Solving Hazardous Waste Problems - ACS Publications - American

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Chapter 16

Case Study and Proposed Decontamination of a Closed Herbicide Plant in the Federal Republic of Germany H.-J. Jürgens and R. Roth Dekonta GmbH, Lotharstrasse 26, D-6500 Mainz, Federal Republic of Germany

This chapter describes the background to the closing of a $50 million chemical plant in Hamburg, Federal Republic of Germany, and proposed decontamination steps.

History The plant, on the outskirts of Hamburg, began in 1923 as a branch for chemical pharmaceutical production of morphine and codeine. In 1951, production of herbicides began with the manufacture of hexachlorocyclohexane (HCH) and the corresponding isolation of lindane. The inactive isomers from this production were stored on site. In 1953, recycling efforts for these waste isomers began, and thermal decomposition of these residues led to integration of several process steps (see figure). Thermal decomposition of the HCH isomers led to a 75% yield of 1,2,4-trichlorobenzene, which opened the process for production of 2,5-dichlorophenol and the corresponding bromination product. In addition to 2,5-dichloro-4-bromophenol production, the recycled trichlorobenzene was converted to 1 , 2,4,5-tetrachlorobenzene which could then be converted to 2,4,5-trichlorophenoxyacetic acid. Formulation out also.

of

insecticides

and

herbicides

was

carried

The residues from the thermal decomposition were significantly smaller than the inactive HCH isomers. Although 2,3,7,8-TCDD content in 2,4,5-T production was known, the presence of polychlorinated dioxins in the residue from the thermal decomposition of HCH isomers was not demonstrated until 1984 (Table I).

0097-6156/87/0338-0221 $06.00/0 © 1987 American Chemical Society

Exner; Solving Hazardous Waste Problems ACS Symposium Series; American Chemical Society: Washington, DC, 1987.

222

SOLVING HAZARDOUS WASTE PROBLEMS

Oj


Benzene

*3Q, j n.D

He»chlorocyclohe*ine (HCH)

y -HCH Lindane sales product

60 - 70 %

a aee e e

5 - 12 %

e eeee e

10 - 15 %

aaaeee

6 - 10 %

ae eee e

3 - U %

ae e ae e

position of CI-atom '

OL, fr.cf. I -HCH

thermal destruction

2. U. 5-Trichlorophenoxyaceticacid sales product f ROH

ichlorophenole 2.4.5 -Trichloroi ues product

2.5-Dichoro -L - bromophenole intermediate product tor Bromophos -J-l- HCH residue waste = 351

Figure

1. R e c y c l i n g p r o d u c t i o n

o f the Hamburg c h e m i c a l

plant.


16.

JURGENS AND ROTH

Table

Decontamination of a Closed Herbicide Plant

I: Analysis of the Thermal D e s t r u c t i o n Compound

Residue

Concentration

2,3,7,8-TCDD other isomers


o f HCH

(1) (ppm)

O.3 12

1,2,3,7,8-Penta-CDD other isomers

7 200

1,2,3,4,7,8-Hexa-CDD 1.2.3.6.7.81.2.3.7.8.9other isomers

45 150 65 680

1,2,3,4,6,7,9-Hepta-CDD 1,2,3,4,6,7,8-

14 0 0 3000

Octa-CDD

7600

2,3,7,8-TCDF other isomers

13 10

1,2,3,7,8-Penta-CDF 2,3,4,7,8other isomers

1-2 15 40

1,2,3,4,7,8-Hexa-CDF 1,2,3,6,7,82,3,4,6,7,8other isomers

65 17 13 230

1 . 2 . 3 . 4 . 6 . 7 . 8 - Hepta-CDF 1.2.3.4.6.7.91,2,3,4,6,8,91,2,3,4,7,8,9-

370 15 100 10

Octa-CDF

200

T h e r e f o r e , an e x c e p t i o n a l r e c y c l i n g proc e s s , w h i c h c o n v e r t e d w a s t e HCH isomers to u s e f u l product, l e d to the c l o s i n g o f the l i n d a n e p l a n t .


