Appendix C

Oil Concentration Analysis

Techniques
Studies are currently under way to
Introduction find a replacement solvent.
Several analytical techniques Potential candidates include
measure the amount of oil and hexane
grease in water.
cyclohexane
These techniques may be broadly
classified as either gravimetric or methylene chloride
infrared (IR) absorbance methods
perchloroethylene
and are described in detail here.
a commercial
These methods are based on the
hydrochlorofluorocarbon
extraction of oil and grease into a
(DuPont 123)
solvent. A sample may contain
suspended solids, which have to be When the gravimetric technique
filtered. is used for analysis, 1,1,1-
trichloroethane or dichloroethylene
In this case, the sample must
may also be used.
first undergo solvent
extraction followed by “Total oil and grease” is defined by
filtration of the extract. the measurement procedure
stipulated by the authorities having
Several different solvents have
jurisdiction. Important variations
been used. These include the
that could give different results for
following:
the same sample are:
petroleum ether
Number of extractions
diethyl ether performed on the water
sample. Multiple extractions
chloroform with Freon on the same water
carbon tetrachloride sample will generally give a
higher oil concentration than
Of these, petroleum ether and a single extraction.
diethyl ether are highly flammable,
whereas chloroform (although a The solvent-to-sample
very good solvent) and carbon ratio. A higher solvent-to-
tetrachloride are toxic. sample ratio will also give a
higher oil concentration.
Thus, these solvents are not
recommended for use. Currently, Determination of IR
1,1,2-trichloro, trifluoroethane absorbance at multiple
(Freon 113) is used when wavelengths. This variation
infrared (IR) absorbance is used for will give a higher oil
analysis. concentration as opposed to
absorbance measurement at
However, these solvents are being a single wavelength.
phased out because of potential
interference with the ozone layer in Use of silica gel. This
the atmosphere. variation is discussed below.

DOI: 10.1016/B978-1-85617-984-3.00005-5
212 Produced Water Treatment Field Manual

Determination concentration of dissolved oil

and grease.
of Dissolved Oil
However, measurement
and Grease techniques are strictly
specified in some countries
The dissolved oil and grease
(e.g., the United States)
content is first determined by
and left open to negotiation
measuring the total oil and grease
or operator discretion in
content and then subtracting the
others.
measured dispersed oil and grease
content.
The measured dispersed oil is
obtained by removal of the Gravimetric Method
dissolved oil and grease from the
This method is the U.S. EPA-
solvent with silica gel.
required method to measure oil and
This can be expressed by the grease in produced water for
following equation: regulatory compliance purposes in
the United States.
dissolved oil and grease ¼ total oil
and grease  dispersed oil and A detailed procedure can be
grease found in EPA 413.1. In this
method the water sample is
Dissolved organic matter is extracted with Freon 113 and
generally either polar or of low the extract evaporated to remove
molecular weight. the solvent.
To remove the dissolved organic The weight of the residue is related
matter, the solvent extract is to the concentration of oil in the
contacted (either in an adsorption water sample.
column or by intimate mixing) with
activated silica gel (e.g., Florisil) or Generally, for the same water
alumina. sample, this method gives a
lower value for oil and grease
The materials not adsorbed by the concentration than the IR
silica gel are described as absorbance method because
“dispersed” oil and grease. of the loss of volatile organics
In the absence of silica gel, filtration during the evaporation process.
can be used to remove the dispersed
oil and grease.
In this technique the filtrate, Advantages
obtained after passing through a
Stipulated by the EPA as the
0.45-m filter paper, is left behind on
technique to be used to measure oil
the filter paper.
in produced water discharge for
The U.S. EPA uses the term regulatory purposes.
“petroleum hydrocarbons” for
Method is simple and well
dispersed oil and grease.
understood.
The choice of measuring total oil
and grease versus dispersed oil and
grease is important from an Disadvantages
operational standpoint because
conventional water treating Requires samples be collected and
technology can reduce the preserved according to EPA
concentration of dispersed oil protocol for shipment to an onshore
and grease, but not the laboratory.
 Appendix C: Oil Concentration Analysis Techniques 213

Is time-consuming. Analysis of Variance

Uses Freon (a CFC) as a solvent. of Analytical Results
Lower limit of measurement is In 1975, the U.S. EPA had a set of
5 mg/l. six different samples analyzed by
Not applicable to light a number of laboratories using
hydrocarbons that volatilize both the gravimetric and IR
below 70 C. methods.
Scatter in reported analysis included
sampling errors as well as analytical
Infrared (IR) errors.

