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.     

Extent and magnitude of copper contamination in marinas of the San Diego region, California, USA

Marinas are areas of special water quality concern because of the potential for pollutant accumulation within their protected waters. Perhaps the largest contaminant source to marinas is antifouling paints that leach copper to prevent the growth of encrusting organisms on vessel bottoms. Very little monitoring of marinas is typically conducted despite the potential environmental risk, particularly in the San Diego region of California, USA where as many as 17,000 recreational vessels are berthed. The objective of this study was twofold: (1) determine the extent and magnitude of dissolved copper concentrations in marinas throughout the San Diego region, and (2) determine if elevated copper concentrations in marinas of the San Diego region are resulting in adverse biological impacts. A probabilistic study design was used to sample water column copper concentrations and toxicity (using Mytilus galloprovincialis) at 30 stations. Results indicated that exceedence of state water quality objectives was widespread (86% of marina area), but that toxicity was much less prevalent (21% of marina area). Toxicity identification evaluations (TIEs) conducted at the most toxic sites indicated that toxicity was largely due to trace metals, most likely copper. Toxicity was reduced using TIE treatments that chelated trace metals such as cation exchange column, ethylenediaminetetraacetic acid (EDTA), and sodium thiosulfate (STS). Moreover, increasing dissolved copper concentrations correlated with increasing toxicity and these copper concentrations were high enough to account for virtually all of the observed toxicity.     

Chemical contamination of a coral reef by the grounding of a cruise ship in Bermuda

Bulk metal analyses of surficial sediments collected around the Norwegian Crown cruise ship grounding site in Bermuda indicated significant but localized contamination of reef sediments by copper and zinc, caused by the stripping of the tri-butyltin (TBT)-free antifouling (AF) paint (Intersmooth 460) from the underside of the hull. Highest copper and zinc values were found in heavily compacted and red-pigmented sediments inside the impact scar and were comparable to levels found close to slip ways of local boat yards where AF paints from hull stripping and cleaning processes are washed into the sea. The re-distribution of AF contaminated sediments by storms and deposition on nearby reefs constitutes a significant ecological risk that could delay recovery processes and reduce the effectiveness of remediation efforts. Whilst the ecotoxicological effects of AF paint particles interspersed with sediment is unknown, and in need of further study, it is argued that the significance of AF paint contamination of grounding sites has been overlooked.     

Organotins (TBT and DBT) in water, sediments, and gastropods of the southern Venice lagoon (Italy)

The release of tributyltin (TBT) from maritime traffic represents one of the main problems of direct, diffuse, and continued contamination of the marine environment. In the present survey, the concentrations of TBT and dibultytin (DBT) in brackish waters, sediments, and the gastropods Nassarius nitidus were evaluated in order to estimate the contamination of the southern part of the Venice lagoon. TBT and DBT were determined by GC-MS/MS. Recent contamination of TBT was found in brackish waters near marinas, whereas the highest concentrations of TBT and DBT were observed in surface sediments at dockyards and harbours. High content of organotin in the gastropods sampled near the dockyards, harbours, and marinas showed a mobilisation from the sediments through the food web. The present study allowed assessment of whether, despite the ban on the use of TBT paints, waters, sediments, and biota were still being contaminated by organotin compounds in the southern Venice lagoon.     

Hydrocarbons in coastal sediments from the Mediterranean sea (Gulf of Fos area, France)

Sedimentary hydrocarbons have been studied quantitatively and qualitatively in 11 coastal stations located in the Gulf of Fos (French Mediterranean coast). Hydrocarbon levels ranged from 10 to 260 mg kg(-1) sed. dry weight. A new parameter "NAR" (Natural n-alkane ratio) is proposed to evaluate the contribution of terrestrial inputs of hydrocarbons in the sediments. The origins of hydrocarbons are multiple: terrestrial inputs, biogenic, pyrolytic (industry emissions mainly steel and iron industries, ship and road traffic). Generally, the main source of contamination is not petroleum. Several ratios between parent polycyclic aromatic hydrocarbons show that the sources of hydrocarbons in the sediments are generally much more pyrolytic than petrogenic.     

