Use of Nanotechnology in Remediation of Radionuclides and Heavy - - PowerPoint PPT Presentation

Use of Nanotechnology in Remediation of Radionuclides and Heavy Metals Frank (Fengxiang) X. Han

• Dept. of Chemistry and Biochemistry

Jackson State University

Global Perspective

• f Pollution by Heavy Metals/Trace

Elements

Driving Force

 Global Population Increase and Civilization (6.91 billion, by 1.1% in 2009)

by Heavy Metals/Trace Elements? How is the Earth Surface polluted Heavy Metal/Trace Element Production

= ?

Pollution

GlobalAnnual Production of Zn, Pb,

Cu, Cr, Ni, and Cd since Industrial Age

Zn

2 4 6 8 10 12

1850 1875 1900 1925 1950 1975 2000 2025

Million Tons

Actual Estimated

Pb

2 4 6

1850 1875 1900 1925 1950 1975 2000 2025

Cu

2 4 6 8 10 12 14 16

1850 1875 1900 1925 1950 1975 2000 2025

Cr

1 2 3 4 5 Million Tons

Ni

0.0 0.5 1.0 1.5

Cd

0.000 0.006 0.012 0.018 0.024

1850 1875 1900 1925 1950 1975 2000 2025 1850 1875 1900 1925 1950 1975 2000 2025 1850 1875 1900 1925 1950 1975 2000 2025

Year Year Year

Cumulative Production of Zn, Pb, Cu,

Cr, Ni, and Cd since Industrial Age

100 200 300 400 500

M i l l i o n T o n s

Zn Cr Cu

Pb Ni

1.25 250 1.00 200 0.75 150 0.50 100 0.25 50 0.00

1850 1875 1900 1925 1950 1975 2000 2025 1850 1875 1900 1925 1950 1975 2000 2025 1850 1875 1900 1925 1950 1975 2000 2025

Year Year Year

Cd

Annual production of As since Industrial Age since Industrial Age

Thousand Tonnes 0.00 0.25 0.50 0.75 1.00 Thousand Tonnes (c) As in Petroleum 10 20 30 40 50 60 1850 1900 1950 2000 Year Thousand Tonnes Measured Fitted As Mine Thousand Tonnes (a) (b) 30 25 As in Coal 1850 1900 1950 2000 Year 20 15 10 5 (d) 80

Gross Annual As

1850 1900 1950 2000 Year 60 40 20 1850 1900 1950 2000 Year

Gross As Production, As Production from Petroleum and Coal since Industrial Age

(a)

%, As from coal and petroleum

• ver gross As

100 Annual 75 Cumulative 5 50 25 4 0.04 0.03 0.02 A s from petroleum

Gross As

1850 1900 1950 2000 Year (b) 10.0

Million Tonnes As

0.01 3 0.00 1850 1875 1900 1925 1950 1975 2000 2 As from mining

%, As from petroleum

• ver As from coal and petroleum

7.5 1 5.0

As from coal

2.5 1850 1875 1900 1925 1950 1975 2000 0.0 1850 1900 1950 2000 Year Year

Annual and Cumulative Hg Production

12

0.80

Annual Hg Mine Annual Hg in Coal

Thousand Tons

Thousand Tons

Thousand

Thousand Tons 10

0.60 0.40 Actual

8

Simulated

6 4 2

Actual Simulated

0.20 0.00

1850 1875 1900 1925 1950 1975 2000 2025 1850 1875 1900 1925 1950 1975 2000 2025

Year Year 800

800

Cumulative Hg Cumulative Total Hg

Hg-coal/Total, %

600

8 6 4 2

1850 1900 1950 2000

600 400

Tons

400

Hg Mine

200

200 Hg in Coal

1850 1875 1900 1925 1950 1975 2000 2025 1850 1875 1900 1925 1950 1975 2000 2025

Year Year

Potential Cumulative Anthropogenic Inputs to Global Arable Soil (0-10 cm)

