Ecotoxicological Assessment and Biodegradation Potential of Epoxidised Methyl Oleate (EMO) as a Bio-Based Plasticiser in Aquatic Environment
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Abstract
Bio-based plasticisers have been developed as sustainable alternatives to phthalate-based plasticisers. However, limited information on their potential ecotoxicological effects on aquatic organisms could hinder their widespread adoption in the market. This study addresses this gap by providing ecotoxicological data on epoxidised methyl oleate (EMO), a potential bio-based plasticiser. This study evaluated the acute toxicity of EMO on five aquatic species (Moina macrocopa, Daphnia magna, Chlamydomonas reinhardtii, Chlorella vulgaris and Macrobrachium lanchesteri) to develop a species sensitivity distribution (SSD) curve for determining the predicted no-effect concentration (PNEC) of EMO for ecological risk assessment. Additionally, the biodegradation potential of EMO in aquatic environments was assessed using the OECD 301F Manometric Respiratory Test. These results indicate that EMO exhibits a concentration-dependent toxic effect on all tested species. The SSD curve, developed using a normal distribution and a Maximum Likelihood Estimation fit model, yielded 0.359 mg/L for hazardous concentration for 5% of species (HC05). This HC05 value suggests that EMO poses a minimal ecological risk, as it exceeded the water solubility limit (0.012 mg/L). Furthermore, EMO demonstrated favourable biodegradation potential under aerobic conditions. At a concentration of 30 mg/L, EMO achieved 60% biodegradation within four days of incubation, whereas at 100 mg/L, the same level of biodegradation was achieved by Day 11. These findings underscore the importance of assessing the environmental impact of bio-based plasticisers and highlight the EMO’s potential as an eco-friendly alternative to less biodegradable, petroleum-based plasticisers.
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References
Alhanish A and Abu Ghalia M. (2021). Developments of biobased plasticizers for compostable polymers in the green packaging applications: A review. Biotechnology Progress 37(6): e3210. https://doi.org/10.1002/btpr.3210
Asma Liyana S, Siti Afida I, Noorazah Z, Zulina A M and Razmah G. (2024). Ecotoxicology perspective of epoxidised palm methyl oleate (EPMO): A potential low toxicity plasticizer. 32nd Regional Conference on Solid State Science & Technology, Hotel Grand Continental, Kuala Terengganu, Malaysia. 17–19 September 2024.
Banaee M, Zeidi A, Mikušková N and Faggio C. (2024). Assessing metal toxicity on crustaceans in aquatic ecosystems: A comprehensive review. Biological Trace Element Research 202: 5743–5761. https://doi.org/10.1007/s12011-024-04122-7
Beaman J, Bergeron C, Benson R, Cook A, Gallagher K, Ho K, Hoff D and Laessig S. (2016). A summary of literature on the chemical toxicity of plastics pollution to aquatic life and aquatic-dependent wildlife. Washington: United States Environmental Protection Agency.
Bocqué M, Voirin C, Lapinte V, Caillol S and Robin J. (2016). Petro‐based and bio‐based plasticizers: Chemical structures to plasticizing properties. Journal of Polymer Science Part A 54: 11–33. https://doi.org/10.1002/pola.27917
Bodaghi A. (2020). An overview on the recent developments in reactive plasticizers in polymers. Polymers Advanced Technologies 31: 355–367. https://doi.org/10.1002/pat.4790
Bondarenko S and Gan J. (2009). Simultaneous measurement of free and total concentrations of hydrophobic compounds. Environmental Science and Technology 43: 3772–3777. https://doi.org/10.1021/es8037033
Bonifacio A, Bonetti L, Piantanida E and De Nardo L. (2023). Plasticizer design strategies enabling advanced applications of cellulose acetate. European Polymer Journal 197: 112360. https://doi.org/10.1016/j.eurpolymj.2023.112360
Fox D R, van Dam R A, Fisher R, Batley G E, Tillmanns A R, Thorley J, Schwarz C J, Spry D J and McTavish K. (2020). Recent developments in species sensitivity distribution modeling. Environmental Toxicology and Chemistry 40: 293–308. https://doi.org/10.1002/etc.4925
Geng W, Xiao X, Zhang L, Ni W, Li N and Li Y. (2022). Response and tolerance ability of Chlorella vulgaris to cadmium pollution stress. Environmental Technology 43: 4391–4401. https://doi.org/10.1080/09593330.2021.1950
Globe Newswire (2023). Plasticizers Global Market Report 2023: Growing demand for plasticizers in construction industry drives sector. https://www.globenewswire.com/en/news-release/2023/05/02/2659148/28124/en/Plasticizers-Global-Market-Report-2023-Growing-Demand-for-Plasticizers-in-Construction-Industry-Drives-Sector.html (accessed on 23 May 2021).
