Sediment Quality Management under the ICPDR

Igor Li ška ICPDR Secretariat 2 The River Protection Convention

A legal frame for co -operation to assure the protection of water and ecological resources and their sustainable use in the Danube River Basin 3

According to the Article 9 of the DRPC the Contracting Parties to DRPC have agreed to co -operate in the field of monitoring and assessment of the water resources. 4

TNMN

• Based on national monitoring networks • 78 sampling stations (72 provided data in 2002) • 52 determinands in water • Minimum sampling frequency 12/year (chem ) 2/year ( biol ) 5

o o o o o o o o o 10 12 30' 15 17 30' 20 22 30' 25 27 30' 30

o Praha 50 M o PL ra UA v a S D v a it cv a e O v B n b a CZ d a a a v A N l S a P tm v H rut ü J r orn h ih a a ad MD01 l la tk v R va a a h o e r a ra ge D D o it S n yje M V Sla ire 47 30' yj N na t e va Jijia a g a MD e CZ01 m ro z ub SK i d is n D02 R o T Da CZ02 H09 B o j P A03 a a B z r sar S is u r D01 I n T T t i n a So g I A02 Ipel mes o r h A01 SK01 n M c c a o h ld e WienA04 SK04 C ova Kishinev L S ra a Danube a sn lz th a s e SK03 Z a L H Br s München o eg i D04 c gy h H01 v R H03 a B r A lyd is e th tr l - e i l r er tj I H02 D03 e B a s b MD04 o Enn i de re epe 47 30' a t ul R es b h m Cris m a ü a o K e S R tr s S n i In r S rös e io Kö t 3 l Cr 0 H04 tz isu i e l Ne D v n gro M P lo n e Zala T a s i E n s h ic s c Ismail a z Cr o Danube isul A p a lb SL01 M a u K H08 o ra H06 S 45 av Dravina inja Mures RO Sa RO v D ca 05 a ra H05 SCG10 ran HR03 va A HR04 a H07 SCG01 eg Tamis I Ljubljana B ZagrebHR HR01 SCG02 SCG11 SL S Ialomita a HR05 SCG03 HR06 v HR02 BLACK a SCG09 SCG12 Ar HR07 ges Kupa Bucuresti SEA HR08 SCG04 RO04 BIH01 SCG06 J SCG14 SCG07 i SCG05 RO01 u RO09 BIH02 a Beograd o a S in n r BIH04 O 45 U a BIH03 k B SCG13 BG05 n SCG08 l U t a V o va SCG16 SCG17 s r a RO03

b SCG15 S n RO02 BG04

a a

s M BG02 BG08 Be o li r Danube L a BG01 o v R m FRY a u BIH s BG03 . m J L Lo an o t m a S m a ra J t a c o u os k s i z g û s . O t r O o 42 30' a M a t R n k i ri o s I V D ra v Sarajevo a

Z T a a p ra . M Piva o r Sofia a v a BG

FYROM 0 50 100 150 250 250 km

Monitoring location on the Danube River on the tributary 6 Determinand Unit Class I II - TV III IV V Class limit values Oxygen/Nutrient regime Dissolved oxygen * mg.l -1 7 6 5 4 < 4 -1 BOD 5 mg.l 3 5 10 25 > 25 -1 COD Mn mg.l 5 10 20 50 > 50 -1 COD Cr mg.l 10 25 50 125 > 125 pH - > 6.5 * and < 8.5 Ammonium -N mg.l -1 0.2 0.3 0.6 1.5 > 1.5 Nitrite -N mg.l -1 0.01 0.06 0.12 0.3 > 0.3 Nitrate -N mg.l -1 1 3 6 15 > 15 Total -N mg.l -1 1.5 4 8 20 > 20 Ortho -phosphate -P mg.l -1 0.05 0.1 0.2 0.5 > 0.5 Total -P mg.l -1 0.1 0.2 0.4 1 > 1 Chlorophyll -a µg.l -1 25 50 100 250 > 250 Metals (total) Zinc µg.l -1 bg 100 200 500 > 500 Copper µg.l -1 bg 20 40 100 > 100 Chromium (Cr -III +VI) µg.l -1 bg 50 100 250 > 250 Lead µg.l -1 bg 5 10 25 > 25 Cadmium µg.l -1 bg 1 2 5 > 5 Mercury µg.l -1 bg 0.1 0.2 0.5 > 0.5 Nickel µg.l -1 bg 50 10 0 250 > 250 Arsenic µg.l -1 bg 5 10 25 > 25 Toxic substances AOX µg.l -1 10 50 100 250 > 250 Lindane µg.l -1 0.05 0.1 0.2 0.5 > 0.5 p,p´ -DDT µg.l -1 0.001 0.01 0.02 0.05 > 0.05 Atrazine µg.l -1 0.02 0.1 0.2 0.5 > 0.5 Trichloromethane µg.l -1 0.02 0. 6 1.2 1.8 > 1.8 Tetrachloromethane µg.l -1 0.02 1 2 5 > 5 Trichloroethene µg.l -1 0.02 1 2 5 > 5 Tetrachloroethene µg.l -1 0.02 1 2 5 > 5 7

