Der PAH-Metabolit 1-Hydroxypyren in der Galle von Klieschen (Limanda limanda) aus Nord- und Ostsee

Due to their carcinogenic properties, polycyclic aromatic hydrocarbons (PAH) are important environmental contaminants which may lead to increased levels of neoplastic aberrations in fish liver. To measure the PAH contamination of fish, concentrations of PAH metabolites were determined in the bile. The main metabolite 1-hydroxypyrene was determined in concentrations from < 0.8 to 189 ng/ml in bile of dab caught in the North Sea and the Baltic Sea re-spectively. The concentrations are comparable to levels of 1-hydroxypyrene measured in cod and herring from the Baltic Sea. The highest concentrations in dab bile were measured in fish from the inner German Bight and the Kiel Bight.

Analysis of soils and sediments for organic pollutants

20 samples of soil or sediment (7 of which were predominantly sand) from various locations were received for analysis of their content of organic pollutants. These analyses were performed using a capillary column gas chromatograph equipped with an electron impact (E.I.) mass spectrometer as detector and using computerised data storage. In addition to the target compounds, the full scan data were examined to determine the composition of natural organic products and a series of diagnostic fragment ions was used to search for additional anthropogenic products. Organic-rich environmental samples are notoriously difficult to analyse for pollutant organics owing to the presence of high concentrations of many natural organic compounds. A single procedure for extraction and clean-up was adopted. It was designed for chlorinated aliphatic and aromatic hydrocarbons and other pesticides containing acidic functional groups and was based on published methods for the determination of organic pollutants in soils and sediments. 4 soils and 2 sands showed levels of one or two groups of PCBs slightly in excess of the detection limit, one sample showed a similar level of 2,4-D and 3 samples contained dieldrin at or just above the detection limit.

Management of Biesboch reservoirs for quality control with special reference to eutrophication

The three Biesbosch Reservoirs are pumped storage reservoirs, fed with rather polluted and highly eutrophic water from the River Meuse. Air injection at the bottom of the reservoirs prevents thermal stratification, which would otherwise result in serious water quality deterioration. Reservoir mixing also serves as an economic algal control measure; mixing over sufficient depth causes light to play the role of limiting factor and this, combined with zooplankton grazing, keeps the biomass of phytoplankton at acceptable levels. Special problems are caused by benthic, geosmin-producing Oscillatoria species growing on the inner embankment. Rooting up the bottom with a harrow is used as the method of control, based on underwater observations by biological staff trained as SCUBA-divers. With regard to pollutant behaviour the three reservoirs act as a series of fully mixed reactors. This enables the application of kinetic models to describe their behaviour and allows the use of a selective intake policy, e.g. for suspended solids with associated contaminants, ammonia and polynuclear aromatic hydrocarbons. A combination of selective intake and self- purification processes - enhanced by the compartmentalisation of the storage volume in three reservoirs - leads to a striking improvement for many water-quality parameters.

Molecular biomarkers and toxic consequences of impact by organic pollution in aquatic organisms

Organic contaminants are readily bioaccumulated by aquatic organisms. Exposure to and toxic effects of contaminants can be measured in terms of the biochemical responses of the organisms (i.e. molecular biomarkers). The hepatic biotransformation enzyme cytochrome P4501A (CYP1A) in vertebrates is specifically induced by organic contaminants such as aromatic hydrocarbons, PCBs and dioxins, and is involved in chemical carcinogenesis via catalysis of the covalent binding of organic contaminants to DNA (DNA-adducts). Hepatic CYP1A induction has been used extensively and successfully as a biomarker of organic contaminant exposure in fish. Fewer but equally encouraging studies in fish have used hepatic bulky, hydrophobic DNA-adducts as biomarkers of organic contaminant damage. Much less is known of the situation in marine invertebrates, but a CYPlA-like enzyme with limited inducibility and some potential for biomarker application is indicated. Stimulation of reactive oxygen species (ROS) production is another potential mechanism of organic contaminant-mediated DNA and other damage in aquatic organisms. A combination of antioxidant (enzymes, scavengers) and pro-oxidant (oxidised DNA bases, lipid peroxidation) measurements may have potential as a biomarker of organic contaminant exposure (particularly those chemicals which do not induce CYP1A) and/or oxidative stress, but more studies are required. Both CYP1A- and ROS-mediated toxicity are indicated to result in higher order deleterious effects, including cancer and other aspects of animal fitness.

