Speciation of Cu, Cd, Pb and Zn in a contaminated harbor and comparison to environmental quality standards.

The water column of harbors contains significant amounts of (priority) hazardous trace metals that may be released into coastal areas of high societal and economic interests where they may disturb their fragile equilibria. To deepen our understanding of the processes that influence the transport of the various metal fractions and allow for a more rigorous environmental risk assessment, it is important to spatially monitor the relevant chemical speciation of these metals. It is of particular interest to assess their so-called dynamic fraction, which comprises the dissolved chemical forms that are potentially bioavailable to living organisms. In this study this was achieved in the Genoa Harbor (NW Italy) for copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) by applying a multi-method approach. For the first time in this system the dynamic fractions of the target metals (CuDyn, CdDyn, PbDyn, ZnDyn) were observed in real-time on-board by voltammetry using innovative electrochemical sensing devices. Trace metals in the operationally defined dissolved <0.2 µm and <0.02 µm fractions were equally quantified through sampling/laboratory-based techniques. The obtained results showed a clear spatial trend for all studied metals from the enclosed contaminated part of the harbor towards the open part. The highest CuDyn and CdDyn fractions were found in the inner part of the harbor while the highest PbDyn fraction was found in the open part. The proportion of ZnDyn was negligible in the sampled area. Small and coarse colloids were involved in Cu, Cd and Zn partitioning while only coarse colloids played an important role in Pb partitioning. The determined concentrations were compared to the Environmental Quality Standards (EQS) established by the EU and those determined by the Australia and New Zealand to trigger for 99 and 95% species protection values. The results of this work allow us to highlight gaps in the EQS for which metal concentration thresholds are excessively high or non-existent and should urgently be revised. They also reflect the need to quantify the potentially bioavailable fraction of hazardous trace metals instead of just their total dissolved concentrations. The data support the establishment of environmental quality standards and guidelines based on realistic risk assessment to protect aquatic life and resources and ultimately human health.

Phaeocystis antarctica unusual summer bloom in stratified antarctic coastal waters (Terra Nova Bay, Ross Sea).

This study focuses on the potential explanations for a Phaeocystis antarctica summer bloom occurred in stratified waters of Terra Nova Bay (TNB) - which is part of the Antarctic Special Protected Area (n.161) in the Ross Sea - trough a multi-parameter correlative approach. Many previous studies have highlighted that water column stratification typically favors diatom dominance compared to the colonial haptophyte P. antarctica, in the Ross Sea, and this correlation has often been used to explain the historic dominance of diatoms in TNB. To explore the spatial and temporal progression of P. antarctica bloom in coastal waters, four stations were sampled three times each between December 31, 2009 and January 13, 2010. Taxonomic and pigment composition of phytoplankton communities, macro-nutrient concentrations and various different indices, all indicated the relative dominance of P. antarctica. Cell abundances revealed that P. antarctica contributed 79% of total cell counts in the upper 25 m and 93% in the lower photic zone. Similarly, a strong correlation was observed between Chl-a and the Hex:Fuco pigment ratio, corroborating the microscopic analyses. Recent studies have shown that iron can trigger colonial P. antarctica blooms. Based on the Hex:Chl-c3 proxy for iron limitation in P. antarctica, we hypothesize that anomalously higher iron fluxes were responsible for the unusual bloom of colonial P. antarctica observed in TNB.

The effects of dredging and environmental conditions on concentrations of polycyclic aromatic hydrocarbons in the water column.

Sediment dredging can cause damage to the marine environment due to mobilization of sediments and contaminants. The effects of dredging and boundary environmental conditions on the concentration of Polycyclic Aromatic Hydrocarbons (PAHs) in water were evaluated during dredging of the Oil Port of Genoa-Multedo (Italy). Results showed that turbidity and PAH concentrations increased in the water during dredging. However, the scenario was complex due to the high number of interacting physical-chemical factors influencing PAH concentrations and transport. Due to these, PAH distribution is different in water, where low-molecular-weight PAHs were predominant (maximum concentration 0.105 µg L-1), and in bottom sediments, where high-molecular-weight PAHs had the highest concentrations (from 299.3 to 1256.5 ng g-1). Moreover, mainly during dredging the PAH concentrations in water were significantly higher inside than outside the port as a consequence of the lower dynamics within the port basin. Turbidity was the main parameter related to PAH concentrations.

