Marc Tedetti

High penetration of ultraviolet radiation in the south east Pacific waters

We investigated the penetration of solar ultraviolet radiation (UVR) in the surface waters of the south east Pacific (08 - 35 degrees S, 142 - 73 degrees W) from October to December 2004 during the BIOSOPE cruise. In the hyper-oligotrophic waters of the South Pacific Gyre ( near Easter Island), diffuse attenuation coefficients for downward irradiance, K-d(lambda), at 305 nm (UV-B), 325, 340 and 380 nm (UV-A) were 0.083, 0.055, 0.039 and 0.021 m(-1), respectively. The corresponding 10% irradiance depths, Z(10%)(lambda), were 28, 42, 59 and 110 m, respectively. These UVR penetrations are the highest ever reported for oceanic waters and are equal to those measured in the clearest fresh waters. UV-extended inherent optical property (IOP) and radiative transfer (RT) models allowed reliable estimations of K-d(lambda) with the Case 1 water assumption when two values of chromophoric dissolved organic matter (CDOM) absorption spectral slope coefficient (S) were used, i.e. 0.017 nm(-1) at 325, 340 and 380 nm, and 0.023 nm(-1) at 305 nm.

Identification and quantification of known polycyclic aromatic hydrocarbons and pesticides in complex mixtures using fluorescence excitation-emission matrices and parallel factor analysis.

Polycyclic aromatic hydrocarbons (PAHs) and pesticides are among the most widespread organic contaminants in aquatic environments. Because of their aromatic structure, PAHs and pesticides have intrinsic fluorescence properties in the ultraviolet/blue spectral range. In this study, excitation-emission matrix (EEM) fluorescence spectroscopy and parallel factor (PARAFAC) analysis were used to characterise and discriminate fluorescence signatures of nine PAHs and three pesticides at the μg L(-1) level in the presence of humic substances (0.1-10 mgCL(-1)). These contaminants displayed a diversity of fluorescence signatures regarding spectral position (λEx: 220-335 nm, λEm: 310-414 nm), Stokes shift (39-169 nm) and number of peaks (1-8), with detection limits ranging from 0.02 to 1.29μgL(-1). The EEM/PARAFAC method applied to mixtures of PAHs with humic substances validated a seven-component model that included one humic-like fluorophore and six PAH-like fluorophores. The EEM/PARAFAC method applied to mixtures of pesticides with humic substances validated a six-component model that included one humic-like fluorophore and three pesticide-like fluorophores. The EEM/PARAFAC method adequately quantified most of the contaminants for humic substance concentrations not exceeding 2.5 mg CL(-1). The application of this method to natural (marine) samples was demonstrated through (1) the match between the Ex and Em spectra of PARAFAC components and the Ex and Em spectra of standard PAHs, and (2) the good linear correlations between the fluorescence intensities of PARAFAC components and the PAH concentrations determined by GC-MS.

Spatial and seasonal variabilities of dissolved hydrocarbons in surface waters from the Northwestern Mediterranean Sea : results from one year intensive sampling

Dissolved aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analysed from surface water collected in continental, harbour and off-shore marine sites from Marseilles coastal area (Northwestern Mediterranean Sea) from February 2011 to February 2012. AH and PAH concentrations were in the range of 0.04-0.53 μgl(-1) and 8.1-405 ngl(-1), respectively. They both displayed seasonal and spatial variations in their concentrations and molecular composition. The lowest AH concentrations were found in summer and the highest PAH concentrations in winter. Both natural and anthropogenic (pyrogenic and petrogenic) hydrocarbon sources were identified. In winter, concentrations and composition patterns highlighted an increase in the signature of unburned and combusted fossil fuels, while they suggested an enhancement of weathering processes in summer months. Hydrocarbon inputs to the dissolved phase seemed to originate mainly from the atmosphere and the Rhône River. Hydrocarbon additional sources were identified only at the harbour site, emphasising the intense shipping traffic and industrial activities occurring in one of the most important Mediterranean harbours. This study underscores the strong dynamics of dissolved hydrocarbons and the uncoupling of the sources, transport and removing processes affecting AHs and PAHs. It also demonstrates the pertinence of taking this dynamics into account for the budget assessments of organic pollutants in coastal environments.

Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea

Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05-0.41 and 0.04-4.3 μg l(-1) in the SSW, peaking up to 38 and 1366 μg l(-1) in the SML, respectively. Dissolved and particulate PAHs ranged 1.9-98 and 1.9-21 ng l(-1) in the SSW, amounting up 217 and 1597 ng l(-1) in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9-11.5 in the dissolved phase.

