http://www.clu-in.org/conf/tio/nano-iron/ 1 CL:AIRE 2010 Field scale application, case studies from the EU (CZR) Kvapil Petr, Černík Miroslav (Lacinová L., Nosek J., Zbořil R.,) AQUATEST a.s. – TUL – UPOL http://www.clu-in.org/conf/tio/nano-iron/ 2 CL:AIRE 2010 Presentation objectives To start discussion about: the risk management problem being addressed, the practical delivery and use of the technology, the regulatory approval process, the project outcomes and ongoing monitoring. the risks versus the benefits of iron nanoparticle use for remediation. History of nanoiron (nZVI) in First application of nZVI in ČR – in 2004 ČR http://www.clu-in.org/conf/tio/nano-iron/ 3 CL:AIRE 2010 •Spolchemie •source - Zhang •GOLDER Ass. •Laboratory tests •Field tests •ORP decrease •pH increase •CHC decrease 6 months Period of nanoiron activity reduction ~ 70 % Kurivody site – first successfull 2005 FRACTURED BEDROCK FLOW Tracer test Blast fracturing Low final concentrations No rebound 20 000 PW-3 MW-2 MW-3 15 000 sum of ClU [ug/l] remediation limit 2 500 ug/l 10 000 5 000 Zhang´s nZVI 20 09 08 6. 7. .2 0 .1 2 20 08 18 07 .2 0 .1 1 1. 6. 7 20 0 14 .4 . 06 .2 0 .1 0 10 28 6 20 0 24 .3 . 20 05 5 5. 9. 20 0 17 .2 . 20 04 1. 8. .1 . 20 0 4 0 14 http://www.clu-in.org/conf/tio/nano-iron/ 4 CL:AIRE 2010 P W -3 M W -3 A p p lic a tio n w e ll GW f d ir lo w e c t io n - b la st fra ctu rin g - tra ce r te st - Z V I n a n o p . a p p lica tio n M W -2 http://www.clu-in.org/conf/tio/nano-iron/ 5 CL:AIRE 2010 Nanoiron applications - overview Site Contam. Lab/pilot/ Remed. Type of nZVI Spolchemie 2004 Cl-Ethenes L,P ZHANG Kuřívody 2005, 2006 Cl-Ethenes L,P ZHANG, RNIP Piešťany 2005 Cl-Ethenes L,P ZHANG Permon 2006 Cr6+ L,P RNIP Rožmitál 2007 – 2010 PCB L,P RNIP, NANOFER Hluk 2007, 2008 (PRB) Cl-Ethenes L,P RNIP, NANOFER Hořice 2008, 2009 Cl-Ethenes L, P, R RNIP, NANOFER Uherský Brod 2008 Cl-Ethenes P NANOFER Písečná 2008, 2009 Cl-E, Cl-A L, P, R RNIP, NANOFER Spolchemie 2010 Cl-E, Cl-M L, P, R NANOFER Laboratory: AOX, U, As, nitrobenzene, acid mine waters, other CHC Steps to FULL-SCALE http://www.clu-in.org/conf/tio/nano-iron/ 6 CL:AIRE 2010 Feasibility approval - laboratory test Regulatory approval process in CZR Feasibility approval - field pilot test Concentration test Kinetic test Geological & hydrogeological descriptions Tracer tests Applications of nanoiron Full scale http://www.clu-in.org/conf/tio/nano-iron/ 7 CL:AIRE 2010 Feasibility - Laboratory tests Aim: Feasibility approval description: Batch tests: system nanoparticles x water x soil 2 phases: 1. phase – verification of efficient concentration 2. phase – verification of reaction rate 100 80 1,2- c is - DCE % 60 TCE PCE 40 20 0 0 2 4 6 0 g Fe /l 8 10 http://www.clu-in.org/conf/tio/nano-iron/ 8 CL:AIRE 2010 Nano-iron project regullations NZVI injections regulated by WATER law „Ussualy“ Exception for irregular matters injection Subject to decision of regional authorities Ussualy field pilot test required Usually the iron is more easily accepted than soluble materials (oxidants or reductants) Field system – from 2009 http://www.clu-in.org/conf/tio/nano-iron/ 