Report on
dangerous substances in
the aquatic environment
of Lithuania
Prepared within the project “Screening of
dangerous substances in the aquatic environment
of Lithuania”
2007
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
Report on dangerous substances in the aquatic environment of Lithuania
Funded by:
Finnish Ministry of Environment
Produced by:
Zita Dudutytė, Baltic Environmental Forum
Levonas Manusadžianas, Institute of Botany (Ecotoxicity part)
Rasa Ščeponavičiūtė, Center for Environmental Policy (chapters “Practices on
monitoring and screening of hazardous substances in Lithuania 1992-2005”
and “Quality assurance and methods used in the HS screening”)
Editorial team:
Environmental Protection Agency of Lithuania
Finnish Environment Institute (SYKE)
Lithuanian Ministry of Environment
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Content
1.
Introduction ....................................................................................................................... 4
2.
Legal background - existing legislation and a new framework ........................................... 5
3.
Practices of monitoring and screening of hazardous substances in Lithuania 1992-2005 .. 8
4.
Selection of the hazardous substances, sampling sites and matrixes .............................. 12
A. Selection of hazardous substances ............................................................................. 12
B. Selection of the sampling sites .................................................................................... 16
C. Selection of the matrixes ............................................................................................. 19
5.
Quality assurance and methods used in the HS screening .............................................. 25
A. Sampling and handling of samples ............................................................................. 25
B. Analysis of samples .................................................................................................... 26
6.
Results of the analysis .................................................................................................... 32
A. Overview of the results by substances/ groups of substances..................................... 33
B. Overview of the results in the receiving environment .................................................. 39
C. Results of ecotoxicity tests .......................................................................................... 44
7.
Potential sources of hazardous substances .................................................................... 46
8.
Findings and recommendations....................................................................................... 48
9.
List of abbreviations ........................................................................................................ 51
10. References ...................................................................................................................... 52
List of Annexes
Annex I:
ANNEX 1 to the Council Directive on pollution caused by discharges of certain
dangerous substances (76/464/EEC)
Annex II: ANNEX VIII to Water Framework Directive
Annex III: Extract of the Water Framework Directive (2000/60/EC) - Article 16 Strategies against
pollution of water
Annex IV: Annex X of Directive 2000/60/EC - List of priority substances in the field of water policy
Annex V: Environmental quality standards for priority substances and certain other pollutans
Annex VI: List of priority hazardous and hazardous substances of Lithuania
Annex VII: Overall results of the chemical analysis
Annex VIII: Results of the analysis by investigated sites
Annex IX: Results of the ecotoxicity analysis
Annex X: List of laboratories
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
1.
Introduction
This report is the outcome of the project “Screening of Hazardous Substances in the aquatic
environment of Lithuania”, which has started in October 1 2005 and continued till March of 2007. The
project is funded by Finnish Ministry of Environment. The main parties involved into project
implementation are Lithuanian Environmental Protection Agency, Finnish Environment Institute, Baltic
Environmental Forum and Center for Environmental Policy.
The idea of the project derived from the need to comply with EU legal environmental obligations in the water
sector, where a big emphasis is given to the control of pollution by hazardous substances. As EU Dangerous
Substances Directive (DSD, 76/464/EEC and daughter directives) and the Water Framework Directive
(WFD, 2000/60/EC) states, all EU Member States have to control hazardous substances based on European
wide quality standards and should aim at progressive reduction of pollution of the aquatic environment by
hazardous substances and phasing out the emissions of hazardous priority substances.
However existing information on use and discharge of hazardous substances to water environment in
Lithuania is very limited and more information is needed on actual concentrations in main pollution sources
effluents to fulfil these legal requirements. Therefore the aforementioned project was initiated.
The main objective of the project was to investigate the occurrence of selected WFD priority substances and
some other pollutants in wastewater, sewage sludge and the receiving environment (surface water and
sediments) and obtain measurement data on their concentrations.
Data collection concentrated on discharges from largest urban wastewater treatment plants and selected
sampling sites on transboundary rivers and in transitional waters to the Baltic Sea. All together the project
covered 44 sites, where 9 hazardous substances groups were analyzed (metals, phenols and their
ethoxylates, organotin compounds, brominated diphenylethers, phtalates and their ethoxylates, chlorinated
parafins, polycyclic aromatic hydrocarbons, volatile organic compounds, chloroorganic pesticides,
pentachlorphenol and some other substances such as chlorpyrifos, cyanides, AOX at some sites) and
ecotoxicity tests were performed.
By side of fulfilling the major goal of the project, the experience exchange among Lithuanian and Finnish
experts working in the field took place. Experts of Environmental Protection Agency of Lithuania have visited
Finnish Environment Institute (SYKE) to get familiar with analytical methods and assess the possibilities to
develop new method for the analysis of hazardous substances.
This report documents the results of the hazardous substances screening exercise. Furthermore it contains
legal background information, description of the methods used in the screening exercise, information on
potential sources of hazardous substances and their discharges to the aquatic environment.
The report is mainly targeted to the authorities that are responsible for the development and implementation
of policies for hazardous substances control. It is intended to support in fulfilling reporting obligations to
European Commission and HELCOM and improving existing or developing new tools and programmes for
hazardous substances control and reduction in Lithuania. It can also function as a background the permitting
authorities when issuing permits to the commercial/industrial entities.
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
2.
Legal background - existing legislation and a new framework
Existing legislation
Community policy concerning dangerous substances in European waters was introduced with the Council
Directive on pollution caused by discharges of certain dangerous substances (Directive 76/464/EEC).
The scope of the directive involves inland waters, internal coastal waters, territorial and ground waters. This
directive established two lists of dangerous substances:
 List I contains certain individual substances which belong to the following families and groups of
substances, selected mainly on the basis of their toxicity, persistence and bioaccumulation (see Annex I
for whole list). 17 substances from the above presented list regulated under so-called “daughter
directives” with the aim to eliminate pollution by these substances. These 5 “daughter” directives set the
Community-wide specific emission limit values and quality objectives in the surface and coastal waters
for the following substances:
o mercury discharges by the chloralkali electrolysis industry (82/176/EEC);
o cadmium discharges (83/513/EEC);
o mercury discharges by other sectors (84/156/EEC);
o discharges of hexachlorocyclohexane (84/491/EEC);
o discharges of certain dangerous substances (carbon tetrachloride, DDT, pentachlorphenol,
aldrin, dieldrin, endrin, isodrin, hexachlorobenzene, hexachlorobutadiene, chloroform, 1,2dichlorethane, trichloroethylene, perchloroethylene, trichlorobenzene) (86/280/EEC,
amended by 88/347/EEC and 90/415/EEC).
 List II (under Article 7) includes:
a) other substances belonging to the categories listed in List I and for which the limit values have not
been determined;
b) other substances and categories of substances having deleterious effects on the aquatic
environment, which can be confined to a given area and which depend on the characteristics and
location of the water into which they are discharged (see Annex I for whole list).
The Member States are required to reduce pollution by these substances. They need to identify nationally
relevant substances, make emissions inventory, set up monitoring network for reporting, authorise
discharges, control composition and use of substances, establish quality objectives and make information
publicly available.
As part of the ongoing restructuring of the Community water policy, the Directive 76/464/EEC is now
integrated in the Water Framework Directive (WFD) (2000/60/EC) and will be fully repealed on 22
December 2013. There is currently a transitional period until the year 2013. “Daughter” directives are
currently in force but they will be also repealed when all provisions regarding priority substances of WFD will
be in place.
New framework legislation
The Water Framework Directive (WFD) (2000/60/EC) establishes a comprehensive framework for
sustainable management of European waters through the river basins approach. As part of the Directive,
Article 4 sets out the environmental objectives and the deadlines by which these should be achieved. The
key objective of the Directive is to achieve good chemical status for all waters by 2015. The WFD considers
the objective of “good chemical surface water status” to be achieved in a water body if concentrations of
pollutants do not exceed the relevant EQS established at Community level. Environmental quality standard
(EQS) means “the concentration of a particular pollutant or group of pollutants in water, sediment or biota
which should not be exceeded in order to protect human health and the environment” (Article 2 (35)).
Chemical pollutants of concern under the Water Framework Directive (WFD) are divided into:
 priority substances  it is required to progressively reduce pollution from priority substances (by
2015);
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA



