Abstract
There is an urgent global need to develop novel types of environmentally safe dispersing chemicals from renewable resources in order to reduce the environmental impact of oil spills. For this goal, cellulose, the most abundant natural polymeric source, is a promising green, nontoxic alternative that could replace the current synthetic surfactants. In this study, cellulose nanocrystals (CNC) synthesized using a deep eutectic solvent (DES) and two commercially available cellulose nanocrystals were used as marine diesel oil–water Pickering emulsion stabilizers. In particular, oil in water (o/w) emulsion formation and stability of emulsified oil during storing were addressed using a laser diffraction particle size analyzer, image analysis, and oil emulsion volume examination. The particle size of the o/w reference without CNCs after dispersing was over 50 µm and coalescence occurred only a few minutes after the emulsifying mixing procedure. All three investigated CNCs were effective stabilizers for the o/w system (oil droplets size under 10 µm) by preventing the oil droplet coalescence over time (6 weeks) and resulting in a stable creaming layer. The CNCs prepared using green DES systems boasted performance comparable to that of commercial CNCs, and they showed effectiveness at 0.1% dispersant dosage.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abdolmaleki K, Mohammadifar MA, Mohammadi R et al (2016) The effect of pH and salt on the stability and physicochemical properties of oil-in-water emulsions prepared with gum tragacanth. Carbohydr Polym 140:342–348. doi:10.1016/j.carbpol.2015.12.081
Alexandrescu L, Syverud K, Gatti A, Chinga-Carrasco G (2013) Cytotoxicity tests of cellulose nanofibril-based structures. Cellulose 20:1765–1775. doi:10.1007/s10570-013-9948-9
Andresen M, Stenius P (2007) Water-in-oil emulsions stabilized by hydrophobized microfibrillated cellulose. J Dispers Sci Technol 28:837–844. doi:10.1080/01932690701341827
Anon. http://www.environment.fi/en-US, Oil pollution response methods. http://www.ymparisto.fi/en-US/Sea/Environmental_emergency_response_in_Finland/Marine_pollution_response/Oil_pollution_response_methods
Aveyard R, Binks BP, Clint JH (2003) Emulsions stabilised solely by colloidal particles. Adv Colloid Interface Sci 100:503–546
Bhattacharya M, Malinen MM, Lauren P et al (2012) Nanofibrillar cellulose hydrogel promotes three-dimensional liver cell culture. J Controll Release 164:291–298. doi:10.1016/j.jconrel.2012.06.039
Carpenter AW, de Lannoy C-F, Wiesner MR (2015) Cellulose nanomaterials in water treatment technologies. Environ Sci Technol 49:5277–5287. doi:10.1021/es506351r
Chandrasekar S, Sorial G, Weaver J (2006) Dispersant effectiveness on oil spills—impact of salinity. ICES J Mar Sci 63:1418–1430. doi:10.1016/j.icesjms.2006.04.019
Chevalier Y, Bolzinger M-A (2013) Emulsions stabilized with solid nanoparticles: pickering emulsions. Colloids Surf A Physicochem Eng Asp 439:23–34. doi:10.1016/j.colsurfa.2013.02.054
De Gennes PG, Taupin C (1982) Microemulsions and the flexibility of oil/water interfaces. J Phys Chem 86:2294–2304
DeLeo DM, Ruiz-Ramos DV, Baums IB, Cordes EE (2015) Response of deep-water corals to oil and chemical dispersant exposure. Deep Sea Res Part II Top Stud Oceanogr. doi:10.1016/j.dsr2.2015.02.028
Elsaesser A, Howard CV (2012) Toxicology of nanoparticles. Adv Drug Deliv Rev 64:129–137. doi:10.1016/j.addr.2011.09.001
Fang Y, Wang L, Li D et al (2008) Preparation of crosslinked starch microspheres and their drug loading and releasing properties. Carbohydr Polym 74:379–384. doi:10.1016/j.carbpol.2008.03.005
Gong Y, Zhao X, Cai Z et al (2014) A review of oil, dispersed oil and sediment interactions in the aquatic environment: influence on the fate, transport and remediation of oil spills. Mar Pollut Bull 79:16–33. doi:10.1016/j.marpolbul.2013.12.024
Haapala A, Laitinen O, Karinkanta P et al (2013) Optical characterisation of size, shape and fibrillarity from microfibrillar and microcrystalline cellulose, and fine ground wood powder fractions. Appita J J Tech Assoc Aust N Z Pulp Pap Ind 66:331
