Skip to main content
Log in

Mobility of 2,4-Dichlorophenoxyacetic Acid, Glyphosate, and Metribuzine Herbicides in Terra Rossa-Amended Soil: Multiple Approaches with Experimental and Mathematical Modeling Studies

  • Published:
Water, Air, & Soil Pollution Aims and scope Submit manuscript

Abstract

2,4-Dichlorophenoxyl acetic acid (2,4-D), glyphosate, and metribuzine are used extensively as an herbicide in the vicinity of Antalya, Turkey. The objective of this study was to investigate the mobility of such herbicides in terra rossa-amended soil by multiple approaches with batch, miscible-displacement, and mathematical modeling studies. The results indicated that the sorption isotherms exhibited predominantly linear behavior over a wide range (0–100 mg/L) of selected herbicides. The average distribution coefficient (Kd) obtained from linear sorption isotherm was 0.95, 1.20, and 44.15 L/kg for 2,4-D, metribuzine, and glyphosate, respectively. After hydrogen peroxide treatment for eliminating organic carbon content in the soil, the average distribution coefficient (Kd) obtained from the linear sorption isotherm was 0.096, 0.118, and 4.37 L/kg for 2,4-D, metribuzine, and glyphosate, respectively. Miscible-displacement experiments also showed that the sorption of 2,4-D, metribuzine, and glyphosate was described by linear and rate-limited processes in the soil. Transport of metribuzine and 2,4-D was slightly but glyphosate was extensively delayed compared to non-reactive tracer experiments in the soil. Hydrogen peroxide treatment experiments also indicated that the organic carbon content was responsible for the non-ideal sorption behavior of such herbicides. The rapid desorption can be attributed to soft carbon fraction (humic/fluvic acid and lipids), whereas slower desorption can be responsible by hard carbon fraction (black carbon, kerogen) of soils that led to chemically non-ideal behavior. Two-site transport modeling analyses, including linear sorption and rate-limited sorption–desorption, provided a reasonably good match to the herbicide breakthrough curves indicating mathematical modeling results were generally consistent with the results obtained from the batch and column experiments. As a result, sorption of 2,4-D and metribuzine onto terra rossa-amended soil was low which could lead to contamination risk of karstic groundwater resources overlying the Antalya travertine plateau in the region. On the other hand, glyphosate exhibits much more sorption affinity in the soil and leaching risk is limited as with more delay. As a result, investigating the mobility of such herbicides in top soils overlying the karstic aquifer systems in Antalya would be very important to identify the contamination risk of groundwater resources. The results from the present study would also help in the design of effective herbicide management strategies in Antalya, Turkey.

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
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • Accinelli, C., Koskinen, W. C., Seebinger, J. D., Vicari, A., & Sadowsky, M. J. (2005). Effects of incorporated corn residues on glyphosate mineralization and sorption in soil. Journal of Agricultural and Food Chemistry, 53, 4110–4117.

    CAS  Google Scholar 

  • Adams, A.R., 2014. The degradation of atrazine by soil minerals: effects of drying mineral surfaces. Master of Science in the Faculty of Agrisciences at Stellenbosch University.

  • Akyol, N. H. (2015). Characterizing and modeling of extensive atrazine elution tailing for stable manure amended soil. Chemosphere, 119, 1027–1032.

    CAS  Google Scholar 

  • Akyol, N. H., Ozbay, I., & Ozbay, B. (2015). Effect of organic carbon fraction on long-term atrazine elution tailing for two heterogeneous porous media: experimental and modeling approach. Water, Air, and Soil Pollution, 226, 368.

    Google Scholar 

  • Akyol, N. H., Yolcubal, I., & Imer, D. (2011). Sorption and transport of trichloroethylene in caliche soil. Chemosphere, 82, 809–1816.

    CAS  Google Scholar 

  • Akyol, N. H., & Yolcubal, I. (2013). Oxidation of nonaqueous phase trichloroethylene with permanganate in epikarst. Water, Air, and Soil Pollution, 224(1573), 1–19.

    Google Scholar 

  • Albers, C. N., Banta, G. T., Hansen, P. E., & Jacobsen, O. S. (2009). The influence of organic matter on sorption and fate of glyphosate in soil—comparing different soils and humic substances. Environmental Pollution, 157, 2865–2870.

    CAS  Google Scholar 

  • Allison, L. E. (1965). Organic carbon. In C. A. Black (Ed.), Methods of analysis, part 2, chemical and microbiological properties # 9 (pp. 1367–1378). Madison: American Society of Agronomy.

