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OVERVIEW ON HAZARDOUS WASTES AND ITS MANAGEMENT

Dr. I.D. Mall Professor, Department of Chemical Engineering, Indian Institute of Technology- Roorkee,

Roorkee-247667(UA), India INTRODUCTION

� While there is little doubt that humankind’s increasing of natural law has brought us increased life expectancy and higher quality of life for more people than ever known before.

� This has brought the risk of global calamity and impairment of human health. � Hazardous waste management has become an international problem � The environmental and Human Health consequences of the residuals and

wastes: not understood and recognised � Developments in science, epidemiology, toxicology and analytical chemistry

enabled to recognise LAND Mark Episodes

� DDT : Residues in deep sea liquid, Antarctic penguins, and the fatty tissues of Homo sapiens. High levels of DDT in aquatic birds

� Mercury : As liquid mercury to cure constipation. Mercury salts: results in neurological disorder Dutch Hat industry Organic form Methyl Mercury: More Pernicious Minamata Japan episode paralysis and sensory loss recently in coal fire boilers

� Polychlorinated biphenyls (PCB’s): transformer coolants, plasticisers, carbonless paper: Japan and Taiwan Miscarriages and birth defects Poly brominated biphenyls: Michigan mothers milk

� Dioxins and Furan from pulp and paper mill effluent

� Hazardous waste doses pose a real risk to human health and The environment

� But to what magnitude of risk? Relative Risk

Problem EPA experts Public Opinion

Hazardous waste sites Low-Medium High Pesticide residue on foods High Medium Indoor air pollutants High Low Consumer Exposure High Low to chemicals

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HAZARDOUS WASTE ? A solid waste or combination of solid wastes that, because of quantity, concentration or physical, chemical or infectious characteristics, may cause or significantly contribute to an increase in mortality or an increase in serious, irreversible, or incapacitating reversible illness or pose a substantial hazard to human health or the environment when improperly treated, stored, transported, disposed, or otherwise managed. About 290 million tons of hazardous wastes are generated in the U.S. each year. About 4% is recycled. The rest is treated, stored or disposed. Generally the term "hazardous waste" means a solid waste, or combination of solid waste that, because of its quantity, concentration, or physical, chemical or infectious characteristics may:

� Cause or significantly contribute to an increase in mortality or an increase in serious irreversible, or incapacitating reversible, illness; or

� Pose a substantial present or potential hazard to human health or the environment when improperly treated, stored, transported, or disposed of, or otherwise managed.

Hazardous wastes come in many forms. They can be liquid, solids, semisolid, or contained gases. They can be manufacturing process byproducts, sludges or spent materials or simply discarded products. Hazardous waste can be classify on the basis of

� Physico-chemical properties � Toxicological properties � Environmental properties � Specific effects on human health

EPA lists wastes based on three categories:

� Exhibits a hazardous characteristic Ignitibility, Reactivity, Corrosivity, Toxicity

� Acutely hazardous Fatal to humans at low doses

� Toxic If it contains certain hazardous constituents

� Listing is accompanied by a hazard code I, C, R, E, H, T

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Waste Characteristics

CHARACTERISTICS OF HAZARDOUS WASTE � Ignitability

� Flashpoint <60 C � Solid at STP capable of

causing fire through friction, moisture changes or spontaneous chemical changes

� Oxidizer � Corrosivity

� pH < 2 or > 12.5

� Reactivity � Unstable � Reactive with water � Generates toxic fumes � Contains sulfide or cyanide

groups � Capable of detonation

� Toxicity � EPA definition

CLASSIFICATION OF HAZARDOUS WASTE On the basis of various properties of the waste can be classified under the following categories:-

� Explosive, Corrosive, Oxidizing , Flammable , Infectious , Irritant, Toxic, Toxic for reproduction, Harmful, Mutagenic, Exotoxic, Carcinogenic, Residuary hazardous property

GENERATION OF HAZARDOUS WASTE

� Sources of hazardous waste in the country include those from industrial processes, mining extraction, tailings from pesticide based agricultural practices, etc.

