Chemical effect of pesticide application on soils: evidence from rare earth elements

  • Khadija SemhiEmail author
  • Joëlle Duplay
  • Gwenaël Imfeld
  • René Boutin
Original Paper


The main objective of this study is to investigate the distribution of rare earth elements (REEs) in Lolium perenne L. plant species which has been grown on vineyard soils treated with pesticide commonly used in the study area. These plants have been grown on two types of soils: (1) brown calcareous soils developed on loess and (2) brown to calcic brown soils developed on conglomerates. The significant correlation observed between the concentrations of phosphorus and the total amount of REEs, in addition to the enrichment in middle REEs (MREEs), suggests the complexation of REEs with phosphates and organic matter. The soils were enriched in REEs due to pesticide application but the plants were depleted. The ratio of REEs in plant over REEs in soil before application of pesticides is higher than that after application of pesticides. Application of pesticides to crops did not affect the fractionation of REEs neither in leaves nor in roots. No selectivity in uptake of REEs occurred because of pesticides except for Ce and Eu which show a negative anomaly relative to the other REEs.


Rare earth elements Fractionation Grass Soil Pesticides 



The authors wish to thank the Agricultural and Viticulture College of Rouffach, the farmers of the Hohrain domain, Rouffach (France), and F. Huber, A. Aubert, and J.L. Cézard from the mineralogy laboratory of LHYGES. The authors would also like to thank the anonymous reviewer for his constructive comments.

Funding information

This research was funded by the Research Program EC2CO (CNRS-INSU).


