Fullerenols (PHFs) are emerging pollutants with health risks, yet conventional adsorbents suffer from small pore sizes, limited effective pore quantities, and low unit area adsorption capacities. This study used cuttlebone (CB), a fishery waste, to prepare carbonized CB (CCB), acid-modified CB (HCB), and a combined carbonized and acidified CB (HCCB) as adsorbents for PHF. These modified adsorbent materials showed increases in effective pores (50–200 nm) for PHF adsorption: 33% (CCB), 23% (HCB), and 41% (HCCB). The initial adsorption rate and adsorption capacity of CCB for PHF increased with higher pyrolysis temperatures due to reduced electrostatic repulsion, increased π–π interactions, and the transformation of aragonite into calcite of CB calcium carbonate skeleton. Acid modification enhances pore filling and thus capacity but slows kinetics via longer intraparticle diffusion; both effects intensify with higher acid concentration and longer treatment. The unit area adsorption capacities of CCB, HCB, and HCCB for PHF were 3.11, 1.18, and 2.11 mg/m2, much higher than traditional materials. This research effectively removes PHF and upgrades marine waste into a high-value adsorbent, practicing “pollution control through waste utilization.” The results have both pollution control and circular economy value, expanding sustainable and low-cost material paths, promoting the integration of multiple disciplines such as environmental engineering, materials science, and marine science, and providing new ideas for the treatment of nanomaterial pollutants.
AhnS, WernerD, KarapanagiotiHK, et al.Phenanthrene and pyrene sorption and intraparticle diffusion in polyoxymethylene, coke, and activated carbon. Environ Sci Technol2005;39(17):6516–6526; doi: 10.1021/es050113o
2.
AtamanE, AnderssonMP, CeccatoM, et al.Functional group adsorption on calcite: I. Oxygen containing and nonpolar organic molecules. J Phys Chem C2016;120(30):16586–16596; doi: 10.1021/acs.jpcc.6b01349
3.
BolshakovaO, BorisenkovaA, SuyasovaM, et al.In vitro and in vivo study of the toxicity of fullerenols C_(60), C_(70) and C_(120)O obtained by an original two step method. Mat Sci Eng2019;104(109945.1-109945):11.
4.
CalvaresiM, FaliniG, BonacchiS, et al.Fullerenol entrapment in calcite microspheres. Chem Commun (Camb)2011;47(38):10662–10664; doi: 10.1039/c1cc13680a
5.
CeraJSA, LabiosJD, BuladacoMS, et al.Acid modification and characterization of rice straw biochar and its potential as ameliorant for saline-sodic lowland soil. J Ecol Eng2024;25(8):300–316; doi: 10.12911/22998993/189946
6.
CharykovNA, KtitorovaIN, SemenovKN, et al.Impact of polyhydroxy fullerene (fullerol or fullerenol) on growth and biophysical characteristics of barley seedlings in favourable and stressful conditions. Plant Growth Regul2016;79:309–317; doi: 10.1007/s10725-015-0135-x
7.
ChecaAG, CartwrightJHE, Sánchez-AlmazoIM, et al.The cuttlefish Sepia officinalis (Sepiidae, Cephalopoda) constructs cuttlebone from a liquid-crystal precursor. Sci Rep2015;5:11513; doi: 10.1038/srep11513
8.
ChenQ, ZhuR, ZhuY, et al.Adsorption of polyhydroxy fullerene on polyethylenimine-modified montmorillonite. Appl Clay Sci2016;132–133:412–418; doi: 10.1016/j.clay.2016.07.007
9.
ChenW, WangB, LiangS, et al.Fullerenols as efficient ferroptosis inhibitor by targeting lipid peroxidation for preventing drug-induced acute kidney injury. J Colloid Interface Sci2025;680(Pt A):261–273; doi: 10.1016/j.jcis.2024.10.198
10.
DarwishAS, SayedMA, SheblA. Cuttlefish bone stabilized Ag3VO4 nanocomposite and its Y2O3-decorated form: Waste-to-value development of efficiently ecofriendly visible-light-photoactive and biocidal agents for dyeing, bacterial and larvae depollution of Egypt’s wastewater. J Photochem Photobiol A2020;401:112749; doi: 10.1016/j.jphotochem.2020.112749
11.
DhawanA, TaurozziJS, PandeyAK, et al.Stable colloidal dispersions of C60 fullerenes in water: Evidence for genotoxicity. Environ Sci Technol2006;40(23):7394–7401; doi: 10.1021/es0609708
12.
FanS, TangJ, WangY, et al.Biochar prepared from co-pyrolysis of municipal sewage sludge and tea waste for the adsorption of methylene blue from aqueous solutions: Kinetics, isotherm, thermodynamic and mechanism. J Mol Liq2016;220:432–441; doi: 10.1016/j.molliq.2016.04.107
13.