    Google Scholar 

  • Al-Rajab, A. J., Amellal, S., & Schiavon, M. (2008). Sorption and leaching of 14C-glyphosate in agricultural soils. Agronomy for Sustainable Development, 28, 419–428.

    CAS  Google Scholar 

  • Altunbas, S., & Sarı, M. (2009). The relationships of iron contents between Red Mediterranean soils and its parent material in Antalya province, Turkey. Akdeniz Üniversitesi Ziraat Fakültesi Dergisi, 22(1), 15–21.

    Google Scholar 

  • Beltran, J., Gerritse, R. G., & Hernandez, F. (1998). Effect of flow rate on the adsorption and desorption of glyphosate, simazine and atrazine in columns of sandy soils. European Journal of Soil Science, 49, 149–156.

    CAS  Google Scholar 

  • Boivin, A., Amellal, S., Schiavon, M., & Genuchten, M. T. V. (2005). 2,4-Dichlorophenoxyacetic acid (2,4-D) sorption and degradation dynamics in three agricultural soils. Environmental Pollution, 138, 92–99.

    CAS  Google Scholar 

  • Borggaard, O. K., & Gimsing, A. L. (2008). Fate of glyphosate in soil and the possibility of leaching to ground and surface waters: a review. Pest Management Science, 64, 441–456.

    CAS  Google Scholar 

  • Carroll, K. C., Artiolla, J., & Brusseau, M. L. (2006). Transport of molybdenum in a biosolid-amended alkaline soil. Chemosphere, 65, 775–785.

    Google Scholar 

  • Cengiz, M. F., Basancelebi, O., & Kitis, Y. E. (2017). Glyphosate residues in drinking waters and adverse health effects. The Turkish Journal of Occupational/Environmental Medicine and Safety, 2, 247–252.

    Google Scholar 

  • Chakravarty, S, 2014. World agrochemical and pesticide market to grow 8.7% annually from 2014 to 2018. http://www.marketresearchreports.com/blog/2014/01/06/world-agrochemical-andpesti-cide-market-grow-87-annually-2014-2018#sthash.Ah9mn8eN.dpuf.

  • Clausen, L., & Fabricius, I. (2001). Atrazine, isoproturon, mecoprop, 2,4-D and bentazone adsorption onto iron oxides. Journal of Environmental Quality, 30(3), 858–869.

    CAS  Google Scholar 

  • Clausen, L., Fabricius, I., & Madsen, L. (2001). Adsorption of pesticides onto quartz, calcite, kaolinite and alpha-alumina. Journal of Environmental Quality, 30(3), 846–857.

    CAS  Google Scholar 

  • Da Cruz, L. H., de Santana, H., Zaia, C. T. B. V., & Zaia, D. A. M. (2007). Adsorption of glyphosate on clays and soils from Paraná State: effect of pH and competitive adsorption of phosphate. Brazilian Archives of Biology and Technology, 50, 385–394.

    Google Scholar 

  • Damonte, M., Torres Sanchez, R. M., & Dos Santos Afonso, M. (2007). Some aspects of the glyphosate adsorption on montmorillonite and its calcined form. Applied Clay Science, 36, 86–94.

    CAS  Google Scholar 

  • Daniel, P. E., Bedmar, F., Costa, J. L., & Aparicio, V. C. (2002). Atrazine and metribuzin sorption in soil of the Argentinean humid pampas. Environmental Toxicology and Chemistry, 21(12), 2567–2572.

    CAS  Google Scholar 

  • De Jonge, H., & De Jonge, L. W. (1999). Influence of pH and solution composition on the sorption of glyphosate and prochloraz to a sandy loam soil. Chemosphere, 39, 753.

    Google Scholar 

  • De Jonge, H., De Jonge, L. W., Jacobsen, O. H., Yamaguchi, T., & Moldrup, P. (2001). Glyphosate sorption in soils of different pH and phosphorus content. Soil Science, 166, 230–238.

    Google Scholar 

  • Dollinger, J., Dage’s, C., & Voltz, M. (2015). Glyphosate sorption to soils and sediments predicted by pedotransfer functions. Environmental Chemistry Letters, 13, 293–307.

