Effects of anthropogenic activities in a Mediterranean coastland: the case study of the Falerno-Domitio littoral in Campania, Tyrrhenian Sea (southern Italy)

Marine Pollution Bulletin 112 (2016) 271–290

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Marine Pollution Bulletin journal homepage: www.elsevier.com/locate/marpolbul

Effects of anthropogenic activities in a Mediterranean coastland: the case study of the Falerno-Domitio littoral in Campania, Tyrrhenian Sea (southern Italy) Giuseppina Balassone a,⁎, Giuseppe Aiello a, Diana Barra a, Piergiulio Cappelletti a, Alberto De Bonis a, Carlo Donadio a, Marco Guida b, Leone Melluso a, Vincenzo Morra a, Roberta Parisi a, Micla Pennetta a, Antonietta Siciliano b a b

Dipartimento di Scienze della Terra, dell'Ambiente e delle Risorse, Università di Napoli Federico II, Naples, Italy Dipartimento di Biologia, Università di Napoli Federico II, Naples, Italy

a r t i c l e

i n f o

Article history: Received 18 February 2016 Received in revised form 28 July 2016 Accepted 2 August 2016 Available online 7 September 2016 Keywords: Falerno-Domitio littoral (S Italy) Sediments Geological features Metals Meiobenthos Toxicity evaluation

a b s t r a c t The environmental status of the Falerno-Domitio littoral, a sector of the Italian south coast (Campania region) locally affected by an extensive anthropic pressure and pollution, was assessed by a multi-disciplinary approach, consisting of geological vs. biological studies. Geochemical abundance of potentially hazardous trace metals in beach sands is mainly constrained by the nature of the source rocks. Geochemical data of marine sediment quality with regards to possible heavy metal pollution and the enrichment factors of selected potentially toxic metals show that Cr and V values are higher in marine samples than in natural sources, suggesting that they are, at least in part, of anthropic derivation. A relationship between meiobenthos and heavy metals (Cr, Co, and V) has been also observed, providing a valuable biological marker to human-deriving chemical pollution. Ecotoxicological analyses confirm a relationship between enrichment in selected metals and moderate toxicity of some sea-bottom sediments closer to the coastline. © 2016 Elsevier Ltd. All rights reserved.

1. Introduction In the Mediterranean ecoregion, Italian marine coastal environments are areas of invaluable naturalistic relevance, even if locally modified by the anthropogenic pressure/impact effects to various extent. National and European Commission directives have established, mainly starting from the last two decades, strategies for protection and/or improvement/re-establishing of the natural equilibrium status of these areas, trying to balance both socio-economic growth and environmental protection in order to achieve sustainable development (European Commission, 2000, 2008). The European requirements challenge researchers to a) check the ecological status and b) find methods to measure it (Paganelli et al., 2011). Within the politics of landscape safeguard, the shoreline areas represent a sort of natural laboratories, where to test a key interconnection between preservation of natural habitats and anthropogenic activity. In order to fully characterize and monitor the quality and health status of coastal environments, the knowledge of different biotic vs. abiotic factors of sediments, which can be a reservoir for anthropogenic pollutants (Burton, 2002), has a key importance. In particular, sediment pollution by trace metals in estuaries and around coastal areas is an international environmental issue (Alyazichi et al., 2014 and reference therein). The effects and responses ⁎ Corresponding author. E-mail address: [email protected] (G. Balassone).

http://dx.doi.org/10.1016/j.marpolbul.2016.08.004 0025-326X/© 2016 Elsevier Ltd. All rights reserved.

of resident benthos and other aquatic organisms to sediment-bound pollutants depend on a synergy of different parameters, mainly related to the geochemical nature of sediments and to the presence of multiple classes of environmental pollutants. The analysis of benthic foraminifers (Protista) and ostracods (Crustacea), organisms able to secrete calcareous shells that persist in the sea-bottom sediments, allows to obtain data on meiofaunal subrecent assemblages and their interaction with the environmental evolution linked to anthropic activities and to the long-duration consequences related to the presence of pollutants in sea-bottom sediments (Schafer et al., 1975; Samir, 2000; Pascual et al., 2002; Triantaphyllou et al., 2003; Vilela et al., 2003; Bergin et al., 2006; Ruiz et al., 2003, 2005, 2008, 2013; Romano et al., 2008, 2009; Frontalini and Coccioni, 2008, 2011; Frontalini et al., 2009; Armynot du Châtelet and Debenay, 2010; Barras et al., 2014). As the sediment is a complex and heterogeneous matrix, the exposure on solid and elutriate phases was assessed by using a multitrophic battery of ecotoxicity tests to evaluate the impact on the aquatic biota. The ecotoxicological effects can be tested by some biological models such as Vibrio fischeri (bioluminescence inhibition), Phaeodactylum tricornutum (growth inhibition), and Brachionus plicatilis (mortality), to evaluate the impact on the aquatic biota. To outline the factors which influence the main sediment littoral drift as well as the coastal physiography and the morphological variability also related anthropic action (i.e. erosion and recession phenomena, etc.), the geomorphological/sedimentological approach to the littoral deposits is of crucial importance. Environmental

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components of the littoral prism, with a particular attention to the submerged beach, have to be evaluated in detail, because they influence the littoral drift of marine sediments deriving from watercourses and the sedimentary balance of the various costal physiographic units. Besides, the abiotic features of marine and beach sediments can be thoroughly characterized by means of integrated mineralogical, geochemical and petrographic investigations; provenance studies related to major elements and REE concentrations and mineralogical-petrographic composition of beach sediments can indicate their source areas and the geological settings of sedimentary basins, and also identify the main factors in controlling the composition of the beach sands, i.e. rivers and/or longshore currents (Armstrong-Altrin et al., 2012; Papadopoulos et al., 2014). The northern sector of the Campania region littoral (southern Italy) is an area with heterogeneous natural environments and wildlife habitats, with sand dunes and beaches, watercourse mouths, lakes, coastal ponds, marshlands, etc. This area is also well known for its archaeological heritage, represented by many Graeco-Roman sites, such as the Cumae excavation (together with Ischia island, the oldest Greek colonies on the mainland of Italy) southward, and the Sinuessa site northward. Since the second half of the 1950s the Falerno-Domitio coastline, as other areas of the Campania coastline, was affected by an extensive and uncontrolled anthropic pressure, which caused severe land degradation (De Pippo et al., 2008); for instance, its central area called the Domitia coast, due to strong urban and industrial pollution, was classified as one of four sites of national interest (SIN) in the Campania Region to be remediated and reassessed by governmental actions (Verde et al., 2013). A few detailed investigations exist on the Falerno-Domitio littoral under a comprehensive geological-biological-environmental perspective. Previous studies focused on hydrologic, sedimentological and macrobenthic analyses of some areas of the Campania and Latium regions, as Gaeta Gulf - Volturno river mouth area (Ferretti and Setti, 1989), and Circeo cape - Ischia island area (Zurlini and Damiani, 1989). An exhaustive sedimentological, microphytobenthic (diatoms), geochemical, and biological study was carried out by Verde et al. (2013) on both sediments and waters samples coming from a sector of the Falerno-Domitio littoral falling in the Caserta Province (the socalled Litorale Domitio), extending from the Agnena canal to the Patria lake. Moreover, a thorough review study on literature data of chemical contaminants in both waters and sediments mainly in the Gulf of Naples and some nearby coastal areas was carried out by Tornero and Ribera d'Alcalà (2014), with the aim of extracting recommendation for mitigating pollution sources and risks for the Campania region; this work also includes geochemical data (SiDiMar 2001-2004) of some heavy metals related to the Volturno river mouth. The present work describes the results of an interdisciplinary research (FARO 2012 project, Università di Napoli Federico II) focused on the assessment of the environmental quality of the Falerno-Domitio littoral, through the definition of physical and biological aspects of sediments collected from both marine and beach selected sites. Sedimentological and geomorphological survey of the shoreline, analyses on benthic foraminifers/ostracods and ecotoxicological assays on seabed sediments, as well as mineralogical, petrographic and geochemical analyses on both beach and seabed sediments were cross-checked to thoroughly characterize the geological nature and distribution of sediments sampled in this part of the Mediterranean coastal area. The final aim is to update the knowledge of the ecological status of the Falerno-Domitio littoral with new data about biotic and abiotic features on such impacted areas. 2. Materials and methods 2.1. Study area The Falerno-Domitio littoral (hereafter FDL) is a wide shoreline of the Tyrrenhyan Sea (western Mediterranean area), extending for

about 50 km in the northern sector of the Campania region, from Torregaveta (west of Naples) to the mouth of the Garigliano river, which is the natural limit between the Campania and Latium regions (Fig. 1). During the Quaternary, a strong subsidence of this plain was controlled by NW-SE and NE-SW normal faults and accompanied by high sedimentation rate. Hence, the Campanian Plain is filled by thick layers of alluvial deposits of the Garigliano and Volturno rivers, whose supplying areas are the Mesozoic-Tertiary sedimentary carbonates and subordinate Miocene terrigenous deposits of the southern Apennine chain, and volcanic products of Phlegrean Fields, Roccamonfina and Somma-Vesuvius. In the northern sector, the FDL is limited by the Mesozoic carbonates (Massico and Aurunci mounts), and by the Roccamonfina volcano. During upper Pliocene and Quaternary an intense vertical tectonics led to the formation of horst and graben bordered by normal faults; to this phase is also related the formation of the Campania Plain. Roccamonfina is a stratovolcano active between ca. 550 and 150 kyr (Rouchon et al., 2008). The volcanic products belong to the potassic and ultrapotassic series (from shoshonitic basalts to trachytes and from leucite basanites and tephrites to phonolites; Conticelli et al., 2011 and references therein). The growth of the Roccamonfina volcano within the Garigliano and Volturno rivers basins caused the deviation of the two watercourses and was one of the most relevant geomorphological events of the coastal area between Campania and Latium during the Pleistocene. The central-southern part of the FDL (Torregaveta, Cuma and Licola) is within the Phlegraean Fields s.l. volcanic area, and characterized by a Quaternary, highly explosive magmatism of potassic series (from shoshonitic basalts to trachyphonolites). The most important volcanic products are those related to the eruption of the Campanian Ignimbrite (~ 39 kyr BP; De Vivo et al., 2001) and the Neapolitan Yellow Tuff (~ 15 kyr BP; Deino et al., 2004; Fedele et al., 2011). At approximately 20 km to the east of the FDL lies the Somma-Vesuvius complex, which activity started about 25 kyr BP and with magmatic products belonging to the ultrapotassic series (potassic basalts and tephrites, trachytes and phonolites; Santacroce et al., 2008). From the geomorphological point of view, the FDL is characterized by various transition environments that can be observed from the north to Cuma and Torregaveta; these are represented by a sandy beach with a discontinue parallel-to-the-shoreline dune belt (located in the areas of Garigliano river mouth-Mondragone and IschitellaCuma-Torregaveta), the Garigliano and Volturno river mouths, and the Patria and Fusaro lagoons (De Pippo et al., 2004). The FDL is a very important naturalistic site and at least in part still preserves untouched natural areas. As a matter of fact, it partly belongs to the Natural Reserve of the Volturno river mouth - Licola coast, and to the Regional Park of Phlegraean Fields; wide areas colonized by Mediterranean maquis are still present, together with backdune secular pinewood and the Silva Gallinara relict wood, known since the Graeco-Roman Period. As already stated, the FDL is worldwide famous for its archaeological heritage dated from the Graeco-Roman period onward (Balassone et al., 2013; Morra et al., 2013). Ruins of Roman villae and roads and other remains widely occur from the southern FDL seashore named Spiaggia Romana until the Garigliano river. Some remarkable examples are the road named Via Domitiana, the Servilio Vatia Villa Maritima (Caputo, 1995), lying underwater for 3 m below sea level (m bsl), and the Medieval coastal towers of Capodiferro and Patria. On the other side, growing anthropic pressure in the FDL led to a strong erosion of the shoreline, with successive, often tardive, recovery actions (Pennetta et al., 2011). The coastal dynamics, the morpho-sedimentary features, biocenosis and ecology of emerged and submerged beach were modified, triggering an environmental degrade and allochthonous organisms proliferation. The FDL was included in the above mentioned SIN in 1998, due to the long-term contamination mainly related to inputs from the Volturno river, the chronic malfunction of the wastewater treatment plant of Cuma, and some minor outfalls discharging untreated wastewaters. According to Lima et al. (2012), the main contamination sources are

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Fig. 1. A) Schematic geological map of the northern sector of Campania region (southern Italy), with the indication of the Falerno-Domitio littoral. The red lines and circles correspond to the sampling transects: 1 = Garigliano; 2 = Baia Domitia; 3 = Mondragone; 4 = Volturno; 5 = Cuma. B) Location of sediment samples along both the marine transects and the beach areas (see also Table 1).

livestock wastewaters, urban and industrial sludges, which caused accumulation of Al, Cr, Fe, Hg, Mn, Pb in sea-bottom sediments and locally very high concentration of Cd, Cu, Mo, Ni, Zn. Increased levels of As, B, Cd, Cu, Se, V, Zn may originate from agricultural fertilizers; the intensive use of inorganic pesticides, especially during the 1950s and 1960s, led to the accumulation of Cu, Hg, Mn, Pb, Zn; moreover, the illegal discharge of pollutants and hazardous burial in agricultural zones, river banks and Regi Lagni canal system during the last three decades is among the main causes of the environmental degradation of parts of the FDL.

underground in each station. Sea-bottom samples were collected with a manual sampler by divers supported by a boat, that registered pictures and videos of the surrounding sea bottom, the seawater temperature at surface and bottom, and the depth, controlled also with the on board single beam ecograph. Each sample, of about 1 kg, was stored in a double plastic bag with alphanumerical code identification, and subsequently it was divided in sub-samples for the specific physicalchemical, meiofaunal and microbiological laboratory tests. Specific softwares to obtain correlation diagrams and geo-biothematic maps were used to elaborate data.

