Distribution and diagenesis of trace metals in marine sediments of a coastal Mediterranean area: St Georges Bay (Lebanon).

St Georges Bay of Lebanon's coast is an open bay to the Mediterranean Sea. It is exposed to numerous anthropogenic activities such as industrial effluent, untreated wastewater discharge and maritime activities resulting in increasing chemical contamination, especially with trace metals. Contamination with trace metals (Cu, Cd, Co, Pb, As, Ag and Hg) and the influence of early diagenesis on their distribution were studied on both sediments and waters. For this purpose, sediment cores were collected, then treated under inert atmosphere to retrieve pore waters and solid fraction. The area appears to be seriously impacted by the materials transported by the Beirut River and/or by direct inputs, and recent land reclamation using dumpsite material. The sediments showed a significant level of contamination. Element mobility was studied by selective extraction on sediments. The mobility of trace elements from solid fraction to pore waters is controlled by the Fe/Mn cycle and organic matter.

Seasonal and Spatial Variability of Trace Elements in Livers and Muscles of Three Fish Species from the Eastern Mediterranean.

Levels of 20 trace elements (Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Ag, Cd, Sn, Sb, Ba, Hg, Pb, and U) were assessed in livers and muscles of two demersal fish species (Siganus rivulatus and Lithognathus mormyrus) and one pelagic species (Etrumeus teres) from the Lebanese coast located in the Eastern Mediterranean. The samples were collected from three sites along the Lebanese coast during the wet and dry seasons in 2017. The trace elements were more concentrated in livers than in muscles and interspecific differences were also found. The herbivorous species S. rivulatus showed the highest levels for most trace elements, while the carnivorous species L. mormyrus showed the least contamination. Elemental seasonal differences were species dependent and were observed for Ti, Cr, Mn, Fe, Ni, As, and Hg, with higher values during the wet season. Multivariate analysis showed spatial differences mainly during the wet season, while being closely related to species that reflected different accumulation patterns in each site. Levels of most trace metals in livers were higher than those reported in other Mediterranean regions (up to 2 to 3 folds). Nevertheless, the levels of Cd, Pb, and Hg in fish muscle were below the maximum levels set by the European Commission indicating that the consumption of these fish species is not likely to have adverse effect on human health. However, exposure depends on dietary habits of the population and a continuous exposure to these elements may result in adverse effects.

Juvenile fish caging as a tool for assessing microplastics contamination in estuarine fish nursery grounds.

Estuaries serve as nursery grounds for many marine fish species. However, increasing human activities within estuaries and surrounding areas lead to significant habitat quality degradation for the juveniles. In recent years, plastic pollution has become a global environmental issue as plastic debris are found in all aquatic environments with potential adverse impacts on marine biota. Given the important ecological role of estuaries and implications of microplastics (MP) in ecosystems, here we assess the occurrence, number, size, and polymer types of MP ingested by wild and caged juvenile European flounder (Platichthys flesus). We deployed caged fish for 1 month at five sites in three estuaries in the eastern English Channel. The Seine estuary, heavily impacted by manmade modifications and one of the most contaminated estuaries in Europe, was compared to two smaller estuaries (Canche and Liane) less impacted by industrial activities. We found that juvenile flounders (7-9 cm) were vulnerable to plastic ingestion. Seventy-five percent of caged fish and 58% of wild caught fish had the presence of MP items in their digestive tract. Fibers (69%) dominated in the fish's digestive tract at all sites. An average of 2.04 ± 1.93 MP items were ingested by feral juvenile flounder and 1.67 ± 1.43 by caged juvenile flounder. For the caged fish, the three sites impacted by wastewater treatment plant (Liane, Le Havre harbor, and Rouen) were those with the highest percentage of individuals that has ingested MP items. Most of the isolated items were fibers and blue in color. Polymers identified by micro Raman spectroscopy were polycaprolactam, polyethylene terephthalate, and polyurethane. Although other environmental factors may have affected caged fish condition and mortality, we found no significant correlation with the number of ingested MP. However, the high occurrence of MP ingested by juvenile fish on nursery grounds raises concerns on their potential negative effects for fish recruitment success and population renewal. Finally, this study describes, for the first time, the feasibility of using caged juvenile fish as an assessing tool of MP contamination in estuarine nursery grounds.

Microplastics pollution along the Lebanese coast (Eastern Mediterranean Basin): Occurrence in surface water, sediments and biota samples.

