Evaluating a model of the historical behavior of two hexachlorocyclohexanes in the Baltic Sea environment

The POPCYCLING-Baltic model, a non-steady-state multicompartmental mass balance model of long-term chemical fate in the Baltic Sea environment, is evaluated for its capability to simulate the behavior of alpha- and gamma-hexachlorocyclohexane isomers from 1970 to 2000. The model predicts HCH concentrations in air, seawater, marine sediments, and needles well within an order of magnitude, often within a factor of 2, and reproduces major features of the observed differences in space and time. The spatial and temporal patterns of HCHs in the Baltic Sea environment are found to be controlled mostly by chemical input, both through direct emissions within the drainage basin and through advective inflow from adjacent areas, but variable environmental conditions can significantly modify the spatial distribution patterns. Simulations with different boundary conditions, i.e., variable assumptions concerning advective atmospheric inflow, suggest that sources within the drainage basin alone are not capable of explaining the observed HCH levels and that significant transport into the region must occur. Deviations between predicted and measured HCH concentrations can often be explained by uncertain estimates of usage and advective import, illustrating the usefulness of the model for evaluating the reasonability of emission estimates and boundary conditions.     

Fish, fishing, and pollutant reduction in the Baltic Sea

The Baltic Sea is heavily polluted yet supports major commercial fisheries for cod (Gadus morhua), herring (Clupea harengus), and sprat (Sprattus sprattus). Emissions of persistent organic pollutants, such as polychlorinated biphenyls (PCBs) and DDT, were high during the 1960s and 1970s, and concentrations in fish and other fauna are still significant. Several models of the fluxes of these pollutants among the water, sediment, and atmosphere have been developed, but these generally omit the roles of fish and fisheries. We show that the standing stock of the most abundant fish species in the Baltic Sea was a sink for 260 kg of PCBs in the late 1980s to early 1990s and that the fishery removed as much or more PCB (31 kg yr(-1))than other budget components (e.g., degradation in the water column). Accounting for fish and fisheries could increase our understanding of the fluxes of pollutants, and banning the discard of highly contaminated organs such as cod liver could be part of the pollution management.     

The air-sea equilibrium and time trend of hexachlorocyclohexanes in the Atlantic Ocean between the Arctic and Antarctica

Hexachlorocyclohexanes (HCHs) were determined simultaneously in air and seawater during two cruises across the Atlantic Ocean between the Arctic Ocean (Ny-Alesund/ Svalbard, 79 degrees N; 12 degrees E) and the Antarctic Continent (Neumayer Station/ Ekstroem Ice Shelf, 70 degrees S; 8.2 degrees W) in 1999/ 2000. The concentrations of alpha-HCH and gamma-HCH in air and surface waters of the Arctic exceeded those in Antarctica by 1-2 orders of magnitude. The gaseous concentrations of gamma-HCH were highest above the North Sea and between 20 degrees N and 30 degrees S. Fugacity fractions were used to estimate the direction of the air-sea gas exchange. These showed for alpha-HCH thatthe measured concentrations in both phases were close to equilibrium in the North Atlantic (78 degrees N-40 degrees N), slightly undersaturated between 30 degrees N and 10 degrees S and again close to equilibrium between 20 degrees S and 50 degrees S. Y-HCH has reached phase equilibrium in the North Atlantic as alpha-HCH, but the surface waters of the tropical and southern Atlantic were strongly undersaturated with y-HCH, especially between 30 degrees N and 20 degrees S. These findings are significantly different from two earlier estimates around 1990 as a result of global emission changes within the past decade. Therefore, we investigated the time trend of the HCHs in the surface waters of the Atlantic between 50 degrees N and 60 degrees S on the basis of archived samples taken in 1987-1997 and those from 1999. A decrease of alpha-HCH by a factor of approximately 4 is observed at all sampling locations. No decrease of gamma-HCH occurred between 30 degrees N and 30 degrees S, but there was a decrease in the North Atlantic, North Sea, and in the South Atlantic south of 40 degrees S. The constant level of gamma-HCH in the tropical Atlantic confirms the conclusion that the tropical Atlantic acts as a sink for y-HCH at present time. The measured alpha-HCH seawater concentrations were compared with results from a global multimedia fate and transport model. Whereas the time trend over 13 years and the latitudinal gradient were well reproduced by the model, the absolute levels were too high by a factor of 4.5. This may be explained by the zonal averaging employed in the model as well as uncertain emissions and degradation rates.     

