Hazardous Waste Management

1. Hazardous Waste Management CEV 414 E

2. Every year, billions of tons of solid wastes are discarded into our environment. These wastes range in nature from common household trash to complex materials in industrial wastes, range in nature from common household trash to complex materials in industrial wastes, such as hospitals and laboratories. • Waste is defined as 'any material that are no longer desired and has no current or substance that has been discarded or otherwise designated as a waste material, or one that may become hazardous by interaction with other substances

3. Hazardous waste may either be in the form of solid, liquid, semi-solid or contained gaseous material (UNEP 1982). • Turkey had also extricated several catastrophes similar to other countries. • In 1970, hazardous wastes were imported to be utilized as a fuel from foreign countries. People were unaware of the adverse effects of the gas formed through burning. • In 1980 a ship named unaware of the adverse effects of the gas formed through burning. In 1980 a ship named Petersberg had spent 2 moths in Marmara and Black sea to discharge its wastes

4. It was not the legislation’s or governmental acts but the common sense of people that terminated the improper actions. • Great number of fish and other living organisms were found dead at the sea shore of Marmara Sea between Kartal and Kadıköy region. • Drums that were full of hazardous waste were found in Black Sea near Samsun. • Hekimbaşı uncontrolled landfill area was exploded and 40 people died in Istanbul. • A gold mine project, which used cyanide extraction and proposed waste dam is still being problem to make Environmental Impact Assessment Report due to lacking in regulations and their enforcements. Growing concern about the environment in Turkey has focused attention in recent years on the need for vigorous Government action.

5. In consequence, substantial administrative measures have been introduced to improve the environmental concern and to provide a more efficient and rational basis for the management of wastes from all sources. • In 1995 Control of Hazardous Waste legislation has been passed to provide a control over wastes that are generated (Control of Hazardous Waste Regulation-27.08.1995). • The Control of Hazardous Waste Legislation of Turkey has been based on the idea of regulatory approach of EPA. The Turkish legislation then becomes a reproduction of the Resource Conservation and Recovery Act (RCRA). • Studies have not been made to see whether the legislation is suitable for Turkey or not. Thus the legislation cannot be carried out to protect environment due to inappropriate technical evaluations, misplaced definition of effects, contradictions and intersections among the lists in terms of criteria, source, characteristics, as well as subjective descriptions. Practices which will lead to environmental protection legislation's have to be based on political proposals, project planning as well as legal alterations for their ease of applicability.

6. Classification • Classification with Respect to Characteristics • Solid waste has to be examined whether it exhibits a characteristic that makes it hazardous. • All persons who generate a solid waste have to ascertain whether their wastes exhibit one or more of the characteristics as follows: Ignitability, Corrosivity, Reactivity, Toxicity (Hall and others 1993, UNEP 1983, EPA 1990a).

7. Ignitability • The hazardous waste characteristic of ignitability was established to identify solid wastes capable during routine handling of causing a fire, or provoking a fire once started. • A solid waste is deemed to exhibit the characteristics of ignitability if meets one of the four descriptions. It is determined using the test method specified in ASTM Standard D-93- 79 or ASTM Standard D-3278 (EP A 1990a, DEPE 1992, Meyer 1989).

8. Corrosivity • Corrosive substances may exhibit extremes of acidity or basicity or a tendency to corrode steel. Wastes capable of corroding metal could escape their own containers and liberate other wastes. • In addition, wastes with a pH at either the high or low end of the scale can harm human tissue and aquatic life and may react dangerously with other wastes. It is determined using the test method specified in EP A 600/ 4- 79-020.

9. Reactivity • Reactive substances are those, which are extremely unstable and have a tendency to undergo violent chemical change or explode during stages of its management. • The regulation lists several situations where this may happen which guarantee specific consideration like the behavior of the substance when mixed with water, when heated etc. Instead of developing a precise scientific description of this characteristic, EPA has publicized a descriptive, prose definition as a suitable test protocols for measuring reactivity are unavailable (EPA 1990a, 1990b, Meyer 1989).

