Organotins in North Sea brown shrimp (Crangon crangon L.) after implementation of the TBT ban

The organotin (OT) compounds tributyltin (TBT) and triphenyltin (TPhT) are potent biocides that have been used ubiquitously in antifouling paints and pesticides since the mid-1970s. These biocides are extremely toxic to marine life, particularly marine gastropod populations. The European Union therefore took measures to reduce the use of TBT-based antifouling paints on ships and ultimately banned these paints in 2003. Despite sufficient data on OT concentrations in marine gastropods, data are scarce for other species such as the North Sea brown shrimp (Crangon crangon), a dominant crustacean species in North Sea inshore benthic communities. The present study provides the first spatial overview of OT concentrations in North Sea brown shrimp. We have compared these data with historical concentrations in shrimp as well as with sediment concentrations. We have also addressed the effect on the shrimp stock and any human health risks associated with the OT concentrations found. TBT and TPhT in shrimp tail muscle ranged from 4 to 124 and from 1 to 24 μg kg⁻¹ DW, respectively. High levels are accumulated in estuarine areas and are clearly related with sediment concentrations (biota-sediment accumulation factor ∼10). Levels have decreased approximately 10-fold since the ban took effect, coinciding with a recovery of the shrimp stock after 30 years of gradual regression. Furthermore, the OT levels found in brown shrimp no longer present a human health risk.     

A numerical study on the seasonal variability of polychlorinated biphenyls from the atmosphere in the East China Sea

A three-dimensional/high-resolution transport model for persistent organic pollutants (POPs) has been developed for the East China Sea (ECS). The POPs model has four compartments (gaseous, dissolved, phytoplankton-bound, and detritus-bound phases) and includes processes for diffusive air-water exchange, phytoplankton uptake/depuration to POPs, decomposition of dissolved phase, vertical sinking of phytoplankton, detritus production by phytoplankton mortality, and vertical sinking and decomposition of detritus. The POPs model is coupled with an ocean circulation model that can reproduce the seasonal variation in physical variables to represent the advection and diffusion of POPs. We applied the POPs model to the polychlorinated biphenyl congener 153 (PCB 153) from the atmosphere and examined the behavior of PCB 153 in the ocean. The model showed a remarkable seasonal variability of PCB 153. Concentrations in the dissolved and particulate phases are high in winter (January-March) and low in summer (July-September). In coastal regions, where chlorophyll a concentration is high, horizontal and vertical distributions in the dissolved and particulate PCB 153 concentrations are strongly affected by phytoplankton uptake. The sensitivity experiments on the dynamics of PCB 153 suggested that a change of Henry’s law constant associated with water temperature is the major factor controlling the seasonal variability of PCB 153. The model-based yearly mass balance of PCB 153 in the ECS indicated that most of the atmospheric input (35.5 kg year⁻¹) is removed by the horizontal advection outside the ECS (19.0 kg year⁻¹) and accumulates to the sea bottom by vertical sinking (15.7 kg year⁻¹). For comparison with PCB 153, we also conducted simulations for PCB 52, 101, and 180. The seasonal variations are similar to that of PCB 153. The mass balance of PCB 52 that has short half-life time and less hydrophobic property shows the different results compared with PCB 101, 153, and 180.     

Zinc effect on the sea urchin Paracentrotus lividus immunological competence

Pollution by heavy metals has become one of the most important problems in marine coastal areas as a consequence of anthropogenic inputs. Among metal contaminants, zinc, being considered not very toxic, is sometimes released into the sea in appreciable quantities and its concentration is loosely regulated.In this work we analyzed the effects of a high zinc concentration on the sea urchin Paracentrotus lividus immune system. In particular, after 24 h of zinc treatment, we evaluated coelomocytes morphology and composition as well as the zinc influence on some humoral parameters such as hemolysis, lysozyme-like activity and antibacterial activity on Vibrio alginolyticus. Our results evidenced that the presence of zinc affected both cellular and acellular components of the sea urchin immune system. The P. lividus coelomocytes changed in morphology and number; moreover, the amebocytes changed from a petaloid to a filipodial-like shape and the red spherula cells increased in number. Among the considered humoral effectors lysozyme-like activity and antibacterial activity on V. alginolyticus decreased in short-term to zinc treatment. The modifications in the sea urchin immunological competence might give an early indication of disease susceptibility thus suggesting to consider the examined defence mechanisms as potential biological indicators of metal pollution.     

