Brominated flame retardants in the environment of Asia-Pacific: an overview of spatial and temporal trends

In this paper, we summarize spatial and temporal trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in coastal and marine biota, and further assess human exposure to these brominated flame retardants (BFRs) in Asia-Pacific. The review is based mainly on the studies that were conducted in our laboratory and utilized samples archived in the environmental specimen bank (es-BANK) of Ehime University, Japan. The studies suggest that the target BFRs are ubiquitous in the environment of Asia-Pacific. Examination of spatial trends reveals that concentrations of these contaminants are relatively high in samples from Korea, South China and Japan. In general, the magnitude of environmental contamination by PBDEs in Asia-Pacific, as well as human exposure to these contaminants, seem to be comparable to or slightly higher than in Europe, but lower than in North America. Evaluation of temporal trends in concentrations of BFRs in marine mammals from the coastal waters of Japan and China showed drastic increase during the last 30 years. These changes in BFR levels in samples from Japan were in line with trends in production/use of the commercial formulations. Since the withdrawal of some PBDE products from the Japanese market in the 1990s, concentrations of HBCDs appear to exceed those of PBDEs, reflecting increasing usage of HBCDs over PBDEs. The increasing environmental contamination by BFRs in Chinese coastal waters indicates that contamination by BFRs has already become evident, even in developing countries. In view of the rising environmental levels and the high consumption volume of BFRs in Asia, further efforts should be made to monitor environmental contamination by these chemicals in order to identify sources and reduce emissions.     

TBT in California coastal waters: Monitoring and assessment

Butyltins were monitored at over eighty sites, primarily marinas, in surface waters and sediments of the California coast. Values of tributyltin (TBT) in marina waters ranged from 20 to 600 ppt while lower values were usually found in harbors and on the coast. The origin of the tributyltin is in its use as an antifouling agent in marine paints. In those marinas where the concentrations are greater than about 100 ppt, there is usually a conspicuous absence of native organisms, especially molluscs, which are among the most sensitive animals to the highly toxic TBT. The impact of TBT upon not-target organisms recalls the DDT episode of the 1970s. Increasing uses of TBT-containing antifouling paints in the future may have even more drastic effects on coastal organisms than those observed today. The conclusion is inescapable that TBT should be banned for use in commercially available marine paints.     

Monitoring the drastic growth of ship breaking yards in Sitakunda: a threat to the coastal environment of Bangladesh

The vast coastal and marine resources that occur along the southern edge of Bangladesh make it one of the most productive areas of the world. However, due to growing anthropogenic impacts, this area is under considerable environmental pressure from both physical and chemical stress factors. Ship breaking, or the dismantling and demolition of out-of-service ocean-going vessels, has become increasingly common in many coastal areas. To investigate the extent of ship breaking activities in Bangladesh along the Sitakunda coast, various spatial and non-spatial data were obtained, including remote sensing imagery, statistical records and published reports. Impacts to coastal and marine life were documented. Available data show that ship breaking activities cause significant physical disturbance and release toxic materials into the environment, resulting in adverse effects to numerous marine taxonomic groups such as fish, mammals, birds, reptiles, plants, phytoplankton, zooplankton and benthic invertebrates. Landsat imagery illustrates that the negatively impacted coastal area has grown 308.7 % from 367 ha in 1989 to 1,133 ha in 2010. Physicochemical and biological properties of coastal soil and water indicate substantially elevated pollution that poses a risk of local, regional and even global contamination through sea water and atmospheric transport. While damage to the coastal environment of Bangladesh is a recognized hazard that must be addressed, the economic benefits of ship breaking through job creation and fulfilling the domestic demand for recycled steel must be considered. Rather than an outright ban on beach breaking of ships, the enterprise must be recognized as a true and influential industry that should be held responsible for developing an economically viable and environmentally proactive growth strategy. Evolution of the industry toward a sustainable system can be aided through reasonable and enforceable legislative and judicial action that takes a balanced approach, but does not diminish the value of coastal conservation.     

Organotin compounds in surface sediments from seaports on the Gulf of Gda??sk (southern Baltic coast)

Sediment samples were collected in two Polish ports of international significance--the Port of Gdańsk and the Port of Gdynia (Gulf of Gdańsk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdańsk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.     

