Application of a toxicity test battery integrated index for a first screening of the ecotoxicological threat posed by ports and harbors in the southern Adriatic Sea (Italy)

Ports and harbors may represent a threat for coastal ecosystems due to pollutant inputs, especially those derived from maritime activities. In this study, we report a first assessment of the ecotoxicological threat posed by six ports and harbors of opposite coastal regions, Apulia and Albania, in the southern Adriatic Sea (Italy). A bioassay battery consisting of four different species representing different trophic levels, algae Dunaliella tertiolecta, bacteria Vibrio fischeri, crustacean Artemia salina, and echinoids Paracentrotus lividus, has been used to assess sediment elutriates, pore waters, and sediment suspensions. Two different approaches of toxicity data integration, worst case and integrated index, have been used to determine the most appropriate procedure for the investigated sites. All sites with the worst case approach showed high toxicity levels. The chronic test with algae was the most sensitive identifying the highest effects in the battery. This effect can be attributable to contaminants derived from antifouling paints. The sediments, evaluated with V. fischeri test, often showed toxicity not found in the aqueous matrices of the same sites and that can be mainly linked to organic compounds. The test battery used in this study allowed us to perform a preliminary screening of the ecotoxicological risk of the studied area. In fact, the species utilized for toxicity tests responded differently to the investigated samples, showing different sensitivity. The test battery integrated index did not allow highlighting the differences among the sites and showed a general high ecotoxicological risk. A larger number of tests with higher sensitivity together with a tailored attribution of weights to endpoints and matrices will improve the final site evaluation.     

Urban activity and mercury contamination in estuarine and marine sediments (Southern Brazil)

The distribution of mercury in sediments of the Patos Lagoon estuary and nearby coastal marine deposits has been investigated for the period 1998-2008. Polluted urban soils and coastal reclamation fills are the principal sources of high mercury concentrations for shallow estuarine sediments. The shallow sediments that form near the urban area enter the navigation canal and are transported into the ocean. The mercury concentration in sediments of the navigation canal has considerably increased since 2004, due to intense reconstruction activity in the urban area. Periodic dredging of the canal strengthens the preconditions for coastal marine sediment contamination by mercury. However, this does not occur because the resuspended dredged sediments are significantly diluted by natural suspended particulate matter.     

Speciation of inorganic arsenic in coastal seawater from Ionian and Tyrrhenian Seas (Sicily, Italy) using derivative anodic stripping chronopotentiometry

The purpose of this paper was to use derivative anodic stripping chronopotentiometry (dASCP) as a sensitive and accurate technique, to determine the concentrations of dissolved As (III) and As (V) in coastal seawater samples from the Straits of Messina, the Ionian and the Tyrrhenian seas, and to investigate the relationship between the anthropogenic activities on the coastal areas and the concentration of dissolved inorganic arsenic in seawaters. The obtained data indicated that As (V) was the most abundant species, with concentration ranging from 26.7 to 307 nM, whereas As (III) levels were lower than 48 nM in all the samples. In particular, As (III) and As (V) levels significantly decreased from high to low anthropogenic activities zones (p < 0.00001, ANOVA), with the reference samples, from a wildlife reserve, showing the lowest values. Furthermore it was observed that human activities influenced inorganic arsenic speciation, since the zones that received high human input presented the highest As(V)/As (III) ratio.     

Polycyclic aromatic hydrocarbons and ecotoxicological characterization of sediments from the Huaihe River, China

The distribution, source, ecological risk and ecotoxicity of polycyclic aromatic hydrocarbons (PAHs) of sediments from 7 sampling sites, named as Xinyang (XY), Huainan (HN), Bengbu (BB), Xuyi (XuY), Fuyang (FY), Mengcheng (MC) and Zhengzhou (ZZ), in the Huaihe River basin, China, have been investigated. The total concentrations of 16 USEPA priority PAHs ranged from 62.9 to 2232.4 ng g?1 dry weight (d.w.) with a mean concentration of 1056.8 ng g?1 d.w. Through the assessment of ecological risk, we found that the levels of PAHs in the Huaihe River should not exert adverse biological effects. The total benzo[a]pyrene toxicity equivalent (TEQ) values calculated for samples varied from 0.01 to 194.1 ng g?1 d.w., with an average of 65.9 ng g?1. The toxicity data were accordant with the chemical analysis results in this study. HN, BB and ZZ showed the greatest pollution extent both in the chemical analysis and the study of ecotoxicological effects.     

