Laboratory Evaluation of Products of Incomplete Combustion Formed

Chapter 6

Laboratory Evaluation of Products of Incomplete Combustion Formed from Burning of Agricultural Product Bags Downloaded by STANFORD UNIV GREEN LIBR on August 2, 2012 | http://pubs.acs.org Publication Date: October 30, 1992 | doi: 10.1021/bk-1992-0510.ch006

1

B. Adebona, A. Shafagati, E. J. Martin, and R. C. Chawla

School of Engineering, Howard University, Washington, DC 20059

Unused and used empty, aluminum-lined, multiwall bags, utilized as containers for pesticides were burned in an infrared incinerator in the induced air mode, at temperatures ranging from 300 to 1000 °C. Combustion parameters for test conditions were selected to simulate "open burning," a popular disposal option for used pesticide bags. Emissions were analyzed for organic products of incomplete combustion (PICs) using appropriate sampling equipment and a gas chromatograph / mass spectrometer (GC/MS). Preliminary analysis shows the presence of cyclic compounds in the emitted gas streams from burning both used and unused bags. Number and concentration of PICs decreased as the combustion temperature increased. Results illustrating the relationship between PIC formation and combustion temperatures are presented and discussed.

With t h e passage and implementation o f t h e 1988 Amendments t o t h e F e d e r a l I n s e c t i c i d e , Fungicide and R o d e n t i c i d e A c t (FIFRA-88), t h e U.S. Environmental P r o t e c t i o n Agency (EPA) i s proposing t o r e v i s e the r e g u l a t i o n s r e l a t e d t o s t o r a g e , d i s p o s a l , t r a n s p o r t a t i o n and r e c a l l o f p e s t i c i d e s and p e s t i c i d e c o n t a i n e r s , and i n c o r p o r a t e e x i s t i n g a u t h o r i t y i n t o 40 CFR P a r t 165. A s s o c i a t e d data requirements w i l l be i n c o r p o r a t e d i n 40 CFR P a r t 158. Of t h e f o u r elements o f planned a t t e n t i o n by EPA: storage, d i s p o s a l , t r a n s p o r t a t i o n and r e c a l l , d i s p o s a l i s o f i n t e r e s t i n t h i s paper.

Corresponding author

0097-6156/92/0510-0063$06.00/0 © 1992 American Chemical Society In Pesticide Waste Management; Bourke, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1992.

64

PESTICIDE WASTE MANAGEMENT

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The primary options p o t e n t i a l l y u s e f u l f o r d i s p o s a l o f bags a r e r e c y c l e (probably not p r a c t i c a l f o r paper bags), l a n d f i l l (which i m p l i e s c o s t s and r i s k s f o r t r a n s p o r t a t i o n and long term storage) , and open burning a t the p o i n t o f use. Open burning i s the most used o p t i o n because i t i s l e a s t c o s t l y t o the user and i s a v a i l a b l e o n - s i t e . Many p e s t i c i d e users are i n v o l v e d with d i s p o s a l o f t h e 1/4 b i l l i o n p e s t i c i d e containers generated each year (1) . About 30% of the t o t a l number o f c o n t a i n e r s i s estimated t o be 50-lb. bags (2) . T h i s c o n s t i t u t e s use of about 75 m i l l i o n 50-lb. p e s t i c i d e bags per year. B r i e f H i s t o r y o f M u l t i w a l l Shipping Bags Over 100 years ago, shipping sacks f i r s t used t o t r a n s p o r t products such as f l o u r and feed t o the market p l a c e were made o f burlap and/or cotton. P r i o r t o t h i s time, t h e popular method o f shipping bulk m a t e r i a l s was i n b a r r e l s or wooden c r a t e s . When cotton became scarce d u r i n g t h e C i v i l War, manila rope paper made from 100% manila f i b e r was introduced as a s u b s t i t u t e f o r burlap and c o t t o n . Bags were c l o s e d by gathering a t the top and t y i n g with cord. E a r l y i n the 20th Century a manila rope paper bag was invented; i t was pasted a t both ends with a " v a l v e " opening. The bag was o r i g i n a l l y intended t o package s a l t but was soon used f o r cement and limestone. When manila rope became scarce a f t e r World War I, kraft paper was mixed with manila fiber, but t h e combination r e s u l t e d i n a very s t i f f composition. The idea of u s i n g two p l i e s , each of a l i g h t e r weight, was introduced t o g i v e a more acceptable bag c o n s t r u c t i o n . The m u l t i w a l l bag became a r e a l i t y . In 1924, 3, 4, and 5 w a l l bags were introduced, but made e n t i r e l y o f 100% k r a f t paper. The problem of c l o s u r e was solved by sewing the plies together. Today the m u l t i w a l l bag i s very s o p h i s t i c a t e d and contains many other m a t e r i a l s besides paper t o provide properties of s t r e n g t h , moisture r e s i s t a n c e , o i l p e n e t r a t i o n r e s i s t a n c e and odor p r e v e n t i o n (Figure 1) . K r a f t paper may be laminated with low and h i g h d e n s i t y polyethylene, aluminum f o i l , and g l a s s i n e (3) . Bags may be coated with various substances l i k e inks and dyes t h a t a r e used t o provide a wide range o f data and i n f o r m a t i o n t o the user. Thus today's s h i p p i n g bag may be a complex combination of chemicals i n a d d i t i o n t o t h e contained m a t e r i a l ( s ) , adding t o the c o m p l i c a t i o n o f a s s e s s i n g the environmental and h e a l t h conseguences o f bag disposal. Why be Concerned with Bags? Product r e t e n t i o n s t u d i e s by container manufacturers have i n d i c a t e d t h a t some product i s r e t a i n e d i n t h e bag a f t e r emptying. The average q u a n t i t y o f 5% Diazinon f o r m u l a t i o n , f o r example, r e t a i n e d i n the bag i n one study f o l l o w i n g

