Effect of organic matter and selected heavy metals on sorption of acenaphthene, fluorene and fluoranthene onto various clays and clay minerals

  • Mohsen SaeediEmail author
  • Loretta Y. Li
  • John R. Grace
Original Article


The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite + 40% sand, and 43% kaolinite + 42% sand + 15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.


Polycyclic aromatic hydrocarbons Sorption Clay Heavy metal Organic matter 



The authors are grateful to the Contaminated Sites Approved Professionals (CSAP) Society for a Scholarship to Mohsen Saeedi, as well as to the Natural Sciences and Engineering Research Council of Canada (NSERC) for funding (RGPIN 185040-13 and RGPIN 7111-11). The authors also express their appreciation to Iran University of Science and Technology (IUST), School of Civil Engineering, for use of some analytical equipment.

Supplementary material

12665_2018_7489_MOESM1_ESM.docx (194 kb)
Supplementary material 1 (DOCX 193 kb)


  1. ASTM (American Society for Testing and Materials) (2001) Standard test method for pH of soils. ASTM D4972, ASTM International, West Conshohocken, PAGoogle Scholar
  2. ASTM (American Society for Testing and Materials) (2006) Standard specification for standard sand. ASTM C778, ASTM International, West Conshohocken, PAGoogle Scholar
  3. ASTM (American Society for Testing and Materials) (2008) Standard test methods for Loss on Ignition (LOI) of solid combustion residues. ASTM D 7348, ASTM International, West Conshohocken, PAGoogle Scholar
  4. Bhattacharyya KG, Gupta SS (2008) Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review. Adv Colloid Interface Sci 140:114–131CrossRefGoogle Scholar
  5. Brindley GW, Bender R, Ray S (1963) Sorption of non-ionic aliphatic molecules from aqueous solutions on clay minerals clay-organic studies—VII. Geochim Cosmochim Acta 27:1129–1137CrossRefGoogle Scholar
  6. CCME (Canadian Council of Ministers of the Environment) (2008) Canadian soil quality guidelines for carcinogenic and other polycyclic aromatic hydrocarbons (environmental and human health effects), PN 1401, 210 ppGoogle Scholar
  7. CCME (Canadian Council of Ministers of the Environment) (2010) Canadian soil quality guidelines for the protection of environmental and human health. Polycyclic Aromatic Hydrocarbons, 19 pGoogle Scholar
  8. Centre for Land and Biological Resources Research (CLBR) (1993) Clay mineralogical database of Canadian soils, Technical Bulletin 1993-1E. Ottawa, Ontario, 67 p. ISBN 0-662-20249-XGoogle Scholar
  9. Chen W, Hou L, Luo X, Zhu L (2009) Effects of chemical oxidation on sorption and desorption of PAHs in typical Chinese soils. Environ Pollut 157:1894–1903CrossRefGoogle Scholar
  10. Delle Site A (2001) Factors affecting sorption of organic compounds in natural sorbent/water systems and sorption coefficients for selected pollutants: a review. J Phys Chem Ref Data 30:187–439CrossRefGoogle Scholar
  11. Dunnivant FM, Anders E (2005) A basic introduction to pollutant fate and transport: an integrated approach with chemistry, modeling, risk assessment, and environmental legislation. Wiley, HobokenCrossRefGoogle Scholar
  12. Environment Agency (EA) (2003) Review of the fate and transport of the selected contaminants in the soil environment draft technical report P5- 079/TR1Google Scholar
