Environmental Science and Pollution Research

, Volume 21, Issue 7, pp 5098–5120 | Cite as

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India

  • G. P. Gurumurthy
  • K. BalakrishnaEmail author
  • M. Tripti
  • Stéphane Audry
  • Jean Riotte
  • J. J. Braun
  • H. N. Udaya Shankar
Research Article


The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary–Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.


Nethravati–Gurupur Rivers Dissolved trace elements REEs Redox processes Sorption reaction Tropical river Cerium anomaly 



This work is funded by the Ministry of Environment and Forests (19/36/2006-RE), Government of India, through a research project to KB. INSU-EC2CO (CNRS) and IRD, France are also thanked for partially funding this research work. We thank all technical staff at GET, Toulouse for their help during the analysis of samples. The first author (GPG) is thankful to the Embassy of France in India and the International Association of Geochemistry for providing Sandwich Ph.D. fellowship to do a part of this work at GET, Toulouse, France and for providing Ph.D. Student Research Grant, respectively. This work is part of GPG’s Ph D thesis submitted to Manipal University, Manipal and the work is carried out at Department of Civil Engineering, Manipal Institute of Technology, Manipal University, Manipal, India.


  1. Ajmal M, Khan MA, Nomani AA (1985) Distribution of heavy metals in water and sediments of selected sites of Yamuna River (India). Environ Monit Assess 5(2):205–214CrossRefGoogle Scholar
  2. Aries S, Valladon M, Polve M, Dupré B (2000) A routine method for oxide and hydroxide interference corrections in ICP-MS chemical analysis of environmental and geological samples. Geostand Newslett J Geostand Geoanal 24:19–31CrossRefGoogle Scholar
  3. Balistrieri LS, Murray JW, Paul B (1994) Geochemical cycling of trace elements in a biogenic meromictic lake. Geochim Cosmochim Acta 58(19):3993–4008CrossRefGoogle Scholar
  4. Bhaskar Rao YJ, Naha K, Srinivasan R, Gopalan K (1991) Geology, geochemistry and geochronology of the Archean Peninsular Gneiss around Gorur, Hassan District, Karnataka, India. Indian Acad Sci (Earth and Planetary Sciences) Proceedings 100:399–412Google Scholar
  5. Braun J-J, Pagel M, Muller JP, Bilong P, Michard A, Guillet B (1990) Cerium anomalies in lateritic profiles. Geochim Cosmochim Acta 51:597–605Google Scholar
  6. Braun J-J, NdamNgoupayou JR, Viers J, Dupré B, Bedimo Bedimo J-P, Boeglin J-L, Robain H, Nyeck B, Freydier R, SighaNkamdjou L, Rouiller J, Muller J-P (2005) Present weathering rates in a humid tropical watershed: Nsimi, South Cameroon. Geochim Cosmochim Acta 69:357–387CrossRefGoogle Scholar
  7. Brown DA, Sherriff BL, Sawicki JA, Sparling R (1999a) Precipitation of iron minerals by a natural microbial consortium. Geochim Cosmochim Acta 63:2163–2169CrossRefGoogle Scholar
  8. Brown GE, Henrich VE, Casey WH, Clark DL, Eggleston C, Felmy A, Goodman DW, Gratzel M, Maciel G, McCarthy MI, Nealson KH, Sverjensky DA, Toney MF, Zachara JM (1999b) Metal oxide surfaces and their interactions with aqueous solutions and microbial organisms. Chem Rev 99:77–174CrossRefGoogle Scholar
  9. Cao M, Woodward FI (1998) Dynamic responses of terrestrial ecosystem carbon cycling to global climate change. Nature 393:249–252CrossRefGoogle Scholar
  10. Chakrapani GJ, Subramanian V (1996) Fractionation of heavy metals and phosphorus in suspended sediments of the Yamuna River, India. Environ Monit Assess 43(2):117–124CrossRefGoogle Scholar
  11. Davranche M, Pourret O, Gruau G, Dia A (2004) Impact of humate complexation on the adsorption of REE onto Fe oxyhydroxide. J Colloid Interface Sci 277:271–279CrossRefGoogle Scholar
  12. Davranche M, Pourret O, Gruau G, Dia A, Le Coz-Bouhnik M (2005) Adsorption of REE (III)–humate complexes onto MnO2: experimental evidence for cerium anomaly and lanthanide tetrad effect suppression. Geochim Cosmochim Acta 69:4825–4835CrossRefGoogle Scholar
