CHANGES OF HEAVY METALS CONCENTRATIONS IN SUSPENDED MATTER OF THE ODRA RIVER AFTER THE FLOOD IN NOVEMBER 1997. M.Sc. Ewa Adamiec1, Prof. Edeltrauda Helios-Rybicka1 1 University of Mining and Metallurgy, Faculty of Geology, Geophysics and Environmental Protection, Al. Mickiewicza 30, 30-059 Cracow, Poland Fax 00-48-12-6332936, Telephone 00-48-12-6172571, e-mail :
[email protected] ABSTRACT High atmospheric precipitation in July 1997 caused high water stage in Odra River and in father consequence flooding of the huge ground e.g. industrial and agricultural areas, waste dumping, and wastewater treatment plants. Flood catastrophe entailed leaching of pollution e.g. heavy metals into surface and ground waters. In order to estimate level of heavy metal pollution in upper and middle part of the Odra River and its tributaries, in November 1997 -26 samples, in May 1998 -37 samples and in November 1998 -35 samples of suspended matter were taken. Suspended matter after microwave digestions with aqua regia were analysed using inductively coupled mass spectrometer (ICP-MS). Zinc, Lead, Cooper, Cadmium, Arsenic, Chromium, Cobalt, Nickel, Magnesium, Iron and other metals were researched. Results were confirmed with the TXRF measurements. Obtained results, in comparison with background concentration according to Turekian and Wedepohl for shale and clays, show very high heavy metals contamination in suspended matter –particularly for cadmium, arsenic, lead-the most toxic elements. High arsenic concentration is caused mainly due to use of the fertilisers and industrial activity. In November 1997, leaching from flooded industrial and agricultural areas caused high cadmium pollution. Concentration of cadmium in suspended matter ranged from 1,46 to 120 mg/kg. In sampling campaigns –November 1997, May 1998 and November 1998, high level of lead contamination in suspended matter, ranged between 27,6 and 742 mg/kg, was determined. The main contributors of lead in the Odra River Catchment Area are industries such as petrochemicals, petroleum refining, steel works foundries and non-ferrous metal-works. INTRODUCTION Aim of the study is to estimate environmental condition of the upper and middle Odra River and observe changes of heavy metals concentrations in suspended matter of the Odra River after the flood in November 1997. High water stage in July 1997 and next flood entailed leaching of pollution for instance heavy metals from industrial and agricultural areas as well as overflooded wastewater treatment plants into surface and ground waters. OBJECT OF THE STUDY In order to estimate level of heavy metal pollution in suspended matter of the upper and middle part of the Odra River and its tributaries after the flood, in November 1997 -26 samples, in May 1998 -37 samples and in November 1998 -35 samples of suspended matter were taken. Location of sampling points is presented at the maps below- Sampling campaigns-November 97-fig. 1, May 98-fig. 2, November ´98- fig.3 (IOP-documentation).