  13. Fonseca B, Pazos M, Figueiredo H, Tavares T, Sanroman MA (2011) Desorption kinetics of phenanthrene and lead from historically contaminated soil. Chem Eng J 167:84–90CrossRefGoogle Scholar
  14. Food and Agriculture Organization of the United Nations (FAO) (2001) Lecture notes on the major soils of the world. World soil resources reportsGoogle Scholar
  15. Gao YZ, He JZ, Ling WT, Hu HQ, Liu F (2003) Effects of organic acids on copper and cadmium desorption from contaminated soils. Environ Int 29:613–618CrossRefGoogle Scholar
  16. Gao Y, Xiong W, Ling W, Xu J (2006) Sorption of phenanthrene by soils contaminated with heavy metals. Chemosphere 65:1355–1361CrossRefGoogle Scholar
  17. Guo X, Luo L, Ma Y, Zhang SH (2010) Sorption of polycyclic aromatic hydrocarbons on particulate organic matters. J Hazard Mater 173:130–136CrossRefGoogle Scholar
  18. Hemond HF, Fechner-Levy EJ (2014) Chemical fate and transport in the environment. Academic Press, New YorkGoogle Scholar
  19. Hwang SC, Cutright TJ (2004) Adsorption/desorption due to system nonequilibrium and interaction with soil constituents. J Environ Sci Health A 39:1147–1162CrossRefGoogle Scholar
  20. Jones KD, Tiller CL (1999) Effect of solution chemistry on the extent of binding of phenanthrene by a soil humic acid: a comparison of dissolved and clay bound humic acids. Environ Sci Technol 33:580–587CrossRefGoogle Scholar
  21. Karickhoff S (1984) Organic pollutant sorption in aquatic systems. J Hydraulic Eng 110:707–735CrossRefGoogle Scholar
  22. Kaschl A, Römheld V, Chen Y (2002) Cadmium binding by fractions of dissolved organic matter and humic substances from municipal solid waste compost. J Environ Qual 31:1885–1892CrossRefGoogle Scholar
  23. Killops SD, Killops VJ (1993) An introduction to organic geochemistry. Wiley, New YorkGoogle Scholar
  24. Kim D, Petrisor IG, Yen TF (2005) Evaluation of biopolymer-modified concrete systems for disposal of cathode ray tube glass. J Air Waste Manag Assos 55:961–969CrossRefGoogle Scholar
  25. Kim D, Lai H-T, Chilingar GV, Yen TF (2006) Geopolymer formation and its unique properties. Environ Geol 51:103–111CrossRefGoogle Scholar
  26. Ko SO, Schlautman MA, Carraway ER (1998) Partitioning of hydrophobic organic compounds to sorbed surfactants. 1 Experimental studies. Environ Sci Technol 32:2769–2775CrossRefGoogle Scholar
  27. Li Y, Gupta G (1994) Adsorption/desorption of hydrocarbons on clay minerals. Chemosphere 28:628–637Google Scholar
  28. McCarty PL, Rittmann BE, Reinhard M (1981) Trace organics in groundwater. Environ Sci Technol 15:40–51CrossRefGoogle Scholar
  29. Means JC, Wood SG, Hassett JJ, Banwart WL (1980) Sorption of polynuclear aromatic hydrocarbons by sediments and soils. Environ Sci Technol 14:1524–1528CrossRefGoogle Scholar
  30. Morillo E, Romero AS, Madrid L, Villaverde J, Maqueda C (2008) Characterization and sources of PAHs and potentially toxic metals in urban environments of Sevilla (Southern Spain). Water Air Soil Pollut 187:41–51CrossRefGoogle Scholar
  31. National Round Table on the Environment and the Economy (NRTEE) (2003) Cleaning up the past, building the future: A national brownfield redevelopment strategy for Canada, Ottawa, Ontario, Canada, 41 pGoogle Scholar
  32. Nguyen X-P, Cui Y-J, Tang AM, Deng Y, Li X-L, Wouters L (2013) Effects of pore water chemical composition on the hydro-mechanical behavior of natural stiff clays. Eng Geol 166:52–64CrossRefGoogle Scholar