  1. Aide MT, Aide C (2012) Rare earth elements: their importance in understanding soil genesis. ISRN Soil Science. 2012, 11 pagesGoogle Scholar
  2. Añasco N, Uno S, Koyama J, Matsuoka T, Kuwahara N (2010) Assessment of pesticide residues in freshwater areas affected by rice paddy effluents in southern Japan. Environ Monit Assess 160(1):371–383CrossRefGoogle Scholar
  3. Arias-Estévez M, López-Periago E, Martínez-Carballo E, Simal-Gándara J, Mejuto J-C, García-Río L (2008) The mobility and degradation of pesticides in soils and the pollution of groundwater resources. Agric Ecosyst Environ 123(4):247–260CrossRefGoogle Scholar
  4. Babcsányi I, Imfeld G, Duplay J, Chabaux F (Paper in preparation) Copper stable isotopes to evaluate copper in soils and runoff in vineyardsGoogle Scholar
  5. Bhupander K, Richa G, Gargi G, Meenu M, Kumar SS, Dev P, Sanjay K, Sekhar SC (2011) Residues of pesticides and herbicides in soils from agriculture areas of Delhi Region, India. J Environ Earth Sci 1(2) 9 pagesGoogle Scholar
  6. Carlos G, Joaquin Ramos-Miras J, Rodríguez Martín JA, Boluda R, Roca N, Bech Jaume (2013) EGU general assembly 2013, held 7-12 April, in Vienna, Austria, id EGU2013–7419Google Scholar
  7. Censi P, Saiano F, Pisciotta A, Tuzzolino N (2014) Geochemical behaviour of rare earths in Vitis vinifera grafted onto different rootstocks and growing on several soils. Sci Total Environ 473–474:597–608CrossRefGoogle Scholar
  8. Cullers R, Chaudhuri S, Kilbane N, Koch R (1979) Rare-earths in size fractions and sedimentary rocks of Pennsylvanian-Permian age fromthe mid-continent of the U.S.A. Geochim Cosmochim Acta 43(8):1285–1301CrossRefGoogle Scholar
  9. Dawson AH, Eddleston M, Senarathna L, Mohamed F, Gawarammana I, Bowe SJ, Manuweera G, Buckley NA (2010) Acute human lethal toxicity of agricultural pesticides: a prospective cohort study. PLoS Med 7:e1000357CrossRefGoogle Scholar
  10. Delgado J, Pérez-López R, Galván L, Nieto JM, Boski T (2012) Enrichment of rare earth elements as environmental tracers of contamination by acid mine drainage in salt marshes: a new perspective. Mar Pollut Bull 64:1799–1808CrossRefGoogle Scholar
  11. Ding S, Liang T, Zhang C, Yan J, Zhang Z, Sun Q (2005a) Role of ligands in accumulation and fractionation of rare earth elements in plants. Examples of phosphate and citrate. Biol Trace Elem Res 107(1):73–86CrossRefGoogle Scholar
  12. Ding S, Liang T, Zhang C, Yan J, Zhang Z (2005b) Accumulation and fractionation of rare earth elements (REEs) in wheat: controlled by phosphate precipitation, cell wall absorption and solution complexation. J Exp Bot 56(420):2765–2775CrossRefGoogle Scholar
  13. Ding S, Liang T, Yan J, Zhang Z, Zechun H, Yaning X (2007) Fractionations of rare earth elements in plants and their conceptive model. Sci China Ser C Life Sci 50:47–55 (in Chinese)CrossRefGoogle Scholar
  14. Duplay J, Semhi K, Errais E, Imfeld G, Babcsanyi I, Perrone T (2014) Copper, zinc, lead and cadmium bioavailability and retention in vineyard soils (Rouffach, France): the impact of cultural practices. Geoderma 230–231:318–328CrossRefGoogle Scholar
  15. El- Saeid MH, Al- Turki AM, Al- Wable MI, Abdel- Nasser G (2011) Evaluation of pesticide residues in Saudi Arabia ground water. Res J Environ Sci 5(2):171–178CrossRefGoogle Scholar
  16. García Gimeno E, Andreu V, Boluda R (1996) Heavy metals incidence in the application of inorganic fertilizers and pesticides to rice farming soils. Environ Pollut 92(1):19–25CrossRefGoogle Scholar
  17. Gigliotti C, Allievi L (2001) Differential effects of the herbicides Bensulphuron and Cinosulphuron on soil microorganisms. J Environ Sci Health B 36(6):775–782CrossRefGoogle Scholar
  18. Govindaraju K, Roelandst I (1993) Second report on the first three GIT-IWG rock reference samples; anorthosite from Greenland, AN-G; basalte d’Essay-la-Cote, Be-N; granite de Beauvoir, MA-N. Geostand Newslett 17(2):227–294CrossRefGoogle Scholar
  19. Gregoire C, Payraudeau S, Domange N (2010) Use and fate of 17 pesticides at the catchment scale. Int J Environ Anal Chem 90(3–6):406–420. CrossRefGoogle Scholar
  20. Hughes JM (1994) Refinement of the structure of gagarinite-(Y)Na, (Cax,REEx-2) F6. Can Mineral 32:563–565Google Scholar
  21. IUSS Working Group WRB (2006) World reference base for soil resources. World Soil Resources Reports. FAO, Rome, p 103Google Scholar
