Assessment of TBT and organic booster biocide contamination in seawater from coastal areas of South Korea

Seawater samples from major enclosed bays, fishing ports, and harbors of Korea were analyzed to determine levels of tributyltin (TBT) and booster biocides, which are antifouling agents used as alternatives to TBT. TBT levels were in the range of not detected (nd) to 23.9 ng Sn/L. Diuron and Irgarol 1051, at concentration ranges of 35–1360 ng/L and nd to 14 ng/L, respectively, were the most common alternative biocides present in seawater, with the highest concentrations detected in fishing ports. Hot spots were identified where TBT levels exceeded environmental quality targets even 6 years after a total ban on its use in Korea. Diuron exceeded the UK environmental quality standard (EQS) value in 73% of the fishing port samples, 64% of the major bays, and 42% of the harbors. Irgarol 1051 levels were marginally below the Dutch and UK EQS values at all sites.     

A review and assessment of tributyltin contamination in the North Sea,based on surveys of butyltin tissue burdens and imposex/intersex in four species of neogastropods

It is evident from measures of butyltin tissue burdens and imposex or intersex in neogastropods that tributyltin (TBT) contamination of coastal waters and open parts of the North Sea is now low. It has been declining for at least the past decade. This is probably due to two measures. First, regulations prohibiting the use of TBT-based paints on small boats and fish farms have reduced inputs of TBT from these sources so that they are now negligible (except possibly where the regulations are flaunted). Second, there is evidence from sites, where commercial vessels are the sole source of TBT, that the adoption of TBT SPC paints has been effective in reducing environmental levels of these contaminants. However, poor dockyard practices, allowing TBT-contaminated wastes, including paint flakes, to accumulate in sediments have left a legacy of hot-spots of contamination in some ports. The impact is localised so that TBT contamination is low in coastal areas immediately adjacent to ports.     

Continuing observation of disturbed reproductive cycle and ovarian spermatogenesis in the giant abalone, Haliotis madaka from an organotin-contaminated site of Japan

Histological examination of gonads as well as chemical analysis of organotin compounds in tissues of the giant abalone, Haliotis madaka, was conducted to evaluate continuing endocrine disruption in abalone populations in Japan. Abalone specimens were collected from two different areas, Tsushima as a reference site and Jogashima as a site representative of declining abalone populations where serious organotin contamination had been observed, each month from January 1998 to March 1999. Scores were given to the development stages of reproductive cells in the ovary and testis. The degree of sexual maturation was evaluated by calculating the mean value of a histogram of these scores for the reproductive cells of each abalone. The temporal variations in degree of sexual maturation showed that female and male abalone from Tsushima matured synchronously, while those from Jogashima did not, which were similar to results of the previous study during September 1995–November 1996. Approximately 19% of the female abalone from Jogashima were masculinized with an ovo-testis, which was also similar to the result of the previous study. The masculinization of female abalone is reported to be induced by tributyltin (TBT) and triphenyltin (TPhT) from antifouling paints. Concentrations of the sum of butyltins (TBT, dibutyltin (DBT) and monobutyltin (MBT): ΣBTs) and the sum of phenyltins (TPhT, diphenyltin (DPhT) and monophenyltin (MPhT): ΣPhTs) in the muscle of abalone from Jogashima (n = 73) of 7.8 ± 9.0 ng/g wet wt. and 4.5 ± 6.8 ng/g wet wt., respectively, were significantly higher than those from Tsushima (n = 87) of 4.7 ± 4.9 ng/g wet wt. and 0.8 ± 1.7 ng/g wet wt., respectively (p < 0.05 for ΣBTs; p < 0.001 for ΣPhTs), although concentrations of TBT and TPhT in the muscle of abalone from Jogashima (n = 73) of 2.2 ± 2.5 ng/g wet wt. and 5.8 ± 5.1 ng/g wet wt., respectively, were insignificantly and significantly higher than those from Tsushima (n = 87) of 0.4 ± 0.6 ng/g wet wt. and 0.5 ± 0.9 ng/g wet wt., respectively, (p > 0.05 for TBT; p < 0.001 for TPhT). Thus, endocrine disruption as well as contamination by organotins in the giant abalone from Jogashima is still persisting.     

