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CLEANER PRODUCTION GUIDELINES IN
PESTICIDE MANUFACTURING SECTOR
Gujarat Cleaner Production Centre(Established by Industries & Mines Department,ENVIS Centre on: Cleaner Production/TechnologySupported byGovernment of IndiaBlock NoPhone: + 91 (079) 232 44 147Mail: [email protected]: www.gcpcgujarat.org.in, www.gcpcenvis.nic.in
CLEANER PRODUCTION GUIDELINES IN
PESTICIDE MANUFACTURING SECTOR
Gujarat Cleaner Production Centre(Established by Industries & Mines Department, GoG)ENVIS Centre on: Cleaner Production/TechnologySupported by: Ministry of Environment, Forest & Climate Change, Government of IndiaBlock No: 11-12, 3rd Floor, Udhyog Bhavan, Gandhinagar
+ 91 (079) 232 44 [email protected] ; [email protected];
: www.gcpcgujarat.org.in, www.gcpcenvis.nic.in
CLEANER PRODUCTION GUIDELINES IN
PESTICIDE MANUFACTURING SECTOR
: Ministry of Environment, Forest & Climate Change,
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 12th 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 tons during
March 2005, and the production in the financial year 2012-13 was 171000 tons.
020000400006000080000
100000120000140000160000180000200000
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
ENDOSULPHAN 9.31 10.54 11.35 9.9 11.49 1.35 0
(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
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(BAVISTIN)
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
the pesticides exported over the years include Parathion (Methyl), Cypermethrin, Endosulfan,
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.
(Source: DGCIS, Department of Commerce, (Rupees in Crores)
Comparison of pesticide use in India and worldwide
Uses of pesticides in India
Sector UseAgriculture For control of pests, weeds, rodents, etc.
Public Health For control of malaria, dengue, fever, choleraOther than agriculture & Public Health Control of vegetation in forests and factory
sites, fumigation of buildings and shipsDomestic Household and garden spray, control of
animals and birdsPersonal For applications of clothing and skin cure
Material Building Incorporation of paints, glues, plastic
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
protection, sheeting, foundation of buildings etc.
State wise production in India during the year 2005-06
State Production in MT/YearGujarat 36.05
Maharashtra 32.16Andhra Pradesh 2.665
Kerala 2.407Karnataka 0.11
Major Pesticide control legislation in India
Legislation Regulatory BodyInsecticide Act. 1968 and the Insecticides Rules, 1971
Ministry of Agriculture Department of Agriculture & Cooperation
Water (Prevention & control of pollution)Act-1974Bureau of Indian Standards ActAir (Prevention & control of pollution)Act-1981
Ministry of Environment & Forest
Environment Protection Act, 1986 Ministry of Environment & ForestHazardous 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 PersistenceOrganophosphates 7-84 Days
DDT 10 YearsCarbamate 2-8 weeks
Aliphatic Acid 3-10 weeksDiuron 16 monthsBHC 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
process).
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 ShippingMaterial
Vent
Scrubbing
System
Discharge
Figure 1: Technical Grade
Active Ingredient
Wetting Agent Vent to Atmosphere
Shipment
To Waste Treatment Plant
Figure 2: Typical unit operation of Chemical Synthesis
Reactor System
Fractionation System
Dryer Packaging
Scrubber
WasteTreatment Plant
Mill
Mixing Tank
Packaging
Figure 3: Formulating Industry
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 orAqueous)
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 WasteSpent catalysts, spent filters, sludges, wastewater treatment biological sludge, contaminated soil, old equipment/insulation, packaging material, reaction by-products, spent carbon/resins, drying aids.
Ground WaterContamination
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 minimize 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
EquipmentCleaning Wastes
Maximize 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 AreaWash downs
Use of dedicated vacuum system. Use of dry cleaning methods. Use of recycled water for initial cleanup. Actively
involved supervision.
Off-SpecificationProducts
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 washwater
Where multiple washings in a reaction are involved, each cycle wash water to be stored and used in subsequent batches.
Steam condensatefrom 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 pumpseal 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 ofwastes 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 inreactions
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.
