UNDP/GEF Danube Regional Project
Strengthening the Implementation Capacities for Nutrient
Reduction and Transboundary Cooperation in the
Danube River Basin

Final Report
Support for TNMN and EMIS Inventory
Harmonization

Project Component 2.2: Development of operational tools for
monitoring, laboratory and information management with
particular attention to nutrients and toxic substances

December 2003

Support for TNMN and EMIS Inventory Harmonization
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Table of Content

Executive Summary
Part I:
Orientation on environmental quality standards for nutrients and other Danube
specific priority substances
Part II:
Preparation of a proposal for connection/operational link of the data collected
during the Joint Danube Survey into ICPDR Information System, with particular
attention to biological database
Part III:
Analysis of the results of the EMIS inventory and their comparison with TNMN
and JDS results with particular attention to the EU Priority List of Pollutants
Part IV:
Development of the Danube List of Priority Substances and SOPs for newly
included determinands
Part V:
Five-years Report on Water Quality in the Danube River Basin Based on Trans-
National Monitoring Network
Part VI:
Development of a methodological concept for assessment of environment stress
and impacts as a basis for preparation of a computer-based application for stress-
impact analysis

Support for TNMN and EMIS Inventory Harmonization
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Executive Summary
This project assisted DRB countries to develop, upgrade and reinforce capacities of tools for emission
control and monitoring of water quality. Both water quality assessment and emission control
(assessment of pressures/programme of measures) are key issues in implementation of the EU WFD.
The implementation process has a high priority in the work of the ICPDR. Therefore, current activities
of those ICPDR expert groups responsible for water quality (MLIM EG) and emission control (EMIS
EG) reflect the needs of the EU WFD implementation. In line with the Work Programmes of MLIM
and EMIS Expert Groups, following major issues were addressed by the project:
ˇ Development of water quality objectives for nutrients and water quality standards for toxic
substances;
ˇ Development of application for pressure /stress (emissions) and impact (water quality/change
in ecosystems) analysis, based on MLIM and EMIS databases (TNMN, JDS, EMIS Inventory)
including analysis and comparison of data in these databases;
ˇ Improvement of the scope of the Trans-National Monitoring Network and Emission Inventory,
including harmonization of their databases, considering EU and DRPC Priority Substances.
TNMN related activities included analysis and assessment of TNMN results, development of
SOPs and upgrade of web-based databases.
Major deliverables from particular project components are summarized below:

1. Development of a proposal on water quality objectives for nutrients in line with
requirements of EU WFD and development of a proposal on water quality standards
for toxic substances from DRPC list of priority substances in line with requirements
of EU WFD
The study aimed at formulating Environmental Quality Standards (EQSs) for those Danube specific
substances that are not included in the list of priority substances of the EU Water Framework
Directive. The Danube specific priority substances comprise: total nitrogen (Ntot), total phosphorous
(Ptot), ammonium (NH4+), chemical oxygen demand (COD), and the metals As, Cr, Cu and Zn.
For the nutrients (Ntot, Ptot) the study used the following working definition in order to make the
WFD's `good status' description for physico-chemical parameters more operational: "nutrient
concentrations such that chances on the occurrence of eutrophication are minimised, or (preferably)
avoided". The query into existing systems for water quality assessment and standards resulted in the
following preliminary recommendations for EQSs to be used as representing `good status' thresholds
for nutrients: Ntot: 1.0 - 1.5 mg N/l; Ptot: 0.02 0.08 mg P/l. Compared to estimated natural
background levels for the Danube river (Ntot ~ 0.8 mg N/l; Ptot ~ 0.03 mg P/l) the proposed EQSs
seem rather steep. The major comment during the presentation of the previous values was that they do
not meet with the requirements of the type specific approach (which was acknowledged by the study).
Following the type specific approach, the conditions (including natural background) and requirements
of the specific water body should be assessed and taken into account when setting its corresponding
EQS. Therefore, the figures for both the EQS as well as for natural background mentioned in the
report are considered merely indicative.
For ammonium (NH4+) a separate EQS has been proposed, since ammonium can have toxic effects
under certain conditions and concentration levels. The proposed threshold value representing the
physico-chemical `good status' of NH4+ is =0.2 mg N/l.
The proposed threshold value representing the physico-chemical `good status' of chemical oxygen
demand is CODMn =10 mg O2/l.

