An assessment of the pollutant status of surficial sediment in Cork Harbour in the South East of Ireland with particular reference to polycyclic aromatic hydrocarbons

Surface sediment from three polluted sites within Cork Harbour, Ireland, and from a relatively clean reference site were collected and analysed for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), brominated flame retardants (BFRs), organotins (OTs), and heavy metals. PAHs were determined to be the most abundant class of contaminant. Concentrations of the sum (Sigma) of the 21 PAHs measured from the Harbour sites (2877.70 ng g(-1), 1000.7 ng g(-1) and 924.40 ng g(-1) dry weight respectively) were significantly higher than that of the sediment from the reference site (528.30 ng g(-1) dry weight). An inner harbour site, Douglas being the more contaminated of the three harbour sites. A similar pattern was observed with the other contaminants however, these compounds, with the exception of the heavy metals, all tended to be detected at concentrations on or below detection limits.     

The use of steroid markers to assess sewage contamination of the Black Sea

Analyses of faecal steroids in coastal sediments taken from throughout the Black Sea indicate chronic sewage contamination at some locations. These include Sochi, where concentrations of coprostanol up to 5400 ng g(-1) (dry wt) were recorded, and in the coastal areas adjacent to the Danube delta (2600 ng g(-1) dry wt). Comparatively high values of 5beta/(5beta+5alpha) isomeric ratios of cholestan-3-ol and cholestan-3-one are reported at these locations and are characteristic of sediments contaminated with sewage. Lower concentrations of coprostanol are reported for Bosphorus sediments (12-440 ng g(-1) dry wt) and in the region of Odessa (130-290 ng g(-1) dry wt). Isomeric ratios at these locations also confirm sewage as a significant contributor to steroids in the Bosphorus, but lower values of the ratios indicate only minor sewage inputs in Odessa. In contrast, steroid concentrations and compositions from most Ukrainian sites are characteristic of uncontaminated environments. To place these results into perspective, the range in levels of coprostanol in the Black Sea sediments compares to the lower to mid-range of concentrations reported for coastal sediments on a world-wide basis, with Black Sea sedimentary levels substantially below those previously reported for heavily impacted sites.     

Distribution and source apportionments of polychlorinated biphenyls (PCBs) in mariculture sediments from the Pearl River Delta, South China

Surface and core sediments collected from six mariculture farms in the Pearl River Delta (PRD) were analyzed to evaluate contamination levels of polychlorinated biphenyls (PCBs). The ∑PCBs (37 congeners) concentrations ranged from 5.10 to 11.0 ng g(-1) (mean 7.96 ng g(-1)) in surface and 3.19 to 22.1 ng g(-1) (mean 7.75 ng g(-1)) in core sediments, respectively. The concentrations were significantly higher than that measured in the sediments of their corresponding reference sites, whereby the average enrichment percentages were 62.0% and 42.7% in surface and core sediments, respectively. Significant correlations (R2=0.77, p<0.05) of PCB homologue group proportions between fish feeds and surface mariculture sediments suggested that fish feed input was probably the main source for the enrichment of PCBs. Due to the fact that PCBs could be transferred along food chains, PCB contamination in fish feeds and mariculture sediments should not be overlooked.     

Contamination of polychlorinated biphenyls (PCBs) in sediments from Kyeonggi Bay and nearby areas, Korea

To elucidate the characteristic distribution and contamination of polychlorinated biphenyls (PCBs) in sediments, 63 sediments and five benthic organisms from Kyeonggi Bay, Namyang Bay and Lake Shihwa, West coast of Korea, were analysed. Characterization of PCBs distribution in sediments was conducted by correlation between PCBs concentrations and environmental parameters, comparison of contamination level and composition of PCBs homologs between Kanechlor mixture (KC-mix) and sediments. The residues of PCBs in sediments were correlated with total organic carbon (TOC) and particulate organic carbon (POC) contents, not with mud contents and grain size distributions. Elevated concentrations of T-PCBs were found in sediments from Incheon North Harbor (INH) in Kyeonggi Bay. T-PCBs concentrations were decreased with distance increase from inner site of INH. The residues of T-PCBs in sediments from Namyang Bay were either non-detectable or near to detection limit. The contamination by PCBs in sediments from Lake Shihwa was also low. The PCBs congener profiles in INH were similar to those of KC-mix, while those in less contaminated sites showed relatively high percentage of lower chlorinated biphenyls. Sites K18 (580 ng/g or 48 ug/g-OC dry wt) and K19 (330 ng/g or 38 ug/g-OC dry wt) within INH exceeded the sediment quality criteria (SQC) (16 micrograms/g-OC as a KC-mix) derived from equilibrium partitioning (EqP) approach.     