2.2. Sampling strategy 2.3. Mineralogy, petrography and geochemistry In order to define the overall ecological status of the littoral prism, 36 sediment samples, distributed along 5 transects orthogonal to the shoreline, were collected at the end of 2013. Among these, 16 were sampled on the beach, few meters far from the shoreline, and 20 on the sea bottom, down to 20 m bsl (Fig. 1 and Table 1). Beach sediments were sampled both at an average distance of 12 m from the sea level and at the close proximity of the sea level; besides, subsurface samples were taken at depth of 50 cm (Table 1). This latter sample set was considered for the mineralogical, petrographic and geochemical analyses, but not for grain size and morphoscopic analyses (see paragraphs 2.5 and 3.5). It was not possible to collect beach sediments the Volturno river mouth, due to technical problems. Sampling of sediments along the offshore transects was carried out at sites of morphological and sedimentological significance, such as the outer beach on the land (less than 1 m above sea level, m asl), the submerged beach in the bar zone (about 4 m bsl), off the distal bar (about 8 m bsl), and finally offshore (about 15 and 20 m bsl). Sampling points were georeferenced with a GPS radioreceiver (Table 1). Sediment samples were collected directly on the beach with a manual sampler, at the surface and 0.4 m

Modal mineralogy and petrography of the recovered sands were performed by using a plane polarized light optical microscope (Leitz Laborlux 12 POL), equipped with a Leica DFC280 camera and Leica Q Win software (3.5.1 version). Chemical analyses of crystal phases were performed on polished thin sections via Energy Dispersive Spectrometry (EDS) at DiSTAR Labs, Federico II University of Naples, utilizing an Oxford Instruments Microanalysis Unit equipped with an INCA X-act detector and a JEOL JSM-5310 microscope (15 kV primary beam voltage, 50–100 mA filament current, and 50 s net acquisition time). The following standards were used for calibration: diopside (Mg), wollastonite (Ca), anorthoclase (Al, Si), albite (Na), rutile (Ti), almandine (Fe), Cr2O3 (Cr), rhodonite (Mn), orthoclase (K), apatite (P), fluorite (F), barite (Ba), strontianite (Sr), Smithsonian orthophosphates (REE, Y), pure niobium (Nb), pure vanadium (V), zircon (Zr, Hf), Corning glass (Th and U), sphalerite (S), and sodium chloride (Cl). Mineralogical and chemical analyses were performed on samples of beach sands and marine sediments, previously washed with deionized water in order to remove sea salts and then grinded in an agate mill. Mineralogical analyses

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Table 1 Sediment samples collected along the beach and the sea bottom in five transects of the Falerno-Domitio littoral (see Fig. 1 for location of transects and related samples), with locations listed from NW to SE, sediment types, labels and geographic coordinates system is WGS84 (depth for the marine sediments is in meters referred to the mean sea level). Site/transect

Sediment type

Sample labela

Latitude N

Longitude E

Distance from the shoreline (m)

Garigliano river mouth

Beach sediments

FGF1 FGF1a FGF2 FGF2a F1 F2 F3 F4 BDF1 BDF1a BDF2 BDF2a F5 F6 F7 F8 MDF1 MDF1a MDF2 MDF2a F9 F10 F11 F12 F13 F14 F15 F16 CUF1 CUF1a CUF2 CUF2a F17 F18 F19 F20

41°13′21.12″ 41°13′21.12″ 41°13′20.40″ 41°13′20.40″ 41°11′26.70″ 41°12′04.62″ 41°12′58.08″ 41°13′11.88″ 41°11′32.24″ 41°11′32.24″ 41°11′31.97″ 41°11′31.97″ 41°11′24.06″ 41°11′10.74″ 41°10′12.24″ 41°09′45.90″ 41°08′27.92″ 41°08′27.92″ 41°08′27.69″ 41°08′27.69″ 41°07′17.28″ 41°07′49.44″ 41°08′14.04″ 41°08′25.98″ 41°00′05.70″ 41°00′36.32″ 41°01′05.64″ 41°01′16.86″ 40°51′01.38″ 40°51′01.38″ 40°51′01.33″ 40°51′01.33″ 40°51′03.18″ 40°51′05.58″ 40°51′10.68″ 40°51′05.46″

13°45′48.10″ 13°45′48.10″ 13°45′47.42″ 13°45′47.42″ 13°43′43.56″ 13°44′22.44″ 13°45′18.18″ 13°45′32.52″ 13°48′15.60″ 13°48′15.60″ 13°48′15.21″ 13°48′15.21″ 13°48′07.14″ 13°47′46.44″ 13°46′38.76″ 13°45′59.16″ 13°51′07.80″ 13°51′07.80″ 13°51′07.35″ 13°51′07.35″ 13°48′55.92″ 13°49′56.82″ 13°50′29.34″ 13°50′50.22″ 13°52′37.50″ 13°53′50.34″ 13°54′56.10″ 13°55′20.82″ 14°02′49.69″ 14°02′49.69″ 14°02′49.40″ 14°02′49.40″ 14°01′30.24″ 14°01′53.94″ 14°02′14.04″ 14°02′31.50″

12 12a 0 0a

Offshore sediments

Baia Domitia

Beach sediments

Offshore sediments

Mondragone

Beach sediments

Offshore sediments

Volturno river mouth

Offshore sediments

Cuma

Beach sediments

Offshore sediments

a

Depth (m)

−20.0 −15.7 −8.6 −5.0 12 12a 0 0a −4.6 −9.8 −15.8 −19.7 12 12a 0 0a −19.9 −14.0 −8.9 −5.0 −20.5 −15.0 −10.2 −5.0 12 12a 0 0a −20.0 −15.0 −9.5 −4.6

The beach sediment labeled with ‘a’ is from the same site of the preceding sample, but collected at ca. 50 cm in depth.

were performed by X-ray powder diffraction (XRPD). Data were acquired at DiSTAR, Federico II University of Naples, with a PANalytical X'Pert PRO diffractometer (CuKα radiation, 40 kV, 40 mA, scanning interval 4–50°2θ, equivalent step size 0.017°2θ, equivalent counting time 120 s per step, RTMS X'Celerator detector). Diffraction patterns were elaborated and interpreted using the X'Pert HighScore Plus 3.0 software for PC. Major and trace elements composition of beach sands was analysed by X-ray fluorescence spectrometry (XRF) at DiSTAR, Federico II University of Naples, using a PANalytical Axios instrument (the analytical procedures have been described in Melluso et al., 2011). Loss on ignition (LOI) was determined gravimetrically by predrying 1 g of powder of the sample overnight at 110 °C and then heating to 1000 °C. Chemistry of marine samples was determined at Activation Laboratories LTD (Ancaster, Canada). One sample (labeled as F17 tq) was also analyzed without preliminary washing with deionized water for comparison. Major elements were analyzed via ICP-OES (Inductively Coupled Plasma-Optical Emission Spectrometry) using a Thermo Jarrell-Ash ENVIRO II ICP. Trace elements were determined by ICP-MS (Inductively Coupled Plasma-Mass Spectrometry) with a Perkin Elmer SCIEX ELAN 6000. Uncertainty is less than 3% for major oxides, less than 15% for Co, Y, Zr and Tb, and less than 5% for all other trace elements (see www.actlabs.com). For six representative offshore samples (F2, F3, F7, F10, F15, F20) the Hg and Cd concentrations were also analyzed. 2.4. Grain size and morphoscopic analyses The sediment samples of beach and sea bottom were subjected to grain-size analysis and the results processed by a granulometric

software (Blott and Pye, 2001) to obtain distribution and statistical parameters. After washing with vacuum pump, all samples were oven dried at 110 °C for 24 h, then weighed with an analytical balance and subjected to dry sieving through a series of stacked sieves, with 1/4 ϕ class interval, up to 63 μm, in a Ro-Tap mechanical sieve shaker for 15'. For each sample histograms and cumulative curves were plotted, as well as calculated statistical parameters Mz (mean size) σI (sorting), SKI (skewness) and KG (kurtosis) (Folk and Ward, 1957; Friedman, 1967; Valia and Cameron, 1977). Furthermore, the grain size fraction of 250–350 μm of each sample was observed through an optical microscope for the recognition of morphoscopic characters of quartz grains present (Bui et al., 1990). 100 granules of quartz were selected in these granulometric fractions, and classified as 1) not abraded, but transparent and angular (NA), 2) blunt edged translucent, with subrounded to rounded edges, more or less hyaline (BT) and 3) rounded opaque, with well-rounded edges and opaque (RO). For futher methodological details see Pennetta et al. (2016a) and references therein). 2.5. Meiobenthos Benthic foraminifers (Protista) and ostracods (Crustacea), both part of meiobenthos, have been studied to test the impact of anthropic activities on organism living in/on sea-bottom sediments. Assemblage composition, diversity and abundance, are strictly related to the recent/ subrecent environmental conditions. Twenty sea-bottom samples (200 g dried weight), sampled along five transects, have been washed through 230 and 120 mesh sieves (63 μm and 125 μm respectively) and splitted; both foraminifer and ostracod shells have been picked up from the coarsest fraction, classified and counted (ostracod both as

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

suspensions prepared for solid samples were serially diluted to a series of 12 concentrations, then 20 μl of reconstituted bacterial reagent was added to dilutions series of samples. After a contact time with the bacteria of 20 min at 15 ± 2 °C, the samples were filtered and transferred into glass cuvettes in the Microtox analyzer (model 500) and equilibrated for 10 min. The emission of bioluminescence after 30 min was recorded through analyzer. The results were expressed as S.T.I. (Sediment Toxicity Index) that represents real acute toxicity of sample as to the natural toxicity of a sample with the same granulometric characteristics. The S.T.I. was calculated according to Onorati et al. (1999). (iii) Acute toxicity test with the rotifer Brachionus plicatilis: the test with B. plicatilis allowed to evaluate the toxicity of the elutriate sample using the mortality of the rotifer as a response. Nauplii hatched from cysts were used for an assay of 48 h (ASTM-, 2012). After this time, the dead rotifers in each well have been counted and the percentage mortality determined. (iv) Algal growth inhibition test: the assay with mono-specific diatom strain (Phaeodactylum tricornutum) is carried out according to the protocol UNI EN ISO 10253 (2006). In this assay exponentially growing P. tricornutum are exposed in a static plate system to a sample over several generations generally 72 h, under defined conditions. The growth of the algae exposed to the sample is compared with the growth of the algae in a negative control.

Minimum Number of Individuals, MNI and Total Number of Valves, TNV) for quantitative analysis. 2.6. Ecotoxicological analyses A series of bioassays were used to determine the potential impact of the samples of FDL marine sediments collected in the various transects (Fig. 1). In order to cover a range of trophic levels for ecological relevance, the assays in the test battery were selected to monitor biological responses in marine bacteria, algae and invertebrates. The effects on FDL samples were studied using a battery of ecotoxicological model systems, including mortality of rotifer Brachionus plicatilis, bioluminiscence inhibition in the bacterium Vibrio fischeri and growth inhibition of the alga Phaeodactylum tricornutum. The analyses were performed on whole sediment in assay with the bacteria, and its elutriate on the algae and the rotifer, according the guideline reported in the “Manual for the handling of marine sediments” (APAT-ICRAM, 2007), and as explained hereinafter. For each site, the qualitative judgment of samples was tabulated as toxicity class by using a scale as reported in Table 2 (APATICRAM, 2003). (i) Preparation of elutriate samples: elutriate was prepared by adding homogenized sediment to artificial seawater (Instant Ocean®) in a 1:4 volumetric ratio (dry weight/volume, w/v). Determination of dry weight of each sample was obtained with the use of a thermobalance with drying temperature of 80 °C. The solution was stirred for 1 h at room temperature. Then the sample was centrifuged at 3500 rpm for 1 h and the supernatant was siphoned off for toxicity testing. Preparation of solid-phase sample: the solid phase was obtained by centrifugation (3500 rpm for 30 min) to eliminate the interstitial water and then a subsample of 7 g was suspended with 35 ml of diluent solution (35‰ NaCl solution) and subsequently shaken by a magnetic stirrer for 10–15 min. The suspension obtained was used to perform serial dilution with the diluent. (ii) Solid phase test (SPT) with Vibrio fischeri: the assays with the bacterium were performed using the Microtox® SPT procedure according the standard procedure (Azur Environmental, 2001) and evaluated the acute toxicity of a sediment using as endpoint the bioluminescence inhibition of the naturally emitted by marine bacteria of the species V. fischeri (strain NRRL-B-11177) after a contact time of 30 min with the test sample. The

275

The growth of the algae exposed to the sample is compared with the growth of the algae in a negative control. The cell density in the cultures was measured after 72 h in a Bürker cell counting chamber. The specific growth rate of P. tricornutum in each replicate culture was calculated from the logarithmic increase in cell density in the intervals from 0 to 72 h using the equation: μ¼

ln Nn − ln No t n −t n

where N0 is the cell concentration at t = 0, Nn the final cell concentration after 72 h of exposure, t0 the time of start measurement, and tn the time of last measurement (hours from start). The percentage inhibition of the cell growth at sample (% I) was calculated as the difference between the rate growth of the control and the rate growth of the sample and expressed as the mean (±standard deviation) of the replicates