10 o 12o 30' 15 o 17o 30' 20 o 22o 30' 25 o 27o 30' 30 o

Praha o 50 M o PL ra UA v a S D v i a t cv a e O v B b a n CZ d a a a A v N l S a P tm v H rut ü J r orn h ih a a ad MD01 l R lav tk v e a a ra h a o g D o a tr e y D V i n S S 47 30' n je M N Hro la ire yj na t e va Jijia a g a MD e CZ01 m ro z ub SK i d is n D02 R o T Da CZ02 H09 B o j P A03 a a B z r sar Bratislava S is u r D01 I n T T t i n a So g I A02 Ipel mes o r h A01 SK01 n c M c a o h ld e WienA04 SK04 C ova Kishinev L S ra a Danube s l a n z th a s e SK03 Z München a L o H B s reg i D04 c gy h H01 v R H03 a B r A i lyd st e th r l - e i l r er tj I D03 H02 e B a s b MD04 o Enn i de re epe 47 30' a t Budapest ul R s b h m ris e ü a C om a K e S R tr s S n i In r S rös e io Kö t 3 z l Cr 0 H04 t isu i e l Ne D v n gro M P lo n e Zala T a s i E n s h ic c C Ismail a s z Drava o Danube risul p a Alb SL01 M a u K H08 o ra H06 45 Sav Dravina inja Mures RO Sa RO v D ca 05 a ra H05 SCG10 Aran HR03 HR04 va H07 ga SCG01 Be Tamis I Ljubljana ZagrebHR HR01 SCG02 SCG11 SL S Ialomita a HR05 SCG03 HR06 v HR02 BLACK a SCG09 SCG12 Ar HR07 ges Kupa Bucuresti SEA HR08 SCG04 RO04 BIH01 SCG06 J SCG14 SCG07 i RO01 u RO09 BIH02 SCG05 a Beograd o na S in U BIH03 r BIH04 O 45 a k SCG13 BG05 B n SCG08 l U t a V o va SCG16 SCG17 s r SCG15 a RO03 b S n RO02 BG04 a a

s M BG02 BG08 Be o li r Danube L a BG01 o v R m FRY a u BIH s BG03 . m J L Lo an o S m a tra m J ta a c u os k s i o z g ű s The Danube . O t r O o 42 30' a M a t R n k i ri o s I V D ra v 0 50 100 150 250 250 km Sarajevo a

Z a Ta p ra . M Piva o r Sofia a v a Legend BG class I class II class III FYROM class IV class V Figure 6.5: no data - The classification of NO3 - N in 2002 10 o 12o 30' 15 o 17o 30' 20 o 22o 30' 25 o 27o 30' 30 o

