Air-sea gas exchange of HCHs and PCBs and enantiomers of alpha-HCH in the Kattegat Sea region

Concentrations and air-water gas exchange of polychlorinated biphenyls (PCBs) and hexachlorocyclohexanes (HCHs) were determined in nine paired air and water samples. The samples were collected monthly in the Kattegat Sea between December 1998 and November 1999. Average fugacity and flux values indicated that PCBs were oversaturated in the water, while HCHs were net deposited. Variations were large over the year, especially during spring and summer. Air parcel back trajectories suggested that air concentrations over the Kattegat Sea are largely dependent of air mass origin. Seasonal trends were detected for airborne HCHs and for PCBs in water. The air and water enantiomeric compositions of alpha-HCH indicated that a larger portion of alpha-HCH in air originated from the underlying water during summer than during winter.     

Evidence for bioamplification of nine polychlorinated biphenyl (PCB) congeners in yellow perch (Perca flavascens) eggs during incubation

This study investigated bioamplification of polychlorinated biphenyls (PCBs) in yellow perch (Perca flavescens) eggs resulting from nutrient utilization by developing embryos during incubation. Newly fertilized eggs containing trace levels of PCBs via maternal deposition were collected from an aquaculture pond in which adult broodstock had been reared over their natural lives. The eggs were incubated using a flow through system that received the same pond water at in-situ temperatures from which they were spawned. Replicate samples of eggs were collected at six time points throughout incubation, ranging from day 0 (newly fertilized eggs) to post-hatch larvae (2-d old). Congener specific PCB fugacities in pooled egg samples showed increases over the incubation period. Just prior to hatching, incubated eggs averaged 2.7-fold higher PCB fugacities compared to fresh eggs. The increase in PCB fugacity with egg incubation time was independent of chemical K_OW. After hatching, PCB residues were lost from the larvae, attenuating the maximum chemical fugacity achieved in late-incubated eggs. However, the rate of PCB elimination in the early larvae stages was K_OW dependent such that a significant larvae/egg fugacity ratio was still evident for intermediate and highly hydrophobic compounds 2 d post-hatching. This study provides the first evidence of in-ovo PCB bioamplification in eggs of an aquatic species and suggests that incubating fish embryos are exposed to higher chemical fugacities in-ovo than would be predicted by maternal deposition alone.     

Levels of polychlorinated biphenyls and organochlorine pesticides in some edible marine organisms from the Central Adriatic Sea

Concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) were found in tissue of marine organisms such as Mediterranean mussel, Norway lobster, red mullet, common cuttle-fish, European flying squid, European anchovy, European pilchard and Atlantic mackerel, coming from two sites along the Abruzzo coast of the Adriatic Sea. Species were selected due to their habitat, trophic level, feeding behaviour and their use in the Italian diet. Mussels, filter feeder and sedentary organisms, were used in order to test water pollution whereas Norway lobster and red mullet (benthic fish) were used in order to test sediment pollution. The concentration of ?PCBs exceeded that of ?OCs in the samples analysed. The highest concentrations of ?PCBs (1415 ng/g lipid weight) and ?OCs (507 ng/g lipid weight) were found in pilchard while the lowest concentrations of the same pollutants were found in cephalopods. Our results have shown that species such as anchovy, pilchard and mackerel, were the most polluted due to their location at the last level of the trophic chain. All samples contained different concentrations of PCBs and among these, congeners 153 and 138 were the most representative. Among the OCs, except for the cuttle-fish, the highest concentrations were found for p,p(')-DDE and p,p(')-DDD that are metabolite of DDT. The prevailing DDE presence, compared to DDT (high DDE/DDT ratio), suggested that the biotransformation rate of pollutants was very efficacious in fish and above all in crustaceans. Results have also been interpreted in terms of geographical distribution and organisms' biological cycle. None of the samples analysed exceeded the tolerance limits established by the OCs Italian legislation.     

Extremes of Temperature, Oxygen and Blooms in the Baltic Sea in a Changing Climate

In the future, the Baltic Sea ecosystem will be impacted both by climate change and by riverine and atmospheric nutrient inputs. Multi-model ensemble simulations comprising one IPCC scenario (A1B), two global climate models, two regional climate models, and three Baltic Sea ecosystem models were performed to elucidate the combined effect of climate change and changes in nutrient inputs. This study focuses on the occurrence of extreme events in the projected future climate. Results suggest that the number of days favoring cyanobacteria blooms could increase, anoxic events may become more frequent and last longer, and salinity may tend to decrease. Nutrient load reductions following the Baltic Sea Action Plan can reduce the deterioration of oxygen conditions.     