priority hazardous substances (sub-group included in the list of the priority substances)  more
stringent requirements on phasing out emissions, discharges and losses of these substances within 20
years to be applied (by 2025);
other pollutants  they are not in the priority substances list; they are included to maintain the
regulation of the substances at Community level;
“river basin specific substances”  Member States shall set quality standards for river basin specific
pollutants based on the indicative list in Annex VIII (see Annex II of this report for the whole list) and take
action to meet those quality standards by 2015 as part of ecological status (Article 4, 11 and Annex V,
WFD). For this purpose a programme of measures shall be in place by 2009, and become operational by
2012. This procedure will then replace Directive 76/464/EEC upon its repeal.
Article 16 of the Water Framework Directive 2000/60/EC (WFD) sets out a strategy for dealing with chemical
pollution of water (see the extract from the directive in Annex III).
As a part of this strategy, on 17 July 2006, the Commission adopted a proposal for a new Directive to
protect surface water from pollution:
 setting environmental quality standards for the priority substances which Member States must achieve
by 2015 to ensure "good chemical surface water status";
 requiring progressive reduction of emissions, losses and discharges of all priority substances, and
phase-out or cessation of emissions, losses and discharges of priority hazardous substances by 2025;
an inventory of discharges, emissions and losses have to be established for the river basins to check
whether the objectives of reduction or cessation are met.
Furthermore the proposed Directive amends Directive 2000/60/EC by updating a list of priority substances in
the field of water policy - Annex X (see Annex IV of this report for the whole list).
When adopted, this Directive will also repeal the five specific “daughter” directives (82/176/EEC,
83/513/EEC, 84/156/EEC, 84/491/EEC and 86/280/EEC as amended by Directive 88/347/EEC and
90/415/EEC) to the directive 76/464/EEC from 22 December 2012.
The proposed Directive sets environmental quality standards for surface waters of 41 dangerous chemical
substances that pose a particular risk to animal and plant life in the aquatic environment and to human
health. It includes:
 33 priority substances including 13 priority hazardous substances,
 8 other pollutants (they fall under the scope of Directive 86/280/EEC and are included in List I of the
Annex to Directive 76/464/EEC, they are not in the priority substances list; the environmental quality
standards for these substances are included in the Commission proposal to maintain the regulation of
the substances at Community level).
See Annex V of this report for the comprehensive list of EQS for priority substances and selected other
pollutants.
Environmental quality standards (EQS) are differentiated for inland surface waters (rivers and lakes) and
other surface waters (transitional, coastal and territorial waters). Two types of EQS are set:
 annual average concentrations for chronic effects, i.e. protection against long-term irreversible
consequences;
 maximum allowable concentrations for short-term ecotoxic effects due to the direct and acute
exposure.
For metals, the compliance regime is adapted by allowing Member States to take background levels and
bioavailability into account. Member States shall have to use compulsory calculation methods, if set up by
the Commission. EQS are also established for biota of certain selected substances. Some EQS may need to
be revised shortly in the light of the outcome of ongoing risk assessments under other Community legislation
(in particular an amendment of the provisional EQS for nickel and lead are likely).
The following table gives an overview on the linkage and differences of the lists of substances regulated by
“old” and “new” framework directives.
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Table 1. Linkage between Directive 76/464/EEC and Directive 2000/60/EC regarding lists of substances.
Priority hazardous substances
(Annex X)
Priority substances
(Annex X)
Other pollutants with specified EQS on
Community level
River basin specific substances
(Annex VIII)
CHEMICAL STATUS
List I
Cd, Hg, Hexachlorobutadiene,
Hexachlorocyclohexane,
Hexachlorobenzene
List I
1,2-dichlorethane, Trichloromethane
(Chloroform), Pentachlorphenol,
Trichlorobenzene
List I
Carbontetrachloride, DDT, aldrin, dieldrin,
endrin, isodrin, trichloroethylene,
perchloroethylene
List II
 other substances belonging to the
categories listed in List I
 other substances and categories of
substances having deleterious effects on
the aquatic environment
 Member States’ specific substances
Water Framework Directive
Directive 2000/60/EC (WFD)
ECOLOGICAL
STATUS
Dangerous Substances Directive
Directive 76/464/EEC (DSD)
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
3.
Practices of monitoring and screening of hazardous substances in
Lithuania 1992-2005
This chapter describes monitoring practices of hazardous and priority hazardous substances, which are
comprised into the national lists based on the requirements of the EU Directives 2000/60/EC and 76/464/EC.
A list of 74 specific pollutants (see Annex VI of this report for the complete list) was fixed in the Order of the
Minister of Environment No. 624 of 21 December 2001 approving the Rules of reduction of water pollution by
hazardous substances, Order of the Minister of Environment No. 623 of 21 December 2001 approving the
Rules of reduction of water pollution by priority hazardous substances (updated by the order of the Minister
of Environment No. 267 of 22 may 2002), replaced by Order of the Minister of Environment No. D1-236 of 17
May 2006 on Regulation on wastewater treatment).
1. Water monitoring during 1992 – 2004
The first ecological monitoring system was established in Lithuania in 1991- 1992 and it included water
monitoring programme. Later on, in 1997 the first State environmental monitoring programme was prepared
and approved. Both state environmental monitoring programmes included water monitoring part, comprising
of rivers and lakes monitoring, Curonian lagoon and Baltic sea monitoring, as well as groundwater
monitoring.
Hazardous substances analysed during 1997-2004
River water quality was assessed in 47 rivers until 2003 and in 51 river in 2004, number of lake monitoring
stations varied from 7 to 13 in different years. Approximately 70 parameters were included in water
monitoring programme. Hazardous or priority hazardous substances, included in the first State
environmental monitoring programme are listed in the Table 2.
Table 2. Hazardous and priority hazardous substances assessed in Lithuanian rivers and lakes during 19972004.
Group
Matrixes
Parameter
Frequency
Monitoring sites
Heavy
metals
Surface
waters;
Bottom
sediments
Surface
waters;
Bottom
sediments
Surface
waters;
Bottom
sediments
Zn, Cu, Cr, Pb, Ni, Hg, Cd
4 times/year in
rivers
2 times/year in
lakes
2-4 times/year
40-50 river monitoring
stations
7-9 lake stations
2-4 times/year in
rivers
2 times/year in
lakes
20-40 river monitoring
stations
7-9 lake stations
Phenols
Pesticides
Pentachlorphenol
DDT, polychlorbiphenyl,
hexachlorocyclohexanes (,,),
simazine, lindane, atrazine
20-40 river monitoring
stations
Water quality with regard to hazardous substances during 1997- 2004
Metals
 Five metals: zinc, copper, chromium, lead and nickel were monitored throughout the period of 19952003. During this period average annual concentrations of heavy metals in all the rivers except of Kulpė
river were similar and did not exceed the annual average maximum allowable concentrations (AA-MAC).
 Only in 2002 concentrations increased insignificantly, and concentration of lead in Nemunas below
Smalininkai and Sidabra river at the border exceeded AA-MAC. The increase of concentrations of heavy
metals was caused by the decreased of water flow in rivers, point sources of pollution and transboundary
pollution.
 In river Kulpė AA-MAC of Cr and Ni were exceeded a number of times during 9 years.
 In 2003 there were few cases when concentrations of Cu, Zn, Cr, Ni and Pb exceeded AA-MAC. Higher
concentrations of these metals occurred in rivers Nemunėlis, Kulpė, Šventoji, Jūra, Buka and Birvėta.
 In 2003 Kulpė remained to be polluted by nickel and chromium, what can be explained by the point
sources of pollution, situated along the upper part of the river.
 In 2004 concentrations of heavy metals in the rivers not exceeded AA-MAC with some exceptions. In
Nevėžis river average annual concentration of lead was 6,1 μg/l. In Kulpė river concentrations of nickel
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
and chromium, similarly to previous years, were higher than in other rivers and were close to AA-MAC.
Chromium concentrations in this river ranged from 7,4 μg/l to 7,9 μg/l, Ni – from 7,7 μg/l to 9,6 μg/l.
Pesticides
 Simazine was once detected in Nemunas river (1,15 μg/l) and exceeded AA-MAC (1g/l).
 Lindane was detected in Nemunas, Lokysta and Nemunėlis water, where concentrations ranged from
0,01 μg/l to 0,06 μg/l.
 Lindane was detected in bottom sediments in 4 rivers - Neris, Jūra, Laukesa and Daugyvenė, where
concentrations varied from 0,004 mg/kg to 1.000 mg/kg. There was only one lake Lūkšto, were lindane
was detected in bottom sediments (0,002 mg/kg).
 DDT was detected 23 times in 15 rivers, where concentrations varied from 0,01 μg/l to 0,96 μg/l.
 In bottom sediments DDT was detected in 6 rivers (Žeimena, Tatula, Šešupė, Daugyvenė, Nevėžis and
Bartuva), here concentrations of DDT varied from 0,0003 μg/kg to 0,010 mg/kg. DDT in bottom
sediments in lakes was detected in Šventas, Lūkštas and Vištytis.
 DDE – was detected 31 times in 17 rivers, where concentrations ranged from 0,005 mg/kg to 0,120
mg/kg.
Phenols
 Pentachlorphenol was detected in 9 rivers (Nemunas, Šešupė, Šventoji, venta, Mūša, Sidabra,
Nemunėlis, Lėvuo, Birveta) where concentrations varied from 0,01 μg/l to 0,4 μg/l, and in two lakes
(Tauragnų and Žuvinto).
Other hazardous substances included in the monitoring programme in rivers were detected rarely or never.
2. Water monitoring after 2004
Since 2005 water quality in Lithuanian rivers and lakes is being monitored according to a new State
environmental monitoring programme for 2005-2010. The new water monitoring programme was prepared
according to the requirements of the Water Framework Directive (2000/60/EC).
Water monitoring programme like the previous one, includes rivers and lakes monitoring, Curonian lagoon
and Baltic sea monitoring and the groundwater monitoring. The monitoring programme is further subdivided
into reference monitoring, operational monitoring and surveillance monitoring.
According to new monitoring programme, water quality will be monitored in 360 river monitoring sites and 80
lake monitoring sites. Monitoring network is subdivided into intensive and extensive monitoring stations,
where monitoring in intensive stations will be carried out several times every year, while in the extensive
monitoring stations – once every 3 or 6 years, based on the rotation principle.
Hazardous substances in the State Environmental Monitoring Programme 2005-2010
A number of hazardous substances to be analysed has been expanded with several additional metals, series
of organic chlorinated compounds, benzene, additional pesticides, etc. The list of the substances is provided
in the Table 3.
Table 3. Hazardous and priority hazardous substances included in the State water monitoring programme
for 2005-2010
Group
Matrixes
Parameter
Heavy metals
Surface waters
Bottoms sediments
Surface waters
Zn, Cu, Cr, Pb, Ni, Hg, Cd, As, Sn, V
Organic chlorinated
compounds
PAH
Phenols
Pesticides
Surface waters
Bottoms sediments
Surface waters
Surface waters
Tetrachlormethane, trichloromethane, 1,2-dichloroethane,
trichloroethylene, perchloroethylene, dichloromethane, benzene
Anthracene, benzo(a)pyrene, benzo(b)fluoranthene,
benzo(g,h,i)pertylene, benzo(k)fluoranthene, fluoranthene,
indeno(1,2,3-cd)pyrene, naphthalene
Pentachlorphenol
DDT, polychlorbiphenyl, hexachlorocyclohexanes (,,),
hexachlorobenzene, endosulphan, endosulphan(alpha), simazine,
lindane, atrazine, aldrin, dieldrin, endrin
Not all of 74 substances from the national list of pollutants are included in the Monitoring programme for
2005-2010 and Water monitoring plans for 2005 and 2006, mainly due to the reason that some of them
cannot be analysed in the Environmental Research Department of EPA. These substances are:
hexachlorbutadiene, C10-13-chloralkanes, brominated diphenylethers, pentabromobiphenylether,
pentachlorobenzene, tributyl compounds, tributyl-cation, chlorfenvinphos, chlorpyrifos, diuron, isoproturon,
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
nonylphenols, 4-(para)-nonylphenol, octylphenols, para-tert-octylphenols, di(2-ethylhexyl)phthalate, cyanides
and tensides:non-ionic.
However the annual average maximum allowable concentrations (AA-MAC) for hazardous substances
released into sewerage, natural environment and AA-MAC in receiving water body are set for all the
substances (see Annex VI of this report for the complete list). In the future, at least those substances, which
are identified as of concern during current screening exercise, should be included into monitoring system,
concidering the analysis in the external laboratories.
Water quality in 2005 with regard to hazardous substances
Water monitoring according to the new monitoring programme was first carried out in 2005. Samples of
water and bottom sediments for analysis of dangerous substances were taken in 51 stations (42 rivers).
As in previous years, the AA-MAC for all parameters was not exceeded except Zn. When speaking about the
parameters, included in the water monitoring for the first time, only concentrations of trichloromethane
(chloroform) exceeded AA-MAC (12 μg/l) in few monitoring stations (Šušvė at estuary - 48,3 g/l; Venta
below Mažeikiai – 149,2 g/l; Varduva at Griežė – 38,8 g/l; Ašva at the border - 117,3g/l). It was also
detected in some more places but in lower concentrations.
Some other hazardous substances were also detected (trichlorethylene, perchloroethylene,
endosulphan(alpha), anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene,
fluoranthene, naphthalene), however their concentrations were low and not exceeded AA-MAC.
Water quality in rivers and lakes is currently assessed according to the corresponding requirements for
fisheries (Order of the Minister of Environment No. D1-633 of 21 December 2005), which sets maximum
allowable concentrations for dissolved oxygen, organic, nutrients and some dangerous substances, see
Table 4 below.
Table 4. Maximum allowable concentrations set in the requirements for fisheries
Maximum allowable concentrations in water bodies for
Parameter
salmons
carps
O2
 9 mg/l
 7 mg/l
BDS7
 4 mg/l
 6 mg/l
PO4
 0,2 mg/l
 0,4 mg/l
NO2
 0,1 mg/l
 0,15 mg/l
Phenols
No phenols taste in the fish
PAH
No film on water and no taste in the fish
NH3
 0,025 mg/l
 0,025 mg/l
NH4
 1 mg/l
 1 mg/l
Zn
 0,03-0,5* mg/l
 0,3-2,0* mg/l
Cu
 0,005-0,112* mg/l
 0,005-0,112* mg/l
* depending on the hardness of water
3. Analysis of priority substances in wastewater
According to Wastewater treatment regulation, approved by the Order of the Minister of Environment No. D1236 on May 17, 2006, economic entities, discharging their wastewater into the sewerage systems have to
determine, which hazardous substances and priority hazardous substances and at what concentrations they
are present in wastewater. Furthermore, the Regulation also provides a list of parameters to be controlled
according to the type of industry. Water pollution with dangerous substances reduction programme,
approved by the Minister of Environment by Order No. D1-71 on February 12, 2004, also includes a list of
substances, which may be discharged by certain types of industries, however in both cases not all
hazardous and priority hazardous substances are covered in the lists, especially those of “new-generation”
as organotin compounds, phtalates, phenols and their ethoxylates etc. Most of the substances or groups of
the substances being priority or priority hazardous substances on EU level are not considered (Table 5
illustrates, which of priority or priority hazardous substances on EU level are covered/recommended at least
for single industry branch in the lists of the above-mentioned legislation).
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Table 5. Hazardous and priority hazardous substances to be considered by certain industries
No.
1
2
3
4
5
6
7
8
10
11
12
13
14
15
16
Substances
Metals (Zn, Ar, Cu, Cr, Pb, Hg, Ni)
Halogenated VOC
Tetrachlormethane
Trichlormethane (chloroform)
Hexachlorbenzene
Hexachlorbutadiene
1,2,4-trichlorbenzene
Pentachlorphenol
Cyanides
Di(2-ethilhexyl)phthalate
1,2-dichlorethane
Tetrachlorethylene
Trichloroethylene
Dichlormethane
PAH
Reg. No. D1-236
(to be controled)
Reg. No. D1-71
(indicative list)
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Furthermore, the economic entities have to make an inventory of dangerous substances, applicable to their
industrial sector and present this inventory in the application for IPPC permit (Order of the Minister of
Environment No. 80 of 27 February 2002, changed by No. D1-330 of 29 June 2005). The frequency of
monitoring of hazardous substances by industries is set in the IPPC permit. If MAC of these substances are
exceeded the reduction programmes should be prepared and implemented.
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
4.
Selection of the hazardous substances, sampling sites and matrixes
A. Selection of hazardous substances
Lithuania has established a list of 74 pollutants, which covers 33 priority substances of WFD as well as some
other pollutants indicated in the Annex VIII WFD and Lists I and II of DSD. In addition, some more physicalchemical parameters were fixed in the list. See the full list in Annex VI. The project has focussed on the
selected substances from this list.
The major criteria for the selection of hazardous substances to be screened in the frame of the project were
the following:
 the priority was given for the substances or groups of substances’ identified among those where the
limits on concentrations in surface waters will be set on European level (i.e. 33 priority substances and 8
other pollutants);
 the biggest gaps of information of occurrence of priority substances in the waste water and receiving
environment;
 the facts that certain substance or group of substances occur on the market;
 the facts on occurrence of substances in the environment from Finnish experience (e.g. dibutylphtalate,
butylbenzylphtalate);
 in order to narrow the scope project has focused on industrial and consumer chemicals, the agricultural
pesticides were excluded from the survey;
 the measurements of some other parameters, such as cyanides, halogenated organic compounds (AOX)
were performed only in the specific places, i.e. in Nemunas after Sovietsk (Kaliningrad region), based on
the concern that they might be emitted directly to the river with the effluents from metal processing (metal
cutting) industry, mirror production (CN) and pulp and paper industry (AOX).
The scope of the investigated substances was very much widened by the fact that the chosen laboratory
provided the possibility to analyse more substances with the same method. In total 102 substances or
groups of substances were screened. They are divided into 9 groups:
1) metals,
2) phenols and their ethoxylates,
3) polycyclic aromatic hydrocarbons,
4) chloroorganic pesticides,
5) volatile organic compounds,
6) organotin compounds,
7) phtalates and their ethoxylates,
8) brominated diphenylethers,
9) other: short chain chlorinated parafins, pentachlophenol, chlorpyrifos, cyanides, AOX.
The complete list of substances or groups of substances analysed within the project is provided in the Table
6 below.
12
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Table 6. Substances/ groups of substances analyzed within the project
Explanations:
* These substances were proposed by the chosen laboratory (GALAB) to be analysed in addition by the same method.
** Information based on findings from data searches in years 2003-2006 (including findings from other projects carried
out by Baltic Environmental Forum).
No.
CAS Nr.
Name
WFD Used
Information source
Use
in
LIT**
I. Metals
Database of dangerous ch.
1.
7440-43-9
Cadmium and its compounds
X
yes
Permits for toxics
IPPC permits
Permits for toxics
2.
7439-92-1
Lead and its compounds
X
yes
Industry
Database of dangerous ch.
3.
7440-02-0
Nikel and its compounds
X
yes
Permits for toxics
IPPC permits
Biocides register
4.
7440-66-6
Zink and its compounds
yes
IPPC permits
Industry
5.
7440-38-2
Arsenic and its compounds
yes
Permits fro toxics
Biocides register
PPP register
6.
7440-50-8
Copper and its compounds
yes
Wood impregnation
IPPC permits
Industry
7.
7439-97-6
Mercury and its compounds
X
yes
Permits for toxics
II. Phenols and their ethoxylates
8.
104-40-5
4-Nonylphenol
X
Textile: printing, finishing,
PPP register
dyeing chemicals and
9.
25154-52-3
Nonylphenols (mixture of izomers)
X
yes
Industry
auxiliaries
Co-formulant in PPP
10.
11066-49-2
iso-Nonylphenol*
Nonylphenolmonoethoxylate
11.
27986-36-3
(NP1EO)
12.
--iso-Nonylphenolmonoethoxylates*
Car care products
13.
20427-84-3
Nonylphenoldiethoxylate (NP2EO)
Professional cleaners,
detergents (industry)
14.
--iso-Nonylphenoldiethoxylates
15.
--iso-Nonylphenoltriethoxylate*
16.
--iso-Nonylphenoltetraethoxylate*
17.
--iso-Nonylphenolpentaethoxylate*
18.
--iso-Nonylphenolhexaethoxylate*
19.
1806-26-4
4-octylphenol
X
20.
140-66-9
4-tert-octylphenol
X
21.
9036-19-5
Octylphenolmonoethoxylate
22.
--Octylphenoldiethoxylate
23.
--4-t-Octylphenoltriethoxylate*
24.
--4-t-Octylphenoltetraethoxylate*
25.
--4-t-Octylphenolpentaethoxylate*
26.
--4-t-Octylphenolhexaethoxylate*
27.
98-54-4
4-t-Butylphenol*
28.
80-46-6
4-t-Pentylphenol*
III. Polycyclic aromatic hydrocarbons (PAH)
29.
120-12-7
Anthracene
X
30.
50-32-8
Benzo(a)pyrene
X
31.
205-99-2
Benzo(b)fluoranthene
X
32.
191-24-2
Benzo[ghi]perylene
X
33.
207-08-9
Benzo(k)fluoranthene
X
34.
193-39-5
Indeno[1,2,3-cd]pyrene
X
13
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
No.
CAS Nr.
Name
WFD
Used
in
LIT**
Information source
yes
Database of dangerous ch.
yes
yes
Permits for toxics
Permits for toxics
yes
Permits for toxics
Use
35.
91-20-3
Naphtalene
36.
206-44-0
Fluoranthene
IV. Chloroorganic pesticides
37.
309-00-2
Aldrin
38.
60-57-1
Dieldrin
39.
72-20-8
Endrin
40.
50-29-3
DDT
41.
58-89-9
Lindane
42.
118-74-1
Heksachlorobenzene
43.
608-73-1
Hexachlorocyclohexanes (,,)
V. Volatile organic compounds (VOC)
X
X
44.
71-43-2
Benzene
X
yes
45.
107-06-2
1,2-dichloroethane
X
yes
46.
75-09-2
Dichlormethane
X
yes
Database of dangerous ch.
47.
56-23-5
Tertrachlormethane
yes
Database of dangerous ch.
Permits for toxics
Industry
Laboratory
48.
127-18-4
Tetrachloroethylene
yes
Database of dangerous ch.
Degreasing details, chemical
cleaning of clothes, polygraphy,
import
49.
67-66-3
Chloroform (trichloromethane)
50.
79-01-6
Trichlorethilene
VI. Organotin compounds
51.
688-73-3
Tributyltin
52.
3664-73-3
Tributyltin kations
53.
78763-54-9
Monobutyltin*
54.
1002-53-5
Dibutyltin*
55.
1461-25-2
Tetrabutyltin*
56.
--Monooctyltin*
57.
--Dioctyltin*
58.
--Tricyclohexyltin*
59.
--Monophenyltin*
60.
--Diphenyltin*
61.
668-34-8
Triphenyltin*
VII. Phtalates and their ethoxylates
62.
117-81-7
Di-2-ethylhexyl phthalate - DEHP
63.
84-74-2
Dibutylphtalate - DBP
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
113-11-3
84-66-2
120-51-4
84-69-5
117-82-8
--605-54-9
131-18-0
84-75-3
85-68-7
---
Dimethyl phthalate*
Diethyl phthalate*
Benzyl benzoate*
Diisobutyl phthalate*
Dimethoxyethyl phthalate*
Diisohexyl phthalate*
Di-2-ethoxyethyl phthalate*
Dipentyl phthalate*
Di-n-hexyl phthalate*
Benzylbutyl phthalate*
Hexyl-2-ethylhexyl phthalate*
14
X
X
X
X
yes
yes
X
X
yes
X
yes
yes
Database of dangerous ch.
Permits for toxics
Database of dangerous ch.
Permits for toxics
Database of dangerous ch.
Biocides register
Permits for toxics
Database of dangerous ch.
Industry
Database of dangerous ch.
Industry
Database of dangerous ch.
Permits for toxics
Laboratory
Laboratory
Laboratory
Gluing of organic glass, specific
chemical technologies, import
Chemical fibre, films, plastics;
cleaners of paints, solvent in
technological processes, import
Laboratory, biocides, import
To improve quality of asphalt for
roads, import
Antifouling paints
Dispersed water paint, sealants
Plasticizer for paints and
coatings)
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
No.
CAS Nr.
Name
75.
76.
117-83-9
84-61-7
Dibutoxyethyl phthalate*
Dicyclohexyl phthalate*
77.
28553-12-0
Diisononyl phthalate*
78.
117-84-0
Di-n-octyl phthalate*
79.
26761-40-0
Diisodecyl phthalate*
VIII. Brominated diphenylethers
80.
32534-81-9
Pentabromdiphenylether, sum
81.
60348-60-9
Pentabromdiphenylether, PBDE-99*
Pentabromdiphenylether, PBDE82.
189084-66-0
100*
83.
32536-52-0
Octabrombiphenylethers
84.
1163-19-5
Decabrombiphenylethers
85.
79-94-7
Tetrabromobisphenol A, TBBPA*
86.
59080-37-4
Tetrabromobiphenyl, PBB-52*
87.
67888-96-4
Pentabromobiphenyl, PBB-101*
88.
59080-40-9
Hexabromobiphenyl, PBB-153*
89.
--Tribromodiphenyl ether, PBDE-28*
90.
5436-43-1
Tetrabromodiphenyl ether, PBDE-47*
Hexabromodiphenyl ether, PBDE91.
182677-30-1
138*
Hexabromodiphenyl ether, PBDE92.
68631-49-2
153*
93.
207122-15-4
Hexabromdiphenyl ether, PBDE-154*
Heptabromodiphenyl ether, PBDE94.
207122-16-5
183*
Heptabromodiphenyl ether, PBDE95.
189084-68-2
190*
96.
87-82-1
Hexabromobenzene*
97.
25637-99-4
Hexabromocyclododecane*
IX. Other substances/ groups of substances
C10-13 chloralkanes (Short chain
98.
85535-84-8
chlorinated parafins (SCCP))
99.
87-86-5
Pentachlorphenol - PCP
100.
2921-88-2
Chlorpyrifos
101.
102.
-----
Cyanides -CN
AOX
WFD
Used
in
LIT**
Information source
Use
Database of dangerous ch.
Rubber industry
Metal cutting fluids
X
X
yes
X
X
yes
Biocides register
PPP register
Preparations for cockroaches
15
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
B. Selection of the sampling sites
Primarily the sampling has concentrated on:
 urban waste water treatment plants (WWTP)
 as review of industrial discharges made by Danish EPA financed project 1 showed that vast
majority of industries discharge their effluent into the public sewer;
 WWTP of biggest cities were considered to contribute to the pollution most, therefore all
biggest cities of Lithuania were covered;
 smaller towns were selected based on the knowledge on industry concentrated in the town
and the results of the screening of certain hazardous substances (metals, PAH, VOC)
performed by Environmental Protection Agency of Lithuania in year 2005; the towns with
higher pollution by screened substances were considered first.
 transboundary rivers
 the sites in the rivers (both flowing in and out of the country) close to the border were
selected in order to have an opportunity to estimate whether any hazardous substances gets
into the Lithuania from neighbouring countries or are passed to neighbouring countries.
 rivers inflowing to the Curonian Lagoon/ Klaipėda Chanell (Nemunas and Akmena)
 the sites at the estuary were selected to check whether hazardous substances gets with the
inland waters to the Baltic Sea.
 transitional waters to the Baltic Sea (harbour area, Malkų bay)
 these sites were chosen due to the reason that some of the selected substances for
screening have very high potential to occur specifically in this areas, e.g. organotin
compounds, phenols and their ethoxylates in harbours area; furthermore, it is the main way
of the pollutants from inland activities to enter the Baltic Sea waters.
The first analysis round has shown that some of the cities are discharging highly polluted wastewater to the
rivers. Therefore at the second step some more sites on the rivers below the most polluting cities have
been added in order to check potential influence of the discharged wastewater to the quality of the surface
waters.
In total 44 sites were screened for the selected hazardous substances:
 25 WWTP,
 8 sites on transboundary rivers at the border,
 2 sites on the rivers before inletting into the Curonian Lagoon and Klaipėda Channel,
 4 sites at the transitional waters of Klaipėda Channel,
 5 sites on the rivers after polluting cities.
Ecotoxicity tests were performed for 37 sites: 25 WWTP and 12 for the surface water.
The detailed list of the sampling sites and analysed matrixes is provided below in the Table 7.
1
Danish EPA financed Project to Assist the Republic of Lithuania to Transpose EU Requirements in the Water Sector (implemented by
DHI, CarlBro and CEP (Center for Environmental Policy)).
16
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Table 7. Sampling sites and analysed matrixes
Site
No.
Sampling site
Sampling site description
Matrixes
1.
WWTP Dzūkijos vandenys
WW to Nemunas river, Alytus
WW/SW WS/BS
ET