Comparison of different methods for extraction of polycyclic aromatic hydrocarbons (PAHs) from Sicilian (Italy) coastal area sediments

This paper describes a work aimed at improving the conditions of an extraction method, coupling GC-MS determination, for the analysis without cleanup phase, of polycyclic aromatic hydrocarbons (PAHs) from sediment samples. The automatic Soxhlet extraction in warm mode (using Extraction System B-811 Standard, Büchi) has demonstrated advantages for automation, reduced extraction time, and lower solvent use than for conventional Soxhlet extraction. Under these conditions, the recoveries are very good as they resulted greater than 85 % and, in most of the cases, near 100 %. The repeatability is also satisfactory (relative standard deviation less than 15 %). The detection limits are also acceptable and ranged from 0.001 to0.01 μg/kg dry weight. Fifty-four sediment samples were collected. The total concentration of the 17 compounds investigated, in samples of sediments collected from three Sicilian coastal areas, expressed as the sum of concentrations, varies from 99 to 11,557 μg/kg of dry matrix; concentrations of total PAHs in the sediments of Cala are two to three times higher than the other stations.     

PBDE,HBCD, and novel brominated flame retardant contamination in sediments from Lake Maggiore (Northern Italy)

The reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) has opened the way for the introduction of novel brominated flame retardants (NBFRs) in place of the banned formulations. Important representatives of this group are decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB). In this study, the contamination due to NBRFs was investigated for the first time in Italy in the sediments of Lake Maggiore. The aim of the research was to characterize in detail the possible presence of temporal trends and/or to identify potential sources of contamination. The study also considered the PBDE and HBCD lake sediment’s current contamination. The analytical results showed that sediments in Lake Maggiore and its tributary rivers had weak concentrations of PBEB, HBB, and BTBPE, but they did not have a negligible/insignificant contamination of HBCD (up to 23.7 ng/g dry weight (d.w.)). The determination of PBDEs in sediments showed that BDE-209 was the predominant congener (up to 217 and 28 ng/g d.w. in river and lake sediments, respectively). DBDPE was detected in the sediments with relevant concentrations (up to 280 ng/g d.w in the River Boesio sediments). The positive correlation of DBDPE with BDE-209 confirmed the wide and important use of this compound in the Lake Maggiore basin and the hypothesis that this compound will soon become one of the most important NBFRs used in Northern Italy. The contamination of Lake Maggiore sediments due to PBDEs, HBCD, and NBFRs were comparable to other worldwide situations.     

Evaluation of a fluorometric screening method for predicting total PAH concentrations in contaminated sediments

A fluorometric screening method was used to estimate total polycyclic aromatic hydrocarbon (t-PAH) concentrations in sediments collected from the St. Louis River Area of Concern (AOC) in northeastern Minnesota. Sediments were collected as part of a Regional Environmental Monitoring and Assessment Program (R-EMAP) study to assess sediment quality in the AOC. The screening method was calibrated using a PAH surrogate standard consisting of eight PAHs commonly found in the St. LouisRiver system, at their approximate proportions. Estimated PAHconcentrations were compared to GC/MS measured `true' PAH concentrations to evaluate the overall predictive power of thescreening method. Regression analysis of log transformed estimated versus true PAH concentration yielded an r² of 0.72 (n = 86). In addition, the rates of false positive and false negative predictions associated with the screening methodwere determined relative to different sediment effects concentrations (SECs) for total PAHs. In general, the rate of false positive predictions was shown to increase as the SEC criteria value decreased, while false negative rates remainedconsistently low (below 7%). Methodological recommendations which led to a three-fold reduction in false negatives, and theimproved prediction of both high and low PAH samples, are presented.     

