Hazardous wastes - Characterisation & TCLP

Prof. M.R.Ezhilkumar
Assistant Professor
Department of Civil Engineering
Sri Krishna College of Engineering and Technology
Coimbatore
ezhilkumar@skcet.ac.in
I only feel angry when I see waste.
When I see people throwing away
things we could use. – Mother
Teresa
1
17CE413
SOLID AND HAZARDOUS
WASTE MANAGEMENT
3.7 – Hazardous waste
characterisation

SHWM – Module 3 – SANITARY LANDFILL AND HAZARDOUS WASTE MANAGEMENT  Mr.M.R.Ezhilkumar 2
Learning Outcomes
☼ HW Characterisation
☼ HW generation estimation
☼ TCLP
☼ HW sampling
3.7 – Hazardous waste characterisation

Characterization of Waste
Important component of hazardous waste management. Why?
 To identify hazardous wastes
 To provide useful information primarily about the chemical substances
 To provide data for selection of treatment and disposal methods
 To develop regulatory standards and criteria

Quantifying waste generation:
by measurement
 Factory visits/records
 Interviews with contractors & suppliers
 On - site inspections
 Raw materials and product records
 Waste disposal records at generating, treatment & disposal sites
 Industry associations
 Local government staff/inspectors
 Surveys

Waste Characteristics in relation to intermediary treatments
Problems of Combustion
 Calorific value
 Moisture content
 Flash point
 Halogen and Sulphur content
 Heavy metals
Problems of Waste transformation
 Mobility of waste
 Waste persistence
 Solubility
 Biodegradability
 Sorption
 Redox potential

Where to find descriptions (recipes) for laboratory methods?
 SW 846
 Test Methods for
 Evaluating Solid Waste
 Available on line at the EPA
web site
 Example: TCLP is EPA Method
1311

EPA publication SW-846
 SW-846 contains over 200 documents, including the Table of Contents,
Disclaimer, Preface, Chapters One through Thirteen, and many different
methods for the sampling and analysis of wastes.
 All of the documents found in the Third Edition of SW-846, as updated by
Updates I, II, IIA, IIB, III, IIIA and IIIB are located at the web.

Hazardous characteristics: Ignitability
Ignitable wastes:
 can create fires under certain conditions
 or are spontaneously combustible
Examples:
 Waste oils
 Used solvents
 Organic cleaning materials
 Paint wastes

Ignitable wastes:
 Materials that have a “flash point” of less than 140oF (60oC)
Examples are:
 gasoline, alcohols, acetone, toluene, xylene and enamel paints
Flash Point: The lowest temperature at which evaporation of a substance produces
sufficient vapor to form an ignitable mixture with air.

It is a liquid, other than an aqueous solution, containing < 24% alcohol by volume,
and it has a flash point < 60oC (140oF), as determined by a Pensky-Martens
Closed Cup Tester, using the test method specified in ASTM Standard D-93-79 or
D-93-80, or a Set a flash Closed Cup Tester, using the test method specified in
ASTM standard D-3278- 78, or as determined by an equivalent test method

It is not a liquid and is capable, under standard temperature and pressure, of
causing fire through friction, absorption of moisture, or spontaneous chemical
changes and, when ignited, burns so vigorously and persistently that it creates a
hazard.
It is an ignitable compressed gas, as determined by the test methods described in
49 CFR 173.300 or by equivalent test methods approved by the Administrator
under Sections 260.20 and 260.21.

It is an oxidizer (any material that yields oxygen readily to stimulate the
combustion of organic matter (e.g., chlorate, permanganate, inorganic peroxide,
or a nitrate).

Hazardous characteristics: Corrosivity
Acids or alkalis that are capable of dissolving human flesh and corroding metal
such as storage tanks and drums
Examples:
• acids from metals cleaning processes eg. ferric chloride from printed circuit
board manufacture
• liquor from steel manufacture

Applies only to Liquids
 If unsure about physical state do a paint filter liquids test
 pH is greater than 12.5 or less than 2.0
 or it corrodes steel at 6.35 mm/year

• It is aqueous and has a pH < 2 or > 12.5, as determined by a pH meter
(Method 9040)
• It is a liquid and corrodes steel (SAE 1020) at rate > 6.35 mm (0.250 in.) per
year at a test temperature of 55EC (130EF), as determined by the test method
specified in NACE (National Association of Corrosion Engineers) Standard TM-
01-69) - (SW 846 Method 1110)

Hazardous characteristics: Reactivity
Reactive wastes are unstable under ‘normal conditions’
They can cause:
• explosions
• toxic fumes
• gases or vapours
Examples:
• Peroxide solutions
• Hypochlorite solutions or solids
The reactivity characteristic identifies wastes
that readily explode or undergo violent
reactions.

