4.

0 SOLIDIFICATION and STABILIZATION

# refers to processes that transform hazardous wastes into a more manageable or less
toxic form
" waste ----> binder ----> solid

# solidification
" material or substance added to hazardous waste to produce a new solid material

# stabilization
" hazardous waste is converted to a more chemically stable form

# objectives include
" improving the handling and physical characteristics of haz waste
" minimize the solubility of the hazardous constituents in a waste

# USEPA believes that it has the potential to have a major impact on the management
of haz wastes
" lower permeability
" lower leaching rates
" lower volatility
" possibility the banned wastes may be suitable for land disposal

# majority of wastes are liquids and sludges

" binder such as cement and polystyrene to solidify
" organic and inorganic systems

waste ---> source reduction ---> resource recovery ---•••

•••---> incinerator ---> landfill (sanitary or secure)

4.1 Points of interest

# renders waste chemically non-reactive and environmentally inert

# encapsulates wastes
# ideal for metal bearing wastes (Cu, Zn, Hg, Se, Cr, Pb, As, etc.)
! electroplating
! metal finishing
! chemical industries sludges

# also successfully used when wastewater is the hazardous waste (CSCE- May 1995)
! electro-plating wastewater with 815 mg/L Cr, 7.9 mg/L Cu, 20 mg/L Pb, 478
mg/L Ni and 180 mg/L Zn with pH of 2.3
! passed LEP test with flying colours
! compressive strength > 20 Mpa, which makes it suitable for construction
material
# organic wastes only if incineration not feasible

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# difficult to treat anions (SO4-, Cl-)
# irreversible vs reversible
! metal recovery

# long term life

! disposal site should not become unusable
! resistance to leaching
! mechanically stable
! resistant to U.V. radiation

# should be easy and very economical

" consume very little energy

4.2 Processes

4.2.1 Cement Based Technology

# addition of Portland cement

! calcium, aluminum silicate, gypsum, silicon form a powder called cement,
which form a gel on the addition of water which acts as a binder

# through hydration, the cement forms a crystalline structure consisting of calcium

alumino-silicate (reaction completion is slow)
# obtain a monolithic rock- like block or crumbly soil
# secondary containment necessary or encapsulate with a polymer to make it impervious
# cheap, successful and relatively safe to implement
# asbestos, latex residue, metal filings are desirable as they strengthen block
# organics, clay, silt will delay the setting and curing time
# anions can break down binder
# borate, arsenates, phosphates retard the process

4.2.2 Organically Modified Clay

# developed to assist with organic wastes

# natural clays (organophobic) are modified to become organophilic
! replacement of inorganic cations within the clay crystalline structure by an
organic cation, typically quaternary ammonium ions
! organic wastes are now sorbed within the crystalline structure

# very effective in stabilizing the waste, which inturn can be encapsulated by cement or
other binders

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# Example
! saturated sandy soil is contaminated with TCE
porosity is 50%
C wet density of 2000 kg/m3
C pore water contains TCE @ 500 g/m3

! how much tetramethylammiom (TMA)-clay is needed per tonne of soil

! lab studies have shown that 2.75 mg of TCE can be sorbed per g of TMA-clay

! volume of soil = 1000/2000

= 0.5 m3

! volume of water = 0.5 x 0.5

= 0.25 m3

! amount of TCE = 0.25 x 500

= 125 g

! required TMA-clay = 125 x 1000 / 2.75

= 45.5 kg

! if benzyltriethylammonium(BTA)-clay were used, which can sorb 17.5 mg/g

of TCE, 7.1 kg would be required

4.2.3 Lime Based Technology

# ideal for sludges

# calcium hydroxide (Ca(OH)2), lime, fly ash or silicates are added to the waste sludge
# form:
! soil like material when calcium hydroxide or lime are added
! pozzolanic concrete (very durable- used by Romans) when fly-ash or silicates
are added

# secondary containment or encapsulation required

# only for inorganic wastes
" oil and grease may interfere with bonding of waste particles
" water left in matrix stays as water, and can leach out

# caution required when mixing materials

" dust
" lime and water can cause exothermic condition

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4.2.4 Thermoplastic Technology

# used for both organic and inorganic wastes

# binders are used

" waste dried to 100°C
" binder heated
" mix together
" after cooling can encapsulate
" reversible

# common binders
" bitumen (1:1 to 2:1 addition ratio)
" plastic (PE, PP, Nylon)
! certain solvents can soften binders
! incompatible with oxidizers like perchlorate and nitrates

# finished blocks can be used for foundations and roads

" unsuitable were solvents can attack binder
" resistant to water and microbial attack

# EPA has been difficult in accepting the “new material” as non-hazardous

4.2.5 Thermoset

# used for both organic and inorganic wastes

# most cost advantage because of wide range of chemicals that can be treated

# use organic polymers with a catalyst (peroxides)

" urea formaldehyde
" styrene
" polyester
" phenolic
" polybutadiene (ideal)
" excellent chemical stability
" hydrophobic (resists water)
" nonpolar (large active range, providing more mechanical flexibility)