Table 2 % humidity (h) and % dry weight (Wd) analyzed in the FDL marine sediments; toxicity of sediment bioassays based on the decrease of bacterial bioluminescence in V. fischeri, on the inhibition of growth of P. tricornutum and the mortality of B. plicatilis; toxicity classes of sediments: N (no toxicity), L (low toxicity), M (moderate toxicity) and H (high toxicity). Transect

Garigliano river mouth

Baia Domitia

Mondragone

Volturno river mouth

Cuma

Sample ID

F1 F2 F3 F4 F5 F6 F7 F8 F9 F10 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20

h (%)

35 34 27 33 25 26 30 31 35 40 40 35 25 38 42 25 29 30 29 31

Wd (%)

65 66 73 67 75 74 70 69 65 60 60 65 75 62 58 75 71 70 71 71

Toxicity

Toxicity classes

V. fischeri

P. tricornutum

B. plicatilis

N

Absent Absent Low Absent Absent Absent Absent Absent Absent Absent Absent Low Low Absent Absent Absent Absent Absent Absent Absent

Absent Absent Absent Biostimulant Moderate Absent Biostimulant Biostimulant Biostimulant Absent Biostimulant Moderate Absent Biostimulant Absent Biostimulant Biostimulant Biostimulant Absent Moderate

Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent Absent

• • • •

L

• • • • • • • • • • • • • • • •

M

H

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for p ≤ 0.05. The results was formulated as % I and as EC50 (percentage of dilution of original elutriate) with their 95% confidence intervals (95%CI) in the case was computable. Miscellaneous physical and ecotoxicological features of the analyzed FDL sediments are summarized in Table 2. 3. Results 3.1. Beach sediments 3.1.1. Mineralogical, petrographic, geochemical and morphosedimentary features Combined XRPD (Supplementary Table 2a–i), modal and EDS data (Supplementary Table 2a–i) indicate that sands of the Garigliano river mouth (Fig. 2a and b) are mostly formed by volcanic lithics, mafic minerals (clinopyroxene, minor amphibole and olivine), and carbonates (calcite and dolomite). Felsic phases are quartz, alkali feldspar, plagioclase and minor leucite; rare sandstone fragments were also observed, along with minor amounts of garnet and biotite. Sands from Baia Domitia (Fig. 2c and d) are formed by mafic minerals (clinopyroxene, minor amphibole, olivine, biotite and garnet) followed by carbonates. Felsic phases are represented by quartz, feldspars (alkali feldspars and plagioclase), and minor feldspathoids (leucite and rare nepheline). Volcanic and sandstone lithics were also observed. Mondragone sands (Fig. 2e and f) are mostly composed of felsic phases (quartz, alkali feldspar, and rare plagioclase), sandstone lithics and carbonates (sporadically represented by bioclasts). Volcanic lithics and mafic phases (clinopyroxene, rare amphibole and garnet) are subordinate. Sands from Cuma (Fig. 2g and h) are composed of felsic phases (quartz, alkali feldspars), scarce sandstone lithics and carbonates. Mafic phases (mostly clinopyroxene) and volcanic lithics and are present in minor amounts, along with sporadic pumices. The accessory minerals identified in most FDL sands are opaque oxides, apatite, analcime, barite, rutile and arsenopyrite. The chemical composition of the observed phases and the macroscopic aspect of the studied beach sands are reported in the Supplementary Table 2a–i and Supplementary Fig. S1. These analyses evidenced a compositional variability of the sediments of FDL emerged beach along the shoreline. Generally, mafic minerals together with plagioclase, alkali feldspar and volcanic lithics decrease southwards. Quartz and calcite increase southwards, whereas dolomite is in greater amounts in the northern part of FDL (see Supplementary Table 1a). The geochemistry of the beach sands of the FDL area (Table 3) clearly indicates a terrigenous nature of these sands, which plot in the arkose field (Fig. 3a and b). Under the morphosedimentary aspect, samples from the emerged beach are mainly formed by fine sand along the shoreline, generally well sorted with a secondary mode of medium sand (see Supplementary Table 3 and Supplementary Figs. S2 and S3), with characteristics indicating a reworking in a high-energy hydrodynamic environment. Quartz grains features are interpreted as subjected to wave action of medium to high energy, typical of a beach environment. The coexistence with grains affected by irregular depressions or smooth, rounded surfaces, due to reciprocal collisions at high energy typical of eolic environment, testifies to an active exchange between sediments of beach and coastal dune. 3.2. Submerged sediments 3.2.1. Mineralogical composition and morphosedimentary features Submerged sediments are characterized by a rather homogeneous mineralogical composition (see Supplementary Table 1b). The predominant phase is quartz, with the exception of samples F2, F13, and F14, which show a moderate content, and sample F10 where is scarce. Feldspars were generally detected in low to moderate amounts or in traces (samples F2, F10, F13, F14). Calcite is frequent in almost all samples. Sample F10 also contains magnesian calcite and low amounts of aragonite. Dolomite occurs in moderate to low amounts in samples from the

northern FDL (Garigliano river mouth and Baia Domitia), while southwards it is detected only in trace amounts. Pyroxene was identified in traces in three samples (F4, F7, F11). Illite/mica (we refer this term to an illite-like mixed-layer clay mineral, illite-smectite, with a strong non-expandable component; Moore and Reynolds, 1997 and references therein) and other clay minerals (kaolinite and chlorite) were detected in all submerged sediments, generally decreasing southwards from low to trace amounts southwards (see Supplementary Table 1b). From a morphosedimentological point of view, a substantial lack of distal granulometric gradation was observed in the marine sediments, due to an irregular decrease seawards in the mean size (Mz); on the contrary, very fine sand and secondarily fine sand are widespread (estimated silt and clay fractions are b3–5% on average). The deposits of shoreface, up to the depth of closure (Hallermeier, 1981), around about 10 m bsl, are composed of very fine sands, generally well sorted, These processes are mainly driven by incident waves and NW-SE littoral drift due to longshore currents (Cocco et al., 1996; Pennetta et al., 2016b). Exchanges between sediments of seabottom with those of emerged beach are confirmed both by morphological analysis of granule surfaces (Supplementary Table 3 and Fig. S2). Shallow water deposits, down to 3 m bsl, are influenced by river discharge, while those offshore present the characteristics of beach sediments. Off the depth of closure, between 10 and 20 m bsl, the seabed deposits respectively consist of fine and very fine distal sands. 3.2.2. Geochemistry The geochemical composition of the FDL submerged sediments is reported in Table 4. These sediments are generally characterized by a narrow range of compositions (e.g., SiO2, 46–61 wt.%; Fe2O3, 2.4–5.4 wt.%; K2O, 1.1–2.6; CaO. 9–15 wt.%), with the exception of sample F10, which shows a high CaO concentration (~ 30 wt.%). The non-washed sample (F17 tq) does not show any appreciable effect of seawater or salt contamination with respect to its treated counterpart, i.e. sample F17. The trace element concentration of the samples (Table 4) is nearly indistinguishable from that of the average marine pelagic sediments (Fig. 4a), and is characterized by high concentration of Rb, Ba, U, Pb, and K, as typical of clayey sediments worldwide. In multi-element diagrams normalized to mantle abundances, elements such as Nb, Ta, Sr, P and Ti have a marked trough, while heavy rare earth elements show a nearly flat pattern. The pattern of sample F10 has a peak at Sr, consistent with the high carbonate content. The samples from different transects are variably enriched in Zr and Hf. The concentration of some heavy metals, such as Cr, Zn, and V, is consistent with that of worldwide sea sediments used for reference in Table 4 (GLOSS, Plank and Langmuir, 1998; GLOSS-II, Plank, 2014; PAAS, Taylor and McLennan, 1985; NASC, Gromet et al., 1984), whereas Co, Cu and Ni show lower values than the reference standards or are below the detection limits. The amount of As also has limited variation (5 to 15 ppm), with the exception of sample F10 (54 ppm), that has also the highest LOI value, likely caused by the abundance of carbonates (Supplementary Table 1b). The diagrams of Fig. 4b and c indicate the role of clay minerals in shaping the absolute concentration of major oxides (and trace elements), with dilution of detrital quartz and carbonates, as already pointed out by XRPD patterns, and in other Mediterranean clayey sediments (Saccà et al., 2011; Leoni et al., 1991) and around the FDL coastline (e.g., De Bonis et al., 2013, 2014; Ferretti and Setti, 1989). Table 5 compares average contents of selected heavy metals (Cd, Co, Cr, Cu, Hg, Ni, Pb, V, Zn plus As) in marine sediments from the five transects (mean values from Table 4) with Italian legal limits (D.M. 367/03; Official Bulletin of the Italian Republic, 2004), as well as with the reference values of natural background detected by Sprovieri et al. (2006), the average concentrations for shale after Wedepohl (1978) and the regional values defined by De Vivo et al. (2003). The concentration of Cd and Hg are determined for only six representative marine sediments deposits (Table 4). Hg content ranges from 0.02 to 0.04 ppm, always below the values of the Italian regulatory guidelines (D.M. 367/03; Official

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277

Fig. 2. Representative PLM images of the FDL beach sands. (a) Sample FGF1, Garigliano river mouth, parallel polars. (b) Sample FGF2, Garigliano river mouth, crossed polars. (c) Sample BDF2, Baia Domitia, parallel polars. (d) Sample BDF1a, Baia Domitia, crossed polars. (e) Sample MDF2a, Mondragone, parallel polars. (f) Sample MDF2, Mondragone, crossed polars. (g) Sample CUF2, Cuma, parallel polars. (h) Sample CUF2a, Cuma, crossed polars. Abbreviations: Q, quartz/sandstone fragments; CF, carbonate fragments/bioclasts; VL, Volcanic lithic; Afs, alkali feldspar; Cpx, clinopyroxene; Am, Amphibole; Lct, leucite; Grt, garnet.

Bulletin of the Italian Republic, 2004) and also the typical concentration recorded in Tyrrhenian surficial sediments (Covelli et al., 2001). The concentration of Cd is below the detection limit of the analytical technique employed (0.5 ppm), hence a more accurate comparison with the above mentioned legal limits (0.3 ppm, Table 5) could not be performed. The concentration of Ni and Pb are always below the legal limits, as well as As, except for the Mondragone transect whose average is affected by the outlier sample F10. The Cr concentration (52–80 ppm)

are always higher than those of the Italian legal value of the D.M. 367/03 (50 ppm); only at Cuma the mean Cr concentration in the sediments are slightly lower (46 ppm). Higher concentrations of some potentially toxic metals were observed in correspondence of river mouths; in these areas, the related samples F1 and F2 (Garigliano mouth) and F13 and F14 (Volturno mouth) show higher concentration of Cr, Co, Ni and Cu compared to all the other samples. Taking into account the sole Volturno area, a chronological trend of selected heavy metal

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Table 3 Major oxides, LOI (wt.%) and trace elements (ppm) composition of FDL beach sands (see text and Table 1 for sample details). Site Sample ID

FGF1

SiO2 TiO2 Al2O3 Fe2O3 MnO MgO CaO Na2O K2O P2O5 LOI Total Rb Sr Y Zr Nb Ba Cr Ni Sc V La Ce

40.33 1.39 5.85 14.78 0.22 8.81 21.82 0.42 0.61 0.16 5.41 99.80 27 357 44 369 13 169 308 83 47 548 41 115

Garigliano river mouth FGF1a FGF2 FGF2a 38.20 0.49 6.80 4.96 0.12 7.80 24.58 0.72 2.21 0.11 13.80 99.79 119 649 29 204 7 474 179 59 33 182 58 101

41.31 0.34 9.69 3.35 0.10 6.29 16.90 1.29 4.60 0.12 15.74 99.73 292 1005 26 213 10 828 44 23 8 124 103 152

41.59 0.46 8.63 4.71 0.11 6.32 19.36 1.08 3.50 0.11 13.87 99.75 199 821 29 231 9 687 113 35 24 175 76 140

BDF1

Baia Domitia BDF1a BDF2

BDF2a

MDF1

Mondragone MDF1a MDF2

MDF2a

CUF1

Cuma CUF1a CUF2

CUF2a

41.81 0.62 5.21 5.65 0.12 7.18 25.97 0.43 0.93 0.10 11.81 99.83 42 445 34 243 8 273 248 61 34 201 36 89

39.35 0.50 5.32 4.88 0.12 7.03 27.07 0.47 1.26 0.09 13.72 99.82 64 518 28 201 5 337 219 64 35 177 42 82

43.14 0.33 9.73 3.06 0.10 2.91 20.69 1.07 4.44 0.09 14.21 99.77 233 904 23 186 12 758 61 20 22 64 82 107

46.58 0.23 4.99 2.08 0.10 2.46 24.70 0.58 1.60 0.07 16.46 99.84 79 588 20 106 5 492 88 32 19 43 35 49

50.31 0.19 6.17 1.82 0.09 1.66 21.85 0.75 2.34 0.06 14.57 99.81 124 661 18 101 6 631 49 25 14 40 40 49

50.23 0.17 6.55 1.73 0.09 1.63 21.55 0.78 2.64 0.06 14.38 99.83 128 668 17 94 5 641 45 18 10 38 41 59

49.90 0.20 6.47 2.08 0.18 1.31 21.74 0.90 2.39 0.10 14.56 99.83 113 539 21 86 8 605 60 23 14 44 42 62