Continuing observation of disturbed reproductive cycle and ovarian spermatogenesis in the giant abalone, Haliotis madaka from an organotin-contaminated site of Japan

Histological examination of gonads as well as chemical analysis of organotin compounds in tissues of the giant abalone, Haliotis madaka, was conducted to evaluate continuing endocrine disruption in abalone populations in Japan. Abalone specimens were collected from two different areas, Tsushima as a reference site and Jogashima as a site representative of declining abalone populations where serious organotin contamination had been observed, each month from January 1998 to March 1999. Scores were given to the development stages of reproductive cells in the ovary and testis. The degree of sexual maturation was evaluated by calculating the mean value of a histogram of these scores for the reproductive cells of each abalone. The temporal variations in degree of sexual maturation showed that female and male abalone from Tsushima matured synchronously, while those from Jogashima did not, which were similar to results of the previous study during September 1995–November 1996. Approximately 19% of the female abalone from Jogashima were masculinized with an ovo-testis, which was also similar to the result of the previous study. The masculinization of female abalone is reported to be induced by tributyltin (TBT) and triphenyltin (TPhT) from antifouling paints. Concentrations of the sum of butyltins (TBT, dibutyltin (DBT) and monobutyltin (MBT): ΣBTs) and the sum of phenyltins (TPhT, diphenyltin (DPhT) and monophenyltin (MPhT): ΣPhTs) in the muscle of abalone from Jogashima (n = 73) of 7.8 ± 9.0 ng/g wet wt. and 4.5 ± 6.8 ng/g wet wt., respectively, were significantly higher than those from Tsushima (n = 87) of 4.7 ± 4.9 ng/g wet wt. and 0.8 ± 1.7 ng/g wet wt., respectively (p < 0.05 for ΣBTs; p < 0.001 for ΣPhTs), although concentrations of TBT and TPhT in the muscle of abalone from Jogashima (n = 73) of 2.2 ± 2.5 ng/g wet wt. and 5.8 ± 5.1 ng/g wet wt., respectively, were insignificantly and significantly higher than those from Tsushima (n = 87) of 0.4 ± 0.6 ng/g wet wt. and 0.5 ± 0.9 ng/g wet wt., respectively, (p > 0.05 for TBT; p < 0.001 for TPhT). Thus, endocrine disruption as well as contamination by organotins in the giant abalone from Jogashima is still persisting.     

The distribution of acid-volatile sulfide and simultaneously extracted metals in sediments from a mangrove forest and adjacent mudflat in Zhangjiang Estuary, China

The distribution of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) were studied in sediments collected from mangrove forest, forest fringe and adjacent mudflat in the Zhangjiang Estuary, China. The aim was to examine the spatial distribution of AVS and SEM in sediments of the Estuary and determine the influence of mangrove trees on AVS and SEM concentrations in the sediments. The results indicated that AVS concentrations in forest sediments were significantly lower than those in mudflat sediments. There was a significant positive correlation between AVS values and moisture contents in forest sediments, while LOI played an important role in AVS concentrations of mudflat sediments. In the forest sediment core, the peak value of AVS appeared deeper in the sediment profile compared to it appeared in the mudflat core. The distribution of SEM showed different trends from that of AVS, and potential toxicity existed in the upriver forest sediments.     

Sedimentary record of polycyclic aromatic hydrocarbons in a sediment core from the Pearl River Estuary, South China

Owing to the hydrodynamic and sedimentation conditions, the western shoal of the Pearl River Estuary (PRE) is known to be an important sink of terrestrial substances including particle-associated pollutants from the Pearl River Delta (PRD) region. In this study, we report the sedimentary record of polycyclic aromatic hydrocarbons (PAHs) during the 20(th) century in a sediment core from the western shoal of the PRE. The summation PAH concentration ranged from 59 ng g(-1) to 330 ng g(-1) in the core with two distinct peaks. An initial increase of summation PAH concentration was found around the 1860s. The amounts of PAHs remained relatively constant for roughly 100 years, followed by the first peak in the 1950s. Then, there was a decrease in PAH concentration and flux in the 1960s and 1970s. A sharp increase of PAH concentration was observed in the early 1980s with a maximum concentration in the 1990s. The PAH diagnostic ratios indicated that the PAHs in the sediment core were mainly of pyrolytic origin, and that atmospheric deposition and land runoff may serve as the important pathways for PAHs input to the sediment. The Gross Domestic Product (GDP) was used as an index of socioeconomic development in the PRD region, which was correlated positively with the changes of PAH concentration and flux in the sediment core. The rapid increase in vehicle numbers and energy consumption in the region in the last two decades may have contributed to the rapid PAH increase since the early 1980s. The results clearly elucidated the impact of regional economic development on the estuarine environment.     

