Distribution and relationships between selected chemical elements in green alga Enteromorpha sp. from the southern Baltic

The concentrations of heavy metals (Cd, Cu, Ni, Pb, Zn and Mn) and macroelements (K, Na, Ca and Mg) were determined in green alga Enteromorpha sp. from the coastal zone of the southern Baltic including Gulf of Gdańsk and Vistula Lagoon in 2000-2003. In order to estimate the degree of accumulation of each element by the green alga, concentration and discrimination factors (CFs) with respect to seawater were calculated. The results of factor analysis (FA) and ANOVA clearly indicate geographical differences between concentrations of chemical elements. Enteromorpha sp. from Vistula Lagoon and the southern Baltic exhibited higher levels of Mn and Ni, and Na and K, respectively. Anthropogenic impact of Cu, Pb and Zn, possibly originated from municipal sewage, was identified in alga samples collected in the Gulf of Gdańsk, especially in the vicinity of Gdynia. From comparison our data with those published earlier results that Pb content in Enteromorpha sp. from the Gulf of Gdańsk decreased within 1978-2003 reflecting reducing use of leaded petrol in Baltic countries in this period. The alga Enteromorpha sp. can be used for biomonitoring surveys of metal contaminants in coastal areas of the Baltic Sea.     

Heavy metals in zooplankton from the Southern Baltic

Samples of zooplankton and suspended matter were collected using a Bongo net (0.33/0.50 mm mesh net), and Nucleopore filters, respectively, from the Southern Baltic off Poland. Major classes of zooplankton, and selected heavy metals (Fe, Co, Ni, Mn, Pb, Cd, Cu, Zn, Cr) were determined in the collected samples. Concentrations of heavy metals in zooplankton were corrected for metals contributed by particulate matter adhering to zooplankton organisms. Heavy metals levels measured in nearshore samples (Bay of Gdańsk, Pomeranian Bay) were higher than those in the samples from the open sea. The only exception was cadmium exhibiting larger concentrations in the offshore as compared to the nearshore samples (0.8 vs. 1.3 microg/g d.w.). This was attributed to decreased concentrations, of both dissolved and particulate cadmium, caused by algal bloom. Larger concentrations of heavy metals in the Bay of Gdańsk in comparison with the Pomeranian Bay (e.g. Cd-1.3 vs. 0.8 microg/g, Cu-20.5 vs. 8.3 microg/g, Pb-12.9 vs. 1.2 microg/g, Cr-12.4 vs. 1.4 microg/g) were attributed to the direct discharge of the Vistula river to the Bay of Gdańsk, while the Pomeranian Bay receives the Odra river runoff indirectly, via the Szczecin Lagoon. The nonlinear estimation of the data set was used to evaluate concentrations of heavy metals in Copepoda and Cladocera. Copepoda proved to be enriched with heavy metals in comparison with Cladocera.     

Determination of volatile organohalogen compounds in urban precipitation in Tricity area (Gdańsk, Gdynia, Sopot)

Chlorinated and brominated derivatives of methane and ethene were determined in samples of atmospheric precipitation collected between November 2000 and May 2001 at four sites in two cities, Gdańsk and Sopot, located on the Gulf of Gdańsk (Baltic Sea, Poland). The analytes were determined by direct aqueous injection of the samples to the capillary column using ECD detection (DAI-GC-ECD). Chloroform and carbon tetrachloride were detected the most often at all sites. The highest concentrations of the analytes were recorded at the intersection of two major streets (no. 3), next to a major route leading to two subdivisions (no. 2) and at Narutowicza Street (no. 1). In general, analyte concentration levels were lower during the spring months. During precipitation, concentrations of the analytes were higher in samples collected at the beginning of the event due to scavenging of the volatile compounds from the atmosphere. After a period of 75 min from the beginning of the precipitation event, analyte concentrations were lower by 10-80%, depending on the initial concentration and nature of the analyte.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Trace metals in flounder, Platichthys flesus (Linnaeus, 1758), and sediments from the Baltic Sea and the Portuguese Atlantic coast