10. Toxicity • One of the most significant dangers posed by hazardous wastes is the leaching of toxic constituents (of land disposed wastes) into the ground water (Christensen 1971, EPA 1981). • EPA designed the (Toxicity Characteristic) TC Toxicity, to identify wastes that pose a threat to human health or the environment resulting from ground water contamination by simulating the leaching process that occurs in a municipal landfill. • EP A treats mixtures of a characteristic hazardous waste and a solid waste differently than it does a mixture of a listed hazardous and solid waste. Toxicity can be determined by fish bioassay tests. Toxicity value defined by LC50.

11. The LC50 for a contaminant is the concentration being lethal to 50 per cent of an exposed population of test fish with a given time. For estimation of LCso values, various procedures using different test species and experimental conditions can be found in literature • (EPA 1990a, 1990b, OECD 1982, Council on Environmental Quality 1971, Manahan 1990). • The entire volume of a mixed waste is treated as hazardous if; the listed hazardous waste in the mixture was not listed separately due to its hazardous characteristics or mixture does not consist of certain specified hazardous wastes.

12. Building Up Criteria to Define Hazardous Waste • Waste can have the potential of being hazardous due to; substances present in the waste, their concentration, their chemical reactivity, physical form in which the substances are present, quantity and recurrent rate of arising of potentially hazardous material, mobility and persistence of the potentially hazardous materials in the environment in which they are placed, targets available in that environment and their vulnerability to the potentially hazardous materials, possibility of remedial measures and their costs. • The short-term acute and long-term environmentally hazardous properties of a waste are a function of the chemical species present. In some cases, wastes have well-defined dangerous properties and are unequivocally hazardous. Such wastes generally result from the use of commonly encountered chemical compounds. The majority of wastes considered, however are likely to be complex mixtures, which do not readily lend themselves to chemical characterization (UNEP 1982, EPA 1990a, 1990b, Hall and others 1993).

13. Composition • Concerning the composition of the waste, the individual components of a waste should be known before a complete assessment of its hazard potential is made. • This knowledge however is often very difficult and may be impossible in practical terms, particularly for solid wastes. To demand, either directly or by implication, that all waste be analyzed for all potentially hazardous species is quite impractical (UNEP 1982).

14. Physical Form • Three major categories of wastes based upon their physical forms are; organic materials, aqueous waste and sludge (UNEP 1982). • These forms largely determine the course of action taken in treating and disposing of the wastes. • It is relatively easy to deal with wastes that are not mixed with other kinds of wastes. The physical form of the waste as relevant to a consideration of both potential acute or long-term environmental hazards. • In general, liquid or sludge waste is more liable to cause water pollution problems than is solid waste. Where an inhalation hazard exists, as with asbestos, fibrous waste is inherently more dangerous than is matrix-bonded asbestos waste, e.g. asbestos cement. Small particle size by itself may confer hazard on a material that is non- hazardous in larger pieces; many finely divided metals are acutely hazardous while the massive material is harmless. • Solids formed by cooling from the molten state may often have their potential hazard much reduced, e.g. metal slags are often considered non-hazardous despite often relatively high concentrations of toxic metals (UNEP 1982).

15. Quantity • The quantity of the waste and its recurrent rate of arising are important. The handling and disposal of a few hundred kilograms of a particular waste as and isolated arising may demand totally different solution to the disposal of similar material arising on a regular basis in quantities, which may be orders of magnitude greater or smaller. • Some countries have introduced requirements that a waste must be present at more than a predefined minimum quantity before it is considered hazardous. This approach is administratively convenient as it reduces the amount of paperwork associated with the regulatory process, but has certain dangers (UNEP 1982). • The potential for environmental damage at a waste disposal site is c1early related not only to the concentration of the substance released but also to the total quantity released at a given time (Kolaczkowski and Crittenden 1987, Exner 1 989).

