Organotins in the sediments of the Zuari estuary, west coast of India

Industrial use of organotins such as butyltins and phenyltins has increased several folds during the last two decades. Butyltins and phenyltins are synthetic, multipurpose chemicals, which have been extensively used in marine antifouling paints. They have been known to be extremely poisonous to mollusc fishery resources (oysters, clams, etc.). Contamination of Zuari estuary sediments was assessed by quantitative determination of butyltins and phenyltins by using GC-MS using the electron ionization mode. Butyltins predominated in the whole area over phenyltins. Butyltins contributed about 70-90% of the organotins in general. The concentration of butyltins in sediments ranged from 20 to 7621 ng Sn/g. The concentration of phenyltins in sediments ranged from 0 to 46 ng Sn/g. Degradation indices for butyltins and phenyltins were calculated. The Butyltin degradation index (BDI) for the Zuari sediments ranged from 0 to 2.7 indicating a lot of fresh input of butyltins in the estuary and a lower degradation rate. The phenyltin degradation index (PhDI) ranged from 1 to 10 implying that different processes were prevalent at different stations. The observed organotin levels in the Zuari estuary indicate some highly localized areas of contamination which are severe enough to cause harmful effects on marine flora and fauna. Therefore, there is a need to regulate the use of butyltins and phenyltins as biocides in marine antifouling paints.     

Organotin pollution in China: an overview of the current state and potential health risk

In recent years, considerable amounts of organotin compounds have entered the environment due to the wide industrial applications in China. Organotins were found in various environmental media. An overview of organotin contamination and distribution in China from various environmental samples, including waters and sediments, is presented to better understand the current state of organotin pollution in China and to improve environmental monitoring and management of organotin contamination. Exposure to organotin contaminated water and sediments induces accumulation of organotins in molluscs and biological effects such as imposex. Potential harmful effects on human health may also result from consumption of contaminated seafoods. Detailed information on distribution, impacts and assessment of risk to human health and marine ecosystems is discussed and monitoring of TBT using biomarkers is described. This review highlights the serious organotin contamination of coastal cities in China and emphasizes the need for long-term monitoring and the development of an effective regulatory program.     

Implications of the ban on organotins for protection of global coastal and marine ecology

Organotin-based antifouling paints are highly effective against most fouling organisms, and their application results in a large amount of savings for the shipping industry. On the other hand, TBT (tributyltin) in antifouling paints is described as the most toxic substance ever introduced into the marine environment. Consequential environmental impacts of TBT led to its regulation in many countries, although concerns were raised regarding the complete prohibition of organotin-based compounds in antifouling paints. Serious concerns were also raised regarding the complete banning of organotins. After long deliberations, the AFS Convention (convention to control the use of harmful antifouling systems on ships) was adopted on 5 October 2001. The Convention, which prohibits the use of harmful organotins in antifouling paints used on ships, will enter into force on 17 September 2008. In view of the concerns raised against the prohibition of organotin-based compounds in antifouling paints, this paper focuses on a review of the AFS Convention, with a gap analysis on the difficulties in implementation of the Convention. It also offers some recommendations for improved policies.     

Conceptual issues in designing a policy to phase out metal-based antifouling paints on recreational boats in San Diego Bay

In marine areas throughout the world where recreational boats are densely located, concentrations of copper in the water are being found to be in excess of government standards, due to the hull coatings used on these boats. Copper-based hull coatings are intended to be antifouling in that they retard the growth of algae, barnacles and tubeworms; but alternatives exist that can eliminate the harm that copper contamination does to marine organisms. A variety of policy options are available to mandate or provide economic incentives to switch to these less harmful alternatives. This paper puts forth a conceptual framework for thinking about how to design and evaluate alternative policies to transition to nontoxic boat hulls, drawing from the authors' experience designing a policy for use in San Diego Bay. Many of the issues raised are broadly applicable to environmental problems where the solution involves a large-scale replacement of durable consumer goods.     