Metal concentrations in the milk and tissues of a nursing Tursiops truncatus female

Metal concentrations measured in the organs of beached whales are published regularly. Few of these, however, describe metal levels in nursing females. In the present study, mercury, lead, copper and zinc levels were measured in the milk and tissues of a female Bottlenose dolphin. Results reveal that metal pollutants pass from the tissue into the milk.     

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.     

Spatial patterns of chemical contamination (metals, PAHs, PCBs, PCDDs/PCDFS) in sediments of a non-industrialized but densely populated coral atoll/small island state (Bermuda)

There is a recognized dearth of standard environmental quality data in the wider Caribbean area, especially on coral atolls/small island states. Extensive surveys of sediment contamination (n = 109 samples) in Bermuda revealed a wide spectrum of environmental quality. Zinc and especially copper levels were elevated at some locations, associated with boating (antifouling paints and boatyard discharges). Mercury contamination was surprisingly prevalent, with total levels as high as 12 mg kg⁻¹ DW, although methyl mercury levels were quite low. PAH, PCB and PCDD/PCDF contamination was detected a several hotspots associated with road run-off, a marine landfill, and a former US Naval annexe. NOAA sediment quality guidelines were exceeded at several locations, indicating biological effects are possible, or at some locations probable. Overall, and despite lack of industrialization, anthropogenic chemicals in sediments of the atoll presented a risk to benthic biodiversity at a number of hotspots suggesting a need for sediment management strategies.     

Mercury contamination history of an estuarine floodplain reconstructed from a Pb-dated sediment core (Berg River, South Africa)

Mercury deposition histories have been scarcely documented in the southern hemisphere. A sediment core was collected from the ecologically important estuarine floodplain of the Berg River (South Africa). We establish the concentration of Hg in this ²¹⁰Pb-dated sediment core at <50 ng g⁻¹ Hg_T throughout the core, but with 1.3 ng g⁻¹ methylmercury in surface sediments. The ²¹⁰Pb dating of the core provides a first record of mercury deposition to the site and reveals the onset of enhanced mercury deposition in 1970. The ratio of methylmercury to total mercury is relatively high in these sediments when compared to other wetlands.     

Trace metals in harbour and slipway sediments from the island of Malta, central Mediterranean

Sediment samples collected from large harbours and public slipways on the island of Malta have been analysed for geochemically important metals (Al, Ca, Fe, Mn) and contaminant metals (As, Cd, Co, Cr, Cu, Ni, Pb, Sn, Zn) following fractionation (<63 μm) and digestion in aqua regia. Absolute and Al-normalised concentrations of contaminant metals exhibited relatively little dispersion both among different samples from the same location and between samples from different locations, notable exceptions including lower concentrations of Cr and Sn on the slipways than in the harbours. Sources of contaminant metals are attributed to diffuse and specific waste inputs from urban surroundings and boating and shipping activities. Overall, concentrations are similar to those reported for other large harbours in urban settings where equivalent sample fractionation-digestion has been performed. Relative to various sediment quality guidelines, Pb is predicted to exert the greatest threat to the marine environment of Malta.     

In situ heavy metals (copper, lead and cadmium) in different plankton compartments and suspended particulate matter in two coupled Mediterranean coastal ecosystems (Toulon Bay, France)

We monitored the concentrations of copper, lead and cadmium in seawater, in suspended particulate matter (SPM) and in bacteria, phyto- and zooplankton communities separated from abiogenic particles, over a one year cycle in two coupled Mediterranean coastal ecosystems (Little Bay (LiB) and Large Bay (LaB)). Metals were present in seawater in the order Cu > Pb > Cd in both bays and showed important variations within the same month than among months. In LiB, their concentrations were between 0.62 and 2.82 μg Cu l⁻¹, 0.16 and 19 μg Pb l⁻¹ and 0.007 and 0.14 μg Cd l⁻¹, respectively, whereas in LaB, they were between 0.23 and 2.11 μg Cu l⁻¹, 0.09 and 0.76 μg Pb l⁻¹ and not detected and 0.65 μg Cd l⁻¹. SPM play an important role on metal adsorption, especially for copper. Bioaccumulation factors showed that bacteria and phytoplankton accumulate metals whereas zooplankton tends to biodiminish them in the plankton food web.     

