Polycyclic aromatic hydrocarbons in the Baltic Sea - Pre-industrial and industrial developments as well as current status.

We report on Baltic Sea polycyclic aromatic hydrocarbon (PAH) pressure based on the U.S. EPA PAHs in view of millennial and decadal developments utilizing data from sediment deposits and seawater. Pre-industrial PAH contents ranged from 500 to 4500 ng/g TOC. Maximum PAH contents were up to 100,000 ng/g TOC and date back to the 1960s to 1970s with maximum pollutant inputs. Contemporary sediment PAH contents with 10,000 to 35,000 ng/g TOC and seawater concentrations with about 1 to 16 ng/l show spatial variability due to different local inputs and sediment characteristics. Pre-industrial compositional change from low molecular weight to high molecular weight (HMW) PAH indicates changing sources from mostly petroleum to combustion. Application of diagnostic ratios reveals petroleum and combustion as contemporary PAH sources and that traffic emissions continuously contribute to the Baltic PAH profile. Medium to high toxicological risk to the marine community might arise from current HMW PAH contents.

Effect of large magnetotactic bacteria with polyphosphate inclusions on the phosphate profile of the suboxic zone in the Black Sea.

The Black Sea is the world's largest anoxic basin and a model system for studying processes across redox gradients. In between the oxic surface and the deeper sulfidic waters there is an unusually broad layer of 10-40 m, where neither oxygen nor sulfide are detectable. In this suboxic zone, dissolved phosphate profiles display a pronounced minimum at the upper and a maximum at the lower boundary, with a peak of particulate phosphorus in between, which was suggested to be caused by the sorption of phosphate on sinking particles of metal oxides. Here we show that bacterial polyphosphate inclusions within large magnetotactic bacteria related to the genus Magnetococcus contribute substantially to the observed phosphorus peak, as they contain 26-34% phosphorus compared to only 1-5% in metal-rich particles. Furthermore, we found increased gene expression for polyphosphate kinases by several groups of bacteria including Magnetococcaceae at the phosphate maximum, indicating active bacterial polyphosphate degradation. We propose that large magnetotactic bacteria shuttle up and down within the suboxic zone, scavenging phosphate at the upper and releasing it at the lower boundary. In contrast to a passive transport via metal oxides, this bacterial transport can quantitatively explain the observed phosphate profiles.

Sulfurimonas subgroup GD17 cells accumulate polyphosphate under fluctuating redox conditions in the Baltic Sea: possible implications for their ecology.

The central Baltic Sea is characterized by a pelagic redox zone exhibiting high dark CO2 fixation rates below the chemocline. These rates are mainly driven by chemolithoautotrophic and denitrifying Sulfurimonas GD17 subgroup cells which are motile and fast-reacting r-strategists. Baltic Sea redox zones are unstable and a measurable overlap of nitrate and reduced sulfur, essential for chemosynthesis, is often only available on small scales and short times due to local mixing events. This raises the question of how GD17 cells gain access to electron donors or acceptors over longer term periods and under substrate deficiency. One possible answer is that GD17 cells store high-energy-containing polyphosphate during favorable nutrient conditions to survive periods of nutrient starvation. We used scanning electron microscopy with energy-dispersive X-ray spectroscopy to investigate potential substrate enrichments in single GD17 cells collected from Baltic Sea redox zones. More specific substrate enrichment features were identified in experiments using Sulfurimonas gotlandica GD1T, a GD17 representative. Sulfurimonas cells accumulated polyphosphate both in situ and in vitro. Combined genome and culture-dependent analyses suggest that polyphosphate serves as an energy reservoir to maintain cellular integrity at unfavorable substrate conditions. This redox-independent energy supply would be a precondition for sustaining the r-strategy lifestyle of GD17 and may represent a newly identified survival strategy for chemolithoautotrophic prokaryotes occupying eutrophic redox zones.

Benthic Bacterial Community Composition in the Oligohaline-Marine Transition of Surface Sediments in the Baltic Sea Based on rRNA Analysis.