Absorbance The true values were taken to be the

average of the reported values
Method (excluding those of extreme scatter)
and are as follows:
For infrared absorbance methods
(e.g., EPA 413.2 and EPA 418.1), (Note: Error is defined as the
the water sample is extracted difference of an observation from
with Freon 113. the best obtainable estimate of the
true value, which in this case is the
The IR absorbance of the extract is
arithmetic mean.)
measured at single, or multiple,
wavelength(s) to give the oil It is interesting to note that the
concentration. gravimetric value is lower than
the infrared value of each of the
In this method, the water sample is
samples.
often acidified to prevent any salts
from precipitating out (e.g., iron This is expected since the solvent
sulfide). evaporation step in the gravimetric
process causes some loss of volatile
IR absorbance at multiple
organics, leading to lower results
wavelengths results in a higher
than the IR method. Errors ranged
oil concentration measurement
from 0 to 241%.
than if a single wavelength was
used. The worst laboratory had errors
between 49% and 98%, whereas
the best laboratory had errors up
Advantages to 8%.

Fast and convenient for offshore

surveillance.
Particle Size Analysis
The lower limit of measurement
is 0.2 mg/l. The oil droplet size distribution is
one of the key parameters
influencing water treating
Disadvantages equipment selection.
Therefore, accurate measurement
Uses Freon (a CFC).
of the oil droplet size distribution is
The lower limit is 0.2 mg/l. an important task.

Sample 1 2 3 4 5 6
Gravimetric 201.7 209.3 95.5 77.6 33.7 19.1
Infrared 261.3 265.4 131.0 110.0 50.7 23.0
214 Produced Water Treatment Field Manual

Another important parameter is electrode through the

quantifying the size distribution orifice.
upstream and downstream of
When a nonconductive
production equipment, such as
particle passes through
control valves.
the orifice, a change in
Oil and other particles in produced electrical resistance
water range in size from less occurs between the
than 1 m up to several hundred two electrodes, which
microns. is proportional to the
particle volume.
Although many particles found in
produced water are not spherical, A fixed volume of water
for practical purposes, the particles containing suspended
are represented by equivalent particles is forced
spheres. through the orifice.
As each particle passes
through the orifice, the
increased resistance
Droplet Size results in a voltage that
Measurement is proportional to the
particle volume.
Equipment
The series of pulses
Three different types of equipment produced by a series of
are commonly used for droplet size particles passing
measurement. through the orifice are
electronically scaled and
Each has its advantages and
counted, yielding a
disadvantages. First, establish the
particle size distribution.
information desired before selecting
the equipment type: One must realize that
the particle “diameter”
1. Coulter counter. The
given by the counter is
Coulter counter
the diameter of a
consists of two
fictitious equivalent
electrodes immersed in
sphere with the same
a beaker of sample
volume as the real
water, which contains a
particle.
sufficient number of
dissolved ions to easily This equipment has
conduct an electrical some limitations
current. because the size range
is limited. In addition,
The negative electrode
the samples have to be
is located inside a glass
suspended in an
tube, which is sealed
electrolyte solution,
except for a tiny hole or
which can prove
orifice on the side of the
difficult if the sample is
tube.
totally soluble in the
The positive electrode is solution.
located in the water
However, the Coulter
sample beaker.
counter does provide
A constant electrical both frequency and
current is passed from volume distributions
the positive electrode against volumetric
to the negative particle size.
 Appendix C: Oil Concentration Analysis Techniques 215

2. Light (laser) percent of total particle

scattering counters. volume within a given
These include size range).
instruments that are
3. Microscopy. In this
based on the principle
technique, the droplet
of light absorption/total
size distribution is
scatter, or light
determined by
blockage, to detect
observing the water
particles in a fluid.
sample under a
Water flows through a microscope and visually
sensor cell, and as each measuring the size of
particle passes through the droplets.
the intense beam of
Often a magnified
light in the sensor, light
photograph is also
is scattered.
used for visual
The instrument determination.
measures the
This technique has the
magnitude of each
advantage of being
scattered light pulse,
able to distinguish
which is proportional to
between oil droplets
the surface area of the
and non-oil particles.
particle.
A microscope also helps
The particle diameter
to see first hand if there
determined by the
are any extreme shape
instrument in this case
factors.
is the diameter of a
sphere with the same However, the
surface area as the technique generally
particle. uses a very small
sample volume and
Laser diffraction
therefore may not
systems are widely
be representative.
accepted due to their
ease of use, wide size
range, and simple
sample preparation. References
However, as an optical
Kawahara, F.K (1991). A study to select
technique, it is still
a suitable replacement solvent
subject to variations in
for Freon 113 in the gravimetric
response from particle
determination of oil and grease.
shape and refractive
EPA (2 October).
index and is unable
Patton, C.C (1986). Water sampling and
to give frequency
analysis. Applied Water Technol-
information (that is, the
ogy. Campbell Petroleum Series,
number of particles
Norman, OK.
within a given size
Particle sizing: Past and present. Parti-
range).
cle Sizing Review, Filtration and
However, these Separation Journal, (July/August).
techniques can provide API RP 45. (1981). Recommended prac-
relative frequency tice for analysis of oil-field waters.
information (that is, Washington, DC: API.