50.01 0.20 6.51 2.11 0.19 1.29 21.61 0.91 2.36 0.10 14.54 99.84 120 554 22 85 8 621 43 28 13 41 37 59

53.64 0.21 8.86 2.10 0.15 1.07 16.77 1.23 3.73 0.11 11.90 99.79 172 569 19 105 14 805 28 19 10 41 38 56

42.61 0.34 6.76 3.20 0.09 3.68 24.64 0.69 2.44 0.08 15.26 99.80 128 723 22 151 7 574 124 43 28 59 38 75

concentrations (As, Cr, Cu, Hg, Pb and Zn) can be estimated by comparing average data of this study (Table 5) with those of Verde et al. (2013) and the SiDiMar values (2001–2004) in Tornero and Ribera d'Alcalà (2014). Even though based on three datasets only, a decrease with time of the average As and Hg concentration is recorded in the studied samples, when compared to previous literature values, whereas higher Cr, Cu, Pb and Zn amounts in the samples of this study point to an increase of these potentially toxic elements from the 2001–2004 period onward. Further inferences concerning the heavy metal concentrations are discussed in the paragraph 4.2. 3.2.3. Meiobenthic assemblages Benthic foraminifer assemblages detected in the marine bottom sediments (labeled with F1 to F2, Table 1), include 147 species pertaining to 74 genera; 13 species are left in open nomenclature. Ostracod assemblages consist of 87 species referred to 49 genera; 14 species are in open nomenclature. Thirty-nine benthic foraminifer and 6 ostracod species have been considered allochthonous on the basis of the state of preservation and distribution data. Assemblages are generally rich and well diversified (Table 6) showing variations depending on anthropic and non-anthropic conditions. The benthic foraminifer assemblages consist mainly of species pertaining to the genera Quinqueloculina and Elphidium

50.93 0.17 6.09 1.66 0.09 1.76 21.66 0.73 2.34 0.06 14.34 99.82 107 609 17 92 5 598 55 18 11 38 40 54

54.53 0.22 9.52 2.20 0.15 1.07 15.42 1.30 4.05 0.12 11.21 99.80 193 602 19 98 14 888 36 26 9 44 43 50

(13 species), Adelosina (7 species) and Ammonia (5 species). The most abundant species are Ammonia tepida (28771 specimens), A. parkinsoniana (25455) and Cribroelphidium cuvillieri (19261); other common species are: Triloculina trigonula (9716), Quinqueloculina seminulum (8869), Bulimina elongata (8428), Elphidium excavatum (6819) and Q. lata (6188). The best represented ostracod genera are Semicytherura (8 species), Leptocythere (7), Callistocythere e Xestoleberis (5). The most abundant species are: Semicytherura incongruens (2797 MNI, 11775 TNV), Palmoconcha turbida (1379 MNI, 8079 TNV), Leptocythere macella (1392 MNI, 2979 TNV), Leptocythere bacescoi (1144 MNI, 2556 TNV); other common species are: Pontocythere turbida (765 MNI, 6142 TNV) Cytherois uffenordei (742 MNI, 1458 TNV), Loxoconcha ovulata (732 MNI, 4295 TNV), Carinocythereis whitei (792 MNI, 4491 TNV). Statistical analysis was performed using the freeware PAST version 3.01 (Hammer et al., 2001). Cluster analysis was applied to benthic foraminifer and ostracod assemblage data using the Bray-Curtis similarity coefficient. Pearson's correlation coefficient was used to test for correlation between assemblage features, depth, granulometry, distance from the coastline, major and trace elements and toxicological analysis (P. tricornutum) results. For the statistic analyses we have considered the benthic foraminifer and ostracod species with relative abundance greater than 5% in at least one sample. Ostracod assemblage

Fig. 3. Geochemical classification of FDL beach sands based on (a) the Log (SiO2/Al2O3) vs. Log (Fe2O3/K2O) classification diagram of Herron (1998) and (b) on the Log (SiO2/Al2O3) vs. Log (Na2O/K2O) diagram of Pettijohn et al. (1972). Abbreviations: FGF, Garigliano river mouth; BDF, Baia Domitia; MDF, Mondragone; CUF, Cuma.

Table 4 Geochemical composition of FDL sediments from the submerged beach. Major oxides and LOI are expressed in wt.%, trace elements in ppm, except where otherwise indicated. Compositions of the Global Subducting Sediments GLOSS (Plank and Langmuir, 1998) and GLOSS-II (Plank 2014), Post-Archean Australian Shale (PAAS; Taylor and McLennan, 1985), and North American shale composite NASC (Gromet et al., 1984) are included for reference. Transect Sample ID

Garigliano River mouth F2 F3 F4

50.74 0.50 10.75 3.80 0.08 2.06 12.08 1.61 2.02 0.17 15.37 99.17 8.0 3.0 84.0 70.0 10.0 30.0 20.0 70.0 15.0 2.0 10.0 107.0 291.0 22.0 204.0 12.0 1.5 3.0 0.5 8.1 324.0 44.6 85.9 9.7 36.6 7.1 1.3 5.0 0.8 4.2 0.8 2.4 0.4 2.3 0.3 4.8 0.9 3.0 0.6 30.0 16.7 2.9

46.35 0.66 14.41 5.34 0.09 2.21 9.08 1.52 2.10 0.24 17.80 99.80 12.0 5.0 127.0 90.0 14.0 40.0 40.0 90.0 21.0 2.0 10.0 138.0 219.0 28.0 214.0 18.0 1.5 4.0 0.6 13.1 317.0 61.6 115.0 13.4 50.9 9.2 1.8 6.3 1.0 5.3 1.0 2.9 0.4 2.6 0.4 5.1 1.2 4.0 0.9 35.0 25.0 3.7 b 0.5 41

F5

Baia Domitia F6 F7

F8

F9

Mondragone F10 F11

54.07 0.76 8.35 3.82 0.10 2.12 12.49 1.31 1.74 0.17 13.66 98.60 8.0 3.0 87.0 100.0 9.0

56.69 0.42 7.90 2.62 0.07 2.05 12.37 1.32 1.95 0.12 13.17 98.67 6.0 2.0 56.0 60.0 7.0

56.23 0.77 6.68 5.42 0.13 2.36 13.53 1.00 2.08 0.08 10.76 99.06 9.0 2.0 154.0 120.0 12.0

54.67 0.38 8.74 2.92 0.09 1.88 12.70 1.34 2.07 0.12 13.84 98.75 6.0 3.0 59.0 60.0 9.0

58.16 0.46 8.44 2.89 0.08 2.03 11.74 1.38 1.88 0.14 12.98 100.20 7.0 2.0 61.0 60.0 8.0

56.68 0.45 8.68 3.02 0.08 2.02 12.12 1.45 1.93 0.15 13.12 99.68 6.0 2.0 59.0 40.0 7.0

53.74 0.48 10.17 3.40 0.09 1.94 11.97 1.51 2.08 0.14 14.26 99.77 7.0 3.0 72.0 60.0 9.0

23.28 0.26 5.99 3.60 0.42 2.63 29.97 0.84 1.11 0.16 30.49 98.74 6.0 2.0 71.0 30.0 9.0

20.0 60.0 12.0 2.0 8.0 83.0 311.0 32.0 745.0 14.0 4.7 3.0

20.0 50.0 10.0 2.0 7.0 87.0 298.0 18.0 256.0 8.0 1.5 3.0

60.0 10.0 2.0 8.0 80.0 385.0 20.0 490.0 10.0 3.0 4.0

10.0 50.0 11.0 2.0 7.0 97.0 316.0 17.0 167.0 10.0 0.9 2.0

10.0 50.0 11.0 2.0 10.0 84.0 285.0 22.0 274.0 9.0 1.4 4.0

10.0 50.0 10.0 2.0 10.0 80.0 299.0 20.0 253.0

10.0 50.0 8.0 1.0 54.0 52.0 1623.0 24.0 131.0

1.7 2.0

20.0 60.0 14.0 2.0 7.0 101.0 297.0 21.0 216.0 11.0 1.1 2.0

5.7 317.0 59.7 119.0 13.7 52.0 9.8 1.5 7.0 1.1 6.0 1.1 3.4 0.5 3.6 0.6 18.7 1.2 2.0 0.5 27.0 21.6 5.2 b 0.5 37

5.4 342.0 32.5 63.2 7.4 27.9 5.3 1.0 3.9 0.6 3.2 0.6 1.9 0.3 1.8 0.3 6.0 0.7 2.0 0.5 24.0 11.7 2.6

3.7 401.0 34.6 70.4 8.6 34.1 6.2 1.2 4.4 0.6 3.7 0.7 2.1 0.4 2.2 0.4 11.4 0.9 2.0 0.4 19.0 12.1 3.3

6.1 358.0 37.4 71.5 8.1 30.3 5.7 1.1 4.0 0.6 3.4 0.6 1.7 0.3 1.6 0.2 4.1 0.7 2.0 0.5 24.0 13.2 2.4

4.9 333.0 36.5 71.6 8.4 30.9 6.1 1.2 4.4 0.7 3.8 0.8 2.2 0.4 2.1 0.3 6.5 0.8 2.0 0.5 25.0 13.7 2.9 b 0.5 29

5.3 336.0 36.1 68.7 8.0 28.3 5.6 1.1 4.2 0.6 3.5 0.7 2.0 0.3 2.2 0.3 5.5 0.4 2.0 0.6 26.0 13.3 2.8

6.1 346.0 38.5 74.9 8.5 33.4 6.0 1.2 4.5 0.7 3.8 0.8 2.2 0.3 2.1 0.3 5.1 0.9 1.0 0.5 25.0 14.0 2.7

4.2 165.0 42.3 79.0 8.9 32.3 6.0 1.2 5.1 0.7 4.0 0.7 2.1 0.3 2.0 0.3 2.6 0.0 2.0 0.3 19.0 9.2 2.4 b 0.5 29

F13

54.46 0.52 7.25 3.09 0.13 1.89 15.42 1.27 1.85 0.13 14.03 100.00 7.0 2.0 67.0 70.0 9.0

58.10 0.33 7.79 2.57 0.10 1.61 12.19 1.39 2.18 0.10 12.40 98.76 5.0 2.0 55.0 50.0 8.0

61.78 0.43 7.41 2.65 0.11 1.50 12.34 1.37 2.07 0.14 9.92 99.72 7.0 2.0 60.0 60.0 7.0

40.0 10.0 2.0 12.0 90.0 333.0 16.0 186.0 7.0 0.9 2.0

46.26 0.62 13.53 4.89 0.10 2.06 10.85 1.41 2.19 0.20 17.28 99.40 11.0 3.0 107.0 90.0 13.0 30.0 50.0 100.0 20.0 1.0

60.65 0.72 7.12 4.18 0.14 1.74 12.15 1.24 1.92 0.16 9.04 99.07 10.0 2.0 108.0 90.0 10.0

50.0 9.0 2.0 15.0 77.0 668.0 25.0 394.0 11.0 2.0 2.0

46.24 0.65 14.13 5.17 0.12 2.19 9.30 1.63 2.26 0.18 16.92 98.77 12.0 3.0 114.0 100.0 15.0 40.0 40.0 100.0 21.0 2.0 7.0 124.0 237.0 23.0 158.0 17.0 0.6 3.0

50.0 10.0 2.0

40.0 9.0 2.0

120.0 259.0 23.0 183.0 18.0 0.7 4.0

74.0 279.0 41.0 900.0 12.0 5.4 4.0

78.0 287.0 20.0 276.0 7.0 1.1 2.0

3.5 343.0 40.3 81.1 9.3 35.3 6.8 1.2 4.9 0.8 4.4 0.9 2.5 0.4 2.5 0.4 9.4 0.9 1.0 0.4 19.0 12.4 3.2

3.8 400.0 27.0 52.8 6.2 23.3 4.5 1.0 3.3 0.5 2.8 0.5 1.6 0.2 1.6 0.2 4.5 0.6 2.0 0.5 20.0 9.0 2.1

7.9 318.0 40.2 78.2 8.9 34.2 6.6 1.4 5.0 0.8 4.2 0.8 2.4 0.4 2.2 0.4 3.9 1.2 2.0 0.5 22.0 14.0 2.7

7.7 330.0 40.6 81.3 9.1 34.9 6.6 1.3 5.1 0.7 4.5 0.9 2.4 0.4 2.3 0.4 4.5 1.2 2.0 0.5 23.0 14.4 2.9

2.0 487.0 63.2 130.0 15.0 58.6 11.4 1.3 8.4 1.3 7.3 1.5 4.3 0.7 4.6 0.8 21.6 1.0

2.3 428.0 26.1 53.4 6.2 24.1 4.8 0.9 4.0 0.6 3.4 0.7 2.0 0.3 2.0 0.3 7.1 0.7

0.4 14.0 23.1 5.1 b 0.5 20

0.4 14.0 8.2 2.1

F17 tq*

Cuma F18

F19

F20

GLOSS

54.55 0.41 9.74 3.08 0.09 1.59 11.97 1.65 2.38 0.16 13.30 98.92 7.0 3.0 61.0 60.0 9.0

53.93 0.39 9.39 2.90 0.09 1.59 11.95 2.26 2.36 0.16 13.93 98.95 6.0 3.0 56.0 50.0 8.0

59.20 0.35 9.01 2.73 0.09 1.39 12.20 1.62 2.49 0.16 11.04 100.30 5.0 2.0 53.0 40.0 3.0

59.68 0.29 8.24 2.36 0.10 1.21 12.11 1.44 2.50 0.12 10.76 98.81 5.0 2.0 46.0 40.0 8.0