    CAS  Google Scholar 

  • Dousset, S., Jacobson, A. R., Dessogne, J. B., Guichard, N., Baveye, P. C., & Andreux, F. (2007). Facilitated transport of diuron and glyphosate in high copper vineyard soils. Environmental Science & Technology, 41, 8056–8061.

    CAS  Google Scholar 

  • Dubus, I. G., Barriuso, E., & Calvet, R. (2001). Sorption of weak organic acids in soils: clofencet, 2,4-D and salicylic acid. Chemosphere, 45, 767–774.

    CAS  Google Scholar 

  • Duchaufour, P. (1976). Dynamics of organic matter in soils of temperate regions: its action on pedogenesis. Geoderma, 15(1), 31–40.

    Google Scholar 

  • Farenhorst, A., Papiernik, S. K., Saived, I., Messing, P., Stephens, K. D., Schumacher, J. A., Lobb, D. A., Li, S., Lindstrom, M. J., & Schumacher, T. E. (2008). Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie. Journal of Environmental Quality, 37(3), 1201–1208.

    CAS  Google Scholar 

  • Gamerdinger, A.P., & Kaplan, D.I. (2001). Physical and chemical determinants of colloid transport and deposition in waterunsaturated sand and Yucca Mountain tuff material. Environmental Science & Technology 35, 2497–2504.

  • Gamerdinger, A. P., Kaplan, D. I., Wellman, D. M., & Serne, R. J. (2001). Two-region flow and decreased sorption of uranium (VI) during transport in Hanford groundwater and unsaturated sands. Water Resources Research, 37, 3155–3162.

    CAS  Google Scholar 

  • Gaultier, J., Farenhorst, A., & Crow, G. (2006). Spatial variability of soil properties and 2,4-D sorption in a hummocky field as affected by landscape position and soil depth. Canadian Journal of Soil Science, 86(1), 89–95.

    CAS  Google Scholar 

  • Geronimo, E. D., Aparicio, V. C., & Costa, J. I. (2018). Glyphosate sorption to soils of Argentina. Estimation of affinity coefficient by pedotransfer function. Geoderma, 322, 140–148.

    Google Scholar 

  • Gimsing, A. L., & Borggaard, O. K. (2002). Competitive adsorption and desorption of glyphosate and phosphate on clay silicates and oxides. Clay Minerals, 37, 509–515.

    CAS  Google Scholar 

  • Gimsing, A. L., Borggaard, O. K., & Bang, M. (2004). Influence of soil composition on adsorption of glyphosate and phosphate by contrasting Danish surface soils. European Journal of Soil Science, 55, 183–191.

    CAS  Google Scholar 

  • Gimsing, A. L., Szilas, C., & Borggaard, O. K. (2007). Sorption of glyphosate and phosphate by variable-charge tropical soils from Tanzania. Geoderma, 138, 127–132.

    CAS  Google Scholar 

  • Goss, K. U. (1992). Effects of temperature and relative humidity on the sorption of organic vapors on quartz sand. Environmental Science & Technology, 26(11), 2287–2294.

    CAS  Google Scholar 

  • Gurson, A.P., 1999. Su sorunu ve GAP çerçevesinde Türkiye-Suriye ilişkilerine analitik yaklaşım, İstanbul Üniversitesi Sosyal Bilimler Enstitüaü, Yüksek Lisanz Tezi, 177 s.

  • Hu, M. Q., & Brusseau, M. L. (1998). Coupled effects of nonlinear rate-limited sorption and biodegradation on transport of 2,4-dichlorophenoxyacetic acid in soil. Environmental Toxicology and Chemistry, 17, 1673–1680.

    CAS  Google Scholar 

  • Hutchison, J. M., Seaman, J. C., Aburime, S. A., & Radcliffe, D. E. (2003). Chromate transport and retention in variably saturated soil columns. Vadose Zone Journal, 2, 702–714.

    CAS  Google Scholar 

  • Karagüzel, R., Scholz, R., & Ebel, B. (1999). Hydrogeological investigation of Antalya basin concerning the future domestic water needs of Antalya City (Turkey). Environmental Geology, 38(2), 159–167.

    Google Scholar 

  • Kasozi, G. N., Nkeddi-Kizza, Li, Y., & Zimmerman, A. R. (2012). Sorption of atrazine and ametryn by carbonatic and non-carbonatic soils of varied origin. Environmental Pollution, 169, 12–19.

    CAS  Google Scholar 

  • Kaymak, S., & Serim, A. T. (2015). Pestisit Sektöründe Araştırma ve Geliştirme. Fruit Science, 2, 27–34.