Hu Z, Ballinger S, Pelton R, Cranston ED (2015a) Surfactant-enhanced cellulose nanocrystal Pickering emulsions. J Colloid Interface Sci 439:139–148. doi:10.1016/j.jcis.2014.10.034
Hu Z, Patten T, Pelton R, Cranston ED (2015b) Synergistic stabilization of emulsions and emulsion gels with water-soluble polymers and cellulose nanocrystals. ACS Sustain Chem Eng 3:1023–1031. doi:10.1021/acssuschemeng.5b00194
Hu Z, Marway HS, Kasem H et al (2016) Dried and redispersible cellulose nanocrystal Pickering emulsions. ACS Macro Lett 5:185–189. doi:10.1021/acsmacrolett.5b00919
Hua K, Carlsson DO, Ålander E et al (2014) Translational study between structure and biological response of nanocellulose from wood and green algae. RSC Adv 4:2892–2903. doi:10.1039/C3RA45553J
Jiang F, Hsieh Y-L (2015) Holocellulose nanocrystals: amphiphilicity, oil/water emulsion, and self-assembly. Biomacromolecules 16:1433–1441. doi:10.1021/acs.biomac.5b00240
Jung JH, Yim UH, Han GM, Shim WJ (2009) Biochemical changes in rockfish, Sebastes schlegeli, exposed to dispersed crude oil. Comp Biochem Physiol Part C Toxicol Pharmacol 150:218–223. doi:10.1016/j.cbpc.2009.04.009
Kalashnikova I, Bizot H, Cathala B, Capron I (2011) New Pickering emulsions stabilized by bacterial cellulose nanocrystals. Langmuir 27:7471–7479. doi:10.1021/la200971f
Kalashnikova I, Bizot H, Cathala B, Capron I (2012) Modulation of cellulose nanocrystals amphiphilic properties to stabilize oil/water interface. Biomacromolecules 13:267–275. doi:10.1021/bm201599j
Kalashnikova I, Bizot H, Bertoncini P et al (2013) Cellulosic nanorods of various aspect ratios for oil in water Pickering emulsions. Soft Matter 9:952–959. doi:10.1039/C2SM26472B
Kangas H, Lahtinen P, Sneck A et al (2014) Characterization of fibrillated celluloses. A short review and evaluation of characteristics with a combination of methods. Nord Pulp Pap Res J 29:129–143
Katz S, Beatson RP, Scallan AM (1984) The determination of strong and weak acidic groups in sulfite pulps. Sven Papperstidning 87(6):R48–R53
Kim I-Y, Joachim E, Choi H, Kim K (2015) Toxicity of silica nanoparticles depends on size, dose, and cell type. Nanomed Nanotechnol Biol Med 11:1407–1416. doi:10.1016/j.nano.2015.03.004
Kujawinski EB, Kido Soule MC, Valentine DL et al (2011) Fate of dispersants associated with the deepwater horizon oil spill. Environ Sci Technol 45:1298–1306. doi:10.1021/es103838p
Laitinen O, Niinimaki J (2014) Fractional study of the microfibrillated cellulose. Tappi J 13:49–55
Laitinen O, Kemppainen K, Ämmälä A et al (2014) Use of chemically modified nanocelluloses in flotation of hematite and quartz. Ind Eng Chem Res 53:20092–20098. doi:10.1021/ie503415t
Laitinen O, Hartmann R, Sirviö JA et al (2016) Alkyl aminated nanocelluloses in selective flotation of aluminium oxide and quartz. Chem Eng Sci 144:260–266. doi:10.1016/j.ces.2016.01.052
Lou Y-R, Kanninen L, Kuisma T et al (2014) The use of nanofibrillar cellulose hydrogel as a flexible three-dimensional model to culture human pluripotent stem cells. Stem Cells Dev 23:380–392. doi:10.1089/scd.2013.0314
Lyu B, Wang H-D, Ma J et al (2016) Preparation and application of castor oil/nano-TiO2 composite fatliquoring agent via a Pickering emulsion method. J Clean Prod 126:711–716. doi:10.1016/j.jclepro.2016.02.099
Malinen MM, Kanninen LK, Corlu A et al (2014) Differentiation of liver progenitor cell line to functional organotypic cultures in 3D nanofibrillar cellulose and hyaluronan-gelatin hydrogels. Biomaterials 35:5110–5121. doi:10.1016/j.biomaterials.2014.03.020
Ojala J, Sirviö JA, Liimatainen H (2016) Nanoparticle emulsifiers based on bifunctionalized cellulose nanocrystals as marine diesel oil–water emulsion stabilizers. Chem Eng J 288:312–320. doi:10.1016/j.cej.2015.10.113
Pitkänen M, Kangas H, Laitinen O et al (2014) Characteristics and safety of nano-sized cellulose fibrils. Cellulose. doi:10.1007/s10570-014-0397-x
Prendergast DP, Gschwend PM (2014) Assessing the performance and cost of oil spill remediation technologies. J Clean Prod 78:233–242. doi:10.1016/j.jclepro.2014.04.054
