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Project leader Ciglenecki-Jusic Irena
Project co-leader: Prof. Dr. Nikola Batina
Administering organization: Rudjer Bošković Institute, Bijenička 54, 10000 Zagreb Department for Marine and Environmental Research (DMER) Laboratory for Physical Chemistry of Aquatic systems (LPCAS)
Partner Institution/Company: Laboratorio de Nanotecnología e Ingeniería Molecular, Área de Electroquímica, Departamento de Química, CBI
Grant type: 1B
Project title: Nanoparticles in aqueous environment: electrochemical, nanogravimetric, STM and AFM studies
Project summary: In order to evaluate potential exposure of ecosystems to engineered as well as natural aquatic colloids and nanoparticles (NPs), methods must be available for measuring spatial and temporal trends in the concentration, size distribution, metal content of these NPs and their interaction in the different environmental compartments. Here we propose an electrochemical and piezo-nanogravimetric study of metal, metal-oxides and chalcogenide nanoparticles in combination with sophisticated methods such as atomic force and scanning tunneling microscopy, ICPMS and separation techniques such as ultrafiltration and Diffusion Gradients in Thin Films. We offer electrochemistry due to its simplicity and prompt response, low cost and relatively high sensitivity and selectivity, as alternative analytical technique for characterization and quantification of different here preferably chalcogenide based NPs. Voltammetric measurements in combination with electrochemical nanogravimetric measurements (EQCM) and Scaning Tunneling Microscopy (STM) as well as Atomic Force Microscopy (AFM) on different electrode surfaces (Hg and Au electrode) will give more details and information related to attachment, adsorption, deposition and interaction between selected NPs and functionalized electrode surfaces. By following changes in the resonance frequency which will be in the same time accompanied with some changes in current produced during oxido-reduction processes it is possible to characterize physico-chemical properties and to calculate the mass of NPs deposited on the Au surface over a broad range of environmentally relevant solution chemistries including variation in ionic strength, composition, pH, ion valence, particle sizes. The particle deposition mechanisms will be studied in relation with variations of particle charge, particle sizes and applied electrode potential all with the aim to improve and develop new analytical method for fast, selective qualitative and quantitative NPs characterization in natural waters. Method which development is planned in the laboratory will be tested and intercalibrated on the field. We expect that understanding of the environmental impact of engineered NPs will significantly benefit from the lessons learnt with natural NPs. As study sites we offer four types of samples: 1) oxic seawater samples from North Adriatic as the source of natural aquatic colloids and NPs mainly produced during intensive phytoplankton bloom and occasionally appearance of mucous aggregates; 2) hypoxic/anoxic samples of stratified seawater Lake Rogoznica on the eastern Adriatic coast enriched by FeS; 3) industrial waste waters including sea-marinas of engineered NPs; 4) wet deposition from atmosphere. We expect that research proposed here would contribute to further studies and applications of NPs in chemical/biochemical sensing.
Hrvatski sažetak: S obzirom na sve veću proizvodnju nanočestica i nanomaterijala, te na potencijalni risk koji proizvedene kao i prirode nanočestice mogu imati na prirodni ekosustav, potrebno je razviti odgovarajuće metode kojima bi se pratili prostorni i vremenski trendovi u koncentraciji te veličini nanočestica, sadražaju metala te njihovoj interakciji u različitom uvjetima u prirodnom okolišu. U okviru ovog projekta predlaže se elektrokemijsko i piezo-nanogravimetrijsko istraživanje nanočestica metala, metalnih oksida i metalnih sulfida u kombinaciji sa „state of the art“ tehnikama poput mikroskopije atomskih sila (AFM), „scaning tunneling mikroskopije“ (STM), spektrometrije masa s induktivno spregnutom plazmom velikog razlučivanja (HR-ICPMS) te tehnikama odvajanja poput ultrafiltraticije i difuzijskog gradijenta u tankom filmu (DGT). Elektrokemija kao jedna od jeftinijih i jednostavnijih analitičkih tehnika koja omogućava vrlo brzu analizu s relativno velikom selektivnošću i osjetljivosti pokazala se kao dobra alternativna analitička tehnika za karakterizaciju i kvantifikaciju različitih nanočestica. Voltametrija u kombinaciji s elektrokemijskim nanogravimetrijskim mjerenjima (EQCM) te AFM i STM na različitim površinama elektroda (Hg,Au) dati će uvid u procese vezanja, adsorpcije, depozicije te interakcije između različitih nanočestica i elektrodnih površina. Promjene rezonantne frekvencije koje će istovremeno biti popraćene s promjenama u struji oksidacije ili redukcije omogućiti će karakterizaciju fizičko-kemijskih svojstava kao i izračun mase nanočestica deponiranih na površini elektrode. Sve te promjene pratiti će se u razlučitim kemijskim uvjetima (ionska jakost, sastav elektrolita, pH, valencija iona, veličina čestica). Mehanizmi deponiranja i adsorpcije nanočestica na elektrodi također će se pratiti u ovisnosti o naboju i veličini čestica te primjenjenom potencijalu depozicije a sve s ciljem poboljšanja i razvoja novih analitičkih tehnika za brzu, selektivnu kvalitativnu i kvantitativnu karakterizaciju i analizu nanočestica u prirodnim vodama. Metoda koja se planira razviti u laboratoriju testirati će se i interkalibrirati na prirodnim uzorcima. Kao prirodni modeli predlažu se četiri tipa uzoraka: 1) oksični uzorci mora Sjevernog Jadrana kao izvor prirodnih koloida i nanočestica proizvedenih tijekom fitoplanktonskog cvata i sporadične pojave mukoznih nakupina; 2) hipoksično/anoksični uzorci Rogozničkog jezera obogaćeni nanočesticama FeS; 3) industrijske otpadne vode uključujući morske marine kao izvor proizvedenih nanočestica; 4) oborine (kiša, aerosol) kao izvori prirodnih i proizvedenih nanočestica. Očekujemo kako će predloženo istraživanje doprinesti budućim studijama posebno aplikaciji nanočestica u proizvodnji kemijskih/biokemijskih senzora.
Amount requested from UKF: 798.948,00 HRK
Amount of matching funding: 389.947,00 HRK
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