Untargeted approach for the evaluation of anthropic impact on the sheltered marine area of Portofino (Italy).

Seawater passive sampling with Polar Organic Chemical Integrative Samplers (POCIS) combined with Gaschromatography-Mass Spectrometry analysis were employed as a tool for screening unknown contaminants in a complex Ligurian marine coastal area. The untargeted approach allowed recognizing different classes of compounds, mainly hydrocarbons from C20 to C30. Besides, two chemicals, deriving from anthropic activities, N-butylbenzenesulfonamide (NBBS) and diphenyl sulfone (DPS), were identified and quantified in all samples. Both analytes showed decreasing concentrations from the more confined site to the outer one. The oceanographic characterization of the area performed with multiparametric probes provided useful information, in agreement with chemical analyses. The presence of NBBS and DPS in the site presenting lower continental inputs demonstrated the usefulness of the integrative sampling approach for temporal and spatial monitoring, especially for low level and/or short-term pollution events that traditional monitoring can fail to detect.

Plankton dynamics across the freshwater, transitional and marine research sites of the LTER-Italy Network. Patterns, fluctuations, drivers.

A first synoptic and trans-domain overview of plankton dynamics was conducted across the aquatic sites belonging to the Italian Long-Term Ecological Research Network (LTER-Italy). Based on published studies, checked and complemented with unpublished information, we investigated phytoplankton and zooplankton annual dynamics and long-term changes across domains: from the large subalpine lakes to mountain lakes and artificial lakes, from lagoons to marine coastal ecosystems. This study permitted identifying common and unique environmental drivers and ecological functional processes controlling seasonal and long-term temporal course. The most relevant patterns of plankton seasonal succession were revealed, showing that the driving factors were nutrient availability, stratification regime, and freshwater inflow. Phytoplankton and mesozooplankton displayed a wide interannual variability at most sites. Unidirectional or linear long-term trends were rarely detected but all sites were impacted across the years by at least one, but in many case several major stressor(s): nutrient inputs, meteo-climatic variability at the local and regional scale, and direct human activities at specific sites. Different climatic and anthropic forcings frequently co-occurred, whereby the responses of plankton communities were the result of this environmental complexity. Overall, the LTER investigations are providing an unparalleled framework of knowledge to evaluate changes in the aquatic pelagic systems and management options.

Linking environmental forcing and trophic supply to benthic communities in the Vercelli Seamount area (Tyrrhenian Sea).

Seamounts and their influence on the surrounding environment are currently being extensively debated but, surprisingly, scant information is available for the Mediterranean area. Furthermore, although the deep Tyrrhenian Sea is characterised by a complex bottom morphology and peculiar hydrodynamic features, which would suggest a variable influence on the benthic domain, few studies have been carried out there, especially for soft-bottom macrofaunal assemblages. In order to fill this gap, the structure of the meio-and macrofaunal assemblages of the Vercelli Seamount and the surrounding deep area (northern Tyrrhenian Sea - western Mediterranean) were studied in relation to environmental features. Sediment was collected with a box-corer from the seamount summit and flanks and at two far-field sites in spring 2009, in order to analyse the metazoan communities, the sediment texture and the sedimentary organic matter. At the summit station, the heterogeneity of the habitat, the shallowness of the site and the higher trophic supply (water column phytopigments and macroalgal detritus, for instance) supported a very rich macrofaunal community, with high abundance, biomass and diversity. In fact, its trophic features resembled those observed in coastal environments next to seagrass meadows. At the flank and far-field stations, sediment heterogeneity and depth especially influenced the meiofaunal distribution. From a trophic point of view, the low content of the valuable sedimentary proteins that was found confirmed the general oligotrophy of the Tyrrhenian Sea, and exerted a limiting influence on the abundance and biomass of the assemblages. In this scenario, the rather refractory sedimentary carbohydrates became a food source for metazoans, which increased their abundance and biomass at the stations where the hydrolytic-enzyme-mediated turnover of carbohydrates was faster, highlighting high lability.

