Field and laboratory studies on sources and persistence of chlordane contamination in the Missouri aquatic environment

Chemosphere, Vol.20, Nos.lO-12, P r i n t e d in Great Britain

pp 1581-1588,

1990

0 0 4 5 - 6 5 3 5 / 9 0 $3.00 P e r g a m o n Press plc

+ .00

FIELD AND LABORATORYSTUDIES ON SOURCESAND PERSISTENCE OF CHLORDANE CONTAMINATION IN THE MISSOURI AQUATIC ENVIRONMENT C.E. Orazio, S. Kapila*, R.K. Puri, J. Meadows and A.F. Yanders Environmental Trace Substances Research Center University of Missouri Columbia, MO 65203

ABSTRACT Field

and

laboratory

studies

were

chlordane in the aquatic and t e r r e s t r i a l

conducted environment.

to

investigate

the

persistence

of

The laboratory data show that the

transformation and loss of the chlordane constituents is dependent on soil c h a r a c t e r i s t i c s . The overall rate of loss is also dependent on the depth of a p p l i c a t i o n , being s i g n i f i c a n t l y lower

at

greater

depths.

The f i e l d

data

show a

strong

correlation

between

urban

development and residue concentration levels.

INTRODUCTION The i n s e c t i c i d e chlordane is a mixture of chlorinated hydrocarbons which has proven to be quite

persistent

in

the

approximately f o r t y years.

environment. It

It

has been used in

the

United States

for

is estimated that over ten m i l l i o n kilograms of chlordane

were produced and applied for control of a v a r i e t y of a g r i c u l t u r a l pests.

Chlordane has

also been used extensively for control of termites and ants in and around domiciles.

Due

to i t s carcinogenic a c t i v i t y in laboratory animals, i t s use was suspended as of April

]987

by the U.S. EPA. Residue levels as high as 3-4 parts per m i l l i o n (ppm) have been detected in fish from many lakes and rivers in Missouri.

These levels are well in excess of the

Food and Drug Administration (FDA) "action l e v e l " of 0.3 ppm. (1-3). A wide v a r i a b i l i t y reported and h a l f - l i f e (4-6).

in the rate of chlordane loss from the a p p l i c a t i o n s i t e has been estimates of chlordane have ranged from a few days to several years.

This study was i n i t i a t e d to discern the sources of chlordane contamination and to

estimate the persistence of the pesticide in t e r r e s t r i a l and aquatic environments.

1581

1582

EXPERIMENTAL

Various sample matrices including fish tissue, soil/sediment and water were analyzed for chlordane residues during the course of these investigations.

A flow diagram of the

analytical methodologies used during the course of the study is given in Figure i.

COLUMN LEACHING AND TRANSFORMATION STUDIES

These studies were conducted in soil columns packed with a layer of chlordane-spiked soil (Figure 2).

All experiments were performed with the following three different types

of soils: Times Beach, Missouri; Visalia, (San Joaquin) California; and Eglin, Florida. Each soil batch was thoroughly homogenized, air dried and passed through a 20 mesh sieve. The moisture content of the soil was adjusted to 5.0%. The soils were then packed into 20 cm x 7.8 cm i.d. aluminum columns. Careful attention was paid to ensure uniformity of column packing.

The air dried soil was characterized for the following typical parameters. TABLE - I

Soil Sample

% Sand

%Silt

% Clay

Times Beach, MO

11.4

52.7

35.9

2.4

6.9

Eglin, FL

91.7

6.3

2.0

1.6

4.7

Visalia, (San Joaquin) CA 44.1

34.3

21.2

1.7

8.1

% Organic Matter

An aliquot of each soil was taken and spiked with 500 ppm of technical chlordane.

pH

In

one set of experiments, this contaminated soil was placed on top of the soil-packed column in a 5 mm thick layer, while in another set of experiments the contaminated soil was packed between layers of uncontaminated soil.

The soil

columns were placed in a controlled

environment chamber described earlier (7). The effect of a surfactant on the leachability of chlordane was measured by periodic application of water containing 0, 10 or 100 ppm sodium lauryl sulfate to the columns of soil.

The columns were sectioned and the chlordane constituents analyzed after a set

incubation period.