Factors determining the fluctuation of fluoride concentrations in PM10 aerosols in the urbanized coastal area of the Baltic Sea (Gdynia, Poland)

Fluoride concentrations were determined in PM10 samples collected in the urbanized coastal area of the Baltic Sea (Gdynia) in the period between 1 August 2008 and 8 January 2010. F^? concentrations remained within the range of 0.4–36.6 ng?·?m^?3. The economic transformations which have taken place in Poland increasing ecological awareness have had an excellent effect on the levels of fluoride pollution in the air of the studied region. In our measurements, fluoride concentrations increased in wintertime, when air temperature dropped, at low wind speeds (<1 m?·?s^?1) and with low dispersion of pollutants originating from local sources (traffic, industry, domestic heating). At times when wind speed grew to >10 m?·?s^?1, fluorides were related to marine aerosols or else brought from distant sources. Apart from wind speed and air temperature, other significant meteorological parameters which determined the variability of F^? turned out to be air humidity and precipitation volume. Aerosols were washed out effectively, even with small precipitation (h?=?4 mm), and if a dry period lasted for several days, their concentrations grew rapidly to over 30.0 ng?·?m^?3.     

Climate change influence on POPs distribution and fate: a case study

Climate change has the potential of affecting the behaviour and distribution of organic pollutants, including POPs. Direct effects of climate change, like temperature increase, modification of wind and precipitation patterns, sea level rise, snow and ice cover, may be very effective in altering the partitioning of POPs among the environmental compartments. Other consequences of future climate scenarios may imply the alteration of degradation rates, soil properties (and hence land use), air-particle partitioning of chemicals and so forth. A case study is here presented to illustrate the major implications of climate change on the long term at the local scale. A dynamic multimedia model was applied to selected PCB and PCDD/F congeners to simulate the effects of climate change on their distribution and fluxes over the next 50 y in the Venice Lagoon (Italy). Different climate change scenarios were tested, finding noticeable variations in POPs concentration even for minor environmental changes. PCBs and PCDFs environmental concentrations may differ by a factor two in a moderate climate change scenario, compared to a situation with stable climate over the next 50 y. However, model results also suggest that if global warming may have the potential of reducing the environmental levels of these chemicals, it would probably enhance their mobility and hence their potential for long range atmospheric transport.     

Seasonal air-water exchange fluxes of polychlorinated biphenyls in the Hudson River Estuary

Polychlorinated biphenyls (PCBs) were measured in the air and water over the Hudson River Estuary during six intensive field campaigns from December 1999 to April 2001. Over-water gas-phase SigmaPCB concentrations averaged 1100 pg/m3 and varied with temperature. Dissolved-phase SigmaPCB concentrations averaged 1100 pg/L and displayed no seasonal trend. Uncertainty analysis of the results suggests that PCBs with 5 or fewer chlorines exhibited net volatilization. The direction of net air/water exchange could not be determined for PCBs with 6 or more chlorines. Instantaneous net fluxes of SigmaPCBs ranged from +0.2 to +630 ng m(-2) d(-1). Annual fluxes of SigmaPCBs were predicted from modeled gas-phase concentrations, measured dissolved-phase concentrations, daily surface water temperatures and wind speeds. The net volatilization flux was +62 microg m(-2) yr(-1), corresponding to an annual loss of +28 kg/yr of SigmaPCBs from the Hudson River Estuary for the year of 2000.     

PCBs and chlorinated hydrocarbon pesticides in Antarctic atmosphere and hydrosphere

PCBs and chlorinated hydrocarbon pesticides such as DDTs and HCHs (BHCs) were measured in air, water, ice and snow samples collected around the Japanese research stations in Antarctica and adjacent oceans during December 1980 to March 1982. The atmospheric concentrations of chlorinated hydrocarbons decreased in the transport process from northern lands to Antarctica, but the compositions of PCBs, DDT compounds and HCH isomers were relatively uniform throughout this process. Regional and seasonal variations were found in aerial concentrations of these pollutants at Syowa Station and adjacent seas in Antarctica. Chlorinated hydrocarbons were also detected in snow, ice, lake water and sea water samples, in which rather high concentrations were found in snow and ice samples. This suggests that snow and ice serve as media of supply of these pollutants into Antarctic marine environment. Most interestingly, the concentrations of DDTs and higher chlorinated biphenyls were much lower in sea water under fast ice than in that from outer margin of pack ice. This indicates that the active removal of these pollutants is occurred in the sea under fast ice, and that is strongly associated with high primary productivity. It is, therefore, presumed that the concentrations of PCBs and DDTs in marine organisms living under fast ice in Antarctica could be lower than those in other oceans.     

