HEAVY METALS

IN THE UPPER AND MIDLE ODRA RIVER SYSTEM

RECOMMENDATIONS FOR TRANSBOUNDRY RIVER

CHEMICAL MONITORING

E. Adamiec, E. Helios –Rybicka, M. Skwarczek

University of Mining and Metallurgy,

Faculty of Geology, Geophysics and Environmental Protection Al. Mickiewicza 30, Cracow, Poland

The Odra River catchment area

136 528 km2

84.9 % in Poland,

10.4 % in Germany,

4.7 % in the Czech Republic.

Study area - about 70 % of the total Odra catchment

the upper and middle Odra river section –

from Chałupki to the Nysa Klodzka river outlet.

Objectives

(1) To establish the spatial variability in concentrations

of heavy metals (Cd, Zn, Pb, Cu, Ni, Cr, Mn, Fe, As)

for PSM and bottom sediments in the upper and

middle Odra river system.

(2) To assess the level and extent of contamination by

comparison with the river solids classification or

geochemical background standards, and to identify

any need for monitoring and/or remediation.

(3) To estimate the mobility and potential bioavailability

of metals in the river PSM and sediments.

(4) To define kind and measuring frequency of the

parameters for an improvement of the river chemical

monitoring.

Sampling and Methods

In the Years 1997 - 2001 totally about 100 samples of each component

in five sampling campaign: 11’97, 05’98, 11’98, 06’99, 05’2000

(1) water

(2) suspended matter – (filters of 0.45 µm diameter)

(3) bottom sediments - (the < 20 µm)

Analysis

• Total amount of heavy metals concentration

• Mobile fraction - exchangeable and carbonatic bound metals

• Buffer capacity of sediments

• Acidic metal leachibility from sediments

Data quality control

• Analyses were subject to sampling and analytical quality program

Robust Analysis of Variance, with ROB2 program

(1) Cd, Ni, Cr, Cu measurements indicates an excellent

precision - percentage of the analytical and technical

variances is < critical value of the total variances 4% and

20%, respectively,

(2) Analytical variance for Pb (5%) slightly exceeds. For Mn

and Zn analytical variance is 7 % and 9%, respectively.

(3) Analytical variance for As and Fe - not enough satisfying.

(4) Sampling variances for all samples in both cases for

suspended matter and sediments are satisfying and not

exceed 16% of total variances.

(5) Sediments - analytical precision is satisfying for Cu, Zn,

and Mn and not enough satisfying. for Cd, Pb.

Reagent blanks and certified reference materials

• (Lake Sediment LSKD-4, River Sediment 1645, Sediment CRM 7002)

were used to assure quality criteria. ICP-MS was confirmed for PSM

by TXRF, and for sediments with AAS measurements.

As Cd Cu Ni Pb Zn mg/kg

SPM n= 101

SPM Conc. mg/l

min 1,2 8,0 1,8 6,2 22,1 24,4 351 max 116 302 39,8 493 1287 401 31369 arithm.mean 28,9 63,8 9,3 98,4 133 110 1867 geom.mean 23,0 50,5 8,0 77,9 88,9 98,0 1321 median 26,5 52,9 7,3 79,2 81,6 97,2 1221 SD 18,9 47,4 6,2 76,3 165 55,9 3430 Sediments n= 90

fr.<20 µm %

min 2,2 5,0 3,0 31,3 37,0 19,2 333 max 63,8 516 21,7 298 108 343 2591 arithm.mean 28,6 92,1 9,4 110,0 51,6 123 1158 geom.mean 24,0 52,2 8,9 97,9 50,8 114 1098 median 28,4 67,9 8,9 92,7 49,9 119 1158 SD 14,3 113 2,98 55,1 10,0 49,6 359

Tab. 1. Statistical parameters of heavy metals concentrations in the suspended particulate matter (SPM) and bottom sediments of the upper and middle Odra river; SPM concentrations and content of the <20 µm sediment fraction.

As

44 39

13 1 2 10

10

20

30

40

50

<50 <100 <150 <200 <250 > 250mg/kg

Cd

16

54

18 6 3 30

10

20

30

40

50

60

<5 <10 <15 <20 <25 > 25mg/kg

Pb

10

45

23 183 1

0

10

20

30

40

50

<50 <100 <150 <200 <250 >250mg/kg

Zn

38 43

13 2 2 20

10

20

30

40

50

<1000 <2000 <3000 <4000 <5000 > 5000mg/kg

As

3726

161 7

0

10

20

30

40

<50 <100 <150 <200 > 200mg/kg

Cd

4

62

22 1 20

10

20

30

40

50

60

70

<5 <10 <15 <20 > 20mg/kg

Pb

1

35 37

123 3

0

10

20

30

40

<50 <100 <150 <200 <250 >250mg/kg

Zn

422

53

10 1 10

10

20

30

40

50

60

<500 <1000 <1500 <2000 <2500 >2500mg/kg

Frequency distribution of Zn, Cd, Pb and As occurring in suspended matter

and sediments samples of the upper and middle Odra River.