PARTITION STUDIES

The p a r t i t i o n behavior of chlordane constituents in a soil/water system was studied with batch experiments with the three types of soils described above.

The chlordane

concentrations used ranged from I to 500 ppm, in organic-free water or water containing 0.01% sodium lauryl sulfate under three pH regimes (4.5, 7.0 and 8.5).

1583

HF°m~gfylZ~t~nVin~e°r~eltsa~aSndmPr ide(p,p'....)]

1 I

I

I

Florisil Clean-up Florisll Clean-up 21g of 3.5% deactivated Florisil log of 3.5% deactivated Florisil 200ml of 6% ethyl ether in hexane ll0ml of 6% ethyl ether in hexane

1I

1 I ................ 1

I

10q of Bio-Bead S-X3 Fract. I : 30ml C/D (Discard) Fract. II: 40ml C/D

l

I

F

1 I .............. 1

~dI

I

to remove elemental sulfur

I

i

I

Iconcentrate to 2mlI

1

1

L

Silica Gel rractienation 5g of 2.5% deactivated Silica Gel 923 Fraet. I : 45mi he×ane (PCBs) Fract. II: 55mi H/D (Pesticides)

;

I

]

1

HighconflrmationReSolution G O / E l e c t r o n capture Detector High Resolution GC/Mass Spectrometer for

* C/D = Cyclohe×ane/Dichloromethane (i:i) H / D = Hexane/Dichloromethane (I:i)

Fig. ]:

Sample extraction and cleanup procedure used for determination of chlordane residues in environmental samples.

>4]

/ '~!ii~I~ii~!iFi !~i~¸i!¸,!

~Coo n t ~ e

~

Fig. 2:

soi~lh-

/U . . . . t a m i nea~t, ~ I soil p a c k e d t o ~ 80% n a t u r a l ~_ density J

~Plunger

~n

d

-

-

'

~

I

head~

~or l e ~

~

~ -

II

~

Schematic of soil column used for simulating surface/subsurface application of chlordane.

1584

RESULTS AND DISCUSSION A fish contamination survey conducted in a parallel with the present studies has shown that only a moderate, i f

any, decrease in chlordane levels had occurred at most sites

across Missouri during the past five years (Table I I ) . Table Chlorinated

Hdyrocarbon

Residue

II

Levels

in Fish T i s s u e

from M i s s o u r i

River 1

Chlordane Fish

Species

Aldrin

BHC*

ITech)

Hept. p,p'DDD

p,p'DDE

p,D'DDT

Dieldrin

Epox.

PCBs

1984 Shovelnose

Sturgeon

Carp Channel River

Catfish

Carpsucker

<2.0

5.0

610

ii.0

39.0

5.0

126

37.0

310

<2.0

<5.0

160

<5.0

12.0

<5.0

80

22.0

80

<2.0

<5.0

310

i0.0

56.0

<5.0

93

14.0

56

<2.0

<5.0

160

<5.0

20.0

<5.0

80

14.0

80

62

198__~6 Shovelnose

Sturgeon

Carp Channel River

Catfish

Carpsucker

<2.0

<5.0

860

15.0

67.0

5.0

17.0

560

<2.0

<5.0

120

<5.0

9.0

<5.0

3,5

<2.0

<50

<2.0

<5.0

520

<5.0

20.0

<5.0

<2.0

17.0

75

<2.0

<5.0

140

<5.0

16.0

<5.0

33

l!.0

70

1987 Shovelnose

Sturgeon

Carp Channel River

i. 2. 3.

catfish

Carpmucker

<2.0

<5.0

749.0

<2.0

<5.0

180

<2.0

<5.0

<2.0

<5.0

6.0

47.0

<5.0

i00

19.0

303

<5.0

ii.0

<5.0

41

¢.5

70

295

8.0

22.0

<5.0

85.0

i~.0

ii0

234

<5.0

16.0

.<5.0

14.0

".0

<50

C o l l e c t i o n site Easley, MS. All s a m p l e s w e r e <;omposite of f i l l e t s a m p l e s from All s a m p l e s w e r e cf c o m p a r a b l e size and m a t u r i t y .

5 fish.

The chlordane residue profiles in fish tissues showed a rough correlation with the technical chlordane formulations used for termiticide application.

