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.     

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in seawater from the Western Taiwan Strait, China

Seawater samples (including surface water and bottom water) were collected from the Western Taiwan Strait (WTS) during June 24-25, 2009; polycyclic aromatic hydrocarbons (PAHs) in dissolved phase and particulate phase were analyzed, respectively. The results showed that the total concentrations of PAHs in the dissolved phase and particulate phase were ranged from 12.3 to 58.0 ng L(-1), and 10.3-45.5 ng L(-1), which showed a low-middle contamination level in the China Seas. The spatial variability of PAHs may be related to the complicated currents of WTS, especially the Min-Zhe coastal current. PAHs diagnostic ratios suggested that PAHs mainly originated from the inputs of pyrolytic (combustion) sources, which might be contributed to land-based atmospheric deposition. The particle-water partition coefficients of individual PAH showed that partitions were not correlated with suspended particulate matter content, dissolved organic carbon or salinity, similar to the Yangtze coastal area.     

Occurrence and effects of organotins on adult common whelk (Buccinum undatum) (Mollusca, Gastropoda) in harbours and in a simulated dredging situation.

Transplanted common whelk (Buccinum undatum) (Mollusca, Gastropoda) accumulated fairly high levels of organotins (tributyltin (TBT) and triphenyltin (TPT)) during exposure in three harbours with different TBT contamination. This did not though lead to an increase in imposex frequency in the adult females studied. Simulating harbour dredging in an experiment using suspended sediment from one of the harbours only resulted in a low concentration of TBT in the tissues of the common whelk and subsequently no changes in the occurrence and degree of imposex. The common whelk seemed to receive the main part of TBT from the water column and the limited bioaccumulation in the experiment indicates that desorption of TBT from the suspended sediment was slow. After TBT has been totally banned, dredging of contaminated sediments will cause increased exposure of the biota to TBT. Due to slow desorption the increase may however, be slight and temporary to pelagic and epibenthic species unless the settled particles are resuspended.     

Polycyclic aromatic hydrocarbons loads into the Mediterranean Sea: estimate of Sarno River inputs

The polycyclic aromatic hydrocarbons (PAHs) pollution in the Sarno River and its environmental impact on the Gulf of Naples (Tyrrhenian Sea, Central Mediterranean Sea) were estimated. The 16 PAHs identified by the USEPA as priority pollutants and perylene were determined in the water dissolved phase (DP), suspended particulate matter (SPM) and sediments. Total PAHs concentrations ranged from 23.1 to 2670.4 ng L(-1) in water (sum of DP and SPM) and from 5.3 to 678.6 ng g(-1) in sediment samples. Source analysis revealed that PAHs mainly came from combustion process. Contaminant discharges of PAHs into the sea were calculated in about 8530 gd(-1) showing that this river should account as one of the main contribution sources of PAHs to the Tyrrhenian Sea.     

Assessment of tributyltin contamination in a shipyard area using a mussel transplantation approach

Mussels (Mytilus galloprovincialis) were transplanted to seven stations around a large shipyard for 126 days to evaluate tributyltin (TBT) contamination. Although the application of TBT-based paints to ships is totally banned in Korea, butyltin compounds were found to accumulate in mussels following transplantation. Concentrations of TBT and total butyltins in transplanted mussels near the shipyard were in the range of 40-350 ng Sn/g and 74-530 ng Sn/g on a dry weight basis, respectively. Obviously, low TBT concentrations (6.0-53 ng Sn/gdw) were determined in mussels at four stations outside the shipyard. A negative gradient of TBT concentrations and TBT portion to total butyltin concentrations were found in both the surface water and transplanted mussels according to distance from the shipyard. In addition, TBT concentrations in surface water and transplanted mussels showed significant correlation (r(2) = 0.71; p < 0.001). These results indicate that the shipyard still releases fresh TBT into surrounding waters even after TBT regulation in Korea, and mussel transplantation is useful in evaluating TBT contamination in shipyard area.     