Fluorescence properties of dissolved organic matter in coastal Mediterranean waters influenced by a municipal sewage effluent (Bay of Marseilles, France)

Environmental context. Marine dissolved organic matter plays a key role in the global carbon cycle. Questions remain, however, as to the influence of anthropogenic activities on its composition and distribution in coastal waters. It was found that dissolved organic matter in the vicinity of a municipal sewage effluent (Marseilles City, France) contained a high proportion of protein-like material, thereby demonstrating the influence of human activities on coastal dissolved organic matter. Abstract. Fluorescent dissolved organic matter (FDOM) in coastal marine waters influenced by the municipal sewage effluent (SE) from Marseilles City (France, north-western Mediterranean Sea) has been characterised. Samples were collectedeleventimesfromSeptember2008toJune2010intheBayofMarseillesalongacoast-openseatransectfromthe SEoutletinthe SouthBayandatthe MediterraneanInstitute Observationsiteinthe centralBay. Fluorescenceexcitation- emission matrices combined with parallel factor analysis (PARAFAC) allowed the identification of two protein-like (tyrosine C1, with excitation maxima (lEx) and an emission maximum (lEm )o f,230, 275/306nm; tryptophan C2, lEx/ lEm,230, 270/346nm)andthreehumic-likecomponents(marinehumic C3,lEx/lEm280/386nm; C4,lEx/lEm235, 340/ 410nm;C5,lEx/lEm255,365/474nm).FromtheSEoutlettothecentralBay,agradientappeared,withdecreasingFDOM intensities, decreasing dissolved organic carbon, particulate carbon, nutrients and faecal bacteria concentrations and increasing salinity values. This gradient was associated with decreasing abundances in protein-like fluorophores and rising abundances in humic-like (C3 and C5) materials. This shift in FDOM composition illustrated the decrease in wastewater inputs and the increase in marine sources of DOM along the transect. FDOM data showed that the Marseilles SE spread up to 1500m off the outlet, but it did not reach the central Bay. Tryptophan-like material was the dominant fluorophoreintheSEanddisplayedthehighestcorrelationswithbiogeochemicalparameters(organiccarbon,phosphates, faecal bacteria). Therefore, it is proposed to use its fluorescence intensity to detect and track SE inputs in the Marseilles coastal marine waters. Additional keywords: Cortiou, EEM fluorescence, PARAFAC, tryptophan.

Variability of Solar Radiation and CDOM in Surface Coastal Waters of the Northwestern Mediterranean Sea

Atmospheric and in‐water solar radiation, including UVR‐B, UVR‐A and PAR, as well as chromophoric dissolved organic matter absorption [aCDOM(λ)] in surface waters were monthly measured from November 2007 to December 2008 at a coastal station in the Northwestern Mediterranean Sea (Bay of Marseilles, France). Our results showed that the UVR‐B/UVR–A ratio followed the same trend in the atmosphere and at 2 m depth in the water (P < 0.0001) with an increase (eight‐fold higher) during summer. The low diffuse attenuation coefficients for downward irradiance [Kd(λ)] of UVR‐B, UVR‐A and PAR indicated that the waters were highly transparent throughout the year. The relationships between aCDOM(λ) and Kd(λ) in this oligotrophic system suggested that CDOM contributed to UVR attenuation in the UVA domain, but also played a significant role in PAR attenuation. Mean UV doses received in the mixed layer depth were higher by a factor 1.4–33 relative to doses received at fixed depths (5 and 10 m) in summer (stratified period), while the inverse pattern was found in winter (mixing period). This shows the importance of taking into account the vertical mixing in the evaluation of UVR effects on marine organisms.

Assessment of anthropogenic inputs in the surface waters of the southern coastal area of Sfax during spring (Tunisia, Southern Mediterranean Sea)

The coastal marine area of Sfax (Tunisia), which is well-known for its high productivity and fisheries, is also subjected to anthropogenic inputs from diverse industrial, urban and agriculture activities. We investigated the spatial distribution of physical, chemical and biogeochemical parameters in the surface waters of the southern coastal area of Sfax. Pertinent tracers of anthropogenic inputs were identified. Twenty stations were sampled during March 2013 in the vicinity of the coastal areas reserved for waste discharge. Phosphogypsum wastes dumped close to the beaches were the main source of PO4(3-), Cl(-) and SO4(2-) in seawater. The high content in total polyphenolic compounds was due to the olive oil treatment waste water released from margins. These inorganic and organic inputs in the surface waters were associated with elevated COD. The BOD5/COD (<0.5) and COD/BOD5 (>3) ratios highlighted a chemical pollution with organic load of a low biodegradability.