The concentration of

readily metabolized, transformed constituents such as chlordene-C, heptachlor and other dienes in fish tissue is considerably less than in the technical chlordane formulations. The residue patterns,

i.e.,

the relative

distribution of chlordane constituents,

are

dependent on the partition behavior and transformation rates of the constituents in the environment.

Generally,

a higher bioconcentration factor is observed for the persistent

constituents with greater numbers of chlorines. The

chlordane constituents

trans-chlordane,

cis-chlordane,

trans-nonachlor,

and

cis-nonachlor were invariably found to be the major chlorinated hydrocarbon contaminants in all environmental samples. The chemical structure of the major constituents is shown in Figure 3. evident:

A correlation between chlordane concentration and urban development was quite concentrations were appreciably higher in samples from urban areas than rural

areas, as can be clearly observed in Figure 4. Column studies show clear differences in the downward movement and transformation rate of chlordane constituents.

During the one-month time period, the decrease in heptachlor

was coupled with the appearance of 1-hydroxychlordene and was found to be highest in the clay soil followed by the s i l t loam soil and then the sandy soil (Figure 5).

1585

C

l

~

~

el C1

el

Cl

cZ Z

ZZ cis-ghlordane

trans-Chlordane

Cl

Cl

III trans-Nonachlor

Fig. 3:

IV cis-Nonachlor

Structure of the major chlordane constituents found in environmental samples.

The concentration of 1-hydroxychlordane was reduced considerably a f t e r six months; at the twelve month period the 1-hydroxychlordane was e s s e n t i a l l y absent.

The concentrations

of the major constituents at the various time periods versus soil column depth are shown in Figure 6.

A s i g n i f i c a n t decrease in the concentration of chlordene-C and heptachlor was

observed in the top layer of s o i l ,

especially in the Missouri s o i l .

The degree of t h e i r

downward movement was higher in the six and twelve month time period soil

columns.

The

application of 100 ppm sodium l a u r y l sulfate resulted in a s i g n i f i c a n t increase in downward m o b i l i t y of a l l

of the chlordane constituents as compared to controls

(Figure 7).

This

e f f e c t was evident in the Eglin sandy soil and in the San Joaquin soil columns; however, due to crack formation in the Missouri clayey s o i l , the greatest c o n t r i b u t i o n to downward movement was through particle-bound transport,

and the r e l a t i v e e f f e c t of the surfactant

was minimal.

/

~. . . .

L

N 9K 5001; AO ~

A

~

A

~ A

~

_o ),3K),3K

~ ~r~~°

Fig. 4:

Ai~m_~"IE St. Louis

^

"~

A

~£ I

Chlordane concentration and urban population in Missouri.

1586

COLUMN DEPTH 0-6 MM

3 00

6 00

9 30

12 CD 15 00 18 00 21 00

ao

27 ~0

3P ,~o

3 00

~ 00

9 00

12 00

15 00

18 30 21 00 2~ 00 27 OC 30 00

COLUMN ~

DEPTH

~

18-24

MM

.

i i m

3 C3

S 00

i

i

9 C0

12

~

00 15 00 18 GO

~T~TIOM

TI~

C3 24 00 27 00

30 0C

3 O~

DEPTH 24-34

i

] oo

J

e Go

i

~ ,?

~

12 oo

-

(MI~C~ES)

MM

-

:

15 c,o

SANDY

Fig. 5:

TIME

i

]¢ oo

21 oa

2a oo

z? ~0

3~ ~c

3 o0

~ 00

~ETeNT~ON ~ : m : mI~vTes*

EGLIN

12 00 i~ 00 18 00 21 00 2~ 00 27 00 30 00

~TENTION

COLUMN

- -

~ eL', ~ 00

IMIN~ESl

SOIL

~ 00

ig 0a

15 00

t~ ,0

21 00 24 C,0 27 00

RETZ~TIO~ ~Is~ (MIaU~ES)

TIMES

BEACH

-

CLAYEY

Chromatograms of chlordane residues from clayey and sandy soil.

