Fraction distribution and risk assessment of heavy metals in waste clay sediment discharged through the phosphate beneficiation process in Jordan

  • Mohammad Salem Al-Hwaiti
  • Hans Jurgen Brumsack
  • Bernhard Schnetger


Heavy metal contamination of clay waste through the phosphate beneficiation process is a serious problem faced by scientists and regulators worldwide. Through the beneficiation process, heavy metals naturally present in the phosphate rocks became concentrated in the clay waste. This study evaluated the concentration of heavy metals and their fractions in the clay waste in order to assess the risk of environmental contamination. A five-step sequential extraction method, the risk assessment code (RAC), effects range low (ERL), effects range medium (ERM), the lowest effect level (LEL), the severe effect level (SEL), the redistribution index (U tf), the reduced partition index (I), residual partition index (I R), and the Nemerow multi-factor index (PC) were used to assess for clay waste contamination. Heavy metals were analyzed using high-resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Correlation analyses were carried out to better understand the relationships between the chemical characteristics and the contents of the different phase fractions. Concentrations of Cd and Cu confirmed that both were bound to the exchangeable fraction (F1) and the carbonate fraction (F2), presenting higher mobility, whereas Pb was most abundant in the Fe–Mn oxide fraction (F3) and organic matter fraction (F4). The residual fraction (F5) contained the highest concentrations (>60 %) of As, Cr, Mo, V, and Zn, with lower mobility. Application of the RAC index showed that Cd and Cu should be considered a moderate risk, whereas As, Cr, Mo, Pb, and Zn presented a low risk. Cadmium and Cu contents in mobile fractions F1 and F2 were higher than ERL but lower than ERM. On the other hand, As, Pb, and Zn contents of mobile fractions F1 and F2 were lower than ERL and ERM guideline values. Moreover, total Pb concentrations in the clay waste were below the lowest effect level (LEL) threshold value period, Cr and Zn values in the clay waste were determined to have exceeded the severe effect level (SEL) limit values, whereas Cd and Cu level ranges between LEL and SEL indicate moderate contamination. I R values of heavy metals in the clay waste confirmed that Cd and Cu were bound to the exchangeable and carbonate fractions and presented higher mobility, whereas As, Cr, Mo, Pb, V, and Zn were bound to organic or residual fractions and consequently exhibit lower mobility. A Nemerow multi-factor index revealed that the mine site contains high levels of Cd, Cu, V, and Zn pollution. As and Cr were found at a moderate level of contamination, whereas Pb was present at a safe level of contamination. The order of the comprehensive contamination indices was Cd > Cu > Mo > Zn > V > Cr > As > Pb, indicating that the assessment of clay waste, especially with Cd and Cu, should be undertaken to control heavy metal contamination in adjacent urban and mine areas at the Eshidiya mines.


Fractionation Heavy metal distribution Risk assessment Mining waste disposal Beneficiation process 



This project was funded by DFG, Germany (project no: BR 775/28-1). The authors are indebted to C. Lehners, E. Gründken, and M. Schulz for their assistance during laboratory work at ICBM. We thank D. Monien, Ann K. Meinhardt, R. Martin, and S. Eckert for their valuable help and fruitful discussion during research work. Y. Dassin and M. Al-Samadi are thanked for providing slurry samples from Eshidiya beneficiation phosphate process.