11'97 05'00 11'97 05'00 11'97 05'00 11'97 05'00Cd Cu Zn

ŚwinoujscieSPM

Pb

11'97 05'00 11'97 05'00 11'97 05'00 11'97 05'00

n.s n.s n.s n.s

n.s n.s n.s n.s

LAWA classes [mg/kg] Cu Cd Zn PbIV Very strongly contaminated 640 9.6 3200 800

III-IV Strongly to very strongly contaminated 320-640 4,8-9,6 1600-3200 400-800III Strongly contaminated 160-320 2,4-4,8 800-1600 200-400

II-III Moderately to strongly contaminated 80-160 2,4-1,2 400-800 100-200II Moderately contaminated 40-80 1,2-0,6 200-400 50-100

I-II Unpolluted to moderately contaminated 20-40 0,6-0,3 100-200 25-50I Uncontaminated <20 <0,3 <100 <25

IV Brama TorowaRoztoka Od.

PoliceGryfino

II Brama TorowaŚwinoujscie

ChałupkiKrapkowice

II Brama TorowaŚwinoujscie

Opole

WiduchowaKrajnik

Osinów DlnCzelin

Ścinawa

SłubiceAurith

Eisenhuttenstadt

Zn Pb

IV Brama Torowa

Opole-Gr.

Krosno Od.Nowa SólBrzeg Gł.

Głogów

Wrocław J.

Roztoka Od.Police

GryfinoWiduchowa

KrajnikOsinów Dln

Czelin

GłogówŚcinawa

SłubiceAurith

EisenhuttenstadtKrosno Od.

Chałupki

SedimentCd Cu

Wrocław J.Opole

Opole Gr.Krapkowice

Nowa SólBrzeg Gł.

The heavy metals situation in the Odra River suspended matter and bottom

sediments from November 1997 and May 2000, expressed in LAWA classes.

ODRA RIVER SEDIMENTS (<20µm)

Optimisation procedure for four years results 1. Demonstration of the metal “trend” lines for every

sampling campaign on the basis of each metal distribution in the solids samples, over the five sampling campaigns.

2. Calculation of metal arithmetical mean values from five

sampling campaigns. 3. Selection of the samples groups, based on the results of

arithmetical means for each metal, from five sampling campaigns.

4. Calculation of metal arithmetical mean values from

selected sample sets in the particular groups, which allow to proposed only one sampling point for each of the selected Odra river sections (at the most six sampling points).

0

5

10

15

20

25

30

35

40

45

OR01CH OR03CS OR05KR OR06OG OR07OP OR08KP OR12WB OR13WJ OR16MA OR17SC OR19GL OR20BG OR21BO OR22NS OR23CI OR24NI OR25KO

mg/kg

0

4

8

12

16

20

21 55 84 127 144 156 184 247 268 334 397 407 430 471 490 516 km

mg/kg

0

5

10

15

20

to 99 99-127 127-247 247-268 268-407 407-516

km

mg/kg

0

5

10

15

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Suspended matter

Cd

I

II

III

IV

As

0

20

40

60

80

100

120

21 55 84 127 144 156 184 247 268 334 397 407 430 471 490 516 km

mg/kg

Pb

0

50

100

150

200

21 55 84 127 144 156 184 247 268 334 397 407 430 471 490 516km

mg/kg

Cd

0

4

8

12

16

20

21 55 84 127 144 156 184 247 268 334 397 407 430 471 490 516km

mg/kg

Cu

0

40

80

120

160

21 55 84 127 144 156 184 247 268 334 397 407 430 471 490 516 km

mg/kg

Zn

0

1000

2000

3000

4000

5000

21 55 84 127 144 156 184 247 268 334 397 407 430 471 490 516 km

mg/kg

Odra River Course

Distribution of As, Cd, Pb, Cu and Zn (arithmetical mean values of metal

concentration in the suspended matter samples from five sampling campaigns)

with their “trend” lines along the upper and middle Odra river course.

Cu

0

30

60

90

120

150

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Zn

0

500

1000

1500

2000

2500

3000

to 99 99-127 127-247 247-268 268-407 407-516km

mg/kg

Pb

0

50

100

150

200

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Cd

0

5

10

15

20

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

As

0

20

40

60

80

100

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Odra River Course

Mean concentration of As, Cd, Pb, Cu and Zn for suspended matter samples grouped in six sets along the upper and middle Odra river course (each bar

correspond with arithmetical mean value of metals from five sampling campaigns).

As

0

20

40

60

80

100

120

140

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Cd

0

2

4

6

8

10

12

14

16

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Pb

0

20

40

60

80

100

120

140

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Cu

0

40

80

120

160

200

240

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Zn

0

500

1000

1500

2000

2500

3000

to 99 99-127 127-247 247-268 268-407 407-516 km

mg/kg

Odra River Course

Mean concentration of As, Cd, Pb, Cu and Zn for suspended matter samples of each

from the six samples group in the upper and middle Odra river course.