SOIL

3¢ a0

1587

SAN JOAQUIN SOIL- 6 MONTHS 2O

SAN JOAQUIN- 12 MONTHS CONCENTR ~,TION (ug/g}

CQNCENTRATIOH (ug/g)

15

10

5;

0 10

20

30

40

~0

50

20

30

40

DEPTH (mm)

DEPTH (mm)

EGLIN SOIL- 6 MONTHS

EGLIN SOIL- 12 MONTHS

CONCENTRATIO: J [ug/g}

50

CONCENTRATION (ug/g}

~2

i 0

10

20

80

40

50

DEPTH (mm)

0

10

40

50

MISSOURI SOIL- 12 MONTHS

CON CE NTR ATO,N' (ug/g) 10'

CONCEb!TRATION (ug/gJ

~o! 8! .

20

30

40

50

heptachlor(×|0),

"t"

.

.

.

.

.

.

.

.

lO

DEPTH (ram)

Fig. 6:

30

DEPTH (mm)

MISSOURI SOIL- 6 MONTHS

10

20

.

.

.

.

20

.

.

.

.

.

30

40

DEPTH (mm) Y-chlordene

~

t-chlordane

~

c-nen2chler i

Concentration of chlordane constituents vs. soil depth in column.

50

1588

Table

III

Relative Stability of Tech-Chlordane Constituents in Soil/Water Systems*

. ~ ] i n Soi~ Chlordane Corstituents Chlordene L Heptachlor Chlordene Chlordene Chlordene Heptachlor isamer trans- Chlordane c i s Chlordane trans Ronachl~r cis Nonachlor Component K Hydroxychlordene

Perceilt Residue 17.6 3,4 8.0 17.6 ]3.4 29.0 51.0 53.0 50.0 49.5 52.0

Times Beach Soil Percent Residue 25.0 <0.5 0.8 24.5 23.0 35.0 47.0 53.0 53.0 47.C 62.0

Koc 5.0 NO NO 5.1 5.0 4.9 4.9 4.9 5.0 5.0 5.0 ~,9

Visalia

Soi !

Percent Koc 5.0 ND NO 5,0 5,0 5.0 5.i 5.i 5.1 5.2 5.2 3.1

Residue

33.0 <0.5 1.0 48,0 45.0 47.0 61,0 57.0 49,0 50.0 56.0

Koc 5.3 NO NO 5.4 5,4 5,2 5.4 5.3 5.4 5.3 5.3 3.5

Expressed a: percent residual concentration. RO - Not de-ermined

The partition coefficient (log Kd) of the chlordane constituents ranged from 2.9 to 3.7 in surfactant-free systems (Table I l l ) ;

addition of 0.01% lauryl sulfate resulted in an

increase in the concentration of "dissolved" chlordane.

There was no effect of pH on the

partition coefficients of the chlordane profile constituents. From these results, we conclude that chemical/biochemical transformation and erosion of the particle-bound pesticide are likely to play the dominant role in determining the mode of transport and fate of chlordane used for subterranean applications. (~}

:]

-!

i :i

! :) )

Fig. 7:

It2 ¢C' 1; ?

~ooPP:.1 ;UR~'Acr;,xT

i/

;

:6 EO ~ C'C, 21 2O 21 4O 25 6O 27 ~

,'

i

I

3'1

d rl lJ' 11

3C ,C

Effect of surfactant on the concentration of chlordane constituents. REFERENCES

i.

Arruda, J.A., M.S. Crigan, W.G. Layher, G. Kersh, and C. Bever, Environ. Contam. Toxicology, 41, 6]7 (1988).

2.

Johnson, M.G.J.R. Kelso, S.E. George, Can J. Fish Aquat. Sci. Occup. Environ. Toxicoloqy., 10, (supp. I ) , 170-178 (1988).

3.

U.S. Food and Drug Admin. Fed. Registr. Jan., ]5, 1980, 45 (i0), 2904.

4.

Beeman, R.W., F. Matsumara, J. Agri. Food Chem., 29, 84 (1981).

5.

Bennett, D.L., R. Ballee, R.C., Hall, W.L. Butts, J.V. Osmen., Bull Environ. Contam. 30xicol., 11 64 (1974).

6.

Harris, C.R., W.W. Sans, Prec., Entomol. Soc. of Ontario, 106, 34-38 (1975).

7.

Kapila, S., A.F. Yanders, C.E. Orazio, J. C Meadows, S. Cerlesi and T.E. Clevenger, Chemosphere, L8, 1297 (1989).