Organotin levels in Nazaré canyon (west Iberian Margin, NE Atlantic) and adjacent coastal area

Organotin compounds (OTs) are ubiquitous in the marine environment and high concentrations (μg g(-1) range) in sediments from different coastal areas around the world have been reported. However, few reports have described the OTs contamination status in the offshore and deep sea environment. This work investigated organotin levels in Nazaré canyon for the first time. Levels of monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), diphenyltin (DPT), triphenyltin (TPT), dioctyltin (DOT) and trioctyltin (TOT) were quantified in sediment samples from the upper flanks of the canyon and from the adjacent coastal area. TBT levels detected in the canyon flanks are about two to three orders of magnitude lower than those found in the coastal area. Nevertheless, when quantifiable, TBT levels in the canyon samples were higher than the Environmental Assessment Criteria set for TBT in sediments by the OSPAR Commission indicating that at those locations negative ecological impacts are likely to occur.     

Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Levels of estrogenic compounds in Xiamen Bay sediment, China

Concentrations of seven estrogenic compounds, i.e., estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol(EE2), diethylstilbestrol (DES), nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), were determined in sediments and pore water from Xiamen Bay in China, and their distributions and potential risks in the Bay were assessed. Total estrogenic compounds concentrations varied from 49.20 to 1230.69 ng/g dw in sediments and from 102.33 to 4376.60 ng/L in pore water. The highest levels of these compounds were found at Yundang Lagoon. The results showed that estrogenic compounds in Xiamen Bay originated mainly from municipal wastewaters. Compared with other areas, Xiamen Bay was contaminated with high levels of estrogen hormones. This contamination poses a potential threat to benthic organisms. Although a good relationship (r = 0.94) was observed between the estrogenic compounds concentrations and total organic carbon (TOC) contents in sediments, which did not indicate that the sediment organic matter favors the accumulation of the detected estrogenic compounds.     

Occurrence of polycyclic aromatic hydrocarbons (PAHs) in seawater from the Western Taiwan Strait,China

Seawater samples (including surface water and bottom water) were collected from the Western Taiwan Strait (WTS) during June 24–25, 2009; polycyclic aromatic hydrocarbons (PAHs) in dissolved phase and particulate phase were analyzed, respectively. The results showed that the total concentrations of PAHs in the dissolved phase and particulate phase were ranged from 12.3 to 58.0 ng L⁻¹, and 10.3–45.5 ng L⁻¹, which showed a low-middle contamination level in the China Seas. The spatial variability of PAHs may be related to the complicated currents of WTS, especially the Min-Zhe coastal current. PAHs diagnostic ratios suggested that PAHs mainly originated from the inputs of pyrolytic (combustion) sources, which might be contributed to land-based atmospheric deposition. The particle-water partition coefficients of individual PAH showed that partitions were not correlated with suspended particulate matter content, dissolved organic carbon or salinity, similar to the Yangtze coastal area.     

Distribution of organochlorines in the dissolved and suspended phase of the sea-surface microlayer and seawater in Hong Kong, China

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were measured in the dissolved and suspended particulate phase in the sea-surface microlayer (SML) and subsurface water (SSW) collected from Hong Kong's coastal environment. The concentration ranges (pg/L) for summation sigmaHCHs, summation sigmaDDTs and summation sigmaPCBs in the SSW dissolved phase (DP i.e. sum of truly dissolved and colloidal phase) were 409-940 (mean 602), 774-5583 (mean 1908) and 266-433 (mean 278), respectively. The concentration ranges (pg/L) for summation sigmaHCHs, summation sigmaDDTs and summation sigmaPCBs in SSW suspended particulate matter (SPM) were <5-85 (mean 59), 358-1369 (mean 787) and 85.6-273 (mean 172), respectively. The enrichment factor of PCBs and OCPs in the SML varied between 1.1 and 4.5 for the DP, and 0.4-8.2 for the SPM. The distribution of contaminants between DP and SPM in both the SML and SSW indicates that particulate matter plays an important role in the distribution and fate of DDTs and PCBs, but not for HCH isomers. The Pearl River Estuary is likely to be a major source of contaminants transported to Hong Kong.     

