A survey of antifoulants in sediments from Ports and Marinas along the French Mediterranean coast

Due to deleterious effects on non-target organisms, the use of organotin compounds on boat hulls of small vessels (<25 m) has been widely prohibited. The International Maritime Organisation (IMO) resolved that the complete prohibition on organotin compounds acting as biocides in antifouling systems should commence in 2008. As a result of restrictions on the use of organotin based paints, other antifouling formulations containing organic biocides have been utilised. This survey was conducted to assess the contamination of replacement biocides in the marine environment following the ban of TBT-based paints. Surface sediments samples were collected in the major ports and marinas along the France Mediterranean coastline (Cote d’Azur) and analysed for organotin compounds, Irgarol 1051, Sea-nine 211^TM, Chlorothalonil, Dichlofluanid and Folpet. Every port and marina exhibited high levels of organotin compounds, with concentrations in sediments ranging from 37 ng Sn g⁻¹dry wt in Menton Garavan to over 4000 ng Sn g⁻¹dry wt close to the ship chandler within the port of Villefranche-sur-Mer. TBT degradation indexes suggested that fresh inputs are still made. Among the other antifoulants monitored, only Irgarol 1051 exhibited measurable concentrations in almost every port, with concentrations ranging from 40 ng g⁻¹dry wt (Cannes) to almost 700 ng g⁻¹dry wt (Villefranche-sur-Mer, ship chandler).     

Occurrence and distribution of phthalate esters in riverine sediments from the Pearl River Delta region,South China

Sixty-eight sediment samples collected from Dongjiang River, Xijiang River, Beijiang River and Zhujiang River in the Pearl River Delta (PRD) region, Southern China, were analyzed for 16 phthalate esters (PAEs). PAEs were detected in all riverine sediments analyzed, which indicate that PAEs are ubiquitous environmental contaminants. The Σ₁₆PAEs concentrations in riverine sediments in the PRD region ranged from 0.567 to 47.3 μg g⁻¹ dry weight (dw), with the mean and median concentrations of 5.34 μg g⁻¹ dw and 2.15 μg g⁻¹ dw, respectively. Elevated PAEs concentrations in riverine sediments in the PRD region were found in the highly urbanized and industrialized areas. Of the 16 PAEs, diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP) and di(2-ethylhexyl) phthalate (DEHP) dominated the PAEs, with the mean and median concentrations of 1.12 μg g⁻¹ dw, 0.420 μg g⁻¹ dw and 3.72 μg g⁻¹ dw, and 0.429 μg g⁻¹ dw, 0.152 μg g⁻¹ dw and 1.55 μg g⁻¹ dw, respectively, and accounted for 94.2–99.7% of the Σ₁₆PAEs concentrations. Influenced by local sources and the properties of PAEs, a gradient trend of concentrations and a fractionation of composition from more to less industrialized and urbanized areas were discovered. As compared to the results from other studies, the riverine sediments in the PRD region were severely contaminated with PAEs. Information about PAEs contamination status and its effect on the aquatic organisms in the PRD region may deserve further attention.     

Anthropogenic lead concentrations and sources in Baltic Sea sediments based on lead isotopic composition

The Gulf of Gdańsk is influenced by heavy metals of anthropogenic origin. In this study, temporal concentration changes of Pb, Zn, Cd, and Cu were studied in six, 50 cm long sediment cores. The main aim of the study was to concentrate on the history of Pb fluxes and Pb isotopic composition (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb) to trace Pb sources. The lowest Pb concentrations (19 μg g⁻¹) were measured in sediments deposited circa 1860, while the highest Pb concentrations (63–147 μg g⁻¹) were measured in sediments deposited between 1960s and 70s. Pre-industrial Pb fluxes were 7 Pb m² year⁻¹, while after WWII they reached 199 Pb m² year⁻¹. Highest ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.22) were measured in the oldest sediment layers, and the lowest ²⁰⁶Pb/²⁰⁷Pb ratios (∼1.165) were measured in the sediments deposited in 1970s–90s. During the period of highest Pb contamination, the anthropogenic Pb fraction reached up to 93%. A general discussion of the Pb sources, emissions, and loads for Poland is included.     