Polychlorinated biphenyls in marine sediments from the southern North Sea and Scheldt estuary: a ten-year study of concentrations, patterns and trends

The paper reports the concentrations and patterns of CBs in sediments of the Belgian part of the southern North Sea and the Scheldt estuary for the period 1991-2001. The long-term analytical performance was well within the quality assurance boundaries set at the outset of the study and is consistent with the state of the art for this type of analysis. The CB concentrations (given as the median of the sum of IUPAC Nos 28, 52, 101, 118, 138, 153 and 180) vary between 0.1 microg kg(-1) and 50 microg kg(-1) dry weight in the total sediment and it could be demonstrated that CB patterns in the fine fraction of the sediment were closely similar throughout the investigated area. Isolation of the fine fraction (<63 microm) by sieving can be regarded as a physical normalisation to reduce the differences in sediment granulometric composition. It allows for a better understanding of CB distribution and patterns and improves the trend analysis. A significant downward trend could not be found at any of the stations, which suggests that CB levels have not been changing in the area of interest in the past decade.     

Immunoassay-based screening of polychlorinated biphenyls (PCB) in sediments: requirements for a new generation of test kits

Polychlorinated biphenyls (PCBs) have been proposed for the inclusion in the European Water Framework Directive (WFD) priority list, currently under revision. Various screening methods have been employed for PCB determination in different environmental matrixes in the last decades, immunoassays being one of the most employed. A literature review reveals that the enzyme-linked immunosorbent assay (ELISA) is the most commonly applied immunoassay for PCB determination in the environment. However, its application to sediments is very limited. A suitability assessment of immunoassay-based analysis for PCB screening in sediments is presented in this work. The significance of available immunoassay-based test kits under the current environmental pollution scenario and their performance against the sensitivity and specificity requirements dictated by the WFD for PCB analysis in sediments is discussed. For example, current detection limits of available test kits for PCB determination in sediments may not be enough for compliance checking under the WFD. In addition, concentration expressed as Aroclor equivalents does not seem to be the way forward. A proposal for adapting available test kits in order to become more suitable tools for PCB screening in sediments is also presented in this study.     

Association of metals (mercury, cadmium and zinc) with metallothionein-like proteins in storage organs of stranded dolphins from the Mediterranean sea (Southern Italy)

Selected toxic and essential metals (mercury, Hg; cadmium, Cd; and zinc, Zn) were determined in the liver and in the kidney collected from 13 dolphins (Stenella coeruleoalba and Tursiops truncatus) stranded along the southern coasts of Italy from 1991 to 1999. Liver samples were also analysed for their methyl mercury (MeHg) and selenium (Se) contents. For subcellular fractionation, liver and kidney samples were homogenized in Tris-HCl buffer; after centrifugation, the supernatant (cytosol) was separated from pellets (insoluble fraction), heated at 80 degrees C for 10 min and centrifuged in order to separate the precipitate containing the thermolabile high molecular weight proteins. The cytosol heat-stable fraction, including metallothionein-like proteins (MTLPs), was then purified by gel filtration chromatography on Sephadex G-75 column. The three subcellular fractions collected (insoluble fraction, thermolabile fraction and purified heat-stable fraction) were analysed for their Hg, Cd and Zn contents. The analytical results confirm previous similar studies on toothed whales in showing that: (1) in the liver, as well as in the kidney, Hg was mainly found in the insoluble fraction, therefore, metallothioneins seem to have no role in the Hg detoxification; (2) in the liver, the molar ratio between Se and inorganic Hg was very close to 1; this suggests that the final compound of MeHg detoxification could be HgSe (tiemannite); (3) in almost all the samples, Cd and Zn were detected in the purified heat-stable fraction (including MTLPs). The mechanism of Cd detoxification and Zn homeostasis is also discussed.     

