Wood biochars and vermicomposts from digestate modulate the extent of adsorption-desorption of the fungicide metalaxyl-m in a silty soil

  • Marco Parlavecchia
  • Valeria D’Orazio
  • Elisabetta LoffredoEmail author
Research Article


This study aimed to investigate changes in metalaxyl-M sorption-desorption capacity of soil following the addition of two types of amendments. Two biochars (BC) from grapevine pruning residues (BC-G) and spruce wood (BC-S) and two vermicomposts (VC) obtained vermicomposting digestates from a mixture of manure and olive mill wastewater (VC-M) and buffalo manure (VC-B) were used. Using a batch equilibration method, the materials and a silt loam soil non-amended or amended with each material at 2% (w/w) were interacted with the fungicide at a concentration of 2 mg L−1 for kinetics study and in the range 1–20 mg L−1 for sorption isotherms. Kinetics results showed that metalaxyl-M onto the amendments and non-amended soil followed preferentially a pseudo-second-order model, thus indicating a chemisorption process. Sorption isotherm data of the product on BC and VC fitted well the Freundlich equation, whereas those on non-amended and amended soil followed preferentially a linear model. The KFads values were 995.2, 788.5, 55.2, 52.1, 6.4, 6.0, 3.4, 2.6 and 1.5 L kg−1 for BC-G, BC-S, VC-M, VC-B, soil-BC-G, soil-BC-S, soil-VC-M, soil-VC-B and non-amended soil, respectively. Product desorption from each soil sample occurred to a lesser extent than sorption. Highly significant correlations (P < 0.005) were found between the values of sorption and desorption constants of all adsorbents and organic C content, thus confirming the prominent role of organic matter in the sorption process of metalaxyl-M.


Soil Soil amendment Fungicide adsorption Sorption kinetics Sorption isotherm Desorption pesticide 



This work was founded by University of Bari Aldo Moro, Italy. The authors thank C&F Energy Società Agricola s.r.l., Altavilla Silentina, Italy, for providing the two vermicomposts used in this study. The authors are grateful to the anonymous reviewers for their valuable suggestions.


