Treating Pesticide-Contaminated Wastewater - American Chemical

9 Treating Pesticide-Contaminated Wastewater Development and Evaluation of a System JOHNC.NYE

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Purdue University, West Lafayette,IN47907

Over the past five years, a system for removing pesticides from the wash water produced by pesticide applicators as they clean their equipment has been developed. The system incorporates a two-stage treatment process. The first step is the flocculation/coagulation and sedimentation of the pesticide contaminated wash water. The supernatant from the f i r s t step i s then passed through activated carbon columns. This paper describes the development of the system, the evaluation of the system's adequacy to handle a wide variety of pesticides, and the recommendations on the implementation of this system to commercial pesticide applicators.

Commercial p e s t i c i d e a p p l i c a t o r s are faced with a serious problem in the proper d i s p o s a l of the l a r g e volumes of p e s t i c i d e contaminated wastewater that are produced during the cleanup of a p p l i c a t i o n equipment. Various studies (Whittaker etal.1982) have reported that the t y p i c a l a g r i c u l t u r a l p e s t i c i d e applicator will produce between 100 and 400 liters of pesticide-contaminated wash water each time he cleans the equipment. For a t y p i c a l applicator, t h i s amounts to approximately 20,000 liters o f waste annually from each piece of equipment (i.e., airplane or truck) that he uses. Very few techniques are a v a i l a b l e f o r p e s t i c i d e applicators to use to handle t h i s volume of concentrated wastewater. The technology used by chemical manufacturers f o r handling large volumes of low concentrations o f wastewater is too expensive to be feasible f o r agricultural applicators. Techniques such as evaporation ponds and g r a v e l d i s p o s a l p i t s have been proposed but these methods r e q u i r e s u i t a b l e weather c o n d i t i o n s f o r evaporation and degradation of the p e s t i c i d e s . The o v e r a l l o b j e c t i v e of the research work that began i n 1978 a t Purdue was to develop a system to a s s i s t chemical a p p l i c a t o r s i n managing p e s t i c i d e contaminated 0097-6156/84/0259-0153$06.00/0 © 1984 American Chemical Society

Krueger and Seiber; Treatment and Disposal of Pesticide Wastes ACS Symposium Series; American Chemical Society: Washington, DC, 1984.

154

TREATMENT A N D DISPOSAL O F PESTICIDE WASTES

wastewater so that the water could be reused and the could be disposed of i n an economical manner. The s p e c i f i c o b j e c t i v e s were: 1.


2.

contaminants

I n v e s t i g a t e a l t e r n a t i v e methods of removing p e s t i c i d e s from contaminated wastewater and design an i n t e g r a t e d treatment system that would be t e c h n i c a l l y and economically f e a s i b l e . Demonstrate the system to commercial p e s t i c i d e a p p l i c a t o r s and provide them with g u i d e l i n e s f o r i n s t a l l i n g the system.

The accomplishment of these o b j e c t i v e s involved two different r e s e a r c h g r a n t s : Grant No. R 805 466010, " C o l l e c t i o n and Treatment of Wastewater Generated by P e s t i c i d e A p p l i c a t o r s " , from the O i l and Hazardous S p i l l s Branch, U.S. Environmental P r o t e c t i o n Agency; and "Removal of F i v e R-PAR and Near R-Par Herbicides from Wastewater", from North C e n t r a l Regional P e s t i c i d e Impact Assessment Program. In the EPA sponsored p r o j e c t (Whittaker, et a l . 1982) the extent of the problem was i n v e s t i g a t e d and a l t e r n a t i v e means of removing p e s t i c i d e s from contaminated wastewater were e v a l u a t e d . F i r s t the c h a r a c t e r i s t i c s of t y p i c a l wash water was measured. Several aircraft were washed and Table I presents the r e s u l t s of the a n a l y s i s of t h i s wastewater.

Table I .