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UNDP/GEF Danube Regional Project
For the metals As, Cr, Cu and Zn it was not possible to extract common denominators from the
existing systems of water quality standards. Firstly, existing systems can differ for the matrices
included in the defined standards (total, dissolved, suspended solids and/or sediment). Secondly,
differences in an order of magnitude of 10 can be observed between comparable water quality
standards, like the `No Observed Effect Level' for zinc applying in the Netherlands (total= 12 ľg/l)
versus the one used by the US-EPA (dissolved= 120 ľg/l). Since comparing existing systems is not
expected to provide a common ground for reaching consensus, for possible follow-up it has been
proposed to a) `pragmatically' adopt of one existing system of EQSs, or b) to infer EQSs for the
Danube specific metals applying the methodology used by the Fraunhofer Institute for setting the
EQSs for the WFD priority pollutants. As it turned out, Austria already has implemented option b) for
dissolved concentrations of As, Cr, Cu and Zn. The final report is expected to be made public around
the end of the year 2003.

2. Preparation of a proposal for connection/operational link of the data collected
during the Joint Danube Survey into ICPDR Information System, with particular
attention to biological database
Primary objective of this project component was to develop a proposal for an operational link between
the JDS and TNMN databases. The project team with a help of selected MLIM experts and
UNDP/GEF Information Specialist, who participated at the development of the original JDS Database,
undertook an approach of on-line introduction of suggested changes/recommendations into the web-
based ICPDR Information System. This gave an instant feedback on the practicality and usefulness of
the JDS database upgrades and improvements. Prior to the final interlinking of databases, numerous
efforts were made consisting of completion of the database for missing parameters and thorough check
on the quality of stored data.
As a result recommendations for a link between the JDS and TNMN databases and harmonisation of
their query templates were made and incorporated into their New Draft Versions. A proposal of the
new central page on the ICPDR website comprising of all ICPDR databases (TNMN, EMIS,
Bucharest Declaration Database, JDS, JDS Investigation of the Tisa River) was drafted. During the
project, the JDS Database was gradually improved and developed into the stage, that it is ready for the
public use (for latest version, see www.icpdr.org [Databases/New Draft Versions]).
Several suggestions, which go beyond the scope of this project component, were made by the project
team and MLIM experts to improve the ease-of-use of the JDS and TNMN databases. A principal
upgrade and Europe-wide harmonisation of the coding system and systematic tracking of taxonomical
changes in the biological part of the database was proposed in order to assure its sustainability. Also,
further upgrade of the GC-MS screening part of the database was suggested to allow proper evaluation
of the screening data on emerging, unknown and Danube River Basin specific pollutants as required
by the WFD. A specific recommendation was made to perform similar upgrade at the JDS
Investigation of the Tisa River database, containing valuable data from survey conducted in October
2001, however, not being ready for public use in its present form.
Final goal of all the above efforts is to create a fully interlinked ICPDR Information System. This
would require future harmonization of the coding system between the TNMN and EMIS databases and
further development of the link between the two databases. The knowledge obtained at the
development and upgrade of the JDS Database created a solid base for extension of the TNMN
Database for new chemical parameters, parameters measured in other matrices than water, GC-MS
screening and biological data.

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3. Analysis of the results of the EMIS Inventory and their comparison with TNMN and
JDS results, with particular attentions to EU Priority List of Pollutants
The main objective of this activity was to prepare a background material for future harmonization of
the ICPDR databases (EMIS, TNMN). Therefore, a comparative analysis of determinands (i) included
in the EMIS inventories/database, (ii) routinely measured in the TNMN and (iii) analyzed within the
Joint Danube Survey (JDS) was made. A particular attention was given to a comparison with the
determinands from the EU Water Framework Directive (WFD) List of Priority Substances. The
analysis made also a comparison with the recently agreed provisional Danube List of Priority
Substances.
At present, for water matrix 26 determinands from EU & Danube Priority Lists are not in the
analytical programme of TNMN and 29 are not in the EMIS inventories. In the JDS, 17 out of these 26
determinands were included in the analytical programme for the water matrix. Eight JDS determinands
that are listed in the Decision No. 2455/2001/EC showed results below detection limit (n.d.). Mercury
was below detection limit in the JDS datasets (due to relatively high LOD of the analytical method
applied), however, it is reported in the TNMN list. For 14 determinands (all organic micropollutants)
listed in the Decision No. 2455/2001/EC no data in water exists in the ICPDR databases (TNMN and
JDS; data from PHARE Applied Research Programme for DRB exist for PAHs).
For sediment / suspended solids altogether 20 determinands of the EU WFD Priority Substances Lists
are not in the analytical programme of TNMN while 22 are not in the EMIS inventories. Ten, out of
these 20 non-TNMN determinands, were included in the analytical programme of the JDS for
sediments/suspended solids. For ten determinands present in the EU WFD Priority Substances list no
data are available in suspended solids/sediments analysed within the TNMN and JDS.
In the technical report results are discussed in detail for each (group of) determinand(s).
Considerations are presented for each determinand whether to include it or not in either the EMIS
inventories or the analytical programme of TNMN. Comments on possible emission sources were
made as well, based on current versions of respective EC documents (source screening). The
considerations were used as a basis for the recommendations. Recommendations referred also to
monitoring matrices agreed until now by EAF PS.

