Gujarat Cleaner Production Centre-ENVIS Centregcpcenvis.nic.in/Experts/Pesticide Sector.pdf · demand and exports. India is a net exporter of pesticides. The export destination markets

Gujarat Cleaner Production Centre-ENVIS Centre

Introduction

Pesticides are defined as the substance or mixture of substances used to prevent, destroy, repel,

attract, sterilize, mitigate any insects. Generally pesticides are used in three sectors viz.

agriculture, public health and consumer use. The consumption of pesticide in India is about 600

gm/hectare, where as that of developed countries is touching 3000 gm/hectare.

There are about 150 industrial units manufacturing pesticides (technical) and about 500 industrial

units engaged in formulations in the country. India is the 4thlargest producer of agrochemicals

after USA, Japan and China.

There is a wide range of pesticides found used in non-agricultural situations such as industries,

public health and for a number of purposes in the home. Domestic use of pesticides is mainly as

fly killer, repellants, rodenticides and fungicides etc. By and large industrial use of pesticide is of

vital importance in the industries such as wood and carpet, wood preservation etc.

Pesticide commonly used in the agriculture can be grouped as

Insecticides – It control the insects that damage the crops. The classes are chlorinated

hydrocarbons, organophosphates, carbamates. They are used on lawns, vegetables,

grapes, tobacco, forest trees etc.

Organic fungicides and bactericides – They control plant molds & other diseases.

Fungicides protects plants from fungal growth. They are used on grain, vegetables,

grapes etc.

Organic herbicides – Herbicides are used to control the weeds which compete with crop

plants with water, nutrients, space & sunlight. They used on the grapes, fruit trees, sugar

beets, beans, rice etc.

Other Categories of Pesticides are :

Mineral Oils,

Seed Treatment – Fungicides And Insecticides

Plant Growth Regulators


Rodenticides

Pesticide Production In India

India is the largest producer of pesticides in Asia and ranks twelveth in the world for the use of

pesticides.

Pesticide is manufactured as technical grade products and consumable pesticides are then

formulated. The installed capacity of technical grade pesticide was 1,45,800 tonnes during

March 2005, and the production in the financial year 2012-13 was 171000 tonnes.

0

20000

40000

60000

80000

100000

120000

140000

160000

180000

200000

Production Tones/Year in India

Production

Tones/Year

Major Groups Production in (000 MTs)

Pesticide and

Insecticides 2006-07 2007-08 2008-09 2009-10 2010-11 2011-12

2012-13 (April to

Sep)

D.D.T. 4.5 3.44 3.31 3.61 3.09 3.62 0.98

MALATHION 4.3 6.3 3.38 1.67 3.05 2.54 0.67

PARATHION

(METHYL) 0 0 0 0 0 0 0.00

DIMETHOATE 1 0.89 0.57 0.98 1.17 0.73 0.32

D.D.V.P. 3.89 3.48 3 3.87 3.48 4.64 2.37

QUINALPHOS 0.82 0.52 0.84 0.99 1.01 0.99 0.85

MONOCROTOPHOS 4.91 5.12 4.57 5.74 9.93 9.58 5.44

PHOSPHAMIDON 0.37 0.71 0.85 1 0.29 0.06 0.01

PHORATE 8.45 6.08 4.67 4.73 5.36 4.61 2.5

ETHION 2.6 2.2 1.41 1.5 1.92 1.33 0.49


(Source : Annual Report 2011-12 of Department of Chemical and Petrochemical)

Export and Import

The indigenous capacity in pesticides sector is adequate to meet the domestic requirement of

demand and exports. India is a net exporter of pesticides. The export destination markets are

USA, UK, France, Netherlands, South Africa, Bangladesh, Malaysia and Singapore, etc. Some of

the pesticides exported over the years include Parathion (Methyl), Cypermethrin, Endosulfan,

