Water contamination issues in Estonia: a review/Vee saastumise probleemid Eestis (ulevaade).
There is a need for general and simultaneous action by the Member States of the European Union (EU) to protect the aquatic environment from pollution, particularly that caused by certain persistent, toxic, and bio-accumulative substances. The Republic of Estonia is one of the smallest countries in the EU. Estonia joined the EU in 2004 . With the Water Framework Directive (WFD; Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000) a framework for Community action in the field of water policy was established. Directive 2008/105/EC of the European Parliament and of the Council of 16 December 2008 sets the environmental quality standards of priority substances and certain other pollutants. The directive calls for the monitoring of the concentrations of these compounds in surface water. On 9 September 2010 the Estonian Ministry of Environment adapted the directive as Regulation No. 49 'The environmental quality standards for hazardous substances in surface water, including priority substances and priority hazardous substances and certain other pollutants, methods of application of environmental quality standards for priority substances and priority hazardous substances in surface water and biota'.
The oil shale mining region in north-east Estonia continues to be of concern in terms of hazardous substances. In this region the largest industrial (Kunda Nordic Cement, Viru Keemia Grupp AS, Kivioli Keemiakombinaat, etc.) and energy (Baltic and Estonian thermal power plants) enterprises in Estonia are located . The environmental monitoring of hazardous substances originating in the Estonian environment was conducted as part of the Estonian National Environmental Monitoring Programme (NEMP) . It was recommended that among the priority hazardous substances in Estonia, the substances that need more attention and periodic monitoring should include monobasic phenols (sum of p-, m-, o-cresols; 3,4-, 3,5-, 2,3-, 2,6-dimethyl phenols, and phenol), dibasic phenols (sum of resorcinol, 2,5-dimethyl resorcinol, and 5-methyl resorcinol), some heavy metals [4,5] and, for geological reasons, barium . The NEMP includes inland, marine, and groundwater sub-programmes, but does not embrace all water environments and substances; impacts of pesticides in the intensive agricultural areas, effluent and sewage sludge are not surveyed in the framework of the NEMP.
In recent years the monitoring of hazardous substances has become more exhaustive as new substances have been included in the survey because of new requirements by the EU. Therefore, the Estonian priority substance list is not final. The objective of this article is to provide an overview of hazardous substances contaminating Estonia's aquatic environment. Upon receipt of new information, additional hazardous substances should be included in the list. Alternatively, if it can be shown that a listed substance poses no risk, the compound may be removed from the list [7-13]. Revised environmental quality standards (EQS) for existing priority substances could be taken into account for the first time in river basin management plans covering the period 2015-2021. The newly identified priority substances and their EQS should be taken into account in the establishment of supplementary monitoring programmes and in preliminary programmes of measures to be submitted by the end of 2018 .
MATERIALS AND METHODS
Selection of hazardous substances and sampling matrices
The results were obtained during the course of international and national monitoring projects coordinated by the Estonian Ministry of the Environment. The concentrations of hazardous substances were studied at different Estonian sampling sites and matrices (Table 1).
The analytes, 130 hazardous substances from 12 groups (Table 1), were chosen from the list of LIFE07ENV/EE/ 000122 BaltActHaz (Baltic Actions for Reduction of Pollution of the Baltic Sea from Priority Hazardous Substances) Project. Many of these substances have not been investigated in Estonia previously. For the selection of sampling matrices, three main criteria were taken into account: solubility of substances in water, potential for bio-concentration, and persistence in the environment [7-10,15-18,20].
1. Solubility of substances in water (hydrophilic and hydrophobic chemicals) is described by the octanol-water partitioning coefficient (KOW). Generally, chemicals with KOW < 1000 are considered hydrophilic and characterized by good solubility in water, low absorption to soil and sediments, and low propensity for bio-concentration. Chemicals with KOW > 1000 are considered hydrophobic and characterized by low solubility in water, high absorption to soil and sediments, and high propensity for bio-concentration. As a rule, hydrophobic substances cannot be found dissolved in water, and for practical reasons there is no point in looking for them there.
2. The bio-concentration factor BCF of substances characterizes their ability to bio-accumulate. The BCF is the ratio of the concentration
in an organism to the concentration in the environmental matrix (in this case water). It describes a chemical's propensity to transfer from the aquatic environment to tissues of a living organism. A substance is classified as bio-accumulative if its BCF value exceeds 2000. Generally, the propensity of a substance to bio-accumulate is considered low if it has a log [K.sub.OW] [less than or equal to] 3.
3. The persistence of compounds in the environment is accessed based on its half-life (t12). A compound is considered persistent if [t.sub.1/2] > 2 months in water or [t.sub.1/2] > 6 months in soil or sediment. Alternatively, a compound is persistent if its BCF > 5000 and/or log Kow > 5 [2,15-18].
The sampling matrices were chosen based on guidance documents on chemical monitoring of sediment and biota under the WFD [21,22]. The matrices are classified as preferred, optional, and not recommended.
* Preferred: monitoring should be performed in this matrix.
* Optional: monitoring can be performed in this matrix, but also in other compartments/matrices; the choice will also be made on the basis of the degree of contamination of a particular matrix.
* Not recommended: monitoring in this matrix is not recommended unless there is evidence of the possibility of accumulation of the compound in this matrix .
Based on the aforementioned criteria and considering the potential occurrence of various substances in certain parts of the environments, the analyses of hazardous substances were carried out in the following matrices:
* surface water
* effluent (treated wastewater)
* bottom sediment of surface waters
* sewage sludge.
The analyses of samples were performed using appropriate quality assurance and quality control protocols. As the Estonian Environmental Research Centre (EERC) or any other national laboratory was not capable or certified to analyse all listed substances in Estonia, analyses were subcontracted to laboratories in Germany. The chemical analyses were carried out in two German laboratories: GALAB Laboratories GmbH and Gesellschaft fur Bioanalytik Hamburg GmbH. The activity of German laboratories has been declared to be in conformity with the requirements of the standard EN ISO/IEC 17025.
