Skip to main content
Log in

Speciation of Metals in Soils and Water: Risk Assessment

  • Original Article
  • Published:
Environmental Processes Aims and scope Submit manuscript

Abstract

Scarce management of solid wastes, excessive wastewater discharge and irrigation with noxious water are among the main causes of heavy metal contamination in agricultural soils. The soils of upper Litani basin in Lebanon are subjected to these sources, beside soil irrigation by Litani river water, contaminated by wastewater. However, the metal mobility, bioavailability, or potential risk can be elucidated by metal soil and water chemical speciation. This study involved the metal speciation in soils of the upper Litani basin, and computation of pollution indices for risk assessment. A modified BCR sequential extraction technique was implemented to soil samples that operationally extract metals sequentially from fractions termed as acid soluble, reducible, oxidizing, and residual. Beside, soil pH, Eh and TOC, macro-water parameters, and metal water content were measured. The geochemical computer model PHREEQC was used to predict water metal species. Data indicated that Mn, Zn, Cr, and As had their highest average percentage from total metal in the reducible and acid soluble soil fractions, while Cu, Ni, Cd, Hg were in the oxidizing and acid soluble soil fractions. Metal speciation was related to TOC, Eh and water BOD. The average values for the indices indicated: enrichment factor and geo-accumulation of severe enrichment and very strong contamination for Cd and Hg; risk assessment high risk for Cr, Ni, and Cd; and 50% of sites suffered from considerable contamination according to the global contamination factor. The highest percentage of water species were for Mn, Zn, Ni, and Cd, the free metal aqua ion.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1

Similar content being viewed by others

References

  • Abdel-Satar AM, Goher ME (2015) Heavy metals fractionation and risk assessment in surface sediments of Qarun and Wadi El-Rayan Lakes, Egypt. Environ Monit Assess 187:346–358

    Google Scholar 

  • Acosta JA, Gabarrón M, Faz A, Martínez-Martínez S, Zornoza R, Arocena JM (2015) Influence of population density on the concentration and speciation of metals in the soil and street dust from urban areas. Chemosphere 134:328–337

    Google Scholar 

  • APHA (2005) Standard methods for the examination of water and wastewater, 21st edn. American Public Health Association/American Water Works Association/Water Environment Federation, Washington DC

    Google Scholar 

  • Ahmed IAM, Taylor JH, Bieroza M, Zhang H, William Davison W (2014) Improving and testing geochemical speciation predictions of metal ions in natural waters. Water Res 67:276–291

    Google Scholar 

  • Ahmad JU, Abdul Goni M (2010) Heavy metal contamination in water, soil, and vegetables of the industrial areas in Dhaka, Bangladesh. Environ Monit Assess 166:347–357

    Google Scholar 

  • Bavec Ŝ, Gosar M (2016) Speciation, mobility and bioaccessibility of Hg in the polluted urban soil of Idrija (Slovenia). Geoderma 273:115–130

    Google Scholar 

  • Benson NU, Asuquo FE, Williams AB, Essien JP, Ekong CI, Akpabio O, Abaas A, Olajire AA (2016) Source evaluation and trace metal contamination in benthic sediments from equatorial ecosystems using multivariate statistical techniques. PLoS One 1–19. https://doi.org/10.1371/journal.pone.0156485

    Google Scholar 

  • Bîrsan E, Luca C (2010) Speciation of heavy metals in surface waters polluted by anthropogenic activities. In: Proceeding of the 6th edition of Colloque Franco-Roumain de Chimie Appliquée, COFrRoCA 2010, 7–10 July 2010, Orléans, France

  • Brown P, Markich SJ (2000) Evaluation of the free ion activity model of metal organism interaction: extension of the conceptual model. Aquat Toxicol 51(2):177–194

    Google Scholar 

  • Chakraborty P (2012) Speciation of Co, Ni and Cu in the coastal and estuarine sediments: some fundamental characteristics. J Geochem Explor 115:13–23