Fig.1 Sampling Campaign 11’ 97 Fig.2 Sampling Campaign 05’ 98 Fig.3 Sampling Campaign11’ 98 OR-62 OR-62
OR-53 OR-51
OR-53 OR-51
OR60SW
OT-41 OR44PC OR42SZ OR41PO OR39GR
OR36WI
OR35SK
OT32WA
OR29AU
OR24NI
OT-30
OT26BO
OR28EI
OR22NS OT27NE OR25KO
OT-39 OT43KK
OT-40
OT-32.11 OT-32.9
OT-28 OT-27
OR20BG
OR19GL
OR26PO OT19RU
OT16KA
OR-31 OT-32.10 OR-30 OR-29 OR-28 OR-24 OR-26OR-25 OR-23
OT17ZI OR17SC OR15BD OR13WJ OT13BI OT11OA
OT-26
OT-32.N OT-32.4 OT-32.5 OT-32.6
OR32KK OT24OB OR31LE WA05SR OR25KO OT31IL OR24NI OR29AU OR22NS OR19GL OR20BG OT18BA
OR30FS
OR06OG OR05KR OT05KL OR02RM
OR01CH
OTO1L
WT02NE WA04KO WT03PR WA03SI WT01WI
OT30BR OR28EI
OT28OS
OR23CI OR26PO OT27NEOT26BO OR21BO OT19RU
OR-17 OT-32.W OT-32.3 OR-16OR-15 OR-13 OR-12 OT-14 OR-11 OT-13 OR-9 OT-12 OT-11 OT-32.2 OR-8 OR-7 OT-9 OT-8 OR-6 OR-5 OR-4 OT-7 OT-5 OT-32.1 OR-3 OT-4
OT-17 OT-16
OR11OL ORO8SK OTO8MP
WA08(A)B WA07PO
WT04OB
OT-32.7
22 OT-24 OROR-21 OR-20
WA08PZ
OR33GC OR34HO OT32WA
OT-32.8
OR-19 OT-19 OT-18
OR12WB
OT09NK ORO7OP
OR41SZ OR43AB OR42GR OR38ME OR39BA OR37GA WT05NO OT42KB OR36WI OT36HF WA09MI OR35SK WA10GW OR40BS
OT34HW
OT-32.0
OR32KK OR30FS
OT-41
OR-34 OT-32.12 OR-33 OR-32
OR34HO OR33GC
OR44PO
OR-44 OT-40 OT-39 OR-41 OR-40 OR-39 OT-36 OR-38 OR-36 OR-35 OT-34
OR17SC OT14WI OR15BD OR13WJ WA02CZ OR12WB OR08KP OR-9 WA01ZA OT08MP OT13BY OT16KA OT12SL OR06OG OR11OL OR16MA OT-11 OR10BR OR04KZ OR07OP OR05KR OT09NK OT05KL OT04BI OT07OS
OT17ZI
OR03CS OR02RM OTO1OL OR01CH
OR-2 OT-1
OR-1
POTENTIAL SOURCES OF POLLUTION There are about 1700 potential sources of pollution in the Odra catchment area. About 700 significantly influence the condition of the Odra River and its tributaries. The most dangerous polluters are; RAFAKO (Racibórz)-steam factory, HUTMAN (Wrocław), KGHM (Lubin)-metallurgy, Glass-works in Piechowice, Rokita (Brzeg), Wizów (Bolesławiec), Inorganic Chemicals (Kędzierzn Koźle), POLIFARB (Wrocław)- chemical plants, Paint Factory in Złoty Stok, Jelcz (Jelcz)-Cars factory, tannery in Prochowice and others. Figure 4 present potential industrial sources of pollution in the Odra River Catchment.
Fig. 4 Location potential industrial sources of pollution in the Odra River Catchment Area.