224

Plant


Closing


How d i d i t happen? The p r o d u c t i o n f a c i l i t i e s were n o t outmoded s i n c e the p r o d u c t i o n p l a n t was c o n t i n u a l l y m o d e r n i z e d a c c o r d i n g to b e s t a v a i l a b l e t e c h n o l o g y , and between 1980 - 1984 a t o t a l o f 30 m i l l i o n DM were i n v e sted in environmental p r o t e c t i o n . A major r e a s o n f o r the c l o s i n g was p r e s s u r e by the p u b l i c on g o v e r n m e n t . The p l a n t i s s e p a r a t e d by a r o a d from a n e i g h b o r h o o d w i t h many s m a l l v e g e t a b l e g a r d e n s . Increased a i r e m i s s i o n s o f HCH, w h i c h l e d t o i n c r e a s e s o f HCH i n v e g e t a b l e s , g a i n e d e x t e n s i v e media a t t e n t i o n i n 1979, alt hough the HCH c o n t e n t i n v e g e t a b l e s was n o t d e m o n s t r a t e d to be h a z a r d o u s to h e a l t h . In 1981, a s p e c t a c u l a r o c c u p a t i o n o f a s t a c k i n the p l a n t by G r e e n p e a c e l e d t o the b e g i n n i n g o f the p r e s s u r e by p u b l i c i n t e r e s t g r o u p s and e c o l o g i s t s (Green P a r t y ) on the p l a n t and on the a p p r o p r i a t e a g e n c i e s o f the F r e e and H a n s e a t i c C i t y o f Hamburg. In 1983, the a t t e n t i o n r e s u l t i n g from t h e 41 drums o f waste from S e v e s o , l o s t d u r i n g t r a n s p o r t , l e d to p r o h i b i t i o n of t r a n s p o r t of residues c o n t a i n i n g 2 , 3 , 7 , 8 - T C D D i n Germany. In t h i s manner, i n c i n e r a t i o n o f the l i q u i d r e s i d u e s a t sea became e l i m i n a t e d as a d i s p o s a l o p t i o n . C o n s e q u e n t l y , the H a m b u r g - M o o r f l e e t p l a n t s t o p p e d p r o d u c t i o n o f 2 , 4 , 5 - T , f o r w h i c h a new b u i l d i n g and p r o c e s s had been e r e c t e d i n 1978. The newly f o u n d e d d e p a r t m e n t o f e n v i r o n m e n t a l p r o t e c t i o n i n Hamburg i n c r e a s e d i t s search for d i o x i n i n p r o d u c t i o n , waste, aqueous d i s c h a r g e s , and i n s o i l . A f t e r s o i l from the p l a n t was f o u n d t o c o n t a i n about 30 ppb o f 2 , 3 , 7 , 8 - T C D D , and b e c a u s e o f the known TCDD c o n t e n t s i n r e s i d u e s from 2 , 4 , 5 - T p r o d u c t i o n , the company r e m a i n e d i n the headlines. R e f e r e n c e s t o the company a p p e a r e d i n a l m o s t e v e r y p u b l i c a t i o n r e l a t i n g to TCDD, e i t h e r m u n i c i p a l i n c i n e r a t o r s , l a n d f i l l s , o r r e s i d u e s i n f i s h . When i t was d e m o n s t r a t e d t h a t the r e s i d u e from the t h e r m a l d e c o m p o s i t i o n o f HCH contained, unexpectedly, 2 , 3 , 7 , 8 - T C D D and o t h e r p o l y c h l o r i n a t e d d i o x i n s and f u r a n s , the company was r e q u i r e d by the Hamburg e n v i r o n m e n t a l p r o t e c t i o n d e p a r t m e n t to meet t h e f o l l o w i n g e f f l u e n t l i m i t s TCDD c o n t e n t s i n r e s i d u e 1 u g / k g , i n a i r 1 pg/m and i n aqueous d i s c h a r g e 1 ng/l(2). These l i m i t s , w h i c h had been s u g g e s t e d by E p s t e i n and o t h e r s a t t h e G e o r g s w e r d e r - S y m p o s i u m , i n June 1984, were opposed by the company b u t u p h e l d by the Hamburg c o u r t s . Since these l i m i t s represented a n a l y t i c a l d e t e c t i o n l i m i t s i n Germany, and s i n c e f u t u r e l o w e r i n g o f the d e t e c t i o n l e v e l s was p r o b a b l e , i t was u n c e r t a i n whether t h e s e v a l u e s c o u l d e v e r be met. C o n s e q u e n t l y , p r o d u c t i o n was s t o p p e d a t the s i t e . F o r c o m p a r i s o n , a t the same time the a l l o w e d e m i s s i o n s from two Hamburg m u n i c i p a l i n c i n e r a t o r s were 200 p g / m and 650 p g / m (3). :