In Pesticide Waste Management; Bourke, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1992.

6. ADEBONAETAL.

Laboratory Evaluation of PICs PINCH BOTTOM

- OPEN MOUTH


4 PLY EXAMPLE

PLY 1 = ADHESIVE + METALLIZED FILM PLY 2 = ADHESIVE + PAPER PLY 3 = ADHESIVE + PAPER PLY 4 = PAPER 4- INK Figure

1 Multiwall

Bag


66


s t a n d a r d i z e d opening, emptying and shaking t e s t s , was about 0.12 grams or 2.64 χ 10" l b . ( L e t t e r from E. Tytke t o B. Omilinsky of Formulogics on Stone Container C o r p o r a t i o n Product R e t e n t i o n Evaluation, August 7, 1990). In a 50 l b . bag t h i s represents about 33.6 χ 10" l b o f D i a z i n o n . Using t h i s value, the amount of Diazinon remaining i n bags on a nationwide b a s i s would be about 2600 l b s . ( r o u g h l y one ton) annually. I f a l l of the bags and contents were burned a t 99% d e s t r u c t i o n e f f i c i e n c y , about 25 l b s . / y e a r would be discharged t o the atmosphere. Other estimates of m a t e r i a l r e t a i n e d i n bags s i m i l a r t o the one i n v e s t i g a t e d i n t h i s study range as high as 2 grams or 4.4 χ 10" l b . ( 3 ) . In a d d i t i o n t o the bag contents - i n t h i s case a p e s t i c i d e - t h e bag and i t s c o n s t r u c t i o n components may be sources of PICs. Table I shows the p o s s i b l e sources of PICs among the bag components. The bag used f o r t h i s study c o n t a i n s only the components shown with an a s t e r i s k (*). A r i s k a n a l y s i s f o r i n c i n e r a t i o n o f used p e s t i c i d e c o n t a i n e r s has not been performed as y e t . I t would p r o v i d e an i n d i c a t i o n of the p o t e n t i a l impact o f t h e r e s i d u a l pesticide (in this case Thimet) material left in containers. The r i s k a n a l y s i s would proceed i n s e v e r a l e s t i m a t i o n steps: 4

6


3

• • • • • •

r e s i d u a l p e s t i c i d e i n container number of c o n t a i n e r s used number of c o n t a i n e r s burned types and q u a n t i t i e s of emissions based on t h i s and other combustion s t u d i e s p o t e n t i a l l y exposed p o p u l a t i o n d i s p e r s i o n t o the exposed p o p u l a t i o n

