Professional Documents
Culture Documents
3 Hazardous Waste
3.1 Hazardous Wastes Incidents
Figure 3-1: Workers in protective clothing clearing the toxic waste from a hole in the landfill on Pulau Pangkor, Perak, Malaysia. Some 92 drums containing potassium cyanide were brought there by the owner ScientificTex Sdn Bhd from Penang, Malaysia, and dumped illegally. (The Straits Times, Friday, March 24,1995)
3-1
April 2011
NTU
EM107 Environmental Health and Safety deposited fly ash there. Biological warfare agents and residues may also had been buried there, an accusation the US Pentagon has denied. In 1952 Hooker Chemical closed and capped the canal.
In 1953, the Niagara Falls School Board and city officials ordered Hooker Chemical to sell canal to city. Reportedly Hooker Chemical tried to dissuade the sale and not to build on the site citing possible dangers of building over the chemical landfill - but School Board and the city were determined, and the final sale was for US$1. In the deed Hooker stated that chemical wastes were buried there and Hooker should bear no liability for them.
The 99th Street School was built in 1954 over the unused northern part of the canal. Following soon housing developments, and utilities that resulted in digging into the protective clay covering and laying sewer lines through the waste. In 1978, some 97 families lived immediately adjacent to the landfill , in the homes immediately adjacent to the landfill, and the school had 410 students. In a study published in 2008, an estimated 6,200 persons were affected by the waste dump.
The aftermath
Children playing at the park would occasionally pick up chunks of rocks and would throw them against rocks to see the brilliant explosion. These rocks turned out to be chunks of phosphorus. Soon more horror stories abound birth defects, mental retardation, enlarged livers, cancer, swimming pool swelling up, black stuff oozing out of basements, etc. A large number of chemicals were found at the sites tests showed a variety of chlorinated solvents, benzenes, toluenes, pesticides, dioxin, etc.
The US Superfund Program was created by the Comprehensive Environmental Response, Compensation and Liability Act of 1980 (CERCLA). With the polluter pays principle, the US government would take legal action to get the former owners and users of contaminated site to cleanup the contamination or pay for the cleanup. If the responsible parties cannot be identified or are now bankrupt, the costs are paid from a Superfund created by a tax on manufacturers of petroleum and chemicals. The Occidental Chemical Corporation (which had become the parent company of Hooker Chemical) paid $129 million to cover the federal government's cleanup costs at Love Canal, New York.
3-2
April 2011
EM107 Environmental Health and Safety In October of 1981, the Love Canal was listed on the EPAs National Priorities List (NPL). Note: The National Priorities List (NPL) is the list of national priorities among the known releases or threatened releases of hazardous substances, pollutants, or contaminants throughout the United States and its territories. The NPL is intended primarily to guide the EPA in determining which sites warrant further investigation.
Minamata Disease
3-3
April 2011
NTU
NTU
EM107 Environmental Health and Safety the right to prohibit the import of hazardous wastes or other wastes for disposal from other Parties. There are at present 175 parties to the treaty, with only Afghanistan, Haiti and the United States of America having signed but not ratified the treaty.
NTU
A waste will be consider hazardous by the following two ways: Listed in regulations as hazardous wastes; or Exhibit one or more of the following characteristics ignitable (flash point < 60 oC), oxidizing, corrosive (pH < 2 or > 12.5, or corrodes steel at a rate > 6.35mm per year at a test temperature of 55 oC), reactive, toxic (LD50 < 500 mg/kg) or explosive. One should note that the characteristics listed above could vary between countries. Unknown wastes should be considered hazardous unless proven by known origin or by testing.
In Singapore, the key elements for the management of hazardous wastes are: avoid generation of intractable wastes; encourage waste minimisation; encourage waste reuse, recovery and recycling; regulate collection, treatment and disposal; monitor and audit collection, treatment and disposal; and promote and support educational and training programmes. In Singapores planning process, proposed industrial development will be screened for waste generation to eliminate the generation of wastes that cannot be safely disposed of in Singapore.