3

3

3


16.

JURGENS AND ROTH

Cleanup


225

Plans

Dekonta i s engaged i n p l a n n i n g and c a r r y i n g o u t a p p r o p r i ate measures f o r c o n v e r t i n g the plant site into a reusable i n d u s t r i a l s i t e . T h e p r o j e c t i s d i v i d e d i n t o two p a r t s , d e c o n t a m i n a t i o n o f s o i l and u n d e r l y i n g a r e a s , and c l e a n i n g and d i s m a n t l i n g o f b u i l d i n g s and equipment. are operating


We

Soil

under

the following

wastes c o n t a i n i n g landfills.

-

Liquid normal

-

Incineration i n land-based f a c i l i t i e s that are capable of destroying d i o x i n s i s n o t a l l o w e d by l o cal authorities.

-

Incineration

-

I f permits f o r d i s p o s a l i n a secure l a n d f i l l could be o b t a i n e d , t r a n s p o r t a t i o n o f w a s t e s containing d i o x i n a b o v e 10 u g / k g i s p r o h i b i t e d . E x c e p t i o n s t o this transportation prohibition are possible but not specified. Therefore, on-site destruction of liquid wastes remains t h e only a l t e r n a t i v e , however, s p e c i fic procedures are not defined.

-

S o l i d wastes c o n t a i n i n g d i o x i n s c a n be d i s p o s e d i n one s e c u r e l a n d f i l l , an o l d s a l t mine l o c a t e d a t Herfa-Neurode i n Hessen. There a r e three major r e strictions :

a t sea also

dioxins

guidelines:

cannot

are not allowed i n

be

permitted.

1.

Only wastes from are accepted.

2.

The l a n d f i l l imposes t i o n s which, i n case disposal weight.

3.

The p o s s i b l e e x c e p t i o n of the transportation proh i b i t i o n i s tied to specific packaging requirem e n t s . A d i s t i n c t i o n i s made b e t w e e n t h o s e w a s t e s containing greater t h a n 10 u g / k g a n d t h o s e b e l o w t h a t number.

and

the Federal

Republic

o f Germany

special packaging restricof our wastes, double the

Groundwater

The 80,000 s q m e t e r a r e a h a s b e e n d i v i d e d i n t o a g r i d a n d , s i n c e May 1985, 46 e x p l o r a t o r y d r i l l i n g s t o 30 t o 60 met e r s a n d 118 d r i l l i n g s t o 8 m e t e r d e p t h s h a v e b e e n c a r r i e d o u t . I n a d d i t i o n , 32 w e l l s a r e b e i n g d r i l l e d t o 30 m e t e r d e p t h i n t h e i m m e d i a t e v i c i n i t y o f t h e p l a n t s i t e . The s o i l samples a r e b e i n g a n a l y s e d f o r t o t a l e x t r a c t a b l e halide, specific production m a t e r i a l s by gas c h r o m a t o g r a p h y ,


226


and t o t a l PCDD*s. T h e g e o l o g i c a l a n d h y d r o g e o l o c i a l knowledge from t h i s i n v e s t i g a t i o n , coupled with t h e a n a l y t i c a l r e s u l t s , w i l l be t h e b a s i s f o r a d e c o n t a m i n a t i o n p l a n .


