence Hopkinson, Andrew Cundy, Ross Pollock.................................31 Session 3: New Applications Inorganic Pollutants S31 Delivery and activation of nano-iron by DC electric field. Sibel Pamukcu, Laura Hannum, J.Kenneth Wittle ............................................................35 S32 Electro-reclamation of cyanide, impossibility or opportunity? Bas Godschalk, Wiebe Pool..............................................................................................37
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INDEX
S33 Electrokinetically enhanced removal and degradation of nitrate in the subsurface using nanosized Pd/Fe slurry. Gordon C. C. Yang, Chih-Hsiung Hung, Hsiu-Chuan Tu ................................................. 39 S34 Spent caustic oxidation using electrogenerated Fentons reagent in a batch reactor. Henrik Hansen, Patricio Nuez, Nicols Rodrguez ......................................................... 41 S35 Physicochemical study of clay soil using inert and steel electrodes. C. Liaki, C.D.F. Rogers and D.I. Boardman ..................................................................... 43 S36 Microstructural changes in a cementitious membrane due to the application of an electrical field. A. Covelo, B. Daz, L. Freire, X. R. Nvoa, M. C. Prez .................................................. 45 S37 Effect of the electrolysis time in the movement of nitrates in an andisol of Antioqua (Colombia). Diego A. Vasco, Felipe Hernndez-Luis, Carmen D. Arbelo, Mario V. Vzquez ............. 47 S38 Comparative cost analysis of the electro-Fenton and the photoelectro-Fenton processes. Ahmet Altin, Eyp Atmaca, Sreyya Altin, Vural Evren.................................................... 49 Session 4: New Applications Bioremediation S41 Assessment of electrode materials for an integrated bio-electro-process. Lohner S.T., Becker D., Schell H., Augenstein T., Weidlich C. ........................................ 53 S42 Electrokinetic transport and processing of bone repair agents. Henry E. Cardenas, Satya S.Vasam, Yu Zhao, Deepika Morishetti................................. 55 S43 Electro-bioremediation: influence of direct current on the physiology and dispersion of pollutant degrading bacteria in model soil. Lei Shi, Susann Mller, Hauke Harms, Lukas Y. Wick..................................................... 57 S44 Electrokinetic remediation of biosolids through inactivation of Clostridium perfringens spores. Maria Elektorowicz, Elham Safaei, Jan Oleszkiewicz, Robert Reimers ........................... 59 S45 Electrokinetic enhancement of phytoremediation in Zn, Cd, Cu and Pb contaminated soil using potato plants. R. Bi, H. Aboughalma, M. Schlaak ................................................................................... 61 S46 Tetrachloroethylene bioremediation by electrochemical injection of an electron donor. Xingzhi Wu, David B.Gent, Akram Alshawabkeh Jeffrey L. Davis ................................... 63 Session 5: Organic Pollutants S51 Influence of electroosmotic flow on the PAH release from model soil matrices. Lei Shi, Hauke Harms, Lukas Wick .................................................................................. 67 S52 Electrokinetic removal of molinate from soils: experimental and modeling. A. B. Ribeiro, J. S. Santos, E. P. Mateus, J. M. Rodrguez-Maroto, M. D. R. Gomes da Silva, L. M. Ottosen ..................................................................................................... 69 S53 Remediation of hexachlorobenzene in soil by enhanced electrokinetic Fenton process. Oonnittan, A., Shrestha, R., Sillanp, M......................................................................... 71 S54 Integrated electrokinetic process with BDD electrode for degradation of phenol from contaminated soil. You-Jin Lee, Jong-Young Choi, Ji-Won Yang .................................................................. 73 S55 Electrokinetic remediation of the oil-contaminated soils. V. A. Korolev, O.V. Romanyukha & A.M. Abyzova........................................................... 75
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INDEX
Session 6: Modelling and other Applications S61 Prediction of the performance of EKR based on speciation analysis and mathematical modeling. C. Vereda-Alonso, A. Garca-Rubio, C. Gmez-Lahoz, J. M. Rodrguez-Maroto and F. Garca-Herruzo..............................................................................................................79 S62 Electrokinetic remediation model: electric resistivity heating with dc electric fields. Zorn, R., & Steger, H. ........................................................................................................81 S63 Strengthening of soft clay with electrokinetic stabilization method. Dilek Turer, Ayten Genc ....................................................................................................83 S64 Induced electrical gradients by hyperfiltration in clays. J.P. Gustav Loch and Katja Heister ..................................................................................85 Session 7: Electrokinetic and Electrochemical Degradation S71 Electrochemical treatment of pharmaceutical wastewater by combining electrochemical oxidation with ozonation. Menapace, Hannes; Daz, Nicols ....................................................................................89 S72 Soil remediation by electro synthesis of oxidants and their electrokinetic distribution. Heidi Mikkola, Wolfgang Wesner, Julia Schmale, Slagjana Petkovska ............................91 S73 On site and in situ production of oxidants for soil remediation. W. Wesner, A. Diamant, B. Schrammel, M. Unterberger, H. Mikkola ...............................93
Posters
P01 Electrokinetic dewatering and remediation of river dredged contaminated high water sediments. Ha Ik Chung, Jun Yu .........................................................................................................97 P02 Electrokinetic ultrasonic remediation of contaminated admixed soils with various clay and sand contents. Ha Ik Chung, Masashi Kamon...........................................................................................99 P03 The use of an airlift reactor with in-situ electrogeneration of Fentons reagent in the treatment of spent caustic from a petroleum refinery. Patricio Nuez, Henrik K. Hansen, Jaime Guzman ........................................................101 P04 Arsenic removal from copper smelter wastewater by electrocoagulation in an airlift reactor. Henrik K. Hansen, Patricio Nuez, Sandra Aguirre, Alejandro Jeria, Cesar Jil ..............103 P05 Integrated electrokinetic remediation technologies: opportunities and challenges. Krishna R. Reddy, Ph.D., P.E. ........................................................................................105 P06 Electrokinetic nutrient transport to stimulate microbial contaminant degradation in sandy soils. Lohner S.T., Katzoreck D., Augenstein T., Schell H., Tiehm A.......................................107 P07 A new electrode backfill material for electrokinetic soil remediation. Steger, H., Zorn, R. .........................................................................................................109 P08 Electrolytic generation of an alkaline barrier for in-situ degradation of munition constituent (RDX) contaminated groundwater. David B. Gent, Akram Alshawabkeh, Jeffrey L. Davis ....................................................111 P09 Drying brick masonry by electroosmosis Small pilot plant. Lisbeth M. Ottosen, Inge Rrig-Dalgrd..........................................................................113
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INDEX
P10 Electrokinetic settling & sedimentation behaviour of cohesive soil in dilute suspension. MyungHo Lee, Dae-Ho Kim, Soo Sam Kim.................................................................... 115 P11 Corrosion remediation using chloride extraction concurrent with electrokinetic pozzolan deposition in concrete. Henry E. Cardenas, Kunal Kupwade-Patil...................................................................... 117 P12 Electrokinetic treatment for freezing and thawing damage remediation within limestone. Henry E. Cardenas, Pradeep Paturi ............................................................................... 118 P13 Remediation of oil-polluted soils by the electrochemical lixiviation. V. A. Korolev & O.V. Romanyukha................................................................................. 119 P14 Assessment of electrokinetic metal removal from biosolids. Elektorowicz Maria, Hadhir Aboli, Jan A. Oleszkiewicz.................................................. 121 P15 Electrokinetic removal of bentazone from soils: experimental and modeling. A. B. Ribeiro, C. S. Abreu, E. P. Mateus, J. M. Rodrguez-Maroto, M. D. R. Gomes da Silva, H. K. Hansen.................................................................................................... 122 P16 Electrochemical degradation of PAHs from water in the presence of surfactants. T. Alcntara, J. Gmez, M. Pazos, S. Gouveia, C. Cameselle and M. A. Sanromn .... 123 P17 Electrokinetic remediation of benzo[a]pyrene from contaminated kaolinite. J. Gmez, T. Alcntara, M. Pazos, C. Cameselle and M. A. Sanromn ........................ 125 P18 Electrokinetic remediation and electrochemical treatment of dye polluted kaolinite. M. Pazos, C. Cameselle and M. A. Sanromn ............................................................... 127 P19 Removal of organic pollutants and heavy metals in soils by electrokinetic remediation. M.T. Ricart, M. Pazos, S. Gouveia, C. Cameselle and M.A. Sanromn ........................ 129 P20 Electrokinetic desorption processes of soft soil contaminated with heavy metal. MyungHo Lee, Jung-Geun Han and Jai-Young Lee ...................................................... 131 P21 Electrokinetic bleaching of kaolin clay. C. Cameselle, M. Pazos, I. Vazquez, F. Moscoso and M. A. Sanromn ....................... 133 P22 Electromigration of Mn, Fe, Cu and Zn with citric acid in polluted clay. M. Pazos, A. Huerga, J. L. Prieto, S. Gouveia, M. A. Sanromn, C. Cameselle ........... 135 P23 Electrodialytic remediation of suspended mine tailings. Henrik K. Hansen, Adrian Rojo, Lisbeth M. Ottosen, Alexandra Ribeiro ....................... 137 P24 Electrodialytic remediation of copper mine tailings using bipolar electrodes. Adrin Rojo, Henrik K. Hansen....................................................................................... 139 P25 Enhanced electrokinetic soil remediation of heavy metals. Ayten Genc, George Chase............................................................................................ 141 P26 Preliminary treatment of MSW fly ash as a way of improving electrodialytic remediation. Clia Ferreira, Lisbeth Ottosen, Alexandra Ribeiro ........................................................ 143 P27 An enhanced electrokinetic remediation for lead removal from soils polluted from a zinc production plant. Ahmet Altin, Mustafa Degirmenci ................................................................................... 145 P28 Electrolyte conditioning for electrokinetic remediation of arsenic from mine tailing. Do-Hyung Kim, Byung-Gon Ryu, Sung-Woo Park, Jung-Seok Yang, Kitae Baek......... 147 P29 Anolyte conditioning-enhanced electrokinetic remediation of fluorine-contaminated soil. Do-Hyung Kim, Kitae Baek, Sung-Hwan Ko................................................................... 149
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INDEX
P30 Electrokinetic remediation of Ni and Zn contaminated soil: catholyte conditioning. Do-Hyung Kim, Hyun-Duck Choi, Min-Chul Shin, Chil-Sung Jeon, Kitae Baek..............151 P31 Straw ash Electrodialytic removal of Cd in a pilot scale. A. T. Lima; Ottosen, L.M.; Ribeiro, A.B.; H.K. Hansen....................................................153 P32 Electrokinetic remediation of metal and surfactant from sewage sludge. Violetta Ferri, Sergio Ferro, Claudio Anzalone, Achille De Battisti .................................155 P33 Dialytic and electrodialytic removal of heavy metals from MSW fly ash: experimental and modeling. A. T. Lima, A. B. Ribeiro, J. M. Rodrguez-Maroto, A. Varela-Castro, L. M. Ottosen .....157 P34 Electrochemical re-impregnation of wood with copper. Iben V. Christensen, Lisbeth M. Ottosen, Simon R. Jensen; Morten B. Jacobsen.........159 P35 Transport of boron in wood - an electrokinetic accelerated wood impregnation process. Iben V. Christensen, Lisbeth M. Ottosen, Inge Rrig-Dalsgaard ....................................161 P36 Remediation of a chromium (VI) contaminated soil by electrodialysis. Ana M. Nieto Castillo, Juan J. Soriano, Rafael A. Garca-Delgado ................................163 P37 A simple computer model for the electrodialytic remediation of a chromium (VI) contaminated soil. Rafael A. Garca-Delgado ,Ana M. Nieto Castillo, Juan J. Soriano ................................165 P38 Implementation of a iodide enhanced EKR to a mercury contaminated soil. A. Garca-Rubio, J. M. Rodrguez-Maroto, F. Garca-Herruzo, C. Vereda-Alonso, C. Gmez-Lahoz, J. M. Esbr and P. Higuera .................................................................167 P39 Electrokinetic remediation of a radionuclid- contaminated soils. V. A. Korolev, Y.E. Barkhatova, E.V. Shevtsova.............................................................169 P40 Electrokinetic remediation of a soil contaminated with heavy metals in a scale pilot experiment. Lobo, M.C, Martinez-Iigo, M.J, Prez-Sanz, A, Plaza, A, Alonso, J, Perucha, C .........171 P41 Electrokinetic remediation of metal-contaminated soil. Larisa L.Lysenko, Nataliya A.Mishchuk...........................................................................173 P42 Electrokinetic remediation of copper contaminated clay soils. Nataliya Mishchuk, Larysa Lysenko, Boris Kornilovich ...................................................174 P43 Fundamental problems of soil and sludge decontamination by application of an electric field. Nataliya A. Mishchuk .......................................................................................................175 P44 Remediation of cadmium contaminated paddy soils by washing with calcium chloride in Pindi-Bhatian (Punjab) Pakistan. Tahir Mehmood, Syed Tasawar Abbas, Kashif Shahbaz and Muhammad Bashir .........177 P45 Comparative leaching reagent effects in the course of an electroremediation of a soil contaminated by lead. S. Amrate, B. Hamdi, D. E. Akretche, M. Pazos, C. Cameselle and C. Innocent ...........179 P46 From electroremediation to metal valorisation. N. Sabba and D. E. Akretche ..........................................................................................181
xix
Plenary Lectures
Some plants with tolerance to heavy metals could be used to remove these pollutants from soil, when the application of the electrokinetic technologies doesnt allow the total removal. Even, bioremediation and phytoremediation can be enhanced by the effect of the direct current on the soil (Acar et al., 1996, Maini et al., 2000, OConnor et al., 2003, Both remediation strategies, biological and electrokinetic, could be used in combination, but more effort must be done in field conditions, in order to demonstrate their efficency, evaluating the impact on the soil. Ecotoxicological assays must be carried out during and after the remediation process to assess the environmental impact on the ecosystem.
References:
Alef, K. and Nannipieri, P. 1995. Methods in Applied Soil Microbiology and Biochemistry. Academic Press, London Acar, Y.B and Alshawabkeh, A.N., 1993. Principles of Electrokinetic Remediation. Enviornmental Science and Technology. Vol 27. N 13, 2638-2647. Brombacher, C, Bachofen, and R, Brandl, H. 1998. Development of a Laboratory Scale leaching plant for metal extraction from fly ash by Thiobacillus Strains. Applied and Environmental Microbiology. 64 (4), 1237-1241. Comission of the European Communities. COM. 2006, 232. Proposal for a Directive of the European Parliament and of the Council. http://ec.europa.eu/comm/environment/soil/index.htm Gadd, G. M. 2000. Bioremedial potential of microbial mechanism of metal mobilization and inmobilization. Current Opinion in Biotechnology. 11, 271-279. Kalbitz, K and Wenrich, R. 1998. Mobilization of heavy metals and arsenic in polluted wetland spills and its dependence of dissolved organic matter. The Science of the Total Environment. 209. 27-39. Kim, S, Moon, SH, and Kim, K.W. 2001. Removal of heavy metals from soils using enhanced electrokinetic soil processing. Water, Air, Soil Pollut. 125 (1-4). 259-272. Lobo, M.C, Sanchez, M, Garbi, C, Ferrer, E, Martinez Iigo, M.J, Allende, J.L, Martn, C, Casasus, L, Alonso-Sanz, R, Gibello, A and Martn, M. 2003. Bioremediation of soils and waters by using inmobilized native bacteria :implementation and modeling. Water, Air & Soil: Focus, 3(3)35-46. 2003 Maini, G, Sharman, AK, Sunderland, G, Knowles, CJ, and Jackman, S.A. 2000. An integrated method incorporating sulphur-oxidizing bacteria and electrokinetic to enhance removal of copper from contaminated soil. Environm. Sci. Technol. 34 (6). 1081-1087. .Martin, M. Mengs, G. Garbi, M. Snchez, A. Gibello, F. Gutierrez, and E. Ferrer. (2000). Propachlor removal by pseudomonas strain GCH1 in an inmobilixzed cell system. Applied Envriron, Microbiol., 66, 3, 1190-1194 OConnor, CS, Lepp, NW, Edwards, S.R., Sunderland, G. 2003. The combined use of electrokinetic remediation and phytoremdiation to decontaminate metal-polluted soils: a laboratory-scale feasibility study. Environm. Monitor. Assess. 84 (1-2) 141-148. Page, MM. and Page, CL. 2002. Electroremediation fo contaminated soil J. Environm. Eng. 128. (3).208219. Pazos, M; Sanroman, MA and Cameselle, C. 2006. Improvement in the electrokinetic remediation of heavy metals spiked caolin with the polarity inversion technique. Chemosphere. 62 (5) 819-822. Reddy, K.R, Saichek, R.E, Maturi, K and Ala, P, 2002. Effects of soil moisture and heavy metals concentrations on electrokinetic remediation. Indian Geotechnical Journal. 32 (2). Saichek, RE, and Reddy, KR. 2003. Effect of pH control at the anode or the electrokinetic removal of phenanthrene from kaolin. Chenosphere. 51. 273-287. Ugaz, A, Puppah, S, Gale, R.J, and Acar, YB. 1994. Electrokinetic soil processing. Complicating features of elecgtrokinetic remediation of soils and slurries: saturation effects and the role of the cathode electrolysis. Chem. Eng. Commm. 129. 183-200. Willaert, R. G., Baron, G. V, and De Backer, L. 1996. Inmobilised Living Cell Systems. Wiley and Sons, Sussex Zhou, DH, Zorn, and R, Kurt, C. 2003. Electrochemical remediation of copper contaminated kaolinite boy conditioning analyte and catholyte pH simultaneously. J. Environ. Science-China. 15 (3). 396- 400.
Environmental engineering. Electromigration is mainly used for transporting pollutants out from contaminated matrices and here soil is the most investigated material, but also the transport of ions into the matrices can be of value in some situations. Removal of heavy metals. Such processes have shown successful for remediation of different
materials such as soil, sediment, fly ash, waste water sludge and waste wood. Removal of salt (NaCl) from soil to improve the quality of saline-sodic soils to hinder land degradation Improved bio-remediation organic soil pollutants. There are different ways electromigration can improve the conditions for the microorganisms e.g. supplying surfactants or increase bioavailability of the pollutant.
There is no doubt from the experiences obtained with the above mentioned processes that electromigration is a powerful tool to remove ions, supply ions or to change chemical conditions in porous media even very fine porous media where other processes based on e.g. pressure gradients fails. It could certainly be advantageous to share knowledge and know how obtained in the two fields of electrokinetics, both in order to increase the understanding of electrokinetics in various porous media and the effect that can be expected on the porous media itself, but there are also situations where direct collaboration is necessary. Further also some subjects within construction of electrodes and control of the process could be beneficial to share. An example where collaboration is necessary is a situation where electrokinetic soil remediation is planned under a house. In such action it is of crucial importance to the environmental engineer to know how/if the building materials is influenced by the applied electric field. Another situation could be electrokinetic salt removal from a basement wall where one of the electrodes is placed in the soil outside the building. Here knowledge on electrokinetics in soil is important to the civil engineer. The issue of pH changes from the electrode processes is a common key issue. An alkaline and an acidic front develop from the cathode and anode, respectively, if no precautions taken. Acidification from the anode is aiding heavy metal release and is thus very important in remediation of e.g. soil and sediments but the alkaline front prevents full remediation due to precipitation of the heavy metals. Concrete has a natural high pH and it is very important to avoid acidification since concrete is destroyed by acidification. The alkaline front in concrete, on the other hand, is only of concern because the transference number of Cl- decreases due to competition with OH-. Combining the fields of soil remediation and chloride removal from concrete, know how is available on possible electrode constructions that can hinder pH changes in the porous matrix, which is necessary in e.g. re-impregnation and beneficial when removing salts from masonry. An important issue to every process that involves applying an electric DC field to a porous media is transport of non-target ions and matrix changes. In every process it is necessary to know the properties of the matrix after the treatment, either to find use of the material (e.g. fly ash or sediment) or to be certain that the materials properties have not been changed unacceptably (e.g. wood, concrete or bricks). It is certain, that the applied electric field is not only transporting the target ions out from the matrix (or into). Non-target ions are also transported, and non-target ions of interest in most matrices are e.g. Ca, K and Na. These are common soil elements and it has been shown, that these elements are removed during electrokinetic soil remediation which is of no concern except for the current wasted in transporting these ions. When treating straw ash from biomass combustion the removal of K is unwanted since K is adding significantly to the fertilizer value of the remediated ash. In concrete, on the other hand, the transport of Na and K can be a limitation to the process due to the danger of alkali-kisel reaction. The literature survey has surely underlined that it could be beneficial to collaborate and exchange knowledge of electrokinetics within the two fields civil and environmental engineering in order to raise the common understanding of the processes.
ELECTROKINETIC DELIVERY OF NANOSCALE IRON PARTICLES FOR REMEDIATION OF PENTACHLOROPHENOL IN CLAYEY SOIL
Krishna R. Reddy1, Amid P. Khodadoust2, and Madhusudhana R. Karri3 1 Professor, 2Associate Professor and 3Graduate Research Assistant University of Illinois at Chicago, 842 West Taylor Street, Chicago, Illinois 60607, USA Tel: 312-996-4755; Fax: 312-996-2426; E-mail: kreddy@uic.edu Several researchers have synthesized different types of nanomaterials for a wide range of engineering applications. However, only recently nanoscale iron particles (NIPs) have received the attention of environmental professionals to remediate contaminated sites. This paper investigates: (1) the reactivity of NIPs to promote the reductive degradation of pentachlorophenol (PCP) in clayey soils, and (2) potential to deliver NIPs into PCPcontaminated clayey soils using electrokinetics and resulting PCP reduction efficiency. Kaolin was used as a model low permeability clayey soil and was artificially spiked with PCP at initial concentration of 500 mg per Kg of dry soil (mg/Kg) or 1000 mg/Kg. PCP was chosen because it is one of the common contaminants found at former wood preserving contaminated sites. To spike the soil, hexane was used to dissolve solid PCP, and this hexane-PCP mixture was slowly added to dry kaolin soil. The mixtures were stirred with stainless steel spoons within glass beakers and then placed beneath a ventilation hood for nearly a week until the hexane completely evaporated and the contaminated soil was dry. The dry soil was then mixed with 35% deionized water to simulate typical field moisture conditions. The NIPs used for this study were produced using the the patented method by Uegami et al. (US2003/0217974A1) and consisted of an elemental iron core (Fe) and a magnetite shell (Fe3O3) in approximately same amounts by weight. The aqueous NIP suspension with 25.6 wt.% solid concentration had density of 1.27 g/mL. The average particle size and surface area of NIPs was 70 nm (0.07 m) and 28.8 m2/g, respectively. A series of laboratory batch experiments was conducted on PCP-contaminated kaolin with different contact time (1, 2, 8, 12, 24 and 48h) and different NIPs concentrations (1, 2, 4, 5, 8, 10, 20, 40, 60, 80 and 100 g/L) to investigate the reactivity and optimum concentration of NIPs. These experiments were conducted in 40-mL glass vials containing 25 mL of NIPs suspension of known concentration (5, 10 and 20 g/L) and 5 g of PCP spiked kaolin soil (with PCP concentration of 1000 mg/Kg). The soil-NIPs suspensions were shaken for 48 hours. The aqueous suspension was centrifuged at 4000 rpm for 30 min to separate the solids from the liquid. The supernatant and the residual soil were analyzed for PCP concentration using GC-MS. These results showed that 80 to 98% PCP was removed from the soil within an hour, but PCP reduction was increased from 50 to 78% at 1h to 40 to 90% at 24 h reaction time for different NIP concentrations. There was no significant effect of NIPs concentration on the PCP removal, but the amount of PCP reduction increased with increase concentration of NIPs with 30% at 1 g/L to 98% at 100 g/L. There appears to be an optimal NIPs concentration beyond which benefits are diminished. A series of electrokinetic experiments was conducted to investigate electrokinetic delivery of NIPs and resulting PCP reduction efficiency. The testing equipment and the procedure were the same as that used in previous studies at University of Illinois at Chicago (UIC). Kaolin spiked with PCP with an initial concentration of 500 mg/Kg was tested under different NIP concentrations, voltage gradients, operating duration, and enhancement
7
conditions as summarized in Table 1. Except for the control test, the anode reservoir was filled with NIPs suspension and recirculated with a pump, while the cathode reservoir was filled with deionized water. During the application of electric potential, current and the electroosmotic flow were recorded. At the end of each test, aqueous samples from the electrodes and dissected soil sections were analyzed for pH, iron and PCP. Table 1. Testing Program to Investigate Electrokinetic Delivery of NIPs Voltage Test Test Test Anode Flushing Pore Gradient Duration Date Designation Solution Volumes (VDC/cm) (Hours) March 31, 2003-April 18, 2003 August 28, 2003October 7, 2003 NIP0 NIP1 NIP2 NIP3 NIP4 NIP5 NIP6 1.0 1.0 1.0 2.0 2.0 1.0 1.0 Distilled Water 5 g/L NIP 10 g/L NIP 5 g/L NIP 10 g/L NIP 0.5% Tween 80 + 5 g/L NIP 5% Ethyl Alcohol + 5 g/L NIP 427 427 427 937 936 936 936 1.2 2.1 2.2 0.9 1.5 2.4 2.5
The test results showed that the current increased rapidly during the first few hours, then decreased over a period of time. The measured electroosmotic flow varied depending on the test conditions as shown in Table 1. Very low amounts of iron and PCP were detected in the effluent. The dissected soil sections revealed that soil pH decreased in the first four sections from the anode but was the highest in the section closer to the cathode. The iron concentrations in soil increased from the anode to the cathode, indicating the delivery of NIPs into the soil using electrokinetics. Visual observations also revealed the presence of iron particles within the first two sections from the anode. A low concentration of PCP was observed in the first section away from the anode that increased up to the third section and then further decreased towards the cathode end, indicating the migration of PCP occurring from anode to cathode. The amount of PCP reduction by NIPs was calculated based on the initial mass in the soil, the mass removed in the effluent, and the mass remaining in the soil and it ranged from 100% near the anode to 5% near the cathode. The enhanced electrokinetic experiments results showed that high electroosmotic flow was obtained in the cosolvent enhanced system (2.5 pore volume) as compared to surfactant enhanced system (2.4 pore volume) resulting in the increased injection of nanoiron into the soil. Further it was also evaluated that the transport and dispersion of nanoiron particle was more uniform in surfactant enhanced system as compared to cosolvent enhanced system. Overall, the results from this study revealed that the extent of delivery and reactivity of NIPs were limited by passivation and aggregation of NIPs under the oxygenated and low pH conditions that exist at the anode as well as complex geochemical reactions occurring simultaneously at different rates. The NIPs transport may be affected by probable dissolution of substrate minerals and possible precipitation of secondary solids as well as changes in the surface charge of all solids as the solution composition changes. Parameters controlling these reactions include pH, Eh, solution composition, and solid (both NIPs and substrate) composition and structure. Besides these considerations, the system parameters such as voltage gradient, mode of voltage gradient application (pulsed versus continuous), and pH control at the anode and cathode should be optimized.
About 20 years ago the first full and pilot scale electrokinetic soil remediation processes to remove heavy metals were reported [1,2]. The electrokinetic phenomenon electroosmosis together with electromigration of heavy metal ions were key factors in this remediation technique. Industry, remediation companies and academics worked together in the successful development of the remedation method. Since then only a few soil remediation companies have continued to offer electrokinetic remediation as treatment solution [3]. Why has the interest stopped? Is the method to complicated? Patent rights restrictions? Is it too expensive? Is it not efficient? Does heavy metal contaminated soil not cause sufficient risk for society? On the other hand, the research during the last 5 10 years in the area of electroremediation is increasing and showing that we are turning into other waste mateials such as ashes, wood waste, sewage sludge and even wastewater. Furthermore, we are combining different effects using the electric current to enhance other remediation processes. Soil has become less important since regulatives generally is getting less strict when it comes to heavy metal contamination in soils. Only toxic organic contaminants and radioactive elements are of great concern, and researchers are turning their interest into these cases. The aim with this presentation is to start a discussion whether or not true electrokinetic remediation of soil still has potential and interest to be a reference remediation technology.
[1] US-EPA Report 402-R-97-006 (1997). [2] Lageman, R., Environmental Science and Technology, 27 (1993) 2648-2650. [3] Lageman, R., Clarke, RL., Pool, W., Engineering Geology 77 (2005) 191-201.
Oral Contributions to
session 1 Electrokinetic Barriers
IN-SITU ELECTROKINETIC PERMEABLE REACTIVE BARRIER: field investigation in the vicinity of unregulated landfill site
MyungHo Leea and Ha-Ik Chungb a BK Research Associate, Dept. of Civil & Environ. Eng., Hanyang Univ., South Korea E-mail: mhleecok@paran.com b Research Fellow, Geotechnical Eng. Research Dept., KICT, South Korea ABSTRACT This paper presents preliminary field investigations on the electrokinetic remediation coupled with permeable reactive barrier system. Unregulated and old-fashioned landfills are one of the primary contributors to various contaminated soil problems. Insitu electrokinetic remediation technology has been successfully applied to the environs of unregulated landfill site, located in Kyeong-Ki province, Korea. Atomizing slag was adopted as a PRB reactive material for the remediation of groundwater contaminated withinorganic and/or organic substances. From the preliminary investigations, the coupled technology of EK with PRB system would be effective to remediation contaminated grounds without the extraction of pollutants from subsurface due to the reactions between the reactive materials and contaminants. Keywords: atomizing slag, clayey soil, electrokinetics, landfill, permeable reactive barrier
(-) Zeolite
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Fig. 1. Testing apparatus for electrokinetic permeable reactive barrier system: (a) electrode array; (b) perforated electrode chamber and drainage system
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[1] Acar, Y. B. and Alshawabkeh A. N. (1993), Principles of electrokinetic remediation, Environ. Sci. Technol., 27(13), pp. 2638-2647. [2] Lee, M. (2007), New concept of remediation technique for the contaminated ground and groundwater: Electrokinetic Permeable Reactive Barrier System (EKPRBS), Korea Society of Waste Management, 24(2), pp. 134-140. (in Korean) [3] Melitas, N., Conklin, M. and Farrell, J. (2002), Electrochemical study of arsenate and water reduction on iron media using for arsenic removal from potable water, Environ. Sci. Technol., 36(14), pp. 3188-3193. [4] Mitchell, J. K. (1993), Fundamentals of soil behaviour, Wiley Inter. Science [5] Morrison, S. (2003), Performance evaluation of a permeable reactive barrier using reaction products as tracers, Environ. Sci. Technol., 37(10), pp. 2302-2309. [6] Simon, F. G. and Meggyes, T. (2000), Removal of organic and inorganic pollutants from groundwater using permeable reactive barriers: part 1. treatment processes for pollutants, Land Contamination Reclamation, Vol. 8, No. 2. [7] Yeung, A. T. (1994), Electrokinetic flow processes in porous media and their applications, Advances in porous media, Elsevier, 2, pp. 309-395.
