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H2S and TRS Measurements – Continuous and Integrated Methods
Prepared by Sanjay Prasad, Yu-Mei Hsu, Michael Martineau, Kendra Thomas
Wood Buffalo Environmental Association
April 25, 2018
1. Background information
Hydrogen sulfide (H2S) is a colourless gas which has the odour of rotten eggs. H2S is considered
an odour nuisance at low levels, and can result in discomforting physiological symptoms of
headache and nausea. Total Reduced Sulfur (TRS) is a collection of H2S and a number of other
sulfur compounds (e.g Carbonyl Sulphide (COS), Carbon Disulphide (CS2) and Methyl
Mercaptan (CH3SH)). The current Alberta Ambient Air Quality Objectives for H2S are:
1-hour average of 14 μg m-3 (or 10 ppb)
24-hour average of 4 μg m-3 (or 3 ppb).
The principle of operation accepted by the Alberta Air Monitoring Directive (AMD) for
continuous ambient air H2S and TRS monitoring methods is Ultraviolet (UV) pulsed
fluorescence: H2S and TRS analyzers are basically Sulfur dioxide (SO2) analyzers with a SO2
scrubber and a converter to convert either H2S or TRS to SO2 for analysis. Some analyzers are
capable of cycling between SO2, H2S, and TRS measurements by switching between sample
pathways with and without SO2 scrubbers and converters. After sulfur compounds are converted,
the SO2 is measured proportional to UV absorption and fluorescence, which is related back to the
H2S or TRS concentration for detection and reporting (USEPA 2017).
2. Current Method for Continuous Measurements
The common method used for a continuous ambient H2S or TRS monitor is based on UV pulsed
fluorescence which is also required by the Alberta AMD (Alberta Environment and Parks 2017).
2.1 Principle of the Method
H2S/TRS is measured using thermal oxidation to convert H2S or TRS molecules to SO2 and the
converted SO2 molecules are then analyzed using continuous fluorescent SO2 analyzers.
H2S
H2S molecules will be oxidized to SO2 in the presence of Oxygen and heat. This is accomplished
by diverting the sample flow through the H2S converter, after a scrubber is used to remove
hydrocarbons. The converter has a stainless-steel body heated to at least 320 °C. Prior to the
converter, the sample flow passes through a scrubber to remove all SO2, and to allow only the
H2S molecules to pass through and enter the H2S converter. The H2S molecules are then
converted to SO2 as Equation 1.
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H2S + O2 + heat → SO2 + H2O Equation 1
The converted SO2 molecules then return to the standard SO2 analyzer for detection and are
reported as H2S (Alberta Environment and Parks 2011a, Alberta Environment and Parks 2011b).
TRS
TRS compounds include a variety of airborne compounds which contain Sulfur. Some of the
common compounds found in Alberta are: Carbonyl Sulphide (COS), Carbon Disulphide (CS2)
and Methyl Mercaptan (CH3SH). Similar to H2S, TRS molecules will be oxidized to SO2 in the
presence of Oxygen and heat. The difference between H2S and TRS is the TRS conversion
requires a higher temperature. This is accomplished by diverting the sample flow through a TRS
converter, after the flow has passed through the hydrocarbon scrubber. The TRS converter is a
Quartz tube heated to a minimum of 800 °C. Prior to the converter, the sample flow must pass
through a scrubber to remove all SO2, and to allow only the TRS molecules to pass through to
enter the TRS converter. The TRS molecules are then converted to SO2 as Equation 2.
TRS + O2 + heat → SO2 + H2O Equation 2
The converted SO2 molecules then return to the standard SO2 analyzer for detection and are reported as
TRS (Alberta Environment and Parks 2011a, Alberta Environment and Parks 2011b).
The primary detection principle utilized in SO2 analyzers is UV fluorescence. Where a valence
electron absorbs UV at a wavelength of 214 nm and enters an excited state (*). When the
electron drops back into its usual state, a photon is emitted at a lower energy wavelength of 390
nm as Equation 3.