The distribution of organochlorine pesticides (OCPs) in surface sediments of Bohai Sea Bay,China

The residues of organochlorine pesticides (OCPs) in 19 surface sediments of Bohai Sea Bay were determined in this study. Total OCP concentration in surface sediment ranged from 9.01 to 18.04 ng/g dry weight, with a mean concentration of 12.50 ng/g. These findings are in the mid-range of pesticide concentrations compared to those reported in other regions worldwide. DDTs and HCHs were the predominant species. The α-HCH/β-HCH ratios and the predominant γ-HCH indicate that the technical HCH contamination was due mainly to historical usage, although there appeared to be a fresh input of lindane. The results from \(\left( {\mbox{DDD}\,\mbox{+}\,\mbox{DDE}} \right)\mbox{/}\sum {\mbox{DDTs}} \) and DDD/DDE calculations suggest that the usage of DDT in agricultural activities was not terminated, and the historical/fresh inputs of DDT in these areas could be more easily degraded into DDD under an anoxic condition. PCA implies that the recent usage of DDT could serve as important fresh input sources for OCPs.     

Organochlorine pesticides and polychlorinated biphenyl residues in reared and wild Dicentrarchus labrax from the Mediterranean Sea (Sicily, Italy)

The aim of this research was to compare the levels of organochlorine pesticides and PCBs in samples of Dicentrarchus labrax living in the Straits of Messina with samples cultivated in cages in the Mediterranean Sea. Muscles and liver tissues sampled over the months, within the same year, were analyzed. The quantitative determination of the organochlorine compounds was performed by GC-ECD and confirmed with GC–MS. The results showed that the concentrations of DDTs in muscles and livers as such of reared sea bass were in the range 0.2–1.3 μg/kg and 9.6 –48.4 μg/kg, respectively. In wild fish the concentrations of DDTs were very much lower: 0.1 μg/kg in muscles, 5.1–9.0 μg/kg in livers. Total PCBs levels were higher in cultivated sea bass than in wild fish; the concentration ranges were 5.3–59.7 μg/kg and 74.4–267.4 μg/kg in muscle and liver of reared samples, respectively, and 1.1–1.5 μg/kg and 63.2–109.4 μg/kg in muscle and liver of wild samples, respectively.     

Metal levels in sediments and transplanted mussels in Pagassitikos Gulf (Aegean Sea, Eastern Mediterranean)

Metal concentrations were determined in surface sediments and transplanted mussels in a shallow semi-enclosed bay, Pagassitikos Gulf, Aegean Sea. Cu, Zn, Pb, Hg, and As levels in sediments were enriched close to point sources of pollution, i.e., Volos Port and cement plant. Fe, Mn, Cr, and Ni spatial distributions in sediments were rather uniform with increasing concentrations towards deeper sites, suggesting natural enrichment, whereas levels found in the port, although elevated, were not the highest in the study area. Spatial variations in concentrations of most metals in mussels transplanted nearshore were generally in accordance to those in sediments, with the highest Fe, Mn, Cr, Ni, and Cu levels in the port and the highest Hg levels close to the cement plant. Concentrations of metals in sediments and transplanted mussels were comparable to those reported in Mediterranean areas. Results indicate that pollution point sources contribute to anthropogenic metal enrichment in the study area.     

Evaluation of germination, root growth and cytological effects of wastewater of sugar factory (Afyonkarahisar) using Hordeum vulgare bioassays

In this study, the effect of Afyonkarahisar Sugar Factory's discharge water on germination percentage, root growth and mitotic divisions of the root tip cells of Hordeum vulgare L. were investigated. Six concentrations of wastewater and ranging from 10(0), 10(?-1), 10(?-2), 10(?-3), 10(?-4), 10(?-5), were applied for 6, 12, 18 and 24 h, respectively. It was observed that the treatments reduced the germination percentages of H. vulgare grains and inhibited the root growth as well as reduced mitotic index compared to the control group at all concentrations. It was also observed that the increase of the concentrations of wastewater decreased the cell division, and several mitotic anomalies such as c-mitosis, lagging chromosomes, multipolar anaphases and chromosome bridges increased.     