  1. Alves MR, Landgraf MD, de Rezende O, MO (2001) Sorption and desorption of the herbicide alachlor on humic acid fractions from two vermicomposts. J Environ Sci Health B 36:798–808. CrossRefGoogle Scholar
  2. Andrades MS, Sánchez-Martín MJ, Sánchez-Camazano M (2001) Significance of soil properties in the adsorption and mobility of the fungicide metalaxyl in vineyards soils. J Agric Food Chem 49:2363–2369. CrossRefGoogle Scholar
  3. Atmaca N, Arikan S, Essiz D, Kalender H, Simsek O, Bilmen FS, Kabakci R (2018) Effects of mancozeb, metalaxyl and tebuconazole on steroid production by bovine luteal cells in vitro. Environ Toxicol Pharmacol 59:114–118. CrossRefGoogle Scholar
  4. Barriuso E, Laird DA, Koskinen WC, Dowdy RH (1994) Atrazine desorption from smectites. Soil Sci Soc Am J 58:1632–1638. CrossRefGoogle Scholar
  5. Beesley L, Moreno-Jiménez E, Gomez-Eyles JL, Harris E, Robinson B, Sizmur T (2011) A review of biochars’ potential role in the remediation, revegetation and restoration of contaminated soils. Environ Pollut 159:3269–3282. CrossRefGoogle Scholar
  6. Bermúdez-Couso A, Arias-Estévez M, Nóvoa-Muñoz JC, López-Periago E, Soto-González B, Simal-Gándara J (2007) Seasonal distributions of fungicides in soils and sediments of a small river basin partially devoted to vineyards. Water Res 41:4515–4525. CrossRefGoogle Scholar
  7. Bermúdez-Couso A, Fernandez-Calviño D, Pateiro-Moure M, Garrido-Rodríguez B, Novoa-Muñoz JC, Estėvez MA (2011) Adsorption and desorption behavior of metalaxyl in intensively cultivated acid soils. J Agric Food Chem 59:7286–7293. CrossRefGoogle Scholar
  8. Bhat SA, Singh S, Singh J, Kumar S, Bhawana VAP (2018) Bioremediation and detoxification of industrial wastes by earthworms: vermicompost as powerful crop nutrient in sustainable agriculture. Bioresour Technol 252:172–179. CrossRefGoogle Scholar
  9. Chen B, Zhou D, Zhu L (2008) Transitional adsorption and partition of nonpolar and polar aromatic contaminants by biochars of pine needles with different pyrolytic temperatures. Environ Sci Technol 42:5137–5143. CrossRefGoogle Scholar
  10. Fernandes MC, Cox L, Hermosín MC, Cornejo J (2003) Adsorption-desorption of metalaxyl as affecting dissipation and leaching in soils: role of mineral and organic components. Pest Manag Sci 59:545–552. CrossRefGoogle Scholar
  11. Fernandes MC, Cox L, Hermosín MC, Cornejo J (2006) Organic amendments affecting sorption, leaching and dissipation of fungicides in soils. Pest Manag Sci 62:1207–1215. CrossRefGoogle Scholar
  12. Gámiz B, López-Cabeza R, Facenda G, Velarde P, Hermosín MC, Cox L, Celis R (2016a) Effect of synthetic clay and biochar addition on dissipation and enantioselectivity of tebuconazole and metalaxyl in an agricultural soil: laboratory and field experiments. Agric Ecosyst Environ 230:3241. CrossRefGoogle Scholar
  13. Gàmiz B, Pignatello JJ, Cox L, Hermosín MC, Celis R (2016b) Environmental fate of the fungicide metalaxyl in soil amended with composted olive-mill waste and its biochar: an enantioselective study. Sci Total Environ 541:776–783. CrossRefGoogle Scholar
  14. Garcia-Sanchez M, Tausnerova H, Hanc A, Tlustos P (2017) Stabilization of different starting materials through vermicomposting in a continuous-feeding system: changes in chemical and biological parameters. Waste Manag 62:33–42. CrossRefGoogle Scholar
  15. Ho YS (2006) Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods. Water Res 40:119–125. CrossRefGoogle Scholar
  16. Ho YS, Mckay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465. CrossRefGoogle Scholar
  17. Hrelia P, Maffei F, Fimognari C, Vigagni F, Cantelli-Forti G (1996) Cytogenetic effects of metalaxyl on human and animal chromosomes. Mutat Res 369:8–86. CrossRefGoogle Scholar
  18. Ignatowicz K (2018) Chloroorganic pesticide adsorption from water solution using sewage sludge vermicompost as natural sorbent. J Ecol Eng 19:123–129. CrossRefGoogle Scholar
  19. International Humic Substances Society (IHSS) Accessed 10 July 2019
  20. Koch A, McBratney A, Adams M, Field D, Hill R et al (2013) Soil security: solving the global soil crisis. Global Policy 4:434–441CrossRefGoogle Scholar
  21. Komárek M, Čadkova E, Chrastný V, Bordas F, Bollinger J-C (2010) Contamination of vineyard soils with fungicides: a review of environmental and toxicological aspects. Environ Int 36:138–151. CrossRefGoogle Scholar
  22. Kumar KV (2006) Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon. J Hazard Mater B137:1538–1544. CrossRefGoogle Scholar