Preliminary

results

from

the exploratory borings are:

-

The p l a n t area c o n t a i n s areas t h a t a r e h i g h l y t a m i n a t e d , w i t h EOX v a l u e s u p t o 2 8 4 , 0 0 0 ppm.

-

The p o l l u t i o n chlorophenols

-

A few samples from t h e s u r f a c e a r e a T C D D . One s a m p l e c o n t a i n s 9 ppm.

-

Groundwater below contaminated minated, 2,3,7,8-TCDD has been

-

Contamination decreases markedly EOX-values i n s o i l are g e n e r a l l y

-

Geologic c o n d i t i o n s l i m i t the groundwater n a t i o n t o a r e a s o n a b l y w e l l - d e f i n e d plume the South.

r e s u l t from c h l o r o b e n z e n e s , and 2 , 4 , 5 - T - a c i d .

con-

HCH,

contain

2,3,7,8-

soil i s also contanot detected. outside the plant. l e s s t h a n 2 0 ppm. contamitowards

1 4 % o f t h e b o r i n g s a t d e p t h c o n t a i n EOX a t g r e a t e r t h a n 2 0 ppm, w h e r e a s 4 0 % o f t h e s h a l l o w b o r i n g s h a v e similar contamination levels. S o i l c o n t a m i n a t e d w i t h l e v e l s o f TCDD u p t o 9 ppm a r e s u b j e c t t o immediate r e s p o n s e . About 2,000 m o f such s o i l w i l l be e x c a v a t e d a n d p l a c e d i n t o an i n t e r i m s t o r a g e a r e a upon a p p r o v a l by t h e Hamburg a u t h o r i t i e s . T h e s e contaminated s o i l s w i l l be s t o r e d u n t i l a d e s t r u c t i o n method b e c o m e s a v a i l a b l e . S u c h a m e t h o d w i l l be p r o p o s e d upon c o n c l u s i o n o f t h e d r i l l i n g t e s t p r o g r a m . S o i l decont a m i n a t i o n methods must a l s o t a k e a c c o u n t o f t h e b u i l d i n g and equipment cleanup p r o c e d u r e s . 3

Buildings

and Equipment

E q u i p m e n t i s t o be c l e a n e d f o r o f f - s i t e reuse or scrapp i n g . B u i l d i n g s a r e t o be c l e a n e d o r d e m o l i s h e d . The d e g r e e o f c o n t a m i n a t i o n o f t h e b u i l d i n g s a n d t h e equipment i s being determined a c c o r d i n g t o t h e p r i n c i p l e of w o r s t c a s e . S e l e c t i o n o f s a m p l e s from a r e a s most likel y t o be c o n t a m i n a t e d w i l l l e a d t o t h e e s t a b l i s h m e n t o f p e r s o n a l p r o t e c t i o n measures and t o t h e a p p r o p r i a t e decont a m i n a t i o n method. Four l e v e l s o f worker p r o t e c t i o n have been e s t a b l i s h e d w i t h a p p r o p r i a t e p r o t e c t i v e equipment:


16.


JURGENS AND ROTH

227

0

no c h e m i c a l ea r e q u i r e s

contamination n o r m a l work c l o t h i n g .

A

Chemical contamination a n d 2,3,7,8-TCDD e q u i v a l e n t s < 0,01 ppm Work i n t h i ^ a r e a w i l l b e c a r r i e d o u t i n c o a t e d T y v e x , safety shoes with b o o t i e s c h e m i c a l l y resis t a n t g l o v e s , p a r t i a l f a c e mask w i t h particulate a n d o r g a n i c v a p o r r e s p i r a t o r s , a n d safety glasses.


/

B

Chemical contamination a n d 2,3,7,8-TCDD e q u i v a l e n t s b e t w e e n 0 , 0 1 - 1,0 ppm In t h i s a r e a , t h e a r e a A p r o c e d u r e s w i l l be expand e d t o i n c l u d e f u l l f a c e mask a n d more f r e q u e n t clothing changes.

