DETERMINATION OF EMISSION FACTORS OF DIOXINS FROM OPEN BURNING

OF MUNICIPAL SOLID WASTES IN KERALA

Report- April 2016 – March 2018

Submitted by

Environmental Technology Division

CSIR- National Institute for Interdisciplinary Science & Technology (NIIST)

1
 Executive Summary

Kerala is one of the most densely populated states in India. Solid waste management is a major
issue in Kerala. The semi-urban population spread, acute scarcity of land and inadequate
investments in waste management has created a crisis situation in Kerala. Kerala generates
6000 T of waste every day as per the survey done in 2006. The quantum of waste generated will
be higher in 2016 due to improvement in quality of life. Unscientific & unhealthy practices such
as open burning of municipal solid waste are prevailing in the state due to lack of organized
waste management plan. Waste incineration is a major source of unintentional production of
dioxins and furans, which are highly toxic and persistent in the environment. It is reported
elsewhere that the emission of dioxins and furans are much higher during open burning of
wastes in comparison to well-engineered waste incinerators. No reports are available in India
on the emission factors of dioxins from such open burning practices.
CSIR- NIIST has the state of the sophisticated analytical testing facilities and technical know –
how on the monitoring of dioxins and furans. Kerala State Pollution Control Board has awarded
CSIR-NIIST a project on “Determination of emission factors of dioxins from open burning of
municipal solid wastes in Kerala”. The prime objective of the project is to generate authentic
data and to create an inventory of dioxin emission from open burning of municipal solid wastes
in Kerala.
The formation of dioxins depends on combustion conditions and waste composition. The
typical waste composition of major cities in Kerala was collected from literature. A simulated
waste burning facility (Burn Hut) was constructed at CSIR-NIIST to carry out the waste
combustion experiments. There are several difficulties to determine the emission factor of
dioxins by sampling and analysing from typical open burn sites. It includes (a) no control on the
composition of waste (b) variation in air flow rates and wind direction and (c) dispersion of the
target analyte into soil, ash and other sorbents in the waste making it difficult to quantify. The
simulated burn hut combustion experiments can overcome such practical difficulties. The burn
hut is equipped with blower fan to discharge desired air flow, platform with load cells to
monitoring the weight losses, thermocouples to monitor temperature and a stack sampling

2
port to insert the isokinetic probe and a railed platform to set the sampling equipments.
Isokinetic dioxin stack samplers were employed for the particulate and vapour sampling.
In addition to the simulated burn hut experiments, 2- 3 waste dump yards field sampling were
also carried out to understand the emission factors observed in the real field samples. The
waste dump yards were selected after assessing the current/previous history of open burning
at such sites. It will give us a comparative evaluation of data generated by simulated
combustion experiments vis-à-vis field sample experiments.
A series of experiments were carried out to optimize the analytical workflow and
procedures for the sample extraction, cleanup and quantification of samples. We have focussed
on three types of samples (a) stack air (b) residual ash and (c) real waste dump yard soil.
Manual as well as automated methods were employed for the extraction and cleanup. A state
of the art High resolution gas chromatography coupled with triple quadruple mass
spectrometer was employed for the quantification of dioxins and furans. The obtained
concentrations of individual congeners were multiplied with its corresponding toxicity
equivalence factor to obtain the toxicity equivalence (TEQ) and the summed up to get the total
TEQ.

In a typical experiment, about 10 kg of composite waste is burned under simulated conditions

in the burn hut and the stack sample and residual ash samples were collected. A representative
quantity of ash (10 g) and the stack sample were analysed following the optimized workflow.
The obtained dioxin levels in ash as well as stack air is then multiplied with total residual ash
and the total stack air volume respectively to obtain the total quantity of dioxins. It is then
normalized to per kg of waste burned to obtain the emission factor of dioxins in air and residual
ash respectively.

In the study, we carried out emission factor determination during burning of wet and dry
composite MSW.

3
The emission factors of dioxins determined were:

Wet waste -1 (77 % moisture) open burning

Land (residual ash): 41.9 µg PCDD-F TEQWHO/ ton of waste burned

Wet waste -2 (67.8 % moisture) open burning

Land (residual ash): 27.52 µg PCDD-F TEQWHO/ ton of waste burned

Air emission: 5.1 µg PCDD-F TEQWHO/ ton of waste burned

Dry waste (14 .7 % moisture)open burning

Land residual ash: 0.86 µg PCDD-F TEQWHO/ ton of waste burned

Air emissions 4.2 µg PCDD-F TEQWHO/ ton of waste burned.

For emission factor calculation, we considered only the emission under wet condition, as MSW
open burning is carried out using wet waste and the average moisture level is between 60% and
80%.
Hence, the average emission factor of dioxins to air and land is 5.1 & 34.71 µg PCDD-F TEQWHO/
ton of waste burned.
The estimated annual emission of dioxins in Thiruvananthapuram city is 0.19 g TEQ per annum
to air and 1.27 g TEQ per annum to residual ash (land). It was calculated assuming an average
quantity of 100 tons of wastes is being openly burned in Thiruvananthapuram.

4
1. Introduction
th
India ratified Stockholm Convention on Persistent Organic Pollutants (POPs) on 13 January
th
2006, and the convention came into force on 12 April 2006. The objective of the Stockholm
Convention is to protect humans and the environment through elimination of POPs. Some POPs
like chlorinated pesticides are industrially produced. Others like dioxins are unintentional The
Convention originally included twelve POPs of which eight are pesticides (aldrin, chlordane, DDT,
dieldrin, endrin, heptachlor, mirex, and toxaphene), two are industrial chemicals
(hexachlorobenzene, HCB, and polychlorinated biphenyls, PCB), and two are unintentional POPs
(polychlorinated dibenzo-para-dioxins, PCDD, and polychlorinated dibenzofurans, PCDF).
However also the two industrial POPs, namely HCB and PCB, are included in the list of
unintentional POPs since they can be formed and released as byproducts in the same processes
that also generate PCDD and PCDF. At its 4th meeting in May 2009, the Conference of the
parties listed nine new POPs, including pentachlorobenzene (PeCBz) in annex C as an
unintentional POP.

The member nations of the convention developed National Implementation Plans (NIPs), which
is the country’s roadmap on measures and strategies to implement the obligations of the
convention. India, being a signatory has developed a National Implementation Plan with the aid
from United Nations Industrial Development Organisation (UNIDO). CSIR-NIIST is one of the
participant institutes in developing inventories of polychlorinated dibenzodioxins and furans [1].
The issue of polychlorinated dibenzodioxins and dibenzofurans (PCDD/PCDF) represents one of
the largest difficulties countries in general and developing countries especially have to face. The
national (or regional) action plan to be developed for unintentional POPs includes release
inventories where countries have to identify and quantify all their PCDD/PCDF sources. UNEP’s
Standardized Toolkit groups the dioxin sources into ten broad categories such as waste
incineration, production and use of chemicals and consumer goods, production of minerals,
production of ferrous and non-ferrous metals [2]. The Toolkit categories and the main release
vectors are shown in Table 1.

5
 Table 1: Main source categories in the UNEP Standardized Toolkit and the five vectors of
release

Cat. Source Categories Annual Releases (g TEQ/annum)

No. Air Water Land Products Residue
1 Waste Incineration  
Ferrous and Non Ferrous Metal
2  
Production
3 Power generation and heating  
4 Production of Mineral Products   
5 Transportation  
6 Open burning Processes    
Production and use of chemicals &
7    
consumer goods
8 Miscellaneous   
9 Disposal/ Landfilling    
Site specific evaluation is required to identify
10 Potential Hot-Spots
release pathways

India’s inventorization was evaluated by independent experts and the report is available in
public domain [3]. The overall rating of the project is “unsatisfactory” and several shortcomings
were pointed out. As per the report, key sources such as open burning of municipal solid wastes
and MSME were not sampled at all and simply omitted from the inventory.
Reports from about sixty countries that have quantified their PCDD/F emission shows that bad
waste management practices such as open burning of municipal solid wastes without any
technical measures is the largest source of dioxin emission. It is a common practice in
developing countries and economies in transition to burn municipal wastes, agricultural wastes
and industrial residues in open places. Most often municipal solid waste open burning occurs in
densely populated areas. The possibilities of human exposure is much higher to such sources

6
than any other industrial sources, as the dispersion of pollutants occurs at ground level
compared to industrial stacks culminating in shorter pathways to enter the food chain. Reports
of dioxin emission factor determination from such open burning activity, shows alarmingly high
levels of emission from such sources [4, 5]. The default emission factors given in the latest
version of UNEP standardized toolkit is based on laboratory and simulated waste combustion
experiments done in OECD countries. Wide variation in the emission factors are observed in the
data reported elsewhere from a few micrograms TEQ to 150,000 micrograms per ton of waste
burned. The wide differences in the waste combustion conditions and ways of burning (eg: burn
barrels, dump yard, pit burning) in developing countries vis-a- vis developed countries causes
wide discrepancies in the default emission factors. The emission factors have been reviewed
based on latest study conducted by UNEP in the waste compositions in China and Mexico in
2010, to 40 µg PCDD-F TEQWHO & 300 µg PCDD-F TEQWHO per ton waste in air and land
respectively [5]. It shows that country wise or region wise emission factors are essential.

Kerala faces a crisis in the management of municipal solid wastes because of the absence of
modern urban waste collection, transportation, treatment and disposal. With no other
alternatives in place, citizens are forced to find own means to dispose waste, such as by open
burning. As a first step understanding the dangers of open burning of MSW, KSPCB has awarded
CSIR-NIIST, a project entitled “Determination of emission factors of dioxins from open burning
of municipal solid wastes in Kerala”. It is the first study in India on quantifying dioxins from
MSW burning.
The main objectives of the project are
(1) Determination of dioxin emission factors from open burning of typical Kerala municipal
solid waste composition, by laboratory waste burning facility (Burn Hut)
(2) Quantifying the effect of waste composition and combustion conditions and
(3) Open burn dumpsite sample studies to analyse the background dioxin levels.

7
2. Equipments and Materials

2.1. Burn hut

A “burn hut” is constructed to simulate the waste burning under different combustion
conditions with provision for controlled supply of combustion air inlet and stack sampling port,
and collection of combustion residues. The design of the proposed burn hut is given in Fig 1.
The burn hut has an area of 270 cm * 340 cm and a roof with a minimum height of 196 cm. The
burn hut was made out of aluminum sheets fitted to galvanized iron frame and painted with
aluminium. The air is supplied by a rectangular duct on all four sides at floor level connected to
an axial air flow blower. A variable frequency drive (VFD) was connected to regulate the air flow
rate from the blower. The air discharge rate can be set between 14 m3/min to 55 m3/min, using
a flow tube designed as per IS 4894-1987 specification. It is supplied from four sides to ensure
the thorough mixing of the smokes and to maintain a positive pressure inside the burn hut. The
burn hut is provided with a cylindrical stack of 2.5m height and 30 cm diameter to expel the
smoke and combustion gases.

The sampling port was set in the stack 165 cm downstream (5.5 stack diameter) and 45 cm
upstream (1.5 stack diameter). 4 thermocouples were placed in line with the air flow (core of
the fire, top of the flame, middle of the pathway and opening of the stack) to make the
temperature profiling of the burn hut. All the wires and cables for connecting load cells and
thermocouples were passed through an aluminium pipe to protect from combustion
temperature. Railed platform was provided to facilitate sampling and to place dioxin stack
sampling equipment.