� Industrial operations generate considerable quantities of hazardous waste and in rapidly industrializing countries such as India the contribution to hazardous waste from industries is largest. Since industrial units are spread all over the country, the impacts are region-wide.

� States such as Gujarat, Maharashtra, TamilNadu, and Andhra Pradesh, which and have undergone relatively greater industrial expansion, face problems of toxic and hazardous waste disposal far more acutely than less developed states.

Characteristics of waste:

Ignitability

Corrosivity

Reactivity

Toxicity

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INDUSTRIAL HAZARDOUS WASTE GENERATION � Timber product processing � Leather tanning and finishing � Iron and steel manufacturing � Petroleum refining � Inorganic chemicals � Textile mills � Organic chemical manufacturing � Adhesives � Gum and wood chemicals � Pharmaceuticals � Explosives � Pesticides � Pharmaceuticals � Non-ferrous metal manufacturing � Paint and ink formulation and printing � Soap and detergent manufacturing � Auto and other laundries � Plastic and synthetic materials � Pulp mills, paper products � Rubber processing � Machinery & mechanical products manufacturing

STATUS OF HAZARDOUS WASTE GENERATION IN INDIA (Source Hazardous waste management in India)

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State wise comparative HW Generation Units as per HWM Rules 1989 & 2003 State wise comparative HW Generation Units as per HWM Rules 1989 & 2003

501

1532

2984

6052

454

1589

3953

4571

700

14481100

2177

1036

1633

0

1000

2000

3000

4000

5000

6000

7000

AP

Guj

arat

Kar

nata

ka

Mah

ara

shtr

a

Pun

jab

TN

UP

State

No. of HW units as per HWM Rules, 1989No. of HW units as per 2003

No.

of H

W g

ene

ratin

g U

nits

309

47116 133

183 16357

271

889

575

423

753

257207

0100200300400500600700800900

1000

Cha

ndig

arh

Har

yana

Him

acha

l

Ker

ala

MP

Oris

sa

J& K

STATE

No

. of

HW

gen

erat

ing

Un

its

HW generating Units as per HWM RULES, 1989HW generating Units as per HWM RULES, 2003

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Sources & Quantum of Waste from Major Industrial Sources Fate of Hazardous Waste in India Solid Wastes that are not hazardous wastes:

� Household wastes � Ag waste if used as fertilizer � Mining spoils return to mine � Wastes from exploration, development or production of crude oil, gas,

geothermal � Cement Kiln wastes � Leather Industry, Trivalent Chromium Process

Landfilling 58%

Incineration 4%

Recycling 38%

Recycling Incineration Landfilling

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Summery of different bioremediation strategies for typical hazardous wastes Hazardous Waste Assessment Methodology (Source Revision of criteria and protocols of assessment and classification of hazardous waste Public Consultation Document R&D Project No P1-482 September 2002)

Nitrogen compounds

Examples Ammonia,Nitrate,

Nitro-aromatics etc.

• Phytoremediation•Injection wells •Aeration

Hydrocarbons

• Compositing• Surfactants • Fungi• Plants • Fertilizers

Examples Dibenzothiophenone,

Toluene,phenanthrene,Carbazole, octane etc.

Hazardous Wastes

Halogenated organic

compounds

•Nutrient application•Aeration •Bioaugmentation •Phytoremediation

Examples Carbonatetra chloride,Tetrachloro ethylene,Trichloro ethylene,PCBs, DDT etc

Herbicides/pesticides

• Microbial,• Bioaugmentation • Phytoremediation

Examples Atrazine, metachlorDinoseb,

Aldicarb etc.

Metals

• Phytoremediation•Injection wells •Constructed wetlands

Examples Iron,Lead,

Chromium,Copper,

mercury etc.