Trace metals in antifouling paint particles and their heterogeneous contamination of coastal sediments

Antifouling paint residues collected from the hard-standings of a marine leisure boat facility have been chemically characterised. Scanning electron microscopy revealed distinct layers, many containing oxidic particles of Cu and Zn. Quantitative analysis indicated concentrations of Cu and Zn averaging about 300 and 100 mg g⁻¹, respectively, and small proportions of these metals (<2%) in organometallic form as pyrithione compounds. Other trace metals present included Ag, Cd, Cr, Ni, Pb and Sn, with maximum concentrations of about 330, 75, 1200, 780, 1800 and 25,000 μg g⁻¹, respectively. Estuarine sediment collected near a boatyard contained concentrations of Cu and Zn an order of magnitude greater than respective concentrations in “background” sediment, and mass balance calculations suggested that the former sample was contaminated by about 1% by weight of paint particles. Clearly, antifouling residues represent a highly significant, heterogeneous source of metallic contamination in the marine environment where boating activities occur.     

Metal concentrations in sediments from tourist beaches of Miri City,Sarawak, Malaysia (Borneo Island)

Forty-three sediment samples were collected from the beaches of Miri City, Sarawak, Malaysia to identify the enrichment of partially leached trace metals (PLTMs) from six different tourist beaches. The samples were analyzed for PLTMs Fe, Mn, Cr, Co, Cu, Ni, Pb, Sr and Zn. The concentration pattern suggest that the southern side of the study area is enriched with Fe (1821–6097 μg g⁻¹), Mn (11.57–90.22 μg g⁻¹), Cr (51.50–311 μg g⁻¹), Ni (18–51 μg g⁻¹), Pb (8.81–84.05 μg g⁻¹), Sr (25.95–140.49 μg g⁻¹) and Zn (12.46–35.04 μg g⁻¹). Compared to the eco-toxicological values, Cr > Effects range low (ERL), Lowest effect level (LEL), Severe effect level (SEL); Cu > Unpolluted sediments, ERL, LEL; Pb > Unpolluted sediments and Ni > ERL and LEL. Comparative results with other regions indicate that Co, Cr, Cu, Ni and Zn are higher, indicating an external input rather than natural process.     

Baseline heavy metals and metalloid values in blood of loggerhead turtles (Caretta caretta) from Baja California Sur, Mexico

Environmental pollution due to heavy metals is having an increased impact on marine wildlife accentuated by anthropogenic changes in the planet including overfishing, agricultural runoff and marine emerging infectious diseases. Sea turtles are considered sentinels of ecological health in marine ecosystems. The objective of this study was to determine baseline concentrations of zinc, cadmium, copper, nickel, selenium, manganese, mercury and lead in blood of 22 clinically healthy, loggerhead turtles (Caretta caretta), captured for several reasons in Puerto López Mateos, Baja California Sur, Mexico. Zinc was the most prevalent metal in blood (41.89 μg g⁻¹), followed by Selenium (10.92 μg g⁻¹). The mean concentration of toxic metal Cadmium was 6.12 μg g⁻¹ and 1.01 μg g⁻¹ respectively. Mean concentrations of metals followed this pattern: Zn > Se > Ni > Cu > Mn > Cd > Pb and Hg. We can conclude that blood is an excellent tissue to measure in relatively non-invasive way baseline values of heavy metals in Caretta caretta.     

Selenium in sediments and biota from estuaries of southwest England

Selenium concentrations have been measured in sediment, fucoid macroalgae and macroinvertebrates from four estuaries of SW England (Yealm, Plym, Looe, Fal). Sediment concentrations ranged from about 0.4 μg g⁻¹ in the Yealm to 1.49 μg g⁻¹ at one site in the Plym. Concentrations in Fucus vesiculosus (0.05–0.31 μg g⁻¹) and F. ceranoides (0.05–0.51 μg g⁻¹) were significantly lower than corresponding concentrations in sediment but there was no correlation between algal and sediment concentrations. Selenium concentrations in Littorina littorea (∼4 μg g⁻¹), Hediste diversicolor (2.82–12.68 μg g⁻¹), Arenicola marina (∼17 μg g⁻¹) and Scrobicularia plana (1.18–6.85 μg g⁻¹) were considerably higher than concentrations in macroalga or sediment, suggesting that Se is effectively accumulated from the diet. Although Se concentrations in some invertebrates exceed toxicity thresholds for the diet of predacious birds and fish, no specific evidence for Se toxicity exists in these estuaries.     