SO2 + hv1 → SO2* → SO2 + hv2 Equation 3
* = Excited State
hv1 = Exposure Light at 214 nm
hv2 = Emitted Light at 390 nm
The light emitted by the decaying SO2 electrons is filtered and channeled into a photo multiplier
tube and amplified and converted to an electrical signal (Alberta Environment and Parks 2011c).
2.2 Operations/Diagram
The continuous H2S/TRS monitor measures H2S/TRS concentrations in ambient air by thermal
conversion of H2S/TRS to SO2 with a molybdenum catalytic converter and UV fluorescence of
the SO2 gas (Sumner et al. 2005). H2S measurements are made using a low temperature
converter operating typically between 300 to 350 °C. For TRS measurements, the conversion of
sulfur compounds to SO2 occurs at a much higher temperature typically between 800 and 1000
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°C. To maximize converter performance, it is important to operate the analyzers with converters
in the appropriate temperature ranges as specified by manufacturers (Alberta Environment and
Parks 2017).
Figure 1 illustrates a pneumatic diagram of Teledyne Instruments T101 H2S Analyzer. The air
sample is drawn into the monitor through the sample gas inlet and then flows through a sample
filter and a hydrocarbon scrubber (hydrocarbon kicker) to remove particles and hydrocarbons,
respectively, from the air sample. A H2S/SO2 mode valve is used to control the air flow for SO2
measurement or H2S measurement (Table 1).
The air sample then flows into the sample chamber, where pulsating UV Light excites the SO2
molecules. The condensing lens focuses the pulsating UV light into the mirror assembly. The
mirror assembly contains four selective mirrors that reflect only the wavelengths which excite
SO2 molecules. As the excited SO2 molecules decay to lower energy states they emit UV light
that is proportional to the SO2 concentration. The bandpass filter allows only the wavelengths
emitted by the excited SO2 molecules to reach the photomultiplier tube (PMT). The PMT detects
the UV light emission from the decaying SO2 molecules (Thermo Scientific 2015).
Figure 1. Pneumatic Diagram of Teledyne Instruments T101 Analyzer (Adapted from Teledyne
Monitor Labs (2016))
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Table 1. H2S – SO2 Switching Valve Operating States (Adapted from Teledyne Monitor Labs
(2016))
GAS MODE CONDITION OF H2S –SO2 SWITCHING
VALVE
VALVE PORT
CONNECTION
H2S Open to SO2 Scrubber and Molybdenum
Converter COM → NO
SO2 Open to directly to Sample Chamber. Bypasses
SO2 Scrubber and Molybdenum Converter COM → NC
H2S –SO2 Switches between above two states every 10
minutes.
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2.3 Interferences
It should be noted the Ultraviolet (UV) pulsed fluorescence method for measuring H2S/TRS is
subject to interference from a number of sources, including SO2, hydrocarbons (Luke 1997) and
other species which absorb at about 190 - 230 nm and fluoresces at 340 - 410 nm. Obviously,
since the analyzer measures H2S by converting it to SO2, the most significant interfering gas for
this measurement would be ambient SO2 which is present in the sample gas. A SO2 chemical
scrubber is applied to remove SO2 from the sample gas before the H2S → SO2 conversion takes
place.
The second most common source of interference is from other gases which fluoresce in a similar
fashion to SO2 when exposed to UV Light. The most significant of these gases is a class of
hydrocarbons called aromatic hydrocarbons (Luke 1997) of which xylene and naphthalene are
two prominent examples. A hydrocarbon scrubber (kicker) mechanism removes aromatic
hydrocarbons present in the sample gas before it the reaches the sample chamber.
Because ozone absorbs UV Light over a relatively broad spectrum it could cause a measurement
offset by absorbing some of the UV given off by the decaying SO2* (* = excited state) in the
sample chamber. This can be prevented from occurring by having a very short light path between
the area where the SO2* fluorescence occurs and the PMT detector (Teledyne Monitor Labs
2016).