Conserving biodiversity in a human-dominated world: degradation of marine sessile communities within a protected area with conflicting human uses.

Conservation research aims at understanding whether present protection schemes are adequate for the maintenance of ecosystems structure and function across time. We evaluated long-term variation in rocky reef communities by comparing sites surveyed in 1993 and again in 2008. This research took place in Tigullio Gulf, an emblematic case study where various conservation measures, including a marine protected area, have been implemented to manage multiple human uses. Contrary to our prediction that protection should have favored ecosystem stability, we found that communities subjected to conservation measures (especially within the marine protected area) exhibited the greatest variation toward architectural complexity loss. Between 1993 and 2008, chronic anthropogenic pressures (especially organic load) that had already altered unprotected sites in 1993 expanded their influence into protected areas. This expansion of human pressure likely explains our observed changes in the benthic communities. Our results suggest that adaptive ecosystem-based management (EBM), that is management taking into account human interactions, informed by continuous monitoring, is needed in order to attempt reversing the current trend towards less architecturally complex communities. Protected areas are not sufficient to stop ecosystem alteration by pressures coming from outside. Monitoring, and consequent management actions, should therefore extend to cover the relevant scales of those pressures.

Organic matter features, degradation and remineralisation at two coastal sites in the Ligurian Sea (NW Mediterranean) differently influenced by anthropogenic forcing.

Organic matter (OM) features, degradation and remineralisation were studied in the seawater of a natural coastal site (Marine Protected Area of Portofino) and at an urbanised coastal site (Quarto, Genoa city) of the Ligurian Sea. The accumulation of low trophic value OM and the persistence of phytoplanktonic biomass throughout the year were observed only at the urbanised site. Efficient OM degradation and remineralisation via high-activity (two times higher than at the Portofino site) hydrolytic enzymatic activities (alkaline phosphatase and leucine aminopeptidase) were recorded. This active degradation indicated a generally good resistance of the Quarto system to environmental pressures (coastal inputs and anthropogenic influence). However, the high potential release of recycled inorganic nutrients and the favourable environmental conditions (i.e. higher seawater temperature at the Quarto site and allochthonous inputs), could encourage unpredictable development of the autotrophic fraction, including an already observed dystrophic blooming of toxic microalgae.

Characteristics of the mesophotic megabenthic assemblages of the vercelli seamount (north tyrrhenian sea).

The biodiversity of the megabenthic assemblages of the mesophotic zone of a Tyrrhenian seamount (Vercelli Seamount) is described using Remotely Operated Vehicle (ROV) video imaging from 100 m depth to the top of the mount around 61 m depth. This pinnacle hosts a rich coralligenous community characterized by three different assemblages: (i) the top shows a dense covering of the kelp Laminaria rodriguezii; (ii) the southern side biocoenosis is mainly dominated by the octocorals Paramuricea clavata and Eunicella cavolinii; while (iii) the northern side of the seamount assemblage is colonized by active filter-feeding organisms such as sponges (sometimes covering 100% of the surface) with numerous colonies of the ascidian Diazona violacea, and the polychaete Sabella pavonina. This study highlights, also for a Mediterranean seamount, the potential role of an isolated rocky peak penetrating the euphotic zone, to work as an aggregating structure, hosting abundant benthic communities dominated by suspension feeders, whose distribution may vary in accordance to the geomorphology of the area and the different local hydrodynamic conditions.