It is obvious that industrial activities are important sources of heavy metal pollution in environment, resulting in high contamination of suspended matter. Heavy metals employed in major industry are presented in table 1. Table 1 Heavy metals employed in major industries(after Dean et al. 1972)
As Pulp, papermills, Organic chemicals, petrochemicals Alkalis, chlorine, inorganic chemicals Fertilisers Petrolum refining Basic steel works foundries Basic nonferrous metalworks, foundries Motor vehicles, aircraftplating Flat glass, cement, asbestos products Textile mill products Leather tanninig Steam generation power plants
Cd Cr Cu Fe Mn x
x
Pb
Ni
x
x
x
x
x
x
x
x
Zn x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x x
x
x x
x
x x x x
x
ANALYTICAL PROCEDURE Membrane filters with weighed suspended matter were digested with aqua regia (3 cm3 HCl and 1 cm3 HNO3 ) in the microwave oven with SW 3051 EPA procedure application characterised by: pressure - 70 psi; ramp - 15 min; hold - 5 min; power 100%. After digestion procedure, the samples were placed to the volumetric flasks and filled up to the volume 20 cm3 and acidified with nitric acid. Rh+ was applied as an internal standard. METHODS Suspended matter after microwave digestions were analysed using inductively coupled mass spectrometer (ICP-MS). ICP-MS-Inductively coupled plasma mass spectrometry is an analytical technique that performs elemental analysis with excellent sensitivity and high sample throughput. The ICP-MS instrument employs plasma (ICP) as the ionisation source and a mass spectrometer (MS) analyser to Zinc, Lead, Cooper, Cadmium, Arsenic, Chromium, Cobalt, Nickel, Magnesium, Iron and other metals were researched. Results were confirmed with the TXRF measurements. Fig.5 The schematic diagram of the ICP-MS HP-4500 (AGILENT TECHNOLOGIES, 1999)
RESULTS AND DISCUSSION Obtained results, in comparison with background concentration according to Turekian and Wedepohl for shale and clays, show very high heavy metals contamination in suspended matter –particularly for cadmium and lead-the most toxic elements. Cadmium seems to be of
particular concern because of extremely high level and its high mobility. The determined levels of heavy metals in suspended matter samples from the Odra River and its tributaries exceed the geochemical background values of the fine grained sedimentary rocks (TUREKIAN, WEDEPHOL, 1961). High metals concentration is caused mainly due to use of the fertilisers and industrial activity. In November 1997, leaching from flooded industrial and agricultural areas caused high cadmium pollution. The main contributors of lead in the Odra River Catchment Area are industries such as petrochemicals, petroleum refining, steel works foundries and non-ferrous metal-works. Results of heavy metals determination are presented in table 2. Table 2. Heavy metals concentration in suspended matter of the Odra River and its tributaries Range of heavy metals concentration in suspended Background matter concentration according Metal to Turekian and mg/kg Wedepohl* November November May 1998 mg/kg 1997 1998 357-3278 576-31369 169-1789 95 Zn 68,8-401 65,2-673 27,6-742 20 Pb 38,3-907 15,0-1276 28,2-1372 45 Cu 1,46-120 0,50-41,5 0,25-21,6 0,3 Cd 15,9-193 13,5-1927 8,0-97,4 As 64,1-331 88,0-1613 52,4-256 90 Cr 17,2-377 66,4-3317 23,3-383 68 Ni 1228-9024 1510-19247 1064-6615 850 Mn
*(TUREKIAN, WEDEPHOL, 1961) The Odra River and its tributaries suspended matter samples are very high contaminated with heavy metals. The contents of pollution vary in the wide ranges. Concentration of cadmium in suspended matter ranged from 1,46 to 120 mg/kg. In sampling campaigns – November 1997, May 1998 and November 1998, high level of lead contamination in suspended matter, ranged between 27,6 and 742 mg/kg, was determined. Significant amounts of other metals were measured in suspended matter. Ranges of heavy metals concentration in suspended matter are presented in table 1. The highest concentrations of heavy metals were found in the suspended matter samples taken in May ’98 from the Odra River tributaries: Kłodnica, Oława, Osobłoga and extremely high - 31369 mgkg-1 of Zn in the Odra River in Oława whereas of Cd in the sample from the Rudna River 120 mg/kg, taken in November ’97. Figure 6 presents the results of Cadmium measurements in suspended matter in sampling campaign –November 97. Fig.6 Cadmium concentration in suspended matter-November 1997.
