Assessment of organotin (butyltin species) contamination in marine biota from the Eastern Aegean Sea, Turkey

The marine environment continues to be adversely affected by tributyltin (TBT) release from maritime traffic. Therefore the concentrations of TBT, dibutyltin (DBT) and monobutyltin (MBT) were measured in barnacles, mussels and fish along the Eastern Aegean coastline. The average concentrations of TBT ng Sn g⁻¹ were found to be 235 in fish, 116 in mussels and 635 in barnacles. The highest concentrations of TBT, DBT and MBT were observed in the barnacles which had been sampled in marinas and harbors. All mussels sampled showed values of TBT + DBT, which were below the “tolerable average residue level (TARL)” as currently accepted. This indicates a lack of risk to the consumer. However, 7 out of the 15 fish sampled displayed TBT + DBT levels above the TARL, which indicates that a fish consumer group may be at risk. Barnacles have high potential as biomonitors for the presence of organotin in the Aegean Sea.     

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.     

Evaluation of the contamination of platinum in estuarine and coastal sediments (Tagus Estuary and Prodelta, Portugal)

Platinum contamination in estuarine and coastal sediments has been evaluated in three cores collected from the Tagus Estuary and Prodelta shelf sediments. Elevated concentrations, up to 25-fold enrichment compared to background values, were found in the upper layers of the estuarine sediments. The degree of Pt enrichment in the estuarine sediments varied depending on the proximity to vehicular traffic sources, with a maximum concentration of 9.5 ng g⁻¹. A considerable decrease of Pt concentrations with depth indicated the absence of significant contamination before the introduction of catalytic converters in automobiles. Platinum distribution in the Tagus Prodelta shelf sediment core showed no surface enrichment; instead a sub-surface maximum at the base of the mixed layer suggested the possibility of post-depositional mobility, thereby blurring the traffic-borne contamination signature in coastal sediments.     

Distribution,fluxes and bacterial consumption of total organic carbon in a populated Mediterranean Gulf

Saronikos Gulf (Greece) practically constitutes the sea border of the metropolitan city of Athens and the alongshore outskirts, and it receives the treated wastes of ∼4 million people from a point source that discharges on the sea bottom at ∼65 m water depth. Total organic carbon (TOC) was measured in 477 seawater samples collected in the Saronikos Gulf, during 10 cruises, from August 2001 to May 2004 and analyzed with the High Temperature Catalytic Oxidation method (HTCO). TOC concentrations ranged from 49 to 198 μmol C L⁻¹ in agreement with other Mediterranean coastal waters. The highest TOC concentrations were found in the upper waters (0–75 m), whereas in the deeper parts of the Gulf (between 100 and 400 m) TOC concentrations were kept constantly low (49–70 μmol C L⁻¹). A general pattern towards higher TOC concentrations during summer was also observed. Calculations of non-refractory (labile+semi-labile) organic material based on a one-dimensional (1D) conceptual model showed that it corresponds to 33% of the bulk TOC during summer and to 27% during winter. Bacterial production (BP) was measured at selected stations of ∼70–80 m depth using the [³H] leucine method. Depth integrated BP values varied from 2.8 to 10.9 mmol m⁻² d⁻¹, whereas extraordinary high integrated BP values (126 and 140 mmol m⁻² d⁻¹) were observed at the station over the treated sewage outflow. From the turnover time, τ, of the non-refractory TOC by bacteria it was implied that organic matter in the effluents is extremely labile (2–58 days). Moreover, τ values at the other sites showed that during summer non-refractory organic material resisted bacterial degradation (1–8 months), whereas during early spring it was easily degradable (20–50 days). The balance of TOC fluxes for the Inner Gulf for June and September 2003 showed that the Inner Gulf acts as a net producer of TOC during summer. Our results suggest that the presence of the Athens treated sewage outfall does not contribute to the observed summer accumulation of TOC in the Inner Gulf and other causes such as increased bacteria predation and/or nutrient limitation must be responsible.     

Temporal and spatial trends of total petroleum hydrocarbons in the seawater of Bohai Bay, China from 1996 to 2005

The temporal and spatial distribution of total petroleum hydrocarbons (TPH) in the seawater of Tianjin Bohai Bay during 1996-2005 was investigated for the first time. TPH concentrations in 480 seawater samples collected from 16 stations during a 10-year span were quantified by ultra-violet fluorescence spectroscopy. Petroleum hydrocarbons were ubiquitous in the seawater, and their concentrations were highly variable, ranging from 23.7 to 508 μg L⁻¹. TPH concentrations in the seawater varied with seasons, showing a decreasing order of winter > spring > summer. Over the 10-year period, TPH at all stations steadily decreased. The highest values obtained were at stations near the port areas and Dagu outfall where shipping activities and land-based waste water discharges were the major sources of pollution. Our results provided the background information on the extent of TPH contamination in the seawater and highlighted the need to further control TPH pollution in Tianjin Bohai Bay.     