Grand View Research (2017). Bio plasticizers market size worth $2.68 billion by 2025 CAGR 10.7%. https://www.grandviewresearch.com/press-release/global-bio-plasticizers-market. (accessed on 9 May 2021).
Handoh I C and Kawai T. (2014). Modelling exposure of oceanic higher trophic-level consumers to polychlorinated biphenyls: Pollution ‘hotspots’ in relation to mass mortality events of marine mammals. Marine Pollution Bulletin 85: 824–830. https://doi.org/10.1016/j.marpolbul.2014.06.031
Hiltunen M, Vehniäinen E R and Kukkonen J V K. (2021). Interacting effects of simulated eutrophication, temperature increase, and microplastic exposure on Daphnia. Environmental Research 192: 110304. https://doi.org/10.1016/j.envres.2020.110304
Hutchinson T H, Shillabeer N, Winter M J and Pickford D B. (2006). Acute and chronic effects of carrier solvents in aquatic organisms: A critical review. Aquatic Toxicology 76: 69–92. https://doi.org/10.1016/j.aquatox.2005.09.008
Jadhav P D, Girase C D, Kulkarni R D, Patwardhan A V and Unnithan U R. (2024). Synthesis and properties of a bio-based plasticizer derived from fatty acid methyl ester of erucic acid. Journal of Polymers and the Environment 32: 4371–4384. https://doi.org/10.1007/s10924-024-03231-7
Jaikumar I M, Periyakali S B, Rajendran U, Joen-Rong S, Thanasekaran J and Tsorng-Harn F. (2021). Effects of microplastics, polystyrene, and polyethylene on antioxidants, metabolic enzymes, HSP-70, and myostatin expressions in the giant river prawn Macrobrachium rosenbergii: Impact on survival and growth. Archives of Environmental Contamination and Toxicology 80: 645–658. https://doi.org/10.1007/s00244-021-00833-3
Ji M, Giangeri G, Usman M, Liu C, Bosaro M, Sessa F, Canu P, Treu L and Campanaro S. (2023). An integrated Metagenomic-Pangenomic strategy revealed native microbes and magnetic biochar cooperation in plasticizer degradation. Chemical Engineering Journal 468: 143589. https://doi.org/10.1016/j.cej.2023.143589
Jiang Q, Jiang Z, Ao S, Gao X, Zhu X, Zhang Z and Zhang X. (2021). Multi-biomarker assessment in the giant freshwater prawn Macrobrachium rosenbergii after deltamethrin exposure. Ecotoxicology and Environmental Safety 214: 112067. https://doi.org/10.1016/j.ecoenv.2021.112067
Juergens M T, Deshpande R R, Lucker B F, Park J J, Wang H, Gargouri M, Holguin F O, Disbrow B, Schaub T, Skepper J N, Kramer D M, Gang D R, Hicks L M and Shachar-Hill Y. (2015). The regulation of photosynthetic structure and function during nitrogen deprivation in Chlamydomonas reinhardtii. Plant Physiology 167: 558–573. https://doi.org/10.1104/pp.114.250530
Juneau A, El Berdey R and Popovic P. (2002). PAM fluorometry in the determination of the sensitivity of Chlorella vulgaris, Selenastrum capricornutum, and Chlamydomonas reinhardtii to copper. Archives of Environmental Contamination and Toxicology 42: 155–164. https://doi.org/10.1007/s00244-001-0027-0
Jüppner J, Mubeen U, Leisse A, Caldana C, Wiszniewski A, Steinhauser D and Giavalisco P. (2018). The target of rapamycin kinase affects biomass accumulation and cell cycle progression by altering carbon/nitrogen balance in synchronized Chlamydomonas reinhardtii cells. The Plant Journal 93: 355–376. https://doi.org/10.1111/tpj.13787
Kim L, Cui R, Kwak I J and An Y J. (2022). Sub-acute exposure to nanoplastics via two-chain trophic transfer: From brine shrimp Artemia franciscana to small yellow croaker Larimichthys polyactis. Marine Pollution Bulletin 175: 113314. https://doi.org/10.1016/j.marpolbul.2021.113314
