Chemical composition of natural sea salt from the Secovlje salina (Gulf of Trieste, northern Adriatic).

In our research the concentrations of major and minor elements were determined in natural sea salts from the Se~ovlje salina (Piran salts, Slovenia) and compared to those of selected samples of commercially available unrefined salts with different geographical origins (Croatia, Austria, Italy, Portugal, India, and Pakistan). In the case of major element contents such as sodium (Na), iron (Fe), aluminum (Al), manganese (Mn), and titanium (Ti) many similarities were observed among the analysed salt samples. On the other hand, Piran salts are characterized by lower silicon (Si) values. Among the salts from the Secovlje salina, the salt with the trade name Piran salt has a higher Mg content while Flower of salt has a lower concentration of calcium (Ca). In Slovenian samples the majority of trace element values were lower than 0.5 µg g-1, which was comparable to the results from commercially available unrefined salts. The salt composition differences observed indicate area-specific signatures related to geographic origin and diverse salt production processes. The quality of the studied salt samples is in accordance with standards established by the Codex Alimentarius Commission and the Piran salts are also suitable regarding issues of national food control.

Elemental Composition of Plankton Exometabolites (Mucous Macroaggregates): Control by Biogenic and Lithogenic Components.

Among the various exometabolitic effects of marine microorganisms, massive mucilage events in the coastal zones of temperate and tropical seas are the most spectacular and environmentally important. Abundant mucilage material in the form of aggregates appears in late spring/early summer in the water column of the Adriatic Sea. These macroaggregate biopolymers originate mainly from plankton exometabolites, with both autochthonous and allochthonous components, and strongly impact the tourism, fisheries, and economy of coastal countries. In contrast to extensive studies on the structural and chemical nature of macroaggregates performed over past decades, the full elemental composition of these substances remains poorly known, which does not allow for a complete understanding of their origin, evolution, and necessary remediation measures. Here, we report the results of comprehensive analyses of 55 major and trace elements in the composition of macro aggregates collected at the surface and in the water column during massive mucilage events. Through normalization of the elemental chemical composition of the upper earth crust (UCC), river suspended material (RSM), mean oceanic plankton, and mean oceanic particulate suspended material, we demonstrate that the water column macroaggregates reflect a superposition of the signal from plankton and marine particulate matter. The surface macroaggregates were preferentially enriched in lithogenic component, and carried the signature of planktonic material. The rare earth element (REE) signal was strongly dominated by plankton and, to a lesser degree, by oceanic particulate matter, while at the same time being strongly (>80 times) impoverished compared with UCC and RSM. Taken together, the elemental composition of macroaggregates allows for distinguishing the lithogenic and biogenic impacts on the occurrence of these unique large-scale mucilage events, linked to the exometabolism of marine plankton combined with the input of allochthonous inorganic material.

"Kisanje" severnega Jadrana.

The present knowledge of the carbonate system in the northern Adriatic is described in this short overview. Its buffer capacity is rather high, due to riverine input of carbonates dissolved from Alpine and Karstic watersheds, and the waters should have a higher resilience to acidification. In the shallow eutrophic areas, the combined effect of rising atmospheric CO2, warming and river-induced anthropogenic CO2 with the associated decrease in buffer capacity could act to acidification process. Significant effect on calcifying organisms is expected in the future.

Nature and lability of northern Adriatic macroaggregates.

The key organic constituents of marine macroaggregates (macrogels) of prevalently phytoplankton origin, periodically occurring in the northern Adriatic Sea, are proteins, lipids and especially polysaccharides. In this article, the reactivity of various macroaggregate fractions in relation to their composition in order to decode the potentially ¼bioavailable« fractions is summarized and discussed. The enzymatic hydrolysis of the macroaggregate matrix, using α-amylase, ß-glucosidase, protease, proteinase and lipase, revealed the simultaneous degradation of polysaccharides and proteins, while lipids seem largely preserved. In the fresh surface macroaggregate samples, a pronounced degradation of the α-glycosidic bond compared to ß-linkages. Degradation of the colloidal fraction proceeded faster in the higher molecular weight (MW) fractions. N-containing polysaccharides can be important constituents of the higher MW fraction while the lower MW constituents can mostly be composed of poly- and oligosaccharides. Since the polysaccharide component in the higher MW fraction is more degradable compared to N-containing polysaccharides, the higher MW fraction represents a possible path of organic nitrogen preservation. Enzymatic hydrolysis, using α-amylase and ß-glucosidase, revealed the presence of α- and ß-glycosidic linkages in all fractions with similar decomposition kinetics. Our results indicate that different fractions of macroaggregates are subjected to compositional selective reactivity with important implications for macroaggregate persistence in the seawater column and deposition.