Characterization of the pesticide chlordane in estuarine river sediments

Sediments are increasingly recognized as both carrier and potential source of contaminants in aquatic environments. This study investigated the characteristics and spatial distribution of total chlordane and its three most abundant compounds, including alpha-chlordane, gamma-chlordane, and trans-nonachlor, in sediments from the Cedar and Ortega rivers, Florida, USA, using geographic information system (GIS)-based kriging analyses and field measurements. Kriging analysis showed that two areas, one from the Cedar River area and the other from the northern end of the Ortega River area, were contaminated. The maximum concentrations of total chlordane, gamma-chlordane, alpha-chlordane, and trans-nonachlor in the sediments were, respectively, 101.8, 20.1, 26.3, and 19.2 microg/kg. A plot of total organic carbon (TOC)-normalized chlordane concentrations showed that effects of grain size on sediment chlordane contamination were negligible. A principal axis analysis further revealed that a linear correlation existed between alpha-chlordane and total chlordane as well as between gamma-chlordane and total chlordane, whereas no correlation existed between trans-nonachlor and total chlordane. Comparison of total chlordane concentration with Florida Sediment Assessment Guidelines showed that the Cedar River and the northern end of the Ortega River had total chlordane concentrations above the probable effect level (4.79 microg/kg), which could pose a potential risk to aquatic life.     

A Risk-Based Predictive Tool to Prevent Accidental Introductions of Nonindigenous Marine Species

Preventing the introduction of nonindigenous species (NIS) is the most efficient way to avoid the costs and impacts of biological invasions. The transport of fouling species on ship hulls is an important vector for the introduction of marine NIS. We use quantitative risk screening techniques to develop a predictive tool of the abundance and variety of organisms being transported by ocean-going yachts. We developed and calibrated an ordinal rank scale of the abundance of fouling assemblages on the hulls of international yacht hulls arriving in New Zealand. Fouling ranks were allocated to 783 international yachts that arrived in New Zealand between 2002 and 2004. Classification tree analysis was used to identify relationships between the fouling ranks and predictor variables that described the maintenance and travel history of the yachts. The fouling ranks provided reliable indications of the actual abundance and variety of fouling assemblages on the yachts and identified most (60%) yachts that had fouling on their hulls. However, classification tree models explained comparatively little of the variation in the distribution of fouling ranks (22.1%), had high misclassification rates (∼43%), and low predictive power. In agreement with other studies, the best model selected the age of the toxic antifouling paint on yacht hulls as the principal risk factor for hull fouling. Our study shows that the transport probability of fouling organisms is the result of a complex suite of interacting factors and that large sample sizes will be needed for calibration of robust risk models.     

Spatial distribution of DDT in sediments from estuarine rivers of central Florida

Sediments may act as both a carrier for and a potential source of contaminants such as toxic organics in aquatic environments. This study investigated the spatial distribution of the pesticide DDT [1,1, 1-trichloro-2,2-bis(p-chlorophenyl)ethane] in sediments from the Cedar and Ortega Rivers located in the lower St. Johns River basin, Florida, USA, using field measurements and three-dimensional kriging analysis. High DDT concentrations were found near the junction of the Cedar and Ortega Rivers and at the north end of the Ortega River in the upper 0.5 m of the sediments, indicating that the sediment was enriched with DDT in the top layer although use of this chlorinated compound was banned in 1972. Further study revealed that the influence of sediment grain size or texture on DDT contamination was negligible in this river system and no linear correlations existed among DDT and its metabolites such as DDD [1,1-dichloro-2,2-bis(p-chlorophenyl)ethane] and DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene]. Comparison of three-dimensional distribution of DDT content to the Florida sediment quality assessment guideline or probable effect level (PEL) showed several "hot spots" in the Ortega River sediments, where DDT contents exceeded the PEL value of 4.78 microg kg(-1). Such contamination may pose a significant hazard to aquatic life.     

