Marine oil pollution and beached bird surveys: the development of a sensitive monitoring instrument

One of the most obvious adverse effects of (chronic) pollution of the world's oceans and seas with mineral oil is the mortality of seabirds. Systematic surveys of beachcast corpses of birds ('beached bird surveys') have been used in many parts of the world to document the effect of oil pollution, but particularly so in Western Europe and in parts of North America. In this paper, the history, current schemes, methods and possible (future) use of beached bird surveys are described and discussed, because the value of beached bird surveys has been hotly disputed. Oil pollution is known since the late 19th century, while the first beached bird surveys were conducted in the 1920s. Due to the amount of man-power needed for these surveys, most beached bird survey programs thrived only through the work of a large number of volunteers. However, most programs have resulted in substantial amounts of high quality data, often covering many consecutive years. One of the main shortcomings of many beached bird survey programs was the emphasis on stranded bird numbers rather than on relative measures, such as oil rates (percentage of corpses oiled of all corpses found). Sources of pollution, particularly so in chronically polluted regions such as the North Sea, the Baltic, the Mediterranean and the waters around Newfoundland, are insufficiently known, but could be studied through a sampling program connected to beached bird surveys. Suggestions for standardization of methods are presented, which could lead to a global and highly sensitive monitoring instrument of marine oil pollution.     

Estimation of the net air-sea flux of ammonia over the southern bight of the North Sea

Measurements of airborne gaseous ammonia and total dissolved ammonium in sea water determined on cruises on the North Sea have been used to calculate net fluxes of ammonia between air and sea. The system is finely balanced with the majority of net fluxes from air to sea, but some periods occur when the sea becomes a net source of ammonia in air. Examination of the field data suggests that the main factor determining the direction of flux is the airborne ammonia concentration, which when elevated causes ammonia deposition to the sea. It is calculated that ammonia deposition to the southern bight of the North Sea (below 56°N) amounts to 7.6 x 103 tonnes N per year, about one-half of an earlier upper limit estimate. Comparison with studies from the Pacific Ocean, in which the sea acts as a source of atmospheric ammonia, reveals that the major differences arise from much higher concentrations of airborne ammonia in the North Sea atmosphere caused by advection from adjacent land.     

Airborne trichloroacetic acid and its deposition in the catchment area of the Caspian Sea

The main sources of pollution discharge into the Caspian Sea are metal and oil processing plants in the catchment areas of the Ural and Volga rivers, as well as the coastal and offshore oil industry in the countries bordering the sea. The high evaporation from the surface of this largest inland sea introduces highly volatile C₂-chlorohydrocarbons into the atmosphere. Subsequent reactions with OH radicals and other oxidants results in the formation of secondary pollutants, such as phytotoxic trichloroacetic acid (TCA), which are then delivered by the air or rain into the neighbouring ecosystems of various vegetation zones. Biomonitoring investigations in the catchment area of the Caspian Sea have revealed that differences in pollution levels in the southern Russian area between the Black Sea and the Caspian Sea, resulting from TCA originating in the atmosphere, are attributable to climatic conditions and the geographical position of the measuring sites. ©     

A Multivariate Baltic Sea Environmental Index

Since 2001/2002, the correlation between North Atlantic Oscillation index and biological variables in the North Sea and Baltic Sea fails, which might be addressed to a global climate regime shift. To understand inter-annual and inter-decadal variability in environmental variables, a new multivariate index for the Baltic Sea is developed and presented here. The multivariate Baltic Sea Environmental (BSE) index is defined as the 1st principal component score of four z-transformed time series: the Arctic Oscillation index, the salinity between 120 and 200 m in the Gotland Sea, the integrated river runoff of all rivers draining into the Baltic Sea, and the relative vorticity of geostrophic wind over the Baltic Sea area. A statistical downscaling technique has been applied to project different climate indices to the sea surface temperature in the Gotland, to the Landsort gauge, and the sea ice extent. The new BSE index shows a better performance than all other climate indices and is equivalent to the Chen index for physical properties. An application of the new index to zooplankton time series from the central Baltic Sea (Latvian EEZ) shows an excellent skill in potential predictability of environmental time series.     

Evaluation of modifications of the simple spectrofluorometry method for estimating petroleum hydrocarbon levels in fresh and waste water samples

The monitoring of petroleum hydrocarbons in the water environment is very often performed using complicated methods. There are many difficulties encountered in analyzing a long number of samples in the monitoring programme. In such cases, a simpler though less precise and specific technique using inexpensive equipment to monitor a large number of water samples, might be more desirable.

This idea was realized in the assessment of the state of pollution of the Mediterranean Sea by petroleum hydrocarbons where the pollution of sea water with oil (dissolved and/or dispersed in sea water) was measured by spectrofluorometry. The paper describes an analytical evaluation of three modifications of simple the spectrofluorometry method, applied on numerous river and waste water samples collected from various areas of Croatia.     

