Environmental Science and Pollution Research

, Volume 25, Issue 11, pp 10956–10965 | Cite as

Aqueous aggregation and stability of graphene nanoplatelets, graphene oxide, and reduced graphene oxide in simulated natural environmental conditions: complex roles of surface and solution chemistry

  • Nan Ye
  • Zhuang Wang
  • Se Wang
  • Hao Fang
  • Degao Wang
Research Article


Graphene-family nanomaterials (GFNs) exhibit universal applications and consequently will inevitably enter aquatic systems. However, both the fate and behavior of GFNs in aquatic environments have not been completely explored at field relevant conditions. Herein, we have systematically investigated the aqueous aggregation and stability of graphene nanoplatelets (GNPs), graphene oxide (GO), and reduced graphene oxide (RGO) under varied solution chemistry parameters (pH, divalent cations, and dissolved organic carbon (DOC)) during 21 days of incubation in simulated natural environmental conditions. Results indicate that pH values from 6 to 9 had a notable impact on the aqueous behaviors of the three GFNs. Divalent cations (Ca2+ and Mg2+) at the concentrations of 2.5 and 10 mM remarkably increased the extent of aggregation of the three GFNs and resulted in severe sedimentation, independently of surface chemical functionalization. The presence of only DOC ranging from 0.5 to 2 mg C/L significantly elevated the dispersion stability of GNPs and RGO in a dose-dependent manner, whereas no effects were observed on GO. Furthermore, DOC at the studied concentrations and surface functionality were insufficient to counterbalance the impact of the divalent cations. Direct visual and in situ observations further supported the conclusions on the effects of divalent cations or/and DOC. These findings further underline that the environmental behaviors of GFNs are controlled by the complex interplay between water chemistry parameters and GFN surface properties.


Graphene-family nanomaterials Surface chemistry Water chemistry Physicochemical property Aggregation Stability 



Funding for this work was supported by the National Natural Science Foundation of China (21407080 and 41601519) and the Natural Science Foundation of Jiangsu Province (BK20150891 and BK20140987). We also thank the anonymous reviewers for helping to improve the manuscript.

Supplementary material

11356_2018_1326_MOESM1_ESM.doc (2.3 mb)
ESM 1 (DOC 2351 kb)