  33. Obuekwe IS, Semple KT (2013) Impact of Zn, Cu, Al and Fe on the partitioning and bioaccessibility of 14C-phenanthrene in soil. Environ Pollut 180:180–189CrossRefGoogle Scholar
  34. Ontario Ministry of Agriculture, Food and Rural Affairs (OMAFRA) (2016) Classifying prime and marginal agricultural soils and landscapes: guidelines for application of the Canada land inventory in Ontario. Accessed 26 Aug 2016
  35. Organization for Economic Cooperation and Development (OECD) (2000) Adsorption-desorption using a batch equilibrium method. OECD guideline for the testing of chemicals. Test No. 106, 45 pGoogle Scholar
  36. Ping L, Luo Y, Wu L, Qian W, Song J, Christie P (2006) Phenanthrene adsorption by soils treated with humic substances under different pH and temperature conditions. Environ Geochem Health 28:189–195CrossRefGoogle Scholar
  37. Polubesova M, Chen Y, Stefan C, Selle M, Werner P, Chefetz B (2009) Sorption of polyaromatic compounds by organic matter-coated Ca2 + and Fe3 + montmorillonite. Geoderma 154:36–41CrossRefGoogle Scholar
  38. Portal for Soil and Water Management in Europe (EUGRIS) (2016) Accessed 08 Nov 2016
  39. Prieto-Taboada N, Ibarrondo I, Gómez-Laserna O, Martinez-Arkarazo I, Olazabal MA, Madariaga JM (2013) Buildings as repositories of hazardous pollutants of anthropogenic origin. J Hazard Mater 248–249:451–460CrossRefGoogle Scholar
  40. Saicheck RE, Reddy KR (2005) Electrokinetically enhanced remediation of hydrophobic organic compounds in soils: a review. Crit Rev Environ Sci Technol 35:115–192CrossRefGoogle Scholar
  41. Saison C, Perrin-Ganier C, Amellal S, Morel JL, Schiavon M (2004) Effect of metals on the adsorption and extractability of 14C-phenanthrene in soils. Chemosphere 55:477–485CrossRefGoogle Scholar
  42. Schwarzenbach RP, Westall J (1981) Transport of nonpolar organic compounds from surface water to groundwater. laboratory sorption studies. Environ Sci Technol 15:1360–1367CrossRefGoogle Scholar
  43. Shaker AM, Komy ZR, Heggy SEM, El-Sayed MEA (2012) Kinetic study for adsorption humic acid on soil minerals. J Phys Chem A 116:10889–10896CrossRefGoogle Scholar
  44. Soler-Rovira P, Madejon E, Madejon P, Plaza C (2010) In situ remediation of metal-contaminated soils with organic amendments: role of humic acids in copper bioavailability. Chemosphere 79:844–849CrossRefGoogle Scholar
  45. Stevenson F, Goh K (1971) Infrared spectra of humic acids and related substances. Geochim Cosmochim Acta 35:471–483CrossRefGoogle Scholar
  46. Su C, Jiang LQ, Zhang WJ (2014) A review on heavy metal contamination in the soil worldwide: situation, impact and remediation techniques. Environ Skept Critics 3:24–38Google Scholar
  47. Thavamani P, Megharaj M, Krishnamurti GSR, McFarland R, Naidu R (2011) Finger printing of mixed contaminants from former manufactured gas plant (MGP) site soils: implications to bioremediation. Environ Int 37:184–189CrossRefGoogle Scholar
  48. Thavamani P, Megharaj M, Naidu R (2012) Multivariate analysis of mixed contaminants (PAHs and heavy metals) at manufactured gas plant site soils. Environ Monit Assess 184:3875–3885CrossRefGoogle Scholar
  49. Traina J, Spontak SA, Logan TJ (1989) Effects of cations on complexation of naphthalene by water-soluble organic carbon. J Environ Qual 18:221–227CrossRefGoogle Scholar
  50. Troeh FR, Thompson LM (2005) Soils and soil fertility, 6th edn. Wiley, HobokenGoogle Scholar