8
Where is the duct , blower, flow
measurement apparatus, flow
calibration reading?

Fig 1: Design of Burn Hut

9
2.2 Load Cells & Temperature detectors

Beam load cells having a working range of 10 – 8000 kg is used for monitoring the weight loss
during combustion. The strain due to the weight is converted into an electric signal by strain
gauge in the load cell apparatus.

A load cell mounted platform was placed inside (centre) the burn hut. The platform is made of
Aluminium sheet and is riveted onto a rectangular iron frame. The platform surface area is 107
cm * 107 cm. The whole platform is mounted on four load cells so as to get the real time
change in the mass of the waste burned. The total height of the platform is 21.2 cm from
ground (load cell stand + load cell + platform). The design of the platform & exterior view of
constructed burn hut is shown in Fig 2 & 3 respectively.

Fig 2: Design of the Platform

10
 Fig 3: Exterior view of burn hut

Custom made Nickel-chromium and Nickel- aluminum alloy based resistant temperature
detectors (70 cm long, 6 mm dia) supplied by HEAT TEMP, Thiruvananthapuram were used to
monitor the temperature changes during combustion at the waste pile and in the air flow
pathway. The measurement range is 32 – 450 0C. The thermo-electric effect due to the
difference in the temperatures at the inter-junction is measured using a RTD at the inter-
junction.

2.3 Blower Fan

A high pressure axial fan ( MJ Air Supplies Model: MAX-500-6-6/21.5/AL/4ZL) of 3000 m3/hr
capacity is installed outside the burn hut to provide controlled air discharge during combustion.
The air discharge is provided inside the burn hut through a duct having 80 holes of 5 cm
diameter as shown in Fig 1. It ensures uniform distribution of air inside the burn hut.

11
The air discharge rate of the blower fan is measured as per the IS 4894- 1987 method. The inlet
side of the blower fan is fitted with a cylindrical airway of diameter D and minimum length 4D;
a conical expander or reducer of 15” maximum included angle being used to connect the fan to
the airway. To the inlet end of the test airway shall be fitted a conical inlet and four side
tappings in accordance with Fig. 4 and with the following provisions: The four side tappings
shall be equally spaced at 900 on the cylindrical duct. The bore at the surface of the airway shall
not exceed 4.76 mm in diameter and shall be straight, uniform and at right angles to the duct
for at least 2 bore diameters. The openings shall be flush with the duct and free from burrs and
countersinks. The four side tappings shall be connected to one limb of the manometer, each
connection being of the same length, bore and arrangement of tubing to minimize the effect of
flow due to difference of pressure at the tappings. The other limbs of the manometer shall be
opened to the ambient atmosphere and the manometer reading shall be taken as equal to the
average static pressure in the airway.

Fig 4: Air discharge rate measurement set up of blower

12
2.4 Isokinetic Dioxin stack sampler

Fig 5a – b: Schematic diagram of dioxin sampling train & Photograph of meter console

Isokinetic sampling is the recommended technique for stationary source sampling of dioxins.
USEPA Method 23 [6] was followed for sampling and analysis of stack air. The sampling train &
Meter console of Method 23 Dioxin stack sampler is shown in Fig 5a & 5b respectively. The
equipment was procured from KNJ Engineering Inc., Korea. The sampling train consists of a
heated probe and filter box kept at 120 oC, followed by water cooled condenser and pre-
cleaned XAD cartridge. Empty and deionized water filled impinger trains are connected
following the XAD cartridge. The stack velocity and air flow rate is measured using the s-type
pitot tube following the Bernoulli’s principle.

The sampling flow rate is adjusted at the manometer so as to attain isokinetic sampling. (Refer
USEPA Method 23 & CPCB stack sampling guidelines for detailed protocol) [6,7].

2.5 Extraction and Cleanup apparatus/equipments

The stack air as well as ash samples obtained from the simulated waste combustion
experiments and the soil samples collected from waste dump yards are extracted with organic
solvents. Soxhlet extraction apparatus is use for the manual extraction of samples (Fig 6).

13
  The source material containing the compound to be extracted is placed inside the
thimble.

 The thimble is loaded into the main chamber of the Soxhlet extractor.

 A condenser is fitted about the main chamber

 The extraction solvent to be used is placed in a distillation flask.

 The flask is placed on the heating element

 Upon heating the solvent in distillation flask will be evaporated and will be condensed
down to the main chamber. The hot solvent will dissolve off the organic content in the
sample. The solvent will flush out to the flask by siphoning action. The process is
repeated for several cycles so as to ensure maximum extraction of contaminants.

Fig 6: Manual & Automated Extraction System

Accelerated solvent extraction equipment can also be used for the automated and faster
extraction of dioxins and PCBs from samples. Dionex ASE-350 Accelerated Solvent Extraction
System supplied by M/s. Thermofisher Corporation is used. ASE is a technique that uses liquid
solvents at elevated temperatures and pressures. These conditions allow extractions to take
place in short periods of time with small solvent volumes as compared to conventional
techniques such as sonication and Soxhlet extraction. ASE is equivalent to U.S. EPA Methods
14
3540, 3541, and 8150 for the extraction of organochlorine pesticides (OCPs), organophosphorus
pesticides (OPPs), semivolatiles or base, neutral, acids (BNA), chlorinated herbicides, polycyclic
aromatic hydrocarbons (PAHs), and polychlorinated biphenyls (PCBs).

2.6. Automated sample cleanup system

The removal of unwanted matrix components such as lipids, fats and other organic impurities
prior to GC- MS quantification is essential to avoid interferences. Also the Non-dioxin like PCBs,
Non-ortho PCBs and Mono- ortho PCBs has to be separated from the dioxin fraction. Manual
cleanup methods are available. However, it is tedious and time consuming. To ensure fast and
better cleanup efficiencies, we have also employed DEXTech Automated Dioxin clean up system
(Make: LCTech) (Fig 7).

Fig 7: Automated Dioxin clean up

2.7. GC-MS/MS

A triple quadruple mass spectrometer (GC-MS/MS) is used for the quantification of dioxins and
furans. Agilent Technologies Make 7890 Series gas chromatrograph coupled to 7000C
Quadrupole MS/MS is used for the analysis (Fig 8).

15
 Fig 8: Gas Chromatography – Triple Quadruple Mass Spectrometer

2.8. Standards, Chemicals and Solvents

All native dioxins, furans and PCB standards were procured from Cambridge Isotope
Laboratories, UK. C13 labelled mixture of dioxins (DF-LCS-C200), non-ortho PCBs (MBP-CP) ,
mono - ortho PCBs (MBP-MO) and cleanup standard spiking solution (37Cl4 - 2,3,7,8-TCDD) (Cat
No: S13CSSA ) were procured from Wellington Laboratories, England. Unlabelled and C13
labelled non-dioxin-like PCBs were procured from CIL.

All manual clean up materials such as 22 % H2SO4 treated silica gel, 44 % H2SO4 treated silica
gel, 2 % KOH treated silica gel, 10 % AgNO3 treated silica gel, sodium sulphate, florisil columns
and reversible carbon columns, were procured from Sigma- Aldrich, Milwaukee, USA. Reagents
such as Silica gel, high purity grade, type 60, 70-230 mesh and basic alumina was obtained from
MP Biochemicals. All high purity solvents such as toluene, hexane, dichloro methane were
procured from Spectrochem, India. Keeper solvents such as nonane and isooctane were
obtained from E-Merck, Germany. High purity reagents such concentrated H2SO4 (98%), HCl,
NaCl, NaOH were procured from E-Merck, India. MilliQ denionized water was used to prepare
all aqueous solutions for cleanup.

16
2.9. Preparation of standard calibration mixture

Calibration solutions were produced by serial dilution of individual congeners of dioxins and
furans. The quantification of dioxins and furans in samples were carried out against the
standard calibration curve. Nine point calibration mixture contain 10 - 2560 ppt of tetra, penta,
hexa chlorinated congeners of dioxins and furans, 1234678 HpCDF, 1234789 HpCDF and OCDF
each, and 50- 12800 ppt of 1234678 HpCDD and 500-128000 ppt of OCDD respectively. Each of
the calibration mixture contain 500 ppt of 15 C13 labelled congeners and 1000 ppt of
OCDD/OCDF respectively which was used to quantify the internal standard recovery in samples.
Syringe/recovery standard mixtures of 100 ppt of C13 labelled 1278 TCDF, 123469 HxCDF and
1234689 HpCDF each and clean up spike standard of 500 ppt Cl37 2378 TCDD was added in each
of the calibration mixtures. An isotope labelled sampling standard (C13 labelled 1234 TCDD &
1234 TCDF) was also present in the calibration mixtures. The sampling standard was spiked in
XAD -2 resin prior to stack sampling, so as to check any breakage in the sampling train. The
cleanup standard was spiked prior to cleanup steps to check sample loss during cleanup and
finally a syringe standard was spiked just before injection in GC-MS/MS to quantify the
performance of instrument. The recoveries of sampling and cleanup standards were calculated
as per the equations given in sec. 3.11.4 & 3.11.5 respectively, whereas the syringe/recovery
standard data is used for internal standard recovery calculation given in sec. 3.11.3.

3. Experimental Procedures

3.1 Waste combustion studies

Municipal solid wastes for the combustion experiments were prepared by hand mixing of
different types of waste materials. The typical composition of MSW in Thiruvananthapuram city
was selected based on the report of Dr. R. Ajaykumar Varma, Executive Director, Suchitwa
Mission entitled “Status of municipal solid waste generation in Kerala and their
characteristics”[8]. The selected composition is given in table 2.

17
 Table 2 : Typical composition of municipal solid waste in Kerala
SL. No Waste category Percentage Weight taken for 10 kg of
composite waste

1 Paper 2.25 0.23

2 Plastic 2.79 0.28

3 Metals 1.02 0.10

4 Glass 1.30 0.13

5 Rubber and leather 2.11 0.21

6 Compostable organics 69.09 6.91

7 Others – textiles, inert 21.44 2.14

and domestic hazards

The moisture content of compostable organics in the waste is calculated during each set of
experiments. Experiments were conducted using dry waste as well, by prior drying of
putrescible waste. The moisture content of the dried waste was also determined.

Typically, 10 kg of the composite waste (wet/dry) is placed on the platform inside the burn hut.
The air flow rate of the blower is adjusted to the desired level using the variable frequency
drive device. The combustion is initiated with a flame generated at a gas flame torch. The gas
flame torch is made by coupling liquefied petroleum gas and oxygen at appropriate rate and
the nozzle tip is ignited. The waste pile is then set to fire. The photographs of waste ignition
inside burn hut and sampling set up is shown in Fig 9.

3.2 Air discharge rate measurement

The air discharge rate was measured using the measurement set up shown in section 2. 3.,
following IS – 4894- 1987 method [9]. The blower fan was calibrated at various rpm adjusted
using the variable frequency drive (VFD). The air discharge rate was set to required rates during
18
waste combustion experiments. The air discharge rate of the blower was adjusted to 0.52 m3/s
by adjusting the VFD.
Air Discharge Rate of Blower Fan

Where,
Q - Flow rate in m3/hr
Cd - discharge coefficient
D - diameter of the airway (m)
ΔP - difference between the ambient pressure and the pressure in the side
tapings (mm H2O)
Wt - weight of air in the airway (kg/m3)
The air flow rate at the stack sampling port was also measured using anemometer as well as
using the pitot tube of stack sampler.