Organotins in a medium-size Mediterranean basin (the Herault River)

This study reports the first assessment of organotin pollution in the Hérault watershed, a medium size Mediterranean basin. Organotin compounds were analyzed in surface waters, wells supplying drinking water and sewage treatment plants (STPs). In surface and ground waters, a background contamination by total organotin compounds has been identified in the range of 0.51 +/- 0.02-71 +/- 2 ng(Sn) L(-1), which is of the same order of magnitude as those observed in other European areas. Organotins were systematically present in STP influents and sludge. Total or partial elimination of organotin compounds from treated wastewater was observed. STP effluents appeared nevertheless to be a non-negligible source of contamination not only of rivers but also of aquifers tapped for drinking water supply.Tributyltin concentration was higher than the maximum allowable concentration proposed by the European Commission in some surface waters and wells supplying drinking water. This could compromise the water resource and have serious and irreversible consequences for the aquatic eco-system. As it was the case for the ban of antifouling paints, a regulatory regime in decreasing point-source emissions of these harmful compounds used in household products might be applied.     

Assessment of Climate Change Effects on Canada's National Park System

To estimate the magnitude of climate change anticipated forCanada's 38 National Parks (NPs) and Park Reserves, seasonaltemperature and precipitation scenarios were constructed for 2050and 2090 using the Canadian Centre for Climate Modelling andAnalysis (CCCma) coupled model (CGCM1). For each park, we assessed impacts on physical systems, species, ecosystems andpeople. Important, widespread changes relate to marine andfreshwater hydrology, glacial balance, waning permafrost, increased natural disturbance, shorter ice season, northern andupward altitudinal species and biome shifts, and changed visitation patterns. Other changes are regional (e.g., combinedEast coast subsidence and sea level rise increase coastal erosionand deposition, whereas, on the Pacific coast, tectonic upliftnegates sea level rise). Further predictions concern individualparks (e.g., Unique fens of Bruce Peninsular NP will migratelakewards with lowered water levels, but structural regulation of Lake Huron for navigation and power generation would destroythe fens). Knowledge gaps are the most important findings. Forexample: we could not form conclusions about glacial massbalance, or its effects on rivers and fjords. Likewise, for theEast Coast Labrador Current we could neither estimate temperature and salinity effects of extra iceberg formation, nor the further effects on marine food chains, and breeding park seabirds. We recommend 1) Research on specific large knowledge gaps; 2) Climate change information exchange with protected area agencies in other northern countries; and 3) incorporating climate uncertainty into park plans and management. We discuss options for a new park management philosophy in the face of massive change and uncertainty.     

Biomarkers of environmental contaminants in the coastal waters of Estonia (Baltic Sea): effects on eelpouts (Zoarces viviparus)

The eastern Baltic Sea near the Estonian coast is heavily navigated by numerous cargo ships and oil tankers. Hundreds of accidents and oil spills happen yearly in this area. Yet, there is a lack of data concerning the distribution and effects of the environmental contaminants, especially polycyclic aromatic hydrocarbons (PAHs). Different parts of the Baltic Sea have different levels of contamination; therefore a wide range of monitoring stations in coastal areas in the Gulf of Finland and Gulf of Riga were chosen. The aim of the present research was to document the responses of chosen biomarkers of environmental contaminants in different unstudied areas of the Estonian coastal sea. During 2009 and 2010 we measured PAH metabolites, EROD activities, geno- and cytotoxicity, histology, parasites and other biomarkers from the eelpout (Zoarces viviparus), a resident benthic fish species. The results showed that fish from the Gulf of Riga emitted lower levels of fluorescence in fixed wavelength analyses (representing equivalents of PAH metabolites in bile and urine), and consistently, showed less geno- and cytotoxicity and parasite infection, higher liver somatic index (LSI) and a higher condition factor (CF) than fish inhabiting areas close to the Baltic proper and in the Gulf of Finland. The results point to the effect of long-range contaminant transportation, whether atmospheric or hydrodynamic, and also to the intensive shipping activity in international routes. This study fills the gap of knowledge in this area that has persisted until now. Nevertheless, more studies in this area on the different groups of contaminants are necessary, to specify the factors that are responsible for observed biological effects.     

Spatial and temporal distribution of tributyltin (TBT) in seawater, sediments and bivalves from coastal areas of Korea during 2001–2005

Tributyltin (TBT) concentrations were determined in seawater, sediments and bivalve samples collected from Korean coastal areas during 2001-2005, to investigate the levels and temporal variation in TBT contamination in relation to the timing of the imposition of regulations on TBT use in Korea. TBT concentrations ranged from <5.0 to 164 ng/L in seawater, from <7.0 to 9,576 ng/g dry weight in sediments, and from <7.0 to 6,296 ng/g dry weight in bivalves. The highest concentrations of TBT were found at locations close to intensive shipping traffic and industrial complexes, and the contamination at some hot spot areas was high enough to cause harmful effects on marine organisms. TBT concentrations and their occurrence in Korean coastal waters have been decreasing annually. In particular, TBT concentrations in seawater have dramatically decreased. This result is consistent with regulations and bans on the use of TBT in Korea.     