4. Development of the Danube List of Priority Substances and SOPs for newly included
determinands
The main objective of this activity was to develop the Danube List of Priority Substances, based on the
EU List of Priority Substances, determinands of TNMN and JDS; and taking into account the results
of Phare project ZZ-97-25 Component VI in line with work of EMIS EG on this topic. However, the
activities concerning developing the Danube List of Priority Substances had started long time before
the Danube Regional Project began and the list was finalized by the ICPDR during course of the
project. Therefore, a summary is provided of the activities performed and milestones achieved.
Moreover, general recommendations are given for the follow-up actions.
In line with the Decision No 2455/2001/EC of the European Parliament and of the Council of 20
November 2001 establishing the list of priority substances in the field of water policy and amending
Directive 2000/60/EC, and taking into account determinands analysed within TNMN and JDS as well
as the results of Phare project ZZ-97-25 Component VI, the EMIS EG prepared the draft Danube List
of Priority Substances. At the 1st Meeting of the Joint MLIM/EMIS Working Group in February 2003
this draft was discussed and it was suggested to keep the Annex A as prepared by the EMIS EG
(identical with the EU WFD list). The Annex B was proposed to be divided into two groups General
Parameters (COD, NH4, N, P) and Danube Specific Priority Substances (As, Co, Zn, Cr). The ICPDR
at its 1st Standing Working Group meeting in June 2003 agreed with the proposed Danube List of
Priority Substances but considered it only as provisional. To arrive at a final list the national targeted
screenings for EU WFD Priority Substances will have to be performed to prove their relevance for the
specific area/region.

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UNDP/GEF Danube Regional Project
For the determinands, which newly appeared in the proposed Danube List of Priority Substances it
was necessary to make available the respective standard operational procedures (SOPs). The overview
of SOPs provided in the technical report takes into account the results of the review on possibilities to
analyze the EU WFD priority substances in the Danube countries, which was performed by the MLIM
EG in 2002. An attention was also paid to the activities of the Expert Group on Analysis and
Monitoring of Priority Substances (AMPS) working under the "EU Expert Advisory Forum on Priority
Substances and Pollution Control". The recommended standard operational procedures are divided
into two groups - priority substances from the DECISION No. 2455/2001/EC and geneneral
parameters and priority substances specific for the Danube River Basin.

