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Benzene, Toluene, Ethyl Benzene and Xylene (BTEX) are the volatile

components commonly associated with petroleum products. Benzene, toluene and


xylenes are found naturally in petroleum products like crude oil, diesel fuel and gasoline.
Ethylbenzene is a gasoline and aviation fuel additive. The term BTEX reflects that
benzene, toluene, ethylbenzene and xylenes are often found together at contaminated
sites. Because they are all highly toxic and soluble in water, they represent a significant
hazard for humans.The main source of BTEX contamination is the leakage of gasoline
from faulty and poorly maintained underground storage tanks. They are considered one of
the major causes of environmental pollution because of widespread occurrences of
leakage from underground petroleum storage tanks and spills at petroleum production
wells, refineries, pipelines, and distribution terminals.

Because of the high concentration of BTEX compounds in petroleum and the


massive use of petroleum products as energy source, as solvents and in the production of
other organic chemicals, their presence in water creates a hazard to public health and the
environment. Contamination of groundwater with the BTEX compounds is difficult to
remedy because these compounds are relatively soluble in water and can diffuse rapidly
once introduced into an aquifer.

Advanced detection methods of BTEX contamination are being developed


nowadays. This paper describes one of the advanced methods namely Detection using
microchip induced laser fluorescence (LIF). It is a very compact system and can be used
to detect contamination in both soil and water. Thus even though one of the BTEX
compounds (ethylbenzene) cannot be detected by this method, it is most commonly used.

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BTEX is the abbreviation used for four compounds found in petroleum products.
The compounds are benzene, toluene, ethylbenzene and xylenes. These organic chemicals
make up a significant percentage of petroleum products like crude oil, diesel, gasoline
etc. Ethylbenzene is a gasoline and aviation fuel additive. They are also used extensively
in manufacturing processes. is used in the production of synthetic materials and
consumer products, such as synthetic rubber, plastics, nylon, insecticides and paints. is
used as a solvent for paints, coatings, gums, oils and resins. may be present in consumer
products such as paints, inks, plastics and pesticides. are used as a solvent in printing,
rubber and leather industries.

The BTEX chemicals are present in a standard gasoline blend in approximately


18%(w/w), and the group is considered to be the largest one that is related to any health
hazards. Naphthalenes make up only 1%(w/w) of gasoline. Benzene, which is recognized
as the most toxic compound among BTEX, represents 11%, toluene represents 26%,
ethylbenzene 11% and xylene 52% of the total BTEX fraction in gasoline.

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BTEX contamination of soil and groundwater can occur by the accidental spill of
gasoline, diesel fuel and leakage from underground storage tanks in pumping stations.
Once released to the environment, BTEX can volatilize, dissolve, attach to soil particles
or degrade biologically. Volatilization occurs when chemicals evaporate, allowing them to
move from a liquid into the air. Volatilization of the BTEX components of gasoline
commonly occurs when you pump gasoline into your car, and is responsible for the
characteristic odour. This phenomenon can also occur within the air pockets present in
soils. BTEX can also dissolve into water, allowing it to move in the groundwater. Since
BTEX can "stick" to soil particles, these chemicals move slower than the groundwater.
BTEX can also dissolve into water, allowing it to move in the ground water. Because of
their polarity and very soluble characteristics, BTEX will be able to enter the soil and
groundwater systems and cause serious pollution problems. If oxygen is present in
sufficient quantities, BTEX can also degrade biologically, though very slowly.

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Exposure to BTEX can occur by ingestion, inhalation or absorption through the
skin. Inhalation of BTEX can occur while pumping gasoline or while showering or
bathing with contaminated water. Absorption of these chemicals can occur by spilling
gasoline onto one's skin or by bathing in contaminated water. Acute exposures to high
levels of gasoline and its BTEX components have been associated with skin and sensory
irritation, central nervous system depression and effects on the respiratory system. These
levels are not likely to be achievable from drinking contaminated water, but are more
likely from occupational exposures. Prolonged exposure to these compounds has similar
effects, as well as the kidney, liver and blood systems. According to the U.S.
Environmental Protection Agency (U.S. EPA), there is sufficient evidence from both
human and animal studies to believe that benzene is a human carcinogen. Workers
exposed to high levels of benzene in occupational settings were found to have an increase
incidence in leukaemia.