Hypoxia in the Baltic Sea and basin-scale changes in phosphorus biogeochemistry

Deep-water oxygen concentrations in the Baltic Sea are influenced by eutrophication, but also by saltwater inflows from the North Sea. In the last two decades, only two major inflows have been recorded and the lack of major inflows is believed to have resulted in a long-term stagnation of the deepest bottom water. Analyzing data from 1970 to 2000 at the basin scale, we show that the estimated volume of water with oxygen, <2 mL L(-1), was actually at a minimum at the end of the longest so-called stagnation period on record. We also show that annual changes in dissolved inorganic phosphate water pools were positively correlated to the area of bottom covered by hypoxic water, but not to changes in total phosphorus load, thus addressing the legacy of eutrophication on a basinwide scale. The variations in phosphorus pools that have occurred during the past decades do not reflect any human action to reduce inputs. The long residence time and internally controlled variation of the large P pool in the Baltic Sea has important implications for management of both N and P inputs into this eutrophicated enclosed basin.     

Polychlorinated naphthalene levels,distribution, and biomagnification in a benthic food chain in the Baltic Sea

The scientific literature contains little information regarding bioaccumulation and biomagnification of polychlorinated naphthalenes (PCNs) in food webs. Here we present new information on the food chain transfer of PCNs within a food chain in a subarctic environment PCNs (tetra- to hepta-chloro congeners) were measured in surface sediments and in a marine benthic food chain, comprising amphipods, isopods, and fourhorned sculpins. Samples were collected from five locations in the Gulf of Bothnia, northern Baltic Sea. PCN concentrations in the sediments were similar to background levels determined previously in sediments from the northern hemisphere. Measurement of the carbon content of the sediments allowed the calculation of biota to sediment accumulation factors (BSAFs). Tetra- and penta-CNs exhibited BSAF values greater than one, while BSAFs for the more chlorinated PCNs were less than one. This suggests more efficient assimilation, by amphipods, of the less chlorinated PCNs. A decrease in sigmaPCN concentrations from the lowest to the highest trophic level was demonstrated (amphipods: 10-69 ng/g lw, isopods: 3.9-16 ng/g lw; fourhorned sculpins: 0.54-1.5 ng/g lw). Biomagnification factors (BMFs) were calculated based on the concentrations of the congeners. These indicated that a few congeners biomagnified significantly: the highest BMFs (0.09-1.4) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms.     

Temporal trends of PFOS and PFOA in guillemot eggs from the Baltic Sea, 1968--2003

Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have recently been identified as ubiquitous environmental contaminants. Although they have been produced for 50 years, little is known about when they first appeared in the environment and how their concentrations have changed over time, particularly in response to the phase-out of PFOS, which began in 2000. In this study temporal trends in the concentrations of PFOS and PFOA in the Baltic Sea marine environmentwere measured using archived guillemot eggs. Samples collected from Stora Karls? (Sweden) between 1968 and 2003 were received from an environmental specimen bank and concentrations of PFOS and PFOA were analyzed using HPLC coupled to ESI-MS/MS. PFOA was not detected in any of the samples (LOD 3 ng/g), but there was an almost 30-fold increase in PFOS concentrations in the guillemot eggs during the time period, from 25 ng/g in 1968 to 614 ng/g in 2003 (wet weight). Regression analysis indicated a significant trend, increasing on average between 7 and 11% per year. A sharp peak in PFOS concentrations was observed in 1997 followed by decreasing levels up to 2002, but this cannot be linked to the PFOS phase-out, which occurred at the end of this period.     