The Potential of Current- and Wind-Driven Transport for Environmental Management of the Baltic Sea

The ever increasing impact of the marine industry and transport on vulnerable sea areas puts the marine environment under exceptional pressure and calls for inspired methods for mitigating the impact of the related risks. We describe a method for preventive reduction of remote environmental risks caused by the shipping and maritime industry that are transported by surface currents and wind impact to the coasts. This method is based on characterizing systematically the damaging potential of the offshore areas in terms of potential transport to vulnerable regions of an oil spill or other pollution that has occurred in a particular area. The resulting maps of probabilities of pollution to be transported to the nearshore and the time it takes for the pollution to reach the nearshore are used to design environmentally optimized fairways for the Gulf of Finland, Baltic Proper, and south-western Baltic Sea.     

Sea salt concentrations across the European continent

The oceans are a major source for particles that play an important role in many atmospheric processes. In Europe sea salt may contribute significantly to particulate matter concentrations. We have compiled sodium concentration data as a tracer for sea salt for 89 sites in Europe to provide more insight in the distribution of sea salt across Europe. The annual average sea salt concentrations above land were estimated to range between 0.3 and almost 13 μg m^?3. Maximum concentrations are found at the Irish coast. At coastal sites along the Atlantic and North Sea coast concentrations tend to be around 5 μg m^?3. More inland locations up to about 300 km away from the coast tend to show concentrations between 2 and 5 μg m^?3, whereas sites further away from the coast are characterized by lower concentrations. An analysis of the representativity of the data with respect to a long term average showed that the long average is associated with a standard deviation of around 15%. The compilation of observations provides an improved overview of sea salt concentrations in Europe as well as an improved basis for model validation. Verification of the results of the LOTOS-EUROS model learned that the model represents well the spatial variability of the observed sea salt concentrations very well. However, the absolute concentrations are significantly overestimated due to large uncertainties in the emission and dry deposition parameterizations. Using the high explained variability in the gradients across Europe, the bias-corrected modelled distribution serves as a best estimate of the sea salt distribution across Europe for 2005.     

Historical marine ecology: examining the role of fisheries in changes in North Sea benthos

The organisms living on and in the sea floor, the benthos, represent an important ecological group. Although some (shellfish) have an economic value, most do not, and so little long-term data are available. We have identified three sources of historic benthic data for the North Sea, a regional sea that has been subjected to multiple human impacts for at least several hundred years. Each dataset has its limitations, but by their use together some issues emerge. Wider community shifts were observed in the shorter term and a number of extirpations at the scale of the North Sea were seen over longer time scales. The extirpated taxa share a number of characteristics consistent with an effect of fisheries such as fragile morphology. We must concentrate now on furthering our understanding of the ecological significance of shifts in dominance of particular functional units and protecting those habitats and species most vulnerable to fisheries-driven extirpation.     

Simulated sea surface temperature and heat fluxes in different climates of the Baltic Sea

The physical state of the Baltic Sea in possible future climates is approached by numerical model experiments with a regional coupled ocean-atmosphere model driven by different global simulations. Scenarios and recent climate simulations are compared to estimate changes. The sea surface is clearly warmer by 2.9 degrees C in the ensemble mean. The horizontal pattern of average annual mean warming can largely be explained in terms of ice-cover reduction. The transfer of heat from the atmosphere to the Baltic Sea shows a changed seasonal cycle: a reduced heat loss in fall, increased heat uptake in spring, and reduced heat uptake in summer. The interannual variability of surface temperature is generally increased. This is associated with a smoothed frequency distribution in northern basins. The overall heat budget shows increased solar radiation to the sea surface, which is balanced by changes of the other heat flux components.     

Monitoring contaminants from oil production at sea by measuring gill EROD activity in Atlantic cod (Gadus morhua)

An ex vivo gill EROD assay was applied in Atlantic cod (Gadus morhua) as a biomarker for waterborne CYP1A-inducing compounds derived from oil production at sea. Exposure to nominal concentrations of 1 ppm or 10 ppm North Sea crude oil in a static water system for 24 h caused a concentration-dependent gill EROD induction. Further, exposure of cod for 14 days to environmentally relevant concentrations of produced water (PW, diluted 1:200 or 1:1000) from a platform in the North Sea using a flow-through system resulted in a concentration-dependent induction of gill EROD. Crude oil (0.2 ppm) from the same oil field also proved to induce EROD. Finally, gill EROD activity in cod caged for 6 weeks at 500-10 000 m from two platforms outside Norway was measured. The activities in these fish were very low and did not differ from those in fish caged at reference sites.     

