Organophosphorous and carbamates pesticide residues in the aquatic system of ioannina basin and Kalamas river(Greece)

Chemosphere, Vol.15, No.8, pp 1023-1034, 1986 Printed in Great Britain

0045-6535/86 $3.00 + .OO Pergamon Journals Ltd.

ORGANOPHOSPHOROUS~D CARBAMATESPESTICIDE RESIDUES IN THE AQUATIC SYSTEMOF IOANNIHA BASIN AND KALAMASRIVER(GREECE) T.A.Albanis, P.J.Pomonis, A.Th.Sdoukos Cepartment of Chemistry, University of Ioannina, Ioannina 45110, Greece

ABSTRACT Organophosphorus and carbamates pesticide residues have been monitored in the aquatic system of Ioannina basin and its natural outlet, Kalamas river, for the period September 1984, to October 1985. The concentrations of detected molecules of azinphos-methyl, parathion-methyl, diazinon, carbofuran and carbaryl were found to follow a seasonal fluctuation with maxima during summer and minima during winter months. The results are discussed in relation to the am• ounts of those pesticides used for farming as well as the seasonal rainfall in the vicinity of Ioannina basin. INTRODUCTION Ioannina basin is located in the northwest part of Greece and its aquatic center is considered to be the Ioannina lake Pamvotis (Fig.l). The lake is 8Km long (NNW-SSE) and its maximal width is 5Km at the southern end and approximately IKm near the city of Ioannina. The lake occupies an area of about 23Km2 and its height above sea level is about 470m. The maximum frequency depth is approximatly tom. The total colume of water is between 8.107 (summer) and 12.5.107 (winter) m3 (I). The natural outlet of the lake is Kalamas river (Fig.l) connected with the lake through the Lapsista's canal (17.11
1023

1024

GREECE

b ALBANIA

i Lake Pamvotis Ioannina

IONIAN SEA

,%

Tuner Katamas K1 River ~<,)~

/ ~ . , ~ x 4//Canat

l//

x~3 _

_,"

-%~

\

Figure 1: Geographical situation of sampling

....

area.

Lake Pamvotis

/

"-~2 ka

1025

annina basin the following quantities of such pesticides, taken as the active compound, were sold to the local farmers: Azinphos-methyl 400kgr, parathion-methyl 350kgr, diazinon 550kgr, carbofuran 2800kgr and carbaryl 3400kgr (2). These molecules show a rather decreased stabil i t y in aquatic environment, having a persistence time in natural waters between 4-12 weeks, depending on temperature, pH e.t.c. (3,4). Nevertheless, the presence of even trace quantities in natural waters may generate public concern since i t is kown that such materials induce phosphorylation or carbamylation of acetylcholinesterase enzyme at nerve endings(5,6). Their toxicological evaluation according to WHO (6) shows that the maximum acceptable daily intake for man should be in mg/kg W: azinphos 0.0025, parathion-methyl 0.001, diazinon 0.002, carbofuran and carbaryl 0.01. The limits of organophosphorus and plus carbamates insecticides in drinking waters should be less that 0.100 mg/It (7). Since measurements of organophosphorus and carbamates pesticides in the above noticed aquat i c system have not been carried out previously, we decided to start a program of monitoring such pesticides contaminats. This paper reports results from such measurements. EXPERIMENTAL Figure I shows the sampling stations in the !oannina lake(points LI,L2,L3,L4,L5,L6) , the Kalamas r i v e r (points RI,R2,R3) as well as in the canal connecting them (points CI,C2,C3,C4,C5). The method of sampling was similar to that described in (8). Briefly they were carried out as follows: 2L samples were collected during September and November 1984, March, l:ay, July and September 1985 in bottles previously cleaned with 15% methylene chloride in n-hexane(v:v). They were stored in amber glass bottles at 4°C prior to extraction, normally within 24h of collection. All glassware used in the analyses was heated at 250°C up to 40min and repeatedly washed with solvents in order to remove all the pesticide traces (g). The solvents used were suitable for pesticide residue analysis, while the glass wool was silanized to avoid contamination (10). For the organophosphorus

insecticides an one l i t e r sample of water was extracted with 140ml

of a mixture of 15% methylene chloride in hexane (v:v) in sealed jars placed horizontally on a Fisher-Kahn shaker (280 oscillations/min;