16. Acute Hazard • The acute hazard posed by the waste may be expressed in terms of oral, inhalation or dermal toxicity, flashpoint, explosivity, concentration of known corrosive species, etc. Physical characteristics, such as vapor pressure and boiling point, may be important. • To avoid dangerous interactions with co-deposited materials, highly reactive materials, e.g. powerful oxidants, should also be considered. However, unless toxicity tests are performed on the waste itself, acute hazards posed by the waste can only be predicted by the hazards of its components.

17. Long-term Hazard • The long-term hazard posed by the waste will depend upon the chosen disposal route. • For example, such properties as volatility, water solubility and solubility in organic chemicals will influence the mobility of wastes deposited in landfill. The persistence of a particular material will depend upon its vulnerabİ1İty to various natural breakdown mechanisms like microbiological, photochemical, oxidation/reduction, etc. • The toxicity of a deposited material and its metabolites and organoleptic factors, such as taste and smell, are relevant.

18. Exclusive List of Hazardous Wastes. • One alterative approach to the problem of adequately defining what constitutes a hazardous • waste is to draw up a list of known wastes, which present no significant short-term handling or long-term environmental hazards, and to define hazardous waste by exclusion, as any wastes not listed. • While one advantage of the exclusive list approach is that it is relatively simple to ensure that the listed materials are not hazardous, materials not listed and, marginally so. In addition, when reliance is placed upon qualitative, subjective criteria, different interpretations will inevitably possible. • Thus, waste producers, waste disposers and regulatory authorities are denied the certainty they need.

19. Inciusive List of H azardous‘ Wastes • More widely employed for regulatory purposes are listings of hazardous waste, either with or without accompanying criteria. This approach is currently used in Belgium, Denmark, France, the Federal Republic of Germany, the Netherlands, Sweden, United Kingdom and the United States. • The lists comprise wastes from certain industries, wastes containing specific components or specific waste streams identified by the processes from which they originate. The United States also uses this approach but combines it with prescribed test procedures, such that hazardous wastes are so defined by their presence in a list of waste materials or providing certain results when subjected to the test protocol (EP A 1980, EP A 1990a, 1990b, Hall and others 1993). • The inclusive list offers a greater degree of certainty but suffers from the disadvantage that exclusions may well be significantly hazardous. The greater the degree of specificity, the more the list approaches catalogue proportions (UNEP 1983).

20. § 261.31 Hazardous wastes from non-specific sources. F001 .. The following spent halogenated solvents used in degreasing: Tetrachloroethylene,trichloroethylene,methylene chloride, 1,1,1-trichloroethane, carbon tetrachloride,and chlorinated fluorocarbons; all spent solvent mixtures/blends used indegreasing containing, before use, a total of ten percent or more (by volume) ofone or more of the above halogenated solvents or thosesolvents listed in F002,F004, and F005; and still bottoms from the recovery of these spent solvents andspent solvent mixtures.(T) F006 ... Wastewater treatment sludges from electroplating operations except from the followingprocesses: (1) Sulfuric acid anodizing of aluminum; (2) tin plating on carbonsteel; (3) zinc plating(segregated basis) on carbon steel; (4) aluminum or zinc-aluminumplating on carbon steel; (5) cleaning/stripping associated with tin, zinc andaluminum plating on carbon steel; and (6) chemical etching and milling of aluminum. (T)

21. § 261.32 Hazardous wastes from specific sources. Wood preservation: K001 ...... Bottom sediment sludge from the treatment of wastewaters from wood preservingprocesses that use creosote and/or pentachlorophenol.(T) Inorganic pigments: K002 .......Wastewater treatment sludge from the production of chrome yellow and orange pigments.(T) K003 .....Wastewater treatment sludge from the production of molybdate orange pigments ...... (T) K004 ..... Wastewater treatment sludge from the production of zinc yellow pigments ................. (T) K005 ...... Wastewater treatment sludge from the production of chrome green pigments ............ (T) K006 ...... Wastewater treatment sludge from the production of chrome oxide green pigments(anhydrous and hydrated).(T) K007 .....Wastewater treatment sludge from the production of iron blue pigments ..................... (T) K008 ......Oven residue from the production of chrome oxide green pigments ............................ (T)

