Antifouling biocides in discarded marine paint particles

Antifouling paint fragments collected from marinas and leisure boat maintenance facilities and in the vicinity of abandoned boats have been chemically characterised. High concentrations of Cu (23-380 mg g⁻¹) and Zn (14-160 mg g⁻¹) in the samples (n = 14) are consistent with the use of these metals in the principal biocidal and non-biocidal pigments in contemporary antifouling formulations. Up to about 2% and 7% of the respective metals were solvent-extractable, suggesting that organo-forms of Cu and Zn (e.g. pyrithiones) were also present. Of the organic biocides, dichlofluanid was present in most samples and at concentrations up to about 20 mg g⁻¹. Chlorothalonil and Irgarol 1051® were only detected in one and four cases, respectively, and Sea Nine 211® was not detected in any sample. Results are discussed in terms of UK legislation regarding biocide usage and the likely effects and fate of discarded paint particles in coastal environments where boats are repaired or moored.     

A study of marine pollution caused by the release of metals into seawater following acid spills

This study examined the potential metal pollution induced by the accidental spill of different acids into seawater. The acids sink to the bottom according to their densities and subsequently react with marine sediments. The acids selected for this study were acetic, hydrochloric, nitric, sulfuric, and phosphoric acids; the metallic elements selected were Cr, Cu, Fe, Mn, Pb and Zn. The sediment was collected in Brest Harbour. The percentages of metals released from this sediment in the presence of various concentrations of acids in seawater were important; concentrations of approximately 7 mg L⁻¹ for Mn and 60 mg L⁻¹ for Zn were observed under our experimental conditions. We also examined the rate of release of these metals from the sediment into the seawater in the presence of the different acids and under different experimental conditions. We found that most of the metallic elements were released from the sediments into the seawater during the first fifteen minutes of exposure. After this time, a high degree of pollution was induced if acids leached into seawater were not rapidly diluted.     

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.     

Trace elements in the sediments of a large Mediterranean marina (Port Camargue,France): Levels and contamination history

The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 μg g⁻¹ of Cu, 475 μg g⁻¹ of Zn, 0.82 μg g⁻¹ of Hg, 94 μg g⁻¹ of Pb and over 10,000 ngSn g⁻¹ of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.     

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.     

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.     

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.     

Persistence and metallic composition of paint particles in sediments from a tidal inlet

Concentrations of Cu, Pb, Sn and Zn have been determined in sediment (<500 μm) and macroscopic paint particles (>500 μm) retrieved from sections of two cores collected from a tidal inlet of the Plym estuary, southwest England. Paint particles contributed up to about 0.2% of the total mass retrieved from each section and were most abundant towards the base of the cores where, according to (210)Pb dating, deposition took place about a decade prior to sampling. Metal concentrations in the paint particles pooled from the sections were highly variable, typically spanning two orders of magnitude in each core, and were greatest for Cu and Zn (up to 460,000 and 170,000 μg g(-1), respectively) due to their use in contemporary antifouling formulations applied to boat hulls. Concentrations of metals in the sediment were, however, relatively invariant, an effect attributed to the abundance and dispersion of microscopic paint particles throughout the cores.     

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.     

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.     

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.     

Metals contamination along the watershed and estuarine areas of southern Bohai Sea,China

Distributions and magnitude of metals in water, sediment and soil collected from the watershed and estuarine areas of southern Bohai Sea, were investigated. The largest dissolved concentrations of As, Cu and Zn in water were 347.70, 2755.00, 2076.00 μg/L, respectively, much higher than corresponding drinking water guidelines. The greatest concentrations of Cu, Zn, Cr, Ni, Pb, As and Cd in sediments were 1462.2, 1602.17, 196.43, 67.15, 63.54, 73.86 and 1.41 mg/kg, dw, respectively. The mean concentrations of Cu, Ni, Cd, Zn, Cr, Pb and As in soils were 24.67, 24.73, 0.14, 64.75, 56.52, 25.12 and 9.34 mg/kg, dw, respectively. Land use was confirmed to be an important factor of influence on soil metal concentrations. Metal contents along the watershed of Jie River were significantly greater than in other locations. The detection of metals in relatively high concentrations from different environmental matrices in this region indicates the necessity of further studies.     

Animal-sediment relationships: Evaluating the ‘Pearson-Rosenberg paradigm’ in Mediterranean coastal lagoons

We investigated the applicability of the Pearson-Rosenberg (P-R) conceptual model describing a generalized pattern of response of benthic communities in relation to organic enrichment to Mediterranean Sea coastal lagoons. Consistent with P-R model predictions, benthic diversity and abundance showed two different peaks at low (>2.5-5 mg g⁻¹) and high (>25-30 mg g⁻¹) total organic carbon (TOC) ranges, respectively. We identified TOC thresholds indicating that risks of reduced benthic diversity should be relatively low at TOC values < about 10 mg g⁻¹, high at TOC values > about 28 mg g⁻¹, and intermediate at values in-between. Predictive ability within these ranges was high based on results of re-sampling simulation. While not a direct measure of causality, it is anticipated that these TOC thresholds should serve as a general screening-level indicator for evaluating the likelihood of reduced sediment quality and associated bioeffects in such eutrophic systems of the Mediterranean Sea.     