  1. Al-Hwaiti, M. (2000). Geostatistical and geochemical investigation on Eshidiya phosphorites, Western Orebody, South Jordan: variation in ore composition and its content of toxic heavy metals available for plant absorption. Ph.D thesis. University of Jordan. 255 p.Google Scholar
  2. Al-Hwaiti, M. & Ranville, J. (2010). Distribution of heavy metal and radionuclide contamination in soils related to phosphogypsum waste stockpiling in the Eshidiya Mine, Jordan. The International Journal Geochemistry: Exploration, Environment, Analysis, 10, 419-433.Google Scholar
  3. Al-Hwaiti, M., & Khashman, O. (2014). Health risk assessment of heavy metals contamination in tomato and green pepper plants grown in soils amended with phosphogypsum waste materials. Environmental Geochemistry and Health. doi: 10.1007/s10653-014-9646-z.Google Scholar
  4. Al-Hwaiti, M., Matheis, G., & Saffaini, G. (2005). Mobilization, redistribution and bioavailability of potentially toxic elements in Shidiya phosphorites, southeast Jordan. Journal of Environmental Geology, 47, 431–444.CrossRefGoogle Scholar
  5. Al-Hwaiti, M., James, T., Hailey, R., & Suresh, B. (2013). Selectivity assessments of a sequential extraction procedure for potentially trace metals mobility and bioavailability in phosphate rocks from Jordan Phosphate Mines. Soil and Sediment Contamination: An International Journal, 23(4), 417–436.CrossRefGoogle Scholar
  6. Al-Hwaiti, M., Al, Q. M., Saffarini, G., & Al-Zhughoul, K. (2014). Assessment of elemental distribution and heavy metals contamination in phosphate deposits: potential health risk assessment of finer-grained size fraction. Journal Environmental Geochemistry and Health, 36, 651–663.CrossRefGoogle Scholar
  7. Alonso Castillo, M. L., Vereda Alonso, E., Siles Cordero, M. T., Cano Pavon, J. M., & Garcia de Torres, A. (2011). Fractionation of heavy metals in sediment by using microwave assisted sequential extraction procedure and determination by inductively coupled plasma mass spectrometry. Microchemical Journal, 98(2), 234–239.CrossRefGoogle Scholar
  8. Al-Slaity, F. A. (2005). Environmental aspects of phosphate beneficiation processes in Al-Abeid mine, central Jordan: migration and dispersion of heavy metals in the sediment, soil and water systems. Jordan: M.Sc. Thesis, The Hashemite University.Google Scholar
  9. Altschuler, Z. (1980). The geochemistry of trace elements in marine phosphorites. Part 2: characteristics, abundances and enrichment. SEPM Special Publication, 29, 19–30.Google Scholar
  10. Al-Zoubi, H. S., & Al-Thyabat, S. S. (2012). Treatment of a Jordanian phosphate mine wastewater by hybrid dissolved air flotation and nanofiltration. Mine Water and the Environment, 31, 214–224.CrossRefGoogle Scholar
  11. Ashraf, M. A., Maah, M. J., & Yusoff, I. (2012). Chemical speciation and potential mobility of heavy metals in the soil of former tin mining catchment. Scientific World Journal. doi: 10.1100/2012/125608.Google Scholar
  12. Aslıhan, K., Feza, K., Hüseyin, S., Başkaya, S., & Sonay, S. (2012). Fraction distribution and risk assessment of heavy metals and trace elements in sediments of Lake Uluabat. Environmental Monitoring and Assessment, 184, 5399–5413.CrossRefGoogle Scholar
  13. Baeyens, W., Monteny, F., Leermakers, M., & Bouillon, S. (2003). Evaluation of sequential extractions on dry and wet sediments. Analytical and Bioanalytical Chemistry, 376, 890–901.CrossRefGoogle Scholar
  14. Banin, A., Han, F. X., Serban, C., Ben-Dor, E., & Schachar, Y. (1997). The dynamics of heavy metals partitioning and transformations in arid-zone soils. In I.K. Iskandar, S.E. Hardy, A.C. Chang, G.M. Pierzynski (Eds.), (pp. 713–714). Proceedings of the 4th International Conference on the Biogeochemistry of Trace Elements, Berkeley.Google Scholar