The Howard Program The Howard U n i v e r s i t y Combustion Research Laboratory (HUCORL) i s dedicated t o the a n a l y s i s and d i s c o v e r y o f t h e requirements f o r e f f e c t i v e combustion o f wastes and t h e understanding of the combustion process. HUCORL was e s t a b l i s h e d t o develop and r e f i n e combustion technology and i t s a p p l i c a t i o n s t o a l l i n d u s t r i a l and commercial processes t h a t r e q u i r e burning as an i n t e g r a l p r a c t i c e . Because hazardous waste d e s t r u c t i o n i s an important n a t i o n a l need a t t h i s time, the primary t h r u s t of t h e work o f t h e Laboratory i s d i r e c t e d a t t h i s area. I n c i n e r a t i o n i s a d e s t r u c t i o n technology t h a t has been developed f o r the permanent d i s p o s a l of hazardous wastes. On t h e other hand, open burning of p e s t i c i d e c o n t a i n e r s r e p r e s e n t s u n c o n t r o l l e d combustion without t h e advantages of a i r p o l l u t i o n c o n t r o l . One of t h e combustors a v a i l a b l e a t HUCORL, t h e i n f r a r e d u n i t can be operated i n a manner t o simulate open burning, i . e . , the temperature p r o f i l e r can be s e t t o range from room temperature t o a p r e s e t maximum. In t h e case of low preset temperatures, e.g., 300 °C, t h e temperature i n the furnace w i l l sometimes exceed the p r e s e t


6. ADEBONAETAL.

Laboratory Evaluation of PICs

TABLE I


POTENTIAL SOURCES OF PICs

LAMINATES * PAPER HDPE - high d e n s i t y p o l y e t h y l e n e LDPE - low d e n s i t y p o l y e t h y l e n e * METALLIZED FILM * MYLAR POLYPROPYLENE NYLON * ADHESIVES * INKS * DYES GLASSINE * ADDITIVES -

f o r strength, d u r a b i l i t y , appearance, e t c .

( c l a s s i f i e d chemicals,

i n general)


67


68


maximum when a flame i s present. D i f f e r e n t s e t t i n g s of the maximum temperature during t e s t i n g can be e s t a b l i s h e d i n order t o simulate the exposure of v a r i o u s segments of a p i l e of unburned bags, as might occur i n a f i e l d where d i s p o s a l by burning i s being p r a c t i c e d . Samples of a c t u a l m u l t i w a l l bags t h a t had contained a g r a n u l a r formulation of phorate (Thimet 10G/15G; d i e t h y l S[ ( e t h y l t h i o ) methyl] phosphoro-dithioate) were sent t o Howard U n i v e r s i t y by EPA a f t e r being emptied u s i n g normal f i e l d p r a c t i c e s . The bags were sampled by c u t t i n g v a r i o u s p o r t i o n s which might represent d i f f e r e n t q u a n t i t i e s of r e s i d u a l Thimet formulation. These samples were then burned i n the i n f r a r e d combustor under v a r i o u s o p e r a t i n g c o n d i t i o n s s e l e c t e d t o cover the range of c o n d i t i o n s expected during open burning c o n d i t i o n s . Table I I presents a range of commonly used p e s t i c i d e s along with Thimet. Experimental

Setup

The primary component of the i n f r a r e d combustor i s a small s c a l e (100 gram capacity) e l e c t r i c powered i n s u l a t e d and c o n t r o l l e d furnace shown i n Figure 2. I t i s possible to r e c o r d the weight change of a sample d u r i n g and a f t e r combustion u s i n g a balance on the top of the u n i t . The furnace i s a l s o equipped with a temperature r e c o r d e r . The i n f r a r e d u n i t i s r e l a t e d t o other a n c i l l a r y equipment i n the l a b o r a t o r y as shown i n Figure 3. The temperature profiler c o n t r o l s the rate of temperature increase during a burn and the maximum temperature t h a t may be p r e s e t . An ? ^rburner with a separate temperature c o n t r o l l e r insures it any r e s i d u a l s which are created i n the furnace are burned t o a high degree of e f f i c i e n c y before hot gases e x i t the l a b through the b u i l d i n g stack (dedicated e x c l u s i v e l y t o HUCORL). Induced r a t h e r than f o r c e d d r a f t provides t h a t any leaks i n the system are i n t o the duct work and a f t e r b u r n e r and f i n a l l y through the stack r a t h e r than i n t o the room. Sampling i s performed from the duct work between the furnace and the a f t e r b u r n e r ; v o l a t i l e s are sampled u s i n g the v o l a t i l e organic sampling t r a i n (VOST), and semi- and n o n - v o l a t i l e s are sampled using M o d i f i e d Method 5 (MM5 or Method 23). MM5 i s the method used as a "standard" technique f o r years t o gather p a r t i c u l a t e and nonp a r t i c u l a t e , n o n - v o l a t i l e compounds from a i r samples u s i n g a combination of c o l l e c t i o n i n l i q u i d and a d s o r p t i o n on s o l i d medium. The VOST i s s i m i l a r but used f o r sampling v o l a t i l e compounds. The two systems o f t e n e x h i b i t some "crossover," i . e . , both v o l a t i l e and n o n - v o l a t i l e compounds may be c o l l e c t e d on each. S i m u l a t i n g an Open Burn The p r o f i l e r brings the temperature i n the furnace up t o the p r e s e t value w i t h i n a few minutes as shown i n F i g u r e 4,