  13. Divakra Rao V, Naqvi SM, Sathyanarayana K, Hussain SM (1974) Geochemistry and origin of the Peninsular Gneisses of Karnataka. J Geol Soc India 15:270–277Google Scholar
  14. Dupré B, Viers J, Dandurand JL, Polve M, Bénézeth P, Vervier P, Braun J-J (1999) Major and trace elements associated with colloids in organic-rich river waters: ultrafiltration of natural and spiked solutions. Chem Geol 160(1):63–80CrossRefGoogle Scholar
  15. Dwarakish G S, Abdu Rahiman K U, Natesan U (2009) Changes in river hydrology and coastal sedimentation by dams in Periyar River basin Keraa, India. Proceedings of the 4th IASME/WSEAS International Conference on Water Resources, Hydraulics and Hydrology (WHH-09).Google Scholar
  16. Eby GN (2004) Principles of environmental geochemistry, 1st edn. Brooks Cole, StamfordGoogle Scholar
  17. Elbaz-Poulichet F, Seyler P, Maurice-Bourgoin L, Guyot JL, Dupuy C (1999) Trace element geochemistry in the upper Amazon drainage basin (Bolivia). Chem Geol 157:319–334CrossRefGoogle Scholar
  18. Froelich P, Klinkhammer GP, Bender MAA, Luedtke NA, Heath GR, Cullen D, Maynard V (1979) Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis. Geochim Cosmochim Acta 43(7):1075–1090CrossRefGoogle Scholar
  19. Fuller CC, Harvey JR (2000) Reactive uptake of trace metals in the hyporheic zone of a mining-contaminated stream, Pinal Creek, Arizona. Environ Sci Technol 34:1150–1155CrossRefGoogle Scholar
  20. Gaillardet J, Dupré B, Allègre CJ (1995) A global geochemical mass budget applied to the Congo Basin Rivers: erosion rates and continental crust composition. Geochim Cosmochim Acta 59:3469–3485CrossRefGoogle Scholar
  21. Gaillardet J, Viers J, Dupré B (2003) Trace element in river waters. In: Drever JI, Holland HD, Turekian KK (eds) Surface and groundwater, weathering, erosion and soils, treatise on geochemistry, vol. 5. Pergamon, New YorkGoogle Scholar
  22. Geological Survey of India (1981) Geological and mineral map of Karnataka and Goa. Compiled by Swaminath et al. published under the direction of Krishnamurthy, V.S., Director General, Geological Survey of IndiaGoogle Scholar
  23. Gunnars A, Blomqvist S, Johansoon P, Andersson C (2002) Formation of Fe(III) oxyhydroxide colloids in freshwater and brackish seawater, with incorporation of phosphate and calcium. Geochim Cosmochim Acta 66:745–758CrossRefGoogle Scholar
  24. Gurumurthy GP, Balakrishna K, Riotte J, Audry S, Braun JJ, Shankar UHN, Manjunatha BR (2012) Controls on intense silicate weathering in a tropical river, Southwestern India. Chem Geol 300–301:61–69CrossRefGoogle Scholar
  25. Heimburger A, Tharaud M, Monna F, Losno R, Desboeufs K, Nguyen EB (2013) SLRS-5 elemental concentrations of thirty-three uncertified elements deduced from SLRS-5/SLRS-4 ratios. Geostand Geoanal Res 37(1):77–85CrossRefGoogle Scholar
  26. Honeyman BD, Santschi PH (1988) Metals in aquatic systems. Environ Sci Technol 22:862–871CrossRefGoogle Scholar
  27. Ingri J (1985) Geochemistry of ferromanganese concretions and associated sediments in the Gulf of Bothnia. Ph.D. thesis, Luleå University, Luleå, SwedenGoogle Scholar
  28. Ingri J, Widerlund A (1994) Uptake of alkali and alkaline-earth elements on suspended iron and manganese in the Kalix River, northern Sweden. Geochim Cosmochim Acta 58:5433–5442CrossRefGoogle Scholar
  29. Jenkinson DS, Adams DE, Wild A (1991) Model estimates of CO2 emissions from soil in response to global warming. Nature 351:304–306CrossRefGoogle Scholar
  30. Johannesson KH, Lyons WB (1994) The rare earth element geochemistry of Mono Lake water and the importance of carbonate complexing. Limnol Oceanogr 39:1141–1154CrossRefGoogle Scholar
  31. Kirschbaum MUF (1995) The temperature dependence of soil organic matter decomposition, and the effect of global warming on soil organic C storage. Soil Biol Biochem 27(6):753–760CrossRefGoogle Scholar
  32. Lion LW, Altmann RS, Leckie JO (1982) Trace-metal adsorption characteristics of estuarine particulate matter: evaluation of contributions of iron/manganese oxide and organic surface coatings. Environ Sci Technol 16(10):660–666CrossRefGoogle Scholar