Variability of particulate (SS,POC) and dissolved (DOC,NO3) matter during storm events in the Alegria agricultural watershed

The temporal variability of suspended sediment, nitrates (NO₃) and dissolved (DOC) and particulate organic carbon concentrations was analysed in the Alegria agricultural watershed over a 2‐year period. Nine storm events were studied, including an exhaustive analysis of hydrometeorological conditions, quantification of fluxes, and concentration‐discharge hysteresis loop characterization. The overall aim was to study the variability in these components during storm events and determine the mechanisms (flow paths) affecting the trajectories, from the source to the stream. The forms, rotational patterns and trends of hysteretic loops were investigated, and relationships between hysteresis features and hydrological parameters were studied. The results revealed clear differences between particulate (suspended sediment, particulate organic carbon) and dissolved (DOC, NO₃) matter transport responses. Movement of the particulate matter was attributed to surface water, as reflected in clockwise hysteresis loops, whereas dissolved matter showed, in general, counterclockwise hysteresis loops, indicating a time delay in the arrival of solutes to the stream. This could be related to subsurface flow paths for DOC and a groundwater source for NO₃. Copyright © 2013 John Wiley & Sons, Ltd.     

Distribution and accumulation of organotin species in seawater, sediments and organisms collected from a Taiwan mariculture area

The present study was undertaken to evaluate the distribution and accumulation of tributyltin (TBT) and triphenyltin (TPhT) in seawater, sediments and selected organisms from a cage mariculture area in southern Taiwan, Hsiao Liouchiou Island. Our results show that ΣOTs were found in concentrations as high as 196 ng/L in seawater collected from the sites in Pai-Sa harbor, and up 1040 ng/g dry wt. in sediments dredged from sites within Da-Fu harbor. Also, ΣOTs concentrations of 859 ng/g dry wt. were observed in the liver of cobia (Rachycentron canadum) from mariculture cages. As most published studies have focused on the acute toxicity and bioaccumulation of organotins in mussels, the effects of organotins on cobia and other marine fauna are still poorly understood. This study highlights the significance of ΣBTs accumulation in cobia, as well as in the sediments and seawater surrounding their culture facilities.     

On the significance of wind event frequency for particulate resuspension and light attenuation in coastal waters

Wind-induced resuspension of particulate matter was investigated in a shallow coastal region off southwestern Australia, chosen for its isolation from the complexity of other confounding physical processes. The site had negligible river discharge, low nutrient concentrations and was largely devoid of tidal currents. Moorings were deployed in the micro-tidal waters to measure current speed, wave parameters, backscatter, subsurface irradiance and dissolved oxygen concentration. Two contrasting sites were chosen as representative of high and low wave-energy environments. Turbulent kinetic energy, recorded by the instruments, was dominated by the wind-wave signal. During wind events, at the most exposed site, bed shear stress exceeded the critical stress required to lift and resuspend sediments. At the most enclosed site, bed shear stresses only exceeded the critical stress required to suspend less dense material such as benthic fluff. Wind-waves were found to be the dominant mechanism driving the vertical redistribution of particulate matter. Low frequency storm events and high frequency (daily) sea breezes were found to differ significantly in their retention of particulate matter suspended in the water column. Long periods of calm generally followed the passage of a storm, allowing suspended particulate matter to settle out, while consecutive daily sea breezes were more effective in holding particulate matter in suspension. Linear correlations were found between the backscatter (a proxy for suspended particulate matter), light attenuation and dissolved oxygen concentration. Approximately half the variability in dissolved oxygen concentration could be attributed to the variability in light attenuation, with a decline in concentration during wind resuspension events. Variability in dissolved oxygen concentration was interpreted as a possible indicator of the moderation of pelagic phytoplankton productivity during wind events.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

小白洋淀水-沉积物系统多环芳烃的分布、来源与生态风险

以端村小白洋淀为研究对象,利用GC-MS测定了6个样点水、悬浮物和沉积物中15种优控多环芳烃(PAHs)的含量,分析了其组成与来源特征,探讨了不同多环芳烃单体的生态风险,结果表明:(1)15种优控多环芳烃的总含量(PAH15),水相为40.1-74.0ng/L,算术均值51.0ng/L;悬浮物为2438.0-5927.0ng/g,算术均值4528ng/g;沉积物为466.9-1366.4ng/g,算术均值为755.6ng/g;与国内外有关研究相比,污染较轻,(2)三相中均以2、3环PAHs为主,其比例均高于80%;并且,从水相、悬浮物相到沉积物相,2环PAHs依次降低,3环、4环依次升高,高环检出率和含量也依次升高,(3)沉积物中多环芳烃的来源以生物质燃料(秸秆、薪材)和煤的燃烧为主,以液体化石燃料(汽油、柴油和原油)的燃烧为辅,(4)沉积物中的芴(FLO)、菲(PHE)含量在潜在生态风险效应区间低值(ERL)与中值(ERM)之间,其生态风险几率介于10%-50%之间;其他PAHs单体的含量均低于ERL,其生态风险几率均低于10%.     