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Graphical Representation of State wise Generation of Hazardous Waste

Water Pollution in Yamuna Hazardous Waste from Industries causes Water Pollution

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DIFFERENT INDUSTRIAL HAZARDOUS WASTE And Many More….And Many More….And Many More….And Many More….

Sludge from Industries as a Hazardous Waste Societal waste

Household Waste

Municipal Solid Waste

Waste from Paint Industries

Hazardous Waste from Battery Manufacturing &

Recycling

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BASEL CONVENTION ON THE CONTROL OF TRANSBOUNDARY MOVEMENT OF HAZARDOUS WASTE AND THEIR DISPOSAL The convention is ratified by 35 countries, it entered into force on 5th May, 1992. The main principle of the convention is to regulate the Transboundary movement of hazardous wastes with prior informed consent of the importing country and to ensure environmentally sound management of hazardous wastes. The convention seeks to prohibited the export of hazardous wastes without the consent of the importing country. Basel Convention

� Basel convention is an international environment agreement on “control of trans boundary movement and disposal of hazardous waste” which was drafed on 22nd March, 1989.

� Basel BAN On 31st Dec, 1997 a “total ban” on the trans boundary movement was decided rather than “control” or the “partial transboundary movement” of hazardous waste from OECD (Organisation for Economic Corporation and Development) to non OECD.

GLOBAL SCENARIO

� Large manufacturing industries like chemical, metal, electrical, petroleum, transportation etc., generate hazardous wastes at the rate of more than 1000 kg/month/unit.

� More than 80% of the world's hazardous waste is produced in the United States and other industrial countries.

� 300-500 million tons of heavy metals, solvents, toxic sludge, and other wastes accumulate every year from industry.

� In developing countries, 70% of industrial wastes are dumped untreated into waters where they pollute the usable water supply.

INDIAN SCENARIO

� India has grown as 2nd fastest growing economy. It accounts for 20% of Asian and 10% of global growth.

� At the same time it is producing around 7.2 mt of hazardous waste out of which, 1.4 mt are recyclable, 0.1 mt to be incinerated and 5.2 mt to be disposed on land.

Country constitutes of : � Global population 16% � Global land mass 2.4% � Population growth >1.6% � Polluted surface water 70% � Diseases due to water 70%

Environment Legislation in India

� Article 48 (A) and 51 (A) (g) of Directive � Principles of State Policy (1976) � Article 21 Right to Life � Precautionary and Polluter Pays Source http://greenbusinesscentre.com

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� Principles � Environment (Protection) Act, 1986

The Hazardous Wastes (Management & Handling) Rules, 1989, Aments. 2000, 2003

� “Hazardous Waste” means any waste which by reason of any of its physical, chemical, reactive, toxic, flammable, explosive or corrosive characteristics cause danger to health or environment, whether alone or when in contact with other wastes or substances and shall include:

� Wastes listed in column (3) of Schedule 1 � Wastes having constituents listed in Schedule 2 if their concentrations equal to

or more than the limit indicated in the said Schedule; and � Wastes listed in Lists A and B of Schedule 3 (Part-A) applicable only in

case(s) of import and export of hazardous wastes in accordance with rule 12,13, 14 if they posses any of the hazardous characteristics listed in Part `B’ of Schedule 3. The rules do not apply to the following: � waste water and exhaust gases as covered under the provisions of Water

(Prevention and Control of Pollution) Act, 1974 and the Air (Prevention and Control of Pollution) Act, 1981.

� Wastes arising out of the operation from ships beyond 5 kms as covered under the provisions of the Merchant Shipping Act, 1958 and the rules there under.

� Radio-active wastes covered under the provisions of the Atomic Energy Act, 1962 and rules there under.