Arsenic and trace metal contents in sediment profiles from the Admiralty Bay, King George Island, Antarctica

Admiralty Bay (Antarctica) hosts three scientific stations (Ferraz, Arctowski and Macchu Picchu), which require the use of fossil fuel as an energy source. Fossil fuels are also considered the main source of pollution in the area, representing important inputs of major pollutants (organic compounds) and trace metals and metalloids of environmental interest. Accordingly, this work presents the results of As, Cd, Cr, Cu, Ni, Pb and Zn in sediment profiles from Admiralty Bay. The sediment results from Ferraz station were slightly higher than the other sampling sites. The highest contents were observed for Cu and Zn (from 44 to 89 mg kg⁻¹). Otherwise, by using enrichment factors and geochronology analysis, the most relevant enrichment was observed for As in the samples collected close to the Ferraz station, indicating that increasing As content may be associated with the activities associated with this site.     

Polychlorinated biphenyls and organochlorine pesticides in plastics ingested by seabirds

The occurrence of plastic objects in the digestive tract was assessed in eight species of Procellariiformes collected in southern Brazil and the occurrence of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the ingested plastics pellets and plastic fragments was evaluated. PCBs were detected in plastic pellets (491 ng g⁻¹) and plastic fragments (243-418 ng g⁻¹). Among the OCPs, p,p′-DDE had the highest concentrations, ranging from 68.0 to 99.0 ng g⁻¹. The occurrence of organic pollutants in post-consumer plastics supports the fact that plastics are an important source carrying persistent organic pollutants in the marine environment. Although transfer through the food chain may be the main source of exposure to POPs to seabirds, plastics could be an additional source for the organisms which ingest them, like Procellariiformes which are the seabirds most affected by plastic pollution.     

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.     

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).     

Persistent organochlorine pollutants in Korean offshore waters: Squid (Todarodes pacificus) as a biomonitor

Persistent organochlorine pollutants (POPs) such as polychlorinated biphenyls (PCBs), dichlorodiphenyl trichloroethane and its metabolites (DDTs), chlordane compounds (CHLs), and hexachlorocyclohexanes (HCHs) were determined in Japanese common squid collected from the offshore waters of Korea. Liver accumulated higher levels of contaminants than mantle. The sums of DDTs, PCBs, CHLs and HCHs in liver were in the ranges of 164-4430 ng g⁻¹, 95-1030 ng g⁻¹, 15-121 ng g⁻¹, and 13-98 ng g⁻¹ on a lipid weight basis, respectively. Among the POPs, DDTs showed distinct regional difference in concentration levels and composition between the western and eastern offshore of Korea. One of the highest concentrations of DDTs so far recorded in the western offshore of Korea, that is Yellow Sea. This implies ongoing fresh input of technical DDT to this regional sea. HCHs were relatively high in the Yellow Sea as well, with an enhanced signal of γ-HCH indicating recent input of lindane. In contrast, CHLs showed higher level in the eastern offshore of Korea, that is East Sea, but PCBs showed an even distribution in both regions. Squid could be a useful bio-indicator for monitoring offshore water contamination by POPs.     

Spatial and temporal variations of heavy metal contamination in sediments of a mangrove swamp in Hong Kong

Spatial and temporal variations of heavy metal contamination in sediments of a small mangrove stand in Hong Kong were examined by laying two transects perpendicular across the shore. Surface sediment samples were taken along the two transects running landward to seaward at intervals of 5 or 10 m during December 1989, and March, July and September 1990. Total concentrations of Cu, Zn, Mn and Pb did not show any specific trend along each transect, although the maximum concentration of heavy metals tended to occur at the landward edge. There was a high level of variability among locations within each transect; for instance, the Cu concentrations fluctuated from 1 to 42 μg g⁻¹. Certain sites contained exceptionally high levels of total metals. Total concentrations of Cu, Zn, Mn and Pb as high as 42, 150, 640 and 650 μg g⁻¹, respectively, were recorded, implying contaminated sediment. A comparison of the two transects indicated that the sediments of Transect B seemed to contain higher total Zn but lower Cu and Mn concentrations than those of Transect A. Most of the heavy metals accumulated in the sediments were not extractable with ammonium acetate and no Cu or Pb was detected in these extracts. The concentrations of extractable Zn and Mn were low, less than 10% of the total metal concentration in the sediment, and appeared to decrease from the landward to seaward samples. For both total and extractable metals, there were significant seasonal fluctuations for both transects, but no specific trends could be identified. These spatial and temporal variations suggest that the scale and representativeness of sampling require careful planning, and a single sample might not give a satisfactory evaluation of the levels of heavy metal contamination in mangrove ecosystems.     

Distribution and bioaccumulation of polychlorinated biphenyls and organochlorine pesticides residues in sediments and Manila clams (Ruditapes philippinarum) from along the Mid-Western coast of Korea

The distribution and bioaccumulation features of PCBs, DDTs, and HCHs were investigated in the sediments and Manila clams collected from along the Mid-Western coast of Korea. The measured concentrations of ΣPCBs, ΣDDTs and ΣHCHs were 1.08–3.5, 0.12–0.35 and 0.090–0.30 ng g⁻¹ dw in sediment, and 33–390, 7.4–46 and 6.3–27 ng g⁻¹ lipid in Manila clam, respectively. Their levels were found to be relatively lower than those of other contaminated areas and the consumption of Manila clam from these areas seems to be safe for human health according to calculated lifetime cancer risk and hazard indices. The ΣPCBs and ΣDDTs concentrations in sediments showed a significant relationship to those in clams. The significant correlation was observed between BSAF in clams and K_ow for each PCB congeners and DDT metabolites. These findings support that the PCBs and DDTs levels, which are highly hydrophobic chemicals, in clam reflect the sediment pollution through bioaccumulation.