Aquatic organotin pollution in Taiwan

The current status of aquatic organotin pollution in Taiwan is reviewed. In freshwater sediments and biota, especially in rice-field related habitats, phenyltins (PTs) were dominant among the organotin pollutants, whereas butyltins (BTs) were usually predominant in marine environments. Among the marine habitats, contamination levels were found to be in the descending order of harbour and estuary>fish cultural site>coastal>offshore>coral reefs. Imposex snails were observed in all the sampling years (1990-2003). Meanwhile, organotin concentrations were greater in winter than those in summer, whereas proportions of PTs were much higher in summer than in winter. Due to the lack of continuous monitoring data, the effectiveness of the ban on TPT usage in agriculture in 1999 and the prohibition of TBT use on small boats in 2003 is still not known.     

Spray deposition of two insecticides into surface waters in a South African orchard area

Drift from pesticide spray application can result in contamination of nontarget environments such as surface waters. Azinphos-methyl (AZI) and endosulfan (END) deposition in containers of water was studied in fruit orchards in the Western Cape, South Africa. Additionally, attention was given to the contamination in farm streams, as well as to the resulting contamination of the subsequent main channel (Lourens River) approx. 25 km downstream of the tributary stream inlets. Spray deposit decreased with increasing distance downwind and ranged from 4.7 mg m(-2) within the target area to 0.2 mg m(-2) at 15 m downwind (AZI). Measured in-stream concentrations of both pesticides compared well with theoretical values calculated from deposition data for the respective distances. Furthermore, they were in the range of values predicted by an exposure assessment based on 95th-percentile values for basic drift deposition (German Federal Biological Research Centre for Agriculture and Forestry [BBA] and USEPA). Pesticide deposition in the tributaries was followed by a measurable increase of contamination in the Lourens River. Mortality of midges (Chironomus spp.) exposed for 24 h to samples obtained from the AZI trials decreased with decreasing concentrations (estimated LC50 from field samples = 10 microg L(-1) AZI; lethal distance: LD50 = 13 m). Mortality in the tributary samples averaged 11% (0.5-1.7 microg L(-1) AZI), while no mortality was discernible in the Lourens River samples (0.041 microg L(-1)). The sublethal endpoint failure to form tubes from the glass beads provided was significantly increased at all sites in comparison with the control (analysis of variance [ANOVA], Fisher's protected least significant difference [PLSD], p < 0.01).     

Sediment Quality Assessment in the Gulf of Gdańsk (Baltic Sea) Using Complementary Lines of Evidence

Sediments from Polish coastal environments were classified by a quality assessment approach that took into account trace metal and organic micropollutant concentrations, grain-size distribution, and organic carbon content. Generally, no benthic organisms were found at sites where sediments were classified as heavily polluted. However, areas characterized by a moderate contamination showed a variable composition of the benthic community and changing bioaccumulation patterns; therefore, no single species found in the Gulf of Gdańsk could be considered representative of the whole benthic environment. Although sediment monitoring must be considered a suitable tool to detect hot-spot pollution areas in coastal and inland waters, it should be complemented by bioaccumulation measurements to evaluate the actual risk posed by contaminants to benthic organisms. This “biological information” allows a better appreciation of the real benthic infaunal community exposure to chemicals and can usefully complement the existing sediment quality guidelines.     

Bioluminescent bacteria as indicators of chemical contamination of coastal waters