While the decay of SO2* to SO2 happens quickly, it is not instantaneous. Since it is not
instantaneous, it is possible for the extra energy possessed by the excited electron of the SO2*
molecule to be given off as kinetic energy during a collision with another molecule. This
process, in effect, heats the other molecule slightly and allows the excited electron to move into a
lower energy orbit without emitting a photon. The most significant interferents in this regard are
nitric oxide (NO), carbon dioxide (CO2), water vapor (H2O) and molecular oxygen (O2). In
ambient applications the quenching effect of these gases is negligible (Teledyne Monitor Labs
2016).
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To monitor H2S/TRS concentrations in ambient air, the H2S/TRS is oxidized to SO2 by a
Molybdenum converter. However, the converter unit does not oxidize all H2S/TRS to SO2, rather
it uses a conversion efficiency determined by the manufacturer. The conversion efficiency varies
from instrument to instrument, and is typically above 80% (Bluhme et al. 2016).
Sumner et al. (2005) have assessed the effect of potential interferant gases (Table 2) on the
response of the SO2 analyzer ( Teledyne Model 101E) with seven (7) gases in zero air and a 100-
ppb H2S standard. No interference effect was observed in the Model 101E response to SO2, a
blend of C1 to C6 alkanes, and ammonia. The Model 101E showed an interference effect for
carbonyl sulfide in zero air of 20% and in 100-ppb H2S of 6%. Carbon disulfide resulted in an
interference effect of 6% in zero air and 9% in the 100-ppb H2S matrix. The interference effect
of methyl mercaptan on the Model 101E was 33% in both zero air and 100-ppb H2S. Dimethyl
sulfide resulted in a 12% interference effect in both matrices.
Table 2. Interference Effect Evaluation (adapted from Sumner et al. (2005))
Interferant Approximate
concentration (ppb)
Interference Effect (%)
Zero Air Matrix 100-ppb H2S Matrix
Sulfur dioxide 100 0 0
Carbonyl sulfide 100 20 6
Carbon disulfide 100 6 9
Methyl mercaptan 100 33 33
Dimethyl sulfide 100 12 12
Hydrocarbon blend 500 (total) 0 0
Ammonia 500 0 0
3. Designations – US, Australia, New Zealand, Europe
H2S or TRS are not criteria pollutants in the United States of America, therefore the United
States Environmental Protection Agency (USEPA) does not have a Federal Reference Method
(FRM) for H2S or TRS (USEPA 2017).
4. AMD and Manufacturer Performance Specifications
In Alberta, as required by the Alberta AMD, Chapter 4: Monitoring Requirements and
Equipment Technical Specifications, the operating principle for measurement of H2S and TRS is
UV pulsed fluorescence. The minimum performance specifications required by the AMD are
listed in Table 3. The manufacturer performance specifications of two analyzers including
Teledyne T101 and Thermo Scientific Model 450i are listed in Table 4 and Table 5, respectively.
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Table 3. Alberta AMD performance specifications for H2S and TRS continuous analyzers
(adapted from Alberta Environment and Parks (2017))
Criteria Performance Specification
Required Operating Range* (Full Scale): 0.1 ppm, 0.5 ppm or 1.0 ppm
Zero Noise: 0.5 ppb RMS
Lower Detection Limit: 1.0 ppb
Zero Drift (24-hr): 1.0 ppb
Span Drift (24-hr) 1% of full scale
Linearity: 1% of full scale
Precision: 1.0 ppb or 1% of reading
Rise time: Maximum of 120 seconds
Fall time: Maximum of 120 seconds * The typical operating range is 0.1 ppm with 0.5 ppm and 1.0 ppm used in unique circumstances such as
emergency monitoring. RMS is the root mean square of differences.