32cm strock distance) for 15min (10). For the car-

bamates the pH of an one l i t e r sample was adjusted to 3-4 with 50% H2S04, 10g of ~a2SO4 dissolved in i t and extracted with the same procedure noticed above (11). The extracts were removed by decanting and the water extracted two additional times by shaking for 15min with 140mi of 30% methylene chloride in n-hexane. The three extracts were combined in a 500ml bott l e containing 5gr of anydrous Na2SO4. Next the extracts were evaporated in a rotary evaporator (Buchi 011) and concetrated

down to 4ml (40°C water bath). For hydrolysis to take place

2ml 10% methanolic KOH was added to methylene

chloride extracts and the mixture was l e f t to

be hydrolyzed at room temperature. Next the solution was acidified and extracted with benzene (2x50ml). The combined extracts were passes through a 10g Na2SO4 column and concentrated in a rotary evaporator as previously (11). As a clean up system for organophosphorus insecticides a microcolumn (14xO.5cm) was used f i l led with Frorosil stored at 130°C (12,13). Two fractions were obtained after elution with 10ml portions of 6 and 15% ethyl ether in petroleum ether. For carbamates a microcolumn f i l led with 5mm of anydrous Na2SO4 on top of silica gel was used. The column was eluted with" 5ml of 5 and 25% benzene in n-hexane. The f i r s t elution fraction is the wash fraction and was

1026

Table I, Detected concentrations of Azinphos methyl (ng/It) Lake station

Date LI

L3

L4

L5 ND

L6 ND

ND

HD

ND

ND

ND

ND 3

HD 2

ND

ND

1

ND 2

ND

1

16

14

13

13

9

8

5

9

11

4

3

4

C5 HD 9

12-Sept.1984

3

lO-Nov

ND

10-Mar.1985

ND

11-May

12-July 14-Sept.

Canal station 3-Aug.1985

C1 ND

Cz ND

C3 ND

C4 HD

11-Jun.

12

17

14

7

River station R2

R3

8

ND 2

NO 5

25

20

18

20 3

16

17

4

1

26-Nov.1984

R1 ND

11-Jun.1985 11-Jul, 3-Au 9. 13-Sept. (a) Hot detected.

Table 2. Detected concentrations of M.parathion (ng/It) Date

Lake station

12-Sept.1984

L1 ND

L2 ND

L3 ND

L4 1

L5 1

L6 ND

lO-Nov

ND

ND

ND

ND

ND

HD

10-Mar-1985

ND

ND

ND

ND

2

6

8

4

HD 9

ND

11-May 12-July

12

9

!1

6

3

5

14-Sept.

ND

ND

8

4

1

0,5

3-Au9,1985

C! ND

C2 0.5

C3 1

C4 ND

C5 0.5

11-Jun

1

3

2

4

3

Canal station

River station RI

R2

R3

26-Nov,1984

ND

ND

NO

11-Jun.1985 11-aul.

2 8

7 14

8 32

3-Aug.

15

9

6

13-Sept.

NO

ND

ND

7

1027

Table 3. Detected concentrations of Diazinon (ng/It) Date

Lake station

12-Sept.1984

LI 2

L2 3

L3 1

L4 1

L5 2

t6 0.5

lO-Nov.

1

|

ND

ND

NO

liD

10-Mar.1985

ND

ND

ND

ND

ND

ND

2

12

11-May

6

22

14

6

12-July

35

57

45

25

13

18

23

8

7

C4 ND

C5 ND

13

14

14-Sept.

12

22

3-Apr.1985

C1 ND

C2 ND

11-Jun.

12

6

RI

R2

R3

ND

NO

ND

26-Nov.1984

13 Canal station C3 ND 7 River station

11-Jun.1985

10

14

4

11-Jul.

52

42

9

3-Aug.

7

8

2

13-Sept.

4

2

2

Table 4. Detected concentrations of Carbofuran (ng/It) Date

Lake station L1

L2

t3

t4

L5

L6

12-Sept.1984

ND

2

10

4

3

1C-Nov.

ND

NO

NO

NO

1 ND NO

ND

lO-Mar.1985

ND

ND

ND

ND

11-May

4

6

7

5

1

ND 2

17 13

8

9

3

7

C4 ND 19

C5 ND 17

12-July 14-Sept.

23 ND

35 4

3-Apr.1985 11-Jun

C1 ND 7

C2 ND 14

42 12 Canal station C3 ND 21 River station

R1

R2

R3

26-Nov.1984 11-jun

ND 5

ND 4

ND 2

11-Jul. 3-AUg,

12 3

11 6

14 5

13-Sept.