Congener profiles of polychlorinated biphenyls in core sediments of Sunderban mangrove wetland (N.E. India) and their ecotoxicological significance

The paper presents the first comprehensive survey of congener profiles of polychlorinated biphenyls (PCBs) in core sediment samples (<63 microm particle size) covering seven sites in Sunderban mangrove Wetland, north-eastern part of the Bay of Bengal. Results pointed out a non-homogenous contamination of the wetland with Sigma23PCB values ranging from 0.5 to 26.9 ng g(-1) dry weight, reflecting very low to moderate contamination closely in conformity to other Asian coastal environment. The general decreasing order of the dominant congeners to the total load was: CB138 > 153 > 149 > 101, indicating the predominance of hexa-chlorinated congeners. The spatial distribution revealed significant differences in concentration related to local urbanization with industrial and land-based sources. No uniform temporal trend on PCB levels was recorded probably due to particular hydrological characteristics of the wetland and/or non-homogenous inputs from point sources. Strong positive correlations between the seven dominant congeners suggest their common sources and similar environmental behaviors. These results were also used for a risk assessment evaluation in the Sunderban wetland, showing that the present PCB levels were exceeding in few cases the lower limit of sediment quality guidelines of Environmental Protection Agency and Canadian Council of Ministers of the Environment.     

Distribution of trace metals in marine sediments of the Bay of Palma de Mallorca (Mallorca Island, Spain)

Metals were determined in surface bottom marine sediments of the Bay of Palma de Mallorca (Spain) by microwave-assisted acid-oxidant digestion and inductively coupled plasma–optical emission spectrometry in order to assess the level and distribution of potentially metallic pollutants. Average concentrations found were 1.2?±?0.3 Al and 1.9?±?0.9 Fe (in milligrams per gram), and 8?±?2 Cr, 2?±?1 Cu, 60?±?10 Mn, 4?±?1 Ni, 6?±?4 Pb, 50?±?7 Sn and 10?±?3 Zn (in micrograms per gram). Enrichment factors using normalized values to Al were also calculated which indicated that sediments were Sn and Pb enriched. Sediments were fractionated by grain size: <63, 63–250, 250–500 and >500 (in micrometres), and the metals' affinity towards the different fractions was studied. The metals' affinity to the finer fraction was evidenced, excluding Sn and Mn that showed practically no affinity for fine grains. Latent variables were extracted from the data using principal components analysis. It allowed samples to be grouped in two clusters, and most of the metals (Al, Cr, Cu, Fe, Ni, Pb and Zn) showed a similar distribution pattern. Sn and Mn showed a distinct pattern.     

The response of nematode assemblages to intensive mussel farming in coastal sediments (Southern Brazil)

The impact of mussel farms on the benthic environment was investigated using free-living nematode assemblages as indicators of environmental condition of the Enseada do Brito, a shallow embayment in South Brazil. The studied area is located at the State of Santa Catarina, responsible for 90% of the production of mussel farmed in the country. Samplings were carried out quarterly, from July 2004 to May 2005, below mussel ropes and at control sites located 300 m apart from the longlines. The results suggested that the mussel culture changed ecological functioning of the benthic environment at studied coastal embayment. The intense organic loads due to the biodeposition of the mussel farms, which had been in production for more than 10 years, have turned fine and well-sorted sand bottoms into a muddy deposit with significantly higher total organic content than the control. The number of nematode genera, diversity, dominance and trophic diversity were significantly lower under the mussel farms than at the control sites. The mussel farms biodeposition had also affected the temporal variability of nematode assemblages, which was detected only for samples at the control sites. The low depth and environmental energy, together with the age of the farms, were probably responsible for the observed changes in the nematode assemblages.     

Polybrominated diphenyl ethers (PBDEs) in the riverine and marine sediments of the Laizhou Bay area, North China