14
CHROMATE ADSORBTION IN A TRANSFORMED RED MUD PERMEABLE REACTIVE BARRIER USING ELECTROKINESIS
Giorgia De Gioannisa, Aldo Muntonia*, Romano Ruggerib, Hans Zijlstrab and Matteo Florisa a University of Cagliari, Department of Geoengineering and Environmental Technologies, Piazza dArmi 09123 Cagliari, Italy; bVirotec Italia, Via Alessandria 112 00198 Roma, Italy e-mail: amuntoni@unica.it Seawater neutralized Red Mud with soil neutral pH and acid neutralizing capacity of about 4 moles per kg is used in environmental remediation for treatment of acid to slightly alkaline, metal contaminated water and soil [1, 2, 3]. It has been observed that the micron sized etched mineral particles with high specific surface, containing up to 35 wt% of hematite, are excellent adsorbents for metal oxyanions such as arsenate, antimonate, and chromate. However, significant adsorption capacities of more than 1 mg/g are only observed after the seawater neutralized Red Mud is activated by acid and fluid pH is less than 6.5 [4, 5]. For treatment of metal oxyanion contaminated acid waters such conditions can be readily attained, however for metal oxyanion contaminated neutral soils, costly soil acidification or acid pre-treatment of seawater neutralized Red Mud could be required. During electrokinetic remediation of metal contaminated soil, hydrogen ions are generated at the anode and hydroxyl ions at the cathode [6, 7, 8]. Thus it is hypothesised that metal oxyanions can be removed from contaminated soil by an electric field, in order to accumulate at the oppositely charged anode, where they can be readily adsorbed on seawater neutralized Red Mud that is acid activated by the hydrogen ions produced by the anode. In order to test the hypothesis, a laboratory-scale electrochemical cell of about 30 cm length is filled with about 2 kg of clayey soil of pH 5.5 that is artificially contaminated with 1000 mg chromate per kg dry weight [9]. Subsequently, a 30 V electric field is maintained during 12 days and afterwards, the pH and chromium concentrations of 6 soil slices are assessed. As the clayey soil has a fairly high adsorption capacity for chromate due to the presence of ferrous iron and the reduction of soluble chromate to insoluble chromium III, in particular at lower pH conditions near the anode, two different setups using seawater neutralized Red Mud were investigated, and compared to an electrokinetic test with only chromate contaminated clayey soil. In the first test, a modest amount of 30 g of seawater neutralized Red Mud is mixed with the clayey soil adjacent to the anode. The quantity is chosen such that it just neutralizes the acid produced at the anode during the duration of the test. The idea is that in doing so, acidification of the soil near the anode is prevented; the hydroxyl front produced by the cathode can advance as far as possible towards the anode promoting desorbtion of the chromate; and chromate adsorption and chromate chromium III conversion are hampered near the anode. In the second test, a considerable amount of acid activated seawater neutralized Red Mud is mixed with the clayey soil adjacent to the anode. In this case, the idea is to provide an optimum adsorbent for chromate adsorption, allowing electrokinetic removal of chromate from clayey soil, without the need of electrolyte purification and the ex-situ disposal of the recovered chromate contaminant. The latter should substantially reduce the costs of electrokinetic remediation of, for instance, metal oxyanion contaminated
15
mining waste dumps in remote mountainous areas, which are common in Sardinia that is characterized by numerous abandoned metal ore mines, exploited since Roman times. The results of both laboratory-scale tests using seawater neutralized Red Mud permeable reactive barrier in combination with electrokinetic remediation of artificially chromate contaminated clayey soil are compared to electrokinetic remediation alone and discussed with respect to the possibility of field-scale application.
[1] McConchie D., Saenger P., and Fawkes R., (1996). An environmental assesment of the use of seawater to neutralise bauxite refinery wastes. In: V. Ramachandran and C.C. Nesbitt (eds.) Proceedings of the 2nd Internat. Symp. On Extraction and Processing for the Treatment and Minimisation of Wastes. The Minerals, Metals, and Materials Soc., Scottsdale Arizona, 407 416. [2] McConchie D., Clark M., Hanahan C. and Fawkes R. (1999) The use of seawaterneutralised bauxite refinery residues (red mud) in environmental remediation programs. IN: I. Gaballah, J. Hager and R. Solozabal (eds.) Proceedings of the 1999 Global Symposium on Recycling, Waste Treatment and Clean Technology, San Sebastian, Spain. The Minerals, Metals and Materials Society, 1: 391-400. [3] Zijlstra J.J.P., Bello V., Ruggeri R. And Teodosi A. (2005). The BAUXSOLTM Technology: An innovative solution for environmental remediation problems. In; R. Cossu and R. Stegmann (eds), Proceedings Sardinia 2005 Tenth International Waste Management and Landfill Symposium, 1019 1020. [4] Cenc-Fuhrmann H., Tjell J.C., and McConchie D., (2004). Adsorption of Arsenic from Water Using Activated Neutralized Red Mud. Environ. Sci. Technol., 38 (8), 2428 -2434. [5] Mureddu, M (2006). Indagini di laboratorio sulla capacit del BAUXSOLTM di migliorare la rimozione del Cromo da acque contaminate. Universita degli Studi di Cagliari, Facolt di Scienze Matematiche, Fisiche e Naturali Dipartimento di Scienze Chimiche. Tesi di Laurea, 63 p. [6] Lindgren, E.R., Mattson, E.D., & Kozak, M.W. (1992). Electrokinetic remediation of unsaturated soils. In D.W. Tedder & F.G. Pohlan (Eds.), Emerging technologies in hazardous waste management IV: ACS symposium series, Atlanta, GA (pp. 3350). [7] Mascia M., Muntoni A., Palmas S.,1, Polcaro A.M., Vacca A., 2006. Experimental study and mathematical model on remediation of Cd polluted soils by electrokinetics. Electrochimica Acta (Elsevier), (M. Mascia et al., Electrochim. Acta (2006), doi:10.1016/j.electacta.2006.04.066), Vol. 52, Issue 10, ISSN 0013-4686, febbraio 2007. [8] Lynch R.J., Muntoni A., Ruggeri R., Winfield K.C., 2006. Preliminary tests of an electrokinetic barrier to prevent heavy metal pollution of soils. Electrochimica Acta (Elsevier), Vol. 52, Issue 10, ISSN 0013-4686, doi:10.1016/j.electacta.2006.06.049, febbraio 2007. [9] Reddy, K.R., & Parupudi, U.S. (1997). Removal of chromium, nickel and cadmium from clays by in-situ electrokinetic remediation. Journal of Soil Contamination, 6(4), 391407.
16
ELECTROKINETIC PERMEABLE REACTIVE BARRIER FOR THE REMOVAL OF HEAVY METAL AND ORGANIC SUBSTANCE IN CONTAMINATED SOIL AND GROUNDWATER
Ha Ik Chunga, Yong Soo Leeb a Research Fellow, Korea Institute of Construction Technology, 2311 Daewha-dong Ilsan-gu Goyang-shi Gyeonggi-do, Korea, Tel +82-31-910-0216, Fax +82-31-910-0211 E-mail: hichung@kict.re.kr b Senior Researcher, Korea Institute of Construction Technology, 2311 Daewha-dong Ilsan-gu Goyang-shi Gyeonggi-do, Korea E-mail: yslee@kict.re.kr
This paper presents a study on an electrokinetic permeable reactive barrier which is electrokinetic remediation coupled with permeable reactive barrier system. In this study, electrokinetic permeable reactive barrier is filled with reactive materials such as atomizing slag & sand mixture, zeolite & sand mixture, and iron powder & sand mixture for remediation of soil and groundwater contaminated with heavy metal and organic substance. A series of laboratory experiments including variable conditions such as concentration of contaminants, magnitude of applied electrical current, operating duration, and reactive materials were performed with the contaminated soil and groundwater. Investigated are volume of water flow through soil specimen, the concentration changes of soil specimen, the current and voltage changes, and the concentration changes of groundwater inflow and outflow. The efficiency of heavy metal and organic substance removal by the proposed method was evaluated under various operating conditions. The test setup used in this study was made to combine the electrokinetic processor with permeable reactive barrier processor. The test chamber was made of a plexiglas box having an insider scale of 10cm x 10cm with a height of 10cm. The elecrokinetic with permeable reactive barrier processor consists of four parts: anode electrode, cathode electrode, electric power supplier, and permeable reactive material. Ethylene glycol and Cd were used as a surrogate contaminant to demonstrate the groundwater and soil contaminated by heavy metal and organic substance. The following left side figure shows the electrokinetic permeable reactive barrier test cell and the reactive material of black color is situated at right side reservoir of this cell. The following right side figure shows the volume of cumulative effluent passing through sediment specimen with different reactive material conditions.
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The tests were conducted for two conditions: electrokinetic remediation test (EK) and electrokinetic with permeable reactive barrier test (EK+PRB). In the tests, the clay soil specimens were thoroughly mixed with Ethylene glycol of 300ppm and Cd of 50ppm. The test specimen was then subjected to electric power at 2.0V/cm from electrokinetic test setup. Tests were continued to maximum 200 hr. The test result shows that the contaminant in soil and groundwater was effectively removed by composite reaction of electroosmosis, electromigration, washing efficiency, and reactive adsorption efficiency generated from electric power and reactive material. [1] Kyung Kook Lee, Ha Ik Chung, etc., Remediation of contaminated soil by electrokinetic reactive washing ecopile, Fall Conference of Korea Geotechnical Society, 2006.10
18
Cathode Anode
Fig.1 A schematic representation of an electrokinetic barrier A one dimensional electrokinetic cell test was used, as shown in Fig.2.
Power supply +
19
Fig.2 Schematic diagram of a cylindrical electrokinetic cell test of the barrier The tube diameter is 11cm, and the length of the soil compartment is 22 cm. There is an electrode compartment on each side of the soil compartment which was filled with a fine sand of particle size range 90 - 150 microns. The copper-polluted water which is fed from a constant head device is driven through the cell in the absence of an electric field. An electric field of 1.7V/cm was applied when the copper reached sampling point (tap) 2. The effect of the field on the copper movement through the soil was monitored at the four sampling points distributed along the column, and also at the outlet.
Concentration of Copper at each port w ith tim e
70 60
Conc (mg/l)
Power on
Time (mins)
Tap 2
Tap 3
Tap 4
Output
Fig.3. Copper concentrations observed at the sampling points, and at the outlet of the soil compartment It is observed in Fig. 3 that hardly any copper reaches sampling points 3 or 4 when the power is applied, and that hardly any copper emerges from the outlet. The incoming copper concentration was 10 g/l, so about 99.95% copper has been excluded. Further results of these experiments and a more complete analysis will be presented in the full paper. Results obtained so far indicates that a pulsed electric field barrier should be possible. References J K Mitchell and T C Yeung, Electrokinetic flow barriers in compacted clay, Transportation Research Record No.1228, Geotechnical Engineering 1-9, (1990) Narasimhan and Sri Ranjan, Electrokinetic barrier to preventing subsurface contaminant migration: theoretical model and validation Journal of Contaminant Hydrology, 42, 117, (2000), R.J. Lynch, A. Muntoni, R. Ruggeri and K.C. Winfield, Preliminary tests of an electrokinetic barrier to prevent heavy metal pollution of soils, Electrochimica Acta 52 (2007) 34323440.
20
Oral Contributions to
session 2 Metal Removal
23
(instead of acetic acid), while a micropore PET membrane is used to separate the ash from the cathode compartment to favour the movement of phosphate anions from the cathode towards the anode. The humidity of bottom ash has been increased up to 24% (w/w) for chlorides solubilization and the coarse ferrous and non-ferrous metals have been manually separated before the electrokinetic treatment. The test duration was varied between 24 and 48 h, applying 2-2.8 V/cm (DCV). The UNI EN 12457/2 method was followed to compare the leaching of pollutants from untreated and treated specimens, getting a considerable stabilizing effect for Ba and Pb by phosphatation, with a leachate reduction of 95-98%, while Cu leaching remained quite high and dependent on the solubility of Cu-organocomplexes. Phosphation did not show a significant effect in stabilizing these particular species, even if a measurable reduction of Cu-leaching (65 %) was found after the electrokinetic treatment. Chlorides extraction ranged between 50-85%, depending on the Amperage and the time of treatment. References [1] Acar Y.B. & Alshawabkeh A.N. (1993) Environ. Sci. Technol., 46, 2638. [2] Traina G., Persano Adorno G., De Battisti A. (2005) Electrokinetic Remediation: un nuovo approccio alla valorizzazione di cenere di fondo (bottom-ash) da incenerimento RSU. Atti di Ecomondo, pp. 434 - 442 , Volume 2 Maggioli Editore. [3] Piantone P., Bodnan F., Derie R. & Depelsenaire G. (2003) Monitoring the stabilization of municipal solid waste incineration fly ash by phosphation: mineralogical and balance approach, Waste Management, 23, 225.
24
Fig. 1. Schematic view of a cell used for experimental EDR remediation of freshwater sediments. AN = anion-exchange membrane, CAT = cation-exchange membrane. I = anolyte compartment, II = compartment containing sediment slurry, III = catholyte compartment.
25
The slurry was kept in suspension by constant stirring with plastic-flaps attached to a glass-stick and connected to an overhead stirrer. The anolyte was separated from the soil specimen by an anion-exchange membrane, and the catholyte was separated from the soil specimen by a cation-exchange membrane. Figure 1 shows a schematic drawing of the setup. Platinum coated electrodes were used as working electrodes. The catholyte and the anolyte initially consisted of 0.01M NaNO3 adjusted to pH 2 with HNO3. pH in the electrolytes was kept between 1 and 2 by manual addition of HNO3 (7M) or NaOH (6M). The liquid to solid ratio (L/S) was 4 (100g soil and 400ml distilled water), and the current density was 0.8mA/cm2 (40mA). Four experiments of variable duration were made with each sediment. Results and discussion Figure 2 illustrates the results of EDR of sediment from the Millpond Raadvaddammen as a function of time. All elements could be reduced in concentration to values approximating background values. The current efficiency was high compared to remediation of harbour sediments [1], reducing the costs of the remediation. The high current efficiency probably relies on the lower concentration of soluble salts competing for the current in fresh water sediments. Unsatisfactory remediation could have been anticipated due to the immobilisation of heavy metals by high levels of phosphate and organic matter as described for Pb in previous works [4]. This effect was, however absent, and the release of metals caused by the shift in redox potential when the sediment was exposed to oxygen may be partly responsible for the successful remediation.
Concentration in sediment [%] 100 90 80 70 60 50 40 30 20 10 0 0 50 100 150 200 250 300 350 time/hours
Ni Zn Cr Cu Pb
Figure 2: Remediation results obtained with sediment from the Millpond Raadvaddammen from the fresh water system Mlleen north of Copenhagen. [1] Nystroem G.M., Ottosen L.M., Villumsen A. (2005) Acidification of harbour sediment and removal of heavy metals induced by water splitting in electrodialytic remediation. Separation Science and Technology; 40, 2245-2264. [2] Jensen P.E., Ottosen L.M., and Ferreira C., (2007), Electrodialytic Remediation of Pb-Polluted Soil Fines (< 63my) in Suspension, Electrochimica Acta, 52, 3412-3419. [3] Jakobsen M.R., Fritt-Rasmussen J., Nielsen S., Ottosen L.M. (2004) Electrodialytic removal of cadmium from wastewater sludge. Journal of Hazardous Materials, 106, 127-132. [4] Jensen P.E., Ottosen L.M., Pedersen A.J. (2006) Speciation of Pb in industrially polluted soils. Water Air and Soil Pollution 170, 359-382.
26
(voltage, test duration) as well as cathodic and anodic solutions were adopted and tested in order to accomplish the main objective of mobilizing metals from sediments, favoring migration and avoiding precipitation. The enhanced electrokinetics made use of chelating agents (EDTA, citric acid), pH adjustment through the use of nitric acid solutions, and application of a hydraulic gradient. The evolution over time of circulating current intensity and density, of electrosmotic flow as well as the evaluation of pH and metal concentration in the electrode solutions was evaluated through periodical measurements over the treatment period. The efficiency of the process was evaluated on the basis of the achieved cathodic flow and of the residual concentration values of salt and contaminants in the solid sample measured at the end of the treatment. The results of the tests proved that EK is a suitable process in order to achieve either dewatering and removal of salts or the mobilization of the pollutants. The different characteristics of the sediments mirrored in the achieved heavy metal removal. In general, the enhancement of the process proved to be necessary in order to improve the overall efficiency of the process since prompt depolarization of cathode and higher heavy metals removal can be achieved. The results obtained indicated that in the case of real contaminated sediment, as compared to the results typically reported for spiked materials, the remediation efficiency is significantly affected by the buffer capacity of the sediment and by partitioning and speciation of metals in the less mobile fractions.
Removal efficiency (%) 80
W2 CIT4 EDTA1
70 60 50 40 30 20 10 0 Pb Zn Cu Cr Ni Cd
Figure Metal removal efficiency using different process fluids (W2: deionized water; CIT4: 0.2M citric acid; EDTA1: 0.2M EDTA)
[1]
[2]
Ceremigna, D., Polettini, A., Pomi, R., Rolle, E., De Propris, L., Gabellini, M., Tornato, A. Comparing sediment washing yields using traditional and innovative biodegradable chelating agents, Proc. 3rd International Conference on Remediation of Contaminated Sediments, New Orleans, Louisiana, USA, January 24-27, 2005. Ceremigna, D., Polettini, A., Pomi, R., Rolle, E., De Propris, L., Gabellini, M., Tornato, A. A kinetic study of chelant-assisted remediation of contaminated dredged sediment, submitted to J. Hazard. Mater., 2005.
28
29
BENCH SCALE EVALUATION OF HEXAVALENT CHROMIUM REDUCTION AND CONTAINMENT USING FIRS (FERRIC IRON REMEDIATION AND STABILISATION) TECHNOLOGY
Anne Hansena, Laurence Hopkinsonb, Andrew Cundyb, Ross Pollocka a Churngold Remediation Limited, St Andrews House, St Andrews Road, Avonmouth, Bristol,BS11 9DQ, UK; bSchool of the Environment, Civil Engineering Division, University of Brighton, Moulscoomb, Brighton, BN2 4GJ, UK E-mail: anne.hansen@churngold.com Introduction The aim of this study was to investigate if FIRS, a novel electrokinetic technique, can be used to reduce the carcinogenic and mobile Cr(VI) to the less toxic and less mobile Cr(III), and lock up the Cr(III) in iron. FIRS is a, low energy contaminant reduction/containment technique that has the potential to be used to remediate heavy metal contaminated soils and sediments. The FIRS technique involves the application of a low magnitude direct electric potential between opposite polarity iron electrodes emplaced in or either side of a contaminated soil or sediment. The electric potential is used to generate a strong pH (and Eh) gradient within the soil column, promote dissolution of the anodic electrode(s) and force the precipitation of an iron rich barrier in the soil at the point of the pH jump. The iron-band generated by the technique contains iron in its elemental Fe, Fe(II) and Fe(III) valence states[1], held within a variety of iron mineral phases, which constitute the precipitated iron stone barrier. Chromium usually exists in two different valences in the near surface environment; Cr(III) and Cr(VI), depending on the redox state of the local environment. Cr(III) exists as cations, while Cr(VI) usually existed as toxic oxyanions. Cr(VI) species are soluble over a wide pH range and will migrate towards the anode during electrokinetic treatment [2]. It has been estblished that reduction of Cr(VI)in the presence of Fe(II)occurs instantaneously as shown by the following reaction: Cr2O7 +14H + +6 Fe2+
2-
2Cr
3+
+ 6 Fe + 7H2O
3+
When Cr(VI) enters the acid anode zone, developed by the FIRS technology, it comes into contact with Fe(II), which is migrating in solution, away from the dissolving anodic electrode(s) and is reduced to less mobile Cr(III) which accumulates near the anode electrode, Fe(II) and Feo is simultaneously oxidised, and stable inert Cr(III) bearing ferric iron mineral phases are produced. Presented below are the results of a laboratory experiment on the remediation properties of FIRS, with respect to Cr(VI) contaminated soils. Chemical analyses were conducted at a certified laboratory. Results 50kg soil was treated in a 700mmx300mmx300mm test cell. The initial concentration of total Cr and Cr(VI) in the soil was 9300mg/kg soil 740mg/kg respectively. After running the experiment for 5 weeks at 75V the concentration of Cr(VI) was 240 mg/kg and 35 mg/kg near the anode and cathode respectively. Concentration of total Cr was 24000 mg/kg and 6300mg/kg near the anode and cathode respectively. The results are presented in figures 1 and 2. These figures show the initial concentrations and the concentrations across the experimental cell after 5 weeks.
31
20000
mg/kg
5cm
Initial conc.
Total Cr
The experiment was terminated before an iron band had formed. Scanning electron microscopy (SEM) reveals the presence of abundant chromium bearing iron minerals within the treated soil (Figure 3).
Figure 3 SEM photo and graph In summary the experiment results show that FIRS treatment, over comparatively short experimental time frames has resulted in a 96% reduction in the concentration of Cr(VI) within the soil, and an 27% build up of precipitated iron within the anodic compartment, association with an 100% build up of chromium within the same zone. Moreover, SEM images suggest that the precipitated chromium is locked up in poorly crystalline fine grained iron-rich minerals. Conclusions While the efficiency of all electrokinetic techniques are in measure a function of soilspecific properties, e.g., buffering capacity, etc, the experimental results are highly promising in that they clearly show that FIRS shows considerable potential to remediate Cr(VI) contaminated soil and groundwater. An in-situ pilot scale test is being developed to follow up these results [1] A.B Cundy and L. Hopkinson, Applied Geochemistry.20 (2005) 841-848. [2] K.R. Reddy and S. Chinthamreddy, Advances in Environmental Research. 7 (2003) 353365 [3] K.R. Reddy, U.S. Parupudi, S.N. Devulapalli, C.Y. Xu, J. Hazard. Mater.55 (1997) 135158
32
Oral Contributions to
session 3 New Applications Inorganic Pollutants
35
It was determined that the redox potential reduced across the soil bed from anode to cathode, indicative of nano-iron transport from anode to cathode, as shown in Figure 1. The presence of nano-iron pushed the redox potential to higher positive values at low pH (anode side), while lowering it to higher negative values at high pH (cathode side) than the electrokinetic effects alone. The diffusion of nano-iron without the electrical field showed no activation of the iron, as indicated by little or no change in the redox potential for the diffusion sample in Figure 1. These results showed that nano-iron was both transported and activated by the applied electrical field.
Figure 1: Redox Potential vs. Distance - Test Comparison The electrokinetically enhanced transport and activation of nano-iron were evidenced by the higher negative potentials achieved in nano-iron specimens on the cathode side, at the same pH for the same test durations of the control specimens. Figure 2 shows the variation of redox potential (Eh) versus pH. The variation of Eh vs. pH in the electrokinetics only specimen follows closely the lower bound for electrolysis of water, while when nano-iron is transported using electrokinetics the system displays higher oxidation potential for iron.
(a)
(b)
Figure 4: Soil Bed at 46.0 hrs (a) Diffusion Only (b) Electrokinetically Enhanced ______________________________________________________________________ [1] Pamukcu, S., Weeks, A., and Wittle, Kenneth J. (2004). Enhanced Reduction of Cr (VI) by Direct Electric Field in a Contaminated Clay. Environ. Sci. Technol., 38, 1236-1241. [2] Sun, Y.P., Li, X.Q., Cao, J., Zhang, W.X , and Wang, H.P. (2006). Characterization of Zero-valent Iron Nanoparticles. Advances in Colloid and Interface Science, 120:47-56.
36
In the middle of many cities company grounds are situated of former gas plants. The gas plants have been used for decades in the previous century. Today, the gas plants are closed or used as storage or parking place. Many municipalities are planning to redevelop these areas for living or shopping areas. However, the soil is heavily contaminated with PAH, mineral oil, acids and very common cyanide. The gas factories have produced city gas by transforming coal into gas. During this process, the gas had to be cleaned before use. One of the pollutants is hydrocyanic. It has been removed by dry washing of the gas with ferruginous earth (bog ore). Hydrocyanic will react with iron and form iron cyanide complexes. The ferruginous earth has been regenerated many times. When the activity of ferruginous earth has been reduced, the earth will be sold or used as raising material around the factory. The ferruginous earth contains after use about 10 % iron cyanide complexes. The iron cyanide complexes will dissolve during by the weather conditions and start to spread over the site through water canals and through pores of the soil. Today, the cyanide will be mainly present as iron cyanide complexes (such as Berlins Blue), thiocyanate and the very soluble ionic cyanide. Especially free cyanide could spread very easily through the soil. Due to the great interest in redeveloping these plants, effective and economic solutions are required. One common method is excavation of the whole plant. Especially, PAH and tar should be treated by excavation. However, cyanide soluble in groundwater could be present in a big volume and at great depths. Therefore, a in situ method will be desirable. Holland Milieutechniek has developed and successfully applied the in situ Electro-Reclamation method for the cyanide contaminants. Electro-Reclamation is developed as an in situ method for removing contaminants like heavy metals, cyanides and other electrical charged components from low permeable soil types. Electrodes are installed in the contaminated soil and by creating a DC current electrical charged particles like ions and ion complexes will move to and captured at the special designed electrodes. Electro-Reclamation can easily take out the ionic cyanide and thiocyanate. But low soluble iron cyanide complexes, such as Berlins Blue have to be transformed in ionic form before they can be transported to the electrodes. Laboratory and field research, has shown that the Berlins Blue complex could easily dissolve at a pH of 7 or higher. Therefore, the pH of the soil has to be increased. Electro Reclamation can also be used
37
as an in situ method to change the soil pH. In this way the soil pH could be increased and the Berlins blue will dissolve in iron and ionic cyanide complexes which will be transported by the electro kinetic processes. Holland Milieutechniek has tested the technology in the laboratory and proven the proper working of this method. Efficiency up to 99% is common in all types of soil. Therefore, the method has been demonstrate in a pilot, which was successful. ElectroReclamation has shown to overcome the impossibilities of iron cyanide complexes and will have great opportunities to be the in situ method of cyanide contaminations.
38
ELECTROKINETICALLY ENHANCED REMOVAL AND DEGRADATION OF NITRATE IN THE SUBSURFACE USING NANOSIZED Pd/Fe SLURRY
Gordon C . C. Yanga, Chih-Hsiung Hunga, Hsiu-Chuan Tua a Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan. E-mail: gordon@mail.nsysu.edu.tw 1. Introduction In recent years injection of nanoiron (nanoscale zero-valent iron) slurry to the groundwater for remediation of various contaminants (e.g., trichloroehylene, nitrate, and pesticides) has been demonstrated in more than 20 sites worldwide [1]. However, only limited studies had forcused on the transport of nanoiron in the subsurface environment [2, 3]. Yang [2] employed a slurry of nanoiron modified by an anioinc surfactant to evaluate its ability to transport through vertical and horizontal soil columns. It was found that the specific nanoiron slurry could easily travel through a 15cm vertical silica sand column without difficulty. However, it took more than 25 hr to travel through the same vertical column filled with a real loamy sand soil. Based on the experimental data and deep-bed filtration theory, a sticking coefficient was calculated. Further, a transport distance of 0.25 m was estimated for such nanoiron slurry to travel under typical groundwater conditions. An additional study conducted in a horizontal loamy sand column saturated with a simulated groundwater by applying an electric field gradient of 1 V/cm revealed that the transport distance of the nanoiron slurry was 10fold greater. After analyzing the mass balance of iron, it was postulated that a certain amount of nanoiron had been transported in the groundwater saturated loamy sand by the electroosmotic flow. In a separate laboratory-scale study [4] using a hybrid technology of injecting surface-modified nanoscale Pd/Fe slurry into the anode reservoir of an electrokinetic (EK) remediation system, it was found that 92.44% of trichloroethylene (TCE) in the loamy sand soil body has been degraded as compared with the blank test of 2.09% reduction in TCE due to evaporation during the 6-day test period. This work was aimed to further evaluate the effectiveness of in situ removal and degradation of nitrate in the subsurface using the slurry of Pd/Fe bimetallic nanoparticles under an electric field. 2. Experimental All chemicals used in this work are reagent grade unless otherwise specified. The same surface-modified nanoscale Pd/Fe slurry as used elsewhere [4] was selected and tested in this work. Fig. 1 shows the schematic diagram of the EK system used in this work. In which, the soil compartment was packed with a simulated nitrate-contaminated loamy sand (850 g soil + 150 mL of nitrate solution having a concentration of 150 mg/L) that was saturated with a simulated groundwater. Except Test 1 (i.e., applying only electric field without any addition of dispersant), in all other tests (see Fig. 1) a daily addition of 20 mL of surface-modified nanoscale Pd/Fe slurry (@ 4 g/L) was practiced. More specifically, 10 mL/day of the aformentioned slurry was added to each injection port for Tests 4 and 5. In all tests, a constant electric field gradient of 1 V/cm and treatment time of 6 days were employed.