ENDOSULPHAN 9.31 10.54 11.35 9.9 11.49 1.35 0

FENVALERATE 0.52 0.72 0.49 0.53 0.8 0.55 0.24

CYPERMETHRIN 5.06 4.66 4.03 6.23 4.95 8.79 2.72

ANILOPHOS 0.02 0 0 0 0 0 0.00

ACEPHATE 9.27 10.73 10.25 11.55 14.28 15.97 8.72

CHLORPYRIPHOS 6.17 6.55 6.55 6.12 6.41 5.11 3.22

PHOSALONE 0.25 0.5 0 0 0 0 0.00

METASYSTOX 0.63 0 0 0 0 0 0.00

FENTHION 0.12 0 0 0 0 0 0.00

TRIAZOPHOS 1.84 1.84 2.06 0.88 1.58 0.72 0.6

LINDANE 0.25 0.08 0 0 0 0 0

TEMEPHOS 0.1 0.23 0.27 0.08 0.12 0.13 0.08

DELTAMETHRIN 0.34 0.26 0.03 0.02 0.52 0.33 0.2

ALPHAMETHRIN 0.17 0.21 0.02 0 0.31 0.32 0.15

CAPTAN & CAPTAFOL 0.19 0 0 0 0.72 0.92 0.28

ZIRAM(THIO

BARBAMATE) 0.24 0.19 0.07 0 0.49 0.53 0.22

CARBENDZIM(BAVIST

IN) 0.14 0.07 0.2 0.38 0.59 0.43 0.19

CALIXIN 0.03 0 0 0 0 0 0.00

MANCOZAB 22.88 27.12 35.34 31.49 26.05 43.71 21.35

COPPER-

OXYCHLORIDE 0 0 0 0 0 0 0.00

2, 4-D 0 0.27 0.21 0 0 0 0.00

BUTACHLOR 0.18 0.03 0.12 0.24 0.29 0.11 0.14

ISOPROTURON 3.15 2.96 2.98 2.91 3.68 2.53 1.96

GLYPHOSATE 2.89 2.58 4.34 4.66 4.86 5.24 3.33

DIURON 0 0.08 0.01 0.13 0.2 0.3 0.1

ATRAZIN 0.09 0.22 0.26 0.26 0.24 0.66 0.2

FLUCHLORALIN 0.1 0 0 0 0 0 0.00

ZINC PHOSPHIDE 1.11 0.95 0.91 0.92 0.86 0.89 0.29

ALUMINIUM 2.08 2.53 2.58 3.25 2.82 3.14 2.2

DICOFOL 0.05 0.09 0.09 0.02 0.04 0.08 0.05


DDT, etc. Exports consist mostly of patent products. The major manufacturers in the pesticide

sector include M/s United Phospharus Ltd., M/s Syngenta, M/s Rallis India and M/s Hindustan

Insecticides Ltd., a Public Sector Undertaking under the Government of India. The value of

exports and imports during the last five years is given below. (Rupees In Crores)

(Source: DGCIS, Department of Commerce)

Comparison of pesticide use in India and worldwide

Uses of pesticides in India

Sector Use

Agriculture For control of pests, weeds, rodents, etc.

Public Health For control of malaria, dengue, fever, cholera

Other than agriculture & Public Health Control of vegetation in forests and factory

sites, fumigation of buildings and ships

Domestic Household and garden spray, control of

animals and birds

Personal For applications of clothing and skin cure

Material Building Incorporation of paints, glues, plastic

protection, sheeting, foundation of buildings

etc.

0

2000

4000

6000

8000

2007-08 2008-09 2009-10 2010-11 2011-12

Export

Import

0%

10%

20%

30%

40%

50%

60%

70%

Insecticides Herbicides Fungicides Others

India

World


State wise production in India during the year 2005/06

State Production in MT/Year

Gujarat 36.05

Maharashtra 32.16

Andhra Pradesh 2.665

Kerala 2.407

Karnataka 0.11

Major Pesticide control legislation in India

Legislation Regulatory Body

Insecticide Act. 1968 and the Insecticides

Rules, 1971

Ministry of Agriculture Department of

Agriculture & Cooperation

Water (Prevention & control of pollution)Act-

1974

Bureau of Indian Standards Act

Air (Prevention & control of pollution)Act-

1981

Ministry of Environment & Forest

Environment Protection Act, 1986 Ministry of Environment & Forest

Hazardous waste(management & handling)

Rules-1989

Ministry of Environment & Forest

Prevention of Food Adulteration Act, 1954 Ministry of Health & Family Welfare

Persistence in soil of some pesticides

Insecticides, Herbicides and their groups Persistence

Organophosphates 7-84 Days

DDT 10 Years

Carbamate 2-8 weeks

Aliphatic Acid 3-10 weeks

Diuron 16 months

BHC 11 Years

Toxaphene 6 Years

Manufacturing Process :

