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Crayfish Waste-shells Integrated Valorization for Added Value Materials Production: Calcium Hydroxide, Calcium Carbonate, Chitin, Chitosan, and N-S co-doped Carbon Quantum Dots

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Waste and Biomass Valorization Aims and scope Submit manuscript

Abstract

Purpose

Crayfish treatment leads to the production of waste and byproducts up to 80% of the total initial seafood amount. The current common method to handle such waste is the landfilling practice which produces remarkable amounts of hazardous gasses and substances due to the anaerobic decomposition process. In this study, an integrated procedure is proposed for the valorization of wastes produced by a fish and crustaceous enterprise.

Methods

According to the circular economy and environmentally friendly practices spirit, integrated vertical production and waste valorization methods are adopted globally to reduce food waste. In this study, a process consisting of four sequential steps was proposed to valorize crayfish-treatment waste. Four final added-value materials were produced during this study. The first was chitosan which was identified via the NMR technique exhibiting 91% deacetylation degree. The other two were calcium hydroxide particles of size 6.32 μm and calcium carbonate particles of size 16.9 μm exhibiting meso-macro-pore structure with Sg = 46m2/g and Sg = 20m2/g respectively. Pore specific surface area values of these two products are similar to values reported in the literature for applications such as drug carriers etc. The last product was nitrogen/sulfur-doped carbon quantum dots which exhibited an identified via AFM technique mean size of 5.01 nm. This material was successfully tested for its advanced antioxidant capabilities via the DPPH assay and for its antimicrobial properties via MIC routine measurements with E. coli and L. monocytogenes.

Results

Experimental data indicated that the valorization process proposed in this study could lead to a yield of 10% w/w for chitosan after three stages treatment, to a yield of 35% w/w for Ca(OH)2 or CaCO3 after 1 stage treatment, and to a yield of 5% w/w N-S co-dopped Carbon QDs.

Conclusion

The globally big amount of waste-shells from Crayfish and other crustaceous could be integratedly exploited for added-value materials production yielding economic and environmental benefits.

Highlights

Crayfish waste shells are valorized.

Integrated valorization of waste shells of crustaceous is feasible.

Calcium carbonate and Calcium hydroxide powders exhibiting very good properties for different applications could be produced from waste shells valorization.

High added value materials such as chitin and chitosan biopolymers could be produced from waste shells valorization.

Advanced quantum dots such as nitrogen/sulfur dopped could be produced from waste shells valorization.

AbstractSection Graphical Abstract

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Data Availability

Data are presented in the manuscript.

Abbreviations

AFM:

Atomic Force Microscopy

BET:

Brunauer Emmett Teller

CaCO3:

Calcium Carbonate

Ca(OH)2:

Calcium Hydroxide

CHN:

Chitin

CPSM:

Corrugated Pore Structure Model

CQDs:

Carbon Quantum Dots

CS:

Chitosan

DD:

Deacetylation Degree

DFT:

Density Functional Theory

DPPH:

2,2-DiPhenyl-1-PicrylHydrazyl

FTIR:

Fourier Transform Infra Red

NMR:

Nuclear Magnetic Resonance

QDs:

Quantum Dots

UV:

Ultra Violet

UV–Vis-NIR:

Ultra Violet-Visible-Near Infra Red

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Acknowledgements

The authors acknowledge Flerianos S.A. fish and seafood processing company as well as Ms. Athina Evmorfopoulou for the waste-shells supply.

Funding

This research received no external funding.