Permitting
Many countries require the generator of hazardous to obtain a permit or notify the environment authorities of the generation of hazardous wastes. Likewise, companies that would like to be involved in the business of collection, transportation, storage, treatment and disposal of hazardous wastes are also required to obtain a permit before they may engage in such activities. Typically, the companies concerned must have the knowledge and expertise to manage their hazardous wastes. In Singapore the permit holder is required to attend and passed a prescribed training (Management of Hazardous Substances conducted by the Singapore Environment Institute at NEA). Further, only companies with the appropriate level of expertise to handle, treat and disposed of hazardous wastes may be granted licenses. Each license is also limited in its scope, i.e. the license would specify the type of waste the company may accept for treatment and disposal.
Manifest
A manifest system was created by the US EPA to track the movement of hazardous waste to ensure that the waste actually reach their intended treatment and disposal facility. This system has been widely adopted by 3-6 April 2011
NTU
EM107 Environmental Health and Safety many countries. In Singapore it is known as the consignment note system and is e-tracked. The manifest is a form that contains detailed information about the waste, including: generator name and nature of the wastes (e.g. hazard classification) quantity of wastes shipped information about the transporter and final destination of the waste
Crade-tograve
The concept of cradle-to-grave tracking system came from US regulation: the Resource Conservation and Recovery Act (RCRA). Generators must manage hazardous wastes from the moment they are generated until their ultimate disposal. In the paper version, multiple copies of the manifest are generated at source the transporter signs the manifest and provide 2 copies of the manifest to the generator, who sends a copy to the environmental authority. If there are more than 1 transporter, at the handing over of the waste the second transporter is to sign and return a copy of the manifest to the first transporter, and the process is repeated until the waste arrives at the designated treatment and disposal facility. The treatment and disposal facility must returned a signed copy of the manifest to the environmental authority, and in many countries, also return a copy of the manifest to the generator. This is illustrated in the diagram below.
Figure 3-2: Cradle-to-Grave It should be noted that in the US, the government always views the waste as belonging to the generator, a responsibility that may go beyond the grave, i.e. the waste generator is responsible (in part) for the waste handlers actions. Thus, if the handler does a poor job and pollutes the environment, the generator may be responsible for cleanup.
3-7
April 2011
EM107 Environmental Health and Safety The storage of hazardous wastes should be handled in a similar fashion as the storage of hazardous substances or chemicals. See Chapter 6 for further details.
Figure 3-10: pH control for batch neutralization of acidic wastewater Neutralization agents for acidic wastewaters Lime: Low cost Disadvantage: sludge and scale production (maintenance issues) Sodium hydroxide (NaOH) solution (caustic soda): More expensive; lower system capital and maintenance cost Significantly less sludge production; sodium salts produced are usually highly soluble Sulfuric acid Economical and requires conventional materials for storage, handling and feeding
3-8
April 2011
NTU
EM107 Environmental Health and Safety Highly corrosive need to consider safety and material handling precautions Could also create a sulfide problem downstream Hydrochloric acid (HCl) More expensive; lower system capital and maintenance cost
Figure 2-11: Typical chemical precipitation system Typical metal hydroxide precipitation process flow Collect wastewater in equalization tank pH adjustment Oxidation or reduction (as needed) or certain constituents, e.g. reduction of Cr6+ to Cr3+ (less toxic) pH adjustment (for optimum precipitation pH)
3-9
April 2011
NTU