FlorekM, FornalE, Gómez-RomeroP, et al.Complementary microstructural and chemical analyses of Sepia officinalis endoskeleton. Mater Sci Eng C2009;29(4):1220–1226; doi: 10.1016/j.msec.2008.09.040
14.
GaiK, ShiB, YanX, et al.Effect of dispersion on adsorption of atrazine by aqueous suspensions of fullerenes. Environ Sci Technol2011;45(14):5959–5965; doi: 10.1021/es103595g
HenryTB, MennFM, FlemingJT, et al.Effect of aqueous C60 nano-aggregates on tetrahydrofuran decomposition products in larval zebrafish by gene expression assessment. Environ Health Perspect2007;115(7):1059–1065; doi: 10.1289/ehp.9757
17.
JungHS, KimM, ShinH, et al.Electrospinning and wound healing activity of beta-chitin extracted from cuttlefish bone. Carbohydr Polym2018;193:205–211; doi: 10.1016/j.carbpol.2018.03.100
18.
KhazriH, Ghorbel-AbidI, KalfatR, et al.Removal of drugs by cuttlefish bone powder: Equilibrium, kinetics and thermodynamic study. J Environ Anal Chem2016;03(01); doi: 10.4172/2380-2391.1000176
19.
LaskarII, HashishoZ. Insights into modeling adsorption equilibria of single and multicomponent systems of organic and water vapors. Sep Purif Technol2020;241:116681; doi: 10.1016/j.seppur.2020.116681
20.
LingZ, NanZ, LihongT, et al.Structural and adsorption characteristics of potassium carbonateactivated biochar. RSC Adv2018;8:21012–21019; doi: 10.1039/C8RA03335H
21.
LiuJ, ZhuR, LaipanT, et al.Interaction of polyhydroxy fullerenes with ferrihydrite: Adsorption and aggregation. J Environ Sci2018;59:72–82; doi: 10.1016/j.jes.2017.06.016
22.
MalakootianM, ShiriAM. Investigating the removal of tetracycline antibiotic from aqueous solution using synthesized Fe3O4@cuttlebone magnetic nanocomposite. Desalination Water Treat2021;230:207–216; doi: 10.5004/DWT.2021.27033
23.
MaoZ, ZengZ, XueW, et al.Adsorption of reactive brilliant blue dye from aqueous solution using modified walnut shell: Kinetics, equilibrium, and thermodynamics. Environ Eng Sci2021;38(10):965–973; doi: 10.1089/ees.2020.0364
24.
Mchedlov-PetrossyanNO, MarfuninMO, KriklyaNN. Colloid chemistry of fullerene solutions: Aggregation and coagulation. Liquids (Basel)2023;4(1):32–72.
25.
MousaviSZ, NafisiS, MaibachHI. Fullerene nanoparticle in dermatological and cosmetic applications. Nanomedicine2017;13(3):1071–1087; doi: 10.1016/j.nano.2016.10.002
26.
NakamuraH, NozakiY, KoizumiY, et al.Effect of number of hydroxyl groups of fullerenol C60(OH)n on its interaction with cell membrane. J Taiwan Inst Chem Eng2018;90:18–24; doi: 10.1016/j.jtice.2017.11.016
27.
OlsenR, LeirvikKN, KvammeB. Adsorption characteristics of glycols on calcite and hematite. AIChE J2019;65.
28.
RaifF, AkouzA, HasibA, et al.Adsorption of methylene blue onto raw wastes of argan, date, and olive: Study of kinetics and isotherms. Environ Eng Sci2025;42(4):166–176; doi: 10.1089/ees.2024.0316
29.
SarinP, LeeSJ, ApostolovZD, et al.Porous biphasic calcium phosphate scaffolds from cuttlefish bone. Int J Appl Ceram Technol2011;94(8):2362–2370; doi: 10.1111/j.1551-2916.2011.04404.x
30.
ShiL, ZhangD, YangM, et al.New discovery of extremely high adsorption of environmental DNA on cuttlefish bone pyrolysis derivative via large pore structure and carbon film. Waste Manag2024;175:286–293; doi: 10.1016/j.wasman.2024.01.016
31.
ShiQ, WangC, ZhangH, et al.Trophic transfer and biomagnification of fullerenol nanoparticles in an aquatic food chain. Environ Sci: Nano2020;7:3564–3571; doi: 10.1039/C9EN01277J
32.
ShuaiD, Xiao-XueK, Zai-DongS, et al.Fish scale-based biochar with defined pore size and ultrahigh specific surface area for highly efficient adsorption of ciprofloxacin. Chemosphere2022;287:131962; doi: 10.1016/j.chemosphere.2021.131962
33.
