Environmental Science and Pollution Research

, Volume 22, Issue 11, pp 8224–8234 | Cite as

Groundwater arsenic removal using granular TiO2: integrated laboratory and field study

  • Jinli Cui
  • Jingjing Du
  • Siwu Yu
  • Chuanyong JingEmail author
  • Tingshan ChanEmail author
Research Article


High concentrations of arsenic (As) in groundwater pose a great threat to human health. The motivation of this study was to provide a practical solution for As-safe water in As geogenic areas using granular TiO2 (GTiO2). The kinetics results indicated that the As (III/V) adsorption on GTiO2 conformed to the Weber-Morris (WM) intraparticle diffusion model. The Langmuir isotherm results suggested that the adsorption capacities for As (III) and As (V) were 106.4 and 38.3 mg/g, respectively. Ion effect study showed that cationic Ca and Mg substantially enhanced As (V) adsorption, whereas no significant impact was observed on As (III). Silicate substantially decreased As (V) adsorption by 57 % and As (III) by 50 %. HCO3 remarkably inhibited As (V) adsorption by 52 %, whereas it slightly reduced As (III) adsorption by 8 %. Field column results demonstrated that ∼700 μg/L As was removed at an empty bed contact time (EBCT) of 1.08 min for 968 bed volumes before effluent As concentration exceeded 10 μg/L, corresponding to 0.96 mg As/g GTiO2. Two household filters loaded with 110 g GTiO2 in the on-off operational mode can provide 6-L/day As-safe drinking water up to 288 and 600 days from the groundwater containing ∼700 μg/L As and ∼217 μg/L As, respectively. Integration of batch experiments and column tests with systematic variation of EBCTs was successfully achieved using PHREEQC incorporating a charge distribution multisite complexation (CD-MUSIC) model and one-dimensional reactive transport block.


Groundwater arsenic Granular TiO2 Adsorption Empty bed contact time CD-MUSIC PHREEQC XANES 



We thank Dr. David Parkhurst for the helpful discussion on PHREEQC modeling. We acknowledge the financial support of the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB14020201), the National Natural Science Foundation of China (41373123, 21337004), and RCEES (YSW2013A01).

Supplementary material

11356_2014_3955_MOESM1_ESM.docx (1.7 mb)
ESM 1 (DOCX 1764 kb)