Characterization of colloidal and particulate matter transported by the magela creek system,Northern Australia

The composition and amount of colloidal and suspended participate matter transported during a small flood event in Magela Creek in tropical northern Australia was investigated. The flood studied constituted approximately 3 % of the total annual flow, most (90%) of which occurred between mid-January and mid-February of the study year. Three fractions were separated from water samples using a sequential method involving a continuous flow centrifuge to separate suspended particulate matter (SPM; nominally > 1 μm) followed by hollow fibre filtration, first using a 0.1 μm filter to separate course colloidal matter (CCM; nominal size 1–0.1 μm) and then a 0–015 μm filter to separate fine colloidal matter (FCM; nominal size 0.1–0.015 μm). The SPM was predominantly inorganic (organic matter 21 %), whereas the colloidal fractions were dominantly organic matter (CCM 60%; FCM 83%). Analysis of individual particles using electron microprobe and automated image analysis indicated that the mineral fractions in both the SPM and CCM were dominated by iron-enriched aluminosilicates (including kaolinite) (72–82%) and quartz (9–10%), indicative of a highly weathered and extensively laterized catchment. Surprisingly there was very little difference in the composition of the SPM or CCM fractions during the flood event studied, which may indicate either that sediment availability was restricted following the major run-off events in January and February, or that all the sediment sources within the catchment are geochemically similar. Approximately the same amounts of particulate (20 tonne), colloidal (21 tonne) and dissolved material (17 tonne) were transported during the 25 hour period of the main flood peak; over 90% of the colloidal matter was 0.1–1.0 μm in size. These data suggest that previous estimates of the amounts of particulate (and colloidal) matter transported by Magela Creek, which were based on suspended solids measurements, may have underestimated the particulate matter load by as much as 50%. It is possible that the relatively high proportion of colloidal matter is unique to Magela Creek because coagulation and aggregation of colloidal matter to particulate matter is slow due to the very low concentations of calcium and magnesium in these waters. However, if the result is more widespread, there are important implications for the global estimates of fluvially transported particulate and dissolved materials as many of the previous studies may have underestimated the particulate load and overestimated the dissolved load.     

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).     

Inshore/offshore gradients of imposex and organotin contamination in Nassarius reticulatus (L.) along the Portuguese coast

Imposex and organotin (OT) tissue contamination of the netted whelk Nassarius reticulatus (L.) were assessed in the continental shelves around the main estuaries of the central coast of Portugal (Lisbon: Tagus estuary; Setúbal: Sado estuary) and the main coastal lagoon in the Southern of Portugal (Faro: Ria Formosa). Pollution levels were higher in areas of more intense boat traffic and shipyard activities and imposex showed a clear decreasing gradient from the estuaries to the offshore, in relation to a similar gradient of tissue contamination by tributyltin. Remarkably, imposex was extensively spread over the adjacent continental shelves of Tagus and Sado estuaries. The current work shows that TBT pollution is undoubtedly a matter of concern not only for the above estuaries where harbours are implanted but also for the adjacent continental shelves, regardless the massive dilution of contaminants that may occur in these deeper areas.     

Mercury partition in the interface between a contaminated lagoon and the ocean: The role of particulate load and composition

After having estimated the patterns of flow to the ocean and found some seasonal and tidal differences, mainly with regard to the relative importance of dissolved and particulate fractions, mercury partitioning at the interface between a contaminated lagoon and the Atlantic Ocean was investigated during four tidal cycles in contrasting season and tidal regimes. Mercury was found to be located predominantely in the particulate fraction throughout the year, contributing to its retention within the system. Seasonal conditions, variations in marine and fluvial signals and processes affecting bed sediment resuspension influenced the character and concentration of suspended particulate matter in the water column. Variation in the nature, levels and partitioning of organic carbon in the particulate fraction affected levels of particulate mercury as well as mercury partitioning. These results highlight the dominant role of suspended particulate matter in the distribution of anthropogenic mercury and reinforce the importance of competitive behavior related to organic carbon in mercury scavenging.