The ratio of bioluminescent to total bacteria (bioluminescent ratio, BLR) as an indicator of a variety of types of anthropogenic contamination of estuarine ecosystems was evaluated through a series of laboratory and field studies. Laboratory studies indicated that the BLR of natural bacterioplankton communities was proportionally reduced in the presence of a number of contaminants including diesel fuel and saltmarsh sediments co-contaminated with mercury and polychlorinated biphenyls (PCBs). Bioluminescent ratio inhibition was observed after short-term exposure to a contaminant suggesting a physiological rather than a population response of native microbial communities. Simulated eutrophication did not suppress the BLR. Field observations of the BLR were conducted weekly for a 2-yr period in the Skidaway River estuary, Georgia, USA. These observations revealed considerable seasonal variability associated with the BLR. Bioluminescent ratios were highest during the summer (25 +/- 15%), lower in the fall (6 +/- 5%) and spring (3 +/- 2%), and near zero during the winter. Although the BLR was not significantly correlated to salinity at a single site (Skidaway River estuary), the BLR was significantly correlated with salinity when sites within the same estuary system were compared (r2 = 0.93). Variation in BLR was not correlated to standard bacteriological indicators of water quality including total and fecal coliform bacteria. Comparison of the BLR from impacted and pristine estuarine sites during the fall suggested that anthropogenically impacted sites exhibited lower BLR than predicted from salinity versus BLR relationships developed in pristine systems. These observations suggest that the BLR could be used as a simple and reliable initial indicator of chemical contamination of estuarine systems resulting from human activity.     

Optimal Environmental Management Strategy and Implementation for Groundwater Contamination Prevention and Restoration

An innovative management strategy is proposed for optimized and integrated environmental management for regional or national groundwater contamination prevention and restoration allied with consideration of sustainable development. This management strategy accounts for availability of limited resources, human health and ecological risks from groundwater contamination, costs for groundwater protection measures, beneficial uses and values from groundwater protection, and sustainable development. Six different categories of costs are identified with regard to groundwater prevention and restoration. In addition, different environmental impacts from groundwater contamination including human health and ecological risks are individually taken into account. System optimization principles are implemented to accomplish decision-makings on the optimal resources allocations of the available resources or budgets to different existing contaminated sites and projected contamination sites for a maximal risk reduction. Established management constraints such as budget limitations under different categories of costs are satisfied at the optimal solution. A stepwise optimization process is proposed in which the first step is to select optimally a limited number of sites where remediation or prevention measures will be taken, from all the existing contaminated and projected contamination sites, based on a total regionally or nationally available budget in a certain time frame such as 10 years. Then, several optimization steps determined year-by-year optimal distributions of the available yearly budgets for those selected sites. A hypothetical case study is presented to demonstrate a practical implementation of the management strategy. Several issues pertaining to groundwater contamination exposure and risk assessments and remediation cost evaluations are briefly discussed for adequately understanding implementations of the management strategy.     

Use of Integrated Landscape Indicators to Evaluate the Health of Linked Watersheds and Coral Reef Environments in the Hawaiian Islands

A linkage between the condition of watersheds and adjacent nearshore coral reef communities is an assumed paradigm in the concept of integrated coastal management. However, quantitative evidence for this "catchment to sea" or "ridge to reef" relationship on oceanic islands is lacking and would benefit from the use of appropriate marine and terrestrial landscape indicators to quantify and evaluate ecological status on a large spatial scale. To address this need, our study compared the Hawai'i Watershed Health Index (HI-WHI) and Reef Health Index (HI-RHI) derived independently of each other over the past decade. Comparisons were made across 170 coral reef stations at 52 reef sites adjacent to 42 watersheds throughout the main Hawaiian Islands. A significant positive relationship was shown between the health of watersheds and that of adjacent reef environments when all sites and depths were considered. This relationship was strongest for sites facing in a southerly direction, but diminished for north facing coasts exposed to persistent high surf. High surf conditions along the north shore increase local wave driven currents and flush watershed-derived materials away from nearshore waters. Consequently, reefs in these locales are less vulnerable to the deposition of land derived sediments, nutrients and pollutants transported from watersheds to ocean. Use of integrated landscape health indices can be applied to improve regional-scale conservation and resource management.     