Pesticides are produced in two stages the manufacturing consists of chemical synthesis of active

ingredients for crop protection, which is very often the synthesis of complex organic chemical


compounds, and subsequent formulation of these active ingredients (usually mixing and grinding

processes). Major chemical reactions involved in production of technical grade pesticides are:

alkylation, carboxylation, acetylation, condensation, cyclization, dehydration, halogenation,

oxidation, sulphonation, nitration and amination. Main physical (mostly separation or

purification) operations, which are usually called as “unit operations” include: Liquid/liquid

extraction, liquid/liquid separation, liquid/solid separation, gas/solid separation, distillation,

crystallization, gas absorption, drying, grinding and mixing (Figure 1). After a pesticide is

manufactured in its relatively pure form (the technical grade material) the next step is

formulation-processing a pesticide compound into liquids, granules, dusts and powders to

improve its properties of storage, handling, application, effectiveness, or safety. The technical

grade material may be formulated by its manufacturer or sold to a formulator/packager (Figure

2). Very often, during these operations, wastewater and solid waste is separated, whereas waste

gas is directly released from the reaction itself. Typical unit operations of chemical synthesis

with its associated emissions are depicted in Figure 3.

Raw Shipping

Material Vent

Scrubbing

System

Discharge

Reactor

System

Fractionati

on System

Dryer Packaging

Scrubber

Waste

Treatment

Plant


Figure 1 : Technical Grade

Active Ingredient

Wetting Agent Vent to Atmosphere

Shipment

To Waste

Treatment Plant

Figure 2 : Formulating Industry

Mill

Mixing Tank

Packaging


Figure 3 : Typical unit operation of Chemical Synthesis

Pesticides Banned for manufacture, import and use in India

Aldrin

Benzene Hexachloride

Calcium Cyanide

Chlordane

Copper Acetoarsenite

Cibromochloropropane

Endrin

Ethyl Mercury Chloride

Ethyl Parathion

Heptachlor


Menazone

Nitrofen

Paraquat Dimethyl Sulphate

Pentachloro Nitrobenzene

Pentachlorophenol

Phenyl Mercury Acetate

Sodium Methane Arsonate

Tetradifon

Toxafen

Aldicarb

Chlorobenzilate

Dieldrin

Maleic Hydrazide

Ethylene Dibromide

Trichloro Acetic Acid

Metoxuron

Chlorofenvenphos

Lindane (Banned for use from 25 March,2013

Pesticides Restricted For Use In India

Lindane

Methyl Bromide

Aluminium Phosphide

Methyl Parathion

Sodium Cyanide

Monocrotophos

Endosulfan

Fenitrothion

Diazinon


Fenthion

Dazomet

Methoxy Ethyl Mercuric Chloride (MEMC).

Pollution Outputs During Manufacturing of Organic Chemical

Media Potential Source of Emissions

Air Point source emissions: stack, vent (e.g., laboratory hood,

distillation unit, reactor, storage tank vent), material

loading/unloading operations (including rail cars, tank trucks, and

marine vessels) Fugitive emissions: pumps, valves, flanges, sample

collection, mechanical seals, relief devices, tanks Secondary

emissions: waste and wastewater treatment units, cooling tower,

process sewer, sump, spill/leak areas.

Liquid wastes

(Organic or

Aqueous)

Equipment wash solvent/water, lab samples, surplus chemicals,

product washes/purifications, seal flushes, scrubber blow down,

cooling water, steam jets, vacuum pumps, leaks, spills, spent/used

solvents, housekeeping (pad wash down), waste oils/lubricants

from maintenance.

Solid Waste Spent catalysts, spent filters, sludges, wastewater treatment

biological sludge, contaminated soil, old equipment/insulation,

packaging material, reaction by-products, spent carbon/resins,

drying aids .

Ground Water

Contamination

Unlined ditches, process trenches, sumps, pumps/valves/fittings,

wastewater treatment ponds, product storage areas, tanks and tank

farms, aboveground and underground piping, loading/unloading

areas/racks, manufacturing maintenance facilities

Cleaner Production Opportunities For Waste Reduction in Pesticide

Manufacturing Process

The best way to reduce pollution is to prevent it in the first place. Pollution prevention

techniques improve efficiency and increase profits. This can be done in many ways such

as reducing material inputs, re-engineering processes to reuse by-products, improving

management practices, and substituting toxic chemicals with those which are less toxic.

In the waste management hierarchy, if source reduction is not feasible, the next

alternative is recycling of wastes followed by recovery, and waste treatment as the last

alternative.