Praha o 50 M o PL ra UA v a S D v i a t cv a e O v B b a n CZ d a a a A v N l S a P tm v H rut ü Ji r orn h hl a a ad MD01 l R av tk v e a a ra h a o g D o a tr e y D V i n S S 47 30' n je M N Hro la ire yj na t e va Jijia a g a MD e CZ01 m ro z ub SK i d is n D02 R o T Da CZ02 H09 B o j P A03 a a B z r sar Bratislava S is u r D01 I n T T t i n a So g I A02 Ipel mes o r h A01 SK01 n c M c a o h ld e WienA04 SK04 C ova Kishinev L S ra a Danube a sn lz th a s e SK03 Z München a L o H B s reg i D04 c gy h H01 v R H03 a B r A lyd is e th tr l - e i l r er tj I H02 B a D03 e MD04 s b o Enn i de re epe 47 30' a t Budapest ul R s b h m ris e ü a C om a K e S R tr s S n i In r S rös e io Kö t 3 z l Cr 0 H04 t isu i e l Ne D v n gro M P lo n e Zala T a s i E n s h ic c C Ismail a s z Drava o Danube risul p a Alb SL01 M a u K o ra H06 H08 S Dra 45 avin vina Mures RO S ja RO av D ca 05 a ra H05 SCG10 ran HR03 va A HR04 a H07 SCG01 eg Tamis I Ljubljana B ZagrebHR HR01 SCG02 SCG11 SL S Ialomita a HR05 SCG03 HR06 v HR02 BLACK a SCG09 SCG12 Ar HR07 ges Kupa Bucuresti SEA HR08 SCG04 RO04 BIH01 SCG06 J SCG14 SCG07 i RO01 u RO09 BIH02 SCG05 a Beograd o na S in U BIH03 r BIH04 O 45 a k SCG13 BG05 B n SCG08 l U t V o a a v SCG16 SCG17 s a r SCG15 RO03 b S n RO02 BG04 a a

s M BG02 BG08 Be o li r Danube L a BG01 o v R m FRY a u BIH s BG03 . m J L Lo an o S m a tra m J ta a c u s k s i o z go ű s The Danube . t r O o 42 30' a O M a t R n k i ri o s I V D ra v 0 50 100 150 250 250 km Sarajevo a

Z a Ta p ra . M Piva o r Sofia a v a BG Legend class II class III FYROM class IV class V Figure 6.9: no data The classification of Cd in 2002 9 Analytical Quality Control

Variation in the reported values of NO 3-N and TP in AQC water samples 10

Load assessment programme

• Integrated with the TNMN

• Load s are calculated for BOD 5, inorganic nitrogen, ortho -phosphate -phosphorus, dissolved phosphorus, total phosphorus, suspended solids and chlorides (voluntary) • Minimum sampling frequency - at least 24 per year 11 Annual loads of suspended solids at monitoring stations along the Danube River in 2002

7 8000

7000 6 RO02 6000 5 tons) 6 ) 5000 -1 .s 4 3 4000 3 SK01 A04 3000 H05 RO05 discharge (mdischarge

2 D02+A01 2000 suspended solids (x 10 (x solids suspended RO04 H03 1 1000

0 0 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400 200 0 distance from the mouth (km)

suspended solids discharge TNMN sediment monitoring

Determinands in sediments Unit Minimum Principal Target Limit Tolerance (dry matter) likely level level of of Detection of int erest interest Organic Nitrogen mg/kg 50 500 10 10 or 20% Total Phosphorus mg/kg 50 500 10 10 or 20% Calcium (Ca 2+ ) mg/kg 1000 10000 300 300 or 20% Magnesium (Mg 2+ ) mg/kg 1000 10000 300 300 o r 20% Iron (Fe) mg/kg 50 500 20 20 or 20% Manganese (Mn) mg/kg 50 500 20 20 or 20% Zinc (Zn) mg/kg 250 500 50 50 or 20% Copper (Cu) mg/kg 2 20 1 1 or 20% Chromium (Cr) – total mg/kg 2 20 1 1 or 20 % Lead (Pb) mg/kg 2 20 1 1 or 20 % Cadmium (Cd) mg/ kg 0.05 0.5 0.05 0.05 or 20% Mercury (Hg) mg/kg 0.05 0.5 0.01 0.01 or 20% Nickel (Ni) mg/kg 2 20 1 1 or 20 % Arsenic (As) mg/kg 2 20 1 1 or 20 % Aluminium (Al) mg/kg 50 500 50 50 or 20% TOC mg/kg 500 5000 100 100 or 20% Petroleum hydrocarbons mg/kg 10 100 1 1 or 20 % Total Extractable matter mg/kg 100 1000 10 10 or 20 % PAH – 6 (each) mg/kg 0.01 0.1 0.003 0.003 or 30% Lindane mg/kg 0.01 0.1 0.003 0.003 or 30% pp’DDT mg/kg 0.01 0.1 0.003 0.003 or 30% PCB – 7 (each) mg/kg 0.01 0.1 0.003 0.003 or 30 % 13 TNMN sediment monitoring