  23. Lagergren S (1898) Zur theorie der sogenannten adsorption gelöster stoffe, Kungliga Svenska Vetenskapsakademiens. Handlingar 24:1–39Google Scholar
  24. Lehmann J, Joseph S (2009) Biochar for environmental management: science and technology. Earthscan, LondonGoogle Scholar
  25. Loffredo E, Parlavecchia M, Perri G, Gattullo R (2019) Comparative assessment of metribuzin sorption efficiency of biochar, hydrochar and vermicompost. J Environ Sci Health B (online, in press). CrossRefGoogle Scholar
  26. Loffredo E, Senesi N (2006) Fate of anthropogenic organic pollutants in soils with emphasis on adsorption/desorption processes of endocrine disruptor compounds. Pure Appl Chem 78:947–961. CrossRefGoogle Scholar
  27. Loffredo E, Taskin E (2017) Adsorptive removal of ascertained and suspected endocrine disruptors from aqueous solution using plant-derived materials. Environ Sci Pollut Res 24:19159–19166. CrossRefGoogle Scholar
  28. Marín-Benito JM, Sanchez-Martín MJ, Andrades MS, Perez-Clavijo M, Rodríguez-Cruz MS (2009) Effect of spent mushroom substrate amendment of vineyard soils on the behavior of fungicides: 1. Adsorption desorption of penconazole and metalaxyl by soils and subsoils. J Agric Food Chem 57:9634–9642. CrossRefGoogle Scholar
  29. Mendes CB, Lima GF, Alves VN, Coelho NMM, Dragunski DC, Tarley CRT (2012) Evaluation of vermicompost as raw natural adsorbent for adsorption of pesticide methylparation. Environ Technol 33:167–172. CrossRefGoogle Scholar
  30. Mohan D, Sarswat A, Ok YS, Pittman CU Jr (2014) Organic and inorganic contaminants removal from water with biochar, a renewable, low cost and sustainable adsorbent – a critical review. Bioresour Technol 160:191–202. CrossRefGoogle Scholar
  31. Monkiedje A, Spiteller M (2002) Sorptive behavior of the phenylamide fungicides, mefenoxam and metalaxyl, and their acid metabolite in typical Cameroonian and German soils. Chemosphere 49:659–668. CrossRefGoogle Scholar
  32. Nikologianni A, Andreou P, Nektarios PA, Markoglu AN (2010) Metalaxyl-M leaching from different substrates and drainage systems in intensive green roofs. Acta Hortic 881:725–728. CrossRefGoogle Scholar
  33. Qian K, Kumar A, Zhang H, Bellmer D, Huhnke R (2015) Recent advances in utilization of biochar. Renew Sust Energ Rev 42:1055–1064. CrossRefGoogle Scholar
  34. Rani R, Sharma VK, Rattan GS, Singh B, Sharma N (2012) Dissipation of residues of mancozeb and metalaxyl in tomato (Solanum lycopersicum L.). Bull Environ Contam Toxicol 90:248–251. CrossRefGoogle Scholar
  35. Senesi N, Loffredo E (2018) The Chemistry of soil organic matter. In: Sparks DL (ed) Soil Physical Chemistry, 2nd edn. CRC Press, Boca Raton FL, pp 239–370Google Scholar
  36. Sharma D, Awasthi MD (1997) Adsorption and movement of metalaxyl in soils under unsaturated flow conditions. Plant Soil 195:293–298. CrossRefGoogle Scholar
  37. Sharma K, Garg VK (2018) Comparative analysis of vermicompost quality produced from rice straw and paper waste employing earthworm Eisenia fetida (Sav.). Bioresour Technol 250:708–715. CrossRefGoogle Scholar
  38. Taskin E, de Castro BC, Allegretta I, Terzano R, Rosa AH, Loffredo E (2019) Multianalytical characterization of biochar and hydrochar produced from waste biomasses for environmental and agricultural applications. Chemosphere 233:422–430. CrossRefGoogle Scholar
  39. Tomlin C (2006) The Pesticide Manual, 14th edn. British Crop Protection Council, Hampshire, U.K.Google Scholar
  40. Villar I, Alves D, Mato S (2017) Product quality and microbial dynamics during vermicomposting and maturation of compost from pig manure. Waste Manag 69:498–507. CrossRefGoogle Scholar
  41. Wang Y, Xu Y, Li D, Tang B, Man S, Jia Y, Xu H (2018) Vermicompost and biochar as bio-conditioners to immobilize heavy metal and improve soil fertility on cadmium contaminated soil under acid rain stress. Sci Total Environ 621:1057–1065. CrossRefGoogle Scholar
  42. White PM Jr, Potter TL, Lima IM (2015) Sugarcane and pinewood biochar effects on activity and aerobic soil dissipation of metribuzin and pendimethalin. Ind Crop Prod 74:737–744. CrossRefGoogle Scholar
  43. WHO (2009). The WHO recommended classification of pesticides by hazard and guidelines to classification.

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Dipartimento di Scienze del Suolo, della Pianta e degli AlimentiUniversità degli Studi di Bari Aldo MoroBariItaly

Personalised recommendations