Volume and C h a r a c t e r i s t i c s of Wastewater Generated by A e r i a l Pesticide Applicators Characteristics

Source p e s t i c i d e formulation left in aircraft hopper r i n s e water used to c l e a n spray boom wash water to c l e a n a i r c r a f t hopper wash water to c l e a n a i r c r a f t surface T o t a l wastewater

Voume liters 5-20

COD Soluble

Total mg/1 60,000

mg/

TSS

SVS

mg/1

mg/1

40-100

13,000

9,600

11,600

8,900

20-40

88,500

5,000

18,000

14,000

75-200

1,200

500

600

350

150-360

1,200

900

1,100

950

Next s e v e r a l methods of f i l t e r i n g the p e s t i c i d e contaminated wastewater were e v a l u a t e d . P a r t i c l e s i z e f i l t e r s were i n e f f e c t i v e s i n c e many of the p a r t i c l e s are m i c r o c o l l o i d a l i n s i z e . Likewise coalescer type f i l t e r s were g e n e r a l l y inadequate. A f t e r studying these f i l t r a t i o n techniques, flocculation procedures were


9. N Y E

Treatment of Contaminated Wastewater

155


assessed. Table I I presents data from one of the t y p i c a l t e s t s conducted to determine the r e s u l t of alum (aluminum s u l f a t e ) on sedimentation.

Table I I . Use of Aluminum S u l f a t e to Remove M e t r i b u z i n by Sedimentation alum F i n a l cone. I n i t i a l cone. of M e t r i b u z i n dosage of M e t r i b u z i n (mg/1) (mg/1) (mg/1) 200 81 100 500 90 100 200 330 500 500 315 500 200 750 585 500 585 750 200 1050 1250 500 1125 1250 200 2000 996 500 982 2000 200 920 3000 500 1000 3000

Alum dosages between 200 and 500 mg/1 were not s i g n i f i c a n t l y different. Table I I a l s o i l l u s t r a t e s that sedimentation i s e f f e c t i v e i n lowering the c o n c e n t r a t i o n of the p e s t i c i d e s to the solubility limit. Metribuzin is soluble i n water to a c o n c e n t r a t i o n of about 1200 mg/1 and the sedimentation step reduced the c o n c e n t r a t i o n from 2000 and 3000 mg/1 to about 1000 mg/1. At lower c o n c e n t r a t i o n s sedimentation was not e f f e c t i v e . Other coagulants and f l o c c u l a n t a i d s such as hydroxide and f e r r i c c h l o r i d e , were tested but alum with an a n i o n i c polymer (Watcon 1255) was the most e f f e c t i v e . A c t i v a t e d carbon a d s o r p t i o n was s e l e c t e d as the means f o r the final polishing of the p e s t i c i d e contaminated wastewater. F i l t r a s o r b 300 (Calgon) was used i n these t e s t s . One of the major questions regarding activated carbon adsorption was the e f f e c t i v e n e s s of t h i s system on mixed groups of m a t e r i a l s . Whittaker (1980) conducted an extensive study to determine how much p e s t i c i d e could be adsorbed by a c t i v a t e d carbon using both isotherm and continuous column systems. Whittaker used b i s o l u t e mixtures of p e s t i c i d e s to determine the e f f e c t i v e n e s s of 25 gm activated carbon columns i n removing combinations of p e s t i c i d e s from wastewater. Table I I I shows the r e s u l t s of these s t u d i e s and indicates that a c t i v a t e d carbon can be used to remove mixtures of p e s t i c i d e s . The lowest exhaustion c a p a c i t y found i n t h i s study was 69 mg of m e t r i b u z i n adsorbed on 1 gm of a c t i v a t e d carbon.