SongR, ChenQ, YanL, et al.Response surface optimization of an extraction method for the simultaneous detection of sulfamethoxazole and 17β-estradiol in soil. Molecules2020;25(6):1415; doi: 10.3390/molecules25061415
34.
TanXF, ZhuSS, WangRP, et al.Role of biochar surface characteristics in the adsorption of aromatic compounds: Pore structure and functional groups. Chin Chem Lett2021;32(10):2939–2946; doi: 10.1016/j.cclet.2021.04.059
35.
TangH, WuX, XianH, et al.Heterogeneous nucleation and growth of CaCO3 on calcite (104) and aragonite (110) surfaces: Implications for the formation of abiogenic carbonate cements in the ocean. Minerals2020;10(4):294; doi: 10.3390/min10040294
36.
TangL, YuJF, PangY, et al.Sustainable efficient adsorbent: Alkali-acid modified magnetic biochar derived from sewage sludge for aqueous organic contaminant removal. Chem Eng J2018;336:160–169; doi: 10.1016/j.cej.2017.11.048
37.
TrpkovicA, Todorovic-MarkovicB, TrajkovicV. Toxicity of pristine versus functionalized fullerenes: Mechanisms of cell damage and the role of oxidative stress. Arch Toxicol2012;86(12):1809–1827; doi: 10.1007/s00204-012-0859-6
38.
WangC, ZhangH, RuanL, et al.Bioaccumulation of 13C-fullerenol nanomaterials in wheat. Environ Sci: Nano2016;3(4):799–805; doi: 10.1039/C5EN00276A
39.
WangY, WangK, WangX, et al.Effect of different production methods on physicochemical properties and adsorption capacities of biochar from sewage sludge and kitchen waste: Mechanism and correlation analysis. J Hazard Mater2024;461:132690; doi: 10.1016/j.jhazmat.2023.132690
40.
XuJ, CaoR, LiM, et al.Superhydrophobic and superoleophilic cuttlebone with an inherent lamellar structure for continuous and effective oil spill cleanup. Chem Eng J2021;420:127596; doi: 10.1016/j.cej.2020.127596
41.
YangLY, GaoJL, GaoT, et al.Toxicity of polyhydroxylated fullerene to mitochondria. J Hazard Mater2016;301:119–126; doi: 10.1016/j.jhazmat.2015.08.046
42.
YangT, JiaZ, ChenH, et al.Mechanical design of the highly porous cuttlebone: A bioceramic hard buoyancy tank for cuttlefish. Proc Natl Acad Sci USA2020;117(38):23450–23459; doi: 10.1073/pnas.2009531117
43.
YangY, SunC, LinB, et al.Surface modified and activated waste bone char for rapid and efficient VOCs adsorption. Chemosphere2020;256:127054; doi: 10.1016/j.chemosphere.2020.127054
44.
YuJ, FengH, TangL, et al.Insight into the key factors in fast adsorption of organic pollutants by hierarchical porous biochar. J Hazard Mater2021;403:123610; doi: 10.1016/j.jhazmat.2020.123610
45.
YuanY, PengX. Fullerol-facilitated transport of copper ions in water-saturated porous media: Influencing factors and mechanism. J Hazard Mater2017;340:96–103; doi: 10.1016/j.jhazmat.2017.07.001
46.
ZhangH, WangJ, ZhouB, et al.Enhanced adsorption of oxytetracycline to weathered microplastic polystyrene: Kinetics, isotherms and influencing factors. Environ Pollut2018;243(Pt B):1550–1557; doi: 10.1016/j.envpol.2018.09.122
47.
ZhangP, LiZ, ChengX, et al.Modeling Analysis of Two Common Organic Pollutants’ Adsorption and Desorption from Activated Carbon, C60, and Soil Organic Carbon. Environ Eng Sci2019;36(1):136–147; doi: 10.1089/ees.2018.0265
48.
ZhuL, ZhaoN, TongL, et al.Structural and adsorption characteristics of potassium carbonate activated biochar. RSC Adv2018;8(37):21012–21019; doi: 10.1039/C8RA03335H
49.
ZhuR, ChenQ, ZhouQ, et al.Adsorbents based on montmorillonite for contaminant removal from water: A review. Appl Clay Sci2016;123:239–258; doi: 10.1016/j.clay.2015.12.024
50.
ZhuY, ZhuR, ChenQ, et al.Calcined Mg/Al layered double hydroxides as efficient adsorbents for polyhydroxy fullerenes. Appl Clay Sci2018;151:66–72; doi: 10.1016/j.clay.2017.10.018
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