Koivisto S. (1995). Is Daphnia magna an ecologically representative zooplankton species in toxicity tests? Environmental Pollution 90: 263–267. https://doi.org/10.1016/0269-7491(95)00029-Q
Kumari A, Rajput S, Raina P, Chaudhary G and Kaur R. (2024). The ubiquity of microplastics and phthalates in aquatic ecosystems and toxicological concerns. In A Kumari, V D Rajput, S S Mandzhieva, T Minkina and V Hullebusch (eds.), Emerging contaminants. Elsevier, 113–129. https://doi.org/10.1016/B978-0-443-18985-2.00009-2
Kusumaningtyas R D, Prasetiawan H, Anggraeni N D, Anisa E D N and Hartanto D. (2022). Conversion of free fatty acid in Calophyllum inophyllum oil to fatty acid ester as precursor of bio-based epoxy plasticizer via SnCl2-catalyzed esterification. Polymers (Basel) 15: 123. https://doi.org/10.3390/polym15010123
Lenzi L, Degli Esposti M, Braccini S, Siracusa C, Quartinello F, Guebitz G M, Puppi D, Morselli D and Fabbri P. (2023). Further step in the transition from conventional plasticizers to versatile bioplasticizers obtained by the valorization of levulinic acid and glycerol. ACS Sustainable Chemistry and Engineering 11: 9455–9469. https://doi.org/10.1021/acssuschemeng.3c01536
Li J, Zhang J, Yadav M P and Li X. (2019). Biodegradability and biodegradation pathway of di-(2-ethylhexyl) phthalate by Burkholderia pyrrocinia B1213. Chemosphere 225: 443–450. https://doi.org/10.1016/j.chemosphere.2019.02.194
Luo X, Chu H and Liu M. (2020). Synthesis of bio-plasticizer from soybean oil and its application in poly(vinyl chloride) films. Journal of Renewable Materials 8: 1295–1304. https://doi.org/10.32604/jrm.2020.011026
Manatunga D C, Sewwandi M, Perera K I, Jayarathna M D, Peramune D L, Dassanayake R S, Ramanayaka S and Vithanage M. (2024). Plasticizers: Distribution and impact in aquatic and terrestrial environments. Environmental Science: Processes and Impacts 26: 2114–2131. https://doi.org/10.1039/D4EM00317A
Marttinen S K, Hänninen K and Rintala J A. (2004). Removal of DEHP in composting and aeration of sewage sludge. Chemosphere 54: 265–272. https://doi.org/10.1016/S0045-6535(03)00661-1
Maurad Z A, Bakar Z A, Hazmi A S A and Idris Z. (2019). Palm-based plasticiser. http://palmoilis.mpob.gov.my/TOTV3/wp-content/uploads/2020/02/TT658-ZULINAABDMAURAD
Maurad Z A, Idris Z, Hazmi A S A, Ismail R, Bakar Z A, Chooi F C and Yee L W. (2021). Epoxidized palm-based methyl oleate plasticizers, (PI 2016702567/PCT/MY2017/050039) granted MY183650A, Malaysia.
Muobom S S, Umar A M S, Brolin A P and Soongseok Y. (2020). A review on plasticizers and eco-friendly bioplasticizers: Biomass sources and market. International Journal of Engineering Research & Technology 9(5): 1138–1144. https://doi.org/10.17577/IJERTV9IS050788
Najera-Losada L, Narváez-Rincón P C, Orjuela A, Gomez-Caturla J, Fenollar O and Balart R. (2025). Plasticization of polylactide using biobased epoxidized isobutyl esters derived from waste soybean oil deodorizer distillate. Journal of Polymers and the Environment 33: 125–144. https://doi.org/10.1007/s10924-024-03415-1
Navarro-Barranco C, Ros M, Tierno de Figueroa J M and Guerra-García J M. (2020). Marine crustaceans as bioindicators: Amphipods as case study. In G Lovrich and M Thiel (eds.), Fisheries and aquaculture. Oxford University Press, 436–462. https://doi.org/10.1093/oso/9780190865627.003.0017
OECD (1992). OECD guidelines for the testing of chemicals. Section 3: Degradation and accumulation. Test 301: Ready biodegradability. Updated guideline, adopted 17 July 1992.