9 CL:AIRE 2010 Z V Iron pow der D isperg ator Water Water PRETreatm ent R em oval O x ygene C ontam . D osing system Su rface M odif. Iron suspension GW head •Advantage of initial high reactivity •Mobility and reactivity control Dry powder stored and brought to the site Reduced surface oxidation by Oxygen (pretreatment) http://www.clu-in.org/conf/tio/nano-iron/ 10 CL:AIRE 2010 Case #1: PCB – Rozmital p.T. 20 years of hydraulic barrier Former tarmacadam plant, DELOR 103 Recently contaminated soil waste deposit Iron is feasible, but only nanoscale is efficient No exception from Water law needed for this site Case #1: PCB – Rozmital p.T. 100% 80% initial 4 days 60% 30 days 40% 20% 0% 17 26 31 49 48 44 96 74 70 Kinetics: Nanofer25 – indicative congeners TODA (0.5g Fe) Nanofer (0.5g Fe) 100% 90% congeners 80% 70% 60% 50% 40% 30% 20% 10% 180 138 153 118 101 77, 110 70 66, 88, 95 74 96 41, 64 44 37, 42, 59 48 49 47, 75 52 22, 51 28 20, 33, 53 31 26 17 0% 16, 32 •Significant decrease after 4 days •NanoFe active during whole period •TODA x Nanofer similar •Lower efficiency for more chlorinated •Sorption questions? 5.8 • • Laboratory experiments • kinetics for 4, 10, 30, 60 days • concentration dependency Indicative congeners x all RNIP x Nanofer25S 15, 18 http://www.clu-in.org/conf/tio/nano-iron/ 11 CL:AIRE 2010 • sum of congeners 7.0 concentration (ug/l) http://www.clu-in.org/conf/tio/nano-iron/ 12 CL:AIRE 2010 Case #1: PCB – pilot test shaft ring 6.0 J-6 5.0 4.0 3.0 2.0 1.0 0.0 X-08 XI-08 XII-08 I-09 datum II-09 III-09 IV-09 http://www.clu-in.org/conf/tio/nano-iron/ 13 CL:AIRE 2010 Case #2 – Horice Provided by MEGA and TUL Tested nanoiron vs. Lactates During first stages nanoiron more efficient, later simillar efficiency Decission of client to use nanoiron, no toxic intermediate degradation product observed. No Water law exception needed for this site http://www.clu-in.org/conf/tio/nano-iron/ 14 CL:AIRE 2010 Case #2 – Horice – full scale system • PCE, TCE, DCE, 70 mg/l • 120 x 60 m • I.stage (11/2008) • 82 injection wells • depth 10 m • 300 kg nZVI • II.stage • 300 kg nZVI (11/2009) http://www.clu-in.org/conf/tio/nano-iron/ 15 CL:AIRE 2010 Case #2 – Horice - PCE: ini, 3m, 6m, 9m http://www.clu-in.org/conf/tio/nano-iron/ 16 CL:AIRE 2010 Case #2 – Horice - DCE: ini, 3m, 6m, 9m http://www.clu-in.org/conf/tio/nano-iron/ 17 CL:AIRE 2010 Case #2 – Horice – I. stage economics Direct push well network – 80 w x 10 m x 40€ = 32 k€ nanoFe - 300 kg x 5 x 23€ = 35 k€ Other (water, electricity, management) - 30 k€ Monitoring (not part of remediation) - 100 k€ TOTAL = 200 k€ II. Stage = 100 k€ (shared monitoring) http://www.clu-in.org/conf/tio/nano-iron/ 18 CL:AIRE 2010 Case #3: Pisecna site Former dangerous waste landfill Fractured – bedrock area CLE and CLA contamination Drinking water sources in the neighbourhood High reactivity needed for TCA degradation No exception from Water law needed http://www.clu-in.org/conf/tio/nano-iron/ 19 CL:AIRE 2010 Case #3 – Pisecna Comparative lab-tests Comparative test for 5 nZVI types: prepared by Zhang (2003) RNIP (Toda) NANOFER 25 – without surfactant NANOFER 25S – modifyed