The limits of detection (LOD), limits of quantification (LOQ), and measurement uncertainties (MU%) of the EERC and GALAB laboratories are presented in [15-18]. For more detailed specification of COHIBA project methods, LOQ, LOD, and MU% can be found in .
Within the BaltActHaz project, samples were collected from Estonian inland surface waters (SW), from surface waters along coastal areas (SW), from the bottom sediment (BS), and from effluents (treated wastewater, E), and sewage sludge of wastewater treatment plants (wastewater sludge, WS). Sampling was performed all over Estonia in May and September 2010. Sampling points and the respective matrices where samples were taken are shown in Fig. 1 and Appendix 1.
Hazardous substances were quantified at a total of 33 sampling locations, of which 8 were at wastewater treatment plants (WWTPs) (Nos 1-8), 11 were rivers (Nos 9-19), 5 were coastal regions (Nos 20-24), 2 were Lake Peipsi (Nos 25 and 26), and 7 were regions engaged in intensive agriculture (Nos 27-33) (Fig. 1).
Wastewater treatment plants:
1. Tallinn WWTP--E, WS
2. Kohtla-Jarve WWTP--E, WS
3. Narva WWTP--E, WS
4. Parnu WWTP--E, WS
5. Kuressaare WWTP--E, WS
6. Haapsalu WWTP--E, WS
7. Keila WWTP--E, WS
8. Tartu WWTP--E, WS.
9. Narva state monitoring station No. 32--SW, BS
10. Kohtla flowing into the Purtse River--SW, BS
11. Puhajogi state monitoring station No. 33 (the mouth of the river)--SW, BS
12. Kunda state monitoring station No. 36 (the mouth of the river)--SW, BS
13. Mustajogi state monitoring station No. 60--SW, BS
14. Jagala state monitoring station No. 42 (the mouth of the river, Linnamae)--SW, BS
15. Keila state monitoring station No. 47--SW, BS
16. Vaana state monitoring station No. 45 (the mouth of the river)--SW, BS
17. Vasalemma (the mouth of the river)--SW, BS
18. Kasari state monitoring station No. 49--SW, BS
19. Parnu state monitoring station No. 52--SW, BS.
[FIGURE 1 OMITTED]
20. Coast of Sillamae Bay (eastern part of the Gulf of Finland)--SW, BS
21. BLRT Grupp AS (Baltic Ship Repair Company), Tallinn, effluents flow into Tallinn Bay--E
22. BLRT Grupp AS Company Baltic Premator dock No. 2, effluents flow into Tallinn Bay--E, WS
23. BLRT Grupp AS Company Baltic Premator dock No. 34, effluents flow into Tallinn Bay--E
24. BLRT Grupp AS Company Baltic Premator dock No. 3, effluents flow into Tallinn Bay--as dock No. 3 was not open during the time of planning sampling, it was not possible to take effluent samples from there.
25. Lake Peipsi State monitoring point Peipsi No. 17 SW, BS
26. Lake Peipsi State monitoring point Peipsi No. 38 SW, BS.
27. Alastvere. Main ditch of Alastvere (Vohma-Nomme Village)--SW
28. Torve. Outlet to the Pedja River--SW
29. Voisiku state monitoring station No. 61 (the main ditch of Voisiku)--SW
30. Pedja River state monitoring station No. 14 (Jogeva Plant Breeding Station)--SW
31. Janijogi River state monitoring station No. 64--SW
32. Rannu. Main ditch of Konguta before flowing into Lake Liivaku (Tartu County)--SW
33. Rohu. Rohu Stream before the collection lake (Tartu County)--SW.
The regulation prescribes the methods and installations for collecting sea water, surface water, effluent, bottom sediments, and sewage sludge in the process of trace level analyses described precisely in [15-20].
The samples were transported to the laboratory in thermo boxes with cold batteries and were placed in the refrigerator immediately after arrival. All samples were taken as two replicates, in case during transportation to Germany one of the sample bottles or jars should break. The samples were packed by the chemists of the EERC, who have previous experience in such activity.
RESULTS AND DISCUSSION
Levels of hazardous substances in surface waters
At the beginning of the 2000s the list of priority substances included first-rate heavy metals and phenols (monobasic and dibasic phenols) .
In 2008, within the framework of the international project 'EU Wide Monitoring Survey of Polar Persistent Pollutants in European River Waters', 122 water samples from 27 European Union Member States were studied [12,13]. Three rivers from Estonia were included in the project: the Narva, Purtse, and Emajogi. The Narva River on the Estonian-Russian border has the largest catchment area--56 225 [km.sup.2]--in the Estonian territory; its area is 17 145 [km.sup.2], and the mean flow rate at the river mouth is 380-400 [m.sup.3]/s. The Purtse River in the oil-shale region has a catchment area of 784 [km.sup.2] and the mean flow rate 6.7 [m.sup.3]/s. The catchment area of the Emajogi (together with the catchment area of Lake Vortsjarv and the catchment in Latvian territory) is 9740 [km.sup.2], and its mean flow rate is 70 [m.sup.3]/s.
A first EU-wide data set has been created on the occurrence of polar persistent pollutants in river surface waters to be used for continental-scale risk assessment and related decisions. The level of contamination of a total of 100 European rivers and other similar bodies of flowing water were tested for 35 selected polar persistent organic compounds (POS). These included pharmaceuticals (e.g. carbamazepine, diclophenac), antibiotics (sulphamethoxazole), pesticides (e.g. 2,4-D, mecoprop, bentazone, tefbutylazine), perfluorinated compounds (PFCs, e.g. perfluorooctane sulphonate (PFOS), perfluorooctanoic acid (PFOA)), benzotriazoles (corrosion inhibitors), hormones (estrone, estradiol), and alkylphenolics (bisphenol A, nonylphenol). Only dissolved (liquid) in the water phase, and not suspended, material was investigated. The content of the majority of substances in three Estonian rivers included in the international project remained below the LOD (Table 2).