Investigation of taste tainting in salmon flesh in the Ribble catchment

This report presents the findings of the first phase of an investigation into the cause(s) of taints in salmonid fish in the River Ribble, commissioned by the North West Region of the Environment Agency. There have been reports of tainting in fish taken from both the estuary and the freshwater river for many years, but the contaminants involved and their source and transport pathway are unknown. Tainting by phenols has been of specific concern in the past. The work programme comprised: examination of tainting reports; collection of salmonids; their submission for taste testing; literature review; analysis of fish flesh using gas chromatography-mass spectrometry (GCMS) and analysis of river bed sediments. From enquiries, three common descriptors of the 'taint' were identified: disinfectanty; diesely; and muddy. The incidence of taints appears transient/irregular and may therefore relate to the incidence of discharges and specific threshold concentrations of pollutants. The literature review showed that a wide range of organic compounds including many industrial chemicals, and others which are naturally occurring, can taint fish flesh. Taste testing confirmed the presence of tainted salmon and trout in the Ribbie Catchment. It identified a low incidence of 'untainted' fish but demonstrated the 'taint' to be not specific to one tainting substance. Differences were found both between the species and fish from different parts of the catchment. Overall, most fish exhibited an unpleasant flavour, though this may have been influenced to some extent by the fact that most were sexually mature. The worst tainting was found in trout from the river Calder: a soapy/chemical aftertaste. An unpleasant earthy/musty flavour distinguished the salmon from the trout. Phenol was shown to have been a minor issue during the present study, whilst no hydrocarbon taints were identified. Examination of tissue from the eight salmon exhibiting the worst taints revealed the presence of aromatic hydrocarbons, but no phenolic compounds. Other notable substances present in the fish were siioxanes and benzophenone. Data from sediment analysis is presented which shows the main compounds present to be aromatic and polyaromatic hydrocarbons, that concentrations at two locations R. Darwen and R. Calder were significantly higher than at other sites, and that some phenolic compounds were detected at low levels. A paucity of fish flesh taste descriptors linked to specific compounds prevented an obvious correlation to be made between the tastes observed and the organic compounds detected. Descriptors frequently used by the taste testing panel (e.g. earthy, musty, astringency, chemical) cannot be linked to any of the compounds identified in the tissue analyses. No taste information was available from the literature on siioxanes. Aromatic hydrocarbons though present in tissue and sediments were not identified as tainting.

Effects of the Santa Barbara, Calif., Oil Spill on the Apparent Abundance of Pelagic Fishery Resources

Many studies have been made of the effects of oil on marine invertebrates, plants (marine algae and phytoplankton), and vertebrates such as seabirds and marine mammals. An excellent review of these findings, which includes some references to fish and pathological effects of aromatic hydrocarbons, has been published by the Royal Society, London (Clark, 1982). That review dealt with the environmental effects of such major oil spills or releases such as those by the tankers Torry Canyon (119,000 t) on the south coast of England, Metula (50-56,000 t) in the Straits of Magellan, Argo Merchant (26,000 t) off Cape Cod, and the super tanker Amoco Cadiz (223,000 t) on the coast of northern Brittany. Those spills were studied to determine their effect on living resources. In contrast there are few references on the impact of oil spills on pelagic fishery resources.

