APPLICATION OF NANOSCALE ZERO VALENT IRON (nZVI) FOR GROUNDWATER REMEDIATION

Presented by

Misnagama Gamage Aruna Jayamanjula S194373

Master of Petroleum Engineering

OUTLINE OF PRESENTATION
1. Introduction
2. Implementation of Field Application of nZVI 3. Field Application of nZVI 4. Costs 5. Conclusion

1. INTRODUCTION
1.1 Current Situation of Contaminant Remediation
In Europe polluted sites to be remediate - 20,000 + Identified potentially contaminated sites 350,000 ----- European Environment Agency. In USA polluted sites to be remediate 235,000 to 355,000 ----- U.S. EPA 2005.

a) Pump and Treat Method

An ex-situ treatment technology. The predominant technology for addressing groundwater contamination until 1992 (Karn et al. 2009; U.S. EPA 2005). Operates for about 18 years as very expensive and slow It is expected that ex situ remediation techniques will be phased out over the coming decade. (Karn et al. 2009).

b) Permeable Reactive Barrier

Passive in-situ treatment method using granular zero valent iron (ZVI) Metallic iron very effective in transforming a wide variety of common contaminants (chlorinated methanes, brominated methanes, trihalomethanes, chlorinated ethenes, chlorinates benzenes, other polychlorinated hydrocarbon pesticides, and dyes) into less toxic compounds.

1. INTRODUCTION (contd.)
ZVI reduces inorganic anions also such as nitrate reduces to ammonia, perchlorate (plus chlorate or chlorite) reduces to chloride, selenate, arsenate, arsenite, and chromate. ZVI also efficient in removing dissolved metals from solution. The major drawback: PRBs can only address contaminant plumes that flow through the barrier and hence they do not contribute to the active removal of the source. This has a direct impact on the duration of the remediation and the availability of the land for reuse. c) Nanoscale Zero Valent Iron (nZVI) Nanoscale iron particles arebased on the large specific surface areasignificantly more reactive than conventional ZVI and are to some extent able to migrate below ground, which allows active remediation of the contaminated plume and the source. These beneficial properties led to a rapid increase of site remediation with nZVI. Other types of nanoparticles have also been tested - zeolites, calcium oxide, iron oxides, and (bi)metallic iron. nZVI (nanoscale zero valent iron) is the most commonly used nanomaterial for soil and groundwater remediation at the present.

1. INTRODUCTION (contd.)
Principle Zero-valent iron reacts chemically as reductive agent (it is oxidized = get rusty)

Feo Fe2 2e
CHC are reduces with overall reaction

5Fe o C 2 HCl 3 5H 5Fe 2 C 2 H 6 3Cl

It was confirmed in laboratory that > 70 compounds can be reduced (Zhang, 2003): o Chlorinated Hydrocarbons (CHC): TCE, PCE, DDT, PCB, PCM, PCP, lindane, o Heavy Metals: Pb, Hg, Ni, Cd, Cr, As, U, etc. o others: nitrates, TNT

1. INTRODUCTION (contd.)
1.2 NZVI Modifications & Types used for Soil and Groundwater Remediation
Abbrev. ZVI NZVI Description Zero valent iron Nanoscale zero valent iron (surface modified, e.g., with starch, carboxymethylene cellulose, polyacrylic acid, cellulose, inhicor-T, Tween 60 or 80) Bimetallic NZVI (NZVI combined with a metal catalyst such as Ni, Pd, Pt, Cu, Ag) NZVI on carbon support (NZVI combined with active carbon platelets of 50200 nm diameter) Emulsified NZVI [NZVI core in water coated by foodgrade surfactants and biodegradable vegetable oil which form an oilliquid membrane (about 15 m in diameter)] Amorphous type of NZVI made from borohydride reduction of dissolved Fe(III) NZVI produced from nanosized ferrihydrite by the Czech company NANOIRON Reactive nanoscale iron particlea crystalline type of nano-iron made by gas phase reduction of FeOOHproduced by TODA Inc. Japan. Characteristics Microscale Surface modification mobility in the ground aims to increase

BNZVI c-NZVI

ENZVI

BNZVI has high reaction rate than NZVI but consequently a shorter lifetime c-NZVI may be used to enhance the NZVI distribution in contaminated aquifers (no field tests carried out yet) ENZVI was designed for the in situ treatment of dense non-aqueous phase liquids (DNAPLs). Due to the hydrophobic coating, ENZVI can mix with organic contaminants.

Fe(B) NANOFER RNIP

Sources: Muller et al. (2010), Quinn et al. (2005), EPA

1. INTRODUCTION (contd.) 1.3 Pilot Tests in Europe Comparison Table

Source: Muller et al. (2012)

2. IMPLEMENTATION OF FIELD APPLICATION OF nZVI

Laboratory Experiments feasibility approval Batch experiments: groundwater + soil + nZVI concentration Concentration dependency (efficient concentration) in g/L Kinetic (reaction rate) Comparison of different products Regulatory Approval Subjected to decision of local authority Field Pilot Study Usually 100-500kg of nZVI Before a full-scale application of nZVI, a precise site investigation and pilot tests are needed, to evaluate the site hydrogeology as well as the geochemistry. The hydrogeology influences the transportability of the particles. The geochemistry indicates potential substances that nZVI could react with other than the target compounds and thus determines the lifetime of the reactive particles. Pilot tests are conducted to provide information on the amount of nZVI needed and possible unanticipated challenges. Full Scale Remediation

3. FIELD APPLICATION OF nZVI

3.1 Site Condition
Site Location: Kara Trutnov in Czech Republic Source: Fur processing site Contaminant: Chlorinated ethenes (PCE, TCE, DCE, VC) and chromium (Cr6+) Previous treatment: pump & treat, venting, vapour deposition, potassium permanganate In Situ Chemical Oxidation (ISCO)

3.2 Specification and Characteristics of the Nano-material

Nano-material applied : NanoFer 25S Average particle size : 50nm Narrow particle size distribution : 20-100nm Average surface area : 20-25m2/g Surface Modification : by combining biodegradable organic and inorganic stabilizers.