    Google Scholar 

  • Chakraborty P, Babu PV, Vudamala K, Ramteke D, Chennuri K (2014) Mercury speciation in coastal sediments from the central east coast of India by modified BCR method. Mar Pollut Bull 81:282–288

    Google Scholar 

  • Chavez E, He ZL, Stoffella PJ, Mylavarapu RS, Li YC, Baligar VC (2016) Chemical speciation of cadmium: an approach to evaluate plant available cadmium in Ecuadorian soils under cacao production. Chemosphere 150:57–62

    Google Scholar 

  • Chen H, Teng Y, Lu S, Wang Y, Wang J (2015) Contamination features and health risk of soil heavy metals in China. Sci Total Environ 512-513:143–153

    Google Scholar 

  • Chopra AK, Pathak C, Prasad G (2009) Scenario of heavy metal contamination in agricultural soil and its management. J Appl Nat Sci 1(1):99–108

    Google Scholar 

  • Darwish T, Zurayk RR (1997) Distribution and nature of red Mediterranean soils in Lebanon along an altitudinal sequence. Catena 28:191–202

    Google Scholar 

  • Deshmukh SK, Singh AK, Datta SP (2015) Impact of wastewater irrigation on the dynamics of metal concentrations in the vadose zone: monitoring: part I. Environ Monit Assess 187:695. https://doi.org/10.1007/s10661-015-4898-3

    Article  Google Scholar 

  • Ebong GA, Dan EU, Inam E, Offiong NO (2018) Total concentration, speciation, source identification and associated health implications of trace metals in Lemna dumpsite soil, Calabar, Nigeria. Journal of King Saud University – Science. https://doi.org/10.1016/j.jksus.2018.01.005

  • Elgallal M, Fletcher L, Evans B (2016) Assessment of potential risks associated with chemicals in wastewater used for irrigation in arid and semiarid zones: a review. Agric Water Manag 177:419–431

    Google Scholar 

  • Emad Farahat E, Linderholmb HW (2015) The effect of long-term wastewater irrigation on accumulation and transfer of heavy metals in Cupressus sempervirens leaves and adjacent soils. Sci Total Environ 512–513:1–7

    Google Scholar 

  • EPA (2014) SESDPROC-300-R3, Soil sampling. https://www.epa.gov/sites/production/files/2015-06/documents/Soil-Sampling.pdf. Accessed 2 Dec 2017

  • Favas PJC, Pratas J, Gomes MEP, Cala V (2011) Selective chemical extraction of heavy metals in tailings and soils contaminated by mining activity: environmental implications. J Geochem Explor 111:160–171

    Google Scholar 

  • Forghani G, Mokhtari AR, Kazemi GA, Fard MD (2015) Total concentration, speciation and mobility of potentially toxic elements in soils around a mining area in Central Iran. Chem Erde-Geochem 75(3):323–334

    Google Scholar 

  • Frohne T, Rinklebe J, Diaz-Bone RA, Du Laing G (2011) Controlled variation of redox conditions in a floodplain soil: impact on metal mobilization and biomethylation of arsenic and antimony. Geoderma 160:414–424

    Google Scholar 

  • Gabarrón M, Faz A, Martínez-Martínez S, Zornoza R, Acosta JA (2017) Assessment of metals behaviour in industrial soil using sequential extraction, multivariable analysis and a geostatistical approach. J Geochem Explor 172:174–183

    Google Scholar 

  • Gogoi A, Chaminda T, An KJ, Snow D, Li Y (2016) Influence of ligand metal speciation, transport and toxicity in a tropical river during wet (monsoon) period. Chemosphere 163:322–333

    Google Scholar 

  • Gu Y-G, Gao Y-P, Lin Q (2016) Contamination, bioaccessibility and human health risk of heavy metals in exposed-lawn soils from 28 urban parks in southern China's largest city, Guangzhou. Appl Geochem 67:52–58

    Google Scholar 

  • Gusiatin ZM, Kulikowska D (2014) The usability of the IR, RAC and MRI indices of heavy metal distribution to assess the environmental quality of sewage sludge compost. Waste Manag 34:1227–1236