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Table 4. Teledyne Model T101 Basic Unit Specifications (adapted from Teledyne Monitor Labs
(2016))
Parameter Description
Ranges
H2S: Min 0-50 ppb Full scale; Max 0-10 ppm Full scale
SO2: Up to 0-20 ppm Full scale
(selectable, independent ranges and auto ranging supported)
Measurement units ppb, ppm, µg/m3, mg/m3 (selectable)
Zero Noise
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Table 5. Thermo Scientific Model 450i Specifications (adapted from Thermo Scientific (2018))
Parameter Description
Preset Ranges
0-0.05, 0.1, 0.2, 0.5, 1, 2, 5, and 10 ppm,
0-0.2, 0.5, 1, 2, 5, 10, 20, and 25 mg/m3
Extended Ranges
0-0.5, 1, 2, 5, 10, 20, 50, and 100 ppm,
0-2, 5, 10, 20, 50, 100, 200, and 250 mg/m3
Custom Ranges 0-0.05 to 100 ppm, 0-0.2 to 250 mg/m3
Zero Noise
Manual SO2 or
Combine Sulfur
Automatic mode
SO2 or H2S
1.0 ppb 3.0 ppb (10 second averaging time)
0.5 ppb 1.5 ppb (60 second averaging time)
0.25 ppb 0.75 ppb (300 second averaging time)
Lower Detectable
Limit
Manual SO2 or
Combine Sulfur
Automatic mode
SO2 or H2S
2.0 ppb 6.0 ppb (10 second averaging time)
1.0 ppb 2.0 ppb (60 second averaging time)
0.5 ppb 1.5 ppb (300 second averaging time)
Zero Drift (24 hour) Less than 1 ppb
Span drift (24 hour) ± 1% Full Scale
Response Time 80 seconds (10 second average time)
110 seconds (60 second average time)
320 seconds (300 seconds average time)
Precision 1% of reading or 1 ppb (whichever is greater)
Linearity ±1% full scale 80% H2S to SO2 (Note: Various other Sulfur compounds can be converted
at varying %)
Operating
Temperature 20⁰C to 30⁰C
Power Requirements 100 VAC, 115 VAC, 220-240 VAC ±10% @ 300W
Size and Weight 16.75"(W) x 8.62"(H) x 23"(D), 48 lbs. (21.8 kg)
Outputs
Selectable Voltage, RS232/RS485, TCP/IP, 10 Status Relays, and Power
Fail Indication (standard). 0-20 or 4-20 mA Isolated Current Output
(optional)
Inputs 16 Digital Inputs (standard), 8 0-10 Vdc Analog Inputs (optional)
Available Options Teflon particulate filter, Rack mounts, Rear extenders
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5. Other Methods for H2S and RSC Measurements
Both passive and active measurements have been developed for H2S and Reduced Sulfur
Compounds (RSCs) measurements. A general outline of the analytical protocols commonly
employed in RSC analysis is illustrated in Figure 2.
Figure 2. General protocols of Reduced Sulfur Compounds (RSCs) analysis in air matrices. The
abbreviations used in figure are as follows: LC-AFS = liquid chromatography-atomic
fluorescence spectrometer, IC = ion-chromatography, SPME = solid phase microextraction, FPD
= flame photometric detector, PFPD = pulsed flame photometric detector, MS = mass
spectrometer, AED = atomic emission detector, SCD = sulfur chemiluminescence detector, and
TD = thermal desorber. (adapted from Pandey and Kim (2009).)
5.1 H2S Passive Measurement
Many H2S passive samplers are made commercially available (Shooter et al. 1995, Tang et al.
2002, Venturi et al. 2016) for the remote locations with no power accesses. The H2S passive
collection media are coated with chemicals (e.g., Silver nitrate, zinc acetate) to collect H2S for
sample analysis (Tang et al. 2002, Pavilonis et al. 2013).
Sampling stage Preconcentration stageDetection stage
(Detector type)
LC-AFS
IC
Conductomery
Potentiometry
Coulometry
Voltametry
FPD
PFPD
MS
AED
SCD
Bag or Canister
Non-GC methods
GC method
Alkaline aqueous Phase
Diffusion scrubbers
SPME
Tube
TD
Cryogenic trappingSolid sorbentsSorption on metal
surfaces
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5.2 Gas Chromatograph (GC) Methods
For RSC analysis in the air, the gas chromatography (GC) technique has been and is the most
common methodology because of its excellent separation capability and quantitative recovery
(Helmig 1999, Willig et al. 2004). The GC-based analysis commonly involves a sample
collection stage, injection, and separation on a chromatographic column. The final detection can
then be carried out through various Sulfur-selective (or universal) detectors.