Ramachandran SD, Hodson PV, Khan CW, Lee K (2004) Oil dispersant increases PAH uptake by fish exposed to crude oil. Ecotoxicol Environ Saf 59:300–308. doi:10.1016/j.ecoenv.2003.08.018
Ramachandran SD, Sweezey MJ, Hodson PV et al (2006) Influence of salinity and fish species on PAH uptake from dispersed crude oil. Mar Pollut Bull 52:1182–1189. doi:10.1016/j.marpolbul.2006.02.009
Rattaz A, Mishra SP, Chabot B, Daneault C (2011) Cellulose nanofibres by sonocatalysed-TEMPO-oxidation. Cellulose 18:585–593. doi:10.1007/s10570-011-9529-8
Ruka DR, Sangwan P, Garvey CJ et al (2015) Biodegradability of poly-3-hydroxybutyrate/bacterial cellulose composites under aerobic conditions, measured via evolution of carbon dioxide and spectroscopic and diffraction methods. Environ Sci Technol 49:9979–9986. doi:10.1021/es5044485
Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794
Sirviö JA, Visanko M, Liimatainen H (2015) Deep eutectic solvent system based on choline chloride-urea as a pre-treatment for nanofibrillation of wood cellulose. Green Chem 17:3401–3406. doi:10.1039/C5GC00398A
Sirviö JA, Visanko M, Liimatainen H (2016) Acidic deep eutectic solvents as hydrolytic media for cellulose nanocrystal production. Biomacromolecules. doi:10.1021/acs.biomac.6b00910
Smith EL, Abbott AP, Ryder KS (2014) Deep eutectic solvents (DESs) and their applications. Chem Rev 114:11060–11082. doi:10.1021/cr300162p
Van Hoecke K, De Schamphelaere KA, Van der Meeren P et al (2008) Ecotoxicity of silica nanoparticles to the green alga Pseudokirchneriella subcapitata: importance of surface area. Environ Toxicol Chem 27:1948–1957
Vartiainen J, Pöhler T, Sirola K et al (2011) Health and environmental safety aspects of friction grinding and spray drying of microfibrillated cellulose. Cellulose 18:775–786. doi:10.1007/s10570-011-9501-7
Vikman M, Vartiainen J, Tsitko I, Korhonen P (2015) Biodegradability and compostability of nanofibrillar cellulose-based products. J Polym Environ 23:206–215. doi:10.1007/s10924-014-0694-3
Visanko M, Liimatainen H, Sirviö JA et al (2014) Amphiphilic cellulose nanocrystals from acid-free oxidative treatment: physicochemical characteristics and use as an oil–water stabilizer. Biomacromolecules 15:2769–2775. doi:10.1021/bm500628g
Wagle DV, Zhao H, Baker GA (2014) Deep eutectic solvents: sustainable media for nanoscale and functional materials. Acc Chem Res 47:2299–2308. doi:10.1021/ar5000488
Wang M (2010) In Gulf Spill, BP Using Dispersants Banned in U.K. ProPublica. https://www.propublica.org/blog/item/In-Gulf-Spill-BP-Using-Dispersants-Banned-in-UK
Wu Y, Sun Q, Kong L, Fang H (2014) Properties and microstructure of polymer emulsions modified fibers reinforced cementitious composites. J Wuhan Univ Technol Mater Sci Ed 29:795–802. doi:10.1007/s11595-014-0999-z
Xhanari K, Syverud K, Stenius P (2011) Emulsions stabilized by microfibrillated cellulose: the effect of hydrophobization, concentration and o/w ratio. J Dispers Sci Technol 32:447–452. doi:10.1080/01932691003658942
Yang JS, Jiang B, He W, **a YM (2012) Hydrophobically modified alginate for emulsion of oil in water. Carbohydr Polym 87:1503–1506. doi:10.1016/j.carbpol.2011.09.046
Yildirimer L, Thanh NTK, Loizidou M, Seifalian AM (2011) Toxicology and clinical potential of nanoparticles. Nano Today 6:585–607. doi:10.1016/j.nantod.2011.10.001
Zhang Y, Chen D, Ennis AC et al (2013) Chemical dispersant potentiates crude oil impacts on growth, reproduction, and gene expression in Caenorhabditis elegans. Arch Toxicol 87:371–382. doi:10.1007/s00204-012-0936-x
Acknowledgments
This work was conducted as part of the ERDF-funded VIKE project (“Improvement of the oil spill prevention and response with the green chemicals”) and also financed by the Academy of Finland (“Arcrespo project”). We acknowledge Neste Oil Inc. for kindly providing the marine diesel oil sample used in our experiments.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Laitinen, O., Ojala, J., Sirviö, J.A. et al. Sustainable stabilization of oil in water emulsions by cellulose nanocrystals synthesized from deep eutectic solvents. Cellulose 24, 1679–1689 (2017). https://doi.org/10.1007/s10570-017-1226-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-017-1226-9