Janusz Pempkowiak

EXTRACTION STUDIES OF HEAVY-METAL POLLUTANTS IN SURFICIAL SEDIMENTS FROM THE SOUTHERN BALTIC SEA OFF POLAND

Surficial sediment samples from the Gulf of Gdansk and the southern Baltic Sea were analyzed for Cu, Zn, Cd, Pb, Ag, Cr, Co, Ni, Mn, Cs, Rb, Fe, Ca, Mg, K, Na, Li, Sr, Al and P. Extraction techniques were used to establish the association of the elements with specific phases in the sediments. Elimination of grain size effects was achieved by analyzing the size fraction 60% of the total Zn, Cd, Pb and Na, ∼60% of the Cu, Cr, Mn, Sr, Ca and Mn, and <50% of the Ag, Co, Ni, Cs, Rb, Li, Fe, Al, K and P in the sediment. Up to 45% of the total Cu was extracted from the sediments by 0.1 M NaOH and appears to be associated with the humic acid fraction. Areal variations of element contents were observed. Most elements in total and HCl leachates were enriched in sediments from near the mouth of the Vistula River. Correlation studies indicated that the trace elements are partitioned among several phases such as Fe- and Mn-oxyhydroxides and clay minerals in the sediments.

Heavy‐metal pollution in surficial sediments from the Southern Baltic sea off Poland

Abstract The Gulf of Gdansk is one of the pollution “hot spots”; of the Baltic Sea. In order to investigate heavy‐metal pollution there, 31 bulk (<2 mm), surficial sediments from the Gulf of Gdansk and the southern Baltic Sea were analyzed for 20 elements. Cobalt, Ni, Cs, Rb, Fe, Mg, Li, and K covary with Al and display an enrichment factor EFAl M of about one, indicating that these elements occur in the sediments dominantly in the clay mineral fraction. Zinc, Cd, Pb, and Ag display an enrichment factor much greater than one and are thought to be dominantly anthropogenic in origin. Grain size plays a significant role in determining element concentrations within the sediments. Systematic trends in the distribution of the heavy metals away from the mouth of the Vistula River were therefore not observed in bulk sediments. However, R‐mode factor analysis discriminated between sediments taken from near the mouths of the Vistula and Reda Rivers and the other sediments and indicated that sediments from near the ...

Assessment of organotin pollution along the Polish coast (Baltic Sea) by using mussels and fish as sentinel organisms

Levels of tributyltin (TBT) and its degradation products, mono- (MBT) and dibutyltin (DBT), as well as triphenyltin (TPT), were monitored in 10 stations along the Polish coast (Baltic Sea). Mussel-Mytilus edulis-and fish-Platichthys flesus-were used as sentinel organisms. The bioaccumulation patterns of butyltin and phenyltin compounds varied substantially. Butyltins were detected in mussel tissue from all the sampled stations. Among them, organisms from the Gulf of Gdansk showed the highest residues (68 ng/g w.w. as Sn) in conjunction with elevated TBT/DBT ratios, which suggest recent inputs of TBT in the area. Additionally, flatfish were sampled in the Gulf of Gdansk, and different tissues (liver, digestive tube and gills) were analyzed separately. TPT, although undetected in mussels, was always present in fish. The highest organotin concentration was observed in the liver (369 ng/g w.w. as Sn) of fish caught near Gdansk port. Relatively high concentrations were observed in digestive tube, which points out the ingestion of organotin contaminated food as an important uptake route of those compounds in P. flesus.

Horizontal and vertical variabilities of mercury concentration and speciation in sediments of the Gdansk Basin, Southern Baltic Sea

The mercury compounds introduced to the environment because of anthropogenic activity are accumulated, mainly, in marine sediments. Both distribution of mercury in the Baltic Sea and factors affecting it are remain largely unknown. Due to its complex chemistry and variable conditions in the Baltic Sea bottom sediments, mercury may be reemitted to the overlaying water, and thus to the environment. The aim of this study was twofold. Total mercury contents were measured in sediments of the Gdansk Basin along a Vistula mouth (main source)--Gdansk Deep (deposition area) transect in order to assess spatial distribution of the element. Soft and sandy bottom sediment cores were collected and cut into slices. The mercury measurements consisted of acid digestion followed by CV-AAS determination. A five-step sequential extraction procedure involving measurements of mercury species water soluble, bound to humic substances and insoluble, was employed in order to investigate mercury speciation. On the basis of speciation results stability and remobilisation potential was assessed. The second aim was demonstrating that mercury gradients in vertical profiles of the investigated sediment cores exist. Total mercury contents varied in range from 28 ng/g x dw to 844 ng/g. Mercury associated with organic matter and sulphides, (respectively 39% and 49%) were the dominant species of the element. The results indicated that the river run-off is a source of mercury in the area. Vertical gradients of both total content and speciation of mercury in the soft sediments were attributed to both remobilisation from sediments, and decreasing trend in the anthropogenic load of the element deposited to sediments.

Mercury and major essential elements in seals, penguins, and other representative fauna of the Antarctic.