Development of Tools for Integrated Monitoring and Assessment of Hazardous Substances and Their Biological Effects in the Baltic Sea

The need to develop biological effects monitoring to facilitate a reliable assessment of hazardous substances has been emphasized in the Baltic Sea Action Plan of the Helsinki Commission. An integrated chemical–biological approach is vitally important for the understanding and proper assessment of anthropogenic pressures and their effects on the Baltic Sea. Such an approach is also necessary for prudent management aiming at safeguarding the sustainable use of ecosystem goods and Services. The BEAST project (Biological Effects of Anthropogenic Chemical Stress: Tools for the Assessment of Ecosystem Health) set out to address this topic within the BONUS Programme. BEAST generated a large amount of quality-assured data on several biological effects parameters (biomarkers) in various marine species in different sub-regions of the Baltic Sea. New indicators (biological response measurement methods) and management tools (integrated indices) with regard to the integrated monitoring approach were suggested.     

A Comprehensive Inventory of the Ship Traffic Exhaust Emissions in the Baltic Sea from 2006 to 2009

This study addresses the exhaust emissions of CO₂, NO_x, SO_x, CO, and PM_2.5 originated from Baltic Sea shipping in 2006–2009. Numerical results have been computed using the Ship Traffic Emissions Assessment Model. This model is based on the messages of the automatic identification system (AIS), which enable the positioning of ships with a high spatial resolution. The NO_x emissions in 2009 were approximately 7 % higher than in 2006, despite the economic recession. However, the SO_x emissions in 2009 were approximately 14 % lower, when compared to those in 2006, mainly caused by the fuel requirements of the SO_x emission control area (SECA) which became effective in May 2006, but affected also by changes in ship activity. Results are presented on the differential geographic distribution of shipping emissions before (Jan–April 2006) and after (Jan–April 2009) the SECA regulations. The predicted NO_x emissions in 2009 substantially exceeded the emissions in 2006 along major ship routes and at numerous harbors, mostly due to the continuous increase in the number of small vessels that use AIS transmitters. Although the SO_x emissions have been reduced in 2009 in most major ship routes, these have increased in the vicinity of some harbors and on some densely trafficked routes. A seasonal variation of emissions is also presented, as well as the distribution of emissions in terms of vessel flag state, type, and weight.     

A western gray whale mitigation and monitoring program for a 3-D seismic survey, Sakhalin Island, Russia