  15. Bordas, F., & Bourg, A. C. M. (1998). A critical evaluation of sample for storage of contaminated sediments to be investigated for the potential mobility of their heavy metal load. Water, Air, and Soil Pollution, 103, 137–149.CrossRefGoogle Scholar
  16. Bradl, H. B. (2005). Heavy metals in the environment: origin, interaction and remediation (p. 269). Elsevier.Google Scholar
  17. Camel, V. (2000). Microwave-assisted solvent extraction of environmental samples. Trends in Analytical Chemistry, 19(4), 229–248.CrossRefGoogle Scholar
  18. Cheng, Z., Leda, L., Sara, D., Michael, G., & Richard, S. (2011). Speciation of heavy metals in garden soils: evidences from selective and sequential chemical leaching. Soils and Sediments, 11, 628–638.CrossRefGoogle Scholar
  19. Cuong, T. D., & Obbard, J. P. (2006). Metal speciation in coastal marine sediments from Singapore from Singapore using a modified BCR-sequential extraction procedure. Applied Geochemistry, 21, 1335–1346.CrossRefGoogle Scholar
  20. Dudka, S., Piotrowska, M., & Chlopecka, A. (1994). Effect of elevated concentrations of Cd and Zn in soil on spring wheat yield and the metal contents of the plants. Water, Air, and Soil Pollution, 76, 333–341.CrossRefGoogle Scholar
  21. El-Hasan, T. (2006). Geochemical dissociation of major and trace elements in bed and suspended sediment phases of the phosphate mines effluent water, Jordan. Environmental Geology, 51, 621–629.CrossRefGoogle Scholar
  22. El-Noman, J. (1995). Lithologisch anorganisch-und organisch-geochemische Merkmale von Phosphoriten der Lagerstaetten, El-Hasa, El-Abied und Esh-Shidiyas, Jordanien und ihre genetische Interpretationen. Unpubl. Thesis (D 83), Technische Universitaet Berlin, Germany. 97 p.Google Scholar
  23. Erika-Andrea, K., Frentiu, T., Michaela, P., & Cordo, E. (2005). Use of sequential extraction to assess metal fractionation in soils from Bozanta Mare, Romania. Acta Universitatis Cibiniensis Seria F Chemia, 8(2), 5–12.Google Scholar
  24. Fan, W., Wang, W. X., Chen, J., Li, X. D., & Yen, Y. F. (2002). Cu, Ni and Pb speciation in surface sediments from a contaminated bay of northern China. Marine Pollution Bulletin, 44, 816–832.CrossRefGoogle Scholar
  25. Fatoki, O. S., & Mathabatha, S. (2001). An assessment of heavy metal pollution in the East London and Port Elizabeth harbours. Water SA, 27(2), 233–240.Google Scholar
  26. Fernandes, H. M. (1997). Heavy metal distribution in sediments and ecological risk assessment: the role of diagenetic processes in reducing metal toxicity in bottom sediments. Environmental Pollution, 97, 317–325.CrossRefGoogle Scholar
  27. Flores, A., Navarro, S., & Martınez, F. (2010). Evaluation of metal attenuation from mine tailings in SE Spain (Sierra Almagrera): a soil-leaching column study. Mine Water and the Environment, 29(1), 53–67.CrossRefGoogle Scholar
  28. Florida Institute of phosphate Research (FIPR) (1988). Reclamation of phosphatic clay waste ponds. Research Project: FIPR 82-02-030. Prepared by. Department of Civil Engineering. University of Florida. Gainesville, Fla. 32611. IMC, Bartow.Google Scholar
  29. Guerra-Garcıa, J. M., & Garcıa-Gómez, J. C. (2005). Oxygen levels versus chemical pollutants: do they have similar influence on macrofaunal assemblages. A case study in a harbour with two opposing entrances. Environmental Pollution, 135, 281–291.CrossRefGoogle Scholar
  30. Guevara-Riba, A., Sahuquillo, A., Rubio, R., & Rauret, G. (2004). Assessment of metal mobility in dredged harbour sediments from Barcelona, Spain. Science of the Total Environment, 321, 241–255.CrossRefGoogle Scholar
  31. Han, F. X., Banin, A., Kingery, W. L., Triplett, G. B., Zhou, L. X., Zheng, S. J., & Ding, W. X. (2003). New approach to studies of heavy metal redistribution in soil. Advances in Environmental Research, 8, 113–120.CrossRefGoogle Scholar