1983 Biscayne Bay hydrocarbon study: final report

A two year, comprehensive, quantitative investigation was conducted to analyze and identify the spatial distribution of petrogenic and biogenic hydrocarbons in sediments, surface waters, fish and shellfish of Biscayne Bay, Florida. The goal for the first year of the project was to establish baseline information to support oil spill impact assessment and clean-up. One hundred fifty-five sediment and eleven biota samples were collected. The areas sampled included the Miami River, Intracoastal Waterway, tidal flats, access canals and environmentally sensitive shorelines. The second year of the study centered on areas exhibiting petroleum contamination. These areas included the Miami River, Little River, Goulds Canal, Black Creek and Military Canal. Surface and subsurface sediment, biota and surface water were collected. Sample collection, analyses, and data handling for the two year project were conducted so that all information was court-competent and scientifically accurate. Chain of custody was maintained for all samples. Total hydrocarbon content of surface sediments ranged from below detection limits to a high of 2663.44 pg/g. Several sample stations contained petroleum contamination. The majority of biota samples exhibited hydrocarbon concentrations and characteristics that indicated little, if any, petroleum contamination. Surface water samples ranged from 0.78 to 64.47 μg/L and several samples contained petroleum hydrocarbons. Our results indicate several areas of petroleum contamination. These areas are characterized by industrial complexes, port facilities, marinas, major boating routes and many of the major tributaries emptying into Biscayne Bay.

Protocols for conducting dolphin capture-release health assessment studies

Marine mammals, such as dolphins, can serve as key indicator species in coastal areas by reflecting the effects of natural and anthropogenic stressors. As such they are often considered sentinels of environmental and ecosystem health (Bossart 2006; Wells et al. 2004; Fair and Becker 2000). The bottlenose dolphin is an apex predator and a key component of many estuarine environments in the southeastern United States (Woodward-Clyde Consultants 1994; SCDNR 2005). Health assessments of dolphins are especially critical in areas where populations are depleted, show signs of epidemic disease and/or high mortality and/or where habitat is being altered or impacted by human activities. Recent assessments of environmental conditions in the Indian River Lagoon, Florida (IRL) and the estuarine waters surrounding Charleston, South Carolina (CHS) highlight the need for studies of the health of local bottlenose dolphins. While the condition of southeastern estuaries was rated as fair in the National Coastal Condition Report (U.S. EPA 2001), it was noted that the IRL was characterized by poorer than expected benthic communities, significant sediment toxicity and increased nutrient concentrations. Similarly, portions of the CHS estuary have sediment concentrations of aliphatic aromatic hydrocarbons, select inorganic metals, and some persistent pesticides far in excess of reported bioeffect levels (Hyland et al. 1998). Long-term trends in water quality monitoring and recent scientific research suggest that waste load assimilation, non-point source runoff impacts, contaminated sediments, and toxic pollutants are key issues in the CHS estuary system. Several ‘hot spots’ with high levels of heavy metals and organic compounds have been identified (Van Dolah et al. 2004). High concentrations of anthropogenic trace metals, polychlorinated biphenyls (PCB’s) and pesticides have been found in the sediments of Charleston Harbor, as well as the Ashley and Cooper Rivers (Long et al. 1998). Two superfund sites are located within the CHS estuary and the key contaminants of concern associated with these sites are: polycyclic aromatic hydrocarbons (PAH), lead, chromium, copper, arsenic, zinc and dioxin. Concerns related to the overall health of IRL dolphins and dermatologic disease observed in many dolphins in the area (Bossart et al. 2003) initiated an investigation of potential factors which may have impacted dolphin health. From May-August 2001, 35 bottlenose dolphins died in the IRL during an unusual mortality event (MMC 2003). Many of these dolphins were diagnosed with a variety of skin lesions including proliferative ulcerative dermatitis due to protozoa and fungi, dolphin pox and a vesicular dermatopathy of unknown etiology (Bossart et al. 2003). Multiple species from fish to dolphins in the IRL system have exhibited skin lesions of various known and unknown etiologies (Kane et al. 2000; Bossart et al. 2003; Reif et al. 2006). On-going photo-identification (photo-ID) studies have documented skin diseases in IRL dolphins (Mazzoil et al. 2005). In addition, up to 70% of green sea turtles in the IRL exhibit fibropapillomas, with the highest rates of occurrence being seen in turtles from the southern IRL (Hirama 2001).