Temporal and spatial biomonitoring of heavy metals in eastern Aegean coastal waters using Amphibalanus amphitrite

This biomonitoring study presents the spatial and temporal distributions of heavy metals in the soft tissues of a major fouling species Amphibalanus amphitrite living on hard substrate at different sites along the eastern Aegean coast. A. amphitrite has been chosen as a strong candidate for monitoring heavy metals. Sediment and seawater samples were also collected to detect their metal contents in order to gain more information on the environmental conditions and possible bioaccumulation patterns. The physico-chemical characteristics of sampling stations have been measured in order to characterize the sampling area. The order of metal concentrations in barnacles, sediment and seawater decreased in the following order Cu > Fe > Zn > Mn > Cd > Cr > Pb > Hg, Fe > Mn > Zn > Cu > Pb > Cr > Hg > Cd and Fe > Zn > Mn > Cu > Pb > Cr > Cd > Hg, respectively. These results showed that barnacles accumulate Cu in a higher degree than both sediment and seawater. Moreover, metal concentrations in barnacle have the potential for use in any future regulatory framework monitoring and eventually controlling ambient metal pollution levels.     

Biomarker responses in pelagic and benthic fish over 1 year following the Hebei Spirit oil spill (Taean, Korea)

After the Hebei Spirit oil spill incident (7th December, 2007) in the west coast of Korea, contamination of biliary PAH metabolite and hepatic biomarkers in a pelagic and a benthic fish was monitored for 1 year. Concentrations of 16 PAHs and alkylated PAHs in fish muscle were highest (22.0 ng/g d.w. for 16 PAHs and 284 ng/g d.w. for alkylated PAHs) at 5 days after the spill and then decreased rapidly to background levels at 11 months after the spill. Fish from the oiled site had elevated biliary PAH metabolite concentrations immediately after the spill; these declined steadily in both species, but were still above reference site concentrations 2 months after the spill. Oiled-site fish showed hepatic CYP 1A induction whose trend closely followed those of biliary PAH metabolite concentrations, implying continuous exposure to PAHs. Brain acetylcholinesterase activity was not related to oil exposure.     

U, Th, K and Cs activity concentrations along the southern coast of the Caspian Sea, Iran

The determination of activity concentrations of the radioactive elements ²³⁸U, ²³²Th, ⁴⁰K and ¹³⁷Cs was performed on grab samples taken from a polluted environment. The samples were sliced into strata from 5 cm depth, dried and ground to sieved through a 170 mesh size prior to the analysis. Activity concentration was quantified using gamma spectroscopy. The results showed that the concentrations of activity in the sediment samples are 177 ± 12.4, 117 ± 11.5, 1085 ± 101.6 and 131 ± 4.8 Bq kg⁻¹ for ²³⁸U, ²³²Th, ⁴⁰K and ¹³⁷Cs, respectively. In general, the distribution of activity concentrations along the southern coast of the Caspian Sea area exceeded international limits. The hazard index of the samples was 0.19-0.88, with an average of 0.49. The mean values of radium equivalent activity and dose rate are 176 Bq kg⁻¹ and 63 nGy h⁻¹, respectively.     

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.     

Fumarole compositions and mercury emissions from the Tatun Volcanic Field,Taiwan: Results from multi-component gas analyser,portable mercury spectrometer and direct sampling techniques

Gas emissions from Tatun volcanic group, northern Taiwan, were studied for the first time using a multi-component gas analyser system (Multi-GAS) in combination with Giggenbach flask methods at fumaroles and mud pools at Da-you-keng (DYK) and Geng-tze-ping (GZP). CO₂/S molar ratios observed at DYK ranged from 3–17, similar ratios were observed using a Multi-GAS sensor box of 8–16. SO₂ at GZP was low, higher concentrations were observed at DYK where SO₂/H₂S ratios were close to 1 for both methods. A lower CO₂/H₂S ratio was measured via Giggenbach flask sampling (7.2) than was found in the plume using the gas sensor at GZP (9.2). This may reflect rapid oxidation of H₂S as it mixes with background air. Gaseous elemental mercury (GEM) levels were observed in the fumarole gases using a portable mercury spectrometer. These are the first such measurements of mercury at Tatun. Mean GEM concentrations in the fumarole plumes were ∼ 20 ng m^− 3, with much higher concentrations observed close to the ground (mean [GEM] 130 and 290 ng m^− 3 at DYK and GZP, respectively). The GEM in the fumarole plume was elevated above concentrations in industrial/urban air in northern Taiwan and the increase in GEM observed when the instrument was lowered suggests high levels of mercury are present in the surrounding ground surface. The GEM/CO₂ (10^− 8) and GEM/S (10^− 6) ratios observed in the fumarole gases were comparable to those observed at other low-temperature fumaroles. Combining the Hg/CO₂ ratio with a previous CO₂ flux value for the area, the annual GEM flux from the Tatun field is estimated as 5–50 kg/year.     

