Hazardous substances in the aquatic environment of Estonia.

The Water Framework Directive (WFD) aims to regulate the management of European surface water bodies. Directive 2008/105/EC, which establishes the environmental quality standards of priority substances and certain other pollutants, the content of which in the surface water should be monitored, has been transposed by the Estonian Ministry of Environment 9 September 2010 Regulation No. 49. Sampled hazardous substances were selected primarily based on their toxicity, as well as their lifetime in environment and ability to accumulate in living organisms (bioaccumulation). The contents of hazardous substances and their groups determined from Estonian surface waters remained below the limits of quantifications of used analysis methods in most cases. However, the content of some heavy metals, mono- and dibasic phenols in the surface water/waste water and sewage sludge/bottom sediments can still reach the delicate levels in the Estonian oil shale region in particular. Among new substances analysed in Estonia historically first time in 2010, amounts of organotin compounds in sediments and some alkylphenols, their ethoxylates and phthalates were found in various sample matrices.

Distribution pattern of PCBs, HCB and PeCB using passive air and soil sampling in Estonia.

BACKGROUND, AIM, AND SCOPE: Passive air sampling survey of the Central and Eastern Europe was initiated in 2006. This paper presents data on toxic organic compounds such as polychlorinated biphenyls (PCB 28, 52, 101, 118, 153, 138, and 180), hexachlorobenzene (HCB), pentachlorobenzene (PeCB), hexachlorocyclohexane compounds (alpha-HCH, beta-HCH,gamma-HCH, delta-HCH), and dichloro-diphenyl-trichloroethane (DDT) compounds (p,p'DDE, p,p'DDD, p,p'DDT, o,p'DDE, o,p'DDD, and o,p'DDT) determined in ambient air and soil samples collected at Estonian monitoring stations. MATERIALS AND METHODS: Ambient air and soil samples were collected in five sites in northern Estonia. Passive air samplers were deployed four times over 4-week periods covering the period April-August 2006. Samples were analyzed using gas chromatography-electron capture detector (HP 5890) supplied with a Quadrex fused silica column 5% Ph for organochlorine pesticides (OCPs). Local ground-boundary wind field was modeled for each monitoring station and sampling period on the basis of observed wind data from the nearest meteorological station with a high quality of time series and compared with upper air (at 850- and 500-hPa level) data from Tallinn-Harku aerological station. RESULTS: Median levels of PCB at Estonian stations varied between 3 and 9 ng/filter, although the maximum in Kohtla-Järve reached as high as 28 ng/filter. Sampling rates about 3.5 m(3)/day were determined by empirical measurements, making approximately 100 m(3) for a 28-day sampling cycle. In general, OCP levels in soil were at the limit of detection, except Tallinn site and Muuga Port affected mainly by local sources. However, the atmospheric PCB concentrations are in agreement with the soil analyses where highest PCB levels were found in the soil sample for Tallinn (12.0 ng/g dry weight). For HCB, the atmospheric distribution was quite uniform, with the background levels sometimes higher than the urban ones. HCB and PeCB concentrations were very low in May and June when meridional airflow from the southern sector dominated, and concentrations were slightly higher in July and August, most probably due to revolatilization of adsorbed HCB (with PeCB impurities) from former industrial applications during the summer month and possibly enhanced by forest fires in Russia. Also, the highest summary HCH and DDT levels (63.5 and 2.5 ng/filter, respectively) in Estonian monitoring stations were determined at the end of July and beginning of August when the ground-boundary wind direction was from NE with relatively high speed (4-7 m/s). The highest DDT levels in ambient air (3.5 ng/filter) were determined in the spring samples. For DDT and HCH, long-range atmospheric transport clearly dominates persistent OCP, atmospheric input to Estonia as well as for the Scandinavian countries. The DDE/DDT ratio was >1, indicating no fresh input. DISCUSSION: The passive air sampling demonstrates uniform distribution of OCPs. In the regional context, there is no indication of increased levels of concentrations of OCPs in the industrial Northeast Estonia where the oil shale processing causes certain pollution impacts. Though the passive sampling does not apply for monitoring of short-term fluxes, the method is capable of reflecting background levels in long-term prospective for potential effect on human health due to long-term exposition of OCPs. CONCLUSIONS: PCB and its congeners, HCB, PeCB, HCH, and DDT were very low in Estonia. None of the persistent organochlorine pesticides have ever been produced in Estonia, and as of today, all old OCP stocks in the country have been destroyed. Highest concentrations could be expected in March and April when southwestern airflow is still strong and dominant, but air humidity is lower and deposition takes place far from the place of origin of OCPs. In summer, the share of locally formed organic compounds increases and deposition depends strongly on weather conditions. In some cases in Tallinn and Muuga where local anthropogenic impact occurs, HCB and PeCB stem from revolatilization of industrial application. RECOMMENDATIONS AND PERSPECTIVES: The passive air sampling could be employed more widely to explore long-term human exposure to OCP deposition and assess potential health risks. The survey based on passive air sampling could be extended from Central and Eastern Europe to other European regions to get methodically adjusted cross-European data coverage. Based on the results of the survey, the Lahemaa reference station is a feasible option to represent background monitoring of persistent organic pollutants.