Concentrations of two organic contaminants in precipitation, soils and plants in the Essex region of Southern Ontario

Recent research has indicated that the atmosphere is an important pathway by which pollutants enter terrestrial and aquatic ecosystems. We report here concentrations of PCBs and octachlorostyrene (OCS) in precipitation, soils and plants in Essex County, Ontario. The average PCB concentration in urban precipitation (23 ng litre(-1)) was lower than that previously reported for urban areas in the Great Lakes basin. Differences between sites and with varying wind directions were not significant. OCS concentrations in precipitation averaged 1.6 ng litre(-1). Concentrations of PCBs in soils were 2-3 orders of magnitude greater than in precipitation. Concentrations of these pollutants in city soils and plant roots were consistently higher than those from suburban and rural sites. Ratios of urban to suburban concentrations in soils and precipitation were approximately 5:1 for PCBs. However, concentrations of OCS were similar in urban and suburban samples of precipitation, soils and plant tissues. These comparisons suggest an urban source for PCBs, but not OCS. Concentrations of all contaminants in plant leaves, unlike those in precipitation, roots and soils, were relatively similar in urban and suburban areas. That similarity suggests that direct foliar uptake is not an important pathway for pollutant uptake in plants.     

Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment

Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011–2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069–2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air–sea gas exchange and “bulk” (precipitation + dry particle) deposition, resulting in net gains of 53 and 46 kg year^?1 for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year^?1 for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.     

PCB in soils and estimated soil-air exchange fluxes of selected PCB congeners in the south of Sweden

PCB concentrations were studied in different soils to determine the spatial variation over a region of approximately 11 000 km(2). PCB congener pattern was used to illustrate the spatial differences, as shown by principal component analysis (PCA). The relationship to different soil parameters was studied. PCB concentrations in soil showed a large variation between sampling-areas with median concentrations ranging between 2.3 and 332 ng g(-1) (dw). Highest concentrations were found at two sites with sandy soils, one with extremely high organic carbon content. Both sites were located on the west coast of southern Sweden. Soils with similar soil textures (i.e. sandy silt moraine) did not show any significant differences in PCB concentrations. PCB congener composition was shown to differ between sites, with congener patterns almost site-specific. PCB in air and precipitation was measured and the transfer of chemicals between the soil and air compartments was estimated. Soil-air fugacity quotient calculations showed that the PCBs in the soil consistently had a higher fugacity than the PCBs in the air, with a median quotient value of 2.7. The gaseous fluxes between soil and air were estimated using standard modelling equations and a net soil-air flux estimated by subtracting bulk deposition from gaseous soil-air fluxes. It was shown that inclusion of vertical sorbed phase transport of PCBs in the soil had a large effect on the direction of the net soil-air exchange fluxes.     

Modeling Nutrient Transports and Exchanges of Nutrients Between Shallow Regions and the Open Baltic Sea in Present and Future Climate

We quantified horizontal transport patterns and the net exchange of nutrients between shallow regions and the open sea in the Baltic proper. A coupled biogeochemical-physical circulation model was used for transient simulations 1961-2100. The model was driven by regional downscaling of the IPCC climate change scenario A1B from two global General Circulation Models in combination with two nutrient load scenarios. Modeled nutrient transports followed mainly the large-scale internal water circulation and showed only small circulation changes in the future projections. The internal nutrient cycling and exchanges between shallow and deeper waters became intensified, and the internal removal of phosphorus became weaker in the warmer future climate. These effects counteracted the impact from nutrient load reductions according to the Baltic Sea Action Plan. The net effect of climate change and nutrient reductions was an increased net import of dissolved inorganic phosphorus to shallow areas in the Baltic proper.     

Ensemble Modeling of the Baltic Sea Ecosystem to Provide Scenarios for Management

We present a multi-model ensemble study for the Baltic Sea, and investigate the combined impact of changing climate, external nutrient supply, and fisheries on the marine ecosystem. The applied regional climate system model contains state-of-the-art component models for the atmosphere, sea ice, ocean, land surface, terrestrial and marine biogeochemistry, and marine food-web. Time-dependent scenario simulations for the period 1960–2100 are performed and uncertainties of future projections are estimated. In addition, reconstructions since 1850 are carried out to evaluate the models sensitivity to external stressors on long time scales. Information from scenario simulations are used to support decision-makers and stakeholders and to raise awareness of climate change, environmental problems, and possible abatement strategies among the general public using geovisualization. It is concluded that the study results are relevant for the Baltic Sea Action Plan of the Helsinki Commission.     

