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Vol. 42 No. 2

GENERAL PAPERS Organized by T. Mill Symposia Papers Presented Before the Division of Environmental Chemistry American Chemical Society Boston, MA August 18-22, 2002

REMOVAL OF ARSENIC FROM WATER BY ZERO-VALENT IRON Sunbaek Bang, Xiaoguang Meng and George P. Korfiatis Center for Environmental Engineering Stevens Institute of Technology, Hoboken, NJ 07030 E-mail:

Introduction Arsenic is a carcinogenic contaminant in the groundwater and drinking water of some regions, including Bangladesh, India, Japan, New Zealand, Taiwan, and United States1-6. Arsenic may be concentrated in liver, kidney, lung, and skin tissues by ingestion of arsenic in drinking water1. The World Health Organization (WHO) has recommended less than 0.01 mg/L of arsenic concentration in drinking water to minimize the effect of health. The U.S. Environmental Protection Agency (US EPA) reduced maximum contaminant level (MCL) of arsenic from 0.05 to 0.01 mg/L on October 2001. Arsenic is found as As(III) and As(V) species in natural systems. In oxygenated water, As(V) species (H3AsO4, H2AsO4-, HAsO42-, and HAsO43-) are stable while As(III) species (H3AsO3, and H2AsO3-) are becomes stable under slightly reducing conditions7. Main difference between As(III) and As(V) is that As(V) has the double bond oxygen in molecular structure. The double bond oxygen in the As(V) molecule may increase the ability to be ionized through the loss of hydrogen ions8. The propensity for ionization is expressed by pKa. The pKa values for As(III) and As(V) are as follows: As(III) H3AsO3, pK1 = 9.20, pK2 = 14.22 , pK3 = 19.22 As(V) H3AsO4, pK1= 2.19, pK2 = 6.94, pK3 = 11.5 8 Numerous techniques have been developed to remove arsenic from water, using ferric salts, alum, lime, activated alumina, activated carbon, and ion exchange9-15. The most common technique for the removal of arsenic is coagulation with ferric salts.


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Zero-valent iron (Fe0) has been used to treat both organic and inorganic contaminants16-18. Recently, some researchers have studied removal of arsenic with zero-valent iron19-21. The objective of this study is to determine the efficiency of iron filings for arsenic from water. Materials and Methods All chemicals were analytic grade and all stock solution was prepared with deionized water (DI) by a Milli-Q water system. The As(III) and As(V) stock solutions were prepared by dissolving NaAsO2 (Fisher, Fairlawn, NJ) and As2O53H2O (Aldrich, Milwaukee, WI) respectively. Iron filings (80-120 mesh) were obtained from U.S. metals Inc (Mentune, IN). Sand used in sand column was obtained from Ricci bros sand Inc (Port Norris, NJ). Arsenic-containing groundwater from a Superfund site in Washington State was used in this study. Typical chemical characteristics of the groundwater are listed in Table 1. Arsenic in the groundwater exists primarily in As(V) form. Table 1. Chemical characteristics of the arsenic-containing groundwater Total As 26 ppm Total SiO2 375 ppm Total Fe 0.65 ppm PH 10 DO 8 mg/L

In the batch experiments, 1 g/L of iron filings (100 mesh) were placed in a conical beaker containing 200 ml of water spiked with arsenic or arsenic-contaminated groundwater. The solution was continuously mixed with a magnetic stirring bar in the open to air or under the nitrogen system. At different mixing times, 1.5 ml of samples were taken and centrifuged for 10 min to separate the solution from precipitate for analysis of soluble arsenic. In each batch test, the pH was adjusted to desirable values by adding hydrochloric acid or sodium hydroxide. Column experiments were conducted using acrylic columns packed with iron filings (100 mesh) and granular iron. The arsenic-spiked solution or contaminated groundwater was passed through the iron columns upward with different flow rate, using peristaltic pump. An iron column was conjugated with a sand column in a series to remove the particles generated in the iron column. The sand column was packed with 2 in of gravel and 2 ft of sand. Effluent water samples were collected and acidified with nitric acid for analysis of arsenic and iron. Arsenic concentration in the solution was determined with a graphite furnace atomic absorption spectrometer (Varian Zeeman 400). Iron analysis was performed using a graphite furnace atomic absorption spectrometer and Inductively Coupled Plasma (Varian Liberty 200). In all experiments, pH was measured with Orion pH meter (290A and 410A) and the pH electrode was calibrated with three buffers (pH 4.0, 7.0, and 10.0) daily.


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Results and Discussion The batch results in Figure 1 indicate that the kinetics of As(V) removal with iron filings is faster than that of As(III). Greater than 98 % of the As(V) was removed after 5.5 hours of mixing while 93 % of the As(III) was removed within 9 hours of mixing from DI water. A linear regression of the first-order kinetic from Eq (1) was performed on each data set. As illustrated by the regression in Figure 1, the kinetics of As(III) and As(V) removal could be described by pseudo first-order kinetics model. The similar results were observed in the investigation for the reaction of iron with nitrate and halogenated compounds22-23. More than 0.953 of R2 was obtained in this modeling work. The value of kobs was 0.494/h and 0.266/h for 100 ppm of As(V) and As(III), respectively. According to Eq (2), the half-lives(t1/2) were 1.40 hours and 0.953 hours for an initial concentration of 100 ppm of As(V) and As(III), respectively.
5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 0 2 4 6 Time (hr) 8 10

A s (III) A s (V) Linear (As (III)) Linear (As (V))

Figure 1. The kinetics of As(III) and As(V) removal by Fe0. (As = 100 ppm, pH=6, Iron filings = 1 g/L (100 mesh), DI water)