2

1

2

I028

discarded. To access the possible losses during the above procedures a number of tests were run with blanks containing a known amount of standard pesticide mixtures. Blanks containing Varian supplied mixtures, and spiked in the G.C. showed losses between 8-16% after the above procedure of extraction concentration and clean up The following abbreviations were used for the five compounds studied: Organophosphorus:azinphos methyl(phosphorothioic acid, O,O-dimethyl S-(4-oxo-l,23,-benzotriazin-3(4H) yl)methyl ester), parathion methyl(phosph~rothioic acid, O,O-dimethyl O-(4-nitrophenyl)ester), diazinon(phosphorothioic, O,O,diethyl O-(-6-methyl-2(l-methymethyl)-4-pyrimidinyl)ester).Carbamates:carbofuran (2,3-dihydro-2,2-dimethyl-benzofuranyl-7-N-methylcarbamate), carbaryl(1-naphtyl N-methyl carbamate). Gas chromatographic analyses were carried out mainly on a Varian 3300 G.C. equipped with a );i 63 E.C.D. Different columns were used as 6% QF-I plus 4% SE-30 and 4% SE-20 plus 6% OV-210, both on 80/100 chromosorb Wfor organophosphorus insecticides and 3% 0V-17 on 100/120 HP chromosorb W ( I I ) . The temperatures set in the column, the injector and the detector of the aeriograph were 210-270 and 300°C respectively. All samples were run in dublicate and their concentrations determined by direct comparison with pure analytical standards and mixtures of them. The results obtained from such analyses are shown in tables I-5 and sum, r.arized in tables 6 and 7. Table 5. Detected concentrations of Carbaryl(b) (ng/It) Lake station

Date

12-Sept.1984 12-Jui.1985 14-Sept,

L1

L2

L3

L4

L5

L6

ND 28

2

I

ND

ND

32

38

ND 13

13

18

I

ND

3

i

2

3

Canal station

11-Jun.1985

CI

C2

C3

C4

C5

6

7

8

11

12

River station R1

R2

R3

ll.july.1985

15

24

26

3-Aug.

2

3

2

(b) Not detected in other dates in lake,canal and river stations. DISCUSSION The overall picture obtained from table 6 is shown in fig.2 which includes the mean values of the detected molecules in all the stations in the lake and in the river over one year period. This picture shows the seasonal(time)fluctuations of pesticides in the analyzed samples. On the contrary fig.3 summarizes the data of table 7 and shows the local (space) average levels for the analyzed molecules over the same time. From. fig.2 i t is apparent that the concentration of pesticides is low both in the lake and in the river during the winter months because of dilution effects due to the rainfall which

ND

ND-3

8-16

3-11

ND

7-17

ND

2-8

18-25

16-20

1-4

10-Mar.1985

12-July

14-Sept.

3-Apr.1985

11-July

2G-Nov.1984

11-Jun-1985

17-July

3-Aug.

13-Sept.

ND

11-May

ND-3

lO-Nov.

2.7

17.7

21.0

5.0

ND

11.8

ND

6.0

12.1

1.5

ND

ND

0.8

ND

6-15

8-32

2-8

ND

I-4

ND-I

ND-8

3-12

2-9

ND

ND

ND-1

ND

10.0

18.0

5.6

ND

2.6

0.4

2.2

7.7

6.0

ND

ND

0.3

mean

range

range

mean

Parathion-methyl

Azinphos methyl

12-Sept.1984

Date

2-4

2-8

9-52

4-14

ND

6-14

ND

7.23

13-57

2-22

ND

ND-1

1-3

range ND-IO

ND-13

8-42

I-7

ND

ND

7-21

ND

2.6

5.7

34.3

9.3

ND

1-2

3-6

11-4

2-5

ND

In the r i v e r

10.4

ND

Carbaryl

1.7

4.7

12.3

3.7

ND

15.6

ND

6.5

22.3

4.2

ND

ND

3.3

ND

ND

ND

0.5

HD

ND

8.8

ND

1.7

HD

2-3

ND

2.3

1 5 - 2 6 21.7

HD

ND

6-12

ND

ND-3

13-38 23.7

ND

ND

ND

ND-2

r a n g e mean range mean

Carbofuran

In the canal

14.2

32.1

10.3

ND

0.3

1.6

mean

Diazinon

In the lake

Table 6: Maximum, minimum and mean values of pesticides (no/It) on different samplings dates

3

3

3

3

3

5

5

6

6

6

6

6

6

(stations)