by TWEEN NANOFER …– modifyed by axilate Tested properties: aggregation - DLS sedimentation – column tests mobility - column tests reactivity – kinetic tests, various nZVI concentration 3 real ground water 2 artifficaly mixed water 19 http://www.clu-in.org/conf/tio/nano-iron/ 20 CL:AIRE 2010 Case #3 – Pisecna – mobility tests 20 Case #3 – Pisecna – reactivity tests PCE TCE 1,20 c/c0 0,80 0,60 0,40 0,20 0,00 0 100 200 300 400 500 600 1,20 1,00 0,80 0,60 0,40 0,20 0,00 0 700 100 200 300 time (hrs) NANOFER 25 NANOFER25S AXILAT TODA NANOFER 25 ZHANG 1,00 0,80 0,60 0,40 0,20 0,00 NANOFER 25 100 200 300 400 time (hrs) NANOFER25S 500 AXILAT 600 TODA 700 ZHANG 1,2-DCA 1,20 0 400 time (hrs) NANOFER25S 1,2-DCE c/c0 c/c0 http://www.clu-in.org/conf/tio/nano-iron/ 21 CL:AIRE 2010 c/c0 1,00 AXILAT 500 600 TODA 700 ZHANG 2,30 2,10 1,90 1,70 1,50 1,30 1,10 0,90 0,70 0 100 NANOFER 25 200 300 400 time (hrs) NANOFER25S AXILAT 500 600 TODA 700 ZHANG 21 Case #3 – Pisecna – pilot application GEO-Group a.s. site • RNIP x NANOFER25 •CHC concentrations similar •Cl-Ethenes O.K. both (o) •Cl-Ethanes TODA worse (∆) 1.20 RNIP_ethanes RNIP_ethenes NANOFER_ethanes NANOFER_ethenes XII-08 II-09 1.00 0.80 C/C0 http://www.clu-in.org/conf/tio/nano-iron/ 22 CL:AIRE 2010 •Geological conditions not equal 0.60 0.40 0.20 0.00 IX-08 X-08 XI-08 XI-08 date I-09 I-09 III-09 III-09 Case #3 – Pisecna – full-scale http://www.clu-in.org/conf/tio/nano-iron/ 23 CL:AIRE 2010 Pretreatment of technological water Preparation nZVI slurry: Contaminant removal Oxygen removal 1000 kg dry powder iron NANOFER25N (containers in N2 atmosphere) diluting by field slurry dispergator to 5000 kg of 20% suspension of nZVI NANOFER 25 and NANOFER 25S On-site Semi-automatic dosing system 23 http://www.clu-in.org/conf/tio/nano-iron/ 24 CL:AIRE 2010 Case #3 – Pisecna – Full scale system ClU [%] ClA [%] AV-23 AV-22 AV-21 AV-20 AV-19 AV-18 AV-17 AV-16 AV-15 AV-14 AV-13 AV-12 AV-11 AV-10 AV-9a AV-9 AV-8 AV-7 AV-6 AV-5 AV-4 AV-3 AV-2 AV-1 [%] initial concentration http://www.clu-in.org/conf/tio/nano-iron/ 25 CL:AIRE 2010 Case #3 – Pisecna – full-scale results in application wells 250,0 200,0 150,0 100,0 50,0 0,0 ClE [%] 25 Case #3 – Pisecna – economics http://www.clu-in.org/conf/tio/nano-iron/ 26 CL:AIRE 2010 Estim. contaminants = 1 ton Contam. Area = 2000 m3 Depth of contam.= 20 -35 mbs nZVI plan = 1.3 tons Number of wells = 30 Duration = 1 test + 2 full a. cost: nZVI Wells Other Monitoring = 140 k€ = 60 k€ = 40 k€ = 120 K€ TOTAL = 360 K€ Case #4 – Spolchemie http://www.clu-in.org/conf/tio/nano-iron/ 27 CL:AIRE 2010 Exception from Water law needed Exploited cellars in contaminated area CLE and CLM contamination Clay, sand, gravel aquifer Chemical factory Date 23 16 .6 .20 10 10 20 10 .20 6. .6 9. 10 10 10 20 10 .20 .20 .20 6. .5 .5 .5 2. 26 19 12 10 10 10 20 10 .20 .20 .20 5. .4 .4 .4 5. 28 21 14 10 10 10 20 10 .20 .20 .20 4. .3 .3 .3 7. 31 24 17 Concentration (ug/L) Date Total ClM RW5-31 6 000,0 AW5-7 3 000,0 2 000,0 1 000,0 0,0 23 16 .6 .2 01 0 0 20 10 .2 01 6. .6 9. 0 0 0 20 10 .2 01 .2 01 .2 01 6. .5 .5 .5 2. 26 19 12 0 0 0 20 10 .2 01 .2 01 .2 01 5. .4 .4 .4 Total CHC 5. 