Contamination status and accumulation profiles of organotins in sea otters (Enhydra lutris) found dead along the coasts of California, Washington, Alaska (USA), and Kamchatka (Russia)

Organotin compounds (OTs) including mono- to tri-butyltins, -phenyltins, and -octyltins were determined in the liver of adult sea otters (Enhydra lutris) found dead along the coasts of California, Washington, and Alaska in the USA and Kamchatka, Russia. Total concentrations of OTs in sea otters from California ranged from 34 to 4100ng/g on a wet weight basis. The order of concentrations of OTs in sea otters was total butyltins>total octyltins> or = total phenyltins. Elevated concentrations of butyltins (BTs) were found in some otters classified under 'infectious-disease' mortality category. Concentrations of BTs in few of these otters were close to or above the threshold levels for adverse health effects. Total butyltin concentrations decreased significantly in the livers of California sea otters since the 1990s. Based on the concentrations of organotins in sea otters collected from 1992 to 2002, the half-lives of tributyltin and total butyltins in sea otters were estimated to be approximately three years.     

Environmental behavior of organotin compounds in the coastal environment of Xiamen, China

In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L(-1) dissolved in the water, 0.14-6.7 ng (Sn) L(-1) in suspended particulate matter and nd approximately 26 ng (Sn) g(-1) (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen's coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of (210)Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.     

Petroleum and PAH contamination of the Black Sea

Concern has been expressed regarding the extent of contamination of the Black Sea. Analyses of coastal sediments taken from throughout the region indicate, however, that levels of petroleum hydrocarbons (2-300 microg g(-1) dry wt total hydrocarbons) are generally comparable to those encountered in the Mediterranean and are lower than concentrations reported for highly contaminated areas such as the Gulf, Hong Kong, Taiwan and New York Bight. Highest concentrations of total hydrocarbons (>100 microg g(-1) dry wt) were associated with discharges from Odessa, Sochi and the River Danube. Chronic/degraded petroleum was the major contributor at these sites. Samples from the Ukrainian coastline were comparatively clean (<10 microg g(-1) dry wt total hydrocarbons). Major contributions of fresh oil (as indicated by sigma n-C14-34) occur through the River Danube. Concerning total PAH, concentrations (7-638 ng g(-1) dry wt) compare to relatively unpolluted locations in the Mediterranean and are much lower than levels reported for polluted UK estuaries (e.g. Mersey, Tyne, Thames). Both pyrolytic and petrogenic PAH are present in most samples, although petroleum derived PAH are dominant at Sochi and pyrolytic sources are prevalent in the Bosphorus region. The absence of a correlation between total hydrocarbons and PAH (R2 = 0.04) indicates different primary sources for the two.     

Antifouling biocides in water and sediments from California marinas

Irgarol 1051 is a common antifouling biocide and is highly toxic to non-target plant species at low ng/L concentrations. We measured up to 254 ng/L Irgarol in water and up to 9 ng/g dry weight Irgarol in sediments from Southern California recreational marinas. Irgarol’s metabolite, M1, concentrations were up to 62 ng/L in water and 5 ng/g dry weight in sediments. Another antifouling biocide, diuron, reached up to 68 ng/L in water and 4 ng/g dry weight in sediments. The maximum Irgarol concentrations in water were greater than the Irgarol concentration recommended as the plant toxicity benchmark (136 ng/L), suggesting that Irgarol concentrations may be high enough to cause changes in phytoplankton communities in the sampled marinas. Irgarol concentrations measured in sediments were greater than calculated Environmental Risk Limits (ERLs) for Irgarol in sediments (1.4 ng/g). Antifouling pesticide accumulation in sediments may present a potential undetermined risk for benthic organisms.     