3.3 Isokinetic sampling protocol

The stack sampling and analysis of dioxins and furans were carried out following USEPA
method 23 and CPCB guidelines for stack monitoring. The glass lined sampling probe is
introduced at the sampling port provided in the burn hut stack (see sec. 2.1). Precleaned XAD-2
resin and glass fiber filter paper is used for vapour phase & particulate sampling respectively. A
sample is withdrawn from the gas stream isokinetically and collected in the sample probe, on a
glass fiber filter, and on a packed column of XAD-2 resin.
The isokinetic sampler probe records the flue gas temperature. The stack velocity and air flow
rate is measured using the s-type pitot tube following the Bernoulli’s principle. The sampling
flow rate is adjusted at the manometer so as to attain isokinetic sampling. These adjustments
are done prior to setting of fire in the waste sample. Setting fire to the waste pile and switching
on of sampling pump is done simultaneously. The isokinetic sampling is carried out from
initiation till completion of combustion or until the seizure of smoke emission, whichever is

19
later. The sampling train is shown in scheme 1 and exterior view of sampling train set up at
stack in the background of smoke expulsion from burn hut is shown in Fig. 9.

The calculation of stack sampling parameters such as stack velocity, stack flow rate, sampling
nozzle flow rate, and volume of sampled gas is as given below

3.3.1 Calculation of stack sampling parameters

1. Ps – static pressure in the stack

Where,

ΔPs - stack gas velocity pressure

13.6 - density of Hg

Pbar - barometric pressure

2. Us - stack gas velocity inside the stack (m/s)

Where,

Kp - constant, 33.5

Cp - S-type pitot tube coefficient, 0.84

Ts - Absolute stack gas temperature, deg K

ΔP - stack gas velocity pressure, mm Hg

Ps - absolute stack gas pressure, 760 mm Hg

Ms - Mol weight of stack gas on wet basis, 28.8484 Kg/kg mole

3. Qs – Stack gas discharge (m3/s)

Where,

As - area of the stack, 0.07065 m2

Bwo - proportion by volume of water vapor in stack gas

20
 Tref - 298 deg K

Pref - 760 mm Hg

Ts - absolute stack gas temperature, deg K

Ps - absolute stack gas pressure, 760 mm Hg

Us – stack gas velocity, m/s

4. Rs - sampling rate at nozzle (LPM)

Where,

Us - stack gas velocity, m/s

An - Area of nozzle. m2

60000 - Conversion factor

5. Rm – flow rate through meter

Where,

Rs - sampling rate at nozzle

Tm - temperature at metering condition, K

Ts - absolute stack temperature, K

Ps - absolute stack gas pressure, mm Hg

Pbar - barometer pressure, mm Hg

Pm - suction at meter, mm Hg

Vm - volume of gas sampled at meter conditions, m3

Vv - equivalent vapor volume of condensate at meter conditions, m3

21
6. Vsam – total sampled gas (m3)

Where,

Tm - temperature at metering condition, K

Pbar - barometer pressure, mm Hg

Pm - suction at meter, mm Hg

Vm - volume of gas sampled at meter conditions, m3

Y - calibration factor of dry gas meter, 1.004

7. Oxygen correction

Where,

Es - calculated emission concentration at the standard oxygen concentration

Em - measured emission concentration

Os - standard oxygen concentration

Om - measured oxygen concentration * moisture correction

22
 Scheme 1: Dioxin stack sampling train

The particulate matter will be collected in quartz filter in the filter box and dioxin in the
condensed air is trapped by XAD resin cartridge. Upon completion, the sampling train is
dismantled. The filter paper as well as XAD resin is removed and kept separately. The sampling
train from the probe nozzle till the filter box is washed out using different solvents and kept
separately. The PCDD's and PCDF's are extracted from the sample, clean up carried out using
automated clean up system, separated by high resolution gas chromatography, and measured
by triple quadruple mass spectrometer.

23
Fig 9: Photographs of waste combustion experiments & isokinetic sampling

24
3.4. Burn Hut ash sampling

Upon completion of each simulated waste burn experiment in the burn hut, the residual ash on
the platform, was weighed and recorded. A representative sample ash (100 g) was taken, and
preserved at 4 oC in an amber coloured bottle till analysis (USEPA method 8290 [10]).

3.5. Waste dump yard soil sampling protocol

The major waste dump yards and waste burning sites in the Thiruvananthapuram city sampled
were Attakulangara, Manacaud and Palayam. All the sites were having an area less than 100 ft
x 100 ft. The sites were not having a regular geography and hence the representative point
selection was very difficult. In Attakulangara and Manacaud, samples were not collected from
wet areas. Samples were taken from 4 to 6 points. At each point surface soil was scratched
within the area of a 0.5 – 1 ft diameter. It was impossible to separately collect soil and ash from
the sites, as it was intermixed with various components in the waste such as vegetable peelings,
plastic, paper, rubber and other diverse kinds of wastes. Hence a composite mixture of soil, ash
and other components in the site was collected. The scratched soil was sieved (2 mm sieve) into
a clean tray and homogenized by coning and quartering method. Then the samples
approximately 2 kg were transferred into a pre-cleaned, amber colored glass jar till analysis.

3.6. Sample Extraction

(a) Stack sample extraction

The samples were extracted by soxhlet extraction as per USEPA method 23. The XAD-2 resin,
glass fiber filter and solvent washings from the nozzle tip till the filter cartridge were
transferred to the extraction chamber. The filter paper and any particulates that adhere to the
filter holder gasket were stored along with XAD-2 resin (container 1). All particulates sticking to
the nozzle, sample probe lines and filter holder were collected and stored along with acetone
and DCM washings of those parts (container 2). Finally, all the sample lines were washed with
toluene and stored in container no.3. The material in container no. 1 was transferred to an
extraction thimble. Labelled internal standard mixture containing 100pg of each congener (17

25
nos) was spiked and placed inside the extraction chamber. The solvent in the container no. 2
was concentrated to less than 5 mL and transferred to the extraction chamber. The toluene
washing in container no.3 was transferred to distillation flask and filled up to 250 ml with
additional toluene. The distillation flask, chamber and condenser were fitted together and
placed on a heating mantle. The extraction was carried out for 16 hr. The extract was
concentrated and taken to cleanup steps as mentioned in method 23.

(b) Ash extraction (Refer USEPA Method 8290)

About 10 g of the residual ash sample is weighed, spiked with internal standard mixture (100
pg of each congener) and transferred to an extraction jar. It was then treated with 150 ml of 1
M HCl in a shaker for 3 hr at room temperature. The sample was filtered through a pre-cleaned
glass fiber filter paper, followed by washing the ash cake with 500 mL of organic-free reagent
water and the filter cake was dried overnight in a desiccator.

The filter cake was then mixed with 10 g of anhydrous powdered sodium sulfate in a closed
container and intermittently remixed (2 -3 times) for 2 hrs. The ash sample along with the filter
paper was placed in a thimble and kept inside the extraction chamber of soxhlet apparatus,
charged with 200 mL of toluene and extracted at 110 0C for 16 hr.

Upon completion, the toluene extract was cooled and filtered using a glass fibre filter paper.
The filter paper was rinsed 2-3 times with minimum amount of toluene (10 mL) and combined
with the filtrate. Further, it was concentrated to near dryness in a rotary evaporator at 50 oC
and transferred to a separating funnel using 15 mL of hexane, followed by transfer of RB flask
rinsates (2-3 times) to separating funnel. The combined solution in the separating funnel was
shaken for two minutes with 50 mL of 5 % NaCl solution, discard the aqueous layer. The hexane
layer was concentrated to 10 mL and clean up was carried out as per the procedure given in
sec.3.7.

26
(c ) Dump yard soil extraction (Refer USEPA method 8290 for detailed procedure)

Briefly, about 10 g of the dump yard soil sample is weighed, and mixed thoroughly with 10 g of
anhydrous powdered Na2SO4 with a stainless steel spatula. The soil/sodium sulfate mixture was
transferred to an extraction thimble, spiked with labelled internal standard mixture containing
100pg of each congener (17 nos and placed in soxhlet apparatus. It was then extracted with 250
ml of toluene and refluxed at 110oC for 16 hours.

The extract was filtered as per the procedure. It was then cleaned up as per sec. 3.7 /3.8.

3.7. Manual sample cleanup procedure

The samples (stack, ash, dump yard soil) were taken for cleanup steps upon completion of
extraction. In certain cases, a liquid-liquid partition step was followed. Detailed procedure can
be referred to USEPA method 23 & 8290. The followed procedure is briefly given below.

The partition step (a) was followed for ash and soil samples. The partition step was not required
for stack sample and was taken directly to silica/alumina column cleanup upon extraction.

(a) Partition

The extracted sample in hexane was partitioned against 40 mL of concentrated H2SO4 in a

separating funnel. The darkened sulfuric acid bottom layer was discarded (repeated 2-3 times
until color was visible). The hexane fraction is then partitioned against 40 mL of 5 percent (w/v)
aqueous NaCl, followed with against 40 mL of 20 percent (w/v) aqueous KOH) and against 40
mL of 5 percent (w/v) aqueous sodium chloride as per the procedure. The extract was then
dried with anhydrous Na2SO4 and concentrated to near dryness on a rotary evaporator (Refer
USEPA method 8290). It was then taken to silica/alumina column cleanup.

(b) Silica/Alumina Column Cleanup

A glass column (approx 30 cm x 10.5 mm), fitted with a teflon stopcock was used to pack silica
materials. The column was packed with glass wool plug, 1 g silica gel, 2 g NaOH-impregnated
silica gel, 4 g H2SO4-impregnated silica gel, 3 g AgNO3 impregnated silica and 2 g silica gel from
bottom to top. It was then used for cleanup.
27
Similarly an alumina column was prepared by packing glass wool plug, 4 g layer of anhydrous
Na2SO4, 4 g layer of activated basic alumina and 4 g of anhydrous Na2SO4 from bottom to top.
Both the columns were examined for channeling by eluting with 10 mL hexane. The column was
discarded if found unsuitable.
The residue obtained from acid-base-salt partitioning was dissolved in 2 mL hexane and applied
to the top of the silica gel column. It was then eluted with 90 mL hexane, concentrated to 1mL
and applied to the top of the alumina column. The alumina column was eluted with 20 mL of
hexane, followed by 15 mL of 60 % CH2Cl2. The 2nd fraction was concentrated to 2 mL in a
nitrogen stream and taken to carbon column clean up (Refer USEPA method 8290)
(c ) Reversible Carbon Column Cleanup
A dual layer carbon column was used for the separation of dioxins and PCBs. The readymade
column procured from M/s. Suppelco is made of bi-layers of activated carbon having different
affinities for dioxin compounds. The two carbon materials are Carboxen 1016 having a surface
area of 75 m2/g and carboxen 1000 having a surface area of 1200 m2/g (Scheme 2). The dual
layer reversible column was connected with a glass column and placed inside a vacuum
manifold system and the vacuum was adjusted to about 100-400mm Hg (0.013- 0.053 MPa) .
The column was conditioned by solvent washings as per procedure given in Suppleco’s
instruction manual [11].