The effects of urbanization on populations of grass shrimp Palaemonetes spp. in small, high salinity estuaries

High salinity estuaries in the southeastern U.S. have experienced increased inputs of contaminants from nonpoint source (NPS) urban runoff and decreases in habitat due to filling of wetlands and dock/bulkhead construction. Urbanization may pose significant risks to estuarine fauna, particularly crustaceans. The grass shrimp of the genus Palaemonetes, is one of the dominant species found in estuarine tidal creeks, accounting for greater than 50% of all macropelagic fauna on an annual basis. Spatial analytical and geographic information system techniques were used to determine which factors influenced the Palaemonetes population structures in a South Carolina bar-built estuary surrounded by urban development. Impacts from land use practices were investigated using concentric circular buffers around study sites. Factors investigated included sediment-associated polycyclic aromatic hydrocarbons concentration, land use classification, percent impervious surfaces, and other selected urban factors. Geographic information system and statistical modeling showed quantitative relationships between land use class and impacts on Palaemonetes density. The study suggests that habitat loss is a major factor influencing grass shrimp densities. Multiple regression modeling suggests a significant relationship between habitat alterations and Palaemonetes densities.

Deepwater Horizon oil spill: assessment of potential impacts on the deep soft-bottom benthos; interim data summary report

A study was initiated in May 2011, under the direction of the Deepwater Horizon (DWH) Natural Resource Damage Assessment (NRDA) Deepwater Benthic Communities Technical Working Group (NRDA Deep Benthic TWG), to assess potential impacts of the DWH oil spill on sediments and resident benthic fauna in deepwater (> 200 meters) areas of the Gulf. Key objectives of the study were to complete the analysis of samples from 65 priority stations sampled in September-October 2010 on two DWH Response cruises (Gyre and Ocean Veritas) and from 38 long-term monitoring sites (including a subset of 35 of the original 65) sampled on a follow-up NRDA cruise in May-June 2011. The present progress report provides a brief summary of results from the initial processing of samples from fall 2010 priority sites (plus three additional historical sites). Data on key macrofaunal, meiofaunal, and abiotic environmental variables are presented for each of these samples and additional maps are included to depict spatial patterns in these variables throughout the study region. The near-field zone within about 3 km of the wellhead, where many of the stations showed evidence of impaired benthic condition (e.g. low taxa richness, high nematode/harpacticoid-copepod ratios), also is an area that contained some of the highest concentrations of total petroleum hydrocarbons (TPH), total polycyclic aromatic hydrocarbons (total PAHs), and barium in sediments (as possible indicators of DWH discharges). There were similar co-occurrences at other sites outside this zone, especially to the southwest of the wellhead out to about 15 km. However, there also were exceptions to this pattern, for example at several farther-field sites in deeper-slope and canyon locations where there was low benthic species richness but no evidence of exposure to DWH discharges. Such cases are consistent with historical patterns of benthic distributions in relation to natural controlling factors such as depth, position within canyons, and availability of organic matter derived from surface-water primary production.