EM107 Environmental Health and Safety Precipitation by adding hydroxide (OH-) Solids separation, sludge handling
3.4.3 Oxidation-Reduction
Redox Oxidation is an increase of the oxidation state, reduction is a reduction of the oxidation state. In a reduction reaction, the reducing agent is oxidized. Chromium removal from industrial wastewater involves the reduction of Cr6+ to Cr3+, using a suitable reducing agent (e.g. Fe2+ which itself is oxidized to Fe3+), then precipitating Cr(OH) 3 . Cr6+ + 3Fe2+ Cr3+ + 3Fe3+ Cr3+ + 3Fe3+ + 12OH- Cr(OH) 3 +3Fe(OH) 3 Calculate the quantity of FeSO4 and NaOH required to remove 99% chromium in 100 L/min of a wastewater containing 200 mg/L of Cr6+. What is the quantity of sludge produced? (Atomic mass Cr = 52, Fe = 55.8, Na = 23, O = 16, H = 1, S = 32) Cr6+ + 3FeSO 4 + 12NaOH Cr(OH) 3 +3Fe(OH) 3 + 12Na+ + 3SO 4 2Atomic mass Cr = 52, Fe = 55.8, Na = 23, O = 16, H = 1, S = 32 From the equation above, 1 mole Cr6+ reacts with 3 moles of Fe2+ and 12 moles of OH- to produce 1 mole of Cr(OH) 3 and 3 moles of Fe(OH) 3 . Or 52 g Cr6+ : 3 x 55.8 g Fe2+ : 12 x 17 g OH- : (52 + 17 x 3) g Cr(OH) 3 : 3 x (55.8 + 17 x 3) g Fe(OH) 3 Amount of Cr6+ to be removed = 0.99 X 200 (mg/L) x 100 L = 19,800 mg = 19.8 g/min Amount of Fe2+ required = 19.8/52 x 3 x 55.8 g = 63.7 g/min Amount of FeSO 4 required = 63.7/55.8 x (55.8 + 32 + 16 x 4) = 173 g/min = 173 x 60 x 24 g/day = 249120 g/day = 249 kg/day The amount of NaOH required, and the quantity of sludge produced can similarly be worked out.
Example
3-10
April 2011
NTU
EM107 Environmental Health and Safety (PAC) to remove them from the wastewater as well as providing significantly lengthen its retention time to enable the biomass to degrade them.
3.5 Problems
1. Cyanide (CN-) is important in metal removal because cyanide forms complexes with metals and prevents them from precipitating as hydroxides. In addition, cyanide is extremely toxic and is likely to interfere or poison the biological treatment systems employed by municipal treatment plants. A common method for cyanide destruction is through chlorine oxidation at high pH. The reaction is as follows: 2CN- + 5Cl 2 + 8OH- 2CO 2 + N 2 + 10Cl- + 4H 2 O a. Propose a reason why the oxidation reaction has to be carried out at high pH. b. Calculate the daily amount of chlorine required to completely destroy cyanides in an industrial wastewater stream containing 80 mg/L of cyanide flowing at 25 L/min. [19.67 kg/day] 2. Which of the following statements on hazardous wastes is TRUE? a. Toxic industrial wastes as defined by Singapore regulations are industrial wastes that exhibit toxicity to human and other organisms. b. The key benefit of the consignment note system in Singapore is the systematic collection of revenue derived from the monitoring of the movement of hazardous wastes. c. Hazardous wastes cannot be treated using biological treatment methods. d. Transporters are required to apply for a permit for the transport of hazardous waste. (0910S2)
3-11
April 2011
NTU
3. A key concept for the management of hazardous substances is the cradle-to-grave approach. Briefly describe the approach and the key elements involved in this approach of hazardous substances management. (8 marks)(0607S2) 4. What are some parameters typically used to define wastes as hazardous wastes? (6 marks)(0809S2) 5. Briefly discuss how a permit, licensing and manifest system may be used to manage the transport, treatment and disposal of hazardous waste. (8 Marks)(0910S2)
3.6 References
1. American University, Washington D.C., TED Case Studies: Minamata Disaster, http://www1.american.edu/TED/MINAMATA.HTM, accessed 2 April 2011. 2. Basel Convention on the Control of Transboundary Movements of Hazardous Wastes and their Disposal, http://www.basel.int/convention/basics.html, accessed 30 March 2011. 3. NEA, Controlled Toxic Industrial Wastes, http://app2.nea.gov.sg/NEADownload.aspx?res_sid=20100505422108755681, accessed 3 April 2011. 4. University of Minnesota, Douglas Allchin, The poisoning of Minamata, http://www1.umn.edu/ships/ethics/minamata.htm, accessed 2 April 2011. 5. Wentz C A (1995), Hazardous waste management, 2nd Ed, McGrawHill Internationsl.
3-12
April 2011