Seasonal and spatial characteristics of seawater and sediment at Youngil Bay, southeast coast of Korea

The seasonal geochemical characteristics of the seawater and sediments and the major factors causing heavy metal contamination were investigated at the Youngil bay and the Hyungsan river estuary in the Southeast Coast of Korea, where a world-scale steel-industry complex (Pohang iron and steel industrial complex, POSCO) is located. The seasonal and spatial distribution characteristics of temperature, dissolved oxygen (DO), pH, and nutrients of the seawater were studied at 45 fixed stations, especially focusing on the river mouth area. Sediments at 27 stations were examined during winter and summer to determine the major controlling factors for the distribution of metals, using correlation matrix and R-mode factor analyses, and to evaluate the pollution status, using the modified geoaccumulation (I(geo)(')) index. Temperatures for the effluent from the POSCO located at the Hyungsan river mouth were 2-3 degrees C higher compared to other sampling areas, due to the thermal discharge from the POSCO. The DO concentration of the surface water at the Pohang old port was as low as 2-4 mg/L. In spring, the DO value at the Hyungsan river mouth was higher than 12 mg/L, by the mass multiplication of phytoplanktons at the river mouth where seawater temperature and nutrients concentrations were relatively high, resulting in the pH value of higher than 8.3. The nitrogen to phosphorus (N/P) ratios at the river mouth were 20-150 times higher compared to other areas, implying that the nitrogen loading into this semi-enclosed bay is significantly higher than phosphorus and the major nitrogen sources are not only the domestic sewage from the city but the industrial wastewater from the POSCO and other steel factories nearby. The phosphorus concentrations at the Pohang old port were shown 3-10 times higher than those at other stations, due to the inflow of pollutants generated from the nearby ships anchoring and the release of phosphate from the bottom sediment. Results from the sediment analysis showed that the major controlling factors for the distribution pattern of each metal are grain size and organic carbon (C(org)) content. Based on the factor analysis, Al, Fe, Cr, Li, and Pb were shown strongly correlated with the mean grain size (Mz), whereas Cd, Cu, Zn, and Sn with the C(org) content. Results from the fractionation of the sedimentary metals into lattice and labile fractions to characterize the mobility of sediment metals showed that the mineral lattice fraction was high in the order of Al=K>Cr>Li>Sr>Fe, while the labile fraction, which might be released to the overlying water, was in the order of Pb>Zn>Cd>Cu>Ca>Sn. Evaluation of the sediment pollution status by applying (I(geo)(')) of 13 metals showed Cd, Cu, and Zn as high as 1-3 range at the old port. Even though the overall marine pollution mainly by the world-class steel industrial complex in this semi-enclosed bay area studied does not currently pose a serious threat, due to the seawater circulation and the large influx of river discharge, the countermeasures to implement the sediments concentrated with heavy metals, especially at the old port with no seawater circulation, are still warranted for this coastal water environment.     

Physico-chemical and biological sediment properties determining erosion resistance of contaminated riverine sediments – Temporal and vertical pattern at the Lauffen reservoir/River Neckar, Germany

In order to contribute to a reliable, easy-to-handle and economically viable erosion risk assessment of contaminated riverine sites, the present study aims to implement master-variables best characterising the sediment stability. Thus, a wide range of sediment properties was related to the critical shear stress for mass erosion, determined in the SETEG (Stroemungskanal zur Ermittlung der tiefenabhaengigen Erosionsstabilitaet von Gewaessersedimenten) pressurised channel, with special emphasis on vertical and temporal gradients in the Lauffen reservoir on the River Neckar. Over the course of 1 year, positive impacts of some macrofauna species and benthic diatoms on the sediment stability were detected for the sediment surface (0.5 cm). However, a high seasonal variability of biological parameters caused varying relations with erosion resistance in the upper sediment layers as shown for the colloidal carbohydrates. Considering only deeper sediment layers (5–35 cm), a more general pattern could be revealed with correlations between the critical shear stress and single sediment properties such as depth, grain size, total organic carbon (TOC), cation exchange coefficient (CEC), carbohydrates and proteins. Firstly, the influence of physico-chemical and biological properties on erosion resistance became evident, even over depths at 0–35 cm. Secondly, inter-particle forces are most important for erosion resistance. These are enhanced in fine-grained sediment layers, offering high binding capacities but also strengthened by polymeric substances permeating the void space and coating particles. These covariance patterns of sedimentological and biological parameters are addressed by multivariate statistical tests (principal component analysis), resulting in a higher magnitude of the correlation coefficient between critical shear stress and the master-variables in main component II (polymeric substances, grain size, TOC, CEC; R=0.77) compared to single correlations.     