Baseline of butyltin pollution in coastal sediments within the Basque Country (northern Spain), in 2007-2008

Tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) were measured in surficial sediments at, the ports of Pasaia and Bilbao, together with other mid- and small-size harbours of the Basque Country (northern Spain), in 2007-2008. The highest values of the sum of the three measured butyltin species (3523-3640 ng g⁻¹, as Sn) were found at sampling stations near to shipyards located within the port of Pasaia. The highest value of TBT concentration (3143 ng g⁻¹, as Sn) was found at the marina of Getxo, in the port of Bilbao. The degree of TBT degradation varied greatly between sampling stations, being found to be generally higher in those sediments with higher values of redox potential and lower values of TBT concentration (normalized by organic matter content).     

Distribution of rare earth elements in marine sediments from the Strait of Sicily (western Mediterranean Sea): evidence of phosphogypsum waste contamination

Concentrations of rare earth elements (REE), Y, Th and Sc were recently determined in marine sediments collected using a box corer along two onshore-offshore transects located in the Strait of Sicily (Mediterranean Sea). The REE + Y were enriched in offshore fine-grained sediments where clay minerals are abundant, whereas the REE + Y contents were lower in onshore coarse-grained sediments with high carbonate fractions. Considering this distribution trend, the onshore sediments in front of the southwestern Sicilian coast represent an anomaly with high REE + Y concentrations (mean value 163.4 μg g⁻¹) associated to high Th concentrations (mean value 7.9 μg g⁻¹). Plot of shale-normalized REE + Y data of these coastal sediments showed Middle REE enrichments relative to Light REE and Heavy REE, manifested by a convexity around Sm-Gd-Eu elements. These anomalies in the fractionation patterns of the coastal sediments were attributed to phosphogypsum-contaminated effluents from an industrial plant, located in the southern Sicilian coast.     

Hydrocarbon composition and distribution in a coastal region under influence of oil production in northeast Brazil

Waters and sediments from the Potiguar Basin (NE Brazilian coast) were investigated for the presence and nature of polycyclic aromatic hydrocarbons (PAH) and aliphatic hydrocarbons. The region receives treated produced waters through a submarine outfall system serving the industrial district. The total dispersed/dissolved concentrations in the water column ranged from 10-50 ng L⁻¹ for ∑16PAH and 5-10 μg L⁻¹ for total aliphatic hydrocarbons. In the sediments, hydrocarbon concentrations were low (0.5-10 ng g⁻¹for ∑16PAH and 0.01-5.0 μg g⁻¹ for total aliphatic hydrocarbons) and were consistent with the low organic carbon content of the local sandy sediments. These data indicate little and/or absence of anthropogenic influence on hydrocarbon distribution in water and sediment. Therefore, the measured values may be taken as background values for the region and can be used as future reference following new developments of the petroleum industry in the Potiguar Basin.     

Anthropogenic organic matter inputs indicated by sedimentary fecal steroids in a large South American tropical estuary (Paranaguá estuarine system, Brazil)

Urban sewage is considered one of the most important sources of marine pollution in South America, because most coastal cities do not have proper facilities to treat and dispose of sewage. The Paranaguá estuarine system is an important estuarine environment of the South American coast where fishing, urban and tourist activities, industries and the main Brazilian grain shipping port are potential sources of pollution in this area. The anthropogenic input of sedimentary organic matter, represented by sewage contribution, was evaluated by fecal steroid concentrations. The coprostanol levels were comparatively low (<0.10 μg g⁻¹), except at the sites close to Paranaguá city, where the coprostanol concentration reached 2.22 μg g⁻¹ showing strong sewage contamination. Fecal steroid levels were comparable to the lower to midrange concentrations reported for coastal sediments worldwide. The results of this work demonstrated that sewage pollution can be considered a problem for a small part of the Paranaguá estuary.     

Lead in blood and eggs of the sea turtle, Lepidochelys olivacea, from the Eastern Pacific: Concentration, isotopic composition and maternal transfer

Concentrations of lead were assessed in the sea turtle, Lepidochelys olivacea, from a nesting colony of the Eastern Pacific. Twenty-five female turtles were sampled and a total of 250 eggs were collected during the “arribada” event of the 2005-2006 season. Considering the nesting season, the maternal transfer of lead (Pb) via egg-laying, in terms of metal burden in whole body, was 0.5%. Pb concentrations (in dry weight) in blood (0.95 ± 0.18 μg g⁻¹) and egg samples (yolk, 0.80 ± 0.10 μg g⁻¹; albumen, 1.08 ± 0.20 μg g⁻¹; eggshell, 1.05 ± 0.20 μg g⁻¹) were comparable or even lower than those found in other sea turtles. The isotope ratios (²⁰⁶Pb/²⁰⁷Pb and ²⁰⁶Pb/²⁰⁸Pb) in blood (1.183 ± 0.0006 and 2.452 ± 0.0006, respectively) were comparable to that of natural Pb-bearing bedrock in Mexico (1.188 ± 0.005 and 2.455 ± 0.008, respectively). According to international norms of Pb, the health of this population and its habitats is acceptable for Pb and corresponds to basic levels of a nearly pristine environment.     