Namber of determinations

~0

o t,J

~J

Azinphos-methyl Methyl-parathion Diazinon Carbofuran Carbaryl

Azinphos-methyl ~thyl-parathion Diazinon Carbofuran Carbaryl 0.5 6.0 3.5 3.0

ND-12 ND-7

ND-6

11.2 5.0 14.6 3,4 3.4

ND-25 ND-15 ND-52

ND-12 ND-15

R1

6.0

ND-12

ND-1

C1 1.7

3.5

ND-11 4.4 ND-24 5,7

ND-20 8.4 ND-14 6.0 ND-42 13.2

R2

ND-7

ND-6 3.0 N D - 1 4 7.0

0.5-3

ND-17 8.5

C2

ND-35 7.8 ND-32 6.0

1.5

7.0

11.8 7.0

ND-14 ND-26

: ND-18 ND-32 ND-9

R3

ND-8

4.6 5,6

8,2 9.2 3.4

4.0

ND-7 3.5 ND-21 10.5

1-2

ND-14

C3

ND-42 ND-38

6.5 2.3

2.5 9.1

3.5

5.5

6.5 9.5

2.0

ND-11

ND-13 ND-17

0.5-3

ND-9

Stations in the River

ND-11

ND-13 ND-19

ND-4

ND-7

C4

C5

ND-8 ND-13

ND-9 ND-13

Stations in the canal

ND-17 ND-13

ND-6 ND-25

5.0

7.0 8,5

1.7

4.5

2.2 2.2

2.3 4.1

2.0

ND-9 ND-18

ND-7 ND-18

ND-8

3.5 3.5

2.1 6.2

2.1

2

2 E

2

2

6 6

6 6

6

4.5 4.8

ND-11 4.5 ND-45 12o2

ND-9

ND-23 ND-28

ND-9 2.5 ND-57 17.5

3.3

2.3 9.3

ND-13

ND~12 ND-35

4.6

ND-13

4.1

ND-16

Azinphos-methyl Methyl-parathion Diazinon Carbofuran .Carbar¥1

N D - 1 4 4.1

L3 L4 L5 L6 m i n a t i o n s(samr a n g e mean range mean range mean range mean oling(dates)

LI L2 range mean range mean

Number of deter-

Compound

Stations in the lake

Table 7: Range and mean values of pesticides detected (ng/It) in different sampling stations

0

0

1031

40

Carbofuran

Diazinon

20~

i r-~ i i

I8

,

" i -D L..,,,~

,

20

[ =~l_]

150-

14

I

I

i

'

IL..

I I -- I !

t

I

I !

I I L---

;

- 0

i-,,t

I ! !

12

C

I

I0

°

I,,.

I '

L.~,

I~-

7 i )

'

]

_J

:

1

.~°

L,

:E

r

N

/.12_

v

c 0

I

Cl

1

I

I

I

I

I

I

I

I

I

.Azinphos-methyl

C

I

I

t

,!

.- ~.00 -

I

-'1

I

I

r

•

'1

I

Parothion-methyL

8

8 L) m- : t

14-,

-~

L.,

--.~

I

I E150--', I

~ I.

~2 ,

!

~o~ , I

I

¢=

I

,

-~[ II •

.

•

,

, I

I,--

!

~l

r/\ l~oo--:

2~-

./ /

-''-/' /" ~

JI

,

I L-

:

--i-i

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*

,,

"1 I

I

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L - - -h0

--

16

..

j

;. !!

I I

li I4

!!

1~2

~ ~

I~o

~

"l".I..

i5o-:J

.i

, ,

6Lj

ii

--n

,

-I I I ~

Ii

L_~

l '

I~!

8"-,

I

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, '-Lr\i

=,

I

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-18

.

.

6

•

,!

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,,'t -~-

/"

iI

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I S'O'N )~J 'F 'M'A'M'J 'J 'A'S'0 iS'0' N'D~ 'P 'M kM'j P 1954 N ~ 1955 ~1984 ~-1985

I

--

~

I

"i~' -12 •

I

5~01 '

Figure 2: Mean values of the pesticides Diazinon, Carbofuran, Azinphos-methyl and Parathionmethyl in the Ioannina lake ~ ~ and in the Kalamas r i v e r (o-r-.oO) over one year period. Data are from table 6. The dotted l i n e (-o-) represents the average height of r a i n f a l l (m/month) i n . t h e area f o r a f i f t e e n year period.

I !

I

I

I

I

I

I I I I I

I

¢

Lake

0, R3 R2R1 C5C4C3C2C1 L6 L5L4L3 L2L1 R3 R2R1 C5C4C3C2C1 L6 L5 L4 L3 L2 L1 Sampling stations

.i '2

t I I I

I I I I

t

!

Lake

Parathion- methyl River ~ C a n a l I

Lake - - - - - . .