• Only few countries participated • Regular sediment monitoring considered as superfluous in some countries (low cost/information gain) • Therefore – regular monitoring replaced by investigative surveys (each 5 -6 years) Joint Danube Survey - Objectives

• To produce a homogenous data set for the Danube River based on a single laboratory analysis of selected determinands; • To identify and confirm specific pollution sources;

• To screen the pollutants as specified in the proposed EU Water F ramework Directive; • To provide a forum for riparian/river basin country participatio n for sampling and intercomparison exercises; • To facilitate specific training needs and improve in -country experience; • To promote public awareness. 15 JDS – activities

• Surface water, sediment, mussels and biological (macrozoobenthos, phytobenthos , macrophytes , phytoplankton, zooplankton) samples were collected from 98 sampling sites • Suspended solids samples were collected from 63 sections of the Danube • Fifteen parameters ( e.g., conductivity, dissolved oxygen, nitrites, nitrates, total coliforms , faecal coliforms ) were analysed on -board • All samples were sent in regular intervals to the JDS Reference Laboratories for analyses of more than 80 additional determinands • JDS National Teams worked together with the JDS Core Team, collected samples from the respective national stretches of the Danube and analyzed them in parallel 16

JDS 21,22 Sap; Ásványráró UA 1812 JDS 17 UA JDS 02 JDS 04 Bratislava Kelheim Kachlet 1869 JDS 23 2412 2233 JDS 12 Medvedov D JDS 16 Klosterneuburg 1806 1942 tr. JDS 24 JDS 06 Moson Danube arm / end JDS 01 1880 Jochenstein JDS 14 1794 Neu l 2204 Wildungsmauer müh JDS 29 2581 lt 1895 M SK JDS 30 A JDS 08 tr. Hron JDS 10 o JDS 26 r tr. Ipoly Asten Ybbs a 1716 v tr. Vah 1708 2120 2061 a JDS 25 1766 JDS 03 r h a Komarno c Geisling Is e 1768 L 2358 Bratislava JDS 31 MD n n V Szob JDS 32,33 I a Kishinev r h e JDS 11 Szetendre Island s ll JDS 05 1707 is I Greifenstein 1691 R tr. s JDS 34 Munich A n 1950 2225 n upstr. Budapest E H JDS 09 JDS 13 1659 JDS 07 Wallsee JDS 27 tr. Schwechat JDS 36 Aschach 2096 a Iza/Szony Budapest 1913 b tr. Rackeve arm start 2165 a 1761 JDS 28 R JDS 37 JDS 15 1642 downstr.Budapest upstr. Morava 1719 JDS 96 1881 1632 JDS 38 Vilkova JDS 94 Chilia arm JDS 40 tr. Rackeve arm end JDS 18,19 56 Dunafoldvar JDS 39 1586 Hrusov reservoir Tass 135 1560 P 1856,1852 JDS 41 r JDS 95 1586 u JDS 20 Paks S t Reni Ismail i JDS 43 r Gabcikovo reservoir 2 JDS 42 1533 e 130 1846 Baja JDS 64 JDS 93 t tr. Sio tr. 1497 1497 Banatska Palanka/Bazias JDS 44 154 Hercegszanto 1071 JDS 63 JDS 45 1434 JDS 46 RO upstr. Drava Starapalanka - Ram JDS 92 JDS 98 BLACK Batina JDS 52 JDS 65 JDS 82 1384 1077 Braila St. Gheorghe arm 1424 downstr. Irongate reservoir downstr. Jantra SEA Zagreb JDS 48 JDS 54 167 64 D 1252 (Golubac/Koronin) 532 ra tr. Tisa va downstr. Drava 1040 JDS 89 JDS 97 1367 T 1215 Chiciu/Silistra arm HR i JDS 80 JDS 47 s JDS 66 a 378 12 T Svishtov ita tr. Drava a Irongate reservoir m m o 1379 JDS 49 JDS 55 550 al i (Tekija/Orsova) Bucurest I Borovo s downstr. Tisa 956 JDS 75 JDS 91 1337 JDS 53 1202 Danube downstr. Giurgeni upstr. Tisa JDS 67 Arg 235 Vrbica/Simijan 629 es 1216 JDS 87 JDS 50 924 0 50 100 150 250 250 km tr. Arges /Backa Palanka a JDS 73 JDS 77 JDS 51 v 432 JDS 88 1300 a JDS 68 upstr. Iskar tr. upstr. Novi Sad S downstr. Arges JDS 90 a upstr. 640 O 605 1262 v 429 upstr. Cernavoda a J lt JDS 86 r 849 iu 295 o R upstr. Arges M us 434 JDS points Danube . L JDS 69 om O BIH a r s tr. Timok r JDS 85 a t a t JDS points tributary i k s m n 845 m S I V downstr. Ruse o ta a s k J JDS 83 L go û 488 tr. = tributary JDS 70 O t JDS 74 JDS 79 upstr. Ruse Sarajevo Novo Selo tr. Iskar Nikopol 500 upstr. = upstream 834 637 579 JDS 84 JDS 71 JDS 72 JDS 81 tr. Russenski Lom downstr. = downstream tr. Jantra 498 FRY downstr. Kozloduy JDS 76 795 537 685 upstr. Olt Number JDS point 606 JDS 01 JDS 78 Neu Ulm Location Sofia downstr. Olt BG 602 2581 Danube km