  32. Hseu, Z. Y. (2006). Extractability and bioavailability of zinc over time in three tropical soils incubated with biosolids. Chemosphere, 63, 762–771.CrossRefGoogle Scholar
  33. Idris, A. M., Eltayeb, M. A. H., Potgieter-Vermaak, S. S., Grieken, R., & Potgieter, J. H. (2007). Assessment of heavy metal pollution in Sudanese harbours along the Red Sea coast. Microchemical, 87, 104–112.CrossRefGoogle Scholar
  34. Itoh, A., Nagasawa, T., Zhu, Y., Lee, K. H., Fujimori, E., & Haraguchi, H. (2004). Distributions of major-to-ultratrace elements among the particulate and dissolved fractions in natural water as studied by ICP-AES and ICP-MS after sequential fractionation. Analytical Sciences, 20, 29–36.CrossRefGoogle Scholar
  35. Iwegbue, C. M. A., Arimoro, F. O., Nwajei, G. E., & Eguavoen, O. I. (2012). Concentrations and distribution of trace metals in water and streambed sediments of Orogodo River, southern Nigeria. Soil and Sediment Contamination, 21, 382–406.CrossRefGoogle Scholar
  36. Jain, C.K., Gupta, H., & Chakrapani, G. (2008). Enrichment and fractionation of heavy metals in bed sediments of River Narmada, India. Environ Monit Assess 141, 35–47Google Scholar
  37. Jaradat, Q. M., Massadeh, A. M., Zaitoun, M. A., & Maitah, B. M. (2006). Fractionation and sequential extraction of heavy metals in the soils of scrap yard of discarded vehicles. Environmental Monitoring and Assessment, 112, 197–210.CrossRefGoogle Scholar
  38. Jiries, A., ElHasan, T., Al-Hwaiti, M., & Seiler, K. B. (2004). Evaluation of the effluent water quality produced at phosphate mines in central Jordan. Mine Water and the Environment, 23, 133–137.CrossRefGoogle Scholar
  39. Jones, B., & Turki, A. (1997). Distribution and speciation of heavy metals in surficial sediments from the Tees Estuary, north-east England. Marine Pollution Bulletin, 34, 768–779.CrossRefGoogle Scholar
  40. Katip, A., Karaer, F., Başkaya, H. S., Ileri, S., & Sarmaşik, S. (2012). Fraction distribution and risk assessment of heavy metals and trace elements in sediments of Lake Uluabat. Environmental Monitoring and Assessment, 184, 5399–5413.CrossRefGoogle Scholar
  41. Kersten, M., & Frostner, U. (1986). Chemical fractionation of heavy metals in anoxic estuarine and coastal sediments. Water Science and Technology, 18, 121–130.Google Scholar
  42. Korfali, S. I., & Jurdi, M. S. (2011). Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon. Environmental Monitoring and Assessment, 178(1–4), 563–579.CrossRefGoogle Scholar
  43. Li, X. D., Shen, Z. G., Wai, W. H. O., & Li, Y. S. (2001). Chemical forms of Pb, Zn and Cu in the sediment profile of the Pearl River Estuary. Marine Pollution Bulletin, 42(3), 215–223.CrossRefGoogle Scholar
  44. Liu, H., Li, L., Yin, C., & Shan, B. (2008). Fraction distribution and risk assessment of heavy metals in sediments of Moshui Lake. Environmental Sciences, 20, 390–397.CrossRefGoogle Scholar
  45. Long, E., Macdonald, D., Smith, S., & Calder, F. (1995). Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments. Environmental Management, 19, 81–97.CrossRefGoogle Scholar
  46. Lucas, J., Flicoteaux, R., Nathan, Y., Prevot, L., & Shahar, Y. (1980). Different aspects of phosphorite Weathering. In Z. Bentor (Ed.), SEPM Special Publication, 29, 41–51.Google Scholar
  47. McClellan, G. H. (1980). Mineralogy of carbonate-flouriteapatites. Journal of the Geological Society (London), 137, 675–681.CrossRefGoogle Scholar
  48. Miretzky, P., Avendano, M. R., Munoz, C., & Carrillo-Chavez, A. (2011). Use of partition and redistribution indexes for heavy metal soil distribution after contamination with a multi-element solution. Soils and Sediments, 11, 619–627.CrossRefGoogle Scholar