Pisani X G, Lompré J S, Pires A and Greco L L. (2022). Plastics in scene: A review of the effect of plastics in aquatic crustaceans. Environmental Research 212: 113484. https://doi.org/10.1016/j.envres.2022.113484
Prempeh N, Li J, Liu D, Das K, Maiti S and Zhang Y. (2014). Plasticizing effects of epoxidized sun flower oil on biodegradable polylactide films: A comparative study. Polymer Science Series A 56: 856–863. https://doi.org/10.1134/S0965545X14060182
Righetti G I C, Nasti R, Beretta G, Levi M, Turri S and Suriano R. (2023). Unveiling the hidden properties of tomato peels: Cutin ester derivatives as bio-based plasticizers for polylactic acid. Polymers (Basel) 15: 1848. https://doi.org/10.3390/polym15081848
Salinas J, Carpena V, Martínez-Gallardo M R, Segado M, Estrella-González M J, Toribio A J, Jurado M M, López-González J A, Suárez-Estrella F and López M J. (2023). Development of plastic-degrading microbial consortia by induced selection in microcosms. Frontiers in Microbiology 14: 1143769. https://doi.org/10.3389/fmicb.2023.1143769
Santhi V A and Mustafa A M. (2013). Assessment of organochlorine pesticides and plasticisers in the Selangor River basin and possible pollution sources. Environmental Monitoring and Assessment 185: 1541–1554. https://doi.org/10.1007/s10661-012-2649-2
Sharma I. (2021). Bioremediation techniques for polluted environment: Concept, advantages, limitations, and prospects. In M A Murillo-Tovar, H Saldarriaga-Noreña and A Saeid (eds.), Trace metals in the environment: New approaches and recent advances. IntechOpen. https://doi.org/10.5772/intechopen.90453
Sharma K, Nayarisseri A and Singh S K. (2024). Biodegradation of plasticizers by novel strains of bacteria isolated from plastic waste near Juhu Beach, Mumbai, India. Scientific Reports 14: 30824. https://doi.org/10.1038/s41598-024-81239-8
Shen C, Wei J, Wang T and Wang Y. (2019). Acute toxicity and responses of antioxidant systems to dibutyl phthalate in neonate and adult Daphnia magna. PeerJ 7: e6584. https://doi.org/10.7717/peerj.6584
Skariyachan S, Taskeen N, Kishore A P and Krishna B V. (2022). Recent advances in plastic degradation: From microbial consortia-based methods to data sciences and computational biology driven approaches. Journal of Hazardous Materials 426: 128086. https://doi.org/10.1016/j.jhazmat.2021.128086
Souaf B, Methneni N, Beltifa A, Turco V L, Danioux A, Litrenta F, Sedrati M, Mansour H B and Di Bella G. (2023). Occurrence and seasonal variation of plasticizers in sediments and biota from the coast of Mahdia, Tunisia. Environmental Science and Pollution Research 30: 48532–48545. https://doi.org/10.1007/s11356-023-25687-1
Sprague J B. (1971). Measurement of pollutant toxicity to fish-III. Water Research 5: 245–266. https://doi.org/10.1016/0043-1354(71)90171-0
Staples C A, Adams W J, Parkerton T F, Gorsuch J W, Biddinger G R and Reinert K H. (1997). Aquatic toxicity of eighteen phthalate esters. Environmental Toxicology and Chemistry 16: 875–891. https://doi.org/10.1002/etc.5620160507
Sun S, Weng Y and Zhang C. (2024). Recent advancements in bio-based plasticizers for polylactic acid (PLA): A review. Polymer Testing 140: 108603. https://doi.org/10.1016/j.polymertesting.2024.108603
Sustaita-Rodríguez A, Vega-Rios A, Bugarin A, Ramos-Sánchez V H, Camacho-Dávila A A, Rocha-Gutiérrez B and Chávez-Flores D. (2021). Chemoenzymatic epoxidation of highly unsaturated fatty acid methyl ester and its application as poly(lactic acid) plasticizer. ACS Sustainable Chemistry and Engineering 9: 17016–17024. https://doi.org/10.1021/acssuschemeng.1c05934
Thomas Johnson B, Heitkamp M A and Jones J R. (1984). Environmental and chemical factors influencing the biodegradation of phthalic acid esters in freshwater sediments. Environmental Pollution Series B, Chemical and Physical 8: 101–118. https://doi.org/10.1016/0143-148X(84)90021-1
Wang Y, Wang T, Ban Y, Shen C, Shen Q, Chai X, Zhao W and Wei J. (2018). Di-(2-ethylhexyl) phthalate exposure modulates antioxidant enzyme activity and gene expression in juvenile and adult Daphnia magna. Archives of Environmental Contamination and Toxicology 75: 145–156. https://doi.org/10.1007/s00244-018-0535-9
Weber S, Grande P M, Blank L M and Klose H. (2022). Insights into cell wall disintegration of Chlorella vulgaris. PLoS ONE 17: e0262500. https://doi.org/10.1371/journal.pone.0262500
Wu X, Zhang X, Yang S, Chen H and Wang D. (2000). The study of epoxidized rapeseed oil used as a potential biodegradable lubricant. Journal of the American Oil Chemists’ Society 77: 561–563. https://doi.org/10.1007/s11746-000-0089-2
Zanotelli V R T, Neuhauss S C F and Ehrengruber M U. (2010). Long‐term exposure to bis(2‐ethylhexyl) phthalate (DEHP) inhibits growth of guppy fish (Poecilia reticulata). Journal of Applied Toxicology 30: 29–33. https://doi.org/10.1002/jat.1468
Zappaterra F, Renzi M, Piccardo M, Spennato M, Asaro F, Di Serio M, Vitiello R, Turco R, Todea A and Gardossi L. (2023). Understanding marine biodegradation of bio-based oligoesters and plasticizers. Polymers (Basel) 15: 1536. https://doi.org/10.3390/polym15061536