Alkylphenols and their ethoxylates in seafood from the Tyrrhenian Sea

The present study reports the results of an investigation on occurrence of octylphenols (OPs), nonylphenols (NPs) and their respective ethoxylates (with 1-6 ethoxylic group) in aquatic species of commercial interest from the Tyrrhenian Sea. Samples were collected at Livorno, Fiumicino and Salerno commercial harbors, during September-October 2003. The data obtained showed that almost all of the tested compounds were found in all the samples. NP was generally detected at the highest concentrations. Among the tested species common to the three sampling sites, mullets and seabreams generally showed high values of total alkylphenols (APs) and alkylphenol ethoxylates (APEOs) (44-55 ng g(-1) and 27-525 ng g(-1) fw), yet, the maximum concentrations were found in shrimps from Fiumicino (1255 ng g(-1) fw). On the contrary, the lowest concentrations were observed in hakes and anchovies (34-36 ng g(-1) and 6-37 ng g(-1) fw). Tuna, exhibited very high concentrations of total alkylphenolic compounds (APEs) (889 ng g(-1) fw). Seafood from Fiumicino fishing area, which is under the influence of the River Tiber, showed a degree of contamination of at least one order of magnitude higher than the other two sites. On the basis of the results of this study, the corresponding daily intakes of NPs are much lower than the TDI proposed by the Danish Environmental Agency.     

Polycyclic aromatic hydrocarbons in marine organisms from the Adriatic Sea, Italy

Polycyclic aromatic hydrocarbons (PAHs) were analyzed in bivalves (Mitylus galloprovincialis), cephalopods (Todarodes sagittatus), crustaceans (Nephrops norvegicus) and fish (Mullus barbatus, Scomber scombrus, Micromesistius poutassou, Merluccius merluccius) in several pools coming from the Central Adriatic Sea. These marine organisms were selected because of their multitude, wide distribution and common use in the Italian diet, they were sampled and analyzed during the year 2004. Acenaphthene, benzo(a)pyrene, dibenz(a,h)anthracene, benzo(ghi)perylene and indeno(1,2,3-cd)pyrene showed levels below the instrumental detection limit in all samples. Fluorene, phenanthrene, anthracene, fluoranthene, benz(a)anthracene, benzo(b)fluoranthene and benzo(k)fluoranthene were detected at different concentrations in analyzed samples. Chrysene was detected only in mussels with very low values (average 0.74ngg(-1) wet weight). PAHs composition pattern was dominated by the presence of PAHs with 3-rings (62%) followed from those with 4-rings (37%) and 5-rings (1%). Atlantic mackerel, European hake and blue whiting showed the highest PAH concentrations, ranging from 44.1 to 63.3ngg(-1) wet weight, the group of invertebrate organisms showed a level of contamination about three times lower than those of the vertebrate groups. Mediterranean mussels that did not present very high levels of contamination expressed as sum of PAHs showed one of the highest values of benzo(a)pyrene equivalents (BaPEs). Conversely the latter value was very low in Atlantic mackerel even if this species reported the highest total PAH concentrations. No significant correlation was observed between weight, length and trophic levels and total PAHs.     

Concentrations and composition of organochlorine contaminants in different species of cephalopod molluscs from the Italian waters (Adriatic Sea)

Persistent organochlorines, such as polychlorinated biphenyls including coplanar congeners and DDT compounds were measured in the liver of different species of mollusc cephalopods: broadtail squid (Illex coindetii), horned octopus (Eledone moschata) and spider octopus (Octopus salutii) collected in two different areas of the Adriatic Sea (central and southern Adriatic Sea). The concentration of PCBs exceeded DDT ones in horned octopus (PCBs: 617.0 ngg(-1) lipid weight, DDTs: 188.0 ngg(-1) lipid weight) and in spider octopus (PCBs: 590.0 ngg(-1) lipid weight, DDTs: 293.0 ngg(-1) lipid weight), while in broadtail squid PCB load (748.0 ngg(-1) lipid weight) was similar to those of DDTs (514.5 ngg(-1) lipid weight). No significant difference in PCB levels was observed among species, while DDT concentrations were higher in broadtail squid than in horned octopus and spider octopus. DDTs composition showed slight differences in relation to species, thought p,p'-DDE was the predominant compound in all cephalopod species (broadtail squid: 88.1%, horned octopus 94.1%, spider octopus: 97.5%). PCB isomer profiles were similar among species being hexachlorinated isomers the most abundant, followed by penta- and heptachlorobiphenyls, while tri- and tetrachlorobiphenyls made up a small percentage of the total PCB residues. Regarding coplanar congeners, non-ortho PCBs were below the detection limit in all samples and the 2,3,7,8-TCDD toxic equivalent (TEQ) concentrations were very low. The influence of biological and ecological factors (size/weight and location) on the bioaccumulation of organochlorine compounds has been discussed.     