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Authors and Affiliations

  1. Department of Material Science and Engineering, University of Ioannina, 45110, Ioannina, Greece

    Constantinos E. Salmas & Viktoria Sakavitsi

  2. Department of Food Science and Technology, University of Patras, 30100, Agrinio, Greece

    Stavros Georgopoulos, Areti Leontiou, Konstantinos Zaharioudakis, Efthymia Ragkava, Vasilios K. Karabagias, Nikolaos D. Andritsos, George Kehayias & Aris E. Giannakas

  3. Department of Pharmacognosy and Natural Products Chemistry, Faculty of Pharmacy, National and Kapodistrian University of Athens, Panepistimiopoli Zografou, 15771, Athens, Greece

    Antigoni Cheilari

  4. Laboratory of Food Chemistry, Department of Chemistry, National and Kapodistrian University of Athens Zografou, 15771, Athens, Greece

    Eleni Kollia & Charalampos Proestos

  5. Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece

    Ioannis Konstantinou

Authors
  1. Constantinos E. Salmas
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  2. Stavros Georgopoulos
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  4. Viktoria Sakavitsi
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  7. Konstantinos Zaharioudakis
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  8. Efthymia Ragkava
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  9. Vasilios K. Karabagias
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  11. Ioannis Konstantinou
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  12. Charalampos Proestos
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  13. George Kehayias
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  14. Aris E. Giannakas
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Contributions

“Conceptualization, methodology, writing—original draft preparation, writing—review and editing, and overall supervision, A.E.G., and C.E.S.; formal analysis, S.G., V.S., A.C., E.K., K.Z., V.K.K., N.D.A., A.K., A.K., C.L, G.K., I.K., and C.P.; investigation, S.G., V.S., E.K., K.Z., V.K.K., N.D.A., A.K., A.K., C.L, V.K.K., I.K., and C.P.; resources, N.D.A., data curation, S.G., V.S., A.C., E.K., K.Z., V.K.K., N.D.A., A.K., A.K., C.L, V.K.K.; G.K.; I.K.,C.P.;A.E.G., and C.E.S., visualization, Α.L., E.K., C.P., Ι.Κ.;and S.G.; All authors have read and agreed to the published version of the manuscript.”

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Correspondence to Constantinos E. Salmas or Aris E. Giannakas.

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Statement of Novelty

Nowadays, approximately 8 million tons of waste shells are produced globally from crab, shrimp, lobster, crayfish, and other crustaceans. Until recently such waste was landfilled or dumped at sea with unfavorable side effects on soil and water. This study aims to develop an integrated process to fully valorize such food byproducts according to the circular economy and sustainability spirit. According to our proposed process, the seafood waste valorization was achieved via the following sequence of process steps: 1st, Demineralization process of waste to extract chitin and to isolate CaCO3 and Ca(OH)2 solution; 2nd, Deacetylation process of the produced via the demineralization process chitin to produce chitosan, and to isolate a rich in proteins solution; 3rd, Precipitation process of the produced via the demineralization process CaCO3 and Ca(OH)2 solution to produce high-quality CaCO3 and Ca(OH)2; 4th, Hydrothermal treatment of the produced via the deacetylation process proteins solution to produce N-S co-dopped carbon quantum dots. The experimental measurements showed recovery of a remarkable amount of calcium carbonate or calcium hydroxide which exhibited high purity and preferable pore structure characteristics. This material has gradually gained widespread attention because of its suitability for advanced applications such as cancer treatment, bone repair, and other medical purposes. The obtained amount of this material was achieved via a greener method using smaller quantities of chemicals or chemical reactions. Furthermore, the attractive biopolymers chitin and chitosan which are eligible for numerous applications, were recovered and identified via NMR technique. Finally, advanced nitrogen/sulfur carbon quantum dots were produced via further exploitation of liquid byproducts produced from the above two process stages without the need for nitrogen or sulfur chemical sources. As an overall conclusion this study confirmed that added-value materials such as Chitin/Chitosan, Ca(OH)2, CaCO3, and Nitrogen/Sulfur co-dopped Carbon Quantum Dots, are possible to take place via a greener way, with a total valorization of waste shells from crustaceans in three process stages using reduced chemical agents and chemical reactions.

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Salmas, C.E., Georgopoulos, S., Leontiou, A. et al. Crayfish Waste-shells Integrated Valorization for Added Value Materials Production: Calcium Hydroxide, Calcium Carbonate, Chitin, Chitosan, and N-S co-doped Carbon Quantum Dots. Waste Biomass Valor (2024). https://doi.org/10.1007/s12649-024-02559-4

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