This pollution prevention, recycle, reuse, and water conservation practices fall into three

groups: production practices, housekeeping practices, and practices that use equipment

that –by design – promote pollution prevention. Some of these practices and equipment

conserve water, others reduce the amount of pesticide product in the wastewater, and

some others may prevent the generation of a wastewater altogether. The list of common

pollution prevention practices is given below:

Triple-rinsing raw material shipping containers directly into the formulation

Scheduling production to minimise cleanouts

Segregating processing/formulating/packaging equipment by ̇ (1) Individual product

(2) Solvent-based versus water-based formulations

(3) Products that contain similar active ingredients in different concentrations

(4) Storing interior equipment rinse waters for use in formulating the same product

(5) Packaging products directly from formulation vessels

(6) Using raw material drums for packaging final products

(7) Dedicating equipment (possibly only mix tank or agitator) for “hard-to-clean”

formulations

Housekeeping practices include:

(1) Performing preventive maintenance on all valves, fittings, and pumps

(2) Placing drip pans under leaky valves and fittings or under any valves or fittings

where hoses or lines are routinely connected and disconnected

(3) Cleaning up spills or leaks in outdoor bulk containment areas to prevent

contamination of stormwater.

Equipment that promotes pollution prevention by reducing or eliminating

wastewater generation includes:

(1) Low-volume/high-pressure hoses

(2) Spray nozzle attachments for hoses

(3) Squeezes and mops

(4) Low-volume/recirculating floor scrubbing machines

(5) Portable steam cleaners


(6) Drum triple rinsing stations

(7) Roofs over outdoor tank farms

Equipment Cleaning

(1) Shipping container/drum cleaning operations

(2) Bulk tank and equipment cleaning

(3) Aerosol container leak testing

(4) Laboratory equipment cleaning

Process changes

(1) Storage tanks

(2) Air emission control systems

(3) Microprill formation

Good housekeeping

(1) Floor/wall/equipment exterior cleaning

(2) Leaks and spills clean-up

(3) Pollution prevention opportunities

(4) Precipitation runoff

(5) Containment pad in the loading/unloading

General Cleaner Production Options During Manufacturing of Pesticide

Meter and control the quantities of active ingredients to minimize wastage.

Reuse by-products from the process as raw materials or as raw material substitutes in

other processes.

• Use automated filling to minimize spillage.

• Use “closed” feed systems for batch reactors.

Use nitrogen blanketing where appropriate on pumps, storage tanks, and other

equipment to minimize the release of toxic organics.

Give preference to nonhalogenated and nonaromatic solvents where feasible.

Use high-pressure hoses for equipment cleaning to reduce wastewater.

Use equipment washdown waters and other process waters (such as leakages from pump

seals) as makeup solutions for subsequent batches.


Use dedicated dust collectors to recycle recovered materials.

• Vent equipment through a recovery system.

Maintain losses from vacuum pumps (such as water ring and dry) at low levels.

Return toxic materials packaging to the supplier for reuse or incinerate/destroy in an

environmentally acceptable manner.

Minimize storage time of off-specification products through regular reprocessing.

Find productive uses for off-specification products to avoid disposal problems.

Minimize raw material and product inventory to avoid degradation and wastage that

could lead to the formation of inactive but toxic isomers or by-products.

Label and store toxic and hazardous materials in secure, bunded areas.

In case of formulation industries, the levels of wastewater generation are either

considerably lower than in the ‘technical’ production or sometimes non-existent. It

is observed that most of these industries do not generate any process wastewater.

Best Available Waste Minimization Methods For Manufacturing Aspects

Waste Stream Waste Minimization Method

Equipment

Cleaning Wastes Maximise production runs.

Store and reuse cleaning wastes.

Use of wiper blades and squeegees.

Use of low-volume, high-efficiency cleaning.

Use of plastic or foam “pigs.” Spills and Area

Wash downs Use of dedicated vacuum system.

Use of dry cleaning methods.

Use of recycled water for initial cleanup. Actively

involved supervision.

Off-Specification

Products Strict quality control and automation. may be

reprocessed at appropriate stage, to recover the

product.

Containers Return containers to supplier and or reuse as

directed.

Triple rinse containers. Drums with liners versus

plastic drums or bags.


Segregating solid waste.

Air Emissions Control bulk storage air emissions.

Dedicate dust collection systems.

Use automatic enclosed cut-in hoppers.

Eliminate emissions of ammonia from reaction of

anhydrous ammonia and phosphoric acid.

Miscellaneous Wastewater

Streams Pave high spillage areas.