Scheme 2: Reversible carbon column cleanup set up

28
The column was conditioned with 40 mL of toluene and two cycles of 50 mL of n-hexane. The
column solvent reservoir was capped to minimize evaporation, thereby keeping the column bed
wetted with non- polar solvent after conditioning. The dual layer reversible carbon column was
connected as per the manual. The 2nd fraction of alumina column was eluted in the forward
mode using 30 mL of 3.3 % DCM- Hexane mixture and mono- ortho PCBs were collected. The
carbon column was reversed and eluted with 80 mL of toluene to obtain the dioxin, furans and
non- ortho PCB fraction [11]. The eluate solution was concentrated to 0.2 mL by nitrogen blow
down prior to GC-MS/MS analysis.

An overview of the cleanup procedure is given in scheme 3.

Scheme 3: Manual clean up flow sheet

29
3.8. Semi-Automated Cleanup System for Dioxins

A semiautomated clean up system (DEXTech) was also used to avoid the tedious and time
consuming manual cleanup system. It was used for stack sample and dump yard soil extract
cleanup, whereas ash extracts were cleaned manually, as better recoveries were obtained in
the latter method. The DEXTech dioxin sample cleanup system is capable of effectively
completing the cleanup process in 1 hr. The system consisted of readymade multilayer silica,
florisil and two carbon columns. The sample upon extraction by Soxhlet was concentrated to 2
mL toluene in rotary evaporator and made into 10 mL with n-hexane in an RB flask. The four
plug and play column cartridges are loaded in the system. The extract is then loaded into
LCTech loop. The flask was washed 2 times with 2mL of hexane and was also fed into the loop.
The method was selected from the library and the process was started. The syringe pumps in
the system will flush the sample through different columns and the final cleaned sample is
separated into four fractions. Total run time is 90 minutes. The work flow of semi- automated
sample preparation system is given in scheme 4.

The system had four outlets. The first fraction (140 mL) corresponds to non-dioxin-like PCBs,
second fraction (56 mL) contains mono-ortho PCBs, third fraction (56 mL) contains non-ortho
PCBs and fourth fraction (56 mL) represents PCDD/F. The fractions were collected and
concentrated using nitrogen purging. The final volume was made into 200 µL and was taken for
GC-MS/MS analysis.

30
 Scheme 4: Automated dioxin cleanup system flowsheet

3.9. Quantification using GC-MS/MS system

Agilent 7890B GC system coupled to an Agilent 7000C series triple quadrupole GC/MS system
was used for quantification of dioxins and furans [12]. The sample upon cleanup is mixed with
20 pg labelled syringe/recovery standard before making it upto 200 µL. The syringe standard is
used to gauge the performance of the instrument. Thus the internal standard recovery studies
will monitor the analyte loss during extraction & cleanup steps, while the syringe standard will
monitor the instrumental losses. Separate labelled standards as mentioned in sec. 2.8 was used
to monitor cleanup & sampling efficiencies - ‘surrogate recovery studies’. The GC-MS run
conditions are as given in table 3.

31
 Table 3: GC/MS run conditions
GC Conditions
Column Agilent DB-5 MS UL, 60 m*250 um*0.25um
Fused silica capillary column
Inlet Programmed temperature vaporization inlet
(PTV)
Outlet Vacuum
Injection volume 4 uL
Injection port Multi-Mode Inlet (MMI)
Injection port liner Multi-baffle, deactivated PTV liner
Injection mode Solvent vent
Vent flow 100 mL/min; pressure 5 psi
Purge flow 60 mL/min
Carrier gas Helium
Carrier gas mode Constant flow
Column flow 1.02 mL/min
Retention time locking 15.192 for TCDD
Oven program 60 0C (1 minutes)
30 0C/min to 2700C (9 minutes)
2 0C /min to 310 0C (29 minutes)
10 0C/min to 325 0C (35.5 minutes)
Total run time 35.5 minutes
MS conditions
Operation mode Electron ionization (EI), Multiple reaction
monitoring (MRM)
Transfer line temperature 280 0C
Source temperature 330 0C
Quadrupole temperature 150 0C

A triple quadruple mass spectrometer consists of three quadrupoles. The first (Q1) and third
(Q3) quadrupoles act as mass filters, and the middle (q2) quadrupole is employed as a collision
cell. The collision cell is an RF-only quadrupole (non-mass filtering) using Ar, He, or N2 gas
(~10−3 Torr, ~30 eV) for collision induced dissociation of selected parent ion(s) from Q1. The
precursor ion selected by Q1(Ist mass filter) is fragmented at Q2 (collision cell at a given energy)
to produce product ions. The Q3 (2nd mass filter) detects the product ion. Thus by judiciously
selecting the precursor and product ion, specific molecules can be quantified with negligible
background noise and better sensitivity. Thus the quadrupoles does the mass filtering of
32
multiple ions in each time segments and hence known as multiple reaction monitoring (MRM).
In Dioxin and PCB analysis, two MRM transitions were monitored for each target for
quantitation (‘Quant transition’) and qualification (‘Qual transition’) purposes. Each Quant/Qual
transitions were recorded from two specific precursor ions (usually 2 Da offset) and two distinct
product ions. Dwell times (time for which a particular ion is monitored usually in milliseconds)
were selected and acquisition windows adjusted to optimize acquisition frequency to get ten
data points per peak. Calibration and tune of the instrument were per-formed in the EI high
sensitivity autotune mode every ten days and performances of the instrument were checked at
the same time. The retention times of all native and labelled congeners are known and it may
slightly vary with respect to each column/instrument. A selected compound (eg: 2378-TCDD)
was quantified under different carrier gas flow rates and RT vs flow rate is plotted. The slope of
the curve was used to calculate the appropriate flow rate to obtain the actual retention time
using the column/instrument under consideration. Upon adjusting the flow rate, all congeners
will elute in fixed retention time window, and this procedure is called retention time locking
(RTL). This procedure has to be done, whenever column is replaced or trimming is carried out.

3.10 Toxicity Equivalence factor and Quantification and Recovery calculation

The toxicity of a mixture is stated as TEQ (TCDD equivalents) and is equal to the sum of the
concentration of individual congeners multiplied by their toxicity equivalent factors (TEF).

TEQ =  PCDDi TEFi  + PCDFi TEFi  +  PCBi TEFi 

The 2005 World Health Organization re-evaluated the human toxicity equivalency factors for
dioxins and dioxin like PCBs and is given in Table 4.

33
 Table 4: Toxicity equivalency factors for dioxins and dioxin like PCBs as per WHO2005
SL. No Target Analytes (PCDD/ WHO-Toxic Equivalent Factor (WHO-
PCDF/PCB) TEF05)
PCDDs
1 2,3,7,8- TCDD 1
2 1,2,3,7,8- PeCDD 1
3 1,2,3,4,7,8- HxCDD 0.1
4 1,2,3,6,7,8 – HxCDD 0.1
5 1,2,3,7.8.9 – HxCDD 0.1
6 1,2,3,4,6,7,8-HpXDD 0.01
7 OCDD 0.0003
PCDFs
8 2,3,7,8 –TCDF 0.1
9 1,2,3,7,8-PeCDF 0.03
10 2,3,4,7,8-PeCDF 0.3
11 1,2,3,4,7,8-HxCDF 0.1
12 1,2,3,6,7,8- HxCDF 0.1
13 1,2,3,7,8,9- HxCDF 0.1
14 2,3,4,6,7,8-HxCDF 0.1
15 1,2,3,4,6,7,8- HpCDF 0.01
16 1,2,3,4,7,8,9- HpCDF 0.01
17 OCDF 0.0003

3.11 Calculations

3.11.1 Calculation of response factor & relative response factor of native and labelled
Compounds
Response factor is the ratio of area of the peak of a particular compound to its concentration or
quantity. Relative response factor of native compound (RRF (n)) is the ratio of response factor of
native congener with respect to that of labelled congener (also called internal standard).

The relative response factor of labelled compound is the ratio of response factor of internal
standards with respect to that of recovery or syringe standard. The recovery or syringe
standard is used to quantify the instrument efficiency.
34
 Ax Qis
(a) RRF( n) 
Q x Ais

A Q
(b) RRF(l )  is rs
Qis Ars

Where
Ax is the response (sum of two m/z’s) of native compounds;
Ais is the response (sum of two m/z’s) of corresponding internal standard
Ars is the response (sum of two m/z’s) of recovery standard;
Qis is the amount of internal standard pg/mL;
Qrs is the amount of recovery standard pg/mL;
Qx is the amount of native component pg/mL.
The average relative response factor is calculated as


1 m
RRF  x RRF( n)
m i 1

Where
m is the number of standards (concentration levels);
n is the native component;
i is the calibration level.
The average relative response factor for labelled compounds is calculated as


1 m
RRF  x RRF(l )
m i 1

Where
m is the number of standards (concentration levels);
l is the labelled compound;
i is the calibration level.

35
3.11.2 Calculation concentration component of interest

Ax Qis
The content component of interest is calculated by = C x  where
Ais DIV RRF(n)

Cx is the content of the component of interest in ng/kg;

Ax is the response (sum of two m/z values) of native compounds in sample extracts
Ais is the response (sum of two m/z values) of corresponding labelled internal standard in
sample extracts;
Qis is the amount of injected labelled internal standard pg/mL;
DIV is the calculation factor from concentration (pg/mL) to content on sample basis (ng/kg) =
M/V, where
V is final volume in μl;
M = sample intake in g.
RRF(n) is the relative response factor of native congeners
3.11.3. Internal Standard Recovery
The recovery for the internal standards used is calculated by:
A Q 100
Percentage recovery (%)  is rs x where
Qis Ars RRF(l )

Ais is the response (sum of two m/z’s) of the internal standard in the sample;
Ars is the response (sum of two m/z’s) of the recovery standard in the sample,
Qis is the Amount of internal standard pg/mL;
Qrs is the Amount of recovery standard pg/mL;
RRF(l) is the relative response factor of labelled congeners
3.11.4 Sampling Standard Recovery
The recovery for the sampling standards used is calculated by:

Ass Qis 100

Percentage recovery (%)  x where
Qss Ais RRF( ss / is )

Ass is the response (sum of two m/z’s) of the sampling standard

36
Ais is the response (sum of two m/z’s) of the internal standard in the sample,
Qss is the amount of sampling standard, pg/mL
Qis is the amount of internal standard, pg/mL
RRF(ss /is) is the relative response factor of sampling standard w.r.t internal standard
3.11.5 Cleanup Standard Recovery
The recovery for the cleanup standard used is calculated by:

Acleanup Qis 100

Percentage recovery (%)  x
Qcleanup Ais RRF(cleanup / is )

where
Acleanup is the response (sum of two m/z’s) of the cleanup standard
Ais is the response (sum of two m/z’s) of the internal standard in the sample,
Qcleanup is the amount of cleanup standard, pg/mL
Qis is the amount of internal standard, pg/mL
RRF(cleanup /is) is the relative response factor of cleanup standard w.r.t internal standard

3.12 Estimation of emission factors

Emission factor is the TEQ of dioxin generated during the combustion of unit quantity of
material under consideration. In case of burning of municipal solid wastes, it is the quantity of
dioxin emitted per ton of waste burned. The quantification is not possible at actual open
burning site due to (a) wind flow rates & direction is not controlled and (b) varying means of
dispersion to the surrounding environment. The emission factor of dioxins can be obtained
from the burn hut simulation studies where the total emission factor is the sum of EFair and
EFresidual ash. Unlike the real open burning conditions, quantitative sampling of air and ash is
possible from the simulated burn hut experiments.