The U.S. EPA has established permissible levels for chemical contaminants in
drinking water supplied by public water systems. These levels are called Maximum
Contaminant Levels (MCLs). To derive these MCLs, the US EPA uses a number of
conservative assumptions, thereby ensuring adequate protection of the public The MCL is
set so that a lifetime exposure to the contaminant at the MCL concentration would result
in no more than 1 to 100 (depending on the chemical) excess cases of cancer per million
people exposed.

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The U.S. EPA recommends that exposure to BTEX be minimized. To avoid
or reduce exposure to BTEX, people should use water supplies having
concentrations of these compounds that are below the MCL or apply appropriate
water treatment or filtration systems. If necessary, short-term reductions in
exposure may be accomplished by using bottled water for food and beverage
preparation and avoiding bathing or showering with the contaminated water. With
in-home treatment processes, such as activated charcoal filtration, it is usually
possible to remove sufficient BTEX from water to meet the MCL and thereby
minimize health risks. If benzene is present above the MCL, treatment should be
applied to all household water because of inhalation hazards.

Since the BTEX compounds are very toxic to humans and aquatic life, their
sensitive and rapid determination is of critical importance. There are lots of established
methods for determining BTEX contaminants in water namely liquid-liquid extraction,

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solid phase extraction, gas chromatography, air stripping etc. But these methods exhibit
high levels of sensitivity and selectivity. So they require well-trained personnel for its
successful operation. If a small error occurs during sampling, the analytical result
obtained using the best instrument will be inevitably wrong. Most existing methods for
detecting BTEX are time-consuming, complicated and very expensive for routine
screening. Also these methods require skill for its operation. There has been a lot of
development in this area recently and many advanced techniques for the detection of
BTEX contaminations have been developed. The use of lasers and optic fibres are some
among them.

Three advanced techniques of detection of BTEX contamination are:


1. Raman Dipstick method
2. Bioassay method
3. Detection using Microchip Induced Fluorescence Sensor

Raman dipstick method is the detection of BTEX contamination using long path
length fibre optic Raman dipstick. Determination of BTEX components via optical
remote sensing is attractive because eliminates many of the problems in other established
methods. Samples are interrogated through the long-path length ‘dip-stick’. It is directly
inserted into the liquid of interest or an extension hose is attached to the end of the ‘dip-
stick’, providing a low profile and more flexible means of sample interrogation. Fibre-
optic spectroscopic techniques used for detection include visible absorption, infrared
absorption, fluorescence and Raman spectroscopy. Of these techniques,

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Raman spectroscopy is particularly strong candidate for detecting BTEX analytes in
water because it offers a high degree of selectivity and is compatible with aqueous
matrices. Even though this method is very simple and cheaper, practically a lot of
problems are there. Turbidity of the sample could block collection of Raman scattering
from the sample. Also the presence of interfering compounds can lead to diminished
sensitivity. If the interfering compounds are fluorescent it will mask Raman signals.

Detection of BTEX compounds using Toluene Dioygenese peroxide coupling


reaction is called bioassay method. It is simple, sensitive, whole-cell-based bioassay
system for detection of bio-available BTEX compounds based on a method developed for
screening of oxygenese activity. This bioassay system requires no sophisticated
instruments and exquisite techniques. The bioassay has long term storage stability so that
it can be used for field monitoring of BTEX compounds and its tracking in contaminated
water. The convenience of multiple sample-handling makes this whole cell assay an
attractive candidate to be developed as a field diagnostic method for on-site BTEX
contamination.

The Laser-Induced Fluorescence (LIF) method takes advantage of both time and
wavelength information to investigate the contamination of BTX compounds in soil and
water. This method is studied in detail in the next chapter.

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Most organic molecules when excited with ultra rays re emit less energetic optical
radiation. This emitted radiation is known as fluorescence and is characterized by its
intensity as a function of both time and wavelength. Since this information is linked to
the physical characteristics of an individual molecular species, it provides a powerful
means to perform chemical analyses. By the observation of wavelength and time we can
detect, identify and quantify the chemical species within an aqueous solution.

The Laser-Induced Fluorescence (LIF) takes advantage of both time and


wavelength information to investigate the contamination of BTX compounds in soil and
water. The device provides excitation using a passively Q-switched microlaser pumped
by fibre-coupled near-infrared diode laser and generates short pulses of 266nm radiation
at a repetition rate near 10 kHz. The microchip laser focusing optics and collection
system are very compact and the entire assembly can be placed in a monitoring well or
contained within the shaft of a cone penetrometer. Thus the UV radiation necessary to
excite fluorescence in environmental pollutants such as gasoline is generated at the point
of contamination while the infrared diode pump laser remains above the ground. This
configuration takes advantage of the excellent transmission of infrared energy through
fibre optics cable and minimizes the ultraviolet attenuation.