The fact that hazardous substances are transported to the Baltic Sea from the whole catchment area was taken into account. Within the BaltActHaz project, the samples were collected from Estonian inland surface waters and from surface waters along coastal areas, from the bottom sediment, and from effluents and sewage sludge of WWTPs. In the first round (21 Apr.-3 May 2010) all chosen substances were analysed, and in the second (13-14 Sep. 2010) and third (May 2011) rounds only those substances were analysed that had very high values in the first round or for which the results were questionable for some reason. Special attention was paid to rivers with valuable food fishes (Fig. 2). The Vasalemma River (food fishes salmon and trout), which had previously not been a part of the national environmental monitoring programme, was added (Table 3).
In most cases, the concentrations of hazardous substances remained below the LOD  and did not exceed the environmental quality limit values . The concentrations of the substances that exceeded the LOD but remained below the Estonian EQS are presented in Table 4. However, the oil shale mining region continues to be problematic in terms of the concentrations of hazardous substances.
The concentrations of hazardous substances in the rivers in most cases did not exceed the established environmental quality standards and were prevailingly below the LOQ. Only the contents of a few phthalates, e.g. diisobutylphthalate, di-(2-ethylhexyl)-phthalate, and dimethylphtalate, exceeded the LOQ but still remained below the environmental quality standard. However, high concentrations of monobasic phenols were found in the water samples taken from the Kohtla, Vasalemma, Narva, and Keila rivers. Mono- and dibutyltin were found in samples from the Narva, Keila, and Kasari rivers. A high content of benzene was measured in the water of the Kunda and Puhajogi rivers. The concentrations of hazardous substances in the bottom sediment of rivers were in most cases below the LOQ. However, heavy metals, such as nickel, chromium, zinc, and copper, were found in sediment from the Narva River, and high concentrations of 2.5-dimethylresorcinol were found in the sediments of the Keila, Narva, and Puhajogi rivers [15,16].
[FIGURE 2 OMITTED]
During 2008, as an assignment from the Helsinki Commission (HELCOM), a screening study was performed in the eastern Baltic Sea environment on the occurrence of eight substances/substance groups (organotin compounds (OT), polybrominated diphenyl ethers (PBDE), hexabromocyclododecane (HBCDD), perfluorinated substances (PFAS), chlorinated paraffins, endosulphan, and phenolic substances) identified as priority hazardous substances under the Baltic Sea Action Plan. The project was funded by the Nordic Council of Ministers. Estonian coastal waters were sampled at four places: eastern (Narva Bay near Sillamae) and western (near Dirhami) parts of the Gulf of Finland, western coast of Saaremaa Island, and Parnu Bay .
In all Estonian coastal water samples analysed, PFAS (PFOS, PFOA, etc.), phenolic substances (nonylphenols and nonylphenol ethoxylates, octylphenols and octylphenol ethoxylates), bisphenol A, and triclosan were below the LOQ. From phenolic substances only 4-NP was detected above the LOQ (<10 ng/L) in some Estonian coastal water samples (from <10 ng/L to 66 ng/L in the coastal area near Sillamae). Based on the results, it can be concluded that the concentrations found for different substances in the coastal waters of Estonia were low. A single sampling and analysis of a single random sample at different sampling dates for coastal water does not enable to draw essential conclusions about the state of Estonian coastal waters .
In a previous study , the maximum concentrations of nickel and iso-nonylphenol in a water sample taken in September 2010 from coastal waters of Parnu Bay were 0.66 [micro]g/L and 0.39 [micro]g/L, respectively. However, other analytes such as cadmium, lead, octylphenol, chloroform, (aminomethyl)phosphoric acid (AMPA), glyphosate, and pyrene were below the LOQs .
The concentrations of organotin compounds are high in the harbour areas (sampling point 20--Sillamae Bay) and shipyards (sampling points 21-24): EQS for tributyltin compounds is 0.0002 [micro]g/L, but its maximum measured concentration in water samples was 0.06 [micro]g/L. Water samples taken from Tallinn Bay in the coastal area adjacent to the Baltic Ship Repair Company contained very high concentrations of organotin compounds. Additional studies are required to check the occurrence of these substances in the Estonian aquatic environment.
Organochlorine pesticides (OCPs) have never been produced in Estonia and their import was banned in Estonia beginning in October 1967 [2,25]. Under the BaltActHaz project, there were seven sampling points (Nos 27-33) in intensive agricultural regions at which pesticides were determined. Samples were taken in spring, from the end of April to the beginning of May 2010. All together 23 pesticides (among them endosulfan, chlorfenvinphos, alachlor, atrazine, isoproturon, chlorpyriphos, trifluralin, simazine, glyphosate, AMPA and MCPP and some chlorinated pesticides such as aldrin, dieldrin, endrin, isodrin, hexachlorocyclo-hexanes, etc.) were investigated. The concentrations of all these compounds were below the LOQs [15,16].
The highest concentrations of AMPA and glyphosate were found in the Rapu River in September 2010: 0.93 [micro]g/L and 0.29 [micro]g/L, respectively . However, in most cases the concentrations of pesticides were below the LOQs. These findings suggest that the status of the majority of Estonian surface water bodies is good with respect to pesticides.