Changes in zooplankton communities along a mercury contamination gradient in a coastal lagoon (Ria de Aveiro,Portugal)

The main objective of this paper was to evaluate the impact of mercury on the zooplankton communities’ structure and functioning and their bioaccumulation patterns along a contamination gradient in a temperate coastal lagoon. Our results demonstrated that total abundance was not negatively affected by Hg contamination, since the most contaminated areas presented the highest values, being the copepod Acartia tonsa the dominant species, which means that it is a very well adapted and tolerant species to mercury. Nevertheless, negative effects were observed in terms of species diversity, since the most contaminated areas presented the lowest values of species richness, evenness and heterogeneity. Moreover, the spatial mercury gradient was reflected on the bioaccumulation patterns of the zooplankton communities. This reinforces the idea that zooplankton can be considered as an important vehicle of mercury transfer through the food pelagic web since it constitutes a primordial food resource for several commercial fish species.     

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).     

The relationship of Irgarol and its major metabolite to resident phytoplankton communities in a Maryland marina, river and reference area

The objectives of this study were to: (1) measure water column concentrations of Irgarol 1051 and its major metabolite GS26575 annually (2004-2006) during mid-June and mid-August at 14 sites in a study area comprised of three sub-regions chosen to reflect a gradient in Irgarol exposure (Port Annapolis marina, Severn River and Severn River reference area); (2) use a probabilistic approach to determine ecological risk of Irgarol and its major metabolite in the study area by comparing the distribution of exposure data with toxicity-effects endpoints; and (3) measure both functional and structural resident phytoplankton parameters concurrently with Irgarol and metabolite concentrations to assess relationships and determine ecological risk at six selected sites in the three study areas described above. The three-year summer mean Irgarol concentrations by site clearly showed a gradient in concentrations with greater values in Back Creek (400-500 ng/L range), lower values in the Severn River sites near the confluence with Back Creek (generally values less than 100 ng/L) and still lower values (<10 ng/L) at the Severn River reference sites at the confluence with Chesapeake Bay. A similar spatial trend, but with much lower concentrations, was also reported for GS26575. The probability of exceeding the Irgarol plant 10th centile of 193 ng/L and the microcosm NOEC (323 ng/L) suggested high ecological risk from Irgarol exposure at Port Annapolis marina sites but much lower risk at the other sites. There were no statistically significant differences among the three site types (marina, river and reference) with all years combined or among years within a site type for the following functional and structural phytoplankton endpoints: algal biomass, gross photosynthesis, biomass normalized photosynthesis, chlorophyll a, chlorophyll a normalized photosynthesis and taxa richness. Therefore, based on the above results, Irgarol adverse effects predicted from the plant 10th centile and the microcosm NOEC in the high Irgarol exposure area (Back Creek/Port Annapolis marina) were not confirmed with the actual field data for the receptor species (phytoplankton). These results also highlight the importance of unconfined field studies with a chemical gradient in providing valuable information regarding the responses of resident phytoplankton to herbicides.     

Hg, Zn and Cu levels in the muscle and liver of tiger sharks (Galeocerdo cuvier) from the coast of Ishigaki Island, Japan: relationship between metal concentrations and body length

We analyzed Hg, Zn and Cu concentrations in the liver and muscle of tiger sharks (Galeocerdo cuvier) from the coast of Ishigaki Island, Japan. The Hg concentration in the muscle increased proportionally with body length in the tiger sharks, whereas that in the liver increased rapidly after maturity (defined by a length of over 2.7 m). Muscle Hg levels were higher than liver concentrations in immature sharks, with the inverse trend observed in mature sharks. Notably, the Zn and Cu concentrations in the liver tended to decrease with increasing body length. This rapid increase in hepatic Hg concentration concurrent with the onset of maturity in sharks may result from the continuous intake of Hg via food and the slower growth of mature sharks. The high concentrations of the essential metals Zn and Cu in immature sharks may be explained by the physiological demands related to rapid growth.