28 21 14 0 0 20 10 .2 01 4. .3 7. 31 0 0,0 .2 01 5 000,0 Concentration (ug/L) 10 000,0 .3 0 0 15 000,0 .2 01 .2 01 .2 01 20 10 AW5-7 24 .3 .6 .6 6. 20 000,0 17 23 16 9. 0 0 0 20 10 .2 01 .2 01 .2 01 6. .5 .5 .5 2. 26 19 12 0 0 0 20 10 .2 01 .2 01 .2 01 5. .4 .4 .4 5. 28 21 14 0 0 0 20 10 .2 01 .2 01 .2 01 4. .3 .3 .3 7. 31 24 17 Concentration (ug/L) http://www.clu-in.org/conf/tio/nano-iron/ 28 CL:AIRE 2010 Case #4 – Spolchemie - Pilot Total ClE RW5-31 RW5-31 14 000,0 12 000,0 10 000,0 8 000,0 6 000,0 4 000,0 2 000,0 0,0 AW5-7 Date 30 kg of pure iron injected 6 months period of monitoring 5 000,0 4 000,0 Reduction CHC – 30 – 40% Reduction ClE – 20 – 30% Reduction ClM – 70 – 80% http://www.clu-in.org/conf/tio/nano-iron/ 29 CL:AIRE 2010 Case #4 – Spolchemie – full scale Full scale: •10 direct pushed wells •3 rotary drilled wells •3-12m bgs •1000 kg of pure iron •In 2-3 injection steps •3 years Case #5 – Combination – NZVI - lactate HJ -9 08 RW -9 RW -3 7 C o nta m in an t co mp o siti on P CE (1 0 0% ) P CE (3 0 % ), TC E (2 6% ), DC E (3 9% ) c -DC E (8 2 % ), V C ( 16 % ) Fi rst in je ctio n L ac ti c ac id (2 0 0 9) NZ V I (2 0 09 ) L ac ti c ac id (2 0 0 8) 2 00 kg 5 0 kg 2 00 kg 0 ,5% 0 ,2% 0 ,2% L ac ti c ac id (2 0 1 0) L ac ti c ac id (2 0 1 0) NZ V I (2 0 09 ) 2 00 kg 2 00 kg 3 0 kg -- -- -- NA N O FE R 2 5 S NA N O FE R 2 5 S Q u an tity In je cted co nc en tra tio n NANOIRON pilot test site r ne a le yc r D Application MW-19 MW-3 Groundwater flow direction PW-3 S e con d in je ctio n Q u an tity MW-2 Us ed Garden NZ VI Application PW-2 PJ-808 MW-1 Groundwater flow direction g/l CH C 20 m g /l C HC 100 m g LACTATE pilot test site y od riv Ku 2,5 m HJ-906 n mo Mi http://www.clu-in.org/conf/tio/nano-iron/ 30 CL:AIRE 2010 W ell /l C HC Source area (DNAPL zone) Legend: Groundwater monitoring point CHC concentration contourlines in mg/l Scale bar: 0 20 40 60 80m G flo rou w nd di wa re te ct r io n Case #5 - combination TOTAL molar concentrations [C/C0] http://www.clu-in.org/conf/tio/nano-iron/ 31 CL:AIRE 2010 10,00 1,00 Pure lactate Pure nanoiron RW-9 0,10 RW-37 HJ-908 0,01 Lactate -> Nanoiron 0,00 26.7.09 24.9.09 23.11.09 22.1.10 23.3.10 22.5.10 21.7.10 19.9.10 18.11.10 Time [date] http://www.clu-in.org/conf/tio/nano-iron/ 32 CL:AIRE 2010 Perspectives of nanoiron For contaminations types where high reactivity is needed (for ex. PCB) For sites where presence of toxic intermediates (VC) is hazardous (also buildings and cellars) In the proximity of used cellars or underground facilities (where also the bad smell is undesirable) In the proximity of water sources, the iron is not much soluble, the Iron will not harm the quality of water (bad smell, black color). To enhance remediation proceess started by other technologies. UPOL Radek Zbořil Jan Filip kvapil@aquatest.cz Geologická 4 15200, Praha 5 radek.zboril@upol.cz Svobody 26, 77146 Olomouc http://www.clu-in.org/conf/tio/nano-iron/ 33 CL:AIRE 2010 AQUATEST a.s. Petr Kvapil, Miroslac Černík TUL Miroslav Černík, Lenka Lacinová, Jaroslav Nosek, Štěpánka Klimková miroslav.cernik@tul.cz Hálkova 6, Liberec Thanks for your attention