Food contamination control in European new Member States and associated candidate countries: data collected within the SAFEFOODNET project.

This paper reports the results obtained from the data collected within the European Commission funded project SAFEFOODNET regarding the state of the art in the control of chemical food contaminants in twelve European New Member States and one Associated Candidate Country (Turkey). Information has been gathered on institutions involved in food chemical contamination control, types of contaminants and matrices analyzed, procedures for data quality assurance, purposes of the analyses and accessibility of data in the participant countries. The resulting picture points out the general availability of adequate capabilities for the analysis of food contaminants in the laboratories in charge of control and the performance of the analysis of a large variety of chemicals (persistent organic pollutants, polycyclic aromatic hydrocarbons, pesticides, mycotoxins, heavy metals, radionuclides) in almost each country with few exceptions (dioxins in Bulgaria, Turkey, Latvia, persistent organic pollutants in Lithuania and Malta, polycyclic aromatic hydrocarbons in Malta). The application of validated analytical methods and the process of laboratory accreditation are partially fulfilled within the investigated countries, but still forthcoming for some countries, as in Romania, Turkey and Malta. Information collected on food controls is only partially available online and the language used is prevalently local and English to a lesser extent.

Profiles of polybrominated diphenyl ethers in aquatic biota.

The profiles (concentrations scaled to a sum of 100) of polybrominated diphenyl ethers (PBDEs) in aquatic fauna differ from those of the commercial PBDE formulations, particularly by a much higher proportion of the congener 47. At the same time, the profiles reported by different authors vary a great deal and no patterns related to species, localities, etc. are obvious. It seems that there are systematic differences among the reporting laboratories, and measurement errors within the same laboratory may also play a role. However, the profiles of PBDEs in fish from the Baltic are very similar and form a tight "cluster". PBDE profiles in crustaceans appear different from those in fish.

PCDD/Fs in sprat (Sprattus sprattus balticus) from the Gulf of Finland, the Baltic Sea.

The concentrations and congeners pattern of the polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in sprat collected by the commercial catches in the Gulf of Finland, Baltic Sea. Based on the toxic equivalent concentrations 2,3,4,7,8-PeCDF prevailed among the congeners of PCDD/Fs. The significance of age- and season-specific relationship between the concentration of lipids and dioxins was demonstrated. On lipid weight basis the concentration of PCDDs was significantly higher in spring than in autumn. This difference was not statistically significant for PCDFs. On lipid weight basis the concentration of dioxins decreased with rising content of lipids. PCDD/Fs toxic equivalent concentration increased with the age of sprat exceeding the EU maximum limit value at more than 5-year-old fish.

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill.

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.

Chlorinated dibenzo-p-dioxins and dibenzofurans in the Baltic herring and sprat of Estonian coastal waters.

BACKGROUND, AIMS AND SCOPE: The concentration of chlorinated dibenzo-p-dioxins and dibenzofurans in many fish from the Baltic requires monitoring, since it approaches or exceeds the European Union threshold limit value of 4 pg TEQ/g wet weight of fish for human consumption. The concentrations, expressed in TEQs, are important for toxicology and regulations, but hide the concentrations of the individual congeners, which are important for other environmental sciences, source allocation, and for the detection of measurement errors. This report evaluates the results of a survey reported earlier only in the terms of the TEQ concentrations. METHODS: Principal Component Analysis (PCA) was used to reduce the dimensions of the data (17 = 7 chlorinated dibenzo-p-dioxin and 10 chlorinated dibenzofuran congeners) to three principal components. This facilitated the interpretation of the congener profiles. Slopes of the congener concentrations as a function of age of the fish were estimated by least squares regression. The results were compared with a large set of data for lake trout from Lake Ontario. RESULTS AND DISCUSSION: The congener profiles of Baltic herring are less scattered than those of sprat. The profiles of herring from the central Baltic differ from those of herring from the Gulf of Riga and both appear to be affected relatively minimally by the age of the fish. The congener profiles of herring from the western Gulf of Finland are similar to those from the central Baltic, those from middle Gulf of Finland are similar to those from the Gulf of Riga. Both seem to be more affected by age of the fish than the profiles of the first two groups. The concentrations of several pentachloro- and hexachloro-dibenzo-p-dioxins and dibenzofurans increase with the age of the fish CONCLUSION: PCA is a good technique for the evaluation of the congener profiles. The resulting loading and score plots provide a good graphic summary of the multidimensional data. Additional analyses are needed to confirm the observed profile patterns. A comparison with the results of a long-term monitoring from another area shows that the age of the fish is a more important factor than the year of capture. RECOMMENDATION AND OUTLOOK: The surveys should continue for a number of years and the results should be presented and evaluated both in terms of the TEQs as well as in terms of weight concentrations. Since the concentrations do not appear to change very much from year to year, it would be better to carry out surveys only every 3-4 years and, instead, stratify the sampling according to age and gender of the fish, and to analyze replicate extracts by replicate measurements. The inclusion of unmarked replicate samples would be a good quality assurance measure. It would be desirable to analyze additional parts of the food chain in order to understand the fate of the compounds in the ecosystem.