Krueger and Seiber; Treatment and Disposal of Pesticide Wastes ACS Symposium Series; American Chemical Society: Washington, DC, 1984. Q

8.0 10.0

E

14.0 28.0 109.2 127.7

19.5 16.5

159.5 174.7

HO

21.0

186.0

2.7 4.0

117.8 29.9

1220 (20°C) 250

1100 189.0

MetribuzinPropham (Soin. Β)

> E

E

T o t a l a d s o r p t i o n c a p a c i t y where e f f l u e n t cone. ( C ) e q u a l s .1 o f influent concentration ( C ) JVolume passed where C = .1 C T o t a l a d s o r p t i o n c a p a c i t y where C = .75 C ÎVolume passed when C = .75 C 'The e x h a u s t i o n c a p a c i t y o f a c t i v a t e d c a r b o n f o r prophram i n c o m b i n a t i o n w i t h m e t r i b u z i n and monocrotophos c o u l d n o t be determined. Q

64.5 151.6

300 g/100g 250

272.0 224.9

2,4-DPropham

9.5 30.5

65.8 55.8

1220 (20°C) 58,000

535.9 307.2

MetribuzinMet homy 1

85.0 215.4

7.0 4.40 109.8 72.2 3.1 2.75

67.0 52.0

1220 (20°C) misc.

513.3 493.9

MetribuzinMonocrotophos

6.0 17.0

7.2 7.2 119.5 70.6 3.3 2.65

77.4 65.2

misc. 260 (20°C)

244.0 167.7

MonocrotoposDiphenamid

5

5 250 misc.

206.0 266.7

ProphamMonocrotophos

4.5 15.2

151.9 71.4

-

1Ç.0

6^.0

7.3 11.8

56.4 57.0

1220 (20°C) 250

194.3 122.0

MetribuzinPropham ( S o i n . A)

-

38.0 28.4

88.5 150.0

16.0 14.5

53.0 102.2

90 (20°C) 260 (27°C)

83.7 178.0

FluometuronDiphenamid

23.4 23.4

142.0 136.3

11.8 11.8

96.5 93.0

250 260 (27°C)

205.7 197.4

23.0 23.0

111.2 119.2

(Ϊ)

12.0 12.0

3 Exhaustion Capacity (mg/g)

d)

Breakghrough^" Capacity (mg/g) 76.14 81.1

ProphamDiphenamid

185 (20°C) 250

Water Solubility (mg/L)

160.0 171.5

Concentration (mg/L)

S t u d i e s on B i - S o l u t e P e s t i c i d e S o l u t i o n s

AmetrynePropham

Solution

T a b l e I I I . C a p a c i t y Data from Column A d s o r p t i o n



9.

NYE

Treatment of Contaminated Wastewater

157

R u g g i e r i (1981) found that a mixture of f i v e h e r b i c i d e s could be removed from contaminated wastewater with the combined treatment system of alum f l o c c u l a t i o n and sedimentation followed by a c t i v a t e d carbon a d s o r p t i o n as shown i n F i g u r e 1. The wastewater s o l u t i o n contained approximately 180 mg/1 trifluralin, 460 mg/1 alachlor, 700 mg/1 dinoseb, 180 mg/1 paraquat, and 90 mg/1 2,4-D. In these t e s t s trifluralin and paraquat were completely removed through the sedimentation treatment. To remove paraquat, benonite c l a y was added i n the i n i t i a l sedimentation step. Paraquat s t r o n g l y attaches to the c a t i o n exchange s i t e s on the benonite c l a y . The t r i f l u r a l i n i s e s s e n t i a l l y insoluble i n water and i s e a s i l y s e t t l e d a f t e r the emulsion i s broken. The procedure followed f o r f l o c c u l a t i o n i s shown below. 1. 2.

3.

4.

Prepare 350 L of s y n t h e t i c wash water. Add bentonite, alum, and a n i o n i c polymer to the s y n t h e t i c wash water. The dosage was 2 L of powdered bentonite c l a y , 100 ml of 10 Ν Ν OH, 20 ml of 57% alum s o l u t i o n and 25 ml of a n i o n i c polymer. Mix the s o l u t i o n of wastewater, b e n t o n i t e , alum, c a u s t i c , and polymer f o r 10 minutes and then f l o c c u l a t e at a mixing speed of about 10 rpm f o r 30 minutes. S e t t l e f o r 1 h.