C d - 1 1 '9 7
35
T h e O d r a R iv e r
K r a p k o w ic e 4 0 u g /g
Bac k g r o u d
30
5
Kaczawa
Oława
Bystrzyca
Olza
10
Mała Panew
15
Nysa Kłodzka
20
Zimnica
120u g /g
Kłodnica
25
Bóbr
R a c ib ó r z C h a łu p k i
T h e O d r a T r ib u t a r ie s
Rudna
ug/g
40
0 0
100
200
300
400
500
O d ra km
In the following tables, statistical parameters of heavy metals in suspended particulate matter of the Odra River and its tributaries –Table 3 and in the Odra River –Table 4 are presented. Table 3. The Odra River and its tributaries-metals campaign 11’97, 05'98, 11’98
11 97
in suspended particulate matter -sampling
As
Cd
Cr
Cu
Ni
Pb
Zn
Mn
[µg/g] 15,9 193 64,3 49,4 59,5 45,5
[µg/g] 1,46 120 18,0 11,5 11,9 23,3
[µg/g] 64,1 331 175 168 166 53,1
[µg/g] 38,3 907 173 135 128 170
[µg/g] 17,2 377 94,5 60,6 42,8 102
[µg/g] 68,8 401 185 171 171 75,0
[µg/g] 358 3278 1804 1618 1734 732
[µg/g] 1228 9024 4704 4259 4876 1951
As
Cd
Cr
Cu
Ni
Pb
Zn
Mn
13,5 1927 151 79,8 80,8 318
0,50 41,5 8,05 6,18 6,84 6,85
88,0 1613 248 180 151 326
10,4 2462 200 101 104 412
66,4 3317 421 259 247 607
65,2 673 129 112 102 102
576 31369 3190 1726 1297 5896
1510 19247 5247 4642 5049 3112
11 98
As
Cd
Cr
Cu
Ni
Pb
Zn
Mn
Minimum Maximum Arithmetical mean Geometrical mean Median Standard deviation
8,00 97,4 33,6 28,6 29,8 19,2
0,25 21,6 6,89 5,21 5,20 4,96
52,4 256 111 104 103 43,8
28,2 1372 128 79,6 63,2 226
23,3 383 118 105 108 63,0
27,6 742 123 98,9 89,6 119
169 1789 805 706 814 379
1064 6615 2199 1999 1939 1100
Minimum Maximum Arithmetical mean Geometrical mean Median Standard deviation
05 98 Minimum Maximum Arithmetical mean Geometrical mean Median Standard deviation
Table 4. The Odra River and its tributaries-metals campaign 11’97, 05'98, 11’98
11 97 Minimum Maximum Arithmetical mean Geometrical mean Median Standard deviation
in suspended particulate matter -sampling
As
Cd
Cr
Cu
Ni
Pb
Zn
Mn
[µg/g] 15,9 122 60,2 48,6 58,2 36,0
[µg/g] 10,1 39,8 18,4 16,6 12,8 9,1
[µg/g] 125 303 172 169 166 39,7
[µg/g] 65,4 248 137 123 122 63,5
[µg/g] 22,8 377 114 75,2 66,0 110
[µg/g] 133 401 190 182 171 62,7
[µg/g] 1572 3240 2106 2061 2101 450
[µg/g] 1228 9024 4704 4259 4876 1951
05 98
As
Cd
Cr
Cu
Ni
Pb
Zn
Mn
Minimum Maximum Arithmetical mean Geometrical mean Median Standard deviation
13,5 235 89,5 70,0 79,5 61,0
3,89 13,7 7,56 7,15 7,16 2,60
88,4 327 159 152 148 53,2
20,7 493 119 89,7 100 105
66,4 1287 293 218 230 271
69,2 224 117 111 105 40,7
576 31369 3621 1768 1252 7087
2388 6336 4501 4315 4582 1226
11 98
As
Cd
Cr
Cu
Ni
Pb
Zn
Mn
Minimum Maximum Arithmetical mean Geometrical mean Median Standard deviation
8,00 97,4 32,8 26,7 31,4 21,5
1,75 14,3 6,15 5,58 5,23 2,80
60,3 206 108 103 103 38,1
28,3 186 75,7 68,2 61,0 36,7
58,0 214 109 102 103 42,3
43,9 200 92,4 86,1 80,4 37,5
351 1735 903 855 883 289
1152 4210 2245 2099 2047 857
In order to estimate the heavy metal situation in the Odra River –concentrations of heavy metals in suspended matter are expressed and presented in Lava Classes (Irmer, 1997). Sampling Campaign November 1997, May 1998 and November for Cd-fig.7 and Sampling Campaign –November 1997 for Cu, Cd, Zn, Pb- fig. 8. Fig.7 LAWA classification for Cd-11’97, 05’98, 11’98 Fig.8 LAWA classification for Cu, Cd, Zn, Pb IV III-IV III II-III II I-II I