39
P ow er S u pply
A
Test 4 Test 2
Test 5 Test 3
(-)
C a th o d e R eserv o ir
Fig. 1. The schematic diagram showing the electrokinetic remediation system and slurry injection locations for various tests 3. Results and Discussion In the case of applying EK alone (i.e., Test 1), about 90% of nitrate was removed from the soil compartment to the anode reservoir. The EK results for Tests 2-5 are shown in Fig. 2. Test 4 was found to yield the best result of nitrate removal and degradation.
3 000
2 500
5 4 3 2
2 000
1 500
1 000
500
A n od e R eserv oir
A -05
A -10
A -15
P osition
Fig. 2. Residual nitrate in different locations of the electrode reservoirs and soil compartment for Tests 2-5. 4. Conclusions By injecting 0.05 wt% of surface-modified nanoscale Pd/Fe slurry into the anode reservoir of the EK system an over 99.2% efficiency of nitrate removal and degradation for the entire system was achieved. The cathode reservoir is the worst injection spot. [1] Li, X.Q.; Elliott, D.W.; Zhang, W.X. Zero-valent iron nanoparticles for abatement of environmental pollutants: materials and engineering aspects, Crit. Rev. Solid State Mat. Sci. 2006, 31, 111-122. [2] Yang, G.C.C. In Stability of Nanoiron Slurries and Their Transport in the Subsurface Environment, Proceedings of International Symposium on Environmental Implications and Applications of Nano-sized Materials, Taichung, Taiwan, Dec. 1415, 2006. [3] Saleh, N.; Sirk, K.; Liu, Y.; Phenrat, T.; Dufour, B.; Matyjaszewski, K.; Tilton, R.; Lowry, G.V. Surface modifications enhance nanoiron transport and DNAPL targeting in saturated porous media, Environ. Eng. Sci. 2007, 24, 45-57. [4] Yang, G.C.C.; Chang, D.G. Degradation of trichloroethylene in the subsurface by nanoscale bimetallic Pd/Fe slurry under an electric field. In EnviroNano 2006, Yang, G.C.C. Ed.; Kaohsiung, Taiwan, 2006; 40-47.
40
Figure N1. Upper view of Electro-Fentons reactor Figure N2. Vertical view of Electro-Fentons reactor
41
Background The Fentons main reactions are showed in the following equations proposed by Cheves Walling [4]:
(1) H 2 O 2 + Fe + 2 Fe + 3 + HO ( 2 ) HO ( 3 i ) HO ( 3 j ) HO
* k1
+ HO
+ Fe + 2 Fe + 3 + HO + R i H H 2 O + Ri *
k3i
k2
+ R j H H 2 O + Rj *
k3
Fentons reagent is a strong oxidizing agent, because of the OH radicals produced in (1). Its oxidizing rate is 2.06 times Chlorine (Cl2) relative oxidation power. The oxidation occurred mostly close to the layers of the electrolytes. Considering Grahames Double Layer schema it occurred in the Internal Region, between the Internal and External Helmholtz Even Layer. Because of the less amount of catalyst, Fe+2, the oxidation in the External Region had a slower oxidation rate. The Electro-Fenton reactor was proved varying a) the Ferrous ion concentration ([Fe+2]), b) the Spent Caustics initial Temperature and c) the initial pH. Results Removal of close to 95% of the COD was achieved with a pH of 4, a temperature of 30C and 100 [mg/L] of Fe+2(1[A]). The treatment time was between 10 to 60 minutes, showing that 40 minutes was suffiencient for efficient treatment. Phenol content was equally reduced with 95 %. Conclusions The removal of COD showed that Electro-Fentons reactor is a very useful process for this waste treatment. Its safety and costs advantages make it a process that has to be considered in Petroleum Refineries.
[1]
Cordonnier, F.B.a.J., Refining, Petrochemicals and Gas Processing Techniques. INDUSTRIAL WATER TREATMENT. 1 ed. Vol. 1. 1995, Houston, Texas, USA: Gulf Publishing Company. 248. ENAP Refinerias Aconcagua, I.d.P., Produccion de Sodas Gastadas. 2005: Con Con. Nikolai Markovich Emanuel, E.T.D., Zinada Kushelevna Maizus, Liquid-Phase Oxidation of Hydrocarbons. 1st ed. 1967, Moscow, USSR: Plenum Press. Walling, C., Fenton's Reagent Revisited. Acc. Chem. Res., 1974. 8: p. 125. Weng, S.-H.S.a.H.-S., Treatment of Olefin Plant Spent Caustic by Combination of Neutralization and Fenton Reaction. Water Research, Elsevier Science Ltd., 2000. 35: p. 2017-2021.
42
43
Water Chambers
Industrial Filters Anode Cathode Power Supply Clay Specimen Collecting Beaker
FIGURE 1. Electrokinetic Treatment Arrangement with the Consolidated Clay Specimen Formed and the Solid Tank Base in Position.
14
12
10
Control
6
0 45 50 55 60 65 70
FIGURE 2. Relationship between Soil Undrained Shear Strength and Water Content (NB The control data are for untreated clay consolidated from a slurry to different water contents)
44
0.5 0.4 - Imaginary part 0.3 0.2 0.1 40 MHz 0.0 0.0 2 days 28 days
0.2 0.1
28 days 24 weeks
100 Hz
100 Hz
0.2
0.3
0.4
2
0.5
0.1
0.2
0.3
0.4
-2
0.5
Real Part / k . cm
Real part / k cm
Figure 1. Nyquist spectra from natural diffusion (left) and migration experiments (right) through a mortar sample. Finally, MIP results corroborate EIS measurements. After migration experiments an important increase on the capillary pore size (10-100 nm) is detected. However, after natural diffusion tests no relevant variations are found.
M. Keddam, H. Takenouti, X. R. Nvoa, C. Andrade, C. Alonso, Cem. Concr. Res. 27, 1191 (1997). 2 C. Andrade, V. M. Blanco, A. Collazo, M. Keddam, X. R. Nvoa, H. Takenouti, Electrochim. Acta 44, 4313 (1999). 3 M. Cabeza, M. Keddam, X. R. Nvoa, I. Snchez, H. Takenouti, Electrochim. Acta 51, 1831 (2006).
46
EFFECT OF THE ELECTROLYSIS TIME IN THE MOVEMENT OF NITRATES IN AN ANDISOL OF ANTIOQUIA (COLOMBIA)
Diego A. Vascoa, Felipe Hernndez-Luisb, Carmen D. Arbeloc, Mario V. Vzqueza* a Instituto de Qumica, Univ. de Antioquia, A.A. 1226, Medelln, Colombia b Departamento de Qumica Fsica, Univ. de La Laguna, 38206 Tenerife, Espaa c Departamento de Edafologa y Geologa, Univ. de La Laguna, 38206 Tenerife, Espaa Introduction The electrorremediation has been used in the last years as method of decontamination of soils, taking advantage that the application of an electrical field gives origin to a series of phenomena of transport that propitiate the pollutants' removal [1] And also has proved to be a useful in order to obtain parameters of agricultural interest [2]. The use of fertilizers in excess can provoke alterations in the environment that they can affect even the human health. These fertilizers can drive, for example, to an important increase in the concentration of nitrates in the solution of soil. Given the high solubility of this ion and his low retention for the soils can accumulate in the residual waters, being the agricultural practices the principal pollution source in this respect. Due to their charge it is possible to study his movement by means of the use of electrical fields. These kind of studies of electro-migration have been reported in different types of soils [3, 4] In the present work results obtained in the study of mobility of ions nitrate in samples of Andisol from the Department of Antioquia, a zone where takes place an important activity of culture of flowers, are presented. Experimental The samples of soils were prepared following the procedure developed in the laboratory [1,2]. It consists basically of the preparation of a humid paste that is left to balance 24 hours before beginning the electrokinetic study. This paste is incorporated later into the electrorremediation cells where an electrical field of 1,20V.cm-1 is applied. This study was realized to different conditions, treatment time, nitrate concentrations, etc. After the electrochemical treatment, the samples were fragmented to be able to evaluate the residual composition of nitrate to different distances of the electrodes. This quantification is obtained by means of the employment of a solution extractante the posterior evaluation using a selective electrode to ions nitrate. On the other hand pH, conductivity and electrolysis current variation was evaluated. These electrodynamics studies, they were compared with analysis of movement of nitrate in columns of the soil under study. All the experiments were performed by duplicate. Discussion The following figures show the pH variation inside the soil after the electrochemical experiment as well as the electrolysis current variation during the treatment. For comparison the results obtained with a soil without nitrate ion added is presented.
47
0,200 8,00 6,00 pH 4,00 2,00 1 2 3 4 5 relative position to cathode 0,150 0,100 I (mA) 0,050 10 20 30 40 50 Time (h)
KNO3 100ppm Blank
Residual pH at different position from the electrode and electrolysis current variation during de treatment Chamber [NO3-], M Anode 0.01580 Cathode 0.00016 Nitrate concentration at the electrode chambers after the electrochemical treatment In spite of the major content of ions when nitrate ion is present, the regulatory capacity of the soil keeps the pH invariable, though there is an important increase of the current of electrolysis. The analysis of the residual nitrate concentration in the electrode chamber after the treatment allows verify the effect of the electrical field applied to mobilize the pollutant. References [1] Vzquez MV, Hernndez-Luis F, Lemus M, Arbelo CD. Integral Analysis of the Process of Electro-Remediation of Andisols Polluted by Heavy Metals. Portugaliae Electrochimica Acta 2004; 22: 387-398. [2] M.V.Vazquez, F.Hernndez-Luis, D. Benjumea, D.Grandoso, M.Lemus, C.D.Arbelo; Science of the Total Environment (2007) in press [3] N. Eid, W.Elshorbagy, D.Larson, D.Slack; Journal of Hazardous Materials, B79(2000)133-149. [4] T.B.S. Rajput, N. Patel; Agricultural Water Management 79(2006)293-311
48
49
EF process increases within the pH range 2-3, whereas the effectiveness of the PEF process increases substantially when the current applied to electrodes is increased. In addition, minimum cost of both processes for an acceptable COD removal varies between 2.5$ and 4$ for per kg COD removal from the landfill leachate.
pH Value
1,5 20 2,0 2,5 3,0 3,5 4,0 4,5 20 1,5 20 2,0 2,5
pH Value
3,0 3,5 4,0 4,5 20
15
$ / kg COD removal
$ / kg COD removal
$ / kg COD removal
10
10
10
10
a)
0,5 1,0 1,5 2,0 2,5 3,0
b)
0,5 1,0 1,5 2,0 2,5 3,0
0 0,0
0 3,5
0 0,0
0 3,5
Current (A)
0 500 1000 1500 2000 2500 3000 3500 0 500 1000
Current (A)
1500 2000 2500 3000 3500
H 2 O 2 Concentration (m g/L)
H 2 O 2 Concentration (m g/L)
Fig.1. The effects of the operating parameters of the EF (a) and the PEF (b) processes on the costs of the per kg COD removal.
In order to determine the percents of the cost items within the total costs of both processes, several calculations were done and the results are given in the Table 1. According to the results, the COD removal of the PEF process is 22.5% higher than that of the EF process for initial H2O2: 2500 mg.L-1, whereas the total costs of both processes are much closed. Another important result concluded from the table is that the costs of H2O2 consumptions are 86.9% and 93.2% of the total costs for the EF and the PEF processes, respectively.
Table 1. The effects of the cost items on the total costs of the both processes for different H2O2 concentrations (Test conditions; current: 2A, initial pH: 3) Used H2O2 (mg.L-1) 1500 2000 2500 1500 2000 2500 Energy (%) 6.8 5.5 5.1 6.7 3.0 2.7
3 H2O2 (%) Electrode (%) Total cost ($/m ) COD removal (%) Photoelectro-Fenton (PEF) Process 83.3 9.9 8.7 79.4 85.9 8.5 11.3 85.1 86.9 8.0 13.9 94.4 Electro-Fenton (EF) Process 86.9 6.4 8.4 60.8 91.9 5.0 10.5 70.4 93.2 4.1 13.0 71.9
CONCLUSION Based on the results, it may be concluded that the PEF process can be proposed as a promising approach for treatment of the landfill leachates, when it is compared to EF process. Although, the high operating costs of the PEF process due to high concentrations of used H2O2 limits its commercial usage, it can be applied for the treatment of wastewaters heavily polluted with organic compounds.
[1] S. Irmak, H.I. Yavuz, O. Erbatur, Degradation of 4-chloro-2-methylphenol in aqueous solution by electro-Fenton and photoelectro-Fenton processes, Appl. Cataly. B-Environ. 63(3-4) 2006 243-248. [2] APHA-AWWA-WEF, Standard Methods for the Examination of Water and Wastewater, nineteenth ed., Am. Public Health Assoc., Washington, DC, 1995.
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$ / kg COD removal
Oral Contributions to
session 4 New Applications - Bioremediation
An integrated Bio-Electro-process for groundwater remediation is developed in order to stimulate microbial degradation of groundwater contaminants by the application of electrodes in the subsurface. The main focus in this project is on chloroethenes as these compounds occur at the most contaminated sites and are known to form groundwater plumes of several kilometres (Wiedemeier et al., 1999; Bradley, 2003). Microbial degradation of chloroethenes has repeatedly been demonstrated during the last years. The degradation mechanisms comprise (i) anaerobic reductive dechlorination (e.g. halorespiration) of perchloroethene (PCE) and trichloroethene (TCE) with hydrogen as electron donor and (ii) oxidative dechlorination in particular of cisdichloroethene (DCE) and vinyl chloride (VC) using oxygen as electron acceptor. Under in-situ conditions, a limited availability of electron donors and acceptors results in limited bioremediation efficacy (Tiehm et al., 2002). The scope of this study was on the selection of a suitable electrode material for electrolytical hydrogen and oxygen formation without undesirable side reactions. For example, previous studies indicated that some side reaction products generated at the electrodes have detrimental effects on microbial VC degradation activity (Lohner et al., 2005). Therefore, inhibiting and competitive reactions such as chlorine formation, nitrate reduction, precipitation of carbonates, and corrosion had to be considered. Different electrode materials like dimension stable anodes (DSA: titanium with specific oxide coatings), stainless steel, graphite, vitreous carbon and others were tested according to these criteria. The reactivity of the electrode materials was characterized by cyclic voltammetry and by chemical analysis of reaction products (e.g. hydrogen, hydrogen peroxide, oxygen, chlorine) in mineral medium simulating worst case electrolysis conditions (app. 4 mA/cm2 current density, 100 mg/L chloride concentration). The experiments demonstrated that the side reactions differed significantly depending on the material composition of the electrodes. At the cathode only minor side reactions could be observed, the main reaction was hydrogen production. However, at graphite, vitreous carbon and some DSA electrodes (depending on their coating composition) significant amounts of hydrogen peroxide were detected as these materials have a high overpotential for hydrogen generation. Precipitation reactions at the cathode were detected but did not affect the hydrogen generation efficiency. Nitrate reduction was not observed under the applied experimental conditions.
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The rate of oxygen generation was similar at most electrode materials. Only at graphite and vitreous carbon very low oxygen formation efficiencies were measured. Chlorine formation and corrosion proved to be the most important anodic side reactions. Chlorine generation was most pronounced at the DSA electrodes and increased with increasing current density and chloride concentration in the electrolyte. Minor corrosion was observed when stainless steel was used as anode material, even at high current densities. The results show that the selection criteria for a suitable electrode material were best fulfilled with stainless steel electrodes which had a good hydrogen and oxygen generation efficiency and did not show significant chlorine and hydrogen peroxide production. Corrosion can be minimized when using low current densities as they are used in the Bio-Electro-process. DSA electrodes were less suitable because of their high chlorine and hydrogen peroxide formation rates. Vitreous carbon and graphite did not show high hydrogen and oxygen production efficiencies, in addition high hydrogen peroxide concentrations were measured at these materials. In conclusion, stainless steel proved to be the best material for the application in microbiological remediation systems. Therefore this material was used in further studies combining electrolysis with microbial degradation.
Acknowledgement: We gratefully acknowledge financial support by the Federal Ministry of Economics and Technology and the German Federation of Industrial Research Associations "Otto von Guericke" e.V. (AiF) (Frderkennzeichen: 150 ZN)
[1] Wiedemeier T.H., Rifai H.S., Newell C.J., Wilson J.T. (1999) Natural attenuation of fuels and chlorinated solvents in the subsurface, John Wiley & Sons, Inc., New York [2] Bradley P.M. (2003) History and ecology of chlorethene biodegradation: A review. Bioremediation Journal 7(2): 81-109 [3] Tiehm A., Gozan M., Mller A., Schell H., Lorbeer H., Werner P. (2002) Sequential anaerobic/aerobic biodegradation of chlorinated hydrocarbons in activated carbon barriers. Water Science & Technology: Water Supply 2(2): 51-58 [4] Lohner S.T., Tiehm A. (2005) Influence of electric fields on VC dechlorinating microorganisms. In: 5th Symposium on Electrokinetic Remediation (EREM), Fundamental and Industrial Aspects (book of abstracts), Ferrara/Italy, 22-25 May 2005, 40
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ELECTRO-BIOREMEDIATION: INFLUENCE OF DIRECT CURRENT ON THE PHYSIOLOGY AND DISPERSION OF POLLUTANT DEGRADING BACTERIA IN MODEL SOIL
Lei Shi, Susann Mller, Hauke Harms, Lukas Y. Wick UFZ Helmholtz-Center for Environmental Research, Department of Environmental Microbiology, 04318 Leipzig, Germany; E-mail: lukas.wick@ufz.de Heterogeneous distribution of hydrophobic organic contaminants (HOC) and HOC-degrading organisms limits the bioavailability and bioremediation efficiency of soil-bound HOC. As a consequence there has been increasing interest in employing electro-bioremediation, a hybrid technology of bioremediation and electrokinetics, to overcome the limited HOC-bioavailability by physically homogenizing both immobilised microorganisms and diffusion-retarded HOC. For in-situ electrobioremediation small scale dispersion of HOC is intended rather than macroscopic HOC-transport (HOC-extraction), as bacteria are ubiquitous in soil. Assuming average separation distances of 100 microns [1] between individual bacterial microcolonies, short distance transport may drastically improve the contact between pollutant molecules and bacteria and, concomitantly, biodegradation [2]. Present electrobioremediation approaches mainly aim at pollutant transport over large distances and tend to neglect both the impact of direct current (DC) on organism-soil interactions and microscale HOC release rates. Accordingly, few data are available on bioavailability changes acting via DC-driven effects on organismcompound and organismsoil-interactions. However, detailed investigations of the influences of weak electric fields on the relevant bioremediation processes of soil-bound HOC, in particular its influence on microbial physiology and the physico-chemistry of organismmatrix and organismcompound interactions, are scarce [3]. Up to now, investigations of the impact of weak electric fields on microorganism-matrix interactions have solely focused on the electrokinetics-driven bacterial transport in subsurface, as a result of either electrophoretic movement of negatively charged bacteria to anode and/or electroosmotically-stimulated bacterial translocation to the cathode. Detailed studies of population-heterogeneity-based bacterial electrokinetic dispersion, and dispersioninduced bacterial adhesion and cell physiology changes are still missing. Here we present an extended investigation of the role of electrokinetics on bacterial subsurface behaviors, namely population-heterogeneity-based dispersion, adhesion and cell physiology, of fluorene-degrading sphingomonads in bench scale model aquifers filled with glass beads in presence of weak electric field (1 V cm-1). Flow cytometry was applied to quantify the total number of cells, cell size, as well as the propidium iodide (PI) uptake and the DNA-patterns on a single-cell level. Furthermore, as highly transport relevant cell properties, the physico-chemical cell surface characteristics (surface hydrophobicity and charge) were investigated by contact angle and zeta potential measurements. No negative effects of DC on the cells physiology were found. During 15.5 h of DC-treatment 57% of all cells recovered were dispersed at the centimetre-scale relative to 27% in the absence of DC leading to an approximately sevenfold enhanced DC-driven homogenization efficiency relative to bacteria dispersed by bulk random motility only. Interestingly however, cells mobilised by electrophoresis and electroosmosis exhibited significantly changed adhesion
57
properties. No overall negative effect of DC on the cell viability was found as 6.8% of the DC-treated bacteria exhibited PI-staining relative to 6.0% in the control. Minor differences however were observed in the sub-population that had been mobilised by electroosmosis exhibiting an about two-fold increased PI-% relative to the control. Enhanced PI-staining however did not correlate with reduced culturability of the cells on rich medium agar plates; Relative to the control DC-treated cells mobilised by electroosmosis were even three-fold more culturable and confirm earlier data that PIpermeability does not always indicate reduced viability of oligotrophic environmental bacteria [4]. Our findings thus suggest that electroosmosis is a valuable mechanism to transport viable and culturable PAH-degrading bacteria in the subsurface. Whereas our studies have demonstrated an effective DC-driven homogenization of physiologically active bacteria on the mesoscale, the main thrust of our ongoing research lies in the investigation of the electrokinetic influence at the microscale, i.e. the homogenization processes at the soil pore-water interfaces.
[1] T.N.P. Bosma, P.J.M. Middeldorp, G. Schraa, A.J.B. Zehnder, Environ. Sci. Technol. 31 (1997) 248. [2] K.T. Semple, A.W.J. Morriss, G.I. Paton, Europ. J. Soil Sci. 54 (2003) 809. [3] L.Y. Wick, L. Shi, H. Harms, Electrochim. Acta. 52 (2007) 3441. [4] L. Shi, S. Gnther, T. Hbschmann, L.Y. Wick, H. Harms, S. Mller, Cytometry A (2007), in press.
58
University of Manitoba, School of Engineering, Winnipeg, Canada, R3T 5V6 Tulane School of Public Health and Tropical Medicine, New Orleans, LA, USA
Municipal wastewater treatment facilities convert soluble organics into biosolids. Millions of tons of this nutrient-rich material are being added to soil each year. The governmental agencies in North America encourage biosolids recycling. US EPA (40 CFR Part 503) regulations for the use and disposal of sewage sludge, defines two types of biosolids with respect to pathogen reduction: Class A and Class B. Class A biosolids can be applied in the same way as commercial fertilizer, without the restrictions that govern Class B sludge. Class A status can be achieved by decreasing helminthes, viruses and pathogenic bacteria counts below threshold levels or maintaining certain conditions of e.g. time, temperature or pH. A considerable effort has been made to identify indicator microorganisms whose presence would suggest that human pathogens might also be present. Clostridium perfringens has been suggested as a better indicator organism to assess the efficiency of biosolids disinfection while screening for parasites that may or may not be present. C. perfringens is a spore-forming thermophilic bacterium and has been suggested as an indicator for inactiavtion mechanisms other than temperature (as it is resistant to temperature). This organism is found in densities of 106 colony forming units (CFUs) per gram of solids in raw biosolids and has been suggested as an excellent surrogate for the Ascaris ova in biological systems such as composting and anaerobic digestion. C. perfringens spores exhibits similar resistance to physical and chemical agents and is hardier than Ascaris in high temperatures. Our previous research showed that Electrokinetics (EK) successfully inactivate total coliforms (TC) in sewage sludge; the aim of this study was to examine the impact of EK on C. perfringens vis a vis criteria for Class A biosolids. In order to assess different stressors affecting the inactivation of C. perfringens, series of electrokinetic cells, filled with anaerobically digested sludge were investigated in bench scale in an attempt to simulate possible future full scale process. A number of factors including electric field strengths, enhancement of oxidizing conditions, duration of exposure, and response to different conditioners were investigated. The pH, electrical parameters, as well as quality of catholyte and anolyte were measured daily. Total volatile fatty acids, total solids content, phosphorus and nitrogen compounds were analyzed after each treatment. The enumeration of the fecal coliforms (FC) and spores of C. perfringens in treated sewage sludge was carried out by M-CF method and non-commercial Tryptose-sulfite-cycloserine (TSC) agar culture medium, respectively. Result showed a relationship between C. perfringen inactivation and type of oxidants, pH gradient, and electric field strength. A decrease in volatile solids, nutrients and phosphorus contents were observed in all electrokinetic cells. No viable FC was observed in treated sludge. The electrokinetic method was demonstrated to be a successful technique for biosolids disinfections.
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Figure 1: Experiment set up with potato plants under three different treatments
Nine potato tubers were planted in nine experimental vessels (each 340 x 340 x 280 mm) filled with soil from a cultivated area near a metal smelter in Nordenham/Germany. The experiment was conducted in a chamber under artificial light at the University of Applied Sciences in Emden/Germany. Thirty days after the tubers were planted, direct current (DC) was applied in three vessels, and alternating current (AC) was applied in another three vessels. Three vessels without electrical fields were used as the control (figure 1). The electrical fields were applied for 60 days and the current was kept about 500 mA until harvesting. The soil profiles were investigated for one of the AC and one of the DC vessels. Plant physiological parameters, such as water content, chlorophyll content and biomass production were determined. The metal content of the soil and
61
plant samples were determined by flame AAS after microwave digestion. The pH in the soil profile samples was determined using a pH meter. Result and Discussion The water content and the chlorophyll content of leafs of plants growing under the electrical field (AC and DC) were higher than those without electrical treatment. The biomass production of the plants growing under AC treatment was the highest at 1.8 kg, followed by the control plant at 1.0 kg, and the plant growing under DC treatment at 0.75 kg.
Figure 2: Metal content in the potato plants under three different treatments
The plants growing under AC treatment had the highest metal content (Cu, Cd, Pb and Zn) compare to those under DC treatment or the control. When the biomass production and the metal contents are combined, the AC field showed the highest enhancement of phytoremediation. The plants growing under the DC treatment showed the lowest biomass production, Cd and Pb contents. This could be explained by the observed change of pH condition (3.8 near anode and 7.8 near cathode), resulting in inhibition of plant growth and metal uptake. Never the less, there was a higher Zn and Cu content in the plant under DC treatment than in the control plant. Conclusion Combination with electrical field application, especially using alternating currents, represents a promising approach to enhance the decontamination of metal polluted soils using phytoremediation. The application of direct current field requires optimisation in order to overcome the lower pH conditions induced and resulting phytotoxicity and potential metal mobility.
[1]
I. Raskin and B. Ensley (1999). 2nd Ed Phytoremediation of Toxic Metals: Using plants to Clean Up the Environment. Wiley & Sons. [2] Luo Q S, Zhang X, Wang H and Qian Y, (2005). Journal of Hazardous Materials B121: 187-194. [3] OConnor C S, Lepp N W, Edwards R and Sunderland G, (2003). Environ. Moni. And Ass. 84: 141-158.
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63
70 60 50 DCE (mg/L)
(b)
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Port 2 Port 4
control
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electrochemical injection
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5,000 4,000
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(c)
Lactate (mg/L)
7.3
pH
EC-B
Control A
Figure 2. Results from biological experiments (a) DCE in control, (b) DCE in electrochemical injection (EC-1), (c) Final pore water lactate (d) Final pH of Electrochemical (EC)and Control A
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Oral Contributions to
session 5 Organic Pollutants
INFLUENCE OF ELECTROOSMOTIC FLOW ON THE PAH RELEASE FROM MODEL SOIL MATRICES
Lei Shi, Hauke Harms, Lukas Wick UFZ Helmholtz-Center for Environmental Research, Department of Environmental Microbiology, 04318 Leipzig, Germany; E-mail: lei.shi@ufz.de The basic principles of electrokinetic extraction and the electrokinetically enhanced bioremediation of contaminants from fine-grained soil have been experimentally proven to be feasible. Although empirical electro-bioremediation appears to be safe, effective and economically interesting compared to other remediation techniques there is still a need for mechanistic understanding of the molecular processes affecting the release and transport of hydrophobic organic contaminants, such as polycyclic aromatic hydrocarbons (PAH) in soil. Due to their hydrophobicity PAH are mainly dissolved in non aqueous liquids (NAPL) or associated with the surface or the intra-particle pores of the solid phase in soil. Limited release of PAH has been proven to dramatically decrease the PAH-bioavailability, and consequently the efficiency of bioremediation. The release rate of PAHs from the solid to the aqueous phase is limited by the slow diffusion through the unstirred boundary layer around soil particle [1] or the stagnant water phase in intra-particle nanopores. Electroosmotic flow (EOF) is used in capillary electrochromatography (CEC) as a pumping aid instead of hydraulic flow (HF) to enhance mass transfer of solute between mobile and stationary phase [2]. Based on the knowledge from CEC, we hypothesize that EOF is likely to overcome mass-transfer bottlenecks in low permeable soil matrices by i) increasing the release of sorbates by inducing liquid flow at the immediate exterior of soil particles, ii) creating flow in nanopores in the organic sorbent phase, which are inaccessible by hydraulic flow, and iii) influencing the pore or surface diffusion among aggregated minerals [3]. Here we present an investigation of the effect of EOF on the dissolution and release of surface- and intra-particle-bound phenanthrene using well defined model aquifers of known solid matrix structures (e.g. alginate beads). EOF-facilitated PAH release was compared to the PAH release in presence of HF of similar flow rates (1 mL h-1). Our data indicate an approximately fourfold enhanced EOF-induced release of phenanthrene from alginate beads. This effect is explained by a (theoretically expected) significantly decreased thickness of effective diffusion layer of phenanthrene. Ongoing research focuses on EOF-facilitated phenanthrene release from intra-particle nanopores of well defined model aquifers with high tortuosity.
[1] P. Mayer, U. Karlson, P. Christensen, A. Johnsen, S. Trapp, Environmental Science and Technology 39 (2005) 6123. [2] M. M. Robson, M. G. Cikalo, P. Myers, M. R. Euerby, K. D. Bartle, Journal of Microcolumn Separations 9 (1997) 357. [3] L.Y. Wick, L. Shi, H. Harms, Electrochimica Acta 52 (2007) 3441.