Determining the native/non-native status of newly discovered terrestrial and freshwater species in Antarctica - current knowledge, methodology and management action

Continental Antarctic terrestrial and freshwater environments currently have few established non-native species compared to the sub-Antarctic islands and other terrestrial ecosystems on Earth. This is due to a unique combination of factors including Antarctica's remoteness, harsh climate, physical geography and brief history of human activity. However, recent increases in national operator and tourism activities increase the risk of non-native propagules reaching Antarctica, while climate change may make successful establishment more likely. The frequency and probability of human-assisted transfer mechanisms appear to far outweigh those of natural propagule introductions by wind, water, birds and marine mammals. A dilemma for scientists and environmental managers, which is exacerbated by a poor baseline knowledge of Antarctic biodiversity, is how to determine the native/non-native status of a newly discovered species which could be (a) a previously undiscovered long-term native species, (b) a recent natural colonist or (c) a human-mediated introduction. A correct diagnosis is crucial as the Protocol on Environmental Protection to the Antarctic Treaty dictates dramatically different management responses depending on native/non-native status: native species and recent natural colonists should be protected and conserved, while non-native introductions should be eradicated or controlled. We review current knowledge on how available evidence should be used to differentiate between native and non-native species, and discuss and recommend issues that should be considered by scientists and managers upon discovery of a species apparently new to the Antarctic region.     

The legal design of the international and European Union ban on tributyltin antifouling paint: direct and indirect effects

The Convention on the Control of Harmful Anti-fouling Systems on Ships (AFS Convention), which was adopted in 2001 and will come into force in September 2008, bans the use of TBT (tributyltin) antifouling paint on ships. The EU (European Union) effectively implemented the Convention on 1 January 2008 by enforcing a similar ban. Several states have national restrictions and bans in place. The regulation on TBT antifouling paint aims at checking the risk of adverse effects on marine ecosystems. The legal and political situation is, however, characterized by complex relations between different layers of legislation, the use of several different legal techniques, and levels of ambition. The international and EU bans thereby cause some indirect effects, which are only partly included in what is seen as 'the TBT issue' and so only partly assessed in the legal process of the ban. This article discusses the expediency of the existing legislation and legal strategies aimed at reducing the negative environmental effects of TBT-like toxins in marine ecosystems and indirect effects of such actions. It considers the adequacy and limits of current regulatory approaches for handling complex environmental problems, such as TBT in antifouling paint.     

Chemical Characteristics of Urban Stormwater Sediments and Implications for Environmental Management, Maricopa County, Arizona

On the basis of published guidelines, urban stormwater sediments do not appear to constitute a major regional environmental problem with respect to the chemical characteristics investigated here. At individual sites, high concentrations of organic compounds—chlordane, dieldrin, PCBs, and toxaphene—may require some attention. The possible environmental hazard presented by low-level organochlorine contamination is not addressed in this paper; however, high levels of toxicity in urban sediments are difficult to explain. Sediment toxicity varied significantly with time, which indicates that these tests should be evaluated carefully before they are used for management decisions.     

Environmental management aspects for TBT antifouling wastes from the shipyards

Tributyltin (TBT)-based antifouling paints have been successfully used for over 40 years to protect a ship's hull from biofouling. However, due to its high toxicity to marine organisms, the International Maritime Organization (IMO), in 1990, adopted a resolution recommending governments to adopt measures to eliminate antifouling paints containing TBT. High concentrations of TBT are detected in the vicinity of ports and shipyards. TBT is also usually detected in the sediment, in which it accumulates. This study reviews recent literature for the best management practices (BMPs) in order to minimize the environmental effects of TBT. The paper focuses on the evaluation of the available techniques for the removal of TBT from shipyard wastes and from the sediment. The most effective treatment methods are highlighted. BMPs include recycling of abrasive materials, use of cleaner abrasive materials, reuse of spent abrasive materials, substitution of hydroblasting by vacuum blasting or containment or ultra-high-pressure water blasting and confinement of pollution by enclosure and containment systems. The treatment of the TBT wastes by conventional biological wastewater treatment processes is probably not suitable, because the concentrations of TBT found in shipyards' wastewaters are toxic to microorganisms. Advanced technologies such as activated carbon adsorption and dissolved air flotation, in combination with filtration and coagulation-clarification, photodegradation and electrochemical treatment, are required to remove TBT. However, advanced methods should be further optimized to meet the regulatory limit of 200 ng/L. To date, only one published work examines the efficiency of incineration for the treatment of solid sandblast wastes. Regarding the treatment of sediment, land deposition of the less polluted fraction of sediment is a feasible option. Such treatment must take into account the risk of contamination of groundwater and the surroundings, and it requires extended areas of land. Other treatment methods, such as thermal and electrochemical treatment, are promising options but due to the large amounts of dredged material, they have high capital and operational costs.     