2.
WWTP Varėnos vandenys
WW to Derežnyčia river



3.
WWTP Birštono vandentiekis
WW to Nemunas river



4.
Nemunas at the Belarus border
at Švendubrės village



5.
WWTP Klaipėdos vanduo
WW to Baltic sea/Curonian lagoon



6.
WWTP Silutės vandenys
WW to Nemunas/Šyša river



7.
WWTP Tauragės vandenys
WW to Nemunas/Jūra river



8.
Nemunas at Rusnė
up the Leitė



9.
Bartuva at the border
below Skuodas



10.
Akmena-Danė at the estuary
0,1 km from estuary



11.
Šventoji at the border
at Senoji Įpiltis



12.
Malkų bay at Klaipėda
point of regular monitoring

 
13.
Harbour area
at the gates


14.
Harbour teritory
at JSC Klaipėdos kartonas

 
15.
Nemunas after Sovietsk
at Pagėgiai



16.
WWTP of Marijampolė
WW to Nemunas/Šešupė river



17.
WWTP of Vilkaviškis
WW to Širvinta/Žeimena river



18.
WWTP of Šakiai
WW to Šešupė/Siesartis river



19.
WWTP of Kazlų Rūda
WW to Pilvė/Jūrė river






20.
WWTP Aukštaitijos vandenys
WW to Nevėžis river, Panevėžys

21.
WWTP Rokiškio vandenys
WW to Laukupė river



22.
Nemunėlis river at the border
at Tabokinė



23.
Mūša river at the border
below Saločiai



24.
WWTP Utenos vandenys
WW to Šventoji/Vyžuona



25.
WWTP Anykščių vandenys
WW to Šventoji river



26.
Dysna river at the border
at Kačerginė



27.
WWTP Šiaulių vandenys
WW to Mūša/Kulpė river



28.
WWTP Plungės vandenys
WW to Minija/Mažoji Sruoja river



29.
WWTP Mažeikių nafta
WW of town to Venta/Skutulas river



30.
WWTP Radviliškio vanduo
WW to Kruoja/Obelė river



31.
Venta river at the border
at Mažeikiai



32.
Neris river at the border
at Buivydžiai



33.
WWTP Vilniaus vandenys
WW to Neris river



34.
WWTP Ukmergės vandenys
WW to Šventoji river



35.
WWTP of Švenčionėliai
WW to Sudatėlis lake



36.
WWTP of Pabradė
WW to Žeimena river



37.
WWTP Kauno vandenys
WW to Nemunas river



38.
WWTP Kėdainių vandenys
WW to Nemunas river





39.
WWTP Jonavos vandenys
WW to Neris river

40.
Šventoji river
after Anykščiai



41.
Siesartis river
after Šakiai



42.
Nemunas river
after Kaunas



43.
Nevėžis river
after Panevėžys



  
44. Klaipėda Channel
at “Baltijos kolūkis”
Matrixes: WW - waste water, SW - surface water, WS - sludge from WWTP, BS - bottom sediments, ET - ecotoxicity test
Sampling rounds: number of sampling rounds is indicated by number of 
Other abbreviations: WWTP - Waste Water Treatment Plant
17
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
The maps below provide a detailed overview on the location of the sampling sites as well as general
information on the sampled matrixes.
Picture 1. Location of the sampling sites.
22
31 29
9
23
11
28
27
21
30
5
43 20
10
See
Picture 2
25
40
6
8
26
38
7
15
24
34
35
39
41 18
36
42 37
32
19
17
33
3
16
1
2
4
Surface water/
bottom sediments
Wastewater/
sewage sludge
Picture 2. Location of sampling sites in Klaipėda Channel.
18
Ecotoxicity
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
C. Selection of the matrixes
In the frame of this project the analysis of the hazardous substances were performed in the following
matrixes:
 wastewater,
 sewage sludge,
 receiving waters (mainly rivers and some sites at transitional waters in Klaipėda channel), and
 sediments in the receiving environment.
The selection of the matrixes for the specific substances/ groups of substances was based on the potential
occurrence of the substance in the specific matrix, i.e. particularly hydrophobic substances will not be found
in significant concentrations in liquid phase. Therefore the practical approach was taken to save the
resources and to limit analysis to the most relevant matrixes. The relevant matrixes were determined
based on different literature sources (Report of the expert group on analysis and monitoring of priority
substances) and by the chemical-physical properties of the substances influencing their fate in the
environment (solubility in water, partitioning, bioaccumulation etc., see Table 8).
Table 8. The main criteria considered determining the potential occurrence of the substances in different
matrixes.
Criteria
Koc>2700
Log Koc >3.5
BCF >2000
Log Pow = 4.5-9
Meaning
Interpretation
 high potential of sorption of substance to
soil/sediments
 higher Koc values - less mobile organic chemicals
 Koc <500 no or little adsorbtion
 already starting from BCF>1300 substance is liable to
bioaccumulate in fatty tissue
 BCF>2000 shows that substance bioaccumulates in
fatty tissue
 BCF>5000 shows that substance strongly
bioaccumulates in the fatty tissue
 liable to bioaccumulate in fatty tissue
The partitioning coefficient between
water and organic carbon. It indicates
potential to adsorb to the soil/
sediments.
Bioconcentration factor
Coefficient indicating partitioning of
substance between octanol and water.
The table below gives an overview on the potential of the occurrence of substances or groups of substances
in different matrixes. In case of the group of substances the matrixes were determined based on the key
representative substances (e.g. for brominated diphenylethers, organotin compounds, phenols, phtalates
and their ethoxylates).
Table 9. Priority matrixes to be analysed for different substances/ groups of substances
* Potential that substance occurs in the selected matrix: H- high, M- medium
Priority matrixes where substances should be analysed
No.
CAS Nr.
Name
Waste
water
Sewage
sludge
Receiving
water
Sediments Biota
H-M*
H-M
H-M
H-M
H-M
H-M
H-M
H-M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
H-M
M
H-M
M
M
M
M
M
M
M
H
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
M
I. Metals and their compounds
1.
2.
3.
4.
5.
6.
7.
7440-43-9
7439-92-1
7440-02-0
7440-66-6
7440-38-2
7440-50-8
7439-97-6
Cadmium and its compounds
Lead and its compounds
Nickel and its compounds
Zinc and its compounds
Arsenic and its compounds
Copper and its compounds
Mercury and its compounds
II. Phenols and their ethoxylates
8.
9.
104-40-5
25154-52-3
10.
27986-36-3
11.
20427-84-3
4-Nonylphenol
Nonylphenols (mixture of izomers)
Nonylphenolmonoethoxylate
(NP1EO)
Nonylphenoldiethoxylate (NP2EO)
19
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
Priority matrixes where substances should be analysed
No.
12.
13.
14.
15.
CAS Nr.
1806-26-4
140-66-9
9036-19-5
---
Name
4-octylphenol
4-tert-octylphenol
Octylphenolmonoethoxylate
Octylphenoldiethoxylate
Waste
water
M
M
M
M
Sewage
sludge
M
M
M
M
Receiving
water
M
M
M
M
H-M
M
M
H
Sediments Biota
M
M
M
M
M
M
M
M
III. Polycyclic aromatic hydrocarbons (PAH)
16.
120-12-7
Anthracene
17.
50-32-8
Benzo(a)pyrene
H
M
H
M
18.
205-99-2
Benzo(b)fluoranthene
H
M
H
M
19.
191-24-2
Benzo[ghi]perylene
H
M
H
M
20.
207-08-9
Benzo(k)fluoranthene
H
M
H
M
21.
193-39-5
Indeno[1,2,3-cd]pyrene
H
M
H
M
22.
91-20-3
Naphtalene
H-M
M
M
M
M
23.
206-44-0
Fluoranthene
M
M
M
H
M
IV. Chloroorganic pesticides
24.
309-00-2
Aldrin
M
M
M
M
M
25.
60-57-1
Dieldrin
M
M
M
M
M
26.
72-20-8
Endrin
M
M
M
M
M
27.
50-29-3
DDT
M
M
H
H
28.
87-68-3
Heksachlorobutadiene
H-M
M
M
M
M
29.
608-73-1
Hexachlorocyclohexane
M
M
M
M
M
30.
58-89-9
Lindane
M
M
H
H
H
M
V. Volatile organic compounds (VOC)
31.
71-43-2
Benzene
H
32.
107-06-2
1,2-dichloroethane
H
H
33.
75-09-2
Dichlormethane
H
H
34.
118-74-1
Heksachlorbenzene
M
M
35.
608-93-5
Pentachlorbenzene
M
M
36.
120-82-1
Trichlorobenzene
H
H
37.
56-23-5
Tertrachlormethane
H
H
38.
127-18-4
Tetrachloroethylene
H
H
39.
67-66-3
Chloroform (trichloromethane)
H
H
40.
79-01-6
Trichlorethilene
H
H
M
VI. Organotin compounds
41.
688-73-3
Tributyltin
M
M
H
H-M
42.
3664-73-3
Tributyltin kations
M
M
H
H-M
43.
668-34-8
Triphenyltin
M
M
H
H-M
VII. Phtalates and their ethoxylates
44.
117-81-7
Diethylhexylphtalate - DEHP
H-M
H-M
M
M
M
45.
84-74-2
Dibutylphtalate - DBP
M
M
M
M
M
VIII. Brominated diphenylethers
46.
32534-81-9
Pentabrombifenilethers - PBDE
H
H
M
47.
32536-52-0
Octabrombiphenylethers
M
M
M
48.
1163-19-5
Decabrombiphenylethers
M
M
M
M
M
H
H
H
H
IX. Other substances/ groups of substances
49.
85535-84-8
50.
87-86-5
C10-13 chloralkanes (Short chain
chlorinated parafins (SCCP))
Pentachlorphenol - PCP
51.
---
Cyanides - CN
20
M
M
M
M
M
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Priority matrixes where substances should be analysed
No.
CAS Nr.
Name
52.
2921-88-2
Chlorpyrifos
53.
---
AOX
Waste
water
M
Sewage
sludge
H
Receiving
water
M
Sediments Biota
M
H-M
H
The analysis within the project focused on the matrixes where the substances or groups of substances can
occur most likely, i.e. only matrixes indicated in the table above as H or M were considered. The only
considerable exception was made for the chloroorganic pesticides, which were analysed only in the receiving
environment. It was based on the facts that these substances are not anymore in use therefore they can
hardly occur in the wastewater treatment plants. Furthermore, the analysis of Environmental Protection
Agency of year 2005 has proved the absence of this group of substances in wastewater and sewage sludge
in some of the selected sites.
Initially in the project proposal it was planned to analyse hazardous substances also in the biota (fish).
During the inception phase of the project the biota analysis were cancelled mainly due to difficulty to interpret
and evaluate the results of biota (fish) analysis gained within such project:
 in rivers fish is highly migrating, therefore it is very difficult to correlate the occurrence of hazardous
substances in the fish to any specific source of hazardous substances;
 due to limited resources only very random samples could be taken and analysed what leads to even
more complicated interpretation of the results and decrease the added value to the general results of the
project and their practical applicability.
Thus, the priority was given to the chemicals analysis in the wastewater and sewage sludge and receiving
environment.
However in the later stage the biota (fish) tests were replaced by the series of microbiotests - Algaltoxkit,
Thamnotoxkit, Microtox, Charatox, Rotoxkit at most of the sites where chemical analysis has been
performed. The major reasons to consider the microbiotests were following:
 chemical tests alone are not sufficient to assess potential effects of complex wastes mixtures on aquatic
environment because of difficulties to screen all possible chemicals in water and limited knowledge on
chemicals toxicity and their interactions;
 the complete chemical composition of water is not known, some other toxic substances may have great
negative influence on the aquatic organisms, therefore the measurement of ecotoxicity in addition to
chemical analysis in the same sites should give more complete view on the status of toxicity of waste
water and status of surface water and lead to the better evaluation of the results;
 due to the reason that not all species respond identically to different type of pollutants, it was decided to
choose series of biotests with different organisms to get more valuable results.
The principal strategy proposed for the analysis and the evaluation of the results is the following:
Microtox + Thamnotox
[/Charatox]
Chemical
analysis
Yes
Slightly toxic/
toxic
Strongly toxic
Algaltoxkit/ Rotoxkit/
Protoxkit
EVALUATION
The complete overview on the specific substances/ groups of substances analyzed in the different matrixes
at the different sites is given in the Table 10. The duplicates required for the quality control are not counted
as independent samples. Also a series of the ecotoxicity tests are considered as one sample.
21
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
Sampling and analysis were performed in two big rounds in order to get a flexibility to choose additional
sampling sites or to repeat suspicious analysis after screening the results of the first round. Additionally third
sampling round was carried out in 3 sites (only sediments). More information on the reasoning of repeated
samples at different sites is presented in the chapter on results of the analysis.
Table 10. An overview on sampling sites, analysed substances/groups of substances, matrixes and number
of analysis
MET – metals, Hg – mercury, Ph&E - phenols and their ethoxylates, PAH - polycyclic aromatic hydrocarbons, COP chloroorganic pesticides, VOC - volatile organic compounds, OT - organotin compounds, BDPE -brominated
diphenylethers, Pht&E - phtalates and their ethoxylates, SCCP - short chain chlorinated parafins, PCP –
pentachlophenol, ChP – chlorpyrifos, CN – cyanides, AOX – halogenated organic compounds, ET – ecotoxicity test
X – analysis have been done by EPA in 2005.
No.
Site/Matrixes
MET
Hg
Ph&E PAH
1. WWTP Dzukijos vandenys
Wastewater
X
X
1
Sludge
1
1
1
2. WWTP Varėnos vandenys
Wastewater
X
X
1
Sludge
1
X
1
3. WWTP Birštono vandentiekis
Wastewater
X
X
1
Sludge
1
1
1
4. Nemunas at Belarus border
Receiving water
1
1
2
Sediments
1
1
2
5. WWTP Klaipėdos vanduo
Wastewater
1
1
2
Sludge
1
1
1
6. WWTP Šilutės vandenys
Wastewater
X
X
1
Sludge
X
1
1
7. WWTP Tauragės vandenys
Wastewater
X
X
1
Sludge
X
1
1
8. Nemunas river at Rusnė
Receiving water
X
X
1
Sediments
X
X
2
9. Bartuva river at the border
Receiving water
X
X
1
Sediments
X
X
1
10. Akmena river at estuary
Receiving water
X
X
1
Sediments
X
X
1
11. Šventoji river at the border
Receiving water
X
X
1
Sediments
X
X
1
12. Malkų bay at Klaipėda
Receiving water
1
1
2
Sediments
1
3
3
13. Harbours area (at gates)
Receiving water
X
X
1
Sediments
X
X
1
14. Harbours area (at JSC Klaipėdos kartonas)
Receiving water
2
2
2
Sediments
2
3
3
15. Nemunas river after Sovietsk
VOC
OT
X
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
X
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
1
2
2
COP
2
2
2
ChP
ChP
ET
1
2
1
1
1
2
2
2
2
2
2
2
2
1
1
1
1
X
1
1
1
1
1
1
1
1
1
1
1
1
X
1
1
1
1
1
1
1
1
1
1
2
1
2
2
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
3
3
2
3
3
1
1
1
1
1
1
1
X
X
1
1
1
X
X
1
1
1
X
X
1
1
1
X
X
1
2
2
1
1
2
1
1
X
X
1
2
2
2
2
2
1
3
1
3
2
3
2
1
1
2
2
Receiving water
2
2
2
2
2
Sediments
2
2
2
2
2
22
BDPE Pht&E SCCP PCP Other
ChP
ChP
2
1
1
1
1
2
2
2
1
1
1
3
2
2
1
2
1
2
2
2
1
CN
AOX
CN
AOX
1
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
No.
Site/Matrixes
MET
16. WWTP of Marijampolė
Wastewater
X
Sludge
X
17. WWTP of Vilkaviškis
Wastewater
X
Sludge
X
18. WWTP of Šakiai
Wastewater
X
Sludge
X
19. WWTP of Kazlų Rūda
Wastewater
X
Sludge
X
20. WWTP Aukštaitijos vandenys
Wastewater
1
Sludge
1
21. WWTP Rokiskio vandenys
Wastewater
1
Sludge
1
22. Nemunėlis river at the border
Receiving water
X
Sediments
X
23. Mūša river at the border
Receiving water
X
Sediments
X
24. WWTP Utenos vandenys
Wastewater
X
Sludge
X
25. WWTP Anykščių vandenys
Waste water
X
Sludge
1
26. Dysna river at the border
Receiving water
1
Sediments
1
27. WWTP Šiaulių vandenys
Wastewater
1
Sludge
1
28. WWTP Plungės vandenys
Wastewater
1
Sludge
1
29. WWTP Mažeikių nafta
Wastewater
1
Sludge
1
30. WWTP Radviliškio vanduo
Wastewater
1
Sludge
1
31. Venta river at the border
Receiving water
X
Sediments
X
32. Neris river at Buivydžiai
Receiving water
1
Sediments
1
33. WWTP Vilniaus vandenys
Wastewater
2
Sludge
2
34. WWTP Ukmergės vandenys
Wastewater
1
Sludge
1
35. WWTP of Švenčionėliai
Wastewater
1
Hg
Ph&E PAH
COP
VOC
OT
BDPE Pht&E SCCP PCP Other
ET
X
X
1
1
1
1
1
1
1
1
1
1
1
1
1
X
1
X
X
1
1
1
1
1
1
1
1
1
1
1
1
1
X
2
X
X
1
1
1
1
1
1
1
1
1
1
1
1
1
X
2
X
X
1
1
1
1
1
1
1
1
1
1
2
1
1
X
2
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
X
X
1
1
1
1
X
X
1
1
1
1
1
1
X
X
1
1
1
1
X
X
1
1
1
1
1
1
X
X
1
1
1
1
X
1
1
1
1
1
2
1
1
1
1
X
1
1
2
1
1
1
1
2
1
2
2
2
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
X
X
1
1
1
1
X
X
1
1
1
1
1
1
1
1
X
2
X
X
1
1
1
1
X
X
1
1
1
1
1
1
1
1
X
1
X
X
1
1
X
1
X
X
1
1
1
1
1
1
1
1
X
2
X
X
1
1
X
1
X
X
1
1
1
1
2
1
1
1
X
1
X
X
1
1
1
1
X
X
1
1
1
1
1
1
1
1
2
2
2
2
1
1
2
2
2
2
2
2
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
2
1
1
1
2
1
1
1
1
2
1
2
1
2
1
2
1
1
2
1
1
1
1
1
1
2
1
1
1
1
1
1
1
23
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
No.
Site/Matrixes
MET
Hg
Ph&E PAH
Sludge
1
1
2
36. WWTP of Pabradė
Wastewater
1
1
1
Sludge
1
1
2
37. WWTP Kauno vandenys
Wastewater
1
1
1
Sludge
1
1
1
38. WWTP Kėdainių vandenys
Wastewater
X
X
1
Sludge
1
1
1
39. WWTP Jonavos vandenys
Wastewater
1
1
1
Sludge
1
1
1
40. Šventoji river after Anykščiai
Receiving water
1
1
1
Sediments
1
1
1
41. Siesartis river after Šakiai
Receiving water
1
1
1
Sediments
1
1
1
42. Nemunas river after Kaunas
Receiving water
1
1
1
Sediments
1
1
1
43. Nevėžis river after Panevėžys
Receiving water
1
1
1
Sediments
1
1
1
44. Klaipėda channel at "Baltijos" kolūkis
Sediments
1
24
COP
VOC
1
OT
BDPE Pht&E SCCP PCP Other
2
2
2
2
1
ET
1
1
1
1
2
1
2
1
2
1
2
1
1
1
1
1
1
1
1
1
1
2
2
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
ChP
ChP
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
5.
Quality assurance and methods used in the HS screening
A.
Sampling and handling of samples
Sampling time. Sampling during the project was carried out in three phases:
1) April-June 2006, in total 25 wastewater samples, 25 wastewater sludge samples, 14 surface water
and 14 bottom sediments samples;
2) October 2006, in total 14 waste water samples, 10 wastewater sludge samples, 10 surface water
samples, 10 bottom sediments;
3) November 2006, 3 samples of sediments.
Samples for the ecotoxicity tests were taken in parallel to samples for chemical analysisi during first and
second phases; in total 36 samples of wastewater and 14 samples of surface water.
Sampling time for different Regional departments is indicated in the Table 11.
Table 11. Sampling time in Regional environmental protection departments
Regional Environmental
Protection Department
Alytus
Kaunas
Klaipeda (MRC)
Marijampolė
Panevėžys
Utena
Šiauliai
Vilnius
1st sampling
2-4 May
24-26 April
5-8 June
2-4 May
15-17 May
5-8 June
8-10 May
12-15 June
2nd sampling
16-19 October
9-12 October
9-12 October
16-19 October
23-26 October
23-26 October
9-12 October
9-12 October
3rd sampling
16-17 November
Sampling was carried out by the specialists of the Regional environmental protection departments (REPD).
Sampling was performed following Standard Activity Procedures, which are based on ISO/EN standards, see
Table 12 below.
Table 12. List of Standard activity procedures and corresponding ISO/EN standards
Matrix
Method
Standards followed for the preparation of SAP
Surface
water and
bottom
sediments
Standard activity
procedure (SAP) for
taking surface water
and bottom sediments
sample