  51. US EPA (United States Environmental Protection Agency) (1986a) Polynuclear aromatic hydrocarbons. EPA-Method 8100 (SW-846)Google Scholar
  52. US Environmental Protection Agency (1986b) Cation exchange capacity of soils (Sodium Acetate, EPA-Method 9081 (SW-846)Google Scholar
  53. US EPA (United States Environmental Protection Agency) (1996a) Acid digestion of sediments, sludges and soils. EPA-Method 3050B (SW-846)Google Scholar
  54. US Environmental Protection Agency (1996b) Soxhlet extraction. EPA-Method 3540C (SW-846)Google Scholar
  55. US Environmental Protection Agency (2004) Cleaning up the nation’s waste sites: markets and technology trends, Office of solid waste and emergency response, Washington. DC. EPA 542-R-04-01Google Scholar
  56. Wang G, Mielke H, Quach V, Gonzales C, Zhang Q (2004) Determination of polycyclic aromatic hydrocarbons and trace metals in New Orleans soils and sediments. Soil Sediment Contam 13:1–15CrossRefGoogle Scholar
  57. Weber WJ Jr, McGinley PM, Katz LE (1992) Distributed reactivity model for sorption by soils and sediments. 1. Conceptual basis and equilibrium assessments. Environ Sci Technol 26:1955–1962CrossRefGoogle Scholar
  58. Weber WJ Jr, Kim SH, Johnson MD (2002) Distributed reactivity model for sorption by soils and sediments: 15. High-concentration co-contaminant effects on phenanthrene sorption and desorption. Environ Sci Technol 36:3625–3634CrossRefGoogle Scholar
  59. Wu P, Tang Y, Wang W, Zhu N, Li P, Wu J, Dang Z, Wang X (2011) Effect of dissolved organic matter from Guangzhou landfill leachate on sorption of phenanthrene by montmorillonite. J Colloid Interface Sci 361:618–627CrossRefGoogle Scholar
  60. Yu H, Huang GH, An CJ, Wei J (2011) Combined effects of DOM extracted from site soil/compost and biosurfactant on the sorption and desorption of PAHs in a soil–water system. J Hazard Mater 190:883–890CrossRefGoogle Scholar
  61. Yu H, Xiao H, Wang D (2014) Effects of soil properties and biosurfactant on the behavior of PAHs in soil–water systems. Environ Syst Res 3:1–11CrossRefGoogle Scholar
  62. Yuan S, Tian M, Lu XH (2006) Electrokinetic movement of hexachlorobenzene in clayed soils enhanced by Tween 80 and—cyclodextrin. J Hazard Mater B137:1218–1225CrossRefGoogle Scholar
  63. Yuan S, Shu Z, Wan J, Lu X (2007) Enhanced desorption of hexachlorobenzene from kaolin by single and mixed surfactants. J Colloid Interface Sci 314:168–175CrossRefGoogle Scholar
  64. Zhang MK, Ke ZX (2004) Copper and zinc enrichment in different size fractions of organic matter from polluted soils. Pedosphere 14:27–36Google Scholar
  65. Zhang W, Zhuang L, Yuan Y, Tong L, Tsang DC (2011a) Enhancement of phenanthrene adsorption on a clayey soil and clay minerals by coexisting lead or cadmium. Chemosphere 83:302–310CrossRefGoogle Scholar
  66. Zhang L, Luo L, Zhang S (2011b) Adsorption of phenanthrene and 1, 3-dinitrobenzene on cation-modified clay minerals. Colloids Surf A 377:278–283CrossRefGoogle Scholar
  67. Zhu D, Herbert BE, Schlautman MA, Carraway ER, Hur J (2004) Cation– π bonding: a new perspective on the sorption of polycyclic aromatic hydrocarbons to mineral surfaces. J Environ Qual 33:1322–1330CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of Civil EngineeringThe University of British ColumbiaVancouverCanada
  2. 2.Department of Chemical and Biological EngineeringThe University of British ColumbiaVancouverCanada

Personalised recommendations