  22. Johannesson KH, Stetzenbach KJ, Hodge VF (1996) Rare earth element complexation behavior in circumneutral pH groundwaters: assessing the role of carbonate and phosphate ions. Earth Planet Sci Lett 139(1–2):305–319CrossRefGoogle Scholar
  23. Johannesson KH, Chevis DA, Burdige DJ, Cable JE, Martin JB, Roy M (2011) Submarine groundwater discharge is an important net source of light and middle REEs to coastal waters of the Indian River Lagoon, Florida, USA. Geochim Cosmochim Acta 75:825–843CrossRefGoogle Scholar
  24. Kastori RR, Maksimovic IV, Zeremski-Skoric TM, Putnik-Delic MI (2010) Rare earth elements—yttrium and higher plants. Zbornik Matice srpske za prirodne nauke 118:87–98CrossRefGoogle Scholar
  25. Köhler H-R, Triebskorn R (2013) Wildlife ecotoxicology of pesticides: can we track effects to the population level and beyond? Science 341:759–765CrossRefGoogle Scholar
  26. Krneta S, Ciobanu CL, Cook NJ, Ehrig K, Kontonikas-Charos A (2017) Rare earth element behaviour in apatite from the Olympic Dam Cu–U–Au–Ag deposit, South Australia. Minerals 2017(7):135. CrossRefGoogle Scholar
  27. Lepland A, Arrhenius G, Cornell CD (2002) Apatite in early Archean Isua supracrustal rocks, southern West Greenland: its origin, association with graphite and potential as a biomarker. Precambrian Res 118(2002):221/241Google Scholar
  28. Liang T, Zhang S, Wang L, Kung HT, Wang Y, Hu A, Ding S (2005) Environmental biogeochemical behaviors of rare earth elements in soil-plant system. Environ Geochem Health 27:301–311CrossRefGoogle Scholar
  29. Liang T, Ding S, Song W, Chong Z, Zhang C, Li H (2008) A review of fractionations of rare earth elements in plants. J Rare Earths 26:7–15CrossRefGoogle Scholar
  30. Liebich J, Schäffer A, Burauel P (2003) Structural and functional approach to studying pesticide side-effects on specific soil functions. Environ Toxicol Chem 22(4):784–790CrossRefGoogle Scholar
  31. Lima e Cunha MC, Pereira VP, Stoll Nardi LV, Bastos Neto AC, Vedana LA, Formoso MLL (2012) REE distribution pattern in plants and soils from Pitinga Mine—Amazon, Brazil. Open J Geol 2:253–259Google Scholar
  32. Luo YR, Byrne RH (2004) Carbonate complexation of yttrium and the rare earth elements in natural waters. Geochim Cosmochim Acta 68:691–699CrossRefGoogle Scholar
  33. Lutz SR, van der Velde Y, Elsayed OF, Imfeld G, Lefrancq M, Payraudeau S, van Breukelen BM (2017) Pesticide fate on catchment scale: conceptual modelling of stream CSIA data. Hydrol Earth Syst Sci 21:5243–5261CrossRefGoogle Scholar
  34. Matini L, Ossebi JG, MBedi R, Moutou JM (2012) Rare earth elements in soil on spoil heap of an abandoned lead ore treatment plant in the District of Mfouati, Congo-Brazzaville. Int Res J Environ Sci 1(2):33–40Google Scholar
  35. Nyakairu GWA, Koeberl C (2002) Variation of mineral, chemical, and rare earth element composition in size fractions of clay-rich sediments from the Kajjansi and Ntawo clay deposits, central Uganda. Chem Erde 62(1):73–86CrossRefGoogle Scholar
  36. Pal R, Chakrabarti K, Chakraborty A, Chowdhury A (2005) Pencycuron application to soils: degradation and effect on microbiological parameters. Chemosphere 60(11):1513–1522CrossRefGoogle Scholar
  37. Reimann C, Englmaier P, Fabian K, Gough L, Lamothe P, Smith D (2015) Biogeochemical plant–soil interaction: variable element composition in leaves of four plant species collected along a south–north transect at the southern tip of Norway. Sci Total Environ 506–507:480–495CrossRefGoogle Scholar
  38. Rosenbauer RJ, Foxgrover AC, Hein JR, Swarzenski PW (2013) A Sr–Nd isotopic study of sand-sized sediment provenance and transport for the San Francisco Bay coastal system. Mar Geol 345(1):143–153CrossRefGoogle Scholar
  39. Samuel J, Rouault R, Besnus Y (1985) Standardized multi-element analysis of geological material by inductively coupled plasma atomic emission spectrometry and mass spectrometry. Analusis 13:312–317Google Scholar
  40. Semhi k, Chaudhuri S, Clauer N (2009) Fractionation of rare-earth elements in plants during an experimental growth in varied clay substrates. Appl Geochem 24(3):447–453CrossRefGoogle Scholar
  41. Semhi K, Al-Khirbash S, Abdallah O, Khant T, Duplay J, Chaudhuri S, Al-Saidi S (2010) Dry atmospheric contribution to the plant-soil system around a cementfactory: spatial variations and sources—a case study from Oman. Water Air Soil Pollut 205:343–357CrossRefGoogle Scholar
  42. Semhi K, Clauer N, Chaudhuri S (2012) Variable element transfers from an illite-rich substrate to a growing plant during a three-month experiment. Appl Clay Sci 57:17–24CrossRefGoogle Scholar