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This is a case study done by Bloch. J, Germaine J.T, Hemond H.F and
Johnson.B.Sinfield.

The experimental apparatus used to evaluate the performance of the LIF probe
includes spectroscopic hardware, a test cell and a data acquisition system.

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The microchip laser is pumped by a 1 W continuous wave 808nm diode laser
through a fibre optic cable. The microchip laser is mounted in the probe using a threaded
fitting that contains a sapphire window and an UV silica focusing optic. This laser is
passively Q-switched and provides 200ps pulses of 1064nm light at a repetition rate of
approximately 10 kHz. After two stages of frequency doubling and subsequent filtering to
remove 1064 and 532nm lights, a fourth harmonic is generated in the UV at 266nm
which is focused just outside the probe’s sapphire window. Molecular fluorescence
excited by the UV microchip laser is imaged through the same window onto the tip of a
550µm diameter silica return fibre. The output of the fibre is focused on the entrance slit
of a 1/8m scanning monochromator.

A fast photomultiplier tube (PMT) is used to detect light intensity at the exit slit of
the monochromator. A trigger signal is generated using an UV silica beam splitter
mounted within the monochromator to direct a small fraction of the light entering the
spectrometer on to a second PMT. The PMTs are operated at approximately 800 V.

The test cell employed in the laboratory experiments is used to simulate


immersion of the probe in a liquid. The cell consists of a rectangular stainless-steel block
clamp that is placed around the probe. The test sample is placed in a cylindrical hole in
the clamp located directly above the laser output window of the probe. The hole contains
approximately 1.5cm3 of sample solution, although only a small fraction of this volume is
actually interrogated by the laser. Sample loss around the probe/clamp interface is
prevented using a Teflon gasket. Volatilization is prevented by a stainless steel cap fitted
with a fluorocarbon rubber o-ring.

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A 1.5 GHz digital storage oscilloscope is used as a fast analog-to-digital converter
to acquire fluorescence signals at a sampling rate of 5 giga-samples per second for a
period of 50ns referenced to the trigger; 500 traces are typically averaged for each
measurement. The PMT output signal is measured across a 50Ω load. A personal
computer is used to control the monochromator grating and the oscilloscope.

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Test solutions were prepared by dilution of stock solutions, which comprised
distilled demineralised water maintained in equilibrium with reagent-grade compounds.
During each test, a volume of the desired sample was sealed in the test cell with zero
headspace. This procedure minimized loss by leakage or volatilization throughout the
duration of a LIF test. Fresh solutions were used for each test. In addition, blanks of
distilled demineralised water were measured whenever test solutions were changed, to
demonstrate that no residual contamination remained in the test cell.

A series of tests were performed to determine the sensor’s sensitivity to BTX


compounds and its time-response. Each test involved recording the time-dependent
fluorescence spectrum (from 275 to 350nm) of one of the BTX compounds at a particular
concentration in water. The spectra from each test were analyzed to determine:

1. The total fluorescence signal gathered from the test medium


2. The fluorescence lifetime of the compound in solution
3. The wavelength of the peak fluorescence emission
4. The peak fluorescence intensity

The total fluorescence signal was determined by integrating over time and
wavelength using trapezoidal integration; results are presented in arbitrary units. Absolute
signal amplitudes were typically on the order of 101mV at the oscilloscope input for peak
concentration levels. A plot of the fluorescence signal, integrated in time, versus emission
wavelength is referred to as an emission wavelength spectrum.

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A plot of fluorescence signal versus time, at any individual emission wavelength, is
termed as an intensity-time trace. The collection of all of the information available from a
fluorescence test, in terms of both the time and wavelength, can be presented in a three-
dimensional plot referred to as a wavelength-time-intensity (WTI) profile. The peak
fluorescence signal is defined as the highest intensity observed at any wavelength.
Further, the total fluorescence signal is the volume under the WTI profile.

Each compound has different fluorescence lifetime. Over the majority of the
concentration ranges, each compound is having a linear relationship among the peak
signal, the total fluorescence signal and the concentration of a compound in solution. The
slopes of the lines relating compound concentration to either peak signal (the highest
intensity observed at any wavelength) or total fluorescence signal (volume under the WTI
profile) differ among the three compounds.