1900 1950 1990 2000 Hg Cd As 0.0 0.5 1.0 1.5 2.0 2.5

mg/kg

Ni Cr Pb Zn Cu 50 100 150 200 250 mg/kg

Compared to Global Soil and Lithosphere

1 900 1 950 1 990 2000

As Cr Ni Cd Pb Zn Cu Hg 1 2 3 4 5 6 7 8 9

1900 1950 1990 2000

Ni Cr As Zn Cu Cd Hg Pb 1 2 3 4 5 6 7 8 9 10

Ratios of Anthropogenic Cumulative Input /World Soil Ratios of Anthropogenic Cumulative Input /Lithosphere

Global Metal Burden per Capita

1950 1990 2000 Cd As 80 0.8 70 0.7 60 0.6 50 0.5 Kg 40 0.4 Cumulative 30 0.3 Metal/Capita 20 0.2 10 0.1 0.0 Ni Hg 1900 1950 1990 2000 Cr Pb Zn Cu 1900

Global Nuclear Radionuclide Pollution

Nuclear Energy

 With the fast growth of global population, the world consumption of

energy has been continuously increasing at an annual rate of 2-3%. Fossil fuel energy is the major source of current global energy consumption (37% petroleum, 25% coal and 22% natural gas)

 Due to increasing cost of fuel energy supplies and global warming,

nuclear energy has become a promising emission-free clean energy. Currently, nuclear energy accounts for 6% and 8% of the total energy consumption in the world and the U.S., respectively

Nuclear Power Plant Accidents

 99 nuclear power plant accidents worldwide  4 major accidents including the most recent Fukushima Daiichi

nuclear disaster (2011), Chernobyl disaster (1986), Three Mile Island accident (1979), and the SL-1 accident (1961).

 Chernobyl: 137Cs, 90Sr, 238Pu and 241Am  Fukushima Daiichi: 134Cs, 137Cs, 60Co and 131I  On the other hand, radionuclides were in colloids of groundwater of

nuclear ground detonation sites such as the Nevada Test Site. Dissolved organic carbon mobilized actinides (Am, Pu, Np and U) in the groundwater of these sites.

Developing Novel Nanomaterials for Removing Radionuclides and Heavy Metals from Water

To functionalize meso silica for adsorption

• f Cs, Co, and Sr in contaminated water

MCM-41 (Mobil Composition of Matter No. 41) is a mesoporous alumosilicate with a hierarchical structure.

TEM pictures of MCM-41-SH (a and b). The pore sizes were indicated as arrows, measured as 3 nm or 6 nm.

 Characterization

Particle Size and Zeta Potential FTIR and Raman Spectroscopy TEM Images

Adsorption of Cs, Sr, and Co on thiol- functionalized MCM-41

Prepare a mix solution of CsNO3, Sr(NO3)2, and Co(NO3)2 at serial concentrations. Add sorbents, shake and filter supernatant. Inductively coupled plasma-mass spectrometry (ICP-MS) was applied.

FTIR spectra of MCM-41-SH and MCM-41. The weak peak around 2600 cm-1 indicated the presence of the SH group

Raman spectra of MCM-41 and MCM-41-

• SH. Aliphatic carbon chains appeared from

600 cm-1 to 1300 cm-1; the peak around 2600cm-1 confirmed the existence of –SH function group.

y = 0.0342x + 0.2768 R² = 0.9329 1.2 Equilibrium Conc. /Adsorption Capacity (Ce /Q, g L-1 ) y = 0.752x + 0.7223 R² = 0.932

• 4
• 2

2 4

• 4
• 2

2 4 LogQ LogCe

Cs adsorption isotherm from water on MCM-41-SH

0.8 0.4 10 20 30 Equilibrium Concentration (Ce, mg L-1) Langmuir model of Cs adsorption from water on MCM-41-SH Freundlich model of Cs adsorption from water on MCM-41-SH

Table 1 Comparison of adsorption of Cs on MCM-41-SH as described with Langmuir and Freundlich models

Langmuir Model Freundlich Model R2 0.93 R2 0.93 b, L mg-1 0.12 n 1.33 Q, mg g-1 29.24 Kf 5.28

This study indicated that commercially available MCM-41 after being functionalized became more selective on Cs, one

• f elements with the most difficult to remove. For the next stage study, I consider to make sorbent recyclable.