6. ADEBONA ET AK

Laboratory Evaluation ofPICs

TABLE I I PESTICIDE TYPES EXAMPLES


TYPE

ORGANIC Phosphorus-containing

THIMET (Phorate) Parathion Malathion

Nitrogen-containing

Carbamates Alachlor Captan Diquat

Sulfur-containing

Chlorobenside EXD

Chlorophenoxy

CPA 2,4-D

Polyhalogen

DDT DDD

Polygen-Aromatic

Toxaphene

ORGANO-METALLICS

Carbon-metal bonded

INORGANICS Heavy Metal-High Tox

A r s e n i c , Cadmium

Heavy Metal-Mod. Tox

Copper

F l u o r o Compounds

Sodium f l u o r i d e

Miscellaneous

A l , Zn, Cyanide


69



WEIGHT BALANCE DUCT TO AFTERBURNER

."-| r-ODO

VOST

Ο




72



6. ADEBONAETAL.

73

Laboratory Evaluation ofPICs

r e g a r d l e s s of the temperature s e t t i n g . R e f e r r i n g t o F i g u r e 4, a t lower temperature s e t t i n g s (300 °C i n t h i s c a s e ) , the flame temperature as the sample burns may exceed the p r e s e t p r o f i l e r value. The VOST and MM5 samplers may be operated f o r about 20 minutes i n a given c y c l e ; the sampling p e r i o d t h e r e f o r e , extends beyond the completion of a sample burn d u r i n g a t e s t ( t y p i c a l l y 5 t o 15 minutes). The c o l l e c t e d sample contains a p o r t i o n of the emissions from the e n t i r e sample burn. PICs produced at lower temperatures are thus a p a r t of the sample as w e l l as PICs from h i g h e r temperatures. Indeed, there are s i m i l a r i t i e s among PICs a t both high and low temperatures as d i s c u s s e d i n the r e s u l t s . The o v e r a l l time p e r i o d of a simulated burn was r e p r e s e n t a t i v e of an a c t u a l open burn. W i t h i n a few minutes of l i g h t i n g bags with a match i n the f i e l d , flames spread t o engulf the e n t i r e p i l e and then recede. Most of the bag m a t e r i a l i s completely burned, some i s charred ( p a r t i a l l y burned), and some i s l e f t unburned. Samples recovered a f t e r a simulated t e s t burn showed s i m i l a r characteristics. R e s u l t s and D i s c u s s i o n On a p r e l i m i n a r y b a s i s (before c o n f i r m a t i o n of the i d e n t i t y of a l l compounds), the f o l l o w i n g t o t a l numbers of PICs were found by GC/MS a n a l y s i s using the N a t i o n a l I n s t i t u t e of Standards and Technology (NIST) l i b r a r y of r e f e r e n c e s p e c t r a f o r comparison: PICs from unused bags at 300 °C PICs from unused bags a t 1000 °C PICs from used bags at 1000 °C

7 8 14

More PICs were found from burning used bags than unused bags. About the same number of PICs (although some q u a l i t a t i v e d i f f e r e n c e s e x i s t ) were found from unused bags at both 300 °C and 1000 °C. T h i s i n d i c a t e d as p o i n t e d out earlier, that a l l PICs produced during temperature p r o f i l i n g over the f u l l range are gathered by the sampling systems. Almost a l l of the compounds - from used and unused bags - were p o l y c y c l i c aromatic ( m u l t i p l e benzene r i n g ) compounds i n d i f f e r e n t c o n f i g u r a t i o n s and w i t h d i f f e r e n t s u b s t i t u t i o n s , as shown i n Table I I I . The presence of these compounds suggested o r i g i n s other than the paper bag i t s e l f , or even the phorate (Thimet) molecule. A d d i t i o n a l burns are c o n c e n t r a t i n g on the inks and adhesives used t o laminate the bag l a y e r s d u r i n g construction. On the other hand, the sources of PICs may be more d i f f i c u l t t o determine. Table IV compares some of the PIC compounds from t h i s study to two others. A complementary study done by Science Applications International C o r p o r a t i o n (SAIC) f o r EPA used a f u l l s c a l e open burning s i m u l a t i o n of Thimet bags i n F l o r i d a (4) . The HUC0RL