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The fluorescence-to-concentration relationship, essentially a calibration factor,
varies among compounds for two reasons. First, the UV absorptivity varies for different
compounds. Under equivalent conditions, a solution of benzene, for example, absorbs an

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order of magnitude less at 266 nm than does an equimolar concentration of xylene.
Second, the quantum yield (ratio of the number of emitted photons to absorbed photons)
also differs among compounds. The quantum yield of benzene, for example, is less than
one-third of that for o-xylene.

Detection of the presence of a contaminant relative to a baseline or background is


the least challenging operation for a sensor. To achieve this goal the sensor need only
reliably indicate the presence of a signal in excess of the "uncontaminated" background.
The criterion for the detection of a compound was defined to be a minimum signal level
of approximately three times the standard deviation of the background. Assuming that the
random noise component of the background, which cannot be effectively subtracted from
the fluorescence signature, can be characterized by a normal distribution, the three times
standard deviation criterion should include approximately 99.9% of the noise. Thus any
signal above this threshold could reasonably be interpreted as the product of
fluorescence. The background associated with this LIF system was evaluated from ten
full-spectrum scans of water blanks. The ten background scans has to be carried out on
different days over a period of 3 months. The standard deviation of the background signal
can be found out. The corresponding detection limits for benzene, toluene and o-xylene
can be calculated. These values were obtained by dividing the three times standard
deviation minimum required signal level by the slope of the plot relating peak
fluorescence signal to aqueous concentration for each of the BTX compounds.

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Even though we can detect the presence of various BTEX compounds in water,
the LIF can detect only Toluene and Xylene effectively. Benzene is notably more
challenging top detect while Ethyl benzene cannot be detect at all. The LIF sensor can
accurately measure fluorescence lifetimes as short as 2.5 ns. Also there is a clear straight-
line relationship between contaminant concentration and observed fluorescence intensity
that can be used to calibrate the LIF sensor for quantitative analyses over
environmentally relevant concentration ranges. It is recognized that the performance of
the LIF sensor will degrade in natural environments involving contaminant mixtures and
non aqueous media.

These experiments also highlight that the capabilities of the LIF sensor are
directly linked to the performance characteristics of the data acquisition system and, more
importantly, illustrate the need to distinguish among a contaminant sensor’s ability to
detect, to identify and to quantify chemical compounds. Each of these capabilities
requires data of a different nature and quality, and success in achieving any of these
levels of measurement can enable valuable practical applications.

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1. It is a very compact collection system. So it can be placed in a monitoring well or
within a cone penetrometer.
2. LIF can be used for the detection of contamination both in water as well as in soil.
3. The intensity of fluorescence is a function of wavelength and time, which is
linked to the physical characteristics of an individual molecular species, provides
a powerful means to detect the contaminants.
4. It has the ability to detect the presence of a compound in solution or recognize a
change in state, relative to background conditions. So it helps in finding leaks in
landfill systems or indicates the presence of harmful agents in water.
5. Since it is possible to detect, identify and quantify the contamination, it is easy to
select the type and extent of treatment to be given.

1. It is very difficult to detect the presence of Benzene in water. Also Ethylbenzene


cannot be detected at all.
2. The entire system is costly as it has sophisticated instruments.

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This treatment is used after groundwater has been pumped out of the aquifer.
The contaminated water is passed through the organoclay and carbon unit where the
organics are adsorbed and collected. This is accomplished through the adsorption of the
chemical substance onto a carbon matrix. The effectiveness of this process is related to
the quality of the organoclay and the properties of the contaminants. This process can be
extremely effective when using a high quality organoclay such as Aqua Technologies ET-
1 Activated Clay.

Because of the health concerns


surrounding soil and
groundwater contamination from
petroleum products, there is a
high interest in researching this
area. The continual release of
petroleum products into the
subsurface environment
requires the need for monitoring
and remediation
techniques. Even though there
has been a lot of research going on
within this area the problem of
how to set up actual remediation
processes is still very complex

Direct push groundwater circulation wells (DP-GCW) are a promising


technology for remediation of groundwater contaminated with dissolved hydrocarbons
and chlorinated solvents. In these wells, groundwater is withdrawn from the formation at
the bottom of the well, aerated and vapor stripped and injected back into the formation at
or above the water table. Previous field studies have shown that: (a) GCWs can circulate
significant volumes of groundwater; and (b) GCWs can effectively remove volatile
compounds and add oxygen

In this work, we describe the development and field-testing of a


system of DP-GCWs for remediation of volatile organics such as benzene, toluene,
ethylbenzene, and toluene (BTEX). The GCWs were constructed with No. 20 slotted well
screen (2.4 cm ID) and natural sand pack extending from 1.5 to 8.2 m below grade. Air is
introduced ~ 7.5 m below grade via 0.6 cm tubing. Approximately 15% of the vertical
length of the air supply tubing is wrapped in tangled mesh polypropylene geonet drainage
fabric to provide surface area for biological growth and precipitation of oxidized iron.