Trace metals were examined in the muscle tissue of flatfish species of flounder, Platichthys flesus (Linnaeus, 1758), sediments from two southern Baltic Sea sites (Gdańsk Bay and Ustecko-?ebskie as a reference) and in two areas of the Portuguese Atlantic coast (Douro River estuary and Atlantic fishing ground as a reference) to evaluate spatial differences in trace metals. Additionally, the accumulation of trace metals in flounder of different length classes was assessed. Flounder from the Gdańsk Bay area contained twofold more cupper (Cu), lead (Pb) and mercury (Hg) than did flounder from the Douro River estuary, but zinc (Zn) and cadmium (Cd) were at similar concentrations. The sediments from Gdańsk Bay contained significantly more Zn and threefold more Cd, while concentrations of Cu and Pb were twofold lower. The concentrations of metals in the sediments did not correlate with those in the flounder. Spatial differences were noted in metal concentrations in flounder from the southern Baltic Sea and the Portuguese Atlantic coast as well as within these regions, with higher concentrations in the flounder from the Baltic Sea Gdańsk Bay. The flounder in length class 25–30 cm from Gdańsk Bay contained metal concentrations comparable to those of class 40–45 cm specimens from the Atlantic coast. The accumulation of metals in flounder length classes differed in the two regions.     

Distribution and relationships of trace metals in soft tissue,byssus and shells of Mytilus edulis trossulus from the southern Baltic

Concentrations of Hg, Cd, Pb, Ag, Cu, Zn, Cr, Ni, Co, Mn, and Fe in soft tissues, shells and byssus of blue mussel (Mytilus edulis trossulus) from 23 sites along the Polish coast of the Baltic Sea were determined by AAS method. Byssus, as compared with the soft tissue, concentrated more effectively Pb, Cu, Cr, and especially Ag, Ni, Mn and Fe, moderately Hg and Zn and less effectively Cd. Significant inter-regional and inter-size differences in metal concentrations in both soft tissues and byssus were recorded. Highly significant correlations (P<0.01, P<0.05) were observed between tissue and byssal concentrations of Cd, Pb, Ni and Ag. Factor analysis showed clear separation of both the tissue and byssi samples based on their geographic distribution, possibly reflecting a different rate of deposition of clay minerals at the head of the Pomeranian Bay and the Gulf of Gdańsk. The Pomeranian Bay differs from the Gulf of Gdańsk in respect to geological structure of bottom sediments as a substrata for the M. edulis trossulus as well as in relation to various sources of metallic pollutants. From the data obtained in the present study and those reported previously the soft tissue and especially byssus of M. edulis, in contrast to shells, appear to be a significantly better bioindicator for identification of coastal areas exposed to metallic contaminants.     

Concentrations and profiles of PCDD/Fs in sediments of major Polish rivers and the Gdansk Basin--Baltic Sea

The present state of contamination of bottom sediments in southern part of the Baltic Sea with PCDD/Fs was compared to the findings made for the north-western and eastern Baltic Sea coastal areas of Finland, Sweden and Denmark. The extent of the study area--from marine the Gdańsk Basin, the lower Oder and Vistula Rivers up till W?oc?awek reservoir--allowed to obtain the sediment samples with diversified properties. Dioxin's concentrations in sediments examined in the Polish costal area allows us to evaluate this zone as relatively less contaminated. Higher dioxin concentration has been found in Wloclawek Dam Reservoir. Differences in congener patterns and temporal changes in marine sediment profiles were examined. The highest concentrations of tetra- and penta-congeners still remain in the surface layer of Gdansk Deep, whereas the decline in concentrations of these most toxic congeners, have been observed in the sediments from some other parts of the Baltic coast. Excess concentration of dioxins in sediments has a great impact on human being due to special ability of accumulation in the trophic chain as well as in water (fishes) and land (milk, meat).     