58.16 0.32 9.33 2.83 0.10 1.39 12.38 1.51 2.60 0.13 11.34 100.10 6.0 2.0 54.0 40.0 9.0

58.57 0.62 11.91 5.78 0.32 2.48 5.95 2.43 2.04 0.19 10.30 100.59 13.1

20.0 80.0 13.0 2.0 5.0 106.0 309.0 20.0 199.0 13.0 0.8 3.0

20.0 70.0 12.0 1.0 5.0 101.0 305.0 19.0 190.0 12.0 0.6 2.0

40.0 50.0 10.0 2.0 6.0 98.0 317.0 14.0 135.0 8.0

10.0 60.0 11.0 2.0 7.0 104.0 330.0 14.0 119.0 9.0

4.0

2.0

5.3 409.0 31.6 63.0 7.2 27.2 5.2 1.0 4.1 0.6 3.5 0.7 2.0 0.3 2.0 0.3 5.1 0.9 1.0 0.5 24.0 11.3 2.8

4.9 404.0 31.7 63.4 7.2 27.0 5.1 1.1 4.0 0.6 3.6 0.7 1.9 0.3 2.0 0.3 4.9 0.8 1.0 0.4 23.0 11.3 2.7

4.1 450.0 28.3 55.3 6.3 22.5 4.3 0.9 3.7 0.6 3.5 0.7 1.9 0.3 1.8 0.3 4.0 0.7

3.3 452.0 23.2 46.8 5.3 20.2 4.2 0.8 3.1 0.5 2.6 0.5 1.3 0.2 1.4 0.2 3.4 0.6

4.0 460.0 23.9 47.1 5.3 20.7 4.2 0.9 3.0 0.5 2.7 0.5 1.4 0.2 1.4 0.2 2.9 0.7

21.0 9.3 2.6

0.5 18.0 7.3 1.9

0.5 19.0 7.5 1.9 b 0.5 24

F17

50.0 10.0 2.0 99.0 329.0 16.0 168.0 10.0 1.5 2.0

Reference standards GLOSS-II PAAS

NASC

110 78.9 21.9 70.5 75 86.4

56.6 0.64 12.51 6.29 0.43 2.75 6.22 2.50 2.21 0.2 10.16 100.51 15 1.99 116 68.8 26.9 73 116 93

57.2 327 29.8 130 8.94

83.7 302 33.3 129 9.42

3.48 776 28.8 57.3

2.92

4.9 786 29.1 57.6 7.15 27.6 6 1.37 5.81 0.92 5.43 1.1 3.09

2.76 0.413 4.06 0.63

3.01 0.459 3.42 0.698

2.8 0.43 5 1.2

3.1 0.46 6.3 1.1

19.9 6.91 1.68

21.2 8.1 1.73

20 14.6 3.1

20 12.3 2.7

27 5.78 1.31 5.26 4.99

62.8 1.00 18.9 7.22

64.8 0.7 16.9 6.29

2.20 1.30 1.20 3.70 0.16

2.86 3.63 1.14 3.97 0.13

98.48 16

100.42 15

150 110 23 55

130 125 26 58

160 200 27 210 19

125 142 35 200 13

650 38 80

636 31 67

32 5.6 1.1 4.7 0.77

27.4 5.6 1.2 5.2 0.85

279

*F17 tq, sample F17 analyzed without preliminary washing with deionized water.

0.7 1.0

Volturno river mouth F14 F15 F16

F12

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

SiO2 TiO2 Al2O3 Fe2O3(t) MnO MgO CaO Na2O K2O P2O5 LOI Total Sc Be V Cr Co Ni Cu Zn Ga Ge As Rb Sr Y Zr Nb Ag Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Tl Pb Th U Cd Hg (ppb)

F1

280

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

Garigliano Baia Domitia Mondragone Volturno Cuma

Fig. 4. Geochemical characteristics of FDL marine sediments from the submerged beach related to the five transects of Garigliano, Baia Domitia, Mondragone, Volturno and Cuma (see Tables 1 and 4). Compositions of the Global Subducting Sediments GLOSS (Plank and Langmuir, 1998) and GLOSS-II (Plank, 2014), Post-Archean Australian Shale (PAAS; Taylor and McLennan, 1985), and North American shale composite NASC (Gromet et al., 1984) are included for reference. (a) Primitive mantle-normalized (normalization values from Lyubetskaya and Korenaga, 2007) trace element patterns. (b) Triangular diagram (after Klaver et al., 2015) showing the relative concentrations of Al2O3, SiO2 and CaCO3 in the samples. Dilution trends from the detrital clay fraction by silica and carbonate are reported. (c) K/Al vs. Mg/Al diagram (after Klaver et al., 2015). Ideal compositions of chlorite, kaolinite, smectite and illite are shown for reference (Deer et al., 1992).

analyses were carried out considering both the minimum number of individuals (MNI) and the total number of valves (TNV). As regards cluster analysis of benthic foraminifers, the analysis shows two significant clusters, For1 and For2; For1 is subdivided in two subclusters For1a and For1b (Fig. 5a). The cluster analysis of ostracods (MNI) revealed a low diversity, low abundance cluster (Osi1) and a high diversity, high abundance cluster (Osi2). They have been subdivided in four subclusters (Osi1a, Osi1b, Osi2a, Osi2b; Fig. 5b). Regarding the TNV parameter of ostracods, we have pointed out two clusters, i.e. Osv1 and Osv2 (Fig. 5c), the latter divided into two subclusters (Osv2a and Osv2b). Comparison among the cluster analysis carried out on foraminifer and ostracod assemblages (MNI and TNV) shows that the features of the meiobenthic assemblages allow the discrimination of four groups of samples. The first group includes the very low-diversity, low-abundance, high dominance assemblages F15 and F16. These sampling stations are the nearest to the mouth of the Volturno river, on fine and very fine sandy bottom sediments, at a depth of 5 and 10.2 m bsl. The foraminifer-ostracod (TNV) ratio is relatively high (12–13). The samples pertaining to the second group, F5, F13 and F14, are characterized by low-diversity, low-abundance and high-dominance assemblages. Two of them (F13, 20.5 m bsl and F14, 15 m bsl) pertain to the Volturno river estuary transect; the third, F5, is the sampling station nearest to the coastline in the Baia Domizia transect, at 4.6 m bsl. The sea-bottom sediments are fine and very fine sands. The third group consists of the largest number of samples (12), yielding assemblages representing the prevailing ecological conditions in the Falerno-Domitio coastal area. No sample of the Volturno river estuary transect is present in this group. Average diversity and abundance values characterize the foraminifer and ostracod assemblages. High diversity, high abundance and low dominance assemblages

occur in the samples of the fourth group. F1, F8 and F9 are the outermost sampling stations of the Garigliano river estuary, Mondragone and Baia Domizia transects in sandy bottom sediments with a depth around 20 m bsl. The foraminifer-ostracod (TNV) ratio is low. These assemblages reflect the optimum of the ecological conditions in the Falerno-Domitio upper infralittoral zone. Pearson's coefficient analysis of benthic foraminifers showed the following correlations (Table 7): As with Lobatula lobatula, Siphonaperta aspera, diversity (S and H) and equitability (J); Cr with dominance D; Ni with Cribroelphidium cuvilleri, Elphidium excavatum; Pb with Ammonia parkinsoniana, A. tepida, Bulimina elongata, Elphidium granosum, Quinqueloculina seminulum and with abundance. Abundance (Ind.) correlates with depth and distance from the coastline; distance and coastline correlate with some foraminifer species as shown in Table 7. The analysis displays the following anticorrelations: Co with Quinqueloculina lata, Cr with L. lobatula and Q. lata, S and H, V with Q. lata and S, and finally Q. lata with con Co, Cr and V. The Pearson's coefficient analysis correlations of ostracods (MNI) (Table 8) shows the following results: As shows significant positive correlation with the species Cytheroma variabilis, Loxoconcha affinis, Neonesidea mediterranea, Xestoleberis communis, and with diversity (S and H); Cr with dominance (D); Pb with Callistocythere flavidofusca, Leptocythere crepidula, Loxoconcha ovulata, Palmoconcha turbida, Semicytherura incongruens and abundance; abundance correlates with depth, granulometry and distance. The observed anticorrelations are: Ba with C. variabilis, N. mediterranea, X. communis; simple diversity S, Co with Neocytherideis muelleri; Cr with diversity S and H; Pb with equitability. The TNV analysis of ostracods (TNV) shows the following correlations (Table 9): As correlates with Aurila convexa, Callistocythere flavidofusca, Cytheroma variabilis, Loxoconcha affinis, Neonesidea mediterranea, Xestoleberis

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

281

Table 5 Average contents of selected heavy metals from Table 7 calculated for the FDL marine sediments sampled in each transect (see Fig. 1). Reference values are represented by the benchmark levels from the Italian regulatory guidelines (D.M. 367/03; Official Bulletin of the Italian Republic, 2004), the natural background calculated for the southern Campania shelf (Sprovieri et al., 2006), the Regional values of sediment dataset for Campania region (De Vivo et al., 2003) and the mean values for Shale by Wedepohl (1978). Element (ppm)

As Cda C Cr Cu Hga Ni Pb V Zn a

This work

Reference concentrations

Garigliano river mouth

Baia Domitia

Mondragone

Volturno river mouth

Cuma

Regulatory limit for sea sediments

Background value

8.8 b0.5 10.0 80.0 25.0 0.039 17.5 29.0 88.5 67.5

8.8 b0.5 9.0 70.0 7.5 0.029 0.0 23.5 83.3 52.5

22.0 b0.5 8.8 52.5 7.5 0.029 0.0 20.8 66.3 50.0

1.8 b0.5 11.3 85.0 22.5 0.020 17.5 18.3 97.3 72.5

4.6 b0.5 7.4 46.0 18.0 0.024 0.0 21.0 54.0 62.0

12 0.3

20.18 0.10

7.60 0.35

1.50 0.11

50

42.37 18.81 0.04 25.36 16.44 68.31 73.43

27.19 72.05 0.53 48.16 32.56 40.18 83.41

100.00 50.00 0.05 80.00 14.00 160.00 75.00

0.3 30 30

Regional value

Shale average value

Referred to two samples for Garigliano and just one samples for the other sites, for a total of six selected samples from all the transects (see text and Table 7).

communis, and diversity (S and H); Cr with dominance; Pb Carinocythereis whitei, L. ovulata, P. turbida, and with abundance. Abundance correlates with depth and distance. The anticorrelations pointed out are: As anticorrelates with dominance; Ba with C. flavidofusca, C. variabilis, Loxoconcha affinis, N. mediterranea, X. communis, and diversity S; Co with Semicytherura sulcata; Cr with A. convexa and S. sulcata, diversity (S and H); Pb with equitability; V with S. sulcata. A Pearson's coefficient positive correlation of Ni, Pb and Zn with depth and distance has been recorded. 3.2.4. Ecotoxicity results The results of the ecotoxicological analyses carried out by this study are presented in Fig. 6. V. fischeri tests applied to the solid phase did not show acute toxic effects measurable with the species tested (Fig. 6a). Only, the samples F3, F12 and F13 presented S.T.I. values slightly above 1, showing very low toxicity. As regard sediment toxicity analyses carried out on elutriate, data for P. tricornutum showed a high heterogeneity between samples, with 11 sampling sites induced growth inhibition (positive values) of P. tricornutum cells; while other 9 elutriates induced growth stimulation (negative values). The stimulatory response ranged from 11 to 36% increase in comparison to controls

(p ≤ 0.05). Significant inhibition (p ≤ 0.05) of algal growth following 72 h of exposure to the extract was observed for F5, F12 and F20 samples (Fig. 6b) that showed EC50 values of 61% (42–88% CI), 52% (30– 88% CI), and 100% respectively. Slight toxicity was found in F1, F2, F3, F6, F10, F13, F15 and F19 with values in the range between 17 and 44% of inhibition. In general, the biostimulatory effects can be considered relatively high and attributable to enrichment in nutrients, due to the process itself elutriation which solubilized many substances such as phosphates and nitrates from the sediment. The results of survival of nauplii of B. plicatilis are shown in Fig. 6c. The average mortality of rotifer treated with elutriates was always b20% after 24 h and only the samples F6, F12 and F20 showed toxicity N25% after 48 h of treatment. According to the index proposed by APAT-ICRAM (2003), based on toxicity classes (Table 2), our sediments were not toxic. 4. Discussion 4.1. Coastal geomorphology The sediments of the FDL emerged beach refer to a wave-dominated littoral characterized by a prograding beach along which coastal dunes

Table 6 Data from meiofaunal calcareous assemblages detected in the FDL bottom sediment samples, listed in order of increasing depth and from north to south (see Fig. 1), and related to both benthic foraminifer and ostracod assemblages (minimum number of individuals, MNI, and total number of valves, TNV): simple diversity, Taxa S; individuals per 100 g, Abundance; Dominance D; Shannon H, Shannon's diversity index; Equitability J. The benthic foraminifer-ostracod (MNI) and foraminifer-ostracod (TNV) ratios are also reported. Transect Sample ID Depth (m)

F4 5

Garigliano River mouth F3 F2 F1 8.6 15.7 20.09

Foraminifer Taxa S 41 Abundance 1820 Dominance D 0.13 Shannon H 2.57 Equitability J 0.69 Ostracod MNI Taxa S 16 Abundance 83 Dominance D 0.16 Shannon H 2.20 Equitability J 0.79 Ratio F/O MNI 22.06 Ostracod TNV Taxa S 16 Abundance 200 Dominance D 0.14 Shannon H 2.27 Equitability J 0.82 Ratio F/O TNV 9.10