Odra River Course

11'9705'9811'9806'9905'00

Pb

0

50

100

150

200

250

300

CH KR OG OP OL WB WJ BD SC GL BG NS NI KO

mg/kg

Zn

0

500

1000

1500

2000

2500

3000

CH KR OG OP OL WB WJ BD SC GL BG NS NI KO

mg/kg

As

0

40

80

120

160

200

CH OG OP OL WB WJ BD SC GL BG NS NI KO

mg/kg

Cd

0

5

10

15

20

25

CH KR OG OP OL WB WJ BD SC GL BG NS NI KO

mg/kg

Cu

0

50

100

150

200

250

300

CH OG OP OL WB WJ BD SC GL BG OR NI KO

mg/kg

Distribution of As, Cd, Pb, Cu and Zn (arithmetical mean values of metal content

in the samples from five sampling campaigns) with their “trend” lines for the

bottom sediment, along the upper and middle Odra river.

Cd

0102030405060708090100

0 1 2 3 4 5 6

Leachibility[%]

7pH

Cu

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7

Leachibility[%]

Zn

010

20304050

607080

90100

0 1 2 3 4 5 6 7

Leachibility[%]

pH

Pb

010

20304050

607080

90100

0 1 2 3 4 5 6

Leachibility[%]

7

Suspended matter Sediments

Cu

0

100

200

300

400

Gło

gów

Kacz

awa

Klod

nica

M. P

anew

Rud

na

mg/

kg mobile portion

Cd

0

4

8

12

16

20

mg/

kg

Zn

0

1000

2000

3000

4000

mg/

kg

Pb

0

50

100

150

200

mg/

kg

Cd143 59

0

5

10

15

20

mg/

kg

Zn

0

500

1000

1500

2000

2500

3000

3500

mg/

kg

Pb

0

200

400

600

800

1000

1200

1400

1600

mg/

kg

Cu

0

100

200

300

400

500

Rac

ibór

z

Krap

kow

ice

Opo

le

Oła

wa

Wro

cław

B.

Mal

czyc

e

Cig

acic

e

Gło

gów

Byto

m O

d.

Kros

no O

d.

mg/

kg

Total and mobile content of metals in the suspended matter and sediments

samples of the Odra river.

Pb

0

10

20

30

40

50

0 50 100 150 200 250 300 350 400

total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg) Zn

0

1000

2000

3000

0 1000 2000 3000 4000 5000total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg)

Cu

0

25

50

75

100

125

0 100 200 300 400 500 600total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg)

Mn

0

2000

4000

6000

8000

10000

0 2000 4000 6000 8000 10000 12000

total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg)

Cr

0

5

10

15

20

25

30

35

40

0 50 100 150 200 250

total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg)

Cd

0

2

4

6

8

10

0 5 10 15 20 25

total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg)

As

0

25

50

75

100

0 50 100 150total (mg/kg)

exch

ange

able

+ c

arbo

natic

(mg/

kg)

spm riverspm tributariessediment

SPM Odra RiverSPM TributariesSediments

Variation of the mobile metal contents of the suspended matter and bottom sediments selected samples of the Odra river and its tributaries showing good correlation of Pb , Zn, Cd and Mn

with their total amount in the suspended matter (SPM) and bottom sediments.

Conclusions

The studies were carried out within the International Odra Project, research activities of the Faculty of Geology, Geophysics and Environmental Protection at the University of Mining and Metallurgy in Krakow, and partly within the Jurzykowski Foundation. The authors express also thanks and appreciation to the Polish-German Foundation for founding this research

1. The detected levels of contamination, mainly Zn, Cu, Pb and Cd,

in the most of PSM and sediment samples of the Odra river exceed

the geochemical background or threshold values.

2. The highest metal pollution of the Odra river system was found

with cadmium, zinc, lead and arsenic. The dilution, re–suspension,

and re–deposition processes at extreme high the Odra river water

events in July 1997 caused additional increase of metal

concentrations in the PSM and sediments, immediately after flood.

3. Metals variability in the Odra river sediments was less significant

if compare with PSM, thus the last component will be

recommended for the chemical monitoring. Additional arguments

for selection of PSM are: easy sampling procedure, better

homogenity, less time consuming of sample preparation and its

chemical digestion, and simpler matrix composition for ICP–MS

method.

4. Cadmium, Zn and As appear to be of particular concern because

of the high level, that appear to be bioavailable and their high

mobility. However, from metal mobility procedures,

• buffer capacity of sediments – acidic metal leaching,

• extraction of exchangeable and carbonatic bound metals in solids,

more favourable seems to be the last one, as one extraction step.

5. The results further show that in the contaminated sediments the

great preponderance of heavy metals is held in form, where it is

mainly associated as ion exchangeable and with carbonates, i.e. in

more mobile forms. Particular in the PSM the carbonates play an

important role in metal accumulation processes.

6. Besides total metal concentration, this well definite „mobilisation

test” of metals in river solids, is recommend for monitoring

purposes, allowing to evaluate the most mobile portion of metals,

which can be easy release as soluble and bioavailable fraction. This

mobile portion of metals are crucial for river quality assessment

and remediation method selection, if require.

7. The results of four years, very wide studies of the Odra river

system suggest, that for river monitoring purposes, the frequency

and numbers of samples for chemical analysis of both water and

solids - preferable PSM - could be reduce to twice a year, with few,

correct selected sampling sites.