� Bio-medical wastes covered under the Bio-Medical Wastes (Management and Handling) Rules, 1998 made

� Wastes covered under the Municipal Solid Wastes (Management & Handling) Rules, 2000

� The lead-acid batteries covered under the Batteries (Management & Handling) Rules, 2001

� Ensure proper collection, reception, treatment, storage and disposal of hazardous wastes.

� Apply for renewal of authorization before expiry of the validity period � Maintain records of hazardous wastes handling (Form 3) � Submit “Annual Returns” to the SPCB (Form 4) � Report to the SPCB any accident � Labeling / Packaging / Transportation of HW as per Motor Vehicle Act, 1988

and Rules, 1989 � Clarification on the definition of Hazardous Wastes all wastes mentioned in

Schedule 1 are hazardous irrespective of the concentration limits provided in Schedule 2

� List of hazardous wastes according to Schedule 1 is modified (Process categories under the schedule are realigned and regrouped to 36 from 44 earlier)

� Procedure for registration of re-processors of nonferrous scrap and used oils included in the amendments. CPCB is to issue registration.

� “Used oil” and “waste oil” are defined � A Schedule for hazardous wastes prohibited for import and export from India

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New Amendments Draft circulated by CPCB for amendments in Schedules 3,4 & 8: Schedule 4: Scrap plastic of non-halogenated polymers and copolymers added Schedule 8:Hazardous wastes prohibited for Import and Export. Recent Supreme Court Order 14, October, 2004 “----all industries, involved in the hazardous chemicals and generating hazardous wastes display on-line data outside the factory gate, on quantity and nature of hazardous chemicals being used in the plant, as well as water and air emissions and solid wastes generated within the factory premises. If such data is not made available, the unit should be asked to show cause or even be asked to close down”. National Policy Document to be made by the MoEF / CPCB: “The policy document should emphasis a commitment to the recycling of wastes and materials, and propose incentives for encouraging and supporting recycling. Industries must be given a clear message that they must show tangible and concrete results as for as prevention and reduction of wastes are concerned. If they do not, they should be made to pay a waste regeneration tax------” ISSUES RELATED TO HWM IN INDIA

� Inventorisation of HWs � Guidelines/Codes of practices for categories of hazardous wastes � Design criteria of land-fill sites followed? � Problems with the regulations:

- Schedule 5 & 6 - Oil-Re-fining industry ESTs

� Common Facilities for HW Storage, treatment and disposal CATEGORIES OF HAZARDOUS WASTES SCHEDULE 2 Waste Categories Types of wastes Regulatory Quantities

Waste category No. 1 Cyanide wastes

1 kilogram per year calculated as cyanide

Waste category No. 2 Metal finishing wastes

10 kilograms per year the sum of the specified substance calculated as pure metal

Waste category No. 3

Waste containing water soluble chemical compounds of lead, copper, zinc, chromium, nickel, selenium, barium and antimony

10kilograms per year the sum of the specified substance calculated as pure metal

Waste category No. 4 Mercury, Arsenic, Thallium and Cadmium bearing wastes

5kilograms per year the sum of the specified substance calculated as pure metal

Waste category No. 5 Non-halogenated hydrocarbons including solvents

200kilograms per year calculated as nonhalogenated hydrocarbons

Waste category No. 6 Halogenated hydrocarbon including solvents

50kilograms per year calculated as halogenated Hydrocarbons

Waste category No. 7 Wastes from paints, pigments, glue, varnish and printing ink.