Occurrence,distribution and partitioning of nonionic surfactants and pharmaceuticals in the urbanized Long Island Sound Estuary (NY)

This work deals with the environmental distribution of nonionic surfactants (nonylphenol and alcohol ethoxylates), their metabolites (NP, nonylphenol; NPEC, nonylphenol ethoxycarboxylates; and PEG, polyethylene glycols) and a selection of 64 pharmaceuticals in the Long Island Sound (LIS) Estuary which receives important sewage discharges from New York City (NYC). Most target compounds were efficiently removed (>95%) in one wastewater treatment plant monitored, with the exception of NPEC and some specific drugs (e.g., hydrochlorothiazide). Concentrations of surfactants (1.4–4.5 μg L⁻¹) and pharmaceuticals (0.1–0.3 μg L⁻¹) in seawater were influenced by tides and sampling depth, consistent with salinity differences. Surfactants levels in suspended solids samples were higher than 1 μg g⁻¹, whereas only most hydrophobic or positively charged pharmaceuticals could be found (e.g., tamoxifen, clarithromycin). Maximum levels of target compounds in LIS sediments (PEG at highest concentrations, 2.8 μg g⁻¹) were measured nearest NYC, sharply decreasing with distance from major sewage inputs.     

Metal (Al, Fe, Mn and Cu) distributions and origins of polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of the Marmara Sea and the coast of Istanbul, Turkey

In this study, total metal (Al, Fe, Mn and Cu) and PAHs analyses have been done in the surface sediments. Sediment samples have been collected from seven parts of the Marmara Sea and the coast of Istanbul during 2009. Total Al, Fe, Mn and Cu contents vary between 1.8% and 5.4%; 1.1% and 2.8%; 122 and 259 μg g⁻¹; 27 and 416 μg g⁻¹, respectively. EF and CF values of Fe and Mn are lower than 1.5 and 1, respectively, in all the stations. Total PAH contents range between 135 and 6009 ng g⁻¹ in the surface sediments. The origin of PAHs has been found pyrolitic according to the Phe/Ant ratio in the all stations. Contrastingly, at K0, MKC and MY1 Stations, PAH origins have been observed petrogenic according to the Flu/Pyr ratio.     

Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of São Paulo, Brazil

The State of São Paulo is the most developed area in Brazil and was impacted by persistent organic pollutants for several decades. This study investigated organochlorines in five species of small cetaceans (Pontoporia blainvillei, Stenella frontalis, Sotalia guianensis, Tursiops truncatus and Steno bredanensis) found dead along the coast of São Paulo between 1997 and 2003. DDTs (15.9 μg g⁻¹ lipid; mean for all pooled individuals) and PCBs (8.08 μg g⁻¹) exhibited the highest concentrations in the animals, reflecting large amounts formerly used in Brazil. Lower levels of mirex (0.149 μg g⁻¹), HCB (0.051 μg g⁻¹), CHLs (0.008 μg g⁻¹) and HCHs (0.007 μg g⁻¹) were detected in all species. Residual pattern of DDTs in dolphins suggests that o,p′-DDT is more recalcitrant than p,p′-DDT in the body of the animals and/or the environment. In contrast to p,p′-DDT, residues of o,p′-DDT seem to be preferentially converted into o,p′-DDD rather than o,p′-DDE.     

Spatial patterns of submerged macrophytes and heavy metals in the hypertrophic, contaminated, shallow reservoir Lake Qattieneh/Syria

Our investigation on macrophytes in Lake Qattieneh, a large, shallow reservoir in western Syria, is a first assessment of ecological status of this lake. We studied spatial distribution patterns of aquatic macrophyte vegetation and heavy metal concentrations to determine if they can be used as indicators of point sources of pollution. Industrial and municipal point sources at the lake shore increase nutrient load and contamination by heavy metals. Water analyses revealed high concentrations of some heavy metals at some littoral sites: Ni 88.7 μg L⁻¹, Cr 49.99 μg L⁻¹, Co 14.38 μg L⁻¹, and Cu 11.65 μg L⁻¹. Despite hypertrophic conditions and high heavy metal contamination, we recorded several submerged macrophyte species with heterogeneous spatial distribution patterns. Whereas Potamogeton pectinatus L. dominates in the eastern part of the lake, near industrial point sources, both Myriophyllum spicatum L. and Potamogeton lucens L. form extended patches in the western part of the lake. The shallow, littoral areas near villages are dominated by Ranunculus trichophyllus Chaix in Villars and Ceratophyllum demersum L. The west-east gradient in nutrient and heavy metal concentrations in waters and sediments are reflected by the spatial distribution of submersed species. While the heavy metal concentrations of the water body vary considerably in different seasons, the contents in submersed macrophytes integrate seasonal variations of longer time periods. Spatial distribution and tissue accumulation of littoral macrophyte species reflect the environmental conditions at respective sites such as heavy metal contents in water and sediment.     