The supernatant from f l o c c u l a t i o n was then passed through activated carbon columns. The exact c o n c e n t r a t i o n of dinoseb, a l a c h l o r and 2,4-D used i n the study i s shown i n Table IV. Two carbon column exhaustion studies were conducted. In both cases 300 L of wastewater were pumped through the columns. The carbon adsorbed slightly over 300 mg of p e s t i c i d e per gram of carbon i n both t e s t s . 2,4-D and Dinoseb broke through simultaneously a f t e r 1500 L of supernatant with a c o n c e n t r a t i o n of about 600 mg/L Dinoseb and 90 mg/L 2,4-D had passed through the carbon. The columns were not t o t a l l y exhausted until 3000 L had passed through.


TREATMENT A N D DISPOSAL O F PESTICIDE WASTES


158

4 T 0 8 PVC SEWER PIPES M

M

VARIABLE SPEED MIXER

PESTICIDE CONTAMINATED WASH WATER

55 GALLON DRUM

PUMP PRIMARY CARBON COLUMN

FLOCCULATION

a

SEDIMENTATION

CLEAN EFFLUENT

SECONDARY CARBON COLUMN

ACTIVATED CARBON ADSORPTION

Figure 1. P e s t i c i d e - c o n t a m i n a t e d wastewater treatment f o r commercial a p p l i c a t o r s .

system



798 546 616 745 630 653 572 618 639 641 789

Prim mg/1 768 331 584 653 722 515 722 561 480 389 561 384 377

2

196 364 549 772 961 1154 1319 1473 1595 1619 1639

0 0 0 0 1 10 22 105 231 561 722

Adsorbed^ gm

126 216 376 572 788 885 1096 1220 1349 1431 1521 1548 1563

3

Effl mg/1 0 0 0 0 0 8 21 87 75 102 262 285 308

Prim mg/1 83 83 56 64 59 88 83 54 59 54 57 59 55 76 66 76 68 82 122 110 143 126 108 116

440 440 440 440 440 440 440 1270 510 440 440

1

inf mg/1 610 340 340 440 440 440 440 440 440 440 440 440 440 2

0 0 0 0 0 0 0 0 0 0 0

Effl mg/1 0 0 0 0 0 0 0 0 0 0 0 0 0

Alachlor Concentration

19 39 69 82 107 143 176 219 257 296 324

Adsorbed gm 14 36 52 71 88 105 130 143 161 176 193 209 221

6 300° 90* 90° 110° 155* 155° 100 6

60 48 56 52 167 108 91 220 237 343 283

90 90 110 9 0

Prim mg/1 84 74 52 68 56 79 76 50 58 48 49 54 77

1

inf mg/1 120 70 70 90 90 90 90 90 90 90 90 90 90 0 0 0 0 1 3 9 39 101 243 293

0 0 0 0 0 1 4 8 20 23 45 43 75

Effl mg/1

2,4-D Concentration

Removal o f Three H e r b i c i d e s by the Complete System

^ C o n c e n t r a t i o n o f p e s t i c i d e i n the o r i g i n a l wastewater s o l u t i o n . Concentration of p e s t i c i d e after chemical flocculation and sedimentation (primary treatment). C o n c e n t r a t i o n o f p e s t i c i d e s i n t h e e f f l u e n t a f t e r p a s s i n g through the a c t i v a t e d carbon columns. [Amount o f p e s t i c i d e adsorbed i n t o the a c t i v a t e d c a r b o n . ' E f f i c i e n c y of a c t i v a t e d carbon i n terms o f t o t a l amount o f p e s t i c i d e adsorbed on the c a r b o n . '2,4-D f o r m u l a t i o n was changed from Formula 40 (Dow) t o Weedone 638 (Am Chem).