EFtotal = EFair + EFresidual ash

37
The annual Source Strength is calculated by multiplying the release of PCDD/Fs (eg: in µg I-TEQ)
per tonne of MSW burned, referred to as the Emission factor and the quantity of waste burned
per year. The quantity of waste burned per year will be referred to as the Activity Rate.

Source Strength (Dioxin emission per year) = Emission factor x “Activity Rate”

4. Results & Discussion

4.1 Air flow rate calibration

Since the axial flow blower was controlled by a variable frequency drive, the air discharge rate
of blower fan could be calibrated against frequencies. The air discharge rate was measured
using the measurement set up shown in section. 3.3. as per IS 4894-1987. Fig 10 shows the plot
of air discharge rate against revolutions per minute of the blower. The variable frequency drive
has to be set at 15 Hz to generate an air discharge rate of 0.5 m3/s at blower. The first set of
waste burning experiments was conducted at an air discharge rate of 0.5 m3/s at blower side.

1.0
Blower fan calibration

0.9
air discharge rate (m /s)

0.8
3

0.7

0.6

0.5

0.4

0.3
5 10 15 20 25 30 35
AC Frequency (Hertz)

Fig 10: Plot of blower air discharge rate Vs AC frequency

38
 0.7
stack flow rate (anemometer data)
0.6 stack flow rate (Meter console data)
air flow rate at stack (m /s)
0.5
3

0.4

0.3

0.2

0.1

0.0
5 10 15 20 25 30 35
AC Frequency (Hertz)

Fig 11: Plot of air flow rate at stack against AC frequency of blower fan

The air flow rate at the stack sampling point was measured using an anemometer as well as the
manometer reading at the dioxin sampler meter console. Fig 11 shows the plot of air flow rate
measured using anemometer and sampler meter console against revolutions per minute of
blower. It can be understood that the measurement from anemometer as well as sampler
meter console are quite closer. However, the air discharge rate measured at the blower inlet is
higher than that measured at the stack. Leakage from the burn hut is expected to be small.
More likely is error in pressure measurement at the flow tube

39
 4. 2. Calibration of standard congener mixture

The prepared mixed standard solution containing all 17 congeners of dioxin and furans along
with C13 labelled & Cl37 labelled standards were calibrated. The calibration curves of tetra – octa
chlorinated dioxins and furans are shown in Fig 12 a – d.

180000 123478 HxCDF

350000 2378 TCDF
(a) 123678 HxCDF (b)
2378 TCDD 160000 234678 HxCDF
300000 12378 PeCDF 123478 HxCDD
23478 PeCDF 140000
123678 HxCDD
250000 12378PeCDD 123789 HxCDF

Response Factor
Response Factor

120000
123789 HxCDD
200000 100000

80000
150000
60000
100000
40000

50000 20000

0 0
0 500 1000 1500 2000 2500 3000 0 500 1000 1500 2000 2500 3000

Concentration (ppt) Concentration (ppt)

Fig 12 a & b: Calibration curves of tetra, penta, and hexa chlorinated dioxins and furans in the
range 10 – 2560 ppt
1000000
1234678 HpCDF
1234789 HpCDF (c) 4000000
(d)
1234678 HpCDD
800000 OCDF OCDD

3000000
Response Factor

Response Factor

600000

2000000
400000

1000000
200000

0 0
0 500 1000 1500 2000 2500 3000 0 20000 40000 60000 80000 100000 120000 140000

Concentration (ppt) Concentration (ppt)

Fig 12: Calibration curves of (c ) 1234678 HpCDF, 1234789HpCDF and OCDF in the range 10 -
2560 ppt (d) 1234678 HPCDD in the range 50 – 12800 ppt and OCDD in the range 500- 128000
ppt

40
4.3: Optimisation of analytical protocols and validation of the methodology

Studies for optimizing the analytical protocols for the determination of dioxins and furans in
soil, ash and air samples were conducted. This was to establish optimum sample size, extraction
conditions, clean up steps, concentration/ evaporation steps and GC-MS/MS performance
criteria for the quantification of dioxins and furans. We have optimized both manual and
automated clean up procedures to obtain the specified 60 – 120 % recovery for labelled dioxins
(Table 5). The Manual & Automated cleanup steps are as given in section 3.7 & 3.8
respectively.

41
 Table 5: Experiments and Observations on the optimisation of extraction & clean up methods for real samples
SL. No Experiments conducted Aim Inferences
1 10g of soil sample was fortified with 1000ppt of
TCDD. After 16 hr of soxhlet extraction, cleanup of To estimate the recovery 70 % recovery
extract was carried out as per method 8290. The under the specified As per the method, 60 – 120 %
cleanup steps involves step 3-8 given in Figure 1 conditions recovery is necessary to report
such as multilayer silica, alumina and reversible quantitative recovery
carbon column. All these cleanup steps were
conducted manually ( Refer Scheme 2)

10g of fly ash sample is fortified with 1000ppt of

2 2378-TCDD. After 16hr of soxhlet run, an additional To understand the effect of 68 % recovery
clean up step of washing with H2SO4, KOH and NaCl additional washing step No improvement in the efficiency.
was carried out as mentioned in the method. It was IEmulsion formation makes the
followed by the conventional multilayer silica additional step tedious and time
column, alumina, and reversible carbon column consuming.
clean ups manually as given in steps 3- 8.
(Refer Scheme 2)
3
Prepared a mixture of all 17 native PCDD/Fs and 4 It is required for the Calibration was found to be
non- ortho PCBs and made a 5 point calibration quantification of all the
mixture. satisfactory (See Fig 12 above)
toxic dioxin and dioxin like
Retention time locking of all the 21compounds were
carried out. PCBs in the sample extract.
4 Soil samples collected from Attakkulangara dump To optimize the analytical
42
 site. Municipal wastes are burned periodically. protocols for the
quantification of dioxins in
soil samples collected from
waste dump sites under
the purview of the study
5 Evaluation of effect of acid washing step for dump With acid washing recovery
yard soil samples after extraction.
Carried out to estimate the C13 TCDD = 52.1 %
Carried out extraction of 5g of soil. The extract was effect of acid washing prior
divided into 2 equal parts to automated clean up C13 HxCDD = 57.7 %

First Part: Extract was spiked with C13 TCDD followed Total TEQ = 8.1 pg/g WHOPCDD/F
by acid washing ( refer sec 4.7a ) and carried out Without acid washing recovery
automated cleanup after spiking C13 HxCDD
13
C TCDD recovery – 26.01%
13
C HxCDD recovery – 111.5%

Observation: Acid washing step

shows relatively better recovery than
without washing. Repeatability of
the protocol need to be done.

43
6 As suggested by the application expert in Germany, 77 % recovery
we have carried out automated cleanup by injecting
a solvent blank spiked with 1000 ppt TCDD taken in To improve the efficiency of Improved and is within the specified
8ml hexane and 2 ml toluene. It was done instead of automated clean up recovery of 60 – 120 range
10 ml hexane alone.

7 (1) Multilayer silica column cleanup efficiency Optimisation of manual 109.3 % recovery
methods of cleanup
Spiked solvent blank with 1000 ppt C13TCDD and (within the specified 60 – 120 %
conducted silica column clean up as per the method recovery for labelled dioxins
8290

8 (2) Alumina column clean up - Spiked solvent blank 114.9 % recovery

with 1000 ppt C13 TCDD and carried out cleanup (within the specified 60 – 120 %
recovery for labelled dioxins)

9 (3) Carbon column cleanup 76.4 %

Spiked solvent blank with 1000 ppt C13 TCDD and (within the specified 60 – 120 %
recovery for labelled dioxins)
carried out cleanup

13
10 Total manual column cleanup using sample matrix C TCDD recovery – 21.65%
using the above optimized steps 13
C HxCDD recovery – 107.8 %
10 gm soil was extracted by soxhlet for 16 hrs
HxCDF recovery – 102.9%
followed by the following clean up steps. C13 labelled
spiking was done in each steps It can be concluded that
13 unacceptable recovery was observed
C TCDD before silica column

44
 13
C HxCDD before alumina in silica clean up

Native HxCDF before carbon column Channeling in the silica column was
observed, and it was rectified in
further studies to get better
recovery.

In all other cleanup steps, recovery

was within the specified 60 – 120 %
or

80- 120 %

11 Total cleanup using automated system with spiking 13C TCDD recovery – 71.03%
of C13 labelled before each step 13C HxCDD recovery – 129.46 %
13
(Satisfactory recovery in all the
C TCDD spiked onto soil and extracted.
steps ie extraction, clean up and
No washing steps after extraction
evaporation steps)
13
C HxCDD spiked before cleanup
Total TEQ = 11.2 pg/g -WHOPCDD/F

45
12 Total manual clean up using soil sample matrix
13
(Repetition of exp 10) C HxCDD recovery – 143.8 %
HxCDF recovery – 174.3 %
10 gm soil was extracted by soxhlet for 16 hrs
Experiments 11 & 12 showed that
followed by the following clean up steps. C13 labelled the acid washing step is not essential
spiking was done in each steps during cleanup of dump yard soil.
13 Better recoveries were observed
C TCDD before silica column
using manual and automated
13
C HxCDD before alumina cleanups without acid washing steps.
Native HxCDF before carbon column

13 Calibration mixture using all C13 labelled dioxins and All the above optimization steps
C13 dl- PCBs was prepared and method validation is were monitored using only 2 isotope
labelled congeners Ie C13 TCDD &
completed
C13 HxCDD, as the labelled mixture
of all congeners were not procured.
The recoveries observed in these two
congeners may not fully represent
the trend of other congeners.
However, we could generate
preliminary data on various steps
involved in the analysis. In further
studies, isotopes labelled congeners
of all compounds were used to
assess recovery.

46
4. 4. Simulated waste burning studies (Burn Hut) and dioxin emission factor determination

4.4.1. Dioxin air emission factor

An experimental quantity of 10 kg of municipal solid waste was used for the simulated waste
burning study. 10 Kg of typical composition of municipal solid waste as given in table 2 was
placed on the platform inside the burn hut and waste combustion was carried out as per the
procedure given in section 3.1. The moisture content of the waste was determined prior to the
combustion study. The blower air discharge was set at 0.5 m3/s. The stack air was sampled from
the time of ignition of waste till the completion of combustion as per the procedure given in
section 3.3. The stack gas sampling parameters were calculated as per section 3.3.1 and are
given in Table 6 & 7 respectively.

From table 7, it can be observed that the air emission rate of dioxins during the combustion of
dry waste (% moisture = 14.7) is 18.86 pg TEQ/Nm3 while that of wet waste (% moisture = 67.8)
is 18.07 pg TEQ/ Nm3. The total dioxin emission was calculated by multiplying the obtained air
emission rates (pg/Nm3) with total stack gas volume (Vtotal (Nm3)) and is given in table 7. It is
calculated to be 38357.1 & 49484.7 picogram TEQ for dry and wet waste respectively.