The introduction of anthropogenic sounds into the marine environment can impact some marine mammals. Impacts can be greatly reduced if appropriate mitigation measures and monitoring are implemented. This paper concerns such measures undertaken by Exxon Neftegas Limited, as operator of the Sakhalin-1 Consortium, during the Odoptu 3-D seismic survey conducted during 17 August–9 September 2001. The key environmental issue was protection of the critically endangered western gray whale (Eschrichtius robustus), which feeds in summer and fall primarily in the Piltun feeding area off northeast Sakhalin Island. Existing mitigation and monitoring practices for seismic surveys in other jurisdictions were evaluated to identify best practices for reducing impacts on feeding activity by western gray whales. Two buffer zones were established to protect whales from physical injury or undue disturbance during feeding. A 1 km buffer protected all whales from exposure to levels of sound energy potentially capable of producing physical injury. A 4–5 km buffer was established to avoid displacing western gray whales from feeding areas. Trained Marine Mammal Observers (MMOs) on the seismic ship Nordic Explorer had the authority to shut down the air guns if whales were sighted within these buffers. Additional mitigation measures were also incorporated: Temporal mitigation was provided by rescheduling the program from June–August to August–September to avoid interference with spring arrival of migrating gray whales. The survey area was reduced by 19% to avoid certain waters <20 m deep where feeding whales concentrated and where seismic acquisition was a lower priority. The number of air guns and total volume of the air guns were reduced by about half (from 28 to 14 air guns and from 3,390 in³ to 1,640 in³) relative to initial plans. “Ramp-up” (=“soft-start”) procedures were implemented. Monitoring activities were conducted as needed to implement some mitigation measures, and to assess residual impacts. Aerial and vessel-based surveys determined the distribution of whales before, during and after the seismic survey. Daily aerial reconnaissance helped verify whale-free areas and select the sequence of seismic lines to be surveyed. A scout vessel with MMOs aboard was positioned 4 km shoreward of the active seismic vessel to provide better visual coverage of the 4–5 km buffer and to help define the inshore edge of the 4–5 km buffer. A second scout vessel remained near the seismic vessel. Shore-based observers determined whale numbers, distribution, and behavior during and after the seismic survey. Acoustic monitoring documented received sound levels near and in the main whale feeding area. Statistical analyses of aerial survey data indicated that about 5–10 gray whales moved away from waters near (inshore of) the seismic survey during seismic operations. They shifted into the core gray whale feeding area farther south, and the proportion of gray whales observed feeding did not change over the study period. Five shutdowns of the air guns were invoked for gray whales seen within or near the buffer. A previously unknown gray whale feeding area (the Offshore feeding area) was discovered south and offshore from the nearshore Piltun feeding area. The Offshore area has subsequently been shown to be used by feeding gray whales during several years when no anthropogenic activity occurred near the Piltun feeding area. Shore-based counts indicated that whales continued to feed inshore of the Odoptu block throughout the seismic survey, with no significant correlation between gray whale abundance and seismic activity. Average values of most behavioral parameters were similar to those without seismic surveys. Univariate analysis showed no correlation between seismic sound levels and any behavioral parameter. Multiple regression analyses indicated that, after allowance for environmental covariates, 5 of 11 behavioral parameters were statistically correlated with estimated seismic survey-related variables; 6 of 11 behavioral parameters were not statistically correlated with seismic survey-related variables. Behavioral parameters that were correlated with seismic variables were transient and within the range of variation attributable to environmental effects. Acoustic monitoring determined that the 4–5 km buffer zone, in conjunction with reduction of the air gun array to 14 guns and 1,640 in³, was effective in limiting sound exposure. Within the Piltun feeding area, these mitigation measures were designed to insure that western gray whales were not exposed to received levels exceeding the 163 dB re 1 μPa (rms) threshold. This was among the most complex and intensive mitigation programs ever conducted for any marine mammal. It provided valuable new information about underwater sounds and gray whale responses during a nearshore seismic program that will be useful in planning future work. Overall, the efforts in 2001 were successful in reducing impacts to levels tolerable by western gray whales. Research in 2002–2005 suggested no biologically significant or population-level impacts of the 2001 seismic survey. M. W. Newcomer is deceased.     

Heavy Metal Monitoring Using Bivalved Shellfish from Zhejiang Coastal Waters, East China Sea

The interest of culturing bivalved shellfish (including mussels, clams, oysters etc.), has increased in recent years, but the consumption has been hampered both by high levels of heavy metals and toxic algae. The levels of heavy metals (Hg, Cd, Pb, Zn, Cu and As) were determined in soft tissues of different shellfish from Zhejiang coastal waters, East China Sea. The average concentrations of the heavy metals analyzed exhibited the following decreasing order: Zn > Cu > As > Cd > Pb > Hg. Comparison of heavy metals concentrations among species indicated that Bivalves clearly have significant potential as useful bioindicators; however, the results indicated that no one species is universally suitable, as is true of any organism used in these studies. The distribution of the metals was also investigated along the Zhejiang coast, which the results showed the mean concentration of Hg and Cd detected did not vary greatly and presented a similar spatial pattern at different sampling stations, the concentrations of Zn and Pb were highly variable at different sampling sites. The amounts of heavy metals in soft tissue of shellfish were also compared with those from the related species from other seas in China and world marine waters. The results suggested that the coastal area might be considered relatively unpolluted with heavy metals and the concentrations of metals in shellfish also below the seafood safety limits for human consumption.     