Direct chromatographic analysis or direct injection (DI) of RSCs into a GC injector is highly
recommended when the concentration of samples is in the detectable range of a given GC-setup.
The use of the DI method can reduce possible loss (or gain) due to contact with different surface
types, and reduces analysis time by eliminating time-consuming procedures such as
supplementary sample treatments by which contamination or loss of analytes can occur (Kim
2006, Pandey and Kim 2008, Pandey and Kim 2009). However, the application of the DI
approach is often limited, as most detectors of the GC method are not sensitive enough to cover
ambient samples which are typically below a few ppb in concentration. Therefore, research has
sought to improve and develop GC methods based on Sulfur-specific detectors, including
electron capture detector (ECD), flame photometric detector (FPD), pulsed flame photometric
detector (PFPD), sulfur chemiluminescence detector (SCD), atomic emission detection (AED),
Hall electrical conductivity detector (HECD), and photo ionization detector (PID) with combined
application of a mass spectrometer (MS) and GC system (Nielsen and Jonsson 2002, Dincer et
al. 2006, Oostdijk et al. 2007, Ras et al. 2008). USEPA CFR Promulgated Test Method 15
(USEPA 2017) has employed an online GC-FPD method for monitoring hydrogen sulfide,
carbonyl sulfide, and carbon disulfide emissions from stationary sources
To allow the analysis of increasingly smaller quantities of target compounds, the range of
instrumental detectability needs to be improved. As a means to extend the detectability of a given
GC system, one can increase the total amount of analytes injected by adopting some
preconcentration (or sample enrichment) stages: (1) sorption on certain metal surfaces (Braman
et al. 1978, Barnard et al. 1982, Ferek et al. 1986), (2) sorption on solid adsorbents (Maier and
Fieber 1988, Sunesson et al. 1995, Inomata et al. 1999), and (3) cryogenic trapping (Kim 2005,
Kim 2005, Ras et al. 2008, Pandey and Kim 2009). However, the analysis of low-level sulfur
species through such modifications can be subject to positive blanks (e.g., memory effect) or
sorptive loss in the chromatographic system (Sulyok et al. 2001, Sulyok et al. 2002).
Sampling and Preconcentration Strategies. RSCs from air can be collected in vessels such as
glass bulbs, canister bags, polymer bags, and Tedlar film bags. Considering the highly reactive
nature of Sulfur compounds, the sampling vessels should be inert enough to reduce adsorptive
loss (Sulyok et al. 2001). Moreover, careful attention should be given to tubing and connecting
materials used for the sampling of Sulfur compounds. The reason for this is certain materials
can act as significant sources of bias in the determination of RSC concentrations (Sulyok et al.
2001, Sulyok et al. 2002, Kim et al. 2006, Winkel and Tangerman 2008).
ASTM Method D5504-01(ASTM International 2001) use
canister samples for H2S collection
and require samples to be analyzed by GC-PFPD or GC-SCD within 24 hours. ASTM Method
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D5504-01 has been demonstrated that H2S in passivated canisters does not degrade over 24
hours; therefore, detailed holding time tests are not necessary. However, the acceptability of
this holding time should be verified by analyzing an ambient air sample several times over the
period (at least 24 hours) following sample collection. The H2S concentration at 24 hours
following sample collection should be within 15% of the initial measured value (ASTM
International 2001, Battelle 2005).
A major difficulty in the sampling of RSCs is interference caused by atmospheric oxidants such
as SO2, ozone, and NOx. To help overcome these difficulties, many substances were developed
as scrubbers, including PTFE, Tygon, glass fiber filters, chromosorb, anakrom, and glass beads
with a coating of chemicals (ex., Na2CO3, MnO2, KOH, and NaOH) (Braman et al. 1978,
Andreae et al. 1985, Saltzman and Cooper 1988, Bates et al. 1990, Ayers et al. 1991, Kittler et
al. 1992, Watanabe et al. 1995).
Another considerable difficulty in determining RSCs is relative humidity. Water significantly
lowers the capacity of adsorbents and can clog cryogenic traps (Haberhauer-Troyer et al. 1999).