F5 4.6

Baia Domizia F6 F7 F8 9.8 15.8 19.7

F12 5

Mondragone F11 F10 8.9 14

F9 19.9

F16 5

Volturno River mouth F15 F14 F13 10.2 15 20.5

F20 4.6

F19 9.5

Cuma F18 15

F17 20.2

22 5728 0.24 2.10 0.68

36 9120 0.10 2.81 0.78

45 53120 0.10 2.87 0.75

21 224 0.13 2.42 0.80

39 9312 0.08 2.91 0.79

38 9504 0.07 2.99 0.82

43 24640 0.07 3.09 0.82

53 7872 0.08 3.19 0.80

48 7840 0.05 3.39 0.88

54 8768 0.04 3.54 0.89

48 33088 0.07 3.11 0.80

25 216 0.20 2.11 0.66

27 333 0.12 2.45 0.74

18 289 0.26 1.80 0.62

20 5664 0.22 1.96 0.65

37 4032 0.10 2.86 0.79

38 1192 0.10 2.81 0.77

40 4608 0.09 2.92 0.79

38 8544 0.07 3.01 0.83

18 536 0.30 1.81 0.63 10.69

20 602 0.11 2.43 0.81 15.15

21 3842 0.12 2.37 0.78 13.83

10 34 0.15 2.10 0.91 6.59

29 507 0.22 2.24 0.67 18.38

19 483 0.15 2.17 0.74 19.68

30 2388 0.13 2.45 0.72 10.32

30 271 0.08 2.85 0.85 29.54

34 507 0.06 3.10 0.88 15.48

55 804 0.06 3.36 0.84 10.91

31 1937 0.10 2.80 0.82 17.09

8 11 0.15 1.99 0.96 20.57

7 14 0.25 1.62 0.83 24.67

11 60 0.29 1.61 0.67 4.86

8 13 0.22 1.76 0.84 453.12

18 118 0.12 2.35 0.81 34.17

12 113 0.15 2.10 0.85 10.55

28 372 0.13 2.48 0.75 12.39

27 738 0.14 2.50 0.76 11.58

18 956 0.32 1.69 0.58 5.99

20 2312 0.14 2.26 0.75 3.94

21 16192 0.12 2.34 0.77 3.28

10 56 0.21 1.88 0.81 4.00

29 1360 0.21 2.24 0.67 6.85

19 1904 0.16 2.25 0.76 4.99

30 12560 0.15 2.31 0.68 1.96

30 748 0.09 2.77 0.81 10.52

34 1320 0.07 2.99 0.85 5.94

55 2640 0.07 3.20 0.80 3.32

31 8048 0.13 2.46 0.72 4.11

8 18 0.19 1.88 0.90 12.00

7 25 0.24 1.64 0.84 13.32

11 131 0.29 1.59 0.66 2.21

8 31 0.22 1.76 0.84 182.71

18 318 0.20 2.11 0.73 12.68

12 268 0.19 2.00 0.80 4.45

28 1048 0.13 2.48 0.74 4.40

27 2096 0.15 2.32 0.70 4.08

282

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

were formed, at present almost completely dismantled or anthropized. The deposits of shoreface, down to about −10 m bsl, are composed of very fine sands resulting from erosion of emerged beaches, mixed with beach and/or river sediments transported by longshore currents. Offshore, at the depth of closure, between 10 and 20 m bsl, the seabed deposits consist of fine and very fine distal sand, as also observed - at least in part - by Ferretti and Setti (1989) and Zurlini and Damiani (1989), with the presence of a sand fraction relatively coarser than the main mode. A provenance from ancient emerged beaches could be likely inferred for these sediments. 4.2. Mineralogy, petrology and geochemistry

Fig. 5. Dendrogram based on cluster analyses of (a) benthic foraminifer abundance data, (b) the minimum number of ostracod individuals (MNI) and (c) the total number of ostracod valves (TNV).

The mineralogical and chemical composition of the beach sands is entirely consistent with provenance of these sands from dismantling carbonates, sandstone and volcanic deposits located in the neighbouring of the FDL area. Moreover, the petrography and chemical composition of the sands changes with the location, being richer in volcaniclastic debris in the Garigliano river mouth because of the close supply from Roccamonfina Volcano. In the northern coastline higher amounts of dolomite occur, due to the predominance of carbonate rocks in the Garigliano river basin compared to siliciclastic rock types (cf., Grauso, 1989). In the Volturno river basin siliciclastic rocks are more frequent and, as a consequence, sands from the southernmost sites are characterized by higher amounts of quartz. In this area calcite prevails over dolomite, while feldspars are mostly represented by alkali feldspar, due to the proximity with Phlegrean Fields (Melluso et al., 2012; Morra et al., 2013). The concentration of potentially toxic heavy metals in beach sediments, such as Cr, is directly influenced by clinopyroxene abundance in the samples, as expected from the geochemical behavior or this element. The mineralogical and geochemical features of marine sediments are quite uniform, likely as a consequence of the action of littoral drift, showing very little or no correlation with sands collected in the same transects. Constraints about the possible source of heavy metals in the offshore sediments can be made by comparing their contents in FDL samples with literature reference data following the procedure used by Sprovieri et al. (2007) for the Naples harbor, and Verde et al. (2013) for the Domitia coast. According to these authors, in order to discriminate between natural and anthropogenic contribution to potentially toxic elements concentrations in sediments, an enrichment factor (EF) can be calculated using the equation: EF = Css / Cref, where Css is the amount of the metal in the surface sediment and Cref is the concentration of the same element in a chosen reference material. We have considered as Css the concentrations of selected potentially hazardous metals in sea-bottom sediments, i.e. As, Cr, Cu, Pb, V, Zn (Table 4), whereas as Cref we have used the values of the background levels for the Campania region (Table 5) of Sprovieri et al. (2006). As presented in Fig. 7, the EF values mainly fall below 1 for As, apart from sample F10 in the Mondragone transect; also Hg in the six analyzed samples (not represented in Fig. 7) has an EF b 1. For these two elements a likely natural source can be suggested. Instead, we found EF values that were above 1 for Cr and Pb for most of the samples, varying in the range 1.2–2.8 for Cr and 1.1–2.1 for Pb. Regarding Cu, V and Zn, only some samples show EF N 1. The highest EF values of Cr and V are found in the mouth of the Garigliano and Volturno rivers, as well as in the Baia Domitia area. Cu and Zn show slight to significant enrichments only in some samples from the mouths of the Garigliano (sample F2) and Volturno (samples F13 and F14) rivers, and at Cuma (F19, F17 and F17 tq). Fig. 8 shows the EF average values calculated for selected metals from the FDL transects with reference to Regional concentration values (sensu De Vivo et al., 2003) of Campania and average values for Shale (sensu Wedepohl, 1978) of Table 5, considering that these EF estimations are particularly informative when evaluating the impact of human activity (Verde et al., 2013). The EF calculated versus the Regional values (the red bars of Fig. 8) are greater than 1 for Cr and V in all the investigated transects, showing their concentration in FDL samples higher than the reference levels established for the Campania region by De Vivo et al. (2003). This means that these elements

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

283

Table 7 Bivariate correlation with the Pearson's correlation coefficient (benthic foraminifers); significant correlations (p b 0.05) are indicated in bold. As Adelosina longirostra (d'Orbigny, 1826) Ammonia beccarii (Linnaeus, 1758) Ammonia parkinsoniana (d'Orbigny, 1839) Ammonia tepida (Cushman, 1926) Buccella granulata (Di Napoli Alliata, 1952) Bulimina elongata (d'Orbigny, 1846) Cribroelphidium cuvillieri (Lévy, 1966) Eggerella scabra (Williamson, 1858) Elphidium crispum (Linnaeus, 1758) Elphidium excavatum (Terquem, 1875) Elphidium granosum (d'Orbigny, 1846) Elphidium punctatum (Terquem, 1878) Haynesina depressula (Walker and Jacob, 1798) Lobatula lobatula (Walker and Jacob, 1798) Quinqueloculina lata (Terquem, 1876) Quinqueloculina pygmaea Reuss. 1850 Quinqueloculina seminulum (Linnaeus, 1758) Siphonaperta aspera (d'Orbigny, 1826) Triloculina trigonula (Lamarck, 1804) Vertebralina striata (d'Orbigny, 1826) Wiesnerella auricolata (Egger, 1895) Depth Granulometry Coast distance Taxa S Individuals (Ind.) Dominance D Shannon H Equitability J

Ba

Be

Co

Cr

Cu

Ni

Pb

V

Zn

P. tric

Depth

Gran.

C. dist.

0.063 −0.221

0.004 −0.228 −0.069 −0.292 −0.247

0.221 −0.278 −0.316 −0.109

0.041

0.263

0.056

0.114 −0.301 0.040 −0.299

0.364 0.109 0.054 0.106 0.321 −0.039 −0.047 −0.016

0.421 0.389

0.486 0.085 0.662 −0.066

0.149 −0.201 0.056 −0.215

0.447 0.501

0.428 0.453

0.514 0.611

0.021 −0.220 0.294 0.072 −0.035 0.141 0.375 −0.355 −0.091 −0.276 −0.446 −0.189

0.481 0.060

0.521 0.020 0.168 −0.188 0.312 −0.377 −0.268 −0.047

0.544 0.406

0.359 0.556

0.634 0.477

0.000 −0.198

0.232 −0.040 −0.138

0.095

0.445

0.529 −0.072

0.110 −0.221

0.643

0.419

0.701

0.041 −0.286

0.255

0.117 −0.036

0.182

0.586

0.487

0.030

0.211 −0.231

0.675

0.391

0.793

−0.070 −0.122 0.134 −0.291 0.024 −0.244

0.491 0.326 0.273

0.119 −0.025 0.106 0.054 0.137 0.011

0.218 0.075 0.190

0.343 0.375 0.554

0.469 −0.023 0.493 0.069 0.454 0.067

0.251 −0.214 0.170 −0.192 0.229 −0.205

0.602 0.419 0.593

0.130 0.354 0.351

0.489 0.471 0.694

0.188 −0.016 −0.109

0.021

0.352

0.510 −0.077

0.016 −0.196

0.477

0.389

0.599

0.196 −0.352 −0.301 −0.083

0.189

0.115

0.221

0.379 −0.148 −0.016 −0.166

0.564

0.396

0.592

0.088 −0.272 0.188 −0.219 0.012 −0.171

-0.131 −0.269 −0.314 −0.294 −0.094 0.167 −0.105 −0.212

0.038

0.327

0.749 −0.308 −0.228 −0.130 −0.501 −0.158 −0.320 −0.265 −0.271 −0.109 −0.056 0.076

0.224 −0.195 −0.568 −0.606 −0.241 −0.207

0.117 −0.624 −0.327

0.110 −0.227 −0.295 −0.360 −0.362 −0.226 −0.019 −0.426 −0.374

0.185 −0.372

0.266 −0.070 −0.206

0.206 −0.039

0.062 −0.081

0.467 −0.227 −0.184 −0.181

0.523 −0.145 −0.025 −0.250

0.510

0.634

0.546 −0.487 −0.130 −0.130 −0.149 −0.360 −0.246

0.124 −0.213 −0.313 −0.044 −0.038

0.368

0.027

0.220 −0.357

0.085 −0.133 −0.269 −0.071

0.181

0.335 −0.207 −0.192 −0.188

0.432

0.481

0.520

−0.014 −0.008

0.071 −0.070 −0.129 −0.033

0.094

0.059 −0.125 −0.127

0.141

0.137

0.149

0.066 0.460 0.091 0.533 0.118 −0.425 0.561 0.550

0.328

0.175 −0.182

0.587

0.059

0.024

0.186 −0.024

0.111 −0.155 −0.109 −0.158 −0.220 −0.143 −0.112 −0.182 −0.265 −0.365 −0.382 −0.474 −0.255 −0.300 0.042 −0.201 −0.147

0.440 −0.203 0.419 −0.173 0.239 0.195 −0.184 −0.201

0.212 −0.335 0.344 −0.468 −0.020 0.398 −0.420 −0.301

−0.034 −0.246 0.058 −0.734 −0.153 0.599 −0.663 −0.469

have higher concentration in the marine sediments than in natural sources, suggesting that they are, at least in part, of anthropic derivation. This result agrees with Verde et al. (2013), that similarly registered in the Domitia coast (comparable to our Volturno river mouth site) high values of Cr and V (as well as Cd). The EF values evaluated with respect to the average world Shale (Wedepohl, 1978), namely the blue bars of Fig. 8, show that mean FDL values were less than 1 for all heavy metals, except for Pb. Enrichment of these elements can suggest evidence of anthropogenic contamination, due to both agricultural practices and indiscriminate inputs of wastewater treatment plants located near the mouths of the Garigliano and Volturno rivers and Cuma, which also contribute a high quantity of chlorides, sulphates and Escherichia coli (Lima et al., 2012; Verde et al., 2013). 4.3. Meiobenthic assemblages and environment Cluster analysis discriminated groups characterized especially by distinct diversity, abundance and dominance values of the meiobenthic assemblages. The low-diversity, low-abundance, high dominance assemblages (F15, F16 and, subordinately, F5, F13 and F14) indicate that the Volturno estuary transect is the most environmentally stressed area