Metal(oid) mobility in a hypersaline salt marsh sediment (Secovlje Salina, northern Adriatic, Slovenia).

In this research, sediments from the Secovlje Salina (northern Adriatic, Slovenia) were geochemically investigated in order to decode the mobility of metal(oid)s in the hypersaline environment. The results demonstrated that the concentrations of As, Co, Cu, Mo, Ni, Pb, Sb, Sn and Zn were comparable to those detected in various similar coastal background areas, as well as in the Secovlje salt marsh core sample. The estimated mobility potential of metal(oid)s in sediment decreases in the following order: Mo > As > Cu > Sb > Sn > Co > Pb > Ni > Zn. Since the hypersaline sediment (e.g. healing mud) is used as a healing factor (it can be applied directly on human skin), the study of metal(oid) bioavailability in an interaction between the hypersaline sediments and the artificial sweat was also performed. It is significant that the metal(oid) contents are leached in very low concentrations and are treated as nontoxic for humans according to international norms for cosmetic products. The study provides information in order to assess the role of metal mobility on the potential health impact of the application of natural healing mud.

The structure and role of the "petola" microbial mat in sea salt production of the Secovlje (Slovenia).

Microbial mats are commonly observed in estuaries and in salt marshes but they only rarely represent a significant surface involved in salt production. In the Secovlje salt works in Northern Adriatic, a microbial mat known as the "petola" covers the bottom of salt crystallising pans, highly influencing salt composition and salt production processes. Throughout the year the petola is subjected to numerous co-varying factors that drive changes in its structure and the microbial community. Seasonal modifications were investigated via various methods (cryo-HRSEM, XRD, elemental analysis, carbohydrate content, bacterial community structure). This study provides knowledge on microbial mat compositional characteristics and functional roles in response to seasonal variation in environmental conditions. The in situ characterisation (close-to its natural hydrated state) of the three-dimensional microstructure provides precise information about dominating filamentous cyanobacterium Coleofasciculus chthonoplastes and extracellular polymer secretion (EPS) organisation. This is the first study to address how microbial mat composition and structure, especially 3D EPS network (and microbial diversity), affects the salt production processes within a hypersaline environment.

Periphyton as a bioindicator of mercury pollution in a temperate torrential river ecosystem.

Mercury presents a potential risk to the environment and humans, especially in its methylated form. It is among the highest priority environmental pollutants. River Idrijca (Slovenia) is highly contaminated with mercury due to past mercury mining. The aim of this work was to investigate whether the periphyton community in rivers such as Idrijca is a suitable indicator of Hg pollution and of changes in mercury methylation and could serve as an early warning system of increased input of MeHg in the food chain. Periphyton is the only site of primary production in temperate torrential rivers such as Idrijca and is therefore an important link in the food chain. It is also a potential site of Hg accumulation and its introduction to higher trophic levels. Our aim was to assess the response of the periphyton to seasonal and spatial variations in mercury levels and to evaluate its potential as an early warning system of changes in mercury reactivity and mobilization The results indicate that periphyton in a torrential river is too complex and unpredictable to be used as a sole indicator of mercury concentrations and changes in the river. Nevertheless, it can complement environmental measurements due to its importance in the riverine food web.

Characterization of carbohydrates in mucilage samples from the northern Adriatic Sea.

Carbohydrate contents in seawater, mucilage, and mucilage interstitial waters were analyzed during episodes of mucilage formation in the summers of 2000 and 2001 in the northern Adriatic Sea off Pesaro and in the Gulf of Trieste using 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) and 2,4,6-tripyridyl-s-triazine (TPTZ) assays. The significant presence of polysaccharides in seawater in the presence of mucilage has an important impact on the agglomeration processes forming gelatinous material (macrogels). Characterization of oligosaccharides in the water-soluble fraction of mucilage using HPLC/RI revealed maltose and pentaose as the main components.