710 710 730 710 710 710 710 710 850 715 710

245 554 854 1154 1454 1754 2054 2354 2654 2954 3245

1

inf mg/1 940 545 545 700 700 700 700 700 700 700 700 700 700

Volume 1 164 437 710 1010 1310 1501 1801 2047 2347 2620 2920 3193 3411

Dinoseb Concentration

T a b l e IV.


15 29 46 62 112 143 168 223 263 294 291

14 34 48 69 85 100 122 133 147 154 155 158 158

Adsorbed gm

37 69 105 146 188 230 266 306 338 352 360

25 46 76 114 154 175 215 239 264 281 298 306 310

Efficiency^ mg/gm

160

TREATMENT A N D DISPOSAL OF PESTICIDE WASTES


Implementation of Treatment

System

Following the development of the 2-stage treatment system, demonstrations were performed t o show the adequacy o f the system at two d i f f e r e n t p e s t i c i d e a p p l i c a t o r s bases w i t h i n the s t a t e of Indiana. Over two spraying seasons the system was used a t the Monon A i r p o r t t o handle the wastewater from ADI, Inc. Wastewater generated during cleaning and l o a d i n g of a i r c r a f t was c o l l e c t e d from a concrete pad that was modified so that the water draining off the concrete could be c o l l e c t e d i n a sump and pumped i n t o a 1000 g a l l o n storage tank. Once a month the c o l l e c t e d wastewater was treated with the system. A l l the p e s t i c i d e s i n the wastewater were removed by the sedimentation and a c t i v t e d carbon a d s o r p t i o n process even though a wide v a r i e t y o f chemicals were handled by that a p p l i c a t o r . Further s t u d i e s were conducted a t the Capouch Helicopter o p e r a t i o n near Rensselaer. Over the past two seasons this system has handled a l l of the p e s t i c i d e contaminated wastewater that was produced a t that s i t e . At each of these s i t e s v e g e t a t i o n has developed i n areas that had been assumed t o be s t e r i l e because of contamination by p e s t i c i d e s during previous y e a r s . G e n e r a l l y the procedure that has been developed i s e f f e c t i v e in reducing the volume of waste that must be handled by a p e s t i c i d e a p p l i c a t o r by a f a c t o r of 100. F i v e thousand g a l l o n s o f wastewater can be reduced t o 50 g a l l o n s of sludge and spent a c t i v a t e d carbon. Under current r e g u l a t i o n s these m a t e r i a l s would most l i k e l y have to be disposed of a t a hazardous waste d i s p o s a l site. Literature Cited 1.

2.

3.

4.

Nye, J. C. Whittaker, K. F. 1980. Collection and Treatment of Rinsewater from Pesticide Application Equipment, Paper No. 80-2108, American Society of Agricultural Engineers, St. Joseph, Michigan. Ruggieri, T. J., 1981, Determination of the ability of a flocculation/sedimentation/activated carbon treatment plant to remove herbicides from application equipment wash water, and examination of the feasibility of bioassays for determination of activated carbon exhaustion. MSAE Thesis, Purdue Univesity, West Lafayette, Indiana. Whittaker, K. F., 1980, Adsorption of selected pesticides by activated carbon using isotherm and continuous flow column system, Ph.D. Thesis, Purdue Univesity, West Lafayette, Indiana. Whittaker, K. F., Nye, J. C. Wukasch, K. F., Squires, R. G . , York, A. C. and Kazimier, H. A. 1982. Collection and Treatment of Wastewater Generated by Pesticide Applicators. PB 82-255 365, O i l and Hazardous Materials S p i l l s Branch, MERL-Cincinnati, USEPA, Edison, NY 08837.

RECEIVED April 24, 1984


Treating Pesticide-Contaminated Wastewater - American Chemical

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