47
 Table 6: Stack Sampling Parameters
Experimental Weight % ΔP Ps Ts Ms Bwo As Us Qs Rs Vm Vv Rm Vstd
condition of Moisture (mm (mm (Deg (Kg/kg (%) (m2) (m/s) (m3/s) (LPM) (m3) (m3) (LPM) (Nm3)
waste of waste H2O) Hg) K) mol)
(Kg)
Dry waste 9.1 14.7 1.778 759.86 363 28.85 0.91 0.071 4.83 0.28 9.2 1.07 0.01 7.59 1.06
Wet waste 9.8 67.8 1.778 759.86 323 28.85 0.82 0.071 4.55 0.29 8.7 1.34 0.01 8.05 1.32

Table 7. Air Emission Data

Experimental Weight % Obtained Vstd Stack Run Vtotal Total TEQ TEQ per kg TEQ per ton
3 3
condition of Moisture TEQ (Nm ) Concentration time (Nm ) emitted of waste of waste
waste of waste (pg (pg TEQ/Nm3) (min) (pg (pg (ug
(Kg) TEQPCDD/F) TEQPCDD/F) TEQPCDD/F/kg) TEQPCDD/F/ton)
Dry waste 9.1 14.7 18.86 1.06 17.81 131.5 2153.4 38357.1 4215.1 4.2
Wet waste 9.8 67.8 23.85 1.32 18.07 157.6 2738.5 49484.74 5049.46 5.1

48
The weight of dry and wet waste burned is 9.1 and 9.8 kg respectively. Hence the quantity of
dioxin air emission factor per Kg of waste burned is calculated to be 4215.1pg TEQ per Kg of dry
waste burned & 5049.5pg TEQ per Kg of wet waste burned respectively.

The dioxin air emission calculated per ton of waste burned is 4.2 & 5.1 µg TEQ/ton dry and wet
waste burned respectively. It may be noted that probability of drying the waste and burning at
open places are very unlikely. Hence, we have not considered the emission level from dry waste
for emission factor calculation. Hence, the air emission factor of dioxins from open burning of
MSW is 5. 1 µg TEQ/ton of waste burned.

4. 4.2. Dioxin emission in residual ash samples

Upon completion of waste combustion, the residual ash is allowed to cool down to room
temperatures and the representative samples were collected as per the procedure (sec. 3.4).
The analysis of ash samples were carried out as per the extraction & cleanup procedures given
in sec. 3.6b and 3.7 respectively. The cleanup of ash samples were carried out using manual
method (sec. 3.7) and determination carried out as per the procedure given in sec. 3.9. The
dioxin content in residual ash obtained upon combustion of wet waste samples having moisture
content of 77.4 % was found to be 41.9 ng PCDD/F TEQWHO/Kg of waste burned while that of
waste containing 67.8 % moisture was 27.52 ng PCDD/F TEQWHO/Kg of waste burned.
However, the dioxin content in residual ash obtained upon combustion of dry waste sample
containing 14.7 % moisture content was found to be 0.86 ng PCDD/F TEQWHO/Kg of waste
burned. These results indicate that increased moisture content in fuel is more conducive for
the formation of dioxins.
Table 8 shows consolidated emission factors determined using wet & dry MSW maintaining the
waste composition given in table 2. The emission factor of dioxins and furans released to air as
well as to residual ash per ton of waste burned is calculated. As per the present study, it can be
observed that the emission factor of dioxins in residual ash is higher in case of wet MSW (%
moisture =77.4) in comparison to that of dry MSW (% moisture = 14.7). However, the air
emission remains more or less similar for wet & dry MSW combustion respectively. The better

49
combustion conditions in dry MSW may be a plausible reason for lower dioxin content in
residual ash of dry waste. Further investigation is needed to establish this hypothesis.

As explained in the case of air emission, we have considered the quantity of dioxins emitted
from wet waste of moisture content between 60- 80 % as emission factor. Hence the average
emission factor of dioxins in residual ash is 34.71 µg TEQ/ton of waste burned.

Table 8: Emission factor data from burn hut experiments

SL. Burn Hut Weight Nature Samp Dioxin Stack Ash Air analysis
No. experime of of ling stack air analysis (µg PCDD/F
ntal simulat waste time emission volum (µg PCDD/F TEQWHO/to
conditio ed &% e TEQWHO/ton n
(min) rate
n MSW moistu (Nm3) waste) waste)
(Kg ) re (pg/Nm3)

Waste Recovery
1 composit 10 Wet 41.9 was low- so
not
ion as ( 77.4)
considered
given in
table 2
2 “ 9.1 Dry 131.5 18.86 2153.4 0.86 4.2
(14.7)
3 “ 9.8 Wet 18.05 2738.5 27.52 5.1
(67.8) 157.6

The simulated waste combustion studies shows that there is not much difference in dioxin air
emission levels from the burning of dry waste compared to that of wet waste. However, it may
be noted that the dioxin levels in ash increases with moisture content. The formation of dioxins
is reported to be increased by poor combustion conditions, such as increased levels of moisture
in the fuel [13]. Similarly, enhancement in dioxin formation under smouldering conditions is
also reported elsewhere. Hence, the increase in the dioxin level in ash with increased moisture
50
content could be due to the culmination of poor combustion conditions and possible prolonged
smouldering stage. The present report shows the data using wastes under three different
moisture contents (14.7, 67.8 and 77. 4) only. Few more combustion studies, under different
moisture levels will provide a clear picture.

The absence of this trend in air emission needs to be investigated. The smouldering process
occurs in dense pockets of waste pile and hence there is greater probability of dioxins to adhere
to ash particulates. The air flow rates will also play a role. Further experiment data using
different air flow rates, combustion conditions and moisture levels is required to arrive at a
conclusion.

4.5. Evaluation of analytical quality parameters

4.5.1. Calculation of internal standard recovery and its interpretation

The recovery of C13 labelled internal standards in spiked ash and stack samples were calculated
based on the equation given in section 3.11.3 . The recovery of internal standards should be in
the range 60 – 120 % for dioxins and furans. Internal standard recovery outside this coverage
range is acceptable, in cases where its contribution to TEQ is less than 10 %.

Internal standard spike and its recovery study will compensate the losses of native compounds
occurring during the analysis. The relative response factor term given in the concentration
calculation equation (section 3.11.2) act as the correction factor. Hence, obtaining the
recoveries as per the acceptable conditions is critical for quantitative results.

Table 9 and 10 shows the calculation of internal standard recovery and toxicity equivalence
following the above mentioned criteria for stack air samples (wet & dry waste burning). It can
be observed that the recoveries of most of the internal standards are in the range 60 -120 %. In
case of recoveries outside the range, we have considered its contribution to TEQ and value
were accepted only if its contribution to TEQ < 10 %. These conditions are satisfied in both
these samples (see table 9 & 10).

51
Table 9: Calculation of toxicity equivalence and internal standard recovery of stack sample (wet waste burn expmt)

Concentration of ainternal standard (IS) spiked(except OCDD & 500 OCDD & OCDF 1000
OCDF) (ppt), Qis (ppt), Qis
concentration of syrringe standard (ppt), Qrs 100

sampled volume of air = 1.32

b c d
Compound Conc TEF TEQ Recovery/ Avg Avg RF RF of RRFl Syringe ISTD IS
pg/ Nm3 Syringe response response of IS syringe of IS to spike Resp. in recovery
standard of IS of spike Syringe Resp. in sample %
syringe sample (Ais)
spike (Ars)
1234678- 161.7 0.01 1.62 1234689 12833.0 10992.0 25.7 109.9 0.2 8030.0 8513.4 90.8
HpCDD HpCDF
1234678- 6.3 0.01 0.06 1234689 35426.2 10992.0 70.9 109.9 0.6 8030.0 31257.4 120.8
HpCDF HpCDF
1234789- 9.6 0.01 0.10 1234689 33164.1 10992.0 66.3 109.9 0.6 8030.0 25803.5 106.5
HpCDF HpCDF
123478- 8.2 0.10 0.82 123469 12972.6 10347.0 25.9 103.5 0.3 7252.0 8534.8 93.9
HxCDD HxCDF
123478- 9.1 0.10 0.91 123469 32982.1 10347.0 66.0 103.5 0.6 7252.0 24274.0 105.0
HxCDF HxCDF
123678- 9.5 0.10 0.95 123469 12526.2 10347.0 25.1 103.5 0.2 7252.0 8534.8 97.2
HxCDD HxCDF
123678- 0.6 0.10 0.06 123469 33080.4 10347.0 66.2 103.5 0.6 7252.0 23998.6 103.5
HxCDF HxCDF
123789- 7.1 0.10 0.71 123469 12526.2 10347.0 25.1 103.5 0.2 7252.0 8559.0 97.5
HxCDD HxCDF
123789- 9.0 0.10 0.90 123469 31476.0 10347.0 63.0 103.5 0.6 7252.0 21195.6 96.1
HxCDF HxCDF
12378- 0.8 1.00 0.78 1278 TCDF 14430.4 19510.0 28.9 195.1 0.1 12494.0 6807.7 73.7

52
PeCDD
12378- 0.4 0.03 0.01 1278 TCDF 23836.5 19510.0 47.7 195.1 0.2 12494.0 15699.9 102.9
PeCDF
234678- 9.2 0.10 0.92 123469 34487.1 10347.0 69.0 103.5 0.7 7252.0 13450.7 55.6
HxCDF HxCDF
23478- 8.4 0.30 2.52 1278 TCDF 26266.6 19510.0 52.5 195.1 0.3 12494.0 15699.9 93.3
PeCDF
2378-TCDD 6.8 1.00 6.84 1278 TCDF 18139.6 19510.0 36.3 195.1 0.2 12494.0 11980.0 103.1
2378-TCDF 7.7 0.10 0.77 1278 TCDF 67322.9 19510.0 134.6 195.1 0.7 12494.0 18469.3 42.8
OCDD 282.5 0.00 0.08 1234689 18439.4 10992.0 18.4 109.9 0.2 8030.0 12524.0 93.0
HpCDF
OCDF 30.23 0.00 0.01 1234689 26642.7 10992.0 26.6 109.9 0.2 8030.0 16675.8 85.7
HpCDF

TEQ pg/Nm3 = 18.07

a
Internal standard – 13Cisotope labelled congener spiked to sample prior to extraction
b
Recovery/ Syringe standard – 13C isotope labelled congener spiked to sample prior to GC-MS/MS injection
c
RF – Response factor - Ratio of area of the peak of a particular congener to its concentration
d
RRF – Ratio of response factor of internal standards with respect to that of recovery or syringe standard.