Butyltin concentrations in oysters from the Gulf of Mexico from 1989 to 1991

Oyster samples from 53 Gulf of Mexico coastal sites were collected and analyzed for butyltins during 1989, 1990, and 1991. The geometric-mean tributylin concentrations were 85, 30, and 43 ng Sn/g for 1989, 1990, and 1991, respectively. The tributyltin concentrations are best represented by a log-normal distribution. A decline in the butyltin concentrations at sites with relatively low butyltin concentrations for 1989 compared with 1990 and 1991 was observed, and, at relatively high butyltin concentrations (> 400 ng Sn/g), there was hardly any difference between 1989 and 1991, but lower concentrations were present in 1990. Continued monitoring is needed in order to determine if butyltin contamination of the coastal marine environment is decreasing in response to use limitations.     

Polychlorinated biphenyl and organochlorine insecticide residues in human adipose tissue in Poland

Concentrations of PCBs (polychlorinated biphenyls) and organochlorine insecticides such as DDT, HCHs (hexachlorocyclohexanes), HCB (hexachlorobenzene) and chlordanes were determined in human adipose fat from the provinces of Skierniewice and Gdańsk in Poland collected during 1979 and 1990, respectively. The mean levels (microg g(-1) lipid weight basis) in Skierniewice and Gdańsk were found to be 1.2+/-0.44 and 1.5+/-1.3 for PCBs, 25+/-16 and 15+/-13 for DDT, 0.53+/-0.17 and 0.25+/-0.09 for HCHs, 0.36+/-0.22 and 0.26+/-0.23 for HCB, and 0.11+/-0.08 and 0.07+/-0.04 for chlordanes, respectively. Very high concentrations of DDT were detected, with the maximum value as high as 52 microg g(-1) lipid weight in Skierniewice and 47 microg g(-1) lipid weight in Gdańsk. PCB residues contained in the human fat from Polish cadavers are comparable to those of the levels reported for industrialized nations. It is appraised from the levels of DDT and PCBs in Poles' fat that the Polish environment is still experiencing both types of contamination, arising from agricultural and industrial activities. Contamination of humans by other organochlorine insecticides was relatively lower.     

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.     

On the aliphatic,and polycyclic aromatic hydrocarbon levels in the southern baltic sea atmosphere

Samples of marine aerosols from the S Baltic Sea have been analysed for aliphatic hydrocarbons from pentadecane to dotriacontane, and for polycyclic aromatic hydrocarbons (PAHs) from anthracene and phenantrene to benzo(ghi)perylene. Some of the sampling stations were situated near industrialized areas (Gdańsk Bay, Pommeranian Bay) and some others in the open Baltic Sea. The aliphatic hydrocarbons were analysed by gas chromatography, polycyclic aromatic hydrocarbons by HPLC. Quantitative composition of the hydrocarbons in the Baltic aerosols is presented and discussed.     

Occurrence of organotin compounds in water and sediment in Canada

Water and sediment samples from 265 locations across Canada were analyzed for butyltin and methyltin species, and inorganic tin. In 10% of the water samples the highly toxic tributyltin species was found at concentrations which could cause growth retardation upon chronic exposure to a sensitive organism, rainbow trout yolk sac fry. High concentrations of tributyltin were found in some sediments (up to 10 mg Sn/kg dry weight), but the biological availability of sediment-associated tributyltin is unknown. Tributyltin was mainly found in areas of heavy boating and shipping traffic, which is consistent with its use as an antifouling agent in some paints for boats, ships and docks. The methyltin species were found much less frequently in water and sediment than tributyltin and its degradation products.     