  33. Ludwig W, Probst J-L, Kempe S (1996) Predicting the oceanic input of organic carbon by continental erosion. Glob Biogeochem Cycles 10(1):23–41CrossRefGoogle Scholar
  34. Morel FMM, Hering JG (1993) Principles and applications of aquatic geochemistry. Wiley, New YorkGoogle Scholar
  35. Morford JL, Emerson S (1999) The geochemistry of redox sensitive trace metals in sediments. Geochim Cosmochim Acta 63(11):1735–1750CrossRefGoogle Scholar
  36. Neubraure U, Nowack B, Furrer G, Schulin R (2000) Heavy metal sorption on clay minerals affected by the siderophore desferrrioxamine B. Environ Sci Technol 34:2749–2755CrossRefGoogle Scholar
  37. Nimick DA, Gammons CH, Cleasby TE, Madison JP, Skaar D, Brick CM (2003) Diel cycles in dissolved metal concentrations in streams: occurrence and possible causes. Water Resour Res 39(9):1247–1259CrossRefGoogle Scholar
  38. Nimick DA, Cleasby TE, McCleskey RB (2005) Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream. Environ Geol 47:603–614CrossRefGoogle Scholar
  39. Nimick DA, Gammons CH, Parker SR (2010) Diel biogeochemical processes and their effect on the aqueous chemistry of streams: a review. Chem Geol 283:3–17CrossRefGoogle Scholar
  40. Ohta A, Kawabe I (2001) REE (III) adsorption onto Mn dioxide (δ-MnO2) and Fe oxyhydroxide: Ce (III) oxidation by δ-MnO2. Geochim Cosmochim Acta 65(5):695–703CrossRefGoogle Scholar
  41. Probst JL, Nkounkou RR, Krempp G, Bricquet JP, Thiebaux JC, Olivry JC (1992) Dissolved major elements exported by the Congo and the Ubangui rivers during the period 1987–1989. J Hydrol 135:237–257CrossRefGoogle Scholar
  42. Rajamani V, Tripathi JK, Malviya VP (2009) Weathering of lower crustal rocks in the Kaveri river catchment, southern India: implications to sediment geochemistry. Chem Geol 265:410–419CrossRefGoogle Scholar
  43. Ramesh RV, Subramanian, Van Grieken R (1990) Heavy metal distribution in sediments of Krishna river basin, India. Environ Geol Water Sci 19(3):207–216CrossRefGoogle Scholar
  44. Rao KL (1979) India’s water wealth. Orient Longman, New Delhi, p 276Google Scholar
  45. Rengarajan R, Sarin MM (2004) Distribution of rare earth elements in the Yamuna and the Chambal rivers, India. Geochem J 38(6):551–569CrossRefGoogle Scholar
  46. Rudnik RL, Gao S (2003) Composition of the continental crust. In: Drever JI, Holland HD, Turekian KK (eds) Surface and groundwater, weathering, erosion and soils, vol 5. Treatise on geochemistry. Pergamon, New YorkGoogle Scholar
  47. Seto M, Akagi T (2008) Chemical condition for the appearance of a negative Ce anomaly in stream waters and groundwaters. Geochem J 42:371–380CrossRefGoogle Scholar
  48. Sharma A, Rajmani V (2000) Weathering of gneissic rocks in the upper reaches of Cauvery River, south India: implications to neotectonics of the region. Chem Geol 166:203–223CrossRefGoogle Scholar
  49. Shiller AM (1997) Dissolved trace elements in the Mississippi River: seasonal, interannual, and decadal variability. Geochim Cosmochim Acta 61:4321–4330CrossRefGoogle Scholar
  50. Shiller AM (2002) Seasonality of dissolved rare earth elements in the lower Mississippi River. Geochem Geophys Geosyst 3(11):1–14CrossRefGoogle Scholar
  51. Shiller AM (2010) Dissolved rare earth elements in a seasonally snow-covered, alpine/subalpine watershed, Loch Vale, Colorado. Geochim Cosmochim Acta 74:2040–2052CrossRefGoogle Scholar
  52. Shiller AM, Mao L (2000) Dissolved vanadium in river water: effect of silicate weathering. Chem Geol 165:13–22CrossRefGoogle Scholar
  53. Sholkovitz ER (1995) The aquatic chemistry of rare earth elements in rivers and estuaries. Aquat Chem 1:1–34Google Scholar
  54. Sholkovitz ER, Copland D (1982) The chemistry of suspended matter in estuary water, a biologically productive lake with seasonally anoxic hypolimnion. Geochim Cosmochim Acta 46:393–410CrossRefGoogle Scholar
  55. Sigg L (1985) Metal transfer mechanisms in lakes; the role of settling particles. In: Chemical processes in lakes. Wiley, New York, pp 283–310 (ed. W. Stumm)Google Scholar