22. P021 592–01–8 Calcium cyanide P021 592–01–8 Calcium cyanide Ca(CN)2 P189 55285–14–8 Carbamic acid, [(dibutylamino)- thio]methyl-, 2,3-dihydro-2,2-dimethyl- 7-benzofuranyl ester. P191 644–64–4 Carbamic acid, dimethyl-, 1-[(dimethyl-amino)carbonyl]- 5-methyl-1H- pyrazol-3-yl ester. P192 119–38–0 Carbamic acid, dimethyl-, 3-methyl-1- (1-methylethyl)-1H- pyrazol-5-yl ester. P190 1129–41–5 Carbamic acid, methyl-, 3-methylphenyl ester. P127 1563–66–2 Carbofuran. P022 75–15–0 Carbon disulfide P095 75–44–5 Carbonic dichloride P189 55285–14–8 Carbosulfan.

23. U002 67–64–1 Acetone (I) U003 75–05–8 Acetonitrile (I,T) U004 98–86–2 Acetophenone U005 53–96–3 2-Acetylaminofluorene U006 75–36–5 Acetyl chloride (C,R,T) U007 79–06–1 Acrylamide U008 79–10–7 Acrylic acid (I) U009 107–13–1 Acrylonitrile U011 61–82–5 Amitrole U012 62–53–3 Aniline (I,T) U136 75–60–5 Arsinic acid, dimethyl- U014 492–80–8 Auramine U015 115–02–6 Azaserine

24. Management Strategies for Identification • Management strategies also play an important role in defining a hazardous waste. These steps may include; the source of the waste, generators, waste transport, waste storage, appropriate treatment technologies, Final disposal. • Once a waste is identified as hazardous, quantities must be tracked. In order to identify whether a solid waste is hazardous or not, generator should have to refer to lists or various tests. Effective identification and labelling by the generators are essential for control. Mismanagement of Hazardous Waste leads to a 'cradle to grave' control system (UNEP 1983). • This system regulates the hazardous waste from the time it is first generated through the transport to final treatment or disposal. Some hazardous wastes require special control from the time of generation through their transportation, temporary storage, treatment and disposal.

25. Hazardous wastes should be identified and disposed of in a manner that will most effectively protect the environment. The quick and dirty approach is still employed today by putting wastes in open dumps, landfills or in warehouses. Hazardous wastes can either be tracked according to the amount that is generated (EPA 1990a, DEPE 1992, Phifer and McTigue 1989): • 1.Small quantity generators, 2.Large quantity generators • or can be classified according to their sources: • Point sources, 2.Diffuse sources.

26. Industrial hazardous wastes are a unique problem because they are transportable, and pose hazard either in short or long term basis. Thus it will be appropriate to further classify the wastes: • Industrial hazardous waste generators • Non-industrial hazardous waste generators. • Standard Industrial Classification (SIC) codes have been employed to identify groups of hazardous waste generators. The office of Management and Budget Manual establishes these codes. • However in some cases they were found to be inadequate. The manual and codes do not identify individual facilities or potential generators. They are often not descriptive or inclusive as is necessary for a complete hazardous waste survey.

27. Collection and Transport • These play an important role particularly in terms of disposal cycle and in control. • Most incidents of improper disposal of hazardous waste have occurred during transport and may result from disposal contracts between the waste generator and hauler rather than between the waste generator and disposer. • Thus, any reduction of cost for disposal (e.g. by means of improper dumping) will increase the profit of waste haulage firm.