0.451 −0.257 0.466 −0.225 0.052 0.308 −0.313 −0.388

0.641 0.525 0.080 0.534 −0.076 0.130 −0.082 −0.280 0.789 0.590 0.183 0.513 −0.203 0.128 −0.597 −0.473 0.430 0.531 −0.092 0.061 0.307 −0.045 0.409 0.469 −0.294 0.084 −0.485 −0.467 −0.358 0.004 −0.269 −0.410

0.161

0.546 −0.292 −0.208 −0.234 −0.555 – 0.367 0.898 −0.239 0.367 – 0.361 −0.429 0.898 0.361 – 0.018 0.114 0.292 0.073 −0.190 0.587 0.446 0.677 −0.086 −0.125 −0.273 −0.027 0.071 0.128 0.331 0.039 0.170 0.090 0.338 −0.023

both for benthic foraminifers and for ostracods. They are dominated by the foraminifer species Ammonia parkinsoniana, A. tepida, Cribroelphidium cuvilleri, Quinqueloculina seminulum, Q. lata and by the ostracods Palmoconcha turbida, Semicytherura incongruens, Carinocythereis whitei, Leptocythere crepidula, L. macella and Pontocythere turbida. The best ecological conditions, evidenced by high-diversity, high-abundance, low-dominance assemblages of the samples F1, F8 and F9, occur in the outermost and deepest sampling stations of the Garigliano estuary, Baia Domizia and Mondragone transects. The best represented benthic foraminifer species are Ammonia parkinsoniana, A. tepida, Cribroelphidium cuvilleri and Bulimina elongata; ostracod assemblages are characterized by C. whitei, Cytherois uffenordei, Leptocythere bacescoi, L. macella, Palmoconcha turbida, Semicytherura incongruens and Loxoconcha ovulata. Depth and distance from land are main factors influencing meiobenthic assemblages. Pearson's correlation coefficient analysis shows some correlations among meiobenthic assemblage features, major and trace elements, granulometry and distance/depth of the sampling stations. Results show that meiobenthic assemblage diversity and abundance increase with distance from the coastline and depth, probably due to both natural and anthropic factors. Actually, within the infralittoral zone, abundance and diversity usually increase with depth because of the

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Table 8 Bivariate correlation with the Pearson's correlation coefficient (ostracods, MNI); significant correlations (p b 0.05) are indicated in bold. As Aurila convexa (Baird, 1850) Callistocythere flavidofusca (Ruggieri, 1950) Carinocythereis whitei (Baird, 1850) Cyprideis torosa (Jones, 1850) Cytheretta subradiosa (Roemer, 1838) Cytheridea neapolitana (Kolmann 1958) Cytherois uffenordei (Ruggieri, 1974) Cytheroma variabilis (Müller, 1894) Leptocythere bacescoi (Rome, 1942) Leptocythere crepidula (Ruggieri. 1950) Leptocythere macella (Ruggieri, 1975) Loxoconcha affinis (Brady, 1866) Loxoconcha ovulata (Costa, 1853) Neocytherideis muelleri (Kruit, 1955) Neonesidea longevaginata (Müller.1894) Neonesidea mediterranea (Müller, 1894) Palmoconcha turbida (Müller, 1912) Pontocythere turbida (Muller, 1894) Semicytherura incongruens (Muller.1894) Semicytherura sulcata (Müller, 1894) Urocythereis margaritifera (Muller, 1894) Xestoleberis communis (Muller, 1894) Xestoleberis plana (Müller, 1894) Depth Granulometry Coast distance Taxa S Individuals (Ind.) Dominance D Shannon H Equitability J

Ba

Be

Co

Cr

−0.021 0.193 −0.090 −0.067 −0.173 0.271 −0.414 0.168 −0.008 −0.176

Cu

Ni

Pb

V

0.201 −0.230 −0.189 −0.274 0.042 0.440 0.512 −0.020

Zn

P. tric

Depth

Gran.

C. dist.

0.056 −0.180 0.024 −0.234

0.049 −0.254 −0.196 0.528 0.508 0.677

0.029 −0.192 0.285 0.078 0.016 0.125 0.424 0.480 0.058 0.177 −0.163 −0.358 0.439 −0.138 −0.350 −0.418 0.130 −0.056 −0.017 −0.424 −0.092 0.057 0.024 −0.177 −0.099 −0.313 −0.259 −0.210 0.032 0.278 −0.244 −0.242 −0.167

0.445 0.313 0.516 0.101 −0.082 −0.023 0.315 0.463 0.397

0.041 −0.236

0.112 −0.108 −0.139 −0.018

0.398

0.466 −0.084 −0.021 −0.189

0.500

0.499

0.634

0.036 −0.220

0.124 −0.025 −0.105

0.429

0.492 −0.030

0.044 −0.168

0.491

0.402

0.652

0.832 −0.639 −0.054 −0.033 −0.335 −0.052 −0.068 −0.074 −0.076 −0.137 −0.145 0.033 −0.176 0.204 0.060 0.007 0.088 0.391 0.414 0.044 0.125 −0.130 0.063 −0.266 0.197 −0.070 −0.210 0.053 0.403 0.519 −0.068 0.005 −0.169

0.183 0.390 0.489

0.563 0.320 0.354

0.129 0.488 0.619

0.025 −0.185

0.511

0.429

0.639

0.052

0.002 −0.181 −0.278 −0.011

0.328

0.385 −0.166 −0.097 −0.177

0.750 −0.459 −0.282 −0.124 −0.301 −0.292 −0.260 −0.265 −0.172 −0.276 −0.011 −0.114 0.177 -0.159 0.041 −0.247 0.345 0.074 −0.003 0.125 0.476 0.580 0.050 0.175 −0.209 0.528 0.372 0.610 −0.150 0.313 −0.103 −0.511 −0.371 −0.280 −0.374 −0.086 −0.483 −0.281 0.081 −0.029 −0.103 −0.303 0.244 −0.141 −0.191 −0.042 −0.036 −0.258 −0.180 −0.187 −0.123 −0.186 −0.045 −0.158 −0.176 −0.165 0.863 −0.587 −0.248 −0.001 −0.209 −0.222 −0.229 −0.244 −0.013 −0.199 −0.063 −0.061

0.308 −0.091

0.059 −0.262

0.077

0.416

0.527 −0.009

0.119 −0.211

0.529

0.428

0.602

0.103 −0.163 −0.101 −0.276 −0.355 −0.106

0.170

0.344 −0.268 −0.121 −0.159

0.480

0.383

0.533

0.074 −0.310

0.305

0.615 −0.148

0.606

0.521

0.614

0.266

0.014 −0.044

0.299 −0.132 −0.149 −0.024

0.023 −0.096

−0.076

0.268 −0.049 −0.433 −0.403 −0.238 −0.351 −0.040 −0.482 −0.183 −0.320

−0.028

0.281 −0.146 −0.205 −0.260 −0.201 −0.306 −0.171 −0.309

0.020

0.846 −0.598 −0.085 −0.076 −0.393 −0.079 −0.138 −0.106 −0.141 −0.158 0.287 0.066 0.460 0.091 0.766 0.153 −0.484 0.684 0.131

−0.151 −0.365 −0.382 −0.474 −0.566 −0.317 0.143 −0.391 0.219

−0.127 0.440 −0.203 0.419 −0.062 0.193 0.184 −0.113 −0.290

−0.043 0.212 −0.335 0.344 −0.324 −0.083 0.302 −0.312 0.082

0.011 −0.034 −0.246 0.058 −0.581 −0.189 0.560 −0.574 0.007

diminished water energy. On the other hand, in the vicinity of coastline we noticed some relationships between benthic foraminifer and ostracod assemblages and selected heavy metals contained in the sea-bottom sediments, potential pollutants if occurring in significant amounts. We can observe that Cr has inverse relationship with abundance and diversity of both benthic foraminifer and ostracod assemblages, and positive relationship with dominance. The most sensitive species are the foraminifer Quinqueloculina lata and the ostracod Semicytherura sulcata. An inverse correlation can be also observed between these latter species and Co, Cr and V concentrations (Table 4). In particular, sampling stations with very low diversity, low abundance and high dominance assemblages are located near the mouth of the Volturno river; these features normally indicate a highly stressed environment, also revealed by a high benthic foraminifer/ostracod ratio. In this sector of the FDL, the average Cr content in two marine sediments (i.e. F15 and F16) sampled close to the Volturno river outfall is 75 ppm; if we consider two samples always coming from the Volturno transect (i.e. samples F13 and F14), as well as one sample from the Baia Domitia transect (i.e. sample F5), we reach a mean Cr concentration of ~103 ppm, more than twice the amount allowed by the Italian law environmental criterions (D.M. 367/03; Official Bulletin of the Italian Republic, 2004). Then, if we cross-check the meiobenthos data

−0.308 0.451 −0.257 0.466 −0.254 0.019 0.214 −0.276 −0.159

0.082 −0.134 −0.221

0.109 −0.046 −0.280 −0.257 0.180

0.174

0.502

0.072

−0.301 −0.135 −0.110 −0.105 −0.095 −0.095 −0.152 −0.231 0.641 0.525 0.080 0.534 0.008 0.000 0.367 0.898 −0.076 0.130 −0.082 −0.280 −0.555 0.367 0.000 0.361 0.789 0.590 0.183 0.513 −0.239 0.898 0.361 0.000 −0.176 0.147 −0.394 −0.283 −0.429 0.231 0.441 0.116 0.391 0.528 −0.104 0.027 −0.094 0.590 0.508 0.664 0.121 0.008 0.331 0.362 −0.235 −0.033 −0.151 −0.036 −0.188 0.069 −0.381 −0.347 −0.219 0.083 0.267 0.015 −0.108 −0.532 0.145 −0.229 0.110 −0.330 −0.216 −0.251

with geochemical analyses and particularly with the estimated EF values, we see that not only in fifteen bulk samples chromium has concentrations greater than 50 ppm (Table 4), which is the threshold value established by the Italian government organization "Ministero dell'Ambiente e della Tutela del Territorio" (Official Bulletin of the Italian Republic, 2004) (Table 5), but also the higher EF values calculated for our FDL sediments are just ascribed to both Cr and V, pointing to a direct link between biological activity modifications and human-deriving chemical pollution.

4.4. Ecotoxicity The ecotoxicological test battery used allowed to screen the toxicity of FDL sediment. The algae have been shown to be more sensitive to toxicants than bacteria or rotifer, as confirmed in other studies (Miller et al., 1978). The results obtained for the values of P. tricornutum cell density were subjected to significant changes of response from inhibition to stimulation of the growth. This variability was related to the peculiar sensitivity of diatoms for testing sediment elutriates (Cheung et al., 1997; Mucha et al., 2003) and easily ascribed to the chronic exposure (72 h, UNI EN ISO 10253, 2006).

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285

Table 9 Bivariate correlation with the Pearson's correlation coefficient (ostracods, TNV); significant correlations (p b 0.05) are indicated in bold. As Aurila convexa (Baird, 1850) Callistocythere flavidofusca (Ruggieri, 1950) Carinocythereis whitei (Baird, 1850) Cyprideis torosa (Jones, 1850) Cytheretta subradiosa (Roemer, 1838) Cytheridea neapolitana (Kolmann, 1958) Cytherois uffenordei (Ruggieri, 1974) Cytheroma variabilis (Müller, 1894) Leptocythere bacescoi (Rome, 1942) Leptocythere crepidula (Ruggieri, 1950) Leptocythere macella (Ruggieri, 1975) Loxoconcha affinis (Brady, 1866) Loxoconcha ovulata (Costa, 1853) Neocytherideis muelleri (Kruit, 1955) Neonesidea longevaginata (Müller, 1894) Neonesidea mediterranea (Müller,1894) Palmoconcha turbida (Müller, 1912) Pontocythere turbida (Muller, 1894) Semicytherura incongruens (Muller, 1894) Semicytherura sulcata (Müller, 1894) Urocythereis margaritifera (Muller, 1894) Xestoleberis communis (Muller, 1894) Xestoleberis plana (Müller, 1894) Depth Granulometry Coast distance Taxa S Individuals (Ind.) Dominance D Shannon H Equitability J

Ba

Be

Co

Cr

Cu

Ni

Pb

V

Zn

P. tric

Depth

Gran.

C.dist.