Developing meso-silica templated nano carbon for removing Cs

 Carbon Precursor

 

 Mesosilica has been used as a stable template to

synthesize mesoporous carbon with various functional groups such as hydroxyl, carboxyl, and carbonyl groups, etc.

Ferulic acid, as the carbon precursor, was used for the adsorption of Cs(I) and other several major nuclides such as Co(II) and Sr(II). Ascorbic acid as C precursor and binding to nano magnetite Fe3O4, for removing Hg(II) and Pb(II).

Ferulic acid Ascorbic acid

•  Characterization

TEM, FTIR, and BET are applied to illustrate functional groups and pore structure.

T TE EM M i im ma ag ge es s o

• f

f f fe er ru ul li ic c a ac ci id d-N NC C ( (a a) ) a an nd d a as sc co

• r

rb bi ic c a ac ci id d-N NC C ( (b b) ). .

FTIR

FTIR spectra of ferulic acid-NC (a) and ascorbic acid-NC (b) (upper figure) and BET isotherm of two nano carbons (lower left). Magnetic effect after a permanent magnet was applied to the ascorbic acid- NC (lower right).

Hg on Ascorbic-NC Co, Sr, Cs on Ferulic-NC a d b c f e

Kinetic study of Co, Sr, and Cs with 0.3 g/L ferulic acid-NC at 25 with pH=6~7. Kinetic data (a), pseudo-first

• rder (b), and pseudo-second order (c)

were shown. All three elements fit pseudo-second order well. Kinetic study of Hg with 0.3 g/L ascorbic acid-NC at 25 with pH=6~7. Kinetic data (d), pseudo-second order (e), and pseudo-first order (f) were shown.

Adsorption Kinetics

Adsorption Isotherms of Co, Sr and Cs: Phase I and II

Adsorption isotherms of Co (a), Sr(c), and Cs(e) with 0.3 g/L ferulic acid- NC at 25 with pH=6~7: Langmuir model of Co(b), Sr(d), and Cs(f) for Phase I; Freundlich model of Co(g), Sr(h), and Cs(i) for Phase II.

Adsorption isotherm of Hg(a) and Pb(c), with 0.3 g/L ascorbic acid-NC, at 25 , with pH=6~7: Langmuir model of Hg(b) and Pb(d).

Thermodynamic study of Hg(a) and Pb(c) on ascorbic-

• NC. Van’t Hoff

model linear plot was applied to Hg(b) and Pb(d).

Table 3 Thermodynamic parameters of Hg and Pb at 10 and 20 mg/L, on ascorbic acid- NC with 0.3 g/L at pH~6,7.

Metals Temperature Initial Concentrations of metals

0C

10 mg/L 20 mg/L ΔG lnKC ΔH ΔS R

2

ΔG lnKC ΔH ΔS R

2

(kJ mol

• 1)
• 1

(kJ mol )

• 1 K
• 1

(J mol )

• 1

(kJ mol ) (kJ mol

• 1)
• 1 K
• 1

(J mol ) Hg 15

• 1.51

0.63 1

• 1.83

0.76 0.74 30

• 2.1

0.88 11.6 45.6

• 2.73

1.09 7.93 34.3 45

• 2.6

1.09

• 2.83

1.07 Pb 15

• 0.57

0.24 0.037 1.01

• 0.42

0.38 30 0.8

• 0.32

2.64

• 1.05

45

• 1.07

0.4

• 1.88

0.71

• Δ G and + ΔH indicates spontaneous adsorption process; + ΔH indicates endothermic adsorption process

Adsorption of Cs using magnetic heteroatom-functionalized calixarene complex

Calixarene is a building block material in the macrocyclic molecular group. Its unique character was the three-dimensional pre-organization, making it a potential candidate of receptor to many cations and anions, which exhibited potentials for the treatment of nuclear wastewater.