53
 Table 10: Calculation of toxicity equivalence and internal standard recovery of stack sample (dry waste burn expmt)

Concentration of IS spiked(except OCDD & OCDF) (ppt), Qis 500 OCDD & OCDF 1000
(ppt), Qis
concentration of syrringe standard (ppt), Qrs 100

sampled volume of air = 1.05

Compound Conc TEF TEQ Syringe Avg Avg RF of RF of RRFl of Syringe ISTD IS
pg/ standard response response IS syringe IS to spike Resp. recovery
Nm3 of IS of syringe spike Syringe response (Ais) %
spike (Ars)
1234678- 170.1 0.01 1.70 1234689 12833.0 10992.0 25.7 109.9 0.2 10992 8540.7 66.6
HpCDD HpCDF
1234678- 14.1 0.01 0.14 1234689 35426.2 10992.0 70.9 109.9 0.6 10992 27870.1 78.7
HpCDF HpCDF
1234789- 30.4 0.01 0.30 1234689 33164.1 10992.0 66.3 109.9 0.6 10992 26230.1 79.1
HpCDF HpCDF
123478- 6.8 0.10 0.68 123469 12972.6 10347.0 25.9 103.5 0.3 10347 9744.3 99.0
HxCDD HxCDF
123478- 6.3 0.10 0.63 123469 32982.1 10347.0 66.0 103.5 0.6 10347 27221.9 54.7
HxCDF HxCDF
123678- 7.8 0.10 0.78 123469 12526.2 10347.0 25.1 103.5 0.2 10347 9744.3 77.8
HxCDD HxCDF
123678- 0.5 0.10 0.05 123469 33080.4 10347.0 66.2 103.5 0.6 10347 27221.9 82.3
HxCDF HxCDF
123789- 1.2 0.10 0.12 123469 12526.2 10347.0 25.1 103.5 0.2 10347 9646.5 77.0
HxCDD HxCDF
123789- 6.6 0.10 0.66 123469 31476.0 10347.0 63.0 103.5 0.6 10347 23725.7 75.4
HxCDF HxCDF
12378- 7.0 1.00 7.00 1278 TCDF 14430.4 19510.0 28.9 195.1 0.1 19510 12513.7 86.7
PeCDD

54
 12378- 3.0 0.03 0.09 1278 TCDF 23836.5 19510.0 47.7 195.1 0.2 19510 19620.3 82.3
PeCDF
234678- 8.1 0.10 0.81 123469 34487.1 10347.0 69.0 103.5 0.7 10347 26289.6 76.2
HxCDF HxCDF
23478- 5.6 0.30 1.68 1278 TCDF 26266.6 19510.0 52.5 195.1 0.3 19510 13609.8 51.8
PeCDF
2378-TCDD 3.8 1.00 3.80 1278 TCDF 18139.6 19510.0 36.3 195.1 0.2 19510 14491.2 79.9

2378-TCDF 2.8 0.10 0.28 1278 TCDF 67322.9 19510.0 134.6 195.1 0.7 19510 41509.4 61.7

OCDD 78.9 0.00 0.02 1234689 18439.4 10992.0 18.4 109.9 0.2 10992 12846.8 69.7
HpCDF
OCDF 344.5 0.00 0.10 1234689 26642.7 10992.0 26.6 109.9 0.2 10992 18038.7 67.7
HpCDF

TEQ pg/Nm3 = 18.85

55
Table 11:Calculation of recovery of stack sampling standard

Concentration of IS spiked (except OCDD & OCDF) (ppt) , Qis 500 OCDD & OCDF (ppt), Qis 1000

Concentration of sampling standard (ppt), Qss 500

Sampled volume of air 1.32 Nm3

Compounds Sampling TEF Conc TEQ Avg Avg RF of RF of RRF of Resp of Resp of Rsa
standard pg/ response response IS Sam Sam IS from Sam Std
(SS) Nm3 of IS of SS Std Std to expt from
IS expt

1234678- 0.0100 161.7 1.62 12833.0 18399 25.7 36.8 1.4 8513.4 10885 89.2
HpCDD

123478- 0.1000 8.2 0.82 12972.6 18399 25.9 36.8 1.4 8534.8 10885 89.9
HxCDD

123678- 0.1000 9.5 0.95 12526.2 18399 25.1 36.8 1.5 8534.8 10885 86.8
HxCDD 1234
TCDD
123789- 0.1000 7.1 0.71 12526.2 18399 25.1 36.8 1.5 8559.0 10885 86.6
HxCDD

12378-PeCDD 1.0000 0.8 0.78 14430.4 18399 28.9 36.8 1.3 6807.7 10885 125.4

2378-TCDD 1.0000 6.8 6.84 18139.6 18399 36.3 36.8 1.0 11980.0 10885 89.6

OCDD 0.0003 282.5 0.08 18439.4 18399 18.4 36.8 2.0 12524.0 10885 87.1
56
 1234678- 0.0100 6.3 0.06 35426.2 19466 70.9 38.9 0.5 31257.4 12494 72.7
HpCDF

1234789- 0.0100 9.6 0.10 33164.1 19466 66.3 38.9 0.6 25803.5 12494 82.5
HpCDF

123478- 0.1000 9.1 0.91 32982.1 19466 66.0 38.9 0.6 24274.0 12494 87.2
HxCDF

123678- 0.1000 0.6 0.06 33080.4 19466 66.2 38.9 0.6 23998.6 12494 88.5
HxCDF

123789- 1234 TCDF 0.1000 9.0 0.90 31476.0 19466 63.0 38.9 0.6 21195.6 12494 95.3
HxCDF

12378-PeCDF 0.0300 0.4 0.01 23836.5 19466 47.7 38.9 0.8 15699.9 12494 97.4

234678- 0.1000 9.2 0.92 34487.1 19466 69.0 38.9 0.6 13450.7 12494 164.6
HxCDF

23478-PeCDF 0.3000 8.4 2.52 26266.6 19466 52.5 38.9 0.7 15699.9 12494 107.4

2378-TCDF 0.1000 7.7 0.77 67322.9 19466 134.6 38.9 0.3 18469.3 12494 234.0

OCDF 0.0003 30.2 0.01 26642.7 19466 26.6 38.9 1.5 16675.8 12494 102.5

57
Table 12: Calculation of cleanup standard recovery in residual ash analysis

Concentration of IS spiked(except OCDD & OCDF) (ppt), Qis 500 OCDD & OCDF 1000
(ppt), Qis
concentration of cleanup standard (ppt), Qcs 500

Residual ash amount = 2.91 kg

Compound Conc TEF TEQ Cleanup Avg Avg RF of RF of RRF of Cleanup ISTD Resp. CS
pg/ standard response response IS Cleanup cleanup spike (Ais) recovery
gm of IS of spike to IS response %
Cleanup (Acs)
spike
37
1234678- 500.1 0.01 5.0 Cl TCDD 12833.0 29852.5 25.7 59.7 2.3 26246 8481.4 133.0
HpCDD
37
1234678- 22.5 0.01 0.2 Cl TCDD 35426.2 29852.5 70.9 59.7 0.8 26246 25569.5 121.8
HpCDF
37
1234789- 22.7 0.01 0.2 Cl TCDD 33164.1 29852.5 66.3 59.7 0.9 26246 25451.5 114.6
HpCDF
37
123478- 11.7 0.1 1.2 Cl TCDD 12972.6 29852.5 25.9 59.7 2.3 26246 12726.2 89.6
HxCDD
37
123478- 51.2 0.1 5.1 Cl TCDD 32982.1 29852.5 66.0 59.7 0.9 26246 32877.8 88.2
HxCDF
37
123678- 9.5 0.1 0.9 Cl TCDD 12526.2 29852.5 25.1 59.7 2.4 26246 12726.2 86.5
HxCDD
37
123678- 8.0 0.1 0.8 Cl TCDD 33080.4 29852.5 66.2 59.7 0.9 26246 32878.2 88.5
HxCDF
37
123789- 11.9 0.1 1.2 Cl TCDD 12526.2 29852.5 25.1 59.7 2.4 26246 9998.2 110.1
HxCDD
37
123789- 17.7 0.1 1.8 Cl TCDD 31476.0 29852.5 63.0 59.7 0.9 26246 27893.9 99.2

58
 HxCDF
37
12378- 10.7 1.0 10.7 Cl TCDD 20138.4 29852.5 40.3 59.7 1.5 26246 15460.9 114.5
PeCDD
37
12378- 103.0 0.03 3.1 Cl TCDD 23836.5 29852.5 47.7 59.7 1.3 26246 25278.6 82.9
PeCDF
37
234678- 51.1 0.1 5.1 Cl TCDD 34487.1 29852.5 69.0 59.7 0.9 26246 29987.5 101.1
HxCDF
37
23478- 145.8 0.3 43.7 Cl TCDD 26266.6 29852.5 52.5 59.7 1.1 26246 28764.1 80.3
PeCDF
37
2378-TCDD 3.7 1.0 3.7 Cl TCDD 24453.5 29852.5 48.9 59.7 1.2 26246 22153.1 97.0

37
2378-TCDF 117.2 0.1 11.7 Cl TCDD 85950.7 29852.5 171.9 59.7 0.3 26246 83824.2 90.1

37
OCDD 196.8 0.0003 0.06 Cl TCDD 18439.4 29852.5 18.4 59.7 3.2 26246 7962.3 203.6

37
OCDF 34.3 0.0003 0.01 Cl TCDD 26642.7 29852.5 26.6 59.7 2.2 26246 13202.5 177.4

59
Table 11 shows the evaluation of the stack sampling train performance. The recovery of spiked
isotope labelled sampling standards were calculated (refer sec. 3. 11. 4) The recoveries were in
the range of 60 -130 % as specified for sampling in USEPA method 23. Only 2 congeners show
recovery of higher than 130 %. However, as per method 23, deviation in few congeners can be
neglected.
Similarly Table 12 shows the evaluation of cleanup protocol efficiency. The recovery of cleanup
standard Cl37TCDD used in the study was calculated (refer sec.3.11.5). The recovery of majority
of the congeners were between 60 -130 % , and hence the cleanup protocol was efficient.
4.5.2. Congener abundance profile in simulated waste burning samples (stack & residual ash)
based on toxicity equivalence values

The dioxin congener specific distribution pattern in stack air and corresponding residual ash in
wet as well as dry MSW waste in terms of toxicity equivalence (TEQ) is shown in figure 13 & 14
respectively. The predominant contribution of tetra and penta-chlorinated dibenzo dioxins &
furans can be observed in air as well as residual ash in all cases. The reason for this pattern of
congener profile needs to be investigated further.

Fig 13 a: Dioxin congener distribution pattern in stack sample (Wet waste)

60
Fig 13b: Dioxin congener distribution pattern in residual ash (wet waste)

Fig 14a: Dioxin congener distribution pattern in stack sample (dry waste)

61
 Fig 14b: Dioxin congener distribution pattern in residual ash (dry waste)

4.6 Estimated Annual emission of dioxins and furans in Thiruvananthapuram city

The total quantity of municipal solid waste generated in Thiruvananthapuram city is about 300
tons per day. Since there is no data available on the quantity of MSW burned openly, we have
considered an activity rate of about 100 tons per day is getting burned.Based on this
assumption, the annual emission of dioxins is calculated to be 0.19 g & 1.27 g TEQ in air and
land respectively (See Table 13). It is calculated based on the emission factor of dioxins to air &
residual ash for wet waste burning obtained in our present study is 5.1 µg PCDD-F TEQWHO and
34.71 µg PCDD-F TEQWHO respectively per ton of waste burned. As stated previously, we have
only considered average emission factor of wet waste for emission factor calculation, as the
average moisture level in wastes in Kerala is 60-80 % and probability of open burning of dried
waste is scarce.