Modeling eelgrass spatial response to nutrient abatement measures in a changing climate

For many coastal areas including the Baltic Sea, ambitious nutrient abatement goals have been set to curb eutrophication, but benefits of such measures were normally not studied in light of anticipated climate change. To project the likely responses of nutrient abatement on eelgrass (Zostera marina), we coupled a species distribution model with a biogeochemical model, obtaining future water turbidity, and a wave model for predicting the future hydrodynamics in the coastal area. Using this, eelgrass distribution was modeled for different combinations of nutrient scenarios and future wind fields. We are the first to demonstrate that while under a business as usual scenario overall eelgrass area will not recover, nutrient reductions that fulfill the Helsinki Commission’s Baltic Sea Action Plan (BSAP) are likely to lead to a substantial areal expansion of eelgrass coverage, primarily at the current distribution’s lower depth limits, thereby overcompensating losses in shallow areas caused by a stormier climate.     

Simulating uncertainty in climate-pest models with fuzzy numbers

Inputs in climate-pest models are commonly expressed as point estimates ('crisp' numbers), which implies perfect knowledge of the system in study. In reality, however, all model inputs harbor some level of uncertainty. This is particularly true for climate change impact assessments where the inputs (i.e., climate projections) are highly uncertain. In this study, uncertainties in climate projections were expressed as 'fuzzy' numbers; these are uncertain numbers for which one knows that there is a range of possible values and that some values are 'more possible' than others. A generic pest risk model incorporating the combined effects of temperature, soil moisture, and cold stress was implemented in a fuzzy spreadsheet environment and run with three climate scenarios: (1) present climate (control run); (2) crisp climate change; and (3) fuzzy climate change. Under the crisp climate change scenario, winter and summer temperatures and precipitation were altered using best estimates (averaged predictions from the 1995 assessment report of the Intergovernmental Panel on Climate Change [IPCC]). Under the fuzzy scenario, climate changes were expressed as triangular fuzzy numbers, utilizing the extremes (lowest and highest predictions from the IPCC report) in addition to the best estimates. Under each scenario, environmental favorability was calculated for six locations in two geographical regions (Central North America and Southern Europe) with two hypothetical pest species having temperate or mediterranean climate requirements. Simulations with the crisp climate change scenario suggested only minor changes in overall environmental favorability compared with the control run. When simulations were conducted with the fuzzy climate change scenario, however, important changes in environmental favorability emerged, particularly in Southern Europe. In that region, the possibility of considerably increased winter precipitation led to increased values of environmental favorability. However, the simulations also showed that this result harbored a very broad range of possible outcomes. The results support the notion that uncertainty in climate change projections must be reduced before reliable impact assessments can be achieved.     

Echoes from the Past: A Healthy Baltic Sea Requires More Effort

Integrated sediment multiproxy studies and modeling were used to reconstruct past changes in the Baltic Sea ecosystem. Results of natural changes over the past 6000 years in the Baltic Sea ecosystem suggest that forecasted climate warming might enhance environmental problems of the Baltic Sea. Integrated modeling and sediment proxy studies reveal increased sea surface temperatures and expanded seafloor anoxia (in deep basins) during earlier natural warm climate phases, such as the Medieval Climate Anomaly. Under future IPCC scenarios of global warming, there is likely no improvement of bottom water conditions in the Baltic Sea. Thus, the measures already designed to produce a healthier Baltic Sea are insufficient in the long term. The interactions between climate change and anthropogenic impacts on the Baltic Sea should be considered in management, implementation of policy strategies in the Baltic Sea environmental issues, and adaptation to future climate change.     

Organochlorine residues (PCBs and DDTs) in two Torpedinid species liver from the Southeastern Mediterranean Sea

Purpose  

Polychlorinated biphenyls (PCBs), dichlorodiphenyltrichloroethane (DDT) and PCB congeners accumulation profile were measured in the liver of two torpedinid species (Torpedo nobiliana and Torpedo marmorata) from the Mediterranean Sea (Adriatic Sea) in order to investigate the relative toxicological impact of these highly toxic PCBs in the organisms in question.     