5. Proposal (recommendations for) an upgrade of the TNMN by including the Danube
List of Priority Substances, taking into account the 5 years data of TNMN
The objective of this report was to assess water quality in Danube River basin, including cla ssification
and identification of spatial and temporal changes. The basis for assessment is data on physico-
chemical and biological determinands collected in the frame of TNMN in five-years period 1996
2000. The main assessment objectives were as follows:
ˇ Checking of compliance with water quality target values expressed by joint
classification prepared for Danube River Basin;
ˇ Identification of water quality changes along the Danube River;
ˇ Detection of trends in water quality;
ˇ Assessment of dangerous substances content in water in accordance to EQS
established or proposed for use in EU.
In general, following facts concerning classification and trend evaluation of the processed TNMN data
should be highlighted:
Nutrients
Ammonium-N and nitrite-N concentrations increase from upper to lower Danube. In the Danube
River, 53.3 % of ammonium-N and 37.2 % nitrite-N values were found to be above the target limits
for these determinands. A special concern should be paid to the ammonium-N content recorded on the
Arges river, where all five yearly values of C90 in time period 1996-2000 were above the limit for
Class V; these extremely high values, correlated with BOD5 values, show the impact of untreated or
insufficiently treated waste waters from municipalities. In the Danube River, occurrence of
ammonium-N shows a decreasing tendency from 1996 to 2000 in the upper part and in the middle
section in Slovak monitoring sites.
The spatial distribution of nitrate-N concentrations shows a decrease from upper/middle to lower
Danube. Tributaries with the highest content of nitrate-N are Morava, Dyje, Sio in the upper/middle
part, and Iskar, Russenski Lom, Arges and Prut in the lower part of river basin. For nitrate-N
concentrations the fluctuations in time profile are low for the Danube River, but rather high for the
tributaries.
Orthophosphate-P shows a spatial pattern similar to that of total phosphorous characterized by a slight
increasing profile from upper to lower Danube. In the upper/middle part of the Danube a decreasing
tendency in P concentration is seen in the section from Danube-Bratislava (km 1869) down to
Danube-Szob (km 1708) with an exception at Danube-Medvedov/Medve (km 1806). In general, the
time variance of total P concentrations is much higher than that of ortho-phosphates.
Heavy metals
Except of manganese, for which a maximum of the spatial profile is present in the middle Danube
reach, for most of the discussed heavy metals the general pattern is an increase from the upper and
middle to the lower Danube. Furthermore, the heavy metals content in some tributaries mainly those
located in the lower Danube - is higher than the content in the Danube River itself.
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The contamination of the Danube River by lead and copper was found rather high. A slightly better
was the situation for cadmium and mercury with 47.4% of values exceeding cadmium target level and
36.6% of values exceeding mercury target level. In general, relatively high fluctuations of heavy metal
concentrations were observed along the Danube. Despite these uncertainties the development of heavy
metal content in some tributaries was found positive a decrease is indicated in Drava river
(cadmium, chromium, copper, lead, nickel and zinc), in Arges (cadmium, chromium, copper, lead),
Prut (cadmium, chromium, lead) and in Siret (chromium, copper, lead).
In general, five years trends of heavy metal pollution can hardly been evaluated because a relatively
high deviation of results occurred. High values of heavy metals often result from high loads of
suspended solids caused by flood events. The statistical parameter used in this report (90% percentile)
was certainly influenced by such hydrological processes. For this five-years evaluation report the
data on total concentration of heavy metals in water samples had been used because data related to
dissolved fraction was not available in sufficient amount. Therefore, it must be stressed that such a
rather scattered pattern of the heavy metal pollution data for the water matrix clearly supports future
orientation of TNMN activities on the solid phase, i.e., in TNMN planning activities the analysis of
suspended solids and sediments should be preferred.
Oxygen regime
Dissolved oxygen concentrations show positive results, with only 7.4% of values being below the
quality target in the Danube River and 8.6% being below the quality target in monitored tributaries.
Oxygen concentration decreases from upper to lower part of the Danube River, lowest values being in
the section from Danube-Bazias to Danube-Novo Selo/Pristol. As for the tributaries, rather low
oxygen content was identified in those located in the lower part of the river basin.
As for BOD values 13.3% of them are above the target value in the Danube River (mainly in the
middle and in the lower sections) and 35.9% exceed the target value in tributaries. Organic pollution
expressed by BOD increases along the Danube, reaching its maximum in the secion from Danube-
Dunafoldvar (rkm 1560, H04) to Danube-Pristol/Novo Selo (rkm 834, RO02). The tributaries most
polluted by degradable organic matter are Morava, Dyje and Sio in the upper/middle part of the
Danube mainstream and Russenski Lom and Arges in the lower part.
For CODCr, 22.4% of all values for the Danube mainstream and 39.7% for tributaries were found
above the quality target; the situation is more positive in case of CODMn - no value above this limit
for the Danube River and 18.2% for tributaries. In principle, the results obtained for CODCr and
CODMn show the highest values in the lower part of the Danube River.
Organic micropollutants
The organochlorine compounds (Lindan and p,p'-DDT) showed similar spatial profile, with an
increasing pattern from upper/middle to lower Danube. The polar pesticide Atrazine was undetectable
at most of the monitoring sites along the Danube River, only 12.5% of the data were found above the
target limit. In tributaries, 30% of Atrazine values were above the quality target, the maximum values
were found in rivers Sio and the Sajo.
For the volatile organic compounds, data is available for upper and middle Danube only. Chloroform
and tetrachloroethylene show values above the target limits in a following pattern: 29.0% of the
Danube samples and 39.5% of the samples taken from tributaries exceeded the target values for
chloroform, for tetrachloroethylene the respective numbers were 13.6% for the Danube and 7% for
tributaries. The situation was found to be better for tetrachloromethane and trichloroethylene - in the
Danube River mainstream no value was detected above the target limit for these compounds, while in
tributaries only a small percentage of all data (2.3%) was above the target limits for both these
determinands.

