Burdina zerobalentearen nanopartikulak: promesa edo errealitatea? Kasu-azterketen berrikuspena

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1 Burdina zerobalentearen nanopartikulak: promesa edo errealitatea? Kasu-azterketen berrikuspena Petr Kvapil, Miroslav Černík TUL, AQUATEST a.s., ARTEC

2 First application of nzvi in Europe in 2004 Spolchemie source - Zhang GOLDER Ass. Laboratory tests Field tests ORP decrease ph increase CHC decrease 6 months Period of nanoiron activity reduction ~ 70 %

3 Kurivody site first successfull 2005 FRACTURED BEDROCK FLOW Tracer test Blast fracturing Low final concentrations 20 No 000 rebound sum of ClU [ug/l] PW-3 MW-2 MW-3 remediation limit ug/l MW-3 GW flow direction MW-2 PW-3 Application well - blast fracturing - tracer test - ZVI nanop. application Zhang s nzvi

4 Site Nanoiron applications - overview Contam. Spolchemie 2004 Cl-Ethenes Lab/pilot/ Remed. L,P Type of nzvi ZHANG Kuřívody 2005, 2006, 2009 Cl-Ethenes L,P ZHANG, RNIP Piešťany 2005 Cl-Ethenes L,P ZHANG Permon 2006 Cr6+ Rožmit mitál PCB L,P L,P RNIP 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 2009, 2010 Cl-E, Cl-M L, P, R NANOFER Laboratory: CHC, AOX, U, As, nitrobenzene, acid mine waters, other

5 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)

6 Expectations of successful remediation? Setected method is the best Runs where others failed Fast remediation Within several weeks Cheap remediation For a few tens of thousands Environmental - friendly No toxic No by-products Intermediates do not arise No rebound effect One application is sufficient Expectation: All provide nanofe

7 Nanoiron will help where other methods have failed? No & Yes Nanoiron can substitute bio-enhanced enhanced dechlorination Nanoiron will help in cases of complex mixture contaminants (mixture of ClM, ClE, some metals, saline waters) In areas where are water resources, cellars, danger of explosions, etc.

8 Spolchemie Pilot test Necessary the exception from Water law Exploited cellars in the neighbourhood Contamination by CLE and CLM Aquifer clay, sand, gravel

9 20 000, , , ,0 0,0 Spolchemie Pilot test Total CHC RW5-31 AW , , , , , , ,0 0,0 Total ClE RW5-31 AW Date Date Concentration (ug/l) Concentration (ug/l) 6 000, , , , , ,0 0,0 Total ClM RW5-31 AW kg of pure Fe 6th months monitoring Reduction ClU 30 40% Reduction ClE 20 30% Reduction ClM 70 80% => Now running FULL SCALE Date Concentration (ug/l)

10 Nanoiron cleans soils and waters? Yes & No Iron cleans, NANO increases efficiency Suitable for saturated zone Exemple: : PCB, DCA, AOX, some metals, cyanides Rožmit mitál

11 Case: : PCB Rozmital p.t. Laboratory experiments kinetics for 4, 10, 30, 60 days concentration dependency Indicative congeners x all RNIP x Nanofer25S 100% 80% 60% 40% 20% 0% initial 4 days 30 days Kinetics: Nanofer25 indicative congeners TODA (0.5g Fe) Nanofer (0.5g Fe) 100% 90% 80% congeners 70% Significant decrease after 4 days NanoFe active during whole period TODA x Nanofer similar Lower efficiency for more chlorinated Sorption questions? 60% 50% 40% 30% 20% 10% 0% , , , 33, 53 22, , , 42, 59 41, , 88, ,

12 Case: : PCB pilot test sum of congeners concentration (ug/l) shaft ring J X-08 XI-08 XII-08 I-09 II-09 III-09 IV-09 datum

13 Nanoiron degrades quickly and without intermediates? YES & NO Reaction rate should be confirmed in laboratory tests Fast reactions without intermediates: : PCB, metals (Cr,, As) Slow reactions (cis-dce, DCA) Exemple (Permon,, PíseP sečná)