Changes in trace metals in Thalassia testudinum after hurricane impacts

Major hurricanes Emily and Wilma hit the Mexican Caribbean in 2005. Changes in trace metals in the seagrass Thalassiatestudinum prior to (May 2004, 2005) and following passage of these hurricanes (May, June 2006) were determined at four locations along a ∼130 km long stretch of coast. Before the hurricanes, essential metals were likely limiting and concentrations of potentially toxic Pb were high in a contaminated lagoon (27.5 μg g⁻¹) and near submarine springs (6.10 μg g⁻¹); the likely sources were inland sewage disposal or excessive boat traffic. After the hurricanes, Pb decreased to 2.0 μg g⁻¹ in the contaminated lagoon probably through flushing. At the northern sites, essential Fe increased >2-fold (from 26.8 to 68.3 μg g⁻¹ on average), possibly from remobilization of anoxic sediments or upwelling of deep seawater during Wilma. Thus, hurricanes can be beneficial to seagrass beds in flushing toxic metals and replenishing essential elements.     

Distributions of polycyclic aromatic hydrocarbons in the Daliao River Estuary of Liaodong Bay, Bohai Sea (China)

The distributions of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in the aqueous phase, suspended particulate matter (SPM), sediment, and pore water of the Daliao River Estuary in Liaodong Bay, Bohai Sea (China). Total PAH concentrations ranged from 139.16 to 1717.87 ng L⁻¹ in surface water, from 226.57 to 1404.85 ng L⁻¹ dry weight in SPM, from 276.26 to 1606.89 ng g⁻¹ dry weight in sediments, and from 10.20 to 47.27 μg L⁻¹ in pore water. PAH concentrations were at relatively moderate levels in water, SPM, sediment and pore water in comparison with those reported for other estuary and marine systems around the world. Sedimentary PAH concentrations decreased offshore owing to active deposition of laterally-transported river-borne particles. PCA analysis of the possible PAH source suggested petrogenic and pyrolytic PAH inputs in the studied region.     

Mercury in blood and eggs of the sea turtle Lepidochelys olivacea from a nesting colony in Oaxaca, Mexico

Mercury concentrations were assessed in the sea turtle Lepidochelys olivacea from a nesting colony of Oaxaca, Mexico; 25 female turtles were sampled, a total of 250 eggs were collected during the season 2005-2006. Higher concentrations were found in yolk fraction, while in blood and albumen mean levels were below of 0.0010 μg g⁻¹ dry wt. On the basis of one nesting season, the maternal transfer of Hg via eggs-laying was estimated in 2.0 ± 1.1%. According to international norms, the health of this population and its habitats is acceptable for Hg and corresponds to baseline levels of a nearly pristine environment.     

Biomonitoring of organochlorine compounds and trace metals along the Eastern Adriatic coast (Croatia) using Mytilus galloprovincialis

The paper presents the results of monitoring trace organic contaminants (17 PCBs and 7 OCPs) and 6 trace metals (Cd, Cr, Cu, Hg, Pb and Zn) in the coastal waters of the eastern Adriatic in 2006 using Mytilus galloprovincialis as indicator species. OCPs were found in all samples (0.07-14.3 ng g⁻¹ d.wt.), while in positive samples concentrations of PCBs ranged between 0.16 and 20.5 ng g⁻¹ d.wt. The α-HCH/γ-HCH and DDE/DDT ratios indicated recent input of γ-HCH and DDT. Spatial distributions of HCB, PCBs, DDTs and Hg were significantly correlated with population density. Although elevated concentrations of all trace metals and organic contaminants were recorded in the densely populated and industrialized areas, overall data point to relatively low level of contamination of the eastern Adriatic coast. Evaluation of the risks to human health associated with consumption of the mussels suggested that there is no health risk for moderate shellfish consumers.