# irreversible
" susceptible to acids

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4.2.6 Encapsulating

# very expensive

# dewater waste
" free and combined

# provide jacket of polyethylene

" pellets of HDPE fused to surface of material
" 0.6 cm thick

# wastes treated
< pesticides
< nickel-cadmium battery waste
< chlorine brine sludge (Hg, Na, Cl-)
< SOx scrubber sludge (Ca, SO4=)
< calcium fluoride sludge (Ca, F-)

4.3 Block Testing

# bulk and dry unit weight

# unconfined compressive strength
# permeability
# freeze - thaw durability (cyclic)
# wet - dry durability (cyclic)
# chemical composition of leachate
" exposed to ph of 4.5 for 3 months
" concentrations not to exceed drinking water

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4.4 Vitrification

# ideal for soils contaminated with hazardous materials, plus

" drums containing combustible liquids

" combustible solids

# in-situ

" converts contaminated soil to chemically inert glass

# four electrodes are driven into ground

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# flaked graphite is placed between electrodes to ensure conductivity

# electro-potential applied to graphite which heats surrounding soil to 2000°C

" exceeds soils fusion temperature

# molten soil is conductive, which allows further vitrification

# during process
" nonvolatile components are incorporated into glass
! depth important for metals not to be lost through vaporization

" destruction measured through retention factor (RF)

RF = Ai/Ae

Ai = concentration of element initially present

Ae = concentration of element exiting

Reported RF Factors of Metals

Type of Metal Soil Off-Gas Combination

Particulates
Sr, Pu, U, La, Nd 104 105 109

Semi-Volatiles 102 104 106

Co, Cs, Sb, Te, Mo

Volatiles 2-10 104 105

Cd, Pb

" organic components are destroyed through pyrolysis

! removal greater than 99.9999% if off gases should captured for to
treatment
! includes PCBs and dioxins

# ideal soil permeability is 10-5 to 10-9 cm/s

! even with groundwater

# marginal is 10-5 to 10-4 cm/s

# processing rate is 3 to 5 tons/hr (3 to 5 yds/hr)
# average duration of process lasts 150 to 200 hr at a rate of 3 to 6 in/h
" to obtain a depth of 50 ft, require 300 to 400 h

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# all test sites show a metal leach rate of less than
5 x 10-5 g/cm2/d

" allows delisting of site plus the fact that half life estimated at 18 million yr

# mixed wastes

# cost figure

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5.0 TREATMENT METHODS

5.1 Internet Stuff

5.1.1 USEPA provides a variety of innovative technologies, many of which are linked to:
http://www.epa.gov/epaoswer/osw/. This include but are not limited to:
< biological treatment
< carbon adsorption
< chemical oxidation: strong oxidizing agents (e.g. hypochlorite, peroxides,
persulfates, percholorates, permanganates, etc)
< chemical reduction: strong reducing agents (e.g. sulfur dioxide, alkali salts,
sulfides, iron salts, etc)
< deactivation: removes the hazardous nature of the waste by neutralizing the
characteristics of ignitability, corrosivity, and/or reactivity
< incineration
< steam stripping: apply steam to the liquid and subsequent condensation of the
extracted organic compounds
< vitrification
< wastewater treatment units

5.2 Liquid Waste

5.2.1 PARCON (Plasma Arcing Conversion) (HAZMAT - Oct/96/pg22)

! plasma based technology for the destruction of liquid hazardous waste

< USEPA writes that it is an alternative to thermal

! PCB destruction @ 99.999999996

! process as follows

< plasma refers to any ionized gas which is able to conduct electricity
< at the high temps 5500°C, waste molecules are not burned but rather broken
down into their consituent atoms
< stable molecules can then be removed using conventional treatment, e.g.
C quencher @ 100° to convert C, H, Cl and S to carbon dioxide, H2O,
hydrogen chloride and sulphur dioxide
C followed by scrubbers to remove neutralize

! portable unit that can process 12.5 kg/h or 50 kg/h

! larger ones to be constructed

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5.3 SITE - Superfund Innovative Technology Evaluation

! USEPA has developed the SITE program to evaluate technologies for contaminated
sites
< http://www.epa.gov/ORD/SITE/index.html

5.3.1 Solidification and Stabilization in Hialeah, Florida, SITE (EPA/540/S5-89/004)

! GE service shop facility

! PCBs, VOCs and Heavy Metals
! Soil + HWT-20 + H2O
! Immobilized PCBs and Other contaminants
< compressive strength 410 psi
< k increased 4 orders to 4 x 10-7
< passed wet/dry
< failed freeze thaw cycles
< low porosity, high durability
< 10 X 20 ft areas to 18 ft depth
< $194/ton or $150/yd3

5.3.2 The Carver-Green Field Process, Dehydro-Tech Corporation, SITE EPA/540SR-

92/002

Extracts solvents and separates wastes constituents into three product streams,
clean dry solids, water and solvents. Uses 3 stage evaporation, distillation and
oil/water separator. Successfully used on drilling mud waste.