    Google Scholar 

  • Kempf, A., & Brusseau, M. L. (2009). Impact of non-ideal sorption on low-concentration tailing behavior for transport in two natural porous media. Chemosphere, 77, 877–882.

    CAS  Google Scholar 

  • Koleli, N., Kantar, C., Cuvalci, U., & Yılmaz, H. (2006). Movement and adsorption of methamidophos in clay loam and sandy loam soil. International Journal of Environmental Analytical Chemistry, 86, 1127–1134.

    CAS  Google Scholar 

  • Koleli, N., Demir, A., Eke, M., & Kayışoğlu, N. G. (2010). Topraktaki kadmiyum taşınımına ahır gübresinin etkisi. Biyoloji Bilimleri Araştırma Dergisi, 3, 99–104.

    Google Scholar 

  • Kovaios, I. D., Paraskeva, C. A., Koutsoukos, P. G., & Payatakes, A. C. (2006). Adsorption of atrazine on soils: model study. Journal of Colloid and Interface Science, 299, 88–94.

    CAS  Google Scholar 

  • Lin, K. H., Yen, J. H., & Wang, Y. S. (1997). Accumulation and elimination kinetics of herbicides Butachlor, Thiobencarb and Chlomethoxyfen by Aristichthys nobilis. Pesticide Science, 49, 178–184.

    CAS  Google Scholar 

  • Mamy, L., & Barriuso, E. (2005). Glyphosate adsorption in soils compared to herbicides replaced with the introduction of glyphosate resistant crops. Chemosphere, 61, 844–855.

    CAS  Google Scholar 

  • Maraqa, M. A., Wallace, R. B., & Voice, T. C. (1999). Effects of residence time and degree of water saturation on sorption nonequilibrium parameters. Journal of Contaminant Hydrology, 36, 53–72.

    CAS  Google Scholar 

  • Morillo, E., Undabeytia, T., Maqueda, C., & Ramos, A. (2000). Glyphosate adsorption on soils of different characteristics. Influence of copper addition. Chemosphere, 40, 103–107.

    CAS  Google Scholar 

  • Morrica, P., Barbato, F., Giordano, A., Seccia, S., & Ungaro, F. (2000). Adsorption and desorption of imazosulfuron by soil. Journal of Agricultural and Food Chemistry, 48(12), 6132–6137.

    CAS  Google Scholar 

  • Mudhoo, A., & Garg, V. K. (2011). Sorption, transport and transformation of atrazine in soils, minerals and composts: a review. Pedosphere, 21(1), 11–25.

    CAS  Google Scholar 

  • Munira, S., Farenhorst, A., & Akinremi, A. (2018). Phosphate and glyphosate sorption in soils following long-term phosphate applications. Geoderma, 313, 146–153.

    CAS  Google Scholar 

  • Olalade, I. A., Alomaja, F., Oladaja, N. A., Olalade, O. O., & Oleye, F. F. (2015). Kinetics and isotherm analysis of 2,4-dichlorophenoxyl acetic acid adsorption onto soil components under oxic and anoxic conditions. Journal of Environmental Science and Health. Part. B, 50, 492–503.

    Google Scholar 

  • Ololade, I. A., Oladoja, N. A., Oloye, F. F., Alomaja, F., Akerele, D. D., Iwaye, J., & Aikpokpodion, P. (2014). Sorption of glyphosate on soil components: the roles of metal oxides and organic materials. Soil and Sediment Contamination, 23, 571–585.

    CAS  Google Scholar 

  • Ozbay, B., Akyol, N. H., Akyol, G., & Ozbay, İ. (2018). Sorption and desorption behaviours of 2,4-D and glyphosate in calcareous soil from Antalya, Turkey. Water Environment Journal, 32, 141–148.

    CAS  Google Scholar 

  • Pan G., Ran W., Yuan D., 1993. Red soils in the karst region s.w. China. 2nd International meeting on Red Mediterranean soils, 6–8.

  • Pessagno, R. C., Sanchez, R. M. T., & Afonso, M. D. S. (2008). Glyphosate behavior at soil and mineral-water interfaces. Environmental Pollution, 153, 53–59.

    CAS  Google Scholar 

  • Pineiro, A.L., Pena, D., Albarran, A., Becerra, D., Llerena, J.S., (2013). Sorption, leaching and persitance of metribuzine in Mediterranean soils amended with olive mill waste of different degrees of organic matter maturity, Journal of Environmental Management, 122, 76–84.

