While recording SERS spectra of pure β‐carotene at sub‐micromole concentrations for reference purpose, we discovered an unusual spectral response never reported before. In pre‐resonance conditions with the 532‐nm line, SERS of β‐carotene with AgNPs exhibits among the strong υ(CC) mode at 1512 cm−1 unshifted from normal Raman spectrum, additional strong bands at 1649, 1575 and 1387 cm−1 as well as other medium bands not observed in the Raman spectrum of the crystalline powder. Such behavior is explained in terms of selection rules relaxation upon cyclohexene terminal rings of the β‐carotene interaction with the NP surface. AFM images of the SERS system suggested dimers and trimers clustering of the nanoparticles with adsorbed β‐carotene. In light of the new SERS feature the consequences in correct interpretation of the SERS imaging from complex biosystems containing carotenoids are discussed. Relative intensity ratio of the β‐carotene band at 1512 cm−1 and water against concentration allowed a reliable SERS calibration curve for 50 to 500 nmol l−1 concentration range and provided quantitative SERS assessment of the carotenoid content in the sea urchin (Paracentrotus lividus) gonads extracts. Copyright © 2015 John Wiley & Sons, Ltd.
Samples of the European eel, Anguilla anguilla from two different habitats in the River Neretva estuary region were analysed using two different traditional fishery gear, in the period from 2016 to 2019. The monthly eel catches in ten traditional fyke nets in Parila lagoon varied from 4.4 to 12.7 kg (±2.45 kg) in 2016 and 2.4 to 9.6 kg (±2.01 kg) in 2019. There were no statistical differences between monthly and total weights recorded in 2016 and 2019 (t=1.04; p=0.312). The b-coefficient of the length-weight (LW) relationship for the freshwater eel samples varied from 3,1036 to 3,3206 duringtwo-year period of the sampling. The LW relationship for the brackish population was significantly lower (b-coefficient 2,6513). The dominant eel stage in both sites was yellow eel, while silver stage was scarce. The fishery with traditional devices revealed that efficiency of these artisanal tools is low, pointing to poor abundance of eel in their common habitats. The recorded catch using bigger traditional eel trap gear during autumn spawning migrations was also dominated with yellow stage, while silver eel represented only 15,4% of the catch. The infestation of eels with the parasite,Anguillicoloides crassus was significantly higher in freshwater habitat (41% of eel specimens infested) than in brackish, Parila lagoon (7%). Poor efficiency of traditional gear, bad length and weight structure of the population and low b-coefficients of eels in their most important habitat, indicate poor status of European eel population and River Neretva estuarine ecosystems.
This study reported the efficiency of artificially formulated feed and benthic macrophyte diet on growth and gonad development of cultured stony sea urchin, Paracentrotus lividus (Lamark, 1816). An initial sample of 720 individual urchins was gathered in coastal area of SE Adriatic, near Dubrovnik, Croatia and for the purposes of the experiment, was held in a flow-through system. Sea urchin were fed four test diets A, B, C and D. Diet A consisted of seaweeds collected in the natural habitat of sampled sea urchin, artificial diets B, C, and D contained a different ratio of ingredients. The feed mixtures differed in respect to corn meal content; B (22%), C (30%) and D (35%) as well as the distribution of fish meal content; B (15%), C (5%) and D (0%). Prior to the commencement of feeding, sea urchins in all groups were starved for 15 days. During the period of starvation, recorded total urchin weight, gonadosomatic index (GSI) and gonad weight values for all experimental groups, showed a declining trend except in the control group, where they stayed the same. After 30 days, the declining trend of morphometric values was recorded for treatment A and the control group. During the two months of the intensive feeding conditions in the regimes with artificially prepared feed, B, C and D a growing trend was recorded for all morphometric values, and it was particularly evident in the treatment C. In the last month of the experiment, a significant decline in the GSI and gonad weight values were observed for the groups, A and the control. The differences among the artificially formulated feeds expressed through increase of GSI and gonad mass values revealed that the best among them was artificial feed C whose variance in consistence of essential nutritional components fits between prepared feeds B and D. Based on the results of our study we conclude that the artificially formulated feed is adequate food for sea urchins in a controlled environment, especially when it contains a smaller animal protein component (5-10%) and a larger share of plant components (over 90%).
Live diatoms exposed to AgNPs revealed SERS mechanism dependent on the nanoparticles type while the SERS output allowed detection of extracellular substances.
Raw algae waste naturally thrown on shores could pose serious threats for landfilling and its reuse for composting or further processing as added-value by-products require knowledge-based decisions and management for the sustainable development of local ecosystems. Raw marine waste containing salt (halite) and heavy metals that eventually accumulate in algae hamper their safe applicability in soil fertilization or in other exploitations. Here, the suitability of algal biomass for use as an environmentally safe fertilizer was investigated, thereby supporting sustainable coastal management. The simple extraction of the dry algal biomass of three abundant Mediterranean species, Enteromorpha intestinalis, Corallina elongata, and Gelidium pulchellum, in water containing sodium carbonate resulted in a greenish extract containing a reduced heavy metals content, and nutrients such as K+, PO43−, SO42−, NO3−, Ca2+, and Mg2+. UV-Vis and Raman techniques, including surface-enhanced Raman scattering (SERS), were employed for the fast evidencing of polyphenols, carotenoids, and chlorophylls in the extracts content, while E. intestinalis extract additionally exhibited polysaccharide signals. Heavy metals analysis showed that the major metals in the extracts were Fe, Ni, Zn, and Cu; however, their levels were an order of magnitude lower than in the dry biomass. The extracts also showed a mild antibacterial effect. The combination option of aqueous extracts with powdered crustacean shells to obtain a novel, eco-friendly, solid biofertilizer complex was further shown, which could be pelleted for convenient use. The immersion of solid biofertilizer pellets in water is accompanied by re-solubilization of the compounds originating from algae extracts, presenting the opportunity for dry storage and easier handling and land applicability. In summary, aqueous extracts of marine algae waste present an environmentally safe and attractive way to recycle excessive algal biomass and to formulate a new, eco-friendly biofertilizer complex.
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