Persistent organochlorine residues in sediments from the Black Sea

The extent of contamination of the Black Sea by selected organochlorine compounds has been assessed through the analysis of surficial sediments taken from throughout the region. Concentrations of HCHs at sites influenced by the Danube delta are among the highest recorded on a global basis (up to 40 ng g(-1) dry wt). The ratio between the alpha- and gamma-isomers was relatively low indicating contamination through the use of lindane. Concentrations of DDTs (0.06-72 ng g(-1) dry wt) and PCBs (0.06-72 ng g(-1) dry wt) were not especially high in comparison to levels reported from throughout the world. The DDE/DDT ratio was, however, low indicating fresh inputs and hence current usage of DDT within the Black Sea region.     

Temporal trend, spatial distribution, and terrestrial sources of PBDEs and PCBs in Masan Bay, Korea

Congener specific determination of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) was carried out in 21 surface sediment samples and a sediment core from Masan Bay, Korea. Among the 40 PBDE congeners targeted only 29 were detectable. PBDE congener profile within sediments was dominated by BDE-209 followed by BDEs-99, -47, -153 and -183, sequentially. In surface sediments, the average ΣPBDEs levels approached that of average ΣPCBs values. However, trends observed in the sediment core suggest that this pattern will alter over time and result in higher surface sediment PBDE concentrations than PCBs in future. Various diffuse and point sources for PBDEs and PCBs were identified in this location. Shipping and other industrial activities were associated with PCB contamination while domestic and industrial waste discharges corresponded with PBDE contamination. The average concentration for PBDEs and PCBs in surface sediments were 5.7, 7.2 ng/g dry weight, respectively.     

The effect of mangrove reforestation on the accumulation of PCBs in sediment from different habitats in Guangdong, China

To investigate the influence of mangrove reforestation on the accumulation of PCBs, the concentrations and homologue patterns of polychlorinated biphenyls in surface sediments from different mangrove forests and their adjacent mud flats in Guangdong Province were determined. The total PCB concentrations in the sediments ranged from 3.03 to 46.62 ng g?1 (dry weight). Differences in the accumulation and distribution of PCBs were found between the mangrove sites and the mud flats. Furthermore, the natural forests and restored mangrove forests of native species showed slight PCB contamination, whereas the exotic species Sonneratia apetala exacerbated the PCB pollution at certain sites. It was suggested that the native mangrove species Kandelia candel and Aegiceras corniculatum could represent good choices for the phytoremediation of PCB contamination.     

Environmental behavior of organotin compounds in the coastal environment of Xiamen,China

In 2006, organotins pollution were investigated in the coastal environment of Xiamen, China. Six species of organotin compounds including tributyltin, triphenyltin and their degradation compounds were quantified in the dissolved and particulate phases of the water, and in the sediment using GC-FPD. The concentrations of organotin compounds ranged from 2.2 to 160 ng (Sn) L⁻¹ dissolved in the water, 0.14–6.7 ng (Sn) L⁻¹ in suspended particulate matter and nd ∼ 26 ng (Sn) g⁻¹ (dry weight) in the sediment. The highest concentration of total organotin or tributyltin in water was found in a shipyard and at a station near the inlet of the harbor, indicating fresh inputs of antifouling paints to Xiamen’s coastal environment. Organotin speciation was performed on sediment cores to investigate contamination trends over the past ten years in the harbor. The results of ²¹⁰Pb dating indicated that Xiamen western harbor suffered contamination during 2000. The environmental behavior of organotins such as the enhancement of the microlayer, partitioning between water/suspended particulate matter and between water/sediment are also discussed in this paper.     