Process wash

water Where multiple washings in a reaction are involved,

each cycle wash water to be stored and used in

subsequent batches.

Steam condensate

from ejectors Many places this water can be used as wash water,

without affecting the process.

Steam condensate can also be explored for boiler

feed .

Vacuum pump

seal water Use double stage pumps and recycle seal water

rather than using as once flow system.

Process changes Improvements possible by changing reaction

conditions, solvents

elimination, reduction in processing steps, etc.

Conversion of

wastes into useful

products

Absorption of HCl gases with chilled water to get

HCL acid

Spent H2SO4 from Nitrations to be used for SSP

production.

Absorb NH3 in chilled water to get aqueous

Ammonia.

Emulsions and rag

formation in

reactions

Use of de-emulsifiers and resins for proper

separation of organic and aqueous layers and reduce

the carryover of organics and rag in aqueous layers.

Solvent

Extraction Extraction of aqueous waste layers by suitable

solvents to recover

carryover organics in waste streams.

(Source : Technical Guidance Manual For Pesticide Sector, MoEF, GOI, September, 2010)

Environmental Issues Due To Water Consumption and Waste Generation

Because of the nature of pesticides and their components, waste waters generated from

manufacturing plants usually contain toxic. The pollutants or groups of pollutants likely

to be present in raw wastewater include halomethanes, cyanides, haloethers, phenols,


polynuclear aromatics, heavy metals, chlorinated ethane and ethylenes, pesticides, dienes,

and other common constituents such as BOD, COD, and TSS.

Washing and cleaning operations provide the principal sources of waste water in

formulating and packaging operations. Because these primary sources are associated with

clean up of spills, leaks, area wash downs and storm water run off.

Waste water from formulation and packaging operations typically have low levels of

BOD, COD and TSS, and pH is generally neutral.

In the past, evaporation was the predominant disposal techniques for waste water

generated in formulating plants.

Waste Generation

Manufacture Plant

(Technical Grade)

Kg/ton of active

ingredient manufacture

200

Formulation Plant Kg/ton of formulated

product

3-4

Waste Characteristics of Pesticide Waste

Parameter Dithane(mg/l)

pH 6.9

Total Solids 33000

Suspended Solids 2000

Dissolved Solids 31000

Total Volatile Solids 3220

BOD5 180

COD 1372

Chlorides 1500

Sulphates 2050

Manganese 215

Zinc 4

Central Pollution Control Board Effluent Standards for Pesticide Industry

Parameter Standards

Temperature Shall not exceed 5 ºCAbove the receiving water temp.

pH 6.5-8.5

Oil & grease 10

BOD 3 days 27 ºC Technical Grade

Unit

100

BOD 3 days 27 ºC Formulation Unit 30


Total Suspended Solids 100

Bio assay test 90% survival of fish after 96 Hrs in 100% effluent

Specific Pesticides In mg/l

DDT 0.01

Benzenl Hexachloride 0.01

Endosulfan 0.01

Carbonyl 0.01

Malathion 0.01

Fenitrothion 0.01

Diamethoate 0.45

Phorate 0.01

Sulphar 0.03

2,4 D 0.4

Methyl Parathion 0.01

Phenathoate 0.01

Pyrethrums 0.01

Ziram 1

Paraquate 2.3

Proponil 7.3

Copper Sulphate 0.05

Copper Oxyghloride 9.6

Other Pesticides 0.10

Heavy Metals In mg/l

Copper 1

Manganese 1

Zinc 1

Mercury 0.01

Antimony as sb 0.1

Any other metal like Nickel etc Shall not exceed 5 times the drinking water standards

of BIS

Organics In mg/l

Phenol and Phenolic compounds as

C6H5OH

1

Inorganics In mg/l

Arsenic as As 0.2

Cyanide CN` 0.2

Nitrate as NO3 50

Phosphate as P 5

Emissions In mg/Nm3

HCl 20

Cl2 5

H2S 5

P2O5 as H3PO4 10


HBr 5

NH3 30

Particulate matter with pesticide

compounds CH3Cl

20

HBr 5

Pollution Effects By Pesticide

(1) Effects on Streams

Presence of suspended solids causes odor and lowers the DO level in stream which is

deadly to aquatics. It also increases the turbidity of water course and enhances flooding

by diminishing the stream bed volume.

High BOD values will increase the organic matter and create unpleasant tastes, odors and

general septic conditions due oxidation of organic matters. It decreases DO level and

affects deadly to aquatic life.

