Contamination and toxic effects of persistent endocrine disrupters in marine mammals and birds

In recent years, several species of marine mammals and birds have been affected by uncommon diseases and unusual mortalities. While several possible causative factors have been attributed for these events, a prominent suspect is exposure to man-made toxic contaminants. Particularly, some of these man-made chemicals can disrupt normal endocrine physiology in animals. At CMES, our studies focus on exposure and toxic effects of endocrine disrupting chemicals, particularly organochlorines, in higher trophic level wildlife. Endocrine disrupting chemicals, such as organochlorine insecticides, polychlorinated biphenyls, organotins etc. are found in tissues of a wide variety of wildlife. Extremely high concentrations have been found in animals afflicted with diseases and/or victims of mass mortalities. Elevated contamination by organochlorines has been found in open sea animals such as cetaceans and albatrosses, which seemed to be attributable to their low capacity to metabolize toxic persistent contaminants. Significant correlations between biochemical parameters (serum hormone concentrations and cytochrome P450 enzyme activities) and residues of endocrine disrupting chemicals were found in some species of marine animals, which indicates that these chemicals may impose toxic effects in animals even at the current levels of exposure. In general, water birds and marine mammals accumulated the dioxin-like compounds with much higher concentrations than humans, implying higher risk from exposure in wildlife. The future issues of endocrine disrupting chemicals in humans and wildlife will have to be focused in developing countries.     

Polybrominated diphenyl ethers and their hydroxylated/methoxylated analogs: Environmental sources,metabolic relationships,and relative toxicities

Brominated compounds are ubiquitous in the aquatic environment. The polybrominated diphenyl ether (PBDE) flame retardants are anthropogenic compounds of concern. Studies suggest that PBDEs can be biotransformed to hydroxylated brominated diphenyl ethers (OH-BDE). However, the rate of OH-BDE formation observed has been extremely small. OH-BDEs have also been identified as natural compounds produced by some marine invertebrates. Another class of compounds, the methoxylated BDEs (MeO-BDEs), has also been identified as natural compounds in the marine environment. Both the OH-BDEs and MeO-BDEs bioaccumulate in higher marine organisms. Recent studies have demonstrated that MeO-BDEs can be biotransformed to OH-BDEs and this generates greater amounts of OH-BDEs than could be generated from PBDEs. Consequently, MeO-BDEs likely represent the primary source of metabolically derived OH-BDEs. Given that for some endpoints OH-BDEs often exhibit greater toxicity compared to PBDEs, it is prudent to consider OH-BDEs as chemicals of concern, despite their seemingly “natural” origins.     

Polybrominated diphenyl ethers and their hydroxylated/methoxylated analogs: environmental sources, metabolic relationships, and relative toxicities

Brominated compounds are ubiquitous in the aquatic environment. The polybrominated diphenyl ether (PBDE) flame retardants are anthropogenic compounds of concern. Studies suggest that PBDEs can be biotransformed to hydroxylated brominated diphenyl ethers (OH-BDE). However, the rate of OH-BDE formation observed has been extremely small. OH-BDEs have also been identified as natural compounds produced by some marine invertebrates. Another class of compounds, the methoxylated BDEs (MeO-BDEs), has also been identified as natural compounds in the marine environment. Both the OH-BDEs and MeO-BDEs bioaccumulate in higher marine organisms. Recent studies have demonstrated that MeO-BDEs can be biotransformed to OH-BDEs and this generates greater amounts of OH-BDEs than could be generated from PBDEs. Consequently, MeO-BDEs likely represent the primary source of metabolically derived OH-BDEs. Given that for some endpoints OH-BDEs often exhibit greater toxicity compared to PBDEs, it is prudent to consider OH-BDEs as chemicals of concern, despite their seemingly "natural" origins.     

Flame retardants (PBDEs) in marine turtles, dugongs and seafood from Queensland, Australia

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in numerous products. These compounds have been found to enter the marine environment where they have the potential to bioaccumulate in biota. Limited information is currently available concerning the levels of PBDEs in Australian marine wildlife. This study presents baseline information on PBDE levels in a variety of marine species from Queensland, Australia and considers the influence of species-specific factors on contaminant levels and tissue distribution in marine turtles. Overall, the PBDE levels measured in this study are relatively low compared to marine biota from the northern hemisphere, indicating low level input into the marine system of Queensland. This is in general agreement with global estimates which suggest low PBDE usage in Australia. Previous studies, however, have found relatively high PBDE levels in Australian human milk and sera. This discrepancy in contamination trends between terrestrial and marine biota suggests that future transport of PBDEs may occur to the marine system in Australia.     