    Google Scholar 

  • Hu Y, Liu X, Baim J, Shih K, Eddy Y, Zeng EY, Cheng H (2013) Assessing heavy metal pollution in the surface soils of a region that had undergone three decades of intense industrialization and urbanization. Environ Sci Pollut Res 20:6150–6159

    Google Scholar 

  • Jackson A (2015) Variations in the abundance of photosynthetic oxygen through Precambrian and Paleozoic time in relation to biotic evolution and mass extinctions: evidence from Mn/Fe ratios Togwell. Precambrian Res 264:30–35

    Google Scholar 

  • Jain CK (2004) Metal fractionation study on bed sediments of river Yamuna, India. Water Res 38:569–578

    Google Scholar 

  • Juen LL, Aris AZ, Shan NT, Yousoff FM, Hashim Z (2015) Geochemical modelling in selected tropical estuaries and coastal water of Strail of Melacca. Prog Environ Sci 30:100–114

    Google Scholar 

  • Kabata-Pendias A (2011) Trace elements in soils and plants. CRC Press, Boca Raton

    Google Scholar 

  • Kebonye NM, Eze PN, Akinyemi FO (2017) Long term treated wastewater impacts and source identification of heavy metals in semi-arid soils of Central Botswana. Geoderma Reg 10:200–214

    Google Scholar 

  • Khan J, Samad A, Noor Y, Rashid M, Jan B (2015) In-situ stabilization of heavy metals in agricultural soils irrigated with untreated wastewater. J Geochem Explor 159:1–7

    Google Scholar 

  • Korfali SI, Davies BE (2004) Speciation of metals in sediment and water in a river underlain by limestone: role of carbonate species for purification capacity of rivers. Adv Environ Res 8:599–612

    Google Scholar 

  • Korfali SI, Jurdi M (2007) Assessment of domestic water quality: case study, Beirut, Lebanon. Environ Monit Assess 135:241–251

    Google Scholar 

  • Korfali SI, Jurdi M (2011) Speciation of metals in bed sediments and water of Qaraaoun reservoir, Lebanon. Environ Monit Assess 178(1–4):563–579

    Google Scholar 

  • Korfali SI, Mroueh M, Al-Zein M, Salem R (2013) Metal concentration in commonly used medicinal herbs and infusion by Lebanese population: health impact. J Food Res 2:70–82

    Google Scholar 

  • Korfali SI, Jurdi M, Amacha N (2014) Sources and levels of metals in the upper Litani basin soils: Lebanon. J Environ Sci Eng A 3:55–71

    Google Scholar 

  • Korfali SI, Karaki H (2017) Bioavailability of metals in soils irrigated by synthetic wastewater: metal speciation. Proceeding of European Water Resources Association, 10th World Congress on Water Resoures and Environment “Panta Rhei”, Athens, pp 1353–1360

  • Kouassi LB, You A, Trokourey A, Soro MB (2014) Preliminary assessment of cadmium mobility in surface sediments of a tropical estuary. Bull Chem Soc Ethiop 28(2):245–254

    Google Scholar 

  • Lenoble V, Omanovic D, Garnier D, Mounier S, Donlagic N, Le Poupon C, Pizeta I (2013) Distribution and chemical speciation of arsenic and heavy metals in highly contaminated waters used for health care purposes (Sebrinica, Bosnia, and Herzegovina). Sci Total Environ 443:420–428

    Google Scholar 

  • Li H, Wang J, Wang Q, Qain X, Qian Y, Yang M, Li F, Lu H, Wang C (2015) Chemical fractionation of arsenic and heavy metals in fine particle matter and its implications for risk assessment: a case study in Nanjing, China. Atmos Environ 103:339–346

    Google Scholar 

  • Li H, Ji H (2017) Chemical speciation, vertical profile and human health risk assessment of heavy metals in soils from coal-mine brownfield, Beijing, China. J Geochem Explor 183:12–22