Reactivity
• The most Nebulous characteristic
• No repeatable, sound test method
• Meant to identify wastes that have the potential to explode or release toxic
gases during the waste management process
The determination is based ultimately on the your knowledge of your waste and a
regulatory interpretation.

A solid waste is hazardous by the reactivity characteristic if:
• It is normally unstable and readily undergoes violent change without
detonating.
• It reacts violently with water.
• If forms potentially explosive mixtures with water.
• When mixed with water, it generates toxic gases, vapors, or fumes in a quantity
sufficient to present a danger to human health and the environment.

• It is a cyanide or sulfide bearing waste which, when exposed to pH conditions
between and 12.5, can generate toxic gases, vapors or fumes in a quantity
sufficient to present a danger to human health or the environment.
• It is readily capable of detonation or explosive decomposition or reaction at standard
temperature and pressure
• It is a forbidden explosive

Hazardous characteristics: Toxicity (poisonous chemicals)
Toxic wastes are harmful or fatal when ingested, inhaled or absorbed through the
skin.
Examples:
•Spent cyanide solutions
•Waste pesticides
Wastes with heavy metals; lead, nickel, silver, chromic acid, mercury and volatile organic
compounds (VOC’s)

• The toxicity characteristic is determined using the Toxicity Characteristic
Leaching Procedure (TCLP).
• Method 1310B: Extraction Procedure (EP) Toxicity Test Method and Structural
Integrity Test
• Method 1311: Toxicity Characteristic Leaching Procedure

• A solid waste exhibits the characteristic of toxicity if the TCLP extract from a
subsample of the waste contains any of the listed contaminants at a
concentration greater than or equal to the respective value given in that List.
• If a waste contains <0.5% filterable solids, the waste itself, after filtering, is
considered to be the extract for the purposes of analysis.

FACTORS AFFECTING LEACHABILITY
• Alkalinity of the waste
• Surface to volume ratio of waste
• Leachant to waste ratio
• Type of Leachant
• pH of Leachant
• Contact Time
• Extent of Agitation
• Number of replacements of fresh leachant
• Extraction Vessel
• Extraction Temperature

Toxic Characteristic Leaching Procedure
• US EPA , 1986
• Simulates Landfill Environment
• Particle size < 9.5 mm
• Leachant = Acetic Acid (pH = 2.88+/- 0.05)
• Liquid to Solid Weight = 20:1
• Agitation for 18 h at 30 rpm and 22 oC
• Use a Zero head space extraction vessel for wastes with VOCs

TCLP - Toxicity Characteristic Leaching Procedure
• Purpose – Determine the mobility of both organic and inorganic analytes
present in liquid, solid and multiphasic wastes
• Crush to < 9.5 mm particle size
• Agitate in a weak acetic acid in liquid:solid = 20:1 by wt
• Agitate for18 hrs, filter through 0.6~0.8 μm glass fiber filter
• Analyze sample for constituents

Toxicity Characteristic
• Extract is analyzed to determine if any of these 39 compounds exceed their
regulatory level
• 8 heavy metals, 4 insecticides, 2 herbicides, and 25 other organic compounds

TCLP- Regulatory Levels

EXTRACTION PROCEDURE FLOW CHART

TCLP – 5 STEPS
• Separation Procedure
• Particle Size Reduction
• Extraction of Solid Material
• Final Separation of the Extraction from the Remaining Solid
• Testing (Analysis) of TCLP Extract

TCLP-Summary of Procedure -I
Separation Procedure
• For liquid wastes (i.e., those containing less than 0.5% dry solid material), the
waste, after filtration through a 0.6 to 0.8 Mm glass fiber filter, is defined as the
TCLP extract.
• For wastes containing greater than or equal to 0.5% solids, the liquid, if any, is
separated from the solid phase and stored for later analysis.