Reach 1 Reach 2 Reach 3 Reach 4 Reach 5 Reach 6 Reach 7 Reach 8 Reach 9 17

Cadmium in Sediments

35 Danube Tributaries 30

25

20

15 [µg/g]

10

5

0 3000 2500 2000 1500 1000 500 0 River-km 18

Mercury in Sediments

Danube Tributaries 4

3,5

3

2,5 JDS4R - Kachlet 2 [µg/g] 1,5 JDS96L - Vilkova 1

0,5

0 3000 2500 2000 1500 1000 500 0 River-km 19 Spatial distribution of selected elements (logarithmic scale) in suspended solids samples of the Danube river (without tributaries) 100000

10000

Aluminium Iron Arsenic Chromium Nickel 1000

100

10 Concentration,µg/g

1 2500 2000 1500 1000 500 0 River-km 20 Concentration of Cadmium in the investigated sediments core samples

[µg/g] 0 1 2 3 4 5 6 7 8 0

10

20

30

40

50

60 Depth [cm] 70

80 JDS20 (Gabcikovo Reservoir) < 1.1 µg/g 90 JDS36 (Rackeve Soroksar Danube Arm) JDS63-L (Irongate Reservoir) 100 JDS63-R (Irongate Reservoir) 21 Significant changes in the element concentration between layers of the sediment cores (concentration difference > uncertainty of the analytical procedu re )

Element As Cr Hg Pb Cu Ni Cd Zn Fe Mn Al

Uncertainty of Analytical Method [%] 15 11 14 14 7 8 11 10 11 10 15

Gabcikovo Reservoir (JDS20) ≈ ≈  ≈ ≈ ≈ ≈ ≈ ≈ ≈ ≈

Rackeve -Soroksar Danube (JDS36) ≈ ≈  ≈  ≈  ≈ ≈ ≈ ≈

Irongate Reservoir (JDS63 -L)     ≈    ≈ ≈ ≈

Irongate Reservoir (JDS63 -R)     ≈  ≈  ≈ ≈ ≈

(“” - decreasing temporal trend , “” - increasing temporal trend , “≈” – no significant change )