28. Management, Treatment and Disposal • Waste Reduction • Waste sorting and Recycling • Waste transfer and Transboundry movement • Energy and Material recovery • Thermal Processing/ Waste Incineration • Ultimate Disposal/ H.W. Sites

29. Physical Treatment • Lagooning and tank storage are widely used to seperate oil and water from mixed wastes • Solidification fixation processes are generally used as pretreatment prior to landfill disposal • Air flotation and various filtration and centrifugation techniques

30. Chemical Treatment • Cyanide Oxidation • Heavy Metal Precipitation • Hexavalent Chromium Reduction • Acid neutralization

31. Biological Treatment • The in-plant biological treatment of dilute aqueous effluents is well established, and m.o. Have been developed to selectively degrade specific toxic chemicals • Composting may also be useful for certain organic chemical products

32. Disposal • Landfill • Incinaration • Dumping at sea • Underground disposal • Deep-well disposal

33. Coast of Waste Treatment and Disposal Table 4. Cost to Western Europan Chemical Industry for treating and disposing of waste by different methods : Spring 1979 Methods Cost Range US $ /tonnes Simple Disposal to land 1-20 Disposal to land in a site lined with plastic sheet 10-50 Underground disposal to dropping into old wells or mines 20-150 Land disposal after encapsulation either by mixing the waste 10-100 with cement or other agent or by incarcerating whole drums in cement Coastal sea dumping from ships or 5-15 Deep-ocean dumping beyond the continental shelf 10-150 Simple incineration (without significant heat recovery) 30-150 Incineration with alkaline stack scrubbing 100-350 Incineration onboard ship at sea 50-350 All types of chemical treatment and, in particular : Destruction of cyanide by hypochlorite 300-500 Reduction of chromic acid 100-300 Destruction of cyanide (catalytic) 200-500

35. Hazardous Waste Definition • “Hazardous waste“ is a/any specialized and listed waste; • which has acute or chronic hazard potential described as “Flammable” ,”Toxic”, “Corrosive” and/or “Reactive” criteria, • Which should be managed with all together with the social, political and economical aspects of the eco-system instead of convantional tratment and disposal techniques because of its composition, constituents, physical form, fate and transport in the environment • Which may be in forms of solid, liquid, slurry, sludge and pressurized gas • Which may be a/any hazardous substance that has been discarded or otherwise designated as a waste material, or one that may become hazardous by interaction with other subtances

36. A RATING SYSTEM FOR DETERMINATION OF HAZARDOUS WASTES Ilhan Talinli , Rana Yamanturk, Egemen Aydin, Sibel Basakcilardan

37. Introduction • Hazardous wastes, the main drawbacks of industrialized world, are still keeping their importance because of their potential hazard to human health and environment, when improperly treated, stored, transported and/or disposed. • The unique solution for that kind of wastes is to manage and control them from the point of generation to ultimate disposal.

38. The legislators of each country should create regulations enforcing the safe management of the hazardous waste. • These regulations should appoint the hazardous waste generator as a legal entity who must ensure that the waste is managed in accordance with its regulatory standards [1]. • But a generator who will comply a regulatory program demands a far more precise definition of the term “hazardous waste”.

39. The term “hazardous waste”, originated from US Environmental Protection Agency, does not have a unique and universally accepted definition but the identification of hazardous waste in each country is based on the four characteristics 1) ignitability 2) corrosivity 3) reactivity 4) toxicity [2]. • Although every country has its own regulatory program, the most common violation of the rules, whether willful or inadvertent, is because of the definition of the waste as hazardous waste [3].

40. In most of the countries, the board responsible from the hazardous waste management defines the hazardous waste by using two different mechanisms (1) by listing (2) by identifying characteristics and these definitions are commonly based on the Subtitle C of Resource Conservation and Recovery Act (RCRA) which is the most extensive study done about hazardous waste management.

41. Using lists to define hazardous wastes presents certain advantages and disadvantages. • The main advantage is that lists make the hazardous waste identification easier for generators. On the other hand, hazardous waste lists simply can not include all hazardous wastes. • Another disadvantage is their lack of flexibility. Lists determine a waste as hazardous if it falls within a particular category or class. • The actual composition of the waste is not considered as long as the waste is listed. Thus, the lists can regulate some wastes that do not pose a significant health threat or a really hazardous waste may be not found in the lists [4].