62 riverine and marine sediments were collected from the Laizhou Bay area, where the largest manufacturing base of brominated flame retardants (BFRs) in Asia is located. Eight polybrominated diphenyl ethers (PBDEs) were analyzed to investigate the impact of rapidly-developed bromine industries on the regional aquatic system. PBDE concentrations varied largely in riverine sediments. Σ(7)PBDEs (including BDE 28, 47, 99, 100, 153, 154 and 183) and BDE 209 ranged from 0.01 to 53 ng g(-1) dw and from 0.74 to 285 ng g(-1) dw with a mean value of 4.5 ng g(-1) dw and 54 ng g(-1) dw, respectively, indicating a strong influence of direct pollution discharges from local factories. In marine sediments, Σ(7)PBDEs and BDE 209 ranged from not detected (nd) to 0.66 ng g(-1) dw and from 0.66 to 12 ng g(-1) dw with a mean value of 0.32 ng g(-1) dw and 5.1 ng g(-1) dw, respectively. PBDE concentrations were mostly <10 ng g(-1) dw for Σ(7)PBDEs and <50 ng g(-1) dw for BDE 209, which are at a relatively low level for monitored riverine and coastal sediments around the world. Even at the most contaminated sites in Laizhou Bay area, PBDE concentrations were not among the highest concentrations reported in the literature. Congener compositions were dominated by BDE 209 (57.2-99.9% of the sum of BDE congeners), with minor contributions from penta- and octa-BDE products. Tri- to octa-BDE congeners were well correlated among each other (r > 0.75) and thus sources from similar mixing of penta- and octa-BDE products were suggested in this area. Compared with riverine sediments, a much better correlation between PBDE concentrations with TOC was observed in marine environment. The congener pattern changed and their correlation coefficients among each other were remarkably reduced. Contributions of BDE 28, 47 and 99 to Σ(7)PBDEs were generally the same in almost all the marine sites, while it was distinctively higher for BDE 153. These are probably attributable to several reasons, such as contributions by atmospheric deposition and/or redistribution between particles of various sizes during and/or after fluvial transportation combined with the difference of physiochemical properties of BDE congeners.     

Distribution and ecotoxicological significance of trace element contamination in a ~150 yr record of sediments in Lake Chaohu, Eastern China

This paper presents the concentrations, vertical profiles and possible sources of selected major and trace elements in a sediment core covering ～150 years of sedimentation in Lake Chaohu, eastern China. Element concentrations were measured by portable X-ray Fluorescence Spectroscopy (XRF) and were used to evaluate possible environmental consequences of the recent industrialization in China. Statistical analyses identify four groups: (1) organic carbon (OC), total nitrogen (TN), Pb, Zn, and As associated with the use of chemical fertilizers and pesticides; (2) Mn, Cr, Ni and Cu from industrial and mining activities; (3) Fe, Rb, K, Co, Ti and Ca influenced by post-depositional processes and land exploitation; and (4) Zr and Sr from the soil. The vertical profiles of elements placed in the first two groups show distinct increases in concentrations above depths of 20 cm (~1978), coincident with the timing of industrialization in China, and the anthropogenic-derived fluxes are higher than the lithogenic-derived fluxes over the last three decades. With the exception of Zr and Sr, association of the measured metals with organic carbon and nitrogen suggests that organic matter may act as a carrier phase. The geoaccumulation index (I(geo)) reveals increased contamination from elements in the first two groups in recent years. Element concentrations, compared with the Effects Range-Low (ERL) and Effects Range-Median (ERM) levels set by NOAA, suggest that adverse biological effects from Ni contamination are very likely.     

Evaluation of a temporal trend heavy metals contamination in Posidonia oceanica (L.) Delile, (1813) along the western coastline of Sicily (Italy)

The use of biological species in the monitoring of marine environmental quality allows the evaluation of biologically available levels of contaminants in the ecosystem and the effects of contaminants on living organisms. The seagrass Posidonia oceanica is a useful bioindicator because through the lepidochronology technique it is possible to obtain a historical contamination trend of a given area. This study aims to assess the temporal trend contamination by heavy metal investigations on dead sheaths of 100 samples of P. oceanica collected in the Protected Marine Area of "Plemmirio" (Sicily) and in the Siracusa bay. Important results were obtained because data show a significant negative temporal trend for the metals analysed especially for As, Co, Cr, Hg, Pb, Se, U and V that in the past had higher concentrations, with a stronger contamination in the Plemmirio area, the site much more exposed to the pollution of the nearby petrochemical complex. This study confirms the relevance of the use of P. oceanica as a biological indicator of metal contamination in coastal ecosystems. Thus the usefulness of P. oceanica as a tracer of spatial metal contamination and as a good tool for water quality evaluation is reinforced.