250 kilograms per year calculated as oil or oil emulsions

Waste category No. 8 Wastes from dyes and dye intermediate containing inorganic chemical compounds

200 kilograms per year calculated as inorganic chemicals

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Waste category No. 9 Wastes from dyes and dye intermediate containing inorganic chemical compounds

50 kilograms per year calculated as organic chemicals

Waste category No. 10 Waste oil and oil emulsions 1000 kilograms per year calculated as oil and oil emulsions

Waste category No. 11 Tarry wastes from refining and tar residues from distillation or pyrolytic treatment

200 kilograms per year calculated as tar

Waste category No. 12

Sludges arising from treatment of waste waters containing heavy metals, toxic organics, oils, emulsions and spent chemicals and incineration ash

Irrespective of any quantity

Waste category No. 13 Phenols

5 kilograms per year calculated as phenols

Waste category No. 14 Asbestos

200 kilograms per year calculated as asbestos

Waste category No. 15

Wastes from manufacturing of pesticides& herbicides & residues from pesticides and herbicides formulation units

5 kilograms per year calculated as pesticides and their intermediate products

Waste category No. 16 Acid / alkaline / slurry wastes

200 kilograms per year calculated as acids / alkalis

Waste category No. 17 Off-specification and discarded products

Irrespective of any quantity

Waste category No. 18 Discarded containers and container liners of hazardous and toxic wastes.

Irrespective of any quantity.

HAZARDOUS WASTES GUIDELINES The guidelines for the Management and Handling of hazardous wastes published by the Ministry of Environment & Forests in 1991, are provided to prescribe detailed procedures for handling and disposal of hazardous wastes. The Silent Features of the Bio-medical Wastes (Management & Handling) Rules 1998 & 2000 These rules provide control for the generation, collection, segregation, packaging, storage, transportation, treatment and disposal of the bio-medical waste. These rules include wastes generated from medical and health institutions, biotechnology and biological testing organization, laboratories, animal wastes, etc. The main features rules are: � Bio-medical wastes

Bio-medical means any waste which is generated during the diagnosis treatment or immunization of human beings or animals in research pertaining thereto or in the production or testing biological including the 10 Categories of wastes listed in the schedule I of the Biomedical wastes rules.

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� Authorization � Every occupier of institution generating medical waste is to ensure

handling of such wastes without any adverse effect on human health and environment.

� Every occupier of institution/operator of facility to make application for grant of authorization in form 1 to prescribed authority. Application for authorization to accompany with an authorization fee as prescribed by state Government.

� Prescribed authority appointed in every State and union territory are required to grant authorization within ninety days from the date of applications and to be valid for three years.

� Segregation, packaging & labeling

� Unique feature is it prescribes requirements for segregation of wastes at sources along with appropriate packaging and labelling details.

� Transportation in accordance with the Motor Vehicles Act 1988 and the rules there under.

� Treatment & Disposal

� Treatment and disposal to be in accordance with those given in schedule I and in compliance with standards prescribed in schedule V.

� The specific standards required for various treatment disposal techniques are given within these rules.

� Records & Reporting

� Records of generation, collection, reception, storage, transportation, treatment, disposal, handling ton be maintained of prescribed authority.

� Any accident in the institution or facility to be reported in Form III. HAZARDOUS WASTE LIFE CYCLE

HAZARDOUS WASTE LIFE CYCLE

Process Raw Materials

Catalyst Products

Hazardous Wastes

Wastes other than Hazardous Wastes

for treatment & further reuse / disposal

Recycled in other industries

Treatment

Wastes with Potential reuse

Landfill till HW cycle is complete

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CONCULSIONS The very real problem that hazardous waste has created and is creating is compounded by the commingling of technological obstacles; limited financial resources, a general with an inadequate understanding of basic scientific concepts including risk analysis. However, there has been continuous reduction in hazardous waste generation due to regulatory enforcement, legal liability, exposure to public scrutiny, reputation and image impacts With Source reduction cleaner and greener production, material substitution a, reuse, etc we can have sustainable development and we can all look forward to leaving a smaller footprint for future generations. While we are still in the process of effective implementation of the regulations through creating awareness among the people especially among the waste generators a move towards “Prevention is better than cure” by adopting waste minimization technologies and management of the unavoidable waste in the environmentally sound manner is the NEED OF THE HOUR

“Nature is essence of civilisation, to preserve it in its pristine glory and magnificence becomes our priority”