Toxicity of tire wear particle leachate to the marine macroalga, Ulva lactuca

Tire wear particles filed from the treads of end-of-life vehicle tires have been added to sea water to examine the release of Zn and the toxicity of the resulting leachate and dilutions thereof to the marine macroalga, Ulva lactuca. Zinc release appeared to be diffusion-controlled, with a conditional rate constant of 5.4 μg[L(h)^1/2]⁻¹, and about 1.6% of total Zn was released after 120 h incubation. Exposure to increasing concentrations of leachate resulted in a non-linear reduction in the efficiency of photochemical energy conversion of U. lactuca and, with the exception of the undiluted leachate, increasing accumulation of Zn. Phototoxicity was significantly lower on exposure to equivalent concentrations of Zn added as Zn(NO₃)₂, suggesting that organic components of leachate are largely responsible for the overall toxicity to the alga. Given the ubiquity and abundance of TWP in urban coastal sediments, the generation, biogeochemistry and toxicity of tire leachate in the marine setting merit further attention.     

Environmental Degradation of Blends of Atactic Poly[(R,S)-3-hydroxybutyrate] with Natural PHBV in Baltic Sea Water and Compost with Activated Sludge

Degradation of atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) binary blends with natural poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV, 12 mol% of 3HV units), has been investigated and compared with plain PHBV in the compost containing activated sludge and under marine exposure conditions in the dynamic water of the Baltic Sea. Characteristic parameters of compost and the Baltic Sea water were monitored during the incubation period (6 weeks) and their influence on the degree of biodegradation is discussed. After specified degradation times of the experiments the weight loss of the samples, surface changes, changes in molecular weight and polydispersity as well as changes of the composition and thermo-mechanical properties of the blends have been evaluated. Macroscopic observations of the samples were accompanied by investigations using optical microscopy, size-exclusion chromatography (SEC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and tensile testing. The degree of degradation of blends of a-PHB with PHBV depends on the blend composition and environmental conditions. In both environments studied the weight loss of plain PHBV was more significant than changes the molecular weight. In both environments only enzymatic degradation of the blends, which proceeds via surface erosion mechanisms, was observed during the incubation period.     

Shipboard Measurements of Nitrogen Dioxide,Nitrous Acid,Nitric Acid and Ozone in the Eastern Mediterranean Sea

Measurements of nitrogen dioxide, nitrous and nitric acids as well as ozone were made using newly developed instrumentation onboard the research vessel Aegeon in the Aegean Sea between 25th–29th July 2000. Typical nitrogen dioxide concentrations observed aboard the boat were 4–6 ppb (v/v) with a broad maximum of 20–30 ppb (v/v). Ozone concentrations typically ranged between 40 and 80 ppb (v/v). Mixing ratios of both nitric and nitrous acids in the ambient air of the Aegean Sea were mainly below 50 ppt (v/v). The data also showed a number of short pollution episodes with rapid changes in the concentration of reactive nitrogen compounds [nitrogen dioxide maximum up to 164 ppb (v/v), nitric acid maximum up to 12 ppb (v/v), nitrous acid maximum up to 2.7 ppb (v/v)] and ozone [maximum up to 88 ppb (v/v)]. These episodes were correlated with pollution plumes originating from boats upwind, at short distance, from the R/V Aegeon. The measurements revealed the importance of nitrous and nitric acids for the transport of nitrogen to marine biota in busy ship lanes.