All salts, some even in low concentration, are toxic to certain forms of aquatic life.

Chlorides are toxic to fish in 400 ppm.

Under proper environmental conditions inorganic salts such as nitrogen, phosphorus

induces the growth of microscopic plant life algae in the water. The main disadvantage of

algae is they contribute organic loading after dying.

(2) Effects on Sewers

Suspended solids may cause clogging of sewers by getting accumulated at an invert.

The waste contains sulphates which are converted into H2S gas which can form odour

problem.

The presence of sulphates also forms crown corrosion.

(3) Effects on STPs

BOD exerted by organics imposes a load on treatment plant. Increase in BOD load

requires greater biological unit capacity for its treatment which increases daily operating

expenses.

Suspended solids from industrial waste sometime may settle more rapidly than that of

sewage solids, which are necessary to be removed at shorter intervals, otherwise they will


build up excessively at tank bottom and cause septic conditions. Slower setting of

industrial solids will require longer detention period and larger basins which increase the

unit cost.

(4) Effects on Ecology

Water

Pesticides are found to pollute every source of water including wells. The main routes

through which pesticides reach the water are :

(1) It may drift outside of the intended area when it is sprayed.

(2) It may percolate, or leach, through the soil.

(3) It may be carried to the water as runoff.

(4) It may be spilled accidentally

They may also be carried to water by eroding soil.

Soil

Many of the chemicals used in pesticides are persistent soil contaminants whose impact may

endure for decades and adversely affect soil conservation. The use of pesticides decreases the

general biodiversity in the soil.

Air

Pesticide drift occurs when pesticides suspended in the air as particles are carried by wind to

other areas, potentially contaminating them. Volatile pesticides applied to crops will

volatilize and are blown by winds to nearby areas posing a threat to wildlife. Sprayed

pesticides or particles from pesticides applied as dusts may travel on the wind to other areas,

or pesticides may adhere to particles that blow in the wind, such as dust particles.

(5) Effects on Humans

Pesticides may cause acute and delayed health effects in those who are exposed. Pesticide

exposure can cause a variety of adverse health effects. These effects can range from simple

irritation of the skin and eyes to more severe effects such as affecting the nervous system,

mimicking hormones causing reproductive problems and also causing cancer. Strong

evidence also exists for other negative outcomes from pesticide exposure including

neurological, birth defects, fetal death, and neurodevelopment disorder.

(6) Effects on Biota


Plants

Nitrogen fixation, which is required for the growth of higher plants, is hindered by pesticides

in soil. The insecticides DDT, methyl parathion, and especially pentachlorophenol have been

shown to this effect. It results in reduced nitrogen fixation and thus crop yields.

Animals

Pesticides inflict extremely widespread damage to biota and many countries have acted to

discourage pesticide usage through their Biodiversity Action Plans. Animals may be

poisoned by pesticide residues that remain on food after spraying for example when wild

Animals enter sprayed fields or nearby areas shortly after spraying. Widespread application

of pesticide can eliminate food sources that certain types of animals need, causing the

animals to relocate change their diet. Poisoning from pesticides can travel up the food chain.

It affects on reproductive system of animals.

Aquatic life

A major environmental impact has been the widespread mortality of fish and marine

invertebrates due to the contamination of aquatic systems by pesticides. This has resulted

from the agricultural contamination of waterways through fallout, drainage, or runoff erosion

and from the discharge of industrial effluents containing pesticides into waterways.

Most of the fish in Europe’s Rhine River were killed by the discharge of pesticides and at

one time fish populations in the Great Lakes became very low due to pesticide

contamination.

Pesticide surface runoff into rivers and streams can be highly lethal to aquatic life, sometimes

killing all the fish in a particular stream. Application of herbicides to bodies of water can

cause fish kills when the dead plants rot and use up the water’s oxygen, suffocating the fish.

Some herbicides, such as copper sulfite, that are applied to water to kill plants are toxic to

fish and other water animals at concentrations similar to those used to kill the plants. Some

pesticides can cause physiological and behavioural changes in fish that reduce Insecticides

are more toxic to aquatic life than herbicides and fungicides.

Birds

Pesticides had created striking effects on birds, those in the higher tropic levels of food

chains. Pesticides will also kill grain and plant-feeding birds, and the elimination of may rare


species of ducks and geese. Populations of insect eating birds such as partridges, grouse and

pheasants have decreased due to the loss of their insect food in agricultural fields through the

use of insecticides.