Evaluation of River Water Quality Simulations at a Daily Time Step – Experience with SWAT in the Axe Catchment,UK

The Water Framework Directive (WFD) was established for the protection of surface waters (rivers, lakes, transitional and coastal waters) and ground waters in the European Union. The main environmental objective is to achieve and maintain a good status for all waters by the target date of 2015. Models which are able to address the majority of environmental objectives are proposed within the WFD to inform the management changes required to meet current water policy goals. The use of the Soil and Water Assessment Tool (SWAT) catchment model is widespread throughout the world, especially to support river basin management as required by the WFD. This paper provides a critical evaluation of the use of the model by placing model performance in the Axe catchment, UK, in the context of international performance of the model. Within the constraints of the available data, SWAT represents hydrology, sediment and ortho‐phosphorus concentration well for this heterogeneous catchment, but the representation of daily nitrogen concentration dynamics is poor. Temporal aggregation of model outputs from daily to monthly improved the performance metrics for all the river outputs, including nitrate. Wider review of SWAT studies showed widespread reporting of monthly performance metrics within the SWAT studies, despite the model operating at a daily time step. Poor performance for nitrate identified in this current study may be a significant factor in the choice to not report daily results. This demonstrates the importance of ascertaining the reasons for the use of temporal aggregation in modelling studies.     

Sediment characteristics and macrofauna distribution along a human-modified inlet in the Gulf of Oristano (Sardinia, Italy)

We studied the spatial variability and within-year temporal changes in hydrological features, grain size composition and chemical characteristics of sediments, as well as macrofaunal assemblages, along a heavily modified inlet in the Gulf of Oristano (western Sardinia, Italy). The inlet connects the Cabras lagoon to the gulf through a series of convoluted creeks and man-made structures, including a dam and fish barriers built in the last three decades. Sediments were muddy and mainly composed of the "non-sortable" fraction (i.e., <8 microm particle size) in all four areas investigated: Lagoon, Creeks, Channel and Seaward. Along the inlet, however, the ratio between the <8 microm and the 8-64 microm fractions was highest in Creeks and Channel, between the fish barriers and the dam, suggesting impaired hydrodynamics. Consistently, steep gradients in water salinity, temperature and dissolved oxygen concentrations were found in proximity to the fish barriers. The whole inlet was characterized by a major organic enrichment of sediments, with up to an annual mean of 33.6% of organic matter and 11.7% of total organic carbon in Seaward due to the presence of seagrass leaf litter. Acid-volatile sulphide and chromium-reduced sulphur concentrations were highest throughout the year in Seaward and Lagoon, respectively, with a peak in summer. Consistently, the whole inlet supported low structured macrofaunal assemblages dominated by few opportunist species, with a relatively lower diversity in Lagoon throughout the year and the highest abundances in Seaward in summer. We infer that the presence of artificial structures along the inlet, such as fish barriers and the dam, impair the lagoon-gulf hydrodynamics, sediment exchange and animal recruitment and colonization. We suggest that the removal of these structures would favour water renewal in the Cabras lagoon, but would also increase the outflow of organic C-bonding fine particles into the gulf with serious consequences for Posidonia oceanica and Cymodocea nodosa seagrass meadows. We conclude that all possible consequences of such initiatives should be carefully considered before any action is taken.     

Assessment of future water provisioning and sediment load under climate and LULC change scenarios in a peninsular river basin,India

Assessment of the impact of changes in climate and land use and land cover (LULC) on ecosystem services (ES) is important for planning regional-scale strategies for sustainability and restoration of ES. The Upper Narmada River Basin (UNRB) in peninsular India has undergone rapid LULC change due to recent agricultural expansion. The impact of future climate and LULC change on ES in the UNRB is quantified and mapped using the Integrated Valuation of Ecosystem Services and Tradeoffs (InVEST 3.3.0) tool. Our results show that water yield is projected to increase under climate change (about 43% for representative concentration pathway 4.5 for 2031–2040), whereas it is projected to decrease under the LULC change scenario. Sediment export is projected to increase (by 54.53%) under LULC change for 2031–2040. Under the combined effect of climate and LULC change, both water yield and sediment export are expected to increase. Climate change has a greater impact on projected water yield than LULC change, whereas LULC has greater impact on sediment export. Spatial analysis suggests a similar trend of variation in relative difference (RD) of ES in adjacent sub-basins. The quantified changes in ES provisioning will benefit future land management, particularly for operation of the Rani Avanti Bai Sagar Reservoir downstream of the UNRB.     