Concentrations of total Hg and major essential elements, Ca, Mg, Na, and K, were measured in the muscle, liver, and kidney of three species of seals, crabeater seal (Lobodon carcinophagus), leopard seal (Hydrurga leptonyx), and Weddell seal (Leptonychotes weddelli) collected in the Antarctic. The muscle and liver of three species of penguins, i.e., gentoo penguin (Pygoscelis papua), Adelie penguin (P. adeliae), chinstrap penguin (P. antarctica), and other representative fauna were also analyzed for the elements. Distinct inter-tissue differences in the metal concentration were observed; liver had the greatest concentrations of Hg, kidney showed maximum concentration of Ca and Na, while muscle was characterized by the greatest content of Mg and K. Inter-specimen differentiation of concentrations among the same species was distinctly visualized for Hg but not for the major essential elements. The Hg concentration in the seals analyzed are in keeping with those reported previously by other authors. Such comparison for Ca, Mg, Na, and K was impossible because of the lack of available literature data for their concentrations in marine seals. Numerous significant correlations were observed between concentrations of the several metals analyzed. There was no correlation between Hg, which is a non-essential element and both Zn and Cd which are essential and non-essential elements, respectively in the liver or kidney of seals. However, there were significant correlations between concentration of Zn and the sum of molar concentrations of Hg + Cd in kidney (r=0.82) and liver (r=0.76). The results suggest that several control mechanisms operate to maintain physiologically required levels that decreases any effect of heavy metal toxicants such as Hg and Cd.

Enrichment factors of heavy metals in the Southern Baltic surface sediments dated with 210Pb and 137Cs

Abstract Eight samples of stratified bottom sediments (cores) from the Gdansk Basin, the Bornholm Deep, and the Arcona Deep (Southern Baltic) were collected. The rate of sediment accumulation amounting to 0.1–2.3 mm/y was established by means of the radioactive lead ( 210 Pb) method and confirmed by 137 Cs distribution. The measurements revealed an increase of some heavy metals concentrations in the surface sediments. The enrichment factors for Hg, Cu, Zn, Pb, Cd, Ni, Co, and Cr were found in the ranges of 4.7–4.9, 1.1–2.7, 1.1.–2.5, 1.4–2.8, 1.0–2.2,, 1.0, 1.0, and 1.0–1.2, respectively. An increase of metals inflow to sediments caused by anthropogenic factors, modified by oxidative-reductive conditions, is held responsible for the enrichment.

Distribution and coassociations of selected metals in seals of the Antarctic.

Zinc, Cu, Cd, Pb, Ag, Ni, Co, Cr, Fe and Mn concentrations in some tissues of crabeater seal (Lobodon carcinophagus), leopard seal (Hydrurga leptonyx) and Weddell seal (Leptonychotes weddelli) from the Antarctic were determined. Distinct inter-tissue differences in metal concentrations in seals were observed; liver contained maximum levels of Zn, Cu, Ag and Mn, whilst kidney showed the highest levels of Cd, Ni and Co. Muscle was characterized by low concentrations of all the elements analyzed. The metal concentrations in the vertebrates analyzed were compared with those for organisms originating from various aquatic areas. Significant correlations were found between the levels of several of the metals analyzed, e.g. between renal and hepatic concentrations of Zn and Cd. Strong relationships between the hepatic concentrations of some metals were found, e.g. Cd-Zn. These two metals also showed a significant coassociation in their renal concentrations. The slope of the regression line for renal Cd/Zn was about three times higher than the hepatic one and this may reflect a relatively high Cd exposure, probably from specific food (squid and krill) provenance, of the seals analyzed.

Concentration of selected metals in penguins and other representative fauna of the Antarctica

Concentration of Zn, Cu, Cd, Pb, Ag, Co, Ni, Cr, Mn and Fe were determined in muscle and liver of three species of penguins and other animals of the antarctic region. Liver was characterized by maximum concentrations of all the metals analyzed. The element levels in the samples assayed are in keeping with those reported previously by other authors. It is assumed that specific food habits of penguins are mainly responsible for elevated Cd levels in livers of these birds.

Long-term changes in sewage sludge stored in a reed bed

The problem of the utilization and management of sewage sludge originating from small wastewater treatment plants is still unsolved. A common approach is to store the sludge in plots which in time turn into grassland. This investigation was aimed at evaluating the influence of the storage time in plots on the chemical properties of sewage sludge deposited there. Tests were carried out on samples obtained from discrete layers of stratified sludge that had lain in a hydrophyte facility disused for 7 years after 23 years of continuous sludge discharge. The age of the sludge was established by the lead-210 method. Moisture, organic matter, total nitrogen and total phosphorus contents were measured in samples of dated sewage sludge. The composition of the stored biosolids stabilized with respect to phosphorus, nitrogen and organic matter within 11, 15 and 17 years, respectively.

Biogeochemical Control of the Coupled CO2–O2 System of the Baltic Sea: A Review of the Results of Baltic-C

Past, present, and possible future changes in the Baltic Sea acid–base and oxygen balances were studied using different numerical experiments and a catchment–sea model system in several scenarios including business as usual, medium scenario, and the Baltic Sea Action Plan. New CO2 partial pressure data provided guidance for improving the marine biogeochemical model. Continuous CO2 and nutrient measurements with high temporal resolution helped disentangle the biogeochemical processes. These data and modeling indicate that traditional understandings of the nutrient availability–organic matter production relationship do not necessarily apply to the Baltic Sea. Modeling indicates that increased nutrient loads will not inhibit future Baltic Sea acidification; instead, increased mineralization and biological production will amplify the seasonal surface pH cycle. The direction and magnitude of future pH changes are mainly controlled by atmospheric CO2 concentration. Apart from decreasing pH, we project a decreasing calcium carbonate saturation state and increasing hypoxic area.