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Abstract The contamination of soils, groundwater, and surface waters by chemicals used in agriculture is currently a significant concern. Many of these agrochemical compounds are considered a threat both to the environment and to biota. Molinate (S-ethyl N,Nhexamethylene-1-carbamate), an herbicide, is applied once a year to flooded fields during rice seeding to control the overgrowth of weeds. The removal of molinate was studied when submitted to an electric field. The applicability of the electrokinetic process in molinate soil remediation was evaluated. Two soils were used, being one of them spiked with molinate residues. Several electrokinetic experiments were carried out at a laboratory scale. Determination of molinate residues were performed by chromatography and mass spectrometry. The results show that the electrokinetic process is able to remove molinate in soil solution. A one-dimensional model was developed for simulating the electrokinetic treatment of a saturated soil containing molinate. The movement of molinate was modelized taking into account the diffusion transport resulting from molinate concentration gradients and the eventual reversed electroosmotic flow at acidic soil pH. Keywords Electroremediation, herbicides, modeling, soil
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71
Kaolin
HCB
0.01 M KCl
Kaolin
HCB
15
5 x 24
Kaolin
HCB
30
10 x 24
15 10 5 0 24 48 72 hours 96 120
24
48
72 hours
96
120
H Binso (m /kg C il g )
References [1] Chang, J.H., Qiang, Z, and Huang, C.P. 2006. Remediation and simulation of selected chlorinated organic solvents in unsaturated soil by a specific enhanced electrokinetics. Colloids and surfaces A: Physiochem. Eng. Aspects, Volume 287, Issues 1-3, 15 September 2006, Pages 86-93
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INTEGRATED ELECTROKINETIC PROCESS WITH BDD ELECTRODE FOR DEGRADATION OF PHENOL FROM CONTAMINATED SOIL
You-Jin Lee, Jong-Young Choi, Ji-Won Yang* Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), 373-1 Guseong-dong, Yuseong-gu, Daejeon, 305701, Republic of Korea E-mail: jwyang@kaist.ac.kr
1. Introduction Boron-doped diamond (BDD) electrode has received a great attention as a new anode material in an advanced electrochemical oxidation process because of its extremely wide electrochemical potential window and inert surface [1]. Many papers have reported that various organic contaminants, such as phenols [2] and dyes [3], are completely oxidized during electrolysis by BDD electrode. In this study, a new integrated electrokinetic process was proposed using BDD electrode as anode. It can not only separate organic contaminants from soil by inducing electrokinetic phenomena but also mineralize them electrochemically by producing oxidants on the surface of BDD electrode. To investigate the feasibility of the integrated process, electrokinetic tests using BDD electrode were performed for the remediation of phenol-contaminated soil and the results were compared with those of simple electrokinetic tests. 2. Materials and methods For the test, surface soil (< 1.00 mm) was artificially polluted with phenol and the initial concentration was about 200 ppm (mg/kg dry soil). A rectangular reactor (5*5*20 cm3) was used for both simple and integrated electrokinetic tests. It has a 10 cm-long soil compartment and two electrode chambers (100 mL) placed at each end. In integrated electrokinetic tests, BDD coated Niobium plate electrodes (Nb/BDD, 40*40*2 mm3) purchased from Fraunhofer IST (Germany) were used for anode and platinum coated stainless steel (S.S./Pt) electrodes were used for cathode. To enhance the electrochemical oxidation of organic pollutant in anode compartment, the effluent drained out from cathode reservoir by electroosmosis was circulated to anode reservoir. For a comparative purpose, simple electrokinetic tests were also conducted using S.S./Pt electrodes for both anode and cathode. A DC electric current was applied under the constant current condition, 10 mA or 20 mA, and 0.05 M K2HPO4 was used as an electrolyte. During the operation period, the variation of electric potential was observed and the phenol concentration in electrode reservoirs was measured periodically. After 10 days, to evaluate the removal efficiency, the residual amount of phenol in electrokinetic reactor was analyzed for each compartment: anode and cathode reservoirs, 10 sections of soil specimen, and effluent. [1] M. Panizza, G. Cerisola, Electrochim. Acta 51 (2005) 191. [2] P. Canizares, J. Lobato, R. Paz, M. A. Rodrigo, C. Saez, Water Res. 39 (2005) 2687. [3] X. Chen, G. Chen, Sep. Purif. Technol. 48 (2006) 45.
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3. Results and discussion The electric potential in the integrated system using BDD electrode changed just like that in the simple electrokinetic test. The power consumption was, therefore, almost same for 10 days and was only influenced by the applied current: about 40 and 180 Wh were used for 10 and 20 mA tests, respectively. In general, the velocity of electroosmotic flow is proportional to potential gradient. The higher current was applied, the more electroosmotic flow was produced. In the simple electrokinetic tests, the removal efficiency of phenol was affected by the accumulated amount of electroosmotic flow because phenol is relatively soluble in water. In the test of 20 mA, most of phenol was removed from soil and only 2.1 % remained. When BDD electrode was employed as anode in electrokinetic process, the residual amount of phenol in soil was almost same as that of the comparative test. While most of phenol was contained in effluent in the simple electrokinetic test, the contaminant was effectively degraded in the integrated process: 56.7 and 90.3 % of phenol were oxidized in the tests with 10 and 20 mA, respectively. It demonstrates that the integrated electrokinetic process with BDD electrode can effectively degrade organic contaminants from soil by controlling current density and operation time.
(a)
Anode reservoir Soil Cathode reservoir Effluent
(b)
22.3
8.9
81.5
24.3
5.8
56.7
13.2
96.3 2.0
20 40 60 80 100 120
90.3
9.0
40
60
80
100
Figure 1. Phenol content in electrokinetic reactor after the operation: (a) simple electrokinetic process and (b) integrated electrokinetic process with BDD electrode. 4. Conclusions In this study, the integrated electrokinetic tests using BDD electrode were conducted for the remediation of phenol-contaminated soil for 10 days. Most of phenol was transported toward cathode by electroosmosis and then degraded near the anode compartment of BDD electrode by circulating effluent. The consumed electricity during the operation time was similar to that of the simple electrokinetic test. From the results, it can be concluded that the integrated electrokinetic process is feasible for the treatment of contaminated soil with organic pollutants. It might be an innovative in-situ soil remediation technology to make up for the weak points of electrokinetics such as anode corrosion and effluent treatment. Acknowledgement This subject is supported by Korean Ministry of Environment as "The Eco-technopia 21 project".
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water-soluble salts, since, other conditions being equal, in this case grows the thickness of diffuse DEL, and, therefore, and the speed of electrical osmosis transfer. Furthermore, the obtained data about the efficacy of electrokinetic cleaning clearly correlate with the physico- chemical indices of the investigated soils. The influence of composition and concentration of the electrolyte of the pore solution of soils on the efficacy of electrokinetic cleaning also is reflected in the structure DES. To analyze the relationship between decontamination efficiency of oily soils and concentration of the alkaline solution in pores, NaOH solutions with concentrations of 0.01, 0.05, 0.1 0.25 N, HCl in those concentrations and 0,01 N NaCl were used. The results of studies shows that with an increase in concentration HCl, occurs reduction in the effectiveness in the cleaning, and with the use of solution NaOH as the pore was obtained inverse dependence. Partial solubility of oil in alkali possibly promotes more efficient oil removal from the sample containing NaOH. Apparently, a part of hydrocarbon contaminant dissolves due to the electrokinetic inter-reaction with the alkali solution. With the analysis of the influence of grading of soil on the efficacy of the electrokinetic cleaning of the oil-contaminated soils it is established that the content of the particles, which relate to the fraction > 0,01 mm in quantity 55-75%, is optimum relationship for conducting the electrokinetic cleaning. In this case the effect of cleaning soil of about 40% is achieved. With further increase in the content of the particles of these fractions the effectiveness of cleaning is reduced. To analyze the relationship between decontamination efficiency of oily soils and fractional composition of oil Usinsk's, Tarasovsk's, Yaregsks oil, and also the mixture of the crude oil of West Siberia were used. The results of studies showed that the maximum effect of removal is achieved at removal of light Tarasovsk's oil from soil, and minimum from heavy Yaregsks oil and composes 43% and 29% respectively. The study of the influence of the processes of oil degradation on the efficiency of cleaning they showed that the general effect of cleaning decreases with an increase in the period of pollution. In the conducted investigations the period of petroleum pollution varied from 2 of days to 7th months. The analysis of the obtained results showed that the greatest effect of cleaning - 68% is achieved at the electrokinetic working 2 of day pollution, and with cleaning of models 6 and by the 7 of monthly pollution the degree of cleaning composes only 1-2%. Thus, the received results show that the petropolluted file is more senior, the method will be less effective. Thus, researches carried out by us showed the high efficiency of electrokinetic removal of the petroleum pollution from soils. The studied factors influencing electrokinetic clearing, will allow to understand mechanisms of removal of oil pollution under action of a constant electric current and to develop industrial technology of soil clearing. References [1] Korolev V.A. et al. (2000). The electrochemical remediation of soils. - Proc. of 31st Internat. Geological Congress, Sess.22-3. August 6-17, 2000, Rio-de-Janeiro, Brazil (D-ROM) [2] Korolev V.A. (2001). Laws of the electrochemical soils remediation from petroleum pollution. EREM 2001. 3rd Symposium and Status Report on Electrokinetic Remediation / Schriftenreihe Angewandte Geologie Karlsruhe, 63, 19 (1-12) [3] Korolev V.A. (2001). The Cleaning of Soils from Pollution. Moscow, MAIK/ Interperiodica publishing house, 365 pp. (in Russian);
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Oral Contributions to
session 6 Modelling and other Applications
PREDICTION OF THE PERFORMANCE OF EKR BASED ON SPECIATION ANALYSIS AND MATHEMATICAL MODELING.
C. Vereda-Alonso, A. Garca-Rubio, C. Gmez-Lahoz, J. M. Rodrguez-Maroto and F. Garca-Herruzo Dpto. de Ingeniera Qumica. Fac. de Ciencias. U. de Mlaga. 29071-Mlaga (Spain). Lahoz@uma.es Although some considerations about the future use of a contaminated site may be done, both, the legal definitions to consider it contaminated and remediated, are usually based on the total concentration of regulated toxics. Nevertheless, there is a general agreement to consider that the development of tools for a reliable risk assessment would be desirable so that regulations are based on these risk evaluations. These tools are usually related somehow to bioavailability considerations, but those that have more chances to be used in regulatory texts should be performed using simple and reproducible analytical procedures. Among these techniques a sequential extraction procedure which has a good acceptance among researchers have been used for the speciation of soils contaminated with heavy metals for the determination of their mobility (1). The technique provides four fractions, which here are denominated weak acid soluble (WAS), reducible, oxidizable and residual. On the other hand it is well known that, at a specific contaminated site, the performance of Electrokinetic Remediation (EKR), as happens with all other in situ techniques, is depending heavily on the nature of both the contaminants and the soil. Up to the present moment, few publications have studied the relationship between the maximum remediation that can be achieved and the mobility of the soils as determined by the speciation analysis. For instance, at the contamination case of the Aznalcollar spill (2), it was shown that the speciation of the toxic cations present indicates that their mobility was rather different, as can be seen in figure 1a. It was also shown that, for each metal present, there seems to be a relationship between the maximum remediation that can be achieved by an acid enhanced EKR and the amount initially present as WAS (Fig. 1b).
100
100
Cd Cu Fe Pb Zn
80
80
Cd Zn Cu Fe Pb
% recovered
a
60
60
(%)
b
40
40
20
20
Figure 1. Results for the Azanalcollar spill. a) Speciation analysis. b) Recovery by acid-enhanced EKR.
Regarding that work it was also shown that a mathematical model, with relatively simple transport equations and few equilibrium equations with definitions based on the speciation analysis, was able to describe satisfactorily the behavior of the main parameters of the system. These are the rate of recovery of the toxic ion, the maximum recovery, the rate of acid addition and the energy requirements.
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Nevertheless, it is clear that more field cases should be studied before a relationship can be accepted between the results obtained from the speciation analysis and the remediation degree achievable by EKR. It is also important to determine a) if for those cases for which other enhancements are used (for instance the use of chelating agents instead of acid enhancement) a relationship between the speciation analysis and the maximum remediation efficiency can be also established. And b) if the toxic ions remaining in the soil after the remediation are those fractions which are less mobile. This is important if in the future EKR is to be accepted by the regulatory agencies even if only a certain amount of the toxic ions can be removed. Regarding these two issues we have initiated a research for the study of remediation alternatives for a soil contaminated mainly with Hg. The site is located close to Almadn (Ciudad Real, Spain), and near the mines that have been producing important amounts of mercury for centuries. After carrying out the speciation analysis, our first approach was to determine the fraction of Hg removable by a flushing solution with iodide. We also performed a speciation analysis after the remediation to determine which fraction was more efficiently removed. Our results are indicating that, approximately, a 30 % of the initial metal concentration can be removed at an acceptable rate. Larger amounts can be achieved but with very little concentration in the effluent. A somewhat surprising result was that the total amount of the more mobile fraction (WAS fraction) was not smaller after the remediation. In fact, the one with a more important decrease after the extraction was the reducible one, whereas the WAS fraction increased five fold. Therefore, even if a fraction of Hg was removed, an increase of the hazards of the site could be derived from the remediation procedure. Similar phenomena have been observed before (3). Of course, the effluent concentration could be limited by kinetic phenomena that can be due to several factors such as the rate of dissolution of the different mercury species present in the soil, or to preferential pathways arising during the remediation for the flushing solution. Alternative remediation techniques should be studied for this site, among which EKR enhanced with iodide presents interesting possibilities, and we are accomplishing that work. Of course, variations on the mobility after the remediation would be also studied, and compared with those observed for the flushing approach. Acknowledgements: This research was funded by Project 148/2004/3 (Ministry for Environment). CGL and CVA acknowledge the economic support from the Junta de Andaluca through the program Medidas de Impulso de la Sociedad del Conocimiento en Andaluca References: 1.- A.M. Ure, P. Quevauviller, H. Muntau and B. Griepink, Speciation of heavy metals in soils and sediments. An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the commission of the European Communities, Int. J. of Environ. and Anal. Chem. 51 (1-4) 135-51 (1993). 2.- M.D. Garcia-Gutierrez, C. Gomez-Lahoz, J.M. Rodriguez-Maroto C. Vereda-Alonso and F. Garcia-Herruzo. Electrokinetic remediation of a soil contaminated by the pyritic sludge spill of Aznalcollar (SW, Spain) Electrochimica Acta 52, 3372-3379 (2007) 3.-A.B. Ribeiro and J. M. Rodriguez-Maroto Electroremediation of heavy metal contaminated soils. Processes and application. Chap. 18 in Trace elements in the environment CRC Press (2006).
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Figure 1: dominating mechanism in dependency on the applied energy (after PAMUKCU 2005). Beside other physicochemical effects like electrode reactions the model has to be to extend to unsaturated soil conditions, especially in the presence of volatile organic substances, because then diffusion processes can dominate pollutant transport in the gaseous phase especially at relatively high temperatures. Finally numerical simulations of temperature effects occurring during applying a dc electric field are compared to laboratory and field scale experiments in different soils.
[1] Mitchell, J.K. (1993): Fundamentals of Soil Behavior, 437 S.; New York (Wiley & Sons). [2] HO, S.V., ATHMER, C., SHERIDAN, P.W., HUGHES, B.M., ORTH, R., MCKENZIE, D.,
BRODSKY, P.H., SHAPIRO, A., THORNTON, R., SALVO, J., SCHULTZ, D., LANDIS, R., GRIFFFITH, R. & SHOEMAKER, S. (1999a): The Lasagna Technology for In Situ soil remediation. 1. Small field test. Environ. Sci. Technol., 33(7): 1086-1091. [3] HO, S.V., ATHMER, C., SHERIDAN, P.W., HUGHES, B.M., ORTH, R., MCKENZIE, D., BRODSKY, P.H., SHAPIRO, A., SIVAVEC, T.M., SALVO, J., SCHULTZ, D., LANDIS, R., GRIFFITH, R. & SHOEMAKER, S. (1999b): The Lasagna Technology for In Situ soil remediation. 2. Large field test. Environ. Sci. Technol., 33(7): 1092-1099.
[4] STEGER, H. (2006): Elektrokinetische In-situ-Sanierung LCKW-kontaminierter gering durchlssiger Lockergesteine.- XXXIV-196 S., http://www.ubka.unikarlsruhe.de/eva/index.html, Karlsruhe (Elektronisches Vollarchiv Eva) [Dissertation]. [4] PAMUKCU, S. (2005): Electrically Enhanced Transformation of Contaminants in Clay Rich Subsurface. Presentation at the EREM Conference May 2005, Ferrara, Italy.
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10 cm 10 cm 5 cm
5 cm
10 cm
5 cm
10 cm
Figure 1. Circular electrokinetic Unit (After Turer and Genc, 2005) In the experiments, Ankara clay has been used. First, the liquid limit of the clay was determined and samples were prepared at liquid limit of 73%. After placing the clay in the electrokinetic unit the clay is compacted under 130 kg weights. When there was no more compaction (in the dial gage reading the change in elevation), the weight was lifted. Next, the anode and cathode chamber was filled with distilled water and left for sample to equilibrate in the unit. A day after, the water in the anode compartment was discharged and the compartment was filled with 1 M CaCL2. Constant electrical potential of 10 V was applied to the sample for 3 weeks. At the end of the experiment liquid in the anode and cathode compartments were discharged and shear strength of the sample was measured with a laboratory vane apparatus. Soil was sampled in a radial
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manner at 2.5 cm and 7.5 cm away from anode as it is seen in figure 2. A part of the soil sample was kept untouched for sampling a week after the completion of the experiment. During this period electrokinetic unit was kept in a humidity cabinet.
S oil
Testing points after the treatm ent Testing points one week after the treatm ent
Figure 2. Location of sampling points Results: The measurement obtained at 7.5 cm distance from the anode was showed that shear strength of the samples increased up to 168.3 kPa. The shear strength of the soils at 2.5 cm from the anode did not changed much and the measurements were in average 11 kPa (Figure 3 a). The increase in the strength of the soil at 7.5 cm from anode, relative to 2.5 cm from the anode in the same data set were 703%, 689%, 903% and 1244%. The shear strength measurements taken one week after the completion of the experiment were 182.8 kPa and 101.57 at 7.5 cm and 13.74 kPa and 13.74 kPa at 2.5 cm distance from anode (Figure 3 b). a)
Shear strength (KPa) 160 140 120 100 80 60 40 20 1 2 3 Data sets 4 5
Distance from anode
180
2.5 cm 7.5 cm
b)
2.5 cm 7.5 cm
Figure 3. Shear strength measurements with the addition of 1 M CaCl2 Conclusion: A circular electrokinetic unit with multiple anode arrangement was used to increase the shear strength of the artificially prepared soft soil sample. The aim of using circular eleckrokinetic unit was to increase the area of soil affected from alkaline conditions and decrease the area subjected to acidic conditions. Although with this electrokinetic unit high improvement in the shear strength of the soil was obtained at locations close to cathode the areas close to anode did not show improvement in strength.
[1] Ozkan S, Gale RJ and Seals RK (1999) Electrokinetic stabilization of kaolinite by injection of Al and PO43- ions, Ground Improv 3:135-144. [2] Alshawabkeh ANand Sheahan TC (2003) Soft soil stabilization by ionic injection under electric fields, Ground Improv 7:177-185. [3] Asavadorndeja P and Glawe U (2005) Electrokinetic strengthening of soft clay using the anode depolarization method, B. of Engineering Geology and the Environment [4] Turer D and Genc A (2005) Assessing effect of electrode configuration on the efficiency of electrokinetic remediation by sequential extraction analysis, J. of Hazardous Materials B119, 167-174.
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Introduction Hyperfiltration or salt sieving occurs when a salt solution is forced through a clay layer, e.g. in field aquitards and in clay membranes in technological applications. In the absence of electrical shorting, two types of electrical potential gradients can be induced during hyperfiltration through a clay membrane: Hydraulic flow induces a streaming potential gradient. The positive pole of this electrical gradient is at the downstream side of the membrane. The potential difference hampers the further downstream movement of ions, and therefore of water. Thus, the streaming potential causes an electroosmotic counterflow of solution. A membrane potential gradient develops when the membrane interfaces are in contact with solutions of different salt concentrations. The membrane potential gradient has its positive pole at the low-concentration (i.e. downstream) side of the membrane. Also this potential difference hinders the down-stream movement of ions, be it by convection or diffusion, and works as an electroosmotic counterflow of solution. Streaming potentials Streaming potentials across semi-permeable membranes are induced by water flow in response to hydraulic pressure gradients. Reported streaming potentials per bar in clays range from 0.12 to 180 mVbar -1. Coefficients of electroosmotic conductivity (ke) range from 110-10 to 110-8 m2V-1s-1. Membrane potentials Membrane potentials arise due to a difference in salt concentration across a semipermeable membrane. At perfect semi-permeability the potential difference is given by the Nernst-equation. The positive potential is at the low concentration side of the membrane. Clay membranes are not ideal and therefore the membrane potential difference is smaller than this maximum value. For bentonite, Heister et al. [1] measured membrane potential gradients between 3.9 and 5.8 Vm-1, which are smaller than predicted from the Nernst-equation by a factor 4.5-5.5. Hyperfiltration in bentonite clay Fritz and Whitworth [4] conducted a hyperfiltration experiment with a 0.01M LiClsolution and a 3 mm thick membrane of Li-saturated bentonite of 90 % porosity. A fixed volume flux, Jv , of 1.3710-5 cms-1 was applied. Thus, a hydraulic pressure difference of 20.47 bar developed across the membrane. At steady state they observed a peak concentration of 0.0348 M at the high-pressure interface of the clay membrane, which is ascribed to semi-permeability of the clay. The resulting osmotic pressure difference is calculated to be 1.215 bar.
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Estimation of induced electroosmosis For estimation of the streaming potential gradient in the experiment by Fritz and Whitworth, the conditions of the experiments by Heister et al. [2] are the nearest comparable. To obtain insight in the possible range of induced gradients, we also consider data from others. From the applied hydraulic pressure of 20.47 bar, an induced electrical potential, E, is estimated to be in the range of 0.123 V to 3.68 V. The electroosmotic counterflow (Je) is
J e = ke ( E ) x
(3)
with x positive in the downstream direction. Using the corresponding ke-values reported by these authors, the electroosmotic counterflow (Je) of water is estimated in the range of -1.9610-5 to -2.0510-5 cms-1. The maximum value of the membrane potential gradient in the experiment is negligible in comparison with the streaming potential. Discussion The estimated streaming potential gradient during hyperfiltration creates a counterflow of water of the same order of magnitude as the fixed downstream flow. This counterflow will not have affected the salt sieving observed. However, it will have affected the required pressure on the input solution. This must have been higher than in electrically shorted condition. In the presence of a counterflow Je , the volume flux, Jv , of the solution equals the sum of a hydraulic, a chemico-osmotic and an electroosmotic component. While ignoring induced electroosmosis , Fritz and Whitworth [4] estimated a membrane efficiency for chemico-osmosis, , of 0.55. A chemico-osmotic (counter)flux of 4.6210-7 cms-1 is derived. Since salt sieving was observed, must be >0. However, as was found in earlier studies on bentonite (e.g. Keijzer and Loch [3]), the membrane efficiency probably is a factor 10 to 20 smaller. Although the estimated electroosmotic flux, Je, is is obviously too large, chemical osmosis in hyperfiltration may be small compared to induced electroosmosis. The excess hydraulic pressure characteristic for hyper-filtration may be mainly due to electroosmotic counterflow. Conclusions In clays where hyperfiltration is observed, be it in the field or in the laboratory, a streaming potential gradient and electro-osmotic counterflow may be present if the clay is not electrically shorted. This will result in a larger required hydraulic pressure. If these induced electrical effects are neglected, the role of chemical osmosis and the semipermeability of the clay are overestimated. [1] Heister, K., P.J. Kleingeld and J.P.G. Loch. 2005b. J. Colloid and Interface Sci. 286: 294-302. [2] Heister, K., P.J. Kleingeld, T.J.S. Keijzer and J.P.G. Loch. 2005a. Engineering Geology 77: 295-303. [3] Keijzer, Th.J.S. and J.P.G. Loch. 2001. Soil. Sci. Soc. Am. J. 65: 1045-1055. [4] Fritz, F.J. and T.M. Whitworth. 1994. Water Resources Research 30: 225-235.
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Oral Contributions to
session 7 Electrokinetic and Electrochemical Degradation
Process combination The complete treatment would be done in two steps. In the first one, the wastewater will be treated by electrochemical oxidation with diamond electrodes. Then ozonation completes the process. The ozone will not be produced as the conventional ozone
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producing systems; i.e., with coaxial dielectric-barrier-discharge in air. In this case ozone will be formed by electrolysis with diamond electrodes. The whole process can be described as follows. Firstly, the wastewater under analysis will be taken from the effluent of a wastewater treatment plant (RHV-Leoben) and will be treated in a lab scale unit. In the second phase after approximately one year water from the local hospital in Leoben and a circuit board producer will be sampled. This wastewater will be treated on the pilot plant. Additionally, experiments will be carried on directly at the wastewater treatment plant. To accomplish this, a tech scale unit will be installed in a bypass-system of the facility. The needed amount of ozone will be produced in a non-conventional, separate generator. In this process the ozone will be directly produced from clean water by electrolysis with diamond electrodes. The injection of the concentrated ozonic water to the wastewater will be progressive. After ozone addition, a post mixing chamber for the mixture will be used to install a sensor at this step. With this ozone detector, it will be possible to calculate an ozone balance of the reactor system. This balance in addition to the other parameters (e.g. COD, Chemical Oxygen Demand and DOC, Dissolved Organic Carbon) will allow getting conclusions about the ozone consumption of the substances existing in the sample, which depends on the existing organic matrix of the water samples (scavengers). In the second treatment step, the waste water will be delivered to an electrochemical reactor. Inside, electrodes for an anodic oxidation with doped diamond electrodes are located. In the process OH-radicals will be directly produced and used for the oxidation of the substances (pharmaceuticals and complexing agents). Analysis As shown in Table 1, the samples taken after the treatment modules will be analysed for several different parameters (e.g. DOC, COD, AOX, conductivity, redox potential, pharmaceutical substances and complexing agents content). The pharmaceutical substances and also the complexing agents will be analyzed by the Federal Environment Agency of Austria (this agency has been a project partner in different studies about pharmaceuticals in the ecosystem, as in the ARCEM project). COD and DOC will be analysed by the laboratory of the Institute for Sustainable Waste Management and Technology in Leoben, and the other parameters will be measured using inline instruments during the test runs.
Table 1: Overview of the analytic plan
Substances DOC AOX sum parameter / online Conductivity measurement Redoxpotential pH-Value COD Carbamazepin Coffein Roxithromycin Erythromycin-H2O pharmaceuticals Josamycin Diazepam Trimethoprim Sulfamethoxazol EDTA DTPA complexing agents 1,3-PDTA NTA Analysis made by IAE X X X X X X UBA
X X X X X X X X X X X X
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separately the ion transport caused by electromigration (right cylinder in Fig.1) and by electroosmosis (left cylinder in Fig. 1). Transport caused by capillary force and diffusion takes place in both cylinders.
3 2,5
2-
Transport [cm/h]
2 1,5 1 0,5 0 0 1 2 3 4 5
The influence of field voltage on the transport velocity in sandy soil was investigated by using 1, 1,5, 2 and 4 V/cm. The transport kinetics speeded up linearly with the increasing field voltage (see Figure 2). Also the effect of different soil materials on the transport was tested. Mixtures of pure sand, loam and clay were prepared and the transport in these soils tested. According to the results, electromigration towards the anode was fastest in sandy and loamy soil, whereas transport occurred also in cathode direction in loamy soil. Latter can be explained by electroosmosis. The results of these experiments are presented in Table 1. Table 1. Transport velocities of S2O82- ions in different soil types with 1 V/cm.
Clay (Kaolin) Transport velocity Towards Anode [cm/h] 100 % 100% 100% 50 % 50 % 33 % 50 % 50 % 33 % 50 % 50 % 33 % 2 3,3 0 2,4 0 0 2,1 Towards Cathode [cm/h] 0 1,3 0,7 0,9 0 0,6 0
Sand
Loam (Sialin)
Conclusions The anodic production of oxidizing agents, as well as the transport of these ions in soil has been investigated. The production process has been optimized and needs to be verified in a scaled up system. The results of the transport experiments indicate the importance of laboratory scale tests with existing soil material (from real site) before applying an electrokinetic remediation method in the field.
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necessary, it is not useful to operate these electrodes in situ, but on site. A possible application is in a circular pump and treat remediation, where soil water is pumped trough the cell and released to the soil again. Enriching the solution with ecological compatible inorganic salts (e.g. carbonates, sulphates, nitrates) can help to improve the application. High yields oxidants can be produced this way. Compared with direct production in the soil the lower energy consumption and the high durability of the on site system is of interest for oxidative remediation processes. A demonstration cell will be shown at Vigo.
Reference C. Comninellis et al. 2005. Application of Synthethic Boron-Doped Diamond Electrodes in Electrooxidation Processes. In: A. Fujishima, Y. Einaga, T. N. Rao, D.A. Tryk; 2005 Diamond Electrochemistry. Amsterdam: Elsevier, pp. 449 ff
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Posters
Poster 01
ELECTROKINETIC DEWATERING AND REMEDIATION OF RIVER DREDGED CONTAMINATED HIGH WATER SEDIMENTS
Ha Ik Chunga, Jun Yub a Research Fellow, Korea Institute of Construction Technology, 2311 Daewha-dong Ilsan-gu Goyang-shi Gyeonggi-do, Korea, Tel +82-31-910-0216, Fax +82-31-910-0211 E-mail: hichung@kict.re.kr b Senior Researcher, Korea Institute of Construction Technology, 2311 Daewha-dong Ilsan-gu Goyang-shi Gyeonggi-do, Korea E-mail: yujun@kict.re.kr
Generally, the sediments contain significant water, clay, colloidal fraction and contaminants, and can results in soft strata with high initial void, and its potential hazards in subsurface environments are existed. Electrokinetic technique has been used in dewater process for volume reduction of high water content sediments and in remediation process for extraction of contaminants from contaminated soils. In this research, the coupled effects of dewatering and remediation of contaminated high water content sediments are focused using electrokinetic dewatering and remediation techniques from experimental aspects. A series of laboratory experiments including variable conditions such as water content of sediment specimen, solid content of sediment specimen, concentration level of the contaminant, and magnitude of applied voltage are performed with the contaminated high water sediment specimens sampled from river environment. From the test results, a significant investigation is derived for the mechanisms associated with sediments contaminated with hazardous substance in which simultaneous dewatering and remediation processes are involved by electrokinetic dewatering and remediation system. The coupled effects of dewatering and remediation of slurry type sediment are analysed. The test results show that the dewatering and settlement of specimen is increased with increasing of applied voltage and decreasing of solid content by the process of electrokinetic dewatering mechanism. And the concentration of sediment specimen is decreased with increasing of applied voltage and operating duration by the process of electrokinetic remediation. The contaminated high water sediment can be effectively dewatered and remediated by the coupled effects of electrokinetic dewatering process and remediation process.