  49. Omar, R., Anwar, J., Yasin, Z., & Ali, E. (2008). Reuse of mining wastewater in agricultural activates in Jordan. Environment, Development and Sustainability, 11, 695–703.Google Scholar
  50. Pardo, R., Vega, M., Debán, L., Cazurro, C., & Carretero, C. (2008). Modelling of chemical fractionation patterns of metals in soils by two-way and three-way principal component analysis. Analitica Chimica Acta, 606, 26–36.CrossRefGoogle Scholar
  51. Paulsen, S. C., & List, E. J. (1997). A study of transport and mixing in natural waters using ICP-MS: water–particle interactions. Water, Air, & Soil Pollution, 99, 149–156.Google Scholar
  52. Peng, S. H., Wang, W. X., Li, X. D., & Yen, Y. F. (2004). Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches. Chemosphere, 57, 839–851.CrossRefGoogle Scholar
  53. Prevot, L. (1994). How to interpret trace element contents in phosphorites using the geological data. Revista de Investigacion Cientifica Series Ciencias do Mar, 5(2), 51–61.Google Scholar
  54. Purushothaman, P., & Chakrapani, G. J. (2007). Heavy metals fractionation in Ganga River sediments, India. Environmental Monitoring and Assessment, 132, 475–489.CrossRefGoogle Scholar
  55. Reimann, C., & de Caritat, P. (2005). Distinguishing between natural and anthropogenic sources for elements in the environment: regional geochemical surveys versus enrichment factors. The Science of the Total Environment, 337, 91–107.CrossRefGoogle Scholar
  56. Sakan, S. M., Dordevic, D., Dragan, D., Manojlovic, D., & Predrag, P. (2009). Assessment of heavy metal pollutants accumulation in the Tisza River sediments. Environmental Management, 90, 3382–3390.Google Scholar
  57. Schnetger, B. (1997). Trace element analysis of sediments by HR-ICP-MS using low and medium resolution and different acid digestions, Fresenius. Analytical Chemistry, 359, 468–472.CrossRefGoogle Scholar
  58. Shiller, A. M., & Mao, L. (1999). Dissolved vanadium on the Louisiana Shelf: effect of oxygen depletion. Continental Shelf Research, 19, 1007–1020.CrossRefGoogle Scholar
  59. Shumilin, E., Gordeev, V., Rodrı, G., Figueroa, G., Choumiline, K., & Demina, L. (2011). Assessment of geochemical mobility of metals in surface sediments of the Santa Rosalia mining region, Western Gulf of California. Archives of Environmental Contamination and Toxicology, 60, 8–25.CrossRefGoogle Scholar
  60. Singh, J., & Kalamdhad, A. S. (2011). Effects of heavy metals on soil, plants, human health and aquatic life. International Journal of Research in Chemistry and Environment, 1(2), 15–21.Google Scholar
  61. Singh, S. P., Tack, F. M., & Verloo, M. G. (1998). Heavy metal fractionation and extractability in dredged sediment derived surface soils. Water, Air, and Soil Pollution, 102, 313–328.CrossRefGoogle Scholar
  62. Singh, K., Mohan, D., Singh, V., & Malik, A. (2005). Studies on distribution and fractionation of heavy metals in Gomti River sediments—a tributary of the Ganges. Indian Journal of Hydrology, 312, 14–27.CrossRefGoogle Scholar
  63. Singh, A. P., Srivastava, P. C., & Srivastava, P. (2008). Relationships of heavy metals in natural lake waters with physico-chemical characteristics of waters and different chemical fractions of metals in sediments. Water, Air, and Soil Pollution, 188, 181–193.CrossRefGoogle Scholar
  64. Sofremines. (1984). Ore reserve evaluation and beneficiation of Eshidiya mines, report No. II (p. 149). Amman: Jordan Phosphate Mines Company.Google Scholar
  65. Sofremines. (1987). Ore reserve evaluation and beneficiation of Eshidiya mines, final report (p. 83). Amman: Jordan Phosphate Mines Company.Google Scholar
  66. Sutherland, R. A., Tolosa, C. A., Tack, F. M. G., & Verloo, M. G. (2000). Characterization of selected element concentration and enrichment ratios in background and anthropogenically impacted roadside areas. Archives of Environmental Contamination and Toxicology, 38, 428–438.CrossRefGoogle Scholar