Matrix-bound phosphine in sediments from Lake Illawarra, New South Wales, Australia

Matrix-bound phosphine (MBP) has been measured in sediment from two cores in Lake Illawarra on the south east coast of Australia. The sediments were also dated in the upper layers. MBP concentrations found range from 142 to 1813 ng kg⁻¹, dw (dry weight of sediment) with some values being amongst the highest ever measured. Values of MBP in deeper sediments were higher than for near surface samples, but the patterns with depth were not consistent. Strong correlations were noted between MBP and organic phosphorus (OP, r > 0.8) and with total phosphorus (TP, r > 0.7), but only moderate correlations were found with organic carbon (OC, r > 0.5). No correlations were found between MBP concentrations and the age of the sediments. It was confirmed that high MBP concentrations are indicative of a phosphorus rich environment. The results tend to support the premise that MBP is generated by microbial attack on OP under anaerobic conditions.     

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.     

The measurement of gamma-emitting radionuclides in beach sand cores of coastal regions of Ramsar,Iran using HPGe detectors

Radionuclides which present in different beach sands are sources of external exposure that contribute to the total radiation exposure of human. ²²⁶Ra, ²³⁵U, ²³²Th, ⁴⁰K and ¹³⁷Cs analysis has been carried out in sand samples collected at six depth levels, from eight locations of the northern coast of Iran, Ramsar, using high-resolution gamma-ray spectroscopy. The average Specific activities of natural radionuclides viz., ²²⁶Ra, ²³⁵U, ²³²Th, ⁴⁰K and ¹³⁷Cs, in the 0–36 cm depth sand were found as: 19.2 ± 0.04, 2.67 ± 0.17, 17.9 ± 0.06, 337.5 ± 0.61 and 3.35 ± 0.12 Bq kg⁻¹, respectively. The effects of organic matter content and pH value of sand samples on the natural radionuclide levels were also investigated. Finally, the measured radionuclide concentrations in the Ramsar beach were compared with the world average values, as reported by UNSCEAR (2000). None of the studied beaches were considered as a radiological risk.     

Lead concentrations and isotopes in aerosols from Xiamen, China

To investigate the magnitude and origin of lead (Pb) pollution in the atmosphere of Xiamen, China, 40 aerosol samples were collected from the coast of Xiamen from January to December 2003. All these samples were measured for Pb isotopic compositions (²⁰⁸Pb/²⁰⁶Pb = 2.10897 ± 0.00297, ²⁰⁷Pb/²⁰⁶Pb = 0.85767 ± 0.00159, n = 40) using a Multi-collector-Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS). Thirty-five out of forty samples were also measured for Pb concentrations (79.1 ± 38.3 ng/m³, n = 35) by Atomic Absorption Spectroscopy (AAS). The results indicate that the Pb concentrations display significant seasonal variations while Pb isotopic ratios remain relatively constant. The Pb concentrations were high in January and February, abruptly decreased in March, remained relatively constant (but low) from April to August, and then gradually increased from September to December. This corresponds to the rainless climate in winter and rain scavenging in summer. The higher Pb concentration of Xiamen aerosols in winter and spring may be also caused by long-range transferred anthropogenic Pb during the northeastern monsoon seasons. Although the use of leaded gasoline in Xiamen was banned in 2000, our new data indicate that the Pb annual concentrations of aerosols in Xiamen increased about 12% when compared to the data measured between 1991 and 1993. Thus, Pb pollution in the atmosphere of Xiamen has not receded even after the phase-out of leaded gasoline. Our results further confirm the previous studies’ conclusion that the primary source of atmospheric Pb in China, especially in South China, is the vast combustion of lead-containing coal, not leaded gasoline.     

Occurrence and distribution of microplastics in marine sediments along the Belgian coast

Plastic debris is known to undergo fragmentation at sea, which leads to the formation of microscopic particles of plastic; the so called ‘microplastics’. Due to their buoyant and persistent properties, these microplastics have the potential to become widely dispersed in the marine environment through hydrodynamic processes and ocean currents. In this study, the occurrence and distribution of microplastics was investigated in Belgian marine sediments from different locations (coastal harbours, beaches and sublittoral areas).Particles were found in large numbers in all samples, showing the wide distribution of microplastics in Belgian coastal waters. The highest concentrations were found in the harbours where total microplastic concentrations of up to 390 particles kg⁻¹ dry sediment were observed, which is 15-50 times higher than reported maximum concentrations of other, similar study areas.The depth profile of sediment cores suggested that microplastic concentrations on the beaches reflect the global plastic production increase.     