Levels of hazardous substances in the effluents of wastewater treatment plants
The NEMP does not include effluents from WWTPs and sewage sludge. The results of industrial and domestic wastewater analysis were compared to the limit values for the content of hazardous substances in the effluents discharged into the public sewerage system, laid down with the 16 October 2003 Regulation No. 75 of the Minister of the Environment 'Establishing of requirements for the discharge of hazardous substances into a public sewerage system'. In regard to the content of heavy metals, the effluents of all WWTPs (Fig. 1, sampling points 1-8) were in compliance with the requirements (Table 5). However, the contents of some heavy metals were still high (Fig. 3).
In the first sampling round, in May 2010, the contents of arsenic (0.9 [micro]g/L), lead (6.2 [micro]/L), nickel (9.6 [micro]g/L), and zinc (35 [micro]g/L) were the highest in the effluent of the Tallinn WWTP. The contents of copper (58 [micro]g/L) and chromium (12.5 [micro]g/L) were high in the effluent of the Keila WWTP) (Fig. 3a).
In the second sampling round, in September 2010, the contents of arsenic (5.3 [micro]g/L), lead (1.2 [micro]g/L), nickel (6.7 [micro]g/L), zinc (33.9 [micro]g/L), and copper (59.4 [micro]g/L) were the highest in the effluent of the Kohtla-Jarve WWTP and the content of chromium (16.3 [micro]g/L) in the effluent of the Keila WWTP. The content of mercury remained below the LOQ (0.05 [micro]g/L) in all effluent samples and that of cadmium below the LOQ (0.02 [micro]g/L) in the majority of the effluent samples (Fig. 3b).
In the third sampling round, in May 2011, heavy metals were analysed in the effluent of the Kohtla-Jarve WWTP. The content of arsenic was 3.4 [micro]g/L (parallel sample 3.4 [micro]g/L), lead 0.17 [micro]/L (1.5 [micro]g/L), nickel 4.4 [micro]g/L (5.0 [micro]g/L), zinc 23 [micro]g/L (24 [micro]g/L), cadmium 0.06 [micro]g/L (0.19 [micro]g/L), chromium 0.94 [micro]g/L (0.98 [micro]g/L), and copper 5.2 [micro]g/L (13 [micro]g/L). The content of mercury in the effluent samples remained below the LOQ (0.05 [micro]g/L) [16,17].
In the COHIBA project only mercury and cadmium were measured in the effluent samples from the WWTPs. The mercury concentrations in the effluents were equal to or lower than the LOQ (0.05 [micro]g/L). For cadmium, the highest detected concentration from effluents was 0.15 [micro]g/L . The effluent samples collected in September 2010 from WWTP No. 1 (Kohtla-Jarve WWTP) contained 0.63-21 [micro]g/L of nickel and <0.5-2 [micro]g/L of lead. Cadmium remained below the LOQ .
Levels of hazardous substances in the mining and oil shale region
The north-east Estonian environmental problems are directly related to the mining and processing of oil shale in the region. The concentrations of hazardous substances still cause problems in that region. The largest industrial and energy enterprises are located there (Baltic and Estonian thermal power plants, Kunda Nordic Cement, Viru Keemia Grupp AS, Kivioli Chemical Plant, etc.) [20,25-31].
Ida-Viru county in NE Estonia was chosen as the place for carrying out the monitoring of sources of hazardous substances in May 2011 [17,18]. Ida Viru county is characterized by long-term industrial traditions and an array of manufacturing enterprises. The Kohtla-Jarve WWTP (Jarve Biopuhastus OU) participated in the monitoring as most of the enterprises in the area send their wastewater for treatment to this plant. The type of treatment on Kohtla-Jarve WWTP was mechanical + biological + biological nitrogen and phosphorus + chemical phosphorus separation. In addition to effluent from industrial enterprises, the Kohtla-Jarve WWTP also treats household effluents (domestic wastewater) from the towns of Johvi, Kivioli, Kohtla-Jarve, and Pussi, the municipality of Kohtla-Nomme, and the village of Kukruse.
[FIGURE 3 OMITTED]
During the survey, wastewaters from four participating industrial plants (three chemical industries and one timber industry), leachate from semi-coke and ash deposits, and domestic wastewaters from the towns of Johvi, Kivioli, Kohtla-Jarve, and Pussi, Kohtla-Nomme municipality, and Kukruse village were analysed (Table 6). In NE Estonia, mining and processing of oil shale are considered to be the major sources of hazardous substance contamination to surface water. Additional studies are required to verify the occurrence of the substances identified by the survey in the Estonian aquatic environment.
CONCLUSIONS AND RECOMMENDATIONS
Recent environmental monitoring and screening of the Estonian aquatic environment shows that the concentrations of hazardous substances in surface water are, in most cases, below the LOD and rarely exceed the EQS. However, the concentrations of some heavy metals and monobasic phenols (especially phenols and p- and mcresols) and dibasic phenols in some surface waters and effluents may be of concern. Further, concentrations of organotin compounds are high in ports and shipyards. The concentrations of only some phthalates, e.g. diisobutylphthalate, di-(2-ethylhexyl)-phthalate, and dimethylphtalate, exceeded the LOQ, but were below the EQS. Mono- and dibutyltin and benzene were found in some rivers.
Contamination with hazardous substances from the oil shale industry continues to be a concern in NE Estonia. In this area, surface waters are contaminated with mono- and dibasic phenols, pentachlorophenol, polycyclic aromatic hydrocarbons, organotin compounds, and phthalates. Considering the relatively high quantities of hazardous substances in the wastewater, the Kohtla-Jarve WWTP copes relatively well. Even though the influent contains industrial and domestic wastewater as well as leachate from semi-coke and ash deposits, the effluent meets the environmental quality requirements of Estonian legislation.
Additional studies are required to verify the occurrence of hazardous substances in the Estonian aquatic environment. The priority substances list is not final. Upon receipt of new information, hazardous substances should be added to the list. Compounds may also be removed from the list if environmental monitoring and risk assessment shows that the risk is limited. When monitoring hazardous substances in water bodies, consideration should be given to future emissions, and attention should be paid to improved conditions to minimize unwanted production and transport of hazardous substances. Care must also be taken for proper incineration of disposal of hazardous wastes. Sustainable environmental strategies for the aquatic environment should be developed as well to mitigate exposure to hazardous substances to protect living resources.