Very strongly contaminated Strongly to very strongly contaminated Strongly contaminated Moderately to strongly contaminated Moderately contaminated Unpolluted to moderately contaminated Uncontaminated 11'97
Krosno Odrzanskie Nowa Sól Brzeg-Głogowski Głogów Ścinawa W rocław-Janówek Opole Opole-Groszowice Krapkowice Chałupki
05'98
11'98
Cu
Cd
Zn
Pb
Krosno Odrzanskie Nietków Nowa Sól Brzeg-Głogowski Głogów Ścinawa Brzeg-Dolny Wrocław-Janówek Wroclaw-Bartoszowice Oława Skorogoszcz Opole Opole-Groszowice Krapkowice Chałupki
Obtained results of cadmium concentration in suspended matter classified suspended matter into IV-th class as very strongly contaminated. The upper and middle Odra River is strongly to very strongly suspended matter contamination by zinc (class III-IV). With lead and mainly with copper the situation is not so critical as with cadmium and zinc, and classes II-III and III are most common. With nickel and chromium a contamination of suspended matter of the Odra River is lower in comparison with the metals mentioned above. The suspended matter was moderately to strongly contaminated with nickel, and unpolluted to moderately contaminated with Cr. The highest amount of heavy metals was found in the samples in industrial and/or municipal area e.g. Nysa Kłodzka, Wrocław (WWTP, waste dumping, heavy industry), Opole(WWTP), Kożle(Chemical Industry, Głogów, Brzeg Glogowski, Nowa Sól, Bóbr, Kaczawa, Zimnica-Copper Mining District. CONCLUSIONS Generally suspended matter samples from the upper and middle Odra River have been strongly contaminated with heavy metals, mainly with cadmium, zinc, lead and significantly by copper. The trend of decreasing of Zn, Cu and Pb, but increasing of Cd is evident. It is obvious that significant amount of metals leached from agricultural and industrial area into the Odra River after the flood in 1997, but based on presented research, direct and high impact of mining, smelting, wastewater treatment plants were observed. The content of heavy metals in the Odra River and its tributaries vary in wide range depending mainly on sample location. ACKNOWLEDGMENTS University of Mining and Metallurgy financed researches. Project No.10.10.140.519 REFERENCES ADAMIEC, E., HELIOS RYBICKA, E., BEHRENS, AND K. (2000): Heavy metals in water and suspended matter in the Odra River after the flood in 1997. Intern Research Conference. Physicochemical problems of natural waters ecology. April 2000, Szczecin, Poland, pp. 20.
AGILENT TECHNOLOGIES(1999): Agilent 4500 Series ICP-MS. Publication number 59686345E DEAN, J.G., BOSQUI, F.L., Lanouette, V.H. (1972): Removing heavy metals from waste water. Environ. Sci. Technol. 6, 518-522 IOP DOCUMANTATION. IOP Status Seminar, 31.05 – 01.06.1999, Berlin IRMER, U. (1997): Bedeutung von Hintergrundwerten für Qualitätsanforderung an Oberflächenwassern. IKSE-Workshop: Bewertung der Ergebnisse aus der Elbeschadstofforschung. Geesthacht, pp. 36-40. TUREKIAN, K., WEDEPOHL, K. (1961): Distribution of the elements in some major units of the earth’s crust. Bull. Geol. Soc. Am., 72, pp. 175-192.