5.3.3 Alternating Technology Bulletin, Electro-Pure Systems, Inc. SITE EPA/540/F-92/011

Alternative to primary chemical coagulant or organic polymer addition for breaking

stable emulsions and suspensions. Lab studies have shown it to be effective in
treating contaminated runoff, landfill leachate, truck wash rinses and scrubber
solutions. Electrically induces non-toxic polymeric aluminum hydroxide species into
the solution being treated which neutralizes the electrostatic charges on the substances
being removed.

5.3.4 Low Temperature Thermal Treatment (LT3) System, Roy F Weston,.Inc.SITE

EPA/540/MR-92/019.

Low temp desorbs organic compounds from contaminated soil.

5.3.5 Laser Induced Photochemical Oxidative Destruction, Energy and Environmental

Engineering, Inc. SITE EPA/540/F-92/004.

Photochemically oxidizes organic compounds in wastewater by pplying UV radiation

through a laser.

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5.3.6 Slurry Biodegradation, USEPA EPA/540/2-90/016.

Combining organically contaminated soil and sludge with water to form a slurry to
treat aerobically (like activated sludge). Successful up to 250,000 mg/kg for
pesticides, PCBS, fuels, halogenated organics. Metals inhibit the process.

5.3.7 Chemical Dehalogenation Treatment: APEG Treatment, USEPA EPA/540/2-90/015

An alkaline metal hydroxide/polyethylene glycol (APEG) is added to soils, sludges,

sediments containing halogenated compounds. Converts compounds to non-toxic
materials.

5.3.8 Soil Washing Treatment, USEPA EPA/540/2-90/017.

Extracted mechanically washed to remove undesirable contaminants. Removes

contaminants sorbed to fines but not successful when soil has high clay and silt
content. Shown to have excellent potential for halogenated compounds and metals.
Successfully applied to Toronto Harbour SITE EPA/540/AR-93/517.

5.3.9 Treating Chlorinated Wastes with the KPEG Process. USEPA EPA/600/S2-90/026.

Adding potassium polyethylene glycolate to PCB contaminated soil in a batch

process. PCB concentration reduced by 99% with no individual PCB concentration
exceeding 2 ppm.

5.3.10 Cleaning Excavated Soil Using Extraction Agents: A State-of-the-Art Review,

USEPA EPA/600/S2-89/034.

Shown the potential for removing organics,, PCBS, metals or radioactive materials
from sand, silt, clay or wastefill using three generic types of treatments; la) wash water
augmented with a basic or surfactant to remove organics, lb) wash water with an
acidic or chelating agent to remove organics and heavy metals, 2) solvents to remove
hydrophobic organics and PCBS, and 3) air or steam striping to remove volatile
organics. Site specific.

5.3.11 DuPont/0berlin Microfiltration System Palmerton, Pennsylvania, SITE

EPA/540/S5-90/007

Pressure filter removes zinc solids larger than 0. I um from liquid wastes. Removal
efficiencies around 99.95%. Sludge passed EP and TCLP tests.

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5.3.12 Chemical Technology and Ultrafiltration, Atomic Energy of Canada, Ltd. SITE
EPA/540/ZF-92/002.

High molecular weight polymer is added to the wastewater/groundwater containing

trace metals to form metal-polymer complexes. Solution then passes through a
cross-flow ultrafiltration membrane which retains the metal-polymer complexes.

5.3.13 Constructed Wetlands Treatment for Toxic Metal Contaminated Waters, Colorado
School of Mines, SITE EPA/540/F-92/001.

Man made ecosystem was constructed to accumulate and remove metals from influent
waters. Pilot scale plant won and Engineering Excellence Award.

5.3.14 Removal and Recovery of Metal Ions From Groundwater, Bio-Recovery Systems, Inc.
SITE EPA/540/F-92/003.

Non-living algal are immobilized in silica polymer. Allows packing into a column.
Natural affinity of algae for metals then facilitates removal. Stripped off using an acid
rinse. Inconsistencies in removal.

5.3.15 Electron Beam Treatment for Removal of Trichloroethylene and Tetrachloroethylene from
Streams and Sludge, Florida International University and University of Miami, SITE
EPA/540/F-92/009

Aqueous solution containing hazardous compounds are spilled over a weir so it falls
in a thin sheet (4 mm). Simultaneously, a 1.5 M volt electron accelerator generates
electrons and accelerates then to 97% the speed of light. These travel through a
vacuum tube toward the thin film of water, and on collision treatment occurs. Have
removed 99.9% of TCE and PCE.

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