Future sea ice conditions and weather forecasts in the Arctic: Implications for Arctic shipping

The ability to forecast sea ice (both extent and thickness) and weather conditions are the major factors when it comes to safe marine transportation in the Arctic Ocean. This paper presents findings focusing on sea ice and weather prediction in the Arctic Ocean for navigation purposes, in particular along the Northeast Passage. Based on comparison with the observed sea ice concentrations for validation, the best performing Earth system models from the Intergovernmental Panel on Climate Change (IPCC) program (CMIP5—Coupled Model Intercomparison Project phase 5) were selected to provide ranges of potential future sea ice conditions. Our results showed that, despite a general tendency toward less sea ice cover in summer, internal variability will still be large and shipping along the Northeast Passage might still be hampered by sea ice blocking narrow passages. This will make sea ice forecasts on shorter time and space scales and Arctic weather prediction even more important.     

Simulation of interactions between migrating whales and potential oil spills

A numerical model system was developed to quantify the probability of endangered bowhead and gray whales encountering spilled oil in Alaskan waters. Migration and diving-surfacing models for bowhead and gray whales, and an oil spill trajectory model comprise the system. The migration models were developed from conceptual considerations, then calibrated with and tested against observations. The distribution of whales is represented in space and time by discrete points, each of which may represent one or more whales. The movement of a whale point is governed by a random walk algorithm which stochastically follows a migratory pathway. Stochastic diving-surfacing models are used to stimulate surfacing behavior sequences for each species. The oil spill model accounts for oil transport and spreading in open water and in the presence of sea ice. Historical wind records and ice cover data sets provide the environmental conditions to generate stochastic oil spill scenarios. The oil spill, whale migration and diving-surfacing models are linked to provide quantitative estimates of whale-oil interactions. The model system was applied to the Alaskan Beaufort Sea to investigate the probability that bowhead whales would encounter oil spilled in this region.     

Characterizing the spatiotemporal variability of PM2.5 in Cusco,Peru using kriging with external drift

Advancing the understanding of spatiotemporal aspects of air pollution in the urban environment is an area where improved methods can be of great benefit to exposure assessment and policy support. This paper explores the potential of a technique known as kriging with external drift (KED) to provide high resolution maps of fine particulate matter for a downtown region of Cusco, Peru. There were three stages in this research. The first was to conduct a pilot level monitoring campaign to investigate ambient, regional, and street-level air pollutant concentrations for particulate matter (PM_2.5, PM₁₀) and carbon monoxide (CO) in the Province of Cusco. The second was to compile observations within a geographic information system (GIS) in order to characterize the proximal effect of the local transportation network, elevation, and land use classifications on PM_2.5. Third, regression, ordinary kriging and kriging with external drift were used to model PM_2.5 for three select time periods during a 24-h day. Statistical evaluations indicate kriging with external drift resulted in the strongest models explaining 64% of variability seen with morning particle concentrations, 25% for afternoon particles, and 53% in evening particles. These models capture spatial and temporal variability for air pollution in Cusco. These variations seem to be influenced, to varying degrees, by elevation, meteorological conditions, spatial location, and transportation characteristics. In conclusion, combining GIS, meteorological data and geostatistics proved to be a complementary suite of tools for incorporating spatiotemporal analysis into the air quality assessment.     

Coastal hydrogeological system of Mar Piccolo (Taranto,Italy)

The Mar Piccolo basin is an internal sea basin located along the Ionian coast (Southern Italy), and it is surrounded primarily by fractured carbonate karstic environment. Because of the karstic features, the main continental water inflow is from groundwater discharge. The Mar Piccolo basin represents a peculiar and sensitive environment and a social emergency because of sea water and sediment pollution. This pollution appears to be caused by the overlapping effects of dangerous anthropogenic activities, including heavy industries and commercial and navy dockyards. The paper aims to define the contribution of subaerial and submarine coastal springs to the hydrological dynamic equilibrium of this internal sea basin. A general approach was defined, including a hydrogeological basin border assessment to detect inflowing springs, detailed geological and hydrogeological conceptualisation, in situ submarine and subaerial spring measurements, and flow numerical modelling. Multiple sources of data were obtained to define a relevant geodatabase, and it contained information on approximately 2000 wells, located in the study area (1600 km²). The conceptualisation of the hydrogeological basin, which is 978 km² wide, was supported by a 3D geological model that interpolated 716 stratigraphic logs. The variability in hydraulic conductivity was determined using hundreds of pumping tests. Five surveys were performed to acquire hydro-geochemical data and spring flow-yield measurements; the isotope groundwater age was assessed and used for model validation. The mean annual volume exchanged by the hydrogeological basin was assessed equal to 106.93 10⁶ m³. The numerical modelling permitted an assessment of the mean monthly yield of each spring outflow (surveyed or not), travel time, and main path flow.     