TCLP-Summary of Procedure -II
Particle Size Reduction
• Prior to extraction, the solid material must pass through a 9.5-mm (0.375-in.)
standard sieve, have a surface area per gram of material equal to or greater
than 3.1 cm2 , or, be smaller than 1 cm in its narrowest dimension.
• If the surface area is smaller or the particle size larger than described above,
the solid portion of the waste is prepared for extraction by crushing, cutting, or
grinding the waste to the surface area or particle size described above.
(Special precautions must be taken if the solids are prepared for organic
volatiles extraction.)

TCLP-Summary of Procedure -III
Extraction of Solid Material
• The solid material from Step II is extracted for 18 + 2 hours with an amount of
extraction fluid equal to 20 times the weight of the solid phase.
• The extraction fluid employed is a function of the alkalinity of the solid phase of
the waste.
• A special extractor vessel (Zero Head Space Extractor) is used when testing
for volatile analytes.

TCLP-Summary of Procedure -IV
Final Separation of the Extraction from the Remaining Solid
• Following extraction, the liquid extract is separated from the solid phase by
filtration through a 0.6 to 0.8 Mm glass fiber filter. If compatible, the initial liquid
phase of the waste is added to the liquid extract, and these are analyzed
together. If incompatible, the liquids are analyzed separately and the results
are mathematically combined to yield a volume weighted average
concentration.

TCLP-Summary of Procedure -V
Testing (Analysis) of TCLP Extract
• Inorganic and organic species are identified and quantified using appropriate
methods in the 6000, 7000, and 8000 series of methods in this manual or by
equivalent methods.

Apparatus
 Agitation Apparatus
 Extraction Vessels
 Filtration Device
 Filters
 pH meter
 ZHE extract collection device
 ZHE extraction fluid transfer device
 Laboratory balance
 Beaker or Erlenmeyer flask
 Watch glass
 Magnetic Stirrer

Agitation Apparatus
 Should rotate extraction vessel in
an end-over end fashion at 30+/-
2 rpm
 Millipore Rotary Agitator

Rotary Agitation Apparatus

Zero-Headspace Extractor

CHARECTERISATION IS NOT JUST SAMPLE ANALYSIS

SAMPLING OF HAZARDOUS WASTE
• Sampling of hazardous waste to obtain a representative sample for
characterization presents special problem
• a proper sampling plan is required that ensures that correct samples taken at
appropriate locations, frequency and size of samples.
• Depending on whether the waste to be sampled is a liquid, solid, sludge or soil
the sampling methodologies differ.

Components of a Sampling Program
1. Selection of parameters
2. Selection of sampling location
3. Time & Frequency of sampling
4. Mode of sampling
5. Selection of sampling equipment
6. Sample Handling & Preservation

Sampling strategies
• Random or grab
• Stratified random
• Systematic random

SAMPLING PLAN
Sampling Accuracy
 representative (exhibiting average properties of the whole waste) samples of
waste be collected
Sampling Variability
 enough samples (but in no case less than four samples) be collected over a
period of time sufficient to represent the variability of the wastes.

SAMPLING PLAN
 Generally, high accuracy and high precision are required if one or more
chemical contaminants of a solid waste are present at a concentration that is
close to the applicable regulatory threshold.
 Alternatively, relatively low accuracy and low precision can be tolerated if the
contaminants of concern occur at levels far below or far above their applicable
thresholds.
 Sampling accuracy is usually achieved by some form of random sampling.

SAMPLING PLAN
 Sampling precision is most commonly achieved by taking an appropriate
number of samples from the population.
 Another technique for increasing sampling precision is to maximize the
physical size (weight or volume) of the samples that are collected
 The appropriate number of samples is the least number of samples required to
generate a sufficiently precise estimate of the true mean (M) concentration of
a chemical contaminant of a waste.

Selecting a sampling device
 Identify the medium (e.g., liquid or sludge) that best
describes the material to be sampled.
 Select the location or point of sample collection (e.g.,
conveyor, drum, tank, etc.) for the medium selected.
 Identify candidate sampling devices.
 Select a sampling device based on its ability to obtain the
correct size, shape, and orientation of the samples, and meet
other performance goals specified by the planning team.