Deep-sea benthic footprint of the Deepwater Horizon blowout

The Deepwater Horizon (DWH) accident in the northern Gulf of Mexico occurred on April 20, 2010 at a water depth of 1525 meters, and a deep-sea plume was detected within one month. Oil contacted and persisted in parts of the bottom of the deep-sea in the Gulf of Mexico. As part of the response to the accident, monitoring cruises were deployed in fall 2010 to measure potential impacts on the two main soft-bottom benthic invertebrate groups: macrofauna and meiofauna. Sediment was collected using a multicorer so that samples for chemical, physical and biological analyses could be taken simultaneously and analyzed using multivariate methods. The footprint of the oil spill was identified by creating a new variable with principal components analysis where the first factor was indicative of the oil spill impacts and this new variable mapped in a geographic information system to identify the area of the oil spill footprint. The most severe relative reduction of faunal abundance and diversity extended to 3 km from the wellhead in all directions covering an area about 24 km2. Moderate impacts were observed up to 17 km towards the southwest and 8.5 km towards the northeast of the wellhead, covering an area 148 km2. Benthic effects were correlated to total petroleum hydrocarbon, polycyclic aromatic hydrocarbons and barium concentrations, and distance to the wellhead; but not distance to hydrocarbon seeps. Thus, benthic effects are more likely due to the oil spill, and not natural hydrocarbon seepage. Recovery rates in the deep sea are likely to be slow, on the order of decades or longer.

An assessment of chemical contaminants, toxicity and benthic infauna in sediments from the St. Thomas East End Reserves (STEER)

This report contains a chemical and biological characterization of sediments from the St. Thomas East End Reserves (STEER) in St. Thomas, U.S. Virgin Islands (USVI). The STEER Management Plan (published in 2011) identified chemical contaminants and habitat loss as high or very high threats and called for a characterization of chemical contaminants as well as an assessment of their effects on natural resources. The baseline information contained in this report on chemical contaminants, toxicity and benthic infaunal community composition can be used to assess current conditions, as well as the efficacy of future restoration activities. In this phase of the project, 185 chemical contaminants, including a number of organic (e.g., hydrocarbons and pesticides) and inorganic (e.g., metals) compounds, were analyzed from 24 sites in the STEER. Sediments were also analyzed using a series of toxicity bioassays, including amphipod mortality, sea urchin fertilization impairment, and the cytochrome P450 Human Reporter Gene System (HRGS), along with a characterization of the benthic infaunal community. Higher levels of chemical contaminants were found in Mangrove Lagoon and Benner Bay in the western portion of the study area than in the eastern area. The concentrations of polychlorinated biphenyls (PCBs), DDT (dichlorodiphenyltrichloroethane), chlordane, zinc, copper, lead and mercury were above a NOAA sediment quality guideline at one or more sites, indicating impacts may be present in more sensitive species or life stages in the benthic environment. Copper at one site in Benner Bay, however, was above a NOAA guideline indicating that effects on benthic organisms were likely. The antifoulant boat hull ingredient tributyltin, or TBT, was found at the third highest concentration in the history of NOAA’s National Status and Trends (NS&T) Program, which monitors the Nation’s coastal and estuarine waters for chemical contaminants and bioeffects. Unfortunately, there do not appear to be any established sediment quality guidelines for TBT. Results of the bioassays indicated significant sediment toxicity in Mangrove Lagoon and Benner Bay using multiple tests. The benthic infaunal communities in Mangrove Lagoon and Benner Bay appeared severely diminished.

Assessing the impacts of the Deepwater Horizon oil spill: the National Status and Trends Program response; a summary report of coastal contamination

NOAA’s National Status and Trends Program (NS&T) collected oyster tissue and sediments for quantification of polycyclic aromatic hydrocarbons (PAHs) and petroleum associated metals before and after the landfall of oil from the Deepwater Horizon incident of 2010. These new pre- and post- landfall measurements were put into a historical context by comparing them to data collected in the region over three decades during Mussel Watch monitoring. Overall, the levels of PAHs in both sediment and oysters both pre- and post-landfall were within the range of historically observed values for the Gulf of Mexico. Some specific sites did have elevated PAH levels. While those locations generally correspond to areas in which oil reached coastal areas, it cannot be conclusively stated that the contamination is due to oiling from the Deepwater Horizon incident at these sites due to the survey nature of these sampling efforts. Instead, our data indicate locations along the coast where intensive investigation of hydrocarbon contamination should be undertaken. Post-spill concentrations of oil-related trace metals (V, Hg, Ni) were generally within historically observed ranges for a given site, however, nickel and vanadium were elevated at some sites including areas in Mississippi Sound and Galveston, Terrebonne, Mobile, Pensacola, and Apalachicola Bays. No oyster tissue metal body burden exceeded any of the United States Food and Drug Administration’s (FDA) shellfish permissible action levels for human consumption.