Monitoring of organic pollutants in coastal waters of the Gulf of Gdańsk, Southern Baltic

This paper presents an overview of changes in organic pollution of coastal waters of the Gulf of Gdańsk (Baltic Sea). Toxic pollutants including volatile organic compounds (VOC), volatile organohalogen compounds (VOX), chlorophenols, phenoxyacids, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were determined in seawater from the Gulf of Gdańsk coastal waters in the period 1996-2001. In the case of the Gulf of Gdańsk, non-conservative behaviour of VOC was observed due to random temporal and spatial of inputs along the Vistula estuary and to the dilution of VOC-enriched river water with seawater. The concentrations of VOX in seawater decreased throughout the period and the concentrations of VOX were in the range of few ng dm(-3) up to 250 ng dm(-3), similar to estuaries elsewhere. The average concentrations of chlorophenols and phenoxyacids were between 0.1 and 6.0 and 0.05 and 2.2 microg dm(-3), respectively. However, remarkably high concentrations of 2,4-dichlorophenol (6 microg dm(-3)) were obtained in samples collected from the Vistula River. Generally concentrations of PCBs did not exceed few ng dm(-3) with the exception of 1999, when all samples exhibited elevated concentrations of PCBs. In addition, higher concentrations of PCBs in the open sea compared to river waters suggested localised inputs. Due to the ability of most organic pollutants to bioaccumulate and biomagnify, especially the persistent organic pollutants, continued monitoring is of crucial importance for the health of marine life in the Gulf of Gdańsk.     

Flame retardants (PBDEs) in marine turtles,dugongs and seafood from Queensland,Australia

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in numerous products. These compounds have been found to enter the marine environment where they have the potential to bioaccumulate in biota. Limited information is currently available concerning the levels of PBDEs in Australian marine wildlife. This study presents baseline information on PBDE levels in a variety of marine species from Queensland, Australia and considers the influence of species-specific factors on contaminant levels and tissue distribution in marine turtles. Overall, the PBDE levels measured in this study are relatively low compared to marine biota from the northern hemisphere, indicating low level input into the marine system of Queensland. This is in general agreement with global estimates which suggest low PBDE usage in Australia. Previous studies, however, have found relatively high PBDE levels in Australian human milk and sera. This discrepancy in contamination trends between terrestrial and marine biota suggests that future transport of PBDEs may occur to the marine system in Australia.     

Evaluating legacy contaminants and emerging chemicals in marine environments using adverse outcome pathways and biological effects-directed analysis

Natural and synthetic chemicals are essential to our daily lives, food supplies, health care, industries and safe sanitation. At the same time protecting marine ecosystems and seafood resources from the adverse effects of chemical contaminants remains an important issue. Since the 1970s, monitoring of persistent, bioaccumulative and toxic (PBT) chemicals using analytical chemistry has provided important spatial and temporal trend data in three important contexts; relating to human health protection from seafood contamination, addressing threats to marine top predators and finally providing essential evidence to better protect the biodiversity of commercial and non-commercial marine species. A number of regional conventions have led to controls on certain PBT chemicals over several years (termed ‘legacy contaminants’; e.g. cadmium, lindane, polycyclic aromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Analytical chemistry plays a key role in evaluating to what extent such regulatory steps have been effective in leading to reduced emissions of these legacy contaminants into marine environments. In parallel, the application of biomarkers (e.g. DNA adducts, CYP1A-EROD, vitellogenin) and bioassays integrated with analytical chemistry has strengthened the evidence base to support an ecosystem approach to manage marine pollution problems. In recent years, however, the increased sensitivity of analytical chemistry, toxicity alerts and wider environmental awareness has led to a focus on emerging chemical contaminants (defined as chemicals that have been detected in the environment, but which are currently not included in regulatory monitoring programmes and whose fate and biological impacts are poorly understood). It is also known that natural chemicals (e.g. algal biotoxins) may also pose a threat to marine species and seafood quality. Hence complex mixtures of legacy contaminants, emerging chemicals and natural biotoxins in marine ecosystems represent important scientific, economic and health challenges. In order to meet these challenges and pursue cost-effective scientific approaches that can provide evidence necessary to support policy needs (e.g. the European Marine Strategy Framework Directive), it is widely recognised that there is a need to (i) provide marine exposure assessments for priority contaminants using a range of validated models, passive samplers and biomarkers; (ii) integrate chemical monitoring data with biological effects data across spatial and temporal scales (including quality controls); and (iii) strengthen the evidence base to understand the relationship between exposure to complex chemical mixtures, biological and ecological impacts through integrated approaches and molecular data (e.g. genomics, proteomics and metabolomics). Additionally, we support the widely held view that (iv) that rather than increasing the analytical chemistry monitoring of large number of emerging contaminants, it will be important to target analytical chemistry towards key groups of chemicals of concern using effects-directed analysis. It is also important to evaluate to what extent existing biomarkers and bioassays can address various classes of emerging chemicals using the adverse outcome pathway (AOP) approach now being developed by the Organization for Economic Cooperation and Development (OECD) with respect to human toxicology and ecotoxicology.     