Polycyclic aromatic hydrocarbons in traditionally smoked meat products from the Baltic states

A total of 77 traditionally smoked meat samples produced in Latvia, Lithuania, and Estonia were tested for the occurrence of four EU regulated polycyclic aromatic hydrocarbons (PAHs). Levels of PAHs exceeding the EU maximum levels for benzo[a]pyrene and for the sum of four PAHs (PAH4) were detected in 46% and 48% of the samples originating from Latvia. The detected BaP levels in smoked meats ranged from 0.05 to 166 μg kg^?1, while the PAH4 content ranged from 0.42 to 628 μg kg^?1. The mean dietary exposure to PAHs was estimated at the levels of 5.4 ng BaP/kg bw/day and 36 ng PAH4/kg bw/day. The margin of exposure (MOE) approach was utilised to assess the risks to Latvian consumers due to PAHs and the obtained MOEs were in a range of 7205–24,434, thus indicating a potential concern for consumer health for specific population groups.     

Variability of the gaseous elemental mercury sea-air flux of the Baltic Sea

The importance of the sea as a sink for atmospheric mercury has been established quantitatively through models based on wet and dry deposition data, but little is known about the release of mercury from sea areas. The concentration of elemental mercury (Hg0) in sea surface water and in the marine atmosphere of the Baltic Sea was measured at high spatial resolution in February, April, July, and November 2006. Wind-speed records and the gas-exchange transfer velocity were then used to calculate Hg0 sea-air fluxes on the basis of Hg0 sea-air concentration differences. Our results show that the spatial resolution of the surface water Hg0 data can be significantly improved by continuous measurements of Hg0 in air equilibrated with water instead of quantitative extraction of Hg0 from seawater samples. A spatial and highly seasonal variability of the Hg0 sea-air flux was thus determined. In winter, the flux was low and changed in direction. In summer, a strong emission flux of up to 150 ng m(-2) day(-1) in the central Baltic Sea was recorded. The total emission of Hg0 from the studied area (235000 km2) was 4300 +/- 1600 kg in 2006 and exceeded deposition estimates.     

Atmospheric transport of polybrominated diphenyl ethers and polychlorinated biphenyls to the Baltic Sea

The atmospheric transport of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) was compared by measuring concentrations in air and deposition on an island located in the central basin of the Baltic Sea. Median sigmaPBDE and sigmaPCB concentrations (gaseous + particle) were 8.6 and 7.4 pg m(-3), respectively. Airborne PCBs were mainly found in the gaseous phase, while most of the PBDEs were detected on particles, which agrees with predicted particle/gas distributions. SigmaPBDE levels were dominated by the decabrominated BDE209 followed bythe tetrabrominated BDE47 and pentabrominated BDE99. BDE209 is a marker for the environmental distribution of the commercial deca-BDE formulation (>99.5% BDE209), whereas BDE47 and BDE99 are markers for the commercial penta-BDE mixture. General correlations between PBDEs and PCBs suggested similarities in sources and transport mechanism, while more detailed examination of the data identified notable behaviors and exceptions. Differences in regression slopes among tetra-, penta-, and decabrominated PBDEs may reflect different transport processes and the change in usage pattern. Tetra- and pentabrominated PBDEs may originate from secondary sources such as air surface exchange in a manner similar to that of the PCBs, while the deca-BDE209 formulation still has primary sources. The tribrominated BDE17 was also detected and is proposed to be a breakdown product due to atmospheric debromination processes. PBDEs had higher washout ratios than PCBs, explaining their higher concentrations compared to PCBs in precipitation (median of 6.0 and 0.5 ng L(-1) for sigmaBDE and sigmaPCB concentrations ("dissolved" + particle), respectively) than in air. The calculated yearly deposition of PBDEs and PCBs indicated that the atmospheric input of PBDEs to the Baltic Proper is currently exceeding that of the PCBs by a factor of 40, while that of the PCBs is decreasing.     

Modeled direct photolytic decomposition of polybrominated diphenyl ethers in the Baltic Sea and the Atlantic Ocean

In this study, tetra- (#47), penta- (#99), and decabrominated (#209) diphenyl ethers were exposed (in isooctane) to summer sunlight at 60 degrees N, where their photochemical half-lives ranged from 0.6 to 203 h. Apparent quantum yields, ranging from 0.16 to 0.28, were applied to optical models to calculate the rates of direct photochemical decomposition at the surface (depth of 0 m) and in the mixing layer of the ocean. The calculated photolytic half-lives were 4-100 times as long in the mixing layer of the Baltic Sea and the North Atlantic Ocean as atthe surface of 0 m. Calculation of seasonal photochemical half-lives for the mixing layer of the North Atlantic Ocean from 0 degrees N to 60 degrees N showed that the solar photolysis effectively decomposes the congeners in the tropics. At mid- and high latitudes, where solar irradiances are lower outside summer, the photolysis rates for congeners #47 and #99 were often too low for their effective decomposition in the mixing layer. Although solar radiation can potentially decompose the congeners in the mixing layer of the ocean effectively, seasonal and latitudal variation in solar irradiance as well as optical and mixing properties of the ocean can make the direct photolytic decomposition ineffective at high latitude and the coastal ocean.     