The present study is to synthesize the stable and efficient magnetic calixarene composite for the treatment of Co2+, Sr2+, and Cs+. Two types of commercially available upper-rim sulfur or phosphorous functionalized calixarene were applied and compared. Meso-silica as the anchor was applied to connect the Fe O part 3 4 and the calixarene part.

Characterization TEM, FTIR, SEM, XRD, BET methods will be applied to elucidate the unique structure of the calix complex. Adsorption Cs (from 0 to 2000 mg/L) and Sr solution were prepared.

• Experiment

Synthesis

To examine any competitive behavior with other heavy metals, mix solutions of Sr, Co, Cd, Hg, and Pb from 0 to 2000 mg/L.

TEM images of Fe O NP (a), Si-MN (b), S-Si-MN (c), and P-Si- High resolution TEM pictures showed S-Si-MN (a), P-Si-MN 3 4 MN(d). (b), and Si-MN (c).

SEM results of P-Si-MN (a&b) and S-Si-MN (c&d).

• P Si MN

S Si MN

O

Si P Fe O Si S Fe

Weigh t %

29.98 26.65 26.83 16.54 40.47 32.77 7.01 19.75

Atomi c %

47.02 23.82 21.73 7.43 59.26 27.33 5.12 8.29

Energy Dispersive Spectroscopy (EDS) analysis showed the elemental mapping of each composite. On the top is the SEM image of S-Si-MN, and the corresponding elemental mapping results are on the right. The brighter the color, the higher percentage

• f the element is in that zone. On the bottom are the SEM image of P-Si-MN and the elemental mapping.

FTIR spectra of phosphoryl group calixarene (a), sulfonic group calixarene (b), S- Si-MN (c), P-Si-MN (d), and Si-MN (e).

Cs Adsorption in Cs Alone System

60 120 180 400 800 120 Q

e mg/g

Ce mg/L 100 200 300 400 800 1200 Q

e mg/g

c

y = 0.8017x - 0.2887 R² = 0.8351

• 4
• 2

2 4

• 4
• 2

2 4

LogQe

b

y = 0.7407x + 0.0061 R² = 0.8133

• 4
• 2

2 4

• 4
• 2

2 4 logQ

d

LogCe

e

logCe Ce mg/L

Adsorption of Cs on S-Si-MN. (a) Isotherm; (b) Freundlich model and P-Si-MN (c) isotherm; (d) Freundlich model. Far right shows magnetic separation

Sr Adsorption in Sr Alone System

In the individual system, the adsorption of Sr on P-Si-MN. (a) isotherm; (b) Freundlich model; (c) Langmuir model on Phase I; (d) Langmuir model on Phase II.

Co Adsorption in Multimetal system

In the multi-cation system, the adsorption isotherm of Co on S-Si-MN (a) and P- Si-MN (c); Freundlich model from S-Si-MN (b) and P-Si-MN (d).

Sr Adsorption in a Multimetal System

In the multi-cation system, the adsorption of Sr on S-Si-MN (a) isotherm & (b) Freundlich model; on P-Si-MN (c) isotherm & (d) Freundlich model. The inlet of Fig. d showed the Langmuir model of Phase I.

Cd Adsorption in a Multimetal System

In the multi-cation system, the adsorption isotherm of Cd on S-Si-MN (a) and P-Si-MN (c); Freundlich model from S-Si-MN (b) and P-Si-MN (d).