Estimating contribution of wildland fires to ambient ozone levels in National Parks in the Sierra Nevada, California

Data from four continuous ozone and weather monitoring sites operated by the National Park Service in Sierra Nevada, California, are used to develop an ozone forecasting model and to estimate the contribution of wildland fires on ambient ozone levels. The analyses of weather and ozone data pointed to the transport of ozone precursors from the Central Valley as an important source of pollution in these National Parks. Comparisons of forecasted and observed values demonstrated that accurate forecasts of next-day hourly ozone levels may be achieved by using a time series model with historic averages, expected local weather and modeled PM values as explanatory variables. Results on fire smoke influence indicated occurrence of significant increases in average ozone levels with increasing fire activity. The overall effect on diurnal ozone values, however, was small when compared with the amount of variability attributed to sources other than fire.     

Methanesulphonic acid (MSA) stratigraphy from a Talos Dome ice core as a tool in depicting sea ice changes and southern atmospheric circulation over the previous 140 years

Firn core methanesulphonic acid (MSA) stratigraphy from Talos Dome (East Antarctica) was compared with anomalies of the satellite-measured sea ice extent (1973–1995) in the Ross Sea and Wilkes Land oceanic sector. In spite of the sparseness of sea ice data, the MSA maxima fit with many positive sea ice anomalies in the Ross Sea. This evidence suggests that marine biogenic activity enhanced by large sea ice cover is an important, but not exclusive, factor in controlling MSA concentration in snow precipitation at Talos Dome. Other than source intensity, differences in regional atmospheric transport mechanisms affect the arrival of MSA-rich aerosol at Talos Dome. To clarify the role of transport processes in bringing biogenic aerosol to Talos Dome, a spectral analysis was applied to the MSA, SOI (South Oscillation Index), and SAM (Southern Annular Mode) record. Synchronicity or phase shift between the chemical signature and atmospheric circulation modes were tested. The variations in the MSA profile have a periodicity of 6.9, 4.9, 3.5, and 2.9 years. The 6.9 and 2.9 year periodicities show a strong positive correlation and are synchronous with corresponding SOI periodicity. This variability could be related to an increase in MSA source intensity (by dimethylsulphide from phytoplanktonic activity) linked to the sea ice extent in the Ross Sea area, but also to an increased strength in transport processes. Both of these factors are correlated with La Niña events (SOI positive values). Furthermore, SAM positive values are related to an increased sea ice extent in the Ross Sea sector and show two main periodicities 3.3 and 3.8 years. These periodicities determine the MSA variability at 3.5 years. However, the effect of intensification of the polar vortex and the consequent reduction in transport process intensity, which reduce the delivery of air masses enriched in MSA from oceanic areas to Talos Dome, make the effect of the SAM on the MSA concentration at Talos Dome less active than the SOI. In this way, snow deposition at the Talos Dome records larger MSA concentration by the combined effects of increased source emissions and more efficient transport processes. The MSA record from Talos Dome can therefore be considered a reliable proxy of sea ice extent when the effect of changes in transport processes in this region of Antarctica is considered. Over the previous 140 years, these conditions occur with a periodicity of 6.9 years.     

Atmospheric concentrations and air-sea exchanges of nonylphenol, tertiary octylphenol and nonylphenol monoethoxylate in the North Sea

Concentrations of nonylphenol isomers (NP), tertiary octylphenol (t-OP) and nonylphenol monoethoxylate isomers (NP1EO) have been simultaneously determined in the sea water and atmosphere of the North Sea. A decreasing concentration profile appeared following the distance increasing from the coast to the central part of the North Sea. Air-sea exchanges of t-OP and NP were estimated using the two-film resistance model based upon relative air-water concentrations and experimentally derived Henry's law constant. The average of air-sea exchange fluxes was -12+/-6 ng m(-2)day(-1) for t-OP and -39+/-19 ng m(-2)day(-1) for NP, which indicates a net deposition is occurring. These results suggest that the air-sea vapour exchange is an important process that intervenes in the mass balance of alkylphenols in the North Sea.     

The contribution of ship emissions to air pollution in the North Sea regions

As a consequence of the global distribution of manufacturing sites and the increasing international division of labour, ship traffic is steadily increasing and is becoming more and more important as an origin of air pollution.This study investigates the impact of ship emissions in coastal areas of the North Sea under conditions of the year 2000 by means of a regional chemistry transport model which runs on a sufficiently high resolution to study air pollution in coastal regions. It was found that northern Germany and Denmark in summer suffer from more than 50% higher sulphate, nitrate and ammonium aerosol concentrations due to contributions from ships. The implementation of a sulphur emission control area (SECA) in the North Sea, as it was implemented at the end of 2007, directly results in reduced sulphur dioxide and sulphate aerosol concentrations while nitrate aerosol concentrations are slightly increased.     

The occurrence of xenoestrogens in the Elbe river and the North Sea

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.