14 Case Písečná full-scale Pretreatment of technological water Contaminant removal Oxygen removal Preparation nzvi slurry: 1000 kg dry powder iron NANOFER25N (containers in N 2 atmosphere) diluting by field slurry dispergator to 5000 kg of 20% suspension of nzvi NANOFER 25 and NANOFER 25S 14 On-site

15 Příklad Pisecna full-scale results in remediation wells ,0 Concentration [µg/l] , ,0 0,0 HV-12 HV-13 HV-5 HV-6 WELL HV-7 HV-8 HV-9 TX-3 ClE [before] ClE [6 months after 1. injection] ClE [3 months after 2. injection] ClE [8 months after 2. injection] CIE [9 months after 2. injection] ClE [11 months after 2. injection] ClE [13 months after 2. injection] 15

16 Fast reaction, small doses = low price? NOT yet Strong reductive agent degrades by competitive reactions such as with water Need of repeated injections = higher costs For now the high cost of reagents = higher costs BUT can decrease costs of other technologies (exemple: combined method)

17 Groundwater flow direction Application Application Case Combination NZVI - lactate Well HJ-908 RW-9 RW-37 Contaminant composition First injection PCE (100%) Lactic acid (2009) PCE (30%), TCE (26%), DCE (39% ) NZVI (2009) c-dce (82%), VC (16%) Lactic acid (2008) Quantity 200 kg 50 kg 200 kg Injected concentration 0,5% 0,2% 0,2% Second injection Lactic acid (2010) Lactic acid (2010) NZVI (2009) Quantity 200 kg 200 kg 30 kg Used NZVI NANOFER 25S NANOFER 25S Mimon Kurivody Garden 2,5 mg/l CHC 20 mg/l CHC Source area (DNAPL zone) 100 mg/l CHC Groundwater flow direction NANOIRON pilot test site Dry cleaner MW-19 MW-3 PW-3 MW-2 Groundwater flow direction LACTATE pilot test site HJ-906 PJ-808 PW-2 MW-1 Legend: Groundwater monitoring point CHC concentration contourlines in mg/l Scale bar: m

18 ,00 1,00 0,10 0,01 0,00 case - Kombinace Pure lactate Pure nanoiron Lactate -> Nanoiron Time [date] RW-9 RW-37 HJ TOTAL molar concentrations [C/C0]

19 Nannoparticles migrates in the aquifer without retardation? NO Agglomerates quickly when modified and dosed inappropriately Migration confirmed in laboratory columns Could be transported far away by open fractures Example (results of column tests) => Suspension preparation and surface modification at the site

20 Columnt tests Migrace 37 Vo Fe [mg] 1000 Fe v koloně vs. poloha agregováno 60,7 % měřené Fe Fe frakce I. Fe frakce II. Pozadi mobilní 30,2 % 3,1 % Délka 40 [cm]

21 Real migration of nanoparticles After 45 pore volumes Pure Fe Surf. modified Fe

22 Water Water PRE- Treatment Removal Oxygene Contam. Field system ZVIron powder Dispergator Dosing system system from 2009 Surface Modif. Iron suspension GW head Dry powder stored and brought to the site Reduced surface oxidation by Oxygen (pretreatment) Advantage of initial high reactivity Mobility and reactivity control

23 Case Pisecna Full scale system

24 Nanoiron is toxic? NO, not to use internally!!! ( )( In adition, does not harm the water quality in wider area (does( not change organoleptic properties) Can be projected around the cellars and ground water sources. Exemple Spolchemie, and Písečná

25 Conclusions, perspectives of nanoiron applicability Higher price of nanoiron is compensated by properties, that are missing in other materials and metods. Perspectives: 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 n 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.

26 AQUATEST a.s. Petr Kvapil, Miroslav Černík Geologická , Praha 5 TUL Miroslav Černík, miroslav.cernik@tul.c Hálkova 6, Liberec Thanks for your attention