    Google Scholar 

  • Long Y-Y, Hu L-F, Fang C-R, Wu Y-Y, Shen D-S (2009) An evaluation of the modified BCR sequential extraction procedure to assess the potential mobility of copper and zinc in MSW. Microchem J 91:1–5

    Google Scholar 

  • Ma XL, Zuo H, Tian MJ, Zhang LY, Meng J, Zhou XN, Min N, Chang XY, Liu Y (2016) Assessment of heavy metals contamination in sediments from three adjacent regions of the yellow river using metal chemical fractions and multivariate analysis techniques. Chemosphere 144:264–272

    Google Scholar 

  • Magu MM, Govender PP, Ngila JJ (2016) Geochemical modelling and speciation studies of metal pollutants present in selected water systems in South Africa. Phys Chem Earth 92:44–51

    Google Scholar 

  • Mapanda F, Mangwayana EN, Nyamangara J, Giller KE (2005) The effect of long-term irrigation using wastewater on heavy metal contents of soil under vegetables in Harare, Zimbabwe. Agric Ecosyst Environ 107:151–165

    Google Scholar 

  • Matong JM, Nyaba L, Nomngongo PN (2016) Fractionation of trace elements in agricultural soils using ultrasound assisted sequential extraction prior to inductively coupled plasma mass spectrometric determination. Chemosphere 154:249–257

    Google Scholar 

  • Mehr MR, Keshavarzi B, Moor F, Sharifi R, Lahijanzadeh A, Maryam Kermani M (2017) Distribution, source identification and health risk assessment of soil heavy metals in urban areas of Isfahan province, Iran. J Afr Earth Sci 132:16–26

    Google Scholar 

  • Meng W, Wang Z, Hu B, Wang Z, Goodman RC (2016) Heavy metals in soil and plants after long-term sewage irrigation at Tianjin China: a case study assessment. Agric Water Manag 171:153–163

    Google Scholar 

  • Morel FMM (1983) Principles of aquatic chemistry. Wiley, New York

    Google Scholar 

  • Muchuweti M, Birkett JW, Chinyanga E, Zvauya R, Scimshaw MD, Lester JN (2006) Heavy metal content of vegetable irrigated with mixture of wastewater and sewage sludge in Zimbabwe: implication for human health. Agric Ecosyst Environ 112:41–48

    Google Scholar 

  • Müller G (1969) Index of geoaccumulation in the sediments of the Rhine River. J Geol 2:108–118

    Google Scholar 

  • Naji A, Ismail A, Ismail AR (2010) Chemical speciation and contamination assessment of Zn and cd by sequential extraction in surface sediment of Klang river, Malaysia. Microchem J 95:285–292

    Google Scholar 

  • Naser HM, Mahmud NU, Sultana S, Gomes R, Rahman M (2012) Trace elements content in vegetables grown in industrially polluted and non-polluted areas, Bangladesh. J Agric Res 37(3):515–527

    Google Scholar 

  • Nasr SM, Okbah MA, El Haddad HS, Soliman NF (2015) Fractionation profile and mobility pattern of metals in sediments from the Mediterranean coast, Libya. Environ Monit Assess 187:430–438

    Google Scholar 

  • Ni M, Mao R, Jia Z, Dong R, Li S (2018) Heavy metals in soils of Hechuan county in the upper Yangtze (SW China): comparative pollution assessment using multiple indices with high-spatial resolution sampling. Ecotoxicol Environ Saf 148:644–651

    Google Scholar 

  • Obiefuna GI, Orazuklike DM (2010) Chemical speciation of some metal ions in ground waters of Yola aArea using geochemical model. J Appl Sci Environ Manag 14(2):65–70

    Google Scholar 

  • Pérez AL, Anderson AK (2009) DGT estimates cadmium accumulation in wheat and potato from phosphate fertilizer applications. Sci Total Environ 407:5096–5103

    Google Scholar 

  • Pinedo-Hernandez JB, Marrugo-Negrete J (2015) Speciation and bioavailability of mercury in sediments impacted by gold mining in Colombia. Chemosphere 119:1289–1295