Due to the narrow size distribution of nanoparticles and sophisticated stabilization process, the product exhibits a high reactivity with a large scale of pollutants and very low degree of agglomeration, which implies for excellent migration and sedimentation properties.

TEM images of nanoparticles of NANOFER 25S, stabilized by combination of organic and inorganic phases

3. FIELD APPLICATION OF nZVI (contd.)

Characteristics of Nanofer 25S

XRD pattern of zero-valent nanoparticles of -Fe with weight content of 90 % and average particle size of 50 nm (derived from the Scherrer formula); magnetite - Fe3O4 (m) as a by-product

Primarily produced (non-stabilized) Fe(0) nanoparticles with recordly small size and narrow size distribution by view of scanning electron microscopy (SEM).

X-ray diffraction (XRD) used to investigate the material structure of iron nanoparticles. ZVI presence indicate the narrow peaks at 52o, 78o & 100o and magnetite Fe3O4 (m) as a by product. Specific surface area of the nanoparticle was determined with the classic BET method (the BrunauerEmmettTeller isotherm).
BET adsorption-desorption isotherms of Fe(0) nanoparticles with surface area of 25 m2/g.

3. FIELD APPLICATION OF nZVI (contd.)

3.3 Laboratory Experiment

Samples: 100 samples using real ground water with the addition of soil from the site Three different test conditions: o Soil + 0 g/L nZVI o Soil + Lactate + 0 g/L nZVI o Soil + 1 g/L nZVI Tests: Batch tests

Results of Laboratory Experiment for PCE and Cr(VI)

3. FIELD APPLICATION OF nZVI (contd.) 3.4 Pilot Test

Applied 200kg of NANOFER 25S. Target dosing concentration of 2g/L. Pump into 2 injection wells ME-6 and ME-24.

3. FIELD APPLICATION OF nZVI (contd.) 3.5 Test Results After 2 months

Chemical composition of ground water - well ME-24 parameter pH Total chromium (Cr tot.) Hexavalent chromium (Cr6+) Vinylchloride (VC) trans-1,2-Dichlorethene (t-DCE) 1,1-Dichlorethene (DCE) cis-1,2-Dichlorethene (c-DCE) Trichlorethene (TCE) Tetrachlorethene (PCE) sum of CHC including VC September unit September October 22nd October 31st 8th 20th mg/L mg/L g /L g /L g /L g /L g /L g /L g/L 6,94 42,5 42,2 278 14,1 4,4 2340 642 903 4182 8,58 <0,001 <0,005 70,4 1,9 <1 1060 92,4 62,6 1287 7,98 0,874 0,873 <4 <1 <1 3,1 1,64 3,77 8,5 7,87 <0,001 <0,005 <4 <1 <1 18,9 <0,50 <0,50 18,9

An immediate decrease in concentrations of hexavalent chromium to the detection limit (<0,005mg/L) and there was no rebound effect during the next 45 days. 100% of hexavalent chromium was removed from the application well and its surroundings. A gradual decrease in concentrations of chlorinated hydrocarbons (CHC) in well ME-24 from initial value 4200 g/L to 1300g/L (one week after application) and then further to 20g/L (45 days after application). It was removed 99,55% of CHC sum (up to 100% of PCE, TCE and VC and 99,2% cis-1,2-DCE).

3. FIELD APPLICATION OF nZVI (contd.)

3.6 Full Scale Remediation

First Injection: Winter/2011 o 2000kg of Nanofer was injected using 12 injection wells. Second Injection: Spring/2012 o 1800kg of Nanofer was injected.

06/2012

02/2012

4. COSTS: nZVI COMPARING TO OTHER PRODUCTS

Application cost is important
Lower amount of nZVI is needed Better mobility of nanoparticles = less injection wells Faster application Higher efficiency

All parameters affect remediation cost Absolute cost of material ($/kg) is not representative

5. CONCLUSION
Higher price of nanoiron is compensated by properties that are missing in other materials and methods. However, the site characteristics determine the optimum method. Perspectives: For contaminants types where high reactivity is needed (for PCE) For sites where presence of toxic intermediated (VC) is hazardous. In the proximity of water sources since iron does not harm the quality of water To enhance remediation processes started by other technologies. In Europe, only regular nZVI is applied because of concerns regarding the toxicity of the catalysts in BNZVI. The competitiveness of nZVI for source treatment is in general very limited in comparison with ISCO (in situ chemical oxidation).

REFERENCES
1) Muller N.C., Braun J, Bruns J, Cernik M, Rissing P, Rickerby D, Nowack B (2012), Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe, Environ Sci Pollut Res (2012) 19:550558. (Main Article) 2) Slunsk J (2013), Utilization of Zero-Valent Iron nanoparticles (nZVI) for in-situ groundwater remediation including recent field scale application and remediation experience, Applications of Nanotechnology for Safe and Sustainable Environmental Remediation technical session, USA. 3) Zhang W (2003), Nanoscale iron particles for environmental remediation: an overview, J Nanopart Res 5:323-332. 4) http://www.nanoiron.cz/en/characteristics-of-iron-nanoparticles

THANK YOU