A critical appraisal of PAH indices as indicators of PAH source and composition in Elelenwo Creek,southern Nigeria

The survey of polycyclic aromatic hydrocarbons (PAHs) and their relation to potential pollution sources were investigated in suspended particulate matter (SPM), surface waters, and sediments from Elelenwo Creek, southern Nigeria. Total PAH concentrations varied from 2,021.35 to 3,926.84 μg/kg dry weights in SPM and from 4,238.00 to 5,490.84 μg/kg dry weights in sediments. Furthermore, concentration levels of PAHs varied from 720.46 to 857.65 μg/l in the surface waters, which indicates that the aquatic ecosystem is polluted by PAHs. The 2, 3-ring PAHs were not dominant in SPM (34.73%), surface water (40.09%), and sediments (22.43%). While anthracene was more abundant, of the 2, 3-ring PAHs in SPM, the most abundant in the surface waters and sediments were fluorene and acenaphthylene. Four origin indices or concentration ratios of PAH isomer pairs were used to evaluate the suitability of these compounds as tracers to distinguish between the contamination arising from different sources. A critical appraisal of the PAH indices, therefore, suggested that biomass combustion is the major PAH source in the environmental matrices. Relative PAH patterns in the environmental matrices were also evaluated using principal component analysis, and were found to correlate with the PAH patterns of the different potential contamination sources.     

Fate and toxicity of endosulfan in Namoi River water and bottom sediment

Endosulfan (6,7,8,9,10,10,-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine-3-oxide) sorption (standardized to 1% total organic carbon and dry weight) was significantly (P < 0.05) more concentrated on the large (>63 microm) particle fraction compared with smaller size fractions (<5 microm and 5-24 microm) of bottom sediments from the Namoi River, Australia. Following completion of the particle size fractionation (6 to 12 wk) and a sediment toxicity assessment (2 wk), the sediments showed large decreases in concentrations of alpha-endosulfan that coincided with an increase in endosulfan sulfate concentrations and minimal changes in beta-endosulfan concentrations. In the Namoi River, similar patterns were observed in the composition of total endosulfan in monthly measurements of bottom sediments and in passive samplers placed in the water column following runoff from cotton (Gossypium hirsutum L.) fields. The toxicity of endosulfan sulfate in river water indicated by the nymphs of the epibenthic mayfly Jappa kutera, was more persistent than the alpha- and beta-endosulfan parent isomers due to its longer half-life. This suggests that endosulfan sulfate would contribute most to previously observed changes in population densities of aquatic biota. Measured concentrations of total endosulfan in river water of up to 4 microg L(-1) following storm runoff, exceed the range of the 96-h median lethal concentration (LC50) values in river water for both alpha-endosulfan (LC50 = 0.7 microg L(-1); 95% confidence interval [CI] = 0.5 to 1.1) and endosulfan sulfate (LC50 = 1.2 microg L(-1); 95% CI = 0.4 to 3.3). In contrast, the 10-d LC50 value for total endosulfan in the sediment toxicity test (LC50 = 162 microg kg(-1); 95% CI = 120 to 218 microg kg(-1)) was more than threefold higher than the highest measured concentration of total endosulfan in field samples of bottom sediment (48 microg kg(-1)). This suggests that pulse exposures of endosulfan in the water column following storm runoff may be more acutely toxic to riverine biota than in contaminated bottom sediment.