Accumulation of airborne hexachlorocyclohexanes and DDT in pine needles

The accumulation of alpha- and gamma-hexachlorocyclohexanes (HCHs) and p,p'-DDT in Scots pine needles was measured simultaneously with the concentrations in the surrounding air. All three compounds accumulate during the entire life span of the needles. For p,p'-DDT the general accumulation is overlaid by a concentration peak during winter, probably related to particle deposition. For the HCHs the accumulation is overlaid by a seasonal pattern with rapid accumulation during spring and summer months and constant concentrations during winter months. The concentrations of alpha-HCH in the air were more or less constant during the whole sampling period, whereas gamma-HCH shows an air concentration peak in spring and early summer. Air concentrations of p,p'-DDT were for the most part below the detection limit. There is little evidence of revolatilization from the needles, with the exception of a small decline of gamma-HCH concentration in summer after the peak air concentrations. The high accumulation rate of the HCHs during the warm season correlates with high levels of volatile organic compounds (VOCs) in the needles. We suggest that the variation of VOC content in the needles cause seasonal variation of the air-plant partitioning coefficient. An additional complicating factor is that the dry weight of the needles has to be corrected for the yearly variation of starch content. The results presented here question models of uptake of airborne contaminants by plants that assume rapid equilibria between the air and plants.     

Spatial distribution of hexachlorocyclohexanes in agricultural soils in Zhejiang province, China, and correlations with elevation and temperature

Large quantities of hexachlorocyclohexanes (HCHs) were historically applied to soils in Zhejiang, a hilly province of eastern China, yet very limited information is publicly available for the present levels and residue characteristics of HCHs in the region. In this work, concentrations of HCHs and enantiomeric fractions (EFs) of α-isomer were analyzed in 58 agricultural soil samples (0-20 cm) collected in Zhejiang province. On the basis of the ratio of α-HCH/β-HCH and the fact that HCHs were banned in 1983 for agricultural use in China, fresh application of technical HCHs in a large quantity was unlikely in this province. Significant correlation was found between soil concentrations and elevation (R = 0.52, P < 0.001) and temperature (R = -0.55, P < 0.0001), but not between soil concentrations and total technical usage (R = -0.24, P = 0.1), suggesting a typical secondary distribution pattern. The soil residue inventories of HCHs derived from the relationship between concentration and elevation indicated 14.2 tons of HCHs left in agricultural soils in plain areas with the average elevation less than 100 m, and 61.6 tons of HCHs left in mountain soils with the average elevation higher than 100 m. It was also found that EFs of α-HCH were significantly negatively correlated with carbon biomass (C(bio)) in soils. This implies that C(bio) might have important impact on orientation and extent of enantioselective degradation of α-HCH in the region, which is, according to our knowledge, the first report of this kind.     

Identification of polybrominated dibenzo-p-dioxins in blue mussels (Mytilus edulis) from the Baltic Sea

Polybrominated dibenzo-p-dioxins (PBDDs) are known to be formed as byproducts in connection with the manufacture and combustion of products containing brominated flame retardants. However, to date little is known about the occurrence of PBDDs in biological samples. The aim of the present investigation was to examine the presence of PBDDs in blue mussels (Mytilus edulis) from the Baltic Sea employing a procedure adapted for dioxin analysis. Two triBDDs (1,3,7-triBDD and 1,3,8-triBDD) were identified in biota here for the first time. This identification was based on accurate mass determination and comparison of retention times on three gas chromatographic columns of different polarities (PTE 5, SP-2331, and OV1701/heptakis) with synthesized standards, together with comparisons of electron capture negative ionization (ECNI) and electron ionization (EI) mass spectra. In addition, five PBDDs and one polybrominated dibenzofuran (PBDF) were tentatively identified; altogether, one diBDD, three triBDDs, three tetraBDDs, and one triBDFwere detected in the blue mussels. To our knowledge this is the first time PBDDs have been identified in biota of the Baltic Sea. The sigma triBDD concentration in the blue mussels was estimated to be 170 ng/g lipids. The origin of these PBDDs remains unclear, but a plausible hypothesis could be biogenic formation in the marine environment.     