  1. Chae SR, Xiao Y, Lin S, Noeiaghaei T, Kim JO, Wiesner MR (2012) Effects of humic acid and electrolytes on photocatalytic reactivity and transport of carbon nanoparticle aggregates in water. Water Res 46(13):4053–4062. CrossRefGoogle Scholar
  2. Chen KL, Elimelech M (2007) Influence of humic acid on the aggregation kinetics of fullerene (C60) nanoparticles in monovalent and divalent electrolyte solutions. J Colloid Interface Sci 309(1):126–134. CrossRefGoogle Scholar
  3. Chen Y, Ren C, Ouyang S, Hu X, Zhou Q (2015) Mitigation in multiple effects of graphene oxide toxicity in zebrafish embryogenesis driven by humic acid. Environ Sci Technol 49(16):10147–10154. CrossRefGoogle Scholar
  4. Chowdhury I, Duch MC, Mansukhani ND, Hersam MC, Bouchard D (2013) Colloidal properties and stability of graphene oxide nanomaterials in the aquatic environment. Environ Sci Technol 47(12):6288–6296. CrossRefGoogle Scholar
  5. Chowdhury I, Mansukhani ND, Guiney LM, Hersam MC, Bouchard D (2015) Aggregation and stability of reduced graphene oxide: complex roles of divalent cations, pH, and natural organic matter. Environ Sci Technol 49(18):10886–10893. CrossRefGoogle Scholar
  6. Compton OC, Nguyen ST (2010) Graphene oxide, highly reduced graphene oxide, and graphene: versatile building blocks for carbon-based materials. Small 6(6):711–723. CrossRefGoogle Scholar
  7. Cosgrove T (2005) Colloid science: principles, methods and applications. Blackwell, Publishing Ltd.
  8. Domingos RF, Tufenkji N, Wilkinson KJ (2009) Aggregation of titanium dioxide nanoparticles: role of a fulvic acid. Environ Sci Technol 43:1282–1286CrossRefGoogle Scholar
  9. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39(1):228–240. CrossRefGoogle Scholar
  10. Feng Y, Lu K, Mao L, Guo X, Gao S, Petersen EJ (2015) Degradation of 14C-labeled few layer graphene via Fenton reaction: reaction rates, characterization of reaction products, and potential ecological effects. Water Res 84:49–57. CrossRefGoogle Scholar
  11. Garacci M, Barret M, Mouchet F, Sarrieu C, Lonchambon P, Flahaut E, Gauthier L, Silvestre J, Pinelli E (2017) Few layer graphene sticking by biofilm of freshwater diatom Nitzschia palea as a mitigation to its ecotoxicity. Carbon 113:139–150CrossRefGoogle Scholar
  12. Goldberg E, McNew C, Scheringer M, Bucheli TD, Nelson P, Hungerbühler K (2017) What factors determine the retention behavior of engineered nanomaterials in saturated porous media? Environ Sci Technol 51(5):2729–2737. CrossRefGoogle Scholar
  13. Hu X, Zhou Q (2013) Health and ecosystem risks of graphene. Chem Rev 113(5):3815–3835. CrossRefGoogle Scholar
  14. Hu L, Zeng G, Chen G, Dong H, Liu Y, Wan J, Chen A, Guo Z, Yan M, Wu H, Yu Z (2016a) Treatment of landfill leachate using immobilized Phanerochaete chrysosporium loaded with nitrogen-doped TiO2 nanoparticles. J Hazard Mater 301:106–118. CrossRefGoogle Scholar
  15. Hu L, Zhang C, Zeng G, Chen G, Wan J, Guo Z, Wu H, Yu Z, Zhou Y, Liu J (2016b) Metal-based quantum dots: synthesis, surface modification, transport and fate in aquatic environments and toxicity to microorganisms. RSC Adv 6(82):78595–78610. CrossRefGoogle Scholar
  16. Hu L, Wan J, Zeng G, Chen A, Chen G, Huang Z, He K, Cheng M, Zhou C, Xiong W, Lai C, Xu P (2017) Comprehensive evaluation of the cytotoxicity of CdSe/ZnS quantum dots in Phanerochaete chrysosporium by cellular uptake and oxidative stress. Environ Sci: Nano 4:2018–2029Google Scholar
  17. Hua Z, Tang Z, Bai X, Zhang J, Yu L, Cheng H (2015) Aggregation and resuspension of graphene oxide in simulated natural surface aquatic environments. Environ Pollut 205:161–169. CrossRefGoogle Scholar
  18. Hyung H, Kim JH (2008) Natural organic matter (NOM) adsorption to multi-walled carbon nanotubes: effect of NOM characteristics and water quality parameters. Environ Sci Technol 42(12):4416–4421. CrossRefGoogle Scholar
  19. Jeong SH, Kim KK, Jeong SJ, An KH, Lee SH, Lee YH (2007) Optical absorption spectroscopy for determining carbon nanotube concentration in solution. Synth Met 157(13-15):570–574. CrossRefGoogle Scholar
  20. Jiang Y, Raliya R, Fortner JD, Biswas P (2016) Graphene oxides in water: correlating morphology and surface chemistry with aggregation behavior. Environ Sci Technol 50(13):6964–6973. CrossRefGoogle Scholar
  21. Li Q, Xie B, Hwang YS, Xu Y (2009) Kinetics of C60 fullerene dispersion in water enhanced by natural organic matter and sunlight. Environ Sci Technol 43(10):3574–3579. CrossRefGoogle Scholar
  22. Li X, Chen W, Zhang C, Li Y, Wang F, Chen W (2016) Enhanced dehydrochlorination of 1,1,2,2-tetrachloroethane by graphene-based nanomaterials. Environ Pollut 214:341–348. CrossRefGoogle Scholar
  23. Loh KP, Bao Q, Ang PK, Yang J (2010) The chemistry of graphene. J Mater Chem 20(12):2277–2289. CrossRefGoogle Scholar