Impact of seasonal variations in hydrological stresses and spatial variations in geologic conditions on a TCE plume at an industrial complex in Wonju,Korea

Spatial and temporal variations in a trichloroethylene (TCE) plume at an industrial complex in Wonju, Korea, were examined based on hydrogeological data and seven rounds of groundwater quality data collected over a year. The site has considerable vertical heterogeneities; the top layer of soil is covered by impermeable paving material at several locations, followed by a series of reclaimed or residual soil layers, and with weathered rocks to the crystalline biotite granite at the bottom. Areal heterogeneity in the surface conditions plays an important role in controlling groundwater recharge. The heterogeneity structure is influenced by complex surface conditions paved with asphalt and concrete. Owing to the presence of limited recharge area and concentrated summer precipitation events, the effects of seasonal variations on groundwater hydraulics tend to diminish with distance from the recharge area. This result was established by analysing the influence of the contrasting surface recharge conditions between the near‐source zone and the far zone, and the seasonally concentrated precipitation on the transport patterns of a TCE plume. In addition, variations in the plume's downstream contaminant flux levels were also analysed along a transect line near the source zone. The results show that the general tendency of the TCE plume contaminant concentration and mass discharges were reproducible if we account for seasonal recharge variations and the associated changes in the groundwater level. During recharge events, the TCE concentration variations appear to be influenced by leaching of the residual dense non‐aqueous‐phase liquid (DNAPL) TCE trapped in the unsaturated zone. This result shows that seasonal variations in contaminant plume near the source zone is inevitable at this site, and that these variations indicate the presence of residual DNAPL at or above the water table, at least in some isolated locations. Copyright © 2011 John Wiley & Sons, Ltd.     

The phosphoric acid leak from the wreck of the MV Ece in the English Channel in 2006: Assessment with a ship of opportunity, an operational ecosystem model and historical data

This study evaluates the ship of opportunity (Ferrybox) concept for both sustained monitoring of UK shelf sea waters and numerical model validation. Release of phosphate from the wreck of a chemical tanker (MV Ece) in the western English Channel (49.73 degrees N, 3.25 degrees W) in March 2006 is used to demonstrate the importance of sustained observations in decision support systems and policy development. The Ferrybox system continuously collects sea surface (5m) data from a suite of autonomous electronic sensors installed on a passenger ferry operating year-round between Portsmouth (UK) and Bilbao (Spain). The detection of anomalously high concentrations of phosphate (1.54mmolm(-3), four times the usual level) and onset of phytoplankton growth close to the wreck site in March 2006 was placed in the context of multiple years of measurements (phosphate, nitrate, silicate and chlorophyll) collected from the Ferrybox system (2003-2006) and the long-term time series station E1 (50.03 degrees N, 4.65 degrees W, 1930-1987) in the English Channel. With regard to decision support, release of phosphate from the tanker is unlikely to pose a threat as phytoplankton growth at the end of winter is not unusual in this region and dissolved inorganic nitrogen rather than phosphate (DIN:DIP=10-18) is likely to ultimately limit algal growth in spring 2006. With regard to policy development, the Oslo and Paris (OSPAR) commissions recommendation of sampling every three years in "non-problem areas" is likely to provide statistically inadequate data, given the interannual and decadal variability identified in the Ferrybox and E1 data: the Ferrybox data show that oceanic winter nutrient concentrations varied by 35-50% between 2003/2004 and 2005/2006 due to deeper mixing of water off-shelf in early 2005/2006 and comparisons between the Ferrybox and E1 years show that the western English Channel is currently experiencing a low in phosphate concentrations similar to those in the 1960s. The importance of Ferrybox data in evaluating the reliability of predictive operational models needed in decision support is also demonstrated, by highlighting both strengths and weaknesses in a state-of-the-art ecosystem model designed for UK shelf waters.