Occurrence and fate of alkylphenols and alkylphenol ethoxylates in sewage treatment plants and impact on receiving waters along the Ter River (Catalonia, NE Spain)

The partitioning of alkylphenols in the dissolved and particulate matter of influents, effluents, accumulation onto sludge and the impact of sewage treatment plant upon receiving waters was studied along the Ter River basin (Catalonia, NE Spain). A solid-phase extraction or pressurized liquid extraction followed by liquid chromatography-mass spectrometry was developed and permitted to determine target compounds with high efficiency in waters, particulate material and sludge. Nonylphenol mono- and diethoxylate, nonylphenol and octylphenol partitioned preferably upon particulate matter and sludge, whereas long chain NPE(3-15)O prevailed in the dissolved phase and was released by effluents. Within the treatment process, a net accumulation of alkylphenols in sludge was found, producing up to 148g/t/month. The removal efficiency of alkylphenols was of 37-90% and depended on the treatment. Assessment on the fate of these contaminants within STPs is discussed in terms of flow rates, biological oxygen demand and tons of sludge produced.     

Present status of POP contamination in Lake Maggiore (Italy)

In the last decade, Lake Maggiore has been subject to heavy DDT contamination due to a chemical plant located near the main influent of the Baveno Bay. The freshwater bivalve zebra mussel (D. polymorpha) was used as a bioindicator of several POPs (DDTs, PCBs, HCB, HCHs) to follow their concentration trend after a heavy flood in autumn 2000. Sampling of mollusc specimens were carried out monthly from April 2001 to October 2002 at two different stations in and outside the bay. Results showed worsening of DDT pollution due to the transport of insecticide from contaminated sediments and soils still present in the closed chemical plant site. Levels of about 4.5 microg/g lipids in soft tissues of specimens from the most contaminated site and 2.0 microg/g lipids outside it were found, which are twice those measured before the flood. HCHs and HCB values were always very low, but it was noticed since winter 2001-2002 a sharp increase of PCB pollution, with values of about 3-4 microg/g lipids, not due to the 2000 flood, but probably to improper discharge or release of contaminated sediments from numerous dams located in the watershed. Concentrations of total dioxin-like PCBs reached dangerous levels for the water community. Fish consumption may be a risk for human health especially for resident population, bearing in mind that fish usually have a higher POP concentration than zebra mussel.     

Persistence of polycyclic aromatic hydrocarbons in sediments in the deeper area of the Northern Adriatic Sea (Mediterranean Sea)

The Po Valley is the most important agricultural and industrial area of Adriatic basin. In this area there are several rivers which transport polycyclic aromatic hydrocarbons (PAHs) into the sea via suspended particulate matter. This study describes the persistence of PAHs in the deep and coastal sediments of the Northern Adriatic. Different environmental conditions were studied: salinity, temperature, sunlight, sediment particle size and organic matter in sediment. The average conditions in the deep areas of the Northern Adriatic are: salinity higher than 37, temperature lower than 11 °C, darkness and clayey sediments with a high organic matter content. These conditions increase the persistence of the PAHs in the deep area of the Northern Adriatic.     

Biologic impact on the coastal belt of the province of Venice (Italy,Northern Adriatic Sea): preliminary analysis for the characterization of the bathing water profile

Background, aim and scope  

This paper presents a preliminary study of the water profile with reference to microbiological parameters, required by Directive 2006/07/EC (European Community 2006) concerning the management of bathing water quality, in the coastal belt of the Province of Venice (Italy, Northern Adriatic Sea). A historical database has been implemented with monitoring data for the period 2000–2006 (data on rivers, bathing and marine coastal waters and on the characterization of Wastewater Treatment Plant (WWTP) discharges) from the institutional activity of Veneto Regional Environmental Prevention and Protection Agency (ARPAV). An integrated areal analysis for the microbiological investigation of homogeneous stretches along the coast of the Province of Venice was performed for a preliminary characterization of the bathing water profile considering water quality status and existing pressure sources.     