42. Determination of hazardous waste by detecting the characteristics of the waste is another method which needs proper analyses to define the waste as a hazardous waste. • At first, all the hazardous characteristics including phytotoxicity, teratogenicity, bioaccumulation, mutagenicity are thought to be in characteristics of the hazardous waste, but because of the difficulties in testing protocols of these characteristics mentioned above EPA decided to use 4 common characteristics to identify the hazardous waste.

43. Although EPA introduces the test protocols for ignitability, corrosivity, reactivity and toxicity, there are still gaps which enable a hazardous waste to be determined as conventional waste. • The main gap is seen in toxicity testing, which only 43 of the toxic chemicals are subject to the TCLP test [5]. Thus, if a waste does not bear any of the 43 chemicals, the waste is not considered as hazardous, which may be a really hazardous waste. • The other example is ignitability which does not have a test method for non-liquid wastes. The gaps for the determination of the hazard potential of hazardous waste mixtures are also noticed and an index is prepared to serve as a guide for people who produce, store, transport, dispose, recycle and/or regulate hazardous waste [6].

44. Although lists and characteristics analyses are nearly the same in all countries, the differences in regulations make the determination subjective which creates a serious problem in management of these wastes. • In order to eliminate the subjectiveness of lists and characteristics tests, a quantitative determination system is stated in this study. • Overall Rating Value (ORV) calculates and quantifies a/any waste as regular (conventional) waste, non-regular (solid) waste or hazardous waste by using variables such as Ecological Effect (Ee) (ignitability, reactivity, corrosivity, toxicity), Combined Potential Risk (CPR) (carcinogenic effect, toxic characteristics, infectious characteristics, persistency), Physical Form (f), Listing (L) and Quantity (Q) of the hazardous waste.

45. Discarded Material Reuse Recycle Recover Can it be reused, recovered and/or recycled? Y N Waste Is it defined in your wastewater, municipal solid waste and/or air pollution control regulations? Y N Hazardous Waste Determination Check H.W. Lists Y N Regular Waste Has it hazard criteria? Hazardous Waste Y N Assess CPR Y N Non-Regular Waste Rating System

46. To install the rating system formulation, following assumptions are postulated • 1. If a/any discarded material has been defined as a/any waste, the determination of the waste should be done such as wastewater, municipal solid waste and air emission. The term “non-regular waste” has been considered as intermediate waste which differentiates hazardous and conventional waste defined in regulations. If a waste is non-regular waste, next step is determination of hazardous waste. In Equation 1; the component “D” represents the boundary of the non-regular waste in the scale. Wastes such as hospital and radioactive wastes have been neglected in this inquiry because they have their own control regulations and these wastes are already identified as non-regular wastes.

47. 2. Listing methodology of the hazardous waste and their lists published in different countries cannot be neglected, thus the “L” component is additionally taken into account in order to determine hazardous waste.

48. 3. Ecological effects (Ee) includes primarily impacts from waste associated with their one or more hazard characteristics such as toxicity, ignitability, corrosivity and reactivity. • Physical forms of the waste are also rated according to behaviors of the waste in nature.

49. 4. Accumulative and synergistic effects and uncertain potential risks are included in combined potential risk (CPR) parameter. • Components of this parameter are human health toxicity, carcinogenetic effects, infectious risks, and persistency associated with biodegradability, solubility, and bioaccumulation. • Physical forms of the waste and exposure mode are also taken into account during evaluation of these risks.

50. 5. Four critical components explained above are considered as cumulative functions of “Overall Rating Value” (ORV) due to the higher values of these components, the higher ORV. • On the other hand, the amount of the waste is obviously a basic characteristic of the waste in this rating system, thus it should be a multiplier of the other components. • Rating system equation (Eq. 1) is composed of a cumulative-linear function coupled with 8 sub-equation run the points obtained from ranking tables for each parameter