Determination of Hydrocarbons in Mussels from the Egyptian Red Sea Coast

Mussels (Brachidontes Sp.) collected in April 2000 from the Red Sea coastal of Egypt in order to determine the contamination by hydrocarbons. The study included 11 sampling stations covering about 450 Km of the Egyptian Red Sea coast for the first time. Total concentrations of 20 aliphatics (average 0.105 ng g(-1) of wet weight) and sixteen polycyclic aromatic hydrocarbons (PAHs) (average 5452 ng g(-1) of wet weight) were generally lower in comparison with those reported for some of the published surveillance and monitoring studies of coastal areas from various regions. These results suggest that the coastal area in the Red Sea of Egypt might be considered as a relatively unpolluted.     

Water Quality Modeling of Municipal Discharges from Sea Outfalls,Mumbai

The island city of Mumbai with a population of about 10 million generates about 2000 million liters per day (mld) of sewage from the seven service areas of the city sewerage network and discharges it into the adjoining west coast and the two creeks in the Arabian Sea. This has resulted in degradation of coastal water quality, contamination of the adjoining beaches and seafronts. The Municipal Corporation of Greater Mumbai has therefore, undertaken the task of delineating appropriate sewage disposal system to achieve cleaner marine ecosystem through marine outfalls at specific locations. This paper presents the results of the mathematical simulations on the impacts of discharge is-a-vis the length of the outfall and level of land treatment apriori. The results of the simulation indicate the level of bacterial pollution to be higher near the diffuser locations as compared to nearshore regions. 48 hsimulation result analysis shows that FC counts nearthe diffuser location will be in the range of 2000–8000 counts per 100 ml.     

Return period of enhanced gamma ray dose rates: regional differences observed in Japan

We estimated the return period of an increased gamma ray dose rate (Delta gamma) derived from (222)Rn progeny deposited with precipitation. The approximate probability distribution for Delta gamma followed a Hazen plot, which is an empirical plotting equation, indicating that the distribution of Delta gamma was approximated by a nearly double-exponential. The distribution of Delta gamma was well represented by the Gumbel distribution, and the return period for Delta gamma was estimated theoretically. There was a notable regional difference in the return period between the coast of the Japan Sea and the inland or Pacific coast areas: the return period for a given Delta gamma at monitoring sites on the Sea of Japan coast was 1.5 to 2.5 times shorter than that in the inland or Pacific coast areas. This variation with locality suggests that the rate of wet-deposition of (222)Rn progeny is larger at sites on the Sea of Japan coast than inland or on the Pacific coast areas. The expected return period for the maximum Delta gamma at each site was about 10 years. This estimation of the return period of Delta gamma is a novel approach to the study of environmental science in fields such as radioactivity.     

Metal contamination in water, sediment and biota from a semi-enclosed coastal area

This study identifies and quantifies the spatial variations of metal contamination in water, sediment and biota: the common cockle (Cerastoderma edule) and the Mermaid’s glove sponge (Haliclona oculata), within a heavily anthropogenically impacted semi-enclosed estuarine–coastal area with a low ability to disperse and flush contaminants (Poole Harbour, UK). The results showed that metal contamination was detected in all environmental compartments. Water was polluted with As, and Hg sediment metals were mostly within “the possible effect range” in which adverse effects occasionally occurs. Cockles had considerable concentrations of Ni, Ag and Hg in areas close to pollution sources, and sponges accumulate Cu and Zn with very high magnitude. A systematic monitoring approach that includes biological monitoring techniques, which covers all embayments, is needed, and an integrated management of the semi-enclosed coastal zones should be based on the overall hydrological characteristics of these sensitive areas and their ability to self‐restore which is different than open coastal zones.     

Establishment of a sampling strategy for the use of blue mussels as an indicator of organotin contamination in the coastal environment

The application of the Mussel Watch concept to the assessment of chemical contamination in the coastal environment is still premature, since the relationship between the physiological and ecological aspects of blue mussels and the accumulation of contaminants in their soft tissues remains unclear. We cannot yet directly estimate with known confidence the degree of chemical contamination from the levels of contaminants in the soft tissues of mussels. An understanding of the source and range of variability in the tissue concentrations of contaminants is essential, and the establishment of a biomonitoring sampling strategy to minimize the effect of identified sources of variability is required. The present study was conducted to clarify the characteristics of organotin accumulation in blue mussels under various conditions in Tokyo Bay, and to establish an optimized sampling strategy of mussels as exposure indicators of organotin contamination in Japan. It was clear that the sample number, individual size, spawning activity and vertical habitat were factors causing a variation of tissue concentration. Based on a quantitative estimation of the variability of organotin concentration in mussel tissues under various physiological and natural conditions, we suggest that a composite sample of 30 mussels (3-5 cm in shell length), collected from the infralittoral zone prior to their spawning season, is essential to reduce the variability between individuals and to obtain reproducible analytical values at a sampling site. For monitoring sites where natural blue mussels cannot be collected, an alternative method of transplanting blue mussels from a relatively clean area would be required.     