Estimation of PCDD/F distribution and fluxes in the Venice Lagoon,Italy: combining measurement and modelling approaches

The available experimental information on the occurrence of PCDD/Fs in the Venice Lagoon, Italy, was compiled and used to calculate fugacities for the environmental compartments of sediment, suspended particulate matter (SPM), water and air and then used to estimate fugacity ratios and assess the likely net direction of flux between media. The bottom sediment: SPM fugacity ratios for different PCDD/Fs indicate conditions close to equilibrium, suggestive of the close coupling of SPM with re-suspended sediment. Sediment/water and the sediment/air fugacity ratios suggest that net flux directions vary depending on the congener and the location within the lagoon. Net sediment-water-air movement (i.e. re-mobilisation/volatilisation) is suggested for the lighter congeners from the industrial canals, where the highest PCDD/F concentrations in the lagoon occur. The tendency to volatilise increases with decreasing congener molecular weight. In contrast, net deposition (air-water-sediment) appears to be occurring for the heaviest (hepta- and octa-) substituted PCDD/Fs. OCDF represents a marker of the industrial district of the lagoon, decreasing in concentration and as a fraction of total PCDD/Fs with increasing distance. The fugacity-based quantitative water air sediment interaction (QWASI) mass-balance model was applied to the central part of the lagoon. The key parameters for the determination of the model output, identified by a sensitivity analysis, were: the sediment active depth, the sediment re-suspension and deposition rates, and the total input of PCDD/Fs to the system. The QWASI model also indicates the tendency for the lighter PCDD/Fs to be released from surface sediment to the water column.     

Assessing the impact of weather events at mid-latitudes on the atmospheric transport of chemical pollutants using a 2-dimensional multimedia meteorological model

We investigate the long-range transport potential (LRTP) of five different classes of hypothetical chemical pollutants (volatile, multimedia, semivolatile, particle-associated and hydrophilic) during a low pressure weather event using a novel 2 (x- and z-axis)-Dimensional Multi-Media Meteorological Model (2D4M). The atmosphere (z-axis) is described by three atmospheric layers, where two layers constitute the boundary layer and the third layer the free troposphere. The 2D4M can describe distinct weather events on a regional scale and calculate the LRTP of chemicals as a function of time during these events. Four weather factors are used to model weather events and their influence on the atmospheric transport of chemicals: (1) temperature, (2) wind speed and mixing dynamics of the troposphere, (3) hydroxyl radical concentrations and (4) precipitation. We have modeled the impact of variability in each of these factors on LRTP of pollutants during a front event associated with a low pressure period that interrupts a dominant high pressure system. The physico-chemical properties of the pollutant determine which specific weather factors contribute most to variability in transport potential during the event. Volatile and multimedia chemicals are mainly affected by changing atmospheric mixing conditions, wind speeds and OH radical concentrations, while semivolatile substances are also affected by temperature. Low-vapor-pressure pollutants that are particle-associated, and water-soluble pollutants are most strongly affected by precipitation. Some chemical pollutants are efficiently transported from the boundary layer into the upper troposphere during the modeled low pressure event and are transported by much higher wind speeds than in the boundary layer. Our model experiments show that the transport potential of volatile, multimedia and semivolatile compounds is significantly increased during a front event as a result of efficient tropospheric mixing and fast wind speeds in the upper troposphere, whereas low-volatility and hydrophilic chemicals are largely scavenged from the atmosphere. In future LRTP assessment of chemical contaminants as required by the Stockholm Convention and the convention on long-range transboundary air pollution, it is therefore advised to prioritize volatile, multimedia and semivolatile chemicals that are identified in initial screening.     

What environmental fate processes have the strongest influence on a completely persistent organic chemical's accumulation in the Arctic?

Fate and transport models can be used to identify and classify chemicals that have the potential to undergo long-range transport and to accumulate in remote environments. For example, the Arctic contamination potential (ACP), calculated with the help of the zonally averaged global transport model Globo-POP, is a numerical indicator of an organic chemical's potential to be transported to polar latitudes and to accumulate in the Arctic ecosystem. It is important to evaluate how robust such model predictions are and in particular to appreciate to what extent they may depend on a specific choice of environmental model input parameters. Here, we employ a recently developed graphical method based on partitioning maps to comprehensively explore the sensitivity of ACP estimates to variations in environmental parameters. Specifically, the changes in the ACP of persistent organic contaminants to changes in each environmental input parameter are plotted as a function of the two-dimensional hypothetical “chemical space” defined by two of the three equilibrium partition coefficients between air, water and octanol. Based on the patterns obtained, this chemical space is then segmented into areas of similar parameter sensitivities and superimposed with areas of high default ACP and elevated environmental bioaccumulation potential within the Arctic. Sea ice cover, latitudinal temperature gradient, and macro-diffusive atmospheric transport coefficients, and to a lesser extent precipitation rate, display the largest influence on ACP-values for persistent organic contaminants, including those that may bioaccumulate within the polar marine ecosystems. These environmental characteristics are expected to be significantly impacted by global climate change processes, highlighting the need to explore more explicitly how climate change may affect the long-range transport and accumulation behavior of persistent organic pollutants.