3.2.5 Adsorption isotherms of lanthanides by Buccinum tenuissimum shell biomass

The adsorption data obtained for lanthanides using Buccinum tenuissimum shell biomass were analyzed using Langmuir and Freundlich equations. The correlation coefficient (R2) of Langmuir and Freundlich isotherms for lanthanides using ground original shell biomass is shown in Table 7 along with other relevant parameters.

From this table, it is found that R2 value for lanthanides is comparatively high. It indicates the applicability of these adsorption isotherms satisfactorily for lanthanides in this sample. The dimensionless parameter Hall separation factor (RL) for lanthanides is in the range of 0<Rl<1, which means that the sorption for lanthanides by this shell biomass is favorable. Furthermore, the negative value of ^G indicates that the sorption is spontaneous. The higher R2 value for Freundlich model rather than for Langmuir isotherm (0.638-0.886 for Langmuir isotherm and 0.844-0.932 for Freundlich one) suggests that the adsorption on this sample is due to multilayer coverage of the adsorbate rather than monolayer coverage on the surface. It is noted that the value of 1/n less than unity indicates better adsorption mechanism and formation of relatively stronger bonds between adsorbent and adsorbate [10]. That is to say, favorable adsorption for lanthanides by this shell biomass is presented.

On the other hand, R2 and other parameters of Langmuir and Freundlich isotherms for lanthanides using "heat-treatment (480°C) sample" is shown in Table 8. It is noteworthy that R2 value for REEs in this sample is still more large (0.947-0.982 for Langmuir isotherm and 0.948-0.975 for Freundlich one), compared with the original ground sample (Table 7).

Langmuir

Freundlich

a

b

r2

A Gads/ kJmol-1

Rl

Kf

1/n

r2

La

400

0.490

0.638

-15.3

0.0200

115

0.654

0.844

Ce

370

1.17

0.886

-17.5

0.0084

163

0.583

0.864

Pr

400

0.714

0.750

-16.3

0.0138

145

0.658

0.853

Nd

400

0.610

0.681

-15.9

0.0161

133

0.662

0.846

Sm

417

0.6.32

0.740

-16.0

0.0156

145

0.709

0.863

Eu

417

0.571

0.794

-15.7

0.0172

136

0.723

0.883

Gd

435

0.418

0.788

-15.0

0.0234

114

0.765

0.904

Tb

476

0.328

0.800

-14.4

0.0296

105

0.778

0.912

Dy

476

0.239

0.849

-13.8

0.0367

81.8

0.804

0.932

Ho

476

0.183

0.870

-12.9

0.0519

65.2

0.799

0.924

Er

476

0.148

0.878

-12.4

0.0633

55.6

0.787

0.920

Tm

476

0.135

0.842

-12.2

0.0687

52.6

0.785

0.910

Yb

476

0.136

0.818

-12.2

0.0683

53.3

0.762

0.887

Lu

500

0.119

0.786

-11.8

0.0775

51.3

0.759

0.877

Table 7. Coefficient of Langmuir and Freundlich isotherms for lanthanides using original Buccinum tenuissimum shell biomass

Langmuir Freundlich

a

b

r2

A Gads kJmol-1

Rl

Kf

1/n

r2

La

192

0.243

0.982

-13.6

0.0395

57.2

0.258

0.948

Ce

278

0.234

0.972

-13.5

0.0410

70.4

0.292

0.956

Pr

303

0.229

0.962

-13.5

0.0418

71.5

0.321

0.955

Nd

313

0.225

0.956

-13.4

0.0425

72.5

0.328

0.954

Sm

345

0.266

0.948

-13.8

0.0362

78.4

0.359

0.962

Eu

345

0.248

0.947

-13.7

0.0388

76.0

0.364

0.963

Gd

303

0.231

0.955

-13.5

0.0415

75.0

0.299

0.954

Tb

323

0.221

0.961

-13.4

0.0432

69.8

0.354

0.968

Dy

323

0.195

0.957

-13.1

0.0488

66.3

0.358

0.964

Ho

294

0.178

0.961

-12.8

0.0532

61.0

0.346

0.960

Er

294

0.171

0.963

-12.7

0.0553

59.1

0.355

0.964

Tm

303

0.176

0.964

-12.8

0.0539

59.0

0.372

0.968

Yb

323

0.181

0.960

-12.9

0.0523

60.8

0.395

0.974

Lu

333

0.176

0.966

-12.8

0.0536

62.4

0.389

0.975

Table 8. Coefficient of Langmuir and Freundlich isotherms for lanthanides using Buccinum tenuissimum shell biomass after heat-treatment (480°C/ 6h)

Futhermore, this result indicates the stronger the monolayer adsorption (the surface adsorption) on the heat-treatment sample relative to on the original sample (before heat- treatment). Judging from the value of Rl or 1/n in Table 4, the heat-treatment (480°C) sample also exhibits the favorable property for lanthanides adsorption.