The Use of Mytilus Galloprovincialis Acetylcholinesterase and Glutathione S-Transferases Activities as Biomarkers of Environmental Contamination Along the Northwest Portuguese Coast

With the aim of using Mytilus galloprovincialis acetylcholinesterase (AChE) and glutathione S-transferases (GST) activities as biomarkers of environmental contamination in risk assessment studies along the northwest Portuguese coast, the objective of this study was to provide background information related to: (1) baseline values of these enzymatic activities both in reference and contaminated areas and their responsiveness as indicators of exposure to environmental contaminants; (2) the importance of seasonal variations of such biomarkers in M. galloprovincialis along this area. For this, the activity of these enzymes was seasonally determined in mussels collected from four sites, including a reference and three stations with different contamination sources along the referred area. Statistically significant differences on both enzymatic activities were found among the four sampling stations, at the four sampling periods. In comparison to the reference station, lower AChE and higher GST activity values were found in mussels collected in stations potentially contaminated by pesticides and domestic/industrial effluents and in mussels collected in the vicinity of an oil refinery and an industrial/mercantile harbour, respectively. The results obtained in this work highlighted the potential suitability of these biomarkers to be used as components of environmental monitoring programs in risk assessment studies along the northwest Portuguese coast. Since a seasonal variation in both enzymatic activities was found, the possible implications of such variability in the use of these enzymes as environmental biomarkers are also discussed.     

Organic contaminants and trace metals in flounder liver and sediment from the Amsterdam and Rotterdam harbours and off the Dutch coast

Organic contaminants [polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), nonylphenols], organotin compounds and trace metals (cadmium, chromium, mercury and zinc) were determined in flounder (Platichthys flesus) liver and sediment from the Amsterdam harbour (North Sea Canal) and Rotterdam harbour (Euromonding) and off the Dutch coast between the Amsterdam and Rotterdam harbour mouths in order to assess the level of contamination in these harbours and to study contamination gradients.     

Seasonal variation in physicochemical properties of coastal waters of Kalpakkam, east coast of India with special emphasis on nutrients

A study pertaining to the seasonal variation in physicochemical properties of the coastal waters was carried out at Kalpakkam coast for a period of 1 year (February 2006 to January 2007). It revealed that the coastal water was significantly influenced by freshwater input during North East (NE) monsoon and post-monsoon periods. Concentration of all the nutrients and dissolved oxygen (DO) was relatively high during the NE monsoon, whereas, salinity and chlorophyll-a (chl-a) were at their minimum level during this period. Phytoplankton production peak was observed in summer during which a typical marine condition prevailed. The present observed values of nitrate, phosphate, silicate, and turbidity are significantly high (five to ten times) compared to that of the pre-Tsunami period from this coast. Relatively low DO and chl-a concentration was noticed during the post-Tsunami period. A notable feature of this study is that though nutrient concentration in the coastal waters during post-Tsunami period has increased significantly, turbidity, the most single dominating factor, was found to adversely affect the phytoplankton production during post-Tsunami period as reflected by relatively low chl-a concentration. Thus, the post-Tsunami period may result in a change in coastal biodiversity pattern concomitant with change in coastal water quality.     

Spatial Extent of Sediment Toxicity in U.S. Estuaries and Marine Bays

Acute, laboratory toxicity tests were performed by the National Oceanic and Atmospheric Administration (NOAA) on 1543 surficial sediment samples collected during 1991 through 1997 throughout 25 estuaries and marine bays. Selected areas were sampled along the Atlantic, Gulf of Mexico, and Pacific coasts. The toxicity of each sample was determined with 10-day amphipod survival tests performed with solid-phase (bulk) sediments. Collectively, the 1543 samples tested through 1997 represented a total area of approximately 7300 km². Toxicity was observed with the amphipod survival tests in samples that represented approximately 6% of the combined area. Using similar tests conducted on samples collected in different, but overlapping, study areas, the U.S. Environmental Protection Agency (EPA) estimated that approximately 7% of the combined estuarine area sampled was toxic. Generally, toxicity was most severe in northeastern and southwestern estuaries and least prevalent in southeastern and northwestern areas. However, considerable portions of the Pacific coast have not been tested with the same methods. In tests of CYP1A enzyme induction (n=464), samples were toxic that represented about 5% of the combined study areas. Toxicity was much more widespread, however, when the results of two sub-lethal tests were analyzed. Significant results occurred in samples that represented approximately 25% and 39% of the study areas in tests of sea urchin fertilization (n=1309) and microbial bioluminescence (n=1215), respectively.     