C

2,3,7,8-TCDD e q u i v a l e n t s g r e a t e r t h a n 1 ppm. Work w i l l be c a r r i e d o u t i n a i r - s u p p l i e d suits.

Workers i nthe p r o j e c t a r e b e i n g monitored by a comprehensive occupational health examination on a 6-month-basis. A comprehensive sample t r a c k i n g p r o c e d u r e h a s been developed. F o r example, t h ecomputerised system assigns a number w h i c h c o n t a i n s a s e q u e n t i a l sample number, d a y a n d date, coordinates according t o a s i t e g r i d (length, width, l e v e l ) , b u i l d i n g number, a n d sample t y p e such as :

Sequential sample number

Day+Date

Grid-Coordinates

200002

MI

L 272 B 102 H 4,6

13.02.85

building number

B250

sample typ

02

A d d i t i o n a l i n f o r m a t i o n i sadded t o d e f i n e t h e s p e c i f i c p i e c e o f equipment a n d sample l o c a t i o n . T h i s p r o c e d u r e w i l l a l s o c o n t a i n i n f o r m a t i o n about decontamination procedures, d e m o l i t i o n , d i s p o s i t i o n o f r e s i d u e s , and d i s p o s i t i o n o f cleaned equipment f o r reuse o r scrapping. T a r g e t l e v e l s were e s t a b l i s h e d f o r c l e a n i n g equipment s u r f a c e s . These l e v e l s f o r normal p r o d u c t s were proposed based on a s i m p l e e v a l u a t i o n o f t o x i c o l o g i c a l d a t a , such as ADI ( a l l o w a b l e d a i l y i n t a k e ) o r L D 5 0 , and e s t i m a t e s o f dermal c o n t a c t and p o t e n t i a l s k i n a d s o r p t i o n ( T a b l e I I ) .


228


Table

I I . TARGET

LEVELS

FOR E Q U I P M E N T

Compound

Concentration

HCH 18 1.2.4- T r i c h l o r o b e n z e n e 2000 2 4,5-T-acid 107 2.4.5- T r i c h l o r o p h e n o l 89 2,3,7,8-TCDD 0,000004 f


DECONTAMINATION

-

mg/m

2

77 8800 462 385 0,000155

Cleaning and d i s m a n t l i n g o f t h e lindane p l a n t w i l l begin t h i s s u m m e r . A l t h o u g h t h i s u n i t c o n t a i n s n o PCDD, worker p r o t e c t i o n a n d d e c o n t a m i n a t i o n p r o c e d u r e s w i l l be e s t a b l i s h e d as t r a i n i n g f o rcleanup o f PCDD-containing p l a n t s . C l e a n i n g water a n d s u r f a c e r u n o f f w i l l be c o l l e c ted and t r e a t e d by f i l t r a t i o n through an a c t i v a t e d carbon s y s t e m t h a t i s b e i n g c o n s t r u c t e d b y D e k o n t a . We e x p e c t t o meet o r e x c e e d t h e d i s c h a r g e criteria t o t h e Hamburg waste w a t e r t r e a t m e n t p l a n t o f 1 n g / 1 o f TCDD.

Literature 1) Analysis

Cited was made by:

Dr. H.R. Buser, Eidgenössische anstalt, CH-8820 Wädenswil, 2) Freie

und Hansestadt

ForschungsSchweiz

Hamburg

Behörde für Bezirksangelegenheiten, Naturschutz und Umweltgestaltung -Amt für UmweltschutzNachträgliche Anordnung nach § 17 BImSchG zu den Genehmigungsbescheiden der Fa. C.H. Boehringer Sohn vom 18.06.1984 3) Bürgerschaft der Freien und Hansestadt Hamburg Drucksache 11/3159 vom 30.10.1984 Mitteilung des Senats an die Bürgerschaft

R E C E I V E D November 25, 1986


Solving Hazardous Waste Problems - ACS Publications - American

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