Dissolved organic carbon and surface active substances in the northern Adriatic Sea: Long-term trends, variability and drivers.

The paper presents a unique time series of organic matter content (dissolved organic carbon, DOC, and its surface active substances fraction, SAS) collected in the northern Adriatic along the Po-Rovinj transect between 1998 and 2017. The data were collected on a monthly or bimonthly basis. Seasonal variance of organic matter content does not exceed 30% of its total variance, while the DOC and the SAS trends are significantly negative and positive, respectively, over the whole transect. The organic matter content, however, exhibits pronounced interannual and decadal changes, with periods of high and low carbon content and evident changes in composition of the SAS content. The changes indicate altering episodes between eutrophication and oligotrophication, embedded in the overall oligotrophication trend in the considered period. Both series were correlated with the potential local and regional yearly-averaged drivers in both atmosphere and sea. DOC is most strongly (significant at 99%) correlated with the Po River discharges, at the phase lag of -1 to -2 years. For the SAS, the largest correlations (significant at 99%) are obtained with the Adriatic-Ionian Bimodal Oscillating System index (BiOS index), at the phase lag of -3 to -4 years. Correlations between the organic matter content and the hemispheric or the regional climate indices (North Atlantic Oscillation, East Atlantic/West Russia, East Atlantic, Scandinavian, and Mediterranean Oscillation) are much lower and only sparsely significant at 95% at some phase lags. The same was found for the other local drivers (precipitation and net heat flux). Our analysis highlights the importance of remote processes, like the BiOS, that weren't previously considered to shape the biogeochemical properties of such shallow coastal region impacted by freshwater load. To properly assess such impacts, long-term ecological monitoring and homogenized data series are required.

Dissolved organic carbon as potential indicator of global change: A long-term investigation in the northern Adriatic.

Dissolved organic carbon (DOC) is an essential component of the biogeochemical marine system, effecting biological and chemical reactions that take place in the sea. DOC represents a dynamic component of the global carbon cycle. This paper reports 25years of measurements of DOC content and distribution at seven stations along the transect Po River delta - Rovinj in the northern Adriatic (NA). The results show strong temporal and spatial variability: (1) The highest average DOC concentrations were observed in 1998 and 2002 (143µmol/L and 137µmol/L, respectively); (2) The minimum average DOC was recorded in 2006 (88µmol/L) and (3) The short-term DOC accumulation (up to 203, average 102µmol/L) for the years 2009 to 2012, was observed during the summer and autumn months followed by unusually low DOC concentrations during the winter and spring. The DOC results from the more recent monitoring at the same stations indicate primarily oligotrophic characteristics of the NA seawater (88µmol/L). The results of DOC variability and distribution in the NA appears to be strongly influenced by complex circulation patterns. This paper provides a "link" between the Ionian circulation and the NA ecosystem as a part of the recently identified Adriatic-Ionian Bimodal Oscillating System (BiOS). A good agreement between the BiOS oscillation and other variables related to the DOC concentration, like the NA A and B winter types, the Po River discharge, salinity, chlorophyll a, occurrence of hypoxic-anoxic conditions, eutrophication and oligotrophication, suggests that DOC might be a good tool and indicator of global change.

Physicochemical signatures of natural sea films from Middle Adriatic stations.

Monolayer studies and a force-area quantification approach, in combination with electrochemical methods, are applied for physicochemical characterization of surface active substances (SAS) of the sea surface microlayers (MLs) from Middle Adriatic stations. Higher primary production during late spring-early autumn was reflected in the presence of MLs of higher surfactant activity containing on average molecules of lower molecular masses (M(w) = 0.65 ± 0.27 kDa) and higher miscibility (y = 6.46 ± 1.33) and elasticity (E(isoth) = 18.33 ± 2.02 mN m(-1)) modulus in comparison to structural parameters (average M(w) = 2.15 ± 1.58 kDa; y = 3.51 ± 1.46; E(isoth) = 6.41 ± 1.97 mN m(-1)) obtained for MLs from a period of lower production. A higher inhibition effect on the reduction process of Cd(2+) was observed for SAS abundant MLs from a more productive period. This kind of distribution is explained as the consequence of competitive adsorption of hydrophobic lipid-like substances of lower M(w) that act as end-members, highly influencing the surface structural properties of the natural air-water interface forming there segregated surface films during more productive period.

Copper complexing properties of melanoidins and marine humic material.

Melanoidins, condensation products of sugars and amino acids, represent a key link in the transformation of polysaccharides to humic material in the marine environment. We investigated the complexing capacity of melanoidins that were prepared in deionized water and seawater and separated into different molecular mass fractions. The copper complexing properties of humic material isolated from marine lagoon sediments were determined for comparison. Melanoidins prepared using condensation times longer than two days exibit complexation properties towards copper ions that appear to depend on the basicity of the amino acid precursor and the molecular mass of the product. Pseudomelanoidins, prepared from glucose only, do not complex copper ions at all, regardless of the molecular mass. The highest copper complexing capacity value among melanoidins was measured for a glucose-lysine melanoidin with molecular mass fraction >10 kD (L(T)=2.1x10(-7) molCu(2+)/L). Melanoidin prepared from glucose and glutamic acid >10 kD was similar in complexing capacity to fulvic acid (1-20 kD molecular mass) isolated from lagoon sediments. The presence of calcium and magnesium ions and other macro and microconstituents in the seawater used to prepare melanoidins influences its complexing properties towards metal ions.

Temporal dynamics of dissolved and particulate organic carbon in the northern Adriatic Sea in relation to the mucilage events.

The accumulation of dissolved and particulate organic matter may play an important role in mucilage formation in the northern Adriatic. Distributions of dissolved and particulate organic carbon were therefore investigated during the period June 1999-July 2002, when massive mucilage events occurred: in the summer of 2000 and, to a greater extent, of 2002. The seasonal variations in dissolved organic carbon (DOC) concentrations were significant, doubling in summer (up to 150 micromol L(-1)) with respect to winter. The particulate organic carbon (POC) variations were also very large, with a less pronounced seasonal pattern compared to DOC, because the POC changes are much more dependent both on river discharges and on phytoplankton blooms. The comparison of the concentrations between the period before (March-May) and after the onset of mucilage events (June-August) showed that DOC, but particularly POC, were higher in the period before the event of 2002, more markedly in the surface waters of low salinity. The POC increased, reaching mean concentrations of up to 36 micromol L(-1) in March 2002 before the outbreak of the massive mucilage formation in June. This suggests that POC may have a more important role in the mucilage formation than DOC. The highest seasonal variations of organic matter concentrations took place in the upper layer of lower salinity, stressing the importance of stratification and pycnoclines for accumulation and aggregation of the organic matter in the northern Adriatic. The POC contribution to the total organic carbon was low in the oligotrophic waters (DOC/POC ratio >15) and increased with the phytoplankton biomass in the productive waters (DOC/POC ratio <10). Particulate organic carbon predominated over the dissolved inside the mucilage aggregate (DOC/POC ratio <1), probably because aggregation processes, in which colloidal organic carbon is involved, are important. The organic carbon within the aggregates reached a concentration of 13.6 mmol L(-1) which was about 100 times more than in the surrounding waters or in the waters when the mucilages were absent. This indicates that distributions of organic carbon in the northern Adriatic can be extremely patchy during mucilage events.