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).     

Bioconcentration of selected endocrine disrupting compounds in the Mediterranean mussel, Mytilus galloprovincialis

The occurrence of three endocrine disrupting compounds, 4-n-nonylphenol, triclosan and bisphenol A, was investigated in different bivalves originating from the Aegean Sea (Greece). The bioconcentration potential of these compounds was studied using the Mediterranean mussel (Mytilus galloprovincialis). Tissue samples were extracted by sonication. Analysis was performed by gas chromatography-mass spectrometry. According to the field survey results, the average concentrations of 4-n-nonylphenol, triclosan and bisphenol A, were 158, 461 and 404 ng g⁻¹ (dry weight), respectively. During 28 days of exposure at 300 ng L⁻¹, the tissue concentrations of compounds were constantly increased. Steady state was not observed up to the end of the experiment. Kinetic bioconcentration factors varied from 1.7 (4-n-nonylphenol and triclosan) to 4.5 L g⁻¹ (bisphenol A). Following exposure, mussels were relocated to clean water for 28 days. This experiment revealed that depuration rates for all of the target compounds were lower than uptake rates. The biological half-lives of each compound ranged between 12 days (triclosan) and 26 days (bisphenol A).     

Perfluoroalkyl and polyfluoroalkyl substances in sediments from South Bohai coastal watersheds,China

This study investigated the concentrations and distribution of Perfluoroalkyl and polyfluoroalkyl substances (PFAS) in sediments of 12 rivers from South Bohai coastal watersheds. The highest concentrations of ΣPFAS (31.920 ng g⁻¹ dw) and PFOA (29.021 ng g⁻¹ dw) were found in sediments from the Xiaoqing River, which was indicative of local point sources in this region. As for other rivers, concentrations of ΣPFAS ranged from 0.218 to 1.583 ng g⁻¹ dw were found in the coastal sediments and from 0.167 to 1.953 ng g⁻¹ dw in the riverine sediments. Predominant PFAS from coastal and riverine areas were PFOA and PFBS, with percentages of 30% and 35%, respectively. Partitioning analysis showed the concentrations of PFNA, PFDA and PFHxS were significantly correlated with organic carbon. The results of a preliminary environmental hazard assessment showed that PFOS posed the highest hazard in the Mi River, while PFOA posed a relative higher hazard in the Xiaoqing River.     

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.     

Spatial and temporal variability of seawater properties,current velocity and SPM concentration off Cassino Beach-Rio Grande-Southern Brazil

Water column profiles and near-bed time series of pressure, current velocity, suspended-particulate matter (SPM) concentration and seawater temperature and salinity were collected during three short cruises carried out in May 2005 in the shoreface and inner shelf area adjacent to Cassino Beach, southern Brazil. The measurements were part of the Cassino Experiment, a project conducted at an open, sandy coastal area known for the occurrence of patches of fairly large amounts of muddy sediments that are sporadically fluidized, transported onshore and eventually stranded on the beach. The study area is close to the Patos Lagoon mouth, being influenced by its water and suspended-sediment discharge. The presence of the Patos Lagoon outflow on the inner shelf was detected in one of the cruises (May 13) through measurements of near-surface salinity: while close to shore salinity was 29.4, a minimum value of 13.8 was measured at ∼10 km from the coast. Four days later, no trace of the plume was detected in the area. Regarding seawater temperature, no large temporal or spatial variability was documented with measured values ranging from 19.3 to 20 °C. Water column currents were prominently to N and NE, except at the outermost station, located ∼42 km from the coast, where NW-directed flows were observed at surface and mid-depth. Maximum near-bed current velocity oscillated between 18 and 42 cm s⁻¹ in the east–west direction and between 14 and 42 cm s⁻¹ in the north–south direction. Near-surface concentration of SPM oscillated between 11 and 99 mg L⁻¹, in general one order of magnitude lower than near-bed values. However, near-bed concentration of SPM showed large spatial variability: the highest value (2200 mg L⁻¹) was yielded by a water sample collected at ∼8 m water depth, at a station located ∼2 km away from the shoreline; two water samples collected 500 m, apart from this station, yielded SPM concentrations of 148 and 205 mg L⁻¹, one order of magnitude lower. Spectral analyses of near-bed current speed and SPM concentration indicate the relevance of oscillations in the low-frequency (<0.05 Hz) range. Detailed sampling of bottom sediment indicated that in May 2005 the mud patch was centered at ∼8.5 m water depth.