Organotin compounds in the liver tissue of marine mammals from the Polish coast of the Baltic Sea

Butyltins (BTs) and phenyltins (PhTs) were determined in the livers of marine mammals found by-caught or stranded along the Polish coast of the Baltic Sea. During the investigation an original analytical method was developed. Butyltin compounds were detected in all the liver samples, whereas phenyltins were not detected in any of the samples. The total concentrations of BTs ranged from 43.9 to 7698 ng(Sn) x g(-1) dry weight. Age-related trends to accumulate BTs in immature porpoises were found. At the same time there were no male-female differences in BTs concentrations observed. No statistically significant spatial distribution differences were found between the locations corresponding to the open Baltic Sea waters and inside the Gulf of Gdańsk, which is characterized by high maritime activity. In comparison to butyltin levels in marine mammals from other geographic regions, the samples analyzed indicate a significant degree of tributyltin pollution along the Polish coast of the Baltic Sea. On the basis of a literature review, higher BT levels are usually found in waters close to highly industrialized areas, such as Japan, Hong Kong, and the United States.     

Tissue distribution of perfluorinated surfactants in common guillemot (Uria aalge) from the Baltic Sea

Perfluorinated alkyl surfactants (PFAS) were investigated in tissues and organs of the common guillemot (Uria aalge) from the Baltic Sea. Concentrations of 11 perfluorinated carboxylates, four perfluorinated sulfonates, and perfluorooctane sulfonamide were determined in egg, liver, kidney, and muscle of adult guillemot, as well as in liver from chicks, all sampled in 1989. Additionally, whole herring homogenates from 2005 were analyzed, herring comprising a large part of guillemot's diet. Quantifiable concentrations of PFAS were found in all samples. Perfluorooctane sulfonate (PFOS) was predominant, followed by perfluorotridecanoate (PFTriDA) and perfluoroundecanoate (PFUnDA). The median concentration of PFOS was highest in eggs (325 ng/g wet weight (w wt)) followed by chick liver (309 ng/g w wt), kidney (127 ng/g w wt), adult liver (121 ng/g w wt), and muscle (14 ng/g w wt). Comparatively low levels of PFOS were found in herring, leaving a blurred picture of uptake routes. PFAS concentrations in livers of male and female guillemots did not differ significantly. Some PFAS showed higher concentrations in eggs than in female livers. The ratio of levels in egg/female liver, indicating mother-to-egg transfer capacity, increased with increasing PFAS chain length. PFOS showed a higher tendency for transfer than carboxylates of carbon chain lengths C9-C13.     

Using fluffy layer material to study the fate of particle-bound organic pollutants in the southern Baltic Sea

This paper examines the utility of fluffy layer material for studying and monitoring the environmental levels, transport, and fate of particle-bound contaminants in coastal ecosystems. Fluffy layer material is the very young and mobile layer of particulate matter that accumulates on the sediment surface under quiescent conditions. We used this material to study the behavior of polycyclic aromatic hydrocarbons (PAHs) that are discharged by the Oder River into the Baltic Sea. With the fluffy layer material, it was possible to (i) do fingerprint analysis to trace the sources of PAHs in the river discharge, (ii) follow the modification of the PAHs from the mouth of the river to the depositional basin and identify the responsible processes, (iii) monitor the seasonal variation in the PAH input, (iv) study the influence of a major flood event on the PAH loading to the coastal ecosystem, and (v) conduct a PAH mass balance to estimate the contribution of the Oder River source to PAH accumulation in the depositional basin. The fluffy layer material integrated the particle-bound contaminant signal over a period ranging from several days to several months, depending on the sampling location. As such, fluffy layer material is a valuable addition to the matrixes commonly used for studying particle-associated chemicals: SPM and sediment, which reflect time scales of hours and years, respectively.     