  1. Ali I, Al-Othman ZA, Alwarthan A, Asim M, Khan TA (2014) Removal of arsenic species from water by batch and column operations on bagasse fly ash. Environ Sci Pollut Res 21(5):3218–3229CrossRefGoogle Scholar
  2. Appelo CAJ, Postma D (1999) A consistent model for surface complexation on birnessite (MnO2) and its application to a column experiment. Geochim Cosmochim Acta 63(19–20):3039–3048CrossRefGoogle Scholar
  3. Badruzzaman M, Westerhoff P, Knappe DRU (2004) Intraparticle diffusion and adsorption of arsenate onto granular ferric hydroxide (GFH). Water Res 38(18):4002–4012CrossRefGoogle Scholar
  4. Bang S, Patel M, Lippincott L, Meng XG (2005) Removal of arsenic from groundwater by granular titanium dioxide adsorbent. Chemosphere 60(3):389–397CrossRefGoogle Scholar
  5. Chandrasekaran VRM, Muthaiyan I, Huang PC, Liu MY (2010) Using iron precipitants to remove arsenic from water: is it safe? Water Res 44(19):5823–5827CrossRefGoogle Scholar
  6. Cui JL, Shi JB, Jiang GB, Jing CY (2013) Arsenic levels and speciation from ingestion exposures to biomarkers in Shanxi, China: implications for human health. Environ Sci Technol 47(10):5419–5424CrossRefGoogle Scholar
  7. Dou XM, Mohan D, Pittman CU (2013) Arsenate adsorption on three types of granular schwertmannite. Water Res 47(9):2938–2948CrossRefGoogle Scholar
  8. Du JJ, Che DS, Zhang JF, Jing CY (2014a) Rapid on-site separation of As(III) and As(V) in waters using a disposable thiol-modified sand cartridge. Environ Toxicol Chem / SETAC 33(8):1692–1696CrossRefGoogle Scholar
  9. Du JJ, Jing CY, Duan JM, Zhang YL, Hu S (2014b) Removal of arsenate with hydrous ferric oxide coprecipitation: effect of humic acid. J Environ Sci-China 26(2):240–247CrossRefGoogle Scholar
  10. Erban LE, Gorelick SM, Zebker HA, Fendorf S (2013) Release of arsenic to deep groundwater in the Mekong Delta, Vietnam, linked to pumping-induced land subsidence. Proc Natl Acad Sci U S A 110(34):13751–13756CrossRefGoogle Scholar
  11. Fendorf S, Michael HA, van Geen A (2010) Spatial and temporal variations of groundwater arsenic in South and Southeast Asia. Science 328(5982):1123–1127CrossRefGoogle Scholar
  12. Guan XH, Du JS, Meng XG, Sun YK, Sun B, Hu QH (2012) Application of titanium dioxide in arsenic removal from water: a review. J Hazard Mater 215:1–16CrossRefGoogle Scholar
  13. Hanna K, Rusch B, Lassabatere L, Hofmann A, Humbert B (2010) Reactive transport of gentisic acid in a hematite-coated sand column: experimental study and modeling. Geochim Cosmochim Acta 74(12):3351–3366CrossRefGoogle Scholar
  14. Hiemstra T, Van Riemsdijk WH (2006) On the relationship between charge distribution, surface hydration, and the structure of the interface of metal hydroxides. J Colloid Interface Sci 301(1):1–18CrossRefGoogle Scholar
  15. Hristovski K, Westerhoff P, Crittenden J (2008) An approach for evaluating nanomaterials for use as packed bed adsorber media: a case study of arsenate removal by titanate nanofibers. J Hazard Mater 156(1–3):604–611CrossRefGoogle Scholar
  16. Hug SJ, Leupin OX, Berg M (2008) Bangladesh and Vietnam: different groundwater compositions require different approaches to arsenic mitigation. Environ Sci Technol 42(17):6318–6323CrossRefGoogle Scholar
  17. Jeppu GP, Clement TP, Barnett MO, Lee KK (2012) A modified batch reactor system to study equilibrium-reactive transport problems. J Contam Hydrol 129:2–9CrossRefGoogle Scholar
  18. Jing CY, Cui JL (2011) A synthesis method of granular TiO2 adsorbent for drinking water purification. 201110022984.XGoogle Scholar
  19. Jing CY, Meng XG, Calvache E, Jiang GB (2009) Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent. Environ Pollut 157(8–9):2514–2519CrossRefGoogle Scholar
  20. Jing CY, Cui JL, Huang YY, Li AG (2012) Fabrication, characterization, and application of a composite adsorbent for simultaneous removal of arsenic and fluoride. ACS Appl Mater Interfaces 4(2):714–720CrossRefGoogle Scholar
  21. Kanematsu M, Young TM, Fukushi K, Green PG, Darby JL (2012) Individual and combined effects of water quality and empty bed contact time on As(V) removal by a fixed-bed iron oxide adsorber: Implication for silicate precoating. Water Res 46(16):5061–5070CrossRefGoogle Scholar
  22. Kanematsu M, Young TM, Fukushi K, Green PG, Darby JL (2013) Arsenic(III, V) adsorption on a goethite-based adsorbent in the presence of major co-existing ions: modeling competitive adsorption consistent with spectroscopic and molecular evidence. Geochim Cosmochim Acta 106:404–428CrossRefGoogle Scholar