The correlation coefficient (R2) and other parameters of Langmuir and Freundlich isotherms for lanthanides using "heat-treatment (950°C) sample" is shown in Table 9. It is found that R2 value for lanthanides in this sample is fairly small compared with the values of "ground original sample" or "heat-treatment (480°C) sample" (In case of La, Ce, Yb and Lu, R2 can not be estimated due to the lack of sorption data at low initial concentration). The low correlation coefficient (R2) in this "heat-treatment (950°C) sample" may indicate that the removal of lanthanides occurred not by adsorption mechanism,

Langmuir

Freundlich

a

b

R2 A Gads kJmol-1

Rl

Kf 1/n

La — —

Ce — —

Pr

0.0553

5690

0.999

0.418

Nd

0.0727

10100

1.27

0.375

Sm

0.00190

838

0.724

0.157

Eu

0.2107

41600

1.65

0.521

Gd

0.157

44300

1.69

0.526

Tb

0.0974

7980

1.08

0.599

Dy

0.108

13900

1.32

0.506

Ho

0.101

11100

1.26

0.529

Er

0.110

8290

1.14

0.625

Tm

Yb

0.0915

8830

1.15

0.588

Lu

Table 9. Coefficient of Langmuir and Freundlich isotherms for lanthanides using Buccinum tenuissimum shell biomass after heat-treatment (950°C, 6h)

Particularly R2 value is remarkably small for Langmuir isotherm, and then other relevant parameters can not be estimated. As for Freundlich one, not only R2 value is relatively small (0.157-0.625), but the value of 1/n for most lanthanide is more than unity. That is to say, the almost perfect removal of lanthanides for this sample may be due to other mechanism rather than the adsorption on the biomass. However, the cause or mechanism of lanthanides removal on this sample has yet to be sufficiently clarified in our work, and further investigation to survey the mechanism is needed.

Finally, R2 and other parameters of Langmuir and Freundlich isotherms for lanthanides using "heat-treatment (950°C) and water added sample" is shown in Table 10. It is found that R2 value for lanthanides in this sample is fairly large particularly for Langmuir isotherm (0.992-0.999 for Langmuir isotherm and 0.885-0.951 for Freundlich one). This result is similar to that for "heat-treatment (480°C) sample", and indicates the stronger the monolayer adsorption on this sample. Judging from the value of Rl or 1/n in Table10, this sample also exhibits the favorable conditions for lanthanides adsorption.

Langmuir

Freundlich

a

b

R2

A Gads/ kJmol-1

Rl

Kf

1/n

R2

La

i6i

0.969

0.999

-17.0

0.0102

59.3

0.264

0.951

Ce

200

0.980

0.999

-17.1

0.0101

70.3

0.283

0.950

Pr

217

0.852

0.998

-16.7

0.0116

69.3

0.327

0.919

Nd

222

0.789

0.997

-16.5

0.0125

68.0

0.340

0.930

Sm

233

0.878

0.996

-16.8

0.0113

72.0

0.364

0.937

Eu

233

0.782

0.996

-16.5

0.0126

68.3

0.380

0.917

Gd

227

0.647

0.997

-16.0

0.0152

61.6

0.384

0.937

Tb

227

0.629

0.996

-16.0

0.0157

61.7

0.390

0.937

Dy

233

0.506

0.996

-15.4

0.0194

57.2

0.409

0.936

Ho

227

0.404

0.996

-14.9

0.0242

50.6

0.425

0.931

Er

222

0.372

0.996

-14.7

0.0262

47.5

0.433

0.928

Tm

233

0.352

0.996

-14.5

0.0276

48.0

0.450

0.922

Yb

244

0.398

0.994

-14.8

0.0245

55.3

0.417

0.934

Lu

217

0.495

0.992

-15.4

0.0198

53.2

0.409

0.885

Table 10. Coefficient of Langmuir and Freundlich isotherms for lanthanides using Buccinum tenuissimum shell biomass after heat-treatment (950°C/ 6h) and adding water

As mentioned above, biosorption studies have been mainly focused on toxic metals elements such as Cd, Pb, As and Cr so far, and a few reports are focused on lanthanides. The sorption experiments using shell biomass in this work were carried out under low concentration of lanthanide (i. e., 100 cm3 of multi-element standard solution including known initial lanthanide concentration (10 to 500 qg-dm-3)). Then, sorption experiment for three lanthanides (La, Eu and Yb) in single component system by this shell biomass is being planned using the solution individually prepared by each nitrate salt: La(NO3)3-6№O, Eu(NO3)3-6H2O, or Yb(NO3)3-3H2O as the case of seaweed biomass in our work.

4. Conclusion

From this work, it was first quantitatively clarified that seaweed biomass could be efficient sorbents for lanthanides, and exhibit high ability of chemical adsorption. Particularly, Ulva pertusa is found to be a promising biosorbent for removing La. It is also suggested that the adsorption on seaweed biomass is mainly due to monolayer sorption because of well-fitting for Langmuir model.

Biosorption characteristic of Buccinum tenuissimum shell biomass was also studied for lanthanides. Sorption isotherms were analyzed using Langmuir and Freundlich equations to confirm the efficiency of shell biomass as sorbent. The shell biomass samples showed excellent sorption capacity for lanthanides under our experimental condition, even the presence of diverse ions (Ca2+, Mg2+, Na+ and K+) up to the concentration of 200 mg-dm-3.

From these results, it was quantitatively clarified to some extent that shell biomass can be an efficient sorbent for lanthanides. It is very significant information from the viewpoint of environmental protection that the shell (usually treated as waste material) can be converted into a biosorbent for lanthanides.

The data obtained and the method used in this work can be useful tool from the viewpoint of resource recovery in future work.