Salinity has a strong impact on bacterial community composition such that freshwater bacterial communities are very different from those in seawater. By contrast, little is known about the composition and diversity of the bacterial community in the sediments (bacteriobenthos) at the freshwater-seawater transition (mesohaline conditions). In this study, partial 16S-rRNA sequences were used to investigate the bacterial community at five stations, representing almost freshwater (oligohaline) to marine conditions, in the Baltic Sea. Samples were obtained from the silty, top-layer (0-2.5 cm) sediments with mostly oxygenated conditions. The long water residence time characteristic of the Baltic Sea, was predicted to enable the development of autochthonous bacteriobenthos at mesohaline conditions. Our results showed that, similar to the water column, salinity is a major factor in structuring the bacteriobenthos and that there is no loss of bacterial richness at intermediate salinities. The bacterial communities of marine, mesohaline, and oligohaline sediments differed in terms of the relative rRNA abundances of the major bacterial phyla/classes. At mesohaline conditions typical marine and oligohaline operational taxonomic units (OTUs) were abundant. Putative unique OTUs in mesohaline sediments were present only at low abundances, suggesting that the mesohaline environment consists mainly of marine and oligohaline bacteria with a broad salinity tolerance. Our study provides a first overview of the diversity patterns and composition of bacteria in the sediments along the Baltic Sea salinity gradient as well as new insights into the bacteriobenthos at mesohaline conditions.

TBT and its metabolites in sediments: Survey at a German coastal site and the central Baltic Sea.

Since the 1950s the organotin compound tributyltin (TBT) was intensively used in antifouling paints for marine vessels and it became of concern for the marine environment. Herein, we report on a study from 2015 on TBT and its metabolites monobutyltin (MBT) and dibutyltin (DBT) in sediments from the central Baltic Sea and a Baltic Sea coastal site with strong harbor activities (Warnemünde). Sublayers from a sediment core from the Arkona Basin were analyzed to investigate the long term organotin pressure for the Baltic Sea. For the central Baltic Sea total organotin (MBT+DBT+TBT) ranged from 100 to 500ng/g TOC with distinct areas of high organotin content probably due to historical inputs. For the coastal site total organotin ranged from 10,000 to 60,000ng/g TOC. MBT and DBT were the predominant organotin species detected. Overall, the data obtained indicate the progress of TBT degradation at the investigated sites.

Ecotoxicity assessment of natural attenuation effects at a historical dumping site in the western Baltic Sea.

During the late 1950s and early 1960s of the past century, industrial waste material highly enriched in various contaminants (heavy metals, PAHs) was dumped in the inner Mecklenburg Bay, western Baltic Sea. Large-scale shifts in the spatial distribution of heavy metals in surface sediments were mapped by geochemical monitoring in the mid-1980s and 12 years later in 1997. A further study in 2001 was designed to investigate the small-scale spatial distribution of contaminants inside, on top of, and around the historical dumping ground and to examine possible effects to benthic organisms (Arctica islandica, microbiological toxicity tests). The site is located within an area characterized by a discontinuous deposition of fine sediments, but net sedimentation rate of about 3mm/y led ultimately to a gradual coverage of the dumped material. During the first decades after the dumping, about half of the originally dumped material was already spread over the surrounding area as a result of sediment dynamics and re-suspension processes. Recent sediments of the historical dump site are still significantly enriched in heavy metals and PAHs. Microbiological toxicity test results were positive, though uptake of contaminants in mussels was found to deviate only slightly from that of a non-contaminated reference station due to a gradual dilution and decrease in bioavailability of the contaminants.

Storm disturbance of sediment contaminants at a hot-spot in the Baltic Sea assessed by 234Th radionuclide tracer profiles.

Fly ash sludges from an abandoned metal smelter were dumped into the shallow inner part of the Mecklenburg Bay until 1971, representing the most severe heavy metal contamination hot-spot along the German coast. Half of the dumped Zn (455 t) and Pb (173 t) inventory was found to be spread from the originally 0.5 km2 hot-spot site to a now 360 km2 affected adjacent area. Wave-driven resuspension during gale events produced large pulses of contaminated sediments from this hot-spot due to the only 23 m water depth. Instantaneous sediment mixing down to 10 cm occurs during such a wave event as evidenced by activity profiles of the short-lived radionuclide 234Th in sediment cores. According to these estimated sediment exchange fluxes in the transport bottom area, each wave event may have mobilized Zn and Pb pulses on the order of several hundreds of kilograms from the dump site, sufficient to build up a plume in sediments of the outer bay area. With each centimeter (approximately 5 yr) of additional natural sediment capping, however, the amount of metal remobilization would decrease by about 50%.