Polybrominated diphenyl ethers (PBDEs) in sediments and mussel tissues from Hong Kong marine waters

Sediments and green-lipped mussels, Perna viridis, were used to investigate concentrations of polybrominated diphenyl ethers (PBDEs) in Hong Kong's marine environment. PBDEs have been used extensively over the past two decades as flame retardants in polymer additives for a variety of plastics, computers, furniture, building materials, and fabrics. Many measurements of PBDEs in various environmental matrices have been reported from Belgium, Holland, Japan, Europe and North America, but few measurements are available for the southeast Asian region and Hong Kong. PBDE congeners (n=15) were measured in 13 sediments and nine mussel samples, taken from Hong Kong marine waters. The Sigma15PBDEs in sediments ranged between 1.7 and 53.6 ng g(-1) dry wt, with the highest concentrations located around the most heavily populated areas of Victoria Harbour and Sai Kung, while the lowest concentrations of Sigma15PBDEs were found at more remote locations of Sha Tau Kok, Wong Chuk Bay, Castle Peak Bay, and Gold Coast. Sigma15PBDEs ranged from 27.0 to 83.7 ng g(-1) dry wt of mussel tissues. Although not identical, most of the congeners in sediments were found in mussel tissues, with BDE-47, BDE-99, BDE-153 and BDE-183 being the most prominent in both matrices. On the basis of a literature survey, the concentrations of PBDEs reported in Hong Kong sediments and mussel tissues are amongst the highest in the world.     

Tin and organotin in water, sediments, and benthic organisms of Poole Harbour

Tributyltin (TBT) concentrations in waters of Poole Harbour ranged between 2–139 ng l⁻¹ (as Sn) and increased to 234–646 ng l⁻¹ within marinas. Seasonal trends in contamination coincided with boat usage patterns and peaked during summer months. A combination of poor tidal flushing and removal of TBT to particulates restricts high levels of contamination to areas closest to marinas and moorings; TBT concentrations in benthic sediments decreased from 0.52 μg g⁻¹ near such sites to 0.02 μg g⁻¹ at the harbour mouth. Organotin accumulations in several benthic invertebrates including polychaetes (Nereis diversicolor), snails (Littorina littorea) and clams (Scrobicularia plana, Mya arenaria) reflect the distribution of contamination in the environment, though concentration factors (relative to water) vary considerably between species and were highest in sediment dwelling clams, notably Mya (1.3×10⁵). Compared to organotins, biological availability of inorganic tin is low.

Levels of TBT in parts of Poole Harbour exceed Environmental Quality Targets designed to protect marine life and may be responsible for poor recruitment, particularly in bivalves, at heavily contaminated sites.     

Occurrence of perfluorinated compounds in water, sediment and mussels from the Cantabrian Sea (North Spain)

Perfluorinated compounds (PFCs) have emerged as significant global environmental pollutants with persistent, bioaccumulative and toxic properties. The aim of this study was to determine the occurrence of PFCs in water (wastewater, submarine emissaries and port-waters), sediment and transplanted mussels in estuarine areas of high urban and industrial impact from Northern Spain. Five PFCs of industrial use were studied: perfluorooctanesulfonate, perfluorohexanesulfonate, perfluorobutanesulfonate, perfluorooctanoate acid and perfluorononanoate acid. After selective extraction, samples were analyzed by Ultra Performance Liquid Chromatography coupled to tandem mass spectrometry. ΣPFCs ranged from 0.06 to 10.9 ng/L in water, with higher levels in wastewater treatment plants effluents and port waters than in submarine emissaries. Little accumulation was observed in sediments and mussels with ΣPFCs ranging from 0.01-0.13 ng/g dw and 0.01-0.06 ng/g ww, respectively. Most ubiquitous compounds were PFOS and PFOA. Mass fluxes of PFCs to the Cantabrian Sea are estimated and the impact to the coastal ecosystem is discussed.     

Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay,Japan

Contaminations in sediments by polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs were investigated at 44 sites in Osaka Bay, Japan. Concentrations of total PAHs and alkylated PAHs were in the range 6.40–7800 ng/g dry weights and 13.7–1700 ng/g dry weights, respectively. The PAH concentrations tended to be higher along the shoreline in the vicinities of big ports, industrialized areas, and densely populated regions such as the cities of Osaka and Kobe. The major sources appeared to be pyrogenic or both pyrogenic and petrogenic at most of the sites. PAH concentrations were remarkably high at a site near Kobe, where the concentrations of dibenzo(a,h)anthracene and benzo(g,h,i)perylene exceeded the effects-range-medium concentration and eight PAHs were above the corresponding effects-range-low concentrations. Those PAHs may have been derived from the great fire associated with the large earthquake in 1995.     