Porphyrin detection in denatured cnidarian tissue extracts

Porphyrin metabolic disruption from exposure to xenobiotic contaminants such as heavy metals, dioxins, and aromatic hydrocarbons can elicit overproduction of porphyrins. Measurement of porphyrin levels, when used in conjunction with other diagnostic assays, can help elucidate an organism’s physiological condition and provide evidence for exposure to certain toxicants. A sensitive microplate fluorometric assay has been optimized for detecting total porphyrin levels in detergent solubilized protein extracts from symbiotic, dinoflagellate containing cnidarian tissues. The denaturing buffer used in this modified assay contains a number of potentially interfering components (e.g., sodium dodecyl sulfate (SDS), dithiothreitol (DTT), protease inhibitors, and chlorophyll from the symbiotic zooxanthellae), which required examination and validation. Examination of buffer components were validated for use in this porphyrin assay; while the use of a specific spectrofluorometric filter (excitation 400 ± 15 nm; emission 600 ± 20 nm) minimized chlorophyll interference. The detection limit for this assay is 10 fmol of total porphyrin per μg of total soluble protein and linearity is maintained up to 5000 fmol. The ability to measure total porphyrins in a SDS protein extract now allows a single extract to be used in multiple assays. This is an advantage over classical methods, particularly when tissue samples are limiting, as is often the case with coral due to availability and collection permit restrictions.

National Centers for Coastal Ocean Science (NCCOS) research highlights in the Chesapeake Bay

The Chesapeake Bay is the largest estuary in the United States. It is a unique and valuable national treasure because of its ecological, recreational, economic and cultural benefits. The problems facing the Bay are well known and extensively documented, and are largely related to human uses of the watershed and resources within the Bay. Over the past several decades as the origins of the Chesapeake’s problems became clear, citizens groups and Federal, State, and local governments have entered into agreements and worked together to restore the Bay’s productivity and ecological health. In May 2010, President Barack Obama signed Executive Order number 13508 that tasked a team of Federal agencies to develop a way forward in the protection and restoration of the Chesapeake watershed. Success of both State and Federal efforts will depend on having relevant, sound information regarding the ecology and function of the system as the basis of management and decision making. In response to the executive order, the National Oceanic and Atmospheric Administration’s National Centers for Coastal Ocean Science (NCCOS) has compiled an overview of its research in Chesapeake Bay watershed. NCCOS has a long history of Chesapeake Bay research, investigating the causes and consequences of changes throughout the watershed’s ecosystems. This document presents a cross section of research results that have advanced the understanding of the structure and function of the Chesapeake and enabled the accurate and timely prediction of events with the potential to impact both human communities and ecosystems. There are three main focus areas: changes in land use patterns in the watershed and the related impacts on contaminant and pathogen distribution and concentrations; nutrient inputs and algal bloom events; and habitat use and life history patterns of species in the watershed. Land use changes in the Chesapeake Bay watershed have dramatically changed how the system functions. A comparison of several subsystems within the Bay drainages has shown that water quality is directly related to land use and how the land use affects ecosystem health of the rivers and streams that enter the Chesapeake Bay. Across the Chesapeake as a whole, the rivers that drain developed areas, such as the Potomac and James rivers, tend to have much more highly contaminated sediments than does the mainstem of the Bay itself. In addition to what might be considered traditional contaminants, such as hydrocarbons, new contaminants are appearing in measurable amounts. At fourteen sites studied in the Bay, thirteen different pharmaceuticals were detected. The impact of pharmaceuticals on organisms and the people who eat them is still unknown. The effects of water borne infections on people and marine life are known, however, and the exposure to certain bacteria is a significant health risk. A model is now available that predicts the likelihood of occurrence of a strain of bacteria known as Vibrio vulnificus throughout Bay waters.