  56. Stroh P T, Monrad J R, Fullagar P D, Naqvi S M, Hussain S M and Rogers JJW, (1983) 3000 MY old Halekote trondhjemite: a record of stabilization of the Dharwar craton. In: Naqvi SM, Rogers JJW (eds) Precambrian of South India: Geological Society of India Memorandum 4, 365–376Google Scholar
  57. Stummeyer J, Marchig V, Knabe W (2002) The composition of suspended matter from Ganges-Brahmaputra sediment dispersal system during low sediment transport season. Chem Geol 185:125–147CrossRefGoogle Scholar
  58. Subramanian V, Biksham G, Ramesh R (1987) Environmental geology of peninsular river basins of India. J Geol Soc India 29:205–220Google Scholar
  59. Sudhir K, Jose G, Prakasha H C, Gowda J N A (2006) Organic carbon status of a laterite and a red soil under long term rice cultivation in Karnataka, India. 18th World Congress of Soil Science, July 9–15, 2006 Philadelphia, Pennsylvania, USAGoogle Scholar
  60. Taylor P N, Moorbath S, Chadwick B, Ramakrishnan M and Viswanatha M N (1984) Petrography, chemistry and isotopic ages of Peninsular Gneiss, Dharwar acid volcanic rocks and the Chitradurga Granite with special reference to the late Archean evolution of the Karnataka Craton, southern India. Precambrian Research, 23, 349-375Google Scholar
  61. Tessier A, Fortin D, Belzile N, Devitre BR (1996) Metal sorption to diagenetic iron and manganese oxyhydroxides and associated organic matter: narrowing the between field and laboratory measurements. Geochim Cosmochim Acta 60:387–404CrossRefGoogle Scholar
  62. Tosiani T, Loubet M, Viers J, Yanes C, Dupré B, Tapia J (2004) Major and trace elements in river borne materials from the Cuyuni Basin (southern Venezuela): evidence for organo-colloidal control on the dissolved load and elemental redistribution between the dissolved and suspended load. Chem Geol 211(3–4):305–334CrossRefGoogle Scholar
  63. Tripti M, Gurumurthy GP, Balakrishna K, Chadaga MD (2013a) Dissolved trace element biogeochemistry of a tropical river. Southwest India Environ Sci Pollut Res 20(6):4067–4077CrossRefGoogle Scholar
  64. Tripti M, Lambs L, Otto T, Gurumurthy GP, Teisserenc R, Moussa I, Balakrishna K, Probst JL (2013b) First assessment of water and carbon cycles in two tropical coastal rivers of south-west India: an isotopic approach. Rapid Commun Mass Spectrom 27:1681–1689CrossRefGoogle Scholar
  65. Trumbore SE, Chadwick O, Amundson A (1996) Rapid exchange between soil carbon and atmospheric carbon dioxide driven by temperature change. Science 272:393–396CrossRefGoogle Scholar
  66. van den Berg CM, Merks AG, Duursma EK (1987) Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary. Estuar Coast Shelf Sci 24(6):785–797CrossRefGoogle Scholar
  67. Vasyukova E, Pokrovsky OS, Viers J, Dupré B (2012) New operational method of testing colloid complexation with metals in natural waters. Appl Geochem 27(6):1226–1237CrossRefGoogle Scholar
  68. Viers J, Dupré B, Braun J-J, Deberdt S, Angeletti B, NdamNgoupayou J, Michard A (2000) Major and trace element abundances, and strontium isotopes in the Nyong basin rivers (Cameroon): constraints on chemical weathering processes and element transport mechanisms in humid tropical environments. Chem Geol 169:211–241CrossRefGoogle Scholar
  69. Viers J, Dupré B, Gaillardet J (2009) Chemical composition of suspended sediments in world rivers: new insights from a new database. Sci Total Environ 407(2):853–868CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • G. P. Gurumurthy
    • 1
  • K. Balakrishna
    • 2
    Email author
  • M. Tripti
    • 2
  • Stéphane Audry
    • 3
  • Jean Riotte
    • 3
    • 4
  • J. J. Braun
    • 3
    • 4
  • H. N. Udaya Shankar
    • 2
  1. 1.Manipal Centre for Natural SciencesManipal UniversityManipalIndia
  2. 2.Department of Civil Engineering, Manipal Institute of TechnologyManipal UniversityManipalIndia
  3. 3.GET UMR 5563Université Paul Sabatier, IRD and CNRSToulouseFrance
  4. 4.Indo-French Cell for Water Sciences, Joint IRD-IISc LaboratoryIndian Institute of ScienceBangaloreIndia

Personalised recommendations