    Google Scholar 

  • Perin G, Craboledda L, Lucchese M, Cirillo R, Dotta L, Zanetta ML, Oro AA (1985) Heavy metal speciation in the sediments of northern Adriatic sea – a new approach for environmental toxicity determination. In: Lakkas TD (ed) Heavy metals in the environment, vol 2. CEP Consultants, Edinburgh, pp 454–456

    Google Scholar 

  • Pingitore NE (1978) The behaviour of Zn2+ and Mn2+ during carbonate diagenesis: theory and applications. J Sediment Res 48:799–814

    Google Scholar 

  • Rahman SH, Khanam D, Adyel TM, Islam MS, Ahsan MA, Ahedul Akbor M (2012) Assessment of heavy metal contamination of agricultural soil around Dhaka export processing zone (DEPZ), Bangladesh: implication of seasonal variation and indices. Appl Sci 2:584–601

    Google Scholar 

  • Rauret G, López-Sánchez JF, Sahuquillo A, Rubio R, Davidson C, Ure A, Quevauviller P (1999) Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials. J Environ Monit 1:57–61

    Google Scholar 

  • Reijonen I, Hartikainen H (2016) Oxidation mechanisms and chemical bioavailability of chromium in agricultural soil-pH as the master variable. Appl Geochem 74:84–93

    Google Scholar 

  • Rodríguez I, Ruiz E, Alonso-Azcárate J, Rincón (2009a) Heavy metal distribution and chemical speciation in tailings and soils around a Pb-Zn mine in Spain. J Environ Manag 90:1106–1116

    Google Scholar 

  • Rodríguez L, Ruiz E, Alonso-Azcárate J, Rincón J (2009b) Heavy metal distribution and chemical speciation in tailings and soils around a Pb-Zn mine in Spain. J Environ Monit 90:1106–1116

    Google Scholar 

  • Rong Z, Jiale Z, Zhou Z, Chao MA, Wang L, Xiaojiang G (2016) Land use effects on the distribution and speciation of heavy metals and arsenic in coastal soils on Chongming Island in the Yangtze river estuary, China. Pedosphere 26(1):74–84

    Google Scholar 

  • Sadee BA, Foulkes ME, Hill SJ (2016) A study of arsenic speciation in soil, irrigation water and plant tissue: a case study of the broad bean plant, Vicia faba. Food Chem 210:362–370

    Google Scholar 

  • Shaheen S, Rinklebe J (2014) Geochemical fractions of chromium, copper, and zinc and their vertical distribution in floodplain soil profiles along the central Elbe river, Germany. Geoderma 228–229:142–159

    Google Scholar 

  • Sierra J, Roig N, Papiol GG, Pérez-Gallego E, Schuhmacher M (2017) Prediction of the bioavailability of potentially toxic elements in freshwaters. Comparison between speciation models and passive samplers. Sci Total Environ 605-606:211–218

    Google Scholar 

  • Singh KP, Mohan D, Sinha S, Dalwani R (2004) Impact assessment of treated/untreated wastewater toxicants discharged by sewage treatment plants on health, agricultural, and environmental quality in the wastewater disposal area. Chemosphere 55:227–255

    Google Scholar 

  • Singh PK, Deshbhratar PB, Ramteke DS (2012) Effects of sewage wastewater irrigation on soil properties: crop yield and environment. Agvric Water Manag 103:100–104

    Google Scholar 

  • Simpson SL, Vardanega CR, Jarolimek, Jolley DF, Angel BM, Mosley LM (2014) Metal speciation and potential bioavailability changes during discharge and neutralization of acidic drainage water. Chemosphere 103:172–180

    Google Scholar 

  • Sow AY, Ismail A, Zulkifi SZ (2013) Geofractionation of heavy metals and application of indices for pollution prediction in paddy field soil of Tumpat, Malaysia. Environ Sci Pollut Res 20:8964–8973