Electrode Saturated slurry sample (+) Saturated slurry sample (+) Saturated slurry sample (+)
Electrode
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16. 0 15. 0 , c 14. 0 13. 0 12. 0 11. 0 10. 0 0. 0 20. 0 40. 0 60. 0 80. 0 100. 0 , hr gr ek1 ek2
50
15 vol : t
40 , mA 30 20 10 0 0. 0
ek1 ek2
20. 0
40. 0 60. 0 , hr
80. 0
100. 0
[1] Ha Ik Chung, etc., Electrokinetic Sedimentation and Remediation of River Dredged Contaminated Soil, Spring Conference of Korea Geotechnical Society, 2001.3
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Poster 02
ELECTROKINETIC ULTRASONIC REMEDIATION OF CONTAMINATED ADMIXED SOILS WITH VARIOUS CLAY AND SAND CONTENTS
Ha Ik Chunga, Masashi Kamonb a Research Fellow, Korea Institute of Construction Technology, 2311 Daewha-dong Ilsan-gu Goyang-shi Gyeonggi-do, Korea, Tel +82-31-910-0216, Fax +82-31-910-0211 E-mail: hichung@kict.re.kr b Professor, Kyoto University, Japan Various remediation techniques such as simple soil flushing, electrokinetic flushing, ultrasonic flushing, and electrokinetic + ultrasonic flushing remediation were studied for the removal of heavy metal and organic substance in contaminated clayey soils. The study emphasized the coupled effects of electrokinetic and ultrasonic flushing techniques on migration as well as clean-up of contaminants in clayey soils. The laboratory soil flushing tests combined electrokinetic and ultrasonic technique were conducted using specially designed and fabricated devices to determine the effect of these both techniques. The electrokinetic technique is effective in removal of heavy metal in contaminated cohesive fine soil and the ultrasonic technique is effective in removal of organic substance in contaminated cohesionless granular soil. The removal of heavy metal and organic substance can be achieved by the coupled technique with electrokinetic and ultrasonic remediation. A series of laboratory experiments involving the simple soil flushing, electrokinetic flushing, ultrasonic flushing, and electrokinetic + ultrasonic flushing test for clayey soil were carried out. An admixed soil with sand and clay was used as a test specimen, and lead and phenanthrene were used as contaminants of heavy metal and organic substance. In electrokinetic and ultrasonic flushing tests, an increase in out flow, permeability and contaminant removal rate was observed. Some practical implications of these results are suggested in terms of technical feasibility of in situ implementation of the coupled electrokinetic and ultrasonic remediation technique in clayey soil. An admixed soil in the ratio of sand and clay was used as sandy clay mixtures. The mixing weight ratios of sand and clay were 50 : 50, 20 : 80, 0 : 100 as a percentage, respectively. Test results are shown in the following figures.
800
700
600
500
400
300
200
100
S ( 50 C 50) S E( 50 C 50) S U ( 50 C 50) S E+U ( 50 C 50) S S ( 20 C 80) S E( 20 C 80) S U ( 20 C 80) S E+U ( 20 C 80) S S ( 100) C E( 100) C U ( 100) C E+U ( 100) C
0 50 100 150 200 250 300 350
Accum ul ed out l ( l at f ow m )
Ti e( m h)
C oncentaton r i ( /C o) r i ato C
1. 2 1. 0 0. 8 0. 6 0. 4 0. 2 0. 0 0. 0 0. 2 0. 4 0. 6 0. 8 1. 0 Nor alzed di ance f om anode ( m i st r x/L) S( S20 C 80) U( S20 C 80) E( S20 C 80) E+U ( S20 C 80)
Figure 2. Normalized concentration of lead for mixed soil with sand 20% and clay 80%
1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 S E U S50 C50 S E U S20 C80 S E U C100
Figure 4. Mean concentration of phenanthrene in specimen for clayey soil ---------------------------------------------------------------------------------------------------------[1] Ha Ik Chung, Masashi Kamon, Ultrasonically enhanced electrokinetic remediation for removal of Pb and phenanthrene in contaminated soils, Engineering Geology 77 233-242, 2005.
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Poster 03
THE USE OF AN AIRLIFT REACTOR WITH IN-SITU ELECTROGENERATION OF FENTONS REAGENT IN THE TREAMENT OF SPENT CAUSTIC FROM A PETROLEUM REFINERY
Patricio Nuez, Henrik K. Hansen, Jaime Guzman Universidad Tcnica Federico Santa Mara, Av. Espaa 1680, Valparaiso, Chile E-mail: patricio.nunez@usm.cl An airlift reactor was used to study the kinetics of the COD (chemical oxygen demand) reduction, where the Fentons reactive is generated in situ, using the inlet of air as a source for oxygen supply and agitation. This reactor was used to study the kinetics of spent caustic from a petroleum refinery. Spent caustic is generated as a results of the removal of sulphurs and mercaptans in petroleum refineries. Spent caustic is considered to be a hazardous waste. The main hazardous characteristics of this waste are the high COD (Chemical Oxygen Demand) and the high amount of sulfides. Normally the WAO (Wet Air Oxidation) technology, which uses oxygen to oxidize the Spent Caustic at high temperatures (between 200 and 280[C]) and high pressures (up to 150[bar]), is used. This treatment is expensive and due to operating conditions generates a potential hazard situation [1]. New results show that Fentons reagent (Fe2+ + H2O2) is suitable as on oxidizing agent [2]. In order to reduce reagent addtion, an alternative treatment: a pH reduction followed by an Electro-Fenton process, is recommended for this waste. This reactor was set up as two iron concentric stell cylinders, which function as sacrificial anodes. The Fe2+ produced act as source for Fentons reagent together with added H2O2. An airflow passing between the plates induced the mixing of the two phases - without the need of a stirrer -, generating turbulent conditions. Initial results with electrocoagulation based on this type of reactor of arsenic were published earlier by the authors [3,4]. Figure 1 shows the actual reactor.
a)
b)
Figure 1. Airlift reactor for electrogeneration of Fentons reagent. a) side view, and b) top view.
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The volume of the reactor was 1,2 [L]. The spent caustic solutions were prepared with phenol (2.500 ppm) y sodium sulfhydrate (NaSH) (10.000 ppm). The Electro-Fenton process begins as mentioned with the production of the catalysator Fe+2, in concentration of about 100 mg/L, when connecting the electrodes to a power supply (with 1[A] current. The process continues with the addition of hydrogen peroxid (30 % w/w) in a estequimetric ratio with the initial COD present in the wastewater sample. The operational temperature was kept constant during 60 [min] of experimental running and samples were taken after 15, 30, 45 y 60 [min] for COD and phenol analysis. Results showed that more than 90 % COD reduction could be obtained using this reactor. A set of residence time distribution and kinetic experiments were run on pilot scale with an airlift reactor to determine a model for the hydrodynamic and the kinetic parameters. An overall kinetic model that lumps the different reactions for the real spent caustic and specific reaction model for Sulfide and phenol, were developed and the kinetics parameters were fitted using the fluidynamic model developed by the authors.
[1] Cordonnier, F.B.a.J., Refining, Petrochemicals and Gas Processing Techniques. INDUSTRIAL WATER TREATMENT. 1 ed. Vol. 1. 1995, Houston, Texas, USA: Gulf Publishing Company. 248. [2] A. Ventura, G. Jacquet, A. Bermond, V. Camel. Electrochemical generation of the Fentons reagent : application to atrazine degradation. Water Research, 36 (2002), 3517-3522. [3] Hansen, Nuez and Grandon, Minerals Engineering 19 (2006) 521-524. [4] Hansen, Nuez, Raboy, Schippacasse and Grandon, Electrochimica Acta 52 (2007) 3464-3470.
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Poster 04
Copper smelters and the sulfuric acid plants that are connected to them generate large amount of wastewater containing heavy metals, where arsenic is the key contaminant. Heavy metals such as copper and lead can normally be removed by sulfide precipitation but arsenic needs other treatment. Electrocoagulation to precipitate the arsenic through the in-situ production of ferric hydroxide was tested in an air lift reactor. This reactor was set up as two iron concentric cylinders. An airflow passing between the plates induced the mixing of the two phases without the need of a stirrer -, generating turbulent conditions. Initial results with elecoagulation of arsenic were published earlier by the authors [1,2]. A set of synthetic wastewaters was used to test the performance of the reactor. The initial concentration varied from 10 to 5000 ppm of arsenic. Continuos current with current reversal each 60 or 120 seconds in order to avoid the passivation of the electrodes was applied. The gap between the electrodes was 10 mm for the reactor, and the current density was varied between 0.8 3 mA/dm2 depending on experiment. The reactor was run in continuos and batch wise operation, and the elapsed time for each experiment was 120 to 180 minutes. The results from the batch experiments were used to predict the performance of the continuos experiments and vice versa as a validation procedure. The reactors are showed in Figure 1. The airlift reactor was applied to real wastewater sampled at the El Teniente copper smelter gas treatment plant. The arsenic content in the wastewater was found to be between 6 and 15000 ppm depending on the sampling stage in the treatment plant. Both batch and continuous experiments were carried out. In general the arsenic removal was efficient e.g. a batch reactor experiment run at 1.2 mA/dm2 and initially 100 ppm arsenic showed that a more than 99 % reduction in the arsenic concentration after 3 hours was possible. Initial results were published earlier by the authors [1,2]. Residence time distribution experiments were run on both types of reactors, and a model that takes in account a) the kinetics on the solid phase (electrochemical phenomena), b) the mass transfer process, c) the ferrous ion oxidation with the ferric hydroxide production, and d) residence time distribution models, was developed and the kinetic parameters were fitted.
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a)
A set of residence time distribution and kinetic experiments were run on pilot scale with an airlift reactor to determine a model for the hydrodynamic and the kinetic parameters. Based on these results a scale up procedure was developed to design an actual full scale electrocoagulation reactor. The reactor is compared process wise and cost wise with the conventional industrial reactor that use ferric sulfate addition the precipitate arsenic.
[1] Hansen, Nuez and Grandon, Minerals Engineering 19 (2006) 521-524. [2] Hansen, Nuez, Raboy, Schippacasse and Grandon, Electrochimica Acta 52 (2007) 3464-3470.
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Poster 05
Sharma, H.D., and Reddy, K.R. (2004), Geoenvironmental Engineering: Site Remediation, Waste Containment, and Emerging Waste Management Technologies, John Wiley & Sons, Hoboken, New Jersey, USA, 992p.
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high pH conditions in the soil. This allows the cationic metal contaminants to be transported and removed at the cathode. Alkaline solutions are introduced in the anode to increase pH near the anode. This allows anionic contaminants to exist in soluble form and be transported and removed at the anode. Instead of using acids, complexing agents (e.g., EDTA) can be used in the cathode. When these agents enter the soil, they form negative metal complexes that can be transported and removed at the anode. When addressing organic contaminants (including energetic compounds), solubilizing agents such as surfactants, cosolvents and cyclodextrins are introduced in the anode. When transported into the soil by electroosmosis, these agents solubilize the contaminants. Alkaline solutions are also introduced to maintain soil pH greater than PZC to enhance electroosmotic flow. Mixed contaminants (combinations of cationic and anionic metals and organic contaminants) are commonly encountered at contaminated sites. In general, the presence of multiple contaminants is shown to retard the contaminant migration and removal. Synergistic effects of multiple contaminants should be assessed prior to the selection of an enhancement strategy. It is found that the removal of multiple contaminants in a single step-process is difficult. Therefore, sequential conditioning systems have been developed to enhance removal of mixture of cationic and anionic metal contaminants and/or a mixture of metal and organic contaminants. In addition to the use of electrode conditioning solutions, the magnitude and mode of electric potential application is altered. An increase in the magnitude of electric potential increases the electromigration rate and initial electroosmotic flow rate. Pulsed mode of electric potential application is found to increase the electroosmotic flow due to polarization of soil surfaces and it also allows rate-limited dissolution of contaminants to occur. Although excellent removal efficiencies can be achieved by the use of different enhanced electrokinetic remediation strategies, several practical problems arise in using them at actual field sites. These problems include: high cost of electrode conditioning solutions, regulatory concerns over injecting conditioning solutions into subsurface, high energy requirements and costs, longer treatment time, potential adverse effects on soil fertility, and costs for treatment of effluents collected at the electrodes. As a result of all these problems, the full-scale field applications of electrokinetic remediation are very limited. Despite the challenges, in-situ electrokinetic remediation holds promise to remediate difficult subsurface conditions, particularly low permeability and heterogeneous subsurface environments, where most of other conventional technologies fail. The electrokinetic remediation technology can also be applied to remediate diverse and mixed contaminants even when they are non-uniformly distributed in the subsurface. Standard electrokinetic remediation method is essentially an electrokinetically enhanced flushing process. However, the electrokinetic remediation can be made efficient and practical as well as less expensive by integrating or coupling it with other proven remediation technologies. Such integrated technologies include electrokinetic-chemical oxidation/reduction, electrokinetic-bioremediation, electrokinetic-phytoremediation, electrokinetic-thermal desorption, electrokinetic- permeable reactive barriers, electrokinetic-stabilization, electrokinetic-barriers (fences), and others. These integrated technologies have potential for the simultaneous remediation of mixed contaminants in any subsurface environment. Several successful bench-scale and demonstration projects have been reported recently on integrated electrokinetic remediation technologies; such integrated electrokinetic projects are expected to grow in the near future.
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Poster 06
107
Power supply Cathode Gas outlet Voltmeter Thread rod Passive electrodes Overflow Filter fleece Filter fleece Overflow Collecting bottle Anode Gas outlet
Sampling
Sand / Soil
Sampling
Peristaltic pump
Fig.1: Experimental set-up It could be shown that the breakthrough of sulphate, nitrate and ammonium in the 10 cm sandy soil system was within several hours. Transport rates of app. 1.8 cm/h and 1.5 cm/h were observed for sulphate and nitrate at a voltage gradient of 2 V/cm. Decrease of the voltage to 1 V/cm resulted in a transport rate of about 0.7 cm/h for both ions. Ammonia had a slower transport velocity of about 0.5 cm/h at 2 V/cm and 0.2 cm/h at 1 V/cm, respectively. Migration of phosphate was low because it precipitated in the soil. Using of polyphophates was more successful, however, only low transport rates (between 0.1 and 0.5 cm/h at 2 V/cm) were observed. As the experiments were conducted without pH control, a pH gradient developed as expected. Within several hours the initial pH of 7 dropped about 5 units at the anode and increased up to pH 12 at the cathode. At the end of the experiment a pH gradient in the soil from 12 at the cathode to 2 at the anode was observed. There was a significant difference in transport behaviour when multiple ions were injected compared to single ion transport. When sulphate, phosphate, nitrate and ammonia were added at the same time, the amount and velocity of anion transport decreased slightly whereas the amount and velocity of ammonia transport was significantly enhanced due to competitive transport reactions. These preliminary results demonstrate the feasibility of the concept of electrokinetic transport of microbial nutrients and electron acceptors in the subsurface. The electrokinetic distribution is a promising tool for an in-situ stimulation of microbial degradation which is limited by mass transfer processes. Acknowledgment: We gratefully acknowledge financial support by the Federal Ministry of Economics and Technology and the German Federation of Industrial Research Associations "Otto von Guericke" e.V. (AiF) (project no 15131 N). We thank Hagen Steger and Roman Zorn for providing the electrokinetic test chamber.
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Poster 07
109
Test M1K
Test LVL2
ke [m/Vs]
60
80
100
120
140
160
Zeit [d]
Figure 1: Development of the ke-vaules of two different backfill materials (M1A, M1K) and a natural soil (LVL2).
[1] ACAR, Y. B., GALE, R. J., HAMED, J. & PUTNAM, G. (1990): Acid/Base distributions in electrokinetic soil processing.- Transportation Research Record, 1288: 23-33. [2] STEGER, H. (2006): Elektrokinetische In-situ-Sanierung LCKW-kontaminierter gering durchlssiger Lockergesteine.- XXXIV-196 S., http://www.ubka.unikarlsruhe.de/eva/index.html, Karlsruhe (Elektronisches Vollarchiv Eva) [Dissertation]. [3] STEGER, H., ZORN, R., HAUS, R. & CZURDA, K. (2001): Removal of tetrachlorethylene from fine-graind soils by electrokinetic processes.- In: CZURDA, K., HAUS, R., KAPPELER, C. & ZORN, R. [Hrsg.]: Erem 2001 - 3rd Symposium and status report on electrokinetic remediation, 63: 25-1 25-14; Karlsruhe (Schriftenreihe Angewandte Geologie Karlsruhe).
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Poster 08
ELECTROLYTIC GENERATION OF AN ALKALINE BARRIER FOR IN-SITU DEGRADATION OF MUNITION CONSTITUENT (RDX) CONTAMINATED GROUNDWATER
David B. Genta, Akram Alshawabkehb, Jeffrey L. Davisa a Environmental Laboratory, USACE Engineer Research and Development Center, 3909 Halls Ferry Road, Vicksburg, MS 39180 USA, b Dept. of Civil and Environmental Engineering, 400 Snell Engineering Center, Northeastern University, 360 Huntington Avenue, Boston, MA 02115, USA E-mail: David.B.Gent@erdc.usace.amry.mil Introduction. The use, manufacturing, and storage of nitroaromatic and nitramine explosive compounds resulted in contamination of soil and groundwater. The U.S. EPA lists hexahydro,1-3-5-trinitro-1,3,5-triazine (RDX) under the Unregulated Contaminant Monitoring Regulation for Public in List 2. RDX groundwater contamination disrupts the use of military training areas and impacts local drinking water. Methods and Materials. Sand packed columns in a horizontal flow arrangement were used in laboratory experiments to simulate an in-situ treatment barrier (Figure 1). The simulated barrier was designed as a hybrid treatment process for RDX contamination, initially via reductive transformation at the cathode followed by alkaline hydrolysis downstream of the cathode. Experiments included one-dimensional proof-of-concept (5 cm ID) and scale-up optimized (10-cm ID) columns. The distance between the electrodes for the 5-cm and 10-cm columns was 33-cm and 160-cm, respectively. A seepage velocity of 30.5 cm d-1 was used in all experiments. Mixed metal oxide coated titanium electrodes (anode and cathode) were installed in slotted PVC wells within the column to facilitate the destruction of RDX contaminated water by electrolysis at the cathode and by alkaline hydrolysis downstream of the cathode. Ports placed at 30.5-cm intervals along the column were used for pH and RDX sampling. Results and Discussion. The high pH migrated through the column from cathode to anode in 30 days of treatment (Figure 2a). Over the range of inlet concentrations (500 to 2,500 g/L) for the 5-cm columns, RDX removal was approximately 95% with 75% RDX destruction near the cathode, presumably by electrolysis and 13% RDX destruction downstream of the cathode by alkaline hydrolysis with electrode current densities of 6.2 to 12.3 A/m2. An alkaline hydrolysis first order rate coefficient (0.046 hr-1) was used to estimate the optimized scale-up column length (160-cm) required for complete destruction of RDX and its nitroso-substituted products. Effluent RDX concentrations from the 10-cm diameter scale up column (500 to 4,000 g/L influent) were less than the 2 g/L health advisory standard established by the US EPA (Figure 2 b). The alkaline hydrolysis first order reaction rate coefficient from the 10-cm diameter column was 0.054 h-1 with a half life of 13.1 h. Conclusions. The RDX removal percentage for the last 32 days of operation of 10-cm diameter column was 99.995 percent with an electrode current density of 9.2 A/m2. Nitroso-substituted products (MNX, DNX, and TNX) were below detection limits in the column effluent. The effluent end products of RDX ring cleavage detected were formate, nitrite, and nitrate. The significance of this in-situ electrochemical barrier is that the contaminant can be removed from the groundwater without the addition of external chemical amendments and it can be applied below trenching depths. Electrodes placed at the leading edge of a groundwater plume can act as a barrier to RDX transport.
111
Figure 1. Depiction of an electrochemical barrier: (a) in-situ application of direct current across cathodes and anodes, (b) placement of cathode wells upstream of anode wells, (c) RDX decomposition at cathode by direct electrolysis, (d) alkaline front migration downnstream of cathode toward the anode, and (e) anode oxidation of methanol, formate, and nitrite.
Figure 2. 10-cm ID column results vs. time (a) pH from ports along column (b) effluent RDX (g/L)
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Poster 09
Figure 1 shows two electrodes placed at the experimental wall. As seen, they are placed at the same side of the wall to simulate a situation, where it is only possible to get to the wall at one side as e.g. in a basement. The electrodes were 130 cm long. Between the
113
wall and the metallic electrodes was a clay layer of 1.5 2.0 cm thickness. To keep the metallic electrode in place it was covered with about 1 cm clay. The electrodes were covered by plastic to avoid drying of the clay due to evaporation. RESULTS AND DISCUSSION The water content was between 10% and 15% in the bricks and between 3% and 6% in the mortar and the masonry of the experimental wall must be considered very moist. The chloride and nitrate concentrations were low and thus the moisture in the wall is expected originate from rising dampness rather than of hygroscopic origin. During the experiment 40 mA was applied to the electrodes. A piece of fabric was placed under the cathode, and this fabric was wet after less than 1 hour of applied current. The voltage was 60V at the beginning but after 34 hours the voltage had already decreased to 22 V, showing the main problem of the setup it was difficult to maintain good electric contact. The problematic point was the interface between clay and masonry. If a few water droplets were added here the voltage increased again. Never the less the experiment was continued all together for 1 month. During this period the current was sometimes turned off and few times cathode and anode were changed for 2 hours, both resulting in a lower resistance for a short period. After 30 days it was seen, that about 350 ml water were collected under the cathode (see Figure 2). Unfortunately it was not observed when this water started to be collected and if it continued to arrive. The clay of the cathode was very wet, but the clay at the anode was hard as cement and the experiment was stopped since only 16 V could be obtained when applying 40 mA. From each electrode 10 samples Figure 2: Water collected were taken for measurement of pH and water under cathode content. At the anode pH had not lowered (>7.8) and the clay buffered the acidic front effectively. Water content of the clay at the anode was < 13%. Even under during this experiment, where the electrodes not allowed for good electric contact, electroosmosis was obtained and there is basis for further development of an electrokinetic method for drying brick masonry. However, there are still many questions to be answered and also development of proper electrodes is needed. An optimization of the placement of the electrodes must also be made. In the present work the electrodes were placed vertically and this does not hinder water in continuing entering the wall from the soil. It may be a possibility to place the electrodes horizontally and close to the floor and by this hinder the transport of water further than the anode (placed above the cathode). This work is on-going. In some situations it may be advantageous to combine electroosmotic dewatering with isolation of the masonry from rising dampness by inserting a damp proof course in order to prevent the masonry continuously in receiving new water. In cases where there is a problem with hygroscopic moisture in the masonry, a damp proof course cannot solve the problem alone and in such a situation a combination of damp proof course and an applied electric field could also be advantageous. ACKNOWLEDGEMENT BoligfondenKuben is acknowledged for financial support for this project.
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Poster 10
A
Pressure Port Calibration Reservoir Slurry Sample
Power Supply
PMU
Pressure Measuring Unit
V
Voltmeter
PMU
Column
(a)
(b)
Fig. 1. Electrokinetic settling column: (a) schematic diagram; (b) settling column in use
115
400
case1
Height (mm)
case3
case2
30
40
50
60
Time (hr)
(a)
200
Height (mm)
150 100
case6 case4
50
case5
0 0 2 4 6 8 10 12
Time (hr)
(b)
(*iwc: initial water content, es: electrolyte solution) Fig. 2. Surface settlement vs. time: (a) case1 gravitational settling [iwc*: 500%, es*: distilled water], case2 electrokinetic settling [iwc: 500%, es: distilled water], case3 gravitational settling [iwc: 500%, es: 0.02M NaCl]; (b) case4 gravitational settling [iwc: 2000%, es: tap water], case5 electrokinetic settling [iwc: 2000%, es: tap water], case6 gravitational settling [iwc: 2000%, es: 700 mg/L Zn]
[1] Acar, Y. B. and Alshawabkeh A. N. (1993), Principles of electrokinetic remediation, Environ. Sci. Technol., 27(13), pp. 2638-2647. [2] Bowden, R. K. (1988), Compression behaviour and shear strength characteristics of a natural silty clay sedimented in the laboratory, D.Phil. Thesis, Oxford University [3] Lee, M. (2000), An experimental and analytical study of electrokinetic consolidation, M.Sc. Thesis, Oxford University. [4] McRoberts, E. C. and Nixon, J. F. (1976), A theory of soil sedimentation, Can. Geotech. J., Elsevier, 13(3), pp. 294-305. [5] Mitchell, J. K. (1993), Fundamentals of soil behaviour, Wiley Inter. Science [6] US Environmental Protection Agency (1997), The incidence and severity of sediment contamination in surface waters of the United States, National Sediment Quality Survey, Vol. 1, EPA 823-R-97-006, Office of Water, Washington, DC. [7] Yeung, A. T. (1994), Electrokinetic flow processes in porous media and their applications, Advances in porous media, Elsevier, 2, pp. 309-395.
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Poster 11
CORROSION REMEDIATION USING CHLORIDE EXTRACTION CONCURRENT WITH ELECTROKINETIC POZZOLAN DEPOSITION IN CONCRETE
Henry E. Cardenasa, Kunal Kupwade-Patilb a Trenchless Technology Center, Departments of Mechanical and Nanosystems Engineering at Louisiana Tech University, 600 W. Arizona St., Ruston LA, 71272 USA; b Department of Mechanical Engineering at Louisiana Tech University, 600 W. Arizona St., Ruston LA, 71272 E-mail: cardenas@latech.edu
This work examined the impact on corrosion when 20-nm pozzolanic nanoparticles are driven into the capillary pores of relatively immature concrete. Two types of treatment circuits were used, one driving the particles throughout the concrete specimen and the other driving particles directly to the steel reinforcement. The specimens were initially exposed to saltwater followed by Electrochemical Chloride Extraction (ECE) and Electrokinetic Nanoparticle (EN) treatment. Scanning Electron Microscopy (SEM)
revealed a more densified microstructure due to EN treatment. It was found that the reinforcement targeted treatments performed better than the specimen wide treatments. Following 36 days of saltwater re-exposure, the control specimens exhibited severe corrosion as compared to the reinforcement targeted treatment cases. The treatments reduced porosity by 10% and increased tensile strengths by 25 % while causing the conversion of 8 % of the available calcium hydroxide to a variant of C-S-H.
117
Poster 12
ELECTROKINETIC TREATMENT FOR FREEZING AND THAWING DAMAGE REMEDIATION WITHIN LIMESTONE
Henry E. Cardenasa, Pradeep Paturib a Trenchless Technology Center, Departments of Mechanical and Nanosystems Engineering at Louisiana Tech University, 600 W. Arizona St., Ruston LA, 71272 USA; b Department of Mechanical Engineering at Louisiana Tech University, 600 W. Arizona St., Ruston LA, 71272 E-mail: cardenas@latech.edu ABSTRACT Advances in sustainability can be achieved by extending durability. Freeze and thaw damage is a major source of degradation in limestone structures that causes cracking and increased porosity. The increase in porosity tends to compromise durability further. Organic sealants used to curb the moisture intrusion are associated with ground level ozone production. In addition, the limited penetration of these compounds tends to cause freeze and thaw damage to occur deeper within the wall. This study investigated the application of reactive electrokinetic treatment to improve the strength and durability of limestone. The reactants in this case were sodium silicate and calcium hydroxide. Treatments were applied to vertical surfaces using novel re-circulating flow electrodes. A given treatment was applied for 12 days, during which sodium silicate was driven deeply into the limestone block from one electrode and calcium hydroxide from the other. The reactants met inside the stone and formed pore-blocking phases that increased the strength while reducing porosity. Freeze and thaw damage was induced within specimens in accordance with ASTM D 5312. The treatments prevented
deterioration of porosity and strength. In other cases, the treatments appeared to reverse the effects of freeze and thaw damage. Some treatments yielded strength increases of 100% and higher.
118
Poster 13
would occur the most complete removal of oil from the soil, and from other side, the concentration must not exceed the critical value, with which occurs the sharp compression of dual electrical layer. In our studies washing solutions had the following concentrations NaOH - of 0,01, 0,05, 0,1 and 0,25 N and NaCl of 0,01 N. The study results indicated that the oil remaining in the soil samples after decontamination, as under typical no-flow conditions, is redistributed, reflecting decrease of its concentration from the anode towards the cathode. The estimation of a total quantity of oil remote of the sample confirms the noted by us tendencies in the previously carried out experiments under the non-flow conditions, that with an increase in the concentration of the washing solution NaOH occurs an increase in the effectiveness in the electrokinetic cleaning up to concentration NaOH of corresponding 0,1 N, with further increase in the concentration the effectiveness of cleaning is reduced. Data analysis shows that the method of removal without the washing is considerably more effective in comparison with those previously examined by electrokinetic. The conducted investigations made it possible to establish that the maximum effect of the removal of hydrocarbons from the sod-podzolic soil is achieved at concentration NaOH of 0,25 N and 0,1 N, and composes 81 and 93% respectively, while in the usual (non-lixiviation) regime with the same conditions the degree of cleaning it composed 70% and 82%. In this case in proportion to reduction in the concentration of alkaline washing solution to 0,01 N and 0,05 N the degree of cleaning is reduced and composes 70% and 79% respectively. In the experiments with neutral solution NaCl the degree of cleaning composed only 63%. Partial solubility of oil in alkali possibly promotes more efficient oil removal from the sample containing NaOH. Apparently, a part of hydrocarbon contaminant dissolves due to the electrokinetic inter-reaction with the alkali solution. The dissolution contributes to oil transfer from emulsion to solution. Then, oil fractions, dissolved in alkali, move towards the cathode with pore electroosmotic solution and are more easily removed from the sample. It was found that higher alkalinity of the pore solution results in increase of decontamination efficiency as compared with sample containing NaCl neutral solution. Thus, the application of an electrochemical leaching is more effective in comparison with the electrokinetic cleaning in the usual regime. Furthermore, according to obtained data it is possible to conclude that the use in this method of alkaline solutions as the extractant increases a quantity of moved away hydrocarbons.