Arsenosugars and other arsenic compounds in littoral zone algae from the Adriatic Sea

In 10 different marine algae from the littoral zone (found between the highest and lowest tide marks on the seashore) arsenic compounds were determined by means of a high-performance liquid chromatography (anion and cation exchange)-UV photochemical digestion-hydride generation-atomic fluorescence spectrometry (HPLC-UV-HGAFS) system. Samples (Ceramium sp., Cystoseira barbata, Enteromorpha sp., Fucus virsoides, two different species of Gelidium, Padina pavonica, Polisyphonia sp. and Ulva rigida) were collected along the Adriatic Sea coast of Slovenia. The total arsenic content of the algal samples, as determined by ICP-MS, ranged from 1.35 to 28.1 microg g(-1) (fresh weight). In all algae but two, the most abundant arsenic species found were arsenosugars with minor amounts of other arsenic compounds. Cystoseira barbata and Ceramium sp. contained high amounts of mainly inorganic arsenic. A small quantity of arsenobetaine was detected in most of the investigated Adriatic algae, which probably originates from mesofauna attached to the algae in their natural habitat.     

Toxicity and heavy metal contamination of surficial sediments from the Bay of Thessaloniki (Northwestern Aegean Sea) Greece

Surficial sediments (the fraction < 2000 microm) from the Bay of Thessaloniki, in the Northwestern Aegean Sea, Greece were examined for heavy metal and organic carbon contents, as well as for acute LUMIStox toxicity of pore waters (PWs), wet sediment elutriates (WSEs) and dry sediment elutriates (DSEs) obtained from the solid material remaining after PW extraction. WSEs where not toxic. EC20/50 values could be measured in some DSE and PW samples. In all sediment samples, the DSE toxicity was greater than the corresponding PW toxicity. Sediment concentrations of total and labile Cd, Pb, Cu, Cr, Zn, Mn, Ni and Fe were determined and evaluated in relation to sediment quality guidelines. Pollution levels ranged from low to high for certain metals. A misfit between sediment toxicities calculated from heavy metal concentrations and those biologically measured was observed. Toxicity values were in general poorly correlated with sediment's heavy metal or organic carbon content. As significant correlation was however found between the DSE toxicity with total Ni and labile Fe, as well as for the PW toxicity with total Ni, labile Fe and labile Cr.     

Biomonitoring of element contamination in bees and beehive products in the Rome province (Italy)

Environmental Science and Pollution Research - In this study, we determined the levels of elements (i.e. As, Be, Cd, Cr, Hg, Ni, Pb, U, and Zn) in bees and edible beehive products (honey, wax,...     

Organochlorinated contaminants in decapod crustaceans from the coasts of Brittany and Normandy (France)

The contamination and distribution of organochlorinated compounds were considered in three crustacean species (edible crab, Cancer pagurus; spider crab, Maja brachydactyla; velvet swimming crab, Necora puber) from five sites along the coasts of Brittany and Normandy (Western and North-Western France). PCBs (16 single congeners), pp'-DDE and HCB were measured in hepatopancreas, gonads and muscle: in all, 175 samples were analysed. The spider crab was the only species found in the five sampling sites, thus enabling comparison between areas. Specimens from Antifer were much more contaminated (summation operator 16 PCBs in hepatopancreas=2000-4000 ng g(-1) dry weight) than those from other sites (50-1000 ng g(-1) d.w.). Among all the three species, the spider crab appeared more contaminated by PCBs than the edible crab, by a factor 2-3, probably in relation with specific differences in their life cycle. There was no difference due to the gender of the species. Within the different analysed tissues, contamination levels increased from muscle to gonads and hepatopancreas in relation with the fat content. A very similar PCB composition was observed in all samples, PCB fingerprints being characterised by the relative importance of the more persistent PCB congeners: CB153, 138, 180, 187, and 118. Finally, these results were compared to recent food regulations first of maximum marker PCB intake and secondly of maximum dioxin-like PCB intake. By considering the muscle, all samples were far below the regulatory limits; for hepatopancreas and gonads, however, some samples were unfit for human consumption.     

Accumulation and tissue distribution of mercury and selenium in striped dolphins (Stenella coeruleoalba) from the Mediterranean Sea (southern Italy).

Tissues and organs from Stenella coeruleoalba stranded along the Apulian coasts (southern Italy) during the period April-July 1991 were analyzed for their mercury and selenium content. Analysis showed considerable variations in the mercury concentration in the examined organs and tissues. The highest concentrations of mercury were found in the liver (from 2.27 to 374.50 microg g(-1) wet wt.). After the liver, lung, kidney, muscle and brain were the most contaminated, while the lowest mercury contamination was found in the melon. As mercury, the liver also showed the highest selenium levels. Liver samples were also analyzed for their methyl mercury contents. The role of selenium in detoxification process of methyl mercury has been discussed. Mercury concentrations related to geographic variations and pollution of the marine environment have been examined. The possible implications between mercury accumulation and dolphin death have also been discussed.     