In recent years, the monitoring of hazardous substances has become more exhaustive as new substances have been included in the surveys based on requirements by the European Union. The EU Commission has conducted a review of the list of priority substances and has come to the conclusion that it is appropriate to amend the list of priority substances by identifying new substances for priority action at Union level, setting Environmental Quality Standards (EQS) for those newly identified substances, revising the EQS for some existing substances in line with scientific progress and setting biota EQS for some existing and newly identified priority substances. The revised EQS for existing priority substances should be taken into account for the first time in river basin management plans covering the period 2015 to 2021 (Directive 2013/39/EU).
This study was financed by the Estonian Ministry of the Environment under the Estonian National Water Monitoring Programme, by the Ministry of the Agriculture under the Estonian Food Safety Monitoring Programme, and by the international projects LIFE07ENV/EE/000122 'Baltic Actions for Reduction of Pollution of the Baltic Sea from Priority Hazardous Substances--BaltActHaz' and 'Control of Hazardous Substances in the Baltic Sea Region--COHIBA'.
The publication costs of this article were covered by the Estonian Academy of Sciences.
Table 1A. List of sampling points/monitoring stations Sampling Description Coordinates point N number (a) Wastewater treatment plants 1 Tallinn WWTP 59[degrees]28'6.64" 2 Kohtla-Jarve WWTP 59[degrees]24'16.61" 3 Narva WWTP 59[degrees]23'50.47" 4 Parnu WWTP 58[degrees]23'10.48" 5 Kuressaare WWTP 58[degrees]13'12.67" 6 Haapsalu WWTP 58[degrees]56'38.48" 7 Keila WWTP 59[degrees]18'52.3" Rivers (b) 8 Tartu WWTP 58[degrees]20'28.64" 9 Narva station No. 32 59[degrees]25'13.01" 10 Kohtla 59[degrees]22'44.35" 11 Puhajogi station No. 33 59[degrees]25'12" 12 Kunda station No. 36 59[degrees]30'35" 13 Mustajogi station No. 60 59[degrees]15'42.35" 14 Jagala station No. 42 59[degrees]28'25.31" 15 Keila station No. 47 59[degrees]23'42.99" 16 Vaana station No. 45 59[degrees]25'53" 17 Vasalemma 59[degrees]18'18.75" 18 Kasari station No. 49 58[degrees]44'1.01" Coastal waters 19 Parnu station No. 52 58[degrees]27'18.99" 20 Sillamae Bay 59[degrees]24'39.09" 21 BLRT flow into Tallinn Bay 59[degrees]28'0.92" 22 BLRT flow into Tallinn Bay 59[degrees]27'52.35" 23 BLRT flow into Tallinn Bay 59[degrees]27'30.94" 24 BLRT flow into Tallinn Bay 59[degrees]27'29.37" Lakes (b) 25 Peipsi station No. 17 58[degrees]7'10.99" 26 Peipsi station No. 38 58[degrees]26'36" Agricultural regions (b) 27 Main ditch of Alastvere 58[degrees]39'17.73" 28 Torve. Outlet to the Pedja River 58[degrees]35'42.21" 29 Voisiku station No. 61 58[degrees]45'35" 30 Jogeva Plant Breeding Station 58[degrees]45'48" 31 Janijogi station No. 64 59[degrees]13'59.99" 32 Rannu 58[degrees]15'13.06" 33 Rohu 58[degrees]21'14.32" Sampling Description Coordinates point E number (a) Wastewater treatment plants 1 Tallinn WWTP 24[degrees]42'13.57" 2 Kohtla-Jarve WWTP 27[degrees]14'57.89" 3 Narva WWTP 28[degrees]10'28.41" 4 Parnu WWTP 24[degrees]27'6.96" 5 Kuressaare WWTP 22[degrees]29'49.25" 6 Haapsalu WWTP 23[degrees]33'21.65" 7 Keila WWTP 24[degrees]26'3.93" Rivers (b) 8 Tartu WWTP 26[degrees]44'53.83" 9 Narva station No. 32 28[degrees]8'6.98" 10 Kohtla 27[degrees]2'37.72" 11 Puhajogi station No. 33 27[degrees]31'40.01" 12 Kunda station No. 36 26[degrees]32'18" 13 Mustajogi station No. 60 27[degrees]54'19.67" 14 Jagala station No. 42 25[degrees]9'4.87" 15 Keila station No. 47 24[degrees]17'47.03" 16 Vaana station No. 45 24[degrees]21'51.03" 17 Vasalemma 24[degrees]7'38.99" 18 Kasari station No. 49 23[degrees]59'22.02" Coastal waters 19 Parnu station No. 52 24[degrees]45'48.98" 20 Sillamae Bay 27[degrees]44'52.01" 21 BLRT flow into Tallinn Bay 24[degrees]39'26.2" 22 BLRT flow into Tallinn Bay 24[degrees]39'0.44" 23 BLRT flow into Tallinn Bay 24[degrees]39'29.94" 24 BLRT flow into Tallinn Bay 24[degrees]39'34.1" Lakes (b) 25 Peipsi station No. 17 27[degrees]34'31.98" 26 Peipsi station No. 38 27[degrees]16'35.97" Agricultural regions (b) 27 Main ditch of Alastvere 26[degrees]0'6.35" 28 Torve. Outlet to the Pedja River 26[degrees]21'44.46" 29 Voisiku station No. 61 25[degrees]53'21.98" 30 Jogeva Plant Breeding Station 26[degrees]24'0.98" 31 Janijogi station No. 64 25[degrees]41'48.02" 32 Rannu 26[degrees]14'0.27" 33 Rohu 26[degrees]30'32.5" (a) The numbers correspond to Fig. 1. (b) Monitoring station numbers of the Estonian National Environmental Monitoring Programme (NEMP).