  43. Senthil Kumar K, Priya M, Sajwan KS, Kolli R, Roots O (2009) Residues of persistent organic pollutants in Estonian soil. Estonian J Earth Sci 58(2):109–123CrossRefGoogle Scholar
  44. Smith BM, Gindhart TD, Colburn NH (1986) Possible involvement of a lanthanide-sensitive protein kinase C substrate in lanthanide promotion of neoplastic transformation. Carcinogenesis 7(12):1949–1956CrossRefGoogle Scholar
  45. Spanoghe P, Maes A, Steurbaut W (2004) Limitation of point source pesticide pollution: results of bioremediation system. Commun Agric Appl Biol Sci 69(4):719–732Google Scholar
  46. Squier TC, Bigelow DJ, Fernandez-Belde FJ et al (1990) Calcium and lanthanide binding in the sarcoplasmic reticulum ATPase. J Biol Chem 265(23):13713–13720Google Scholar
  47. Tang J, Johannesson KH (2010) Ligand extraction of rare earth elements from aquifer sediments: implications for rare earth element complexation with organic matter in natural waters. Geochim Cosmochim Acta 74(23):690–6705CrossRefGoogle Scholar
  48. Tournebize J (2001) Impact of grass cover in Alsacian vineyard on nitrate transfer. MSc Thesis, Louis Pasteur University, Strasbourg, FranceGoogle Scholar
  49. Tournebize J, Gregoire C, Coupe RH, Ackerer P (2012) Modelling nitrate transport under row intercropping system: vines and grass cover. J Hydrol 440-441:14–25CrossRefGoogle Scholar
  50. Tricca A, Stille P, Steinmann M, Kiefel B, Samuel J, Eikenberg J (1998) Rare earth elements and Sr and Nd isotopic compositions of dissolved and suspended loads from small river systems in the Vosges Mountains (France), the River Rhine and groundwater. Chem Geol 160(1):139–158Google Scholar
  51. Tyler G (2004) Rare earth elements in soil and plant systems - a review. Plant Soil 267:191–206CrossRefGoogle Scholar
  52. Viet PH, Hoal PM, Min NH, Ngoc NT, Hung PT (2000) Persistent organochlorine pesticides and polychlorinated biphenyls in some agricultural and industrial areas in northern Vietnam. Water Sci Technol 42(7–8):223–229CrossRefGoogle Scholar
  53. Wang Z, Lu P, Liu D (1997) Initial assessment of the effects of rare earth elements on soil intigrity. In Guicherit R, Zhu W (eds) Proc. of the 2nd Sino–Dutch Workshop on the Environ. Behavior and Ecotoxicology of Rare Earth Elements and Heavy Metals. Oct.. TNO Publ., La Delft, the Netherlands, p 1–5Google Scholar
  54. Weissteiner CJ, Pistocchi A, Marinov D, Bouraoui F, Sala S (2014) An indicator to map diffuse chemical river pollution considering buffer capacity of riparian vegetation—A pan-European case study on pesticides. Sci. Total Environ. 484:64–73CrossRefGoogle Scholar
  55. Wyttenbach A, Furrer V, Schleppi P, Tobler L (1998) Rare earth elements in soil and in soil-grown plants. Plant Soil 199:267–273CrossRefGoogle Scholar
  56. Yusoff ZM, Ngwenya BT, Parsons I (2013) Mobility and fractionation of REEs during deep weathering of geochemically contrasting granites in a tropical setting, Malaysia. Chem Geol 349–350:71–86CrossRefGoogle Scholar
  57. Zaharescu DG, Burghelea CI, Dontsova K, Presler JK, Maier RM, Huxman T, Domanik KJ, Hunt EA, Amistadi MK, Gaddis EE, Palacios-Menendez MA, Vaquera-Ibarra MO and Chorover J (2017) Ecosystem Composition Controls the Fate of Rare Earth Elements during Incipient Soil Genesis. Sci Rep. 7: 43208.
  58. Zhang P, Chi R, Lu S (1997) Study of adsorption of rare earth elements by ferric oxide gel. J Cent S Univ Technol 4(2):96–99CrossRefGoogle Scholar
  59. Zhang ZY, Wang YQ, Li FL, Xiao HQ, Chai ZF (2004) Distribution characteristics of rare earth elements in plants from a rare earth ore area. J Radioanal Nucl Chem 252(3):461–465CrossRefGoogle Scholar
  60. Zhu M-Y, Tan S-D, Liu W-Z, Zhang Q-F (2010) A review of REE tracer method used in soil erosion studies. Agric Sci China 9(8):1167–1174CrossRefGoogle Scholar
  61. Zoffoli HJ, do Amaral-Sobrinho NM, Zonta E, Luisi MV, Marcon G, Tolón-Becerra A (2013) Inputs of heavy metals due to agrochemical use in tobacco fields in Brazil’s southern region. Environ Monit Assess 185(3):2423–2437CrossRefGoogle Scholar

Copyright information

© Saudi Society for Geosciences 2018

Authors and Affiliations

  • Khadija Semhi
    • 1
    Email author
  • Joëlle Duplay
    • 2
  • Gwenaël Imfeld
    • 2
  • René Boutin
    • 2
  1. 1.Department of Earth Sciences, College of ScienceSultan Qaboos UniversityMuscatSultanate of Oman
  2. 2.LHyGeS - UMR 7517 CNRS, EOST / UdSStrasbourgFrance

Personalised recommendations