SolventExtraction
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 has 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 GenerationManufacture 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 33000Suspended Solids 2000Dissolved Solids 31000
Total Volatile Solids 3220BOD5 180COD 1372
Chlorides 1500Sulphates 2050
Manganese 215Zinc 4
Central Pollution Control Board Effluent Standards for Pesticide Industry
Parameter StandardsTemperature Shall not exceed 5 ºC above the receiving water temp.
pH 6.5-8.5Oil & grease 10
BOD 3 days 27 ºC Technical Grade Unit
100
BOD 3 days 27 ºC Formulation Unit 30Total Suspended Solids 100
Bio assay test 90% survival of fish after 96 Hrs in 100% effluentSpecific Pesticides In mg/l
DDT 0.01Benzenl Hexachloride 0.01
Endosulfan 0.01Carbonyl 0.01Malathion 0.01
Fenitrothion 0.01Diamethoate 0.45
Phorate 0.01Sulphar 0.03
2,4 D 0.4Methyl Parathion 0.01
Phenathoate 0.01Pyrethrums 0.01
Ziram 1Paraquate 2.3Proponil 7.3
Copper Sulphate 0.05Copper Oxyghloride 9.6
Other Pesticides 0.10Heavy Metals In mg/l
Copper 1Manganese 1
Zinc 1Mercury 0.01
Antimony as sb 0.1Any other metal like Nickel etc Shall not exceed 5 times the drinking water standards
of BISOrganics In mg/l
Phenol and Phenolic compounds as C6H5OH
1
Inorganics In mg/lArsenic as As 0.2Cyanide CN` 0.2
Nitrate as NO3 50Phosphate as P 5
Emissions In mg/Nm3
HCl 20Cl2 5H2S 5
P2O5 as H3PO4 10HBr 5NH3 30
Particulate matter with pesticide compounds CH3Cl
20
HBr 5
Pollution effects by Pesticide
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.
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.
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.
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.
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.
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.
Choice of treatment technologies for effluent based on three environmental parameters i.e.
BOD, COD and TDS is given in table below.
CombinationQuality ofEffluent
Cleaner Production
Treatment Options
High TDS, HighCOD and High BOD
Waste is not easilybiodegradable but toxic
Thermal decomposition (based on calorific value); Chemical
oxidation by hydrogenperoxide, ozone etc;
Evaporation + securedlandfill
High TDS, HighCOD 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 isjust 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 justhigher 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, HighCOD and High BOD
Highly organic effluent, may not be easily biodegradable
Thermal decomposition; Chemical oxidation by
hydrogen peroxide or ozone or
sodiumhypo-chlorite etc.; Chemical +
biologicaltreatment
Low TDS, HighCOD and low BOD
Highly recalcitrantwastewaters ,not
readily suitable forbiological treatmen
Chemical recovery; Chemical oxidation +
biological treatment
Low TDS, COD justhigher than BOD and
high BOD
Organic effluent, fully biodegradable
Anaerobic + aerobic treatment
Low TDS, low CODand low BOD
Low organic and lowinorganic effluent
Recycle and reuse (after preliminarytreatment)
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 Pollutant1 Acephate HCL2 Aluminum phosphide P2O53 Bhutachlor HCl, SO24 Captan HCl, SO25 Cypermethrin HCl, SO26 DDVP CH3Cl7 2,4-D Acid HCl8 Dimethoate CH3OH, H2S9 Endosulfan CH3Cl10 Ethion H2S11 Fenvelarate NH3 HCl, SO212 Isoproturon NH313 Malathion H2S14 Methoxy Ethyl Merc.Chloride HCl15 Methyl Bromide HBr, SO216 Monochrotophos CH3Cl17 Oxychloramide HCl18 Phenyl Merc. Acetate HCl19 Phosalone HCl, H2S20 Phosphamidon NH3 CH3Cl HCl21 Phorate H2S22 Zinc Phosphide P2O5
Clean Technologies and Methods for Recovery of Pollutants
SR. No.
Identified Priority
PollutantsControl System
ExpectedEfficiency
TechnicallyAchievable
average Conc.
(mg/Nm3)
CostRs/Lacs
1. HCl � Water Scrubber� Caustic Scrubber� Water/Caustic Scrubber
90 %99 %99%
8.6517.57.0
9.3713.404.11
2. Cl2 � Caustic Scrubber� Water/Caustic Scrubber
99 %99 %
0.150.01
3.164.06
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
7.720.0
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
Product wise 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 isresulting 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/Aluminiumphosphide
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 thequantity of sodium cyanide used and thereby reduce the load ondetoxification and generation of detoxification sludge.
Fenvalerate In the manufacturing process of Fenvalerate, better heat transfer andtemperature 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.
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