Ott Roots was born in 1946. He graduated from Tallinn Technological University as a chemisttechnologist in 1969. In 1983 he received his PhD degree (Candidate of Chemical Sciences, speciality: Organic Chemistry and Hydrobiology). Dr Roots 's research interests include the distribution of toxic persistent organic pollutants in the ecosystems, food safety, working out and improvement of Estonian Environmental Monitoring Programme, materials corrosion, etc. He has participated in various international scientific programmes such as 1993-2015 UN/ECE International Co-operation Programme on Effects on Materials, including Historic and Cultural Monuments (Estonian Task Force), 2002-2003 UNEP Regionally Based Assessment of Persistent Toxic Substances (European regional team member/expert), 2002-2006 EC FP6 (FOOD-CT-2004-513988) SAFEFOODNET, 2006-2015 Monitoring of persistent organic compounds in the air using the passive air sampling technique (MONET EU), 2010-2012 Baltic Action for Reduction of Pollution of the Baltic Sea from Priority Substances (LIFE+07ENV/EE/000122) BaltActHaz project, 2002-2015 Dioxins and other priority hazardous substances in Estonian food, etc. He has been awarded Estonian and international (Soros Foundation, McArthur Foundation) scientific grants. He was a nominee of the Estonian Science Award in 1997 and 2000. From time to time he has delivered special lectures at different universities and EUROACADMY. He has published more than 260 scientific publications (more information: www.etis.ee or Ott Otto Roots Researchgate).
Tiit Lukki was born in 1948. He graduated from the Faculty of Chemistry and Physics, University of Tartu, in 1972 and received his MSc degree from Tallinn Pedagogical University, Estonia, in 1993. His current scientific research projects involve statistical methods and data analysis in science. His study area is Natural Sciences and Sustainability. At present he is Lecturer of Statistical Methods in Environmental Sciences at Tallinn University School of Natural Sciences and Health.
[1.] Roots, O. Book Chapter: Part III: Chronologies of world countries and regions. Europe. Estonian Republic. In A General World Environmental Chronology (GWEC Editorial Working Committee and Takahashi, M., eds). Suirensha, Hosei, Japan, 2014, 689-692.
[2.] Roots, O., Zitko, V., Kumar, K. S., Sajwan, K., and Loganathan, B. G. Contamination profiles and possible trends of organohalogen compounds in the Estonian environment and biota. In Global Contamination Trends of Persistent Organic Chemicals (Loganathan, B. G. and Lam, P. K. S., eds). CRC Press, 2011, 307-335.
[3.] Roots, O. and Saare, L. Structure and objectives of the Estonian Environmental Monitoring Program. Environ. Monit. Assess., 1996, 40, 289-301.
[4.] Roots, O. and Roose, A. Hazardous substances in the aquatic environment of Estonia. Chemosphere, 2013, 93, 196-200.
[5.] Roots, O. Proposal for selection of national priority hazardous substances for Estonian surface water bodies. Ekologicheskaya khimiya, 2008, 17, 22-34.
[6.] Marandi, A., Karro, E., and Puura, E. Barium anomaly in the Cambrian-Vendian aquifer system in North Estonia. Environ. Geol., 2004, 47, 132-139.
[7.] Roots, O. PCDDs, PCDFs and DL-PCBs in some selected Estonian and imported food samples. Fresen. Environ. Bull, 2007, 16, 1662-1666.
[8.] Roots, O. Nutrition recommendations for Estonian fishermen (dioxins and dioxin-like polychlorinated biphenyls). Latvian Journal of Chemistry, 2012, 51, 316-323.
[9.] Roots, O., Simm, M., Kiviranta, H., and Rantakokko, P. Persistent organic pollutants (POPs): food safety control in Estonia. In The Fate of Persistent Organic Pollutants in the Environment (Mehmetli, E. and Koumanova, B., eds). NATO Science for Peace and Security Series. Springer, 2008, 173-185.
[10.] Roots, O., Roose, A., Kull, A., Holoubek, I., Cupr, P., and Klanova, J. Distribution pattern of PCBs, HCB and PeCB using passive air and soil sampling in Estonia. Environ. Sci. Pollut. Res., 2010, 17, 740-749.
[11.] Tamm, I. Euroopa Parlamendi ja Noukogu 6. detsembri 2008 direktiivi 2008/105/EU nouete taitmiseks prioriteetsete ainete inventuur ning seirekorralduse analuus. Report, 2010 (in Estonian). http://www.envir.ee/ et/ veevaldkonna-uuringud-ja-aruanded (accessed 2015-0123).
[12.] Loos, R., Gawlik, B. M., Locoro, G., Rimaviciute, E., Contini, S., and Bidoglio, G. EU Wide Monitoring Survey of Polar Persistent Pollutants in European River Waters. Publications Office of the European Union, Luxembourg, LU, 2008. http://publications. jrc.ec.europa.eu/repository/handle/JRC48459 (accessed 2015-02-17).
[13.] Loos, R., Gawlik, B. M., Locoro, G., Rimaviciute, E., Contini, S., and Bidoglio, G. EU-wide survey of polar organic persistent pollutants in European river waters. Environ. Pollut., 2009, 157, 561-568.
[14.] Directive 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. Official Journal of the European Union. 24.08.2013, L226/1L2226/17. http://eur-lex.europa.eu/legal-content/EN/ ALL/?uri=CELEX:32013L0039 (accessed 2015-01-02).