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These materials were selected to allow rapid installation of the GCWs using 3.8 cm direct
push Geoprobe® rods, greatly reducing well installation costs.

Laboratory testing of these sparged wells and computational fluid


dynamics (CFD) modeling showed that these wells, although they used only about 1
L/min of air, could circulate about 1 L/min of water through the surrounding aquifer. This
flow was sufficient to capture all of a flowing contaminant if the wells are sufficiently
closely together, about 1 meter on center depending on the air flow rate supplied, in a line
across the plume. The CFD work showed the details of this ability to capture, and also
showed that unforeseen heterogeneities in the aquifer such as a gradient of permeability
or a thin impermeable layer (such as a clay layer) did not prevent the system from
working largely as intended.

The system was tested in a petroleum contaminated aquifer near


Rocky Point, NC. The contaminant plume there is approximately 10 m deep, 50 m wide
and contains up to 4 mg/L total BTEX and 75 mg/L dissolved iron. An extensive pilot test
was first performed to estimate the zone of influence for a single well. At this site an air
injection rate of 1.2 L/min resulted in a water flow rate of 1 to 2 L/min based on bromide
dilution tests in the GCW. The GCW increased the dissolved oxygen concentration in the
discharge water to between 6 and 8 mg/L and reduced contaminant concentrations to less
than 20 μg/L total BTEX. Monitoring results from a 73 day pilot test were then used to
define the zone of influence for a single DP-GCW and to design a full scale barrier
system
IN SITU
ISCO involves the delivery of chemical oxidants directly to the subsurface contamination source
zones and downgradient groundwater contamination plumes. This is commonly achieved by
either temporary injection points or permanent injection wells (see Exhibit 2). Upon direct
contact with organic contaminants, a chemical oxidation reaction occurs, which mineralizes the
contaminant compound and produces non-toxic end products such as carbon dioxide (CO2),
water, and in the case of chlorinated solvents (e.g., trichloroethene), inorganic chloride salts
(Interstate Technology Regulatory Council [ITRC] 2005). The contaminants susceptible to
chemical oxidation include total petroleum hydrocarbons (TPH)

BTEX contamination is a threat to the mankind as well as to animals and plants.


Prolonged exposure to the compounds even in small quantities is highly fatal. The reason
why the BTEX entering our soil and groundwater system, are considered such a serious

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problem is that they all have some acute and long term toxic effects. Benzene is
carcinogenic to humans. So the detection of these compounds is of utmost importance.

There are a lot of advanced methods of detection of BTEX contamination


emerging nowadays. One of the advanced techniques, detection using laser induced
fluorescence (LIF) is studied in this paper. LIF is a very compact system. This method
detects contaminants relative to a baseline or background. This method of detection is
quick compared to the other methods which are time consuming. One of the BTEX
compounds, ethylbenzene cannot be detected using this method. Since it is possible to
detect, identify and quantify the BTX contamination, it is easy to select the type and
extent of treatment to be given. Though this method is a bit costly, it provides a powerful,
accurate and reliable means to detect the contaminants in both water and soil.

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1. Aggarwal. I.D, Sleltman. C.M, “Determination of BTEX
contaminants in water via long path length fibre optic Raman dip
stick”, Sensors and Actuators B: Chemical, vol.53, 1998, pp 173-174.
2. Bloch. B, Germaine., J.T, Hemond, H.F., Johnson. B, Sinfield, J.V,
“Contaminant Detection, Identification, and Quantification Using a
Microchip Laser Fluorescence Sensor”, ASCE journal of
Environmental Engineering, vol.133, 2007, pp 346-351
3. “BTEX Contamination”, A Publication of the Hazardous Substance
Research Centres’ Technical Outreach Services for Communities
(TOSC) program, 2003, pp 1-2.

4. http://www.aquatechnologies.com/info_btex.htm
5. http://www.envirotools.org/factsheets/btex.doc
6. http://www.sciencedirect.com/science

7. http://www.wikipedia.com

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