The Mediterranean Sea is the largest semi-enclosed sea and one of the worst affected regional seas with sub-basin scale heterogeneity in plastics concentration. Few studies on microplastics (MPs) pollution have been conducted in the Eastern part of the Mediterranean basin. This study aims to evaluate, for the first time, the MPs pollution of the Lebanese coast (Levantine Basin) as well as the most common polymers found, and to assess the potential role of coastal landfills in this pollution. Two important seafood species that are wholly consumed by the Lebanese community: the European anchovy, Engraulis encrasicolus, and the spiny oysters, Spondylus spinosus, were sampled in three different sites englobing the littoral (Tripoli, Beirut and Sidon). Sea water and sediment samples were also collected from the same sites. Results showed different patterns of MPs concentration in the analyzed matrices: Sidon water sample was highly contaminated in MPs (6.7 MPs/m3) while Tripoli had the highest MPs in sediments (4.68 MPs/g). The occurrence of MPs in the biota was high (83.4% and 86.3% in anchovies and spiny oysters, respectively). Both anchovies and oysters from Beirut region had the highest ingested MPs/individual (2.9 ±â€¯1.9 and 8.3 ±â€¯4.4 MPs/individual, respectively). This study is the first that investigated microplastics ingestion by Spondylus spinosus while indicating the most common polymers found in the three matrices (water, sediments and biota) in the Eastern Mediterranean. These results highlighted the high MPs pollution found in the Levantine Basin in comparison to other Western Mediterranean regions. In addition, the obtained results indicate a potential contribution of coastal landfills to this pollution.

Sources of microplastics pollution in the marine environment: Importance of wastewater treatment plant and coastal landfill.

This study investigated the role of a municipal wastewater treatment plant (WWTP) effluent and an abandoned coastal landfill as pathways for microplastics (MPs) input into the marine environment. MPs were first analyzed in raw sewage influent, sludge and effluent samples, and their fate was studied along a distance gradient from the WWTP in three matrices: surface water, sediments and wild mussels. All suspected MPs were characterized according to their polymer nature using micro-Raman spectroscopy. The investigated WWTP had an estimated daily discharge of 227 million MPs. MPs were found in all matrices with a decreasing abundance from the effluent. Strong MPs abundances (higher than those found near the WWTP effluent) were observed in the vicinity of the coastal landfill suggesting its importance as a MPs entry route into the marine coastal environment. Our study supports the idea that blue mussels are a promising sentinel species for MPs (<200 µm).

Analysis of polycyclic aromatic hydrocarbons (PAHs) in Lebanese surficial sediments: A focus on the regions of Tripoli, Jounieh, Dora, and Tyre.

This paper aims to identify the concentrations of PAHs in the sediments of four coastal zones in Lebanon and determine their possible sources and effects. For each region (Tripoli, Jounieh, Dora, and Tyre), sampling, lyophilization, Soxhlet extraction, rotary evaporation, and gas chromatography were performed on 11, 10, 7, and 11 samples, respectively. The total PAHs concentrations ranged from 1.22 to 731.93µg/kg dry weight. The lowest concentrations were found in Tyre and the highest in Dora and Jounieh. The level of PAHs was classified as low to moderate and their source was mainly pyrogenic.

Role of Cu and pb on Ni bioaccumulation by Chlamydomonas reinhardtii: Validation of the biotic ligand model in binary metal Mixtures.

Ni, Pb and Cu uptake by Chlamydomonas reinhardtii has been quantified in single and binary metal systems in order to test some of the key assumptions of the biotic ligand model (BLM). Experiments were performed in solutions containing 5×10(-7)M of free metal at 30°C and pH 6. Nickel internalization fluxes (Jint) were measured in the presence of various concentrations of lead or copper from 5×10(-8)M to 5×10(-6)M at pH 6.0. Competition experiments did not show a straightforward antagonistic competition, as would be predicted by BLM. Synergistic and antagonistic effects were observed in binary metal systems which implies that bioaccumulation process is much more dynamic than assumed in the equilibrium models. Ni uptake decreased significantly in the presence of Cu(2+) concentrations higher than 5×10(-7)M. However, a maximum value of Ni uptake was observed at 5×10(-7)M Pb(2+). Cu(2+) was shown to compete strongly with Ni for uptake, having a higher binding affinity to Ni transport sites (KCu-Rs=10(6.95)M(-1)) than to Cu transport sites (KCu-Rs'=10(6.22)M(-1)). In contrast, the effect of Pb(2+) on Ni uptake could not be explained by a simple competitive equilibrium with the transport sites of Ni such as the BLM. On the other hand, internalization fluxes of Cu and Pb were nearly constant in the absence and in the presence of Ni, implying that nickel had no effect on the uptake of copper or lead. The calculated affinity constant of Cu to Ni transport sites in the presence of Ni was similar to that obtained in the absence of Ni (K'Cu-Rs'=10(6.22)M(-1)). It was further concluded that Cu and Pb did not interact with the same active sites on the cell surface. Ni and Cu were shown to interfere with Mg and Na transporters, while Pb uptake was thought to occur by the Ca pathway.

Organochlorines in harbour porpoises (Phocoena phocoena) stranded along the southern North Sea between 2010 and 2013.

7 polychlorinated biphenyls (PCBs), 6 dichlorodiphenyltrichloroethanes (DDXs) and 8 polybrominated diphenyl ethers (PBDEs) were measured in the blubber of 20 harbour porpoises stranded on the coasts of the southern North Sea between 2010 and 2013. The results showed that porpoises that died from infectious diseases displayed significantly higher levels of PCBs in their blubber compared to healthy porpoises that died from physical trauma. ∑7CBs and ∑DDXs were higher in juvenile porpoises compared to adult females. Except for three individuals, PBDE concentrations were below the limit of quantification in the blubber samples treated. In general, levels of PCBs and DDXs obtained in the blubber of porpoises from this study were in the same order of magnitude or even lower than those obtained in the blubber of porpoises stranded along the North East Atlantic Ocean and the Black Sea over the period 1987 and 2013. The results of the present study suggest that even if the status of marine pollution has been improved, a continuous long-term contamination by toxic organochlorines over many generations may be observed.