0,669 −0,256 −0,301 −0,256 −0,514 −0,034 −0,333 −0,324 −0,318 −0,194 −0,133 −0,002 0,790 −0,696 −0,046 −0,062 −0,394 −0,038 0,171 0,209 −0,086 −0,112 −0,217 0,404

0,296 −0,195 0,678 0,476

0,040 −0,225

0,143

0,491

0,544

0,168 −0,186

0,514

0,350

0,612

−0,022 −0,108 0,107 −0,083 −0,118 0,045 −0,002 −0,143 −0,113 −0,261 −0,290 −0,110

0,362 0,117

0,404 −0,069 0,058 −0,140 0,260 −0,239 −0,191 −0,172

0,452 0,403

0,361 0,388

0,530 0,493

0,311

0,077 −0,026

0,054

0,015 −0,212

0,131 −0,064 −0,122

0,037

0,436

0,477 −0,054

0,023 −0,184

0,526

0,466

0,666

0,036 −0,202

0,145

0,008 −0,063

0,060

0,416

0,471 −0,001

0,072 −0,144

0,439

0,354

0,588

0,845 −0,640 −0,074 −0,032 −0,342 −0,055 −0,070 −0,093 −0,078 −0,140 −0,143 0,027 −0,176 0,203 0,058 0,001 0,091 0,403 0,425 0,044 0,123 −0,132 0,069 −0,256 0,209 −0,058 −0,221 0,049 0,379 0,494 −0,076 −0,012 −0,157

0,180 0,397 0,442

0,551 0,319 0,290

0,128 0,504 0,569

0,026 −0,212

0,557

0,467

0,684

0,067 −0,150 −0,255

0,016

0,376

0,431 −0,148 −0,071 −0,191

0,864 −0,546 −0,268 −0,131 −0,363 −0,245 −0,248 −0,253 −0,155 −0,247 −0,058 −0,047 0,036 −0,241 0,255 0,011 −0,094 0,105 0,493 0,559 −0,003 0,110 −0,209 0,575 −0,094 0,106 0,046 −0,433 −0,452 −0,160 −0,004 0,261 −0,450 −0,179 −0,006 0,387

0,325 −0,111 0,412 0,691 0,125 0,226

0,327 −0,271 −0,243 −0,186 −0,292 −0,231 −0,031 −0,006 −0,228 −0,225 −0,147

0,172

0,136

0,204

0,942 −0,666 −0,188 −0,029 −0,341 −0,102 −0,174 −0,158 −0,057 −0,161 −0,098

0,064

0,504

0,030

0,026 −0,222

0,071

0,443

0,506 −0,045

0,075 −0,203

0,567

0,442

0,669

0,043 −0,174 −0,015 −0,197 −0,284 −0,036

0,330

0,387 −0,180 −0,075 −0,164

0,525

0,441

0,635

0,050 −0,250

0,358

0,491 −0,155 −0,039 −0,249

0,596

0,492

0,685

0,082 −0,542 −0,292

0,301

0,140

0,119

−0,004 0,060

0,192 −0,035 −0,111

0,122 −0,154 −0,234 −0,003

0,115 −0,195 −0,554 −0,559 −0,284 −0,214

0,145 −0,064 −0,190 −0,222 −0,152 −0,296 −0,109 −0,274

0,009

0,076 −0,022

0,923 −0,654 −0,172 −0,108 −0,425 −0,176 −0,140 −0,116 −0,176 −0,239 −0,070 0,372 0,066 0,460 0,091 0,765 0,118 −0,509 0,687 0,095

−0,250 −0,365 −0,382 −0,474 −0,562 −0,286 0,243 −0,418 0,188

−0,238 0,440 −0,203 0,419 −0,065 0,150 0,162 −0,166 −0,372

−0,115 0,212 −0,335 0,344 −0,325 −0,085 0,336 −0,368 0,017

−0,149 −0,034 −0,246 0,058 −0,583 −0,202 0,575 −0,607 −0,015

In general, the biostimulatory effects can be considered relatively high, and attributable to: • Enrichment in nutrients, due to the process itself elutriation which solubilized many substances such as phosphates and nitrates from the sediment. • Presence of low concentrations of contaminants (Calabrese, 2004).

It was not possible to correlate the ecotoxicological data with a specific and/or class of contaminants. It is notable that most of heavy metal had concentrations below the values of Basic Chemical Level (BCL) as proposed in the manual APAT-ICRAM, 2007 and that complexation of contaminant by organic ligands could be change the toxicity of the single compound. Furthermore, the growth rate of P. tricornutum showed the maximum percentage of toxicity. However, previous study demonstrated high ammonia concentration was a significant cause in inhibition of algal growth (Cheung et al., 1997). The method SPT assay with V. fischeri was employed to provide information on solid-phase. Direct sediment contact of the bacteria could increase the sensitivity to potential contaminant, whose toxicity cannot be associated in aqueous phase testing. Interference that may occur during the test and consequently

−0,311 0,451 −0,257 0,466 −0,257 0,034 0,192 −0,284 −0,131

0,136 −0,207 −0,175 0,124

0,490

0,077

−0,182 −0,124 −0,175 −0,219 −0,052 −0,026 −0,016 −0,047 0,641 0,525 0,080 0,534 −0,555 0,000 0,367 0,898 −0,076 0,130 −0,082 −0,280 −0,239 0,367 0,000 0,361 0,789 0,590 0,183 0,513 −0,429 0,898 0,361 0,000 −0,178 0,145 −0,397 −0,288 −0,083 0,225 0,436 0,111 0,419 0,501 −0,095 0,016 −0,217 0,588 0,495 0,693 0,082 −0,047 0,380 0,351 −0,026 −0,145 −0,168 −0,117 −0,212 0,066 −0,440 −0,386 0,028 0,085 0,262 0,021 −0,115 −0,550 0,064 −0,258 0,123 −0,295 −0,238 −0,208

the interpretation of results including loss of bacteria adhering to the particles and filter the test suspension, was overcome with the use of S.T.I. (Sediment Toxicity Index). Only three samples showed slight toxicity in whole sediments (Fig. 6a, Table 2) and this effect was comparatively also assessed in elutriate test with the diatom. Marine rotifer B. plicatilis is extensively used in ecotoxicology, due to the commercial availability of dried cysts from which live test organisms can be hatched at will. The acute test with this organism was less sensitive, showing always no toxic effect after 24 h or very low toxicity values after 48 h independently from the sample. A longer exposure could certainly increase its sensitivity (Fig. 6c, Table 2). 5. Conclusions The results of the whole dataset produced by our combined geological and ecotoxicological study of FDL beach and sea bottom sediments are summarized in the geoenvironmental map of Fig. 9. The main final remarks are: 1. the mineralogy, petrology and geochemistry of beach sands of the FDL area is mostly constrained by the nature of the source rocks; the contents of potentially hazardous trace metals detected in the

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Fig. 6. Ecotoxicological results obtained from this study; a) S.T.I. obtained with V. fischeri after 30 min of contact time; b) algal growth, where the stimulation (negative values) or inhibition (positive value) of cell density was statistical significant in comparison with the control (p b 0.05); c) mortality of B. plicatilis nauplii after 24 h (blue) and 48 h (green) of exposure treated with elutriates from sediments.

samples can generally be comparable with those of worldwide sediment compositions. A general decrease of mafic minerals, feldspar and dolomite and an increase of calcite and quartz along the shoreline from northwest to southeast can be highlighted; a slight increase of dolomite and illite-like phases amounts northward has been observed in the marine sediments, together with an offshore

decreasing of mean grain size, in agreement with previously cited researches carried out in parts of FDL and other neighboring areas. These features are related to different factors, as the proximity with mainland areas from which high concentration of those minerals are furnished to the emerged beach and marine environment by watercourses mouths, beach and locally submerged tuff shoal and sea

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287

Fig. 7. Enrichment factors, EF = Css / Cref (after Verde et al., 2013), for selected heavy metals of FDL sea-bottom sediments (blue filling), ordered according to increasing depth: Css is the concentration of metal in the studied sample, and Cref corresponds to the concentration of the same elements in the background after Sprovieri et al. (2006). Av (yellow filling) corresponds to the EF average value for each transect.

cliff erosion processes; the main littoral drift in the same direction, from northwest to southeast; the dispersion offshore of fine and very fine sediments (Mz b 125 μm) eroded from the beach, confirmed by morphoscopy of quartz sand grains.

2. Taking into account the biological effects on the meiofaunal calcareous assemblages in response to contamination due to potentially hazardous substances in the sediments, we observe that a relationship between our meiofaunal community and potentially toxic

Fig. 8. Enrichment factors (EF) calculated for selected heavy metals with reference to Regional values of Campania (De Vivo et al., 2003) and average Shale values (Wedepohl, 1978).

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Dol Fsp Px

Dol I/M

Qtz Cal

Fig. 9. Geoenvironmental map of the FDL, based on mutual relationships between sea-bottom and shoreline mineral concentration, coastal sediment supply by rivers and cliffs, littoral drift, meiobenthic distribution and ecotoxicological parameters. Legend: 1, sedimentary deposits (Holocene); 2, volcanic rocks (Quaternary); 3, carbonate rocks and terrigenous deposits (Meso-Cenozoic); 4, isobaths (−m); 5, direction of increasing mineral concentrations on the shoreline (grey arrows) and on the seabed (white arrow) (Dol, dolomite; Fsp, feldspars; Px, clinopyroxene; Qtz, quartz, Cal, calcite concentration; symbols after Siivola and Schmid, 2007); 6 direction of increasing Mz (mean size) on the seabed, ranging from silt and clay offshore up to medium sand nearshore; 7, main littoral drift; 8, areas with different features of benthic foraminifer and ostracod assemblages: a, highly stressed environment characterized by low diversity, low abundance, high dominance and high benthic foraminifer/ostracod ratio; b, stressed environment, with low diversity, low abundance and high dominance; c, moderately stressed to normal marine environment, with relatively high diversity, high abundance and low dominance; 9, white solid circle, ecotoxicity class: N, no toxicity; L, low toxicity (see Table 2).

trace metals, such as Cr, Co, and V, may exist; in particular, the observed anticorrelation of chromium with abundance and diversity of benthic foraminifers and ostracods, as well as correlation with dominance, can provide a valuable biological marker to test the environmental stress and hence the chemical pollution pressure in the FDL. These data are confirmed by the geochemical results, which point to an anthropic pollution source of some heavy metals (Cr and V). The outermost sampling stations show relatively high diversity, high abundance and low dominance assemblages, parameters reflecting a normal marine environment; the Cr concentration in these investigated samples has a mean value of ~ 57 ppm, only

slightly higher than the Italian Ministry threshold limit of 50 ppm. High abundance and diversity assemblages can also be connected with natural factors related to water energy, sea-bottom sediments and vegetation. 3. A comparison between the ecotoxicological analyses with mainly heavy metal contents in marine sediments highlighted species sensitivity variation. These different effects are ascribed on the one hand on the ability of organisms to accumulate, adsorb and metabolize contaminants, on the other hand on the ability of contaminants to bind to organic compounds, their bioavailability speciation and persistence in the marine sediment. Regarding the association of a

G. Balassone et al. / Marine Pollution Bulletin 112 (2016) 271–290

specific contaminant with toxicity, only sample from Baia Domitia (F5), belonging to the low toxicity class, also shows higher EF values of Cr and V, pointing to a correlation between the enrichment of these heavy metals in the sediments and their ecotoxicological features, as already shown by the meiobenthos data. It is worth noting that this sample, together with two samples from Mondragone (F12) and Cuma (F20) also characterized by low toxicity, are closer to the coastline; instead, offshore sediments are all classified as not toxic, likely due to sea water dilution and offshore dispersion of polluting elements due to marine currents. Finally, the Falerno-Domitio coastline is a sector of Campania region locally affected by an extensive anthropic pressure, and is also neighboring to the highly polluted mainland zones of this region (the so-called ‘Terra dei Fuochi’, land of fires). Our combined geological and biological study has pointed out that some areas of the emerged and submerged beach seem in a moderately good ecological status; particularly, the bottom sediments far from the coastline show meiobenthos parameters corresponding to moderately stressed to normal marine environment, also confirmed by ecotoxicological characteristics. This fact could be linked to various interconnected reasons, such as heavy metal elements dispersion due to marine currents, significant resilience of littoral and digestive capacity of marine environment, low or negligible pollution impact by superficial underground acquifers, and biological factors (i.e. Posidonia oceanica mattes to the southeast which captures and fix with its rhizomes the drifted fine sediments). On the other hand, parts of the investigated littoral area show some critical chemical and biological parameters (for instance the Volturno outfall), mainly due to contamination by hazardous substances ascribable to extensive pollutant human activities. Results of this research emphasize that the multidisciplinary approach, consisting of physical, chemical and biotic analyses, is a very useful tool to determine the environmental quality of complex marine coastal systems with high anthropogenic impact. Acknowledgements This research was funded by the University of Naples Federico II and the Italian Compagnia di San Paolo Foundation, grant FARO 2012 (# E65E12000480007) funded to Dipartimento di Scienze della Terra, dell'Ambiente e delle Risorse, to which all authors express their gratitude. We thank the professional divers V. Morgera and P. Sorvino for the seabed sampling, and the underwater photographs and videos. A special thanks is due to Dr. F. Terlizzi, geologist and technical operator diver, for the assistance during the bathymetric surveys and their processing for 2D and 3D georeferred maps. The skillful technical assistance of dr. R. de Gennaro, V. Monetti and L. Francese (DiSTAR, Università di Napoli Federico II) was highly appreciated. Laboratory support of G. Galdieri, V. D'Ambrosio and D. De Feo is gratefully acknowledged. Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.marpolbul.2016.08.004. References Alyazichi, Y.M., Jones, B., McLean, E., 2014. Environmental assessment of benthic foraminifers and pollution in Gunnamatta Bay, NSW, Australia. In: Shimizu, N., Kaneko, K., Kodama, J. (Eds.), Rock Mechanics for Global Issues-Natural Disasters, Environment and Energy. Proc. 2014 ISRM Intern. Symp, pp. 2495–2504. APAT-ICRAM, 2003. Manuale e Linee guida 29/2003. pp. 1–1187. APAT-ICRAM, 2007. Manuale per la movimentazione di sedimenti marini. pp. 1–72. Armstrong-Altrin, J.S., Lee, Y.I., Kasper-Zubillaga, J.J., Carranza-Edwards, A., Garcia, D., Nelson Ebye, G., Balaramf, V., Cruz-Ortizg, N.L., 2012. Geochemistry of beach sands along the western Gulf of Mexico, Mexico: implication for provenance. Chem. Erde 72, 245–262. Armynot du Châtelet, E., Debenay, J.-P., 2010. The anthropogenic impact on the western French coasts as revealed by foraminifers: a review. Rev. Micropaleontol. 53 (3), 129–137.

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