Hg Adsorption in a Multimetal System

In the multi-cation system, the adsorption isotherm of Hg on S-Si-MN (a) and P-Si-MN (c); Freundlich model from S-Si-MN (b) and P-Si-MN (d).

Pb Adsorption in a Multimetal System

In the multi-cation system, the adsorption isotherm of Pb on S-Si-MN (a) and P-Si-MN (c); Freundlich model from S-Si-MN (b) and P-Si-MN (d).

• Comparison of Adsorption Capacity

Adsorbents Adsorbates pH Maximum adsorption capacity (mg/g) References

aminated graphene oxide NP Co 116.35

Fang et al., 2014

Graphene oxide hydroxyapatite NP Sr 2-4 702.18

Wen et al., 2014

Graphene oxide complexed Cs 184.74

Sun et al., 2013

with nitrogene and oxygene groups Sr 147.20 P Si MN 6-7

This study

Co 900 Sr 30000 Cs 200

Other Soil Remediation in my group

 Phytoremediation  Bioremediation  Electronic Kinetic Remediation  Coupled Electronic Kinetic-Phytoremediation  Soil Washing  Coupled Electronic Kinetic-Soil Washing

contaminated water.

Conclusion

Our lab developed a series of promising meso/nanomaterials for cleaning up Cs, Sr, Co and other radionuclides as well as heavy metals (Cd, Hg, Pb) in This study shows the promise of novel meso/nanomaterials in removing common radionuclides and heavy metals and provides alternative solutions for water pollution from nuclear industry development.

Acknowledgement

 This study was supported by the U.S.

Nuclear Regulatory Commission (NRC-HQ- 84-15-G-0042 and NRC–HQ-12-G-38-0038).

Recent Publications

• .



Meng, et al. 2017. Removing uranium (VI) from aqueous solution with insoluble humic acid derived from

• leonardite. Journal of Environmental Radioactivity 180 (2017) 1-8



Mao, et al. 2017. Effects of operation variables and electro-kinetic field on soil washing of arsenic and cesium with potassium phosphate. Water Air and Soil Pollution 228: 15. doi:10.1007/s11270-016-3199-y



Guo, et al. 2016. Development of novel nanomaterials for remediation of heavy metals and radionuclides in contaminated water. Nanotechnology for Environmental Engineering (Springer). 1:7



Mao, et al.. 2016. The distribution and elevated solubility of lead, arsenic and cesium in contaminated paddy soil enhanced with the electro-kinetic field. International of Journal of Environmental Science and Technology 13: 1641–1652.



Mao, et al. 2016. Remediation of lead, arsenic, and cesium contaminated soil using consecutive washing enhanced with electro-kinetic field. Journal of Soils and Sediments, 10: 2344-2353.



Billa, et al. 2016. Radioactivity Studies on Farm Raised and Wild Catfish Collected in the Vicinity of a Nuclear Power Plant. Journal of Radioanalytical and Nuclear Chemistry. 307: 203-210.



Lawson et al. 2016. Binding, Speciation and Distribution of Cs, Co and Sr in U.S. Coastal Soil under Saturated and Field Capacity Moisture Regimes. Journal of Soils and Sediments 16 (2): 497-508.



Mao, et al. 2016. Electro-kinetic remediation coupled with phytoremediation to remove lead, arsenic and cesium from contaminated paddy soil. Ecotoxicology and Environmental Safety, 125:16-24.



Gao, et al. 2015. Adsorption of Cs from water on surface modified MCM-41 mesosilicate. Water Air and Soil Pollution 226: 288-297



Han, et al. 2003. Assessment of global industrial-age anthropogenic arsenic contamination. Naturwissenschaften 90: 395-401.



Han et al. 2002. Industrial age anthropogenic inputs of heavy metals into the pedosphere. Naturwissenschaften 89: 497-504



Han FX. 2007. Biogeochemistry of Trace Elements in Arid Environments, pp ~ 380, Springer.

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