    Google Scholar 

  • Stumm W, Morgan JJ (1996) Aquatic chemistry: chemical equilibria and rates in natural water, 3rd edn. A Wiley Interscience Publications, New York, pp 1102

    Google Scholar 

  • Suda A, Makino T (2016) Functional effects of manganese and iron oxides on the dynamics of trace elements in soils with a special focus on arsenic and cadmium: a review. Geoderma 270:68–75

    Google Scholar 

  • Sundaray SK, Nayak BB, Lin S, Bhatta D (2011) Geochemical speciation and risk assessment of heavy metals in the river estuarine sediments—a case study: Mahanadi basin, India. J Hazard Mater 186:1837–1846

    Google Scholar 

  • Sungur A, Soylak M, Özcan H (2016) Chemical fractionation, mobility and environmental impacts of heavy metals in greenhouse soils from Çanakkale, Turkey. Environ Earth Sci 75:334. https://doi.org/10.1007/s12665-016-5268-3

    Article  Google Scholar 

  • Tian K, Huang B, Xing Z, Hu W (2017) Geochemical baseline establishment and ecological risk evaluation of heavy metals in greenhouse soils from Dongtai, China. Ecol Indic 72:510–520

    Google Scholar 

  • Tokalioğlu S (2012) Determination of trace elements in commonly consumed medicinal herbs by ICP-MS and multivariate analysis. Food Chem 134:2504–2508

    Google Scholar 

  • Turekian KK, Wedepohl KH (1961) Distribution of the elements in some major units of the Earth’s crust. Geol Soc Am Bull 72:175–192

    Google Scholar 

  • Udechukuw BE, Ismail A, Zulkilfi SZ, Omar H (2015) Distribution, mobility, and pollution assessment of Cd, Cu, Ni, Pb, Zn, and Fe in intertidal surface sediments of sg. Puloh mangrove estuary, Malaysia. Environ Sci Pollut Res 22:4242–4255

    Google Scholar 

  • Wazne M, Korfali SI (2016) Spatial and temporal assessment of metal pollution in the sediments of the Qaraoun reservoir, Lebanon. Environ Sci Pollut Res 23:7603–7614

    Google Scholar 

  • Worms I, Simon DF, Hassler CS, Wilkinson KJ (2006) Bioavailability of trace metals to aquatic microorganisms: importance of chemical, biological and physical processes on bio uptake. Biochimie 88(11):1721–1731

    Google Scholar 

  • Źemberyovà M, Hagarovà I, Zimovà J, Bartekovà J, Kuss HM (2010) Determination of molybdenum in extracts of soil and sewage sludge CRMs after fractionation by means of BCR modified sequential extraction procedure. Talanta 82:582–586

    Google Scholar 

  • Zhang J, Li H, Zhou Y, Dou L, Cai L, Liping Mo L, Jing J (2018) Bioavailability and soil-to-crop transfer of heavy metals in farmland soils: a case study in the pearl river delta, South China. Environ Pollut 235:710–719

    Google Scholar 

  • Zhu X, Li W, Zhan L, Huang M, Zhang Q, Achal V (2016) The large-scale process of microbial carbonate precipitation for nickel remediation from an industrial soil. Environ Pollut 219:149–155

    Google Scholar 

Download references

Acknowledgements

Lebanese National Council for Scientific Research, for funding this research under project number CNRS 674. Lebanese American University – School Research and Development Council (SRDC), for funding all travel of the present research under fund number SRDC-t- 2017-24. An initial shorter version of the paper has been presented at the 10th World Congress of the European Water Resources Association (EWRA2017) “Panta Rhei”, Athens, Greece, 5-9 July, 2017 (http://ewra2017.ewra.net).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Samira I. Korfali.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Korfali, S.I., Karaki, H. Speciation of Metals in Soils and Water: Risk Assessment. Environ. Process. 5 (Suppl 1), 101–125 (2018). https://doi.org/10.1007/s40710-018-0328-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40710-018-0328-1

Keywords

Navigation