Levels and congener profiles of PCBs and PCDD/Fs in blue shark (Prionace glauca) liver from the South-Eastern Mediterranean Sea (Italy)

Liver of blue shark (Prionace glauca) specimens from the South-Eastern Mediterranean Sea were analyzed for the presence of polychlorinated biphenyls (PCBs), including coplanar congeners, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). PCBs were the dominant chemicals, followed by PCDFs and PCDDs. The pattern of PCB congener concentrations in the hepatic tissue was dominated by higher chlorinated compounds. The specific profile of toxic PCDD/F congeners was characterized mainly by 2,3,7,8-TCDF and 2,3,7,8-TCDD, followed by 1,2,3,6,7,8-HxCDD and 2,3,4,6,7,8-HxCDF. The total 2,3,7,8-TCDD toxic equivalent (TEQs) was 149 pg g⁻¹ lipid wt. The profile of TEQ shows that PCDDs present the greatest risk to this species contributing to total toxicity with a percentage approximately of 60%, while the contribution of PCDFs and DL-PCBs is almost the same being 22.4% and 21.6%, respectively. Further investigations are urgently needed to characterize the PCDD/Fs contamination levels not only in elasmobranch fish but in all Mediterranean marine biota.     

Noninvasive characterization of the Trecate (Italy) crude-oil contaminated site: links between contamination and geophysical signals

The characterization of contaminated sites can benefit from the supplementation of direct investigations with a set of less invasive and more extensive measurements. A combination of geophysical methods and direct push techniques for contaminated land characterization has been proposed within the EU FP7 project ModelPROBE and the affiliated project SoilCAM. In this paper, we present results of the investigations conducted at the Trecate field site (NW Italy), which was affected in 1994 by crude oil contamination. The less invasive investigations include ground-penetrating radar (GPR), electrical resistivity tomography (ERT), and electromagnetic induction (EMI) surveys, together with direct push sampling and soil electrical conductivity (EC) logs. Many of the geophysical measurements were conducted in time-lapse mode in order to separate static and dynamic signals, the latter being linked to strong seasonal changes in water table elevations. The main challenge was to extract significant geophysical signals linked to contamination from the mix of geological and hydrological signals present at the site. The most significant aspects of this characterization are: (a) the geometrical link between the distribution of contamination and the site’s heterogeneity, with particular regard to the presence of less permeable layers, as evidenced by the extensive surface geophysical measurements; and (b) the link between contamination and specific geophysical signals, particularly evident from cross-hole measurements. The extensive work conducted at the Trecate site shows how a combination of direct (e.g., chemical) and indirect (e.g., geophysical) investigations can lead to a comprehensive and solid understanding of a contaminated site’s mechanisms.     

PCDDs, PCDFs, PCBs and DDE in edible marine species from the Adriatic Sea

Edible marine species from several areas of the Adriatic sea were analyzed for their content in persistent organic pollutants (POPs), such as polychlorinated dibenzodioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and pp'-DDE (dichlorodiphenyldichloroethylene), a metabolite of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT). On the whole, PCDD/F contamination levels were low. In general, I-TEQ findings were greater for those species at higher levels in the trophic web (mackerel > red mullet > anchovy). Contamination levels were within 0.23 and 1.07 pg TEQ/g fw (fresh weight) in the aforesaid species, while all remaining species exhibited contamination levels ranging from approximately 0.07 to 0.25 pg TEQ/g fw. Besides, TEQ cumulative findings in species from the northern area were in general greater than those from the central and southern areas. PCB cumulative findings in the samples also revealed a detectable difference in contamination levels in species obtained from the northern, central, and southern sampling sites, between 7.6 and 177, 2.3 and 157, and 4.5 and 94 ng/g fw, respectively. The greatest PCB concentrations were found in mackerel (94-177 ng/g fw). Finally, DDE concentration levels varied from 0.7 to 32.4 ng/g fw. The highest levels of contamination were found in mackerel, red mullet and anchovy (17.7-32.4 ng/g fw, 8.1-9.8 ng/g fw, and 6.4-11.9 ng/g fw, respectively).     