Hydroxylated and methoxylated brominated diphenyl ethers in the red algae Ceramium tenuicorne and blue mussels from the Baltic Sea

Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and hydroxylated PBDEs (OH-PBDEs) have recently been identified in fish and wildlife from the Baltic Sea. Both OH-PBDEs and MeO-PBDEs are known natural products, while OH-PBDEs also may be metabolites of PBDEs. The aim of the present study was to determine if the red macroalga Ceramium tenuicorne could be a source for MeO- and OH-PBDEs in the Baltic environment. Blue mussels (Mytilus edulis) from the same area were also investigated for their content of MeO- and OH-PBDEs. Seven OH-PBDEs and four MeO-PBDEs were present both in the red macroalga and the blue mussels. The mussels also contained a monochlorinated OH-tetraBDE. One of the compounds, 6-methoxy-2,2',3,4,4',5-hexabromodiphenyl ether, has never been reported to occur in the environment. The identification was based on comparison of relative retention times with reference standards, on two gas chromatographic columns of different polarities, together with comparisons of full-scan electron capture negative ionization (ECNI) and electron ionization (EI) mass spectra. It is shown that MeO-PBDEs and OH-PBDEs are present in algae, but at this stage it could not be confirmed if the compounds are produced by the alga itself or by its associated microflora and/or microfauna.     

Temporal trend studies on tetra- and pentabrominated diphenyl ethers and hexabromocyclododecane in guillemot egg from the Baltic Sea

Guillemot eggs from the Baltic Sea, sampled between 1969 and 2001, were analyzed for tetra- and pentabromodiphenyl ethers (2,2',4,4'-tetraBDE (BDE-47), 2,2',4,4',5-pentaBDE (BDE-99), and 2,2',4,4',6-pentaBDE (BDE-100)), and hexabromocyclododecane (HBCD). This temporal trend study indicates that the concentrations of the polybrominated diphenyl ether compounds increased from the 1970s to the 1980s, peaking around the mid- to the late-1980s. These peaks are then followed by a rapid decrease in concentrations during the rest of the study period, with the concentrations of the major BDE congener below 100 ng/g lipid weight at the end of the period. This corresponds to less than 10% of its peak values. The concentrations of HBCD show a different pattern over time. After a peak in the middle of the 1970s followed by a decrease, the concentrations increased during the latter part of the 1980s. During the recent 10-yr period no significant change has occurred, and the annual mean concentrations are more or less stable at a higher level as compared to the beginning of the study period.     

Particle-water partitioning of PCBs in the photic zone: a 25-month study in the open Baltic Sea

From previous laboratory and field studies, it remains unclear whether partitioning of hydrophobic organic contaminants (HOCs) to phytoplankton from water is kinetically limited or may be treated as an equilibrium process. Here, we report on the partitioning of polychlorinated biphenyls (PCBs) to particulate organic carbon (POC), dominated by planktonic primary production, in the open Baltic Sea during a 25-month period. The organic carbon-normalized partition coefficient (Koc) was corrected for temperature, salinity, and sorption to filter-passing organic carbon. At all 21 sampling occasions, the log Koc-log Kow regression was significantly linear, despite a large variation in biogeochemical parameters such as POC concentration and composition, primary production, and phytoplankton species composition. These data strongly suggest that partitioning of PCBs to POC in temperate surface waters is equilibrated and therefore not kinetically limited by factors such as rapid phytoplankton growth rate or large cell size. The partitioning of PCBs to the POC was described throughout seasonal cycles by log Koc = 0.88 +/- 0.07 log Kow + 0.90 +/- 0.47 (95% confidence interval). The slope of the log Koc-log Kow regression for the single sampling occasions varied between 0.56 and 1.25, and there was a seasonal variation in the POC sorbent quality (e.g., log Koc for PCB 28 varied between 5.5 and 6.9; median 5.9). These variations reflect the variability in structural composition of the POC pool in such pelagic waters. Being able to predict particle-water partitioning of HOCs significantly reduces the required complexity of both food web uptake models and predictions of POC-mediated export of HOCs to the deep ocean.