Moreover, it can cause baseline perturbations and retention time-shifts in chromatography to
deteriorate detection (Haberhauer-Troyer et al. 1999). To overcome the humidity problem, a
number of approaches have been developed by applying dryers (Juhani and Hannu 1988,
Hofmann et al. 1992, Haberhauer-Troyer et al. 1999).
Sorption on Metal Surfaces. The extent of RSC sorption can be affected greatly by the type of
metals (mainly gold, palladium, and platinum) used for such a reaction (Braman et al. 1978,
Barnard et al. 1982, Ferek et al. 1986, Kagel and Farwell 1986). These metallic materials are
also found in modified forms such as glass or quartz tubes filled with gold wool, gold plated
sand, or metal foils (Braman et al. 1978, Ferek et al. 1986, Davison and Allen 1994, Swan and
Ivey 1994, Davison et al. 1996, Curran et al. 1998).
Sorption on Solid Sorbents. Solid sorbent surfaces are regarded as the most general tools for
the preconcentration of volatile species, e.g., activated charcoal, silica gel, aluminum oxide,
graphitized carbon black, molecular sieves, and porous sorbents (Davison et al. 1996, Wylie
and Mora 1996, Lewis et al. 1997, De Bruyn et al. 1998). Porous sorbents, such as Tenax have
been the most popular choice for Sulfur species (Pio et al. 1996, De Bruyn et al. 1998, Ras et al.
2008), but the breakthrough volume of Tenax is not altered by changes in humidity because of
its hydrophobic property (Steinhanses and Schoene 1990). The trapping efficiency of Tenax
tubes is often limited for organosulfur compounds with low boiling points (Tangerman 1986,
Shooter et al. 1992). The capacity of a sorbent can increase significantly by adding a
cryofocusing system (Kroupa et al. 2004). Many studies have been carried out to determine the
affinity and/or breakthrough volume of different sorbents (Przyjazny 1985, Devai and Delaune
1996, Devai and DeLaune 1997) for the adsorption capacity. The application of various solid
sorbents (i.e., silica gel, molecular sieve, and Carbosieve SIII) has been validated by
measurements of RSC concentrations or fluxes under various environmental settings (Delaune
et al. 2002).
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Cryogenic Trapping. Trapping efficiency of adsorbent traps increases exponentially with a
decrease in temperature (Pollmann et al. 2006). The cryogenic trapping technique can increase
the capacity of sorptive materials effectively. The cryogenic traps (i.e., sampling loops) are
generally composed of PTFE, borosilicate glass, and quartz tubes (Wardencki 1998). For
sampling of RSCs, the cryogenic traps are normally immersed in a strong cryogen such as
liquid nitrogen or in liquid argon (Simo et al. 1993). Cryogenic traps can also be used with a
number of sorbents as packing materials to increase sorption efficiency. Commonly used
packing materials include glass-fiber wool, glass beads, Tenax, Porapack Q, activated carbon,
and carbopack. Based on the technique of cryogenic trapping, and GC-PHD, an automated
Sulfur instrument was developed to analyze RSCs continuously (Von Hobe et al. 2008).
Solid-Phase Microextraction (SPME). The solid-phase microextraction (SPME) method, a
potential solvent-free sample preparation technique, allows a single-step treatment for
sampling, isolation, and enrichment (Xiong et al. 2003, Ouyang and Pawliszyn 2006, Ouyang
and Pawliszyn 2006, Demeestere et al. 2007). For air matrices, the SPME fiber can be used to
extract analytes either by direct exposure to raw samples or by the use of the headspace method
on pretreated samples (Arthur and Pawliszyn 1990, Li et al. 2001, Ouyang and Pawliszyn
2006).
In addition to GC methods, there are alternative methods which include liquid chromatograph
(LC), ion chromatograph (IC), and sensor-based methods. The reliability of these alternative
methods for practical application of real environmental samples has not been sufficiently
researched. Methodologies for online monitoring at ambient concentration levels would help
overcome the time-consuming and tedious processes of sampling, enrichment, and offline
analytical protocols in the laboratory (Pandey and Kim 2009).
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6. References
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