[15.] Roots, O. and Nommsalu, H. Aruanne veekeskkonnale ohtlike ainete soeluuringu tulemustest Eestis (Viisimaa, M., ed.). BEF Estonia, Tallinn, 2011 (in Estonian). www.klab.ee/ wp-content/2011/10/soeluuringu_aruanne.pdf (accessed 2016-05-25).
[16.] Roots, O. and Nommsalu, H. Report on Hazardous Substances Screening in the Aquatic Environment in Estonia (Viisimaa, M., ed.). BEF, Tallinn, 2011. www.baltacthaz.bef.ee/publications (accessed 201605-25).
[17.] Roots, O., Nommsalu, H., and Kislenko, K. Veekesk konnale ohtlike ainete allikate analuus. Report. BEF, Tallinn, 2011 (in Estonian). www.baltacthaz.bef.ee/ publications (accessed 2016-05-25).
[18.] Dydutyte, Z., Buselyte, J., Stance, L., Poikane, R., Kadike, S., Nommsalu, H., et al. Investigation of Sources of Hazardous Substances in Lithuania, Latvia and Estonia. Report. BEF, Tallinn, 2011. http://www.baltacthaz.bef.ee (accessed 2016-05-25).
[19.] Korgmaa, V., Laht, M., Paasrand, K., Parts, L., Pollumae, A., Volkov, E., et al. WP3 Innovative Approaches to Chemical Controls of Hazardous Substances. National Report of Estonia. Estonian Environmental Research Centre, 2011. www.cohiba_project.net/publications (accessed 2015-01-14).
[20.] Erm, A., Voll, M., Buschmann, F., and Roots, O. Profiles of Hg, Cd, Cu, Pb and Zn, PCDDs, PCDFs and dl-PCBs in the bottom boundary layer of some north Estonian coastal areas. Baltic International Symposium (Baltic). IEEE, Tallinn, 2014, 1-12 (978-1-4799-5707-1).
[21.] Guidance Document No. 25, 2010. On Chemical Monitoring of Sediments and Biota under the Water Framework Directive. European Union, 2010 (accessed 2015-03-26).
[22.] Guidance Document No. 32, 2014. Guidance on Biota Monitoring (the Implementation of EQS BIOTA) under the Water Framework Directive. European Union, 2014 (accessed 2015-05-26).
[23.] EE 11, 2002 (http://entsyklopeedia.ee/artikkel/ eesti_j%C3%B5ed) (accessed 2015-02-19).
[24.] Lilja, K., Nordstrom, K., Remberger, M., Kaj, L., Egelrud, L., Junedahl, E., et al. Screening of Selected Hazardous Substances in the Eastern Baltic Marine Environment. IVL Report B187. Nordic Council of Ministers, 2009.
[25.] Muur, J. Taimekaitsevahendite kasutamine Eestis [Use of pesticides in Estonia]. In Keskkond 1995 (Meikas, E., ed.). Tallinna Raamatutrukikoda, Tallinn, 1996, 66-68.
[26.] Roots, O. Polychlorinated biphenyls (PCB), polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in oil shale and fly ash from oil shale-fired power plant in Estonia. Oil Shale, 2004, 21, 333-339.
[27.] Schleicher, O., Jensen, A. A., Roots, O., Herrmann, T., and Tordik, A. Dioxin and emissions from a shale oil processing plant in Estonia. Organohalogen Compounds, 2004, 66, 1665-1671.
[28.] Schleicher, O., Roots, O., Jensen, A. A., Herrmann, T., and Tordik, A. Dioxin emission from two oil shale fired power plants in Estonia. Oil Shale, 2005, 22, 563-570.
[29.] Roots, O., Aps, R., Kuningas, K., and Talvari, A. Monitoring of oil products and hazardous substances in Estonian surface water bodies. Proc. Estonian Acad. Sci. Chem., 2007, 56, 75-86.
[30.] Suursaar, U., Aps, R., Kotta, I., and Roots, O. North-East Estonian coastal sea: recovery from the past anthropogenic pressure and new stressors on the background of natural variability. In Ecosystems and Sustainable Development VII (Brebbia, C. A. and Tiezzi, E., eds). WIT Transactions and the Environment, 122. WIT Press, 2009, 331-342.
[31.] Kumar, K., Priya, M., Sajwan, K., Kolli, R., and Roots, O. Residues of persistent organic pollutants in Estonian soils (1964-2006). Estonian J. Earth Sci., 2009, 58, 109-123.