Environmental monitoring in the Mar Grande basin (Ionian Sea,Southern Italy)

Hydrodynamic and water quality data has been recorded since February 2014 by a meteo-oceanographic station installed in the inner part of the Gulf of Taranto, in the northeastern part of the Ionian Sea (Southern Italy). This monitoring action, managed by the research unit of the Technical University of Bari, DICATECh Department, could play a pivotal role in a vulnerable and sensitive area, affected by massive chemical and biological pollutant discharges due to the presence of heavy industry and intense maritime traffic. Monthly trends of winds, waves, currents, and biochemical parameters, such as dissolved oxygen, chlorophyll, and turbidity, are analyzed and discussed. The analysis exhibits that the wave regime is slightly controlled by wind forcing; rather, topography strongly affects the wave propagation direction. Surface currents appear wind induced in the measuring station, while near the bottom a quasi-steady current directed towards southwest is formed. The selected water quality indicators show monthly trends consistent with the typical seasonal convective fluxes and mixing.     

Trace metal contamination in commercial fish and crustaceans collected from coastal area of Bangladesh and health risk assessment

Environmental Science and Pollution Research - Trace metals contamination in commercial fish and crustaceans have become a great problem in Bangladesh. This study was conducted to determine seven...     

Benthic foraminifera and heavy metals distribution: a case study from the Naples Harbour (Tyrrhenian Sea, Southern Italy)

The analysis of 90 surficial sediments from three docks of the Naples Harbour (Levante, Granili, and Diaz) permits to compare the distribution modes of heavy metals with grain sizes, total organic carbon content (TOC) and distribution patterns of benthic foraminifera. Foraminiferal density and species richness decrease with the increasing toxic elements concentrations from the Levante to the Diaz dock. Median concentrations of Ni, Pb, Zn, and Hg (medians of 21.43 mg/kg, 270.24 mg/kg, 489.65 mg/kg, and 1.18 mg/kg, respectively) were reported for the Diaz dock where foraminifera are absent, thus suggesting a possible impact of toxic elements on the benthic ecosystem balance. Compared to the unpolluted marine sediments of the Granili dock, the Levante area shows higher heavy metals levels and a quasi-oligotypic benthic assemblage. This is dominated by the tolerant species Ammonia tepida that may be used as bio-indicator of pollution of anthropised marine sediments.     

Sediment distribution on the continental shelf in relation to stream inputs and contamination: hydrodynamic,chemical, mineralogical,and sedimentological characteristics (Ligurian Sea,Italy)

River estuaries, continental shelf, and sediment contamination are closely linked from the point of view of sediment transport and diffusion that is governed by different factors such as sea waves and currents, river flows and floods, and sediment characteristics. Taking these factors into consideration, we have examined marine environmental and marine bottom sediments off the mouth of a stream to highlight the main ways of sediment and contaminant transport and diffusion on the continental shelf. For this purpose, we followed a multidisciplinary approach, studying circulation of water masses, hydrological characteristics of water column, distribution and main characteristics of sediment grain size, sediment mineralogical composition, and metal concentrations of bottom sediments. Our results allowed identifying the presence of preferential ways of sediment deposition and areas of sediment spread for the Entella Stream, as well as the origin of some metals.

     

Levels of polychlorinated biphenyls and organochlorine pesticides in some edible marine organisms from the Central Adriatic Sea

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) were found in tissue of marine organisms such as Mediterranean mussel, Norway lobster, red mullet, common cuttle-fish, European flying squid, European anchovy, European pilchard and Atlantic mackerel, coming from two sites along the Abruzzo coast of the Adriatic Sea. Species were selected due to their habitat, trophic level, feeding behaviour and their use in the Italian diet. Mussels, filter feeder and sedentary organisms, were used in order to test water pollution whereas Norway lobster and red mullet (benthic fish) were used in order to test sediment pollution. The concentration of ?PCBs exceeded that of ?OCs in the samples analysed. The highest concentrations of ?PCBs (1415 ng/g lipid weight) and ?OCs (507 ng/g lipid weight) were found in pilchard while the lowest concentrations of the same pollutants were found in cephalopods. Our results have shown that species such as anchovy, pilchard and mackerel, were the most polluted due to their location at the last level of the trophic chain. All samples contained different concentrations of PCBs and among these, congeners 153 and 138 were the most representative. Among the OCs, except for the cuttle-fish, the highest concentrations were found for p,p(')-DDE and p,p(')-DDD that are metabolite of DDT. The prevailing DDE presence, compared to DDT (high DDE/DDT ratio), suggested that the biotransformation rate of pollutants was very efficacious in fish and above all in crustaceans. Results have also been interpreted in terms of geographical distribution and organisms' biological cycle. None of the samples analysed exceeded the tolerance limits established by the OCs Italian legislation.