Best Practicable Cleaner Production Options For Waste Water Treatment

For treatment of effluent from the pesticides industry, there are many options depending on

the type of waste. Best practice may include segregation of streams, characteristics– wise

individual treatment and common treatment subsequently, i.e., separation of toxic and highly

organic streams for incineration; detoxification of moderate streams; directly sending the

easily biological streams to secondary treatment; separation of inorganic streams for separate

treatment/evaporation.

(1) Choice of treatment technologies for effluent based on three environmental parameters i.e.

BOD, COD and TDS is given in Table.

Combination Quality of

Effluent

Cleaner Production

Treatment Options

High TDS, High

COD and High BOD

Waste is not easily

biodegradable but toxic

Thermal decomposition

(based on calorific value);

Chemical oxidation by

hydrogen peroxide, ozone

etc; Evaporation + secured

landfill

High TDS, High

COD and low BOD

May be toxic; not suitable for

biological treatment; mostly

inorganic salts

Chemical treatment

(recovery, precipitation

etc.); Evaporation + secured

landfill of evaporated residue

High TDS, COD is

just higher than BOD and

High BOD

Highly organic effluent fully

biodegradable

Anaerobic + Aerobic

treatment; If quantity is

less, incineration (based on

calorific value) + secure

landfill of incineration ash

High TDS, COD just

higher than BOD and

low BOD

Only inorganic salts, no need

for biological treatment

Solar evaporation; Forced

evaporation (after separation

of volatile organic matter);

Reverse osmosis

Low TDS, High Highly organic effluent, may Thermal decomposition;


COD and High BOD not be easily biodegradable Chemical oxidation by

hydrogen peroxide or ozone

or sodium

hypo-chlorite etc.; Chemical

+ biological

treatment

Low TDS, High

COD and low BOD

Highly recalcitrant

wastewaters ,not

readily suitable for

biological treatmen

Chemical recovery;

Chemical oxidation +

biological treatment

Low TDS, COD just

higher than BOD and

high BOD

Organic effluent, fully

biodegradable

Anaerobic + aerobic

treatment

Low TDS, low COD

and low BOD

Low organic and low

inorganic effluent

Recycle and reuse (after

preliminary

treatment)

(2) Toxic effluent, which is not easily biodegradable, may be treated physico-chemically instead

of treating biologically. This treatment includes detoxification, oil separation, equalization,

stripping, clariflocculation, oxidation with H2O2/NaOCl/KmnO4, etc., neutralisation and

clariflocculation. Depending on the mode of disposal, the options for subsequent treatment

are arrived at. Options include the following:

(1) Pre-concentration followed by incineration:

The wastewater may be subjected to evapouration in an impervious holding arrangement so

as to reduce its quantity and then incinerated.

(2) Solar/forced evaporation:

In cases where the effluent quantity is small (say <10 kld) and the climatic conditions are

favourable, solar evaporation may be adopted. Considering the recurring costs, forced

evaporation may be employed as a stand-by arrangement to the solar evaporation system.

(3) The inorganic and high TDS-bearing effluent which can only be treated by reverse osmosis,

ion-exchange methods, etc, prove to be costly and uneconomical, may also be solar

evaporated.

(4) Various important aspects to be considered for effective functioning of biological treatment

system for pesticide industry effluent are:


The detoxification of waste is essential. Otherwise this waste would kill the micro

organisms, thereby making treatment system defunct.

The functioning of biological treatment system is based on microbial activity and a

record shall be maintained for F/M (food to micro-organism ratio), MLSS influent

BOD and sludge recycle rate in polluted water and hence utmost care is to be taken to

keep the system functioning. An efficient biological system helps in treating the

wastewater economically.

Environmental Issues Due to Air Pollution As Per Product Wise

SR. No, Product Associated Air Pollutant

1 Acephate HCL

2 Aluminum phosphide P2O5

3 Bhutachlor HCl, SO2

4 Captan HCl, SO2

5 Cypermethrin HCl, SO2

6 DDVP CH3Cl

7 2,4-D Acid HCl

8 Dimethoate CH3OH, H2S

9 Endosulfan CH3Cl

10 Ethion H2S

11 Fenvelarate NH3 HCl, SO2

12 Isoproturon NH3

13 Malathion H2S

14 Methoxy Ethyl Merc.Chloride HCl

15 Methyl Bromide HBr, SO2

16 Monochrotophos CH3Cl

17 Oxychloramide HCl

18 Phenyl Merc. Acetate HCl

19 Phosalone HCl, H2S

20 Phosphamidon NH3 CH3Cl HCl

21 Phorate H2S

22 Zinc Phosphide P2O5

Clean Technologies and Methods For Recovery of Pollutants

SR.

