Spettroscopia a banda ultralarga per il rilevamento di contaminanti emergenti nelle Bocche di Cattaro

Responsabili di progetto

Dimitrios Zografopoulos, Danijela Joksimovic

Accordo

MONTENEGRO - MoS-not in force - Ministero della Scienza del Montenegro

Bando

CNR/MoS biennio 2019-2020 2019-2020

Dipartimento

Scienze fisiche e tecnologie della materia

Area tematica

Scienze fisiche e tecnologie della materia

Stato del progetto

Nuovo

Proposta di ricerca

Seawater quality monitoring is of paramount importance for the maintenance of a healthy and sustainable aquatic environment. Sources of marine contamination are becoming increasingly more diversified and invasive owing to the steadily growing anthropogenic activities, urbanization, and industrialization. Well-established techniques for the measurement of seawater properties, such as pH, salinity, dissolved oxygen, detection and measurement of pollutants such as trace metals or inorganic fertilizer nutrients, have to be extended so as to address the detection of emerging contaminants, e.g. plastics, microfibers, pharmaceuticals, and assess their environmental impact.

The Bay of Kotor (Boka Kotorska) is among the most important marine geological formations in Montenegro thanks to its peculiar topography, featuring a 107-km-long shoreline and interconnected smaller bays, and its increased urban, financial, and ecological significance. Its ongoing urbanization and industrialization leads to the inevitable pollution of its waters through the atmosphere, the sewage drain system and overall waste discharge, posing a serious threat to the marine ecosystem.

Seawater properties, including different physicochemical parameters (dissolved oxygen, salinity, pH, inorganic nutrients), trace metals in mussels as bioindicator of water pollution, seasonal variations of different parameters, and zooplankton dynamics are systematically monitored by the Institute of Marine Biology (IMB) [1,2]. Still, their strong expertise for the measurement of such properties has to be extended in order to address the detection of emerging contaminants.

In this project, IMB's expertise in classical and instrumental methods of chemical analysis (UV/VIS spectrophotometry, atomic absorption spectroscopy (AAS)) for seawater monitoring, is synergistically coupled with that of CNR-IMM in advanced spectroscopic techniques, i.e. UV/VIS, Fourier-transform infrared (FTIR), terahertz, and micro-Raman spectroscopy, aiming at an ultra-broadband spectroscopic platform for the detection of both organic and inorganic contaminants in the Bay of Kotor.

Samples of seawater and mussels, key bioindicators known for their capacity to accumulate trace elements and microplastic debris (polysterene, polyethelene, polyamides), will be collected at strategically selected locations in Boka Kotorska and processed by IMB. The basic physicochemical parameters of seawater will be determined. The level of nutrients, such as nitrate and phosphate ions in seawater, and trace metals in mussels will be measured using UV/VIS spectrophotometric methods and AAS, respectively.

Subsequently, the samples will be investigated by CNR-IMM in a series of spectroscopic measurements in the UV/visible (0.19-1.1 um), infrared (1.28-27 um), and terahertz (100-1000 um) spectrum. The spectra will be analyzed in order to identify the molecular fingerprints of relevant organic substances (plastics, pharmaceuticals) in the corresponding windows [6,7], aided by publicly available spectral databases for organic compounds [8]. Principal component analysis algorithms will be employed to correctly identify the individual substances. The investigation will be backed by micro-Raman measurements, a powerful vibration spectroscopic technique capable of revealing not only the type but also the structure of the samples under test, including aqueous solutions. If deemed necessary to increase the sensitivity of the measurements, surface-enhanced Raman spectroscopy (SERS) will be employed by exploiting CNR-IMM's expertise in the engineering and fabrication of plasmonic SERS substrates [9].

The results will be analyzed and cross-referenced in order to provide a reference database of the collected spectra. For instance, near-IR spectroscopy can provide an additional means of measuring the physicochemical properties of water, whereas SERS the concentrations of nutrients. A comprehensive report will be prepared on the current status of the marine ecosystem in Boka Kotorska, and on the possible threats stemming from emerging contaminants against both sea life and humans. The report will provide valuable input to the Montenegrin authorities and policy-makers in view of a potential update of the regulations regarding industrial and urban activities, waste disposal and sewage channels in the surrounding areas of Kotor, Tivat, and Herceg Novi.

In parallel, the knowledge and scientific results gained through this project will lead to a mutual transfer of know-how between IMB and CNR-IMM and the mobility will contribute to the training of the young researchers involved in advanced chemical analysis and spectroscopic techniques. Furthermore, the scientific outcome will serve as a solid basis for scientific publications, as well as for long-term cooperation and future joint applications, for instance, in the frame of the Horizon 2020 program.

[1] D. Joksimovic, I. Tomic, A. R. Stankovic, M. Jovic, and S. Stankovic, Food Chem. 127, 632-637, 2011.
[2] A. Pero?evic, D. Joksimovic, D. Ðurovic, I. Mila?evic, M. Radomirovic, and S. Stankovic, J. Trace Elem. Med. Biol., doi:10.1016/j.jtemb.2018.03.018
[3] A. Ferraro, D. C. Zografopoulos, R. Caputo, and R. Beccherelli, Appl. Phys. Lett. 110, 141107, 2017.
[4] A. Ferraro, D. C. Zografopoulos, R. Caputo, and R. Beccherelli, Photon. Lett. Pol. 9, 2-4, 2017.
[5] V. Mussi, C. Biale, S. Visentin, N. Barbero, M. Rocchia, and U. Valbusa, Carbon 28, 3391-3398, 2010.
[6] A. A. Gowen, R. Tsenkova, M. Bruen, and C. O'donnell, Crit. Rev. Environ. Sci. Technol. 42, 2546-2573, 2012.
[7] B. Gewert, M. Ogonowski, A. Barth, and M. MacLeod, Mar. Pollut. Bull. 120, 292-302, 2017.
[8] The Spectral Database for Organic Compounds (SDBS) is a free online searchable database hosted by the National Institute of Advanced Industrial Science and Technology (AIST) in Japan (http://sdbs.db.aist.go.jp).
[9] A. Convertino, V. Mussi, and L. Maiolo, Sci. Rep. 6, 25099, 2016.

Obiettivi della ricerca

The main scientific goal of the project is to develop a toolbox of spectroscopic and chemical analysis methods for seawater quality monitoring and detection of contaminants in Boka Kotorska Bay.

In particular, the project's objectives are:

[O1] Assembling a repository of seawater and biota samples, collected at key locations in Boka Kotorska Bay for the assessment of the quality of the marine ecosystem.

[O2] Development of spectroscopic measurement techniques, namely UV/VIS, FTIR, THz, and micro-Raman spectroscopy, for the detection of inorganic and organic pollutants, focusing on emerging contaminants, e.g. synthetic polymers and pharmaceuticals.

[O3] Cross-referencing of data obtained by advanced spectroscopic techniques with classical and instrumental methods (UV/VIS, AAS) of chemical analysis, and generation of a comprehensive report on the actual status of Boka Kotorska Bay marine ecosystem.

[O4] Transfer of know-how and expertise between IMB and CNR-IMM and training of young researchers according to the plan of mutual visits.

[O5] Dissemination of the results in the form of scientific publications and raising the awareness of third-bodies, such as the Montenegrin authorities, on the potential dangers of the marine ecosystem.

[O6] Establishing a collaboration between IMB and CNR-IMM, as a prerequisite for future joint projects, combining their complementary expertise in marine environmental monitoring with advanced spectroscopic techniques.

Ultimo aggiornamento: 03/12/2024