Effects of new antifouling compounds on the development of sea urchin

Tributyltin oxide (TBTO) has been used worldwide in marine antifouling paints as a biocide for some time. However, it produced toxic effects, especially in marine water/sediment ecosystems. Consequently, its use in antifouling paints has been prohibited in many countries. In this study, the toxicity of alternative and/or new antifouling biocides compared with TBTO is assessed by a biological method. The effects of these chemicals on marine species have not been well studied. This paper assesses, comparatively, the effects of eight biocides on sea urchin eggs and embryos. The chemicals assessed were TBTO, Irgarol 1051, M1 (the persistent degradation product of Irgarol), Diuron, zinc pyrithione, 'KH101', 'Sea-Nine 211', and copper pyrithione. For these chemicals, toxicity appears to be in the order zinc pyrithione > Sea-Nine 211 > KH101 > copper pyrithione > TBTO > Diuron approximately = Irgarol 1051 > M1. Here, we show that zinc pyrithione, Sea-Nine 211, KH101, and copper pyrithione are much more toxic to sea urchins than TBTO or the other chemicals.     

Quantitative model evaluation of organic carbon oxidation hypotheses for the Ediacaran Shuram carbon isotopic excursion

The largest global carbon-cycle perturbation in Earth history was recorded in the Ediacaran—a persistent negative shift in the global marine dissolved inorganic carbon(DIC) reservoir that lasted for ~25–50 million years, with a nadir of –12‰(i.e.,the Shuram Excursion, or SE). This event is considered to have been a result of full or partial oxidation of a large dissolved organic carbon(DOC) reservoir, which, if correct, provides evidence for massive DOC storage in the Ediacaran ocean owing to an intensive microbial carbon pump(MCP). However, this scenario was recently challenged by new hypotheses that relate the SE to oxidization of recycled continentally derived organic carbon or hydrocarbons from marine seeps. In order to test these competing hypotheses,this paper numerically simulates changes in global carbon cycle fluxes and isotopic compositions during the SE, revealing that:(1) given oxygen levels in the Ediacaran atmosphere-ocean of ≤40% PAL, the recycled continental organic carbon hypothesis and the full oxidation of oceanic DOC reservoir hypothesis are challenged by the atmospheric oxygen availability which would have been depleted in 4 and 6 million years, respectively;(2) the marine-seep hydrocarbon oxidation hypothesis is challenged by the exceedingly large hydrocarbon fluxes required to sustain the SE for 25 Myr; and(3) the heterogeneous(partial) DOC oxidation hypothesis is quantitatively able to account for the SE because the total amount of oxidants needed for partial oxidation(50%)of the global DOC reservoir could have been met.     

Monitoring of toxic substances in the Hong Kong marine environment

A long-term programme for monitoring toxic substances in the marine environment was established in Hong Kong in 2004, focusing on chemicals of potential ecological and health concern. The programme ran on 3-year cycles, with the first two years monitoring marine water, sediment, biota, and the third year monitoring pollution sources. Twenty-four priority chemicals were measured, including dioxins/furans, dioxin-like PCBs, total PCBs, PAHs, DDTs, HCHs, TBTs, phenol, nonylphenol (NP), NP ethoxylates, PBDEs and metals. Results from the first three years of monitoring indicate that toxic substances in the Hong Kong marine environment were within the range reported for the coastal waters in China and other regions, but generally lower than in the Pearl River Estuary. The levels met the standards for protecting aquatic life and human consumption. Sewage effluent, stormwater and river water were possible sources of phenolic compounds; whereas air deposition or regional pollution, rather than local discharges, may contribute to the dioxins/furans, PAHs and PCBs found in the marine environment.     