Hydrocarbons in a coral reef ecosystem subjected to anthropogenic pressures (La Réunion Island, Indian Ocean)

The La Saline fringing reef, which is the most important coral reef complex of La Reunion Island, (south- western Indian Ocean), is subjected to anthropogenic pressures through river and groundwater inputs. Salinity and biogeochemicalparameters(silicates,nitrates,dissolvedorganiccarbon,chlorophyll-a),aswellasaliphatichydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analysed in particulate and dissolved material from ground- waters,rivers,harbour,backreef,forereefandoceanicwatersintheLaSalinereefareaduringtherainyseason(February- March 2012). Particulate and dissolved AH concentration ranges were 0.07-144 and 0.06-0.58 m gL � 1 respectively. Particulate and dissolved PAH concentrations ranges were 4.3-326 and 28-350 ng L � 1 respectively. AHs, dominated by nC15, nC17, nC18 compounds or nC26, nC27, nC29, nC31 compounds, were mainly of biogenic origin (phytoplankton, bacteria, higher-plant debris) although some anthropogenic (petroleum inputs) signatures were recorded in the dissolved phase from the harbour and fore reef areas. PAHs, dominated by two- to three-ring compounds and their alkylated homologues, reflected unburned petroleum inputs, but probably also biogenic sources. From the distribution of salinity, biogeochemical parameters and hydrocarbons, we found that inland waters flowed mainly in the surface and in the southern part of reef waters and that particulate PAHs allowed tracking these inland water intrusions in fore reef waters. Finally, this pilot study highlights the uncoupling between the dynamics of AHs and PAHs in tropical environments. Additionalkeywords: aliphatichydrocarbons,groundwaters,LaSalinefringingreef,polycyclicaromatichydrocarbons, tropical environment.

Origin and distribution of hydrocarbons and organic matter in the surficial sediments of the Sfax-Kerkennah channel (Tunisia, Southern Mediterranean Sea).

We investigated the origin and distribution of aliphatic and polycyclic aromatic hydrocarbons (AHs and PAHs) and organic matter (OM) in surficial sediments of the Sfax-Kerkennah channel in the Gulf of Gabès (Tunisia, Southern Mediterranean Sea). TOC, AH and PAH concentrations ranged 2.3-11.7%, 8-174μgg-1sed.dw and 175-10,769ngg-1sed.dw, respectively. The lowest concentrations were recorded in the channel (medium sand sediment) and the highest ones in the Sfax harbor (very fine sand sediment). AHs, PAHs and TOC were not correlated for most of the stations. TOC/N and δ13C values revealed a mixed origin of OM with both marine and terrestrial sources. Hydrocarbon molecular composition highlighted the dominance of petrogenic AHs and the presence of both petrogenic and pyrogenic PAHs, associated with petroleum products and combustion processes. This work underscores the complex distribution patterns and the multiple sources of OM and hydrocarbons in this highly anthropogenized coastal environment.

Water quality affects the structure of copepod assemblages along the Sfax southern coast (Tunisia, southern Mediterranean Sea)

The Sfax southern coast (Gulf of Gabes, Mediterranean Sea) has been under increased anthropogenic pressure for many years. In the present study we investigated the effects of this anthropisation on the spatial distribution of copepod assemblages in relation to the physicochemical features of seawater at 20 stations sampled on 19 March 2013. Copepods represented 73% of total zooplankton abundance. Small planktonic copepods (<1.45mm), including pollution-tolerant species (e.g. Oithona nana, Paracalanus parvus, Harpacticus littoralis and Tisbe battagliai), proliferated exclusively in stations of ~0.5-m depth characterised by high coastal anthropogenic inputs. The largest copepod species were dominated by Calanus helgolandicus (1.45–2.5mm) in the offshore zone in depths of ~3m. Substantial numbers of Oithona plumifera (7.5%) were found at depths between 0.5 and 3m. Copepod diversity was significantly higher in the southern zone, which is less affected by sewage, than in the northern zone, which was subjected to higher pressure (Shannon–Wiener index H′=1.5–2.5 and ≤1.5 bits individual–1). A shift in the planktonic copepod community between the two zones was linked to deterioration of water quality, with higher phosphorus levels, turbidity and chemical oxygen demand (COD) in the northern zone.