Ott Roots (a) * and Tiit Lukki (b)
(a) Estonian Environmental Research Institute, Marja 4D, 10617 Tallinn, Estonia
(b) Tallinn University, Narva mnt 25, 10120 Tallinn, Estonia
Received 7 September 2015, revised 20 October 2015, accepted 21 October 2015, available online 19 August 2016
* Corresponding author, email@example.com
Table 1. Substances and groups of substances analysed in the water monitoring and screening projects in Estonian aquatic environment International projects Substance group National BaltActHaz (a) COHIBA (b) projects  [15-18]  Heavy metals + + + Phenols, + + + alkylphenols, and their ethoxylates Polycyclic aromatic + + - hydrocarbons Volatile organic + + - compounds Chlorobenzenes - + - Organotin compounds - + + Phthalates + + - Polybrominated - + + biphenyls, diphenylethers, and other polybrominated organic compounds Short-and medium- - + + chain chlorinated paraffins Perfluoro compounds - + + Pesticides + + - Polychlorinated - - + dibenzo-p-dioxins, polychlorinated dibenzofurans (a) Baltic Actions for Reduction of Pollution of the Baltic Sea from Priority Hazardous Substances. (b) Control of Hazardous Substances in the Baltic Sea Region. Table 2. Concentrations (ng/L) of priority substances and certain other pollutants in Estonia's rivers and comparison with other European Union rivers [12,13] Substance LOD * Emajogi Purtse Narva River River River Diuron 1 2 0 2 Simazine 1 0 0 0 Isoproturon 1 0 0 0 Atrazine 1 0 0 0 Nonylphenol 50 0 0 0 4-fert-Octylphenol 10 0 0 0 Perfluorooctanoic acid 1 1 1 0 Perfluorooctane sulphonate 1 1 0 1 Bisphenol A 5 0 0 0 Nitrophenol n.a. 14 6 9 2,4-Dinitrophenol 1 14 0 7 Ibuprofen 1 6 0 3 Diclophenac 1 3 1 2 Bentazone 1 2 0 1 Benzotriazole 1 13 0 0 Caffeine 1 22 22 15 Carbamazepine n.a. 15 0 3 Methylbenzotriazole 1 0 90 0 Nonylphenoxyacetic acid 2 74 16 30 Substance Concentrations in EU rivers Maximum Average Diuron 864 41 Simazine 169 10 Isoproturon 1 959 52 Atrazine 46 3 Nonylphenol 4 489 134 4-fert-Octylphenol 557 13 Perfluorooctanoic acid 174 12 Perfluorooctane sulphonate 1 374 39 Bisphenol A 323 25 Nitrophenol 3 471 99 2,4-Dinitrophenol 174 18 Ibuprofen 31 323 395 Diclophenac 247 17 Bentazone 250 14 Benzotriazole 7 997 495 Caffeine 39 813 963 Carbamazepine 11 561 248 Methylbenzotriazole 19 396 617 Nonylphenoxyacetic acid 7 491 553 * LOD--limit of detection; n.a.--not applicable. Table 3. The list and of sampling points/monitoring stations (site numbers correspond to Fig. 1) and valuable fishes of the rivers [15,16,23] Site No. (a) River Catchment area (a), Valuable fish [km.sup.2] 9 Narva 56 225 (17 145 in Salmon, carp Estonian territory) 10 Kohtla 784 (Purtse River Salmon catchment area) 11 Puhajogi 196 Salmon 12 Kunda 530 Salmon 13 Mustajogi 994 14 Jagala 1573 Salmon 15 Keila 682 Salmon 16 Vaana 316 Salmon 17 Vasalemma 395.6 Salmon 18 Kasari 3210 Carp 19 Parnu 6920 Salmon (a) Keskkonnaregister--http://register.keskkonnainfo.ee/envreg/ main? list=VEE&mount=view Table 4. List of the sampling points/monitoring stations (site numbers correspond to Fig. 1) of the rivers and Lake Peipsi where the concentrations of hazardous compounds are above the limit of detection but below the annual average value of the environmental quality standard of inland surface waters [15,16,23] Site No. Water body Hazardous substances 9 Narva R. Lead, nickel, copper, phenol, pand m-cresol, monobutyltin 10 Kohtla R. Nickel, phenol, bromoform, diisobutylphthalate, di-(2-ethylhexy) phthalate (DEHP) 11 Puhajogi R. Lead, nickel, zinc, benzene, trichloromethane (chloroform) 12 Kunda R. Lead, nickel, zinc, benzene, trichloromethane, diisobutylphthalate, DEHP 13 Mustajogi R. Lead, nickel, cadmium, zinc, copper, naphthalene 14 Jagala R. Nickel, trichloromethane, dimethylphtalate, DEHP 15 Keila R. Lead, nickel, zinc, copper, phenol, p- and ra-cresol, tetrachloromethane (carbon tetrachloride), monobutyltin, dibutyltin 16 Vaana R. Lead, nickel, zinc, diisobutylphthalate, DEHP 17 Vasalemma R. Lead, nickel, zinc, chromium, copper, phenol, diisobutylphtalate 18 Kasari R. Lead, nickel, zinc, chromium, copper, trichloromethane, diisobutylphtalate 19 Parnu R. Lead, nickel, zinc, copper, trichloromethane, diisobutylphtalate 25 Lake Peipsi Lead, nickel, phenol, p- and ra-cresol, dichloromethane, trichloromethane, dibutylphthalate 26 Lake Peipsi Nickel Table 5. Limits for the discharge of heavy metals into the public sewage system Heavy metal Limits, mg/L Lead and its compounds 0.5 Nickel and its compounds 1.0 Mercury and its compounds 0.05 Cadmium and its compounds 0.2 Zinc and its compounds 2.0 Chromium (total) 0.5 Chromium (VI) 0.1 Copper and its compounds 2.0 Arsenic and its compounds 0.2 Table 6. Hazardous substances in wastewaters from north-east Estonia [17,18] Source Hazardous substances Chemical industry Mono- and dibasic phenols, pentachlorophenol, polycyclic aromatic hydrocarbons (naphthalene, anthracene, fluoranthene), phthalates (di-(2-ethylhexyl)-phthalate, diisobutylphthalate, dibutylphthalate) Timber industry Organotin compounds (dioctyltin, monobutyltin), volatile organic compounds (dichloromethane, 1,2-dichloroethane), alkylphenols (isononylphenol, 4-tert-butylphenol), phthalates (di(2-ethylhexyl)phthalate, diisobutylphthalate) Semi-coke and ash deposit Mono- and dibasic phenols, arsenic, pentachlorophenol, polycyclic aromatic hydrocarbons (naphthalene, fluoranthene, anthracene), volatile organic compounds (benzene), organotin compounds (monooctyltin, monobutyltin) Domestic wastewater Phthalates (household effluents) (di(2-ethylhexyl)phthalate, diisononylphthalate, diethylphthalate, diisobutylphthalate), alkylphenols and their ethoxylates (isononylphenol, 4-t-octylphenol-monoethoxylate), organotin compounds (monobutyltin, monooctyltin)
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|Title Annotation:||ENVIRONMENTAL SCIENCE|
|Author:||Roots, Ott; Lukki, Tiit|
|Publication:||Proceedings of the Estonian Academy of Sciences|
|Date:||Sep 1, 2016|
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