Perfluorinated compounds in surficial sediments of the Ganges River and adjacent Sundarban mangrove wetland,India

This study reports the first evidence of the quantification of two dominant perfluorinated compounds (PFCs), namely perfluorooctanesulfate (PFOS) and perfluorooctannoate (PFOA), in surface sediment samples (0–5 cm; n = 13) from the Ganges (Hugli) River including Sundarban wetland, India using HPLC–MS/MS. The concentrations of PFOA exhibited a wide range of concentrations from <0.5 to 14.09 ng/g dry wt, whereas the concentration of PFOS was always below the detection limit of <0.5 ng/g dry wt. A consistent enrichment of PFOA was recorded in all the five sites of Sundarban (mean value 11.61 ± 1.86) whereas it was of moderate concentration or below the detection level in the seven sites along with the lower stretch of the Ganges (Hugli) River estuary (mean value 5.96 ng/g dry wt ± 5.36). Wastewater and untreated effluents are likely the major causes of accumulation of PFCs in sediments. The present paper could be used as baseline study to assess future monitoring programs of the ecosystem.     

Spatial distribution and temporal trends of persistent organochlorine pollutants in sediments from Lake Maryut, Alexandria, Egypt

Organochlorine compounds (OCs) in surface and core sediments collected from Lake Maryut, Egypt, were examined to elucidate their distribution, ecological risk and historical trend. To our knowledge, this is the first study on residue levels of OCs in sediments from Lake Maryut. Concentrations of PCBs and DDTs were higher than other OCs, ranging from 3.06 to 388 and from 0.07 to 106 ng/g dry wt., respectively. The highest concentrations of OCs were found at stations near the discharge point of sewage and close to industrial areas. The distribution of DDT and its metabolites suggest no recent inputs into the lake environment. Contamination levels of sedimentary PCBs and DDTs, can be categorized moderate to high compared to other urbanized regions worldwide. Temporal trends in OCs levels were influenced by input pathways at two sites. Evaluation of ecotoxicological risks suggests that adverse biological effects are expected mainly in the main basin area.     

Distribution and partitioning of polycyclic aromatic hydrocarbons (PAHs) in different size fractions in sediments from Boston Harbor, United States.

The concentrations of 16 US EPA priority pollutant polycyclic aromatic hydrocarbons (PAHs) were analyzed in four size fractions (< 62, 62-125, 125-250, and > 250 microm) in three contaminated Boston Harbor sediments. Total PAH concentrations ranged from 7.3 to 358 microg/g dry wt. and varied largely among the different size fractions in these sediments. For all three sites, the highest PAH concentrations were associated with the large size (> 250 microm) fractions while the fine silt and clay fractions (< 62 microm) contained relatively low PAHs. Despite the great concentration differences, the composition of PAHs in the four size fractions of these sediments showed similar patterns dominated by PAHs with three or more rings. By examining the distribution patterns of selected alkyl homologs to parent compounds, the results indicate that the major PAHs contributing to the high contamination in the inner harbor sediments were from pyrogenic sources. A positive correlation between PAHs and sedimentary organic carbon exists for all size fractions in the sediments. Calculated organic carbon normalized partition coefficients (log K(oc)) for selected major PAHs indicate near-equilibrium partitioning of PAHs among the different size fractions despite their large concentration variations. Sedimentary organic matter associated with different size fractions was the controlling factor for the observed distribution differences of PAHs among the size fractions. Our results also suggest that sedimentary organic matter with different origins and maturities may have somewhat different PAH sorption characteristics. Particulate organic matter of charcoal, plant detritus and Capitella fecal pellets in the sediments appear to sorb PAHs more strongly than organic matter associated with clay minerals. The strong association of PAHs with these organic particles in sediments will have a great influence not only on their distribution but also on long-term environmental impact.     

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).