References [1] Korolev V.A. (2001). Laws of the electrochemical soils remediation from petroleum pollution. EREM 2001. 3rd Symposium and Status Report on Electrokinetic Remediation / Schriftenreihe Angewandte Geologie Karlsruhe, 63, 19 (1-12) [2] Korolev V.A. (2001). The Cleaning of Soils from Pollution. Moscow, MAIK/ Interperiodica publishing house, 365 pp. (in Russian) [3] Korolev V.A., Romanuha O.V. (2005). Research of Factors of the Electrokinetic Clearing Petropolluted Soil. - Mat-ls of VII Intern. Conf. New Ideas in the Ground Sciences, t 4, p. 21 (in Russian) [4] Korolev V.A., Romanuha O.V. (2006). The Electrokinetic clearing of soils from hydrocarbons as the factor of improvement of a resource quality of geological space of the urbanized territories. / Sergeev readings. Youth session. Materials of year session of Scientific advice of the RAS on problems of geoecology, engineering geology and hydrogeology , - Moscow, 8, pp. 128-131 (in Russian)
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Poster 14
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Poster 15
Abstract Rice crop fields are usually submitted to several pesticides during the rice cycle. One of them is the herbicide bentazone. The behaviour of bentazone in soils was studied when submitted to an electric field and the applicability of the electrokinetic process in bentazone soil remediation was evaluated. One soil, collected in the rice fields in central Portugal, was used. Since no old residues were detected from previous rice cycles, the soil was spiked with bentazone. Four electrokinetic experiments were carried out at a laboratory scale. Determination of bentazone residues were performed by HPLC. The results show that the electrokinetic process is able to remove bentazone in soil solution. A one-dimensional model was developed for simulating the electrokinetic treatment of a saturated soil containing bentazone. The movement of bentazone was modelized taking into account the diffusion transport resulting from bentazone concentration gradients and the eventual reversed electroosmotic flow at acidic soil pH. Keywords Electroremediation, herbicides, modeling, soil
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Poster 16
123
used like electrolyte for all of them with a concentration of 0.1M. Experiments were carried out in two electrochemical cells: A) Cubic Plexiglas cell with a working volume of 0.4 L, using graphite electrodes with an immersed area of 52 cm2, and an electrode gap of 8 cm. B) ECO-75 cell from Elchem GmbH has a working volume of 1.5 L, using titanium as cathode and titanium with special platinum coating as anode and surface of 560 cm2. In both cases a constant potential difference (5V) was applied with a power supply (HP model 3662) and the process was monitored with a multimeter (Fluke 175). Samples of reaction mixtures were taken from the electrochemical cells to be analyzed for pH and PAHs concentration. pH was measured with a Sentron pH meter (model 1001). The concentration of PAHs was achieved by using an Agilent 1100 HPLC equipped with a XDB-C8 reverse-phase column and using a diode array detector at 200 to 400 nm. Initially, the PAHs desorption capacity to soil was evaluated. In Anthracene desorption studies have been determined that the highest level of removal for a concentration of 1 g L-1 was around 7.4 % for Tergitol. The desorbed value was increased up to 65.5 % when the concentration of this surfactant was augmented to 10 g L-1. However, the chromatograph obtained showed that the Anthracene peak was surrounded by numerous peaks that interfere in the measure of the concentration. Due to this, it must be chosen to subsequent experiments the surfactant Tyloxapol that showed a clear chromatograph and high removal level (47.5 %). In other hand, the levels of removal of Benzo[a]pyrene were near 84% and 80% when Brij 35 and Tween 80 (10 g L-1) were added, respectively. Thus, Brij 35 (10 g L-1) was selected as the better extracting agent. The electrochemical treatment of PAHs-surfactant solutions obtained in the first stage were carried out in two electrochemical cells with different working volumes 0.4 or 1.5 L and electrode material (graphite or titanium). Time-course of treatment of Anthracene and Benzo[a]pyrene in solutions of Tyloxapol and Brij 35, respectively showed that in both cells similar profiles have been obtained. The kinetic studies of the degradation of the two PAHs fit well (regression 0.98-0.99) to exponential single with three parameters. On the other hand, it is widely recognized that the energy cost is the main drawback when it comes to applying electrochemical processes to the effluents treatment; therefore, the evaluation of both configuration showed a low cost with a medium value of electric power consumption around 0.27 Wh L-1 and 7.95 Wh L-1 to electrochemical treatment in cubic cell and ECO-75, respectively. Thus, the electrochemical oxidation of PAHs-surfactant solutions by electrochemical treatment is an environmental friendly and cost competitive alternative. Acknowledgements: This research was financed by the Spanish Ministry of Science and Technology and European FEDER (Project CTM2004-01539/TECNO).
[1] Luthy, R. G., Aiken, G. R., Brusseau, M. L., Cunningham, S. D., Gschwend, P. M., Pignatello, P. M., Reinhard, M., Traina, S. J., Weber, W.J., Westall, J. C., 1997. Sequestration of hydrophobic organic contaminants by geosorbents. Environ. Sci. Technol. 31, 3341-3347. [2] Sanroman, A., Pazos, M., Ricart, M. T., Cameselle, C., 2004. Electrochemical decolourisation of structurally different dyes. Chemosphere. 57, 233-239. [3] Cameselle, C., Pazos, M., Sanroman, A., 2005. Selection of an electrolyte to enhance the electrochemical decolourisation of Indigo. Optimization and Scale-up. Chemosphere. 60, 1080-1086. [4] Martnez-Huitle, C. A., Ferro, S., 2006. Electrochemical oxidation of organic pollutants for the wastewater treatment: Direct and indirect processes. Chemical Society Reviews. 35 (12): 1324-1340.
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Poster 17
Polycyclic aromatic hydrocarbons (PAHs) are pollutants of major concern in soils and sediments. These hydrocarbons are by-products of incomplete combustion or pyrolysis of organic materials with recalcitrance and strong mutagenic/carcinogenic properties [1]. Despite their very low solubility, once PAHs enter into soil, it is difficult to remediate by conventional treatment methods. Many research efforts have been expended to find suitable method for remediation soil and water environments contaminated with PAHs. Among them, an environmentally friendly approach for PAHs degradation could be based on the use of electrochemical treatment. Much effort is expended world-wide to develop new in-situ remediation methods or principles making remediation of contaminated soils faster and more effective. During the last few years, electrokinetic techniques have been applied successfully for the removal of organic contaminants [2]. In this work an in situ method that consists in the soil electrokinetic remediation had been evaluated in kaolinite spiked with PAHs. Toxic polycyclic aromatic hydrocarbons, such as Phenanthrene, Anthracene, and Pyrene, are persistent and difficult to remove from low permeability clayey soils because these contaminants have low aqueous solubilitys and a tendency to strongly bind with the clay minerals and organic matter present in these soils. These compounds are electrically neutral, so they cannot be transported by electromigration, but they can be removed from the soil by electroosmosis. In order to increase the electroosmotic flow and desorption/solubilization of PAHs some surfactant or cosolvents could be added. The objective of the present study is to evaluate the potential of electro-remediation to remove a model PAHs (Benzo[a]pyrene) from a low permeability soil (such as kaolinite). In order to enhance desorption/solubilization of PAHs in soils mixed of cosolvent or surfactant (ethanol or Brij 35) and electrolyte Na2SO4 were evaluated. The experiments were conducted in the electrokinetic cell (cylindrical glass) that contained a sample compartment of 100 mm length and 32 mm inner diameter. The two electrode chambers were placed at each end of the sample compartment isolated from this one by paper filter and porous stones. Graphite electrodes were used for both anode and cathode [3]. Three auxiliary electrodes allowed measuring the electric field distribution along the sample. Electrode chambers were filled with ethanol (40%) or Brij 35 (1%) and Na2SO4. Recirculation of liquid was applied by pumps to avoid concentration gradients. An electric field (3 V DC/cm) was applied across two inert electrodes of graphite, located at both sides of the soil sample. The soil was artificially contaminated (spiked) with Benzo[a]pyrene at a target concentration of 500 mg/kg (mass of PAHs/mass of dry soil).
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As can be seen in Figure 1, after thirty days, around 75.4% of initial Benzo[a]pyrene was removed from the soil using Brij 35 (1%) and Na2SO4 (0.1 M) as processing fluid (which enhanced the desorption of Benzo[a]pyrene from the kaolinite 1,4 12 matrix) and operating with pH control without pH control 1,2 anode pH control at 4.5 at 4.5. Thus, the presence of Brij 35 10 pH pH control 1,0 and Na2SO4 increases the electric conductivity and favours the 8 0,8 desorption of Benzo[a]pyrene from the 0,6 6 clay particles. Moreover, the effect of 0,4 the soil pH was demonstrated. It was 4 very clear that the pH jump limited the 0,2 current intensity and increased the 0,0 2 electrical resistance of the system S1 S2 S3 S4 S5 reducing the Benzo[a]pyrene Figure 1. Electrokinetic treatment of Benzotransport. [a]pyrene contaminated kaolinite with/without
C/C0
pH control.
In view of the results obtained, it can be concluded that electrokinetic remediation appears to be a promising technique for the removal of PAHs from low permeability soils. However the operating conditions, especially the pH value into the soil sample, are decisive to achieve a full remediation.
Acknowledgements: This research was financed by the Spanish Ministry of Science and Technology and European FEDER (Project CTM2004-01539/TECNO).
[1] Joner, E.J., Johansen, A., Loibner, A.P., Cruz, M.A.D., Szolar, O.H.J., Portal, J.-M., Leyval, C. Rhizosphere effects on microbial community structure and dissipation and toxicity of polycyclic aromatic hydrocarbons (PAHs) in spiked soil. (2001). Environmental Science and Technology, 35 (13): 2773-2777. [2] Reddy, K.R., Ala, P.R., Sharma, S., Kumar, S.N. Enhanced electrokinetic remediation of contaminated manufactured gas plant soil. (2006) Engineering Geology, 85 (1-2): 132-146. [3] Pazos, M., Sanromn, M.A., Cameselle, C. Improvement in electrokinetic remediation of heavy metal spiked kaolin with the polarity exchange technique. (2006). Chemosphere, 62 (5): 817-822.
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pH
Poster 18
Dyes are organic colorants used in textile, pharmaceutical, cosmetic, food, and other industries for imparting different shades of colours. Dye manufacturers and users, particularly the textile industries, release wastewaters in massive quantities containing dye to the extent of 0.001-0.7% (w/v) [1]. Decolourisation of industrial textile effluents can be obtained by chemical, biological and physical methods. Each method has advantages and disadvantages. Biological processes show a limited colour removal due to the toxic nature of some dyes and the high salt concentration. Adsorption in activated carbon, membrane filtration, coagulation-flocculation and chemical oxidation with ozone have a considerable cost [2]. Sometimes, spilling and bad management of those effluents provoked the pollution of soils with this kind of organic pollutants. Biological, physical and chemical processes to remove organic pollutants have been considered for remediation of contaminated soils [3]. However, few reports about dye removal from polluted soils were found in the literature. Hence, there is a great interest in developing a soil remediation technology cost-effective and eco-friendly for those xenobiotic and recalcitrant organics. In this work, it is proposed a novel technique that combined electrokinetic remediation and electrochemical treatment for the removal and degradation of textile dyes from polluted soils. The technique uses the electrokinetic remediation for the extraction of pollutants (dye) from soil. In a second stage, the electrochemical degradation is used to degrade the dye to simpler molecules, reaching even the total mineralization. In order to test the feasibility of the combined purposed treatment, the electrokinetic remediation of kaolinite polluted with an acid diphenylnaphthylmethane dye Lissamine Green B (LGB) and the further electrochemical oxidation of the dye have been studied. The electrokinetic remediation was carried out in the electrokinetic cell (cylindrical glass) that contained a sample compartment of 100 mm length and 32 mm inner diameter. The two electrode chambers were placed at each end of the sample compartment isolated from this one by paper filter and porous stones. Graphite electrodes were used for both anode and cathode [2]. An electric field (3 V DC/cm) was applied across two inert electrodes of graphite, located at both sides of the soil sample. The soil was artificially contaminated (spiked) with LGB at a target concentration of 0.225 g dye kg-1 of dry matter, and its pH was around 4 in all the experiments. The moisture content was around 32%, expressed as weight of water per unit weight of wet kaolinite. The unenhanced electrokinetic treatment did not result in any significant removal of LGB from the kaolinite sample. However, the use of Na2HPO4 as processing fluid increased the electro-osmotic flux, improved the desorption of dye from the surface of kaolinite particles and prevented the acidification of the medium. It resulted in the transportation of 94% of the dye towards the cathode chamber where it was
127
accumulated (Figure 1). The use of K2SO4 in the processing fluid also improve the results compared to the unenhanded experiment but the removal of dye only reached 75% due to the lower electro-osmotic flux registered in this experiment.
1,0 12 0,8 10
0,6
0,4
0,2
0,0 S1 S2 S3 S4 S5
Once the dye was removed from kaolinite clay sample, the dye Lissamine Green B can be decolourized upon the electrodes. This process was studied at different dye concentrations (7.5 150 mg L-1) and with disodium hydrogen phosphate (0 0.01 M) as electrolyte. The presence of Na2HPO4 clearly improves the degradation rate reaching 90% of decolourization in 90 min.
Figure 1. Electrokinetic treatment of LGB spiked kaolinite with Na2HPO4 as processing fluid in the cathode and anode chamber. Normalized concentration (bar) and pH (line).
The results obtained in this work have clearly shown that by the used of this combined treatment, full remediation of dye polluted kaolinite at low cost without operational problems, can be achieved. Therefore, this technique may be an attractive option for treatment of industrial wastes (water and ground) contaminated with dyes. Moreover, the process was improved by addition of an adequate electrolyte such as disodium hydrogen phosphate. This electrolyte has a double utility as: Processing fluid in electrokinetic treatment: its presence in the cathode and anode chambers favoured the electric conductivity and the desorption of LGB in the soil. Electrolyte in electrochemical treatment: there is a relationship between the decolourization rate and electrolyte concentration. When the disodium hydrogen phosphate concentration is augmented, the dye decolourization rate increased. Thus, operating at the optimized conditions determined in the present study an appropriated configuration was designed and the full remediation of polluted kaolin at low cost without operational problems can be achieved.
[1] Zollinger, H. Color Chemistry-Syntheses, Properties and Applications of Organic Dyes and Pigments. 3rd Ed. Wiley-VCH, 2003. [2] Pazos M, Ricart MT, Sanromn MA, Cameselle C. Enhanced electrokinetic remediation of polluted kaolinite with an azo dye. Electrochimica Acta 2007; 52(10): 3393-3398. [3] Gong Z, Wilke BM, Alef K, Li P, Zhou Q. Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: Laboratory column experiments. Chemosphere 2006; 62(5):780-787.
pH
128
Poster 19
The wrong management of the industrial wastes in the past had dealt to the pollution of the surrounding areas of industrial sites. Often, the pollution includes inorganic salts, heavy metals, complex organic compounds, etc. Very few technologies (soil washing) can be applied for the removal of heavy metals and organic pollutants from soil and solid wastes, and in many cases they do not success mainly due to the longer treatment time and the high cost involved. Literature had proved that electrokinetic remediation has the potential to remove either heavy metals or organic compounds from soils, sediments and solid wastes. However, very few research groups deal with the simultaneous removal of organics and heavy metals [1-3]. The different nature of both types of pollutants and their possible interaction made difficult to optimize the operating conditions for their extraction and transportation out of the soil. The aim of this work is to evaluate the feasibility of the electrokinetic treatment of solid matrixes polluted with organics and heavy metals. Tannery industry produces wastes with a high content of chromium and a complex organic pollution, mainly dyes. Chromium is a dangerous heavy metal found in the tannery industry wastes in high concentration. Moreover, about 15% of total world production of wastewater in textile dyeing/finishing and also in food, paper and cosmetic industries are lost in its effluents. The discharge of these highly coloured wastewaters into the ecosystem involves environmental problems. There are more than 10000 of chemically different dyes synthetic and pigments. Among them, azo dyes are a major class of synthetic, coloured organic compounds and account for about half of the textile dyestuffs used today [4]. The optimization of the electrokinetic treatment of this waste is rather difficult due to its complexity in composition and the possible interactions among its components. Therefore, the application of electrokinetics in this kind of wastes was firstly tested in model samples at bench scale. These model samples were prepared with kaolinite clay polluted with Cr and an azo dye such as Reactive Black 5 (RB5). RB5 is a dye commonly used in the industry, its complex structure with several aromatic rings and two azo bonds, make it appropriate as a model organic pollutant. In previous paper, Pazos et al. [5] have determined that the electrokinetic treatment of the RB5 spiked kaolinite sample can result in a complete cleaning of the kaolinite matrix if the operating conditions are adjusted properly. The presence in the processing fluid of salts, which favour RB5 desorption from the kaolinite matrix, and the operation at alkaline pH (which favours the ionization of the molecule), enhanced the migration towards the anode, where the dye is accumulated. On the other hand, the removal of heavy metals by electrokinetics can be achieved in acidic conditions, since low pH favours the solution of metals and they form cationic species that migrate towards the cathode. It is obvious that the optimum conditions for removal of Cr and RB5 do not mach up.
129
In order to improve this electrokinetic process, it is necessary to add an electrolyte that increases the electric conductivity and favours the desorption of dye from the polluted clay sample. Potassium sulphate was found to have been very effective in the extraction of dye from the mineral matrix and its presence increases the electric conductivity and favours the desorption of RB5 from the clay particles. In these experiments potassium sulphate was selected as processing fluid, filling the anode and cathode chamber with 0.1 M potassium sulphate. The operating conditions, especially the pH value into the soil sample, are decisive to achieve a full remediation. It was determined that near complete cleaning of the kaolinite matrix could be obtained when electrokinetic treatment was carried out with pH control on anode. When pH value was controlled at 70.2 on the anode chamber it avoided the formation of an acid environment at the anode side and favoured the advance of the basic front. So, the kaolin sample was alkalised reaching an almost flat pH profile (from 9.2 to 9.6). As can be seen in figure 1, 97% of the initial RB5 was removed from kaolinite by electromigration towards the anode, where the dye was oxidized upon the surface of the electrode by electrochemical oxidation. On the other hand, Cr was transported towards the cathode by electromigration as a cation but also by electroosmosis. About 96% of initial Cr was found in the cathode chamber as a precipitated due to the high pH in the cathodic solution. Only 4% of Cr remained in kaolinite.
100 14 80 12
From these results, it is supposed that the interaction among RB5 and Cr into the kaolinite sample avoid the usual premature precipitation of Cr into the soil and favors its migration and concentrate in the cathode chamber.
60
10 pH
40
20
0 A B C D E
4 Cr RB5 pH
F Figure 1.- Electrokinetic treatment of RB5 and Chromium spiked kaolinite with pH control in the anode
130
Poster 20
Anode
HydraulicHead Equalizer(HHE)
EO w Flo
From HHE
DC Power Supply
Effluent
131
1200
1000
800
600
400
200
Fig. 2. Sorbed zinc concentration after electrokinetic processes as a function of normalised distance from cathode
350
Fig. 3. Aqueous zinc concentration after electrokinetic processes as a function of normalised distance from cathode
[1] Acar, Y. B. and Alshawabkeh A. N. (1993), Principles of electrokinetic remediation, Environ. Sci. Technol., 27(13), pp. 2638-2647. [2] Hamed, J., Acar, Y. B. and Gale, R. J. (1991), Pb(II) removal from kaolinite by electrokinetics, J. Geotech. Eng., 117(2), pp. 241-271. [3] Mitchell, J. K. (1993), Fundamentals of soil behaviour, Wiley Inter. Science [4] Pamukcu, S. and Wittle, J. K. (1992), Electrokinetic removal of selected heavy metals from soil, Environmental Progress, 11, pp. 241-250. [5] Yeung, A. T. (1994), Electrokinetic flow processes in porous media and their applications, Advances in porous media, Elsevier, 2, pp. 309-395.
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Poster 21
were tested for the extraction of iron from kaolin, mainly organic acids [4]. Among the organic acids tested (citric acid, gluconic acid,) only oxalic acid shows a good activity releasing and dissolving the iron from kaolin. The best results were found at low pH and with high oxalic acid concentrations. Oxalic acid dissolves iron from kaolin by direct attack of H+ ions to the minerals that contains iron. Once the iron is in solution as Fe3+, oxalic acid forms a soluble complex that stabilises the metal in solution and prevents its precipitation. It was found a ratio between the amount of oxalic acid used in the extractions and the amount of iron in solution. 3 mol of oxalic acid are needed for dissolving 1 mol of iron. It suggests the formula of the soluble complex (equation 1) 3 (C2O4)2- + Fe3+ [Fe(C2O4)3]3[eq 1]
In the this soluble complex, iron, as ferric ion Fe3+, is bonded to three oxalate ions by one of the oxygens corresponding to the acid groups. The complex has a yellow colour, the same as the supernatant after the leaching of kaolin. The oxalate ion in the complex is oxidized by the action of Fe3+ ion in a reaction catalyzed by light, resulting CO2 and ferrous oxalate, which forms a brown precipitate (equation 2). This explains the precipitate formation after the leaching process is completed. The complex is stable when maintained in darkness. The formation of a precipitate of ferrous oxalate removes the iron from the effluent from a leaching process, so avoiding environmental problems and simplifying effluent treatment.
[eq. 2]
The electrokinetic treatment of iron polluted kaolin was carried out with pH control at 6 in the cathode to suppress the acid front. The electrode chamber were filled oxalic acid 0.1M that acted as electrolyte favouring the electric conductiviy of the system and also favours the extraction and complexation of the iron. Most of the iron was recovered in the cathode assuring the formation of the negatively charged complex. Operating in these conditions the iron was removed from kaolin and its whiteness index increased up to 80% (measured as light reflexion using boric acid as reference for 100% of whiteness). This value is adequate for the main industrial applications of kaolin. Acknowledgements: This research was financed by the Spanish Ministry of Environment (Project number: 294/2006/1-1.2).
[1] Ribeiro, F.R., Mussel, W.N., Fabris, J.D., Novais, R.F., Garg, V.K. Identification of Iron-Bearing Minerals in Solid Residues from Industrial Kaolin Processing. Hyperfine Interactions 148-149 (1-4): 4752. [2] Vegli, F., Passariello, B., Toro, L., Marabini, A.M. (1996). Development of a bleaching process for a kaolin of industrial interest by oxalic, ascorbic, and sulfuric acids: Preliminary study using statistical methods of experimental design. Industrial and Engineering Chemistry Research 35 (5), pp. 1680-1687 [4] C. Cameselle, M.J. Nez, J.M. Lema. (1997). Leaching of kaolin iron-oxides with organic acids. Journal of Chemical Technology and Biotechnology 70 (4): 349-354. [3] Cameselle, C., Ricart, M.T., Nez, M.J., Lema, J.M. (2003). Iron removal from kaolin. Comparison between "in situ" and "two-stage" bioleaching processes. Hydrometallurgy 68 (1-3): 97-105
134
Poster 22
Whereas the citric-Fe complex migrates towards the anode, the electroosmotic flow carries Fe to cathode chamber. Fe transportation will be slower than the other metals because of the electromigration in the opposite direction. In experiment 3, citric acid was used to control de pH in the cathode chamber. So, citric acid acted as neutralising and complexing agent. When pH control was carried out with mineral acids (sulphuric or nitric acid) a precipitated of difficult handling was formed [2] because the metal undergoes further reactions on the electrode. Using citric acid, this precipitated is not created, because citric acid maintains the metal in its soluble form and protect them from further reactions on the electrode. It makes the subsequent handling and treatment easier. Nevertheless Cu was electroplated on the cathode what means that it was separated with a good quality and its recovery can be a possibility. As well as experiment 2, the elimination of Cu, Zn and Mn was complete using citric acid as depolarised agent. On the other hand, the elimination of Fe was poor, similar to that obtained in the control experiment. Fe3+ migrated in the direction of the cathode, while the citrate added to the cathode chamber migrates through the soil in direction to the anode. Citrate principally formed a complex with iron because of the high value of the formation constant. Under the pH conditions into the soil, the citrate-Fe(III) complex is negatively charged and tended to migrate to the anode, although it moved slowly due to its big size. After 7 days of treatment, citrate and iron were principally concentrated in the sections 4th and 5th (the closest to the cathode) as it can be seen in Figure 1. No significant electroosmotic flow was observed in this experiment confirming that the primary transport mechanism was electromigration. When citric acid is added in the electrode chambers no electroosmotic flow change was observed, as it was also reported by Zhou et al. [3], this confirming that the citric concentration in the soil is an important factor to enhance the electroosmosis [1, 4].
1000
60
600
40
400
20
200
0 Anode S1 S2 S3 S4 S5 Cathode
Acknowledgements: This research was financed by the Spanish Ministry of Environment (Project number: 294/2006/1-1.2).
[1] Popov, K.I., Shabanova, N.A., Artemeva, A.A., Urinovich, E.M. and Tulaeva, Y.V. (1997). Influence of Chelating Agents on the Electrokinetic Potential of the Clay Fraction of Soddy Podzolic Soils. Colloid J. 59 (2), 212-214. [2] Pazos, M. (2002). Remediacin electrocintica de suelos contaminados con Mn en condiciones de pH controladas. Master Thesis. Department of Chemical Engineering, University of Vigo. [3] Zhou, D.M., Zorn, R. and Kurt, C. (2003). Electrochemical remediation of copper contaminated kaolinite by conditioning anolyte and catholyte pH simultaneously. J Environ. Sci.-China 15 (3), 396-400.
136
Poster 23
Mining activities in Chile have generated large amounts of solid waste, which have been deposited in mine tailings impoundments. These impoundments cause concern to the communities due to dam failures or natural leaching to groundwater and rivers. The need for remediation or control of these wastes is obvious. Electrokinetic remediation has shown its potential for remediation of a great variety of solid waste materials. A possible mine tailings treament is based on the electrodialytic remediation principle [1], where the introduction of ion exchange membranes improves the electrokinetic remediation process. Electroremediation - both electrokinetic (EKR) or electrodialytic (EDR) - could also be promising with mine tailings. Furthermore, the recovery of metal from the mine tailings could mean a profitable solution. Hansen et al. [2] showed that copper could be removed from tailings using electrodialytic remediation but the process had to be enhanced by optimizing the treatment conditions. One of the most concerning parameters was the remediation time. Lately, Ferreira et al. [3] have shown that the remediation time can be decreased remarkably when treating the solid waste material in suspension. The idea was to have the solid suspended by mechanical stirring in an electrical conducting liquid typically with a liquid-to-solid ratio between 5 and 10. The dissolution is rapid, and thereby the electromigration of dissolved heavy metals towards the electrodes too. The system is homogenous and no concentration and pH gradients are generated in the transport medium. No electroosmosis as in the case of static electroremediation will occur, only transport of ions. The results show that even if the solid material to be treated is occupying a fifth of the volume compared to static electroremediation, the remediation time is shortened by a factor of 20. This means that the overall remediation time for a certain mass to be treated is four times shorter in the suspended cell than with the static cell. The present work suggests the use of neumatical stirring instead of mechanical stirring. The use of air as a stirrer to produce the suspension also provides an oxidizing condition for certain heavy metal species such as sulphides present in tailings. Figure 1 shows the principle in electrodialytic remediation, where the solid waste material is suspended in compartment III. The fine porous material in suspension is stirred by the air flow introduced at the bottom of the cell. The electric field is generated between the anode (comp. I) and cathode (comp. V), and the heavy metal cations, which are released fast to the solution, are transported across membrane c into compartment IV. Here heavy metal
137
anode I II
reagents III
sampling
vent IV
cathode V
Suspended tailings
Cu2+
will continuously be removed from the solution by ion exchange resin, which on the other hand will release protons to neutralize OH- coming from compartment V (cathode reaction). This work shows the laboratory results of six electrodialytic remediation experiments on copper mine tailings. The results show that electric current could remove copper from watery tailings applying 42 mA during 7 days. The liquid-to-solid ratios used were 3, 6 and 9. With addition of sulphuric acid, the process was enhanced because the pH decreased to around 4, and the copper by this reason was released in the solution. The maximum copper removal was 53% with addition of sulphuric acid in 7 days experiment at 42 mA using approximately 137.5 g mine tailings on dry basis. The removal for a static (baseline) experiment only reached 12 % when passing approximately the same amount of charge through 130 g of mine tailings. The use of air bubbling (as stirring mechanism) increased the removal efficiency from 30 % to 53 % compared to no stirring maintaining other operation conditions the same.
[1] Hansen et al., Journal of Chemical Technology and Biotechnology 70 (1997) 67-73. [2] Hansen et al., Journal of Hazardous Materials 117 (2005) 179-183. [3] Ferreira et al., Engineering Geology 77 (2005), 339347.
138
Poster 24
Each tailing section was divided in three zones: anode, center and cathode, in order to evaluate copper removal. Table 1 shows a summary of the experiemental.