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UNDP/GEF Danube Regional Project
Biological determinands
Evaluation of saprobic index of macrozoobenthos using Austrian standard ÖNORM M6232 showed
that the Danube River and most of its tributaries correspond to classes II II-III. Only Sava River was
characterized by a worse quality class (III III-IV), however, within the years the situation improved.
In 1996 2000 the microbiological water quality corresponded to classes I IV in the Danube River
mainstream. Some tributaries, as e.g., Vah, Tisza and Siret can be characterized as extensively
polluted, however, data from many other relevant tributaries is missing. It was observed that
sedimentation had positive effects to number of total coliforms below Gabcíkovo Reservoir, Iron
Gates and in Danube Delta as well.
For biological determinands a slightly positive time trend appeared in case of saprobic index of
macrozoobenthos, but no significant trend in microbiological determinands was observed.

6. Development of a methodological concept for assessment of environment stress and
impacts as a basis for preparation of a computer-based application for stress-impact
analysis
In this activity a concept for a computer based application was developed assessing the relation
between a pressure (the emission of a pollutant by a point source) and the downstream increase of the
concentration of a pollutant ("state"). For this concept the use of existing databases (EMIS, TNMN)
and existing models or modules from these models (MONERIS, DBAM, DWQM) was considered.
Assessing different conceptual choices using the above mentioned models/modules three different
functionalities were defined:
Detection of pressure based on observed concentration increase (accidental pollution pressures)
This application would consist of an "inverse DBAM" model. In its simplest form, the application
could be based on a large database of computed pollutant clouds C(t) by DBAM, for different spill and
observation positions, under different hydrological conditions. By comparing the observed cloud of
pollutants with the database of clouds, given the actual hydrologic conditions, potential spill sites can
be observed. Under the assumption that the removal rate of the pollutant is known, the spill mass can
be back-computed.
Detection of pressure based on observed concentration increase (regular pollution pressures)
The application would start from an observed trend-wise increase of the concentration of a given
substance at a given location from one year to another. Upstream point sources which show a
corresponding increase of their emissions could be detected and listed. The decay rate of the substance
in question could be taken into account to eliminate pollution sources too far away for their emitted
pollutants to reach the observation point.
Effects of pollution reduction measures (only regular pollution pressures)
This application could consist of an application like the present DBAM, with some modifications: a
continuous spill should be modelled instead of an accidental spill, average hydrological conditions
should be used rather than actual conditions. To keep things simple, the application should include
only one particular point source for which reduction measures need to be analysed. The background
pollution from the other point sources and from diffuse sources needs to be back-computed for any
selected observation location. The computed concentration from the point source in question before
the reduction is subtracted from the present concentration at the observation point: the difference is the
background concentration. The total concentration after reduction is obtained by adding the computed
concentration from the point source in question after the reduction to the background concentration.
From assessment of practical implications of the three proposed functionalities it was clear, that the
development of the computer based application for stress-impact analysis, which can calculate a
quantitative relation between a point source and downstream changes in concentration levels or vice
versa, will require a major investment in model/software development.
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Therefore, a simpler practical concept was proposed as an alternative solution. In this case, the data of
the TNMN would be the starting point for further analysis. If for a pollutant a significant concentration
increase is observed during, e.g., 2-3 months, analysis of more upstream stations should indicate
between which two stations the increase has started. In that stretch of the river the discharge should
occur. At that point, a link with the EMIS database should be made to identify the point source.
Such a solution would require a proper coverage by the TNMN, in particular at the discharge of major
tributaries and small tributaries with relevant point sources. A direct link with the EMIS database can
be made through the geographical codes in both databases. Results should be presented in GIS. This
concept would require adjustments in the TNMN as well as the development of a link between TNMN
and EMIS based on GIS.

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UNDP/GEF Danube Regional Project

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