Harbour porpoises (Phocoena phocoena) stranded along the southern North Sea: an assessment through metallic contamination.

Throughout the last few years, the southern North Sea has witnessed an increase in the number of stranded marine mammals, particularly the harbour porpoise (Phocoena phocoena). This species is subject to several potential threats such as exposure to contaminants, changes in food supply, marine traffic and fishery by-catch. The aims of this study were to investigate potential associations between contaminants and health status and to analyze spatial and temporal trends of metal concentrations in harbour porpoises. Selected trace elements (As, Cd, Cr, Cu, Hg, Mn, Se, V and Zn) were measured in kidneys and livers of 105 harbour porpoises stranded along the southern North Sea (French and Belgian coasts from 2006 to 2013) and 27 stranded along the Bay of Biscay (French coast from 2009 to 2012). Porpoises that died from infectious disease displayed significant higher hepatic concentrations of Cd, Hg, Se and Zn compared to healthy porpoises that died from physical trauma. Adult porpoises displayed significant higher concentrations of Cd, Cr, Hg, Se and V in livers compared to juveniles. No spatial or temporal trends in metal concentrations were detected in our study. The results of the present study suggested that chemical contamination may represent one of many threats encountered by harbour porpoises, but it cannot explain alone the increase in the number of stranded individuals.

Mercury distribution and methylmercury mobility in the sediments of three sites on the Lebanese coast, eastern Mediterranean.

Mercury (Hg) contamination in coastal sediments has been widely studied in clay deposits; however, equivalent results on carbonated sediments are scarce. This article aims to study Hg distribution in Lebanese carbonate coastal marine sediments (Eastern Mediterranean) in order to characterize their contamination level and to explore the postdepositional mobility of methylmercury (MeHg) in the deposits. Vertical distribution profiles of total (HgT) and MeHg have been established for the solid phase of sediment cores collected in various near-shore environments chosen for their hypothetical various degrees of anthropization. In addition, dissolved MeHg was determined in sediment pore waters to test its mobility and potential availability for biota. Three sites on the Lebanese coasts--Akkar, Dora, and Selaata--were selected. Akkar is far from any direct contamination source, whereas Dora, located near the Beirut harbor, is a heavily urbanized and industrialized zone including a huge dump site, and Selaata is near a chemical plant that produces phosphate fertilizers. Particulate HgT concentrations in the sediments varied between <0.04 and 0.65 µg/g, with a proportion of MeHg lower than 1%. Based on a sediment quality guideline (MacDonald et al. 2000), we concluded that Dora bay sediments are heavily contaminated by Hg, with concentrations exceeding the "consensus-based threshold effect" level (0.17 µg/g) and almost reaching the "effects range-medium" level (0.71 µg/g). In spite of the low HgT concentration in Akkar and Selaata sediment (similar to natural carbonated sediment: 0.04 µg/g according to Turekian and Wedephol (1961), a closer analysis of the sediment core vertical profile allows one to observe an anthropogenic impact. This impact might be toxicologically insignificant; however, it allows tracing the time increase of Hg diffuse deposition. On the other hand, dissolved MeHg concentrations ranged from 0.04 to 0.09 and from 0.04 to 8.76 ng/l in the Selaata and the Dora sediments, respectively; MeHg vertical profiles in interstitial water enabled us to calculate diffusive fluxes of MeHg from the sediment varying from 0.3 to 1.0 ng/m(2)/day. Thus, the deposited sediments constitute a measurable source of bioavailable Hg for epibenthic organisms.

Formation of lipid oxidation and isomerization products during processing of nuts and sesame seeds.

The aim of the present study was to quantify some nutritional and safety quality parameter changes that take place in nuts (roasting) and sesame seeds (dehulling, roasting, milling, and sterilization) during processing. Such evaluation was based on chemical analysis of various indicators of lipid alteration in raw and processed pistachios, almonds, peanuts, and tahina. Lipid oxidation was assessed by the evolution of lipid oxidation products including hydroperoxides, p-anisidine, and thiobarbituric acid reactive substances, as well as carboxymethyllysine (CML) and trans fatty acids (tFAs). All these parameters were significantly affected by the different processing stages, especially by roasting and sterilization (tahina). Nut roasting and sesame heat treatment increased the primary (hydroperoxides) and secondary (aldehydic compounds) lipid oxidation products, with the p-anisidine value reaching 6-11.5 and thiobarbituric acid reactive substances 3-5 mg/kg (equiv of malondialdehyde) in the different end products. In addition, roasting led to the formation of CML (between 12.7 and 17.7 ng/mg) and tFAs (between 0.6 and 0.9 g/100 g) in nuts and tahina, which were absent in the raw material. Roasting parameters appear as the critical factor to control to limit the CML and tFA formation in the final product.