changes of heavy metals concentrations in ...

1 downloads 0 Views 880KB Size Report
KGHM (Lubin)-metallurgy, Glass-works in Piechowice, Rokita (Brzeg), Wizów (Bolesławiec),. Inorganic Chemicals (Kędzierzn Koźle), POLIFARB (Wrocław)- ...
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.