  24. Novoselov KS, Fal'ko VI, Colombo L, Gellert PR, Schwab MG, Kim K (2012) A roadmap for graphene. Nature 490(7419):192–200. CrossRefGoogle Scholar
  25. Ottofuelling S, Von Der Kammer F, Hofmann T (2011) Commercial titanium dioxide nanoparticles in both natural and synthetic water: comprehensive multidimensional testing and prediction of aggregation behavior. Environ Sci Technol 45:10045–10052CrossRefGoogle Scholar
  26. Petosa AR, Jaisi DP, Quevedo IR, Elimelech M, Tufenkji N (2010) Aggregation and deposition of engineered nanomaterials in aquatic environments: role of physicochemical interactions. Environ Sci Technol 44(17):6532–6549. CrossRefGoogle Scholar
  27. Sanchís J, Olmos M, Vincent P, Farré M, Barceló D (2016) New insights on the influence of organic co-contaminants on the aquatic toxicology of carbon nanomaterials. Environ Sci Technol 50:961–969CrossRefGoogle Scholar
  28. Shih C-J, Lin S, Sharma R, Strano MS, Blankschtein D (2012) Understanding the pH-dependent behavior of graphene oxide aqueous solutions: a comparative experimental and molecular dynamics simulation study. Langmuir 289:235–241CrossRefGoogle Scholar
  29. Su Y, Gao B, Mao L (2017a) Concurrent agglomeration and straining govern the transport of 14C-labeled few-layer graphene in saturated porous media. Water Res 115:84–93. CrossRefGoogle Scholar
  30. Su Y, Yang G, Lu K, Petersen EJ, Mao L (2017b) Colloidal properties and stability of aqueous suspensions of few-layer graphene: importance of graphene concentration. Environ Pollut 220(Pt A):469–477. CrossRefGoogle Scholar
  31. Tang H, Zhao Y, Yang X, Liu D, Shao P, Zhu Z, Shan S, Cui F, Xing B (2017) New insight into the aggregation of graphene oxide using molecular dynamics simulations and extended Derjaguin-Landau-Verwey-Overbeek theory. Environ Sci Technol 51:9674–9682CrossRefGoogle Scholar
  32. Wan J, Zhang C, Zeng G, Huang D, Hu L, Huang C, Wu H, Wang L (2016) Synthesis and evaluation of a new class of stabilized nano-chlorapatite for Pb immobilization in sediment. J Hazard Mater 320:278–288. CrossRefGoogle Scholar
  33. Wan J, Zeng G, Huang D, Hu L, Xu P, Huang C, Deng R, Xue W, Lai C, Zhou C, Zheng K, Ren X, Gong X (2018) Rhamnolipid stabilized nano-chlorapatite: synthesis and enhancement effect on Pb- and Cd-immobilization in polluted sediment. J Hazard Mater 343:332–339. CrossRefGoogle Scholar
  34. Wang H, Hu YH (2013) Electrolyte-induced precipitation of graphene oxide in its aqueous solution. J Colloid Interf Sci 391:21–27. CrossRefGoogle Scholar
  35. Wang J, Chen Z, Chen B (2014) Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets. Environ Sci Technol 48:4817–4825CrossRefGoogle Scholar
  36. Wang Z, Gao Y, Wang S, Fang H, Xu D, Zhang F (2016) Impacts of low-molecular-weight organic acids on aquatic behavior of graphene nanoplatelets and their induced algal toxicity and antioxidant capacity. Environ Sci Pollut R 23(11):10938–10945. CrossRefGoogle Scholar
  37. Wang Z, Zhang F, Wang S, Peijnenburg WJ (2017) Assessment and prediction of joint algal toxicity of binary mixtures of graphene and ionic liquids. Chemosphere 185:681–689. CrossRefGoogle Scholar
  38. Wu L, Liu L, Gao B, Muñoz-Carpena R, Zhang M, Chen H, Zhou Z, Wang H (2013) Aggregation kinetics of graphene oxides in aqueous solutions: experiments, mechanisms, and modeling. Langmuir 29(49):15174–15181. CrossRefGoogle Scholar
  39. Xia T, Fortner JD, Zhu D, Qi Z, Chen W (2015) Transport of sulfide-reduced graphene oxide in saturated quartz sand: cation-dependent retention mechanisms. Environ Sci Technol 49(19):11468–11475. CrossRefGoogle Scholar
  40. Xiao Y, Vijver MG, Peijnenburg WJ (2017) Impact of water chemistry on the behavior and fate of copper nanoparticles. Environ Pollut 234:684–691. CrossRefGoogle Scholar
  41. Xiao Y, Peijnenburg WJ, Chen G, Vijver MG (2018) Impact of water chemistry on the particle-specific toxicity of copper nanoparticles to Daphnia magna. Sci Total Environ 610-611:1329–1335. CrossRefGoogle Scholar
  42. Zeng G, Wan J, Huang D, Hu L, Huang C, Cheng M, Xue W, Gong X, Wang R, Jiang D (2017) Precipitation, adsorption and rhizosphere effect: the mechanisms for phosphate-induced Pb immobilization in soils—a review. J Hazard Mater 339:354–367. CrossRefGoogle Scholar
  43. Zhao J, Wang Z, White JC, Xing B (2014) Graphene in the aquatic environment: adsorption, dispersion, toxicity and transformation. Environ Sci Technol 48(17):9995–10009. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Environmental Science and Engineering, Collaborative Innovation Center of Atmospheric Environment and Equipment TechnologyNanjing University of Information Science and TechnologyNanjingPeople’s Republic of China
  2. 2.School of Environmental Science and TechnologyDalian Maritime UniversityDalianPeople’s Republic of China

Personalised recommendations