•-,.,_._

I i I I

I

I I i

~j--

I l

Carbofuran River ~ Canal

I

-,

Azinphos-Methyl

I !

,

I

I I

I

I I I

DiazTnon tnal --"t*- Lake

6

10

12

14

16

Figure 3- Mean balues of the analyzed molecules over one year period in each station in the Ioannina lake, the Kalamas r i v e r and 1.he cawlal conne(:tln.q thei,l. DaLa are from table 7.

O U

u ¢.-,

(-

,,iv,w

O

c,mO

v

6

8

10

12

14

16

8

t

0

1033

is shown in the same figure. The application of pesticides during the spring months in the farms, coupled with the decrease of rainfalls, results in an icrement of pesticide concentration in the lake and the river this time of the year. Figure 3 shows that the ammount of methyl parathion and diazinon in the lake is, on the average, much higher than in the canal, while in the river their concentration rises again.The rather sharp drop of the concentrations found in the canal seems strange in a f i r s t look.Nevertheless i t might be explained by examining the details of the connection between the canal and the lake. Namely the water overflow from the lake drops into canal from a barrier of 2.5m heightx10m wide forming an intense mixing and aeration. I t might be that this point act. as a kind of biological station for the degradation of the analyzed molecules. Alternatively this step observed in the concentrations of these pesticides between the lake and the canal might be due to the fact that the agricultural areas are mainly located in the south of the lake and the applied pesticides in the farms flow mainly there. The water overflow into canal might then be diluted with some other waters, not polluted with those pesticides, resulting this in the low concentrations observed. Hevertheless for carbofuran and azinphos-methyl we observe from the same figure 3 that their mean concentrations are about equal over a year period in the lake and the canal. I t is hard to explain this contrast but i t might be due to some details of the microdistribution of these compounds in the farms, an hypothesis d i f f i cult to be examined in details. Finally we notice that the more unpolluted part of the lake is the NE one (see points L5 and L6) located near mountaineous area and away from the farmlands and the city of Ioannina. Going into the mean values of the pesticides detected into the river, we observe that they are rather higher than those found in the canal. This is certainly due to the increased concentration of pesticides in the main flow of Kalamas river, collecting waters from the agriculture areas in the N-N~ of Ioannina basin. In conclusion i t might be said that although the concentrations of the analyzed molecules in the aquatic system of the area is rater low during winter months, the situation is rather unpleasant during summer, when they reach high values.Although water from the lake is not used for drinking by people or animals, nevertheless the same can not be said for the river where some cattle might be watered. The influence of the pesticides examined here, as well as of chlorinated ones examined recently in the same area (14), on the wild l i f e of the region will be the task of some future work. AKNOWLEDGEMENTS The authors wish to thank the ministry of Environment for a grant which made possible this study. REFERENCES I. Anagnostidis A.and Economou-Amilli A. Arch Hydrobiology 83, 313-342, (1980), 2. National Statistical Burean of Greece (NSBG), Ministry of Agriculture, paper EOP-I,1984-85. 3. Sharon MS, Miles JRW, Harris CR and McEwen FL. Water Research 14, I089-IC93, (1980). 4. Konrad JG, Chesters G and Armstrong DE. Soil Sci Soc Amer Proc 33, 259-264, (1969). Morgan DR "Recognition and Management of pesticides poisonings", Ed US Environmental Protection Agency EPA, (1982).

1034

6. 7. 8. g. 10. 11. 12. 13. 14.

Ve~torazi G. Residue Reviews 56, 1-44, (1975). Prober R. "Handbook of Environmental Control" Vol II (Water supply and treatment), Eds Bond RG and Stranb CP. Clevelend, Ohio, (1973). Rivera J, Caixach J, Ventura F and Espadaler I. Chemosphere 14, 395-402, (1985). BevenueA, Kelley TW and Hylin JW. J. Chromatography 5-4, 71-76,(1971). Lenardon AM, De Heria MIM, Fuse JA, DeMochetto CB and Pepetris Pj. J. the Science of total Environment. 34, 289-297, (1984). Coburn JA, Ripley BD and Chau ASY. J. of the AVAC59(I), 188-196, (1976). Miles JRW, Harris CR. J. Econ Entomology 7_!I, 125-131, (1978). INTERIM "Pending Issuance of Methods for Organic Analysis of Water and Wastes", US Environmental Protection Agency EPA (1978). Albanis TA, Pomonis PJ and Sdoukos AT. J. the Science of total Environment,(in press)

(Received in Germany 11 June 1986; accepted 25 June 1986)