No.

Identified

Priority

Pollutants

Control System Expected

Efficiency

Technically

Achievable

average

Cost

Rs/Lacs


Conc.

(mg/Nm3)

1. HCl � Water Scrubber

� Caustic Scrubber

� Water/Caustic

Scrubber

90 %

99 %

99%

8.65

17.5

7.0

9.37

13.40

4.11

2. Cl2 � Caustic Scrubber

� Water/Caustic

Scrubber

99 %

99 %

0.15

0.01

3.16

4.06

3. CH3Cl � Liquification & Recovery

System

� Incineration after

distillation

99 %

99 %

Ni

-

107.5

-

4. H2S � Scrubber with NaOCL

media

� Scrubber with NaOH

media

� Charcoal Scrubber

96 %

99 %

97 %

8.5

0.43

5.6

57.7

11.3

11.3

5. SO2 � Water Scrubber

� Water Scrubber (Ring jet

scrubber) + Mist

Eliminator + Demister

� Mist Eliminator

96 %

98 %

99 %

-

12.64

1.1

7.7

20.0

0.8

6. NH3 � Two Stage Water

Scrubber

� Recovery System

98 %

99 %

26.2

-

23.4

79.4

7. HBr � Caustic Scrubber 98 % 11.7 5.84

8. CH3OH Channelised Emission was not observed

Productwise Cleaner Production Options

Product Cleaner Production Options

Monocrotophos In the manufacturing process of Monocrotophos, chlorination

efficiency can be improved by providing multiple entries of chlorine in

the reactor. Process conditions are to be optimized to minimize

formation of dichlorides of Monocrotophos Aceto Acetamide (MMA),

which are, resulting in formation of other products going in the waste.

Purer Trimethyl Phosphite (TMP) is to be used to minimize input of

impurities coming along with TMP leading to waste.

Profenophos In the manufacturing process of Prefenophos, efficiency of bromination


needs to be improved by adopting stagewise bromination and

optimizing the process parameters. This will minimize formation of

other bromides and impurities, which form waste. Recovery of

Trimethyl Ethyl Amine Bromide (TMEABr) from aqueous layer will

reduce the load on ETP and presence of organic impurities in ETP

sludge.

Acephate In the manufacturing process of Acephate, lower overall efficiency of

the process and lower recovery efficiencies for solvent are leading to

waste. There is a scope to optimize process efficiency and improve

solvent recovery system and thereby reduce the waste.

Chloropyrophos In Chlorpyriphos manufacturing process, lower extraction efficiency is

resulting in loss of Chlorpyriphos in the waste. Use of centrifugal

extractors with optimized process conditions will improve extraction of

Chlorpyriphos and thereby reduce the waste.

Ethion In the manufacturing processof Ethion, direct controlled addition of

P2S5 in alcohol and elimination of solvent may result in total

elimination of process waste.

Zinc/Aluminium

phosphide

In the manufacturing process of phosphides of zinc and aluminium part

of the phosphorous is burnt for generating high temperature. This in

turn results in generation of waste. Developing an electric arc furnace

will solve this problem. Dusting of the product also needs to be

minimized.

Endosulfan In the manufacturing process of Endosulfan, recovery of Endosulfan

needs to be improved by improving centrifugation and thereby reducing

Endosulfan in the waste

Cypermetharin In Cypermethrin manufacturing process, there is a scope to reduce the

quantity of sodium cyanide used and thereby reduce the load on

detoxification and generation of detoxification sludge.

Fenvalerate In the manufacturing process of Fenvalerate, better heat transfer and

temperature control will reduce the loss of alkyl in alkyl distillation.

Use of acidic ion exchange resin can minimize requirement of acid and

thereby generation of waste.

Malathion In the manufacturing process of Malathion and Dimethoate, minimizing

water content of methanol, P2S5 and equipment will minimize

generation of phosphoric acid, which results in formation of waste.

Dimethoate Drying of Malathion and Dimethoate at lower temperature, using

higher vacuum will reduce thermal degradation of the product.

Documents

Gujarat Cleaner Production Centre-ENVIS Centregcpcenvis.nic.in/Experts/Pesticide Sector.pdf · demand and exports. India is a net exporter of pesticides. The export destination markets