1 2 3 4 5 6 7
Distilled water / 0 Citric acid / 0 Distilled water / 1 Citric acid / 1 Distilled water / 3 Citric acid / 3 Distilled water / 1
Bipolar plates in electrodialytic remediation (EDR) of copper mine tailings improves the remediation action. This fact occurs even though the electric field is reduced when implementing bipolar electrodes, since some of the electric field is consumed by the electrochemical reactions on the plates. Basically three aspects that improved the process were found: i) reduction of the pathways of ionic migration, ii) increase of the electrode surface and iii) in-situ generation of protons (H+) and hydroxyls (OH-). The citric acid addition together with 1 or 3 bipolar electrodes improved even more the remediation action, reaching copper removal in the anode and center zone up to nine times better, compared to conventional experiences EDR without any plates or addition of citric acid [2,3].
139
Removal obtained in the anode zone as in the center zone could be improved increasing the the remediation time further than 18 days. This is due to the fact that there would still exist a margin to continue removing copper from tailing. These major times of EDR would furthermore be useful to increase the removal in the tailings center zone and, for this reason, to get finally a major amount of remedied material. In addition, the acid and alkaline fronts which are generated when using bipolar plates should reduce the tailing neutralization times posteriors for having a minor migration pathway.
[1] Hansen, H.K., Rojo, A., Ottosen, L.M., Electrochimica Acta, 52 (2007) 3355-3359. [2] Hansen, H.K., Rojo, A., Ottosen, L.M., Journal of Hazardous Materials 117 (2005) 179. [3] Rojo, A., Hansen, H.K., Separation Science and Technology 40(9) (2005) 1947.
140
Poster 25
141
range of 10-15 ml/s. The anode and cathode tanks had the volume capacity of 2 liters each and 1500ml of liquid was always present in the tanks during the experiments. In the first electrokinetic remediation experiment, pH values in anode and cathode electrode cells were kept constant at 4. In the anode cell, pH was adjusted to 4 by acetic acid at the start of the experiment and tap water was added when a decrease in pH was observed. On the other hand, the control of pH in the cathode cell was adjusted by circulating 0.1 M acetic acid solution. After the adjustment of pH in both electrode cells a constant current of 50 mA was applied to the sediment specimen. In the second electroremediation experiment, only the applied current was changed and increased to 70 mA. 2. Results The residual manganese, zinc, copper and lead concentrations in the sediment with recpect to the distance from anode were evaluated by using atomic absorption spectrometer measurements. The lowest amount of manganese (38.6 mg/kg) was observed close to the anode. In addition, close to the cathode the residual manganese concentration (480 mg/kg) was higher than the amount present in the original sediment (355 mg/kg). These observations clearly indicate manganese ions are transported toward to cathode. For copper, zinc and lead, however, the accumulation was observed in the middle section of the sediment. Because of having alkaline sediment, it might take additional time to observe desorption of the metals due to the acidity of the soil, especially in the middle section of the sediment sample. In addition, the reverse electroosmotic flow were observed during the experiments and its direction changed periodically. Therefore, having alkaline sediment, controlling pH at both ends and reverse electroosmotic flow could be some of the reasons for the accumulation of metal ions in the middle. It is also concluded that manganese is mainly present in the form of metal acetates (MnAc+) in the pore fluid and therefore, they only move toward the cathode. When the applied current to the sediment specimen was increased from 50 mA to 70 mA in addition to pH control at electrode cells, no increase in the removal efficiency of metals was observed. Therefore, increasing electric field strength does not necessarily mean an increase in the removal efficiency. The calculated removal efficiencies of manganese, copper, lead and zinc were 18%, 20%, 12%, and almost zero, respectively. On the other hand, depending on the experimental results, the control of pH at both electrode cells can decrease the electrical potential difference across the electrodes in comparison to un-enhanced electrokinetic remediation, and this can result in energy saving. [1] Y.B. Acar and A.N., and A.N. Alshawabkeh, Principles of Elektrokinetic Remediation, Environmental Science and Technology 27 (1993) 2638-2647. [2] S. O. Kim, K.W. Kim, D. Stuben, Evaluation of Electrokinetic Removal of Heavy Metals, Journal of Environmental Engineering 28 (2002)705-715 [3] D. Turer, A. Genc, Assessing effects of electrode configuration on the efficiency of electrokinetic remediation by sequential extraction analysis, Journal of Hazardous Materials B119 (2005) 167-174. [4] A. Giannis, E. Gidarakos, Washing enhanced electrokinetic remediation for removal cadmium from real contaminated soil, Journal of Hazardous Materials B123 (2005) 165-175.
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Poster 26
143
the preliminary treatment is effective in reducing membrane-fouling and in increasing metal removal. The preliminary washing also means that less energy was wasted in the transport of soluble salts. To assess the possible impact of EDR in reducing the environmental risk posed by fly ash it is necessary to evaluate how metals are bond to the ash: more important than the total amount left in the ash after treament is the amount of the easily soluble fraction, since this last fraction poses the highest environmental risk. To evaluate this parameter a sequential extraction was performed to the sample before and after EDR. The procedure is an adaptation of the schemes presented in [4-5] and allows the identification of 6 different fractions, which were further grouped in 3 main categories: readily soluble, strongly bonded and residual. It was seen that after EDR metals in the fly ash are mainly found in the strongly bonded and residual phases, thus indicating that the treatment has been successful in reducing the environmental risk posed by this waste. The treatment by EDR aims at removing the readily soluble fraction, which causes the major impacts on the environment due to its leaching potential. EDR does not intend to remove the more strongly bound fractions since they are not of environmental concern for the current available disposal/reuse options. The efficiency of the remediation was therefore calculated as the percentage of metal from the easily soluble fraction which was removed during treatment. Results show that almost all Zn (88%) and Cd (92%) present in the easily soluble forms were extracted, indicating that treatment was successful for these metals. For lead and copper the results are 31% and 13% respectively. A comparison with a similar experiment [3] without preliminary washing shows that efficiencies, while similar for lead, were higher for the other metals, even though remediation time was 1/3 (14 days instead of 40). The main conclusions of this work are firstly, that the preliminary treatment is successful in reducing fouling of the ion-exchange membranes during EDR of fly ash and increases performance and, secondly, that metals in the EDR-treated fly ash are mainly found in the strongly bonded and residual phases, thus indicating that the treatment has been successful in reducing the environmental risk posed by fly ash. [1] Ferreira, C., Ribeiro, A., Ottosen, L. Possible applications for municipal solid waste fly ash. J Hazard Mater, 2003, B96, 201-216. [1] Ottosen, L.M., Hansen, H.K., Laursen, S., Villumsen, A. Electrodialytic remediation of soil polluted with copper from wood preservation industry. Environ. Sci. Technol, 1997, 31, 1711-1715. [3] Ferreira, C., Ribeiro, A., Ottosen, L. Treatment of MSW fly ashes using the electrodialytic remediation technique, in: Brebbia, C.A, Kungolos, S., Popov, V., Itoh, H. (Eds.), Waste Management and the Environment II. Wit Press, 2004, UK. [4] Wunsch, P., Greilinger, C., Bieniek, D., Kettrup, A. Investigation of the binding of heavy-metals in thermally treated residues from waste incineration. Chemosphere, 1996, 32, 2211-2218. [5] VanHerck, P., VanderBruggen, B., Vogels, G., Vandecasteele, C.,. Application of computer modelling to predict the leaching behavior of heavy metals from MSWI fly ash and comparison with a sequential extraction method. Waste Manag, 2000, 20, 203-210.
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Poster 27
AN ENHANCED ELECTROKINETIC REMEDIATION FOR LEAD REMOVAL FROM SOILS POLLUTED FROM A ZINC PRODUCTION PLANT
Ahmet Altina, Mustafa Degirmencib a Dept. of Environmental Eng., Z. Karaelmas University, 67100-Zonguldak-TURKEY; b Dept. of Environmental Engineering, Cumhuriyet University, 58140-Sivas-TURKEY E-mail: aaltin@karaelmas.edu.tr ABSTRACT The effectiveness of the electrokinetic remediation enhanced with acetic acid (AcH) in sandy soils polluted from a zinc production plant was investigated. Best removal efficiencies were obtained by using 3 molar AcH in the cathode chamber and applying 20 volt constant potential. For these conditions, lead (II) removal efficiencies for sandy soils were varied between 65% and 85% up to 0.6 of normalized distance from anode. Key Words: Electrokinetic remediation, Sandy soil, Lead (II), Zinc production plant INTRODUCTION During the electrokinetic remediation experiments, numerous electrochemical reactions and soil-contaminant interactions can take place, simultaneously [1]. Especially, the precipitation reactions closed to cathode area affect the effectiveness of the remediation, negatively. These reactions can be hindered by using purging solutions (AcH, citric acid, HCl etc.) [2]. The aim of this study is to investigate the treatability of lead (II) from a sandy soil, polluted with solid/gas emissions of a zinc production plant, by electrokinetic remediation process. In order to increase of the removal efficiency, the different concentrations of acetic acid (AcH) were applied as purging solution into the cathode chamber. MATERIALS AND METHODS In this study, samples taken from near by the zinc production plant in Kayseri City (Turkey) were used. For the determination of mineralogical properties of the samples, XRD whole-rock analyses were conducted. According to the results, the soil samples contain significant amounts of quartz (45%) and feldspar (47%) minerals, and contain low amounts of clinoptilolite (6%) and simectite (2%) minerals. The samples can be classified as sandy soil, evaluating grain size distribution of the sample. The lead sorption capacity and the average lead concentration of the samples are 4.7 meq/100g.soil and 2650 mg/L, respectively. Electrokinetic remediation apparatus, adapted from [3], is consisted of an extraction cell, fluid-gas volume measurement devices, a DC power supply and a multimeter. In our experimental works, the anode and the cathode compartments were filled with distilled water and AcH (0.5 and 3.0 M) as purging solution, respectively. The remediation experiments were run under a constant potential (7.5 and 10 volt) during the treatment time of 272 hour. At the end of the each test, the soil samples sliced into six sections, and the values of pH and lead (II) concentration were measured in each slice. RESULTS AND DISCUSSION Puppala et al. [2] determined that pH value less than 6 would be sufficient to dissolve and remove the lead (II) in the soil and aid in lead (II) transport to cathode. Virkutyte et al. [4] also reported that precipitation reactions could be minimized at pH value less
145
than 4.5. As seen in Fig.1a, it is possible to reach these pH values by using the purging solutions. The best removal efficiencies were obtained at the test conditions using 3 M AcH and by applying 20 volt constant potential (Fig.1b). In these test conditions, the lead (II) removal efficiencies were varied between 65 and 85% up to 0.6 of normalized distance. Similarly, Sah and Chen [5] pointed out that this efficiency for sandy soil was 70% up to 0.7 of normalized distance at the end of seventh day by using 0.1 M HCl as purging solution. In another study, Vengris et al. [6] also obtained 70% lead (II) removal up to 0.5 of normalized distance at 220th hours. Another result shown in Fig.1b reveals that the efficiencies increase with the increment of applied current. However, it is also taken into consideration by applicants that the energy expenditure of the process increases proportionally for high voltages [7].
12 10 8 pH value 6 4 2 0 1. Slice 2. Slice 3. Slice 4. Slice 5. Slice 6. Slice Distance between from anode to cathode (15 cm)
Lead(II) conc. rate, (C / C 0) 2,0
Potential: 20 V and AcH: 3.0 M Potential: 20 V and AcH: 0.5 M Potential: 7.5 V and AcH: 3.0 M Potential: 7.5 V and AcH: 0.5 M
a)
1,8 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0
Potential: 20 V and AcH: 3.0 M Potential: 20 V and AcH: 0.5 M Potential: 7.5 V and AcH: 3.0 M Potential: 7.5 V and AcH: 0.5 M
b)
1. Slice
2. Slice
3. Slice
4. Slice
5. Slice
6. Slice
Fig.1. The pH (a) and lead (II) (b) profiles for different test conditions [8]. CONCLUSION Conclusions derived from experimental studies are summarized as follows: In order to removal lead (II) from sandy soils, electrokinetic remediation process enhanced with AcH can be used effectively. The precipitation reactions taken place closed to cathode area may be hindered by using 0.5 M AcH. However, lead (II) removal efficiencies of the tests using 3 M AcH are better than that using 0.5 M. The energy consumption of the process increases significantly, whereas applying high potential affects the effectiveness of the remediation, positively.
[1] Chung, H.I., Kang, B.H., 1999. Lead Removal from Contaminated Marine Clay by Electrokinetic Soil Decontamination, Engineering Geology, 53, 139-150. [2] Puppala, S.K., Alshawabkeh, A.N., Acar, Y.B., Gale, R.J., Bricka, M., 1997. Enhanced Electrokinetic Remediation of High Sorption Capacity Soil, J. of Hazardous Materials, 55, 203-220. [3] Hsu, C.N., 1997. Electrokinetic Remediation of Heavy Metal Contaminated Soils, PhD Dissertation, Texas A & M University, Texas, 285 p. [4] Virkutyte, J., Sillanpaa, M., Latostenmaa, P., 2002. Elektrokinetic Soil Remediation: Critical Overview, The Science of the Total Environment, 289, 97-121. [5] Sah, J.G., Chen, J.Y., 1998. Study of the Electrokinetic Process on Cd and Pb Spiked Soils, J. of Hazardous Materials, 58, 301-315. [6] Vengris, T., Binkiene, R., Sveikauskaite, A., 2001. Electrokinetic Remediation of Lead, Zinc and Cadmium Contaminated Soil, J. of Chemical Technology and Biotechnology, 76, 1165-1170. [7] Azzam, R., Oey, W., 2001. The Utilization of Electrokinetics in Geotechnical and Environmental Engineering, Transport in Porous Media, 42, 293-314. [8] Altin, A., Altin, S., Atmaca, E., Degirmenci, M., (2004), Lead (II) Removal from Natural Sandy Soils By Enhanced Electrokinetic Remediation, B. of Environmental Contamination and Toxicology 73(3), 551-560.
146
Poster 28
147
compared to initial pH (8.47) because the concentration of calcium oxide contained in the mine tailing was high and calcium oxide was dissolved by acid front. This result means that the mine tailing has large buffering capacity to acid. Generally, extraction of arsenic from soil was enhanced by alkaline condition. We can expect high removal efficiency of arsenic. However, mine tailing used in this study contains a lot of CaO (57 wt %). The material caused high pH of mine tailing, and the tailing has high buffering capacity against acidic circulation. Figure 2 shows arsenic distribution in mine tailing after experiment. Overall removal efficiency of arsenic was 59%, 44%, 37% and 37% for Exp. 1, Exp. 2, Exp. 3 and Exp. 4, respectively. In Exp. 1 (electrolyte only) and Exp. 3(circulation with acid), arsenic concentration in anode region was higher than middle section and cathode region. Especially, direction of electroosmotic flow was changed toward anode from cathode after 5 days operation in Exp. 3. Anolyte circulating with alkaline solution was not effective (Exp. 2 and Exp. 4). On the contrary higher concentration of alkaline solution decreased the removal of arsenic. In Exp. 2 and Exp. 4, arsenic concentration in cathode region was slightly higher than anode region because high pH caused more electroosmotic flow. Anolyte circulation with acidic solution was enhanced arsenic removal compared to control experiment. Table 1. Composition of electrolyte for electrokinetic experiments.
Circulating solution for Anolyte Exp. 1 Exp. 2 Exp. 3 Exp. 4 MgSO4 1.0 M NaOH 0.5 M MgSO4 1.0 M NaOH 0.1 M HNO3 0.1 M Circulating solution for Catholyte
12 2.5 11 2.0
pH distribution
C/C0
Initial soil pH : 8.47 Exp. 1 Exp. 2 Exp. 3 Exp. 4 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
10
7 0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
[1] I. Ko, Y.-Y. Chang, C.-H. Lee, K.-W. Kim, Asessement of pilot-scale acid washing of soil contaminated with As, Zn and Ni using BCR three-step sequential extraction, J. Hazad. Mater. A127 (2005) 1-13 [2] M. Jang, J.S. Hwang, S.I. Choi, J.K. Park, Remediation of arsenic-contaminated s oils and washing effluent, Chemosphere 60 (2005) 344-354.
148
Poster 29
The experiments of Exp. 1 and Exp. 2 were carried out to evaluate the effect of current density on the removal of fluorine. The experiments of Exp. 1 and Exp. 3 were executed to study the effect of anolyte concentration on removal of fluorine. Removal efficiency of fluorine increased as sodium hydroxide concentration and current density increased. After 14 days, the soil was sliced into 10 sections. Fluorine of soil sample from each slice was extracted using Korean Standard Test Method, and the extractants was reacted with zirconium, and the complex were analyzed using UV/VIS spectrophotometer(HS3300, Humas, Korea).
149
3. Results and Discussion Figure 1 shows pH distribution of soil sections after experiments. pH of soil sections was ranged from 11 to 12.5 and even anode section was strong alkaline conditions. As concentration of circulating solution(NaOH) increased, the pH in soil section increased compared to lower concentration of the solution. It is well known that the extraction of fluorine from soil was enhanced by alkaline condition[2, 3] because hydroxide(OH-) could be exchanged into fluoride(F-). Figure 2 shows fluorine distribution in soil sections after experiment. Average removal efficiency of fluorine was 51.8%, 67.1%, 64.4% and 75.6% for Exp. 1, Exp. 2, Exp. 3 and Exp. 4, respectively. Electromigration and electroosmosis are major removal mechanisms in electrokinetic removal of fluorine. Electroosmotic flow is enhanced by alkaline condition of soil [4, 5]. Fluorine concentration in soil was homogeneously distributed compared to other electrokinetic experiments because enhanced osmotic flow moved fluoride from anode to cathode and fluoride was transferred from cathode to anode by electromigration. 4. Conclusions Even though anolyte circulation with alkaline solution caused increase of soil pH upto 12.0, this high soil pH enhanced fluoride desorption from soil. Anolyte circulation with alkaline solution in electrokinetic remediation was one of most effective for fluorine removal.
12.5 1.4 Exp. 1 Exp. 2 Exp. 3 Exp. 4
pH distribution
12.0
1.2 1.0
C/C0
Exp. 1 Exp. 2 Exp. 3 Exp. 4 0.8 1.0
11.5
11.0
10.5
10.0 0.0
0.2
0.4
0.6
0.2
0.4
0.6
0.8
1.0
Acknowledgement This research was supported by a grant from Korea Foundation of Science and Technology via National Research Laboratory Program.
[1] M. A. Elrashidi, W. L. Lindsay, Chemical equilibria of fluorine in soils: A Theoretical development, Soil Sci. 141 (1986) 274-280. [2] N. Costarramone, S. Tellier, B. Grano, D. Lecomte, M. Astruc, Effect of selected conditions on fluorine recovery from a soil, using electrokinetics, Environ. Technol. 21 (2000) 789-798. [3] Walter W. Wenzel, Winfried E. H. Blum, Fluorine speciation and mobility in Fcontaminated soils, Soil Sci. 153 (1992) 357-364. [4] Andrew P. Shapiro, Roland F. Probstein, Removal of Contaminants from Saturated Clay by Electroosmosis, Environ. Sci. Technol. 27 (1993) 283-291. [5] Jihad T. Hamed, Ashish Bhadra, Influence of current density and pH on electrokinetic, J. Hazard.Mater. 55 (1997) 279-294.
150
Poster 30
potential of soil from negative to positive due to sorption of hydrogen ion onto soil surface. In the soil with positive surface charge, the direction of electroosmotic flow changes from cathode to anode. Lower pH of soil enhances the desorption of nickel and zinc from soil to pore fluid. However the overall removal of metal ion was not enhanced significantly because the direction of electromigration and electroosmotic flow was opposite. Acidic pretreatment of soil and catholyte conditioning with acidic solution enhance the performance of electrokinetic remediation of nickel and zinc, however there is optimum concentration of acidic solution for catholyte conditioning.
1.6 1.4 1.2 1.6 1.4 1.2
C/C0, Zn
C/C0, Ni
1.0 0.8 0.6 0.4 0.2 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Exp-01 Exp-02 Exp-03 Exp-04 0.9 1.0
1.0 0.8 0.6 0.4 0.2 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Exp-01 Exp-02 Exp-03 Exp-04 0.9 1.0
C/C0, Zn
0.8 0.6 0.4 0.2 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
C/C0, Ni
1.0
1.0 0.8 0.6 0.4 0.2 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Fig. 1. Distribution of Zn and Ni after application of electrokinetic remediation Table 1. Experimental conditions for electrokinetic remediation
Exp. No. Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5 Exp. 6 Exp. 7 Exp. 8 Pre-treatment Anolyte MgSO4 (0.05 M) Acetic acid (0.1 M) + MgSO4 (0.05 M) MgSO4 (0.05 M) EDTA (0.1M) + MgSO4 (0.05M) MgSO4 (0.1 M) MgSO4 (0.1 M) MgSO4 (0.1 M) MgSO4 (0.1 M) HNO3 (0.1 M) HNO3 (0.1M) HNO3 (0.1M) HNO3 (0.1M) HNO3 (0.1 M) HNO3 (0.5 M) HNO3 (1.0 M) Acetic acid (0.1 M) + Sodium Acetate (0.1 M) at pH 4.0 Catholyte of soil
[1] D.M. Zhou, C.-F. Deng, L.Cang, A.K. Alshawabkeh, Chemosphere 61(4), 519-527 (2006) [2] H.K. Hansen, A. Rojo, L.M. Ottosen, J. Hazard. Mater. B117, 179-183 (2005)
152
Poster 31
Reuse as fertilizer
Straw Ash Water Solution exceeding:
Pre-wash
Treatment to reduce Cd
Liquid fraction:
Low Cd content
High Cd content
Figure 1 Ultimate target for the remediation of straw ashes Figure 1 schematizes the ultimate goal of the electrodialytic method for straw ash and its sustainable ideal. The contaminated fly ash is combined with an assisting solution and EP is carried out. The outputs of the process would be a solid fraction with low
153
heavy metal content and a liquid fraction containing the heavy metals. At the end both fractions could be reintroduced in the market. The straw ash solid fraction is added directly to agricultural fields and the liquid fraction is used in the production of fertilizer (K is of interest here) after precipitation of Cd (Figure 1). The scale up of EP has been carried out before by Christensen et al., in a 2 m3 pilot plant for wood waste [1]. In the present study, the application of the EP to fly ashes from the combustion of straw in a medium size prototype scale was preformed. The migration of Cd was studied throughout the remediation time and removal rates were compared. Overall, straw ashes are quite suitable for the removal of Cd through electrodialytic remediation since Cd is readily desorbed. Experiments suggest an evaporable Cd fraction, which may be enhanced by the acidic conditions of the ash suspension at room temperature. The final straw ash achieved a low Cd content, though further adjustments need to be carried out in order to optimize Cd removal rate. EP ultimate target is to remove heavy metals from the central compartment into electrolyte compartments. Due to the continuous electrolyte flow into the central compartment, probably due to high concentrations of salts, Cd removal may have been slowed down. The straw ash after electrodialytic remediation has a low pH (2), low Cd (6.8 mg Cd/kg) content and high K residue. Application to land should be moderate, with special emphasis on the application to neutral/alkaline soils. To achieve the sustainability principle Cd concentration in the solutions should be lowered for further reuse in fertilizers. This could be accomplished through alkalinisation of the solutions. Bottom line, Figure 1 represents the ultimate resource for the remediation of straw ashes. Once Cd is removed from the central compartment/ash and isolated in electrolyte units, the ashes may be considered isolated from the metal. These ashes are of great value in agricultural fields, since its potassium content is high (probably in the form of KCl). The residual solutions from EP might be introduced in the original industry, in this case fertilizers industry. The liquid fraction from pre-wash procedure may also be reused in fertilizer industry.
[1] Christensen IV, Pedersen AJ, Ottosen LM, Ribeiro AB (2006). Electrodialytic remediation of CCA-treated waste wood in a 2 m3 pilot plant. Science of the Total Environment 364:45-54. [2] European Commission DG ENV E3 (2002). Heavy Metals in Waste Final Report, Project ENV.E.3/ETU/2000/0058. [3] Hansen HK, Ottosen LM, Kliem BK, Villumsen A (1997). Electrokinetic Remediation of Soils Polluted with Cu, Cr, Hg, Pb and Zn. J. Chem. Tech. Biotech, 70:67-73. [4] Milj-og Energiministeriet: Bekendtgrelse om anvendelse af aske fra forgasning og forbrnding af biomasse og biomasseaffald til jordbrugsforml. BEK no. 39, 20/02/2000 (in Danish). [5] Ottosen LM, Hansen HK (1992). Electrokinetic cleaning of heavy metals polluted soil. Internal Report,Fysisk-Kemisk Institut for Geologi og Geoteknik, Technical University of Denmark, Denmark, 9pp. [6] Ottosen LM, Hansen HK, Laursen S, Villumsen A (1997). Electrodialytic Remediation of Soil Polluted with Copper from Wood Preservation Industry, Environmental Science & Technology, 31:1711-1715 [7] Pedersen AJ (2003). Characterization and electrodialytic treatment of wood combustion fly ash for the removal of cadmium. Biomass Bioenergy 25:44758.
154
Poster 32
Introduction The disposal of sewage sludge from urban wastewater treatment plants is a growing problem worldwide. The European Community1 has developed the draft of Working document on sludge with the aim to update the regulatory system for the (re)use of sewage sludge. In Italy, sewage sludge could be disposed on agricultural lands but, in last years, this use has been limited by Italian legislation to avoid the contamination by and the accumulation of both heavy metals and organic compounds in the soils. Analogous regional regulations have decreased the maximum attainable limit for these pollutants. In order to increase the recycling of sludge on agricultural lands, thus avoiding their accumulation, we need a powerful treatment as electroremediation2. The present work reports on a laboratory investigation on the use of an electrokinetic method for the removal of anionic surfactants like linear alkylbenzenesulphonate (LAS) and heavy metals from wastewater sludge. Experimental section The sewage sludge was obtained from the HERA urban wastewater treatment plants located in Emilia Romagna. The basic cell for electrokinetic sludge remediation is shown in Fig. 1. The experimental apparatus consisted of the following parts: a sludge bed, two electrode 1 2 3 compartments and a power supply. Each end of the sludge bed was equipped with holes (diameter: 1mm) and a paper membrane (2) to enhance uniform electro-osmotic flow. A titanium plate cathode (3) and a titanium coated platinum anode (1) were used. To find the optimal operating conditions, variable current intensities for different times were applied. To gain information about the process, pH, potential, conductivity and temperature were measured before and after each treatment, in both electrolyte compartments. After treatment, the sludge was dried and analysed to determine the concentration of 1 2 3 heavy metals, by atomic absorption spectroscopy, and organic fraction, by extraction and NMR analysis. In a second experimental session, we focused our attention on the possible removal of surfactants. In the various experiments, current densities of 2, 3, 4 and 5 mA/cm2 have been applied to the electrokinetic cell for 8, 16, 24 and 48 hours, respectively.
155
Table 1
Removal efficiencies (%) [M] As Cd Co total Cr Cu Ni Pb V Zn Fe Mn
1
Table 2
1
Test 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
t (h)
j (mA/cm2)
(mg/ Kg)
Test 3 Test 4 Test 6 Test 72 Test 73 -5% -% -8% -5% -13% 12% -6% -1% -5% -8% -21% -8% -23% -20% -10% -25% -12% -17% -3% -14% -16% -21% -3% -8% -19% -18% -25% -16% -13% -14% -12% -14% -64.9% -47.6% -10.2% 16.7% -71.9% -78.4% -36.3% -30.2% -40.4% -56.7% -44.5% -25.4% -27.7% -5.1% 15.3% -21.1% -54.1% -13.0% -34.9% -21.0% -44.1% -99.4%
concentration of metals before treatment, 2 cathode side, 3 anode side Experimental conditions: test 3 - time 3 h, current density 4 mA/cm2; test 4 time 8 h, current density 2.4 mA/cm2; test 6 - time 16 h, current density 2.4 mA/cm2; test 7 - time 48 h, current density 4 mA/cm2.
24 24 24 24 16 16 16 16 8 8 8 8 48 48 48 48
3 4 5 6 3 4 5 6 3 4 5 6 3 4 5 6
17,3 18,0 19,7 43,2 27,3 28,8 28,3 22,2 22,4 41,7 31,9 24,7 29,1 22,6 18,7 31,2
Results and discussion The concentration of heavy metals in the sludge provided by HERA was below the limit set by the Italian legislation; however, it is interesting to observe that all metal contents could be reduced by the electrokinetic treatment. Values collected in table 1 show that removal efficiencies increase both by prolonging the application time and raising the current density. Also the concentration of surfactants in the sludge was below the limit set by the Italian legislation but, in consideration of their widespread use (household detergents, personal care), their increasing concentration could become a problem in the near future. Looking at the related experimental session, good results were obtained, i.e. LAS removal efficiencies between 18% and 43%. No substantial gain in removal efficiency could be obtained by prolonging the application time to more than 16 hour. The lack of a clear trend for data in table 2 could be due to problems in sample homogeneity and analytical determinations; therefore, the above data must be taken as preliminary results and inspected cautiously. Future work will be focused on scale-up of the electrokinetic process optimization of parameters for increasing the LAS removal efficiency optimization of LAS extraction procedure and their quantification by NMR.