  23. Leupin OX, Hug SJ, Badruzzaman ABM (2005) Arsenic removal from Bangladesh tube well water with filter columns containing zerovalent iron filings and sand. Environ Sci Technol 39(20):8032–8037CrossRefGoogle Scholar
  24. Li Y, Liu JR, Jia SY, Guo JW, Zhuo J, Na P (2012) TiO2 pillared montmorillonite as a photoactive adsorbent of arsenic under UV irradiation. Chem Eng J 191:66–74CrossRefGoogle Scholar
  25. Liu S, Guo XC, Zhang XX, Cui YB, Zhang Y, Wu B (2013) Impact of iron precipitant on toxicity of arsenic in water: a combined in vivo and in vitro study. Environ Sci Technol 47(7):3432–3438Google Scholar
  26. Luo T, Cui JL, Hu S, Huang YY, Jing CY (2010) Arsenic removal and recovery from copper smelting wastewater using TiO2. Environ Sci Technol 44(23):9094–9098CrossRefGoogle Scholar
  27. Luo T, Hu S, Cui JL, Tian HX, Jing CY (2012) Comparison of arsenic geochemical evolution in the Datong Basin (Shanxi) and Hetao Basin (Inner Mongolia), China. Appl Geochem 27(12):2315–2323CrossRefGoogle Scholar
  28. Maiti A, Thakur BK, Basu JK, De S (2013) Comparison of treated laterite as arsenic adsorbent from different locations and performance of best filter under field conditions. J Hazard Mater 262:1176–1186CrossRefGoogle Scholar
  29. Maji SK, Kao YH, Wang CJ, Lu GS, Wu JJ, Liu CW (2012) Fixed bed adsorption of As(III) on iron-oxide-coated natural rock (IOCNR) and application to real arsenic-bearing groundwater. Chem Eng J 203:285–293CrossRefGoogle Scholar
  30. McCleskey RB, Nordstrom DK, Maest AS (2004) Preservation of water samples for arsenic(III/V) determinations: an evaluation of the literature and new analytical results. Appl Geochem 19(7):995–1009CrossRefGoogle Scholar
  31. Meng XG, Bang S, Korfiatis GP (2000) Effects of silicate, sulfate, and carbonate on arsenic removal by ferric chloride. Water Res 34(4):1255–1261CrossRefGoogle Scholar
  32. Michael HA, Voss CI (2008) Evaluation of the sustainability of deep groundwater as an arsenic-safe resource in the Bengal Basin. Proc Natl Acad Sci U S A 105(25):8531–8536CrossRefGoogle Scholar
  33. Parkhurst DL, Appelo CAJ (2013) Description of input and examples for PHREEQC version 3-A computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations, U.S. Geological SurveyGoogle Scholar
  34. Rodriguez-Lado L, Sun G, Berg M, Zhang Q, Xue H, Zheng Q, Johnson CA (2013) Groundwater arsenic contamination throughout China. Science 341(6148):866–868CrossRefGoogle Scholar
  35. Saalfield SL, Bostick BC (2010) Synergistic effect of calcium and bicarbonate in enhancing arsenate release from ferrihydrite. Geochim Cosmochim Acta 74(18):5171–5186CrossRefGoogle Scholar
  36. Shanxi Statistical Bureau (2014) Per capita net income of farmers in Shanxi reaches 7154 CNY in 2013Google Scholar
  37. Stachowicz M, Hiemstra T, van Riemsdijk WH (2008) Multi-competitive interaction of As(III) and As(V) oxyanions with Ca2+, Mg2+, PO4 3−, and CO3 2− ions on goethite. J Colloid Interface Sci 320(2):400–414CrossRefGoogle Scholar
  38. Swedlund PJ, Holtkamp H, Song Y, Daughney CJ (2014) Arsenate–ferrihydrite systems from minutes to months: a macroscopic and IR spectroscopic study of an elusive equilibrium. Environ Sci Technol 48(5):2759–2765CrossRefGoogle Scholar
  39. Williams LE, Barnett MO, Kramer TA, Melville JG (2003) Adsorption and transport of arsenic(V) in experimental subsurface systems. J Environ Qual 32(3):841–850CrossRefGoogle Scholar
  40. Zeng H, Arashiro M, Giammar DE (2008) Effects of water chemistry and flow rate on arsenate removal by adsorption to an iron oxide-based sorbent. Water Res 42(18):4629–4636CrossRefGoogle Scholar
  41. Zhang H, Selim HM (2006) Modeling the transport and retention of arsenic (V) in soils. Soil Sci Soc Am J 70(5):1677–1687CrossRefGoogle Scholar
  42. Zhao K, Guo HM (2014) Behavior and mechanism of arsenate adsorption on activated natural siderite: evidences from FTIR and XANES analysis. Environ Sci Pollut Res 21(3):1944–1953CrossRefGoogle Scholar
  43. Zhao K, Guo H, Zhou X (2014) Adsorption and heterogeneous oxidation of arsenite on modified granular natural siderite: characterization and behaviors. Appl Geochem 48:184–192CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental SciencesChinese Academy of SciencesBeijingPeople’s Republic of China
  2. 2.Guizhou Electric Power Testing and Research InstituteGuiyangPeople’s Republic of China
  3. 3.National Synchrotron Radiation Research CenterHsinChuTaiwan

Personalised recommendations