Waste water
Standard activity
procedure (SAP) for
taking wastewater
samples




Waste water
sludge
No standard activity
procedure


LST EN ISO 5667-6:2005 Water quality -- Sampling -- Part 6:
Guidance on sampling of rivers and streams
LST EN 25667-1:2001 Water quality -- Sampling -- Part 1: Guidance
on the design of sampling programmes
LST EN 25667-2:2001 Water quality. Sampling. Part 2: Guidance on
sampling
LST EN ISO 5667-3:2006 Water quality -- Sampling -- Part 3:
Guidance on the preservation and handling of water samples
ISO 5667-10:1992 Water quality. Guidance on sampling of wastewater
samples
LST EN 25667-1:2001 Water quality -- Sampling -- Part 1: Guidance
on the design of sampling programmes
LST EN 25667-2:2001 Water quality. Sampling. Part 2: Guidance on
sampling
LST EN ISO 5667-3:2006 Water quality -- Sampling -- Part 3:
Guidance on the preservation and handling of water samples
ISO 5667-13:2000 Water quality -- Sampling -- Part 13: Guidance on
sampling of sludge from sewage and water treatment works
LST EN 25667-1:2001 Water quality -- Sampling -- Part 1: Guidance
on the design of sampling programmes
Sampling, transportation and storage of samples is briefly described below.
25
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
Surface water and bottom sediments samples. Surface water samples were taken following the “Standard
Activity Procedure for taking surface waters and bottom sediments samples”.
Dishes for samples analysed at GALAB Laboratories Gmbh. Glass bottles of 2,5 l with plastic screw-cap
were used for water and waste water samples for analysis of 5 or 6 groups of substances (phenols and their
ethoxylates, organotin compounds, brominated diphenylethers, phtalates and their ethoxylates, short chain
chlorinated parafins; chlorpyrifos and AOX). Glass bottles of 1 litre with plastic screw-cap were used for
water and wastewater samples for analysis of 3 or less groups of substances.
Glass bottles of 100 ml with plastic screw-cap were used for bottom sediment and sludge samples. During
the second sampling phase samples was isolated from the cap by aluminum folium.
Dishes for samples analysed at Environmental Research Department laboratory of Lithuanian EPA. Glass
bottles of 250 ml for water and waste water samples for analysis of heavy metals were used; glass bottles of
200 ml for mercury; glass bottles of 50 ml for VOC; glass bottles of 1 l for pentachlorphenol; glass bottles of 1
l for PAH.
Plastic bottles of 200 ml with plastic screw cap were used for bottom sediments and sludge samples for the
analysis of heavy metals, glass bottles of 0,5 l for analysis of PAH.
Sampling site and sampling. Water samples were taken against the current. Sampling dish was washed with
water from the stream before taking the sample. Water samples were taken manually with scoop, bucket or
jar at a depth of approximately 0,3 metres.
Bottom sediment samples were taken manually with jar. Jar was closed immediately after taking a sample in
order not to wash out sediments while taking it out from water.
Transportation and storage of samples. Samples to the laboratory were transported in the mobile freezing
box right after sampling. Samples were stored in the fridge at the temperature of 4-8 OC. For samples
analysed at GALAB Laboratories Gmbh no cooling of samples was required, if samples were stored not
longer than 2 weeks.
Wastewater and wastewater sludge samples. Waste water samples were taken following the “Standard
Activity Procedure for taking wastewater samples”.
Sampling site and sampling. Wastewater samples were taken from the specially established sampling site place where wastewater is mixed. Water samples were taken manually with scoop, bucket or jar. Sampling
dish was washed with wastewater from the site before taking the sample.
Sludge sample is taken according to standard ISO 5667-13:2000 since there is no Standard Activity
procedure for taking wastewater sludge sample. Sludge samples should be taken by the specialist of the
wastewater treatment plant, who has been trained to take samples, however during the project samples
were taken by the specialists of the Regional environmental protection departments.
B.
Analysis of samples
Analysis of the samples were carried out by three laboratories:
1) laboratory of Environmental Research Department of the Lithuanian Environmental Protection Agency:
metals, polycyclic aromatic hydrocarbons (PAH), chloroorganic pesticides, volatile organic compounds
(VOC), pentachlorphenol in water samples and some ecotoxicity tests (MicrotoxR, Algaltoxkit F,
Thamnotoxkit FTM);
2) GALAB laboratories, Germany: phenols and their ethoxylates, organotin compounds, phtalates and their
ethoxylates, brominated diphenylethers, short chain chlorinated parafins (SCCP), pentachlorphenol in
sludge/sediments, cyanides, chlorpyrifos, AOX and mercury for some sites;
3) Laboratory of Institute of Botany: ecotoxicity tests (Thamnotoxkit FTM, Charatox (algal
electrophysiological test), Rotoxkit FTM).
Before the analysis the sample has gone through the obligatory pre-treatment stage, see Table 13 for the
details.
26
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Table 13. Description of samples’ pre-treatment before the analysis
I.
Metals
 Water and wastewater: preservation of sample with concentrated nitric acid; ETAAS/ ICP-OES
 Sediments and sludge: drying of sample; homogenisation and mineralisation with concentrated nitric acid; ETAAS/
ICP-OES
 Mercury: sample preservation with clean (trace select Hg<0,0000002%) nitric acid, pH should be less than 2; urgent
II.
treatment with Br after delivery to laboratory.
Phenols and their ethoxylates
 Water and wastewater: addition of internal standards, LLE dichloromethane, derivatisation, column clean up,
concentration of extract, GC-MSD
 Sediments and sludge: addition of internal standards, SLE ethyl acetate, GPC clean up, derivatisation, column clean
III.
up, concentration of extract, GC-MSD
Polycyclic aromatic hydrocarbons (PAH)
 Water and wastewater: extraction with hexane, concentration up to 1-2 ml, column clean up, concentration, eluation
with 5 ml hexane/methylene chloride (1:1), concentration, addition of 1 ml acetonitril; HPLC
 Sludge and bottom sediments: drying of sample, clean up from mechanical particles, extraction with hexane; column
IV.
clean up, concentration of extract, addition of acetonitril; HPLC
Chloroorganic pesticides
 Water and wastewater: extraction with hexane, concentration up to 1 ml, column clean up, eluation with 30 ml
hexane, GC-ECD
V.
Volatile organic compounds (VOC)
No special treatment applied before analysis
VI.
Organotin compounds
 Water and wastewater: addition of internal standards, derivatisation with sodiumtetraethylborate and SLE hexane,
column clean up, concentration of extract, GC-AED
 Sediments and sludge: addition of internal standards, derivatisation with sodiumtetraethylborate and SLE hexane,
VII.
column clean up, concentration of extract, GC-AED
Phthalates and their ethoxylates
 Water and wastewater: addition of internal standards, LLE dichloromethane, column clean up, concentration of
extract, GCMSD
 Sediments and sludge: addition of internal standards, SLE ethyl acetate, column clean up, concentration of extract,
GC-MSD
VIII.
Brominated diphenylethers
 Water and wastewater: addition of internal standards, LLE dichloromethane, sulfuric acid clean up, concentration of
extract, GC-MSD
 Sediments and sludge: addition of internal standards, SLE sulfuric acid/hexane, derivatisation, column clean up,
IX.
concentration of extract, GC-MSD
Other: Pentachlorphenol - PCP
 Water and wastewater: Extraction of sample within 24 hours after sampling, concentration of sample; eluation with 1
ml acetonitril/acetic acid, liquid chromatography
 Sediments and sludge: addition of internal standards, SLE NaOH, acidification of extract with HCl, LLE
IX.
dichloromethane, derivatisation, concentration of extract, GC-MSD
Other: Short chain chlorinated paraffins (SCCP)
 Water and wastewater: addition of internal standards, LLE dichloromethane, column clean up, concentration of
extract, GCMSD
 Sediments and sludge: addition of internal standards, SLE ethyl acetate, column clean up, concentration of extract,
IX.
GC-MSD
Other: Chlorpyriphos
 Water and wastewater: addition of internal standards, LLE dichloromethane, column clean up, concentration of
extract, GCMSD
 Sediments and sludge: addition of internal standards, SLE ethyl acetate, column clean up, concentration of extract,
IX.
GC-MSD
Other: Cyanides - CN
 Water and wastewater: transported shifted into the continuous flow of a buffer solution of pH 3.8 and with UV-B light
the wavelength for l = 312 Nm illuminated. UV light at 290 Nm is filtered by the use of a spiral from Borsilicatglass, in
order to avoid the formation of Thiocyanaten. Subsequently, the sample is distilled at T = 125°C. The developing
hydrogen cyanide is photometrical measured.
 Sediments and sludge: the cyanide connections are decomposed in presence of copper(I) ions with hydrochloric acid.
Hydrocyane is disposed and absorbed in sodium hydroxide solution (the copper ii-ions are reduced by tin chloride).
The cyanide is determined afterwards titrated with silver nitrate solution.
IX.
Other: AOX
 Water and wastewater: adsorption at activated charcoal, acidified with nitric acid. Addition of sodium nitrate to the
water and treatment of the charcoal with a halide-free sodium nitrate solution inorganic halogen connections are
27
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
displaced by the coal. Loaded activated charcoal in the oxygen current is burned, whereby the organically bound
halogens are converted to hydrogen halides, whose mass is determined.
 Sediments and sludge: drying and milling of the sediment, addition of halide-free sodium nitrate solution inorganic
halogen connections are displaced. Addition of activated charcoal, filtration. Loaded activated charcoal in the oxygen
current is burned, whereby the organically bound halogens are converted to hydrogen halides, whose mass is
determined.
X.
Ecotoxicity
 All samples after arrival to the laboratory were imediately filtered through double paper filter (for Charatox) or
membrane filter of 0,45  , hold in refrigerator (4-60C) and tested according standard procedures within 7 days.
Further treated according the standard procedures as described in the corresponding Toxkit microbiotests.
The methods used for the analysis of samples in different matrixes are presented in the Table 14.
Table 14. Methods of analysis applied
Substance/ group of
substances
Cd
Pb, Ni, As, Cu
Zn
Hg
Phenols and their
ethoxylates
Polycyclic aromatic
hydrocarbons
Chloroorganic
pesticides
Volatile organic
compounds
Organotin compounds
Phtalates and their
ethoxylates
Brominated
diphenylethers
Pentachlorphenol
Short chain chlorinated
parafins
Chlorpyrifos
Cyanides
AOX
Ecotoxicity
Surface water/ wastewater
Atomic absorption spectrometry (ETAAS)
LST EN ISO 5961:2000N
Atomic absorption spectrometry (ETAAS)
LST EN ISO 15586:2004 N
Inducatively coupled plasma spectrometry
(ICP-OES); LST EN ISO 11885:2000 N
Atomic fluorescence spectrometry (AFS)
LST EN 13506:2002N
GALAB laboratory: Inducatively coupled
plasma spectrometry (ICP-MS)
Gas chromatography (GC-MSD)
SOP 23
High performance liquid chromatography
(HPLC); LST EN ISO 17993:2004N
Gas chromatography (GC-ECD)
LST EN ISO 6468:2000N
Gas chromatography (GC-ECD)
SVP 1-1-13:2005N
Gas chromatography (GC-AED)
DIN 38407- 13 (SOP 2); DIN 19744 (SOP 1)
Gas chromatography (GC-MSD)
SOP 42
Gas chromatography (GC-MSD)
SOP 42
High performance liquid chromatography
(HPLC); SVP 1-1-11:2004N
Gas chromatography (GC-MSD)
Gas chromatography (GC-MSD); ISO 6468
CN DIN 38405; DIN EN ISO 14403-D6
AOX DIN 38409; DIN EN 1485-H14
90 min electrophysiological test with
Nitellopsis obtuse (Charatox)
72 hgrowth inhibition test with Selenastrum
capricornutum (Algaltoxkit FTM)
24 h mortality test with Thamnocephalus
platyurus (Thamnotoxkit FTM)
24 h mortality test with Brachionus
calyciflorus (Rotoxkit FTM)
30 min bioluminescence inhibition with Vibrio
fischeri (Microtox).
N - method is not accredited
Sediments/ sewage sludge
Atomic absorption spectrometry (ETAAS)
LST EN ISO 5961:2000N
Atomic absorption spectrometry (ETAAS)
SVP 1-2-2:2005N (sludge)
LST EN ISO 15586:2004 N (sediments)
Inducatively coupled plasma spectrometry
(ICP-OES); SVP 1-2-10:2006N
Atomic fluorescence spectrometry (AFS)
SVP 1-2-4:2004N
GALAB laboratory: Extraction (aqua regia),
CV-AAS
Gas chromatography (GC-MSD)
SOP 23
High performance liquid chromatography
(HPLC); ISO 13877:1998N
Gas chromatography (GC-ECD)
ISO 10382 :2002N; SVP 1-1-9 : 2004N
Gas chromatography (GC-AED)
DIN 38407- 13 (SOP 2); DIN 19744 (SOP 1)
Gas chromatography (GC-MSD)
SOP 42
Gas chromatography (GC-MSD)
SOP 42
Gas chromatography GC-MSD
Gas chromatography (GC-MSD)
Gas chromatography (GC-MSD); ISO 6468
CN DIN 38405; LAGA CN 2/79
AOX DIN 38409; DIN 38414-S18
An overview on the limits of the detection, measurement uncertainties as well as available Environmental
Quality Standards for the analysed substances in given in the Table 15. For some substances/ groups of
substances limit of detection of applied analysis methods was too low to be able to control the quality of
water according EQS or currently applied maximum allowable concentrations expressed as annual average
in Lithuania. These substances are the following:
 PAH: Benzo[ghi]perylene, Indeno[1,2,3-cd]pyrene
28
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007