Methyltins in the marine environment

Methyltins were occasionally observed in some natural waters. The nature of a marine sediment determines its organotin burdens. Mono- and dimethyltin compounds were found in polluted marine sediments whereas non-polluted, oxiccoastal sediments contained primarily trimethyltin. The net methylation rate is evidently independent of the inorganic tin content of a sediment. Methyltin in fish is about 3–6% of the total tin content while limpets contain significant amounts of organotin compounds, ranging between 35 and 75% of the total tin. No trimethyltin was detected in green macro-algae and seawater, although limpets, fish and sediments have measurable levels.     

Monitoring of toxic substances in the Hong Kong marine environment

A long-term programme for monitoring toxic substances in the marine environment was established in Hong Kong in 2004, focusing on chemicals of potential ecological and health concern. The programme ran on 3-year cycles, with the first two years monitoring marine water, sediment, biota, and the third year monitoring pollution sources. Twenty-four priority chemicals were measured, including dioxins/furans, dioxin-like PCBs, total PCBs, PAHs, DDTs, HCHs, TBTs, phenol, nonylphenol (NP), NP ethoxylates, PBDEs and metals. Results from the first three years of monitoring indicate that toxic substances in the Hong Kong marine environment were within the range reported for the coastal waters in China and other regions, but generally lower than in the Pearl River Estuary. The levels met the standards for protecting aquatic life and human consumption. Sewage effluent, stormwater and river water were possible sources of phenolic compounds; whereas air deposition or regional pollution, rather than local discharges, may contribute to the dioxins/furans, PAHs and PCBs found in the marine environment.     

Natural and anthropogenic heavy metals in estuarine cohesive sediments: geochemistry and bioavailability

The geochemistry, mineralogy, and grain size distribution of several estuarine cohesive sediment samples from potentially human-influenced areas without such an influence were analyzed to determine the natural heavy metal content and evaluate its impact on the Bahía Blanca estuarine environment. The data were compared with different ranges of concentrations for heavy metals in marine sediments established by the NOAA Screening Quick Reference Tables in which values range from background levels to those considered toxic to the marine environment. Our total heavy metal contents were below the established hazardous levels in all the analyzed samples, even though the potentially human-influenced areas (harbors, industry, urban spread) showed the highest total concentration values as well as greater percentages of bioavailable compounds. This would imply a low and not extensive anthropogenic input into the environment. The relatively high proportions in which Cd, Pb, and Cr appear as bioavailable compounds at some sites not influenced by human activity suggest the presence of a natural source for these elements. This could be attributed to the weathering of naturally occurring volcanic minerals, indicating that special care must be taken when monitoring of sediment for anthropogenic activity is carried out within this environment. According to the results obtained, and in order to minimize the environmental impact caused by periodic water injection dredging, relocation of sewage outfalls from vessel mooring areas into open waters is strongly recommended.     

Characterization of industrial wastewaters using gel-permeation chromatography with multicomponent detection

The gel-permeation chromatography system with multicomponent detection of organic carbon, organic nitrogen, organic halogen, and UV/vis absorption measurement is shown to be a useful tool for characterization of industrial wastewaters and wastewater treatment processes. The proposed system was used to investigate biologically treated wastewater from chemical industry, whereby one branch stream was identified to be the main source of persistent halogenated organics. Various treatment processes of pulp mill wastewater were also evaluated revealing that precipitation with aluminium is very effective for the removal of the high molecular fraction whereas the biological treatment is generally less selective. In the biological treatment of tannery wastewaters, it has been shown that the aerobic treatment, in contrast to anaerobic step, causes evident alterations of the composition of the polar DOC fraction. The nitrogen containing compounds are also better decomposed in the aerobic step compared to the anaerobic one.     