In comparision, the average emission factor of dioxins to air is reported to be 40 µg PCDD-F

TEQWHO/ ton of waste as per the studies reported in 2010 conducted for wastes in China &
Mexico. Similarly the average emission factor of dioxins to residual ash is reported to be 300 µg
PCDD-F TEQWHO/ ton of waste. The reason for lower emissions obtained is not clear. Further

62
studies, are ongoing using different air flow rates and combustion conditions to arrive at the
final emission factor for open burning of MSW in Kerala.

Table 13: Estimated annual emission of dioxins in Thiruvananthapuram city considering 100
tons of MSW is burned openly per day
SL. Type of Dioxin Dioxin emission Total annual Total annual
No. waste % emission factor in emission to emission to
Moisture factor in residual air residual ash
air/ton of ash/ton of (g/annum) (g/annum)
waste burned waste burned
(µg PCDD-F (µg PCDD-F
TEQWHO/ ton) TEQWHO/ ton)
1 Wet 77.4 - 41.9 - 1.53

2 Dry 14.7 4.2 0.86 0.15 0.03

3 Wet 67.8 5. 1 27.52 0.19 1.00

Average Emission from wet 5.1 34.71 0.19 1.27

waste (60-80 % moisture)

4.7 Dump yard sample analysis

The analyses of waste dump yard soil samples were carried out as per USEPA method 8290. All
the sample preparation steps were carried out as per the protocol and the quantification was
carried out using GC-MS/MS. The results obtained are given in table 14. It was observed that
the quantity of dioxin levels observed is relatively lesser than that of the burn hut emission
factors. It substantiate the diverse dispersion possibilities in the open burn site conditions,
whereas the dioxins formed during burn hut experiments will be retained either in residual ash
or will be expelled in the stack air. The emission through stack air is sampled using isokinetic
dioxin stack sampler and quantified. Hence the burn hut experiment study provides quantified
emission factors, whereas open burn site data is not comprehensive. We have carried out
congener specific profiling of dioxins and furans in the dump yard soil by plotting TEQ value (Fig

63
15). The TEQ contribution of different congeners has shown wide variations in the samples
from three different dump yards.

Table 14 : Dioxin Emission Analysis of dump yard soil

SL. No Sampling site Sample type PCDD/Fs (% )
(Dump yard) (ng TEQ /Kg) Recovery
1 Attakulangara Residual soil 8.2 52
(Chalai Market)
2 “ “ 11.4 71

3 “ “ 5.5 51.5

4 Palayam Market “ 6.3 89.5

5 Manacaud “ 17.8 57.7

Another noticeable point is the predominant presence (concentration wise) of OCDD in all the
samples (not shown here). However, since the toxicity equivalence factor (TEF) value of OCDD is
much lower, its contribution to TEQ is negligible. The higher concentration wise presence of
OCDD is in tune with the data reported elsewhere. The differences could be due to the
differential losses of PCDD/Fs through reactions with a hydroxyl radical during atmospheric
transport and deposition and the additional photochemical generation of OCDD.

Table 15 shows the PCDD/Fs concentrations (pg/g dry wt) in soils from dumping and control
sites in Asian developing countries with those in general and contaminated soils from other
locations in the world. It is the first such study reported. It was the first comprehensive data of
PCDD/Fs and related compounds in dumping soils from Asian developing countries, which were
comparable or greater than those in soils from dioxin-contaminated sites reported in developed
nations. It highlighted the role of dumping sites as a significant source of PCDD/Fs.

64
 Fig 15: Distribution pattern of dioxin congeners in the dump yard soil

The present study reported dioxin levels of 5.5 – 17.8 pg TEQ/g in the dump yard soil collected
from Thiruvananthapuram city. The dioxin level reported elsewhere in Indian dump yard soil is
52 pg TEQ/g[13]. The variation in the levels may be due to difference in sampling sites and
number of samples studied. The samplings in previous studies were carried out at Perungudi
Dump yard, Chennai, which is much larger and is one of the infamous dump yard sites in India.

The table shows that data is not available in many developed countries on dump yard samples,
because there are no such sites in most of those countries. However, the dioxins levels
reported in contaminated sites and general soil (control - non contaminated) sites of in India is
higher than that of general soil in UK.

65
 Table 15: Comparison of PCDD/Fs Concentrations (pg/g dry wt) in soils from Dumping and Control Sites in Asian Developing countries
with those in General and Contaminated Soils from Other Locations in the World [13]

Soils from contaminated sites General soils

Country Year Mean pg/g Concentration Mean pg/g WHO Concentration Remark
concentration WHO range concentration TEQ range
TEQ
Phillippines 1999 6100 546 44000-75000 57 na 14 - 100 Dumping sites,
uncontrolled burning
Cambodia 1999 30000 402 330-20000 130 1.9 40 - 370 Dumping sites,
uncontrolled burning
India 2000 7400 52 22000-34000 32 0.22 18 - 79 Dumping sites,
uncontrolled burning
Hanoi, 2000 6100 102 125-50500 370 1.1 na Dumping sites,
Vietnam uncontrolled burning
Hochiminh, 2002 370 2.7 21-880 190 1.27 130 - 260 Dumping sites,
Vietnam uncontrolled burning
Rio de 1999 na 13900 na na na na HCH plant waste site
Janeiro,
Brazil
Crete, 1996 37000 410 2900-105000 na na na Open landfill dump
Greece sites, uncontrolled
burning
Barcelona, 1999 700 11.85 na na na na Municipal waste
Spain incinerator
The 1989 na 3-252 na na na na Municipal waste
Netherlands /90 incinerator
Ohio, USA 1995 15700 458 na na na na Municipal waste
/96 incinerator

66
 Thailand 1997 na na na 15 na na na

Australia 1998 na na na 37 na 31 - 42 na

Lake Baikal, 1997 na na na 73 na na na

Russia
Japan 1997 na na na 3700 42.8 na na
/98
Hong Kong 1996 na na na 6100 na 2500 - 8650 na
Brazil 1997 na na na 20 na na na

British 1997 na na na 460 na 49 -1900 na

Columbia,
Canada
Michigan, 1998 na na na 230 na 94 - 490 na
USA
Indiana, USA 1996 na na na 2000 na 1600 - 2400 na
Norway 1997 na na na 130 na na na

Spain 1996 na na na 315 na 130 - 500 na

United 1997 na na na 290 na 286-600 na

Kingdom
United 1990 na na na 4660/324 21 /19 na na
Kingdom
Germany 1996 na na na 649 na 647-650 na
/97
*na – not available

67
5. Conclusions:
1. Manual and automated extraction & clean up methods for the quantitative recoveries of
dioxins and furans in stack air, ash and waste dump yard soil/residue samples were
optimized as per specified methods ( 60 -120 % recovery for labelled congeners)

2. Emission factor of dioxins was determined using simulated burn hut experiments using 2
different types of waste (wet & dry). The typical composition of municipal solid wastes
in Thiruvananathapuram district as reported elsewhere was used for the study.

3. The emission factor of dioxins in air was found to be 5.1 µg PCDD/F TEQWHO/ton for wet
municipal solid waste composition with a moisture content of 67.8 %

4. The emission factor of dioxins in residual ash was found to be 41.9 & 27.52 µg PCDD/F
TEQWHO/ton for wet municipal solid waste composition with moisture content of 77.4 &
67.8 % respectively.

5. The emission factor of dioxins in air & residual ash was found to be 4.2 & 0.86 µg
PCDD/F TEQWHO/ton respectively for dry municipal solid waste composition having a
moisture content of 14.7 %.

6. A large decrease of dioxin levels in residual ash of dry waste combustion compared to
wet waste was observed. It indicates that moisture levels and poor combustion
conditions play a major role in enhancing dioxin formation. Further studies are ongoing
to understand this phenomenon.

7. The average annual emission of dioxins in Thiruvananthapuram city was calculated

assuming an average quantity of 100 tons of wastes is being openly burned. It is
calculated to be 0.19 g TEQ per annum to air and 1.27 g TEQ per annum to residual ash.

8. Our studies shows higher dioxin levels in the range 5.5 -17.8 pg WHO2005 PCDD/F- TEQ/g
(ppt) in the soil samples collected from open burning site at Attakulangara, Palayam and
Manacaud, Thiruvananthapuram. It is comparatively lesser than previous reported levels
in contaminated sites in Combodia, Philippines, Vietnam, Greece etc, whereas the levels
are higher than general soil in developed countries.

68
9. The congener specific distribution of dioxins and furans in simulated burn hut studies
reveals the predominant contribution of penta & tetra chlorinated dibenzodioxins &
furans to the total toxicity equivalence. Eventhough higher concentrations of octa and
hepta chlorinated congeners are present in all samples, the lower TEF value compared
to that of tetra & penta congeners results to their reduced contribution to total TEQ.

Further investigation is ongoing to understand the influence of various parameters such

as waste composition, air flow rates and temperature. All those results will be included
in the final report.

69
6. References

1. Development of a National Implementation Plan in India as a first step to Stockholm

convention on persistent organic pollutants (UNIDO project GF/IND/07/004), Government
of India, April, 2011

2. Toolkit for identification and quantification of releases of Dioxins, Furans and other
unintentional POPs under Article 5 of the Stockholm Convention, United Nations
Environmental Programme, January 2013

3. Development of a National Implementation Plan in India as a first step to Stockholm

convention on persistent organic pollutants (UNIDO project GF/IND/07/004),Final
Independent Evaluation, United Nations Industrial Development Organisation, Vienna,
November, 2011

4. Evaluation of emissions from the open burning of household waste in barrels, Volume
1.Technical Report, November 1997. Prepared by: Paul M. Lemieux, U.S Environmental
Protection Agency, National Risk Management Research Laboratory, Air Pollution
Prevention and Control Division, Research Triangle Park, NC 27711

5. Hazardous Chemicals from Open Burning of Waste in Developing Countries Final Report,
United Nations Environment Programme, Division of Division of Technology, Industry, and
Economics Chemicals Branch, June 2010.
6. USEPA Method 23: Determination of polychlorinated dibenzo-p-dioxins and
polychlorinated dibenzofurans from stationary sources
7. Methods and standard operating procedures (SOPs) of emission testing in hazardous
waste incinerator, Central Pollution Control Board, Parivesh Bhavan, East Arjun Nagar,
New Delhi.
8. Status of municipal solid waste generation in kerala and their characteristics Dr. R.
Ajaykumar Varma Executive Director, Suchitwa Mission

9. IS: 4894-1987, Indian standard specifications for centrifugal fans.

70
10. USEPA Method 8290: Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated
dibenzofurans (PCDFs) by high-resolution gas chromatography/high resolution mass
spectrometry (HRGC/HRMS)

11. Instructions for Supelco Multi-Layer Silica Gel Column and Dual-Layer Carbon Reversible
Column.
https://www.sigmaaldrich.com/content/dam/sigma aldrich/.../Supelco/.../t704007.pdf

12. EU regulations 2017/644 of 5 April 2017 laying down methods of sampling and analysis
for the control of levels of dioxins, dioxin-like PCBs and non-dioxin-like PCBs in certain
foodstuffs
13. Open Dumping Site in Asian Developing Countries: A Potential Source of Polychlorinated
Dibenzo-p-dioxins and Polychlorinated Dibenzofurans, Environmental Science &
Technology, 2013 ( 1=37) 1493- 1503.

71