  67. Tao, D., & AL-Hwaiti, M. (2010). Beneficiation study of Eshidiya phosphorites using a rotary triboelectrostatic separation. The Mining Science and Technology, 20(3), 357–371.Google Scholar
  68. Templeton, D. M., Ariese, F., Cornels, R., & Sahuquillo, A. (2001). IUPAC guidelines for terms related to chemical speciation and fractionation of elements. Pure and Applied Chemistry, 72, 1453–1470.Google Scholar
  69. Tessier, A., Campbel, P. G. C., & Bisson, M. (1979). Sequential extraction procedure for the speciation of particulate trace metals. Analytical Chemistry, 51, 844–851.CrossRefGoogle Scholar
  70. Tooms, J. S., Summerhayes, C. P., & Cronan, D. S. (1969). Geochemistry of marine phosphate and manganese deposits. Oceanography and Marine Biology. Annual Review, 7, 49–100.Google Scholar
  71. Van der Sloot, H. A., Hoede, D., Wijkstra, J., Duinker, J. C., & Nolting, R. F. (1985). Anionic species of V, As, Se, Mo, Sb, Te and W in the Scheldt and Rhine estuaries and the Southern Bight (North Sea). Estuarine, Coastal and Shelf Science, 21, 633–651.CrossRefGoogle Scholar
  72. Van Kauwenbergh, S. (1997). Cadmium and other minor elements in world resources of phosphate rock. Muscle Shoals: The Fertilizer Society. IFDS. 41 p.Google Scholar
  73. Wang, J., Liu, W., Yang, R., Zhang, L., & Ma, J. (2013). Assessment of the potential ecological risk of heavy metals in reclaimed soils at an opencast coal mine. Disaster Advances, 6 (S3).Google Scholar
  74. Wedepohl, K. H. (1971). Environmental influences on the chemical composition of shales and clays. In L. H. Ahrens, F. Press, S. K. Runcorn, & H. C. Urey (Eds.), Physics and Chemistry of the Earth, vol. 8 (pp. 307–333). Oxford: Pergamon Press.Google Scholar
  75. Wedepohl, K. H. (1991). The Composition of the upper earth's crust and the natural cycles of selected metals. Metals in natural raw materials. Natural resources. In E. Merian (Ed.), Metals and their compounds in the natural environment (pp. 1–17). VCH-Verlag: Weinheim.Google Scholar
  76. Wepener, V., & Vermeulen, L. A. (2005). A note on the concentrations and bioavailability of selected metals in sediments of Richards Bay Harbour, South Africa. Water SA, 31, 589–595.Google Scholar
  77. Wuana, R. A., Okieimen, F. E., & Imborvungu, J. A. (2010). Removal of heavy metals from a contaminated soil using organic chelating acids. International Journal of Environmental Science and Technology, 7(3), 485–496.CrossRefGoogle Scholar
  78. Ying, X., & Jing-Ling, L. (2010). Study on form distribution and correlation of heavy metals in the sediment of urban water. International Conference Bioinformatics and Biomedical Engineering (iCBBE), 18–20 June. Chengdu.Google Scholar
  79. Zakir, H. M., & Shikazono, N. (2008). Metal fractionation in sediments: a comparative assessment of four sequential extraction schemes. Journal of Environmental Science for Sustainable Society, 2, 01–12.CrossRefGoogle Scholar
  80. Zakir, H. M., & Shikazono, N. (2011). Environmental mobility and geochemical partitioning Fe, Mn, Co, Ni and Mo in sediments of an urban river. Journal of Environmental Chemistry and Ecotoxicology, 3(5), 116–126.Google Scholar

Copyright information

© Springer International Publishing Switzerland 2015

Authors and Affiliations

  • Mohammad Salem Al-Hwaiti
    • 1
  • Hans Jurgen Brumsack
    • 2
  • Bernhard Schnetger
    • 2
  1. 1.Environmental Engineering Department, Faculty of EngineeringAl-Hussein Bin Talal UniversityMa’anJordan
  2. 2.Mikrobiogeochemie, Institut für Chemie und Biologie des Meeres (ICBM)Carl von Ossietzky UniversitätOldenburgGermany

Personalised recommendations