Historical trends of organic pollutants in sediment cores from Hong Kong

Recent studies have indicated the occurrence of a wide range of trace organic contaminants, including polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the Hong Kong environment. These contaminants are potentially harmful to ecological systems, particularly in coastal areas. In this study, two sediment cores (4m) were collected from southern waters of Hong Kong in 2004 to study the historical trends, distribution patterns, and potential sources of trace organic contaminants. DDTs (p,p'-DDT, o,p'-DDT, p,p'-DDD, o,p'-DDD and p,p'-DDE), hexachlorohexanes (HCHs) (alpha and gamma), hexachlorobenzene (HCB), and PCBs were detected in the samples, whereas other target compounds were all below detection limits. Many OCPs have not been produced or used for many years due to toxicological or environmental concerns and PCB use is prohibited in Hong Kong. However, some compounds were still detectable in recent years, and were found to be widely distributed in the environment, likely because of pollutant inputs from the highly industrialized Pearl River Delta region. These results provide important information on current and historical contamination in Hong Kong, and help to reconstruct the pollution history of these trace organic pollutants in Hong Kong coastal waters.     

Natural and anthropogenic hydrocarbons in the Antarctic marine environment

The Antarctic marine environment contains a range of hydrocarbons at low concentrations, which are generally biogenic in origin. All major classes of hydrocarbons have been found in the Antarctic ecosystem. At present, anthropogenic input is very low and difficult to resolve from background levels. Pollution in the Antarctic is limited to only a few sources and although contamination can be locally chronic it is very restricted in extent. To date there have been few studies of hydrocarbon pollution and those available have been patchy in spatial coverage and generally lack time-series data. The low levels of natural hydrocarbons and restricted human activity make the Antarctic ecosystem suitable as an indicator of global hydrocarbon pollution.     

Biological invasions as a component of global change in stressed marine ecosystems

Biological invasions in marine environment are the lesser known aspect of global change. However, recent events which occurred in the Mediterranean Sea demonstrate that they represent a serious ecological and economical menace leading to biodiversity loss, ecosystem unbalancing, fishery and tourism impairment. In this paper we review marine bioinvasions using examples taken from the Mediterranean/Black Sea region. Particular attention is given to the environmental status of the receiving area as a fundamental pre-requisite for the colonisation success of alien species. The spread of the tropical algae belonging to the genus Caulerpa in the northwestern basin of the Mediterranean Sea has been facilitated by pre-existing conditions of instability of the Posidonia oceanica endemic ecosystem in relation to stress of both natural and anthropogenic origin. Human interventions caused long-term modification in the Black Sea environment, preparing a fertile ground for mass bioinvasion of aquatic nuisance species which, in some cases, altered the original equilibrium of the entire basin. Finally, the Venice lagoon is presented as the third example of an environment subjected to high propagule pressure and anthropogenic forcing and bearing the higher "diversity" of non-indigenous species compared to the other Mediterranean lagoons. Stressed environments are easily colonised by alien species; understanding the links between human and natural disturbance and massive development of non-indigenous species will help prevent marine bioinvasions, that are already favoured by global oceanic trade.     

Biological effects in the management of chemicals in the marine environment

Coastal ecosystems are impacted by many stressors, of which chemicals are possibly not the most important. Chemicals differ from most other stressors such as eutrophication and hypersedimentation in the time scale-effects from the latter act on the scale of weeks or months, whereas effects from chemicals may take years to manifest themselves in population or community changes. There are four different approaches available to manage chemicals in marine ecosystems: target contaminant levels, target individual effects, target community impacts (biodiversity) and, finally, target processes. These four differ in the analytical methods available and the analyst's ability to separate effects from chemicals from other environmental factors and natural variation. There is furthermore, a need to develop a framework to integrate biological effects methods with risk assessment methodology. Such integration will improve the basis for risk-based assessment of chemicals. A problematic issue relevant to all aspects of environmental management are the interactions between chemicals, and between chemicals and eutrophication or sedimentation. There is a clear need for more knowledge about such interactions.     

Detecting organic tracers from biomass burning in the atmosphere.

This is a brief review key to the literature on the determination of organic tracers from biomass burning which are detectable even after long-range global transport in total extracts of atmospheric particles. The major tracers are thermal degradation products from the biopolymer cellulose, namely the didehydromonosaccharide derivatives levoglucosan, galactosan and mannosan and the resin acid derivative dehydroabietic acid, with minor beta-sitosterol. Dehydroabietic acid is emitted primarily from burning of conifer fuel and these tracers are found in most aerosol samples from the North American continent. Particulate matter from the atmosphere over oceanic areas contains organic tracers from both natural and biomass burning emissions. The major biomarker compounds characterized are natural products from continental vegetation consisting primarily of epicuticular wax components and trace components from biomass burning emissions. The presence of these tracers in atmospheric particulate matter over the ocean confirms the long-range transport of smoke from biomass burning off the continents.