The U.S. National biomonitoring specimen bank and the marine environmental specimen bank

The National Biomonitoring Specimen Bank (NBSB), established in 1979 at the NIST Neutron Research Facility, Gaithersburg, Maryland, was specifically designed to store environmental specimens over long periods of time (50-100 years). This bank contains specimens (e.g., human livers, marine sediments, fish tissues, mussels, oysters, human diet samples, and marine mammal tissues) collected as part of several monitoring and research programs supported by U.S. Federal agencies. In 2002, NIST completed the construction of a second environmental specimen bank facility specifically designed for supporting monitoring and research on marine environmental health issues. This facility, the Marine Environmental Specimen Bank (Marine ESB) is located at the Hollings Marine Laboratory in Charleston, South Carolina, in partnership with a U.S. Federal resource agency, two universities, and a State of South Carolina resource agency. The Marine ESB provides a resource of research specimens that are used to address questions regarding temporal and geographic trends in environmental contamination, genetic separation of populations of animals, and the health status of various types of marine animals. Specimens banked include marine mammal tissues, bird tissues, mussels, and oysters. Plans are underway to establish protocols and initiate banking procedures for other types of marine organisms and environmental materials as part of an expanded effort to support research on the health of marine biota.     

Spatial variation of potentially toxic elements in different grain size fractions of marine sediments from Gulf of Mannar, India

Marine sediments of the Gulf of Mannar (GoM), India are contaminated by potential toxic elements (PTEs) due to anthropogenic activities posing a risk to the existing fragile coral ecosystem and human health. The current study aimed to assess the distribution of PTEs (arsenic—As; cobalt—Co; copper—Cu, molybdenum—Mo; lead—Pb; and zinc—Zn) in marine sediments of different grain size fractions, viz., medium sand (710 μm), fine sand (250 μm), and clay (<63 μm) among the different coastal regions of Pamban, Palk Bay, and Rameswaram coasts of GoM, using grain size as one of the key factor controlling their concentrations. The concentrations of PTEs were measured in the different size fractions of sediment using inductively coupled plasma mass spectrophotometer. The order of accumulation of all PTEs in the three fractions was ranked as Zn > Cu > Pb > As > Co > Mo and in the three locations as Rameswaram > Palk Bay > Pamban. The concentration of PTEs in Palk Bay and Rameswaram coast was significantly different (P?<?0.05), when compared to Pamban coast. Measured geoaccumulation index (I _geo) and contamination factor (CF) indicated significant enrichment of Co and Pb from Rameswaram coast when compared to other two coasts. Although the concentration of Co was low but the measured I _geo and CF values indicated significant enrichment of this PTE in Rameswaram coast. The increased input of PTEs in the coastal regions of GoM signifies the need to monitor the coast regularly using suitable monitoring tools such as sediments to prevent further damage to the marine ecosystem.     

Fucus spiralis as monitoring tool of metal contamination in the northwest coast of Portugal under the European Water Framework Directives

Metals (Cd, Cr, Cu, Fe, Mn and Zn) in coastal seawaters and soft tissues of macroalga Fucus spiralis from the northwest coast of Portugal were determined to assess spatial variations of metal bioavailabilities and bioaccumulation factors to compare different ecological quality classifications. Both coastal seawaters and soft tissues of F. spiralis showed significant spatial variations in their metal concentrations along the coast. The macroalgae F. spiralis accumulated more efficiently Cd, Mn and Zn and showed low bioaccumulation factors to Cr, Cu and Fe. Regarding the metal guidelines of the Norwegian Pollution Control Authority, the entire northwest (NW) coast of Portugal in April 2013 should be classified as ‘class I—unpolluted’ for all metals, except in Ave for Cu (‘class II—moderately polluted’) and Cavado for Cd and Cu (‘class II—moderately polluted’), revealing the low metal bioavailabilities of these seawaters. As there were always significant positive correlations between all metals in seawaters and F. spiralis, this macroalga species was considered a suitable monitoring tool of metal contamination in the NW coast of Portugal and a useful aquatic organism to be included in the European Environmental Specimen Banks in order to establish a real-time environmental monitoring network under the European Water Framework Directives.