In (C0/C)


d [ As ] = kobs [ As ] dt



[ As ] 0 = k t [ As ] obs 1/ 2


Where [As] is arsenic concentration in the solution, t is reaction time, and kobs is the observed first-order reaction rate constant The effect of the dissolved oxygen (DO) on arsenic removal was evaluated by comparing the removal of arsenic in air and N2 systems. In the As(III) spiked-solution, greater than 93 % of As(III) was removed after 9 hours of mixing when the solution was


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open to air while less than 4 percent of As(III) was removed during 9 hours of reaction under nitrogen system (Figure 2). Similar results were observed in As(V) spiked-solution. Greater than 99 percent of As(V) was removed after 5.5 hours of mixing under open to air system while less than 9 percent of As(V) was removed when the solution was purged with nitrogen.
100 80 Residual As (mg/L)
As (III) N2

60 40 20 0 0 1 2 3 4 5 6 Time (hr) 7

A s (V) N2 A s (III) A ir A s (V) A ir


Figure 2. Effect of DO on arsenic removal by iron filings (As = 100 ppm, Iron filings = 1g/L (100 mesh), pH = 6, Aged tap water)

30 25

Residual As (mg/L)

20 15 10 5 0 0 1 2 3 4 Time (hr) 5 6 7

pH 10 pH 8 pH 7 pH 6

Figure 3. Effect of pH on arsenic removal from the groundwater (Iron filings = 10g/L (100 mesh), Initial As = 26 ppm)

The results of the batch experiments from arsenic-containing groundwater for the effect of pH are presented in Figure 3. The removal of total arsenic occurred rapidly at pH 6.


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Greater than 99 % of arsenic removal was obtained within 2 hours of mixing. The rates of arsenic removal decreased with increasing pH. An Iron column conjugated with a sand column was used to evaluate the effect of DO on arsenic removal. The sand column was used to filter the precipitates generated from the iron column. Influent DO was changed from 0.9 to 5.5 mg/L during the experiment. When Influent DO was 0.9 mg/L, effluent arsenic concentrations were increased to 62 ppb within 24 hours. When influent DO was increased to 2.3 3.7 mg/L, arsenic was removed to 29 ppb within 1.5 hours. As was further reduced to about 15 ppb when the influent DO increased to 4.3-5.5 mg/L. As concentration was reduced to less than 2.6 ppb by the sand filter.
70 60 50 DO 2.3~3.7 mg/L 40 DO 4.3~5.5 mg/L 30 20 10 0 0 20 40 T ime (hr) 60 80 100 DO 0.9 mg/L Fe column San d c o l u m n

Figure 4. Effect of DO on removal of arsenic by iron column and sand column (As(V) = 90 ppb, Iron filings = 150 g (100 mesh), Flow rate = 1.5 gal/min/ft2, Fe column d = 1 in, h = 4.5 in, Sand column d= 3 in, h= 2 in) References 1. Karim M. (2000) Wat. Res. 34, 304-310. 2. Pande S. P., Deshpande L. S., Patni P. M., and Lutade S. L. (1997) J. Environ. Sci. Health A32 1981-1987. 3. Kondo H., Ishiguro Y., Ohno K., Nagase M., Toba M., and Takagi M. (1999) Wat. Res. 33, 1967-1972. 4. McLaren S. J., and Kim N. D. (1995) Environmental Pollution 90, 67-73. 5. Chen S., Dzeng S. R., Yang M., Chiu K., Shieh G, and Wai C. M. (1994) Environ. Sci. Technol. 28, 877-881. 6. Hering J. G., Chen, P., Wilkie J. A., Elimelech M., and Liang S. (1996) J. AWWA 88(4), 155-167. 7. Cullen W. R., and Reimer K. J. (1989) Chem. Rev. 89, 713-764. 8. Vance D. B. (1995) National Environmental Journal 5(3), 60-64. 9. Gulledge J. H. and OConnor J. T. (1973) J. AWWA 65(8), 548-552. 10. Gupta S. K. and Chen K. Y. (1978) J. Water Pollution Control Federation 50(3),

Residual As (



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11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23.

493-506. Harper T. R. and Kingham N. W. (1992) Water Environment Research 64(3), 200-203. McNeill L. S. and Edwards M. (1997), J AWWA 89(1), 75-86. Driehaus W., Jekel M., and Hildebrand U. (1998) J. Water SRT-Aqua 47, 30-35. USEPA (2000) Arsenic removal from drinking water by ion exchange and activated alumina plants, EPA/600/R-00/088. Meng X., Bang S., and Korfiatis G. K. (2000) Wat. Res. 34(4), 1225-1261. Gillhan R. W. and OHannesin S. F. (1994) Ground Water 32(6), 958-967. OHannesin S. F. and Gillhan R. W. (1998) Ground Water 36(1) 164-170. Cantrell K. J., Kaplan D. I., and Wietsma T. W. (1995) J. Hazard. Mat. 42, 201-212. Lackovic J. A., Nikolaidis, N. P., and Dobbs, G. M. (2000) Environ. Eng. Sci. 17, 29-39. Su C. and Puls R. W. (2001) Environ. Sci. Technol. 35, 1487-1492. Farrell, J., Wang J., ODay, P., and Conklin, M. (2001) Environ. Sci. Technol. 35, 2026-2032. Siantar D. P., Schreier C. G., Chou, C., and Martin R. (1996) Wat. Res. 30, 2315-2322. Johnson T. L., and Scherer M. M. and Tratnyek P. G. (1996) Environ. Sci. Technol. 30, 2634-2640.

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