74

TABLE I I I SUMMARY OF PICs FROM BAG BURNS


COMPOUND

UNUSED 300 PC

UNUSED 1000 PC

USED 1000 PC

Napthalene

X

X

X

Azulene

X

X

X

1,3,5,7-cyclo-octatetraene

Χ

X

S u b s t i t u t e d A l k y l Benzenes

Χ

X

2- dodecene

X

2-methy1-2-propenylbenzene

X

Indenes

X

Cyclotetradecane

X

Acenapthalene

X

Diethylbenzene

X

Decahydro-diethylnapthalenes

X

Anthracene

X

Phenanthrene

X

9H-fluorene

X


6. ADEBONAETAL.

75

Laboratory Evaluation of PICs


TABLE IV Confirmed Compounds Recovered from Burns of Bags and P l a s t i c Mulch M a t e r i a l

COMPOUNDS Naphthalene

TYPE

HUCORL

polycyclic

X

Biphenyl Acenaphthalene

LINAK

X

X

X

X

X

-

X

2-methylnaphtha1ene Flouranthene Phenanthrene

SAIC

··

X

X

X

X

X

Diethylbenzene

monocyclic

X

9H-fluorene

polycyclic

X

Benzyl a l c o h o l

monocyclic

X

Pyrene

polynuclear

X

2,4-dimethylphenol

monocyclic

X

Phenol

•1

2-methylphenol

II

X

X

X

X X

Dibenzofuran

polycyclic

X

B i s (2-ethylhexyl) phthalate

monocyclic

X


X

X

76


r e s u l t s d i d not represent PICs from VOST samples, however, w h i l e the SAIC r e s u l t s d i d . The Linak and Ryan e t a l . (5), r e s u l t s are not from bag burning but from simulated f i e l d burns of a g r i c u l t u r a l p l a s t i c s used f o r mulching. Some of the Linak (5) PIC compounds were e x t r a c t e d from the residue a f t e r burning and d i d not appear i n the emissions. There i s a s i m i l a r i t y among the compounds i n a l l three s t u d i e s however, i n t h a t many were mono- and p o l y c y c l i c i n nature.


Conclusions S e v e r a l c o n c l u s i o n s may be drawn from the study thus f a r : •

Most PICs from the simulated open burning of Thimet p e s t i c i d e container bags are p o l y c y c l i c aromatic compounds. Cyclic compounds are produced from simulated open burning of a g r i c u l t u r a l product c o n t a i n e r s i n both the l a b o r a t o r y and large, f i e l d - s c a l e t e s t s .

•

More PICs are produced from burning used Thimet bags than from burning unused bags.

I

PICs are produced unused bags.

•

Naphthalene i s a prominent PIC from burning used and unused bags. Compounds related to naphthalene are common among PICs.

from

burning both used

and

Acknowledgment The work performed was p a r t i a l l y supported by the U.S. EPA, O f f i c e of P e s t i c i d e Programs. The work was executed w i t h i n the scope of the U.S. EPA grant, No. CR 817460-01-0. Literature Cited 1. 2. 3. 4.

Executive Summary for Proposed 40 CFR Part 165. U.S. EPA, May 1990. Pesticide Containers - A Report to Congress. Red Border D r a f t , O f f i c e of P e s t i c i d e Programs, U.S. EPA, Washington, D.C., March 1991. The Bag Packaging Workshop Manual. Stone Container Corporation, Bag D i v i s i o n . Undated, c. 1989. Engleman, V.S., Jackson, T.W., Chapman, J.S.F., Evans, J.B., Martrano, R.J., and Levy, L.L. Field Test of Open Burning of Pesticide Bags in Farm Fields. Draft r e p o r t t o the U.S. EPA, Risk Reduction Engineering Laboratory, C i n c i n n a t i , Ohio, by Science A p p l i c a t i o n s I n t e r n a t i o n a l Corp., August 1991.


6. ADEBONA ET AL. Laboratory Evaluation of PICs 5.

77

Linak, W.P., Ryan, J.V., Perry, E., W i l l i a m s , R.W., and DeMarini, D.W. Chemical and Biological Characterization of Products of Incomplete Combustion from the Simulated Field Burning of Agricultural Plastics. JAPCA, v. 39, No.6, June 1989. 1992


RECEIVED July 20,


Laboratory Evaluation of Products of Incomplete Combustion Formed

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