Accumulation of butyl- and phenyltin compounds in starfish and bivalves from the coastal environment of Korea

Triphenyltin (TPT) and tributyltin (TBT) concentrations were determined in two starfish species (Asteria pectinifera and Asterias amurensis), bivalves (Crassostrea gigas or Mytilus edulis), and seawater samples from sites around the coasts of Korea. Both TPT and TBT concentrations in starfish ranged from 8 to 1560 ng/g and from <2 to 797 ng/g as Sn on a dry weight basis, respectively. TPT concentration accounted for 75.4% and 86.4% of total phenyltin concentration in A. pectinifera and A. amurensis, respectively, while monobutyltin, a degradation product of TBT, accounted for 86.3% and 57.2% of total butyltin, respectively. Triphenyltin concentrations in A. pectinifera were significantly correlated to water and bivalve TPT concentrations, which implies that dietary uptake of TPT from contaminated prey as well as direct uptake from surrounding water contribute to TPT body residues in the starfish. Starfish could be target organisms for monitoring TPT compound in the marine environment, due to their high accumulation and low degradation capacity towards TPT.     

Butyltins in estuarine sediments two years after tributyltin use was restricted

The highly toxic compound tributyltin (TBT) is the active agent in many effective antifouling paints. In 1988 the U.S. regulated its use in such paints. Sediments taken from four sites in Boston Harbor, MA., USA in the summer of 1990 were assayed for organotins. There was significantly less TBT at all sites in 1990 than there was in 1988. Dibutyltin (DBT) and monobutyltin (MBT), were also detected, confirming that TBT degradation occurs in the estuary. It is suggested that the decreases are due to biological and/or chemical mechanisms rather than to photochemical reactions or transport away from the sites on resuspended particulate matter.     

Pesticides in precipitation in the Gdańsk region (Poland)

Selected organonitrogen, organophosphorus and organochlorine pesticides have been determined in precipitation samples collected at 10 sites in the Gdańsk region (northern Poland) over a period of one year (1998). Compounds which were detected most often included simazine (0.11-5.80 ng/l), fenitrothion (0.1-2.10 ng/l), chlorfenvinfos (0.1-1.30 ng/l), gamma-HCH (0.012-5.06 ng/l), heptachlor epoxide (0.05-3.28 ng/l) and aldrin (0.02-3.28 ng/l). The pesticide concentrations in precipitation samples revealed seasonal fluctuations, with higher concentrations observed during the application periods (June and July). The concentrations observed were also affected by the inflow of polluted air masses from the southwest. The total pesticide concentration in the precipitation samples was strongly related to the abundance of green areas in the vicinity of the sampling sites. A weak correlation was also found between the total concentration of organonitrogen and organophosphorus pesticides, and the total concentration of organochlorine pesticides in the samples collected.     

Distribution of selected heavy metals and rare earth elements in surficial sediments from the polish sector of the Vistula Lagoon

The concentrations of 22 trace elements plus the rare earth elements (REE) were determined in the <63 μm fraction of surficial sediments from the Polish sector of the Vistula Lagoon by ICP-MS. For the anthropogenically-enriched elements, the mean element enrichment factors (EF's) decrease in the sequence Ag (9.9) > Sb (7.5) >As (5.8) ≥ Cd (5.2) > Pb (3.7), albeit with large variability in concentration in the sediments from one station to another. These observations demonstrate that sediments from the Vistula Lagoon are locally polluted by these anthropogenically-derived elements. Plots of NASC-normalized REE data show that the REE patterns of the sediments have not been significantly modified during transport from their source with only a minor depletion of the heavy rare earth elements (HUE) compare to the light rare earth elements (LREE). The lack of any significant anomalies for Ce and Eu indicates that redox processes have not played a major role in modifying the distribution of the REE. Factor ananalysis of the compositional data shows that sediments from the Polish sector of the Vistula Lagoon can be divided into three main groups depending on the geographical location and the degree of contamination by heavy metals.     

Occurrence of butyltin compounds in the waters of selected lakes, rivers and coastal environments from China

The presence of butyltin compounds was investigated for the first time in selected lakes, rivers and coastal environments of China. Aqueous samples were pretreated by the technique of headspace solid phase micro-extraction after hydride generation with sodium tetrahydroborate (NaBH4). Quantitative measurement of tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT) concentrations were accomplished by capillary gas chromatography with flame photometric detector using quartz surface-induced luminescence. Experimental data demonstrated the widespread occurrence of butyltin compounds in the Chinese aquatic environment. In some locations, the concentrations of TBT were higher than the acute and chronic toxicity threshold of sensitive fresh water or marine organisms. Although DBT and MBT (which mainly come from the degradation of TBT), are less toxic, their occurrence can still affect the ecosystem over a long time frame.     