VOC: 1,2-dichloroethane
Pentachlorphenol in water
Tributyltin
Pentabromdiphenylether, sum
Table 15. Limits of the detection, measurement uncertainties and Environmental Quality Standards for the
analysed substances
LOD – Limit of detection
MU – measurement uncertainty
SW – surface water, WW – wastewater, BS – bottom sediments, WS – sewage sludge
EQS – Environmental Quality Standard for inland surface water
AA-EQS – Environmental Quality Standard expressed as an annual average value
MAC-EQS – Environmental Quality Standard expressed as a maximum allowable concentration
MPA – Maximum permissible addition; it is applied in case of metals, then EQS sediments=Cbackground + MPA
--not applicable
*
for metals in sediments and sludge measurement unit mg/kg
**
for Cadmium and its compounds the EQS values vary dependent upon the hardness of the water as specified in
five class categories
***
EQS given in the table for the priority substances and other pollutants based on the proposal for the Directive on
EQS (COM(2006) 397 final)
****
EQS for bottom sediments are based on the substance data sheets prepared for the implementation of WFD
(CIRCA website).
LOD
EQS***
EQS****
AA-EQS
MAC-EQS
No.
CAS Nr.
Name
SW/WW BS/WS MU (%)
BS
SW
SW
μg/l
μg/kg
μg/l
μg/l
μg/l
I. Metals
0,080,45MPA=
1.
7440-43-9
Cadmium and its compounds
0,05
0,005*
10
0,25**
1,5**
2.3*
2.
7440-66-6
Zinc and its compounds
5
0,5*
15
7,2
MPA=
3.
7439-92-1
Lead and its compounds
1
0,1*
10
--53.4*
20
4.
7440-02-0
Nickel and its compounds
1
0,1*
10
--2.9*
5.
7440-38-2
Arsenic and its compounds
1
0,1*
10
6.
7440-50-8
Copper and its compounds
0,5
0,05*
10
0,05
MPA =
7.
7439-97-6
Mercury and its compounds
0,03
0,02/0,1* 15
0,07
0,47*
II. Phenols and their ethoxylates
8.
9.
10.
104-40-5
25154-52-3
11066-49-2
11.
27986-36-3
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
--20427-84-3
----------1806-26-4
140-66-9
9036-19-5
----------98-54-4
80-46-6
4-Nonylphenol
Nonylphenols (mixture of izomers)
iso-Nonylphenol*
Nonylphenolmonoethoxylate
(NP1EO)
iso-Nonylphenolmonoethoxylates
Nonylphenoldiethoxylate (NP2EO)
iso-Nonylphenoldiethoxylates
iso-Nonylphenoltriethoxylate
iso-Nonylphenoltetraethoxylate
iso-Nonylphenolpentaethoxylate
iso-Nonylphenolhexaethoxylate
4-octylphenol
4-tert-octylphenol
Octylphenolmonoethoxylate
Octylphenoldiethoxylate
4-t-Octylphenoltriethoxylate
4-t-Octylphenoltetraethoxylate
4-t-Octylphenolpentaethoxylate
4-t-Octylphenolhexaethoxylate
4-t-Butylphenol
4-t-Pentylphenol
0,01
0,05
0,05
10
50
10
0,1
100
0,1
0,1
0,1
0,1
0,1
0,1
0,1
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
0,01
100
100
100
100
100
100
100
10
10
10
10
10
10
10
10
10
10
0,3
2
180
0,1
---
34
15
29
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
LOD
No.
CAS Nr.
Name
III. Polycyclic aromatic hydrocarbons (PAH)
29. 120-12-7
Anthracene
30. 50-32-8
Benzo(a)pyrene
31. 205-99-2
Benzo(b)fluoranthene
32. 207-08-9
Benzo(k)fluoranthene
33. 191-24-2
Benzo[ghi]perylene
34. 193-39-5
Indeno[1,2,3-cd]pyrene
35. 91-20-3
Naphtalene
36. 206-44-0
Fluoranthene
IV. Chloroorganic pesticides
37.
309-00-2
Aldrin
38.
60-57-1
Dieldrin
39.
72-20-8
Endrin
40.
50-29-3
DDT
41.
58-89-9
Lindane
42.
118-74-1
Heksachlorobenzene
43.
608-73-1
Hexachlorocyclohexanes (,,)
V. Volatile organic compounds (VOC)
44.
71-43-2
Benzene
45.
107-06-2
1,2-dichloroethane
46.
75-09-2
Dichlormethane
47.
56-23-5
Tertrachlormethane
48.
127-18-4
Tetrachloroethylene
49.
67-66-3
Chloroform (trichloromethane)
50.
79-01-6
Trichloroethylene
VI. Organotin compounds
51. 688-73-3
Tributyltin
52. 3664-73-3
Tributyltin kations
53. 78763-54-9
Monobutyltin
54. 1002-53-5
Dibutyltin
55. 1461-25-2
Tetrabutyltin
56. --Monooctyltin
--Dioctyltin
57. --Tricyclohexyltin
58. --Monophenyltin
59. --Diphenyltin
60. 668-34-8
Triphenyltin
VII. Phtalates and their ethoxylates
61. 117-81-7
Di-2-ethylhexyl phthalate - DEHP
62. 84-74-2
Dibutylphtalate - DBP
63. 113-11-3
Dimethyl phthalate
64. 84-66-2
Diethyl phthalate
65. 120-51-4
Benzyl benzoate
66. 84-69-5
Diisobutyl phthalate
67. 117-82-8
Dimethoxyethyl phthalate
68. --Diisohexyl phthalate
69. 605-54-9
Di-2-ethoxyethyl phthalate
70. 131-18-0
Dipentyl phthalate
71. 84-75-3
Di-n-hexyl phthalate
72. 85-68-7
Benzylbutyl phthalate
73. --Hexyl-2-ethylhexyl phthalate
30
SW/WW BS/WS
μg/l
μg/kg
0,001
0,002
0,005
0,001
0,01
0,01
0,005
0,005
0,08
0,20
0,50
0,10
1,00
1,00
0,30
0,60
0,005
0,005
0,005
0,005
0,005
0,005
0,005
1
1
1
1
1
0,5
1
0,05
25
0,5
0,5
0,05
0,5
0,05
MU (%)
EQS***
EQS****
AA-EQS MAC-EQS
BS
SW
SW
μg/l
μg/l
μg/l
0,1
0,05
0,4
0,1
=0.03
---
=0.002
---
2,4
0,1
--1
=0,01
---
0.01
---
0,01
0,02
0,05
0,04
10
10
20
50
-----
10
---
10
---
0.0002
0.0015
0.02
1,3
---
100000
15-20
15-20
25
310
2500
1743
--1069
16.9
10.3
12
0,001
1
0,001
0,001
0,001
0,001
0,001
0,001
0,001
0,001
0,001
0,001
1
1
1
1
1
1
1
1
1
1
0,05
0,05
0,05
0,05
0,05
0,05
0,05
0,05
0,05
0,05
0,05
0,05
0,05
50
50
50
50
50
50
50
50
50
50
50
50
50
10
15
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
LOD
No.
CAS Nr.
Name
74. 117-83-9
Dibutoxyethyl phthalate
75. 84-61-7
Dicyclohexyl phthalate
76. 28553-12-0
Diisononyl phthalate
77. 117-84-0
Di-n-octyl phthalate
78. 26761-40-0
Diisodecyl phthalate
VIII. Brominated diethylethers
79. 32534-81-9
Pentabromdiphenylether, sum
Pentabromdiphenylether, PBDE80. 60348-60-9
99
Pentabromdiphenylether, PBDE81. 189084-66-0
100
82. 32536-52-0
Octabrombiphenylethers
83. 1163-19-5
Decabrombiphenylethers
84. 79-94-7
Tetrabromobisphenol A, TBBPA
85. 59080-37-4
Tetrabromobiphenyl, PBB-52
86. 67888-96-4
Pentabromobiphenyl, PBB-101
87. 59080-40-9
Hexabromobiphenyl, PBB-153
88. --Tribromodiphenyl ether, PBDE-28
Tetrabromodiphenyl ether, PBDE89. 5436-43-1
47
Hexabromodiphenyl ether, PBDE90. 182677-30-1
138
Hexabromodiphenyl ether, PBDE91. 68631-49-2
153
Hexabromdiphenyl ether, PBDE92. 207122-15-4
154
Heptabromodiphenyl ether, PBDE93. 207122-16-5
183
Heptabromodiphenyl ether, PBDE94. 189084-68-2
190
95. 87-82-1
Hexabromobenzene
96. 25637-99-4
Hexabromocyclododecane
IX. Other substances/ groups of substances
C10-13 chloralkanes (Short chain
97. 85535-84-8
chlorinated parafins (SCCP))
98. 87-86-5
Pentachlorphenol - PCP
99. 2921-88-2
Chlorpyrifos
100. --Cyanides -CN
101. --AOX
SW/WW BS/WS
μg/l
μg/kg
0,05
0,05
0,05
0,05
1
50
50
50
50
1000
0,005
5
0,005
5
0,005
5
0,05
0,1
0,005
0,005
0,005
0,005
0,005
50
100
5
5
5
5
5
0,005
5
0,005
5
0,005
5
0,005
5
0,02
20
0,02
20
0,005
0,2
5
200
0,4
998
0,9
0,01
0,5
10
5
10
50
1000
MU (%)
EQS***
EQS****
AA-EQS MAC-EQS
BS
SW
SW
μg/l
μg/l
μg/l
15
0,0005
---
310
15
0,4
1,4
998
15/10
10
10
10
0,4
0,03
1
0,1
119
15
15
31
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
6.
Results of the analysis
In total 870 samples from 44 sites were analysed (number of samples exclude the duplicates for the quality
assurance and control; series of the ecotoxicity tests are considered as one sample).
Evaluation of the results is rather difficult due to the absence of clear MAC for the substances discharged to
the receiving environment or in the environment. The current Lithuanian law (Wastewater treatment
regulation) sets the limits expressed as a maximum allowable concentration of hazardous substance to/in
the receiving environment as an annual average (AA-MAC) and indicates the general principle that MAC
cannot exceed AA-MAC more than twice. MAC applied for companies having obligations according IPPC
requirements should be the same if BAT document does not state lower value.
For the evaluation of the results EQS set by the new proposal for EQS under WFD and available limits set by
Lithuanian law were applied (see Table 16). Although EQS for bottom sediments as given in the substance
data sheets prepared for the implementation of WFD are not obligatory, but they are good indicator for the
pollution of bottom sediments and indicate whether there is a potential negative impact for the bentic
community.
The table below also indicates the biggest discrepancies between currently applied Lithuanian standards
(AA-MAC and MAC=2xAA-MAC) for surface water and upcoming AA-EQS, MAC-EQS (these parameters
presented in gray cells and bold font):
 for cadmium, mercury, tributyltin, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, pentachlorphenol and
pentabromdiphenylether the current Lithuanian limits are at least 5-10 times higher;
 for anthracene, benzene, di-2-ethylhexyl phthalate, C10-13 chloralkanes and chlorpyrifos – at least 5-10
times lower.
 slight difference (Lithuanian limits are higher) for nonylphenols and octylphenols, benzo(b)fluoranthene,
benzo(k)fluoranthene, fluoranthene, heksachlorobenzene.
Table 16. EU and Lithuanian standards for the limitation of hazardous substances discharges and
occurrence in the environment.
SW – surface water, BS – bottom sediments
EQS – Environmental Quality Standard
AA-EQS – Environmental Quality Standard expressed as an annual average value
MAC-EQS – Environmental Quality Standard expressed as a maximum allowable concentration
AA-MAC – maximum allowable concentration expressed as an annual average value
MAC –Maximum allowable concentration
MPA – Maximum permissible addition; it is applied in case of metals, then EQSsediments=Cbackground + MPA
--not applicable
*
for metals in sediments measurement unit mg/kg
**
for Cadmium and its compounds the EQS values vary dependent upon the hardness of the water as specified in
five class categories
***
EQS given in the table for the priority substances and other pollutants based on the proposal for the Directive on
EQS (COM(2006) 397 final)
****
EQS for bottom sediments are given based on the substance data sheets prepared for the implementation of
WFD (CIRCA website).
*****
LC – limit concentration; it is maximum concentration (calculated, measured or planned) of the substances that
could be discharged to the environment without obligatory control.
EQS***
EQS****
Current LIT standards
AAAAAA-EQS MAC-EQS
LC*****
No.
CAS Nr.
Name
BS
MAC to MAC in
SW
SW
to SW
μg/l
SW
SW
μg/l
μg/l
μg/l
μg/l
μg/l
I. Metals
0,080,45MPA=
5
1.
7440-43-9
Cadmium and its compounds*
40
--0,25**
1,5**
2.3*
2.
7440-66-6
Zinc and its compounds*
400
100
160
MPA=
3.
7439-92-1
Lead and its compounds*
7,2
--100
5
20
53.4*
4.
7440-02-0
Nickel and its compounds*
20
--2.9*
200
10
40
5.
7440-38-2
Arsenic and its compounds*
50
--20
6.
7440-50-8
Copper and its compounds*
500
10
100
32
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
EQS***
No.
7.
CAS Nr.
7439-97-6
Name
Mercury and its compounds*
II. Phenols and their ethoxylates
8.
104-40-5
4-Nonylphenol
9.
25154-52-3
Nonylphenols (mixture of izomers)
10. 1806-26-4
4-octylphenol
11. 140-66-9
4-tert-octylphenol
III. Polycyclic aromatic hydrocarbons (PAH)
12. 120-12-7
Anthracene
13. 50-32-8
Benzo(a)pyrene
14. 205-99-2
Benzo(b)fluoranthene
15. 207-08-9
Benzo(k)fluoranthene
16. 191-24-2
Benzo[ghi]perylene
17. 193-39-5
Indeno[1,2,3-cd]pyrene
18. 91-20-3
Naphtalene
19. 206-44-0
Fluoranthene
IV. Chloroorganic pesticides
AA-EQS MAC-EQS
SW
SW
μg/l
μg/l
0,05
0,07
EQS****
BS
μg/l
Current LIT standards
AAAALC*****
MAC to MAC in
to SW
SW
SW
μg/l
μg/l
μg/l
MPA =
470
2
1
---
20
----20
1
----1
4
----4
0,01
0,05
0,04
0,04
0,03
0,04
1
0,3
0,04
0,2
0,16
0,16
0,12
0,16
4
1,2
0,3
0,1
2
---
180
34
0,1
0,05
0,4
0,1
310
2500
=0.03
---
=0.002
---
2,4
0,1
--1
--1069
0,2
1
0,8
0,8
0,6
0,8
20
6
20.
118-74-1
Heksachlorobenzene
V. Volatile organic compounds (VOC)
0,01
0,05
16.9
0,6
0,03
---
21.
75-09-2
Dichlormethane
22.
127-18-4
Tetrachloroethylene
23.
67-66-3
Chloroform (trichloromethane)
24.
79-01-6
Trichloroethylene
25.
71-43-2
Benzene
26.
107-06-2
1,2-dichloroethane
27.
56-23-5
Tertrachlormethane
VI. Organotin compounds
28. 688-73-3
Tributyltin
29. 3664-73-3
Tributyltin kations
VII. Phtalates and their ethoxylates
30. 117-81-7
Di-2-ethylhexyl phthalate - DEHP
VIII. Brominated diethylethers
31. 32534-81-9
Pentabromdiphenylether, sum
IX. Other substances/ groups of substances
C10-13 chloralkanes (Short chain
32. 85535-84-8
chlorinated parafins (SCCP))
33. 87-86-5
Pentachlorphenol - PCP
34. 2921-88-2
Chlorpyrifos
35. --Cyanides -CN
36. --AOX
20
10
-----
200
200
200
200
40
200
240
10
10
12
10
2
10
12
40
------8
-----
1743
12
10
10
--50
10
---
0.0002
0.0015
0.02
0,02
0,02
0,001
0,001
0,004
0,004
1,3
---
100000
2
0,1
0,4
0,0005
---
310
---
0,1
---
0,4
1,4
998
0,2
0,01
0,1
0,4
0,03
1
0,1
119
40
--100
2
0,0001
---
----40
Overall results of the chemical analysis of samples are presented in the Annex 7. Site specific results with
the selected substances of concern are presented in the Annex 8.
A.
Overview of the results by substances/ groups of substances
1)
Metals
Analysis of metals and their compounds was performed for 31 sites, including both wastewater/sewage
sludge and receiving environment/sediments. The sites where analysis were performed in 2005 or is
regularly performed within the monitoring programme were excluded. The analysis performed by EPA
33
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
laboratory, excluding analysis of mercury in sediments within the second and third round (they were
analysed by GALAB laboratory).



In most cases the concentrations of metals in wastewater and surface water were in line with the current
Lithuanian requirements, except zinc and copper.
Zinc has exceeded AA-MAC to the discharges of wastewater to surface waters in 1 WWTP – Dzūkijos
vandenys (408 μg/l), however it is not exceeding MAC - 800 μg/l.
Copper exceeded AA-MAC in the surface water in harbour territory at JSC Klaipėdos kartonas (13 μg/l),
however it is not exceeding MAC.
For nickel the concern is raised due to its concentrations in sediments in the receiving environment (if to
compare it to the EQS for bottom sediments as given in the substance data sheets prepared for the
implementation of WFD):
 Nickel exceeds EQS for sediments (2,9 mg/l ) in harbour territory at JSC Klaipėdos kartonas (2,6-9,3
mg/l), Nemunas after Sovietsk (3,3 mg/l), Dysna at the border (5,1 mg/l), Šventoji below Anykščiai (3,0
mg/l), Siesartis below Šakiai (15 mg/l), Nevėžis below Panevėžys (11 mg/l) and Klaipėda channel at
Baltijos kolūkis (4,4 mg/l).
2)
Phenols and their ethoxylates
Analysis of phenols and their ethoxylates was performed for 43 sites, including both wastewater/sewage
sludge and receiving environment/sediments. All samples were analysed by GALAB laboratory.
The major groups of nonylphenols and their ethoxylates detected were: iso-nonylphenol, 4-t-pentylphenol, 4t-octylphenol, nonylphenolmonoethoxylate, nonylphenoldiethoxylate and octylphenolmonoethoxylate,
octylphenoldiethoxylate.
 Iso-nonylphenol was detected in wastewater from 9 WWTP. In most cases concentration has not
exceeded 0,1 μg/l. In three cases the concentration of iso-nonylphenol in wastewater was higher than 1
μg/l: WWTP Radviliškio vanduo – 1,03 μg/l, WWTP of Švenčionėliai – 1,84 μg/l, WWTP Kauno
vandenys – 1,59 μg/l. In the surface water it was detected only in Nevėžis below Panevėžys (0,044
μg/l).
 4-t-octylphenol was detected in wastewater of 6 WWTP and 7 sites in the surface water. It was not
exceeding 0,1 μg/l in any water body and only in 1 WWTP Kauno vandenys it was higher (0.12 μg/l),
however it is far from the set MAC.
 Nonylphenolmonoethoxylate was detected in wastewater of 2 WWTP: WWTP Radviliškio vanduo
(0,41 μg/l) and WWTP Kauno vandenys (2,2 μg/l). It was not detected in surface water.
 Octylphenolmonoethoxylate was detected in wastewater of WWTP Radviliškio vanduo (0,023 μg/l). It
was not detected in surface water.
 The nonylphenols and their ethoxylates (iso-nonylphenol, 4-t-pentylphenol, 4-t-octylphenol,
nonylphenolmonoethoxylate,
nonylphenoldiethoxylate
and
octylphenolmonoethoxylate,
octylphenoldiethoxylate) in the sludge were found in 23 WWTP. The high concentrations identified for
iso-nonylphenol, nonylphenolmonoethoxylate and nonylphenoldiethoxylate in WWTP Dzūkijos
vandenys, WWTP Klaipėdos vanduo, WWTP Utenos vandenys, WWTP Plungės vandenys, WWTP
Vilniaus vandenys, WWTP of Švenčionėliai, WWTP of Pabradė, WWTP Kėdainių vandenys, WWTP
Jonavos vandenys. Especially high concentrations detected in WWTP Radviliškio vanduo and WWTP
Kauno vandenys.
 In the sediments of the receiving environment only iso-nonylphenol was found in high concentrations
at two sites: Nemunas at Rusnė (3220 μg/l) and Nevėžis below Panevėžys (373 μg/l). It substantially
exceeds EQS for nonylphenols for bottom sediments as given in the substance data sheets prepared for
the implementation of WFD (180 μg/l).
NPE are widely used in the surfactants for the degreasing and can be easily discharged to the waters from
industrial and institutional cleaning processes, textile finishing processes (used in the auxiliaries), leather
processing (used as auxiliary), pulp and paper industry (used as retention agent). Furthermore, NPE is
contained in pesticides as co-formulant and could also get easily to the environment. It is likely that
household use also contributes with the discharges of octyl- and nonylphenols and their ethoxylates to the
WWTP and further on to the aquatic environment. As survey from WFD Project on Fact Sheets on Pollutants
indicates the consumers are considered as the main inland pollution source for nonylphenols.
The main use of OP is an intermediate in the production of phenol/formaldehyde resins, OPE are mainly
used as emulsifiers for emulsion polymerisation while producing polymers, as well as emulsifier in finishing
agents (mainly styrene-butadiene copolymers) in leather and textile auxiliaries.
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
It is estimated (EUSES modelling, EU-RAR) that in municipal WWTP 20% of NPE get bound to sludge, 45%
degrade, 25% reach surface water as nonylphenolmono- or diethoxylate and around 2.5% degrade to NP.
The primary source of OP/NP is considered to be cctyl- and nonylphenol ethoxylates, which degrade to the
octyl- and nonylphenols, therefore the nonylphenol levels are usually higher. 34% of NP in WWTP gets
bound to sludge, 24% degrade and around 35% reach surface water.
3)
Polycyclic aromatic hydrocarbons (PAH)
Analysis of phenols and their ethoxylates was performed for 43 sites, including both wastewater/sewage
sludge and receiving environment/sediments. Analysis was performed by EPA laboratory.
 PAH were detected in wastewater of 13 WWTP, in most cases naphthalene. However it was far of
reaching AA-MAC and MAC.
 Wastewater of WWTP Dzūkijos vandenys is quite highly contaminated with PAH. That is also the only
place where the concentration of anthracene (0,6 μg/l) exceeds the MAC (0,4 μg/l).
 The bigger variety of PAH is found in the sewage sludge of the 23 WWTP. It includes naphthalene,
anthracene,
fluoranthene,
benzo(b)fluoranthene,
benzo(k)fluoranthene,
benzo(a)pyrene,
benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, however their concentrations are not very high to raise the
concern.
 From the analysed sites of surface water naphtalene was found at 12 sites, however is far of reaching
AA-MAC or MAC.
 Benzo(a)pyrene and anthracene was detected in surface water at 2 sites but well below the AA-MAC or
MAC.
 High variety of PAH detected in the sediments of the receiving environment, however the amounts are
low comparing the EQS for bottom sediments as given in the substance data sheets prepared for the
implementation of WFD. The highest concentrations identified in the Malkų bay at Klaipėda, however
they are also not exceeding EQS for bottom sediments.
The most important sources of the PAH emission nowadays are combustion of wood in the residential sector
and road transportation (for naphthalene, anthracene, benzo(k)fluoranthene, benzo(a)pyrene,
benzo[ghi]perylene, indeno[1,2,3-cd]pyrene traffic and transportation are assumed to be the main inland
pollution source), therefore the biggest loads to WWTP are assumed to come from atmospheric deposition
onto paved surfaces and runoff.
4)
Chloroorganic pesticides
Analysis of chloroorganic pesticides was performed for 11 sites, which included only receiving environment –
surface water and sediments. Analysis was performed by EPA laboratory.
The only substance detected was heksachlorobenzene in the sediments of Šventoji river below Anykščiai
(22 μg/l). It exceeds EQS for heksachlorbenzene for bottom sediments as given in the substance data
sheets prepared for the implementation of WFD (16,9 μg/l).
5)
Volatile organic compounds
VOC were analysed at 34 sites, including both wastewater/sewage sludge and receiving
environment/sediments. The sites where analysis were performed in 2005 or is regularly performed within
the monitoring programme were excluded.
 Benzene, 1,2-dichlorethane, tetrachlormethane were not detected at any site. However it is important to
notice that LOD of method applied by EPA laboratory for 1,2-dichlorethane analysis is 2,5 times lower
than AA-EQS and current AA-MAC as well as MAC in the receiving environment (LOD - 25 μg/l, AA-EQS
and AA-MAC – 10 μg/l);
 Chloroform was found only at one site – in the surface water of Venta river at the border in the
concentration of 388 μg/l. It exceeded current AA-MAC in receiving environment (12 μg/l) more than 30
times, accordingly MAC – more than 15 times. As the monitoring results of years 2005-2006 shows the
concentration of chloroform in Venta below Mažeikiai was always high, while it was not detected above
Mažeikiai. In order to clarify the reasons for such concentrations further analysis and investigations are
necessary. The potential sources of chloroform could be laboratories, use of chloroform in agriculture as
pesticide, use as solvent in electronics industry.
 Dichlormethane detected in wastewater of 2 WWTP: Varėnos vandenys – 5,9 μg/l, Kėdainių vandenys –
5 μg/l. It does not exceed AA-MAC, MAC or limit concentration for the effluents to the receiving
environment.
 Tetrachlorethylene detected in wastewater of 4 WWTP: Klaipėdos vandenys – 21-27 μg/l, WWTP of
Marijampolė – 0,16 μg/l, WWTP of Vilkaviškis – 0,19 μg/l, Vilniaus vandenys – 0,64 μg/l. It is far from
reaching AA-MAC and MAC for effluents to the water environment (200 μg/l).
35
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA

Trichlorethylene was detected only in WWTP Klaipėdos vanduo – 0,17-0,18 μg/l. It is far from reaching
AA-MAC and MAC for effluents to the water environment (200 μg/l).
6)
Organotin compounds
Organotin compounds were analysed at 43 sites. Analysis was done in the samples of wastewater, sewage
sludge and sediments in the receiving environment.
Tributyltin (TBT) was detected in the sludge from nearly all WWTP (22 from 25), however it was not detected
in the wastewater of any WWTP. Wastewater of many WWTP was mostly contaminated by monobutyltin
(MBT) and dibutyltin (DBT). That might be explained by the microbial transformation of TBT (dealkylation and
methylation). TBT is dealkylated first to dibutyltin and further on to monobutyltin. Based on the conclusions of
Swedish screening study (Sternbeck at al. 2006) products including organotins and urban storm water are
causing significant load (diffuse) of organotins to WWTP in the urban area. In wastewater treatment plants
butyltins can be significantly eliminated from wastewater by adsorption onto suspended matter and further by
sedimentation of sludge.
 In the surface water (rivers) butyltin was measured only at several sites, mainly after bigger cities.
Butyltin was detected in:
o Nemunas below Sovietsk (MBT – 0,008 μg/l, DBT – 0,004 μg/l);
o Nemunas below Kaunas (DBT – 0,01 μg/l, TBT – 0,004 μg/l);
o Nevėžis below Panevėžys (MBT – 0,008 μg/l, DBT – 0,006 μg/l, TBT – 0,004 μg/l);
o Tributyltin in both places exceeded current Lithuanian AA-MAC (0,001 μg/l) and MAC (0,002
μg/l) in surface water as well as proposed EU MAC-EQS (0,0015 μg/l). It is important to
notice that AA-EQS for the inland surface water proposed by EU is very low – 0,0002 μg/l.
 High amounts of tributyltin and its degradation products were found in the sediments of most analysed
rivers:
o Nemunas at Rusnė (TBT – 12,4 μg/l, MBT - 150 μg/l, DBT - 100 μg/l);
o Akmena at the estuary (TBT - 585 μg/l, MBT – 12,9 μg/l, DBT – 22,1 μg/l);
o Neris at Buivydžiai (TBT – 1,6 μg/l, MBT – 2,1-15,8 μg/l, DBT – 1,9);
o Siesartis below Šakiai (TBT – 8,3 μg/l, MBT – 59,5 μg/l, DBT - 25 μg/l);
o Nemunas below Kaunas (MBT – 1,4 μg/l);
o Nevėžis below Panevėžys (TBT – 6,4 μg/l, MBT - 121 μg/l, DBT – 25,9 μg/l).
TBT concentrations in bottom sediments are highly exceeding EQS for bottom sediments as given in the
substance data sheets prepared for the implementation of WFD (0,02 μg/l). It can be explained by the
moderate hydrophobic properties of organotins, therefore they strongly associate to the particles in the
aquatic environment.
 Butyltins concentrations are very high in the sites situated at harbour territory in Klaipėda channel:
o bottom sediments in Malkų bay: TBT – 1920-2400 μg/l, DBT – 11-164 μg/l, MBT – 36,9-56,8
μg/l;
o bottom sediments at the gates: TBT – 35,8 μg/l, DBT – 3,5 μg/l, MBT – 1,5 μg/l;
o bottom sediments at JSC Klaipėdos kartonas: TBT – 12,8-68,5 μg/l, DBT – 1,7-5,4 μg/l,
MBT – 1,9-4,7 μg/l;
o surface water at JSC Klaipėdos kartonas: TBT – 0,011-0,012 μg/l, DBT – 0,007 μg/l, MBT –
0,004-0,005 μg/l;
TBT concentrations exceed both MAC-EQS (0,0015 μg/l) and MAC (0,002 μg/l) for the surface water as well
as EQS for the bottom sediments (0,02 μg/l). Although TBT are not anymore used in antifouling paints, it is
still leaching from the sea ships hulls.
 Triphenyltin and its degradation products were found in the sediments of Malkų bay (6,4-7,4 μg/l),
Nevėžis below Panevėžys (16,3 μg/l) and sewage sludge of of WWTP of Vilkaviškis (2,8 μg/l).
 Octyltins (dioctyltin and monooctyltin) were found in the sludge of most WWTP as well as the sediments
in the receiving environment.
Octyltins can be used for rigid PVC potable water pipes and fittings in countries where lead stabilizers are
not allowed for regulatory reasons. Butyltins are also used for rigid PVC profiles and sidings, Venetian blinds,
rain gutters, window profiles.
7)
Phtalates and their ethoxylates
Phtalates and their ethoxylates were analysed at 43 sites in all 4 matrixes: wastewater, sewage sludge,
surface water and sediments in the receiving environment. All analyses were performed by GALAB
laboratory.
36
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007






Phtalates and their ethoxylates in wastewater were detected in 22 WWTP from 25 investigated and in
the sewage sludge of all 25 investigated WWTP. The most common phtalates detected: dibutylphtalate,
diisobutylphtalate, diisononylphtalate and di-2-ethylhexylphtalate.
Di-2-ethylhexylphtalate was detected in wastewater of 14 WWTP. In 4 WWTP it exceeded currently
applied AA-MAC (2 μg/l) for effluents to the surface water: WWTP Aukštaitijos vandenys – 1,95-3,22
μg/l, WWTP Anykščių vandenys – 0,42-2,75 μg/l, WWTP of Švenčionėliai – 10,4-53,2 μg/l, WWTP
Kauno vandenys – 2,97-4,25 μg/l and nearly reached the limit in WWTP Vilniaus vandenys – 1,55 μg/l. In
WWTP of Švenčionėliai – 10,4-53,2 μg/l is highly exceeding also MAC (4 μg/l). Comparing among the
different phtalates and their ethoxylates di-2-ethylhexylphtalate concentrations were the highest both in
the wastewater and sewage sludge. It was followed by diisononylphtalate and then dibutylphtalate.
Di-2-ethylhexylphtalate was detected nearly in all analysed sites of surface water:
o rivers: Nemunas at the border – 0,18 μg/l, Nemunas after Sovietsk – 0,61 μg/l, Nemunas at
Rusnė – 3,45 μg/l, Akmena at estuary – 2,19 μg/l, Šventoji at the border – 0,98 μg/l,
Nemunėlis at the border – 0,09 μg/l, Dysna at the border – 3,85 μg/l, Venta at the border –
1,33 μg/l, Neris at Buivydžiai – 0,68 μg/l, Siesartis below Šakiai – 0,09 μg/l, Nevėžis below
Panevėžys – 0,41 μg/l; practically in all sites it exceeds or is very closed to current AA-MAC
(0,1 μg/l) and MAC (0,2 μg/l);
o Malkų bay – 0,13-0,81 μg/l, harbour area at the gate – 0,82 μg/l, harbour area at JSC
Klaipėdos kartonas – 0,23-1,27 μg/l; in all sites it exceeds current AA-MAC (0,1 μg/l) and/or
MAC (0,2 μg/l).
The concentration of di-2-ethylhexylphtalate in bottom sediments in rivers never exceeded EQS for
bottom sediments as given in the substance data sheets prepared for the implementation of WFD
(100000 μg/l).
The concentration of diisobutylphtalates in the surface water of rivers varied from 0,24 μg/l to 5,6 μg/l.
The concentration of dibutylphtalate in surface water in rivers detected in most of the rivers and varied
from 0,07 μg/l to 1,25 μg/l.
The phtalates are notorious for being difficult to analyse due to contamination from plastic laboratory and
sampling equipment. During the project the bottles with plastic caps were used, however during the second
sampling/analysis round the plastic caps were isolated from sample by foil. Furthermore, to get an
impression of possible impacts on the results due to the plastic parts 5 parallel samples of wastewater were
performed with and without foil (samples were taken from the places where the concentrations of phtalates
during the first sampling/analysis round were the highest). The comparison of the results (see Table 17) do
not show any clear tendency that phtalates migrated to the samples from plastic parts of the bottles used for
storage of samples.
Table 17. Comparison of the results of samples stored with isolated and non-isolated plastic caps.
Substance
Diethylphtalate
Di-2-ethylhexyl phthalate
Diisobutylphtalate
Dibutylphtalate
Diisononylphtalate
Sample without foil
not detected
0,07
0,08
1,77
1,56
2,52
0,36
0,24
10,4
4,25
0,22
0,46
0,65
1,87
2,89
0,08
not detected
0,2
0,42
not detected
3,78
1,6
Sample with foil
0,1
0,11
0,09
1,92
1,04
1,95
0,42
0,27
11,7
4,19
0,68
1,28
1,64
8,67
1,73
0,23
0,08
0,18
not detected
1,23
8,32
not detected
37
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
Phtalates are very widely used in plastic materials (especially PVC) as softener, plasticizer. They are not
fixed, i.e. they easily migrate from plastic to the environment. Therefore DEHP can result from materials and
run off from buildings and constructions in urban areas (washed out from roofs, storm water pipes, drainage
pipes etc.). They can be discharged with sewage effluents or storm water as a result of household use of
PVC with DEHP as well as landfills.
8)
Brominated diphenylethers
Brominated diphenylethers were analysed at 43 sites in 3 matrixes: wastewater, sewage sludge and
sediments in the receiving environment. All analyses were performed by GALAB laboratory.
4 substances from the list of BDPE were detected in sewage sludge of some WWTP and sediments of
Nemunas river at Rusnė:
 Tetrabromobisphenol A (TBBPA) was found in Nemunas at Rusnė – 14 μg/l, WWTP Aukštaitijos
vandenys – 12,3 μg/l, WWTP Anykščių vandenys – 8,8 μg/l, WWTP Šiaulių vandenys – 8,9 μg/l, WWTP
Plungės vandenys – 37,7 μg/l, WWTP Radviliškio vanduo – 83,7 μg/l, WWTP Vilniaus vandenys – 14,4
μg/l, WWTP of Pabradė - 6 μg/l.
 Tetrabromodiphenyl ether (PBDE-47) was detected in Nemunas at Rusnė sediments – 6,3 μg/l and
WWTP Radviliškio vanduo – 18,2 μg/l.
 Pentabromodiphenyl ether (PBDE-99) was found in WWTP of Pabradė – 5,1 μg/l, WWTP Vilniaus
vandenys – 5,4 μg/l, WWTP Radviliškio vanduo – 29,5 μg/l.
 Decabromodiphenyl ether (PBDE-209) was found in WWTP Vilniaus vandenys – 3410 μg/l, WWTP of
Pabradė – 293 μg/l.
The sewage sludge of 3 WWTP (Radviliškio vandenys, Vilniaus vandenys and WWTP of Pabradė) are
contaminated by several BDPE.
BDPE are mainly used in the imported finished articles. Tetrabromobisphenol A (TBBPA) is the most largely
used BDPE, especially in the printed circuit boards in electrical and electronic equipment. Other important
product groups in which brominated flame retardants are found are insulation materials and textiles,
upholstery, plastics and electronics in cars. The main use of pentaBDPE is the manufacture and different
applications of flexible polyurethane foams. OctaBDPE is mainly used in acrylonitrile-butadiene-styrene
(ABS) polymers. DecaBDPE are mainly used in plastic/polymer applications and textile applications.
TetraBDPE and pentaBDPE may also form from octaBDPE or decaBDPE due to the photochemical
degradation. However BDPE pathway to the water environment is not well known yet but could include
releases from manufacturing or processing of the chemicals into products like plastics or textiles. Residues
from washing clothes and fabrics that have been treated with flame retardants may be flushed away down
the drains, however it is not expected to be substantial amount. Consumers are considered as one of the
main inland pollution source for brominated diphenylethers (survey from WFD Project on Fact Sheets on
Pollutants).
Brominated diphenylethers have a strong affinity to stick to solid particles and most of the residues entering
the sewage treatment system are therefore likely to be bound to the solid materials, which are suspended in
sewage.
LOD of the method applied for the pentabromodiphenyl ether analysis in water (0,005 μg/l) is too low to
comply with the proposed EQS on EU level (0,0005 μg/l). Furthermore, in the future it should be considered
that AA-MAC in the water of the receiving environment currently applied in Lithuania (0,1 μg/l) is very far
from proposed EQS.
9)
Short chain chlorinated parafins
Short chain chlorinated parafins (SCCP) were analysed at 43 sites mainly in 3 matrixes: wastewater, sewage
sludge and sediments in the receiving environment. However several sites included also analysis of SCCP in
surface water. All analyses were performed by GALAB laboratory.
SCCP were not detected at any of the sites. LOD of the method applied for the analysis of SCCP in the
project (0,4 μg/l) is in line with the currently proposed EQS on EU level. However it does not satisfy the MAC
set by Lithuanian legislation in the receiving environment (0,02 μg/l).
10)
Pentachlorphenol
The analysis of pentachlorphenol (PCP) was performed for 33 sites. It covered all 4 matrixes: wastewater,
sewage sludge, surface water and sediments in the receiving environment. Wastewater and surface water
analysis were performed by EPA laboratory and sewage sludge and sediments by GALAB.
38
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007


PCP was detected only at 1 site: sewage sludge of WWTP Anykščių vandenys – 54,7 μg/l.
Furthermore, the attention should be paid to the LOD of the currently applied method for PCP analysis in
wastewater or surface water (by EPA laboratory), since it does not comply with the needs of the
proposed EQS on EU level (LOD=0.9 μg/l, EQS=0.4 μg/l).
11)
Chlorpyrifos
Chlorpyrifos was analysed in 3 WWTP in sewage sludge and wastewater. It was selected by the project for
“testing” based on the fact that chlorpyrifos occurs on the Lithuanian market. It is used as biocide mainly for
fighting cockroaches, thus, it could be used by consumers as well as by professional services. Therefore
analysis was performed for 2 WWTP plants of big cities and 1 WWTP of smaller city with big number of
sanatoriums. The analysis was performed by GALAB laboratory.
Chlorpyrifos was not detected in any of 3 analysed sites. LOD of the method applied within the project (0.01
μg/l) is in the line with proposed EQS on EU level (0.03 μg/l), however it does not satisfy the needs of
Lithuanian requirements of MAC in the receiving environment (0,0002 μg/l).
12)
Cyanides, AOX
Cyanides and AOX were analysed only in 1 site – Nemunas river after Sovietsk. Such decision was based
on the assumption of the potential emissions of these substances from Sovietsk sewage system from the
metal processing and mirror production industry (CN) and pulp and paper industry (AOX) in Sovietsk city
(Kaliningrad region).
 Cyanides were not detected in the receiving environment.
 AOX in the surface water <20 μg/l, in the sediments 16000 μg/l.
B.
Overview of the results in the receiving environment
1)
Transboundary rivers
During the project 8 sites on transboundary rivers at the border were covered:
 4 rivers flowing into Lithuania: Nemunas, Neris, Dysna, Šventoji
 4 rivers flowing out of Lithuania to Latvia: Nemunėlis, Mūša, Bartuva, Venta
The most problematic substance groups for all rivers inflowing to Lithuania are phtalates due to their high
concentrations in surface water. Nickel and tributyltin in bottom sediments are of concern due to their
potential negative impact to the bentic community.
 Nemunas river at the border. Several groups of substances were detected in the surface water and
sediments - metals, octylphenol, naphthalene but their concentrations are well below the existing or
upcoming legal requirements (MAC, EQS). The only substance exceeding existing AA-MAC in surface
water and quite close to MAC is DEHP – 0,18 μg/l (AA-MAC= 0.1 μg/l, MAC=0.2 μg/l). However as
foreseen Europe wide AA-EQS=1.3 μg/l, the quality of the water is still good.
 Šventoji river at the border. The substances detected in the surface water and sediments of the river –
PAH and phtalates. PAH are well below the existing and foreseen limits. DEHP is exceeding existing AAMAC and MAC in surface water – 0,98 μg/l (AA-MAC= 0.1 μg/l, MAC=0.2 μg/). The concentration of
diisobutylphtalate is also high - 2.95 μg/l.
 Dysna river at the border. Substance groups detected in the surface water and sediments of the river
at investigated site – metals, PAH and phtalates. Both metals and PAH are well below of existing and
foreseen limits, except nickel. Its concentration in bottom sediments is 5.1 mg/l, which is exceeding EQS
for sediments 2.9 mg/l. The big concern is raised due to the high concentrations of phtalates in the
surface water. DEHP (3.85 μg/l) is exceeding both existing MAC (0.2 μg/l) and foreseen EQS (1.3 μg/l).
Other phtalates are also in high concentrations: diisononylphtalate – 6.97 μg/l, diisobutylphtalate – 1.61
μg/l, dibutylphtalate – 1.19 μg/l.
 Neris river at the border. Metals, octylphenol and PAH were detected in the river but in low
concentrations far of reaching existing and foreseen limits. DEHP in surface water (0.68 μg/l) exceeds
the existing MAC. The concentration of dibutylphtalate is also high. Another substance of concern –
tributyltin, which was detected in the bottom sediments in the concentration 1.6 μg/l, which is much
higher that EQS for sediments (0.02 μg/l) and may strongly influence bentic community.
With regard to the water quality of the rivers flowing from Lithuania to Latvia the biggest problems are raised
again due to phtalates, although according the newly proposed EQS the quality is not sufficient only in one
river – Venta. In the same river the high concentration of chloroform was detected in high concentration.
39
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA




2)
Bartuva river at the border. The PAH detected both in surface water and sediments are well below the
existing and foreseen limits. The concentration of diisobutylphtalate is very high – 5.12 μg/l.
Diisobutylphtalate is classified as very toxic for the aquatic environment (R50/53).
Nemunėlis at the border. PAH were detected in the bottom sediments but in low concentration, well
below of existing limits. Phtalates raise quite high concern – DEHL (0,09 μg/l) is nearly reaching existing
AA-MAC (0,1 μg/l). Also concentrations of other phtalates are rather high.
Mūša river at the border. The only substances detected were naphthalene and DEHP in the bottom
sediments, both in low concentrations.
Venta river at the border. The detected concentrations of PAH in water and sediments are very low.
Other two substances detected in surface water chloroform (388 μg/l) and DEHP (1,33 μg/l) exceeded
the existing and foreseen limits substantially. The further monitoring and sources tracking of chloroform
must be performed.
Waters inletting into Curonian Lagoon/ Klaipėda Channel
The water quality and bottom sediments of 2 rivers inletting into the Curonian Lagoon and Klaipėda Channel
were investigated within the project: Nemunas at Rusnė and Akmena at the estuary.
The surface water of both rivers is highly polluted with DEHP and bottom sediments with organotin
compounds.
 Nemunas at Rusnė. In the surface water only phtalates were detected. DEHP was found in the
concentration 3,45 μg/l and highly exceeds the existing AA-MAC and MAC (0,2 μg/l) as well as foreseen
EQS (1,3 μg/l). Furthermore the concentrations of organotin compounds and nonylphenol in sediments
are very high. They are much exceeding the EQS for the bentic community: nonylphenol – 3220 μg/l
(EQS=180 μg/l), tributyltin – 12.4 μg/l (EQS=0.02 μg/l).
 Akmena at the estuary. PAH detected in the surface water and sediments are well below the existing
and foreseen limits. Concentration of DEHP in the surface water 10 times exceeds the currently applied
MAC (0.2 μg/l). Also concentration of diisobutylphtalate in the surface water is very high – 5.6 μg/l.
Organotins are of concerns due to their high concentration in the bottom sediments and their potential
negative impact to the bentic community. The concentration of tributyltin in sediments - 585 μg/l highly
exceeds EQS indicated in the substance fact sheet – 0.02 μg/l.
3)
Transitional waters of Klaipėda Channel
4 sites at the transitional waters of Klaipėda Channel were investigated: Malkų bay, harbour area at JSC
Klaipėdos kartonas and at the gates, Klaipėda Channel at Baltijos kolūkis. This area was supposed to be
highly contaminated with many of the investigated substances. Sampling and analysis in two of these sites –
Malkų bay and harbour area at JSC Klaipėdos kartonas were repeated three times due to the specific
environmental conditions. It was problematic to make any conclusions after first two analysis rounds due to
the strong water inflow to the Curronian lagoon from the sea that could highly influence the concentrations of
hazardous substances, especially in water, however also in sediments in the harbour area.
The main substances of concern are phtalates, tributyltin and nickel.
 Malkų bay. The substances from 5 analysed groups of substances were detected: metals, phenols,
PAH, organotin compounds and phtalates. The only group of substances raising concern for the surface
water is phtalates. The detected concentration of DEHP is 0,13-0,81 μg/l and it exceeds the currently
applied MAC (0,2 μg/l). The concentrations of nickel and tributyltin in the sediments are well exceeding
the EQS for sediments in order to ensure good conditions for bentic community: Ni - 13 m/l (EQS=2.9
mg/l), TBT – 1920-2400 μg/l (EQS=0.02 μg/l).
 Harbour territory at JSC Klaipėdos kartonas. This site is highly poluted with organotins and phtalates.
The concentration of phtalates in surface water varies from 0,23 μg/l to 1,27 μg/l and exceeds existing
MAC. The concentration of tributyltin varies from 0,011 μg/l to 0,012 μg/l and exceeds more than 5 times
both MAC (0,002 μg/l) and more than 10 times MAC-EQS (0,0015 μg/l). The concentration of tributyltin in
sediments is also very high 12,8-68,5 μg/l. Furthermore, the concentration of copper in surface water
once exceeded AA-MAC and the concentration of nickel in sediments is higher that EQS for bentic
community.
 Harbour area at the gates. The concentration of DEHP in surface water at the gates gets lower – 0,82
μg/l, however it is still exceeding MAC (0,2 μg/l). The concentration of tributyltin in sediment is still very
high – 35,8 μg/l.
 Klaipėda Channel at Baltijos kolūkis. This site was investigated in the addition and only the analysis of
metals, PAH and chloroorganic pesticides in sediments were performed in EPA laboratory. Only nickel
was found in substantial concentrations – 4,4 mg/l, which exceeds the EQS for the sediments.
40
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
5)
Rivers below polluting cities
5 sites on the rivers below highly polluting cities were analysed: Nemunas below Sovietsk, Šventoji below
Anykščiai, Siesartis below Šakiai, Nemunas below Kaunas and Nevėžis below Panevėžys. Four last sites
were added to the screening programme after the results of the first analysis round in order to check the
potential impact of the polluted effluents. However it cannot be interpreted as the pollution in the rivers is
caused mainly due to the effluents of these specific cities since the analysis in rivers above the cities were
not performed in the project.
Siesartis below Šakiai. The effluents from Šakiai were highly polluted with organotin compounds and some
phtalates:
Group of
Subtances
substances
OT
Pht&E
Monobutyltin
Dibutyltin
Tributyltin
Monooctyltin
Dioctyltin
Diisobutylphtalate
Dibutylphtalate
Di-2-ethylhexyl phthalate
Diisononyl phthalate
WW
WS
μg/L
μg/kg*
11,1
117
2,32
74,6
6,4
15,3
10,3
0,35
295
24900
3010
The water quality of the river below the city was rather good except the contamination with phtalates. DEHP
(0,09 μg/l) nearly reaches AA-MAC (0,1 μg/l), the concentration of benzylbutylphtalate is also high – 1,55
μg/l. The concentration of organotin compounds in the sediments is very high, tributyltin exceeds the EQS for
the bentic community:
Group of
substances
Subtances
Monobutyltin
Dibutyltin
Tributyltin
OT
Monooctyltin
Dioctyltin
WS μg/kg*
59,5
25
8,3
11,3
7,2
Nevėžis below Panevėžys. The effluents of Panevėžys were contaminated with metals, organotin and
phtalates.
Group of
Subtances
substances
MET*
OT
Pht&E
Cadmium
Nickel
Lead
Arsenic
Copper
Zinc
Mercury
Monobutyltin
Dibutyltin
Tributyltin
Monooctyltin
Dioctyltin
Diethylphtalate
Diisobutylphtalate
Dibutylphtalate
Benzylbutylphtalate
Diphenylphtalate
Dibutoxyethyl phthalate
WS
μg/kg*
WW μg/L
5,8
28
1290
0,82
127
1140
0,5
237
128
21,7
85,1
70,8
1,8
4
1,1
28
0,03
0,029
0,004
0,22
0,1
0,68
186
306
0,66
16300
0,1
41
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
Group of
Subtances
substances
WW μg/L
3,22
2,52
Di-2-ethylhexyl phthalate
Diisononyl phthalate
WS
μg/kg*
1,95
73300
17000
Nevėžis river below city is also contaminated by phtalates and tributyltin, which concentration exceeds the
existing standards – MAC and EQS. Furthermore the concentration of nickel, tributyltin and nonylphenol in
the bottom sediments are also well above the EQS for the bentic community.
Group of
Subtances
substances
Cadmium
WW
μg/L
Nickel
1,5
Lead
Arsenic
Copper
Zinc
Mercury
MET*
Ph&E
OT
Pht&E
WS
μg/kg*
1,8
4,1
9,7
iso-Nonylphenol
Monobutyltin
Dibutyltin
0,04
0,008
0,006
Tributyltin
0,004
Monooctyltin
Dioctyltin
Triphenyltin
Diisobutylphtalate
Dibutylphtalate
Benzylbutylphtalate
Di-2-ethylhexyl phthalate
Diisononylphtalate
0,3
0,06
0,41
11
63
0,18
57
240
0,53
373
121
25,9
6,4
19,4
5,6
16,3
1000
356
22000
9470
Šventoji below Anykščiai. The effluents of Anykščiai city were much contaminated with phtalates,
especially DEHP and diisononylphtalate.
Group of
Subtances
substances
WW μg/L
OT
Monobutyltin
Dibutyltin
Tributyltin
Monooctyltin
Dioctyltin
Pht&E
Diethylphtalate
Diisobutylphtalate
Dibutylphtalate
Benzylbutylphtalate
Di-2-ethylhexyl phthalate
Diisononyl phthalate
WS μg/kg*
0,01
0,004
0,83
0,17
2,75
8,93
0,07
0,46
0,08
0,06
0,36
0,42
0,11
1,28
0,23
1,31
0,42
186
65,4
9,3
30,5
26,8
51,5
5,9
1,5
6,8
2,5
1110
271
471
36600
5080
The river below the city is mainly contaminated with phtalates, however not DEHP. Furthermore the
concentration of nickel and heksachlorbenzene in the bottom sediments exceed EQS for the bentic
community as proposed in the fact sheet of the substances.
Group of
Subtances
substances
Cadmium
SW
μg/L
3
Nickel
MET*
Pht&E
42
Lead
Arsenic
Copper
Zinc
Diisobutylphtalate
BS
μg/kg*
0,012
6
1,32
1,7
0,45
1,2
7,8
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Group of
Subtances
substances
Dibutylphtalate
Benzylbutylphtalate
COP
SW
μg/L
BS
μg/kg*
0,06
0,54
22
Heksachlorobenzene
Nemunas below Kaunas. The effluents of Kaunas were mostly contaminated by phenols, organotin
compounds and phtalates, especially DEHP.
Group of
Subtances
substances
4-t-Butylphenol
4-t-Pentylphenol
4-t-Octylphenol
iso-Nonylphenol
Nonylphenolmonoethoxylate
Ph&E
Nonylphenoldiethoxylate
Monobutyltin
Dibutyltin
Tributyltin
Monooctyltin
OT
Dioctyltin
Dimethylphtalate
Diethylphtalate
Diisobutylphtalate
Dibutylphtalate
Benzylbutylphtalate
Dibutoxyethyl phthalate
Di-2-ethylhexyl phthalate
Pht&E
Diisononylphtalate
WW μg/L
0,12
1,59
2,2
6,02
5,32
WS μg/kg*
39
77
730
51800
18200
2070
221
219
13,1
70,1
34,3
351
0,32
1,56
2,89
0,19
1,04
1,73
2,97
4,25
1,03
1,6
0,06
4,19 136000 55900
39700 44100
1,19
0,24
1390
892
426
1030
182
In the river below Kaunas the high amount of tributyltin was detected. Other substances have not reached
the existing limits.
Group of
Subtances
substances
Ph&E
4-t-Octylphenol
Monobutyltin
Dibutyltin
OT
Tributyltin
Pht&E
Diisobutylphtalate
Benzylbutylphtalate
SW
BS
μg/L
μg/kg*
0,02
1,4
0,01
0,004
0,1
0,87
Nemunas below Sovietsk.
The major concern with regard to Nemunas river quality after Sovietsk is due to the phtalates in the surface
water. DEHP – 0.61 μg/l exceeds the currently applied MAC (0.2 μg/l). The other significant pollutants can be
organotin compounds. Metals, phenols, PAH are also detected but well below the existing and foreseen
limits. In addition at this site cyanides and AOX were investigated. Cyanides were not detected, AOX=16000
μg/l. In order to clarify what specific AOX are detected, further investigation is necessary.
43
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
C.
Results of ecotoxicity tests
Toxicity assessment was performed using test battery consisting of 5 biotests for the acute toxicity:
 90 min electrophysiological test with Nitellopsis obtusa (Charatox)
 72 h growth inhibition test with Selenastrum capricornutum (Algaltoxkit FTM)
 24 h mortality test with Thamnocephalus platyurus (Thamnotoxkit FTM)
 24 h mortality test with Brachionus calyciflorus (Rotoxkit FTM)
 30 min bioluminescence inhibition with Vibrio fischeri (Microtox)
36 wastewater and 14 surface water samples were examined in total. All 36 wastewater samples were
tested with Charatox and Thamnotoxkit, 25 samples – with Microtox. To assess and rank water sample
toxicities, the results of these three biotests were integrated into numerical indices. These biotests had
relatively good sensitivity determining the toxicity of wastewater: Microtox 48 % (12 samples of 25), Charatox
58 % (21 of 36) and Thamnotoxkit 68 % (25 of 36). Rotoxkit was not considered for the final evaluation due
to its low sensitivity (only 3 tests of 22 showed the toxic signal). The test-battery used enabled us to cover
entire dynamic range of toxic responses (Tables 1 and 2, Annex IX): from 0 toxicity (all three tests negative,
5 of 36 samples) to maximum toxicity (all three tests positive, 3 of 36 samples) and intermediate toxicity
(when only some test organisms were affected, 22 out of 36, e.g. WWTPs of “Kauno vandenys”, “Dzūkijos
vandenys”, “Mažeikių nafta”, “Radviliškio vandenys” etc.
The results of Charatox, Thamnotoxkit, Microtox were used to calculate an integral index, Toxic Print, which
is Average Toxicity multiplied by the number of positevily responsed tests). According to this index and
toxicity scale [Persoone et al., 2003] 36 wastewater samples (Tables 1 and 2, Annex IX) were classified:
 5 were not toxic;
 13 – slightly toxic;
 17 – toxic;
 1 – very toxic (WWTP of Šakiai, No.9, Table 1, Annex IX).
This index is suitable for the characterisation of the toxicity of wastewater samples, filtrates from landfills,
outwash of sediments or sludge [Férard, Ferrari, 2005].
Further on, PEEP index [Costan et al., 1993], which considers both toxicity (represented by the Toxic Print)
and volume of wastewater discharged to the environment (represented as effluent flow in m 3/h) (their product
is called Toxic Load), was calculated. This index provides more information on potential impact to water
organisms and allows to compare the wastewater not only according to their “statical” (average or toxic print)
but also “dynamic” (average day flow) characteristics.
For example, the toxic print of wastewater from WWTPs “Vilniaus vandenys” and “Dzūkijos vandenys”
(Annex IX, Table 1, No. 24 and 4, respectively) are similar 4.49 and 4.71, however, if to consider their
effluent flow and corresponding parameters of Toxic Loads, the impact of wastewater from WWTP “Dzūkijos
vandenys” is approx. 10 times lower than that of wastewater from WWTP “Vilniaus vandenys”, i.e. 2024 and
21573 TU x m3/h, respectively. Using the latter parameter expressed as percentage from the total
wastewater toxic load it is possible to determine the entities having potentially the highest negative impact to
the recipient environment. During the first round of WW-analysis, in the spring-summer period, the highest
toxicity loads were from WWTP “Vilniaus vandenys” and WWTP “Kauno vandenys” (46.30 and 17.33 %,
respectively, Table 1, Annex IX), while during the second round, in the autumn period – from WWTP
“Aukštaitijos vandenys” (%) and WWTP “Kauno vandenys” (43.37 and 32.75 %, respectively, Table 2, Annex
IX).
Using numerical values of PEEP-index (Table 1 and 2, Annex IX) and newly proposed classification scale
[Ronco et al., 2005], the results were following:
 15 samples were not toxic or minutely toxic;
 10 slightly toxic;
 9 medium toxic
 1 very toxic (WWTP Vilniaus vandenys, Table 1, Annex IX).
The results of the analysis of surface water according to the index of toxic print:
 4 samples of water from 3 sites (Nemunas at Belarussia border, Šventoji river at the border and
Nemunas below Kaunas) were not toxic;
 toxic impact of water to testing organisms from 2 sites (harbour teritorry at the gates and harbour teritory
at JSC “Klaipėdos kartonas”);
44
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007