SAMPLING EQUIPMENT

CONTAINERS AND SAMPLING POINTS
Container Type Sampling Point
Drum, bung on end Through bung opening
Barrel, Fiber drum, buckets,
sacks, bags
Through top of barrel , fill opening of bags and sacks,
center of container at different points diagonally
Trucks Through open hatch
Waste pile Withdraw sample through at least three different points
near the top of pile to points diagonally
Storage tanks Sample from the top through the sampling hole

Chain of Custody
 An essential part of any sampling/analytical scheme is ensuring the integrity of
the sample from collection to data reporting.
 The possession and handling of samples should be traceable from the time of
collection through analysis and final disposition.
 This documentation of the history of the sample is referred to as chain of
custody.

Sample labels
 Sample labels are necessary to prevent misidentification of samples. Gummed
paper labels or tags are adequate and should include at least the following
information:
 Sample number.
 Name of collector.
 Date and time of collection.
 Place of collection.
 Labels should be affixed to sample containers prior to or at the time of
sampling and should be filled out at the time of collection.

Sample seals
 Sample seals are used to detect unauthorized tampering of samples following
sample collection up to the time of analysis. Gummed paper seals may be
used for this purpose. The paper seal should include, minimally, the following
information:
 Sample number. (This number must be identical with the number on the sample label.)
 Name of collector.
 Date and time of sampling.
 Place of collection.
 The seal must be attached in such a way that it is necessary to break it in
order to open the sample container.

Sample Packaging
 Aqueous samples for inorganic analysis and volatile organic analysis may
require chemical preservation. The specific preservation requirements will
depend on the analytical method to be used.
 Make sure all lids/caps are tight and will not leak.
 Make sure sample labels are intact and covered with a piece of clear tape for
protection.
 Enclose the sample container in a clear plastic bag and seal the bag. Make
sure the sample labels are visible.

Log Book
 All information pertinent to a field survey or sampling must be recorded in a
logbook.
 This should be bound, preferably with consecutively numbered pages

Sample Homogenization, Splitting, and Subsampling
 The objective of homogenization (mixing) is to minimize grouping and
segregation of particles so they are randomly distributed within the sample.
 Homogenization, combined with a composite sampling strategy, can be an
efficient method for improving the accuracy and precision in sampling of
particulate material.

Sample Splitting
 The goal of splitting is to reduce the mass of the retained sample and obtain
an aliquot of the field sample that reflects the average properties of the entire
field sample.

SAMPLE STORAGE
 Not only is the sampling and sample preparation important, but the sample
storage is also critical.
 The composition of the sample may change with time due to, for example, the
following:
 reaction with air
 reaction with light
 absorption of moisture
 interaction with the container

SAMPLE STORAGE
 Glass is a notorious ion exchanger which can alter the concentration of trace
ions in solution.
 Thus plastic (especially Teflon) containers are frequently used.
 Ensure all containers are clean to prevent contamination.

QUALITY CONTROL
 In most cases, the laboratory supervisor assigns the sample for analysis. The
supervisor should review the information on the sample analysis request
sheet, which now includes inspection notes recorded by the laboratory sample
custodian.
 The technician assigned to analysis should record in the laboratory notebook
the identifying information about the sample, the date of receipt, and other
pertinent information. This record should also include the subsequent testing
data and calculations.

QUALITY CONTROL
 The sample may have to be split with other laboratories in order to obtain all
the necessary analytical information. In this case, the same type of chain-of-
custody procedures must be employed while the sample is being transported
and at the other laboratory.

Health and safety considerations
 Field personnel should be up-to-date in their health and safety training.
 Field personnel should have a medical examination at the initiation of
sampling activities and routinely thereafter, as appropriate and as required by
the OSHA regulations.
 Unscheduled examinations should be performed in the event of an accident or
suspected exposure to hazardous materials.

Health and safety considerations
 Staff also should be aware of the common routes of exposure at a site and be
instructed in the proper use of safety equipment and protective clothing and
equipment.
 Safe areas should be designated for washing, drinking, and eating.
 To minimize the impact of an emergency situation, field personnel should be
aware of basic first aid and have immediate access to a first aid kit.

Assessment Time
Review
Question Report the hazardous waste generation sources available in
Coimbatore region.

Hazardous wastes - Characterisation & TCLP

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