156
Poster 33
DIALYTIC AND ELECTRODIALYTIC REMOVAL OF HEAVY METALS FROM MSW FLY ASH: EXPERIMENTAL AND MODELING
A. T. Limaa*, A. B. Ribeiroa, J. M. Rodrguez-Marotob, A. Varela-Castroc, L. M. Ottosend a Department of Sciences and Environmental Engineering, Faculty of Sciences and Technology, New University of Lisbon, 2829-516 Caparica, Portugal; bDepartment of Chemical Engineering, University of Mlaga, Campus de Teatinos, 29071-Mlaga, Spain; c National Agricultural Station, Soil Science Department, Av. Repblica, 2784505 Oeiras, Portugal; d Department of Civil Engineering, Brovej, Building 118, Technical University of Denmark E-mail: lima.at@gmail.com Fly ash from municipal solid waste incinerators (MSWI) are considered hazardous waste, being their high concentration of heavy metals a major problem. In Portugal, MSWI fly ash are expected to increase over time which poses a growing concern about the waste management issue they represent. Various ways of valorizing them have been reported. The electrodialytic process (ED) removes heavy metals from fly ash, which eventually enables their further valorisation and the recovery of heavy metals for further reuse. In the present work, the effect of applying a direct current as the cleaning agent for the heavy metals presented MSWI fly ash was investigated. Focus was given to a comparison between performances of dialytic vs. electrodialytic experiments, respectively with ion-exchange membranes as the main driving forces for gradient concentration of heavy metals, and electrodialytic experiments, in which an electric field was applied in order to accelerate heavy metal removal from the central cell compartment. The purpose was to differentiate the transport of heavy metals induced by chemical gradients and potential gradients. Six electrodialytic experiments were carried out differing in several parameters, according to what is presented in Table 1. The time length of the experiments was maintained constant in 14 days. Two assisting agents were studied (0,25M ammonium citrate in 1,25% NH3 and distilled water. The experimental setup also varied according to Figure 1 (without and with stirring). From the heavy metals studied, Cd, Cu and Pb, the best removal rates were obtained for Cd, with 0,25M ammonium citrate in 1,25% ammonia as the assisting agent, presenting the setup design no relevance. For Pb, the electrodialytic experiment with distilled water as saturation media achieved the best results. A one-dimensional model was developed for simulating the electrodialytic and dialytic treatment of a saturated bed of MSW fly ash containing Cd, Pb, Cu and Al. The chemical equilibria precipitation solubilization and the movement of individual ions Cd, Pb, Cu, etc and their complexes, Cd(OH)3-, Pb(OH)3-, etc. was mathematically modeled taking into account the diffusion transport resulting from their concentration gradients and from the electromigration of their ionic, simple and complex species during the operation.
157
Table 1 Experimental conditions Setup Exp. Assisting Agent design 0,25M Ammonium Citrate in 1,25% 1 A Ammonia 0,25M Ammonium Citrate in 1,25% 2 A Ammonia 3 B Distilled Water 4 B Distilled Water 5 B 0,25M Ammonium Citrate in 1,25% Ammonia 6 B 0,25M Ammonium Citrate in 1,25% Ammonia
Current (mA) 40
Anolyte 0,25M Ammonium Citrate in 1,25% Ammonia 0,25M Ammonium Citrate in 1,25% Ammonia 0,01M NaNO3 at pH=2 0,01M NaNO3 at pH=2 0,25M Ammonium Citrate in 1,25% Ammonia 0,25M Ammonium Citrate in 1,25% Ammonia
L/S 1,66
1,66
0 40 0 40
4 4 4
Stirring device
+
I AN
III CAT A
+
I AN
II
L = 3 cm
II III CAT B
Figure 1 Setup design for the studied experiments. AN anion exchange membrane; CAT cation exchange membrane; I anode compartment; II central compartment; III cathode compartment; A unstirred ash; B stirred ash suspension.
158
Poster 34
After the experiments the wood was cut into two halves in longitudinal direction. Chromazurol S was sprayed on one halve (a colour indicator showing Cu in blue) and
159
the other half was cut into 10 slices (that were further separated into hard wood, sap wood and a mixture of these) for chemical analysis. Five experiments were conducted with constant current. The experimental parameters varied were the applied current and the duration: (A) 0 mA, 22 days. (B) 1.5 mA, 29 days, (C) 2.5 mA, 29 days, (D) 3.5 mA, 9 days and (E) 2.5 mA, 16 days. In experiments (A) to (D) a 0.16% Celcure AC800 was supplied and in experiment (E) the concentration was increased to 3.2%. Results and discussion Figure 2 shows the distribution of Cu in the wood after electrokinetic treatment (B-D) and in the reference experiment (A). A C
Figure 2: Experiments (A) to (D). Distribution of Cu in the wood after treatment (sapwood up, Hardwood down). Compared to the reference experiment it is seen that the transport of Cu into the wood is significantly increased by the applied current in the three electrokinetic experiments. The visual distribution found with chromazurol (Figure 2) was confirmed with chemical analysis. The charge transfer in the eletrokinetic experiments was (B) 3800 C, (C) 6300 C and (D) 2700 C and this corresponds well to the depth of which Cu was transported into the wood. By increasing the concentration of the supply solution from 0.16% to 3.2% most of the sapwood was impregnated during 16 days and Cu was measured in the first 4 cm in the hardwood. The Cu concentration was more than 3380 mg/kg in all sapwood and in exp. (C) the highest concentration measured in the first slice only was 1650 mg/kg.
It was clearly shown that re-impregnation can be improved by applying an electric field since Cu is distributed much faster into the wood. Due to these encouraging results optimisation of process parameters as well as development of electrode units are done.
160
Poster 35
161
Figure 1: Boron penetration in wood.. Boron applied to (-) surface. Red colour indicate presence of boron.
Conclusion It is possible to accelerate the ingress of boron in wood by the use of an electric field, compared to ingress based on diffusion. The optimisation of the process is ongoing to investigate the limitations of the method (e.g. moisture content, boron concentration) If the optimisation processs is successful, elelctrokietic accelerated boron ingress may prove to be a suitable alternative to existing methods for reimpregnation of wood. The metod seems especially suited for situations where replacement of wood should be avoided, e.g. cultural heritage buildings. Acknowledgments This work was funded by the Danish Forest and Nature Agency (Skov- og Naturstyrelsen).
[1] Lloyd, J.D. (1997) International Status of Borate Preservative Systems. 2nd international conference on wood protection with diffusible preservatives. pp 45-54 [2] Morrell, J.J.; Forsyth, P.G.; Newbill, M.A. (1994) Distribution of biocides in Douglas-fir poles 42 months after application of groundline preservative systems. Forest Products Journal Vol. 44(6) pp.24-26
162
Poster 36
163
using acetic acid, hydroxylamine, hydrogen peroxide and aqua regia solutions prepared from analytical grade reagents. Chemical analysis of digested soil samples, electrolytes and extracting solutions were carried by spectroscopy methods (AAS and ICP). RESULTS In every test, pH decreases at the anode and increases at the cathode as a consequence of the water electrolysis reactions that take place according to the expressions: 2 H2O 4 e- O2 (gas) + 4 H+ Eo = - 1.229 (anode) (1) (2) 2 H2O + 2 e- H2 (gas) + 2 OH- Eo = - 0.828 (cathode) where Eo is the Standard electrochemical reduction potential. The magnitude of the variation depends on the applied current and can reach values below 2 and above 12 at the anode and cathode respectively. As the treatment proceeds, and the ions concentrate in the anolyte and catholyte, their conductivity increases and the colour of the anolyte turns yellowish because of the Cr (VI). Accumulation of chromium in the anode chamber shows that electromigration is the predominant driving force for the transport of ions. Removals of chromium of 27% at 15V and 57% at 30V have been achieved in one week treatments. Higher voltages yield higher initial removals rates and higher amounts of chromium at the cost of being more energy inefficient. Initially most of the chromium in the soil is located in the most mobile fraction (81%) and similar amounts in the other 2 (7% and 10%) with little chromium in the residual fraction. As the electrodialysis treatment proceeds, the more labile phase (soluble + exchangeable + carbonatic) is depleted first and the amount of chromium in it decreases drastically to less than 7% as it is being removed from the soil into the anolyte solution. Results also show that changes in the total chromium distribution occur due to the treatment. Some of it is being transferred to the oxides and sulphides fractions which first increase and then decrease slowly. ACKNOWLEDGEMENTS This work is part of an R+D project co-financed by Spains Ministry of Environment. [1] Rauret, G., Lopez-Sanchez, J.F., Sahuquillo, A., Rubio, R., Davidson, C., Ure, A. & Quevauviller, Ph. (1999). Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials J. Environ. Monit., 1, 57-61.
164
Poster 37
A SIMPLE COMPUTER MODEL FOR THE ELECTRODIALYTIC REMEDIATION OF A CHROMIUM (VI) CONTAMINATED SOIL
Rafael A. Garca-Delgadoa ,Ana M. Nieto Castilloa, Juan J. Sorianoa a Instituto Geolgico y Minero de Espaa (IGME) Direccin de Recursos Minerales y Geoambiente C/ Rios Rosas, 23. 28003-Madrid (SPAIN) E-mail: r.garcia@igme.es A one-dimensional computer model has been developed to simulate the electrodialytic treatment of a water saturated clayey soil containing chromium (VI). Model calibration has been carried out using previous laboratory tests. Additionally, the influence of different operation parameters and their effects on remediation time and energy use have been explored. MATERIALS AND METHODS A simple one dimensional computer model has been developed for simulating the electroremediation treatment. The model has been coded in FORTRAN. The main objective of this model is to supply an adequate qualitative and quantitative description of the behaviour of the pollutant-soil system and to become a useful predictive tool in improving the systems performance by modifying the operation parameters. In the model formulation the electroremediation system is divided into N+2 compartments corresponding to the soil and the two electrode chambers. The number of soil compartments (N) is selected high enough so to permit the study of electrical transport and diffusion effects in the soil with low numerical dispersion [1]. The model operates in two steps: first simulates species transport by integrating forward in time the one dimensional transport equation, then chemical equilibrium among the transported species is re-established. An iterative process between the two steps is carried out until a convergence criterion is achieved. Four transport phenomena can be considered in the system: electromigration, electroosmotic transport, diffusive transport and advection, and two kinds of reactions, electrochemical and chemical ones. The electromigration includes the movement of ions from the soil and from the electrolyte towards the electrodes of opposite charge as well as of the protons and the hydroxyl generated ions. Electroosmotic flow is calculated using the average drop potential through the soil compartment nad the electroosmotic permeability [2]. Direct and reverse electroosmotic flows can be switched depending on soil pH. Diffusive transport of ionic species is negligible when compared to electromigration. Advective transport is only specifically present in the electrode compartments where electrolyte is renovated but not within the soil because of no head difference between the two electrode compartments. The electrochemical reactions considered are the reduction and oxidation of water on the electrodes that take place according to the expressions:
165
2 H2O 4 e- O2 (gas) + 4 H+
Eo = - 1.229 (anode)
(1) (2)
2 H2O + 2 e- H2 (gas) + 2 OH- Eo = - 0.828 (cathode) where Eo is the Standard electrochemical reduction potential.
No chemical reactions are considered for Cr (VI) but sorption which is taken as linear and pH dependent. pH adjustments at the electrodes can be accounted for in the model by changing the concentration of H+ / OH- and increasing the concentration of nitrate or sodium ions accordingly. As an internal consistency check, the program verifies that the electrical neutrality condition is met in every volume element at every time step [3]. RESULTS The model has been calibrated using the results from several laboratory tests on a chromium (VI) contaminated soil [4]. The modelled system is a 20 cm length soil compartment. Base case conditions are: Chromium (VI) content in the soil: 4000 mg/kg, electrolyte composition 0.05M KNO3, constant voltage operation (15 - 30 V) and remediation time 7 days. The effects of changing voltage, electrolyte ionic strength and pH have been explored and will be presented. ACKNOWLEDGEMENTS This work is part of an R+D project co-financed by Spains Ministry of Environment.
[1] Wilson, D.J., Rodrguez-Maroto, J.M., Gmez-Lahoz, C., (1995). Electrokinetic remediation. I. Modeling of simple systems. Sep. Sci. Technol. 30, 2937-2961. [2] Schultz, D.S., (1997). Electroosmosis technology for soil remediation: Laboratory results, field trial, and economic modelling. J. Haz. Mat. 55, 81-91. [3] Vereda-Alonso,C., Rodrguez-Maroto, J.M., Garca-Delgado, R.A., Gmez-Lahoz, C., Graca-Herruzo, F., (2004). Two-dimensional model for soil electrokinetic remediation of heavy metals. Application to a copper spiked kaolin. Chemosphere 54, 895-903. [4] Nieto Castillo, A.M., Soriano, J. J., Garca-Delgado, R.A. (2006). Changes in chromium distribution during the electrodyalitic remediation of a chromium VI contaminated soil. In Bioavailability of Pollutants and Soil Remediation. Conference Proceedings pag 137.
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Poster 38
167
At the end of the large scale experiments the soil columns were divided into 10 cross slices in which the total mercury content was measured. In addition, the BCR sequential extraction procedure (3) was performed for each of these slices in order to evaluate the mobility and availability of the mercury in the soil after the remediation. Likewise, the same procedure was performed at the end of the small scale experiment, but in this case the soil was not divided into slices. 40 25 As an example, the figure shows the 35 consumption of hydriodic acid (as mmol 20 30 of iodide) at the cathode and sodium 25 hydroxide (as mmol sodium) at the 15 anode, for one of the small scale assays. 20 10 The acid consumption rate (mol [HI] s1) 15 was equal within 2 % to the current Hg (%) 10 5 NaOH intensity (mol [e] s1), whereas the 5 HI NaOH consumption was slightly smaller, 0 0 in agreement with the alkaline 0 50 100 150 200 characteristics of the original soil. The t (h) figure also shows the Hg recovered at the Rate of reagent consumption and Hg recovery. anode (mercury was not significantly recovered at the cathode). The percentage of Hg recovered (below 37%) would suggest that the iodide enhanced electrokinetic treatment is not successful. Nevertheless, a comparison of the BCR results obtained before and after the treatments indicates that after the remediation, the mercury was effectively removed from the fraction of Hg associated to the reducible matter, whereas the one associated to the oxidizable matter was not. This oxidizable fraction together with the residual one are probably associated to cinnabar, which is naturally found at the Almadn district. In addition, the large scale experiments indicate that if the treatment is not completely accomplished, the mobility of mercury in the contaminated soil would increase, as can be concluded from the relative increase of Hg associated to the weak acid soluble fraction that we have obtained in the BCR speciation. Similar results have been found earlier (4).
Hg recovered (%)
Acknowledgements: This research was funded by Grant PPQ2003-01902 (Spanish Ministry of Education and Science) and Project 148/2004/3 (Ministry for Environment). CGL and CVA acknowledge the economic support from the Junta de Andaluca through the program Medidas de Impulso de la Sociedad del Conocimiento en Andalucia. References: (1). A. Hernndez, M. Jbrak; P. Higueras, R. Oyarzun, D. Morata and J. Munha. Mineralium Deposita 34, 539-548 (1999) (2). P. Higueras, R. Oyarzun, J. Lillo, J.C. Snchez-Hernndez, J.A. Molina, J.M. Esbr and S. Lorenzo. Science of the Total Environment 356: 112 124 (2006) (3) A.M. Ure, P. Quevauviller, H. Muntau and B. Griepink. Int. J. of Environ. and Anal. Chem. 51 (1-4) 135-51 (1993). (4) A.B. Ribeiro and J. M. Rodriguez-Maroto. Electroremediation of heavy metal contaminated soils. Processes and application Chap. 18 in Trace elements in the environment CRC Press (2006)
168
mmol Na & I
Poster 39
The experiments on clearing soils from salts of strontium and cesium were made in a single-chamber electrokinetic cell of an open type. The experiences have shown, that in a field of a constant electrical current the redistribution of these ions is carried out from the anode to the cathode both in a loam, and in the modified sand-gel soils. This result allows applying the given method to clearing from the radionuclide of protective sorption screens in the places of warehousing liquid radioactive wastes. In experiments on clearing soils from Cs-137 we used of three-chamber electrokinetic installation. In them the anodic and cathodic chamber were separated from the central, filled by the polluted soils, neutral diaphragms and by the drainage from a polymeric material. The plates from the corrosion-proof steel (cathodes) and platinized titanium (anodes) were used as electrodes. The prepared paste of soils was located in the central chamber of electrokinetic installation. During all experiment we entered into the anodi chamber desorbent reagents (NH4NO3 or KNO3) with the concentration 1 mole/l. For neutralization of alkali, which is formed in a catholite at the electrolyze of water, in the cathodic chambers we created pH< 1 at submission of the concentrated nitric acid. The extraction of Cs-137, acting in the cathodic chamber, we carried out by the replacement of catholite. In the other series of experiments we wanted to increase the efficiency of electrochemical clearing from Cs-137 by the selection of the best reagent for the transforming radionuclide in the mobile form. Simultaneously we achieved reduction of the acidity soils, and revealed more sparing, and the ecologically safe conditions of decontamination. It will allow to lower the charges on the subsequent neutralization acidity, i.e. on more complete rehabilitation of the polluted territories from radioactive infection. On the basis of the data received at research of lixiviation Cs-137 from soils, we carried out experiments in comparison of efficiency of application nitric acid and phosphate electrolytes for the electrokinetic clearing of soils. As a result of preliminary researches we have decided to use as the electrolyte the mixed one-mole solutions of acids and them ammonium salts of the following structure: 1M H3PO4 + 1M NH4H2PO4 and 1M HNO3 + 1M NH4NO3. The received results of a laboratory experiments have shown, that at clearing a radioactive soils as an ion-desorbent cation NH4+ is more effective, than cation K+. The extraction Cs-137 with the use of solutions NH4NO3 almost twice is higher, than with use KNO3. The general degree of extraction Cs-137 in this case has made about 50 % and 30 % for the ammonium nitrate and potassium nitrate accordingly. These meanings almost in 5 and 3 times are higher, than without application of the specified salts. As a result of the spent experiments we was established, that the highest parameters of clearing are formed at use complex reagents solution: 1-1,5 M H3PO4 + 1M NH4H2PO4. On the basis of these researches we propose the phosphate leaching solutions in quality of most perspective. References [1] Shevtsova E.V. The research and development of physical-chemical bases of electrokinetic clearing technology of soils from radionuclides. - Moscow, 2003, GUP MosNPO Radon" (in Russian). [2] Korolev V.A. 2001. The cleaning of soils from pollution. - 365 pp. MAIK/ Interperiodica Publ., Moscow (in Russian)
170
Poster 40
ELECTROKINETIC REMEDIATION OF A SOIL CONTAMINATED WITH HEAVY METALS IN A SCALE PILOT EXPERIMENT.
Lobo, M.Ca, Martinez-Iigoa, M.J, Prez-Sanza, A, Plaza, Aa, Alonso, Ja, Perucha, Cb. a Instituto Madrileo de Investigacin y Desarrollo Rural Agrario y Alimentario. IMIDRA. Finca El Encin A-2. Km 38,2 Alcal de Henares 28800 (Madrid). Spain. E-mail: carmen.lobo@madrid.org b AG Ambiental, S.L. C/ Isabel Colbrand, 10 - Local 57 28050 Madrid Spain.
Soil degradation due to contamination represents an increasing hazard that requires the development of methods for soil remediation. The process of regeneration must guarantee the permanence of the solution adopted, giving precedence whenever possible to in situ treatments that would avoid the generation, transport and elimination of waste products [1]. In the last decades, different authors have demonstrated the efficiency of the application of a electric field to the soil in order to mobilize charged species that migrates in the direction of the opposite charged electrodes [2,3,4,5,6] Electrokinetic technology seems to be an adequate way to reduce heavy metals in the soil to safe pollutant levels or enabling them to be removed by biological technologies [7]. In this work, it has been developed a pilot scale experiment with 1 tons of a clayedsandy soil treated with Pb, Cd, Zn and Cr. The soils were artificially contaminated with heavy metal soluble salts in different remediation assays: A: ZnCl2, B: Pb(NO3)2 + Cd (NO3)2 . 4H20 C: Pb(NO3)2 + Cd (NO3)2 4H20 +K2 Cr2O7. . Heavy metal concentration was calculated as five times the limit value according to European legislation in relation to sewage sludge agriculture application [8]. Remediation experiments were carried out using graphite electrodes for both anode and cathode and applying 100 volts direct current. Citric acid was used as purging solution. Pumping was discontinuous to avoid that soil gets dried and a working pressure of 80 psi. was used. A good mobility of the cationic contaminants was produced in the soil, however the mobility of anion (chromium) was lower in the same conditions. In soils with several pollutants (B and C), migration and removal of heavy metals were depended on their initial concentration.
171
In general, short assays (less than 20 days) and low intensity of direct current were enough to obtain good contaminants mobility in this type of soil. Nevertheless, the total remove of soil pollutant were not achieved in this conditions. The residual content was more difficult to remove being necessary to increase the current intensity and the process time or the use of other complementary technologies.
Acknowledgments
This research was financed by Projects 094/2006/2-1.2 (Ministerio de Medio Ambiente) and EIADES Program S-0505/AMB/0296 (Consejera de Educacin. Comunidad de Madrid).
References
[1]Comission of the European Comnuties 2006. Com (2006) 232. Proposal for a Directive for Soil Protection. http://ec.europa.eu/environment/soil/ [2] Acar, Y.B and Alshawabkeh, A.N., 1993. Principles of Electrokinetic Remediation. Enviornmental Science and Technology. Vol 27. N 13, 2638-2647. [3]Page, M.M., and Page, C.L, 2002. Electroremediation of contaminated soils. J, Environ. Eng. 128, 208-219 [4] Reddy, K.R. 1999 Journal of the Air & Waste Management Association 49 (823830), [5] Reddy, K.R, Xu, Ch. Y and Chinthamreddy S. 2001. Assessment of electrokinetic removal of heavy metals form soils by sequential extraction analysis. Journal of hazardous materials. B84, 279-296. [6]Reddy, K.R, Saichek, R.E, Maturi, K and Ala, P, 2002. Effects of soil moisture and heavy metals concentrations on electrokinetic remediation. Indian Geotechnical Journal. 32 (2). [7] Lobo, M.C., Martnez- Iigo, M.J , Alonso, J. Perucha, C., De Fresno, A , Laguna, J. 2003. Application of electrokinetic remediation to soil contaminated with heavy metals and organic compounds. Procc. 4th European Congress of Chemical Engineering. Granada (Spain) [8] Council of the European Communities.(1986): Directive concerning sludge amendments. Off. J. June, 12, L181/6
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Poster 41
173
Poster 42
174
Poster 43
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decontamination from charged and non-charged pollutants. Theoretical results are compared with experimental data [1, 2, 3]. 1. rnilovich B., Mishchuk N., Abbruzzese K., Pshinko G., lishchenko R., Colloids and Surfaces, A 265 (2005) 114123 2. Mishchuk N., rnilovich B., lishchenko R., J. Colloid Interface Science. (in press) 3. Mishchuk N., Lysenko L. Chemistry and Technology of Water, Ukraine (in press)
176
Poster 44
REMEDIATION OF CADMIUM CONTAMINATED PADDY SOILS BY WASHING WITH CALCIUM CHLORIDE IN PINDI-BHATIAN (PUNJAB) PAKISTAN
Tahir Mehmooda, Syed Tasawar Abbasb, Kashif Shahbazb and Muhammad Bashirc ac Department of Soil Science, University College of Agriculture, Rawalakot, Azad Jammu & Kashmir University, AJK (Pakistan), Phone: 00923216220602; E-mail: tahir_tm2000@yahoo.com b ROYAL CROP SCIENCE (Pvt.) Ltd. Multan, Pakistan. INTRODUCTION The soil in many Pakistani paddy fields (especially Faisalabad Division) has been affected by Cd derived from sludge of different chemical manufacturing industries. To ensure the safety of foods, the concentrations of Cd in staple crops should be below a standard value; this applies particularly to rice because 3450% of the Cd intake by Pakistani people has derived from rice. Therefore, development of remediation methods for Cd-contaminated soil has become an urgent task to ensure food safety. OBJECTIVES 1. Identification of wash chemicals with minimal environmental impact on the paddy field and its surrounding environment, but with high Cd-removal efficiency. 2. Development of a cost-effective and environmentally sound soil-wash and on-site wastewater-treatment system that purifies the heavy metal-contaminated wastewater generated by the washing process. 3. Preservation of soil fertility and plant growth after the wash treatment. MATERIALS AND METHODS It includes the following; 1- Performance evaluation of chelating resin 2- On-site soil washing 3 Chemical washing 4. Water washing The CaCl2 (437 kg) (collected from Sitara Chemicals Industries LTD., Sheikhupura Road, Faisalabad, Pakistan was applied to the bounded experimental field, followed by 11.6 kL of canal water, creating a soil-solution ratio and a CaCl2 concentration of 1:1.5 and 0.1 mol L1, respectively. Following the water addition, the initial water level of the experimental field was 32 cm above the subsurface impervious layer, providing total 29.74 kL of water in the filed. The soil solution was mixed by a 13-metric-hp cultivator for 1 h until it turned into slurry; the slurry was allowed to rest for 1 h and then mixed again for 1 h. After the second mixing, the slurry was allowed to rest again for 2 h, and then the supernatant of the slurry was drained off as wastewater. The experimental field was then filled with canal water until the water level reached the initial point following the reapplication of CaCl2 (147 kg) to the field. The resulting concentration of CaCl2 in the paddy field was 0.1 mol L1. The slurry was then mixed, allowed to rest, and drained.
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Significant at the **0.01 and ***0.001 a Washed without CaCl2. b Washed with CaCl2.
Table 2.
Effects of the washing treatment on yields and Cd concentration of two rice varieties Rice variety Plot Yield (kg ha1) Cd concentration (mg kg1)
Shoot Shaheen Basmati Unwashed Washed Super Basmati Unwashed Washed Significant a No yield at the 1025 999 622 641 *0.05
and
**0.01
CONCLUSION The soil-wash experiment revealed the effectiveness of in situ soil Cd removal, especially exchangeable fraction, with on-site wastewater treatment. However, the washing had no effect on rice yield, although it changed soil fertility properties, and the Cd concentrations in soil and paddy yield were lower in the washed plot than in the unwashed plot, confirming the wash effects.
178
Poster 45
COMPARATIVE LEACHING REAGENT EFFECTS IN THE COURSE OF AN ELECTROREMEDIATION OF A SOIL CONTAMINATED BY LEAD.
S. Amrate1, B. Hamdi2, D. E. Akretche1,*, M. Pazos3, C. Cameselle3 and C. Innocent4 1 Laboratory of Hydrometallurgy and Molecular Inorganic Chemistry, Faculty of Chemistry, University of Science and Technology Houari Boumediene (USTHB), B.P. 32 El Alia, 16111 Bab Ezzouar, Algeria 2 Laboratory of Environmental Applied Materials, University of Science and Technology Houari Boumediene (USTHB), B.P. 32 El Alia, 16111 Bab Ezzouar, Algeria 3 Laborator of Bioprocesses, Dept of Chemical Engineering, University of Vigo, Spain 4 European Institute of Membranes (IEM), Place Eugne Bataillon, 34090 Montpellier, France * Nato Project n98080 (2006) ABSTRACT Soil contamination became a concerned problem giving rise to many laboratory studies in recent years. It is due to the fact that various phenomena and numerous factors can intervene as pollutants provoking serious dangers to the human health. Heavy metals are generated from the factors which are the most difficult to eliminate. Despite the fact that processes adapted to organic compounds are varied, those that treat heavy metals are underdeveloped. Electrokinetic soil remediation is one of in situ process that has been recently developed. It is also called either electrodialytic or electroosmosis, and it combines the technique of electrodialysis with electromigration of ions in the contaminated soil. However, the physico-chemical soilcontaminant interactions that occur simultaneously during the process may limit the efficiency of contaminant transport. In effect, in many cases, the water dissociation near the electrodes produces both H+ and OH- ions. The increase of hydroxyl production can give rise to hydroxides precipitates in some cases. To prevent this phenomenon and enhance the decontamination acids can be added near the cathode to neutralize the OH- produced by water dissociation and complexing agent as EDTA can also be used to facilitate the metal desorption from the contaminated soil. In this work, the electrokinetic remediation of an Algerian soil contaminated by lead is studied. The contaminant results from a battery manufactory located at 12 km in the east of Algiers near an agricultural area. Through collaboration between three laboratories, comparative studies have been performed. To enhance the electrokinetic process, the use of acetic acid, nitric acid, citric acid, oxalic acid and disodium salt of ethylendiaminetetraacetic acid has been examined. All results have shown that this soil presents a high buffering capacity, so it is necessary the addition of complexing agents to metal extraction. Either EDTA concentration tested obtained around 80% of metal extraction. Nevertheless, the extraction with citric acid only obtained 80% of extraction in one tested concentration (0.5M pH 1.5). Furthermore, this acid provokes white precipitate in some concentrations tested, especially at lower values. Oxalic acid or nitric acid were not able to extract significant metal quantities and acetic acid allows to extract until 37% of lead. It has been also noticed that the behaviour of the electric field gives rise to an explanation of the phenomena which take place inside the cell used.
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Thus, Both Voltage and electric current measurements are performed to show the electric field strength variation inside the soil for each case studied. Electrokinetic tests were carried out in a cylindrical cell (Teflon and Glass). *Corresponding author. Tel.: (213) 21.24.72.98 , email : dakretche@usthb.dz
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Poster 46
ABSTRACT Electrokinetic processes have been tested for soil remediation since 1990. Many experiments have been performed at a laboratory scale varying many parameters to improve the process and to treat each case according to the nature of soil. Recently, the new developments of the electromembrane processes in the solid matrix treatment, particularly in the soil remediation field allow expecting a new alternative in the metal extraction from ores. An in situ technique which combines the principle of electrodialysis with electromigration of ions in the solid can be envisaged. This fact has induced us to test it for the metal extraction from ores. In this work, we discuss about electroleaching experiments with membranes similar to electrodialyses which have been carried out using typical samples of a Copper ore from Ougarta, a locality sited in the South West of Algeria. This ore contains copper (average percentage 6.5%) in various mineralogical forms where malachite (Cu2CO3(OH)2) is the predominant. The electromembrane process has been studied through the optimisation of some parameters such current density and liquid-solid ratio and the direct electrodeposition of copper has examined too. All electrokinetic experiments have been performed using a five compartment Plexiglas cell with a working membrane area of 16 cm2. The two extreme compartments are composed of graphite electrodes immersed in a rinsing solution of molar H2SO4. The central compartment contains the ore immersed in an appropriate solution of a leaching reagent where the pH is fixed. On both sides of this compartment, two circuits are located and they contain 250 ml of sulphuric acid 0.1M. The membranes are disposed alternatively as in a classical electrodialysis, but the anion exchange membrane near the cathode is retired to allow the electrodeposition study. Results have shown yields of 97% and the combination of electrolysis to the process gives rise to a promising method where the number of units operation is reduced. It has been shown that a new development of electrokinetic technique can be envisaged.
181