Tin compounds in sediments of Lake Maryut, Egypt

Concentrations of inorganic, methyl- and butyltin compounds were quantified by a hydride derivatization/atomic absorption technique for eleven short sediment cores sampled from Lake Maryut, Alexandria, Egypt. All samples contained inorganic Sn concentrations ranging from 1875 to 8190 ng g(-1) dw, the highest levels occurring in the eastern portion of the lake. Methyltin concentrations were also highest in the eastern lake, decreasing considerably in the western lake. Mono- and dimethyltins were found at all sites, the former species being the highest in concentration. Trimethyltin was much lower than either, and was absent from four out of 11 sites. An opposite trend was observed for the butyltin species, their concentration being highest in the west lake, decreasing eastward. Mono- and dibutyltin were almost equal in concentration. Although tributyltin was absent from one site in the lake, it was much higher in concentration than the two other species, particularly in the western lake. In general, methyl- and butyltin concentrations decreased with depth in the cores. Methyltin compounds appear to form within the lake mainly by methylation of inorganic Sn, and butyltin compounds are derived from anthropogenic sources. No significant correlations were found between organic C and concentrations of methyltin species. A significant negative correlation was found between total butyltin concentrations and organic C in surficial sediments.     

In situ experiments for element species-specific environmental reactivity of tin and mercury compounds using isotopic tracers and multiple linear regression

The fate of mercury (Hg) and tin (Sn) compounds in ecosystems is strongly determined by their alkylation/dealkylation pathways. However, the experimental determination of those transformations is still not straightforward and methodologies need to be refined. The purpose of this work is the development of a comprehensive and adaptable tool for an accurate experimental assessment of specific formation/degradation yields and half-lives of elemental species in different aquatic environments. The methodology combines field incubations of coastal waters and surface sediments with the addition of species-specific isotopically enriched tracers and a mathematical approach based on the deconvolution of isotopic patterns. The method has been applied to the study of the environmental reactivity of Hg and Sn compounds in coastal water and surface sediment samples collected in two different coastal ecosystems of the South French Atlantic Coast (Arcachon Bay and Adour Estuary). Both the level of isotopically enriched species and the spiking solution composition were found to alter dibutyltin and monomethylmercury degradation yields, while no significant changes were measurable for tributyltin and Hg(II). For butyltin species, the presence of light was found to be the main source of degradation and removal of these contaminants from surface coastal environments. In contrast, photomediated processes do not significantly influence either the methylation of mercury or the demethylation of methylmercury. The proposed method constitutes an advancement from the previous element-specific isotopic tracers’ approaches, which allows for instance to discriminate the extent of net and oxidative Hg demethylation and to identify which debutylation step is controlling the environmental persistence of butyltin compounds.     

The stability of butyltin compounds in a dredged heavily-contaminated sediment

A treatment process for marine sediment heavily contaminated with tributyltin (TBT) was designed that included dehydrating, sunlight drying and dumping processes. The time course in butyltin (BTs) compounds, TBT, dibutyltin (DBT) and monobutyltin concentrations were investigated in the sediment treated under various conditions (light (UV, sunlight and light exclusion), moisture (air-drying and water saturation) and wetting and drying cycles). Significant changes in all the BT compound concentrations with time were not found regardless of the sediment conditions for light and moisture. The results indicated the high stabilities of TBT and DBT in the sediments versus light and moisture condition changes, probably taking place in the treatment process. It is also estimated that the BTs in the sediment are resistant to photo-degradation and biochemical degradation and their half lives are relatively long. In contrast, the decreases in the TBT and DBT were observed during the wetting and drying cycle treatment for the water saturated sediment both during exposure to sunlight and under a dark condition. This result suggested the hypothesis that the TBT degradation could be accelerated by the high microbial activity induced by the moisture changing treatments.