7 samples of surface water were slightly toxic (impact to testing organisms in 1 or 2 tests from the test
battery.
The overview on all results is provided in the Annex IX.
The correlation between the results of chemical analysis and biotests is rather difficult since in most cases
the concentrations of analysed chemical substances or groups of substances were below the accepted
limits. The cases for further consideration could be WWTP of Kėdainiai, Varėna, Birštonas, Marijampolė,
Kazlų Rūda (because of organotins) and WWTP of Kaunas, Radviliškis, Panevėžys, Anykščiai and
Švenčionėliai (because of phtalates). Especially in the case of Švenčionėliai the significant toxicity of
wastewater could be influenced by phtalates, which concentration exceeded set limit more than 15 times.
However, further investigations are needed to prove that. In other cases, the toxicity of wastewater can be
partly explained by other exceeded parameters, such as nitrites, nitrates, total phosphorus, COD, BOD
etc.[Manusadžianas et al., 1998, 2003; Vindimian et al., 1999].
45
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
7.
Potential sources of hazardous substances
The table below presents an overview on the potential sources of less known hazardous substances, i.e.
industry branches, processes, products as well as other sources. This information could be used for further
evaluation of the primary sources of hazardous substances occurred in the wastewater/sludge and the
receiving environment during the project. Furthermore, it could serve as preliminary guidance for the
permitting authorities considering the importance of different hazardous substances for the applicant of the
permit.
Table 18. Overview on the potential sources of hazardous substances
Substances
Source/process
Type of products
Metal industry
SCCP/MCCP
Cutting, drilling
NPE/OPE
Cutting, drilling
TBT
Shipbuilding and repairing – removing paint and
painting. Leaching to marine environment from
sea ship hulls.
Shipbuilding and repairing – removing paint and
painting. Leaching to marine environment from
sea ship hulls
High pressure additive in metal
processing fluids (both water and oil
based)
High pressure additive in metal
processing fluids
Antifouling paint
TPhT
Electronic industry
PentaBDPE
NPE
OP
Electrical equipment (electronic circuits, TVs,
monitors etc.)
Antifouling paint
Flame retardant
Production of electrical equipment
Production of electric windings (e.g. in motors,
transformers)
Soldering agent
Electrical insulation varnish and
bonding the windings
Flux agent
Finishing (textile coating)
Flame retardants
Finishing (in most modern printing processes)
Used in printing ink formulations as
emulsifier (mainly in styrenebutadiene copolymers)
Hexabromocyclododecane
(HBCDD)
NPE
SCCP
Finishing
TBT
Plastic industry
Polybrominated diphenyl
ethers (PBDEs) and
polybrominated biphenyls
(PBBs
Finishing
Flame retardant, back coating from
polystyrene
Surfactants, conditioning agent
Flame retardant, agent for water
resistance, antifungal agent
Antifungal agent
Textile
Polybrominated diphenyl
ethers (pentaBDPE,
octaBDPE, decaBDPE)
OP/OPE
Tetrabromobisphenol A
(TBBPA) and its derivatives
46
Finishing
Finishing of technical textile
Formulation (blending Iof polymers with various
additives) and industrial use (production of
finished plastic articles).
Used in polyurethane foams, in thermoplastics
such as ABS, polystyrene and polycarbonate:
(OctaBDPE used in plastics in electrical
installations: acrylonitrile-butadiene-styrene
(ABS) polymers, also high impact polystyrene,
polyamide and polybutylene terphtalate
polymers, insulating wires, cables.
PentaBDPE manufacture and different
applications of flexible polyurethane foams.
DecaBDPE used in plastic/polymer
applications, insulated wires and cables,
different electrical equipment.)
Production of thermoset plastics such as
epoxies, polyurethanes and polyesters
Flame retardants
Flame retardant
REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Substances
Source/process
Type of products
NP
Production of plastic products
Adhesive, binding agent, process
regulator, stabilizer, hardener for
epoxy resins and plastic products for
construction purpose (floor covering
materials, paints, sealing
compounds);
soldering agent in insulated wires
and cables
Adhesive
TBT is an impurity in stabilising
agents containing MBT and DBT
OP, butylphenols
Organotin compounds (TBT,
MBT, DBT)
Octyltins
Butyltins
PVC, polyurethane, polyester production and
processing
Production of rigid PVC potable water pipes
and fittings
Production of rigid PVC profiles and sidings,
Venetian blinds, rain gutters, window profiles
Phtalates (DBP, DEHP)
Softener for different polymer
materials (especially PVC)
Plasticizers and flame retardants
SCCP/MCCP
Rubber industry
Octylphenols, butylphenols
Production of PVC plastics
OP
SCCP/MCCP
Tanneries
SCCP/MCCP
Production of rubber for tyres
Tackifier
Plasticizer, flame retardant, adhesive
Leather processing
NPE
OPE
Chemical industry
NPE/OPE
Degreasing
Leather finishing
Fattening and liquoring agent,
impregnation agent
Degreasing agents
Emulsifier in finishing agents
NP/NPE/OPE
NP
NP/OP
Phtalates (DBP, DEHP)
Chloroform
Hexabromocyclododecane
(HBCD)
SCCP/MCCP
Pulp and paper industry
Phenols (methylphenol,
nonylphenol, butylphenol,
octylphenol)
SCCP
AOX
Agriculture
NPE
OPE
TPhT
Food industry
NP/NPE/OP/OPE
Public institutions
(hospitals, schools,
administration, hotels…)
NP/NPE/OP/OPE
Aviation
TBT
NPE
Furniture industry
PentaBDPE
Adhesive
Industrial and institutional cleaning agents,
polishing preparations
Paints, varnishes and coatings production
Production of cosmetics
Production of NPE/OPE, manufacture of resins,
plastics and stabilisers, manufacture of phenolic
oximes
Production of paints, adhesives, sealants,
cosmetics
Pharmaceuticals
Production of expanded polystyrene
Paints, varnishes and coatings production
Surfactant, cleaning agent
Stabilizer, emulsifying agent,
dispersant
Moisturing, emulsifying agent
Plasticizers, softeners
Flame retardant
Binder, plasticizer, flame retardant
Aid agent, paper coating
Solvent
Only if chlorine is used in process
Pesticides
Pesticides
Fungicide for potatos
Co-formulant
Dispersing agent
Cleaning of equipment
High performance surfactant
Professional cleaning
High performance surfactant
De-icing activities in airport
Marking agent
De-icing agent
Production of soft furniture
Flame retardant
47
2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
8.
Findings and recommendations
This chapter aims at summarizing the major findings of the project on occurrence of hazardous substances
in the aquatic environment, needs of improvements in legislative, implementation and enforcement level in
order to be able to comply with and reach the target set by the WFD as well as provides the
recommendations for the further actions in order to ensure the sustainability and further use of the results of
the project.
 Occurrence of the substances and their significance for the Lithuanian aquatic environment
o
o
o
o
o
As the screening results shows the most problematic “new-generation” substances for Lithuanian
aquatic environment are phtalates and organotin compounds. These substances were
detected both in the wastewater and sewage sludge as well as in the receiving environment,
often exceeding the applied limits. It is obvious that these substances can trigger failure of
reaching good water quality status according WFD. These substances are relevant for
transboundary rivers, for transitional water in the Baltic Sea (Klaipėda Channel) as well as for the
effluents from WWTP. However with regard to tributyltin the evaluation to full extent is not
possible since the LOD of the method applied was still higher than newly proposed EQS.
There were only few cases when other substances exceeded the applied or foreseen limits, e.g.
zinc, copper, anthracene, chloroform.
Nickel and organotin concentrations in bottom sediments in the receiving environment very
often exceeded the EQS for the bottom sediments indicated in the substances fact sheets
developed for the implementation of WFD requirements. Although it is not obliged to comply with
these EQS but it shows their potential negative impact of these substances to the bentic
community.
It is only partly possible to judge on water quality with regard to its contamination with
brominated diphenylethers. Although it was not detected in the surface water, the LOD of the
method applied in the screening exercise was 10 times higher than settled EQS.
Although in most cases the concentrations of analysed chemical substances or groups of
substances were below the existing limits, the ecotoxicity tests showed many of the toxicity
cases. It can be partly explained by other exceeded parameters, such as nitrites, nitrates,
amonium N, total phosphorus, COD, BOD etc. In some cases (especially Švenčionėliai) further
investigations would be helpful to prove correlation between investigated chemical pollutants and
toxicity of wastewater.
 Legal measures related to hazardous substances control
Although the limits for all substances/groups of substances screened during the project are legally available
for many of them the appropriate measures enforcing their control are not in place.
o The list of substances relevant for different industry sectors provided in the programme for the
reduction of pollution by hazardous substances do not indicate many of the substances of high
concern as the results of screening exercise showed, e.g. phtalates and their ethoxylates,
organotin compounds, phenols and their ethoxylates, brominated diphenylethers.
o Furthermore, the regulation on wastewater pollution set the requirements for the entities
discharging their effluents directly to the receiving environment and list the parameters to be
controlled based on the pollution source. The parameters indicated in that list do not include
above-mentioned groups of substances as well.
o The parameters in the effluents of industrial/commercial entities are controlled based on the
parameters listed in the permits (both for IPPC installations and non-IPPC installations), which
are usually “traditional” ones as, for example, metals, BOD, COD, total nitrogen, some PAH, VOC
etc. While issuing the permit the “new-generation” pollutants (phtalates, organotins, phenols and
their ethoxylates, chlorinated parafins, brominated diphenylethers) are not yet considered. The
reasons for that could be different, e.g. too low knowledge and experience from both sites –
industry and permitting authorities to be able to identify the occurrence of these substances in the
raw materials, specify the potentially relevant substances based on the processes applied in the
companies, not available analysis methods for checking and control of these substances in the
effluents and posing sanctions for the exceeded limits.
In order to overcome this situation the following measures could be recommended:
o to update the lists of the sector specific hazardous substances to be considered, screened and
controlled according water legislation; however it should not require each company to analyse all
potentially relevant substances from that sector, such request must be based on the evidence of
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
o
o
occurrence of substance in raw material and/or potential discharge of substance to water
environment;
to request companies to set up the electronic inventory on used dangerous chemicals till the level
of substance (current legislation requires “paper version” of the inventory); it will ease the
identification of any specific substances in raw materials, reporting or complying with other
requirements for companies and provide good basis for better control by companies;
to prepare clear guidance on identification of hazardous substances in raw materials and their
potential occurrence in effluents from specific processes for both industry and permitting and
controlling authorities
 Tracking the primary sources of the hazardous substances
The best way to ensure the sustainability of the project results is to continue with the tracking the primary
sources of the hazardous substances, if succeeded, that would lead to the concrete measures to reduce the
pollution of the waters with these substances.
o Currently available tools – database of dangerous substances and preparations, other databases
(e.g. registered plant protection products), permits for use - do not provide good basis for the
identification of occurrence of hazardous substances on the Lithuanian market and their use. For
example, the number of companies reporting to database on dangerous substances and
preparations is just reaching 300, however the number of relevant actors on the market is
definitely much higher. Here the stronger enforcement is necessary. Furthermore, it provides
good information only on pure substances, while most of the hazardous substances relevant to
aquatic environment are contained in the preparations. This information is not easily available.
With regard to the registered plant protection products the easily accessible information is
available only on active substances, while identification of hazardous substances used as coformulants (e.g. NPE) is hardly possible due to intensive resources needed to screen the
documents. It could be recommended to set up electronic database with the information on full
composition of registered plant protection product (e.g. it is available in Estonia).
o The current discharges monitoring system is not well developed towards the identification of
hazardous substances. Most of the industrial installations discharge their effluents to the
municipal wastewater treatment plants, which are responsible for the reaching parameters for the
treated wastewater discharged to the surface waters. As it was mentioned above the “newgeneration” substances do not appear neither in the permits issued for WWTP, nor in the
contracts between WWTP and entity, and therefore they are not controlled in the effluents.
However as the screening results showed some of the substances are well exceeding the limits
to be complied with. Better control and enforcement of the requirements on discharges of
hazardous substances on WWTP level would force them to track back the sources of the
substances exceeding the limits and to revise the contracts with industrial installations.
o In case of chloroform in Venta river at the border, the actions to track the sources of chloroform
discharges must be taken as soon as possible. That should be the task of Šiauliai Regional
Environmental Department to screen the potential sources of chloroform in Mažeikiai and take the
measures (as obliged according the order D1-71 of 13 Feb. 2004 on Programme on reduction of
water pollution by hazardous substances). Furthermore, the monitoring of chloroform in the river
should continue to check whether the right sources and measures are identified and pollution
reduces.
 Monitoring of discharges polluted with hazardous or priority hazardous substances.
Based on the results of the screening exercise, at least the permits for the WWTP discharging the
hazardous or priority hazardous substances to the environment must be revised and identified
substances included to the permits and appropriate monitoring must take place (either 2 or 4 times a year
as required by regulation on wastewater pollution). Further on, the state control of such objects must be
performed at least once a year.
 Current environmental monitoring programme for years 2005-2010 does not include the “newgeneration” substances as well. However considering the results of the screening exercise at least the
following substances should be monitored focussing on the most relevant matrixes as stated in the
chapter 4 part C:
o DEHP
o Organotin compounds
o Nonylphenol/octylphenol (potentially)
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
 Analytical methods
o
Some of the currently applied methods for the analysis of hazardous substances in the EPA
laboratory are not sufficient to control the occurrence of these substances in the wastewater or
surface water according currently applied AA-MAC/MAC or upcoming EQS:
Substance
Benzo[ghi]perylene +
Indeno[1,2,3-cd]pyrene
1,2-dichlorethane
Pentachlorphenol
o
o
o
o
LOD
0.01 μg/l
25 μg/l
0.9 μg/l
AA-MAC
0.03 μg/l
0.04 μg/l
10 μg/l
2 μg/l
EQS
=0.002 μg/l
10 μg/l
AA-EQS=0.4 μg/l
MAC-EQS=1 μg/l
It would be important to improve LOD at least until the level to ensure adequate control of the
substances according the required limits.
It should be considered that currently applied analysis methods in EPA laboratory for polycyclic
aromatic hydrocarbons and chloroorganic pesticides do not include several substances, which
are regarded as priority hazardous substances under WFD. These are pentachlorbenzene,
trichlorbenzene and heksachlorbutadiene. In order to ensure the control of these substances the
methods for their analysis should be developed.
It is recommended to develop some new methods to be able to control at least a few substances,
which according to the screening results are of significance to Lithuanian water quality. The
potential substances would be DEHP, organotin compounds, also phenols and their ethoxylates.
An alternative option could be use of services of external/abroad laboratories (as the experience
showed, e.g. prices of GALAB laboratory are comparable with prices of EPA laboratory). The list
of laboratories questioned during the project can be found in Annex X.
In case of phtalates, it is important to consider that no plastic parts appear in the sampling,
handling, storage or analysis equipment to avoid the perverted results due to potential leakage of
phtalates from plastics to the analysed sample.
If developing any new analytical method the freshly set EQS must be considered for the LOD
determination.
 Standard sampling procedures. In order to ensure the quality of samples, analysis results and their
further interpretation and comparability (e.g. in case of environmental monitoring, control of separate
entities etc.), it is necessary to ensure the harmonised standard sampling procedures. As the project
experience showed the weakest part related to harmonised standard sampling procedures is with regard
to the sampling of sewage sludge in WWTP. The methodological guidance on this issue could be
performed by the Environmental Research Department of EPA.
 The results of the screening exercise showed that many of the hazardous substances due to their
properties are sticked to solid particles and are suspended in sewage sludge. Current legislation on the
use of sewage sludge for the agricultural or recreational purpose is based on the regulating metals in the
sludge. However, considering the properties of most of the hazardous substances accumulated in the
sludge (most of them are persistent, bioacummulating and toxic – PBT), it is not recommended to use
such sludge for agricultural or recreational purpose since that is direct way polluting environment with
PBT substances, no matter it is not aquatic environment.
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
9.
List of abbreviations
AA-EQS
AA-MAC
AOX
BCF
BDPE
BS
ChP
CN
COP
DBP
DBT
DDT
DEHP
DSD
EPA
EQS
ET
EU
EU-RAR
EUSES
HELCOM
HS
IPPC
LC
LOD
MAC
MAC-EQS
MBT
MCCP
MET
MPA
MU
NP
NPE
OP
OPE
OT
PAH
PCP
PEEP
Ph&E
Pht&E
PPP
PVC
REPD
SCCP
SW
TBBPA
TBT
TPhT
TU
VOC
WFD
WS
WW
WWTP
Environmental Quality Standard expressed as an annual average value
Maximum alowable concentration expressed as an annual average value
Halogenated organic compounds
Bioconcentration factor
Brominated diphenylethers
Bottom sediments
Chlorpyrifos
Cyanides
Chloroorganic pesticides
Dubutylphtalate
Dibutyltin
Dichloro-Diphenyl-Trichloroethane
Di-2-ethylhexylphtalate
Dangerous Substances Directive (76/464/EEC)
Environmental Protection Agency of Lithuania
Environmental quality standard
Ecotoxicity test
European Union
European Union Risk Assessment Report
European Union System for the Evaluation of Substances
Baltic Marine Environment Protection Commission (Helsinki Commission)
Hazardous substances
Integrated pollution prevention and control
Limit concentration
Limit of detection
Maximum alowable concentration
Environmental Quality Standard expressed as a maximum allowable concentration
Monobutyltin
Medium chain chlorinated parafins
Metals
Maximum permissible addition
Measurement uncertainty
Nonylphenols
Nonylphenolethoxylate
Octylphenols
Octylphenolethoxylate
Organotin compounds
Polycyclic aromatic hydrocarbons
Pentachlorphenol
Potential Ecotoxic Effect Probe
Phenols and their ethoxylates
Phtalates and their ethoxylates
Plant protection product
Polyvinylchloride
Regional Environmental Protection Departments
Short chain chlorinated parafins
Surface water
Tetrabromobisphenol A
Tributyltin
Triphenyltin
Toxic Unit
Volatile organic compounds
Water Frameworkk Directive (2000/60/EC)
Sludge from WWTP
Wastewater
Wastewater treatment plant
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2007 REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA
10.
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References
Council Directive of 4 May 1976 on pollution caused by certain dangerous substances discharged into the aquatic
environment of the Community (76/464/EEC)
Proposal for a Directive of the European Parliament and of the Council on environmental quality standards in the
field of water policy and amending Directive 2000/60/EC
Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing framework for
Community action in the field of water policy
Commision staff working document Impact Assessment on Proposal for a Directive of the European Parliament and
of the Council on environmental quality standards in the field of water policy and amending Directive 2000/60/EC
State Environmental Monitoring Programme for 2005-2010, approved by the Governmental Decision No. 130 on
February 7, 2005
River Monitoring Plan 2006, approved by the Minister of Environment Order No. D1-63 on February 1, 2006
Water pollution with dangerous substances reduction programme, approved by the Minister of Environment by
Order No. D1-71 on February 12, 2004
Wastewater treatment regulation, approved by the Order of the Minister of Environment No. D1-236 on May 17,
2006
Rules of reduction of water pollution by hazardous substances approved by Order of the Minister of Environment
No. 624 of 21 December 2001
Rules of reduction of water pollution by priority hazardous substances approved by the Order of the Minister of
Environment No. 623 of 21 December 2001
Programme for the reduction of water pollution with dangerous substances, approved by the Minister of
Environment by Order No. D1-71 on February 12, 2004
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(changed by No. D1-330 of 29 June 2005).
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Draft Final Report of the expert group on Analysis and monitoring of priority substances, 2004
EU-RAR. European Union Risk Assessments (EU-RAR) on different substances
OSPAR background document on different substaces (organic tin compounds, brominated flame retardants,
nonylphenol / nonylphenolethoxylates, short chain chlorinated paraffins, octylphenol).
Draft report on HELCOM Assessment on Hazardous Substances in the development of the HELCOM Baltic Sea
action plan
WFD Project Fact Sheets on Pollutants. Outcome and Evaluation. Executive Summary, 2004
WFD Substances’ data sheets on EQS
Substances’ data sheets on Source screening of priority substances under the WFD
Costan, G., Bermingham, N., Blaise, C., Ferard, F., 1993. Potential ecotoxic effects probe (PEEP): A novel index to
assess and compare the toxic potential of industrial effluents. Environ. Toxicol. Water Qual. 8, 115-140
Férard J.-F., Ferrari B. 2005. WASTOXHAS: A bioanalytical strategy for solid wates assessment. In: C.Blaise and
J.-F.Ferrard (Eds.), Small-scale Freshwater Toxicity Investigations, Vol.2. Springer, pp.331-375
Manusadžianas L., Balkelytė L., Sadauskas K., Põllumaa L., Blinova I., Kahru A. 2003. Ecotoxicological study of
Lithuanian and Estonian wastewaters: selection of the biotests, and correspondence between toxicity and chemicalbased indices. – Aquatic Toxicology, 63:27-41
Manusadžianas, L., Balkelytė, L., Sadauskas, K., Stoškus, L., 2000. Microbiotests for toxicity assessment of various
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screening and biomonitoring. Kluwer Academic/Plenum Publishers, New York, Dordrecht, London, Moscow. pp.
391-399
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Toxicol. Chem. 18, 2386-2391
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REPORT ON DANGEROUS SUBSTANCES IN THE AQUATIC ENVIRONMENT OF LITHUANIA 2007
Annexes
Annex I:
ANNEX 1 to the Council Directive on pollution caused by discharges of certain
dangerous substances (76/464/EEC)
Annex II: ANNEX VIII to Water Framework Directive
Annex III: Extract of the Water Framework Directive (2000/60/EC) - Article 16 Strategies against
pollution of water
Annex IV: Annex X of Directive 2000/60/EC - List of priority substances in the field of water policy
Annex V: Environmental quality standards for priority substances and certain other pollutans
Annex VI: List of priority hazardous and hazardous substances of Lithuania
Annex VII: Overall results of the chemical analysis
Annex VIII: Results of the analysis by investigated sites
Annex IX: Results of the ecotoxicity analysis
Annex X: List of laboratories
53