    Google Scholar 

  • Porro, I., Newman, M. E., & Dunnivant, F. M. (2000). Comparison of batch and column methods for determining strontium distribution coefficients for unsaturated transport in basalt. Environmental Science & Technology, 34, 1679–1686.

    CAS  Google Scholar 

  • Pusino, A., Petretto, S., & Gessa, C. (2004). Sorption of primisulfuron on soil, and inorganic and organic soil colloids. European Journal of Soil Science, 55, 175–182.

    CAS  Google Scholar 

  • Rigi, M. R., Farahbakhsh, M., & Rezaei, K. (2015). Use of solid phase extraction with hydrophilic-lipophilic balance (HLB) cartridge as the appropriate option for metribuzin extraction from contaminated soils. Journal of the Brazilian Chemical Society, 26(1), 156–164.

    CAS  Google Scholar 

  • Russo, A., Johnson, G. R., Schnaar, G., & Brusseau, M. L. (2010). Non-ideal transport of contaminants in heterogeneous porous media: 8. Characterizing and modeling asymptotic contaminant-elution tailing for several soils and aquifer sediments. Chemosphere, 81, 366–371.

    CAS  Google Scholar 

  • Simunek, J., Van Genuchten, M.T.H., Sejna, M., Toride, N., Leij, F.J., 1999. Studio of analytical models for solving convection–dispersion equation (STANMOD). Version 2.2. USDA–ARS. US Salinity Lab., Riverside, CA.

  • Spark, K. M., & Swift, R. S. (2002). Effect of soil composition and dissolved organic matter on pesticide sorption. Science of the Total Environment, 298, 147–161.

    CAS  Google Scholar 

  • Toride, N., Leij, F.J., Van Genuchten, M.T.H., 1995. The CXTFIT code for estimating transport parameters from laboratory or field tracer experiments. Version 2.1. Research report. 137. USDA–ARS. US Salinity Lab., Riverside, CA.

  • Van Genuchten, M. T. (1981). Analytical solutions for chemical transport with simultaneous adsorption, zero-order production and first-order decay. Journal of Hydrology, 49, 213–233.

    Google Scholar 

  • Van Genuchten, M. T. H., & Parker, J. C. (1984). Boundary conditions for displacement experiments through short laboratory soil columns. Soil Science Society of America Journal, 48, 703–708.

    Google Scholar 

  • Vasudevan, D., Cooper, E. M., & Exem, O. L. V. (2002). Sorption-desorption of ionogenic compounds at the mineral-water interface: study of metal oxide-rich soils and pure-phase minerals. Environmental Science & Technology, 36, 501–511.

    CAS  Google Scholar 

  • Wang, Y., Zhou, D., & Sun, R. (2005). Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils. Journal of Environmental Sciences, 17, 711–715.

    Google Scholar 

  • Xu, D., Meyer, S., Gaultier, J., Farenhorst, A., & Pennock, D. (2009). Land use and riparian effects on prairie wetland sediment properties and herbicide sorption coefficients. Journal of Environmental Quality, 38, 1757–1765.

    CAS  Google Scholar 

  • Yolcubal, İ., & Akyol, N. H. (2008). Adsorption and transport of arsenate in carbonate-rich soils: coupled effects of nonlinear and rate-limited sorption. Chemosphere, 73, 1300–1307.

    CAS  Google Scholar 

  • Zhou, D. M., Wang, Y. J., Cang, L., Hao, X. Z., & Luo, X. S. (2004). Adsorption and cosorption of cadmium and glyphosate on two soils with different characteristics. Chemosphere, 57, 1237–1244.

    CAS  Google Scholar 

Download references

Acknowledgments

This research was supported by the Kocaeli University Research Funds (KOU-2018-140 and KOU-2016-063). We also thank anonymous reviewers for their constructive comments.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Nihat Hakan Akyol.

Additional information

Publisher’s Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gurson, A.P., Ozbay, I., Ozbay, B. et al. Mobility of 2,4-Dichlorophenoxyacetic Acid, Glyphosate, and Metribuzine Herbicides in Terra Rossa-Amended Soil: Multiple Approaches with Experimental and Mathematical Modeling Studies. Water Air Soil Pollut 230, 220 (2019). https://doi.org/10.1007/s11270-019-4266-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11270-019-4266-y

Keywords

Navigation